CATALYST SYSTEM FOR POLYMERIZATION OF AN OLEFIN, ITS PREPARATION PROCESS, POLYOLEFIN AND PREPARATION

专利摘要:
catalyst system for polymerization of an olefin. The present invention relates to a process for the preparation of a catalyst system suitable for olefin polymerization where the external electron donor is n-propyl triethoxy silane, and a catalyst system obtained or obtainable through said process. the invention also relates to a process for preparing a polyolefin using said catalyst system. the invention further relates to a polyolefin, in particular polypropylene, obtainable by such a process, and shaped articles made from such a polymer. polymers produced using the catalyst system exhibit low volatiles and therefore have a reduced environmental and health impact.
公开号:BR112016014175B1
申请号:R112016014175-0
申请日:2014-12-19
公开日:2021-06-22
发明作者:Martin Alexander Zuideveld；Aurora Alexandra Batinas-Geurts
申请人:Saudi Basic Industries Corporation；Sabic Global Technologies B.V.；
IPC主号:

专利说明:

[001] The present invention relates to a process for the preparation of a catalyst system suitable for olefin polymerization, said catalyst system comprising an external donor. The invention further relates to a catalyst system obtained or obtainable through said process. The invention also relates to a process for preparing a polyolefin using said catalyst system and to a polyolefin obtained or obtainable through such a system. The invention also relates to a polymer based on propylene. In addition, the invention relates to an article shaped from said polyolefin.
[002] Catalyst systems and their components that are suitable for preparing a polyolefin are generally known. One type of such catalysts are generically referred to as Ziegler-Natta catalysts. The term "Ziegler-Natta" is known in the art and typically refers to catalyst systems comprising a solid transition metal-containing catalyst compound (also typically referred to as a procatalyst); an organometallic compound (also typically referred to as a co-catalyst) and optionally one or more electron donor compounds (eg, external electron donors).
[003] The solid transition metal-containing catalyst compound comprises a transition metal halide (e.g., titanium halide, chromium halide, hafnium halide, zirconium halide or vanadium halide) supported on a metal or metalloid compound ( for example a magnesium compound or a silica compound). A summary of such types of catalysts is, for example, given by T. Pullukat and R. Hoff in Catal. Rev. - Sci. Eng. 41, vol. 3 and 4, 389-438, 1999. The preparation of such a procatalyst is, for example, shown in WO96/32427 A1 .
[004] WO2013/124063 shows a dicarbonate compound and its use as an internal donor. WO01/23441 shows a process for preparing a catalyst component for the polymerization of olefins. WO 2011/106497 shows halogenated amide ester and their use as internal donors. US 5,567,665 shows a bypassed magnesium alkoxide-form for olefin polymerization. WO 2011/106500 shows amide esters and their use as internal donors. EP 0 799 839 shows the preparation of a homopolymer of propylene by thermal conversion with radiation in a multistage fluidized bed reactor. EP 1 717 269 shows alpha olefin homo- or copolymers having a certain relationship between MFR and oligomer content. JP 2008 106889 shows an injection molded polypropylene product.
[005] Polyolefins are known to emit volatiles. The volatile fraction of a polymer is associated with the content of oligomers with a relatively low molecular weight, the so-called oligomer content. The emission of volatiles can eventually lead to deterioration of material properties. Also, emissions are associated with environmental hazards and health hazards.
[006] Therefore, there is an ongoing need in the industry to reduce the fraction of volatiles in polymers.
[007] It is an object of the invention to provide an improved catalyst system for the polymerization of olefins and a process for preparing such a system.
[008] It is still an objective of the present invention to provide a pro-catalyst that shows better performance when used in a catalyst system for the polymerization of olefins, especially with respect to the reduction of a volatile fraction in the polymer product.
[009] One or more of the aforementioned objects of the present invention are obtained through the various aspects of the present invention where n-propyl triethoxy silane (nPTES) is used as an external electron donor.
[0010] It has surprisingly been found by the present inventors that a catalyst system having the external donor according to the present invention shows a lower emission.
[0011] In a first aspect, the present invention relates to a process for the preparation of a catalyst system suitable for olefin polymerization, said process comprising the steps of:
[0012] provision of a magnesium-based support;
[0013] optionally activating said magnesium-based support;
[0014] contact of said magnesium-based support with catalytic species of the Ziegler-Natta type, and optionally one or more internal electron donors to yield a procatalyst, and
[0015] contact of said pro-catalyst with a co-catalyst and at least one external donor;
[0016] where the at least one external electron donor is a compound having a structure in accordance with Formula IV: (R92)Si(OR93)3, where, the groups R92 and R93 are each independently a linear, branched alkyl or cyclic, substituted or unsubstituted having between 1 and 10 carbon atoms, preferably an unsubstituted linear alkyl having between 1 and 8 carbon atoms where R92 is n-propyl and R93 is ethyl, n-propyl being triethoxy silane (nPTES ).
[0017] In one embodiment of said first aspect, the process comprises the steps of i) preparation of a magnesium-based support by heating a carbonated magnesium compound of the formula MgR'R"xCO2 where R' is an alkoxide group or aryloxide, R" is an alkoxide group, aryloxide group or halogen, and has a value between about 0.1 and 2.0 at a temperature above 100oC for a period of time sufficient to cause complete loss of CO2; ii) contact of the resulting product with a tetravalent titanium halide such as Ziegler-Natta catalytic species in the presence of a hydrocarbon halo and an internal electron donor; and iii) contacting the resulting halogenated product with a tetravalent titanium halide; and product contact thus obtained with nPTES as the external donor.
[0018] In another embodiment of said aspect, the process comprises the step of preparing a magnesium-based support through halogenation of a magnesium compound of the formula MgR'R", where R' and R" are alkoxy groups containing from 1 to 8 carbon atoms, with titanium tetrachloride, in the presence of (1) an aromatic hydrocarbon halo containing 6 to 12 carbon atoms and 1 to 2 halogen atoms and (2) a polycarboxylic acid ester derived from a branched or unbranched monohydric alcohol containing 1 to 12 carbon atoms, and a monocyclic or polycyclic aromatic compound containing 8 to 20 carbon atoms and two carboxyl groups that are attached to carbon atoms ortho of the ring structure and product contact thus obtained with nPTES as the external donor.
[0019] In another embodiment of said aspect, the process comprises the steps of preparation of magnesium-based support through formation of a solution of a species containing magnesium from a magnesium carbonate or a magnesium carboxylate, precipitation of particles solids from such a magnesium-containing solution by treatment with a transition metal halide and an organo silane having a formula: Rn SiR'4"n, where n = 0 to 4 and where R is hydrogen or an alkyl radical, a haloalkyl or aryl containing one to about ten carbon atoms or a halo silyl or haloalkyl silyl radical containing one to about eight carbon atoms, and R' is OR or a halogen, and reprecipitating such solid particles from a mixture containing a cyclic ether and product contact thus obtained with nPTES as the external donor.
[0020] In another embodiment of said aspect, the process comprises the steps of:
[0021] A) provision of said pro-catalyst obtainable via a process comprising the steps of:
[0022] i) contacting a compound R4zMgX42-z with a silane compound containing alkoxy- or aryloxy- to yield a first intermediate reaction product, being a solid Mg(OR1)xX12-x, where: R4 is the same as R1 being a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof; where said hydrocarbyl group may be substituted or unsubstituted, it may contain one or more hetero atoms and preferably has between 1 and 20 carbon atoms; X4 and X1 are each independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; z is in a range of greater than 0 and less than 2, where 0 < z < 2;
[0023] ii) optionally contacting the solid Mg(OR1)xX2-x obtained in step i) with at least one activating compound selected from the group formed by activating electron donors and metal alkoxide compounds of formula M1(OR2)vw( OR3)w or M2(OR2)vw(R3)w, to obtain a second intermediate product; where M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; M2 is a metal being Si; v is the valence of M1 or M2; R2 and R3 are each a linear, branched, or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl groups, and one or more combinations thereof; where said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has between 1 and 20 carbon atoms;
[0024] iii) contact of first or second intermediate reaction product, obtained respectively in step i) or ii), with a Ti compound containing halogen, respectively obtained in step i) or ii), with a Ti compound containing halogen and optionally an internal electron donor to obtain said procatalyst;
[0025] B) contact of said pro-catalyst with a co-catalyst and at least one external electron donor being nPTES.
[0026] In another embodiment of said aspect, the process is essentially phthalate-free.
[0027] In another embodiment of said aspect, the internal donor is selected from amino benzoates represented by formula (XI):
Where:
[0028] R80, R81, R82, R83, R84, R85, and R86 are independently selected from the group consisting of hydrogen, straight or branched C1-10 alkyl; C3-10 cycloalkyl; C6-10 aryl; and C7-10 alkaryl and aralkyl; where R81 and R82 are each a hydrogen atom and R83, R84, R85 and R86 are independently selected from a group consisting of a straight and branched C1-10 alkyl group; C3-10 cycloalkyl; C6-10 aryl; and C7-10 alkaryl and aralkyl, preferably from a straight or branched C1-10 alkyl group and more preferably from methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl; where when one of R83 and R84 and R86 has at least one carbon atom, then the other of R83 and R84 and R85 and R86 is each a hydrogen atom; where R87 is selected from the group consisting of hydrogen, a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, benzyl, substituted benzyl, and halo phenyl group; and where R80 is selected from the group consisting of C6-10 aryl; and C7-10 alkaryl and aralkyl; preferably, R80 is a substituted or unsubstituted phenyl, benzyl, naphthyl, o-tolyl, p-tolyl or anisole group, and more preferably R80 is phenyl.
[0029] In another embodiment of said aspect, the internal electron donor is selected from the group consisting of 4-[benzoyl(methyl)amino]pentan-2-yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; 4-[benzoyl(ethyl)amino]pentan-2-yl benzoate, 4-(methylamino)pentan-2-yl bis-(4-methoxy) benzoate; 3-[benzoyl(cyclohexyl)amino] 1-phenyl butyl benzoate; 3-[benzoyl(propane-2-yl)amino]-1-phenylbutyl; 4-[benzoyl(methyl)amino]-1,1,1-trifluoropentan-2-yl; 3-(methylamino)-1,3-diphenyl propane-1-yl dibenzoate; 3-(methyl)aminopropane-1-ol dibenzoate; 3-(methyl)amino-2,2-dimethyl propane-1-ol dibenzoate, and 4-(methylamino)pentan-2-yl bis-(4-methoxy) benzoate.
[0030] In yet another embodiment of said aspect, the internal electron donor is activated by an activator, preferably where the activator is a benzamide according to formula X,
Formula X where: R70 and R71 are each independently selected from hydrogen or an alkyl, preferably an alkyl more preferably having between 1 and 6 carbon atoms; R72, R73, R74, R75, R76 are each independently selected from hydrogen, a heteroatom such as a halide, or a hydrocarbyl group selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkyl groups aryl, and one or more combinations thereof, wherein preferably the activator is N,N-dimethyl benzamide, wherein preferably the benzamide according to formula X is present in the procatalyst in an amount of 0.1 to 4% by weight as determined. using HPLC, for example from 0.1 to 3.5% by weight, for example from 0.1 to 3% by weight, for example from 0.1 to 2.5% by weight, for example from 0.1 to 2.0% by weight, for example from 0.1 to 1.5% by weight.
[0031] In a second aspect, the present invention relates to a catalyst system obtained or obtainable through the process described herein.
[0032] In another aspect, the present invention relates to a process for preparing a polyolefin by contacting at least one olefin, preferably polypropylene or a mixture of propylene and ethylene with the catalyst system as described herein.
[0033] In yet another aspect, the present invention relates to a polyolefin obtained or obtainable through the process as described herein.
[0034] In yet another aspect, the invention relates to a polymer based on propylene, such as propylene homopolymer or propylene-olefin copolymer.
[0035] In yet another aspect, the invention relates to a propylene - ethylene copolymer, for example, having an ethylene content based on propylene - ethylene copolymer in the range of 1 to 10% by weight, preferably in the range of 1 to 8, more preferably in the range of 1 to 5% by weight.
[0036] In yet another aspect, the invention relates to heterophasic propylene copolymers.
[0037] In another aspect, the present invention relates to propylene-based polymers having a melt flow index in the range of 30 to 1000, for example 40 to 500 as determined in accordance with ISO 1133:2005 a 230oC with a load of 2.16 kg.
[0038] In another aspect, the present invention relates to propylene-based polymers having a ratio of the oligomer content in ppm to the log (melt flow index) of less than 1650, e.g. of less than 1550 The oligomer content is measured using the process as shown in the description.
[0039] In another aspect, the present invention relates to propylene-based polymers having log (MFR) = 2.1, an oligomer content of less than 1850 ppm, where this is determined by carrying out a line polymer oligomer content versus log (MFR) calibration test, where the calibration line polymer is produced using a Ziegler Natta catalyst and the same external donor.
[0040] In yet another aspect, the invention relates to a polymer based on propylene, such as propylene homopolymer or propylene-olefin copolymer, for example, propylene-ethylene copolymer, for example, having an ethylene content based on propylene-ethylene copolymer in the range of 1 to 10% by weight, for example in the range of 1 to 8, for example in the range of 1 to 5% by weight; or heterophasic propylene copolymers,
[0041] - having a melt flux index in the range of 30 to 1000, for example 40 to 500 as determined in accordance with the method discussed above;
[0042] - a ratio of the oligomer content in ppm to the log (melt flow index) of less than 1650, eg less than 1550, where the oligomer content is measured according to the process discussed below.
[0043] In another aspect, the invention relates to a shaped article comprising the polyolefin as described herein. These aspects and embodiments will be described in more detail below.
[0044] The procatalyst of the present invention exhibits excellent yield in catalyst preparation, and when used in the preparation of polyolefins, in particular for polypropylene and polypropylene/ethylene copolymers. In addition, the catalyst system according to the present invention produces polyolefins with a reduced volatile fraction as compared to known catalyst systems. Polyolefins prepared using the catalyst system as described herein, as well as shaped products made therefrom, therefore have decreased health and environmental risks compared to polyolefins prepared using known catalyst systems. Polyolefins also show less material deterioration over time compared to similar polyolefins prepared using a different catalyst system. Definitions
[0045] The following definitions are used in the present description and claims to define the established subject matter. Other terms not cited below are intended to have the generically accepted meaning in the field.
[0046] "Ziegler-Natta Catalyst" as used in the present description means: a solid transition metal-containing catalyst compound comprises a transition metal halide selected from titanium halide, chromium halide, hafnium halide, zirconium halide, and vanadium halide, supported on a metal or nonmetal compound (eg a magnesium compound or a silica compound).
[0047] "Ziegler-Natta catalytic species" or "catalytic species" as used in the present description means: a transition metal-containing species comprises a transition metal halide selected from titanium halide, chromium halide, hafnium halide, halide of zirconium, and vanadium halide.
[0048] "Internal donor" or "internal electron donor" or "ID" as used in the present description means: an electron donor compound containing one or more atoms of oxygen (O) and/or nitrogen (N). This ID is used as a reagent in the preparation of a solid procatalyst. An internal donor is commonly described in the prior art for preparing a Ziegler-Natta catalyst system for polymerizing olefins; that is, by contacting a magnesium-containing support with a halogen-containing Ti compound and an internal donor.
[0049] "External donor" or "external electron donor" or "ED" as used herein means: an electron donor compound used as a reactant in the polymerization of olefins. An ED is a compound independent of the procatalyst. It is not added during procatalyst formation. It contains at least one functional group that is capable of donating at least one pair of electrons to a metal atom. ED can influence catalyst properties, its non-limiting examples are affecting catalyst system stereoselectivity in polymerization of olefins having 3 or more carbon atoms, hydrogen sensitivity, ethylene sensitivity, comonomer incorporation randomity and catalyst productivity.
