ETHYLENE POLYMER, ARTICLE AND FILM FORMED FROM SUCH ETHYLENE POLYMER AND POLYMERIZATION METHOD FORME

专利摘要:
novel catalytic compositions and methods for creating and using them. an ethylene polymer having (i) a density defined by equation (1) (ró) > a - b log m (1) where (ró) is a density of the polymer in g/cc, log m is a log molecular weight polymer average, a is about 1.0407 and b is about 0.0145; and (ii) a polydispersity index greater than about 5.
公开号:BR112015009417B1
申请号:R112015009417-1
申请日:2013-10-24
公开日:2021-08-31
发明作者:Mark L Hlavinka；Guylaine St Jean；Qing Yang
申请人:Chevron Phillips Chemical Company Lp；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED ORDERS
[0001] Not applicable. DECLARATION WITH RESPECT TO RESEARCH OR DEVELOPMENT SPONSORED BY THE FEDERAL GOVERNMENT
[0002] Not applicable. FUNDAMENTALS OF THE INVENTION
[0003] The present disclosure generally relates to catalytic systems and polymeric compositions. Especially, the present disclosure relates to original catalytic compositions for producing high density polymeric compositions. FIELD OF THE INVENTION
[0004] Polyolefins are plastic materials useful for creating a wide variety of valued products due to their combination such as stiffness, ductility, barrier properties, temperature resistance, optical properties, availability and low cost. In particular, polyethylene (PE) is one of the largest volume polymers consumed in the world. It is a versatile polymer that offers high performance over alternative polymers and materials such as glass or metal. An important PE product is tubing. There is a continuing need for improved catalytic systems for the production of polymeric compositions. BRIEF SUMMARY
[0005] It is disclosed in this document an ethylene polymer having (i) a density defined by the equation (1) p > a - b Log M (1) Where p is a polymer density in g/cc, log M is a logarithm of the average molecular weight of the polymer, a is about 1.0407 and b is about 0.0145; and (ii) a polydispersity index greater than about 5.
[0006] Also disclosed in this document is a polymerization method comprising contacting a monomer with a catalytic system characterized by the fact that it comprises an imine-phenol compound under suitable conditions for the formation of a polymer and polymer recovery, where the imine-phenol compound is characterized by having the formula:
Where O and N represent oxygen and nitrogen, respectively, R comprises a halogen, a hydrocarbyl group, or a substituted hydrocarbyl group, R2 and R3 may each independently be hydrogen, a halogen, a hydrocarboyl group, or a substituted hydrocarbyl group, and Q is a donor group, and where the polymer is characterized by: i) a density defined by the equation (1) p > a - b Log M (1) Where p is a polymer density in g/cc, log M is a log average polymer molecular weight, a is about 1.0407 and b is about 0.0145; and (ii) a polydispersity index greater than about 5.
[0007] Further disclosed in this document is a polyethylene homopolymer having a density greater than about 0.960 g/cc, a melt index greater than about 0.8 g/10 min, and a polydispersity index greater than about 7 , where a film formed by polyethylene homopolymer exhibits a moisture vapor transmission rate less than or equal to about 0.37 gram-mm per 100 square inches per day. BRIEF DESCRIPTION OF THE FIGURES
[0008] Figure 1 is an NMR spectrum of a salt metal complex of an imine (bis)phenolate compound.
[0009] Figures 2-4 are molecular weight distribution profiles for samples from Example 2.
[0010] Figure 5 is a graph of density versus molecular weight for the samples from Example 2.
[0011] Figures 6-7 are graphs of dynamic viscosity versus frequency for samples from Example 2. DETAILED DESCRIPTION
[0012] Original catalytic and polymeric compositions and methods for creating and using them are disclosed herein. In one embodiment, the catalytic composition comprises an imine-phenol compound, alternatively, an imine (bis)phenol compound, alternatively, a salt metal complex comprising an imine-phenol compound or, alternatively, a salt metal complex comprising an imine (bis) compound )phenol. In one embodiment, a polymerization method comprises contacting an olefin monomer with an imine-phenol compound of the type described herein under conditions suitable for polymer formation and polymer recovery. A polymer of the type disclosed in this document can be characterized by high density characteristics and improved processing. In one embodiment, the polymer comprises a high density polymer having improved barrier characteristics. These aspects of the present disclosure are described later in this document.
[0013] 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 in this document, the definition of the IUPAC Chemical Terminology Compendium, 2nd Ed (1997) may apply provided that definition does not conflict with any other type of disclosure or definition. applied in this document, or renders indefinite or ineligible any claim to which the definition applies. To the extent that any definition or use provided by any document incorporated into this document by reference conflicts with the definition or use provided in this document, the definition or use provided in this document controls.
[0014] The element groups of the table 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 instances, an element group may be indicated using a common name assigned to the group; for example, alkaline earth metals (or alkali metals) for Group 1 elements, alkaline earth metals (or alkali metals) for Group 2 elements, transition metals for Group 3-12 elements, and halogens for Group 17 elements .
[0015] A chemical "group" is described according to how the 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 if the 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 be formally derived by removing one hydrogen atom from an alkane, while an "alkylene group" can be formally 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 derived by removing any number ("one or more") of hydrogen atoms from a parent compound, which in this example can be described. as an "alkane group" and encompassing an "alkyl group", an "alkylene group" and materials having three or more hydrogen atoms, as necessary for the situation, removed from the alkane. Throughout the disclosure, where a substituent, linker or other chemical moiety may constitute a particular "group", implies that well known rules of structure and chemical bonding are followed when the 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 specific synthetic methods or procedures, unless specified by otherwise or when the context requires otherwise.
[0016] The term "substituted" when used to describe a group or chain of carbon atoms, for example, when referring to a substituted analogue of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in in the group and is intended to be non-limiting. A group or groups may also be referred to herein as "unsubstituted" 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 the group. "Substituted" is intended to be non-limiting and includes inorganic or organic substituents.
[0017] Unless otherwise specified, any group containing carbon for which the number of carbon atoms is not specified may possess, in accordance with proper chemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 atoms of carbon, or any variation or combination of ranges between these values. For example, unless otherwise specified, any group containing carbon can have 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, of 1 to 10 carbon atoms, or 1 to 5 carbon atoms, and the like. In addition, other identifiers or qualifying terms may be used to indicate the presence or absence of a particular substituent, a particular regiochemistry, and/or stereochemistry, or the presence or absence of an underlying branched structure or backbone.
[0018] The term "organyl group" is used in this document according to the definition specified by the IUPAC: a group of organic substituents, regardless of functional type, having a free valence on a carbon atom. Similarly, an "organylene group" refers to an organic group, regardless of functional type, derived by removing two hydrogen atoms from an organic compound, whether it be two hydrogen atoms from a carbon atom or a hydrogen atom from each of two different carbon atoms. An "organic group" refers to a generalized group formed by the removal of one or more hydrogen atoms from the carbon atoms of an organic compound. Thus, an "organyl group", an "organylene group" and an "organic group" may contain organic functional group(s) and/or atom(s) except carbon and hydrogen, that is, a organic group may comprise functional groups and/or atoms in addition to carbon and hydrogen. For example, non-limiting examples of atoms other than carbon and hydrogen include halogens, oxygen, nitrogen, phosphorus, and the like. Non-limiting examples of functional groups include ethers, aldehydes, ketones, esters, sulfides, amines, phosphines and so on. In one aspect, the hydrogen atom(s) removed to form the "organyl group", "organylene group" or "organic group" can be attached to a carbon atom belonging to a functional group, for example, an acyl group (-C(O)R), a formyl group (-C(O)H), a carboxy group (-C(O)OH), a hydrocarboxycarbonyl group (-C(O)OR), a group cyano (-C=N), a carbamoyl group (-C(O)NH2), an N-hydrocarbylcarbamoyl group (-C(O)NHR), or an N,N'-dihydrocarbylcarbamoyl group (-C(O)NR2 ), among other possibilities. In another aspect, the atom(s) removed to form the "organyl group", "organylene group" or "organic group" may be attached to a carbon atom that does not belong to, and distant from, a functional group , for example, -CH2C(O)CH3, -CH2NR2, and the like. An "organyl group", "organylene group", or "organic group" can be aliphatic, including being cyclic or acyclic, or it can be aromatic. "Organyl groups", "organylene groups" and "organic groups" also encompass rings containing heteroatoms, ring systems containing heteroatoms, heteroaromatic rings and heteroaromatic ring systems. "Original groups", "organylene groups" and "organic groups" can be linear or branched unless otherwise specified. Finally, it is noted that the definitions of "organyl group", "organylene group" or "organic group" include "hydrocarboyl group", "hydrocarbylene group", "hydrocarbon group", respectively, and "alkyl group", "alkylene group" and "alkane group", respectively, as members.
[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, halogenated alkanes indicate 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. Similarly, an "alkylene group" refers to a group formed by removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms ). An "alkane group" is a general term referring 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" can be acyclic or cyclic groups and/or can 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 # H), R2 CH (R # H) and R3C (R # H) are primary, secondary and tertiary alkyl groups, respectively.
[0020] A "halide" has its common meaning, therefore examples of halides include fluoride, chloride, bromide and iodide.
[0021] Within this disclosure, normal organic naming rules will prevail. For example, when referring to substituted compounds or groups, references to substitution patterns are taken to indicate that the indicated group(s) located at the indicated position and that all other positions not indicated are hydrogen. For example, reference to a 4-substituted phenyl group indicates that there is a non-hydrogen substituent located at position 4 and hydrogens located at positions 2, 3, 5, and 6. As another example, reference to a 3-substituted naphtha-2 -il indicates that there is a non-hydrogen substituent located at position 3 and hydrogens located at positions 1, 4, 5, 6, 7, and 8. References to compounds or groups having substitutions at positions other than the position indicated will be referenced using " understanding" or some other linguistic alternative. For example, a reference to a phenyl group comprising a substituent at position 4 refers to a group having a non-hydrogen atom at position 4 and hydrogen or any non-hydrogen group at positions 2, 3, 5 and 6.
[0022] The modalities disclosed in this document may provide the materials listed as suitable to satisfy particular characteristics of the modality delimited by the term "or". For example, a particular characteristic of the subject matter may be disclosed as follows: Characteristic X may be A, B or C. It is also contemplated that for each feature the statement may also be referred to as a list of alternatives so that the statement "Characteristic X is A, alternatively B or alternatively C" is also an embodiment of the present disclosure, whether or not the statement is explicitly cited.
[0023] In one embodiment, the imine-phenol compound may have the
where O and N represent oxygen and nitrogen, respectively, and Q represents a donor group.
[0024] One or more of R, R2, and R3 may each be the same or different and may be selected from the modalities described in this document. R can be a halogen, a hydrocarboyl group or a substituted hydrocarboyl group. In one modality R is not hydrogen. R2 and R3 can each independently be a hydrogen, a halogen, a hydrocarboyl group or a substituted hydrocarboyl group. These substituents are described in more detail in this document.
[0025] Referring to structure I, generally, R, R2 and R3 may independently be a hydrocarbyl group. In one embodiment, R, R2 and R3 can each independently be a C1 to C30 hydrocarbyl group; a C1 to C20 hydrocarbyl group; a C1 to C15 hydrocarbyl group; a C1 to C10 hydrocarbyl group; or a C1 to C5 hydrocarbyl group. In still other embodiments, R, R2 and R3 can each independently be C3 to C30 aromatic group; a C3 to C20 aromatic group; a C3 to C15 aromatic group; or a C3 to C10 aromatic group.
[0026] In one aspect, R, R2 and R3 may each independently be a C1 to C30 alkyl group, a C4 to C30 cycloalkyl group, a C4 to 30 substituted cycloalkyl group, a C3 to C30 aliphatic heterocyclic group, a C3 to C30 substituted aliphatic heterocyclic group, one C6 to C30 aryl group, one C6 to C30 substituted aryl group, one C7 to C30 aralkyl group, one C7 to C30 substituted aralkyl group, one C3 to C30 heteroaryl group, or one C3 to C30 heteroaryl group substitute. In one embodiment, R, R2 and R3 may each independently give a C1 to C15 alkyl group, a C4 to C20 cycloalkyl group, a C4 to C20 substituted cycloalkyl group, a C3 to C20 substituted heteroacyclic group, a C3 to C20 aliphatic heterocyclic group substituted, a C6 to C20 aryl group, a C6 to C20 substituted aryl group, a C7 to C20 aralkyl group, a C7 to C20 substituted aralkyl group, a C3 to C20 heteroaryl group, or a C3 to C20 substituted heteroaryl group. In other embodiments, R, R2 and R3 may each independently be a C1 to C10 alkyl group, a C4 to C15 cycloalkyl group, a C4 to C15 substituted cycloalkyl group, a C3 to C15 aliphatic heterocyclic group, a C3 to C15 aliphatic heterocyclic group substituted, a C6 to C15 aryl group, a C6 to C15 substituted aryl group, a C7 to C15 aralkyl group, a C7 to C15 substituted aralkyl group, a C3 to C15 heteroaryl group, or a C3 to C15 substituted heteroaryl group. In additional embodiments, R, R2 and R3 can each independently be a C1 to C5 alkyl group.
[0027] In one embodiment, R, R2 and R3 can each independently 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, or a nonadecyl group. In some embodiments, the alkyl groups that can be used as R, R2 and R3 can each independently be substituted. Each substituent of an independently substituted alkyl group can be halogen or a hydrocarboxy group; alternatively, a halogen; or alternatively, a hydroxy group. Halogens and hydrocarboxy groups that can be used as substituents are independently disclosed herein and can be used without limitation to further describe the substituted alkyl group that can be used as R, R2 and/or R3.
[0028] In one embodiment, R, R2 and R3 can each independently be 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 group substituted cycloheptyl, a cyclooctyl group, or a substituted cyclooctyl group. In some embodiments, R, R2 and R3 can each independently be a cyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group, or a substituted cyclohexyl group.
[0029] In one embodiment, each substituent for a substituted cycloalkyl group (general or specific) that can be used as R, R2 and R3 each independently being a halogen, a hydrocarboyl group or a hydrocarboxy group. In some embodiments, each substituent for a substituted cycloalkyl group (general or specific) that can be used as R, R2 and R3 each independently can be a halogen, an alkyl group, or an alkoxy group. Halogens, hydrocarboyl groups, hydrocarboxy groups, alkyl group and alkoxy groups that can be used as substituents are independently disclosed herein and can be used without limitation to further describe the substituents for a substituted cycloalkyl group (general or specific) that can be used as R, R2 and/or R3.
[0030] In one aspect, R, R2 and R3 may each independently have Structure II: characterized by the fact that the unassigned valence (*) represents the point at which the substituent (for example, R, R2 or R3) binds to the inima-phenol compound of Structure I. Generally, R21c, R23c, R24c, and R25c can independently be hydrogen or a non-hydrogen substituent and n can be an integer from 1 to 5.

