LOW DENSITY POLYOLEFIN RESINS AND FILMS MADE FROM THEM

专利摘要:
Low density polyolefin resins and films made therefrom disclosed herein are broad molecular weight distribution olefin polymers having densities in the range of 0.895 to 0.930 g/cm3 and with increased impact and tear resistance. these polymers can have a mw/mn ratio in the range of 8 to 35, a high charge melt index in the range of 4 to 50, less than approximately 0.008 lb per 1000 total carbon atoms, and a reverse comonomer distribution.
公开号:BR112015010241B1
申请号:R112015010241-7
申请日:2013-11-06
公开日:2021-07-20
发明作者:Max P. Mcdaniel；Qing Yang；Guylaine St Jean；Albert P. Masino；Ashish M. Sukhadia；Errun Ding；Chung Ching Tso；Lloyd W. Guatney；Daniel G. Hert
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDER
[0001] This order claims the benefit of U.S. Provisional Order No. Series 61/723,335, filed November 7, 2012, the disclosure of which is incorporated herein by reference in its entirety. FUNDAMENTALS OF THE INVENTION
[0002] The linear polyethylene film market is mainly composed of two main types of film resins: linear low density polyethylene (LLDPE) and high molecular weight high density polyethylene (HMWPE). LLDPE grades typically have a density of 0.913 to 0.928 g/cm3 and a narrow molecular weight distribution. Most of these resins are made with Ziegler catalysts, which often yield a polydispersity (Mw/Mn) of 3.5 to 5. However, a smaller segment of this group is made with Metallocene catalysts, which typically produce a polydispersity of 2 to 4. Since polymers with a narrow molecular weight distribution have poor melt strength and are more difficult to extrude, LLDPE film resins generally have a relatively high melt index, such as from 0.8 to 3 g/ 10 min, and are blown into films about 1 mm thick with a large mold gap, close to zero size freezing line height (also called "in the pocket") and a low burst ratio. These conditions are generally referred to as "Low Density Conditions" or "LLDPE Conditions."
[0003] In contrast, HMWPE grades have a high density, typically from 0.948 to 0.955 g/cm3 and a wide molecular weight distribution, which allows easy processing at very high molecular weight. The molten polymer has excellent melt strength, and the high molecular weight results in improved physical properties, including wear resistance and hardness. Typically, these polymers have a High Charge Melt Index (HLMI) of 5 to 15 g/10 min and a polydispersity greater than 20. The wide molecular weight distribution and high molecular weight mean these films have greater melt strength and can be blown more easily, and line conditions known as "high density conditions" are often chosen, which are quite different from the "low density conditions" described above. Generally, the mold gap is smaller, the burst ratio is larger, and the height of the freezing line is quite high, producing a large expanded bubble during the film blowing process.
[0004] HMWPE film classes generally have a bimodal molecular weight distribution. Typically, a Ziegler catalyst is passed through two reaction zones to produce two narrow molecular weight distribution components, one of higher molecular weight and the other of lower molecular weight. When branching is concentrated on the higher molecular weight component, film strength is generally improved. Thus, these polymers tend to have most of the branching in the long chains. In contrast, LLDPE film grades tend to have more branching (or at least an equal amount) in the lower molecular weight portion of the molecular weight distribution.
[0005] The high density of HMWPE films means that they often have greater modulus strength and yield than LLDPE films. In this sense, HMWPE films may be much less likely to sag and stretch when loaded, such as when formed into a plastic bag. However, the higher molecular weight and different blowing conditions tend to introduce more orientation into HMWPE films compared to LLDPE films. Superior orientation can produce unbalanced tear strength. That is, the tear strength in the transverse direction (TD) is much higher than in LLDPE films, while the tear strength in the machine direction (MD) is generally much worse. This can be an advantage or a disadvantage, depending on the final application. Although the higher molecular weight of HMWPE resins tends to increase puncture resistance, the higher density tends to decrease it. Thus, puncture resistance can sometimes be comparable to LLDPE, although this depends on the choice of samples to be compared.
[0006] In summary, it would be beneficial to produce LLDPE polymers with the broad molecular weight distribution and higher molecular weight normally associated with HMWPE film resins, but with densities (eg, 0.910-0.926 g/cm3) normally associated with film resins. LLDPE film. Therefore, it is to these purposes that the present invention is directed. SUMMARY OF THE INVENTION
[0007] This summary is provided to present a selection of concepts in a simplified form which are described further below in the detailed description. This summary is not intended to identify necessary or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the matter claimed.a. The present invention generally relates to novel catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, polymer resins produced using such catalyst compositions, and articles produced using these catalyst resins. polymer. In particular, aspects of the present invention are directed to catalyst compositions employing two catalyst components. The first catalyst component may include a bridged single-atom metallocene compound with an alkenyl substituent, while the second catalyst component may include an unbridged hafnium- or zirconium-based metallocene compound, or a zirconium-based metallocene compound of two bridged carbons containing two indenyl groups. Such catalyst compositions can be used to produce, for example, ethylene-based copolymers having large molecular weight distributions and low densities.b. In one aspect, a catalyst composition is disclosed which may include catalyst component I which comprises a bridged single atom metallocene compound with an alkenyl substituent; catalyst component II comprising an unbridged hafnium- or zirconium-based metallocene compound, or a bridged two-carbon zirconium-based metallocene compound that contains two indenyl groups; and a support-activator. Optionally, such catalyst composition may further comprise a co-catalyst.
[0008] The present invention also contemplates and encompasses olefin polymerization processes. Such processes may comprise contacting a catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce an olefin polymer. Generally, the catalyst composition employed can encompass any of the single atom bridged metallocene compounds of catalyst component I, any of the metallocene compounds of catalyst component II, and any of the optional activator-supports and co-catalysts disclosed herein. For example, orgonealuminum compounds can be used in catalyst compositions and/or polymerization processes.
[0009] Polymers produced from the polymerization of olefins, resulting in homopolymers, copolymers, terpolymers etc., can be used to produce various articles of manufacture. A representative, non-limiting example of an olefin polymer (e.g., an ethylene copolymer) consistent with aspects of this invention may include a higher molecular weight component and a lower molecular weight component, and this olefin polymer may have a density of less than about 0.930 g/cm 3, a ratio of Mw/Mn in a range of about 6 to about 50, an HLMI in a range of about 4 to about 50 g/10 min and less than approximately 0.008 LCB per 1000 total carbon atoms (less than about 8 LCB per 1,000,000 total carbon atoms). Another representative and non-limiting example of an olefin polymer (e.g., an ethylene copolymer) consistent with aspects of this invention may include a higher molecular weight component and a lower molecular weight component, and this olefin polymer may have a density in a range of about 0.895 to about 0.930 g/cm 3, a ratio of Mw/Mn in a range of about 8 to about 35, an HLMI in a range of about 4 to about 50 g/10 min, less than approximately 0.008 LCB per 1000 total carbon atoms and a reverse comonomer distribution.
[0010] Both precede the summary and the detailed description below provide examples and are explanatory only. In this sense, the above summary and the following detailed description should not be considered as restrictive. Additionally, features or variations may be provided in addition to those set forth herein. For example, some aspects and modalities can be directed to various feature combinations and sub combinations described in the detailed description. BRIEF DESCRIPTION OF THE FIGURES
The. Fig. 1 presents a graphical representation of the expected molecular weight distribution and short chain branching distribution of the polymer of constructive example 2.b. Fig. 2 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer from example 9. e. Fig. 3 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer of example 10.f. Fig. 4 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer of example 11.g. Fig. 5 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer from example 12.h. Fig. 6 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer of example 13.i. Fig. 7 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer of example 14.j. Fig. 8 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer of example 15.k. Fig. 9 presents a graphical representation of the molecular weight distribution and short chain branching distribution of the polymer of example 16. DEFINITIONS
[0011] To more clearly define the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in the disclosure but is not specifically defined herein, the definition of the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) may apply, provided that definition does not conflict with any other type of disclosure or definition applied in this document, or sue indefinitely or unqualified for any claim to have this definition applied. To the extent that any definition or use provided by any document incorporated herein by reference conflicts with definition or use of controls provided in this document.
[0012] Regarding the claim transitional terms or phrases, the transitional term "comprising", which is synonymous with "including", "containing", "having", or "characterized by," is inclusive or open and does not exclude the additional , unrecited elements or method steps. The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consisting essentially of" limits the scope of a claim to the specified components or steps and those that do not materially affect the basic and novel feature(s) of the claimed invention. A claim "consisting essentially of" occupies a middle ground between closed claims that are written in an "consisting of" format and fully open claims that are elaborated in an "comprising" format. For example, a raw material consisting essentially of component A may include impurities typically present in a commercially produced or commercially available sample of component A. When a claim includes different characteristics and/or resource classes (eg a method step , raw material characteristics and/or product characteristics, among other possibilities), the transitional terms comprising, essentially consisting of, and consisting of, apply only to the resource class for which they are used and it is possible to have different terms transients or phrases used with different characteristics within a claim. For example, a method can consist of certain steps, but use a catalyst system that comprises recited components and other non-recited components. While compositions and methods are described herein in terms of "comprising" various components or steps, compositions and methods may also "consist essentially of" or "consist of" the various components or steps, unless otherwise indicated. For example, a catalyst composition consistent with aspects of the present invention may comprise; alternatively, it can consist essentially; or alternatively, it may consist of; (i) a catalyst compound I (ii) a catalyst component II, (iii) an activator and (iv) optionally a co-catalyst.1. The terms "a", "an", "a", etc. are intended to include plural alternatives, for example, at least one, unless otherwise specified. For example, the disclosure of "an activator-support" or "a metallocene compound" is intended to encompass one or mixtures or combinations of more than one activator-support or metallocene compound, respectively, unless otherwise specified. form.
[0013] Groups of elements are indicated using the numbering scheme indicated in the version of the periodic table of elements, published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements may be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.
[0014] For any particular compound or group disclosed herein, the name or general structure shown is also intended to encompass all structural isomers, conformation isomers and stereoisomers that may arise from a particular set of substituents, unless specified otherwise. Thus, a general reference to a compound includes all structural isomers, unless expressly indicated otherwise; for example, a general reference to pentane includes n-pentane, 2-methyl-butane and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-butyl group, a group of iso-butyl and a tert-butyl group. In addition, reference to a name or general structure encompasses all enantiomers, diastereoisomers and other optical isomers, whether in racemic or enantiomeric form, as well as mixtures of stereoisomers, as the context permits or requires. For any given formula or name that is shown, any general formula or name shown also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a given set of substituents.
[0015] A chemical "group" is described according to how that group is formally derived from a reference or "parent" compound, for example, by the number of hydrogen atoms formally removed from the parent compound to generate the group, even that this group is not literally synthesized in this way. These groups can be used as substituents or coordinated or attached to metal atoms. By way of example, an "alkyl group" can formally be derived by removing one hydrogen atom from an alkane, while an "alkylene group" can formally be derived by removing two hydrogen atoms from an alkane. In addition, a more general term can be used to encompass a variety of groups that are formally obtained by removing any number ("one or more") of hydrogen atoms from the parent compound, which in this example can be described as a "alkane group", and which encompasses an "alkyl group," an "alkylene group", and the materials have three or more hydrogen atoms, as needed for the situation, taken from the alkane. The disclosure that a substituent, linker, or other chemical moiety may constitute a particular "group" implies that well-known rules of chemical structure and bonding are followed when that group is employed as described. When describing a group as being "derived by", "derived from", "formed by", or "formed from", such terms are used in a formal sense and are not intended to reflect any specific synthetic methods or procedure , unless otherwise specified or the context requires otherwise.
[0016] The term "substituted" when used to describe a group, for example when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group and is intended to not be limiting. A group or groups may also be referred to herein as "substituted" or by equivalent terms such as "unsubstituted" which refer to the original group, in which a non-hydrogen moiety does not replace a hydrogen within that group. Unless otherwise specified, "substituted" is intended to be non-limiting and includes inorganic or organic substituents as understood by those skilled in the art.
[0017] The term "hydrocarbon" whenever used in this specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers can be used to indicate the presence of particular groups in hydrocarbon (eg, halogenated hydrocarbons which indicate the presence of one or more halogen atoms, replacing an equivalent number of hydrogen atoms in hydrocarbon). The term "hydrocarbyl group" is used herein in accordance with the definition specified by the IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon (ie, a group containing only carbon and hydrogen). Examples of non-limiting hydrocarbyl groups include ethyl, phenyl, tolyl, propenyl and the like. Likewise, a "hydrocarbylene" group refers to a group formed by removing two hydrogen atoms from a hydrocarbon, or two hydrogen atoms from one carbon atom, or one atom from each of two different carbon atoms. Therefore, in accordance with terminology used in this document, a "hydrocarbon group" refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group) from a hydrocarbon. A "hydrocarbyl" group, "hydrocarbylene group" and "hydrocarbon group" may be aliphatic or aromatic, cyclic or acyclic, and/or may be linear or branched. A "hydrocarbyl group", "hydrocarbylene group" and "hydrocarbon group" can include rings, ring systems, aromatic rings and aromatic ring systems, which contain only carbon and hydrogen. "Hydrocarbyl groups", "hydrocarbylene groups" and "hydrocarbon groups" include, by way of example, aryl, arylene, arene groups, alkyl, alkylene, alkane groups, cycloalkyl, cycloalkylene, cycloalkane groups, aralkyl, aralkylene and aralkane groups, respectively, among other groups as members.
[0018] An aliphatic compound is a class of acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds, for example, an aliphatic compound is a non-aromatic organic compound. An "aliphatic group" is a generalized group formed by removing one or more hydrogen atoms (as necessary for the specific group) from carbon atoms from an aliphatic compound. Aliphatic compounds and therefore aliphatic groups may contain organic functional group(s) and/or atom(s) other than carbon and hydrogen, unless otherwise specified (eg an aliphatic hydrocarbon).
[0019] The term "alkanes" whenever used in this specification and claims refers to a saturated hydrocarbon compound. Other identifiers can be used to indicate the presence of particular groups in the alkane (for example, the halogenated alkane which indicates the presence of one or more halogen atoms, replacing an equivalent number of hydrogen atoms in the alkane). The term "alkyl group" is used herein in accordance with the definition specified by the IUPAC: a univalent group formed by removing a hydrogen atom from an alkane. Likewise, an "alkylene group" refers to a group formed by removing two hydrogen atoms from an alkane (two hydrogen atoms from one carbon atom) or one atom from two different carbon atoms. An "alkane group" is a general term that refers to a group formed by the removal of one or more hydrogen atoms (as necessary for the particular group) from an alkane. An "alkyl group", "alkylene group" and "alkane group" may be cyclic or acyclic, and/or may be linear or branched, unless otherwise specified. Primary, secondary and tertiary alkyl groups are derived by removing a hydrogen atom from a primary, secondary and tertiary carbon atom, respectively, of an alkane. The n-alkyl group can be derived by removing a hydrogen atom from a terminal carbon atom of a linear alkane. The groups RCH2 (R Φ H), R2CH (R Φ H), and R3C (R Φ H) are primary, secondary, and tertiary alkyl groups, respectively.
[0020] A cycloalkane is a saturated cyclic hydrocarbon, with or without side chains, eg cyclobutane. Other identifiers can be used to indicate the presence of particular groups in the cycloalkane (for example, the halogenated cycloalkane which indicates the presence of one or more halogen atoms, replacing an equivalent number of hydrogen atoms in the cycloalkane). Unsaturated cyclic hydrocarbons having a triple endocyclic triple bond or a triple bond are called cycloalkenes and cycloalkynes, respectively. Those that have more than one such multiple bond are cycloalkadienes, cycloalkatrienes, and so on. Other identifiers can be used to indicate the presence of particular groups in cycloalkenes, cycloalkadienes, cycloalkatrienes, and so on.
[0021] A "cycloalkyl group" is a univalent group derived by removing a hydrogen atom from a ring carbon atom of a cycloalkane. For example, a 1-methylcyclopropyl group and a 2-methylcyclopropyl group are illustrated as follows:

[0022] Similarly, a "cycloalkylene group" refers to a group derived by removing two hydrogen atoms from a cycloalkane, at least one of which is a carbon ring. Thus, a "cycloalkylene group" includes a group derived from a cycloalkane in which two hydrogen atoms are formally removed from the same carbon ring, a group derived from a cycloalkane in which two hydrogen atoms are formally removed from two different carbon rings, and a group derived from a cycloalkane in which a first hydrogen atom is formally removed from a ring carbon and a second hydrogen atom is formally removed from a carbon atom that is not a ring carbon. A "cycloalkane group" refers to a generalized group formed by removing one or more hydrogen atoms (as necessary for the particular group and at least one of which is a ring carbon) from a cycloalkane.
[0023] The term "alkene" whenever used in this specification and claims refers to a linear or branched hydrocarbon olefin that has a carbon-carbon double bond and the general formula cnH2n. Alkadienes refer to a linear or branched hydrocarbon olefin having two carbon-carbon double bonds and the general formula cnH2n-2 and alkatrienes refer to linear or branched hydrocarbon olefins having three carbon-carbons and the general formula cnH2n-4. Alkenes, alkadienes and alkatrienes can also be further identified by the position of the carbon-carbon double bond. Other identifiers can be used to indicate the presence or absence of certain groups within an alkene, alkadiene or alkatriene. For example, a haloalkene refers to an alkene having one or more hydrogen atoms replaced with a halogen atom.
[0024] An "alkenyl group" is a univalent group, derived from an alkene by removing a hydrogen atom from any carbon atom of the alkene. Thus, the "alkene group" includes groups in which the hydrogen atom is formally removed from an sp2 hybridized (olefinic) carbon atom and groups in which the hydrogen atom is formally removed from any other carbon atom. For example and unless otherwise specified, 1-propenyl (-CH = CHCH3), 2-propenyl [(CH3)C=CH2], and 3-propenyl (-CH2CH=CH2) groups are all encompassed with the term "alkenyl group." Likewise, an "alkylene group" refers to a group formed by formally removing two hydrogen atoms from an alkene, either two hydrogen atoms from one carbon atom or an atom from two different carbon atoms. An "alkene group" refers to a generalized group formed by removing one or more hydrogen atoms (as needed for the special group) from an alkene. When the hydrogen atom is removed from a carbon atom participating in a carbon-carbon double bond, the regiochemistry of the carbon than the hydrogen atom is removed and the regiochemistry of the carbon-carbon double bond can be specified. Other identifiers can be used to indicate the presence or absence of certain groups within an alkene group. Alkene groups can also be identified further by the position of the carbon-carbon double bond.
[0025] An arene is an aromatic hydrocarbon, with or without side chains (eg, benzene, toluene or xylene, among others). An "aryl group" is a group derived from the formal removal of a hydrogen atom from an aromatic ring carbon in an arene. Note that arene may contain a single aromatic hydrocarbon ring (eg benzene or toluene), contain fused aromatic rings (eg naphthalene or anthracene) and contain one or more isolated aromatic rings covalently linked through a linkage (eg biphenyl) or non-aromatic hydrocarbon groups (eg diphenylmethane). An example of an "aryl group" is ortho-tolyl (o-tolyl), the structure of which is shown here.