[0050] "Activator" as used in the present description means: a compound donating electrons containing one or more atoms of oxygen (O) and/or nitrogen (N) that is used during the synthesis of the procatalyst prior to or simultaneous with the addition of an internal donor.
[0051] "Activating compound" as used in the present description means: a compound used to activate the solid support prior to contacting it with the catalytic species.
[0052] "Modifier" or "Transition metal or Group 13 modifier" as used herein means: a metal modifier comprising a metal selected from the Group 13 metals of the IUPAC Periodic Table of Elements and Transition Metals. Where in the description the terms metal modifier or metal-based modifier are used, transition metal or Group 13 modifier is intended.
[0053] "Procatalyst" and "catalyst component" as used in the present description have the same meaning: a component of a catalyst composition generally comprising a solid support, a transition metal-containing catalytic species and optionally one or more internal donors.
[0054] "Halide" as used in the present description means: an ion selected from the group of: fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-).
[0055] "Halogen" as used in the present description means: an atom selected from the group of: fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
[0056] "Heteroatom" as used in the present description means: an atom other than carbon or hydrogen. However, as used herein - unless otherwise specified, as below - when "one or more heteroatoms" is used, one or more of the following is intended: F, Cl, Br, I, N, O, P, B, S or Si.
[0057] "Heteroatom selected from group 13, 14, 15, 16 or 17 of the Periodic Table of the elements of IUPAC" as used in the present description means: a heteroatom selected from B, Al, Ga, In, Tl [Group 13], Si, Ge, Sn, Pb [Group 14], N, P, As, Sb, Bi [Group 15], O, S, Se, Te, Po [Group 16], F, Cl, Br, I, Al [ Group 17].
[0058] "Hydrocarbyl" as used in the present description means: is a substituent containing hydrogen and carbon atoms, or saturated or unsaturated linear, branched or cyclic aliphatic radical, such as alkyl, alkenyl, alkadienyl, and alkynyl; alicyclic radical such as alkyl cycle, alkadienyl cycle, alkenyl cycle; aromatic radical, such as monocyclic or polycyclic aromatic radical, as well as combinations thereof, such as alkaryl and aralkyl.
[0059] "Substituted hydrocarbyl" as used in the present description means: is a hydrocarbyl group which is substituted with one or more non-hydrocarbyl substituent groups. A non-limiting example of a non-hydrocarbyl substituent is a heteroatom. Examples are alkoxy carbonyl groups (viz. Carboxylate). When "hydrocarbyl" is used in the present description it may also be "substituted hydrocarbyl", unless otherwise stated.
[0060] "Alkyl" as used in the present description means: an alkyl group being a functional group or side chain consisting of carbon and hydrogen atoms having only single bonds. An alkyl group can be straight or branched and can be substituted or unsubstituted. It may or may not contain heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si) or sulfur (S). An alkyl group also encloses aralkyl groups where one or more hydrogen atoms on the alkyl group have been replaced by aryl groups.
[0061] "Aryl" as used in the present description means: an aryl group being a functional group or side chain derived from an aromatic ring. An aryl group can be unsubstituted or substituted with straight or branched hydrocarbyl groups. It may or may not contain heteroatoms such as oxygen (O), nitrogen (N), phosphorus (P), silicon (Si) or sulfur (S). An aryl group also includes alkaryl groups where one or more hydrogen atoms on the aromatic ring have been replaced by the alkyl groups.
[0062] "Alkoxide" or "alkoxy" as used in the present description means: a functional group or side chain obtained from an alkyl alcohol. It consists of an alkyl bonded to a negatively charged oxygen atom.
[0063] "Aryloxide" or "aryloxy" or "phenoxide" as used in the present description means: a functional group or side chain obtained from an aryl alcohol. It consists of an aryl bonded to a negatively charged oxygen atom.
[0064] "Grignard reagent" or "Grignard compound" as used in the present description means: a compound or a mixture of compounds of the formula R4zMgX42-z (R4, z, and X4 are as defined below) or it may be a complex having more Mg bunches, eg R4Mg3Cl2.
[0065] "Polymer" as used in the present description means: a chemical compound comprising repeating structural units, where the structural units are monomers.
[0066] "Olefin" as used in the present description means: an alkene.
[0067] "Olefin-based polymer" or "polyolefin" as used in the present description means: a polymer of one or more alkenes.
[0068] "Propylene-based polymer" as used in the present description means: a polymer of propylene and optionally a comonomer.
[0069] "Polypropylene" as used in the present description means: a polymer of propylene.
[0070] "Copolymer" as used in the present description means: a polymer prepared from two or more different monomers
[0071] "Monomer" as used in the present description means: a chemical compound that can undergo polymerization.
[0072] "Thermoplastic" as used herein means: capable of softening or melting when heated and hardening again when cooled.
[0073] "Polymer composition" as used in the present description means: a mixture of two or more polymers or of one or more polymers and one or more additives.
"Mw" and "Mn" in the context of the present invention means the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of a sample as measured in accordance with ASTM D6474-12.
"PDI" in the context of the present invention means the ratio of the weight average molecular weight Mw to the number average molecular weight Mn of a sample as measured in accordance with ASTM D6474-12. As used herein, the terms "PDI" and "polydispersity index" are interchangeable.
[0076] "MWD" in the context of the present invention means distribution of the molecular weight of a sample, as represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn of a sample as measured by ASTM D647412. As used herein, the terms "MWD" and "molecular weight distribution" are interchangeable.
[0077] "XS" as used in the present description means: the fraction soluble in xylene in terms of percentage of polymer that does not precipitate upon cooling of a polymer solution in xylene, said polymer solution having been subjected to reflux conditions, below reflux temperature, which equals the boiling temperature of xylene at 25oC. XS is measured in accordance with ASTM D549210. As used herein, the term "XS" and "xylene soluble fraction" are interchangeable.
[0078] "Polymerization conditions" as used in the present description means: temperature and pressure parameters within a polymerization reactor suitable for promoting polymerization between the catalyst composition and an olefin to form the desired polymer. These conditions depend on the type of polymerization used.
[0079] "Production rate" or "yield" as used herein means: the amount of kilograms of polymer produced per gram of catalyst composition consumed in the polymerization reactor per hour, unless otherwise stated.
[0080] "MFR" as used in the present description means the melt mass flow rate as measured in accordance with ISO 1133:2005, at 230oC under a load of 2.16 kg. As used herein, the terms "MFR", "melt flow rate" and "melt mass flow rate" are interchangeable.
[0081] Unless otherwise stated, when it is stated that any R group is "independently selected from" this means that when several of the same R groups are present in a molecule they may have the same meaning or they may not have the same meaning. same meaning. For example, for the compound R2M, where R is independently selected from ethyl or methyl, both R groups can be ethyl, both R groups can be methyl, or one R group can be ethyl and the other R group can be methyl.
[0082] The present invention is described in more detail below. All embodiments described with respect to one aspect of the invention are also applicable to other aspects of the invention, unless otherwise stated.
[0083] As stated above, the external donor nPTES according to the present invention shows a better result with respect to emission, in other words it has a lower emission.
[0084] The present inventors have observed that catalyst performance was improved by measuring the amount of volatiles in the polyolefin, and comparing this to polyolefins prepared through other catalyst systems having a comparable melt flow rate (MFR). Polymers having a relatively high melt flow rate have a higher volatile content compared to polymers having a low flow rate.
[0085] In particular, nPTES as an external donor results in materials with lower oligomer content compared to materials with similar MFR values, manufactured using other donors. In particular, polypropylene homopolymers having lower emissions can be produced using the catalyst system as described herein.
[0086] One of the functions of the external donor compound is to affect the stereo selectivity of the catalyst system in polymerization of olefins having three or more carbon atoms. Hence it can also be referred to as a selectivity control agent.
Mixtures of external donors may be present and may include from about 0.1 mol % to about 99.9 mole % of a first external donor, nPTES, and from about 99.9 mole % to about 0 .1 mol% of either a second or the additional external alkoxy silane donor shown below. In addition, mixtures of nPTES with other external donors can be used. In one embodiment, nPTES is the only external donor used.
[0088] The aluminum/external donor molar ratio in the polymerization catalyst system preferably is between 0.1 and 200; more preferably between 1 and 100. In a Ti-based catalyst, the molar ratio of Si/Ti in the catalyst system may range from 0.1 to 40, preferably 0.1 to 20, even more preferably from 1 to 20 and most preferably from 2 to 10.
[0089] Alkyloxy alkoxy silanes according to Formula IV can be used as additional external donors. nPTES, the first external donor is also in accordance with Formula IV. (R92)Si(OR93)3 Formula IV
[0090] The groups R92 and R93 are each independently an alkyl having between 1 and 10 carbon atoms. Said alkyl group can be linear, branched or cyclic. Said alkyl group can be substituted or unsubstituted. Preferably, said hydrocarbyl group has between 1 and 8 carbon atoms, even more preferably between 1 and 6 carbon atoms, even more preferably between 2 and 4 carbon atoms. Preferably, all three R93 groups are identical. Preferably R93 is methyl or ethyl. Preferably R92 is ethyl or propyl, more preferably n-propyl.
Typical external donors known in the art (for example, as shown in WO2006/056338A1, EP1838741B1, US6395670B1, EP398698A1, WO96/32426A) are organo-silicon compounds having the generic formula Si(ORa)4-nRbn, where n can is from 0 to 2, and each Ra and Rb independently represents an alkyl or aryl group, optionally containing one or more heteroatoms, for example O, N, S or P, with, for example, 1-20 carbon atoms; such as n-propyl trimethoxy silane (nPTMS), n-propyl triethoxy silane (nPEMS), diisobutyl dimethyl silane (DiBDMS), t-butyl isopropyl dimethyl silane (tBiPDMS), cyclohexyl methyl dimethyl dimethyl silane (CHMDMS), dicyclopentyl dimethyl silane (DCPDMS) or diisopropyl dimethyl silane (DiPDMS). These can also be used as a second external donor, in addition to nPTES.
[0092] The present invention is related to a Ziegler-Natta type catalyst system. A Ziegler-Natta type procatalyst for use in a Ziegler-Natta type catalyst system generally comprising a solid support, a transition metal containing catalytic species and optionally one or more internal donors. The present invention furthermore relates to a catalyst system comprising a Ziegler-Natta type procatalyst, a cocatalyst and nPTES as the external electron donor. The term "Ziegler-Natta" is known in the art. The transition metal-containing solid catalyst compound comprises a half transition halide (eg, titanium halide, chromium halide, hafnium halide, zirconium halide, vanadium halide) supported on a metal or nonmetal compound (eg, a magnesium compound or a silica compound).
[0093] Specific examples of various types of Ziegler-Natta catalyst as shown below.
[0094] Preferably, the present invention is related to a so-called TiNo catalyst. It is a magnesium-based titanium halide catalyst optionally comprising one or more internal donors. Procatalyst III of the examples specifies the process for preparing a TiNO procatalyst.
[0095] EP 1 273 595 by Borealis Technology shows a process for producing an olefin polymerization procatalyst in the form of particles having a predetermined size range, said process comprising: preparing a solution of a complex of a metal of Group IIa and an electron donor by reacting a compound of said metal as said electron donor or a precursor thereof in an organic liquid reaction medium; reacting said complex, in solution, with at least one transition metal compound to produce a dispersed phase emulsion which contains greater than 50 mole % of the Group IIa metal in said complex; maintaining particles of said dispersed phase within an average size range of 10 to 200 microns by stirring in the presence of an emulsion stabilizer and solidifying said particles; and recovering, washing and drying said particles to obtain said procatalyst.
[0096] EP 0 019 330 to Dow shows a Ziegler-Natta type catalyst composition. Said olefin polymerization catalyst composition is prepared using a process comprising: a) a reaction product of an organoaluminum compound and an electron donor, and b) a solid component which was obtained by halogenating a magnesium compound with a formula MgR1R2 where R1 is an alkyl, aryl, alkoxide or aryl oxide group and R2 is an alkyl, aryl, alkoxide or aryl oxide group or halogen, are contacted with a tetravalent titanium halide in the presence of a hydrocarbon halo, and contacting the product halogenated with a tetravalent titanium compound. This production process as shown in EP 0 019 330 is incorporated by reference.
[0097] Examples of US 5,093,415 to Dow show an improved process for preparing a procatalyst. Said process includes a reaction between titanium tetrachloride, diisobutyl phthalate, and magnesium dietoxide to obtain a solid material. This solid material is then slurried with carbon tetrachloride in a solvent and phthaloyl chloride is added. The reaction mixture is heated to obtain a solid material which is again slurried in a solvent with titanium tetrachloride. Again this was heated and a solid collected. Again the solid was again slurried in a titanium tetrachloride solution to obtain a catalyst. The examples of US 5,093,415 are incorporated by reference.
[0098] Example 2 of US 6 825 1452 to Dow shows another improved process for preparing a catalyst. Said process includes a reaction between titanium tetrachloride in solution with a precursor composition - prepared by reaction of magnesium dietoxide, titanium tetraethoxide, and titanium tetrachloride, in a mixture of ortho cresol, ethanol and chlorine benzene - and ethyl benzoate as an electron donor. The mixture was heated and a solid was recovered. To the solid titanium tetrachloride, a solvent and benzoyl chloride were added. The mixture was heated to obtain a solid product. The last step was repeated. The resulting solid procatalyst was worked to provide a catalyst. Example 2 of US 6 825 146.2 is incorporated by reference.
[0099] US 4,771,024 shows the preparation of a catalyst in column 10, line 61 to column 11, line 9. The section "catalyst manufacture on silica" is incorporated in the present patent application by reference. The process comprises combining dry silica with carbonated magnesium solution (magnesium diethoxide in ethanol was bubbled with CO2). The solvent was evaporated at 85°C. The resulting solid was washed and a 50:50 mixture of titanium tetrachloride and chlorobenzene was added to the solvent along with ethyl benzoate. The mixture was heated to 100°C and the liquid filtered. Again TiCl4 and chlorobenzene were added, followed by heating and filtration. A final addition of TiCl4 and chlorobenzene and benzoyl chloride was made, followed by heating and filtration. After washing the catalyst was obtained.
[00100] WO03/068828 shows a process for preparing a catalyst component on page 91 "preparation of solid catalyst components" which section is incorporated in the present patent application by reference. Magnesium chloride, toluene, epoxy chlorine propane and tributyl phosphate were added under nitrogen to a reactor, followed by heating. Then phthalic anhydride was added. The solution was cooled to -25o=C and TiCl4 was added dropwise, followed by heating. An internal donor was added (1,3-diphenyl-1,3-propylene glycol dibenzoate), 2-methyl-1,3-diphenyl-1,3-propylene glycol dibenzoate, 1,3-diphenyl-1 dipropionate ,3-propylene glycol, or 1,3-diphenyl-2-methyl-1,3-propylene glycol dipropionate and after stirring a solid was obtained and washed. The solid was treated with TiCl4 in toluene twice, followed by washing to obtain a catalyst component.
[00101] US 4,866,022 shows a catalyst component comprising a product formed by: A. forming a solution of a magnesium-containing species from a magnesium carbonate or a magnesium carboxylate; B. precipitation of solid particles from such a magnesium-containing solution by treatment with a transition metal halide and an organo silane having a formula: RnSiR'4-n, where n = 0 to 4 and where R is hydrogen or a an alkyl, haloalkyl or aryl radical containing one to about ten carbon atoms or a halo silyl radical or a haloalkyl silyl radical containing one to about eight carbon atoms, and R' is OR or a halogen: C. reprecipitation of such particles solids from a mixture containing a cyclic ether; and D. treating re-precipitated particles with a transition metal compound and an electron donor. This process for preparing a catalyst is incorporated in the present patent application by reference.