[0031] In an embodiment where R, R2 and R3 have Structure II, R21c, R23c, R24c, and R25c may be hydrogen and R22c may be any non-hydrogen substituent disclosed herein, or alternatively, R21c, R23c, and R25c may be hydrogen and R22c and R24c independently may be any non-hydrogen substituent disclosed herein. In one embodiment, n can be an integer from 1 to 4; or alternatively, 2 to 4. In other embodiments, n can be 2 or 3; alternatively, 2; or alternatively, 3.
[0032] In one embodiment, R21c, R22c, R23c, R24c, and R25c can independently be hydrogen, a halogen, a hydrocarboyl group, or a hydrocarboxy group; alternatively hydrogen, a halogen or a hydrocarboyl group. In some embodiments, R21c, R22c, R23c, R24c, and R25c can independently be hydrogen, a halogen, an alkyl group, or an alkoxy group. Halogens, hydrocarboyl groups, hydrocarboxy groups, alkyl group and alkoxy groups which can be used as substituents are independently disclosed herein and can be used without limitation to further describe the group R, R2 or R3 having Structure II.
[0033] In one embodiment, R, R2 and R3 can each independently be a phenyl group or a substituted phenyl group. In one embodiment, the substituted phenyl group can be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4-di-substituted phenyl group, a 2,6-di phenyl group. -substituted, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group.
[0034] In one embodiment, each substituent for a substituted cycloalkyl group (general or specific) which can be used as R, R2 and R3 each independently being a halogen, a hydrocarboyl group or a hydrocarboxy group. In one embodiment, the substituted phenyl group can be a 2-substituted phenyl group, a 3-substituted phenyl group, a 4-substituted phenyl group, a 2,4-di-substituted phenyl group, a 2,6-di phenyl group. -substituted, a 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group. Halogens, hydrocarboyl groups, hydrocarboxy groups, alkyl group and alkoxy groups that can be used as substituents are independently disclosed herein and can be used without limitation to further describe the substituents for the substituted phenyl group.
[0035] In one aspect, R, R2 and R3 may each independently have Structure III:
where the unassigned valence (*) represents the point at which the substituent (eg, R, R2 or R3) binds to the imine-phenol compound of Structure I. Generally, R22, R23, R24, R25, and R26 independently may be hydrogen or non-hydrogen substituent. In an embodiment where R, R2 or R3 has Structure III, R22, R23, R24, R25, and R26 can be hydrogen, R23, R24, R25, and R26 can be hydrogen and R22 can be non-hydrogen substituent, R22, R24, R25, and R26 can be hydrogen and R23 can be a non-hydrogen substituent, R22, R23, R25, and R26 can be hydrogen and R24 can be a non-hydrogen substituent, R23, R25, and R26 can be hydrogen and R22 and R24 can be non-hydrogen substituents, R23, R24, and R25 may be hydrogen and R22 and R26 may be non-hydrogen substituents, R22, R24, and R26 may be hydrogen and R23 and R25 may be non-hydrogen substituents, or R23 and R25 may be hydrogen and R22, R24, and R26 can be non-hydrogen substituents. In some embodiments where R, R2 or R3 has Structure III, R23, R24, R25, and R26 can be a hydrogen and R22 can be a non-hydrogen substituent, R22, R23, R25, and R26 can be hydrogen and R24 can be a non-hydrogen substituent, R23, R25, and R26 can be hydrogen and R22 and R24 can be non-hydrogen substituents, R23, R24, and R25 can be hydrogen and R22 and R26 can be non-hydrogen substituents, or R23 and R25 can be hydrogen and R22, R24, and R26 can be non-hydrogen substituents; alternatively, R23, R24, R25, and R26 can be hydrogen and R22 can be a non-hydrogen substituent, R22, R23, R25, and R26 can be hydrogen and R24 can be a non-hydrogen substituent, R23, R25, and R26 can be hydrogen and R22 and R24 can be non-hydrogen substituents, or R23, R24, and R25 can be hydrogen and R22 and R26 can be non-hydrogen substituents; alternatively, R22, R24, R25, and R26 can be hydrogen and R23 can be a non-hydrogen substituent, or R22, R24, and R26 can be hydrogen and R23 and R25 can be non-hydrogen substituents; alternatively, R23, R24, R25, and R26 can be hydrogen and R22 can be a non-hydrogen substituent, or R22, R23, R25, and R26 can be hydrogen and R24 can be a non-hydrogen substituent; alternatively, R23, R25, and R26 can be hydrogen and R22 and R24 can be hydrogen substituents, R23, R24, and R25 can be hydrogen and R22 and R26 can be non-hydrogen substituents, or R23 and R25 can be hydrogen and R22, R24 , and R26 can be non-hydrogen substituents; or alternatively, R23, R25, and R26 can be hydrogen and R22 and R24 can be non-hydrogen substituents, or R23, R24, and R25 can be hydrogen and R22 and R26 can be non-hydrogen substituents. In an embodiment where R, R2 or R3 has Structure III, R22, R23, R24, R25, and R26 can be hydrogen, R23, R24, R25, and R26 can be hydrogen and R22 can be non-hydrogen substituent, R22, R24, R25, and R26 can be hydrogen and R23 can be a non-hydrogen substituent, R22, R23, R25, and R26 can be hydrogen and R24 can be a non-hydrogen substituent, R23, R25, and R26 can be hydrogen and R22 and R24 can be non-hydrogen substituents, R23, R24, and R25 may be hydrogen and R22 and R26 may be non-hydrogen substituents, R22, R24, and R26 may be hydrogen and R23 and R25 may be non-hydrogen substituents, or R23 and R25 may be hydrogen and R22, R24, and R26 can be non-hydrogen substituents.
[0036] In one embodiment, the non-hydrogen substituents that may be used as R22, R23, R24, R25, and R26 in the R, R2 or R3 group having Structure III independently may be a halogen, a hydrocarboyl group, or a hydrocarboxy group, alternatively , a halogen or hydrocarboyl group. In some embodiments, the non-hydrogen substituents that may be used as R22, R23, R24, R25, and R26 in the R, R2 or R3 group having Structure III may independently be a halogen, an alkyl group or an alkoxy group. Halogens, hydrocarboyl groups, hydrocarboxy groups, alkyl group and alkoxy groups that can be used as substituents are independently disclosed herein and can be used without limitation to further describe the group R, R2 or R3 having Structure III.
[0037] In one aspect, R, R2 and R3 may independently be a benzyl group, a substituted benzyl group, a 1-phenyleth-1-yl group, a substituted 1-phenyleth-1-yl group, a 2-phenyleth- group 1-yl or a substituted 2-phenyleth-1-yl group. In one embodiment, R, R2 and R3 can each independently be a benzyl group or a substituted benzyl group; alternatively, a 1-phenyleth-1-yl or a substituted 1-phenyleth-1-yl group; alternatively, a 2-phenyleth-1-yl group or a substituted 2-phenyleth-1-yl group; or alternatively, a benzyl group, a 1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group. In some embodiments, R, R2 and R3 can each independently be a benzyl group; alternatively a substituted benzyl group; alternatively a 1-phenyleth-1-yl group; alternatively a substituted 1-phenyleth-1-yl; alternatively a 2-phenyleth-1-yl group; or alternatively a substituted 2-phenyleth-1-yl group.
[0038] In one embodiment, each substituent for a substituted benzyl group, a 1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group (general or specific) which can be used as R, R2 and/ or R3 can be a halogen, a hydrocarboyl group or a hydrocarboxy group. In some embodiments, each substituent for a substituted benzyl group, 1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group (general or specific) which can be used as R, R2 and/or R3 independently of be a halogen, an alkyl group or an alkoxy group. Halogens, hydrocarboyl groups, hydrocarboxy groups, alkyl group and alkoxy groups that can be used as substituents are independently disclosed herein and can be used without limitation to further describe the substituents for the substituted benzyl group, 1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group (general or specific) which can be used as R, R2 and/or R3.
[0039] In one aspect, R, R2 and R3 may each independently be a pyridinyl group, a substituted pyridinyl group, a furyl group, a substituted furyl group, a thienyl group or a substituted thienyl group.
[0040] In one embodiment, the pyridinyl (or substituted pyridinyl) R, R2 and/or R3 can be a pyridin-2-yl group, a substituted pyridin-2-yl group, a pyridin-3-yl group, a group substituted pyridin-3-yl, a pyridin-4-yl group, or a substituted pyridin-4-yl group; alternatively, a pyridin-2-yl group, a pyridin-3-yl group, or a pyridin-4-yl group. In some embodiments, the pyridinyl (or substituted pyridinyl) group R, R2 and/or R3 can be a pyridin-2-yl group or a substituted pyridin-2-yl group; alternatively, a pyridin-3-yl group or a substituted pyridin-3-yl group; alternatively, a pyridin-4-yl group or a substituted pyridin-4-yl group; alternatively, a pyridin-2-yl group; alternatively, a substituted pyridin-2-yl group; alternatively a pyridin-3-yl group; alternatively a substituted pyridin-3-yl group; alternatively a pyridin-4-yl group; or alternatively a substituted pyridin-4-yl group. In one embodiment, the substituted pyridinyl group R, R 2 and/or R 3 can be a 2-substituted pyridin-3-yl group, a 4-substituted pyridin-3-yl group, a 5-substituted pyridin-3-yl group, a 6-substituted pyridin-3-yl group, a 2,4-disubstituted pyridin-3-yl group, a 2,6-disubstituted pyridin-3-yl group, or a 2,4,6-trisubstituted pyridine-3 group -il; alternatively, a 2-substituted pyridin-3-yl group, a 4-substituted pyridin-3-yl group, or a 6-substituted pyridin-3-yl group; alternatively, a 2,4-disubstituted pyridin-3-yl group or a 2,6-disubstituted pyridin-3-yl group; alternatively, a 2-substituted pyridin-3-yl group; alternatively, a 4-substituted pyridin-3-yl group; alternatively, a 5-substituted pyridin-3-yl group; alternatively a 6-substituted pyridin-3-yl group; alternatively, a 2,4-disubstituted pyridin-3-yl group; alternatively a 2,6-disubstituted pyridin-3-yl group; or alternatively, a 2,4,6-trisubstituted pyridin-3-yl group.
[0041] In one embodiment, the furyl (or substituted furyl) group R, R2 and/or R3 may be a fur-2-yl group, a substituted fur-2-yl group, a fur-3-yl group, or a substituted fur-3-yl group. In one embodiment, the furyl group R, R2 and/or R3 can be a 2-substituted fur-3-yl group, a 4-substituted fur-3-yl group, or a 2,4-disubstituted fur-3-yl group. ll.
[0042] In one embodiment, the thienyl (or substituted thienyl) group R, R2 and/or R3 can be a thien-2-yl group, a substituted thien-2-yl group, a thien-3-yl group, or a substituted thien-3-yl group. In some embodiments, the thienyl (or substituted thienyl) group R, R2 and/or R3 can be a thien-2-yl group or a thien-2-yl group. In one embodiment, the substituted thienyl group R, R 2 and/or R 3 can be a 2-substituted thien-3-yl group, a 4-substituted thien-3-yl group, or a 2,4-disubstituted thien-3 group. -il.
[0043] In one embodiment, each substituent for a substituted pyrinidyl, furyl or thienyl group (general or specific) which can be used as R, R2 and/or R3 each independently being a halogen, a hydrocarboyl group or a hydrocarboxy group. In some embodiments, each substituent for a substituted pyridinyl, furyl, and/or thienyl group (general or specific) that can be used as R, R2 and R3 can each independently be a halogen, an alkyl group, or an alkoxy group; alternatively a halogen or alkyl group; alternatively a halogen or alkoxy group; alternatively an alkyl group or an alkoxy group; alternatively, a halogen; alternatively an alkyl group; or alternatively, an alkoxy group. Halogens, hydrocarboyl groups, hydrocarboxy groups, alkyl groups and alkoxy groups which may be used as substituents are independently disclosed herein and may be used without limitation to further describe the substituents for substituted pyridinyl, furyl and/or thienyl groups (general or specific ) which can be used as R, R2 and/or R3.
[0044] In a non-limiting embodiment, R, R2 and/or R3 may independently be a phenyl group, a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group. In another non-limiting embodiment, R, R2 and R3 can each independently be a phenyl group, a 2-alkoxyphenyl group, a 3-alkoxyphenyl group, a 4-alkoxyphenyl group, or a 3,5-dialkoxyphenyl group. In other non-limiting embodiments, R, R2 and R3 can each independently be a phenyl group, a 2-halophenyl group, a 3-halophenyl group, a 4-halophenyl group, a 2,6-dihalophenyl group, or a 3-group. ,5-dialkylphenyl; alternatively, a 2-halophenyl group, a 4-halophenyl group, or a 2,6-dihalophenyl group; alternatively a 2-halophenyl group or a 4-halophenyl group; alternatively a 3-halophenyl group or a 3,5-dihalophenyl group; alternatively a 2-halophenyl group; alternatively a 3-halophenyl group; alternatively a 4-halophenyl group; alternatively a 2,6-dihalophenyl group; or alternatively a 3,5-dihalophenyl group. Halides, alkyl group substituents, and alkoxy group substituents are independently described herein and may be used, without limitation, to further describe the alkylphenyl, dialkylphenyl, trialkylphenyl, alkoxyphenyl, dialkoxyphenyl, halophenyl or dihalophenyl groups that may be used for R, R2 and/or R3. Generally, the halides, alkyl substituents, or alkoxy substituents of a dialkyl, trialkyl phenyl, dialkoxyphenyl or dihalogenyl group may be the same; or alternatively, the halo, alkyl substituents or alkoxy substituents of alkylphenyl, dialkylphenyl, trialkylphenyl, dialkoxyphenyl or dihalophenyl groups may be different.
[0045] In a non-limiting embodiment, R, R2 and R3 may each independently be a 2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenyl group, a 4-methylphenyl group , a 4-ethylphenyl group, a 4-isopropylphenyl group, or a 4-tert-butylphenyl group; alternatively, a 2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-isopropylphenyl group, or a 4-tert-butylphenyl group; alternatively a 2-methylphenyl group; alternatively a 2-ethylphenyl group; alternatively a 2-isopropylphenyl group; alternatively a 2-tert-butylphenyl group; alternatively a 4-methylphenyl group; alternatively a 4-ethylphenyl group; alternatively a 4-isopropylphenyl group; or alternatively a 4-tert-butylphenyl group. In another non-limiting embodiment, R, R2 and R3 may each independently be a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a 2-tert-butoxyphenyl group; alternatively, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group; alternatively a 2-methoxyphenyl group; alternatively a 2-ethoxyphenyl group; alternatively a 2-isopropoxyphenyl group; alternatively a 2-tert-butoxyphenyl group; alternatively a 4-methoxyphenyl group; alternatively a 4-ethoxyphenyl group; alternatively, a 4-isopropoxyphenyl group; or alternatively, a 4-tert-butoxyphenyl group. In other non-limiting embodiments, R, R2 and R3 may each independently be a 2-fluorophenyl group, a 2-chlorophenyl group, a 3-fluorophenyl group, a 3-chlorophenyl group, a 4-fluorophenyl group, a 4-group chlorophenyl, a 3,5-difluorophenyl group, or a 3,5-dichlorophenyl group; alternatively a 2-fluorophenyl group or a 2-chlorophenyl group; alternatively a 3-fluorophenyl group or a 3-chlorophenyl group; alternatively a 4-fluorophenyl group or a 4-chlorophenyl group; alternatively a 3,5-difluorophenyl group or a 3,5-dichlorophenyl group; alternatively a 3-fluorophenyl group, a 3-chlorophenyl group, a 3,5-difluorophenyl group or a 3,5-dichlorophenyl group; alternatively a 3-fluorophenyl group or a 3,5-difluorophenyl group; alternatively a 2-fluorophenyl group; alternatively a 2-chlorophenyl group; alternatively a 3-fluorophenyl group; alternatively, a 3-chlorophenyl group; alternatively a 4-fluorophenyl group; alternatively a 4-chlorophenyl group; alternatively a 3,5-difluorophenyl group; or alternatively a 3,5-dichlorophenyl group.
[0046] In one modality, Q is a donor group that can have the Structure (IIQ), (IIIQ) or (IVQ):
where N represents nitrogen, Z can be oxygen or sulfur R4 can be hydrogen, a halogen, a hydrocarbyl group, or a substituted hydrocarbyl group and where the unassigned valence (*) represents the point at which the donor group binds to the imine compound -phenol of Structure I. Generally R4 may be any of the halogens, hydrocarbyl groups or substituted hydrocarbyl groups described herein (for example, in the description of groups suitable for use as R2 and/or R3).
[0047] In one embodiment, the catalytic composition comprises a salt metal complex, alternatively a salt metal complex of an imine bis(phenol) compound, alternatively a salt metal complex of an imine bis(phenol) compound which may have Structure V.
In Structure V, O and N represent oxygen and nitrogen, respectively; Q represents a donor group which may have Structure (VI), (VII) or (VII) and where the unassigned valence (*) represents the point at which the donor group binds to the imine-phenol compound of Structure V,
and M is a Group 3 to Group 12 transition metal or lanthanide. Referring to Structure V, X0 can be a neutral ligand and have a value of 0, 1, or 2; X1 can be a monoanionic ligand, and b has a value of 0, 1, 2, 3, or 4; and X2 can be a dianionic ligand and c have a value of 0, 1, or 2.
[0048] In one embodiment, R, R2, R3, R4, and Q of Structure V corresponds to R, R2, R3, R4, and Q of Structure I respectively so that the groups, characteristics, and aspects used to describe R2, R3, R4, and Q of Structure I can be used to describe the corresponding R, R2, R3, R4, and Q of Structure V. One or more of R, R2, R3, and R4 can each be the same or different .
[0049] Generally, the metal atom of the salt metal complex of the imine-bis(phenol) compound (eg M in Structure V) can be any metal atom. In one aspect, the metal atom can be a transition metal or a lanthanide. In one embodiment, suitable salt metals can comprise or consist essentially of a Group 3-12 transition metal; alternatively, a Group 4-10 transition metal; alternatively, a Group 6-9 transition metal; alternatively, a Group 7-8 transition metal; alternatively, a Group 4 transition metal; alternatively a Group 5 transition metal alternatively a Group 6 transition metal; alternatively, a Group 7 transition metal; alternatively, a Group 8 transition metal; alternatively, a Group 9 transition metal; or alternatively, a Group 10 transition metal. In some embodiments, the salt metal may comprise titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium, platinum, copper or zinc. Alternatively M is a Group 4 transition metal. Alternatively, M is titanium. Alternatively, M is zirconium. Alternatively, M is hafnium.
[0050] Generally, the metal atom of the metal may have a positive oxidation state available for the metal atom. In one embodiment, the oxidation state of M is equal to (b + 2c + 2). In one embodiment, the metal can have an oxidation state of +2 to +6; alternatively, from +2 to +4; or alternatively, from +2 to +3. In some embodiments, the metal can have an oxidation state of +1; alternatively, +2; alternatively, +3; or alternatively, +4. For example, the most common oxidation state for Ti, Zr and Hf might be +4; therefore, c can be equal to zero and b can be equal to 2 (two monoanionic ligands) or it can be equal to zero and c can be equal to 1 (one dianionic ligand). The most common oxidation state for V and Ta might be +5; therefore, for example, b might equal one (a monoanionic ligand) and c might equal 1 (a dianionic ligand).
[0051] Referring to Structure V, X0 may be a neutral ligand and the integer a in Structure V may be 0, 1 or 2. In one aspect, suitable neutral ligands may include sigma-donor solvents that contain an atom ( or atoms) that can coordinate to the metal atom in Structure V. Examples of suitable coordination atoms include, but are not limited to, O, N, S and P, or combinations of these atoms. Neutral bond may not be replaced or may be replaced. Substituent groups are independently described in this document and can be used, without limitation, to further describe a neutral linker that can be used as X0 in Structure V. In some aspects, the neutral linker can be a Lewis base. When an integer a equals 2, it is contemplated that the two neutral binders may be the same or different and the descriptions defined herein apply to each binder independently.
[0052] In one aspect, X0 can be an ether, a thioether, an amine, a nitrile or a phosphine. In another aspect, X0 can be an acyclic ether, a cyclic ether, an acyclic thioether, a cyclic thioether, a nitrile, a cyclic amine, a cyclic amine, an acyclic phosphine, a cyclic phosphine or combinations thereof. In other aspects, X0 can be an acyclic ether or a cyclic ether; alternatively an acyclic thioether or a cyclic thioether; alternatively an acyclic amine or a cyclic amine; alternatively an acyclic phosphine or a cyclic phosphine; alternatively an acyclic ether; alternatively a cyclic ether; alternatively an acyclic thioether; alternatively a cyclic thioether; alternatively a nitrile, alternatively an acyclic amine; alternatively a cyclic amine; alternatively an acyclic phosphine, or alternatively a cyclic phosphine. Additionally, X0 can include substituted analogs of any acyclic ether, cyclic ether, acyclic thioether, cyclic thioether, nitrile, acyclic amine, cyclic amine, acyclic phosphine or cyclic phosphine as disclosed herein.
[0053] And in one aspect, X0 may be a nitrile having the formula R1qC^N, an ether having the formula R2q-O-R3q, a thioether having a formula R4q-S-R5q, an amine having the formula NR6qR7qR8q, NHR6qR7q, or NH2R6q, or a phosphine having the formula PR9qR10qR11q, PHR9qR10q, or PH2R9q; alternatively, a nitrile having the formula R1qC4N, an ether having the formula R2q-O-R3q, a thioether having the formula R4q-S-R5q, an imine having the formula NR6qR7qR8q, or a phosphine having the formula PR9qR10qR11q; or alternatively, a nitrile having the formula R1qC4N, an ether having the formula R2q-O-R3q, a thioether having the formula R4q-S-R5q, an amine having the formula NR6qR7qR8q, or a phosphine having the formula PR9qR10qR11q. In one aspect, X0 can be a nitrile having the formula R1qC^N; alternatively, an ether having the formula R2q-O-R3q; alternatively, a thioether having a formula R4a-S-R5a; alternatively, an imine having a formula NR6qR7qR8q, NHR6qR7q, or NH2R6q; alternatively, a phosphine having the formula PR9qR10qR11q, PHR9qR10q, or PH2R9q; or alternatively, a phosphine having the formula PR9qR10qR11q.
In one aspect, R1q of nitrile having the formula R1qC^N, R2q and R3q of ether having the formula R2q-O-R3q, R4q and R5q of thioether having the formula R4q-S-R5q, R6q, R7q, and Amine R8q having the formula NR6qR7qR8q, NHR6qR7q, or NH2R6q, and R9q, R10q, and phosphine R11q having the formula R9qR10qR11q, PHR9qR10q, or PH2R9q, independently, may be a C1 to C18 hydrocarbon group; alternatively, a C1 to C15 hydrocarboyl group; alternatively, a C1 to C12 hydrocarbyl group; alternatively, a C1 to C8 hydrocaboyl group; or alternatively, a C1 to C6 hydrocarboyl group. It should also be noted that R2q and R3q of ether having formula R2q-O-R3q, R4q and R5q of thioether having formula R4q-S-R5q, either of R6q, R7q, and amine R8q having formula NR6qR7qR8q or NHR6qR7q , and/or either of the two of R9q, R10q, and R11q of the phosphine having the formula PR9qR10qR11q or PHR9qR10q can be joined to form a ring containing the ether oxygen atom, the thioether sulfur atom, the amine nitrogen atom, or the nitrogen atom of phosphine phosphorus to form a cyclic ether, thioether, amine or phosphine, respectively, as described herein with respect to cyclic ethers, thioethers, amines and phosphines.
[0055] In one aspect, R1q of the nitrile having the formula R1qC^N, R2q and R3q of the ether having the formula R2q-O-R3q, R4q and R5q of the thioether having the formula R4q-S-R5q, R6q, R7q, and R8q of the amine having the formula NR6qR7qR8q, NHR6qR7q, or NH2R6q, and R9q, R10q, and R11q of the phosphine having the formula PR9qR10qR11q, PHR9qR10q, or PH2R9q, independently being any hydrocarboyl group disclosed herein. The hydrocarboyl group can be, for example, any alkyl group, cycloalkyl group, aryl group or aralkyl group disclosed herein.
[0056] In another aspect X0, in Structure V independently may be a C2-C30 ether, a C2-C30 thioether, a C2-C20 nitrile, a C1-C30 amine, or a C1-C30 phosphine; alternatively a C2-C18 ether; alternatively a C2-C18 thioether; alternatively a C2-C12 nitrile; alternatively a C1-C18 amine; or alternatively, a C1-C18 phosphine. In some aspects, each independent neutral ligand can be a C2-C12 ether, a C2-C12 thioether, a C2-C8 nitrile, a C1-C12 amine, or a C1-C12 phosphine; alternatively a C2-C10 ether; alternatively a C2-C10 thioether; alternatively a C2-C6 nitrile; alternatively a C1-C8 amine; or alternatively, a C1-C8 phosphine.
Suitable ethers which can be used as X0, alone or in combination, may include, but are not limited to, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, methylethyl ether, methylpropyl ether, methylbutyl ether, diphenyl ether, ditolyl ether, tetrahydrofuran, 2-methyltetrafuran, 2,5-dimethyltetrafuran, 2,3-dihydrofuran, 2,5-dihydrofuran, furan, benzofuran, isobenzofuran, dibenzofuran, tetrahydrofuran, 3,4-dihydro-2H-pyran, 3,6 -dihydro-2H-pyran, 2H-pyran, 4H-pyran, 1,3-dioxane, 1,4-dioxane, morpholine, and the like, including substituted derivatives thereof.
Suitable thioethers which can be used as X0, alone or in combination, may include, but are not limited to, dimethyl thioether, diethyl thioether, dipropyl dioether, dibutyl thioether, methylethyl thioether, methylpropyl thioether, methylbutyl thioether, diphenyl dioether, ditolyl dioether, thiophene, benzothiophene, tetrahydrothiophene, thiano, and the like, including substituted derivatives thereof.
Suitable nitriles which can be used as X0, alone or in combination, may include, but are not limited to, acetonitrile, propionitrile, butyronitrile, benzonitrile, 4-methylbenzonitrile, and the like, including substituted derivatives thereof.
Suitable amines that can be used as X0, alone or in combination, may include, but are not limited to, methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripopilamine, tributylamine, aniline, diphenylamine, triphenylamine, totylamine, xylylamine, ditolylamine, pyridine, quinoline, pyrroline, indole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dipropylpyrrole, 2,5-dibutylpyrrole, 2,4-dimethylpyrrole, 2,4-diethylpyrrole, 2,4-dipropylpyrrole, 2,4-dibutylpyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-dipropylpyrrole, 3, 4-dibutylpyrrole, 2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-butylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, 3-ethyl-2,4-dimethylpyrrole, 2,3, 4,5-tetramethylpyrrole, 2,3,4,5-tetraethylpyrrole, and the like, including substituted derivatives thereof. Suitable amines can be primary amines, secondary amines, or tertiary amines.
Suitable phosphines that can be used as X0, alone or in combination, may include, but are not limited to, trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine, diphenylphosphine,ditolylphosphine, triphenylphosphine, tritolylphosphine, methyldiphenylphosphine, dimethyl ethyldiphenylphosphine, diethylphenylphosphine, and the like, including substituted derivatives thereof.
[0062] In one aspect, X0 can be azetidine, oxetane, thiethane, dioxetane, dithiethane, tetrahydropyrrole, dihydropyrrole, pyrrole, indole, isoindole, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, dihydrofuran, furan, benzofuran, isobenzofuran, tetrahydrothiophene, dihydrothiophene, thiophene, benzothiophene, isobenzothiophene, imidazolidine, pyrazole, imidazole, oxazolidine, oxazole, isoxazole, thiazolidine, thiazole, isothiazole, benzothiazole, dioxolane, dithiolane, triazole, dithiazole, piperidine, dihydroamine, pyridine, dimethyl dihydropyran, pyran, thiano, piperazine, diazine, oxazine, thiazine, dithian, dioxane, dioxin, triazine, triazinane, trioxane, oxepine, azepine, thiepine, diazepine, morpholine, quinoline, tetrahydroquinone, bicyclo[3.3.1]tetrasilotrixane, or acetonitriane ; alternatively azetidine, oxetane, thiethane, dioxetane, dithiethane, tetrahydropyrrole, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrothiophene, imidazolidine, oxazolidine, oxazol, thiazolidine, thiazole, dioxolane, dithiolane, piperidine, pyran, pyran piperazine, oxazine, thiazine, dithian, dioxane, dioxin, triazinane, trioxane, azepine, tiepine, diazepine, morpholine, 1,2-thiazole, or bicyclo[3.3.1]tetrasiloxane; alternatively, tetrahydropyrrole, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrothiophene, oxazolidine, thiazolidine, dioxolane, dithiolane, dithiazole, piperidine, tetrahydropyran, pyran, thiano, piperazine, dithiane, dioxane, dioxin, trioxane, or morpholine; alternatively, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrothiophene, dioxolane, dithiolane, tetrahydropyran, pyran, thiano, dithiane, dioxane, dioxin, or trioxane; alternatively, tetrahydrofuran, dioxolane, tetrahydropyran, dioxane, or trioxane; alternatively, pyrrole, furan, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, triazole, pyridine, dimethyl amine, diethyl amine, diazine, triazine, or quinoline; alternatively, pyrrole, furan, imidazole, oxazole, thiazole, triazole, pyridine, dimethyl amine, diethyl amine, diazine, or triazine; or alternatively, furan, oxazole, thiazole, triazole, pyridine, diazine, or triazine. In some aspects, X0 can be azetidine; alternatively, oxetane; alternatively, thiethane; alternatively, dioxetane; alternatively, dithiethane; alternatively, tetrahydropyrrole; alternatively dihydropyrrole, alternatively pyrrole; alternatively, indole; alternatively, isoindole; alternatively, tetrahydrofuran; alternatively, 2-methyltetrahydrofuran; alternatively, 2,5-dimethyltetrahydrofuran; alternatively, dihydropyrrole; alternatively, furan; alternatively, benzofuran; alternatively, isobenzofuran; alternatively, tetrahydrothiophene; alternatively, dihydrothiophene; alternatively, thiophene; alternatively, benzothiophene; alternatively, isobenzothiophene; alternatively, imidazolidine; alternatively, pyrazole; alternatively, imidazole; alternatively, oxazolidine; alternatively, oxazole; alternatively, isoxazole; alternatively, thiazolidine; alternatively, thiazole; alternatively, benzothiazole; alternatively, isothiazole; alternatively, dioxolane; alternatively, dithiolane; alternatively, triazole; alternatively, dithiazole; alternatively, piperidine; alternatively, pyridine; alternatively, dimethyl amine; alternatively, diethyl amine; alternatively, tetrahydropyran; alternatively, dihydropyran; alternatively, pyran; alternatively, tian; alternatively, piperazine; alternatively, diazine; alternatively, oxazine; alternatively, thiazine; alternatively, ditian; alternatively, dioxane; alternatively, dioxin; alternatively, triazine; alternatively, triazinane; alternatively, trioxane; alternatively, oxepin; alternatively, azepine; alternatively, thiepine; alternatively, diazepine; alternatively, morpholine; alternatively, quinoline; alternatively, tetrahydroquinone; alternatively, bicyclo[3.3.1]tetrasiloxane; or alternatively, acetonitrile.
[0063] In another aspect, X0 may be azetidine, tetrahydropyrrole, dihydropyrrole, pyrrole, indole, isoindole, imidazolidine, pyrazole, imidazole, oxazolidine, oxazole, isoxazole, thiazolidine, thiazole, isothiazole, triazole, benzotriazole, dithiazole, piperidine, pyridine, dimethyl amine, diethyl amine, piperazine, diazine, oxazine, thiazine, triazine, azepine, diazepine, morpholine, quinoline, or tetrahydroisoquinoline. In another aspect, X 0 may be thiethane, dithiethane, tetrahydrothiophene, dihydrothiophene, thiophene, benzothiophene, isobenzothiophene, thiazolidine, thiazole, isothiazole, dithiolane, dithiazole, thiano, thiazine, dithiane, or thiepine. In another aspect, X0 can be tetrahydrofuran, furan, methyltetrahydrofuran, dihydrofuran, tetrahydropyran, 2,3-dihydropyran, 1,3-dioxane, 1,4-dioxane, morpholine, N-methylmorpholine, acetonitrile, propionitrile, butyronitrile, benzonitrile, pyridine , ammonia, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, trimethylphosphine, triethylphosphine, triphenylphosphine, tri-n-butylphosphine, methylisocyanide, n-butyl isocyanide, phenyl isocyanide, SMe2, thiophene, or tetrahydrothiophene. In another aspect, X0 can be tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, 1,4-dioxane, acetonitrile, pyridine, dimethylamine, diethylamine, ammonia, trimethylamine, triethylamine, trimethylphosphine, triethylphosphine, triphenylphosphine, SMe2, or tetrahydrothiophene; alternatively, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, or 1,4-dioxane; alternatively, ammonia, trimethylamine, or triethylamine; or alternatively, trimethylphosphine, triethylphosphine, or triphenylphosphine. In yet another aspect, X0 can be tetrahydrofuran, acetonitrile, pyridine, ammonia, dimethylamine, diethylamine, trimethylamine, trimethylphosphine or triphenylphosphine; alternatively, tetrahydroguran, acetonitrile, pyridine, dimethylamine, diethylamine, trimethylamine, trimethylphosphine, or triphenylphosphine; alternatively, tetrahydrofuran, acetonitrile, dimethylamine, diethylamine or pyridine; alternatively, tetrahydrofuran; alternatively, acetonitrile; alternatively, dimethylamine; alternatively, diethylamine; or alternatively, pyridine.
[0064] X1 in Structure V can be a monoanionic ligand and the integer b in Structure V can be 0, 1, 2, 3, or 4. X1 can be a hydrogen (hydride), a halide, a hydrocarbyl group C1 for C18, a hydrocarbyloxide group, a hydrocarbylamine group, a hydrocarbylsilyl group, or a hydrocarbylaminosilyl group. If b is greater than 1, each X1 group of Structure V can be the same or different. In an embodiment b is greater than 1 and each X1 can independently be a hydrogen (hydride), a halide, a C1 to C18 hydrocarboyl group, a hydrocarbyloxide group, a hydrocarbylamine group, a hydrocarbylsilyl group or a hydrocarbylaminesilyl group
[0065] In one aspect, X1 may be a hydrogen, a halide (eg F, Cl, Br or I), a hydrocarbyl group C1 to C18 a hydrocarbyloxide group, a hydrocarbylamine group, a hydrocarbylsilyl group or a hydrocarbylaminosilyl group. In another aspect, X1 can be a hydrogen, a halide, a C1 to C12 hydrocarbyl group, a hydrocarbyloxide group, a hydrocarbylamine group, a hydrocarbylsilyl group, a hydrocarbylaminesilyl group. In yet another aspect, X1 can be hydrogen, a halide, a hydrocarbyl group C1 to C10, a hydrocarbyloxide group, a hydrocarbylamine group, a hydrocarbylsilyl group or a hydrocarbylaminosilyl group. In yet another aspect, X1 can be hydrogen, a halide, a C1 to C8 hydrocarbyl group, a hydrocarbyloxide group, a hydrocarbylamine group, a hydrocarbylsilyl group or a hydrocarbylaminosilyl group.
The hydrocarbyl group which may be X1 in Structure V may be any C1 to C18 hydrocarbyl group, any C1 to C12 hydrocarbyl group, any C1 to C10 hydrocarbyl group, or any C1 to C8 hydrocarbyl group disclosed herein. A hydrocarbyloxide group is used generically herein to include, for example, alkoxy, aryloxy, and -(alkyl or aryl)-O-(alkyl or aryl) groups and these groups can comprise up to about 18 carbon atoms (for example, hydrocarbyloxide groups C1 to C18, C1 to C12, C1 to C10, or C1 to C8). Illustrative and non-limiting examples of hydrocarbyloxide groups can include methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, acetylacetonate (acac), and the like. The term hydrocarbylamine group is used generically herein to refer collectively to, for example, alkylamine, arylamine, dialkylamine, diarylamine and -(alkyl or aryl)-N-(alkyl or aryl) groups and the like. Unless otherwise specified, hydrocarbylamine groups which may be X1 in Structure V may comprise up to about 18 carbon atoms (for example, hydrocarbylamine groups C1 to C18, C1 to C12, C1 to C10, or C1 to C8). The hydrocarbylsilyl group which may be X1 in Structure V may be any C1 to C18 hydrocarbylsilyl group, any C1 to C12 hydrocarbylsilyl group, any C1 to C10 hydrocarbylsilyl group, or any C1 to C8 hydrocarbylsilyl group disclosed herein. A hydrocarbylaminosilyl group is used herein to refer to groups containing at least one hydrocarbon moiety, at least one nitrogen atom and at least one silicone atom. Illustrative and non-limiting examples of hydrocarbylaminosilyl groups that may be X1 may include, but are not limited to -N(SiMe3)2, -N(SiEt3)2, and the like. Unless otherwise specified, hydrocarbylaminosilyl groups that can be X1 can comprise about 18 carbon atoms (for example, hydrocarbylaminosilyl groups C1 to C18, C1 to C12, C1 to C10, or C1 to C8).
[0067] According to one aspect of this disclosure, X1 in Structure V may be a halide; alternatively, a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarbyloxide group; alternatively, a C1 to C18 hydrocarbylamine group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C18 hydrocarbylaminosilyl group. According to another aspect, X1 can be hydrogen; alternatively, F; alternatively, Cl; alternatively, Br; alternatively, I; alternatively, a C1 to C18 hydrocarbyl group; alternatively, a C1 to C18 hydrocarbyloxide group; alternatively, a C1 to C18 hydrocarbylamine group; alternatively, a C1 to C18 hydrocarbylsilyl group; or alternatively, a C1 to C18 hydrocarbylamiasilyl group. According to yet another aspect, or at least one X1 can be hydrogen, a halide, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylamine, a dialkylamine, a trihydrocarbylsilyl, or a hydrocarbylaminosilyl; alternatively hydrogen, a halide, methyl, phenyl, or benzyl; alternatively an alkoxy, aryloxy, or acetylacetonate; alternatively an alkylamine or a dialkylamine; alternatively a trihydrocarbylsilyl or hydrocarbylaminosilyl; alternatively hydrogen or halide; alternatively, methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylamine, or a dialkylamine; alternatively hydrogen; alternatively, a halide; alternatively, methyl; alternatively, phenyl; alternatively, benzyl; alternatively an alkoxy; alternatively an aryloxy; alternatively, acetylacetonate; alternatively, an alkylamine; alternatively, a dialkylamine; alternatively a trihydrocarbylsilyl; or alternatively a hydrocarbylaminosilyl. In these and other aspects, the alkoxy, aryloxy, alkylamine, dialkylamine, trihydrocarbylsilyl and hydrocarbylaminesilyl can be a C1 to C18, a C1 to C12, a C1 to C10, or a C1 to C8 alkoxy, aryloxy, alkylamine, dialkylamine, trihydrocarbylsilyl or hydrocarbylaminolamino .
[0068] X2 in Structure V can be a dianian ligand and the integer c in Structure V can be 0, 1, or 2. In one aspect, X2 can be =O, =NR2A, or =CR2BR2C. In another aspect, X2 can be =O; alternatively, X2 can be =NR2A; or alternatively, X2 can be =CR2BR2C. Independently, R2A, R2B, and R2C can be hydrogen or any C1 to C18 hydrocarbyl group disclosed herein; alternatively hydrogen or any C1 to C12 hydrocarbyl group disclosed herein; alternatively, hydrogen or any C1 to C10 hydrocarbyl group disclosed herein; or alternatively, hydrogen or any C1 to C8 hydrocarbyl group disclosed herein. As an example, R2A, R2B, and R2C can each independently be hydrogen or any C1 to C12, C1 to C8, or any C1 to C6 alkyl group disclosed herein.
[0069] In one embodiment, an imine (bis)phenol compound suitable for use in the present disclosure comprises a compound having Structure IX:
where the groups used to describe R, R2, and R3 of Structure I can be used to describe R, R2, and R3 respectively of Structure IX.
[0070] In one embodiment, an imine (bis)phenol compound suitable for use in the present disclosure comprises a compound having Structure X:
where the groups used to describe R and R2 of Structure I can be used to describe R and R2 respectively of Structure X. In one embodiment of Structure X, R is a t-butyl group and R2 is hydrogen. Alternatively R and R2 are t-butyl groups, alternatively R is a methyl group and R2 is hydrogen, alternatively R and R2 are chlorides, alternatively R is adamantyl and R2 is methyl, alternatively R is methoxy and R2 is hydrogen, or alternatively R e R2 are hydrogen.
[0071] In one embodiment, an imine (bis)phenol compound suitable for use in the present disclosure comprises a compound having Structure XI:
where the groups used to describe R, R2, and R3 of Structure I can be used to describe R, R2, and R3 respectively of Structure XI.
[0072] In one embodiment, an imine (bis)phenol compound suitable for use in the present disclosure comprises a compound having Structure XII:
where the groups used to describe R and R2 of Structure I can be used to describe R and R2 respectively of Structure XII. In one embodiment of Structure XII, R and R2 are methyl groups, or alternatively R and R2 are hydrogen.
[0073] In one embodiment, a salt metal complex of an imine (bis)phenol compound suitable for use in the present disclosure comprises a compound having Structure XIII:
where M is titanium, zirconium or hafnium and R, R2, R3, X0, and X1 are of the type described in this document. In one embodiment of Structure XIII, M is zirconium and R is a t-butyl group. Alternatively, M is hafnium and R is a t-butyl group; alternatively, M is zirconium and R and R2 are t-butyl groups; alternatively M is zirconium and R is a methyl group, alternatively M is zirconium and R and R2 are chloride or alternatively M is zirconium, R is adamantyl and R2 is methyl.
[0074] In one embodiment, a salt metal complex of a bis(phenol) imine compound suitable for use in the present disclosure comprises a compound having Structure XIV where OEt2 represents ethoxide:
where the groups used to describe R and R2 of Structure I can be used to describe R and R2 respectively of Structure XIV.
[0075] In one embodiment, a salt metal complex of a bis(phenol) imine compound suitable for use in the present disclosure comprises a compound having Structure XV where OEt represents ethoxy:

[0076] In one embodiment, a salt metal complex of an imine bis(phenol) compound suitable for use in the present disclosure comprises a compound having any of Structures XVI, XVII, XVIII, XIX, XX, or XXI where X1 is of the disclosed type in this document:

[0077] In one embodiment, the catalytic composition further comprises a chemically treated solid oxide that can function as an activating support. Alternatively, the chemically treated solid oxide may comprise a clay mineral, a pyramidal clay, a defoliated clay, a defoliated clay hardened in another oxide matrix, a layered silicate mineral, an unlayered silicate mineral, a mineral layered aluminosilicate, an unlayered aluminosilicate mineral, or a combination thereof.
[0078] Generally, chemically treated solid oxides exhibit increased acidity when compared to the corresponding untreated solid oxide compound. Chemically treated solid oxide also functions as a catalytic activator when compared to the corresponding untreated solid oxide. Although the chemically treated oxide activates the salt transition metal complex in the absence of cocatalysts, cocatalysts can also be included in the catalytic composition. The activation function of the activation support is evident in the increased activity of the catalytic composition as a whole, as compared to a catalytic 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.
[0079] The chemically treated oxide may comprise a solid oxide treated with an electron extracting anion. While not intended to be bound by the following statement, it is believed that treatment of solid oxide with an electron extracting component amplifies or increases the acidity of the oxide. Thus, the activating support exhibits a Lewis or Br0nsted acidity that is generally greater than the Lewis or Br0nsted acid strength of the untreated solid oxide, or the activating support has a greater number of acidic sites than the untreated solid oxide, or both. One method to quantify the acidity of untreated and chemically treated solid oxide materials is by comparing the polymerization activities of treated and untreated oxides under acid catalyzed reactions.
[0080] Chemically treated solid oxides of the present disclosure are generally formed from inorganic solid oxide which exhibits Lewis or Br0nsted acid behavior and has a relatively high porosity. Solid oxide is chemically treated with an electron extracting component, usually an electron extracting anion, to form an activating support.
According to one aspect of the present disclosure, the solid oxide used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc/g. In accordance with another aspect of the present disclosure, the solid oxide has a pore volume greater than about 0.5 cc/g. In yet another aspect of the present disclosure, the solid oxide has a pore volume greater than about 1.0 cc/g.
[0082] In another aspect, solid oxide has a surface area of about 100 m2/g to about 1000 m2/g. In yet another aspect, the solid oxide has a surface area from about 200 m2/g to about 800 m2/g. In yet another aspect of the present disclosure, the solid oxide has a surface area from about 250 m2/g to about 600 m2/g.
[0083] The chemically treated solid oxide may comprise a solid inorganic oxide comprising oxygen and one or more elements selected from the group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table or which includes 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 can include oxygen and an element or elements selected from Al, B, Ser, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.
Suitable examples of solid oxide materials or compounds that can be used to form the chemically treated solid oxide 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, including mixed oxides of these and their combinations. For example, solid oxide can encompass silica, alumina, silica-alumina, silica coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides, or any combination thereof.
[0085] The solid oxide of the present disclosure encompasses oxide materials such as alumina, respective "mixed oxides" such as silica-alumina and combinations and mixtures thereof. Mixed oxide compounds like silica-alumina can be single or multiple phases of chemistry with more than one metal combined with oxygen to form the solid oxide compound. Examples of mixed oxides that can be used to form an activator support of the present disclosure may include, but are not limited to, silica-alumina, silica-titania, zirconia-silica, titania-alumina, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia and the like. The solid oxide used herein also encompasses oxide materials such as coated silica alumina, as described in US Patent No. 7,884,163, the disclosure of which is incorporated by reference into the addendum in its entirety.
[0086] The electron scavenger component used to treat solid oxide can be any component that increases the Lewis or Br0nsted acidity of the solid oxide after treatment (compared to solid oxide that is not treated with at least one scavenger anion of electron). In accordance with one aspect of the present disclosure, the electron extracting component can be an electron removing anion derived from a salt, an acid, or other compound, such as a compound, such as a volatile organic compound, that serves as a source or a precursor to the anion. Examples of electron removing anions may include, but are not limited to, sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, counterions, trifluoromethanesulfonate, fluozirconate, fluorotitanate, phosph-tungstate, and the like , including mixtures and their combinations. In addition, other ionic or non-ionic compounds that serve as sources for these electron-withdrawing anions can also be employed in the present disclosure. It is anticipated 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 disclosure. In other embodiments, the electron-withdrawing anion can comprise sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, fluoroacetate, triflate, fluozirconate, fluorotitanate, and the like, or combinations thereof.
[0087] Thus, for example, the activating support (e.g., chemically treated solid oxide) used in the catalytic compositions can be, or can comprise, fluorinated alumina, chlorinated alumina, bromide alumina, sulfated alumina, fluorinated silica-alumina, silica - chlorinated alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, bromide-silica zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated silica, alumina coated with sulfated silica , alumina coated with phosphated silica, and the like, or combinations thereof. In one aspect, the activator support 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 combinations thereof. In another aspect, the activating support comprises fluorinated alumina; alternatively, it comprises chlorinated alumina; alternatively, it comprises sulfated alumina; alternatively, comprise fluorinated silica-alumina; alternatively, it comprises sulfated silica-alumina; alternatively, it comprises fluorinated silica-zirconia; alternatively, it comprises chlorinated silica-zirconia; or alternatively, comprises alumina coated with fluorinated silica.
[0088] When the electron extracting component comprises a salt of an electron extracting anion, the counterion or cation of said salt may be selected from any cation that allows the salt to reverse or decompose back the acid during the calcination. Factors that determine the suitability of the particular salt to serve as a source for electron extraction anion include, but are not limited to, solubility of the salt in the desired solvent, lack of adverse cation reactivity, ion pairing effects between the cation and anion, hygroscopic properties transmitted to the salt by the cation, and the like, and thermal stability of the anion. Examples of suitable cations in the electron extracting anion salt include, but are not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H+, [H(OEt2)2]+, and the like.
[0089] Additionally, combinations of one or more electron extraction anions, in varying proportions, can be used to adapt the specific acidity of the activating support to the desired level. Combinations of electron extracting components can be contacted with the oxide material simultaneously or individually, and in any order that allows for the desired acidity of the chemically treated solid oxide. For example, one aspect of this disclosure is to employ two or more electron extraction anion source compounds in two or more separate contact steps.
[0090] Therefore, an example of said process by which a chemically treated solid oxide is prepared follows: a selected solid oxide, or combination of solid oxides, is contacted with a first electron-removing anion source compound to form a first mixture; this first mixture is calcined and then contacted with a second electron extracting anion source compound to form a second mixture; the second mixture is then calcined to form a treated solid oxide. In this process, the first and second electron extraction anion source compounds can be the same or different.
[0091] According to another aspect of the present disclosure, the chemically treated solid oxide comprises a solid inorganic oxide material, a mixed oxide material, or a combination of inorganic oxide materials, which is chemically treated with an electron extracting component , and optionally treated with a metal source, including saline metal, ionic metal, or other metal-containing compounds. Non-limiting examples of ionic metal or metal 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 an ionic metal or metal include, but are not limited to, chlorinated zinc impregnated alumina, fluorinated titanium impregnated alumina, fluorinated zinc impregnated alumina, chlorinated zinc impregnated silica-alumina, silica-alumina fluorinated zinc impregnated, sulfated zinc impregnated alumina, chlorinated zinc aluminate, fluorinated zinc aluminate, sulfated zinc aluminate, alumina coated with silica treated with hexafluorotitanic acid, alumina coated with silica treated with zinc and then fluorinated, and the like, or any combination of these.
[0092] Any method of impregnating solid oxide material with a metal can be used. The method by which the oxide is kept in contact with a source of metal, generally a salt- or metal-containing compound, can include, but is not limited to, gelation, co-gelation, impregnation of one compound into another, and the like. If desired, the metal-containing compound is added or impregnated into the solid oxide as a solution, and subsequently converted to the supported metal after calcination. Accordingly, the solid inorganic oxide may also 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 is generally used to impregnate solid oxide as it can provide improved catalytic activity at a low cost.
[0093] The solid oxide can be treated with saline metals or compounds containing metals before, after or at the same time that the solid oxide is treated with the electron extraction anion. After any contact method, the contacted mixture of the solid compound, electron extracting anion, and ion metal is usually calcined. Alternatively, a solid oxide material, an electron extracting anion source, and the salt metal or metal-containing compound are brought into contact and simultaneously calcined.
[0094] Various processes are used to form the chemically treated solid oxide useful in the present disclosure. The chemically treated solid oxide can comprise the contact product of one or more solid oxides with one or more electron extracting anion sources. The solid oxide is not required to be calcined prior to contact with the electron extracting anion source. Which contact product is usually calcined during or after the solid oxide is brought into contact with the electron-removing anion source. Solid oxide can be calcined or uncalcined. Various processes for preparing solid oxide activating supports that can be employed in this disclosure have been reported. For example, such methods are described in US Patent Nos. 6,107,230; 6,165,929; 6,294,494; 6,300,271; 6,316,553; 6,355,594; 6,376,415; 6,388,017; 6,391,816; 6,395,666; 6,524,987; 6,548,441; 6,548.442; 6,576,583; 6,613,712; 6,632,894; 6,667.274; and 6,750,302; which disclosures have been incorporated herein by reference in their entirety.
[0095] In accordance with one aspect of the present disclosure, solid oxide material is chemically treated by contact with an electron extracting component, generally an electron extracting anion source. Additionally, the solid oxide material is optionally chemically treated with an ionic metal, and then calcined to form a metal-containing solid oxide or chemically treated solid oxide impregnated with metal. In accordance with another aspect of the present disclosure, the solid oxide material and electron extracting anion source are contacted and simultaneously calcined.
[0096] The method by which the oxide is brought into contact with the electron extracting component, usually a salt or an acid of an electron extracting anion, may include, but is not limited to, gelation, co-gelation, impregnation of one component into another, and the like. Therefore, after any contact method, the contacted mixture of solid oxide, electron extracting anion and optional ionic metal is calcined.
[0097] The activating support of the solid oxide (e.g., chemically treated solid oxide), therefore can be produced by a process comprising: 1) keeping the solid oxide (or solid oxides) in contact with a source compound for extracting anion. electrons (or compounds) to form a first mixture; and 2) calcining the first mixture to form the solid oxide activating support.
[0098] According to another aspect of the present disclosure, the activating support of solid oxide (chemically treated solid oxide) is produced by a process comprising: 1) keeping the solid oxide (or solid oxides) in contact with a first source compound of electron extracting anion to form a first mixture; and 2) calcining the first mixture to produce a calcined first mixture; 3) keeping the calcined first mixture in contact with a second electron extracting anion source compound to form a second mixture; and 4) calcining the second mixture to form the solid oxide activating support.
[0099] According to yet another aspect of the present disclosure, the chemically treated solid oxide is produced or formed by contacting the solid oxide with the source compound of the electron extraction anion, where the solid oxide compound is calcined before, during or after contact with the source of the electron extraction anion, and where there is a significant absence of aluminoxanes compounds, organoborons and organoborates, and ionizing ionic compounds.
[00100] The calcination of the treated oxide is generally conducted in an ambient atmosphere, generally in a dry ambient atmosphere, at a carcass temperature of 200 °C to 900 °C, for a period of about 1 minute to 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 conducted for about 30 minutes to about 50 hours, or 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 is generally 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.
[00101] In accordance with one aspect of the present disclosure, the solid oxide material is treated with a source of ionic halide, ionic sulfate, or combinations of anions, optionally treated with an ionic metal, and then calcined to provide the treated solid oxide chemically in the form of a particulate solid. For example, the solid oxide material can be treated with a sulfide source (called a "sulfating agent"), an ionic chloride source (called a "chlorinating agent"), an ionic fluoride source (called a "fluorinating agent") or a combination of these, and calcined to provide a solid oxide activator. Useful acid activating supports include, but are not limited to, brominated alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, brominated silica-alumina, chlorinated silica-alumina, fluorinated silica-alumina, sulfated silica-alumina, brominated silica-zirconia, silica - chlorinated zirconia, fluorinated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina treated with hexafluorotitanic acid, alumina coated with silica treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, fluorinated boria-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, a pillared clay, such as a pyralized montmorillonite, optionally treated with fluoride, chloride, or sulfate; phosphated alumina or other aluminophosphates optionally treated with sulfide, fluoride, or chloride; or any combination of these above. Additionally, any of these activating supports can optionally be treated with an ionic metal.
[00102] The chemically treated solid oxide may comprise a fluorinated solid oxide in the form of a particulate solid. Fluorinated solid oxide can be formed by contacting the solid oxide with a fluorinating agent. Ionic fluoride can be added to the oxide by forming a slurry of the oxide in a suitable solvent such as alcohol or water including, but not limited to, one or three carbon alcohols due to their volatilities and low surface tension. Examples of suitable fluorinating agents include, but are not limited to, hydrofluoric acid (HF), ammonium fluoride (NH4F), ammonium bifluoride (NH4HF2), ammonium tetrafluoroborate (NH4BF4), ammonium silicofluoride (hexafluorosilicate) ((NH4) 2SiF6), ammonium hexafluorophosphate (NH4PF6), hexafluorotitanic acid (H2TiF6), ammonium hexafluorotitanic acid ((NH4)2TiF6), hexafluorozirconic acid (H2ZrF6), AlF3, NH4AlF4, analogues of these and combinations thereof. Triflic acid and ammonium triflate can also be used. For example, ammonium bifluoride (NH4HF2) can be used as a fluorinating agent due to its ease of use and availability.
[00103] If desired, the solid oxide is treated with a fluorinating agent during the calcination step. Any fluorinating agent capable of maintaining full contact with the solid oxide during the calcination step can be used. For example, in addition to these fluorinating agents described above, volatile organic fluorinating agents can be used. Any fluorinating agent capable of maintaining full contact with the solid oxide during the calcination step can be used. Calcining temperatures should generally be high enough to break down the compound and release fluoride. Hydrogen fluoride gas (HF) or fluorine itself (F2) can also be used with the solid oxide if it is fluorinated during calcination. Silicon tetrafluoride (SiF4) and compounds containing tetrafluoroborate (BF4-) can also be used. A convenient method of maintaining solid oxide contact with the fluorinating agent is to vaporize a fluorinating agent into the gas stream used to fluidize the solid oxide during calcination.
[00104] Similarly, in another aspect of this disclosure, the treated solid oxide comprises a chlorinated solid oxide in the form of a particulate solid. The chlorinated solid oxide is formed by maintaining contact of the solid oxide with the chlorinating agent. Ionic chloride can be added to the oxide by forming a fluid paste 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 maintaining full contact with 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 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 maintaining contact of the solid oxide with the chlorinating agent is to vaporize a chlorinating agent into the gas stream used to fluidize the solid oxide during calcination.
[00105] The amount of fluoride and ionic chloride present before calcining the solid oxide is generally about 1 to 50% by weight, where the weight percentage is based on the weight of the solid oxide, eg silica-alumina, before of calcination. According to another aspect of this disclosure, the amount of ionic fluoride or chloride present prior to calcining the solid oxide is from about 1 to 25% by weight, according to another aspect of this disclosure, from about 2 to 20% by weight . In accordance with yet another aspect of this disclosure, the amount of ionic fluoride or chloride present prior to calcining the solid oxide is about 4 to 10% by weight. Once impregnated with halide, the halide oxide can be dried by any method including, but not limited to, suction filtration followed by evaporation, vacuum drying, spray drying, and the like, although it is possible to start the step immediately. calcination without drying of the impregnated solid oxide.
[00106] The silica-alumina used to prepare treated silica-alumina generally has a pore volume greater than about 0.5 cc/g. In accordance with one aspect of the present disclosure, the pore volume is greater than about 0.8 cc/g, and in accordance with another aspect of the present disclosure, greater than about 1.0 cc/g. Additionally, silica-alumina generally has a surface area greater than about 100 m 2 /g. In accordance with another aspect of the present disclosure, the surface area is greater than about 250 m 2 /g. In yet another aspect, the surface area is greater than about 350 m2/g.
[00107] The silica-alumina used in the present disclosure generally has an alumina content of about 5 to 95% by weight. In accordance with one aspect of the present disclosure, the alumina content of silica-alumina is from about 5 to 50%, or from about 8% to 30%, alumina by weight. In another aspect, high alumina silica-alumina compounds may be employed, the alumina content of which of these silica-alumina compounds typically may range from about 60% to about 90%, or about 65% to about 80% alumina by weight. In accordance with yet another aspect of the present disclosure, the solid oxide component comprises alumina without silica, and in accordance with another aspect of this disclosure, the solid oxide component comprises silica without alumina.
[00108] The sulfated solid oxide comprises sulfide and a solid oxide component, such as alumina or silica-alumina, in the form of a particulate solid. Optionally, the sulfated oxide is further treated with an ionic metal such that the calcined sulfated oxide comprises a metal. In accordance with one aspect of the present disclosure, the sulfated solid oxide comprises sulfate and alumina. In some examples, sulfated alumina is formed by a process where the alumina is treated with a sulfide source, for example, sulfuric acid or sulfide salt such as ammonium sulfide. This process is generally carried out to form a suspension of the alumina in a suitable solvent, such as alcohol or water, to which the desired concentration of sulphating agent has been added. Suitable organic solvents include, but are not limited to, one to three carbon alcohols due to their volatilities and low surface tension.
[00109] According to a disclosure aspect, the amount of sulfate ions present prior to calcination is 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 disclosure, the amount of sulfate ion present before calcining is from about 1 to about 50 parts by weight of sulfate ion to about 100 parts by weight of solid oxide, and in still another aspect. of this disclosure, 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 calcination step. immediately.
[00110] According to another aspect of the present disclosure, the activator-support used in preparing the catalyst compositions of this disclosure comprises an ion replaceable activator-support, including but not limited to silicate and aluminosilicate compounds or minerals, either with structures layered or unlayered, and combinations thereof. In another aspect of this disclosure, layered ion-exchangeable aluminosilicates, such as pillared clays, are used as activating supports. When the acid activator support comprises an ion exchangeable activator support, it may optionally be treated with at least one electron withdrawing anion, such as those disclosed herein, although typically the ion exchangeable activator support is not treated with an anion electron scavenger.
[00111] According to another aspect of the present disclosure, the support-activator of this disclosure comprises mineral clays having exchangeable cations and layers capable of expanding. Typical clay mineral activator supports include, but are not limited to, layered 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, should be considered an active part of the catalyst composition due to its close association with the complex metal salt component of transition.
[00112] According to another aspect of this disclosure, the clay materials of this disclosure encompass materials, either 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 disclosure comprises clays that have had ions exchanged with large cations, including highly charged polynuclear metal complex cations. However, the clay material activating supports of this disclosure also encompass clays that have had ions exchanged with simple salts, including, but not limited to, Al(III), Fe(II), Fe(III) and Zn( II) with binders such as halide, acetate, sulfate, nitrate or nitrite.
[00113] According to another aspect of the present disclosure, the support-activator comprises 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 include, but are not limited to, Keggin ions that can have charges such as 7+, various polyoxometalates, and other large ions. Thus, the term pillarizing refers 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 are then 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 reticular structure is maintained and the porosity is reinforced. 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, pp. 55-99, Academic Press, Inc., (1972); Patent Nos. US4,452,910; US5,376.611; and US4,060.480; which disclosures are incorporated herein by reference in their entirety.
[00114] The pillaring process uses clay minerals having interchangeable cations and layers capable of expanding. Any pillared clay that can enhance the polymerization of olefins in the catalyst composition of the present disclosure can be used. Therefore, clay minerals suitable for pillaring 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 comprises bentonite or montmorillonite. The main component of bentonite is montmorillonite.
[00115] Pillarized clay can be pretreated if desired. For example, a pillared bentonite is 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 disclosure.
[00116] The support-activator used to prepare the catalyst compositions of the present disclosure can be combined with other inorganic support materials, including but not limited to zeolites, inorganic oxides, phosphated inorganic oxides and the like. In one aspect, typical support materials that are used include, but are not limited to silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminum phosphate, silica-titania, silica/titania and - precipitated, mixtures thereof or any combination thereof. In one embodiment, the activator support comprises a sulfated solid oxide activator support (S-SSA).
[00117] The production process of these activator-supports may include precipitation, co-precipitation, impregnation, gelling, pore gelling, calcination (up to 900 °C), spray drying, instant drying, rotary drying and calcining, grinding, sieving and similar operations.
[00118] In one embodiment, the catalyst composition optionally comprises a metal hydride and/or a metal alkyl that can function as a cocatalyst. Generally, the metal alkyl compound that can be used in the catalyst disclosure system can be any heteroplectic or homopletic metal alkyl compound. In one embodiment, the metal alkyl may comprise, consisting essentially of, or consisting of, an alkyl metal halide, an alkyl metal halide, or any combination thereof; alternatively, an alkyl metal halide; or, alternatively, an alkyl metal halide.
[00119] In one embodiment, the metal-to-metal alkyl may include, consist essentially of or consist of a group 1, 2, 11, 12, 13 or 14 metal; or alternatively a group 13 or 14 metal; or, alternatively, a group 13 metal. In some embodiments, the alkyl metal metal (not alkyl metal halide or alkyl metal 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, calcium; alternatively lithium; alternatively, sodium; alternatively, potassium; alternatively, magnesium; alternatively, calcium; alternatively, zinc; alternatively, boron; alternatively, aluminum; or alternatively tin. In some embodiments, the metal alkyl (not metal alkyl halide or metal alkyl halide) may comprise, consist essentially of, or consist of a lithium alkyl, a sodium alkyl, a magnesium alkyl, a boron alkyl, a zinc alkyl, or an aluminum alkyl. In some embodiments, the metal alkyl (not an alkyl metal halide or an alkyl metal halide) can comprise, consist essentially of, or consist of an aluminum alkyl.
In one embodiment, the aluminum alkyl can be an aluminum trialkyl, an alkyl aluminum halide, an alkyl aluminum alkoxide, an aluminoxane or any combination thereof. In some embodiments, the aluminum alkyl can be an aluminum trialkyl, an alkyl aluminum halide, an aluminoxane, or any combination thereof; or, alternatively, an aluminum trialkyl, an aluminoxane or any combination thereof. In other embodiments, the aluminum alkyl can be a trialkylaluminum; alternatively, an alkylaluminum halide; alternatively, an alkylaluminum alkoxide; or, alternatively, an aluminoxane.
[00121] In a non-limiting modality, the aluminoxane may have a repeating unit characterized by formula I:
where R' is a linear or branched alkyl group. Aiquii groups for metal alkyls have been independently described herein and can be used without limitation to describe aluminoxanes having Form I. Generally, n of Form I is greater than 1; or, alternatively, greater than 2. In one mode, n can range from 2 to 15; or alternatively, range from 3 to 10. In one aspect, each haide of any metal alkyl halide disclosed herein may independently be fluoride, chloride, bromide or iodide; alternatively, chloride, bromide or iodide. In one embodiment, each of any metal aikii halides disclosed in this document may be greater; alternatively, chloride from; alternatively, bromide; or alternatively, iodide.
[00122] In one aspect, the aiquii group of any metal aiquii disclosed herein (not a metal aiquii halide or metallic aiquii halide) independently may be an aiquii group C1 to C20; alternatively, an aiquii group from C1 to C10 aiquiia group; or, alternatively, an aikii group from C1 to C6. In one embodiment, each alkyl group(s), independently, can be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a hepti group or an octyl group; alternatively, a methyl group, an ethyl group, a butyl group, a hexii group or an octii group. In some embodiments, the alkyl group can independently be a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, an n-hexyl group, or an n-group. -octii; alternatively, a methyl group, an ethyl group, an n-butyl group or an iso-butyl group; alternatively, a group of metalia; alternatively, an etii group; alternatively, an n-propyl group; alternatively, an n-butyl group; alternatively, an iso-butyl group; alternatively, an n-hexyl group; or, alternatively, an n-octii group.
[00123] In one aspect, each alkyl group of any metal alkyl disclosed herein (not metal alkyl halide or metal alkyl halide) independently may be a C1 to C20 alkyl group; alternatively a C1 to C10 alkyl group; or, alternatively, an alkoxy group from C1 to C6. In one embodiment, each alkoxide group of any metal alkyl alkoxide disclosed herein can be, independently, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a hydroxy group. heptoxy or an octoxy group; alternatively a methoxy group, an ethoxy group, a butoxy group, a hexoxy group or an octoxy group. In some embodiments, each alkoxide group of any metal alkyl alkoxide disclosed herein can independently be a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an iso-butoxy group, an n-hexoxy group or an n-octoxy group; alternatively, a methoxy group, an ethoxy group, an n-butoxy group or an iso-butoxy group; alternatively, a methoxy group; alternatively, an ethoxy group; alternatively, an n-propoxy group; alternatively, an n-butoxy group; alternatively, an iso-butoxy group; Alternatively, an n-hexoxy group; or, alternatively, an n-octoxy group.
[00124] In a non-limiting embodiment, useful metal alkyls may include lithium-methyl, n-butyl lithium, sec-butyl lithium, lithium-tert-butyl, diethyl magnesium, di-n-butylmagnesium, ethylmagnesium chloride, n chloride - butylmagnesium and diethyl zinc.
[00125] In a non-limiting embodiment, useful trialkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum or mixtures thereof. In some non-limiting embodiments, trialkylylaluminum compounds can include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixtures thereof; alternatively triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-octylaluminum or mixtures thereof; alternatively triethylaluminum, tri-n-butylaluminum, trihexylaluminum, tri-n-octlaluminum or mixtures thereof. In other non-limiting embodiments, useful trialkylaluminum compounds may include trimethylaluminum; alternatively triethylaluminum; alternatively tripropylaluminium; alternatively tri-n-butylaluminium; alternatively, triisobutylaluminum; alternatively trihexylaluminum; or, alternatively, tri-n-octylaluminum.
[00126] In a non-limiting embodiment, useful alkylaluminum halides may include diethylaluminum chloride, diethylaluminum bromide, ethylaluminum dichloride, ethylaluminum sesquichloride, and mixtures thereof. In some non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride and mixtures thereof. In other non-limiting embodiments, useful alkylaluminum halides may include diethylaluminum chloride; alternatively, diethylaluminum bromide; alternatively, ethylaluminum dichloride; or alternatively ethylaluminium sesquichloride.
[00127] In a non-limiting embodiment, useful aluminoxanes may include methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylalum butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane or mixtures thereof. In some non-limiting embodiments, useful aluminoxanes can include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutyl aluminoxane, t-butyl aluminoxane or mixtures thereof. In other non-limiting embodiments, useful aluminoxanes can include methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane; alternatively, iso-propyl-aluminoxane; alternatively, n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively, 1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively, 3-pentylaluminoxane; alternatively, iso-pentyl-aluminoxane; or alternatively, neopentylaluminoxane.
[00128] In one embodiment, the metal alkyl comprises an organoboron compound or an organoborate compound. Organoboron and organoborate compounds include neutral boron compounds, borate salts and the like or combinations thereof. For example, fluoroorgano borate compounds and fluoroorgano borate compounds are contemplated.
[00129] Any fluoroorgano boron or fluoroorgano borate compound can be used with the present disclosure. Examples of fluoroorgano borate compounds that can be used in the present disclosure 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 in the present disclosure include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixtures thereof. While not intended to be bound by the following theory, these examples of fluoroorgano borate compounds and fluoroorgano boron and related compounds are intended to form "weakly coordinated" anions when combined with organometal or metallocene compounds as disclosed in the Patent US No. 5,919,983, the disclosure thereof 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.