[0026] An "aralkyl group" is an aryl-substituted alkyl group having a free valence on a non-aromatic carbon atom, for example, a benzyl group or a 2-phenyleth-1-yl group among others.
[0027] A "halide" has its usual meaning. Examples of halides include fluoride, chloride, bromide and iodide.
[0028] The term "polymer" is used generically herein to include olefin homopolymers, copolymers, terpolymers, and so on. A copolymer is derived from one olefin monomer and one olefin comonomer, while a terpolymer is derived from one olefin monomer and two olefin comonomers. In this sense, "polymer" encompasses copolymers, terpolymers, etc., derived from any olefin monomer and comonomer(s) disclosed in this document. Likewise, an ethylene polymer would include ethylene homopolymers, ethylene copolymers, ethylene terpolymers and the like. For example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene or 1-octene. If ethylene and 1-hexene monomer and comonomer, respectively, the resulting polymer can be categorized as ethylene/1-hexene copolymer.
[0029] Likewise, the scope of the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. Therefore, a copolymerization process could involve contacting an olefin monomer (eg, ethylene) and an olefin comonomer (eg, 1-hexene) to produce an olefin copolymer.
[0030] The term "co-catalyst" is used generally in this document to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminium compounds, organozinc compounds, organomagnesium compounds, organolithium compounds and the like, which may constitute a component of a catalyst composition when used, for example, in conjunction with an activator-support. The term "co-catalyst" is used regardless of the compound's function or any chemical mechanism by which the compound may operate.
The terms "chemically treated solid oxide," "treated solid oxide compound" and the like are used herein to indicate a solid oxide, relatively high porosity inorganic oxide, which may exhibit Lewis acid or Br0nsted acid behavior , and which has been treated with an electron withdrawing component, typically an anion, and which is calcined. The electron withdrawing component is typically a composite of the electron withdrawing anion source. Thus, the chemically treated solid oxide can include a calcined contact product of at least one solid oxide and at least one electron withdrawing anion source compound. Typically, the chemically treated solid oxide comprises at least one acidic solid oxide compound. The "activator-support" of the present invention may be a chemically treated solid oxide. The terms "support" and "support-activator" are not used to refer to these components as they are inert, and such components should not be interpreted as an inert component of the catalyst composition. The term "activator", as used herein, generally refers to a substance that is capable of converting a metallocene component into a catalyst that can polymerize olefins, or convert a contact product of a metallocene compound and a component that provides a binder activatable (eg an alkyl, a hydride) to the metallocene, when the metallocene compound no longer comprises such a binder, in a catalyst that can polymerize olefins. This term is used regardless of the actual activation mechanism. Illustrative activators include support-activators, aluminoxanes, organoboron or organoborate compounds, ionic ionizing compounds, and the like. Aluminoxanes, organoboron or organoborate compounds, and ionic ionizing compounds are generally referred to as activators if used in a catalyst composition in which an activator-support is not present. If the catalyst composition contains an activator-support, then aluminoxane, organoboron or organoborate and ionic ionizing materials are generally referred to as co-catalysts.
[0032] The term "fluoroorganic boron compound" is used in this document with its common meaning to refer to neutral compounds of the form BY3. The term "fluoroorganic boron compound" also has its usual meaning to refer to monoanionic salts of a fluoroorganic boron compound of the form [cation]+[BY4]-, where Y represents a fluorinated organic group. Materials of these types are generally and collectively referred to as "organoboron or organoborate compounds."
In this document, the term "metallocene" describes compounds comprising at least an n3 to n5-type-cycloalkadienyl moiety, wherein n3 to n5-icloalkadienyl moieties include cyclopentadienyl binders, indenyl binders, fluorenyl binders and the like, including partially saturated or substituted derivatives or analogues of any of these. Possible substituents on these linkers may include hydrogen, therefore this invention encompasses linkers such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially saturated substituted indenyl, partially saturated substituted fluorenyl, and the like. In some contexts, metallocene is referred to simply as "catalyst", much in the same way that the term "co-catalyst" is used herein to refer, for example, to an organoaluminium compound.
[0034] The terms "catalyst composition", "catalyst mixture", "catalyst system" and the like do not depend on the actual product or composition resulting from the contact or reaction of the initial components of the claimed composition/mixture/catalyst system, to nature of the catalytic active site, or the fate of the co-catalyst, the metallocene compound(s), any olefin monomer used to prepare a pre-contacted mixture, or the activator (eg support-activator) after combining these components. Therefore, the terms "catalyst composition", "catalyst mixture", "catalyst system" and the like encompass the initial starting components of the composition, as well as any product(s) that may be the result of contact with these components of initial start-up, and this is inclusive of both heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition", "catalyst mixture", "catalyst system" and the like are used interchangeably throughout this disclosure.a. The term "contact product" is used here to describe compositions in which the components are contacted together in any order, in any manner and for any length of time. For example, components can be contacted by blending or mixing. Furthermore, coming into contact with some component may occur in the presence or absence of any other component of the compositions described herein. Combining additional materials or components can be done by any suitable method. In addition, the term "contact product" includes mixtures, combinations, solutions, slurries, reaction products, and the like, or combinations thereof. Although the "contact product" may include reaction products, it is not required for the respective components to react with each other. Likewise, the term "contacting" is used in this document to refer to materials that may be combined, mixed, suspended, dissolved, reacted, treated or otherwise contacted in any other way. m. The term "pre-contacted" mixture is used herein to describe a first mixture of catalyst components that are contacted for a first period of time prior to the first mixture being used to form a "post-contacted" mixture or second mixture of the catalyst component. catalyst that are contacted for a second period of time. Typically, the pre-contacted mixture can describe a mixture of the metallocene compound (one or more than one), olefin monomer (or monomers) and organoaluminium (or more compounds), before this mixture is contacted with a support-activator and compound of optional additional organoaluminium. Thus, pre-contacted describes the components that are used to contact each other, but before contacting the second components in the post-contacted mixture. Therefore, this invention can occasionally distinguish between a component used to prepare the pre-contacted mix and that component after the mix has been prepared. For example, according to this description, it is possible for the pre-contacted organoaluminium compound, as it is contacted with the metallocene compound and the olefin monomer, which have reacted to form at least one different chemical compound, formulation or structure of the distinct organoaluminium compound used to prepare the pre-contacted mix. In this case, the pre-contacted organoaluminium compound or component is described as comprising an organoaluminium compound which was used to prepare the pre-contacted mixture.n. In addition, the pre-contacted mixture may describe a mixture of the metallocene compound(s) and organoaluminium compound(s), prior to contacting this mixture with a support-activator(s). This pre-contacted mixture may also describe a mixture of the metallocene compound, olefin monomer(s) and support-activator(s), before this mixture is contacted with an organoaluminium co-catalyst compound or compounds.
[0035] Likewise, the term "post-contacted" mixture is used here to describe a second mixture of catalyst components that are contacted for a second period of time, and a constituent of which is the "pre-contacted" or first mixture of catalyst components that have been contacted for a first period of time. Typically, the term "post-contacted" mixture is used herein to describe the mixture of the metallocene compound(s), olefin monomer(s), organoaluminium compound(s), and activator-support formed to contact the pre-contacted mixture of a portion of these components with any additional components added to make the mixture post-contacted. Often, the activator support can include a chemically treated solid oxide. For example, the additional component added to make up for the post-contacted mixture may be a chemically treated solid oxide (one or more than one) and optionally may include an organoaluminium compound that is the same as or different from the organoaluminium compound used to prepare the premixture. -contacted, as described in this document. Therefore, this invention may also occasionally distinguish between a component used to prepare the post-contacted mixture and that component after the mixture has been prepared.
[0036] Although any methods, devices, and materials similar or equivalent to those described herein may be used in practicing or testing the invention, typical methods, devices, and materials are described herein.
[0037] All publications and patents mentioned in this document are incorporated into the addendum by reference for the purpose of describing, and disclosing, for example, the constructions and methodologies described in the publications, which may be used in connection with the invention currently described. The publications discussed throughout the text are provided solely for your dissemination prior to the filing date of the present application. Nothing in this document is to be construed as an admission that inventors are not authorized to predate such disclosure by virtue of the prior invention.
[0038] Applicants disclose various types of scales in the present invention. When applicants disclose or claim a range of any kind, applicants' intent is to individually disclose or claim every possible number that a range could so reasonably cover, including range endpoints as well as any subranges and combinations of subranges covered therein. For example, when applicants disclose or claim a chemical part having a certain number of carbon atoms, applicants' intent is to individually disclose or claim each possible number that could span a range as consistent with the disclosure herein. For example, the disclosure that a moiety is a C1 to C18 hydrocarbyl group, or in alternative language a hydrocarbyl group having 1 to 18 carbon atoms, as used herein, refers to a moiety that can be independently selected from a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any interval therein two numbers (for example, a C1 to C8 hydrocarbyl group) and also including any combination of intervals between these two numbers (for example, a C2 to C4 hydrocarbyl group and a C12 to C16 hydrocarbyl group).
[0039] Likewise, another representative example follows for the number average molecular weight (Mn) of an olefin polymer produced in one aspect of this invention. By a disclosure that Mn can be in a range of about 8,000 to about 25,000 g/mol, applicants intend to recite that Mn can be equal to 8,000, about 9,000, about 10,000, about 11,000, about 12 thousand, about 13,000, about 14,000, about 15,000, about 16,000, about 17,000, about 18,000, about 19,000, about 20,000, about 21,000, about 22,000, about 23,000, about 24,000, or approximately 25,000 g/mol. In addition, Mn can fall within any range from about 8,000 to about 25,000 (for example, from about 10,000 to about 22,000), and this also includes any combination of ranges between about 8,000 and about 25,000 (For example, Mn can range from about 8,000 to about 10,000, or about 15,000 to about 25,000). Likewise, all other ranges disclosed in this document should be interpreted in a similar way to these two examples.
[0040] Applicants reserve the right to disclaim or exclude any individual members of any group, including any sub-range or combinations of sub-ranges within the group, which may be claimed according to a range or similar, if for any reason the applicant chooses to claim less than the full extent of disclosure, for example, to take into account a reference that applicants may not be aware of at the time of filing the application. Furthermore, Applicants reserve the right to disclaim or exclude any individual substituents, analogues, compounds, linkers, structures, or groups thereof or all members of a claimed group, if for any reason Applicant chooses to claim less than that the full extent of disclosure, for example, to take into account a reference that applicants may not be aware of at the time of filing the application. DETAILED DESCRIPTION OF THE INVENTION
[0041] The present invention is generally directed to novel catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, the present invention relates to dual component catalyst compositions, polymerization processes utilizing such catalyst compositions, and resulting low density olefin polymer and film articles.
[0042] An object of the present invention is to produce a bimodal high molecular weight polymer as an HMWPE film grade, but having a low density as an LLDPE film grade, thus achieving the best attributes of the two types of film grades. The result would be a polymer with beneficial processability and improved physical properties such as tear and impact resistance.
Slurry reactors can produce bimodal HMWPE polymers, but lower density polymers often present difficulties due to polymer swelling and/or partial dissolution, often leading to fouling. In the case of bimodal polymers, however, these issues can become more problematic because one of the polymer components can be made at a much lower density than the other component to achieve a final polymer density of, for example, less. of 0.920 g/cm3.
[0044] The use of two distinct metallocene compounds can overcome these problems. A metallocene compound can be selected to produce a generally higher molecular weight component, and this metallocene compound can be a single-atom bridged metallocene compound and, in addition, can be an efficient comonomer incorporating. The other metallocene compound can be a bridged two-atom metallocene compound or unbridged metallocene compound which is more sensitive to hydrogen, produces the generally lower molecular weight component, and this compound may incorporate the comonomer less efficiently than the bridged single-atom metallocene compound, although this is not a requirement. CATALYST COMPONENT I
The catalyst component I may include a metallocene compound bridged with an alkenyl substituent and more particularly a metallocene compound based on titanium, hafnium or zirconium with a single atom bridged with an alkenyl substituent. In one aspect, for example, catalyst component I may include a zirconium-based metallocene compound with a single atom bridged with a cyclopentadienyl group and a fluorenyl group and with an alkenyl substituent of the bridged group and/or the group cyclopentadienyl. In another aspect, catalyst component I may include a hafnium-based metallocene compound with a single atom bridged with a cyclopentadienyl group and a fluorenyl group and with an alkenyl substituent on the bridged group and/or on the cyclopentadienyl group. In another aspect, catalyst component I may include a single atom bridged metallocene compound with an aryl group substituent on the bridged group. In yet another aspect of this invention, catalyst component I may include a bridged metallocene compound having the formula (A):

[0046] Within formula (A), M2, CpC, E2, RX, RY, and each X are independent elements of the bridged metallocene compound. In that sense, the bridged metallocene compound having formula (A) can be described using any combination of M2, CpC, E2, RX, RY, and X disclosed herein.
[0047] Unless otherwise specified, formula (A) above, any other structural formulas disclosed herein and any metallocene complex, compound, or species disclosed herein are not designed to show stereochemical or isomeric positioning of the parts different (for example, these formulas are not intended to exhibit cis or trans isomers or R or S diastereoisomers), although such compounds are contemplated and encompassed by such formulas and/or structures.
[0048] In accordance with aspects of this invention, the metal in formula (A), M2, may be Ti, Zr or Hf. In one aspect, for example, M2 might be Zr, while in another aspect, M2 might be Hf.
[0049] Each X in formula (A) independently can be a monoanionic ligand. In some aspects, suitable mono-anionic linkers may include, but are not limited to, H (hydride), BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbylsilyl group, a C1 to C36 hydrocarbylaminisilyl group, — OBRA12, or — OSO2R1 where R1 is a C1 to C36 hydrocarbyl group. It is contemplated that each X can be the same or a different monoanionic ligand.
[0050] In one aspect, each X independently may be H, BH4, a halide (e.g. F, Cl, Br, etc.), a hydrocarbyl 1 to C18 group, a C1 to C18 hydrocarboxy group, a C1 hydrocarbylaminyl group to C18, a C1 to C18 hydrocarbylsilyl group, or a C1 to C18 hydrocarbylaminylsilyl group. Alternatively, each independent X can be H, BH4, a halide, OBR12or OSO2R1, where R1 is a C1 to C18 hydrocarbyl group. In another aspect, each independent X may be H, BH4, a halide, a C1 to C12 hydrocarbyl group, a C1 to C12 hydrocarboxy group, a C1 to C12 hydrocarbylaminyl group, a C1 to C12 hydrocarbylsilyl group, a 1 to C12 hydrocarbylaminylsilyl group , OBR12 or OSO2R1, where R1 is a C1 to C12 hydrocarbyl group. In another aspect, each independent X can be H, BH4, a halide, a C1 to C10 hydrocarbyl group, a C1 to C10 hydrocarboxy group, a C1 to C10 hydrocarbylaminyl group, a C1 to C10 hydrocarbylsilyl group, a 1 to C10 hydrocarbylaminylsilyl group , OBR12 or OSO2R1, where R1 is a C1 to C10 hydrocarbyl group. In another aspect, each independent X may be H, BH4, a halide, a C1 to C8 hydrocarbyl group, a C1 to C8 hydrocarboxy group, a C1 to C8 hydrocarbylaminyl group, a C1 to C8 hydrocarbylsilyl group, a 1 to C8 hydrocarbylaminylsilyl group , OBR12 or OSO2R1, where R1 is a C1 to C8 hydrocarbyl group. In yet another aspect, each X independently can be a halide or a C1 to C18 hydrocarbyl group. For example, each X can be Cl.
The hydrocarbyl group which may be an X in the formula (A) may be a C1 to C36 hydrocarbyl group, including, but not limited to, a C1 to C36 alkyl group, a C2 to C36 alkenyl group, a cycloalkyl group C 4 to C36, a C6 to C36 aryl group, or a C 7 to C36 aralkyl group. For example, each X independently can be a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C4 to C18 cycloalkyl group, a C6 to C18 aryl group, or a C7 to C18 aralkyl group; alternatively, each X independently may be a C1 to C12 alkyl group, a C2 to C12 alkenyl group, a C4 to C12 cycloalkyl group, a C6 to C12 aryl group, or a C7 to C12 aralkyl group; alternatively, each X independently may be a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C4 to C10 cycloalkyl group, a C6 to C10 aryl group, or a C7 to C10 aralkyl group; or alternatively, each X independently may be a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5 to C8 cycloalkyl group, a C6 to C8 aryl group, or a C7 to C8 aralkyl group.
[0052] Likewise, in some aspects, the alkyl group, which may be X (one or both) in formula (A) may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group , a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group or an octadecyl group; or, alternatively, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group. In some aspects, the alkyl group, which may be X in formula (A) may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group. , a seg-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, a seg-pentyl group or a neopentyl group; alternatively, a methyl group, an ethyl group, an iso-propyl group, an n-butyl group, a tert-butyl group or a neopentyl group; alternatively a methyl group; alternatively, an ethyl group; alternatively an n-propyl group; alternatively, an iso-propyl group; alternatively an n-butyl group; alternatively a tert-butyl group; or, alternatively, a neopentyl group.
Illustrative alkenyl groups that may be X in formula (I) may include, but are not limited to, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, or an octadecenyl group. Such alkenyl groups can be straight or branched, and the double bond can be located anywhere in the chain. In one aspect, each X in formula (A) may be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group or a decenyl group, while in another aspect, each X in formula (A) may be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group or a hexenyl group. For example, each X independently can be an ethenyl group; alternatively, a propenyl group; alternatively a butenyl group; alternatively, a pentenyl group; or, alternatively, a hexenyl group. In yet another aspect, each X can be a terminal alkenyl group, such as a terminal C3 to C18 alkenyl group, a terminal C3 to C12 alkenyl group, or a terminal C3 to C8 alkenyl group. Illustrative terminal alkenyl groups may include, but are not limited to, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-yl group, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-yl group, a non-8-en-1-yl group, a decec group -9-en-1-il and so on.
[0054] Each X in formula (A) may be a cycloalkyl group, including, but not limited to, a cyclobutyl group, a substituted cyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, a substituted cycloheptyl group, a cyclooctyl group, or a substituted cyclooctyl group. For example, each X in formula (A) can be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group or a substituted cyclohexyl group. Furthermore, each X in formula (A) may be a cyclobutyl group or a substituted cyclobutyl group; alternatively a cyclopentyl group or a substituted cyclopentyl group; alternatively a cyclohexyl group or a substituted cyclohexyl group; alternatively a cycloheptyl group or a substituted cycloheptyl group; alternatively a cyclooctyl group or a substituted cyclooctyl group; alternatively, a cyclopentyl group; alternatively a substituted cyclopentyl group; alternatively, a cyclohexyl group; or, alternatively, a substituted cyclohexyl group. Substituents that can be used for substituted cycloalkyl groups are independently disclosed herein and can be used without limitation to further describe these substituted cycloalkyl groups, which can be an X in formula (A).
[0055] In some aspects, the aryl group which may be X in the formula (A) may be a phenyl group, a substituted phenyl group, a naphthyl group or a substituted naphthyl group. In one aspect, the aryl group can be a phenyl group or a substituted phenyl group; alternatively a naphthyl group or a substituted naphthyl group; alternatively a phenyl group or a naphthyl group; alternatively a substituted phenyl group or a substituted naphthyl group; alternatively a phenyl group; or, alternatively, a naphthyl group. Substituents that can be used for the substituted phenyl group or substituted naphthyl group independently are disclosed herein and can be used without limitation to describe the substituted phenyl group or substituted naphthyl group that can be an X in formula (A).
[0056] In one aspect, the substituted phenyl group which may be X in the formula (A) may be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4 phenyl group -disubstituted, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group. In other aspects, the substituted phenyl group may be a 2-substituted phenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group; alternatively, a 3-substituted phenyl group, or a 3,5-disubstituted phenyl group; alternatively a 2-substituted phenyl group or a 4-substituted phenyl group; alternatively a 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group; alternatively a 2-substituted phenyl group; alternatively a 3-substituted phenyl group; alternatively a 4-substituted phenyl group; alternatively a 2,4-disubstituted phenyl group; alternatively a 2,6-disubstituted phenyl group; alternatively a 3,5-disubstituted phenyl group; or, alternatively, a 2,4,6-trisubstituted phenyl group. Substituents that can be used for these specific substituted phenyl groups independently are disclosed herein and can be used without limitation to further describe these substituted phenyl groups, which can be the X group (one or both) in formula (A).
[0057] In some aspects, the aralkyl group which may be an X group in formula (A) may be a benzyl group or a substituted benzyl group. In one aspect, the aralkyl group can be a benzyl group or, alternatively, a substituted benzyl group. Substituents that can be used for substituted aralkyl groups are independently disclosed herein and can be used without limitation to further describe these substituted aralkyl groups, which can be the X group (one or both) in formula (A).
In one aspect, each non-hydrogen substituent(s) for the substituted cycloalkyl group, substituted aryl group, or substituted aralkyl group which may be X in formula (A) independently may be a C1 to C18 hydrocarbyl group; alternatively, a C1 to C8 hydrocarbyl group; or, alternatively, a C1 to C5 hydrocarbyl group. Specific hydrocarbyl groups are independently disclosed herein and can be used without limitation to further describe the substituents of substituted cycloalkyl groups, substituted aryl groups, or substituted aralkyl groups which can be an X in formula (A). For example, the hydrocarbyl substituent may be an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a seg-butyl group, an isobutyl group, an tert-butyl, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a 3-methyl-1-butyl group, a group 3-methyl-2-butyl, or a neo-pentyl group and the like, including combinations thereof. Furthermore, the hydrocarbyl substituent can be a benzyl group, a phenyl group, a tolyl group, or a xylyl group, and the like.
[0059] A hydrocarboxy group is used generically herein to include, for instance, alkoxy, aryloxy, aralkoxy and -(alkyl, aryl or aryl)-O-(alkyl, aryl or aralkyl) groups, and such groups may up to about 36 carbon atoms (for example, hydrocarboxy groups C1 to C36, C1 to C18, C1 to C10, or C1 to C8). Illustrative examples and not limitation of the hydrocarboxy groups that may be an X in the formula (A) may include, but are not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n group. -butoxy, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2-methyl-1-butoxy group, a tert group. - pentoxy, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group, a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group , a benzoxy group, an acetylacetonate (acac) group and the like. In one aspect, the hydrocarboxy group which may be X in formula (A) may be a methoxy group; alternatively, an ethoxy group; alternatively, an n-propoxy group; alternatively, an isopropoxy group; alternatively an n-butoxy group; alternatively, a sec-butoxy group; alternatively, an isobutoxy group; alternatively a tert-butoxy group; alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group; alternatively, a 3-pentoxy group; alternatively a 2-methyl-1-butoxy group; alternatively, a tert-pentoxy group; alternatively a 3-methyl-1-butoxy group, alternatively a 3-methyl-2-butoxy group; alternatively, a neo-pentoxy group; alternatively, a phenoxy group; alternatively, a toloxy group; alternatively a xyloxy group; alternatively a 2,4,6-trimethylphenoxy group; alternatively, a benzoxy group; or, alternatively, an acetylacetonate group.
The term hydrocarbylaminyl group is used generically herein to refer collectively to, for example, alkylaminyl, arylaminyl, aralkylaminyl, dialkylaminyl, diarylaminyl, diaralkylaminyl and de-(alkyl, aryl or aralkyl)-N-(alkyl, aryl) groups or aralkyl), and unless otherwise specified, hydrocarbylaminyl groups which may be X in formula (A) may comprise up to about 36 carbon atoms (e.g., C1 to C36, C1 to C18, C1 to C10 hydrocarbylaminyl groups , or C1 to C8). In this sense, hydrocarbylaminil is intended to cover the dihydrocarbylaminyl and hydrocarbylaminyl (mono) groups. In some aspects, the hydrocarbylaminyl group that may be X in the formula (A) may be, for example, a methylaminyl group (-NHCH3), an ethylaminyl group (-NHCH2CH3), an n-propylaminyl group (-NHCH2CH2CH3), a group iso-propylaminyl (-NHCH(CH3)2), an n-butylaminyl group (-NHCH2CH2CH2CH3), a t-butylaminyl group (-NHC(CH3)3), an n-pentylaminyl group (-NHCH2CH2CH2CH2CH3), a neo-group pentylaminyl (-NHCH2C(CH3)3), a phenylaminyl group (-NHC6H5), a tolylaminyl group (-NHC6H4CH3), or a xylylaminyl group (-NHC6H3(CH3)2); alternatively, a methylaminyl group; alternatively, an ethylaminyl group; alternatively, a propylaminyl group; or, alternatively, a phenylaminyl group. In other aspects, the hydrocarbylaminyl group which may be X in the formula (A) may be, for example, a dimethylaminyl group (-N(CH3)2), a diethylaminyl group (-N(CH2CH3)2), a di- n-propylaminyl (N-(CH2CH2CH3)2), a di-iso-propylaminyl group (-N(CH(CH3)2)2), a di-n-butylaminyl group (-N(CH2CH2CH2CH3)2), a di-t-butylaminyl group (-N(C(CH3)3)2), a di-n-pentylaminyl group (-N(CH2CH2CH2CH2CH3)2), a di-neo-pentylaminyl group (-NCH2C(CH3)3) 2), a di-phenylaminyl group (-N(C6H5)2), a di-tolylaminyl group (-N(C6H4CH3)2), or a di-xylylaminyl group (-N(C6H3(CH3)2)2) ; alternatively, a dimethylaminyl group; alternatively, a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; or, alternatively, a diphenylaminyl group.
[0061] In accordance with some aspects disclosed herein, each X independently may be a C1 to C36 hydrocarbysyl group; alternatively, a C1 to C24 hydrocarbysyl group; alternatively, a C1 to C18 hydrocarbysyl group; or, alternatively, a C1 to C8 hydrocarbysyl group. In one aspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group can be any hydrocarbyl group disclosed herein (e.g., a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5to C8 cycloalkyl group, a C aryl group 6 to C8, a C7 to C8 aralkyl group, etc.). As used herein, hydrocarbylsilyl is intended to cover hydrocarbylsilyl (mono) (-SH2R), dihydrocarbylsilyl (-SiHR2), and trihydrocarbylsilyl (-SIR3) groups, with R being a hydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C3 to C36 trihydrocarbylsilyl group or a C3 to C18 trihydrocarbylsilyl group, such as, for example, a trialkylsilyl group or a triphenylsilyl group. Illustrative and non-limiting examples of hydrocarbylsilyl groups that may be the X group (one or both) in formula (A) may include, but are not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (for example triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl, alkyldimethylsilyl , and the like.
[0062] A hydrocarbylaminylsilyl group is used herein to refer to groups containing at least one hydrocarbon moiety, at least one N atom and at least one Si atom. may include, but are not limited to -N(SiMe3)2, -N(SiEt3)2, and the like. Unless otherwise specified, hydrocarbylaminylsilyl groups which may be X1 and/or X2 may comprise up to about 36 carbon atoms (for example, hydrocarbylaminylsilyl groups C1 to C36, C1 to C18, C1 to C12, or C1 to C8) . In one aspect, each hydrocarbyl (one or more) of the hydrocarbylaminylsilyl group can be any hydrocarbyl group disclosed herein (e.g., a C1 to C5 alkyl group, a C2 to C5 alkenyl group, a C5 to C8 cycloalkyl group, an aryl group C6 to C8, a C7 to C8 aralkyl group, etc.). In addition, hydrocarbylaminylsilyl is intended to cover groups -NH(S1H2R), -NH(SiHR2), -NH(SiR3), -N(SiH2R)2, -N(SiHR2)2, -N(SiR3)2, among others, with R being a hydrocarbyl group.
[0063] In one aspect, each X independently may be -OBR12 or -OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group, or alternatively, a C1 to C18 hydrocarbyl group. The hydrocarbyl group in OBR12 and/or OSO2R1 independently may be any hydrocarbyl group disclosed herein, such as, for example, a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C4 to C18 cycloalkyl group, a C6 aryl group to C18, or a C7 to C18 aralkyl group; alternatively, a C1 to C12 alkyl group, a C2 to C12 alkenyl group, a C4 to C12 cycloalkyl group, a C6 to C12 aryl group, or a C7 to C12 aralkyl group; or alternatively a C1 to C8 alkyl group, a C2 to C8 alkenyl group, a C5 to C8 cycloalkyl group, a C6 to C8 aryl group or a C7 to C8 aralkyl group.
In one aspect, each X independently may be H, BH4, a halide or a C1 to C36 hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while in another aspect, each X independently may be H , BH4 or a C1 to C18 hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group or hydrocarbylaminylsilyl group. In another aspect, each X independently can be a halide; alternatively a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively, a 1 to C18 hydrocarylaminol group; alternatively, a C1 to C18 hydrocarbysyl group; or alternatively, a C1 to C18 hydrocarbylaminylsilyl group. In yet another aspect, both X1 and X2 can be H; alternatively, F; alternatively, Cl; alternatively, Br; alternatively, I; alternatively, BH4; alternatively a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively, a C1 to C18 hydrocarbylaminyl group; alternatively a C1 to C18 hydrocarbylsilyl group; or, alternatively, a C1 to C18 hydrocarbylaminylsilyl group.
Each X independently can be, in some aspects, H, a halide, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylaminyl, a dialkylaminyl, a trihydrocarbylsilyl or a hydrocarbylaminylsilyl; alternatively H, a halide, methyl, phenyl or benzyl; alternatively an alkoxy, aryloxy or acetylacetonate; alternatively an alkylaminyl or a dialkylaminyl; alternatively a trihydrocarbylsilyl or hydrocarbylaminylsilyl; alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylaminyl or a dialkylaminyl; alternatively, H; alternatively, a halide; alternatively, methyl; alternatively, phenyl; alternatively, benzyl; alternatively an alkoxy; alternatively an aryloxy; alternatively, acetylacetonate; alternatively an alkylaminyl; alternatively a dialkylaminyl; alternatively a trihydrocarbylsilyl; or alternatively a hydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl and hydrocarbylaminylsilyl may be a C1 to C36, C1 to C18, C1 to C12, or C1 to C8 alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbysilylyl, and hydrocarbylsilyl, and hydrocarbylsilyl.
[0066] Furthermore, each X independently may be, in certain respects, a halide or a C1 to C18 hydrocarbyl group; alternatively a halide or a C1 to C8 hydrocarbyl group; alternatively F, Cl, Br, I, methyl, benzyl or phenyl; alternatively Cl, methyl, benzyl or phenyl; alternatively, a C1 to C18 alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl or hydrocarbylaminylsilyl group; alternatively, a C1 to C8 alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl or hydrocarbylaminylsilyl group; or, alternatively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl, triisopropylsilyl, triphenylsilyl or allyldimethylsilyl.
[0067] In formula (A), CpC can be a fluorenyl, or cyclopentadienyl, substituted or unsubstituted indenyl group. In one aspect, CpC can be a substituted cyclopentadienyl group, while in another aspect, CpC can be a substituted indenyl group.
[0068] In some aspects, CpC may not contain additional substituents, eg, beyond bridged E2 group, discussed here below. In other aspects, CpC can still be substituted with one substituent, two substituents, three substituents, four substituents, and so on. If present, each substituent at CpC independently may be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarbyl group, or a C1 to C36 hydrocarbylsilyl group. Importantly, each substituent on CpC can be the same or a different group of substituents. Furthermore, each substituent can be in any position(s) of the respective cyclopentadienyl, indenyl or fluorenyl ring structure in accordance with the rules of chemical valence.
[0069] In some aspects, each substituent on CpC can independently be H; alternatively, a halide; alternatively a C1 to C18 hydrocarbyl group; a C1 to C18 halogenated hydrocarbyl group; alternatively, a C1 to C18 hydrocarboxy group; alternatively a C1 to C18 hydrocarbylsilyl group; alternatively, a C1 to C12 hydrocarbyl group or a C1 to C12 hydrocarbylsilyl group; or alternatively a C1 to C8 alkyl group or a C3 to C8 alkenyl group. The halide, hydrocarbyl group C1 to C36, hydrocarbyl group C1 to C36, and hydrocarbylsilyl group C1 to C36, which can be a CpC substituent in formula (A) and can be any halide, hydrocarbyl group C1 to C36, hydrocarbyl group C1 to C36 , and C1 to C36 hydrocarbylsilyl group described herein (for example, as relative to X in formula (A). A substituent at CpC in formula (A) may be, in certain aspects, a C1 to C36 halogenated hydrocarbyl group, where the group Halogenated hydrocarbyl indicates the presence of one or more halogen atoms, replacing an equivalent number of hydrogen atoms of the hydrocarbyl group. The halogenated hydrocarbyl group often can be a halogenated alkyl group, a halogenated alkenyl group, a halogenated cycloalkyl group, a halogenated aryl group, or a halogenated aralkyl group Representative and non-limiting halogenated hydrocarbyl groups include pentafluorophenyl, trifluoromethyl (CF3), and the like.
[0070] As a non-limiting example, if present, each substituent in CpC independently may be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (eg t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group , a nonenyl group, a decenyl group, a phenyl group, a tolyl group (or other substituted aryl group), a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group; alternatively, H; alternatively, Cl; alternatively, CF3; alternatively a methyl group; alternatively, an ethyl group; alternatively a propyl group; alternatively a butyl group; alternatively a pentyl group; alternatively a hexyl group; alternatively a heptyl group; alternatively an octyl group; alternatively a nonyl group; alternatively a decyl group; alternatively an ethenyl group; alternatively, a propenyl group; alternatively a butenyl group; alternatively a pentenyl group; alternatively a hexenyl group; alternatively, a heptenyl group; alternatively, an octenyl group; alternatively a nonenyl group; alternatively a decenyl group; alternatively a phenyl group; alternatively, a tolyl group; alternatively a benzyl group; alternatively, a naphthyl group; alternatively a trimethylsilyl group; alternatively a triisopropylsilyl group; alternatively a triphenylsilyl group; or, alternatively, an allyldimethylsilyl group.
[0071] Likewise, RX and RY in formula (A) independently may be H or any halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 to C1 to hydrocarbylsilyl group C36 disclosed herein (for example as relating to X or substituents on CpC in formula (A)). In one aspect, for example, RX and RY independently can be H or a C1 to C12 hydrocarbyl group. In another aspect, RX and RY independently can be a C1 to C10 hydrocarbyl group. In yet another aspect, RX and RY can be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (e.g. t-Bu), a pentyl group, a hexyl group, a group heptyl, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group and the like. In yet another aspect, RX and RY independently may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group. , an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group or a benzyl group.
[0072] The bridging group E2 in formula (A) may be (i) a bridging group, having the formula >EARARB, wherein EA may be a single C or Si atom and RA and RB independently may be H or a C1 to C18 hydrocarbyl group; or a bridged chain of 2 to 5 carbon atoms or silicone, each substituent on the atoms of the bridged chain independently may be H or a C1 to C18 hydrocarbyl group.
[0073] In the first option, the bridging group E2 can have the formula >EARARB, where EA can be a single atom of C or Si, and RA and RB independently can be H or any hydrocarbyl group C1 to C18 disclosed in this document. In some aspects of this invention, RA and RB independently may be a C1 to C15 hydrocarbyl group; alternatively, RA and RB independently may be a C1 to C8 hydrocarbyl group; alternatively, RA and RB independently can be an alkyl, alkenyl or aryl group having up to 8 carbon atoms; alternatively, RA and RB independently may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a cyclohexylphenyl group, a group naphthyl or a benzyl group; or alternatively RA and RB independently may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a phenyl group, a cyclohexyphenyl group, a naphthyl group or a benzyl group. These and other aspects, RA and RB can also be the same or different.
[0074] In a certain aspect, E2 can be a bridged group, having the formula >EARARB, where EA is C or Si, and where at least one of RA and RB can be a methyl group or a phenyl group. Furthermore, or alternatively, at least one of RA and RB can be a terminal alkenyl group C3 to C8.
In the second option, for example, E2 can be a bridging group having the formula —CRCRD—CRERF—, wherein RC, RD, RE, and RF independently can be a C1 to C18 hydrocarbyl group; or alternatively, a bridging group having the formula —SiRGRH—SiRIRJ—, wherein RG, RH, RI, and RJ independently may be H or a C1 to C18 hydrocarbyl group. In some aspects, RC, RD, RE and RF independently can be H or a methyl group and RG, RH, RI, and RJ independently can be H or a methyl group.
[0076] Options for M2, CpC, E2, RX, RY and X o with bridged metallocene compound having formula (A) are given above. However, in certain beneficial aspects, CpC has an alkenyl substituent and/or E2 has an alkenyl substituent.
[0077] Illustrative and non-limiting examples of bridged metallocene compounds having formula (A) and/or suitable for use as catalyst component I may include, but are not limited to, the following compounds (Me = methyl, Ph = phenyl , t-Bu = tert-butyl):