[00102] The procatalyst used in the catalyst system according to the present invention can be produced by any process known in the art.
[00103] The procatalyst can also be produced as shown in WO96/324426A; this document shows a process for the polymerization of propylene using a catalyst comprising a catalyst component obtained through a process where a compound with formula Mg(OAlk)xCly where x is greater than 0 and less than 2, y is equal to 2-x and each Alk independently represents an alkyl group, is contacted with a titanium tetra alkoxide and/or an alcohol in the presence of an inert dispersant to yield an intermediate reaction product and where the intermediate reaction product is contacted with titanium tetrachloride in the presence of an internal donor, which is di-n-butyl phthalate (DBP)
[00104] Preferably, the Ziegler-Natta type procatalyst in the catalyst system according to the present invention is obtained through a process as described in WO2007/134851 A1. In Example 1 the process is shown in more detail. Example I including all sub-examples (IA-IE) of WO2007/134851 A1 is incorporated into the present description. More details about the different embodiments are shown starting on page 3, line 29 to page 14, line 29 of WO2007/134851 A1 . These embodiments are incorporated by reference in the present description. This process produces the TiNo procatalyst discussed above.
[00105] In the following part of the description the different steps and stages of the process for preparing procatalyst for use in a catalyst system according to an embodiment of the present invention will be discussed.
[00106] The process for preparing procatalyst for use in a catalyst system according to an embodiment of the present invention comprises the following steps:
[00107] - Phase A): preparation of a solid support for the pro-catalyst;
[00108] - Phase B): optionally activation of said solid support obtained in phase A) using one or more activating compounds to obtain an activated solid support;
[00109] - Phase C): contact of said solid support obtained in phase A) or said solid support activated in phase B) with a catalytic species where phase C) comprises one of the following:
[00110] * contact of said solid support obtained in phase A) or said solid support activated in phase B) with a catalytic species to obtain said pro-catalyst; or
[00111] * contact of said solid support obtained in phase A) or said solid support activated in phase B) with a catalytic species and one or more internal donors to obtain said pro-catalyst; or
[00112] * contact of said solid support obtained in phase A) or said solid support activated in phase B) with a catalytic species and one or more internal donors to obtain an intermediate product; or
[00113] iv) contacting said solid support obtained in phase A) or said solid support activated in phase B) with a catalytic species and an activator to obtain an intermediate product;
[00114] - optionally Phase D: modification of said intermediate product obtained in phase C) where phase D) comprises the following:
[00115] * modification of said intermediate product obtained in phase C) with a transition metal or Group 13 modifier in case an internal donor has been used during phase C), in order to obtain a procatalyst;
[00116] * modification of said intermediate product obtained in phase C) with a transition metal or Group 13 modifier and one or more internal donors in case an activator was used during phase C) in order to obtain a pro- catalyst.
[00117] The procatalyst thus prepared can be used to prepare a catalyst system that can be used in olefin polymerization combined with an external donor and a cocatalyst.
[00118] The various steps used to prepare the procatalyst for use in a catalyst system according to an embodiment of the present invention are described in more detail below. Phase A: Preparation of a solid support for the procatalyst
[00119] In the process for preparing procatalyst for use in a catalyst system according to an embodiment of the present invention preferably a magnesium-containing support is used. Said magnesium-containing support is known in the art as a typical component of a Ziegler-Natta procatalyst. The following description explains the magnesium-based support preparation process. Other supports can be used.
[00120] Synthesis of magnesium-containing supports, such as magnesium halides, magnesium alkyls and aryl magnesium, and also alkoxy magnesium and aryloxy magnesium compounds for polyolefin production, particularly polypropylene production are described, for example, in US4978648, WO96/32427a1 WO01/23441 A1 , EP1283 222A1 , EP1222 214B1 ; US5077357; US5556820; US4414132; US 5106806 and US5077357 but the present case is not limited to the disclosure in these documents.
[00121] Preferably, the process for preparing solid support for the procatalyst for use in a catalyst system according to an embodiment of the present invention comprises the following steps: step o) which is optional and step i). Step o) Grignard reagent preparation (optional)
[00122] A Grignard reagent, R4zMgX42-z used in step i) can be prepared by contacting metallic magnesium with an organic halide R4X4, as described in WO 96/32427 A1 and WO01/23441 A1. All forms of metallic magnesium can be used, but preferably use is made of finely divided metallic magnesium, for example powdered magnesium. To get a quick reaction it is preferable to heat the magnesium under nitrogen before use.
[00123] R4 is a hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkyl aryl, or alkoxycarbonyl groups, wherein said hydrocarbyl group may be linear, branched or cyclic, and may be substituted or unsubstituted; said hydrocarbyl group preferably having between 1 and 20 carbon atoms or combinations thereof. The R4 group can contain one or more heteroatoms.
[00124] X4 is selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-).
[00125] The value for z is in a range of greater than 0 and less than 2; 0 < z < 2.
[00126] Combinations of two or more R4X4 organic halides can also be used.
[00127] Magnesium and organic halide R4X4 can be reacted with each other without the use of a separate dispersant; the R4X4 organic halide is then used in excess.
[00128] Organic halide R4X4 and magnesium can also be brought into contact with each other in an inert dispersant. Examples of these dispersants are: aliphatic, alicyclic or aromatic dispersants containing from 4 to 20 carbon atoms.
[00129] Preferably, in this step o) of preparation of R4zMgX42-z, also an ether is added to the reaction mixture. Examples of ethers are: diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, diallyl ether, tetrahydrofuran and anisole. Dibutyl ether and/or diisoamyl ether are preferably used. Preferably, an excess of chlorobenzene is used as the organic halide R4X4. Thus, chlorobenzene serves as a dispersant as well as the organic halide R4X4.
[00130] The halide / ether ratio acts on the activity of the pro-catalyst. The volume ratio of chlorobenzene/dibutyl ether may, for example, range between 75:25 and 35:65, preferably between 70:30 and 50:50.
[00131] Small amounts of iodine and/or alkyl halides can be added to make the reaction between the metallic magnesium and the R4X4 organic halide proceed at a higher rate. Examples of alkyl halides are butyl chloride, butyl bromide, and 1,2-dibromo ethane. When the organic halide R4X4 is an alkyl halide, iodine and 1,2-dibromo ethane are preferably used.
[00132] The reaction temperature for step o) of preparation of R4zMgX42-z is normally between 20 and 150oC; the reaction time is normally between 0.5 to 20 hours. After the reaction for preparing R4zMgX42-z is completed, the dissolved reaction product can be separated from the solid waste products. The reaction can be mixed. Stirring speed can be determined by those skilled in the art and should be sufficient to stir the reagents. Step i) reaction of a Grignard compound with a silane compound
[00133] Step i): contacting a compound R4zMgX42-z - where R4, X4, and z are as discussed above - with a silane compound containing alkoxy or aryloxy to yield a first intermediate reaction product. Said first intermediate reaction product is a solid magnesium containing support. It should be noted that with "containing alkoxy or aryloxy" is meant containing OR1. In other words said alkoxy- or aryloxy-containing silane compound comprises at least one OR1 group. R 1 is selected from the group consisting of a linear, branched or cyclic hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof; where said hydrocarbyl group may be substituted or unsubstituted, it may contain one or more heteroatoms and preferably has from 1 to 20 carbon atoms.
[00134] In step i) a first intermediate reaction product is thus prepared by contacting the following reagents: * a Grignard reagent - being a compound or a mixture of compounds of formula R4zMgX42-z and * a silane compound containing alkoxy or aryloxy. Examples of these reagents are shown, for example, in WO 96/32427 A1 and WO01/23441 A1.
[00135] The compound R4zMgX42-z used as the starting product is also referred to as a Grignard compound. In R4zMgX42-z, X4 is preferably chloride or bromide, more preferably chloride.
[00136] R4 can be alkyl, aryl, aralkyl, alkoxide, phenoxide, etc., or mixtures thereof. Suitable examples of group R4 are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, octyl, phenyl, tolyl, xylyl, mesityl, benzyl, phenyl, naphthyl , thienyl, indolyl. In a preferred embodiment of the invention, R4 represents an aromatic group, for example a phenyl group.
Preferably, as the Grignard compound R4zMgX42-z used in step i) a phenyl Grignard or a butyl Grignard is used. Selection for either phenyl Grignard or butyl Grignard depends on requirements.
[00138] When a Grignard compound is used, a compound according to the formula R4zMgX42-z is intended. When phenyl Grignard is used a compound according to the formula R4zMgX42-z where R4 is phenyl, e.g. PhMgCl, is intended. When butyl Grignard is used, a compound according to the formula R4zMgX42-z where R4 is butyl, for example, BuMgCl or n-BuMgCl, is intended.
[00139] An advantage of using phenyl Grignard is that it is more active than butyl Grignard. Preferably, when butyl Grignard is used, an activation step using an aliphatic alcohol such as methanol is carried out in order to increase the activity. Such an activation step may not be required with the use of phenyl Grignard. A disadvantage of using phenyl Grignard is that leftover benzene products may be present and that it is more expensive and therefore less commercially interesting.
[00140] An advantage of using butyl Grignard is that it is free of benzene and is commercially more interesting due to its lower price. A disadvantage of using butyl Grignard is that in order to have high activity, an activation step is required.
[00141] The process for preparing the procatalyst for use in one embodiment of the present invention can be carried out using any Grignard compound, but the two set out above are the two that are most preferred.
In the Grignard compound of formula R4zMgX42-z, z is preferably from 0.5 to 1.5.
[00143] The compound R4zMgX42-z can be prepared in an optional step (step o)) which is discussed above, preceding step i) or can be obtained from a different process.
[00144] It is explicitly noted that it is possible that the Grignard compound used in step i) alternatively has a different structure, eg it may be a complex. Such complexes are already known to those skilled in the art; a particular example of such complexes is phenyl4Mg3Cl2.
[00145] The alkoxy- or aryloxy-containing silane used in step i) is preferably a compound or a mixture of compounds with the generic formula Si(OR5)4-nR6n,
[00146] where it should be noted that the R5 group is identical to the R1 group. The R1 group originates from the R5 group during the synthesis of the first intermediate reaction product.
[00147] R5 is a hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably, said hydrocarbyl group is an alkyl group, preferably having between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl or hexyl; more preferably selected from ethyl and methyl.
[00148] R6 is a hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably, said hydrocarbyl group is an alkyl group, preferably having between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl or cyclopentyl.
[00149] The value for n is in the range from 0 to 4, preferably n is from 0 to and including 1.
[00150] Examples of suitable silane compounds include tetramethoxy silane, tetraethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl triethoxy silane, diethyl diphenoxy silane, n-propyl triethoxy silane, diisopropyl dimethoxy silane, n-isobutyl di-isobutyl -propyl trimethoxy silane, cyclohexyl methyl dimethyl dimethyl silane, dicyclopentyl dimethyl dimethyl silane, isobutyl isopropyl dimethyl silane, phenyl trimethoxy silane, diphenyl dimethyl silane, trifluoropropyl methyl dimethyl dimethyl silane, bis(perhydrosilane dimethoxy methoxy silane) , di-(n-propyl) dimethyl silane, di-isopropyl dimethyl silane, di(n-butyl) dimethyl silane and/or di-isobutyl dimethyl silane.
[00151] Preferably, tetraethoxy silane is used as silane compound in the preparation of solid compound containing Mg during step i) in the process according to the present invention.
[00152] Preferably, in step i) the silane compound and the Grignard compound are introduced simultaneously to a mixing device to result in particles of the first intermediate reaction product having advantageous morphology. This is, for example, described in WO 01/23441 A1 . Here, 'morphology' does not only refer to the particle shape of the solid Mg compound and the catalyst made therefrom, but also to the particle size distribution (also characterized as extension, viz. An indicator for the width of the particle size distribution as measured in accordance with ISO 13320:2009), its fines content, spray flowability, and volume density (viz. The weight per unit volume of a material, including inherent voids in the material as tested; measured as bulk density per ASTM D1895-96 Reapproved 2010-e1, test process A) of catalyst particles. Furthermore, it is well known that a polyolefin powder produced in a polymerization process using a catalyst system based on such a procatalyst has a similar morphology as the procatalyst (the so-called "replica effect"; see, for example, S. van der Vem, Polypropylene and other Polyolefins, Elsevier 1990, p. 8-10). Likewise, nearly round polymer particles are obtained with a length/diameter (I/D) ratio of less than 2 and with good spray flowability.
[00153] As discussed above, the reactants are preferably introduced simultaneously. By "simultaneously introduced" it is intended that the introduction of the Grignard compound and the silane compound is done in such a way that the molar ratio of Mg/Si does not vary substantially during the introduction of these compounds into the mixing device, as described in WO 01 /23441 A1.
Silane compound and Grignard compound can be introduced into the mixing device continuously or in batches. Preferably both compounds are continuously introduced into the mixing device.
[00155] The mixing device can take various forms; it can be a mixing device in which the silane compound is pre-mixed with the Grignard compound, the mixing device can also be an agitated reactor, in which the reaction between the compounds takes place. The separate components can be metered into the mixing device by means of peristaltic pumps.
[00156] Preferably, the compounds are pre-mixed before the mixture is introduced into the reactor for step i). In this way, a procatalyst is formed with a morphology that leads to polymer particles with the best morphology (high bulk density, narrow particle size distribution, (virtually) no fines, excellent flowability).
[00157] The Si/Mg molar ratio during step i) can range from 0.2 to 20. Preferably, the Si/Mg molar ratio is 0.4 to 1.0.
[00158] The premix period of the reagents in the reaction step indicated above can vary within wide limits, for example, 0.1 to 300 seconds. Preferably, premixing is carried out for 1 to 50 seconds.
[00159] The temperature during the premix step of the reagents is not specifically critical, and may, for example, range between 0 and 80oC; preferably the temperature is between 10oC and 50oC.
[00160] The reaction between said reagents can, for example, occur at a temperature between -20oC and 100oC; for example, at a temperature of 0oC to 80oC. The reaction time is, for example, between 1 and 5 hours.
[00161] The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by those skilled in the art. As a non-limiting example, mixing can be carried out at a mixing speed between 250-300 rpm. In one embodiment, when a blade mixer is used the mixing speed is between 220 and 280 rpm and when an impeller mixer is used the mixing speed is between 270 and 330 rpm. The stirrer speed can be increased during the reaction. For example, during dosing, the agitation speed can be increased every hour by 20-30 rpm.
[00162] The first intermediate reaction product obtained from the reaction between the silane compound and the Grignard compound is usually purified by decantation or filtration followed by rinsing with an inert solvent, for example, a hydrocarbon solvent with, for example, 1- 20 carbon atoms, such as pentane, isopentane, hexane or heptane. The solid product can be stored and further used as a suspension in said inert solvent. Alternatively, the product can be dried, preferably partially dried, and preferably under mild conditions; for example, at ambient temperature and pressure.
[00163] The first intermediate reaction product obtained through this step i) may comprise a compound of the formula Mg(OR1)xX12-x, where:
[00164] R1 is a hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably, said hydrocarbyl group is an alkyl group, preferably having between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms. More preferably selected from ethyl and methyl.