[00130] In one aspect, the weight ratio of the treated solid oxide component to the transition metal salt complex can be from about 10,000:1 to about 1:1. In another aspect, the weight ratio of the treated solid oxide component to the transition metal salt complex in the catalyst composition can be from about 1,000:1 to about 10:1 and, in yet another aspect, from about 500:1 to about 20:1. These weight ratios are based on the combined weights of the cocatalyst (eg, organoaluminium, treated oxide) and transition metal salt complex used to prepare the catalyst composition, regardless of the order of contact with the catalyst components.
[00131] In one embodiment, catalyst compositions of the type disclosed in this document exhibit a catalytic activity of a polymerization reaction ranging from about 1 g PE/g cat • h to about 1,000,000 kg PE/g cat • h , alternatively from about 1 kg PE/g cat • h to about 100,000 kg PE/g cat • h , or alternatively from about 10 kg PE/g cat • h to about 10,000 kg PE/g cat • h. Catalyst system activity is defined as grams of a product produced per gram of the transition metal salt complex used in the catalyst system over the first 45 minutes of the start of a reaction from the time the catalyst system completes. is in contact with the olefin. The activity of the catalyst system can be indicated in terms of various products of an olefin oligomerization or polymerization.
[00132] In one embodiment, the composition of a catalyst of the type described in this document can function in the polymerization of olefins. In one embodiment, a monomer (eg, ethylene) is polymerized using the methodologies disclosed in this instrument to produce a polymer. The polymer can comprise a homopolymer, copolymer and/or combinations thereof. In one embodiment, the polymer is a copolymer comprising ethylene and one or more comonomers such as alpha olefins. Examples of suitable comonomers include, but are not limited to, unsaturated hydrocarbons having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl -1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and mixtures thereof. In one embodiment, the comonomer is 1-hexene. In one embodiment, the comonomer may be present in the polymer in an amount equivalent to or less than about 0.5% by mol, alternatively less than about 0.4% by mol, alternatively less than about 0.3% by mol or alternatively less than about 0.2% by mol.
[00133] In one embodiment, a catalyst system of the type disclosed in this document is used to prepare a polymer by any method of polymerization of olefins, using various types of polymerization reactors. As used herein, "polymerization reactor" includes any reactor capable of polymerizing olefin monomers to produce homopolymers and/or copolymers. Homopolymers and/or copolymers produced in the reactor can be referred to as resin and/or polymers. The various types of reactors include, among others, those which may be referred to as batch, slurry, gas phase, solution, high pressure, tubular, autoclave, or other reactor and/or reactors. Gas phase reactors can comprise fluidized bed reactors or horizontal stage reactors. Mud reactors can comprise vertical and/or horizontal cycles. High pressure reactors can comprise autoclave and/or tubular reactors. Reactor types can include batch and/or continuous process. Continuous processes can use intermittent or continuous product transfer or discharge. Processes may also include direct partial or complete recycling of unreacted monomer, unreacted comonomer, catalyst and/or cocatalysts, diluents, and/or other materials from the polymerization process. The polymerization reactor systems of the present disclosure can comprise one type of reactor in a system or several reactors of the same or different type, operated in any suitable configuration. Polymer production in multiple reactors can include several steps in at least two separate polymerization reactors, interconnected by a transfer system, making it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. Alternatively, polymerization in multiple reactors can include manual or automatic transfer of polymer from one reactor to the subsequent reactor or reactors for further polymerization. Alternatively, multi-stage or multi-step polymerization can take place in a single reactor, where conditions are changed so that a different polymerization reaction takes place.
[00134] The desired polymerization conditions in one of the reactors may be the same or different from the operating conditions of any other reactors involved in the general process of producing the polymer of the present disclosure. 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 or in parallel. In one embodiment, any arrangement and/or any combination of reactors can be employed to produce the polymer of the present disclosure.
[00135] According to an embodiment, the polymerization reactor system may comprise at least one fluidized cycle reactor. Such reactors are common and can comprise vertical or horizontal cycles. Monomer, diluent, catalyst system and optionally any comonomer can be continuously fed to a slurry loop reactor, where polymerization takes place. Generally, continuous processes can comprise the continuous introduction of a monomer, a catalyst, and/or 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, flash evaporation which can include any combination of heat addition and pressure reduction; separation by cyclonic action into a cyclone or hydrocyclone; centrifugal separation; or other appropriate method of separation.
[00136] Typical slurry polymerization processes (also known as particle form processes) are disclosed in US Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191 and 6,833,415, for example; each of which is incorporated herein by reference in its entirety.
[00137] Suitable diluents used in fluidized polymerization include, but are not limited to the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some cycle polymerization reactions can take place under bulk conditions where no diluent is used. One example is propylene monomer polymerization as disclosed in US Patent No. 5,455,314, which is incorporated herein by reference in its entirety.
[00138] According to yet another embodiment, the polymerization reactor may comprise at least one gas phase reactor. Such 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 new or fresh 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 US Patent Nos. 4,588,790, 5,352,749, and 5,436,304, each of which are incorporated herein by reference in their entirety.
[00139] According to yet another embodiment, 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. 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 intermixed for polymerization. Heat and pressure can be appropriately employed to obtain optimal polymerization reaction conditions.
[00140] According to yet another embodiment, the polymerization reactor may comprise a solution polymerization reactor, in which the monomer comes into contact with the catalyst composition by suitable stirring or other means. A carrier comprising an excess organic diluent or monomer may be employed. If desired, the monomer can be placed, in 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.
[00141] Polymerization reactors suitable for the present disclosure may further comprise any combination of at least one feedstock feed system, at least one feed system for catalyst or catalyst components, and/or at least one recovery system of 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.
[00142] Conditions that are controlled for polymerization efficiency and to provide polymer properties include, but are not limited to, temperature, pressure, type and amount of catalyst or cocatalyst, and concentrations of various reactants. Polymerization temperature can affect catalyst productivity, polymer molecular weight and molecular weight distribution. Suitable polymerization temperatures can be any temperature below the depolymerization temperature in accordance with the Gibbs Free Energy Equation. Typically this includes from about 60°C to 280°C, for example, and/or from about 70°C to 110°C, depending on the type of polymerization reactor and/or polymerization process.
[00143] Appropriate pressures will also vary by reactor and polymerization process. The pressure for liquid phase polymerization in a loop reactor is typically less than 1000 psig (6.90 MPa). Pressure for gas phase polymerization is generally about 200 - 500 psig (1.38 - 3.45 MPa). High pressure polymerization in tubular or autoclave reactors is typically performed at approximately 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.
[00144] The concentration of various reactants can be controlled to produce polymers with certain physical and mechanical properties. The proposed end use product that will be formed by the polymer and the method of forming that product can be varied to determine the properties of the desired end product. Mechanical properties include, but are not limited to, tensile strength, flexural modulus, impact strength, deformation, stress relaxation and hardness testing. Physical properties include, but are not limited to, density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack enhancement, short chain branching, chain branching length and rheological measurements.
[00145] Concentrations of monomer, comonomer, hydrogen, cocatalyst, modifiers and electron donors are generally important in producing specific polymer properties. Comonomer can be used to control product density. Hydrogen can be used to control the molecular weight of the product. Cocatalysts can be used to alkylate, eliminate toxics and/or control molecular weight. The concentration of toxics can be minimized as toxics can impact reactions and/or otherwise affect polymer product properties. Modifiers can be used to control product properties and electron donors can affect stereoregularity.
[00146] In one embodiment, a catalyst composition comprises a transition metal salt characterized by Structure VI, a sulfated solid oxide of the type disclosed herein and an alkyl aluminum complex of the type disclosed herein. The catalyst composition may be in contact with a monomer (eg ethylene and the optional comonomer) under conditions suitable for forming a polymer (eg polyethylene).
[00147] In one embodiment, a monomer (eg, ethylene) can be polymerized using the methodologies disclosed herein to produce a polymer of the type disclosed herein. The polymer can comprise a homopolymer. In one embodiment, the polymer is a homopolymer. It should be understood that an insignificant amount of comonomer may be present in the polymers disclosed herein and the polymer is still considered a homopolymer. Here, an insignificant amount of a comonomer refers to an amount that does not substantially affect the properties of the polymer disclosed herein. For example, a comonomer may be present in an amount less than about 1.0% by weight, 0.5% by weight, 0.1% by weight or 0.01% by weight based on the total weight of the polymer.
[00148] The polymer may include other additives. Examples of additives include, but are not limited to, antistatic agents, dyes, stabilizers, nucleators, surface modifiers, pigments, glidants, anti-adherent agents, tacifiers, polymer processing aids and combinations thereof. Such additives can be used singly or in combination and can be included in the polymer before, during, or after preparation of the polymer as described herein. Such additives can be added by any suitable technique, for example, during an extrusion or compounding step, such as during pelleting or subsequent processing into an end-use article.
[00149] In one embodiment, a polymer of the type described in this document is characterized by a density that can be described according to equation (1) p > a - b Log M (1) where "p" is the density of the polymer in g/cc and "log M" is a log of the weight average molecular weight of the polymer and the coefficients "a" and "b" can be determined by at least a square fit for a data set of log M and values of measured density. In an embodiment "a" has a value of 1.0407 and "b" has a value of 0.0145 where the weight average molecular weight of the polymer (eg PE) is from about 50 kg/mol to about 1000 kg/mol. In another embodiment "a" has a value of 1.0417 and "b" has a value of 0.0145 where the weight average molecular weight of the polymer (eg PE) is from about 20 kg/mol to about 2000 kg/mol. In another embodiment "a" has a value of 1.0427 and "b" has a value of 0.0145 where the weight-average molecular weight of the polymer (e.g. PE) is from about 10 kg/mol to about of 5000 kg/mol. In one embodiment, a polymer of the type disclosed herein has a density greater than or equal to about 0.94 g/cc, alternatively greater than about 0.95 g/cc, alternatively greater than about 0.955 g/cc.
[00150] In one embodiment, a polymer of the type described in this document can be of any embodiment. In this document, polymer "modality" refers to the shape of its molecular weight distribution curve, that is, the appearance of the graph of polymer weight fraction versus its molecular weight. Polymer weight fraction refers to the weight fraction of molecules of a given size. A polymer having a molecular weight distribution curve showing a single peak may be referred to as a unimodal polymer, a polymer having a curve showing two distinct peaks may be referred to as a bimodal polymer, a polymer having a curve showing three distinct peaks may be referred to as trimodal polymer, a polymer with a curve showing two or more peaks may be referred to as multimodal, etc. Polymer modality can be determined using any suitable methodology, such as those described in the examples sections herein.
[00151] In one embodiment, a polymer of the type described herein has a weight average molecular weight (Mw) of about 10 kg/mol to about 5,000 kg/mol; alternatively from about 20 kg/mol to about 2000 kg/mol, or alternatively, from about 50 kg/mol to about 1000 kg/mol. Weighted average molecular weight describes the molecular weight distribution of a polymer and is calculated according to Equation 2:
where Ni is the number of molecules of molecular weight Mi.
[00152] A polymer of the type described herein can be characterized by an average molecular weight (Mw) of about 1 kg/mol to about 1000 kg/mol; alternatively from about 2 kg/mol to about 500 kg/mol, or alternatively, from about 3 kg/mol to about 100 kg/mol. The average molecular weight is the common average of the average molecular weights of the individual polymers and can be calculated according to Equation 3:
where Ni is the number of molecules of molecular weight Mi.
[00153] A polymer of the type described herein may be characterized by molecular weight distribution (MWD) greater than about 5, greater than about 10, alternatively greater than about 12, or alternatively greater than about 15. is the ratio of Mw to Mn, which is also referred to as the polydispersity index (PDI), or more simply as polydispersity.
[00154] A polymer of the type described herein can be further characterized by a z (Mz) to Mw (Mz / Mw ) average molecular weight ratio of greater than about 4, alternatively greater than about 5, or alternatively greater to about 6. The z-average molecular weight is a higher order molecular weight that is calculated according to Equation 4:
where Ni is the amount of substance of species i and Mi is the molecular weight of species i. The Mz/Mw ratio is another indication of the extent of a polymer's MWD.
[00155] In one embodiment, a polymer of the type described herein has a melt index, MI, of about 0.0001 g/10 min. at about 10,000 g/10 min, alternatively from about 0.001 g/10 min to about 1000 g/10 min, or alternatively from about 0.01 g/10 min. at about 100 g/10 min. Melt Index (MI) refers to the amount of a polymer that can be forced through a 0.0825 inch diameter extrusion rheometer orifice when subjected to a force of 2160 grams in ten minutes at 190 °C, as determined in accordance with ASTM D 1238.
[00156] In one embodiment, a polymer of the type described in this document has a high melt index, HLMI, in a range of about 0.1 g/10 min. to about 100,000 g/10 min., alternatively about 0.5 g/10 min. at about 10,000 g/10 min., or alternatively at about 1 g/10 min. at about 1000 g/10 min. High Charge Flow Index (HLMI) refers to the rate of a polymer that can be forced through a 0.0824 inch diameter extrusion rheometer hole when subjected to a force of 21,600 grams at 190 °C, of according to ASTM D1238.
[00157] In one embodiment, a polymer of the type described in this document has a Carreau Yasuda parameter 'a' CY-a (a-eta), in the range of about 0.05 to about 0.5, alternatively of about 0.1 to about 0.4, or alternatively from about 0.15 to about 0.3. The Carreau Yasuda parameter 'a' (CY-a) is defined as the rheological amplitude parameter. Rheological amplitude refers to the amplitude of the transition region between Newtonian and power law shear rate for a polymer or to the frequency dependence of the polymer's viscosity. Rheological amplitude is a function of the relaxation time distribution of a polymer resin, which in turn is a resin's molecular structure or architecture. The CY-a parameter can be obtained by assuming the Cox-Merz rule and calculated by fitting the flow curves generated in linear viscoelastic dynamic oscillatory frequency sweep experiments with a modified Carreau-Yasuda (CY) model, which is represented by Equation 5:
where E = viscosity = (Pa^s) Y = shear rate (1/s) a = rheological amplitude parameter t t = relaxation time (s) [describes the location in time of the transition region] F . x . ... o = zero shear viscosity (Pa.s) [sets Newtonian plateau] n = power law constant [sets final slope of high shear rate region].
[00158] To facilitate model fit, the power law constant n is kept at a constant value. 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, Polymeric Liquid Dynamics, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987), each of which is incorporated by reference in this document in its entirety.
In one embodiment, a polymer of the type described herein may have a zero shear viscosity (no) greater than about 1000 Pa.s, alternatively greater than about 2000 Pa.s, or alternatively greater than about 5000 Pa.s Country In one embodiment, a polymer of the type described herein having a melt index of about 2 may have a zero shear viscosity greater than about 5,000 Pa.s, alternatively greater than about 10,000 Pa.s, or alternatively , greater than about 15,000 Pa.s.
[00160] In one embodiment, a polymer of the type described in this document may have an HLMI of about 7 g/10 min. it can have a zero shear viscosity greater than about 50,000 Pa.s, alternatively greater than about 100,000 Pa.s, alternatively greater than about 500,000 Pa.s. In one embodiment, a polymer of the type described herein with HLMI of about 1 g/10 min. it can have a zero shear viscosity greater than about 100,000 Pa.s, alternatively greater than about 500,000 Pa.s, or alternatively greater than about 1,000,000 Pa.s.
[00161] In one embodiment, a polymer of the type described in this document may have a Mw of about 250 kg/mol, may have a zero shear viscosity greater than about 50,000 Pa.s, alternatively greater than about 100,000 Pa .s, alternatively greater than about 500,000 Pa.s. In an alternative embodiment, a polymer of the type described herein with a Mw of about 175 kg/mol may have a zero shear viscosity of greater than about 25,000 Pa.s, alternatively greater than about 50,000 Pa.s. or, alternatively, greater than about 100,000 Pa.s. In an alternative embodiment, a polymer of the type described herein with a Mw of about 125 kg/mol may have a zero shear viscosity greater than about 8,000 Pa.s, alternatively greater than about 10,000 Pa.s, or , alternatively, greater than about 15,000 Pa.s.
[00162] In one embodiment, a polymer of the type disclosed herein has a density greater than or equal to about 0.960 g/cc, alternatively greater than about 0.962 g/cc, alternatively greater than about 0.966 g/cc. Polymers of the type disclosed herein, having a density greater than about 0.960 g/cc, alternatively greater than about 0.962 g/cc, or alternatively greater than about 0.966 g/cc may exhibit improved barrier properties. These polymers are called polymer compositions with improved barrier properties, PCIB,.
[00163] In an embodiment, a PCIB of the type described in this document can be of any embodiment. In one embodiment, a PCB of the type described herein may have a Mw of less than about 145 kg/mol, alternatively, less than about 135 kg/mol, or alternatively, less than about 125 kg/mol. Alternatively, Mw can range from about 50 kg/mol to about 145 kg/mol, alternatively from about 75 kg/mol to about 135 kg/mol, or alternatively, from about 90 kg/mol to about 125 kg/mol.
[00164] A PCIB of the type described herein can be characterized by Mn of about 1 kg/mol to about 20 kg/mol; alternatively from about 2 kg/mol to about 10 kg/mol, or alternatively, from about 3 kg/mol to about 8 kg/mol.
[00165] A PCB of the type described herein may be characterized by MWD greater than about 7, alternatively greater than about 10, alternatively greater than about 12, or alternatively greater than about 15.
[00166] A PCIB of the type described herein may be further characterized by Mz/Mw greater than about 5, alternatively greater than about 6, or alternatively greater than about 7.
[00167] In one embodiment, PCIB of the type described in this document has MI greater than about 0.8 g/10 min, alternatively greater than about 1.5 g/10 min, or alternatively greater than about 1, 8 g/10 min as determined in accordance with ASTM D 1238.
[00168] In one embodiment, PCIB of the type described in this document may have HLMI greater than about 10 g/10 min, alternatively greater than about 25 g/10 min, or alternatively greater than about 50 g/10 min, as determined in accordance with ASTM D 1238.
[00169] In one embodiment, a PCIB of the type described in this document has a Carreau Yasuda parameter 'a' CY-a (a-eta), in the range of about 0.45 to about 0.4, alternatively of about from 0.15 to about 0.3.
[00170] In one embodiment, PCIB of the type described in this document may have a xero shear viscosity (no) of about 1,000 Pa.s to 65,000 Pa.s, alternatively from about 2,000 Pa.s to about 50,000 Pa.s or, alternatively, from about 5,000 to 30,000 Pa.s.
[00171] PCIBs of the type disclosed herein can be formed into articles of manufacture or articles of end use using techniques known in the art, such as extrusion, blow molding, injection molding, fiber spinning, thermoforming and casting. Polymers of the type disclosed in this document may exhibit increased processability.
[00172] In one embodiment, PCIBs of the type described and disclosed herein are fabricated into a film. Advertising films can be produced by any suitable method and under any conditions suitable for film production. In one embodiment, polymers are formed into films through a tubular film process. In a tubular film process, plastic cast material is extruded through an annular slit mold, usually vertically, to form a thin-walled tube. Air can then be introduced through a hole in the center of the mold to explode the tube like a balloon. Mounted on the mold, a ring of high velocity air blows inside the hot film to cool it. The film tube then continues moving upward, cooling itself continuously, until it passes through pinch rollers where the tube is flattened to create what is known as a flat film tube. This flat or collapsed tube is then taken back down to the extrusion tower via more rollers. In the upper outlet lines, the air inside the bubble is exchanged as well. This is known as Internal Bubble Cooling (IBC).
[00173] The flat film is then kept as such or the edges of the flat film are cut to produce two sheets of flat film and finish on the reels. Typically, the expansion ratio between the mold and the blown film tube would be 1.5 to 4 times the diameter. The drawdown between the wall thickness of the molten material and the thickness of the cooled film occurs in both the radial and longitudinal directions and is easily controlled by changing the air volume inside the bubble and by changing the transport speed. Films formed from the polymer resins of this disclosure (eg, polyethylene) can be of any thickness desired by the user. Alternatively, PCBs of this disclosure can be formed into films having a thickness of from about 0.1 mm to about 5 mm, alternatively from about 0.2 mm to about 1.5 mm, alternatively from about 0. 3mm to about 1.0mm.
[00174] In one embodiment, PCIBs of the type disclosed in this document show improvements in processing so that the pressure required to extrude the polymer is reduced compared to a polymer of the same molecular weight prepared using a metallocene catalyst. For example, the extrusion pressure can be reduced by more than about 25%, alternatively more than about 30%, or alternatively more than about 35%.
[00175] In one embodiment, films formed from PCIBs of this disclosure can exhibit improved barrier properties. For example, such films may have reduced moisture vapor transmission rates (MVTR) and reduced oxygen transmission rates (OTR). In one embodiment, film produced from the polymers of this disclosure has a MVTR of less than or equal to 0.55 gram-mm per 100 square inch per day (g-mm/100 in2/day), alternatively, less than, or equal to about 0.37 g-mm/100 in2/day or alternatively less than or equal to about 0.32 g-mm/100 in2/day, measured in accordance with ASTM F 1249. The MVTR measures the passage of gaseous H2O through a barrier. The MVTR can also be referred to as the water vapor transmission rate (WVTR). Typically, the MVTR is measured in a special chamber, divided vertically by the substrate/barrier material. A dry atmosphere is in one chamber, and a moist atmosphere is in the other. A 24-hour test is run to see how much moisture passes through the substrate/barrier from the "wet" chamber to the "dry" chamber under conditions that can specify any one of five combinations of temperature and humidity in the "wet" chamber.
[00176] Films produced from PCIBs of this disclosure can be used in forming any variety of end-use articles. For example, the polymer can be extruded into a sheet, which is then thermoformed into an end-use article, such as a container, a cup, a tray, a palette, a toy, or a component of another product. Other non-limiting examples of end-use items that can be produced from the films in this disclosure include merchandise bags, t-shirt bags, garbage bags, grocery bags, produce bags, food packaging for contents such as cereals, cookies , cheese, meat, etc., shrinkable plastic and other items known to those skilled in the art. In one embodiment, the polymers disclosed herein (eg, polyethylene) can be formed into films that can be useful in food packaging.
[00177] The following are additional enumerated modalities of the concepts disclosed in this document.
[00178] The first modality is an ethylene polymer with: (i) a density defined by the equation (1) p > a - b Log M (1) where p is a polymer density in g/cc, log M is a log average molecular weight of polymer, a is about 1.0407 and b is about 0.0145; and (ii) a polydispersity index greater than about 5.
[00179] A second embodiment, which is the ethylene polymer of the first embodiment, with weight average molecular weight from about 50 kg/mol to about 1,000 kg/mol.
[00180] A third embodiment, which is the ethylene polymer of the first and second embodiments, with a CY parameter of about 0.05 to 0.5.
[00181] A fourth embodiment, which is the ethylene polymer of the first to third embodiments, with a zero shear viscosity greater than about 1000 Pa.s.
[00182] A fifth embodiment, which is the ethylene polymer of the first to fourth embodiments, a ratio of average molecular weight z to weight average molecular weight greater than about 6.
[00183] A sixth embodiment, which is the ethylene polymer of the first to fifth embodiments, with a melt index of about 1 and zero shear viscosity greater than about 5,000 Pa.s.
[00184] A seventh modality, which is the ethylene polymer of the first to sixth modality, with high charge melt flow index of about 7 and zero shear viscosity greater than about 50,000 Pa.s.
[00185] An eighth embodiment, which is the ethylene polymer of the first to seventh embodiments with a weight average molecular weight of about 250 kg/mol and zero shear viscosity greater than about 100,000 Pa.s.
[00186] A ninth embodiment, which is the ethylene polymer of the first to eighth embodiments, with a weight average molecular weight of about 175 kg/mol and zero shear viscosity greater than about 50,000 Pa.s.
[00187] A tenth modality that is a polymerization method comprising contacting a monomer with a catalytic system characterized in that it comprises an imine-phenol compound under conditions suitable for the formation of a polymer and polymer recovery, where the compound imine-phenol is characterized by having the formula:
where: O and N represent oxygen and nitrogen, respectively; R is composed of a halogen, a hydrocarbyl group or a substituted hydrocarbyl group; R2 and R3 can each independently be hydrogen, halogen, hydrocarbyl group or a substituted hydrocarbyl group; and Q is a donor group; where the polymer is characterized by: i) a density defined by the equation (1) p > a - b Log M (1) Where p is a polymer density in g/cc, log M is a log of the average molecular weight of the polymer , a is about 1.0407 and b is about 0.0145; and (ii) a polydispersity index greater than about 5.
[00188] An eleventh embodiment, which is a composition comprising the ethylene polymer of the first to new embodiments with a density greater than about 0.960 g/cc, wherein a film formed from the composition has a transmission rate of moisture vapor less than or equal to about 0.5 gram-mm per 100 square inch per day.
[00189] A twelfth embodiment is the composition of the eleventh embodiment with a zero shear viscosity of about 1000 Pa.s to about 65,000 Pa.s.
[00190] A thirteenth embodiment which is the composition of the eleventh to twelfth embodiments with a CY parameter from about 0.05 to about 0.45.
[00191] A fourteenth modality, which is the composition of the eleventh to thirteenth modality characterized as unimodal.
[00192] A fifteenth modality, which is the composition of the eleventh to fourteenth modality, with a polydispersity index greater than about 7.
[00193] A sixteenth modality, which is the composition of the eleventh to fifteenth modality, with a ratio of z-average molecular weight to weight-average molecular weight greater than about 5.
[00194] A seventeenth modality, which is the composition of the eleventh to sixteenth modality, with a flow rate greater than about 0.8 g/10 min.
[00195] An eighteenth modality, which is the composition of the eleventh to seventeenth modality, with a density greater than about 0.966 g/cc.
[00196] A nineteenth modality, which is the composition of the eleventh to eighteenth modality, in which the film formation occurs at an extrusion pressure about 25% lower than that of the film formed from a polymer with the same molecular weight prepared using a metallocene catalyst.
[00197] A twentieth embodiment, which is an article formed from the ethylene polymer of the first through ninth embodiments.
[00198] A twenty-third modality, which is a film formed from the ethylene polymer from the eleventh to the tenth new modality.
[00199] A twenty-second embodiment which is a polyethylene homopolymer having a density greater than about 0.960 g/cc, a melt index greater than about 0.8 g/10 min, and a polydispersity index greater than about 7, where a film formed by polyethylene homopolymer exhibits a moisture vapor transmission rate less than or equal to about 0.37 gram-mm per 100 square inches per day.
[00200] A twenty-third embodiment which is the polyethylene homopolymer of the twenty-second embodiment having a weight-average molecular weight of less than about 145 kg/mol.
A fourteenth embodiment, which is the polyethylene homopolymer of the twenty-second to twenty-third embodiments, with a weight average molecular weight of about 125 kg/mol and zero shear viscosity greater than about 8,000 Pa.s. . EXAMPLES
[00202] The present disclosure is further illustrated by the following examples, which should in no way be interpreted as imposing limitations on its scope. On the contrary, it should be clearly understood that the resource can be had for various other aspects, modalities, modifications and equivalents thereof which, after reading the description in this document, may be suggested to a person versed in the technique, without deviating from the scope of the present invention or the scope of the appended claims.
[00203] The data and descriptions provided in the examples below are given to show specific aspects and modalities of the disclosed compounds, catalyst system and olefin oligomerization and/or olefin polymerization methods, and to demonstrate a number of practices and advantages of the disclosed same. The examples are given as a more detailed demonstration of some aspects and arrangements described in this document and are not intended to limit the disclosure or claims in any way.
[00204] Flow index (MI, g/10 min) was determined in accordance with ASTM D 1238, condition E, at 190°C with a weight of 2160 grams.
[00205] High Load Melt Index (HLMI, g/10 min) was determined in accordance with ASTM D1238, condition E, at 190°C, with a weight of 21,600 grams.
[00206] Polymer density was determined in grams per cubic centimeter (g/cc) 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 D 1505 and ASTM D 1928, procedure C.
[00207] 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 Styragel 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 the concentration of polymer solutions was generally maintained in the range of 1.0-1.5 mg/ml, depending on molecular weight. Sample preparation was performed at 150 °C for nominally 4 h with occasional gentle shaking before the solutions were transferred to sample vials for injection. 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 broad standard. The full table of the broad pattern was predetermined in a separate SEC-MALS experiment.
[00208] Rheology measurements were made as follows: Deformations were generally kept to a single value during a frequency sweep, but higher deformation values were used for low viscosity samples to maintain a measurable torque. Lower strain values were used for high viscosity samples to avoid overloading the torque transducer and to keep within the linear viscoelasticity limits of the sample. The instrument automatically reduces strain at high frequencies if necessary to keep the torque transducer out of overload. These data were fitted to the Carreau-Yasuda equation to determine dynamic viscosity (n0), relaxation time (T) and a measure of the relaxation time distribution width (CY-a).
[00209] The MVTR was measured according to ASTM F 1249. Synthesis of Imine-phenol ligands
[00210] Two distinct classes of imine-phenol ligands that incorporate a donor arm have been prepared. The first class utilized a second phenol as the donor arm formally giving a supporting structure of the imine (bis)phenolate ligand. The linkers were prepared by reacting phenol benzylamine and aldehydes as shown in Scheme I. Typically, one equivalent of 3-tert-butyl-2-hydroxybenzylamine was added to one equivalent of 3-tert-butyl-2-hydroxybenzaldehyde to produce (tBu) LH2 as confirmed by NMR spectroscopy.