and the like, as well as their combinations.
[0078] Additional non-limiting examples of bridged metallocene compounds having formula (A) and/or suitable for use as catalyst component I may include, but are not limited to, the following compounds:

and the like, as well as their combinations. CATALYST COMPONENT II
[0079] The catalyst component II may include a metallocene compound based on hafnium or unbridged zirconium, or a metallocene based on zirconium compound with two bridged carbon atoms containing two indenyl groups. In one aspect, catalyst component II can include an unbridged hafnium or zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl group and an indenyl group. In another aspect, catalyst component II may include an unbridged zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl group and an indenyl group. In yet another aspect of this invention, catalyst component II may include a two-atom bridged zirconium-based metallocene compound containing two indenyl groups. In yet another aspect of this invention, catalyst component II may include an unbridged metallocene compound having the formula (B):

[0080] Within formula (B), M1, CpA, CpB and each X are independent elements of the unbridged metallocene compound. In that sense, the unbridged metallocene compound having formula B) can be described using any combination of M1, CpA, CpB and X disclosed herein. The monoanionic ligand selections for X in formula (B) are the same as those described above in this document for formula (A).
[0081] In accordance with aspects of this invention, the metal in formula (B), M1, can be Zr or Hf. In one aspect, for example, M1 might be Zr, while in another aspect, M1 might be Hf.
[0082] In formula (B), CpA and CpB independently may be a substituted or unsubstituted cyclopentadienyl or indenyl group. In one aspect, CpA and CpB independently can be an unsubstituted cyclopentadienyl or indenyl group. Alternatively, CpA and CpB independently can be a substituted indenyl or cyclopentadienyl group, for example, with up to 5 substituents.
If present, each substituent in CpA and CpB independently may be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarbyl group, or a C1 to C36 hydrocarbylsilyl group. Importantly, each substituent on CpA and/or CpB can be the same or a group of different substituents. Furthermore, each substituent can be in any position(s) of the respective cyclopentadienyl or indenyl ring structure in accordance with the rules of chemical valence. In one aspect, the number of substituents in CpA and/or IN CpB and/or the positions of each substituent in CpA and/or in CpB are independent of each other. For example, two or more substituents on CpA can be different, or alternatively, each substituent on CpA can be the same. Additionally, or alternatively, two or more substituents on CpB may be different, or alternatively, all substituents on CpB may be the same. In another aspect, one or more of the substituents on CpA may be different from one or more of the substituents on CpB, or alternatively, all of the substituents on both CpA and/or on CpB may be the same. In these and other aspects, each substituent can be at any position on the respective indenyl and cyclopentadienyl ring structure. If substituted, CpA and/or CpB independently can have one substituent, two substituents, three substituents, four substituents, and so on.
In formula (B) each substituent in CpA and/or in CpB independently may be H or any halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, C1 to C36 hydrocarboxy group, or C1 hydrocarbylsilyl group to C36 disclosed herein (for example as relating to substituents at CpC in formula (A)). In one aspect, for example, each substituent on CpA and CpB independently can be a C1 to C12 hydrocarbyl group or a C1 to C12 hydrocarbylsilyl group. In another aspect, each substituent on CpA and CpB independently can be a C1 to C8 alkyl group or a C3 to C8 alkenyl group. In yet another aspect, each substituent on CpA and CpB may independently be H, Cl, CF3, a methyl group, an ethyl group, a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a group hexyl, a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group or an allyldimethylsilyl group.
[0085] Illustrative and non-limiting examples of unbridged metallocene compounds having formula (B) and/or suitable for use as catalyst component II may include, but are not limited to, the following compounds:


and the like, as well as their combinations.
[0086] In other aspects of the present invention, the catalyst component II may include a metallocene compound with two bridged carbons that contains two indenyl groups, having the following formula:

[0087] In this formula, the monoanionic ligand selections for X are the same as those described above in this document for formula (A), eg both Xs can be Cl. The metal in this formula, M1, can be Ti, Zr or Hf. In one aspect, for example, M1 might be Zr, while in another aspect, M1 might be Hf. SUPPORT-ACTIVATOR
[0088] The present invention encompasses various catalyst compositions containing an activator-support. In one aspect, the support-activator can comprise a chemically treated solid oxide. Alternatively, in another aspect, support-activator may comprise a clay mineral, a pillared clay, an exfoliated clay, an exfoliated clay gelled in another oxide matrix, a layered silicate mineral, an unlayered silicate mineral, a mineral of layered aluminosilicate, an unlayered aluminosilicate mineral or any combination thereof.
[0089] Generally, chemically treated solid oxides show enhanced acidity compared to the corresponding untreated solid oxide compound. Chemically treated solid oxide can also function as a catalyst activator compared to the corresponding untreated solid oxide. While chemically treated solid oxide can activate a metallocene complex in the absence of cocatalysts, it is not necessary to eliminate the cocatalysts from the catalyst composition. The support-activator activation function can enhance the activity of the catalyst composition as a whole, compared to a catalyst composition containing the corresponding untreated solid oxide. However, it is believed that the chemically treated solid oxide can function as an activator even in the absence of an organoaluminium compound, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds and the like.
[0090] Chemically treated solid oxide may comprise a solid oxide treated with an electron withdrawing anion Although not intended to be limited by the following bond, it is believed that treatment of solid oxide with an electron withdrawing component increases or enhances acidity of the oxide. Thus, the support-activator exhibits Lewis or Br0nsted acidity that is typically greater than the Lewis or Br0nsted acid strength of the untreated solid oxide, or the support-activator has a greater number of acidic sites than the untreated solid oxide , or both. One method to quantify the acidity of chemically treated and untreated solid oxide materials can be by comparing the polymerization activities of the treated and untreated oxides under acid-catalyzed reactions.
[0091] Chemically treated solid oxides of this invention can generally be formed from an inorganic solid oxide that does not exhibit Lewis acid or BrOnsted acid behavior and has a relatively high porosity. Solid oxide can be chemically treated with an electron withdrawing component, typically an electron withdrawing anion, to form an activating support.
According to one aspect of the present invention, the solid oxide used to prepare a chemically treated solid oxide can have a pore volume greater than about 0.1 cc/g. According to another aspect of the present invention, the solid oxide can have a pore volume greater than about 0.5 cc/g. In accordance with yet another aspect of the present invention, the solid oxide can have a pore volume greater than approximately 1.0 cc/g.
[0093] In another aspect, solid oxide can have a surface of about 100 to about 1000 m2/g. In yet another aspect, the solid oxide can have a surface area of from about 200 to about 800 m2 /g. In yet another aspect of the present invention, the solid oxide can have a surface of from about 250 to about 600 m2 /g.
[0094] The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and one or more elements selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table, or comprising oxygen and one or more elements selected from the lanthanide or actinide elements (see: Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley & Sons, 1995; Cotton, FA, Wilkinson, G., Murillo , CA, and Bochmann, M., Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999). For example, the inorganic oxide may comprise oxygen and an element or elements selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.
[0095] Suitable examples of solid oxide materials or compounds that can be used to form the chemically treated solid oxide may include, but are not limited to, Al2O3, B2O3, BeO, Bi2O3, CdO, Co3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, and the like, coatings of one oxide with the other and combinations thereof. For example, the solid oxide may comprise silica, alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof .
[0096] The solid oxide of this invention encompasses oxide materials such as alumina, "mixed oxide" compounds thereof, such as silica-alumina, and combinations and mixtures thereof. Mixed oxide compounds, such as silica-alumina, can be single or multiple chemical phases with more than one metal combined with oxygen to form a solid oxide compound. Examples of mixed oxides that can be used in the activator-support of the present invention, either alone or in combination, may include, but are not limited to, silica-alumina, silica-titania, zirconia-silica, zeolites, various clay minerals, titania-alumina, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide of this invention also encompasses oxide materials, such as silica coated alumina, as described in U.S. Patent No. 7,884,163, the disclosure of which is incorporated herein by reference in its entirety.
[0097] The electron withdrawing component used to treat solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide in the treatment (when compared to solid oxide that is not treated with at least one electron withdrawing anion ). In accordance with one aspect of the present invention, the electron withdrawing component may be an electron withdrawing anion derived from a salt, an acid or other compound, such as a volatile organic compound, which serves as a source or precursor for that anion. Examples of electron withdrawing anions may include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluortitanate, phosphotungstate, and the like, including mixtures and combinations thereof. Additionally, other ionic or non-ionic compounds that serve as sources for these electron withdrawing anions can also be employed in the present invention. It is contemplated that the electron withdrawing anion can be, or can comprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate and the like, or any combination thereof, in some aspects of this invention. In other aspects, the electron withdrawing anion may comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate and the like, or combinations thereof.
[0098] Thus, for example, the support-activator (e.g., chemically treated solid oxide) used in the catalyst compositions of the present invention may be, or may comprise, fluorinated alumina, chlorinated alumina, bromide alumina, sulfated alumina, silica- fluorinated alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, bromide-silica zirconia, sulfated silica-zirconia, fluorinated silica-titania, coated fluorinated silica-alumina, silica -coated sulfated alumina, coated phosphated alumina silica and the like, or combinations thereof. In one aspect, the support-activator can be, or can comprise, fluoridated alumina, sulfated alumina, fluoridated silica-alumina, sulfated silica-alumina, fluoridated silica coated alumina, sulfated silica coated alumina, phosphated silica coated alumina, and the like or any combination thereof. In another aspect, the support-activator may comprise fluorinated alumina; alternatively, chlorinated alumina; alternatively, sulfated alumina; alternatively, fluorinated silica-alumina; alternatively, sulfated silica-alumina; alternatively, fluorinated silica-zirconia; alternatively, chlorinated silica-zirconia; or, alternatively, fluorinated silica coated alumina.
[0099] When the electron withdrawing component comprises a salt of an electron withdrawing anion, the counterion or cation of that salt can be selected from any cation that allows the salt to revert or decompose back to acid during calcination. Factors that dictate the suitability of the particular salt to serve as a source for the electron withdrawing anion may include, but are not limited to, the solubility of the salt in the desired solvent, the lack of adverse cation reactivity, ion-pairing effects between the cation and the anion, shigroscopic properties conferred on the salt by the cation and the like, and thermal stability of the anion. Examples of suitable cations in the electron withdrawing anion salt may include, but are not limited to, ammonium, trialkylammonium, tetra-alkylammonium, tetra-alkylphosphonium, H+, [H(OEt2)2]+, and the like.
[0100] Combinations of yet one or more different electron withdrawing anions, in varying proportions, can be used to adjust the specific acidity of the support-activator to the desired level. Combinations of electron withdrawing components can be contacted with the oxide material simultaneously or individually, and in any order that provides the desired acidity of the chemically treated solid oxide. For example, one aspect of this invention may employ two or more electron withdrawing anion source compounds in two or more separate contact steps.
[0101] Thus, a process by which a chemically treated solid oxide can be prepared is as follows: a selected solid oxide, or combination of the solid oxide, can be contacted with a first compound from the electron withdrawing anion source to form a first mixture; this first mixture can be calcined and then contacted with a second compound from the electron withdrawing anion source to form a second mixture; the second mixture then can be calcined to form a treated solid oxide. In such a process, the first and second electron-withdrawing anion source compounds can be the same or different compounds.
[0102] According to another aspect of the present invention, the chemically treated solid oxide may comprise an inorganic solid oxide material, a mixed oxide material or a combination of inorganic oxide materials, which are chemically treated with an electron scavenger component , optionally treated with a metal source, including metal salts, metal ions or other metal-containing compounds. Non-limiting examples of the metal or metal ion may include zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium and the like, or combinations thereof. Examples of chemically treated solid oxides that contain a metal or metal ion may include, but are not limited to, chlorinated zinc-impregnated alumina, fluorinated titanium-impregnated alumina, fluorinated zinc-impregnated alumina, chlorinated zinc-impregnated silica-alumina, silica- fluoridated zinc impregnated alumina, sulfated zinc impregnated alumina, chlorinated zinc aluminate, fluoridated zinc aluminate, sulfated zinc aluminate, silica coated alumina treated with hexafluortitanic acid, silica coated alumina treated with zinc and then fluoridated and the like, or any combination of them.
[0103] Any method of impregnating the solid oxide material with a metal can be used. The method by which the oxide is contacted with a source of metal, typically a salt or metal-containing compound, can include, but is not limited to, gelling, cogealizing, impregnating one compound into another, and the like. If desired, the metal-containing compound can be added to or impregnated into the solid oxide in solution form and subsequently converted to the supported metal by calcining. Accordingly, the inorganic solid oxide may further comprise a metal selected from zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum and the like, or combinations of these metals. For example, zinc can often be used to impregnate solid oxide because it can provide improved catalytic activity at a low cost.
[0104] Solid oxide can be treated with metal salts or compounds containing metals before, after or at the same time as the solid oxide is treated with the electron withdrawing anion. After any contact method, the contacted mixture of solid compound, electron withdrawing anion, and metal ion can be calcined. Alternatively, a solid oxide material, an electron withdrawing anion source and the metal salt or metal-containing compound can be contacted and calcined simultaneously.
[0105] Various processes can be used to form the chemically treated solid oxide useful in the present invention. The chemically treated solid oxide can comprise the contact product of one or more solid oxides with one or more electron withdrawing anion sources. It is not required that the solid oxide be calcined before contacting the electron withdrawing anion source. Typically, the contact product can be calcined during or after the solid oxide is brought into contact with the electron withdrawing anion source. Solid oxide can be calcined or uncalcined. Various processes for preparing solid oxide activator supports that can be employed in this invention have been reported. For example, such methods are described in Patent Nos. US 6,107,230; US 6,165,929; US 6,294,494; US6,300,271; US 6,316,553; US 6,355,594; US 6,376,415; US 6,388,017; US 6,391,816; US 6,395,666; US 6,524,987; US 6,548,441; US 6,548,442; US 6,576,583; US 6,613,712; US 6,632,894; US 6,667,274; and US 6,750,302; which disclosures are incorporated herein by reference in their entirety.
[0106] According to one aspect of the present invention, solid oxide material can be chemically treated by contacting it with an electron withdrawing component, typically an electron withdrawing anion source. Additionally, the solid oxide material may optionally be chemically treated with a metal ion and then calcined to form a chemically treated solid oxide containing metal or impregnated with metal. According to another aspect of the present invention, the solid oxide material and electron withdrawing anion source may be contacted and calcined simultaneously.
[0107] The method by which the oxide is contacted with the electron withdrawing component, typically a salt or an acid of an electron withdrawing anion, may include, but is not limited to, gelling, co-gelling, impregnation of a compound to another, and the like. Thus, after any contact method, the contacted mixture of solid oxide, electron withdrawing anion and optional metal ion can be calcined.
[0108] The support-activator of the solid oxide (i.e., chemically treated solid oxide) can thus be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with a scavenger anion source compound electron (or compounds) to form a first mixture; e2) calcining the first mixture to form the solid oxide activator support.
[0109] According to another aspect of the present invention, the support-activator of solid oxide (chemically treated solid oxide) can be produced by a process comprising: 1) contacting a solid oxide (or solid oxides) with a first compound of electron withdrawing anion source to form a first mixture; 2) calcining the first mixture to produce a calcined first mixture; 3) contacting a calcined first mixture with a second electron withdrawing anion source compound to form a second mixture; e4) calcining the second mixture to form the solid oxide activator support.
[0110] According to yet another aspect of the present invention, the chemically treated solid oxide can be produced or formed by contacting the solid oxide with the electron withdrawing anion source compound, where the solid oxide compound is calcined before, during or after contact with the electron withdrawing anion source, and where there is a substantial absence of aluminoxanes, organoboron or organoborate compounds and ionizing ionic compounds.
[0111] Calcination of treated solid oxide generally can be conducted in an ambient atmosphere, usually in a dry ambient atmosphere, at a temperature from about 200 °C to about 900 °C and for a time of about 1 minute to about 100 hours. Calcination can be conducted at a temperature of about 300°C to about 800°C, or alternatively, at a temperature of about 400°C to about 700°C. Calcination can be carried out for about 30 minutes to about 50 hours, or for about 1 hour to about 15 hours. Thus, for example, calcination can be carried out for about 1 to about 10 hours at a temperature of about 350°C to about 550°C. Any suitable ambient atmosphere can be employed during calcination. Calcination can usually be conducted in an oxidizing atmosphere such as air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.
[0112] According to one aspect of the present invention, the solid oxide material may be treated with a halide ion source, sulfate ion or a combination of anions, optionally treated with a metal ion and then calcined to provide the oxide chemically treated solid in the form of a particulate solid. For example, the solid oxide material can be treated with a sulphate source (referred to as a "sulphating agent"), a bromide ion source (referred to as a "brominating agent"), a chloride ion source (referred to as a "chlorinating agent"), or a combination thereof, and calcined to provide the solid oxide activator. Useful acid activator supports may include, but are not limited to, bromide alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, bromide alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, silica-zirconia bromide, chlorinated silica-zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina treated with hexafluorotitanic acid, alumina coated with silica treated with hexafluorotitanium acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, boria-fluorinated alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pillared montmorillonite, optionally treated with fluoride, chloride or sulfate; phosphated alumina or other aluminophosphates, optionally treated with sulfate, fluoride or chloride; or some combination of those above. Additionally, any of these activator-supports can optionally be treated or impregnated with a metal ion.
[0113] In one aspect, the chemically treated solid oxide may comprise a fluoridated solid oxide in the form of a particulate solid. Fluorinated solid oxide can be formed by contacting a solid oxide with a fluoridating agent. The fluoride ion can be added to the oxide by forming a fluid slurry of the oxide in a suitable solvent such as alcohol or water, including, but not limited to, one to three carbon alcohols due to their volatility and low surface tension. Examples of suitable fluoridating agents may include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorsilicate) ((NH4 )2SiF6), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TiF6), ammonium hexafluorotitanic acid ((NH4)2TiF6), hexafluorozirconic acid (H2ZrF6), AlF3, NH4AlF4, their analogues and combinations. Triflic acid and ammonium triphylate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as the fluoridating agent due to its ease of use and availability.
[0114] If desired, the solid oxide can be treated with a fluoridating agent during the calcination step. Any fluorinating agent capable of fully contacting the solid oxide during the calcination step can be used. For example, in addition to those previously described fluoridating agents, volatile organic fluoridating agents can be used. Examples of volatile organic fluorinating agents useful in this aspect of the invention may include, but are not limited to, freons, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and the like, and combinations thereof. Calcining temperatures generally must be high enough to decompose the compound and release fluoride. Hydrogen fluoride gas (HF) or fluorine (F2) itself can also be used with the solid oxide, if fluoridated during calcination. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4-) can also be used. A convenient method of contacting the solid oxide with the fluoridating agent may be to vaporize a fluoridating agent in a gas stream used to fluidize the solid oxide during calcination.
[0115] Likewise, in another aspect of this invention, the chemically treated solid oxide may include a chlorinated solid oxide in the form of a particulate solid. Chlorinated solid oxide can be formed by contacting a solid oxide with a chlorinating agent. Chloride ion can be added to the oxide by forming a fluid slurry of the oxide in a suitable solvent. Solid oxide can be treated with a chlorinating agent during the calcination step. Any chlorinating agent capable of serving as a source of chloride and completely contacting the oxide during the calcination step can be used, such as SiCl4, SiMe2Cl2, TiCl4, BCl3 and the like, including mixtures thereof. Volatile organic chlorinating agents can be used. Examples of suitable volatile organic chlorinating agents may include, but are not limited to, certain freons, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, and the like or any combination thereof. Hydrogen chloride gas or chlorine itself can also be used with the solid oxide during calcination. A convenient method of contacting the oxide with the chlorinating agent may be to vaporize a chlorinating agent in a gas stream used to fluidize the solid oxide during calcination.
[0116] The amount of fluoride or chloride ion present before calcining the solid oxide generally can be from about 1 to about 50% by weight, where the percentage by weight is based on the weight of the solid oxide, for example, silica-alumina, before calcination. According to another aspect of this invention, the amount of fluoride or chloride ion present prior to calcining the solid oxide can be from about 1 to about 25% by weight, according to another aspect of this invention, from about 2 to about 20% by weight. According to yet another aspect of this invention, the amount of fluoride or chloride ion present prior to calcining the solid oxide can be from about 4 to about 10% by weight. Once impregnated with halide, the halide oxide can be dried by any suitable method, including, but not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible to initiate the step. of calcination immediately without drying the impregnated solid oxide.
[0117] The silica-alumina used to prepare treated silica alumina typically can have a pore volume greater than about 0.5 cc/g. In accordance with one aspect of the present invention, the pore volume can be greater than about 0.8 cc/g, and in another aspect of the present invention, greater than about 1.0 cc/g. Furthermore, silica-alumina can generally have a surface area greater than about 100 m 2 /g. According to another aspect of this invention, the surface area can be greater than about 250 m 2 /g. In yet another aspect, the surface area can be greater than about 350 m2/g.
[0118] The silica-alumina used in the present invention can typically have an alumina content of about 5 to about 95% by weight. In accordance with one aspect of this invention, the alumina content of the silica-alumina can be from about 5 to about 50%, or about 8% to about 30%, alumina by weight. In another aspect, high alumina silica-alumina compounds may be employed, in which the alumina content of such silica-alumina compounds typically ranges from about 60% to about 90%, or from about 65% to about 80% alumina by weight. In accordance with yet another aspect of this invention, the solid oxide component may comprise alumina without silica, and in accordance with another aspect of this invention, the solid oxide component may comprise silica without alumina.
[0119] The sulfated solid oxide may comprise sulfate and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide can be further treated with a metal ion so that the calcined sulfated oxide comprises a metal. According to one aspect of the present invention, the sulfated solid oxide can comprise sulfate and alumina. In some cases, sulfated alumina can be formed by a process in which the alumina is treated with a source of sulfate, for example, sulfuric acid or a sulfate salt, such as ammonium sulfate. This process can generally be performed by forming a fluid slurry of alumina in a suitable solvent, such as alcohol or water, to which the desired concentration of sulphating agent has been added. Suitable organic solvents may include, but are not limited to, one to three carbon alcohols due to their volatility and low surface tension.
[0120] According to an aspect of the invention, the amount of sulfate ions present before calcination can be from about 0.5 to about 100 parts by weight of sulfate ion to about 100 parts by weight of solid oxide . According to another aspect of this invention, the amount of sulfate ion present prior to calcining can be from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and according to yet another aspect of this invention, from about 5 to about 30 parts by weight of sulfate ion to about 100 parts by weight of solid oxide. These weight ratios are based on the weight of solid oxide prior to calcination. Once impregnated with sulfate, the sulfated oxide can be dried by any suitable method, including, but not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is also possible to initiate the step of calcination immediately.
[0121] According to another aspect of the present invention, the activator-support used in preparing the catalyst compositions of this invention may comprise an ion replaceable activator-support, including but not limited to silicate and aluminosilicate compounds or minerals, either with layered or unlayered structures, and combinations thereof. In another aspect of this invention, layered ion-exchangeable aluminosilicates, such as pillared clays, are used as activating supports. Where the acidic activator-support comprises an ion-exchangeable activator-support, it may optionally be treated with at least one electron-withdrawing anion, such as those disclosed in this document, although typically the ion-exchangeable activator-support is not be treated with an electron withdrawing anion.
[0122] According to another aspect of the present invention, the support-activator of this invention may comprise mineral clays having exchangeable cations and layers capable of expanding. Typical clay mineral activator supports may include, but are not limited to, layer-exchangeable ion-exchangeable aluminosilicates, such as pillared clays. Although the term "support" is used, it should not be interpreted as an inert component of the catalyst composition, but rather, it can be considered an active part of the catalyst composition due to its close association with the metallocene complex.
[0123] According to another aspect of the present invention, the clay materials of this invention can encompass materials in their natural states or that have been treated with various ions by wetting, ion exchange or pillaring. Typically, the clay material activator support of this invention may comprise clays that have had ions exchanged with large cations, including highly charged polynuclear metal complex cations. However, the clay material activating supports of this invention may also encompass clays that have had ions exchanged with simple salts, including, but not limited to, Al(III), Fe(II), Fe(III) and Zn salts. (II) with binders such as halide, acetate, sulfate, nitrate or nitrite.
[0124] According to another aspect of the present invention, the support-activator can comprise a pillared clay. The term "pillarized clay" is used to refer to clay materials that have had ions exchanged with large, highly charged metal complex cations, typically polynuclear. Examples of such ions may include, but are not limited to, Keggin ions that may have charges, such as 7+, various polyoxometalates, and other large ions. Thus, the term pillarizing can refer to a simple exchange reaction in which the exchangeable cations of a clay material are replaced by large, highly charged ions, such as Keggin ions. These polymeric cations can then be immobilized within the clay interlayers and, when calcined, are converted to metal oxide "pillars", effectively supporting the clay layers as column-like structures. Thus, once the clay is dried and calcined to produce the supporting pillars between the clay layers, the expanded structure of the network can be maintained and porosity can be improved. The resulting pores can vary in shape and size as a function of the pillaring material and the precursor clay material used. Examples of pillaring and pillaring clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J.M. Thomas, Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.)) Ch. 3, p. 55-99, Academic Press, Inc., (1972); U.S. Patent No. 4,452,910; U.S. Patent No. 5,376,611; and U.S. Patent No. 4,060,480; the disclosures of which are incorporated herein by reference in their entirety.
[0125] Pillarizing process can use clay minerals having exchangeable cations and layers capable of expanding. Any pillared clay that can enhance the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, clay minerals suitable for pillaring may include, but are not limited to, allophanes; smectites, both dioctahedral (Al) and trioctahedral (Mg) and derivatives thereof, such as montmorillonites (bentonites), nontronites, hectorites or Laponites; halloysites; vermiculites; micas; fluoromerics; chlorites; mixed layer clays; fibrous clays including, but not limited to, sepiolites, attapulgites and palygorskites; a serpentine clay; illite; laponite; saponite; and any combination thereof. In one aspect, the pillared clay support-activator may comprise bentonite or montmorillonite. The main component of bentonite is montmorillonite.
[0126] Pillarized clay can be pretreated if desired. For example, a pillared bentonite can be pretreated by drying at about 300°C under an inert atmosphere, typically dry nitrogen, for about 3 hours, before being added to the polymerization reactor. Although an exemplary pretreatment is described herein, it should be understood that preheating can be carried out at many other temperatures and times, including any combination of temperature and time steps, all of which are encompassed by this invention.
[0127] The support-activator used to prepare the catalyst compositions of the present invention can be combined with other inorganic support materials, including, but not limited to, zeolites, inorganic oxides, phosphate inorganic oxides and the like. In one aspect, typical support materials that can be used include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminum phosphate, silica-titania, silica/ co-precipitated titania, mixtures thereof or any combination thereof.
[0128] According to another aspect of the present invention, one or more of the metallocene compounds may be precontacted with an olefin monomer and an organoaluminium compound for a first period of time, before contacting the mixture with the support -activator. Since the pre-contacted mixture of the metallocene complex(s), the olefin monomer and the organoaluminum compound is contacted with the activator-support, the composition further comprising the activator-support may be termed a mixture " post-contacted". The post-contacted mixture can be allowed to remain in contact for a further second period of time before being loaded into the reactor where the polymerization process will take place.
[0129] According to yet another aspect of the present invention, one or more of the metallocene compounds may be precontacted with an olefin monomer and an organoaluminium compound for a first period of time, before contacting the mixture with the compound of organoaluminium, Since the pre-contacted mixture of the metallocene complex(s), the olefin monomer and the support-activator is contacted as an organoaluminium compound, the composition further comprising the organoaluminium may be termed a mixture " post-contacted". The post-contacted mixture may be allowed to remain in additional contact for a second period of time, before being introduced into the polymerization reactor. CO-CATALYST
[0130] In certain aspects directed to catalyst compositions containing a co-catalyst, the co-catalyst may comprise a metal hydrocarbyl compound, examples of which include non-halide metal hydrocarbyl compounds, metal hydrocarbyl halide compounds, compounds of non-halide alkyl metal, alkyl metal halide compounds, and so on. The hydrocarbyl group (or alkyl group) can be any hydrocarbyl (or alkyl) group disclosed herein. Also, in some aspects, the hydrocarbyl metal may be a group 1, 2, 11, 12, 13 or 14 metal; alternatively a group 13 or 14 metal; or, alternatively, a group 13 metal. Therefore, in some aspects, the metal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metal hydrocarbyl halide) may be lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium , calcium, strontium, barium, zinc, cadmium, boron, aluminum or tin; alternatively lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum or tin; alternatively lithium, sodium or potassium; alternatively, magnesium or calcium; alternatively lithium; alternatively, sodium; alternatively, potassium; alternatively, magnesium; alternatively, calcium; alternatively zinc; alternatively boron; alternatively, aluminum; or alternatively tin. In some aspects, the metal or alkyl metal hydrocarbyl, with or without a halide, may comprise a lithium or alkyl hydrocarbyl, a magnesium or alkyl hydrocarbyl, a boron or alkyl hydrocarbyl, a zinc or alkyl hydrocarbyl, or an aluminum or alkyl hydrocarbyl.
[0131] In particular aspects directed to catalyst compositions containing an activator-support and a co-catalyst (eg the activator may comprise a solid oxide treated with an electron removing anion), the co-catalyst may comprise a compound of aluminoxane, an organoboron or organoborate compound, an ionic ionizing compound, an organoaluminium compound, an organomagnesium compound or an organolithium compound, and this includes any combinations of these materials. In one aspect, the cocatalyst can include an organoaluminium compound. In another aspect, the co-catalyst may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionic ionizing compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof. In another aspect, the co-catalyst may comprise an aluminoxane compound; alternatively, an organoboron or an organoborate compound; alternatively, an ionizing ionic compound; alternatively, an organozinc compound; alternatively, an organomagnesium compound; or, alternatively, an organolithium compound. ORGANOALUMINIUM COMPOUNDS
[0132] In some aspects, catalyst compositions of the present invention may comprise one or more organoaluminium compounds. Such compounds may include, but are not limited to, compounds of the formula: (RZ)3Al; where each RZ can independently be an aliphatic group having 1 to 10 carbon atoms. For example, each RZ can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl.
[0133] Other organoaluminum compounds that can be used in the catalyst compositions disclosed herein may include, but are not limited to, compounds of the formula: Al(X7)m(X8)3-m, where each X7 independently can be a hydrocarbyl; each X8 independently can be an alkoxide or an aryloxide, a halide or a hydride; and m can be from 1 to 3, inclusive. Hydrocarbyl is used herein to specify a hydrocarbon radical group and includes, for example, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl and aralkynyl groups.
[0134] In one aspect, each X7 independently can be any hydrocarbyl with about 1 to about 18 carbon atoms disclosed herein. In another aspect of the present invention, each independent X7 can be any alkyl having 1 to 10 carbon atoms disclosed herein. For example, X7 can independently be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl and the like, in yet another aspect of the present invention.
[0135] According to one aspect of the present invention, each X8 independently can be an alkoxide or an aryloxide, any of which has from 1 to 18 carbon atoms, a halide or a hydride. In another aspect of the present invention, each X8 can be independently selected from fluorine and chlorine. In yet another aspect, X8 can be chlorine.
[0136] In the formula, Al(X5)m(X6)3-m, m can be a number from 1 to 3 inclusive, and normally, m can be 3. The value of m is not restricted to being an integer ; therefore, this formula may include sesquihalide compounds or other organoaluminium cluster compounds.
[0137] Non-limiting examples of organoaluminum compounds suitable for use in accordance with the present invention may include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds and combinations thereof . Specific non-limiting examples of suitable organoaluminum compounds may include, but are not limited to, trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri -n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride and the like, or combinations thereof.
[0138] The present invention contemplates a method of pre-contacting metallocene (one or more) with an organoaluminum compound and an olefin monomer to form a pre-contacted mixture, before contacting this pre-contacted mixture with an activator-support to form a catalyst composition. When the catalyst composition is prepared in this way, normally, though not necessarily, a part of the organoaluminium compound can be added to the precontacted mixture and another part of the organoaluminium compound can be added to the postcontacted mixture prepared when the precontacted mixture is in contact with the support-activator of solid oxide. However, any organoaluminium compound can be used to prepare the catalyst composition at any pre-contact or post-contact step. Alternatively, all catalyst components can be contacted in one step.
[0139] Still, more than one organoaluminium compound can be used in the pre-contact or the post-contact step. When an organoaluminium compound is added in several steps, the amounts of the organoaluminium compounds disclosed herein include the total amount of the organoaluminium compound used in both the pre-contacted and post-contacted mixtures, and any additional organoaluminium compound added to the reactor. polymerization. Therefore, the total amounts of organoaluminium compounds are disclosed regardless of whether a single organoaluminium compound or more than one organoaluminium compound is used. ALUMINOXAN COMPOUNDS
[0140] Certain aspects of the present invention provide a catalyst composition, which may comprise an aluminoxane compound. As used herein, the terms "aluminoxane" and "aluminoxane compound" refer to aluminoxane compounds, compositions, mixtures or discrete species, regardless of how such aluminoxanes are prepared, formed or otherwise provided. For example, a catalyst composition comprising an aluminoxane compound can be prepared where the aluminoxane is provided as the poly(hydrocarbyl aluminum oxide), or where aluminoxane is provided as the combination of an alkyl aluminum compound and a source of active protons such as water. Aluminoxanes may also be referred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes.
[0141] The other components of the catalyst can normally be contacted with the aluminoxane in a solvent composed of saturated hydrocarbons, although any solvent that is substantially inert to the reactants, intermediates, and products of the activation step can be used. The catalyst composition formed in this way can be collected by any suitable method, for example, by filtration. Alternatively, the catalyst composition can be introduced into the polymerization reactor without being isolated.
[0142] The aluminoxane compound of this invention may be an oligomeric aluminum compound comprising linear structures, cyclic structures, or cage structures, or mixtures of all three. Cyclic aluminoxane compounds having the formula:
wherein each R in this formula may independently be a linear or branched alkyl, having from 1 to 10 carbon atoms, and p in this formula may be an integer from 3 to 20, are encompassed by this invention. The AlRO fraction shown here may also constitute the repeating unit in a linear aluminoxane. Thus, linear aluminoxanes having the formula:
wherein each R in this formula may independently be a linear or branched alkyl, having 1 to 10 carbon atoms, and q in this formula may be an integer from 1 to 50, are also encompassed by this invention.
[0143] In addition, aluminoxanes can have cage structures of the formula Rt5r+αRbr-αAl4ro3r, where each Rt can independently be a linear terminal or branched alkyl group having from 1 to 10 carbon atoms; each Rb can be a linear bridge or branched alkyl group having from 1 to 10 carbon atoms; r can be 3 or 4; and α can be equal to nAl(3) - no(2) + no(4), where nAl(3) is the number of three coordinated aluminum atoms, no(2) is the number of two coordinated oxygen atoms , eno(4) is the number of 4 coordinated oxygen atoms.
[0144] Thus, aluminoxanes that can be employed in the catalyst compositions of the present invention can generally be represented by formulas such as (R-Al-o)p, R(R-Al-o)qAlR2 and the like. In these formulas, each R group independently can be a linear or branched C1-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples of aluminoxane compounds that can be used in accordance with the present invention may include, but are not limited to, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane and the like or any combination thereof. Iso-butylaluminoxane, ethylaluminoxane and methylaluminoxane can be prepared from trimethylaluminum, triethylaluminum or triisobutylaluminum, respectively, and are sometimes referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide) and poly(isobutyl aluminum oxide) , respectively. Also within the scope of the invention to use an aluminoxane in combination with an aluminum trialkyl, as disclosed in U.S. Patent No. 4,794,096, incorporated herein by reference in its entirety.
[0145] The present invention contemplates many values of p and q in the formulas aluminoxane (R-Al-O)p and R(R-Al-O)qAlR2, respectively. In some respects, p and q can be at least 3. However, depending on how the organoaluminoxane is prepared, stored, and used, the p and q value can vary within a single sample of aluminoxane, and such combinations of organoaluminoxanes are contemplated herein. .
[0146] In preparing a catalyst composition containing an aluminoxane, the molar ratio of the moles of aluminum in the aluminoxane (or aluminoxanes) to the total moles of the metallocene complexes in the composition can generally be between about 1:10 and about 100,000:1. In another aspect, the molar ratio can be in a range from about 5:1 to about 15,000:1. Optionally, aluminoxane can be added to a polymerization zone at intervals from about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, or from about from 1 mg/L to about 50 mg/L.
[0147] Organoaluminoxanes can be prepared by various procedures. Examples of organoaluminoxanes preparations are disclosed in US Patent Nos. 3,242,099 and 4,808,561, the disclosures of which are incorporated herein by reference in their entirety. For example, water in an inert organic solvent can be reacted with an alkyl aluminum compound, such as (RZ)3Al, to form the desired organoaluminoxane compound. While not intending to be bound by this statement, it is believed that this synthetic method can provide a mixture of both linear and cyclic R-Al-O aluminoxane species, both of which are encompassed by this invention. Alternatively, organoaluminoxanes can be prepared by reacting an alkyl aluminum compound, such as (RZ)3Al, with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent. ORGANOBORON & ORGANOBORATE COMPOUNDS
[0148] According to another aspect of the present invention, the catalyst composition may comprise an organoboron compound or an organoborate. Such compounds can include neutral boron compounds, borate salts, and the like, or combinations thereof. For example, boron fluoroorgan compounds and borate fluoroorgan compounds are contemplated.
[0149] Any fluoroorgano boron or fluoroorgano borate compound can be used with the present invention. Examples of fluoroorgano borate compounds that can be used in the present invention may include, but are not limited to, fluorinated aryl borates such as N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate, triphenylcarbenium tetrakis (pentafluorophenyl)borate, lithium tetrakis (pentafluorophenyl) )borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and the like, or mixtures thereof. Examples of fluoroorgano boron compounds that can be used as co-catalysts in the present invention may include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or the like. mixtures. While not intending to be bound by the following theory, these examples of fluoroorgano borate compounds and fluoroorgano boron and related compounds may form "weakly coordinated" anions when combined with a transition metal complex (see, for example, Patent US 5,919,983, the disclosure of which is incorporated herein by reference in its entirety). Applicants also contemplate the use of diboron, or bis-boron, compounds or other bifunctional compounds containing two or more boron atoms in the chemical structure, such as disclosed in J. Am. Chem. Soc., 2005, 127, pp. 14756-14768, the contents of which are incorporated herein by reference in their entirety.
[0150] In general, any amount of organoboron compounds can be used. According to one aspect of this invention, the molar ratio of the total moles of the organoboron or organoborate compound (or compounds) to the total moles of the metallocene compounds in the catalyst composition can be in a range from about 0.1:1 to about of 15:1. Typically, the amount of the fluoroorgano boron compound or fluoroorgano borate used can be from about 0.5 moles to about 10 moles of boron/borate compound per mole of the metallocene complex(s). According to another aspect of this invention, the amount of the fluoroorgano borate compound or fluoroorgano borate can be from about 0.8 moles to about 5 moles of the boron/borate compound per mole of the metallocene complex(s). IONIZING IONIC COMPOUNDS
[0151] In another aspect, catalyst compositions disclosed herein may comprise an ionizing ionic compound. An ionic ionizing compound is an ionic compound that can function as a co-catalyst to improve the compounding activity of the catalyst. Without intending to be bound by theory, it is believed that the ionizing ionic compound may be capable of reacting with a metallocene complex and converting the metallocene complex into one or more cationic metallocene complexes, or incipient cationic metallocene complexes. Again, while not purporting to be bound by theory, it is believed that the ionizing ionic compound can function as an ionizing compound by completely or partially extracting an anionic ligand, such as monoanionic ligand X, from a metallocene complex. However, the ionizing ionic compound can be a co-catalyst regardless of whether it ionizes the metallocene compound, abstracts a ligand X to form an ion pair, weakens the metalX bond in the metallocene, simply coordinates to an X ligand, or activates the metallocene by some other mechanism.
[0152] Additionally, it is not necessary for the ionizing ionic compound to activate only the metallocene compound. The activation function of the ionizing ionic compound may be evident in the enhanced activity of the catalyst composition as a whole, compared to a catalyst composition that does not contain an ionizing ionic compound.
[0153] Examples ionizing ionic compounds may include, but are not limited to the following compounds: tri(n-butyl) ammonium tetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate, tri( n-butyl) ammonium tetrakis(2,4-dimethylphenyl) borate, tri(n-butyl) ammonium tetrakis(3,5-dimethylphenyl) borate, tri(n-butyl) ammonium borate tetrakis[3,5-bis (trifluoromethyl) )phenyl]tri(n-butyl)ammonium tetrakis(pentafluorophenyl), N,N-dimethylanilinium tetrakis(p-tolyl)borate N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2 ,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate , triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis( trifluorm ethyl)phenyl]borate, tetrakis(pentafluorophenyl)borate triphenylcarbenium, tropilium tetrakis(p-tolyl) borate, tropilium tetrakis(m-tolyl) borate, tropilium tetrakis(2,4-dimethylphenyl)borate, tropilium tetrakis(3,5- dimethylphenyl)borate, tropilium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropilium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetrakis(p-tolyl)borate, lithium tetrakis( m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodium tetrakis(p-tolyl)borate , sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetraphenylborate, potassium tetrakis(p -tolyl)borate, potassium tetrakis(m-tolyl) borate, potassium tetrakis(2,4-dimethylphen yl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithium tetrakis (pentafluorophenyl), lithium tetraphenylaluminate, lithium tetrakis(p-tolyl) aluminate, lithium tetrakis(m-tolyl) aluminate, lithium tetrakis (2,4-dimethylphenyl) aluminate, lithium tetrakis(3,5-dimethylphenyl) lithium tetrafluoroaluminate aluminate, sodium tetrakis (pentafluorophenyl), sodium tetraphenylaluminate, sodium tetrakis(p-tolyl) aluminate, sodium tetrakis(m-tolyl) ) aluminate, sodium tetrakis(2,4-dimethylphenyl) aluminate, sodium tetrakis(3,5-dimethylphenyl) sodium tetrafluoroaluminate, potassium tetrakis (pentafluorophenyl) aluminate, potassium tetraphenylaluminate, potassium tetrakis(p-tolyl) aluminate, potassium tetrakis(m-tolyl) aluminate, potassium tetrakis(2,4-dimethylphenyl) aluminate, potassium tetrakis(3,5-dimethylphenyl) aluminate, potassium tetrafluoroaluminate and the like, or combinations thereof. Ionizing ionic compounds useful for this invention are not limited thereto; other examples of ionic ionizing compounds are disclosed in U.S. Patent Nos. 5,576,259 and 5,807,938, the disclosures of which are incorporated herein by reference in their entirety. ORGANOMAGNESIUM, ORGANOZINC AND ORGANOLITHUM COMPOUNDS
[0154] Other aspects are directed to catalyst compositions, which include an organozinc compound, an organomagnesium compound, an organolithium compound or a combination thereof. In some aspects, these compounds have the following general formulas:

[0155] In these formulas, X10, X12, and X14 independently can be a C1 to C18 hydrocarbyl group, and X11 and X13 can independently be H, a halide, or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarbyl group. It is contemplated that X10 and X11 (or X12 and X13) may be the same, or that X10 and X11 (or X12 and X13 may be different.
[0156] In one aspect, X10, X11, X12, X13, and X14 independently may be any C1 to C18 hydrocarbyl group, C1 to C12 hydrocarbyl group, C1 to C8 hydrocarbyl group, or C1 to C5 hydrocarbyl group disclosed herein. In another aspect, X10, X11, X12, X13, and X14 independently may be any of C1 to C18 alkyl group, C2 to C18 alkenyl group, C6 to C18 aryl group, or C7 to C18 aralkyl group disclosed herein; alternatively, any C1 to C12 alkyl group, C2 to C12 alkenyl group, C6 to C12 aryl group, or C7 to C12 aralkyl group disclosed herein; or alternatively, any C1 to C5 alkyl group, a C2 to C5 alkenyl group, C6 to C8 aryl group, or C7 to C8 aralkyl group disclosed herein. Thus, X10, X11, X12, X13, and X14 independently can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group , a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a phenyl group, a naphthyl group, a benzyl group, or a tolyl group and the like. In yet another aspect, X10, X11, X12, X13, and X14 independently may be methyl, ethyl, propyl, butyl or pentyl (e.g. neopentyl), or both or both of X10 and X11 (or both X12 and X13) may be methyl, or ethyl, or propyl, butyl or pentyl (for example neopentyl).
[0157] X11 and X13 may independently be H, a halide or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarboxy group (for example, any C1 to C18, C1 to C12, C1 to C10, or C1 to C8 hydrocarboxy group disclosed herein document). In some aspects, X11 and X13 can independently be H, a halide (for example, Cl), or a C1 to C18 hydrocarbyl or C1 to C18 hydrocarboxy group; alternatively, H, a halide, or a C1 to C8 hydrocarbyl group or a C1 to C8 hydrocarboxy group; or alternatively H, Br, Cl, F, I, methyl, ethyl, propyl, butyl, pentyl (eg neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, phenoxy, toloxy, xyloxy or benzoxy.
[0158] In other aspects, the organozinc and/or organomagnesium compound may have one or two hydrocarbylsilyl fractions. Each hydrocarbyl of the hydrocarbylsilyl group can be any hydrocarbyl group disclosed herein (for example, a C1 to C18 alkyl group, a C2 to C18 alkenyl group, a C6 to C18 aryl group, a C7 to C18 aralkyl group etc.). Illustrative and non-limiting examples of hydrocarbylsilyl groups can include, but are not limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (eg, triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl, trimethylsilylmethyl, and the like.
[0159] Exemplary organozinc compounds that can be used as co-catalysts may include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dynepentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di(triisopropylsilyl)zinc , di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc and the like, or combinations thereof.
[0160] Likewise, exemplary organomagnesium compounds may include, but are not limited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dinepentylmagnesium, di(trimethylsilylmethyl)magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium, neopentylmagnesium chloride, trimethylsilylmethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesium bromide, trimethylsilylmethylmagnesium bromide, methylsilylmagnesium bromide, methylmagnesium iodide, magnesium iodide neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide, methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesium ethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide, trimethylsilylmethylmagnesium ethoxide, methyl propoxymagnesium propoxy, propoxymagnesium propoxide, propoxymagnesium propoxide, propoxymagnesium propoxide of butylmagnesium, neopentylmagnesium propoxide, trimethylsilylmethylmagnesium propoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide, propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesium phenoxide, trimethylsilyl or methylmagnesium phenoxide any combination thereof and the like.
[0161] Likewise, exemplary organolithium compounds may include, but are not limited to, methyllithium, ethyllithium, propyllithium, butyllithium (eg, t-butyllithium), neopentyllithium, trimethylsilylmethyllithium, phenyllithium, tolylithium, xylyllithium, benzyllithium, methyllithium ( dimethylphenyl), allyllithium and the like, or combinations thereof. OLEFIN MONOMERS
[0162] Unsaturated reagents that can be employed with catalyst compositions and polymerization processes of this invention typically can include olefin compounds having from 2 to 30 carbon atoms per molecule and with at least one double-bonded olefin. This invention encompasses homopolymerization processes using a simple olefin, such as ethylene or propylene, as well as copolymerization, terpolymerization, etc. reactions using an olefin monomer with at least one different olefinic compound. For example, copolymers, terpolymers, etc. The resulting ethylene can generally contain a large amount of ethylene (>50 mole percent) and a smaller amount of comonomer (<50 mole percent), but this is not a requirement. Comonomers that can be copolymerized with ethylene often can have 3 to 20 carbon atoms in their molecular chain.
[0163] Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be used in this invention. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention can include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene , 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3 - heptene, the four normal octenes (eg 1-octene), the four normal nonenes, the five normal decenes and so on, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described above. Styrene can also be used as a monomer in the present invention. In one aspect, the olefin monomer can include a C2-C20 olefin; alternatively, the olefin monomer can include a C2-C10 olefin; alternatively, the olefin monomer can include ethylene; or alternatively, the olefin monomer can include propylene.
[0164] When a copolymer (or, alternatively, a terpolymer) is desired, the olefin monomer can comprise, for example, ethylene or propylene, which is copolymerized with at least one comonomer. According to one aspect of this invention, the olefin monomer in the polymerization process can comprise ethylene. In this regard, examples of suitable olefin comonomers may include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1 -pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene and the like , or their combinations. In another aspect, the comonomer may include 1-butene, 1-pentene, 1-hexene, octene-1, 1-decene, styrene or any combination thereof; or alternatively 1-butene, 1-hexene, 1-octene or any combination thereof. In yet another aspect, the olefin monomer can include ethylene and the olefin comonomer can include a C4-C10 alpha-olefin (for example, 1-butene, 1-hexene, 1-octene or a mixture thereof). In yet another aspect, the olefin monomer can include ethylene and the olefin comonomer can include 1-hexene.
[0165] In general, the amount of comonomer introduced into a reactor zone to produce the copolymer can be from about 0.01 to about 50 percent of the comonomer weight based on the total weight of the monomer and comonomer. According to another aspect of the present invention, the amount of comonomer introduced into a reactor zone can be from about 0.01 to about 40% of the weight percent comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into a reactor zone can be from about 0.1 to about 35 percent comonomer weight based on the total weight of monomer and comonomer. In yet another aspect, the amount of comonomer introduced into a reactor zone can be from about 0.5 to about 20% of the weight percent comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the comonomer weight percent based on the total amount of monomer and comonomer can be in a range of from about 4 to about 20 percent by weight, or alternatively, from about 8 to about 15 percent. hundred by weight.
[0166] Although it is not intended to be bound by this theory, where branched, substituted, or functionalized olefins are used as reactants, it is believed that a steric hindrance may impede and/or delay the polymerization reaction. Thus, branched and/or cyclic portion(s) of the olefin removed some of the carbon-carbon double bond would not be expected to hamper the reaction in the way that the same olefin substituent situated closer to the carbon-carbon double bond could. According to one aspect of the present invention, at least one monomer/reagent may be ethylene, so the polymerizations are either a homopolymerization involving ethylene alone, or copolymerizations with a different acyclic, cyclic, terminal, internal, linear, branched, substituted or not replaced. In addition, the catalyst compositions of this invention can be used in polymerizing diolefin compounds, including, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene. CATALYST COMPOSITIONS
[0167] In some aspects, the present invention employs catalyst compositions containing catalyst component I, catalyst component II and an activator-support (one or more than one). These catalyst compositions can be used to produce polyolefins - homopolymers, copolymers and the like - for a variety of end use applications. Catalyst component I and catalyst component II are discussed above. In aspects of the present invention, it is envisioned that the catalyst composition may contain more than one catalyst component I bridge metallocene compound and/or more than one catalyst component II metallocene compound. Additional, additional catalyst compounds - in addition to those specified as catalyst component I or catalyst component II - may be employed in catalyst compositions and/or polymerization processes, provided that the additional catalyst compound(s) does not impair the advantages disclosed herein document. Furthermore, more than one support-activator can also be used.
[0168] The metallocene compounds of catalyst component I, which are discussed above. For example, in some aspects, catalyst component I may include (or consist essentially of or consist of) a bridged single atom metallocene compound having formula (A). Catalyst component II metallocene compounds are also discussed above. For example, in some aspects, catalyst component II may include (or consist essentially or consist of) a metallocene compound having formula (B) or a bridged two carbon metallocene compound having two indenyl groups.
[0169] Catalyst compositions of the present invention generally include catalyst component I, catalyst component II and an activator-support (eg, an activator-support comprising a solid oxide treated with an electron-withdrawal anion). Supports-activators useful in the present invention are disclosed above. Optionally, such catalyst compositions can further comprise one or more co-catalyst compound or compounds (suitable co-catalysts, such as organoaluminium compounds, are also discussed above). Thus, a catalyst composition of this invention may include catalyst component I, catalyst component II, an activator-support and an organoaluminum compound. For example, the support-activator may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, bromide alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, bromide alumina, sulfated silica-alumina , fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated-silica-coated alumina, phosphate-coated alumina, and the like, or combinations thereof . Furthermore, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride , diethylaluminum ethoxide, diethylaluminum chloride and the like, or combinations thereof. Therefore, a catalyst composition consistent with aspects of the invention may include (or consist essentially of, or consist of) a metallocene compound based on hafnium or zirconium with a cyclopentadienyl group and a fluorenyl group and with an alkenyl group substituent. bridge and/or in the cyclopentadienyl group; an unbridged hafnium or zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group, or a bridged two carbon metallocene compound containing two indenyl groups; sulfated alumina (or fluorinated silica-alumina, or fluorinated silica-coated alumina); and triethylaluminum (or triisobutylaluminum).
[0170] In another aspect of the present invention, a catalyst composition is provided which comprises the catalyst component I, the catalyst component II, a support-activator and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxanes , organoboron or organoborate compounds, ionic ionizing compounds, or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, substantially free or organoboron or organoborate compounds; or, alternatively, substantially free of ionic ionizing compounds. In these aspects, the catalyst composition has catalytic activity, to be discussed below, in the absence of these additional materials. For example, a catalyst composition of the present invention may consist essentially of catalyst component I, catalyst component II, a support-activator and an organoaluminum compound, where other materials are not present in the catalyst composition that would increase/decrease activity of the catalyst composition by more than 10% of the catalyst activity in the catalyst composition in the absence of said materials.
[0171] However, in other aspects of the present invention, these activators / co-catalysts may be employed. For example, a catalyst composition comprising catalyst component I, catalyst component II and an activator support may further comprise an optional cocatalyst. Suitable cocatalysts in this aspect may include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionic ionizing compounds, organoaluminium compounds, organozinc compounds, organomagnesium compounds, organolithium compounds and the like or any combination of the same; or alternatively, organoaluminium compounds, organozinc compounds, organomagnesium compounds, organolithium compounds or any combination thereof. More than one co-catalyst can be present in the catalyst composition.
[0172] In a particular aspect contemplated herein, the catalyst composition is a dual catalyst composition comprising an activator-support (one or more than one), a metallocene compound of catalyst component I (e.g., a compound of single atom bridged metallocene with alkenyl substituent) and single catalyst II component metallocene compound (eg only a hafnium or unbridged zirconium based metallocene compound or only a two carbon zirconium based metallocene compound bridged containing two indenyl groups.) In these and other aspects, the catalyst composition may include an activator-support comprising a solid oxide treated with an electron-withdrawal anion; only one metallocene compound having formula (A); and only metallocene compound having formula (B).
[0173] This invention further encompasses all methods of making these catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
[0174] Catalyst component I, catalyst component II, or both, can be pre-contacted with an olefin monomer, if desired, not necessarily the olefin monomer to be polymerized and an organoaluminium compound for a first period of time before contacting with this mixture pre-contacted with a support-activator. The first contact time period, the pre-contacted time, between the metallocene compound, the olefin monomer and the organoaluminum compound typically ranges from a time period of about 1 minute to about 24 hours, for example from about 3 minutes to about 1 hour. Pre-contact times from about 10 minutes to about 30 minutes can also be employed. Alternatively, the pre-contacting process can be carried out in several steps, rather than a single step, in which several mixes can be prepared, each containing a different set of catalyst components. For example, at least two catalyst components can be contacted forming a first mixture, followed by contacting with the first mixture at least one other catalyst component forming a second mixture, and so on.
[0175] Several pre-contact steps can be performed in a single container or in multiple containers. Furthermore, several pre-contact steps can be carried out in series (sequentially), in parallel, or a combination of these. For example, a first mixture of two catalyst components can be formed in a first container, a second mixture comprising the first mixture, plus an additional catalyst component can be formed in the first container or in a second container, which is normally placed at downstream of the first container.
[0176] In another aspect, one or more of the catalyst components can be divided and used in different pre-contact treatments. For example, part of a catalyst component may be fed into a first precontact vessel for precontact with at least one other catalyst component, while the remainder of that same catalyst component is fed into a second precontact vessel. contacting for pre-contacting with at least one other catalyst component, or can be fed directly to the reactor, or a combination thereof. Pre-contacting can be carried out in any suitable equipment, such as tanks, agitated mixing tanks, various static mixing devices, a vial, a container of any type, or combinations of these devices.
[0177] In another aspect of this invention, the various catalyst components (for example, a metallocene compound with a single atom bridged with an alkenyl substituent, metallocene compound based on unbridged zirconium or hafnium or a metallocene compound with two carbons bridged with two indenyl groups, a support-activator, an organoaluminium cocatalyst and optionally an unsaturated hydrocarbon) can be contacted in the polymerization reactor simultaneously while the polymerization reaction is processed. Alternatively, any two or more of these catalyst components can be pre-contacted in a vessel prior to entering the reaction zone. This pre-contact step can be continuous, where the pre-contacted product can be fed continuously into the reactor, or it can be a gradual or batch process, where a batch of the pre-contacted product can be added to make a composition. of the catalyst. This pre-contact step can take place over a period of time that can vary from a few seconds to several days, or more. In this regard, the continuous precontact step can generally last from about 1 second to about 1 hour. In another aspect, the continuous precontact step can last from about 10 seconds to about 45 minutes, or from about 1 minute to about 30 minutes.
[0178] Since the pre-contacted mixture of catalyst component I and/or catalyst component II, olefin monomer and organoaluminium co-catalyst is contacted with the support-activator, this composition (with the addition of the support-activator) is called "post-contacted mix." The post-contacted mixture, optionally, can remain in contact for a second period of time, the post-contact time, before starting the polymerization process. Post-contact times between the pre-contacted mixture and the support-activator generally range from approximately 1 minute to about 24 hours. In another aspect, post-contact time can be in a range of about 3 minutes to about 1 hour. The pre-contact step, the post-contact step, or both, can increase polymer productivity compared to the same catalyst composition that is prepared without pre-contact or post-contact. However, neither a pre-contact step nor a post-contact step is necessary.
[0179] The post-contacted mixture can be heated to a temperature and for a period of time sufficient to allow adsorption, impregnation, or interaction of the pre-contacted mixture and the support-activator, such that a part of the components of the mixture pre -contacted can be immobilized, adsorbed or deposited there. Where heating is employed, the post-contacted mixture generally can be heated to a temperature of between about 18°C (0°F) to about 65°C (150°F), or to about 4°C (40°C). °F) at about 35 °C (95 °F).
[0180] According to one aspect of this invention, the weight ratio of catalyst component I to catalyst component II generally can range from about 20:1 to about 1:20. In another aspect, the weight ratio can range from about 10:1 to about 1:10, from about 10:1 to about 1:8, or from about 10:1 to about 1:5. In yet another aspect, the weight ratio can range from about 8:1 to about 1:8, from about 8:1 to about 1:5, from about 8:1 to 1:4, from about 5:1 to about 1:5; from about 4:1 to about 1:4, from about 3:1 to about 1:3, from about 2:1 to about 1:2, from about 1.5:1 to about 1:1, 5, from about 1.25:1 to about 1:1.25, or from about 1.1:1 to about 1:1.1.
[0181] When a precontact step is used, the molar ratio of the total moles of olefin monomer to the total moles of metallocene(s) in the precontacted mixture can typically be on a scale from about 1:10 to about 100,000:1. Total moles of each component are used in this ratio in view of aspects of this invention where more than one olefin monomer and/or more than one metallocene compound is employed in a precontact step. In addition, this molar ratio can be in a range from about 10:1 to about 1,000:1 in another aspect of the invention.
[0182] In general, the weight ratio of the organoaluminium compound of the support-activator can be in a range of about 10:1 to about 1:1000. If more than one organoaluminium compound and/or more than one support-activator is employed, this proportion is based on the total weight of each respective component. In another aspect, the weight ratio of the compound to the support-activator of the organoaluminium can range from about 3:1 to 1:100, or from about 1:1 to about 1:50.
[0183] In some aspects of the present invention, the weight ratio of the metallocene compound(s) (total catalyst component I and catalyst component II) to the support-activator may be in a range from about 1:1 to about of 1:1,000,000. If more than one support-activator is used, this ratio is based on the total weight of the support-activator. In another aspect, this weight ratio can range from about 1:5 to about 1:100,000, or from about 1:10 to about 1:10,000. In yet another aspect, the weight ratio of metallocene compound(s) to support-activator can be in a range from about 1:20 to about 1:1000.
[0184] Catalyst compositions of the present invention generally have a catalytic activity greater than about 100 grams of polyethylene (homopolymer, copolymer etc., as the context requires) per gram of support-activator per hour (abbreviated g/g/h) . In another aspect, catalyst activity can be greater than about 150, greater than about 250, or greater than about 500 g/g/h. In yet another aspect, catalyst compositions of this invention can be characterized by having a catalytic activity greater than about 550, greater than about 650, or greater than about 750 g/g/hr. In yet another aspect, the catalyst activity can be greater than about 1000 g/g/h. These activities are measured under slurry polymerization conditions using isobutane as the diluent, at a polymerization temperature of about 90°C and a reactor pressure of about 390 psig (2.07 MPa). Generally, reactor pressure is largely controlled by monomer pressure, but other factors that contribute to reactor pressure can include hydrogen (if hydrogen is used), isobutane vapor, and comonomer steam or gas (if comonomer is used ). Furthermore, such catalyst activities can be achieved when the catalyst composition contains a co-catalyst such as an organoaluminum compound (e.g. triethylaluminum, triisobutylaluminum etc.). In addition, in some aspects, the support-activator may include, but not limited to, sulfated alumina, fluorinated silica-alumina, or fluorinated silica-coated alumina.
[0185] As discussed above, any combination of catalyst component I, catalyst component II, the support-activator, the organoaluminum compound and the olefin monomer may be pre-contacted in some aspects of this invention. When any precontact takes place with an olefinic monomer, it is not necessary that the olefin monomer used in the precontact step is the same as the olefin to be polymerized. Furthermore, when a pre-contact step between any combination of catalyst components is employed for a first period of time, that pre-contacted mixture can be used in a subsequent post-contact step between any combination of catalyst components to a second period of time. For example, the one or more metallocene compounds, the organoaluminum compound, and 1-hexene can be used in a pre-contact step for a first period of time, and then this pre-contacted mixture can be contacted with the support-activator to form a post-contacted mixture that can be contacted for a second period of time before starting the polymerization reaction. For example, the first contact time period, the pre-contact time, between any combination of metallocene compounds, the olefinic monomer, the activator support and the organoaluminum compound can be from about 1 minute to 24 hours, from about 3 minutes to about 1 hour or about 10 minutes to about 30 minutes. The post-contacted mixture optionally can be left in contact for a second period of time, the post-contact time, before starting the polymerization process. In accordance with one aspect of this invention, post-contact time between the pre-contacted mixture and any remaining catalyst components can be from about 1 minute to 24 hours, or from about 5 minutes to about 1 hour. POLYMERIZATION PROCESSES
[0186] Catalyst compositions of the present invention can be used to polymerize olefins to form homopolymers, copolymers, terpolymers and the like. One such process for polymerizing olefins in the presence of a catalyst composition of the present invention may include contacting the catalyst composition with an olefin monomer and an olefin comonomer (one or more) under polymerization conditions to produce a polymer of olefin, in which the catalyst composition may include catalyst component I, catalyst component II, an activator-support and a co-catalyst. Catalyst components I and II are discussed above. For example, catalyst component I may include a bridged single-atom metallocene compound having formula (A), and catalyst component II may include an unbridged metallocene compound having formula (B) or a two-atom metallocene compound having formula (B). bridge with two indenyl groups.
[0187] According to one aspect of the invention, the polymerization process can employ a catalyst composition, comprising catalyst component I, catalyst component II and an activator-support. Supports-activators useful in the polymerization processes of the present invention are disclosed above. The catalyst composition optionally further can comprise one or more than one organolauminum compound or compounds (or other suitable co-catalyst). Thus, an olefin polymerization process in the presence of a catalyst composition may employ a catalyst composition comprising catalyst component I, catalyst component II, an activator-support and an organoaluminium compound. In some aspects, the support-activator may comprise (or consist essentially of, or consist of) fluorinated alumina, chlorinated alumina, bromide alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, bromide alumina, silica-alumina sulfated silica, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated-silica-coated alumina, phosphate-coated alumina, and the like, or combinations of the same. In some aspects, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride and the like, or combinations thereof.
[0188] In accordance with another aspect of the invention, the polymerization process can employ a catalyst composition, comprising catalyst component I, catalyst component II, a support-activator and an optional co-catalyst, in which the co-catalyst can include an aluminoxane compound, an organoboron or organoborate compound, an ionic ionizing compound, an organoaluminium compound, an organozinc compound, an organomagnesium compound or an organolithium compound, or any combination thereof. Therefore, aspects of this invention are directed to an olefin polymerization process in the presence of a catalyst composition, the processes comprising contacting a catalyst composition with an olefin monomer and an olefin comonomer (one or more) under polymerization conditions to producing an olefin polymer, and the catalyst composition may include catalyst component I, catalyst component II, a support-activator and an aluminoxane compound; alternatively, catalyst component I, catalyst component II, an activator support and an organoboron compound or an organoborate; alternatively, catalyst component I, catalyst component II, a support-activator and an ionic ionizing compound; alternatively, catalyst component I, catalyst component II, an activator-support and an organoaluminium compound; alternatively, catalyst component I, catalyst component II, an activator-support and an organozinc compound; alternatively, catalyst component I, catalyst component II, an activator-support and an organomagnesium compound; or alternatively, catalyst component I, catalyst component II, an activator-support and an organolithium compound. In addition, more than one co-catalyst may be employed, eg an organoaluminium compound and an aluminoxane compound, an organoaluminium compound and an ionizing ionic compound etc.
[0189] In accordance with another aspect of the invention, the polymerization process can employ a catalyst composition that includes only a bridged metallocene compound of catalyst component I, only an unbridged metallocene compound of catalyst component II, a support -activator and an organoaluminium compound.
[0190] The catalyst compositions of the present disclosure are intended for any method of polymerization of olefins, using various types of polymerization reactors. As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of reactors include those that may be referred to as a batch reactor, slurry reactor, gas phase reactor, solution reactor, high pressure reactor, tube reactor, autoclave reactor and the like, or combinations thereof. Appropriate polymerization conditions are used for the various reactor types. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Slurry reactors can comprise vertical or horizontal circuits. High pressure reactors can include autoclaves or tubular reactors. Reactor types can include batch or continuous processes. Continuous processes could use intermittent or continuous product discharge. Processes can also include direct partial or complete recycling of unreacted monomers, unreacted comonomers and/or diluents.
[0191] The polymerization reactor systems of the present invention can comprise one type of reactor in a system or multiple reactors of the same or different type. Polymer production in multiple reactors can include several steps in at least two separate polymerization reactors, interconnected by a transfer device making it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include manual transfer of polymer from one reactor to subsequent continuous polymerization reactors. Multiple reactor systems can include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase reactors, multiple high pressure reactors, or a combination of high pressure reactors with reactors cycle and/or gas. Multiple reactors can be operated in series, in parallel, or both.
[0192] According to an aspect of the invention, the polymerization reactor system may comprise at least circuit slurry reactor comprising vertical or horizontal circuits. Monomer, diluent, catalyst and comonomer can be continuously fed into a loop reactor where polymerization takes place. Generally, continuous processes can comprise the continuous introduction of a monomer/comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of a suspension comprising polymer particles and the diluent from that reactor. Reactor effluent may be flash evaporated to remove liquids comprising the polymer diluent, monomer and/or solid comonomer. Various technologies can be used for this separation step including, but not limited to, instantaneous evaporation which can include any combination of heat addition and pressure reduction; separation by cyclonic action into a cyclone or hydrocyclone; or separation by centrifugation.
[0193] A typical slurry polymerization process (also known as a particle form process) is disclosed, for example, in Patent Nos. US3,248,179, 4,501,885, 5,565,175, 5,575,979,6,239,235 , 6,262,191 and 6,833,415, each of which is incorporated herein by reference in their entirety.
[0194] Suitable diluents used in slurry polymerization include, among others, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, among others, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some loop polymerization reactions can take place under bulk conditions where no diluent is used. One example is the polymerization of propylene monomer, as disclosed in U.S. Patent No. 5,455,314, which is incorporated herein by reference in its entirety.
[0195] According to yet another aspect of this invention, the polymerization reactor may comprise at least one gas phase reactor. Such reactor systems can employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of catalyst under polymerization conditions. A recycle stream can be taken from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product can be withdrawn from the reactor and fresh or new monomer can be added to replace the polymerized monomer. Such gas-phase reactors may comprise a process for a multi-step gas-phase polymerization of olefins, in which olefins are polymerized in the gas phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. One type of gas phase reactor is disclosed in Patent Nos. U.S. 5,352,749, 4,588,790 and 5,436,304, each of which are incorporated herein by reference in their entirety.
[0196] According to yet another aspect of the invention, a high pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors can have multiple zones where fresh monomer, initiators or catalysts are added. The monomer can be entrained in an inert gaseous stream and introduced into a reactor zone. Initiators, catalysts and/or catalyst components can be entrained in a gaseous stream and introduced into another zone of the reactor. Gas streams can be mixed for polymerization. Heat and pressure can be appropriately employed to obtain optimal polymerization reaction conditions.
[0197] According to yet another aspect of the invention, the polymerization reactor may comprise a solution polymerization reactor, wherein the monomer/monomer is contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer may be employed. If desired, the monomer/comonomer can be brought into the vapor phase in contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Agitation can be employed to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.
[0198] Polymerization reactors suitable for the present invention may further comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components, and/or at least one feed recovery system. polymer. Reactor systems suitable for the present invention may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, offloading, laboratory analysis and process control.
[0199] Polymerization conditions that are controlled for efficiency and to provide the desired polymer properties can include temperature, pressure, and concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. A suitable polymerization temperature can be any temperature below the depolymerization temperature in accordance with the Gibbs Free Energy Equation. Typically, this includes from about 60°C to about 280°C, for example, or from 60°C to about 120°C, depending on the type of polymerization reactor. In some reactor systems, such as slurry processes, the polymerization temperature may generally fall within a range of about 60°C to about 100°C, from about 65°C to about 90°C, or from about 60°C to about 85°C.
[0200] Appropriate pressures will also vary according to the reactor and the type of polymerization. The pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig (6.9 MPa). The pressure for gas phase polymerization is generally about 200 psig to 500 psig (1.4 MPa to 3.5 MPa). High pressure polymerization in tubular or autoclave reactors is generally performed at about 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also be operated in a supercritical region generally occurring at higher temperatures and pressures. Operation above the critical point of a pressure/temperature diagram (supercritical phase) can offer advantages.
[0201] Aspects of this invention are directed to olefin polymerization processes comprising contacting a catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce an olefin polymer. The olefin polymer (for example an ethylene copolymer) produced by the process may contain a higher molecular weight component and a lower molecular weight component, and the olefin polymer may have, for example, a density of less than about 0.930 g/cm 3, a Mw/Mn ratio in a range of about 6 to about 50, and/or an HLMI in a range of about 4 to about 50 g/10 min and less than about 0.008 LCB per 1000 total carbon atoms.
[0202] Aspects of this invention are also directed to olefin polymerization processes performed in the absence of added hydrogen. An olefin polymerization process of the present invention may include contacting the catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce an olefin polymer, in which the catalyst composition may include catalyst component I , catalyst component II, an activator-support and an optional co-catalyst, in which the polymerization process is conducted in the absence of added hydrogen. As those skilled in the art would recognize, hydrogen can be generated in situ by metallocene catalyst compositions in various olefin polymerization processes and the amount generated may vary depending on the specific catalyst composition and metallocene compound(s) used, the type of polymerization process used, the polymerization reaction conditions used, and so on.
[0203] In other respects, it may be desirable to conduct the polymerization process in the presence of a certain amount of added hydrogen. Thus, an olefin polymerization process of the present invention may include contacting the catalyst composition with an olefin monomer and an olefin comonomer under polymerization conditions to produce an olefin polymer, in which the catalyst composition comprises catalyst component I, catalyst component II, an activator-support and an optional co-catalyst, wherein the polymerization process is conducted in the presence of added hydrogen. For example, the ratio of hydrogen and olefin monomer in the polymerization process can be controlled, often by the feed ratio of hydrogen to olefin monomer entering the reactor. The hydrogen added to the olefin monomer ratio in the process can be controlled at a weight ratio that falls within a range of about 25ppm to about 1500ppm, from about 50ppm to about 1000ppm, or about from 100 ppm to about 750 ppm.
[0204] In some aspects of this invention, the ratio of reactant or hydrogen feed to the olefin monomer can be kept substantially constant during the polymerization operation performed for a special polymer class. That is, the hydrogen:olefin monomer ratio can be selected in a particular ratio within a range of about 5 ppm to about 1000 ppm or the like, and maintained at the ratio of about +/- 25% during the operation of polymerization. For example, if the target ratio is 100ppm, then keeping the hydrogen:olefin monomer ratio substantially constant would entail keeping the feed ratio between about 75ppm and about 125ppm. Furthermore, the addition of comonomer (or comonomer) can be, and usually is, substantially constant during polymerization performed for a particular polymer class.
[0205] However, in other respects, it is contemplated that monomer, comonomer (or comonomers) and/or hydrogen may be periodically pulsed into the reactor, for example, in a manner similar to that employed in U.S. Patent no. 5,739,220 and U.S. Patent Publication no. 2004/0059070, the disclosures of which are incorporated into the addendum by reference in their entirety.
[0206] The concentration of reactants entering the polymerization reactor can be controlled to produce resins with certain physical and mechanical properties. The proposed end use product that will be formed by the polymer resin and the method of forming that product ultimately can determine the attributes and properties of the desired polymer. Mechanical properties include tensile strength, bending, impact, creep, wear relaxation and hardness testing. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack enhancement, long chain branching, and rheological measurements.
[0207] This invention is also directed to, and encompasses, polymers produced by any of the polymerization processes disclosed in this document. Articles of manufacture may be formed from and/or may comprise polymers produced in accordance with this invention. POLYMERS AND ARTICLES
[0208] If the resulting polymer produced in accordance with the present invention is, for example, an ethylene polymer or copolymer, its properties can be characterized by different analytical techniques known and used in the polyolefin industry. Articles of manufacture may be formed from and/or may comprise the ethylene polymers of this invention, the typical properties of which are given below. For example, the olefin polymer can be an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer or an ethylene/1-octene copolymer. In particular aspects of the present invention, the olefin polymer is an ethylene/1-hexene copolymer.
[0209] Ethylene copolymers produced in accordance with some aspects of this invention generally can have a high charge melt index (HLMI) of about 3 to about 100 g/10 min. HLMIs in the range of about 4 to about 75 g/10 min, from about 4 to about 50 g/10 min, or about 4 to about 35 g/10 min, are contemplated in other aspects of this invention. For example, a polymer of the present invention can have an HLMI in a range from about 5 to about 75, from about 5 to about 50, from about 7 to about 50, from about 5 to about 35 , from about 7 to about 35, from about 10 to about 35, or from about 10 to about 30 g/10 min.
[0210] Ethylene copolymers produced in accordance with this invention can have an HLMI/MI ratio of more than 25; alternatively, more than about 30; alternatively, more than about 50; alternatively more than about 75; alternatively, more than about 100; alternatively, more than about 150; or, alternatively, more than about 200. Suitable ranges for HLMI/MI may include, but are not limited to, from about 30 to about 350, from about 30 to 300, from about 40 to about 350, from about 50 to 300, from about 70 to about 250, or from about 100 to 200 and the like.
[0211] Densities of ethylene copolymers produced using the catalyst systems and processes disclosed in this document are often less than about 0.930 g/cm3. In one aspect of this invention, the density of an ethylene copolymer can be less than about 0.925, less than about 0.920, or less than about 0.915 g/cm3. In yet another aspect, the density can be in a range from about 0.870 to about 0.930 g/cm3, such as, for example, from about 0.895 to about 0.930 g/cm3, from about 0.905 to about from 0.925 g/cm3, or from about 0.910 to about 0.922 g/cm3.
[0212] Ethylene copolymers consistent with various aspects of the present invention can generally have a broad molecular weight distribution and often with weight average molecular weights (of Mw) greater than approximately 100,000 g/mol, greater than about 150,000 g /mol, or more than about 200,000 g/mol. Typical weight average molecular weights (Mws) of these polymers can be, for example, in a range from 100,000 to about 600,000 g/mol, from about 150,000 to about 600,000 g/mol, from about 150,000 to about 500,000 g/mol, from about 150,000 to about 500,000 g/mol, from about 200,000 to about 500,000 g/mol, or from about 200,000 to about 450,000 g/mol. Likewise, suitable non-limiting ranges of number average molecular weight (Mn) may include from about 7,000 to about 35,000 g/mol, from about 8,000 to about 30,000 g/mol, from about 8,000 to about 28,000 g/mol, from about 8,000 to about 25,000 g/mol, or from about 10,000 to about 25,000 g/mol.
[0213] The Mw/Mn ratio, or polydispersity index, for the polymers of this invention can often be in a range of about 6 to 60. In some aspects, disclosed in this document, the ratio between Mw/Mn can be in a range of about 6 to about 50 of about 8 to about 50, or about 8 to about 35. In other respects, the Mw/Mn ratio may be in a range of about 8 to 30, from about 12 to 25, or from about 15 to 25. In these and other aspects, the olefin polymer can have a bimodal molecular weight distribution. The Mz/Mw ratio for the polymers of this invention can often range from about 3 to 15. For example, the Mz/Mw ratio can be in a range from about 3 to 12, from about 4 to 12. from about 4 to 10, or from about 5 to about 9.
[0214] Generally, ethylene polymers produced in aspects of the present invention have low levels of long branching, with long chain branches typically less than about 0.01 (LCB) per 1000 total carbon atoms, but greater than zero. In some aspects, the number of LCBs per 1000 total carbon atoms can be less than about 0.008, less than about 0.006, less than 0.005 over, or less than about 0.003 LCB per 1000 total carbon atoms.
[0215] Ethylene copolymers produced using the polymerization processes and catalyst systems described above may, in some aspects, have an inverse comonomer distribution, that is, a short chain branching content that increases as the molecular weight increases, by For example, the higher molecular weight components of the polymer generally have greater comonomer incorporation than the lower molecular weight components. Typically, there is an increasing incorporation of comonomer with increasing molecular weight. For example, the number of short chain branches (from SCB) per 1000 total carbon atoms may be greater in Mw than in Mn. In one aspect, the ratio of the number of short chain branches (SCB) per 1000 total polymer carbon atoms in Mw to the number of SCBs per 1000 total polymer carbon atoms in Mn can be in a range of about 1.1:1 to about 5:1, or alternatively, in a range of about 1.5:1 to about 4:1.
[0216] As disclosed in this document, high molecular weight polymers can have a higher molecular weight component and a lower molecular weight component. In some aspects, the ratio of the Mw of the higher molecular weight component to the Mw of the lower molecular weight component can be in a range of from about 2:1 to about 60:1 or from about 5:1 to about 50 : 1. In another aspect, this ratio may be in a range from about 10:1 to about 50:1, from about 20:1 to about 50:1, from about 15:1 to about 45:1 or from about 25:1 to about 40:1.
[0217] The copolymers of this invention can be further characterized in that the Mw/Mn ratio of the higher molecular weight component and/or the Mw/Mn ratio of the lower molecular weight component can be less than about 5; alternatively less than about 4; alternatively less than about 3.5; or alternatively, less than about 3. Likewise, the Mz/Mw ratio of the higher molecular weight component and/or the Mz/Mw ratio of the lower molecular weight component may be less than about 4, less than about 3, less than about 2.5, or less than about 2.
[0218] In some aspects, the catalyst component can incorporate comonomer more efficiently than the catalyst component II. In this sense, the ratio of the number of short chain branches (SCB) per 1000 total carbon atoms of the molecular weight component is greater than the number of short chain branches (SCB) per 1000 total carbon atoms of the lowest molecular weight component it can be greater than about 1.1:1 and in some respects greater than about 1.5:1, or in a range from about 1.5:1 to about 6:1 and the like.
[0219] As with the global polymer, the higher molecular weight component may have low levels of long-chain branching, with long-chain branches (LCB) typically less than about 0.01 in length per 1000 atoms of total carbons, less than about 0.008, about less than 0.006, less than about 0.005, or less than about 0.003 LCB per 1000 total carbon atoms.
[0220] A non-limiting and illustrative example of a copolymer of the present invention may contain a higher molecular weight component and a lower molecular weight component, and the copolymer may be characterized by a density of less than about 0.930 g/ cm3, a Mw/Mn ratio in a range of about 6 to about 50, and/or an HLMI in a range of about 4 to about 50 g/10 min and less than about 0.008 LCB per 1000 carbon atoms totals.
[0221] Another illustrative and non-limiting example of an ethylene copolymer of this invention may include a higher molecular weight component and a lower molecular weight component, and the copolymer may be characterized by a density on a scale of about 0.895 to about 0.930 g/cm3, a Mw/Mn ratio in a range of about 8 to about 35, an HLMI in a range of about 4 to about 50 g/10 min, less than about 0.008 LCB per 1000 total carbon atoms and a reverse comonomer distribution.
[0222] Ethylene polymers, whether homopolymers, copolymers, terpolymers and so on, can be formed into various articles of manufacture. Articles that may comprise polymers of this invention include, but are not limited to, an agricultural film, an automobile part, a bottle, a drum, a fiber or fabric, a food packaging film or container, a food service article. , a fuel tank, a geomembrane, a household container, a liner, a molded product, a medical device or material, a tube, a sheet or tape, a toy, and the like. Various processes can be used to form these articles. Non-limiting examples of these processes can include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. Additionally, additives and modifiers are often added to these polymers to provide beneficial polymer processing or end product attributes. Such processes and materials are described in Modern Plastics Encyclopedia, Mid-November 1995 Issue, Vol. 72, no. 12; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992; the disclosures of which are incorporated herein by reference in their entirety.
[0223] Applicants also contemplate a method for forming or preparing an article of manufacture, consisting of a polymer produced by any of the polymerization processes disclosed in this document. For example, a method can include (i) contacting a catalyst composition with an olefin monomer and an olefin comonomer (one or more) under polymerization conditions to produce an olefin polymer, wherein the catalyst composition can include catalyst component I, catalyst component II, an activator support comprising a solid oxide treated with an electron withdrawing anion and an optional cocatalyst (e.g., an organoaluminium compound); and (ii) forming an article of manufacture comprising the olefin polymer. The forming step may comprise mixing, melt processing, extrusion, molding, or thermoforming and the like, including combinations thereof.
[0224] In some aspects, the article produced from and/or comprising the ethylene polymer of the present invention is a film product. In such aspects, the film can have a puncture impact strength of greater than about 9.85 x 103 kg/m (250 g/mil), a puncture impact strength in a range of about 11.8 x 103 kg/m to 78.75 x 103 kg/m (300 to about 2000 g/mil) or a puncture impact strength in a range of about 17.72 x 103 kg/m to about 59.1 x 103 kg /m (450 to about 1500 g/mil). Additionally or alternatively, the film may have an Elmendorf MD tear strength of more than 3.9 x 103 kg/m (100 g/mil), an Elmendorf MD tear strength in a range of about 3.9 x 103 kg/m to about 29.5 x 103 kg/m (100 to about 750 g/mil), or an MD Elmendorf tear strength in a range of about 4.9 x 103 kg/m to about 19, 7 x 103 kg/m (125 to about 500 g/mil). In addition, or alternatively, the film may have an Elmendorf TD tear strength greater than about 23.6 x 103 kg/m (600 g/mil), an Elmendorf TD tear strength in a range of approximately 25, 6 x 103 kg/m to 78.75 x 103 kg/m (650 to 2000 g/mil), or a TD Elmendorf tear strength in a range of about 27.56 x 103 kg/m to 59.1 x 103 kg /m (700 to about 1500 g/mil). EXAMPLES
[0225] The invention is further illustrated by the following examples, which should in no way be considered to impose limitations on the scope of this invention. Various other aspects, modalities, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one skilled in the art without departing from the sense of the present invention or the scope of the appended claims.
[0226] Melt Index (MI, g/10 min) was determined in accordance with ASTM D1238 at 190°C, with a weight of 2,160 grams. High load melt index (HLMI, g/10 min) was determined in accordance with ASTM D1238 at 190°C, with a weight of 21,600 grams.
[0227] Polymer density was determined in grams per cubic centimeter (g/cm3) in a compression molded sample, cooled at about 15°C per hour and conditioned for about 40 hours at room temperature in accordance with ASTM D1505 and ASTM D4703.
[0228] Molecular weight and Molecular Weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent Company) equipped with an IR4 detector (PolymerChar, Spain) and three Styragéis HMW-6E GPC columns (Waters, MA ) running at 145°C the flow rate of mobile phase 1, 2,4-trichlorobenzene (TCB) containing 0.5 g/L 2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 ml/min and polymer solutions concentrations were generally kept in the range 1.0-1.5 mg/ml, depending on molecular weight. Sample preparation was carried out at 150°C for nominally 4 h with occasional gentle agitation before the solutions were transferred to sample vials for injection. An injection volume of about 200 µL was used. The integral calibration method was used to deduce molecular weights and molecular weight distributions using Chevron Phillips Chemicals Company's HDPE polyethylene resin, and MARLEX ® BHB5003 as a broad standard. The full table of the broad pattern was predetermined in a separate SEC-MALS experiment. MN is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, and Mp is the peak molecular weight.
[0229] Melting rheological characterizations were performed as follows. Small-stem oscillatory measurements were performed on an ARES rheometer (Rheometrics Inc., now TA Instruments) using parallel plate geometry. All rheological tests were performed at 19 °C. Complex viscosity data |^*| versus frequency (O) were then curve fitted using the modified three-parameter Carreau-Yasuda (CY) empirical model to obtain the zero shear viscosity - ^0, characteristic viscous relaxation time - TH and the width parameter - a . The simplified empirical model of Carreau-Yasuda (CY) is as follows.
where: |^* (O) | = magnitude of complex shear viscosity;^0 = zero shear viscosity;TH = viscous relaxation time (Tau(^));a = parameter "width" (parameter CY-a);n = corrects the slope of law of final power, fixed at 2/11; e® = angular frequency of the oscillatory shear strain.
[0230] Details of the significance and interpretation of the CY model and derived parameters can be found in: C.A. Hieber and H.H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R.B. Bird, R.C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in its entirety.
[0231] The long chain branches (LCB) per 1,000 total carbon atoms were calculated using the method of Janzen and Colby (J. Mol. Struct., 485/486, 569-584 (1999)), of shear values viscosity zero, no (determined from the Carreau-Yasuda model, described above), and measured Mw values obtained using a Dawn EOS multi-angle light scattering detector (Wyatt). See also U.S. Patent No. 8,114,946; J. Phys. Chem. 1980, 84, 649; and Y. Yu, D.C. Rohlfing, G.R Hawley, and P.J. DesLauriers, Polymer Preprints, 44, 49-50 (2003). These references are incorporated herein by reference in their entirety.
[0232] Short-chain branching content (SCB) and short-chain branching (SCBD) distribution by molecular weight distribution were determined using an IR5-detected GPC system (GPC-IR5), in which the GPC system was a PL220 GPC/SEC system (Polymer Labs, an Agilent company) equipped with three columns of Styragéis HMW-6E (Waters, MA) for polymer separation. An IR5 MCT thermoelectric refrigeration detector (IR5) (Polymer Char, Spain) was connected to the GPC columns via a hot transfer line. Chromatographic data were obtained from two output ports of the IR5 detector. First, the analog signal goes from the analog output port to a digitizer before connecting to computer "A" to molecular weight determinations via Cirrus software (Polymer Labs, now an Agilent company) and the integral calibration method using a resin from MWD HDPE Marlex™ BHB5003 Broad (Chevron Phillips Chemical) as the Standard Broad Molecular Weight. Digital signals, on the other hand, go via a USB cable directly to computer "B" where they are collected by LabView data collection software provided by Polymer Char. Chromatographic conditions were defined as follows: column oven temperature 145 °C; 1 mL/min flow rate; 0.4 mL injection volume; and the polymer concentration of about 2 mg/ml, depending on the sample molecular weight. The temperatures for the IR5 detector's hot transfer line and sample cell were set at 150°C, while the temperature of the IR5 detector electronics was set at 60°C. Short-chain branching content was determined by an in-house method using the intensity ratio of CH3 (ICH3) to CH22 (iCH2) together with a calibration curve. The calibration curve was a graphical representation of SCB content (xSCB) as a function of the intensity ratio of ICH3/ICH2. To obtain a calibration curve, a group of polyethylene resins (not less than 5) from the SCB level, ranging from zero to ca. 32 SCB/1,000 total carbons (SCB standards). All of these SCB Standards have known SCB levels and flat SCBD profiles pre-determined separately by NMR and solvent-gradient fractionation along with NMR methods (SGF-NMR). Using the SCB calibration curves thus created, short chain branch distribution profiles across the molecular weight distribution were obtained for resins fractionated by the GPC-IR5 system under exactly the same chromatographic conditions as for these SCB standards. A relationship between intensity ratio and elution volume was converted to SCB distribution as a function of MWD using a predetermined SCB calibration curve (ie ICH3/iCH2 intensity ratio vs SCB content) and MW calibration curve (i.e., molecular weight vs. elution time) convert the ICH3/iCH2 intensity ratio and elution time into SCB content and molecular weight, respectively.
[0233] Pilot plant polymerizations were performed in an 87 liter (23-gallon) slurry loop reactor at a production rate of about 25 kilograms of polymer per hour. Polymerization runs were carried out under continuous process conditions to shape the particles in a loop reactor (also known as a slurry process) by contacting a dual metallocene solution in isobutane, an organoaluminum solution and an activator support in a 1-L scrambled autoclave with continuous output to loop reactor. The dual metallocene and organoaluminium solutions were fed as separate streams into a T-tube upstream of the autoclave where they were contacted with each other. The support-activator was released with isobutane in a T-shaped tube between the aforementioned T-tube and the autoclave, contacting the organoaluminium/metallocene mixture just before entering the autoclave. The release of isobutane used to transport the activator holder to the autoclave was set at a rate that would result in a residence time of about 25 minutes in the autoclave. The full flow from the autoclave then entered the reactor in a loop.
[0234] Ethylene used was polymerization grade ethylene that was purified through an alumina column (activated at 250 °C, in nitrogen). 1-Hexene was polymerization grade 1-hexene (obtained from Chevron Phillips Chemical Company), which was purified by purging with nitrogen and storing over activated 13-X molecular sieve at 250°C (482°F) in nitrogen. The loop reactor was a liquid-filled reactor, 15.2 cm diameter, looped, with a volume of 23 gallons (87 liters). Liquid isobutane was used as the diluent. Hydrogen was added to regulate the molecular weight and/or HLMI of the polymer product. The isobutane was polymerization grade isobutane (obtained from Chevron Phillips Chemical Company) which was further purified by distillation and then passed through an alumina column (activated at 250°C, in nitrogen).
[0235] Reactor conditions include a pressure of about 580 psi (4 MPa) and a temperature that has varied from about 70°C (158°F) to about 100°C (212°F), as noted in examples. Furthermore, the reactor was operated to have a residence time of about 1.25 h. Metallocene concentrations in the reactor were within a range of approximately 1 to 2 parts per million (ppm) of the diluent in the polymerization reactor. Polymer was withdrawn from the reactor at a rate of about 11.3 kg/h (25 lb/h) and recovered in a flash chamber. A Vulcan dryer was used to dry the polymer under nitrogen at about 60-80 °C.
[0236] Tri-isobutylaluminum co-catalyst (TIBA, obtained from Akzo Corporation) was also used. The cocatalyst was obtained as a molar solution in heptane, but was further diluted to 1% by weight. The cocatalyst was added at a concentration in a range of about 50 to 60 parts per million of the diluent in the polymerization reactor. To prevent the build-up of reactor static, a small amount (less than 5 ppm by weight of diluent) of a commercial antistatic agent sold as "Stadis 450" was added as needed.
[0237] Metallocene A, phenyl-3-butenylmethylidene(eth5-cyclopentadienyl)(eth5-9,2-7-di-tert-butylfluorenyl)zirconium dichloride, was prepared as described in U.S. Patent No. 7,312,283. Metallocene B, bis(indenyl)zirconium dichloride, was purchased from Witco (Eurecene 5032). Metallocene C, hafnium diphenylmethylidene{n5-[3-(penten-4-yl)cyclopentadien-1-ylidene]}h5-(2,7-di-tert-butylfluoren-9-ylidene)], has been synthesized as reported in US Patent No. 7,732,542. Metallocene D, zirconium dichloride h5-1-(propen-2-yl)indenyl][n5—n-butylcyclopentadienyl], was synthesized as reported in U.S. Patent No. 7,732,542. Metallocene E was rac-ethylene-bis(indenyl)zirconium dichloride, and metallocene F was diphenylmethylidene{n5-[3-(penten-4-yl)cyclopentadien-1-ylidene]}h5-(2,7-di) dichloride -tert-butylfluoren-9-ylidene)]zirconium.
[0238] Alumina A, from W.R. Grace Company, was impregnated in incipient moisture with an aqueous solution of ammonium sulfate. Typically, alumina had a surface area of approximately 330 m2/gram and a pore volume of about 1.3 ml/g. The amount of ammonium sulfate used was equal to 20% of the initial amount of alumina. The volume of water used to dissolve the ammonium sulfate was calculated from the total pore volume of the initial sample (eg 2.6 mL of water for each gram of alumina to be treated). Thus, a solution of about 0.08 grams of ammonium sulfate per mL of water was used. The resulting wet sulfated alumina was dried in a vacuum oven overnight at 120°C and then screened through a 35 mesh screen. Finally, the material was activated in a fluidizing flow of dry air at 550°C for 8 hours. The resulting sulfated alumina was then stored under nitrogen.
[0239] Fluorinated silica-coated aluminas were prepared as follows. Alumina A was first calcined in dry air at about 600°C for approximately 6 hours, cooled to room temperature and then contacted with tetraethylorthosilicate in isopropanol to equal 25 wt% SiO 2 . After drying, the silica-coated alumina was calcined at 600 oC for 3 hours. Fluorinated silica-coated alumina (7 wt % F) was prepared by impregnating the silica-coated calcined alumina with a solution of ammonium bifluoride in methanol, drying and then calcining for 3 hours at 600 oC (unless otherwise indicated) at dry air. Thereafter, fluorinated silica-coated alumina was collected and stored under dry nitrogen and was used without exposure to the atmosphere.
[0240] Some of the blown film samples were made on a laboratory scale blown film line using typical linear low density polyethylene (LLDPE) conditions as follows: 100 mm (4 inch) mold diameter, mold opening 1.5 mm (0.060 inch), 37.5 mm (1.5 inch) diameter single screw extruder equipped with a barrier screw with a Maddock mixing section at the end (L/D = 24, 2.2 :1 compression ratio), output rate about 27 kg/h (60 lb/h), explosion ratio (BUR) 2.5:1, bubble "in the pocket" with a "freeze line height (FLH) of about 28 cm (11 inches), barrel and mold set temperatures of 190°C (375°F) and 1 mil (25 micron) film and 3 mil (75 micron) film. Refrigeration was performed with a Dual Lip air ring using ambient (laboratory) air at approximately 25°C (75-80°F). These specific processing conditions were chosen because the film properties thus obtained are typically representative of those obtained under commercial, larger scale film blowing conditions.
[0241] Other blown film samples were taken on the same film line but under high density polyethylene (HDPE) conditions. Typically, the copolymer was blown into a 1 mil (25.4 microns) of film in a 5.08 cm (2 inch) mold with a 35 mil (889 microns) mold gap at fixed temperatures of 205oC/ 220°C barrel/mold, at a rate of 12.7-13.6 kg/h (28-30 lb/h), with an explosion ratio of 4:1 and a freezing line height of 35, 56 cm (14 inches).
[0242] Puncture impact strength was measured according to ASTM D-1709 (method A). Machine direction (MD) and traverse (TD) Elmendorf tear strengths were measured on a Testing Machines Inc. tear tester (model 83-11-00) in accordance with ASTM D-1922. Film veiling was determined in accordance with ASTM D1003, film-to-film coefficient of friction (COF) was determined in accordance with ASTM D1894, film shrinkage properties were determined in accordance with ASTM D2732, and Spencer Impact was determined in accordance with with ASTM D3420. EXAMPLES 1-7
[0243] In example 1, bimodal polymer was produced in the reactor described above with a solution containing two metallocenes in the following amounts: the first component (producing higher molecular weight) was 45% Metallocene A, and the second (producing lower weight molecular) component was 55% Metallocene B. The total metallocene concentration in the reactor was 1.2 ppm and the activator-support (sulfate-treated alumina, described above) was fed to the reactor at the rate of approximately 0.11 kg/h (0.25 lb/h) to achieve a yield of about 907 kg (2000 lb) polymer per kg (lb) alumina. Triisobutylaluminum was fed to the reactor to maintain a concentration of 50 ppm in the isobutane. 1-Hexene was added to the reactor to maintain a concentration of approximately 0.6 wt% of the isobutane diluent. Ethylene was added to maintain a 15% mol concentration. About 2 g (4.5 mlb) of hydrogen was added to adjust average HLMI to 10.3 g/10 min. Reactor temperature was set at 99°C and reactor polymer concentration was set at 20-30 wt%. Approximately 68 kg (150 lb) of polymer was made under these conditions, having an average HLMI of 10.3 g/10 min and an average density of 0.9502 g/cm 3 . The HLMI/MI ratio was 56, Mw (weight average molecular weight) was 190 kg/mol, polydispersity (Mw/Mn) was 15.3 and the overall polymer had 2.5 long chain branches per million of carbons according to the Janzen-Colby method.
[0244] From the analysis of bimodal GPC curves, the lowest molecular weight component was estimated to have a Mw of 31 kg/mol, while the highest molecular weight component was estimated to have a Mw of 840 kg/mol. Thus, the higher molecular weight component had a Mw that was 27 times greater than the lower molecular weight component.
[0245] When run separately, metallocene A produced polymers having a Mw of about 220 kg/mol, a polydispersity of 2.7, a Mz/Mw of 1.9, and 2.3 long chain branches per million atoms of total carbon. Polymer made with Metallocene A, when run alone under the conditions described above and analyzed by FTIR contained 1.8 branches of butyl per 1000 carbons, while Metallocene B generated 0.5 branches of butyl per 1000 carbons, thus giving a ratio of 1 .8/0.5 = 3.6 (i.e., more branches in the higher molecular weight component than in the lower molecular weight component).
[0246] In constructive example 2, the polymer can be produced in substantially the same way as in example 1, except as follows. The reactor temperature is fixed at 80°C, the 1-hexene feed is increased to equal to 4.5 wt% isobutane diluent and 1.8 g (4.1 mlb) of hydrogen is added to adjust the HLMI average to 8.8. The average density can be 0.9271 g/cm3, the HLMI/MI ratio can be 75, the Mw can be 205 kg/mol and the polydispersity can be 16.2. The global polymer can have 1.5 long chain branches per million carbons according to the Janzen-Colby method.
[0247] GPC analysis of the polymer can be performed, and the lowest molecular weight component can have an estimated Mw of 36 kg/mol, while the higher molecular weight component can have an estimated Mw of 745 kg/mol. Thus, the Mw of the higher molecular weight component can be 21 times greater than the Mw of the lower molecular weight component.
[0248] When run separately, metallocene A can produce polymers having a Mw of about 201 kg/mol, a polydispersity of 2.7, a Mz/Mw of 1.8, and 1.8 long chain branches per million atoms total carbon emissions. Polymer made with Metallocene A, when run alone under the conditions described above and analyzed by FTIR can contain 1.3.3 butyl branches per 1000 carbons, while Metallocene B can generate 3.6 butyl branches per 1000 carbons, thus giving a ratio of 13.3/3.6 = 3.7 (i.e., more branches are expected in the higher molecular weight component than in the lower molecular weight component). Using SEC-FTIR analysis, the short chain branching distribution for the polymer of Constructive Example 2 can be measured, and the expected results are shown in FIG. 1 as a function of molecular weight.
[0249] The bimodal polymer of example 1 was blown into film under the conditions of high density (HD) described above and then again under the conditions of low linear density (LL) described above. Film was produced in a thickness of 1mm and tested for impact and tear resistance. The polymer and film properties of example 1 are shown in table I and table II, respectively. The projected polymer properties of constructive example 2 are shown in table I, while the projected/estimated film properties of constructive example 2 are shown in table II. Example 3 was a commercially available high molecular weight film resin from Equistar Corporation (L5005). Example 4 was a commercially available broad monomodal LLDPE film resin from Chevron Phillips Chemical Company LP (TR257). The lower density of constructive example 2 should considerably improve the mechanical properties.
[0250] In example 5, bimodal polymer was produced in substantially the same way as in example 1. For example 5, a solution containing two metallocenes was fed to the reactor in the following quantities: the first component (producing higher molecular weight) was Metallocene 57% C, and the second (producing lower molecular weight) component was 43% Metallocene D. The total metallocene concentration in the reactor was 1.6 ppm and the activator-support (sulfate-treated alumina, described above) was fed to the reactor at a rate of approximately 0.11 kg/h (0.25 lb/h) to achieve a yield of about 907 kg (2000 lb) of polymer per kg (lb) of alumina. Aluminum triisobutyl was fed to the reactor to maintain a concentration of 55 ppm in the isobutane. 1-Hexene was added to the reactor to maintain a concentration of approximately 0.5 wt% isobutane diluent. Ethylene was added to maintain a 15% mol concentration. About 2g (4.5 mlb) of hydrogen was added to adjust average HLMI to 9.5 g/10 min. Reactor temperature was set at 100°C and reactor polymer concentration was set at 28 wt%. Approximately 113 kg (250 lb) of polymer was made under these conditions, having an average HLMI of 9.5 g/10 min and an average density of 0.9511 g/cm 3 . The HLMI/MI ratio was 185, Mw (weight average molecular weight) was 240 kg/mol, polydispersity (Mw/Mn) was 22.4 and the overall polymer had 1.5 long chain branches per million of carbons according to the Janzen-Colby method.
[0251] From the analysis of bimodal GPC curves, the lowest molecular weight component was estimated to have a Mw of 26 kg/mol, while the highest molecular weight component was estimated to have a Mw of 1200 kg/mol. Thus, the higher molecular weight component had an Mw that was 46 times greater than the lower molecular weight component.
[0252] When run separately, metallocene C produced polymers having a Mw of about 190 kg/mol, a polydispersity of 2.8, a Mz/Mw of 1.8, and 1.5 long chain branches per million atoms of total carbon. Polymer made with Metallocene C, when run alone under the conditions described above and analyzed by FTIR contained branches of 2 butyl branches per 1000 carbons, while Metallocene D generated 0.4 butyl branches per 1000 carbons, thus giving a ratio of 2/ 0.4 = 5 (i.e., more branches in the higher molecular weight component than in the lower molecular weight component).
[0253] In constructive example 6, the polymer can be produced in substantially the same way as in example 5, except as follows. The reactor temperature is set at 80 °C, the 1-hexene feed is increased to equal 5 wt % isobutane diluent and 1.7 g (3.9 mlb) of hydrogen is added to adjust average HLMI to 9.6 g/10 min. The average density can be about 0.9243 g/cm3, the HLMI/MI ratio can be 210, the Mw can be 253 kg/mol and the polydispersity can be 26.1. The global polymer can have 0.7 long chain branches per million carbons according to the Janzen-Colby method.
[0254] GPC analysis of the polymer can be performed, and the lowest molecular weight component can have an estimated Mw of 24 kg/mol, while the higher molecular weight component can have an estimated Mw of 955 kg/mol. Thus, the Mw of the higher molecular weight component may be 40 times greater than the Mw of the lower molecular weight component.
[0255] When run separately, metallocene C can produce polymers having a Mw of about 193 kg/mol, a polydispersity of 2.8, a Mz/Mw of 1.9, and 0.8 long chain branches per million atoms total carbon emissions. Polymer made with Metallocene C, when run alone under the conditions described above and analyzed by FTIR may contain 18 butyl branches per 1000 carbons, whereas Metallocene D generated 4 butyl branches per 1000 carbons, thus giving a ratio of 18/4 = 4 .5 (i.e., more branches are expected in the higher molecular weight component than in the lower molecular weight component).
[0256] The bimodal polymer of example 5 was blown into film under the conditions of high density (HD) described above and then again under the conditions of low linear density (LL) described above. Film was produced in a thickness of 1mm and tested for impact and tear resistance. The polymer and film properties of example 5 are shown in table I and table II, respectively. The projected polymer properties of constructive example 6 are shown in table I, while the projected/estimated film properties of constructive example 6 are shown in table II. The lower density of constructive example 6 should considerably improve mechanical properties, such as puncture impact strength and Elmendorf tear strength. It is expected that the MD punching and tearing impact strengths of constructive example 6 will be comparable or superior to example 4.
[0257] In constructive example 7, the polymer can be produced in substantially the same way as in example 5, except as follows. Reactor temperature is set at 74°C, 1-hexene feed is increased to equal 7.6 wt% isobutane diluent and 1g (2.4 mlb) hydrogen is added to adjust average HLMI to 12 .1 g/10 min. The average density can be about 0.9151 g/cm3, the HLMI/MI ratio can be 168, the Mw can be 202 kg/mol and the polydispersity can be 18.1. The global polymer can have 0.6 long chain branches per million carbons according to the Janzen-Colby method.
[0258] GPC analysis of the polymer can be performed, and the lowest molecular weight component can have an estimated Mw of 23 kg/mol, while the higher molecular weight component can have an estimated Mw of 845 kg/mol. Thus, the Mw of the higher molecular weight component may be 37 times greater than the Mw of the lower molecular weight component.
[0259] When run separately, metallocene C can produce polymers having a Mw of about 187 kg/mol, a polydispersity of 2.7, a Mz/Mw of 1.9, and 0.8 long chain branches per million atoms total carbon emissions. Polymer made with Metallocene C, when run alone under the conditions described above and analyzed by FTIR may contain 24 butyl branches per 1000 carbons, whereas Metallocene D generated 4 butyl branches per 1000 carbons, thus giving a ratio of 24/4 = 4 .8 (i.e., more branches are expected in the higher molecular weight component than in the lower molecular weight component).
[0260] The projected polymer properties of constructive example 7 are shown in table I, while the projected/estimated film properties of constructive example 7 are shown in table II. The lower density of constructive example 7 should considerably improve mechanical properties, such as puncture impact strength and Elmendorf tear strength. It is expected that the MD puncture and tear impact strengths of Constructive Example 7 will be a significant improvement over those of Example 4.