[00165] X1 is selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-). Preferably X1 is chloride or bromine and more preferably X1 is chloride. The value for x is in the range of greater than 0 and less than 2: 0 < z < 2. The value for x is preferably between 0.5 and 1.5. Phase B: Activation of said solid support for the catalyst
[00166] This step of activating said solid support to the procatalyst is an optional step that is not required, but preferred, in the present invention. If this activation step is carried out, preferably the process for activating said solid support comprises the following step ii). This phase can comprise one or more stages. Step ii) activation of solid magnesium compound
[00167] Step ii): contact of solid Mg(OR1)xX12-x with at least one activation compound selected from the group formed by activation electron donors and metal alkoxide compounds of formula M1(OR2)vw(OR3)w or M2(OR2)vw(R3)w, where:
[00168] R2 is a hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably, said hydrocarbyl group is an alkyl group, preferably having between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl or hexyl; more preferably selected from ethyl and methyl.
[00169] R3 is a hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms. Preferably, said hydrocarbyl group is an alkyl group, preferably having between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms; more preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl and cyclopentyl.
[00170] M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; v is the valence of M1; M2 is a metal being Si; v is the valence of M2 and w is less than v.
Electron donors and compounds of formula M(OR2)v-w(OR3)w and M(OR2)v-w(R3)w may also be referred to herein as activating compounds.
[00172] In this step one or both types of activating compounds (viz. Activating electron donor or metal alkoxides) can be used.
[00173] The advantage of using this activation step before solid support contact with the halogen-containing titanium compound (process stage C) is that a higher yield of polyolefins is obtained per gram of procatalyst. Furthermore, the ethylene sensitivity of the catalyst system in the copolymerization of propylene and ethylene is also increased due to this activation step. This activation step is shown in detail in WO2007/134851 to the present applicant.
[00174] Examples of suitable activating electron donors that can be used in step ii) are known to those skilled and described hereinafter, i.e., include carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid halides , alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alkoxides, sulfonamides, thio ethers, thio esters and other organic compounds containing one or more heteroatoms, such as nitrogen, oxygen, sulfur and/or phosphorus.
[00175] Preferably, an alcohol is used as the activating electron donor in step ii). More preferably, the alcohol is a linear or branched aliphatic or aromatic alcohol having 1-12 carbon atoms. Even more preferably, the alcohol is selected from methanol, ethanol, butanol, isobutanol, hexanol, xylenol and benzyl alcohol. More preferably the alcohol is ethanol or methanol, preferably ethanol.
[00176] Suitable carboxylic acids as activating electron donors can be aliphatic or (partially) aromatic. Examples include formic acid, acetic acid, propionic acid, butyric acid, isobutanoic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tartaric acid, cyclohexanoic monocarboxylic acid, cis-1,2-cyclohexanoic acid dicarboxylic acid phenyl carboxylic acid, toluene carboxylic acid, naphthalene carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and/or trimellitic acid.
[00177] Anhydrides of the carboxylic acids mentioned above can be mentioned as examples of carboxylic acid anhydrides, such as, for example, acetic acid anhydride, butyric acid anhydride and methacrylic acid anhydride.
[00178] Suitable examples of esters of the carboxylic acids mentioned above are formats, e.g., butyl formate; acetates, for example ethyl acetate and butyl acetate; acrylates, for example ethyl acrylate, methyl methacrylate and isobutyl methacrylate; benzoates, for example methyl benzoate and ethyl benzoate; methyl p-toluate; ethyl naphthalate and phthalates, for example monomethyl phthalate, dibutyl phthalate, di-isobutyl phthalate, diallyl phthalate and/or diphenyl phthalate.
[00179] Examples of suitable carboxylic acid halides as activating electron donors are the carboxylic acid halides mentioned above, for example, acetyl chloride, acetyl bromide, propionyl chloride, butanoyl chloride, butanoyl iodide, bromide benzoyl, p-tolyl chloride and/or phthaloyl dichloride.
[00180] Suitable alcohols are linear or branched aliphatic alcohols with 1-12 carbon atoms, or aromatic alcohols. Examples include methanol, ethanol, butanol, isobutanol, hexanol, xylenol and benzyl alcohol. Alcohols can be used alone or in combination. Preferably the alcohol is ethanol or hexanol.
[00181] Examples of suitable ethers are diethers, such as 2-ethyl-2-butyl-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane and/or 9,9-bis( methoxy methyl) fluorene. Also, cyclic ethers such as tetrahydrofuran (THF), or tri-ethers can be used.
Suitable examples of other organic compounds containing a heteroatom for use as activating electron donors include 2,2,6,6-tetramethyl piperidine, 2,6-dimethyl piperidine, pyridine, 2-methyl pyridine, 4-methyl pyridine, imidazole, benzonitrile, aniline, diethyl aniline, dibutyl amine, dimethyl acetamide, thiophenol, 2-methyl thiophene, isopropyl mercaptan, diethyl thio ether, diphenyl thio ether, tetrahydrofuran, dioxane, dimethyl ether, diethyl ether, anisole, acetone, triphenyl phosphine, triphenyl phosphite, diethyl phosphate and/or diphenyl phosphate.
[00183] Examples of suitable metal alkoxides for use in step ii) are metal alkoxides of the formulas: M1(OR2)vw(OR3)w and M2(OR2)vw(R3)w where M1, M2, R2, R3, v , and w are as defined herein. R2 and R3 may also be aromatic hydrocarbon groups, optionally substituted with, for example, alkyl groups, and may contain, for example, from 6 to 20 carbon atoms. R2 and R3 preferably comprise 1-12 or 1-8 carbon atoms. In preferred embodiments R2 and R3 are ethyl, propyl or butyl; most preferably all groups are ethyl groups.
Preferably, M1 in said activating compound is Ti or Si. Suitable Si-containing compounds as activating compounds are the same as listed above for step i).
[00185] The value of w is preferably 0, the activating compound being, for example, a titanium tetra alkoxide containing 4-32 carbon atoms in total from four alkoxy groups. The four alkoxide groups in the compound can be identical or they can differ independently. Preferably, the at least one of the alkoxy groups in the compound is an ethoxy group. More preferably the compound is a tetra alkoxide, such as titanium tetraethoxide.
[00186] In the preferred process for preparing the procatalyst, an activating compound can be used, but also a mixture of two or more compounds can be used.
[00187] A combination of a compound of M1(OR2)vw(OR3)w or M2(OR2)vw(R3)w with an electron donor is preferred as activation compound to obtain a catalyst system which, for example, shows high activity, and from which sensitivity to ethylene can be affected through internal donor selection; which is specifically advantageous in preparing copolymers of, for example, propylene and ethylene.
[00188] Preferably, a Ti-based compound, eg titanium tetraethoxide, is used together with an alcohol such as ethanol or hexanol, or with an ester compound such as ethyl acetate (EA), ethyl benzoate (EB) or a phthalate ester, or together with an ether such as dibutyl ether (DBE), or with pyridine.
[00189] If two or more activating compounds are used in step ii) their order of addition is not critical, but can affect catalyst performance depending on the compounds used. Those skilled in the art can optimize their order of addition based on a few experiments. The compounds from step ii) can be added together or sequentially.
[00190] Preferably, an electron donor compound is first added to the compound with formula Mg(OR1)xX12-x where after a compound of formula M1(OR2)vw(OR3)w or M2(OR2)vw(R3)w as defined here be added. Activating compounds preferably are added slowly, for example over a period of 0.1-6, preferably over 0.5-4 hours, more preferably over 1-2.5 hours each.
[00191] The first intermediate reaction product that is obtained in step i) can be contacted - when more than one activating compound is used - in any sequence with the activating compounds. In one embodiment, an activation electron donor is first added to the first intermediate reaction product and then the compound M1(OR2)v-w(OR3)w or M2(OR2)v-w(R3)w is added; in this order no agglomeration of solid particles is observed. The compounds in step ii) are preferably added slowly, for example over a period of 0.1-6, preferably over 0.5-4 hours, more preferably over 12.5 hours each.
[00192] The molar ratio of the activating compound to Mg(OR1)xX12-x can vary within wide limits and is, for example, between 0.02 and 1.0. Preferably the molar ratio is between 0.05 and 0.5, more preferably between 0.06 and 0.4, or even between 0.07 and 0.2.
[00193] The temperature in step ii) may be in the range of -20oC to 70oC, preferably of -10oC to 50oC, more preferably in a range of -5oC to 40oC, and more preferably in a range of between 0oC and 30oC.
[00194] Preferably, at least one of the reaction components is dosed in time, e.g. for 0.1 to 6, preferably for 0.5 to 4 hours, more particularly for 1 to 2.5 hours.
[00195] The reaction time after the activating compounds have been added is preferably between 0 and 3 hours.
[00196] The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by those skilled in the art and should be sufficient to stir the reagents.
[00197] The inert dispersant used in step ii) is preferably a hydrocarbon solvent. The dispersant can be, for example, an aliphatic or aromatic hydrocarbon having 1-20 carbon atoms. Preferably, the dispersant is an aliphatic hydrocarbon, more preferably pentane, isopentane, hexane or heptane, most preferably heptane.
[00198] Starting from a product containing solid Mg of controlled morphology obtained in step i), said morphology is not negatively affected during treatment with the activating compound during step ii). The second solid intermediate reaction product obtained in step ii) is considered to be an adduct of the compound containing Mg and the at least one activating compound as defined in step ii), and is still of controlled morphology.
[00199] The second intermediate reaction product obtained after step ii) can be a solid and can further be washed, preferably with the solvent also used as an inert dispersant; and then stored and further used as a suspension in said inert solvent. Alternatively, the product may be dried, preferably partially dried, preferably slowly and under mild conditions; for example, at ambient temperature and pressure. Phase C: Contact of said solid support with catalytic species and optionally one or more internal donors and/or an activator
[00200] Phase C: solid support contact with a catalytic species. This step can take different forms, such as i) contacting said solid support with a catalytic species to obtain said procatalyst; ii) contact of said support with the catalytic species and one or more internal donors to obtain said pro-catalyst; iii) contact of said solid support with a catalytic species and one or more internal donors to obtain an intermediate product; iv) contact of said solid support with a catalytic species and an activating donor to obtain an intermediate product.
[00201] The contact of solid support with catalytic species can comprise several stages (for example, I, II and/or III). During each of these consecutive stages the solid support is contacted with said catalytic species. In other words, the addition or reaction of said catalytic species can be repeated one or more times. The same or different catalytic species can be used during these stages.
[00202] These stages can be divided into Phase C (eg step iii) and Phase D (eg step v) or step v-a) and v-b). It is possible that Phase C comprises one or more stages and that Phase D also comprises one or more stages.
[00203] For example, during stage I in phase C (step iii) the solid support (first intermediate) or the activated solid support (second intermediate) is first contacted with said catalytic species and optionally subsequently with one or more internal donors and optionally an activator. When a second stage is present, during stage II (both Stage C and Stage D) the intermediate product obtained from stage I will be contacted with additional catalytic species which may be identical or different from the catalytic species added during the first stage and optionally one or more internal donors and optionally an activator.
[00204] In case three stages are present, in one embodiment, stage III is v) of Stage D which is preferably a repeat of stage I or may comprise contacting the product obtained from stage II with a catalytic species (which may be the same or different as above) and one or more internal donors. In other words, an internal donor can be added during each of these stages or during two or more of these stages. When an internal donor is added during more than one stage it can be the same or a different internal donor. In one embodiment, stage I is stage iii) of Stage C, stage II is stage va) of Stage D, and stage III is stage vb) of Stage D.
[00205] An activator according to the present invention - if used - can be added either during stage I or stage II or stage III. An activator can also be added during more than one stage.
[00206] Preferably, the solid support contact process with the catalytic species and an internal donor comprises the following step iii). Step iii) solid support reaction with a transition metal halide
[00207] Step iii) solid support reaction with a transition metal halide (eg titanium halide, chromium, hafnium, zirconium or vanadium) but preferably titanium halide. In the discussion below only the process for a titanium-based Ziegler-Natta procatalyst is shown, however, the present invention is also applicable to other types of Ziegler-Natta procatalysts.
[00208] Step iii): contacting the first or second intermediate reaction product, obtained respectively in step i) or ii), with a Ti-compound containing halogen and optionally an internal electron donor or activator to obtain a third intermediate product.
[00209] Step iii) can be carried out after step i) on the first intermediate product or after step ii) on the second intermediate product.
[00210] The molar ratio in step iii) of the transition metal to magnesium preferably is between 10 and 100, more preferably between 10 and 50.
[00211] Preferably, an internal electron donor is also present during step iii). Also mixtures of internal electron donors can be used. Examples of internal electron donors are shown below.
[00212] The molar ratio of the internal electron donor to magnesium can vary within wide limits, for example, between 0.02 and 0.75. Preferably, this molar ratio is between 0.05 and 0.4; more preferably between 0.1 and 0.4; and more preferably between 0.1 and 0.3.
[00213] During contact of the first or second intermediate product and the halogen-containing titanium compound, an inert dispersant is preferably used. The dispersant is preferably chosen so that virtually all of the by-products formed are dissolved in the dispersant. Suitable dispersants include, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents having, for example, 420 carbon atoms. Examples include toluene, xylene, benzene, heptane, o-chloro toluene and chloro benzene.
[00214] The reaction temperature during step iii) is preferably between 0oC and 150oC, more preferably between 50oC and 150oC, and more preferably between 100oC and 140oC. More preferably, the reaction temperature is between 110°C and 125°C.
[00215] The reaction time during step iii) is preferably between 10 minutes and 10 hours. In case multiple stages are present, each stage can have a reaction time between 10 minutes and 10 hours. Reaction time can be determined by those skilled in the art based on the type and scale of the reactor and catalyst systems.
[00216] The mixing speed during the reaction depends on the type and scale of the reactor used. The mixing speed can be determined by those skilled in the art and should be sufficient to stir the reagents.
[00217] The reaction product obtained can be washed, usually with an aliphatic or aromatic hydrocarbon or halogenated aromatic compound, to obtain the procatalyst of the invention. If desired the reaction and subsequent purification steps can be repeated one or more times. A final wash is preferably performed with an aliphatic hydrocarbon to result in a suspended or at least partially dried procatalyst as described above for the other steps.
[00218] Optionally an activator is present during step ii) of Phase C rather than an internal donor, this is explained in more detail below in the activators section.
[00219] The molar ratio of activator to magnesium can vary within wide limits, for example, between 0.02 and 0.5. Preferably, this molar ratio is between 0.05 and 0.4; more preferably between 0.1 and 0.3; and more preferably between 0.1 and 0.2. Phase D: Modification of said procatalyst with a metal-based modifier
[00220] This phase D is optional in the present invention. In a preferred process for modifying the supported procatalyst, this phase comprises the following steps:
[00221] Step iv) modification of third intermediate product with a modifier - metal to yield a modified intermediate product.
[00222] After step iv) - if it is carried out - an additional step of contact of intermediate product with a catalytic species (in other words, an additional stage).
[00223] Step v) contacting said modified intermediate product with a titanium halide and optionally one or more internal donors and/or activators to obtain the present procatalyst. In case no activator is used during Phase C, an activator is used during step v) of Phase D.
[00224] The order of addition, viz the order of first step iv) and subsequently step v) is considered to be very important for the formation of the correct transition metal or Group 13e titanium clusters forming the most active and modified catalytic center.
[00225] Each of these steps is shown in more detail below.
[00226] It should be noted that steps iii), iv) and v) (viz. Phases C and D) are preferably carried out in the same reactor, viz. In the same reaction mixture, directly following each other.
[00227] Preferably step iv) is carried out directly after step iii) in the same reactor. Preferably, step v) is carried out directly after step iv) in the same reactor. Step iv): Transition Metal or Group 13 Modification
[00228] Modification with transition metal or Group 13, preferably aluminum, ensures the presence of transition metal or Group 13 in the procatalyst, in addition to magnesium (from solid support) and titanium (from titanium treatment).