[00211] The synthesis of three bis(phenolate) imine linkers was carried out as follows: (tBu) LH2: Ao 3-tert-butyl-2-hydroxybenzylamine (0.816 g, 4.55 mmol) and 3-tert-butyl- 2-hydroxybenzaldehyde (0.788 g, 4.42 mmol) was added 30 mL of EtOH forming a yellow solution. The mixture was heated at 85°C for 3 hours. Volatiles were evacuated, leaving (tBu)LH2. 1H NMR (CDCl3): δ 8.47 (1H), δ 7.36 (1H), δ 7.29 (1H), δ 7.13 (1H), δ 7.09 (1H), δ 6.89 (1H), δ 6.85 (1H), δ 5.72 (1H), δ 4.84 (2H), δ 1.46 (9H), δ 1.44 (9H). (tBu)2LH2. To 3-tert-butyl-2-hydroxybenzylamine (0.456 g, 2.54 mmol) and 3,5-di-tert-butyl-2-hydroxybenzaldehyde (0.567 g, 2.42 mmol) were added 15 mL of EtOH forming a yellow solution. The mixture was heated at 85°C for 5 hours. Volatiles were evacuated, leaving (tBu)2LH2 in quantitative yield which was used without further purification. 1H NMR (CDCl3): δ 8.49 (1H), δ 7.43 (1H), δ 7.28 (1H), δ 7.13 (1H), δ 7.08 (1H), δ 6.88 (1H), δ 5.84 (1H), δ 4.83 (2H), δ 1.44 (18H), δ 1.31 (9H). (Me) LH2. To 3-tert-butyl-2-hydroxybenzylamine (0.315 g, 1.76 mmol) and 2-hydroxy-3-methylbenzaldehyde (0.222 g, 1.63 mmol) were added 10 mL of EtOH forming a yellow solution. The mixture was heated at 85°C for 2 hours. Volatiles were evacuated, leaving (Me)LH2 in quantitative yield which was used without further purification. 1H NMR (CDCl3): δ 12.70 (1H), δ 8.46 (1H), δ 7.27 (1H), δ 7.24 (1H), δ 7.08 (1H), δ 6.87 (1H), δ 6.82 (1H), 5.72 (1H), δ 4.84 (2H), δ 2.29 (3H), δ 1.44 (9H).
[00212] The second class utilized pyrrole donor groups and were prepared from the condensation of hydroxybenzylamine and a pyrrole aldehyde as shown in Scheme II. This synthetic pathway was used in the preparation of PyLH2 and MePyLH2.