[0261] Example 8 was a broad monomodal LLDPE film resin, having a melt index of 0.2 nominal and a density of 0.924 g/cm3, commercially available from Chevron Phillips Chemical Company LP. Each of Examples 9-16 utilized a dual catalyst system containing a bridged two-carbon zirconium-based metallocene compound that contains two indenyl groups (Metallocene E) and a bridged single-atom zirconium-based metallocene compound containing a cyclopentadienyl and a fluorenyl (Metalocene F) group.
[0262] In example 9, bimodal polymer was produced in the reactor described above with a solution containing Metallocenes E and F, in an E:F weight ratio of 8:1. The total metallocene concentration in the reactor was 0.8 ppm by weight and the support-activator (fluorinated silica-coated alumina, described above) was fed to the reactor at a rate of approximately 0.11 kg/h (0.25 lb/h ), to achieve a yield of about 907 kg (2000 lb) of polymer per kg (lb) of fluorinated silica-coated alumina. Aluminum triisobutyl was fed to the reactor to maintain a concentration of 50 ppm by weight of isobutane. 1-Hexene was added to the reactor to maintain a concentration of about 2.5% mol and ethylene was added to maintain a concentration of about 12% mol (based on the diluent isobutane). About 2g (4.5 mlb) of hydrogen was added to the reactor per hour. Reactor temperature was set at 7980 °C, reactor residence time was approximately 1.2 h and reactor solids % were 29.4 30.3%. Examples 10-16 were produced in the same way as example 9, generally at 11.4-12.4 mol% ethylene and 2.5-2.9 mol% 1-hexene and with the following different amounts of catalysts of Metallocene: Example 10 (1.12 ppm metallocenes at 12:1 E:F ratio), example 11 (0.92 ppm metallocenes at 8:1 E:F weight ratio), example 12 (1, 02 ppm metallocenes at a weight ratio of 20:1 E:F), example 13 (1.6 ppm metallocenes at a weight ratio of 20:1 E:F), example 14 (0.83 ppm of metallocenes at a 20:1 weight ratio of E:F), example 15 (0.79 ppm metallocenes at a 20:1 weight ratio of E:F) and example 16 (0.66 ppm metallocenes in one 30:1 weight ratio of E:F)
[0263] Table III summarizes the polymer properties of examples 8-16. For example, the polymers of examples 9-14 exhibited a unique combination of density, Mw/Mn, HLMI, LCB content and SCB distribution. The broad molecular weight distribution and reverse comonomer distribution of polymers produced using the dual metallocene based catalyst systems disclosed in this document are illustrated in FIGS. 2-9 for the polymers of Examples 9-16, respectively (for example, there are relatively more short chain branches (SCB) for the higher molecular weights; assume 2 methyl (CE) chain ends). In FIGS. 2-9, the number of SCBs per 1000 total carbon atoms (TC) of the polymer in Mz (or Mw) is greater than in Mn.
[0264] Table IV summarizes the properties of the lowest molecular weight component (LMW) and the highest molecular weight component (HMW) of the polymers of examples 9-15. The respective LMW and HMW component properties were determined by deconvoluting the molecular weight distribution (see FIGS. 2-8) of each polymer. The relative amounts of the LMW and HMW components (area percentages) in the polymer and Mp of the LMW component and Mp of the HMW component were determined using a commercial software program (Systat Software, Inc., Peak Fit™ v. 4.05 ). The other molecular weight parameters of the LMW and HMW components (eg Mn, Mw, Mz, etc. of each component) were determined using the deconvoluted data from the Peak FitTM program and applying a Schulz-Flory mathematical distribution function and a Gaussian peak fit, as generally described in US Patent No. 7,300,983, which is incorporated herein by reference in its entirety.
[0265] LCB of polymers from examples 9-16 were determined using the Colby-Janzen method as described in this document. LCB of the HMW component was determined by first producing a polymer using Metallocene F alone under conditions suitable to produce a polymer with molecular weight (Mw) in the range of 100-125 kg/mol and then determining the LCB content using the Janzen-Colby method. LCB of the LMW component was similarly determined by first producing a polymer using Metallocene E alone under conditions suitable to produce a polymer having a Mw in the range of 100-125 kg/mol and then determining the LCB content using the Janzen-Colby method. The polymerization runs used to produce these polymers were carried out in a one-gallon stainless steel reactor with 1.8 L of isobutane. About 1 mmol of triisobutylaluminum, 100 mg of fluorinated silica-coated alumina and 3 mg of the respective metallocene compound were added in that order through a charging port while slowly venting isobutane vapor. The loading port was closed and isobutane added. The reactor contents were stirred and heated to a polymerization temperature of 80°C, and ethylene and 40 ml of 1-hexene were then introduced into the reactor. Ethylene was fed on demand to maintain a target pressure of 400 psig (2.76 Mpa) for the 30 min extension of the polymerization run. If necessary, hydrogen was added with the ethylene feed to produce a polymer with a Mw in the range of 100-125 kg/range. The reactor was kept at the desired temperature during execution by an automated heating and cooling system. Using Metallocene E, polymers were produced at a Mw of 110 kg/mol and a Mw of 112 kg/mol, and these polymers had LCBs of 12.3 and 12.4, respectively, per million carbon atoms. Using Metallocene F, polymers were produced at a Mw of 107 kg/mol and 122 kg/mol, and both polymers had 1.1 LCB per million carbon atoms. Therefore, the ratio of the number of LCBs of the LMW component to the number of LCBs of the HMW component, per million total carbon atoms, was about 11:1.
[0266] Blown films were produced under the HDPE conditions given above at an output rate of 12.7-13.6 kg/h (28-30 lb/h) and a melting temperature of 191-192 °C. In table V, blown films labeled with an "A" were made without an adjuvant polymer (eg, example 10A), while those labeled with a "B" were made with 400 to 800 ppm of an adjuvant polymer (eg, example , 10B). Gels were measured using an automated camera-based gel counting machine made by the Optical Control System (OCS), model FS-5. The system consisted of a light source and a detector. The film was passed through the system, between the light source and the detector, with an inspection width of 150 mm (6 inches). A total of 10 square meters of film area was inspected and gels with sizes less than or greater than 200 microns were analyzed. The numbers in the table represent the numbers for each gel size category counted per square foot. Films made from the polymers of Examples 9-13, as shown in Table V, exhibited a unique combination of puncture impact strength, MD tear strength, opaque, COF and shrinkage properties. In particular, films made from the polymers of examples 9-13 have 3-7 times higher puncture impact strengths than the film produced from the polymer of example 8.
[0267] Blown films were produced under the LLDPE conditions given above at an output rate of approximately 27 kg/h (60 lb/h) and a melting temperature of 179-184 °C, except for example 9, which was produced at an output rate of 20.41-21.77 kg/h (45-48 lb/h) due to pressure limitations. In tables VI-VII, blown films labeled with an "A" were made without an adjuvant polymer (eg 10A), while those labeled with a "B" were made with 400 to 800 ppm of an adjuvant polymer (eg , example, 10B). Films made from the polymers of Examples 9-15, as shown in Table VI, exhibited a unique combination of puncture impact strength, MD tear strength, cloudiness, COF and shrinkage properties. In particular, films made from the polymers of examples 9-15 have higher puncture impact strengths and lower gels than the film produced from the polymer of example 8.