[00229] Without wishing to be bound by any particular theory, the present inventors believe that one possible explanation is that the presence of transition metal or Group 13 increases active site reactivity and therefore increases polymer yield.
[00230] Step iv) comprises modification of third intermediate product obtained in step iii) with a modifier having the formula M(p)Xp, preferably MX3, where M is a metal selected from the Group 13 metals and transition metals of the table periodicity of IUPAC elements, p is the oxidation state of M, and where X is a halide to yield a modified intermediate product. In case the oxidation state of M, eg aluminum, is three, M(p) is AL(III) and there are three monovalent halides X, eg AlCl3 or AlF3. In the oxidation state case of M, eg copper, to be two, M9p) is Cu(II) and there are two monovalent halides X, CuBr2 or CuCl2. Step iv) is preferably carried out directly after step iii), more preferably in the same reactor and preferably in the same reaction mixture. In one embodiment, a mixture of aluminum trichloride and a solvent, eg, chlorobenzene, is added to the reactor after step iii) has been carried out. After the reaction is completed a solid is left to settle which can be obtained by decantation or filtration and optionally purified or a suspension which in the solvent can be used for the next step, viz. Step v).
[00231] The metal modifier is preferably selected from the group of aluminum modifiers (eg aluminum halides), boron modifiers (eg boron halides), gallium modifiers (eg gallium halides), zinc modifiers (eg , zinc halides), copper modifiers (eg copper halides), thallium modifiers (eg thallium halides), indium modifiers (eg indium halides), vanadium modifiers (eg vanadium halides), chromium modifiers (eg, chromium halides) and iron modifiers (eg, iron halides).
[00232] Examples of suitable modifiers are aluminum trichloride, aluminum tribromide, aluminum triiodide, aluminum trifluoride, boron trichloride, boron tribromide, boron triiodide, boron trifluoride, gallium trichloride, gallium triiodide, trifluoride gallium, zinc dichloride, zinc dibromide, zinc diiodide, zinc difluoride, copper dichloride, copper dibromide, copper diiodide, copper difluoride, copper chloride, copper bromide, copper iodide, copper fluoride, thallium trichloride, thallium tribromide, thallium triiodide, thallium trifluoride, thallium chloride, thallium bromide, thallium iodide, thallium fluoride, indium trichloride, indium tribromide, indium triiodide, indium trifluoride, indium trifluoride , vanadium tribromide, vanadium triiodide, vanadium trifluoride, chromium trichloride, chromium dichloride, chromium tribromide, chromium dibromide, iron dichloride, iron trichloride, iron tribromide, dic iron chloride, iron triiodide, iron diiodide, iron trifluoride and iron difluoride.
[00233] The amount of metal halide added during step iv) may vary according to the desired amount of metal present in the procatalyst. It may, for example, range between 0.1 to 5% by weight based on the total weight of the support, preferably between 0.5 and 1.5% by weight.
[00234] The metal halide is preferably mixed with a solvent prior to addition to the reaction mixture. The solvent for this step can be selected from, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with, for example, 4-20 carbon atoms. Examples include toluene, xylene, benzene, decane, o-chloro toluene and chloro benzene. The solvent can also be a mixture of two or more of them.
[00235] The duration of the modification step can vary from between 1 minute and 120 minutes, preferably between 40 and 80 minutes, more preferably between 50 and 70 minutes. This time is dependent on the modifier concentration, temperature, type of solvent used, etc.
[00236] The modification step is preferably carried out at elevated temperatures (eg between 50 and 120oC, preferably between 90 and 110oC).
[00237] The modification step can be performed while shaking. The mixing speed during the reaction depends on the type and scale of reactor used. The mixing speed can be determined by those skilled in the art. As a non-limiting example, mixing can be carried out at a mixing speed of 100 to 400 rpm, preferably 150 to 300 rpm, more preferably about 200 rpm.
[00238] The weight/volume ratio for the metal halide and the solvent in step iv) is between 0.01 gram-0.1 gram : 5.0-100 ml.
[00239] The modified intermediate product is present in a solvent. It can be kept in this solvent after which the following step v) is directly carried out. However, it can also be isolated and/or purified. The solid can be allowed to settle by stopping stirring. The supernatant can be removed by decanting. Otherwise, filtration of the suspension is also possible. The solid product can be washed once or several times with the same solvent used during the reaction or another solvent selected from the same group described above. The solid can be resuspended or can be dried or partially dried for storage.
[00240] Subsequent to this step, step v) is carried out to produce the procatalyst according to for use in a catalyst system according to an embodiment of the present invention. Step v): titanation of intermediate product
[00241] This step is very similar to step iii). It refers to the additional titanation of the modified intermediate product. It is an additional stage of contact with catalytic species (viz. Titanation in this embodiment).
[00242] Step v) contacting said modified intermediate product obtained in step iv) with a titanium compound containing halogen to obtain the procatalyst. When an activator is used during step iii) a donor is used during this step.
[00243] Step v) is preferably carried out directly after step iv), more preferably in the same reactor and preferably in the same reaction mixture.
[00244] In one embodiment, at the end of step iv) or at the beginning of step v) the supernatant is removed from the solid modified intermediate product obtained in step iv) by filtration or by decantation. To the remaining solid, a mixture of titanium halide (eg tetrachloride) and a solvent (eg chlorobenzene) can be added. The reaction mixture is subsequently kept at an elevated temperature (eg between 100 and 130oC, such as 115oC) for a certain period of time (eg between 10 and 120 minutes, such as between 20 and 60 minutes, for example , 30 minutes). After this, a solid substance is allowed to settle through the stirring interruption.
[00245] The molar ratio of transition metal to magnesium is preferably between 10 and 100, more preferably between 10 and 50.
[00246] Optionally, an internal electron donor is also present during this step. Mixtures of internal electron donors can also be used. Examples of internal electron donors are shown below. The molar ratio of internal electron donor to magnesium can vary within wide limits, for example, from 0.02 to 0.75. Preferably, this molar ratio is between 0.1 and 0.3.
[00247] The solvent for this step can be selected from, for example, aliphatic and aromatic hydrocarbons and halogenated aromatic solvents with, for example, 4-20 carbon atoms. The solvent can also be a mixture of two or more of them.
[00248] According to a preferred embodiment of the present invention this step v) is repeated, in other words the supernatant is removed as described above and a mixture of titanium halide (eg tetrachloride) and a solvent (eg chlorobenzene) is added. The reaction is continued at elevated temperatures for a certain time which may be the same or different from the first time in which step v) is carried out.
[00249] The step can be performed while shaking. The mixing speed during the reaction depends on the type of reactor used and the scale of the reactor used. The mixing speed can be determined by those skilled in the art. This can be the same as discussed above for step iii).
[00250] Thus, step v) can be considered to consist of at least two sub-steps in this embodiment, being:
[00251] v-a) contacting said modified intermediate product obtained in step iv) with titanium tetrachloride - optionally using an internal donor - to obtain a partially titanated procatalyst; (This can be considered, for example, to be stage II as discussed above for a three-stage Phase C).
[00252] v-b) contacting said partially titanated pro-catalyst obtained in step v-a) with titanium tetrachloride to obtain the pro-catalyst. (This can be considered, for example, to be stage III as described above for a three-stage Phase C).
[00253] Additional substeps may be present to increase the number of titanation steps to four or more (eg stages IV, V, etc.).
[00254] The solid substance (procatalyst) obtained is washed several times with a solvent (eg heptane), preferably at elevated temperature, for example between 40 and 100oC depending on the boiling point of the solvent used, preferably between 50 and 70oC. After this, the procatalyst, suspended in solvent, is obtained. Solvent can be removed by filtration or decantation. The procatalyst can be used as such wetted by the solvent or suspended in solvent or it can be first dried, preferably partially dried, for storage. Drying can be carried out, for example, by flowing nitrogen at low pressure for several hours.
[00255] Thus in this embodiment, the total titanation treatment comprises three stages of addition of titanium halide. Where the first addition phase is separated from the second and third phases by metal halide modification.
[00256] The titanation step (viz. The step of contacting a titanium halide) according to this embodiment of the present invention is divided into two parts and a modification step with transition metal or Group 13 is introduced between the two parts or stages of titanation.
[00257] Preferably, the first part of the titanation comprises a single titanation step and the second part of the titanation comprises two subsequent titanation steps. However different procedures can be used. When this modification is carried out before the titanation step, the increase in activity was greater as observed by the inventors. When this modification is carried out after the titanation step the increase in activity was smaller as observed by the present inventors.
[00258] In short, an embodiment of the present invention comprises the following steps: i) preparation of first intermediate reaction product; ii) activation of solid support to yield second intermediate reaction product; iii) first titanation or Stage I to yield a third intermediate reaction product; iv) modification to yield modified intermediate product; v) second titanation or Stage II/III to yield the pro-catalyst. This procatalyst is then combined with at least nPTES as an external donor and a cocatalyst to prepare the catalyst system in accordance with the present invention.
[00259] The procatalyst may have a titanium, hafnium, zirconium, chromium, or vanadium (preferably titanium) content of from about 0.1% by weight to about 6.0% by weight, based on the weight of solids. total, or from about 1.0% by weight to about 4.5% by weight, or from about 1.5% by weight to about 3.5% by weight. Weight percentage is based on the total weight of the procatalyst
[00260] The weight ratio of titanium, hafnium, zirconium, chromium or vanadium (preferably titanium) to magnesium in the solid procatalyst can be between about 1:3 and about 1:160, or between about 1:4 and about 1:50, or between about 1:6 and 1:30.
[00261] The solid catalyst compound containing transition metal according to the present invention comprises a transition metal halide (e.g. titanium halide, chromium halide, hafnium halide, zirconium halide or vanadium halide) supported on a metal or metalloid compound (eg a magnesium compound or a silica compound).
[00262] Preferably, a magnesium-based or magnesium-containing support is used in the present invention. Such a support is prepared from magnesium-containing support precursors, such as magnesium halides, magnesium alkyls and magnesium aryls, and also alkoxy magnesium and aryloxy magnesium compounds.
[00263] Support can be activated using activating compounds as described in more detail above in Phase B.
[00264] The catalyst can still be activated during Phase C as discussed above for the process. This activation increases the yield of the resulting catalyst composition in olefin polymerization.
[00265] Various activators can be used, such as benzamide, alkyl benzoates, and monoesters. Each of these will be discussed below.
[00266] A benzamide activator has a structure according to Formula X:
formula X
[00267] R70 and R71 are each independently selected from hydrogen or an alkyl, preferably an alkyl. Preferably, said alkyl has between 1 and 6 carbon atoms, more preferably between 1-3 carbon atoms. More preferably, R70 and R71 are each independently selected from hydrogen or methyl.
[00268] R72, R73, R74, R75, R76 are each independently selected from hydrogen, a heteroatom (preferably a halide), or a hydrocarbyl group, selected, for example, from alkyl, alkenyl, aryl, aralkyl groups , alkoxy carbonyl, or alkyl aryl, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atom, even more preferably between 1 and 6 carbon atoms.
[00269] Suitable non-limiting examples of "benzamides" include benzamide (R70 and R71 are both hydrogen and each of R72, R73, R74, R75, R76 is hydrogen) also represented as BA-2H or methyl benzamide (R70 is hydrogen; R71 is methyl and each of R72, R73, R74, R75, R76 is hydrogen) also represented as BA- HMe or dimethyl benzamide (R70 and R71 are methyl and each of R72, R73, R74, R75, R76 is hydrogen) also represented as BA-2Me. Other examples include mono ethyl benzamide, diethyl benzamide, methyl ethyl benzamide, 2-(trifluoro methyl) benzamide, N,N-dimethyl-2-(trifluoro methyl) benzamide, 3-(trifluoro methyl) benzamide, N,N-dimethyl- 3-(trifluoromethyl)benzamide, 2,4-dihydroxy-N-(2-hydroxyethyl)benzamide, N-(1H-benzotriazol-1-yl methyl)benzamide, 1-(4-ethyl benzoyl) piperazine, 1- benzoyl piperidine.
[00270] It has surprisingly been found by the present inventors that when the benzamide activator is added during the first stage of the process together with the catalytic species or directly after the addition of the catalytic species (eg within 5 minutes) an even greater increase in yield is observed compared to when the activator is added during stage II or stage III of the process.
It has surprisingly been found by the present inventors that benzamide activator having two alkyl groups (eg dimethyl benzamide or diethyl benzamide, preferably dimethyl benzamide) provides an even greater increase in yield than either benzamide or mono alkyl benzamide.
[00272] Without wishing to be bound by a particular theory the present inventors believe that the fact that the most effective activation is obtained when the benzamide activator is added during stage I has the following reason. It is believed that the benzamide activator will bind the catalytic species and is then replaced by the internal donor when the internal donor is added.
[00273] Alkyl benzoates can be used as activators. The activator, therefore, can be selected from the group of alkyl benzoates having an alkyl group having between 1 and 10, preferably between 1 and 6 carbon atoms. Examples of suitable alkyl benzoates are methyl benzoate, ethyl benzoate according to Formula II, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, 2-butyl benzoate, t-butyl benzoate. Formula II

[00274] Most preferably, the activator is ethyl benzoate. In an even more preferred embodiment, ethyl benzoate as activator is added during step iii) and an internal benzamide donor is added during step v), more preferably 4-[benzoyl(methyl)amino]pentan-2-yl benzoate according to with Formula II: Formula XII

[00275] Monoesters can be used as activators. The monoester according to the present invention can be any ester of a monocarboxylic acid known in the art. Structures according to Formula V are also monoesters but are not explained in this section, see the section on Formula V. The monoester can have the formula XXIII. R94-CO-OR95 Formula XXIII
[00276] R94 and R95 are each independently a hydrocarbyl group selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof. R94 can be a hydrogen. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms. When R94 is an aryl, this structure is similar to Formula V. Examples of aromatic monoesters are discussed with reference to Formula V.
[00277] Preferably, said monoester is an aliphatic monoester. Suitable examples of monoesters include formats, for example, butyl format; acetates, for example ethyl acetate, amyl acetate and butyl acetate; acrylates, for example ethyl acrylate, methyl methacrylate and isobutyl methacrylate. More preferably, the aliphatic monoester is an acetate. Most preferably, the aliphatic monoester is ethyl acetate.
[00278] In one embodiment, the monoester used in step iii) is an ester of an aliphatic mono carboxylic acid having between 1 and 10 carbon atoms. Where R94 is an aliphatic hydrocarbyl group.
[00279] The molar ratio between the monoester in step iii) and Mg may range from 0.05 to 0.5, preferably from 0.1 to 0.4, and more preferably from 0.15 to 0.25.
[00280] The monoester is not used as a stereospecific agent, as usual internal donors are known to be in the prior art. Monoester is used as an activator.
[00281] Without being bound by any theory, the inventors believe that the monoester used in the process according to the present invention participates in the formation of magnesium halogen crystallites (eg MgCl2) during the interaction of Mg-containing support with titanium halogen ( for example, TiCl4). The monoester can form intermediate complexes with Ti and Mg halogen compounds (eg TiCl4, TiCl3(OR), MgCl2, MgCl(OEt), etc.), aiding in the removal of titanium products from solid particles to mother liquor and affect the ultimate catalyst activity. Furthermore, the monoester according to the present invention can also be referred to as an activator.
[00282] As used herein, an "internal electron donor" or an "internal donor" is a compound added during formation of the procatalyst that donates an electron pair to one or more metals present in the resulting procatalyst. Not being bound by any particular theory, it is believed that the internal electron donor assists in regulating active site formation thereby improving catalyst stereo selectivity.