[00213] PyLH2: To 3-tert-butyl-2-hydroxybenzylamine (0.30 g, 1.67 mmol) and (0.788 g, 4.42 mmol) and pyrrole-2-carboxaldehyde were added 10 mL of EtOH forming a yellow solution. The mixture was heated at 85°C for 2 hours. Volatiles were evacuated, leaving PyLH2. 1H NMR (CDCl3): δ 9.1 (1H), δ 8.12 (1H), δ 7.22 (1H), δ 6.97 (1H), δ 6.93 (1H), δ 6.80 (1H), δ 6.60 (1H), δ 6.28 (1H), δ 4.83 (s, 2H), δ 1.46 (9H). Metal complexation of bis(phenol) imine ligands
[00214] The transition metal complex of the type disclosed in this document can be formed in two ways. Treatment of (tBu)LH2 to 1 equivalent of ZrBn4 gives a 50:50 mixture of ((tBu)L)2Zr and ZrBn4 not resulting in the desired monoligate (tBu) LZrBn2. Treatment of (tBu)LH2 with Zr(NEt2)4 also produces the unwanted diligate ((tBu)L)2Zr. However, the desired monoligated complex was ((tBu)LZrCl2(Et2O)) by the disproportion of ((tBu)L)2Zr with ZrCl4(THF)2 (Method A). On the other hand, (tBu)LLZrCl2(Et2O) was prepared by adding (tBu)LH2 to a mixture of ZrCl4/2BzMgCl in the presence of Et2O (Method B). The product formed, (tBu) LZrCl2(Et2 O), was confirmed by NMR spectroscopy. The reactions are summarized in Scheme III.