权利要求:
Claims (18)
[0001]
1. Olefin polymer, characterized in that it comprises a higher molecular weight component and a lower molecular weight component, wherein the olefin polymer has: a density in the range of 0.895 to 0.930 g/cm3 (ASTM D1505 and ASTM D4703); a Mw/Mn ratio in a range of 8 to 35 (GPC); an HLMI in a range of 4 to 50 g/10 min (ASTM D1238); less than 0.008 LCB per 1000 total carbon atoms; and a reverse comonomer distribution.
[0002]
2. Polymer according to claim 1, characterized in that the olefin polymer has an HLMI/MI ratio in a range of 50 to 300.
[0003]
3. Polymer according to claim 1 or 2, characterized in that the olefin polymer has: one Mw in a range of 100,000 to 600,000 g/mol; and one Mn in a range of 10,000 to 25,000 g/mol.
[0004]
4. Polymer according to any one of claims 1 to 3, characterized in that the olefin polymer has a density in a range from 0.905 to 0.925 g/cm3.
[0005]
5. Polymer according to any one of claims 1 to 4, characterized in that the olefin polymer has HLMI in a range of 4 to 35 g/10 min.
[0006]
6. Polymer according to any one of claims 1 to 5, characterized in that the olefin polymer has less than 0.005 LCB per 1000 total carbon atoms.
[0007]
7. Polymer according to any one of claims 1 to 6, characterized in that the olefin polymer has an HLMI/MI ratio in a range from 70 to 250.
[0008]
8. Polymer according to any one of claims 1 to 7, characterized in that the olefin polymer has Mw in a range of 150,000 to 500,000 g/mol.
[0009]
9. Polymer according to any one of claims 1 to 8, characterized in that the olefin polymer has a ratio of Mz/Mw in a range of 3 to 12.
[0010]
10. Polymer according to any one of claims 1 to 9, characterized in that the olefin polymer has a ratio of the Mw of the higher molecular weight component to the Mw of the lower molecular weight component in a range of 5: 1 to 50:1.
[0011]
11. Polymer according to any one of claims 1 to 10, characterized in that a Mw/Mn ratio of the higher molecular weight component and a Mw/Mn ratio of the lower molecular weight component is less than 5.
[0012]
12. Polymer according to any one of claims 1 to 11, characterized in that an Mz/Mw ratio of the higher molecular weight component and an Mz/Mw ratio of the lower molecular weight component is less than 4.
[0013]
13. Polymer according to any one of claims 1 to 12, characterized in that the component with the highest molecular weight has less than 0.003 LCB per 1000 total carbon atoms.
[0014]
14. Polymer according to any one of claims 1 to 13, characterized in that the olefin polymer is a copolymer of ethylene/1-butene, a copolymer of ethylene/1-hexene or a copolymer of ethylene/1- octene.
[0015]
15. Polymer according to any one of claims 1 to 14, characterized in that the olefin polymer is a copolymer of ethylene/1-hexene.
[0016]
16. Film, characterized in that it comprises the olefin polymer as defined in any one of claims 1 to 15.
[0017]
17. Film, characterized in that it comprises the olefin polymer as defined in any one of claims 1 to 15, wherein the film has a dart impact strength (ASTM D1709) greater than 9.85 x 103 kg/m ( 250 g/mil).
[0018]
18. Film, characterized in that it comprises the olefin polymer as defined in any one of claims 1 to 15, wherein the film has a dart impact strength in a range of 11.8 x 103 to 78.75 x 103 kg/m (300 to 2000 g/mil).