[00283] The inner electron donor can be any compound known in the art to be used as the inner electron donor. Suitable examples of internal donors include aromatic acid esters such as monocarboxylic acid ester or dicarboxylic acid esters (for example ortho dicarboxylic acid esters such as phthalic acid esters), starch (N-alkyl) benzoate, 1, 3- diethers, silyl esters, fluorenes, succinates and/or combinations thereof.
[00284] It is preferred to use so-called phthalate-free internal donors due to increasingly strict government regulations on the maximum phthalate content in polymers. This leads to an increased demand on phthalate-free catalyst compositions. In the context of the present invention, "essentially phthalate-free" or "phthalate-free" means having a phthalate content of less than, for example, 150 ppm, alternatively less than, for example, 100 ppm, alternatively less than, for example , 50 ppm, alternatively, for example, less than 20 ppm.
[00285] An aromatic acid ester can be used as an internal donor. As used herein, an "aromatic acid ester" is a monocarboxylic acid ester (also called "benzoic acid ester") as shown in Formula V, an ester of dicarboxylic acid (eg, an o-dicarboxylic acid also called "phthalic acid ester") as shown in Formula VI: Formula V

[00286] R30 is selected from a hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms. Suitable examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkyl aryl, and alkynyl groups.
[00287] R31, R32, R33, R34, R35 are each independently selected from hydrogen, a heteroatom (preferably a halide), or a hydrocarbyl group, selected from, for example, alkyl, alkenyl, aryl, aralkyl, groups, carbonyl alkoxy or aryl alkyl, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
Suitable non-limiting examples of "benzoic acid esters" include an alkyl p-alkoxy benzoate (such as ethyl p-methoxy benzoate, methyl p-ethoxy benzoate, ethyl p-ethoxy benzoate), an ethyl benzoate. alkyl (such as ethyl benzoate, methyl benzoate), an alkyl p-halo benzoate (ethyl p-chloro benzoate, ethyl p-bromo benzoate), and benzoic anhydride. The benzoic acid ester is preferably selected from ethyl benzoate, benzoyl chloride, ethyl p-bromo benzoate, n-propyl benzoate and benzoic anhydride. The benzoic acid ester is most preferably ethyl benzoate.

[00289] R40 and R41 are each independently a hydrocarbyl group selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms. Suitable examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, aralkyl, alkyl aryl, and alkynyl groups.
[00290] R42, R43, R44, R45 are each independently selected from hydrogen, a halide or a hydrocarbyl group, selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and a or more your combinations. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
Suitable non-limiting examples of phthalic acid esters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, phthalate of di-t-butyl, di-isoamyl phthalate, di-t-amyl phthalate, dineopentyl phthalate, di-2-ethyl hexyl phthalate, di-2-ethyl decyl phthalate, bis-(2, 2,2-trifluoroethyl), diisobutyl 4-t-butyl phthalate, and di-isobutyl 4-chloro phthalate. The phthalic acid ester is preferably di-n-butyl phthalate or di-isobutyl phthalate.
[00292] As used herein a "diether" may be a 1,3-di-(hydrocarboxy)propane compound, optionally substituted at the 2-position represented by Formula VII,
Formula VII
[00293] R51 and R52 are each independently selected from a hydrogen or a hydrocarbyl group selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms. Suitable examples of hydrocarbyl groups include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadineyl, aryl, aralkyl, alkyl aryl, and alkynyl groups.
[00294] R53 and R54 are each independently selected from a hydrocarbyl group, selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
Suitable examples of dialkyl ether compounds include 1,3-dimethoxy propane, 1,3-diethoxy propane, 1,3-dibutoxy propane, 1-methoxy-3-ethoxy propane, 1-methoxy-3-butoxy propane, 1- -methoxy-3-cyclohexoxy propane, 2,2-dimethyl-1,3-dimethoxy propane, 2,2-diethyl-1,3-dimethoxy propane, 2,2-di-n-butyl-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-dimethoxy propane, 2-ethyl-2-n-butyl-1,3-dimethoxy propane, 2-n-propyl-2-cyclopentyl-1,3-dimethoxy propane , 2,2-dimethyl-1,3-diethoxy propane, 2-n-propyl-2-cyclohexyl-1,3-diethoxy propane, 2-(2-ethyl hexyl)-1,3-dimethoxy propane, 2- isopropyl-1,3-dimethoxy propane, 2-n-butyl-1,3-dimethoxy propane, 2-sec-butyl-1,3-dimethoxy propane, 2-cyclohexyl-1,3-dimethoxy propane, 2-phenyl -1,3-diethoxy propane, 2-cumyl-1,3-diethoxy propane, 2-(2-phenyl ethyl)-1,3-dimethoxy propane, 2-(2-cyclohexyl ethyl)-1,3-dimethoxy propane, 2-(p-chloro phenyl)-1,3-dimethoxy propane, 2-(diphenyl methyl)-1,3-dimethoxy propane, 2-(1-naphthyl)-,13-dimethoxy propane, 2-(fluorine phenyl)-1,3-dimethoxy propane, 2-(1-decahydro naphthyl)-1,3-dimethoxy propane, 2-(pt-butyl phenyl)-1,3-dimethoxy propane, 2,2-dicyclohexyl-1,3-dimethoxy propane, 2,2- di-n-propyl-1,3-dimethoxy propane, 2-methyl-2-n-propyl-1,3-dimethoxy propane, 2-methyl-2-benzyl-1,3-dimethoxy propane, 2-methyl-2 -ethyl-1,3-dimethoxy propane, 2-methyl-2-phenyl-1,3-dimethoxy propane, 2-methyl-2-cyclohexyl-1,3-dimethoxy propane, 2,2-bis-(p- chlorophenyl)-1,3-dimethoxy propane, 2,2-bis-(2-cyclohexyl ethyl)-1,3-dimethoxy propane, 2-methyl-2-isobutyl-1,3-dimethoxy propane, 2-methyl -2-(2-ethyl hexyl)-1,3-dimethoxy propane, 2-methyl-2-isopropyl-1,3-dimethoxy propane, 2,2-diphenyl-1,3-dimethoxy propane, 2,2-dibenzyl -1,3-dimethoxy propane, 2,2-bis-(cyclohexyl methyl)-1,3-dimethoxy propane, 2,2-di-isobutyl-1,3-diethoxy propane, 2,2-di-isobutyl- 1,3-di-n-butoxy propane, 2-isobutyl-2-isopropyl-1,3-dimethoxy propane, 2,2-di-sec-butyl-1,3-dimethoxy propane, 2,2-di-t -butyl-1,3-dimethoxy propane, 2,2-dinepentyl-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, 2-phenyl-2-benzyl-1,3-dimethoxy propane, 2-cyclohexyl-2-cyclohexyl methyl-1,3-dimethoxy propane, 2-isopropyl-2-(3,7-dimethyl octyl)-1, 3-dimethoxy propane, 2,2-diisopropyl-1,3-dimethoxy propane, 2-isopropyl-2-cyclohexyl methyl-1,3-dimethoxy propane, 2,2-diisopentyl-1,3-dimethoxy propane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxy propane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxy propane, 2,2-dicyclopentyl-1,3-dimethoxy propane, 2-n- heptyl-2-n-pentyl-1,3-dimethoxy propane. 9,9-bis(methoxy methyl) fluorene, 1,3-dicyclohexyl-2,2-bis(methoxy methyl) propane, 3,3-bis(methoxy methyl)-2,5-dimethyl hexane, or any combination of the above. In one embodiment, the internal electron donor is 1,3-dicyclohexyl-2,2-bis(methoxy methyl) propane, 3,3-bis(methoxy methyl)-2,5-dimethyl hexane, 2,2-dicyclopentyl -1,3-dimethoxy propane and combinations thereof.
[00296] Examples of preferred ethers are diethyl ether, dibutyl ether, diisoamyl ether, anisole and ethyl phenyl ether, 2,3-dimethoxy propane, 2,3-dimethoxy propane, 2-ethyl-2-butyl-1,3 -dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene:

[00297] As used herein, an "acid succinate ester" is a 1,2-dicarboxy ethane and can be used as an internal donor. Formula VIII

[00298] R60 and R61 are each independently a hydrocarbyl group, selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof. Said hydrocarbyl group Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[00299] R62, R63, R64, and R65 are each independently selected from hydrogen or a hydrocarbyl group, selected from, for example, alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more their combinations. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms.
[00300] More preferably, R62, R63, R64, and R65 are independently selected from a group consisting of hydrogen, a straight or branched C1-10 alkyl group; C3-10 cycloalkyl; C6-10 aryl; and C7-10 alkaryl and aralkyl.
[00301] Even more preferably, R62, R63, R64, and R65 are independently selected from a group consisting of hydrogen, a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl group , phenyl trifluoromethyl, and halo phenyl. More preferably, one of R62 and R63 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, while the other is a hydrogen atom; and one of R64 and R65 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, while the other is a hydrogen atom.
Suitable examples of acid succinate ester include diethyl 2,3-diisopropyl succinate, diethyl 2,3-di-n-propyl succinate, diethyl 2,3-diisobutyl succinate, 2,3- diethyl di-sec-butyl succinate, 2,3-dimethyl diisopropyl succinate, 2,3-di-n-propyl dimethyl succinate, 2,3-dimethyl diisobutyl succinate, 2,3-di- dimethyl sec-butyl succinate.
[00303] Examples of other compounds containing a heteroatom are thiophenol, 2-methyl triophene, isopropyl mercaptan, diethyl thio ether, diphenyl thio ether, tetrahydrofuran, dioxane, anisole, acetone, triphenyl phosphine, triphenyl phosphite, diethyl phosphate, and phosphate of diphenyl.
[00304] The silyl ester as the internal donor can be any silyl ester or silyl diol ester known in the art, for example as shown in US 2010/0130709.
[00305] When an amino benzoate (AB) according to Formula XI is used as an internal donor this ensures better control of stereochemistry and allows preparation of polyolefins having a broader molecular weight distribution.
[00306] Suitable amino benzoates as internal donors according to the present invention are the compounds represented by Formula XI:
Formula XI
[00307] where R80 is an aromatic group, selected from aryl or alkyl aryl groups and may be substituted or unsubstituted. Said aromatic group can contain one or more heteroatoms. Preferably, said aromatic group has between 6 and 20 carbon atoms. It should be noted that the two R80 groups can be identical but they can also be different.
[00308] R80 may be identical or different from any one of R81-R87 and is preferably an unsubstituted and substituted aromatic hydrocarbyl having 6 to 10 carbon atoms.
[00309] More preferably, R80 is selected from the group consisting of C6-10 aryl unsubstituted or substituted with, for example, an acyl halide or an alkoxide; and C7-10 alkaryl and aralkyl group; for example 4-methoxy phenyl, 4-chloro phenyl, 4-methyl phenyl.
Particularly preferred, R80 is a substituted or unsubstituted phenyl, benzyl, naphthyl, ortho-tolyl, para-tolyl or anisole group. More preferably, R80 is phenyl.
[00311] R81, R82, R83, R84, R85 and R86 are each independently selected from hydrogen or a hydrocarbyl group, selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more of their combinations. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms.
[00312] More preferably, R81, R82, R83, R4, R85 and R86 are independently selected from a group consisting of hydrogen, a straight and branched C1-10 alkyl group; C3-10 cycloalkyl; C6-10 aryl; and C7-10 alkaryl and aralkyl.
[00313] Even more preferably, R81, R82, R83, R4, R85 and R86 are independently selected from a group consisting of hydrogen, a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, trifluoromethyl and halo group phenyl.
More preferably, R81, R82, R83, R4, R85 and R86 are each hydrogen, methyl, ethyl, propyl, t-butyl, phenyl or trifluoromethyl.
[00315] Preferably, R81 and R82 are each hydrogen atom.
[00316] More preferably, R81 and R82 are each hydrogen atom and each of R83, R84, R85, and R86 is selected from the group consisting of hydrogen, a straight and branched C1-10 alkyl group; C310 cycloalkyls; C6-10 aryls; and C7-10 alkaryl and aralkyl.
[00317] Preferably, at least one of R83 and R84 and at least one of R85 and R86 is a hydrocarbyl group having at least one carbon atom, being selected from the group as defined above.
[00318] More preferably, when at least one of R83 and R84 is a hydrocarbyl group having at least one carbon atom then the other one of R3 and R4 and of R85 and R86 is each hydrogen atom.
More preferably, when one of R83 and R84 and one of R85 and R86 is a hydrocarbyl group having at least one carbon atom, then the other one of R83 and R84 and one of R85 and R86 is each a carbon atom. hydrogen and R81 and R82 are each hydrogen atom.
[00320] Preferably, R81 and R82 are each hydrogen atom and one of R83 and R84 and one of R85 and R86 is selected from the group consisting of a straight and branched C1-10 alkyl group; C3-10 cycloalkyl; C6-10 aryl; and C7-10 alkaryl and aralkyl.
[00321] More preferably R85 and R86 are selected from the group consisting of C1-10 alkyl, such as a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, trifluoromethyl, and halo phenyl group; and more preferably, one of R83 and R84, and one of R85 and R86 is methyl.
[00322] R87 is a hydrogen or a hydrocarbyl group, selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrokabyl group may contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1 and 10 carbon atoms. R87, may be identical or different from any one of R81, R82, R83, R4, R85 and R86, with the proviso that R87 is not a hydrogen atom.
[00323] More preferably, R87 is selected from the group consisting of straight and branched C1-10 alkyl; C3-10 cycloalkyl; C6-10 alkaryl and aralkyl.
[00324] Even more preferably, R87 is selected from the group consisting of a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, benzyl, and substituted benzyl and halo phenyl group.
[00325] More preferably, R87 is methyl, ethyl, propyl, isopropyl, benzyl or phenyl; and even more preferably, R87 is methyl, ethyl or propyl.
[00326] Without being limited thereto, particular examples of the compounds of formula (XI) are the structures shown in formulas (XII) - (XXII). For example, the structure in Formula (XII) can correspond to 4-[benzoyl(methyl)amino]pentan-2-yl benzoate; Formula (XII) to 3-[benzoyl (cyclohexyl)amino]-1-phenyl butyl benzoate; Formula (XIV) to 3-[benzoyl(propane-2-yl)amino]-1-phenyl butyl benzoate; Formula (XV) to 4-[benzo(propane-2-yl)amino]penta-2-yl benzoate; Formula (XVI) to 4-[benzoyl(methyl)amino]-1,1,1-trifluoropentan-2-yl benzoate; Formula (XVII) to 3-(methylamino)-1,3-diphenyl propane-1-ol dibenzoate; Formula (XVIII) to 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; Formula (XIX) to 4-[benzoyl(ethyl)amino]pentan-2-yl benzoate; Formula (XX) to 3-(methyl)amino propane-1-ol dibenzoate; Formula (XXI) to 3-(methyl)amino-2,2-dimethyl propane-1-ol dibenzoate; Formula (XXII) 4-(methylamino)pentan-2-yl (4-methoxy)benzoate.
[00327] It has surprisingly been found that the catalyst composition comprising the compound of formula (XI) as an internal electron donor shows better control of stereochemistry and allows preparation of polyolefins, particularly of polypropylenes having wider molecular weight distribution and greater isotacticity.
[00328] Preferably, the catalyst composition according to the invention comprises the compound having formula (XI) as the only internal electron donor in a Ziegler-Natta catalyst composition.