[00215] (tBu)LZrCl2(OEt2). Method A: (tBu)LH2 (0.11 g, 0.324 mmol) and Zr(NEt2)4 (0.062 g, 0.162 mmol) were combined in 3 mL of PhMe forming a yellow solution. The mixture was stirred overnight at room temperature. Volatiles were evacuated, leaving an orange-yellow solid, which was dissolved in Et2O (7 mL) and cooled to -30°C. The cold solution was added to ZrCk^THF (0.055 g, 0.147 mmol) suspended in 5 mL of Et2O. The suspension was allowed to warm with stirring at room temperature overnight. Volatiles were evacuated and the resulting solid was washed with pentane leaving (tBu)LZrCl2(OEt2) as an off-white solid (0.87 g).
Method B: ZrCl4 (1.47 g, 6.31 mmol) was suspended in Et2O (35 mL) and cooled to -30°C. In the dark, 1 M of BnMgCl in Et2O (12.6 mL, 12.6 mmol) was added. The resulting suspension was warmed to room temperature with stirring overnight. Volatiles were evacuated and the residue was extracted with 35 ml of PhMe. The PhMe extract was added to (tBu)LH2 (2.04 g, 6.01 mmol) which causes a precipitate to form. The mixture was left to stand at room temperature for three days. The pale yellow precipitate was filtered and washed with pentane 4X5 mL leaving (tBu)LZrCl2(OEt2) (1.45 g). 1H NMR (CD2Cl2): δ 8.49 (s, 1H), δ 7.61 (d, 1H), δ 7.34 (d, 2H), δ 7.09 (d, 1H), δ 6.98 (t, 1H), δ 6.83 (t , 1H), δ 4.79 (s, 2H), δ 4.07 (q, 4H), δ 1.51 (s, 9H), δ 1.50 (s, 9H), δ 1.23 (t, 6H). An NMR spectrum of the product was shown in Figure 1.
[00217] A series of zirconium and hafnium complexes were prepared as described in Scheme IV using method B.