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112015010241B1|2021-07-20|LOW DENSITY POLYOLEFIN RESINS AND FILMS MADE FROM THEM

---

US10899855B2|2021-01-26|Low density polyolefin resins with low molecular weight and high molecular weight components, and films made therefrom

---

US9371407B2|2016-06-21|Catalyst system with three metallocenes for producing broad molecular weight distribution polymers

---

US8623973B1|2014-01-07|Activator supports impregnated with group VIII transition metals for polymer property control

---

EP3041873B2|2022-03-02|Higher density polyolefins with improved stress crack resistance

---

US8703886B1|2014-04-22|Dual activator-support catalyst systems

---

EP2900705B1|2017-08-02|Metallocene and half sandwich dual catalyst systems for producing broad molecular weight distribution polymers

---

BR112016003161B1|2020-12-22|olefin polymerization process and catalytic composition

---

BR112016027380B1|2021-08-10|POLYMERIZATION PROCESS AND CATALYST COMPOSITION

---

BR112016009743B1|2021-11-16|ETHYLENE POLYMER COMPRISING A HIGHER MOLECULAR WEIGHT COMPONENT AND A LOWER MOLECULAR WEIGHT COMPONENT, ARTICLE, FILM AND BLOW FILM COMPRISING SUCH POLYMER, CATALYTIC COMPOSITION AND OLEFIN POLYMERIZATION PROCESS

同族专利:

---

公开号 | 公开日

---

EP2917267B1|2016-09-07|

---

CN104781319A|2015-07-15|

---

US9006367B2|2015-04-14|

---

BR112015010241A2|2017-07-11|

---

SG11201503462TA|2015-05-28|

---

US20140128563A1|2014-05-08|

---

US20150175726A1|2015-06-25|

---

CN104781319B|2018-04-10|

---

WO2014074622A1|2014-05-15|

---

CA2890027A1|2014-05-15|

---

CA2890027C|2020-04-28|

---

US9334350B2|2016-05-10|

---

ES2606684T3|2017-03-27|

---

EP2917267A1|2015-09-16|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3248179A|1962-02-26|1966-04-26|Phillips Petroleum Co|Method and apparatus for the production of solid polymers of olefins|

---

US3242099A|1964-03-27|1966-03-22|Union Carbide Corp|Olefin polymerization catalysts|

---

US4060480A|1971-09-03|1977-11-29|Chevron Research Company|Hydrocarbon hydroconversion process employing hydroxy-aluminum stabilized catalysts supports|

---

US4501885A|1981-10-14|1985-02-26|Phillips Petroleum Company|Diluent and inert gas recovery from a polymerization process|

---

US4588790A|1982-03-24|1986-05-13|Union Carbide Corporation|Method for fluidized bed polymerization|

---

US4452910A|1982-06-15|1984-06-05|Standard Oil Company |Chromium expanded smectite clay|

---

US4808561A|1985-06-21|1989-02-28|Exxon Chemical Patents Inc.|Supported polymerization catalyst|

---

US4794096A|1987-04-03|1988-12-27|Fina Technology, Inc.|Hafnium metallocene catalyst for the polymerization of olefins|

---

US5565175A|1990-10-01|1996-10-15|Phillips Petroleum Company|Apparatus and method for producing ethylene polymer|

---

US5575979A|1991-03-04|1996-11-19|Phillips Petroleum Company|Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator|

---

AU650787B2|1991-12-09|1994-06-30|Phillips Petroleum Company|Process for preparing a pillared chain silicate clay|

---

US5436304A|1992-03-19|1995-07-25|Exxon Chemical Patents Inc.|Process for polymerizing monomers in fluidized beds|

---

US5352749A|1992-03-19|1994-10-04|Exxon Chemical Patents, Inc.|Process for polymerizing monomers in fluidized beds|

---

US5576259A|1993-10-14|1996-11-19|Tosoh Corporation|Process for producing α-olefin polymer|

---

US5455314A|1994-07-27|1995-10-03|Phillips Petroleum Company|Method for controlling removal of polymerization reaction effluent|

---

DE69611554T2|1995-02-20|2001-07-05|Tosoh Corp|Catalyst for the polymerization of olefins and process for the preparation of olefin polymers|

---

EP0889912B1|1996-03-27|2000-07-12|The Dow Chemical Company|Highly soluble olefin polymerization catalyst activator|

---

US5739220A|1997-02-06|1998-04-14|Fina Technology, Inc.|Method of olefin polymerization utilizing hydrogen pulsing, products made therefrom, and method of hydrogenation|

---

US6239235B1|1997-07-15|2001-05-29|Phillips Petroleum Company|High solids slurry polymerization|

---

KR100531628B1|1998-03-20|2005-11-29|엑손모빌 케미칼 패턴츠 인코포레이티드|Continuous slurry polymerization volatile removal|

---

US6107230A|1998-05-18|2000-08-22|Phillips Petroleum Company|Compositions that can produce polymers|

---

US6300271B1|1998-05-18|2001-10-09|Phillips Petroleum Company|Compositions that can produce polymers|

---

US6165929A|1998-05-18|2000-12-26|Phillips Petroleum Company|Compositions that can produce polymers|

---

US6294494B1|1998-12-18|2001-09-25|Phillips Petroleum Company|Olefin polymerization processes and products thereof|

---

US6262191B1|1999-03-09|2001-07-17|Phillips Petroleum Company|Diluent slip stream to give catalyst wetting agent|

---

US6355594B1|1999-09-27|2002-03-12|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6376415B1|1999-09-28|2002-04-23|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6395666B1|1999-09-29|2002-05-28|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6548441B1|1999-10-27|2003-04-15|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6391816B1|1999-10-27|2002-05-21|Phillips Petroleum|Organometal compound catalyst|

---

US6613712B1|1999-11-24|2003-09-02|Phillips Petroleum Company|Organometal catalyst compositions with solid oxide supports treated with fluorine and boron|

---

US6548442B1|1999-12-03|2003-04-15|Phillips Petroleum Company|Organometal compound catalyst|

---

US6750302B1|1999-12-16|2004-06-15|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6524987B1|1999-12-22|2003-02-25|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6667274B1|1999-12-30|2003-12-23|Phillips Petroleum Company|Polymerization catalysts|

---

US6632894B1|1999-12-30|2003-10-14|Phillips Petroleum Company|Organometal catalyst compositions|

---

US6576583B1|2000-02-11|2003-06-10|Phillips Petroleum Company|Organometal catalyst composition|

---

US6388017B1|2000-05-24|2002-05-14|Phillips Petroleum Company|Process for producing a polymer composition|

---

US7829646B2|2000-08-18|2010-11-09|Chevron Phillips Chemical Company Lp|Olefin polymers, method of making, and use thereof|

---

MY137183A|2001-03-16|2009-01-30|Dow Global Technologies Inc|Method of making interpolymers and products made therefrom|

---

US20040059070A1|2002-09-19|2004-03-25|Whitte William M.|Process and apparatus for controlling molecular weight distribution and short chain branching for olefin polymers|

---

US7041617B2|2004-01-09|2006-05-09|Chevron Phillips Chemical Company, L.P.|Catalyst compositions and polyolefins for extrusion coating applications|

---

US7119153B2|2004-01-21|2006-10-10|Jensen Michael D|Dual metallocene catalyst for producing film resins with good machine direction elmendorf tear strength|

---

US7696280B2|2004-04-30|2010-04-13|Chevron Phillips Chemical Company, Lp|HDPE resins for use in pressure pipe and related applications|

---

US7625982B2|2005-08-22|2009-12-01|Chevron Phillips Chemical Company Lp|Multimodal polyethylene compositions and pipe made from same|

---

US7312283B2|2005-08-22|2007-12-25|Chevron Phillips Chemical Company Lp|Polymerization catalysts and process for producing bimodal polymers in a single reactor|

---

US7226886B2|2005-09-15|2007-06-05|Chevron Phillips Chemical Company, L.P.|Polymerization catalysts and process for producing bimodal polymers in a single reactor|

---

US7517939B2|2006-02-02|2009-04-14|Chevron Phillips Chemical Company, Lp|Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching|

---

US7619047B2|2006-02-22|2009-11-17|Chevron Phillips Chemical Company, Lp|Dual metallocene catalysts for polymerization of bimodal polymers|

---

US7632907B2|2006-06-28|2009-12-15|Chevron Phillips Chemical Company Lp|Polyethylene film having improved mechanical and barrier properties and method of making same|

---

EP2058337A1|2007-11-06|2009-05-13|Total Petrochemicals Research Feluy|Process for preparing a polyethylene resin in a double loop reactor with a mixture of bis-indenyl and bis-tetrahydroindenyl catalyst components|

---

US7884163B2|2008-03-20|2011-02-08|Chevron Phillips Chemical Company Lp|Silica-coated alumina activator-supports for metallocene catalyst compositions|

---

US7884165B2|2008-07-14|2011-02-08|Chevron Phillips Chemical Company Lp|Half-metallocene catalyst compositions and their polymer products|

---

US8114946B2|2008-12-18|2012-02-14|Chevron Phillips Chemical Company Lp|Process for producing broader molecular weight distribution polymers with a reverse comonomer distribution and low levels of long chain branches|

---

US8309485B2|2009-03-09|2012-11-13|Chevron Phillips Chemical Company Lp|Methods for producing metal-containing sulfated activator-supports|

---

GB0918736D0|2009-10-26|2009-12-09|Isis Innovation|Catalysts|

---

US8288487B2|2010-07-06|2012-10-16|Chevron Phillips Chemical Company Lp|Catalysts for producing broad molecular weight distribution polyolefins in the absence of added hydrogen|

---

US8476394B2|2010-09-03|2013-07-02|Chevron Philips Chemical Company Lp|Polymer resins having improved barrier properties and methods of making same|

---

US8309748B2|2011-01-25|2012-11-13|Chevron Phillips Chemical Company Lp|Half-metallocene compounds and catalyst compositions|

---

US8865846B2|2012-09-25|2014-10-21|Chevron Phillips Chemical Company Lp|Metallocene and half sandwich dual catalyst systems for producing broad molecular weight distribution polymers|

---

EP2917267B1|2012-11-07|2016-09-07|Chevron Phillips Chemical Company LP|Low density polyolefin resins ad films made therefrom|

---

US8912285B2|2012-12-06|2014-12-16|Chevron Phillips Chemical Company Lp|Catalyst system with three metallocenes for producing broad molecular weight distribution polymers|

---

US9346897B2|2013-05-14|2016-05-24|Chevron Phillips Chemical Company Lp|Peroxide treated metallocene-based polyolefins with improved melt strength|

---

US9156970B2|2013-09-05|2015-10-13|Chevron Phillips Chemical Company Lp|Higher density polyolefins with improved stress crack resistance|

---

US9181370B2|2013-11-06|2015-11-10|Chevron Phillips Chemical Company Lp|Low density polyolefin resins with low molecular weight and high molecular weight components, and films made therefrom|

---

US9169337B2|2014-03-12|2015-10-27|Chevron Phillips Chemical Company Lp|Polymers with improved ESCR for blow molding applications|

---

US9273170B2|2014-03-12|2016-03-01|Chevron Phillips Chemical Company Lp|Polymers with improved toughness and ESCR for large-part blow molding applications|EP2917267B1|2012-11-07|2016-09-07|Chevron Phillips Chemical Company LP|Low density polyolefin resins ad films made therefrom|

---

US8912285B2|2012-12-06|2014-12-16|Chevron Phillips Chemical Company Lp|Catalyst system with three metallocenes for producing broad molecular weight distribution polymers|

---

US10308776B2|2012-12-18|2019-06-04|Exxonmobil Chemical Patents Inc.|Polyethylene films and method of making same|

---

US10577440B2|2013-03-13|2020-03-03|Chevron Phillips Chemical Company Lp|Radically coupled resins and methods of making and using same|

---

US9156970B2|2013-09-05|2015-10-13|Chevron Phillips Chemical Company Lp|Higher density polyolefins with improved stress crack resistance|

---

US9181370B2|2013-11-06|2015-11-10|Chevron Phillips Chemical Company Lp|Low density polyolefin resins with low molecular weight and high molecular weight components, and films made therefrom|

---

WO2015123166A1|2014-02-11|2015-08-20|Univation Technologies, Llc|Method to prepare ethylene copolymers|

---

US9169337B2|2014-03-12|2015-10-27|Chevron Phillips Chemical Company Lp|Polymers with improved ESCR for blow molding applications|

---

US9079993B1|2014-05-22|2015-07-14|Chevron Phillips Chemical Company Lp|High clarity low haze compositions|

---

US9284389B2|2014-07-29|2016-03-15|Chevron Phillips Chemical Company Lp|Bimodal resins having good film processability|

---

KR101617870B1|2014-09-05|2016-05-03|주식회사 엘지화학|Olefin based polymer having excellent processibility|

---

US9493589B1|2015-09-09|2016-11-15|Chevron Phillips Chemical Company Lp|Polymers with improved ESCR for blow molding applications|

---

US9650459B2|2015-09-09|2017-05-16|Chevron Phillips Chemical Company Lp|Methods for controlling die swell in dual catalyst olefin polymerization systems|

---

US9540457B1|2015-09-24|2017-01-10|Chevron Phillips Chemical Company Lp|Ziegler-natta—metallocene dual catalyst systems with activator-supports|

---

KR102064990B1|2016-03-11|2020-03-02|주식회사 엘지화학|Supported hybrid catalyst system for ethylene slurry polymerization and method for preparing ethylene polymer with the catalyst system|

---

WO2017186728A1|2016-04-26|2017-11-02|Total Research & Technology Feluy|Polyolefin compositions|

---

US10000594B2|2016-11-08|2018-06-19|Chevron Phillips Chemical Company Lp|Dual catalyst system for producing LLDPE copolymers with a narrow molecular weight distribution and improved processability|

---

KR102139364B1|2016-12-20|2020-07-29|주식회사 엘지화학|Olefin polymer and preparation method thereof|

---

KR102087340B1|2016-12-20|2020-03-10|주식회사 엘지화학|Polyolefin-based film|

---

JP2020512467A|2017-03-30|2020-04-23|ボレアリス エージー|Aluminoxane activated metallocene catalysts|

---

US11192963B2|2017-03-30|2021-12-07|Borealis Ag|Borate-activated metallocene catalysts|

---

CN111108130A|2017-08-04|2020-05-05|埃克森美孚化学专利公司|Has the advantages ofcontaining-CH2-SiMe3Hybrid catalysts of partially unbridged hafnocenes|

---

US10844150B2|2017-08-04|2020-11-24|Exxonmobil Chemical Patents Inc.|Mixed catalysts with 2,6-bispyridyl iron complexes and bridged hafnocenes|

---

US10435527B2|2017-09-26|2019-10-08|Chevron Phillips Chemical Company Lp|Dual component LLDPE copolymers with improved impact and tear resistance|

---

US10899860B2|2018-08-30|2021-01-26|Exxonmobil Chemical Patents Inc.|Polymerization processes and polymers made therefrom|

---

EP3700947A1|2017-10-23|2020-09-02|ExxonMobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

US10927205B2|2018-08-30|2021-02-23|Exxonmobil Chemical Patents Inc.|Polymerization processes and polymers made therefrom|

---

WO2020046406A1|2018-08-30|2020-03-05|Exxonmobil Chemical Patents Inc.|Polymerization processes and polymers made therefrom|

---

US20190135960A1|2017-11-07|2019-05-09|Nova ChemicalsS.A.|Process to manufacture ethylene interpolymer products|

---

WO2019094131A1|2017-11-13|2019-05-16|Exxonmobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

WO2019094132A1|2017-11-13|2019-05-16|Exxonmobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

US11130827B2|2017-11-14|2021-09-28|Exxonmobil Chemical Patents Inc.|Polyethylene compositions and articles made therefrom|

---

EP3717525A1|2017-11-28|2020-10-07|ExxonMobil Chemical Patents Inc.|Catalyst systems and polymerization processes for using the same|

---

EP3717527A1|2017-11-28|2020-10-07|ExxonMobil Chemical Patents Inc.|Polyethylene compositions and films made therefrom|

---

US10851187B2|2018-01-31|2020-12-01|Exxonmobil Chemical Patents Inc.|Bridged metallocene catalysts with a pendant group 13 element, catalyst systems containing same, processes for making a polymer product using same, and products made from same|

---

US10865258B2|2018-01-31|2020-12-15|Exxonmobil Chemical Patents Inc.|Mixed catalyst systems containing bridged metallocenes with a pendant group 13 element, processes for making a polymer product using same, and products made from same|

---

EP3755705A1|2018-02-19|2020-12-30|ExxonMobil Chemical Patents Inc.|Catalysts, catalyst systems, and methods for using the same|

---

US10259893B1|2018-02-20|2019-04-16|Chevron Phillips Chemical Company Lp|Reinforcement of a chromium/silica catalyst with silicate oligomers|

---

EP3853268A2|2018-09-17|2021-07-28|Chevron Phillips Chemical Company LP|Modified supported chromium catalysts and ethylene-based polymers produced therefrom|

---

US11014997B2|2019-05-16|2021-05-25|Chevron Phillips Chemical Company Lp|Dual catalyst system for producing high density polyethylenes with long chain branching|

---

US11186656B2|2019-05-24|2021-11-30|Chevron Phillips Chemical Company Lp|Preparation of large pore silicas and uses thereof in chromium catalysts for olefin polymerization|

---

CN113950491A|2019-05-31|2022-01-18|陶氏环球技术有限责任公司|Low density polyethylene with improved processability|

---

US11078143B2|2019-09-16|2021-08-03|Chevron Phillips Chemical Company, Lp|Chromium-catalyzed production of alcohols from hydrocarbons|

---

US11267919B2|2020-06-11|2022-03-08|Chevron Phillips Chemical Company Lp|Dual catalyst system for producing polyethylene with long chain branching for blow molding applications|

---

US11186662B1|2020-07-14|2021-11-30|Chevron Phillips Chemical Company Lp|Metallocene catalyst systems with chemically-treated solid oxides for producing ethylene-based plastomers and elastomers|

法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

---

2020-05-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-02-17| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

---

2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-07-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201261723335P| true| 2012-11-07|2012-11-07|

---

US61/723,335|2012-11-07|

---

PCT/US2013/068785|WO2014074622A1|2012-11-07|2013-11-06|Low density polyolefin resins ad films made therefrom|

---