[00329] The compounds of formula (XII), (XIX), (XXII) and (XVIII) are the most preferred internal electron donors in the catalyst composition according to the present invention when they allow preparation of polyolefins having the weight distribution broader molecular and greater isotacticity. The low melt flow range (MFR) values of polymers obtained through the use of catalyst compositions according to the present invention, i.e., MFR less than 6 dg/minute, less than 4 dg/minute and even less than 3 dg/minute indicate improved process stability in terms of producing polymers having stable MFR values.



[00330] The compound according to formula (XI) can be manufactured by any process known in the art. In this regard, reference is made to J. Chem. Soc. Perkin trans. 1994, 537-543 and Org. Synth. 1967, 47, 44. These documents show a step a) of contacting a substituted 2,4-diketone with a substituted amine in the presence of a solvent to yield a β-enamino ketone; followed by step b) contacting β-enamino ketone with a reducing agent in the presence of a solvent to yield a y-amino alcohol. The substituted 2,4-diketone and substituted amine can be applied in step a) in amounts ranging from 0.5 to 2.0 moles, preferably from 1.0 to 1.2 moles. The solvent in steps a) and b) can be added in an amount of 5 to 15 volumes, based on the total amount of the diketone, preferably 3 to 6 volumes. The molar ratio of β-enamino ketone to diketone in step b) can be 0.5 to 6, preferably 1 to 3. The molar ratio of reducing agent to β-enamino ketone in step b) can be 3 to 8, preferably from 4 to 6; the reducing agent can be selected from the group comprising metallic sodium, NaBH4 in acetic acid, Ni-Al alloy. Preferably, the reducing agent is sodium metal because it is an inexpensive reagent.
[00331] The y-amino alcohol which can be used for manufacturing compound (XI) can be synthesized as described in the literature and also mentioned here above or this compound can be directly purchased commercially and used as a starting material in a reaction for obtain the compound represented by formula (XI). Particularly, the y-amino alcohol can be reacted with a substituted or unsubstituted benzoyl chloride in the presence of a base to obtain the compound represented by formula (XI) (herein also referred to as step c), irrespective of whether y-amino alcohol was synthesized as described in the literature or purchased commercially). The molar ratio of substituted or unsubstituted benzoyl chloride to y-amino alcohol can range from 2 to 4, preferably from 2 to 3. The base can be any basic chemical compound that is capable of deprotonating the y-amino alcohol. Said base may have a pKa of at least 5; or at least 10 or preferably between 5 and 40, where pKa is a constant already known to those skilled in the art as the negative logarithm of the acid dissociation constant ka. Preferably the base is pyridine; trialkyl amine, for example triethyl amine; or a metal hydroxide, eg NaOH, KOH. Preferably the base is pyridine. The molar ratio of base to y-amino alcohol. Preferably the base is pyridine. The molar ratio between the base and the y-amino alcohol can vary from 3 to 10, preferably from 4 to 6.
[00332] The solvent used in any one of steps a), b) and c) can be selected from any organic solvents such as toluene, dichloromethane, 2-propanol, cyclohexane or mixtures of any organic solvents. Preferably, toluene is used in each of steps a), b) and c). More preferably, a mixture of toluene and 2-propanol is used in step b). The solvent in step c) can be added in an amount of 3 to 15 volumes, preferably 5 to 10 volumes based on the y-amino alcohol.
[00333] The reaction mixture in any of steps a), b) and c) can be stirred by using any type of conventional stirrers for more than about 1 hour, preferably for more than about 3 hours and most preferably for more than about 10 hours, but less than about 24 hours. The reaction temperature in any one of steps a) and b) may be room temperature, that is, from about 15 to about 30°C, preferably from about 20 to about 25°C. The reaction temperature in step c) can vary between 0 to 10°C, preferably between 5 and 10°C. The reaction mixture in any of steps a), b) and c) may be refluxed for more than about 10 hours, preferably for more than about 20 hours but less than about 40 hours or until the reaction is complete (completion can be measured by gas chromatography, GC).
[00334] The reaction mixture from steps a) and b) can then be allowed to cool to room temperature, that is, at a temperature from about 15 to about 30oC, preferably from about 20 to about 25oC. The solvent and any excess components can be removed in any of steps a), b) and c) by any process known in the art, such as evaporation or washing. The product obtained in any of steps b) and c) can be separated from the reaction mixture by any process known in the art, such as by extraction over metal salts, for example sodium sulphate.
[00335] The molar ratio of the internal donor of formula (XI) to magnesium to be 0.02 to 0.5. Preferably, this molar ratio is between 0.05 and 0.2.
[00336] A benzamide can be used as an internal donor. Suitable compounds have a structure according to formula X:

[00337] R70 and R71 are each independently selected from hydrogen or an alkyl. Preferably, said alkyl has between 1 and 6 carbon atoms, more preferably between 1-3 carbon atoms. More preferably, R70 and R71 are each independently selected from hydrogen or methyl.
[00338] R72, R73, R74, R75, R76 are each independently selected from hydrogen, a heteroatom (preferably a halide), or a hydrocarbyl group, selected, for example, from alkyl, alkenyl, aryl, aralkyl groups, carbonyl alkoxy or aryl alkyl, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 10 carbon atoms, more preferably between 1-8 carbon atoms, even more preferably between 1 and 6 carbon atoms.
[00339] Suitable non-limiting examples of "benzamides" include benzamide (R70 and R71 are both hydrogen and each of R72, R73, R74, R75, R76 is hydrogen) also represented as BA-2H or methyl benzamide (R70 is hydrogen and each of R72, R73, R74, R75, R76 is hydrogen) also represented as BA-HMe or dimethyl benzamide (R70 and R71 are methyl and each of R72, R73, R74, R75, R76 is hydrogen) also represented as BA -2Me. Other examples include mono ethyl benzamide, diethyl benzamide, methyl ethyl benzamide, 2-(trifluoromethyl) benzamide, N,N-dimethyl-2-(trifluoro methyl) benzamide, 3-(trifluoromethyl) benzamide, N,N-dimethyl- 3-(trifluoromethyl)benzamide, 2,4-dihydroxy-N-(2-hydroxyethyl)benzamide, N-(1H-benzotriazol-1-yl methyl)benzamide, 1-(4-ethyl benzoyl) piperazine, 1- benzoyl piperidine.
[00340] As discussed in WO 201124063 1,5-diesters according to formula XXV can be used as internal donors. These 1,5-diesters have two chiral centers at their C2 and C4 carbon atoms. There are four isomers, being the meso 2R, 4S isomer, the meso 2S, 4R isomers and the 2S, 4S and 2R, 4R isomers. A mixture of all of them is called a "rac" diester.
Formula XXV
[00341] R15 is independently a hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms.
[00342] R16 and R17 are different with respect to each other. Both R16 groups can be identical or different. Both R17 groups can be identical or different. The groups R16 and R17 are independently selected from the group consisting of hydrogen, halogen, and hydrocarbyl group independently selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl, or alkylaryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms.
[00343] An example of a compound according to formula XXV is pentanediol dibenzoate.
[00344] The compound according to Formula XXV has two stereo centers (in C2 and C4), comprises two so-called stereo centers each giving rise to two different configurations and thus a total of four stereoisomers. There are two sets of diastereomers (or diastereomers), each comprising two enantiomers. Enantiomers differ at both stereo centers and are therefore mirror images of each other.
[00345] The groups R16 and R17 can be swapped in position. In other words, the mirror image of the compound of Formula XXV having the two R17 groups to the left of the structure. The compound in formula XXV is the meso-isomer (2R,4S) while the mirror image (not shown) is the meso-isomer (2S,4R). The compound of Formula XXV is a meso-isomer, that is, it contains two stereo centers (chiral centers) but is not chiral.
[00346] The following two other isomers are possible: a (2S,4S) isomer (not shown), a (2R,4R) isomer (not shown). R and S illustrate the chiral centers of the molecules as known to those skilled in the art. When a mixture of 2S, 4S and 2R, 4R is present, this is called "rac". These internal donors are shown in detail in WO 2013/124063 which shows Fischer projections of all isomers.
[00347] In one embodiment, at least one group of R16 and R17 may be selected from the group consisting of hydrogen, halogen, a linear or branched C1-10 alkyl group, C3-10 cycloalkyl, C6-10 aryl, and C7- 10 alkaryl or aralkyl. More preferably, at least one group of R16 and R17 is selected from the group consisting of hydrogen, a methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, and halo phenyl group.
[00348] Preferably, both R16 and R17 represent hydrogen. More preferably, R16 and R17 represent a methyl or ethyl group. It is particularly preferred when either one of R16 and R17 represents hydrogen and the other represents a methyl or ethyl group.
[00349] R15 is preferably independently selected from benzene ring containing groups, such as phenyl, phenyl substituted with alkyl, alkoxy or halogen; optionally the carbon atom(s) on the benzene ring being substituted with an oxygen heteroatom and/or nitrogen atom; alkenyl or alkenyl substituted phenyl such as vinyl, propenyl, styryl; alkyl such as methyl, ethyl, propyl, etc.
More preferably, R15 represents a phenyl group. Particularly preferred is pentane-2,4-diol meso dibenzoate (mPDDB).
[00351] The catalyst system according to the present invention includes a cocatalyst. As used herein, a "cocatalyst" is a term known in the art in the field of Ziegler-Natta catalysts and is recognized to be a substance capable of converting the procatalyst into an active polymerization catalyst. Generally speaking, the cocatalyst is an organometallic compound containing a group 1, 2, 12 or 13 metal of the Periodic System of the Elements (Handbook of Chemistry and Physics, 70th Edition, CRC Press, 1989-1990).
The cocatalyst may include any compound known in the art to be used as a "cocatalyst", such as hydrides, alkyls, or aryls of aluminum, lithium, zinc, tin, cadmium, beryllium, magnesium, and combinations thereof. The cocatalyst may be an aluminum hydrocarbyl cocatalyst represented by the formula R203Al.
[00353] R20 is independently selected from a hydrogen or a hydrocarbyl, selected, for example, from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkyl aryl groups, and one or more combinations thereof. Said hydrocarbyl group can be linear, branched or cyclic. Said hydrocarbyl group can be substituted or unsubstituted. Said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group can contain one or more heteroatoms. Preferably, said hydrocarbyl group has between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms. With the proviso that at least one R20 is a hydrocarbyl group. Optionally, two or three R20 groups are linked in a cyclic radical forming a heterocyclic structure.
Non-limiting examples of suitable R20 groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-methyl pentyl, heptyl, octyl, isooctyl, 2-ethyl hexyl, 5,5-dimethyl hexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxy phenyl, benzyl, tolyl, xylyl, naphthyl, methyl naphthyl, cyclohexyl, cycloheptyl, and cyclooctyl.
Suitable examples of hydrocarbyl aluminum compounds as cocatalyst include triisobutyl aluminum (TIBA), trihexyl aluminum, diisobutyl aluminum hydride (DIBALH), dihexyl aluminum hydride, isobutyl aluminum dihydride, hexyl dihydride aluminum, diisobutyl hexyl aluminum, dihexyl isobutyl aluminum, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, trioctyl aluminum, tridecyl aluminum, tridodecyl aluminum, tribenzyl aluminum, triphenyl aluminum, trinaphthyl aluminum, and tritolyl aluminum. In one embodiment, the cocatalyst is selected from triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diisobutyl aluminum hydride, and dihexyl aluminum hydride. More preferably, trimethyl aluminum, triethyl aluminum, tri-isobutyl aluminum, and/or trioctyl aluminum. More preferably aluminum triethyl (abbreviated as TEAL).
[00356] The cocatalyst can also be an aluminum hydrocarbyl compound represented by the formula R21mAlX213-m.
[00357] R21 is an alkyl group. Said alkyl group can be linear, branched or cyclic. Said alkyl group can be substituted or unsubstituted. Preferably, said alkyl group has between 1 and 20 carbon atoms, more preferably between 1-12 carbon atoms, even more preferably between 1 and 6 carbon atoms.
Non-limiting examples of suitable R21 groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-methyl pentyl, heptyl, octyl, isooctyl, 2-ethyl hexyl, 5,5-dimethyl hexyl, nonyl, decyl, isodecyl, undecyl, and dodecyl.
[00359] X21 is selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-) or an alkoxide (RO-). The value for m is preferably 1 or 2.
Non-limiting examples of suitable aluminum halide compounds for cocatalyst include tetraethyl di-aluminoxane, methyl aluminoxane, isobutyl aluminoxane, tetra isobutyl alumioxane, diethyl aluminum methoxide, di-isobutyl aluminum chloride, methyl aluminum dichloride, diethyl chloride aluminum, ethyl aluminum dichloride and dimethyl aluminum chloride.
Non-limiting examples of suitable compounds include tetraethyl dialuminoxane, methyl aluminoxamino, isobutyl aluminoxane, tetraisobutyl dialuminoxane, diethyl aluminum ethoxide, diisobutyl aluminum chloride, methyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum dichloride and chloride of dimethyl aluminum.
[00362] Preferably, the cocatalyst is triethyl aluminum. The aluminum to titanium molar ratio can be from about 5:1 to about 500:1 or from about 10:1 to about 200:1 or from about 15:1 to about 150:1 or about from 20:1 to about 100:1. The aluminum to titanium molar ratio is preferably about 45:1.
[00363] The invention also relates to a process for manufacturing a catalyst system through contact of a Ziegler-Natta type pro-catalyst, a cocatalyst and the external electron donor according to the present invention. The procatalyst, cocatalyst, and external donor can be contacted in any manner known to those skilled in the art; and also as described herein, more specifically as in the Examples.
[00364] The invention further relates to a process for manufacturing a polyolefin through contacting an olefin with the catalyst system according to the present invention. The procatalyst, cocatalyst, external donor and olefin can be contacted in any manner known to those skilled in the art; and also as described herein.
[00365] For example, the external donor in the catalyst system according to the present invention can be complexed with the cocatalyst and mixed with the procatalyst (premix) before contact between the catalyst composition and the olefin. The external donor can also be added independently to the polymerization reactor. The procatalyst, cocatalyst, and external donor can be mixed or otherwise matched prior to addition to the polymerization reactor.
[00366] Contact of olefin with the catalyst system according to the present invention can be done under standard polymerization conditions known to those skilled in the art. See, for example, Pasquini, N. (ed.) "Polypropylene handbook" 2nd edition, Carl Hanser Verlag Munich, 2005. Chapter 6.2 and references cited therein.
[00367] The polymerization process can be a gas phase, a slurry or volume polymerization process, operating in one or more than one reactor. One or more olefin monomers can be introduced into a polymerization reactor to react with the catalyst composition and to form an olefin-based polymer (or a fluidized bed of polymer particles).
[00368] In the case of polymerization into a slurry (liquid phase), a dispersing agent is present. Suitable dispersing agents include, for example, propane, n-butane, isobutane, n-pentane, isopentane, hexane (e.g. iso- or n-), heptane (e.g., iso- or n-), octane, cyclo hexane, benzene, toluene, xylene, liquid propylene and/or mixtures thereof. Polymerization such as, for example, polymerization temperature and time, monomer pressure, avoid catalyst contamination, choice of polymerization medium in slurry processes, use of further ingredients (such as hydrogen) to control the molar mass of polymer, and other conditions are well known to those skilled in the art. The polymerization temperature can vary within wide limits and is, for example, for the polymerization of propylene, between 0°C and 120°C, preferably between 40°C and 100°C. The pressure during (co)polymerization of (propylene) is, for example, between 0.1 to 6 MPa, preferably between 1-4 MPa.
[00369] Several types of polyolefins are prepared such as homopolyolefins, random copolymers and heterophasic polyolefin. For the latter, and especially heterophasic polypropylene, the following is noted.