[00218] (tBu)LHfCl2(OEt2). Method B: HfCl4 (0.233 g, 0.728 mmol) was suspended in Et2O (35 mL) and cooled to -30°C. In the dark, 1 M of BnMgCl in Et2O (1.46 mL, 1.46 mmol) was added. The resulting suspension was warmed to room temperature with stirring overnight. Volatiles were evacuated and the residue was extracted with 8 ml of PhMe. PhMe extract was added to (tBu)LH2 (0.235, 0.693 mmol) which causes a precipitate to form. The mixture was left to stand at room temperature for three days. The suspension was evacuated to volume and 10 ml of heptane was added. The solution was decanted and the solid washed with heptane (10ml) leaving a pale yellow solution (tBu)LHfCl2(OEt2) (0.22g). 1H NMR (CD2Cl2): δ 8.48 (1H), δ 7.63 (1H), δ 7.34 (2H), δ 7.08 (1H), δ 6.94 (1H), δ 6.80 (1H), δ 4.81 (2H), δ 4.0 (4H), δ 1.50 (9H), δ 1.49 (9H), δ 1.23 (6H).
[00219] (tBu)2LZrCl2(OEt2). Method B: ZrCl4 (0.775, 3.33 mmol) was suspended in Et2O (20 mL) and cooled to -30°C. In the dark, 1 M of BnMgCl in Et2O (6.66 mL, 6.66 mmol) was added. The resulting suspension was warmed to room temperature with stirring overnight. Volatiles were evacuated and the residue was extracted with 20 ml of PhMe. PhMe extract was added to (tBu)2LH2 (1.25 g, 3.17 mmol) which caused an orange-yellow solution to form. The mixture was left to stand at room temperature for three days. The solution was evacuated to % by volume, 25 ml of heptane was added and the solution was cooled to -30°C causing a solid to form. The solution was decanted and the solid washed with heptane 3X5 mL leaving a pale yellow solid (tBu)2LZrCl2(OEt2) (0.5g). 1H NMR (CD2Cl2): δ 8.53 (1H), δ 7.63 (1H), δ 7.36 (1H), δ 7.23 (1H), δ 7.03 (1H), δ 6.84 (1H), δ 5.04 (2H), δ 4.14 (4H), δ 1.44 (18H), δ 1.30 (9H), 1.2 (6H).
[00220] (Me)LZrCl2(OEt2). Method B: ZrCl4 (0.242, 1.04 mmol) was suspended in Et2O (20 mL) and cooled to -30°C. In the dark, 1 M of BnMgCl in Et2O (2.1 mL, 2.1 mmol) was added. The resulting suspension was warmed to room temperature with stirring overnight. Volatiles were evacuated and the residue was extracted with 10 ml of PhMe. PhMe extract was added to (Me)LH2 (0.294, 0.99 mmol) which caused a precipitate to form. The mixture was left to stand at room temperature for three days. The solution was decanted and the solid washed with heptane 2X5ml leaving a pale yellow solid (Me)LZrCl2(OEt2) (0.23g). 1H NMR (CD2Cl2): δ 8.48 (1H), δ 7.45 (1H), δ 7.31 (2H), δ 7.08 (1H), δ 6.93 (1H), δ 6.83 (1H), δ 4.82 (2H), δ 3.84 (4H), δ 2.32 (3H), δ 1.50 (9H), δ 1.15 (6H). Olefin Polymerizations
[00221] The ability of catalyst compositions of the type disclosed in this document to catalyze olefin polymerization reactions was investigated. Specifically, (tBu)LZrCl2(Et2O) was used to catalyze the polymerization of ethylene in the presence of S-SSA. The reaction conditions are shown in Table 1. The reactions used 3 milligrams of (tBu)LZrCl2(Et2O) designated as catalyst A, (tBu)LHfCl2(Et2O) designated as catalyst B, (Me)LZrCl2(Et2O) designated as catalyst C, (tBu)2LZrCl2(Et2O) designated as Catalyst D, Cl2LZrCl2(Et2O) designated as Catalyst E or (Ad)(Me)LZrCl2(Et2O) designated as Catalyst F. Each reaction contained 0.6 ml of TIBA and 1 gram of S-SSA and was run at a temperature of 90°C under a pressure of 420 psig for 45 minutes.

[00222] The results demonstrate that the substitution of the ligand influences the activity of the catalyst as replacement of one of the tert-butyl groups by methyl groups resulting in a drastic decrease in the catalytic activity. Furthermore, the inclusion of additional auxiliary volume through an adamantyl group (catalyst F) increased the activity. Furthermore, catalyst A containing zirconium yielded higher catalytic activities compared to the corresponding complex with hafnium, catalyst B.
[00223] Various properties of the polymer samples obtained are shown in Table II. Polymer samples are designated as sample numbers 1, 2, 3, 4, 5, 6, 7 and 8 corresponding to reaction numbers 1, 2, 3, 4, 5, 6, 7 and 8 in Table 1.

[00224] The results demonstrate that the molecular weight distributions of polyethylene resins produced using catalyst compositions of the type disclosed herein are broad. In addition, the introduction of hydrogen resulted in an increase in the high charge melt flow index (HLMI), a reduction in molecular weight, and a narrowing of the molecular weight distribution. The introduction of 1-hexene did not appear to have a significant effect on resin density or distribution. EXAMPLE 2
[00225] As can be seen from Table I, polymer samples were prepared at 90°C at a pressure of 420 psig in the presence of hydrogen. The hydrogen concentration in samples 2-5 and 8 was provided in a feed. The addition of hydrogen for samples 6 and 7 was provided at the beginning of polymer preparation, which is indicated as a value in brackets in Table III. Samples 1 to 5 indicate a decrease in M w as hydrogen concentration increases in feed. As can be seen, Mw for samples 9-13 is greater than Mw for samples 1-8.
[00226] Various polymer properties were evaluated for Samples 1-8 and the results are shown in Table III. Of note are the densities of samples 1-8, which are greater than about 0.964 g/cc and as high as about 0.973 g/cc for an HLMI range of about 1.1 dg/min. at about 153.85 dg/min.
COMPARATIVE EXAMPLE 1
[00227] The properties of commercial polymers were compared to polymers of the type disclosed in this document. Nine comparative polymer samples designated C1-C9 were investigated. C1-C4 and C5 are prepared from Cr/SiO2 and Ziegler-Natta catalysts, respectively. Metallocene polymers used as comparisons in film applications (C6-C9) were prepared as described in Table V using MTE-A or MTE-B metallocene catalysts which are described below. Metallocene polymers designated MTE1-MTE11 are described in US 20110035193, which is incorporated by reference herein in its entirety.


[00228] The density, MI and HLMI of the comparative samples are presented in Tables VI and VII.

[00229] A comparison of MI, HLMI and density for the polymers of example 2 and the comparative polymers is presented in Table VIII. Figures 2-4 are representations of the MWD for various polymer samples and comparative polymer samples. Comparisons show that the polymer compositions of this disclosure are higher in density than resins commercially prepared from heterogeneous chromium, Ziegler-Natta, and/or metallocene catalysts. This is true over a wide range of melt flow rates and high load fluidity.

[00230] The results also demonstrate that the polymers of the present disclosure have a higher density for a given melt index (MI). Table VIII shows four groups of polymers for density comparison for a given MI. The first group compares samples 8 and 9 with C1. The polymer from sample 3 has an HLMI of about 7.2 dg/min. and a density of about 0.966 g/cc, and the polymer from sample 4 has an HLMI of about 17.2 dg/min. and a density of about 0.967 g/cc. In contrast, the C1 polymer has an HLMI of 11 dg/min. and density of 0.961 g/cc. The data in Table VIII shows polymers prepared in accordance with the present disclosure, when it has the same HLMI value (eg 11) as C1, it has a higher density, for example, between about 0.966 g/cc and about 0.967 g/cc. The second group compares sample 5 with samples C2 and C3. Comparing sample 5 with comparative sample 2 shows that the polymer from sample 10 has an MI of 0.33 dg/min. and a density of 0.968 g/cc, while the comparative polymer from sample C2 has a similar MI of 0.37 dg/min. and density of 0.963 g/cc. Comparing sample 5 with comparative sample C3 shows that the polymer in sample 10 has a higher density than that of comparative sample C3 with a higher MI of 0.7 dg/min. Finally, the fourth group compares sample 6 with comparative samples C4, C5 and C7. Comparing sample 6 with comparative polymers C4, C5 and C7 with similar MI values shows that the polymer in sample 6 has a higher density than any polymers prepared with metallocene catalysts, Ziegler (LBI M6210) and MARFLEX 9659 (Cr/ SiO2).
[00231] These results are represented in Figure 5, which is a graph of three groups of polymer samples as a function of log molecular weight. Referring to Figure 5, polymer comparative samples 1-3 formed a first group, MTE1-MTE11 comparative samples formed a second group while the polymers of this disclosure, Samples 1-7, formed a third group. Particularly for a given molecular weight, the polymers of this disclosure had a higher density than any investigated comparative samples. The results also demonstrate that the polymers of the present disclosure have a broad molecular weight distribution. In table IX, it can be seen that samples 1, 3, 5 and 7 have broader molecular weight distributions than the polymers of the comparative samples prepared with metallocene catalysts, that is, samples C6, C8 and C9.

[00232] In addition, Table IX highlights the improvements of the polymer samples of the present disclosure over comparative samples regarding the molecular weight distribution and at for certain HLMI values. Particularly, for HLMI values of 1.1 dg/min for sample 1 and 1.4 dg/min for comparative sample C9, the Mz value is much higher for sample 1 compared to comparative sample C9. Likewise, it is true for samples 3 and 5, compared to comparative sample C8. For sample 1, it is 5.7E+07 compared to the much lower value of 7.7E+04 for comparative sample C9. For samples 3 and 5, the novalues are 5.3E+06 and 2.4E+05 compared to a value of 2.8E+04 for comparative sample C8. Samples 1, 3, 5, and 7 in Table XII show how HLMI increases and Mz values decrease.
[00233] The rheological behavior of polymers of the present disclosure was investigated and the results are presented in Table IX and in Figure 6 and 7. Figures 6 and 7 demonstrate that these resins have a much greater shear thinning corresponding to metallocene resins than should provide greater melt strength, while processing is easier allowing for high yield. Referring to Table IX, samples 1, 3, 5 and 7 generally had higher values than comparative samples C6, C8 and C9. This higher level of processing power is also suggested by the a-eta (CY-a) parameters for 1, 3, 5 and 7 which denote a high level of processing. The higher values of the polymer of the present disclosure correspond to greater bubble stability and the values are closer to commercial benchmarks than the comparative samples. Without intending to be bound by theory, it is believed that the best values are attributable to a broad molecular weight distribution of the polymer of the present disclosure.
[00234] For larger scale film testing purposes, Catalyst A described herein was used to prepare multiple batches of homopolymer resins according to the procedures for samples 6 and 7. Three blends, 0.9 MI, 2 .0 MI and 2.9 MI, were prepared and designated as B1, B2 and B3, respectively, as described in Table X.

[00235] The barrier properties of polymers of the type disclosed in this document were also investigated and the results are shown in Table XI. In Table XI, it can be seen that polymers from samples B1, B2 and B3 have MVTR values similar to the values for comparative samples C6 and C7. As discussed earlier, densities for samples B1, B2 and B3 are higher than for comparative samples C6 and C7; while the MVTR values are kept similar to the C6 and C7 comparative samples.

[00236] In addition, Tables X and XI demonstrate that the polymers of the present disclosure have higher values while showing similar, if not improved, MVTR performance. These results suggest that the polymers of this disclosure could be blown into films more easily and at higher rates than C6 and C7.

[00237] The processing of polymers of the present disclosure was investigated and is shown in Table XII. Referring to Table XII, it can be seen that blends B1, B2 and B3 had extrusion pressures in a range of about 340 psi to about 500 psi, while the comparative samples had extrusion pressures in a range of about 640 psi to about 700 psi. These lower extrusion pressures can be beneficial in increasing tube film production rates. Without intending to be bound by theory, it is believed that the improved extrusion pressures are attributable, at least in part, to the broad molecular weight distribution of the polymer of the present disclosure.
[00238] Although the modalities of the disclosure have been shown and described, modifications to these may be made by a person skilled in the art without departing from the scope and teachings of the disclosure. The modalities described here are exemplary only and are not intended to be limiting. Many variations and modifications of the disclosure disclosed in this document are possible and are within the scope of the disclosure. Where numerical ranges or limitations are expressly defined, such express ranges or limitations shall be understood to include iterative ranges or limitations of similar magnitude, covering expressly stated ranges or limitations (eg, from 1 to about 10 includes 2, 3, 4 , etc.; greater than 0.10 includes 0.11, 0.12, 0.13, etc.). For example, whenever a numerical range with a lower bound and an upper bound, Ru, R1 is disclosed, any number that is included in the range is specifically disclosed. In particular, the following numbers within the scale are specifically disclosed: R=Rl+k*(Ru-Rl), where k is a variable ranging from 1 percent to 100 percent with a percent increment, ie, k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,...50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent or 100 percent. In addition, any numerical scale defined by two R numbers as defined above is also specifically disclosed. The use of the term "optionally" with respect to any element of the claim is intended to explain that the subject element is required or, alternatively, not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as understand, include, have etc. is to be understood as providing support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc.
[00239] Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims that follow, this scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated in the specification as an embodiment of the present disclosure. Thus, the claims are a further description and are an addition to the detailed description of the present invention. The discussion of the reference in this document is not an admission that it is the prior art of the present disclosure, especially any reference may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited in this document are hereby incorporated by reference to the extent that they provide exemplary procedural details, or other details in addition to those presented in this document.

权利要求:
Claims (21)
[0001]
1. Ethylene polymer characterized by having: (i) a density defined by the equation (1) p > a - b Log M (1) where p is a polymer density in g/cc, log M is a log of weight polymer weight average molecular, a is 1.0407 and b is 0.0145; and (ii) a polydispersity index greater than 7, where the polymer has a density greater than 0.960 g/cc and exhibits a moisture vapor transmission rate less than or equal to 0.37 gram-mm per 100 square inches per day when tested in accordance with ASTM F1249, and where the polymer can be formed into a film at an extrusion pressure that is 25% less than that of a film formed from a polymer of the same molecular weight prepared using a catalyst of metallocene.
[0002]
Ethylene polymer according to claim 1, characterized in that it has a weight average molecular weight of 50 kg/mol to 1,450 kg/mol.
[0003]
Ethylene polymer according to claim 1, characterized in that it has a CY-a parameter from 0.05 to 0.45.
[0004]
Ethylene polymer according to claim 1, characterized in that it has a zero shear viscosity of 1000 Pa-s to 65,000 Pa-s.
[0005]
Ethylene polymer, according to claim 1, characterized in that it has a ratio between z-average molecular weight and weighted average molecular weight greater than 5.
[0006]
Ethylene polymer according to claim 1, characterized in that it has a high charge melt index greater than 10.
[0007]
Ethylene polymer according to claim 1, characterized in that it has zero shear viscosity of 2,000 Pas to 50,000 Pa-s.
[0008]
Ethylene polymer according to claim 1, characterized in that it has a CY-a parameter from 0.1 to 0.4.
[0009]
9. Ethylene polymer according to claim 1, characterized in that it is unimodal.
[0010]
Ethylene polymer according to claim 1, characterized in that it has a polydispersity index greater than 10.
[0011]
11. Ethylene polymer according to claim 1, characterized in that it has a ratio between z-average molecular weight and weighted average molecular weight greater than 6.
[0012]
Ethylene polymer according to claim 1, characterized in that it has a melt index greater than 0.8 g/10 min.
[0013]
13. Ethylene polymer according to claim 1, characterized in that it has a density greater than 0.966 g/cc.
[0014]
Ethylene polymer according to claim 1, characterized in that it has a number average molecular weight from 1 kg/mol to 20 kg/mol.
[0015]
Ethylene polymer according to claim 1, characterized in that it has a melt index greater than 1.5 g/10 min.
[0016]
Ethylene polymer according to claim 1, characterized in that it has an HLMI greater than 25 g/10 min.
[0017]
Ethylene polymer according to claim 1, characterized in that it has a weight average molecular weight of less than 145 kg/mol.
[0018]
18. An article characterized in that it is formed from the ethylene polymer as defined in claim 1.
[0019]
19. Film characterized by being formed from the ethylene polymer, as defined in claim 1.
[0020]
20. Film according to claim 19, characterized in that it has a thickness of 0.1 mm to 5 mm.
[0021]
21. A polymerization method characterized in that it comprises contacting ethylene with a catalytic system comprising an imine-phenol compound under conditions suitable for forming an ethylene polymer as defined in claim 1 and recovering said ethylene polymer, wherein the imine compound -phenol is defined by having the formula: where: O and N represent oxygen and nitrogen, respectively; R comprises a halogen, a hydrocarbyl group or a substituted hydrocarbyl group; R2 and R3 can each independently be hydrogen, halogen, hydrocarbyl group or a substituted hydrocarbyl group; and Q is a donor group; and where the ethylene polymer is defined by: i) a density defined by the equation (1) p > a - b Log M (1) where p is a density of the ethylene polymer in g/cc, log M is a log weight average molecular weight of ethylene polymer, a is 1.0407 and b is 0.0145; and (ii) a polydispersity index greater than 7, where the ethylene polymer has a density greater than 0.960 g/cc and exhibits a moisture vapor transmission rate less than or equal to 0.37 gram-mm per 100 inches squares per day when tested in accordance with ASTM F1249, and where the ethylene polymer can be formed into a film at an extrusion pressure that is 25% less than that of a film formed from a polymer of the same molecular weight prepared using a metallocene catalyst.

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SG11201900461UA|2016-07-21|2019-02-27|ObsEva SA|Oxytocin antagonist dosing regimens for promoting embryo implantation and preventing miscarriage|

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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|

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KR102095523B1|2016-11-24|2020-03-31|주식회사 엘지화학|Method for predicting property of polymers|

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US11149102B2|2017-03-10|2021-10-19|Sumitomo Chemical Company, Limited|Film|

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WO2021043726A1|2019-09-03|2021-03-11|ObsEva S.A.|Oxytocin antagonist dosing regimens for promoting embryo implantation and preventing miscarriage|

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WO2021160597A1|2020-02-10|2021-08-19|ObsEva S.A.|Biomarkers for oxytocin receptor antagonist therapy|

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

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

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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. |

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

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2021-03-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-05-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-08-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-31| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/10/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/660,850|US8937139B2|2012-10-25|2012-10-25|Catalyst compositions and methods of making and using same|

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US13/660,850|2012-10-25|

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PCT/US2013/066583|WO2014066618A1|2012-10-25|2013-10-24|Novel catalyst compositions and method of making and using the same for the polymerizsation of olefin, high density polyethylene|

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