[00370] Heterophasic propylene copolymers are generally prepared in one or more reactors, through polymerization of propylene and optionally one or more other polyephins, for example, ethylene, in the presence of a catalyst and subsequent polymerization of a mixture of propylene -alpha- olefin. The resulting polymeric materials may show multiple phases (depending on monomer ratio), but the specific morphology depends on the preparation process and monomer ratio. The heterophasic propylene copolymers employed in the process according to the present invention can be produced using any conventional technique known to those skilled in the art, for example, multistage process polymerization such as bulk polymerization, gas phase polymerization, slurry polymerization , solution polymerization or any combination thereof. Any conventional catalyst systems, for example Ziegler-Natta or metallocene can be used. Such techniques and catalysts are described, for example, in WO06/010414; Polypropylene and other Polyolefins, by Ser van der Vem, Studies in Polymer Science 7, Elsevier 1990; WO06/010414, US4399054 and US4472524.
[00371] The molar mass of the polyolefin obtained during polymerization can be controlled by adding hydrogen or any other agent known to be suitable for the purpose during polymerization. Polymerization can be carried out in a continuous or batch mode. Pulp, bulk and gas phase polymerization processes, multistage processes of each of these types of polymerization processes, or combinations of the different types of polymerization processes in a multistage process are contemplated herein. Preferably, the polymerization process is a single-stage or a multi-stage gas-phase process, e.g. a two-stage gas-phase process, e.g., where at each stage a gas-phase process is used whether or including one is used. separate prepolymerization reactor (small).
[00372] Examples of gas phase polymerization processes include stirred bed reactors and fluidized bed reactor systems; such processes are well known in the art. Typical gas phase olefin polymerization reactor systems typically comprise a reactor vessel to which an olefin monomer(s) and a catalyst system can be added and which contains an agitated bed of growing polymer particles. Preferably, the polymerization process is a single-stage or multi-stage gas-phase process, for example a 2-stage gas-phase process where at each stage a gas-phase process is used.
[00373] As used herein, "gas phase polymerization" is the manner of an ascending fluid medium, the fluid medium containing one or more monomers, in the presence of a catalyst through a fluidized bed of polymer particles maintained in a fluidized state by fluidizing means optionally aided by mechanical agitation. Examples of gas phase polymerization are fluid bed, horizontal stirred bed and vertical stirred bed.
[00374] "Fluid bed", "fluidized", or "fluidization" is a gas-solid contact process where a bead of finely divided polymer particles is lifted and agitated by an ascending stream of gas optionally aided by mechanical agitation. In In a "stirred bed" upstream gas velocity is less than the fluidization limit.
[00375] A typical gas phase polymerization reactor (or gas phase reactor) includes a vessel (i.e. the reactor), the fluidized bed, a product discharge system and may include a mechanical stirrer, a distribution plate , inlet and outlet piping, a cycle gas cooler or heat exchanger. The vessel may include a reaction zone and may include a velocity reduction zone, which is located above the reaction zone (viz. the bed). The fluidizing medium can include propylene gas and at least one other gas such as an olefin and/or a carrier gas such as hydrogen or nitrogen. Contact can take place by feeding catalyst composition into the polymerization reactor and introducing olefin into the polymerization reactor. In one embodiment, the process includes contacting olefin with a cocatalyst. The cocatalyst can be mixed with the procatalyst (pre-mix) before introducing the procatalyst into the polymerization reactor. Cocatalyst can also be added to the polymerization reactor independently of the procatalyst. Independent introduction of the cocatalyst into the polymerization reactor can occur (substantially) simultaneously with the procatalyst feed.
[00376] The olefin according to the invention can be selected from mono- and diolefins containing from 2 to 40 carbon atoms. Suitable olefin monomers include alpha olefins such as ethylene, propylene, alpha olefins having between 4 and 20 carbon atoms (viz. C420), such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 - heptene, 1-octene, 1-decene, 1-dodecene and the like; C4-C20 diolefins such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-vinyl-2-norbornene (VNB), 1,4-hexadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene ; vinyl aromatic compounds having between 8 and 40 carbon atoms (viz. C8-C40) including styrene, o-, m- and p-methyl styrene, divinyl benzene, vinyl biphenyl, vinyl naphthalene; and halogen substituted C8-C40 vinyl aromatics such as chlorostyrene and fluorostyrene.
[00377] Preferably, the olefin is propylene or a mixture of propylene and ethylene, to result in a polymer based on propylene, such as propylene homopolymer or olefin-propylene copolymer. The olefin can be an alpha olefin having up to 10 carbon atoms, such as ethylene, butane, hexane, heptane, octene. A propylene copolymer is herein intended to include both so-called random copolymers which typically have relatively low comonomer content, for example up to 10 mole %, as well as so-called impact PP copolymers or heterophasic PP copolymers comprising higher contents of comonomer, for example, from 5 to 80 mole %, more typically from 10 to 60 mole %. PP impact copolymers are actually combinations of different propylene polymers; such copolymers can be produced in one or two reactors and can be combinations of a first component of low comonomer content and high crystallinity, and a second component of high comonomer content having low crystallinity or even rubber-like properties. Such random and impact copolymers are well known to those skilled in the art. A random propylene-ethylene copolymer can be produced in a reactor. PP impact copolymers can be produced in two reactors: polypropylene homopolymer can be produced in a first reactor; the contents of the first reactor are subsequently transferred to a second reactor into which ethylene (and optionally propylene) is introduced. This results in production of a propylene-ethylene copolymer (ie, an impact copolymer) in the second reactor.
[00378] The present invention also relates to a polyolefin, preferably a polypropylene obtained or obtainable through a process, comprising contacting an olefin, preferably propylene or a mixture of propylene and ethylene with the procatalyst according to the present invention . The terms polypropylene and propylene-based polymer are used interchangeably herein. The polypropylene can be a homopolymer of propylene or a mixture of propylene and ethylene, such as a copolymer based on propylene, for example, propylene-heterophasic olefin copolymer; propylene-random olefin copolymer, preferably the olefin in propylene based copolymers being a C2 or C4-C6 olefin, such as ethylene, butylene, pentene or hexene. Such propylene-based (co)polymers are known to those skilled in the art; they are also described above.
[00379] The present invention also relates to a polyolefin, preferably a propylene-based polymer obtained or obtainable through a process as described herein above, comprising contacting propylene or a mixture of propylene and ethylene with a catalyst system according to present invention.
[00380] In one embodiment, the present invention relates to the production of a polypropylene homopolymer. For such a polymer, properties such as isotacticity and stiffness and emission can be important.
[00381] "Comonomer content" or ""C2 content" in the context of the present invention means the percentage by weight (% by weight) of respectively comonomer or ethylene incorporated in the total polymer weight obtained and measured with FT-IR. FT-IR process was calibrated using NMR data.
MFR is preferably from about 0.01 g/10 minutes to about 2000 g/10 minutes, or from about 0.01 g/10 minutes to about 1000 g/10 minutes; or from about 0.1 g/10 minutes to about 500 g/10 minutes, or from about 0.5 g/10 minutes to about 150 g/10 minutes, or from about 1 g/10 minutes to about 100 g/10 minutes.
[00383] The olefin polymer obtained in the present invention is considered to be a thermoplastic polymer. The thermoplastic polymer composition according to the invention may also contain one or more of the usual additives such as those mentioned above, including stabilizers, for example thermal stabilizers, antioxidants, UV stabilizers; dyes such as pigments and dyes; clarifiers; surface tension modifiers; lubricants; flame retardants; flow enhancement agents; plasticizers; anti-aesthetic agents; impact modifiers; blowing agents; filling materials and reinforcing agents; and/or components that improve interfacial bonding between polymer and filler material, such as maleated polypropylene, in case the thermoplastic polymer is a polypropylene composition. Those skilled in the art can easily select any appropriate combination of additives and additive amounts without undue experimentation.
[00384] The amount of additives depends on their type and function; typically it is from about 0 to about 30% by weight; preferably from 0 to about 20% by weight; more preferably from 0 to about 10% by weight and more preferably from 0 to about 5% by weight based on the total composition. The sum of all components added in a process to form polyolefins, preferably propylene-based polymers or their compositions should add up to 100% by weight.
[00385] The thermoplastic polymer composition of the invention can be obtained by mixing one or more of the thermoplastic polymers with one or more additives through the use of any suitable means. Preferably, the thermoplastic polymer composition of the invention is manufactured in a form that allows easy processing into an article formed in a subsequent step, such as in pellet or granule form. The composition can be a mixture of different pellets or particles; as a combination of a thermoplastic polymer and a master batch of nucleating agent composition, or a combination of pellets of a thermoplastic polymer comprising one of the two nucleating agents and a particle comprising the other nucleating agent, possibly pellets of a thermoplastic polymer comprising said other nucleating agent. Preferably, the thermoplastic polymer composition of the invention is in pellet or granule form as obtained by mixing all components in an apparatus such as an extruder; the advantage being a composition with homogeneous and well-defined concentrations of the nucleating agents (and other components).
[00386] The invention also relates to the use of polyolefins, preferably propylene-based polymers (also called polypropylenes) according to the invention in injection molding, blow molding, extrusion molding, compression molding, molding, molding of thin wall injection, etc., eg in food contact applications.
[00387] Furthermore, the invention relates to a shaped article comprising the polyolefin, preferably the propylene-based polymer according to the present invention.
[00388] The polyolefin, preferably the propylene-based polymer according to the present invention can be made into shaped (semi) finished articles using a variety of processing techniques. Examples of suitable processing techniques include injection molding, injection compression molding, thin wall injection molding, and extrusion compression molding. Injection molding is widely used for producing articles such as, for example, covers and closures, batteries, buckets, containers, automotive exterior parts such as bumpers, automotive interior parts such as instrument panels, or automotive parts under the hood. Extrusion is, for example, widely used for producing articles such as rods, sheets, films and tubes. Thin wall injection molding can, for example, be used to manufacture thin wall packaging applications for both food and non-food segments. This includes buckets and containers and tubes of margarine/yellow shortenings and dairy cups.
[00389] It is noted that the invention relates to all possible combinations of features recited in the claims. Features described in the description can still be combined.
[00390] Although the invention has been described in detail for purposes of illustration, it is understood that such detail is solely for that purpose and variations may be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the claims.
[00391] It is further noted that the invention relates to all possible combinations of features described herein, in particular those combinations of features which are present in the claims are preferred.
[00392] It is further noted that the term 'comprising' does not exclude the presence of other elements. However, it is also to be understood that the description of a product comprising certain components also shows a product consisting of these components. Similarly, it is also to be understood that a description of a process comprising certain steps also shows a process consisting of these steps.
[00393] The invention will be further elucidated with the following examples without being limited thereto. Brief Description of Figures
[00394] Figure 1 (Fig. 1) shows the oligomer content versus the log (MFR) of propylene homopolymers produced using catalyst I and different external donors.
[00395] Figure 2 (Fig. 2) shows the oligomer content versus the log (MFR) of propylene homopolymers produced using catalyst II and different external donors. Experimental Procatalyst I
[00396] Procatalyst I is prepared according to the process shown in US 4,866,022. This patent shows a catalyst component comprising a product formed by: A. forming a solution of a species containing magnesium from a carbonate of magnesium or a magnesium carboxylate; B. precipitation of oily particles from such a magnesium-containing solution by treatment with a transition metal halide and an organo silane having a formula: RnSiR'4-n, where n = 0 to 4 and where R is hydrogen or a an alkyl, haloalkyl or aryl radical containing one to about ten carbon atoms or a halo silyl radical or a haloalkyl silyl radical containing one to about eight carbon atoms, and R' is OR or a halogen; C. reprecipitating said solid particles from a mixture containing a cyclic ether; and D. treatment of reprecipitated particles with a transition metal composite and an electron donor. This process for preparing a catalyst is incorporated in the present patent application by reference. Procatalyst II
[00397] Procatalyst II was prepared according to the process described in US 5,093,415 to Dow. This patent shows an improved process for preparing a catalyst. Said process includes a reaction between titanium tetrachloride, diisobutyl phthalate, and magnesium dietoxide to obtain a solid material. This solid material is then slurried with titanium tetrachloride in a solvent and phthaloyl chloride is added. The reaction mixture is heated to obtain a solid material which is re-slurried in a solvent with titanium tetrachloride. Again this was heated and a solid collected. Again the solid was slurried once more in a titanium tetrachloride solution to obtain a catalyst. Procatalyst III A. Grignard formation step
[00398] A stirred flask, fitted with a reflux condenser and a funnel, was filled with magnesium powder (24.3 g). The flask was placed under nitrogen. The magnesium was heated to 80°C for 1 hour, after which dibutyl ether (DBE, 150 mL), iodine (0.03 g) and n-chloro butane (4 mL) were added successively. After the iodine color had disappeared, the temperature was raised to 80°C and a mixture of n-chloro butane (110 ml) and dibutyl ether (750 ml) was slowly added over 2.5 hours. The reaction mixture was stirred for another 3 hours at 80°C. Then stirring and heating were stopped and the small amount of solid matter was allowed to settle for 24 hours. By decanting the colorless solution above the precipitate, a solution of butyl magnesium chloride (step A reaction product) with a concentration of 1.0mol Mg/L was obtained. B. Preparation of intermediate reaction product
[00399] 250 mL of dibutyl ether were introduced into a 1 L reactor fitted with an impulse stirrer and two baffles. The reactor was heated with a thermostat to 35oC and the stirring speed was maintained at 200 rpm. Then 360 mL of a cooled (to 15oC) solution of the Grignard reaction product as prepared in A and 180 mL of a cooled (to 15oC) solution of 38 mL of tetraethoxy silane (TES) in 142 mL of DBE were metered into the reactor for 400 minutes with preliminary mixing in a mini-mixer of 0.15 mL volume, which was cooled to 15oC by means of cold water circulating in the mini-mixer jacket. The pre-mix time was 18 seconds in the mini-mixer and the connecting tube between the mini-mixer and the reactor. The agitation speed in the mini mixer was 1000 rpm. At the end of dosing, the reaction mixture was kept at 35oC for 0.5 hours. Then the reactor was heated to 60oC and kept at this temperature for 1 hour. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation. The solid substance was washed three times using 300 ml of heptane. As a result, a white solid reaction product was obtained and suspended in 200 ml of heptane.
[00400] Under an inert atmosphere of nitrogen at 20°C a 250 ml glass flask equipped with a mechanical stirrer is filled with a slurry of 5 g of step B reaction product dispersed in 60 ml of heptane. Subsequently, a solution of 0.86 ml of methanol (MeOH/Mg = 0.5 mol) in 20 ml of heptane is dosed under stirring for 1 hour. After maintaining the reaction mixture at 200oC for 30 minutes, the slurry was slowly allowed to warm to 300oC for 30 minutes and kept at this temperature for another 2 hours. Finally the supernatant liquid is decanted from the solid reaction product which has been washed once with 90 ml of heptane at 300°C. C. Procatalyst Preparation
[00401] A reactor was placed under nitrogen and 125 mL of titanium tetrachloride was added to it. The reactor was heated to 90oC and a suspension, containing about 5.5 g of the support obtained in step C in 15 ml of heptane, was added to it under stirring. The reaction mixture was kept at 90oC for 10 minutes. Then ethyl benzoate was added (molar ratio 4 EB/Mg = 0.15). The reaction mixture was held for 60 minutes. Then the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation, after which the solid product was washed with chloro benzene (125 mL) at 90°C for 20 minutes. The washing solution was removed by decantation, after which a mixture of titanium tetrachloride (62.5 ml) and chloro benzene (62.5 ml) was added. The reaction mixture was kept at 90oC for 30 minutes. After which the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation, after which a mixture of titanium tetrachloride (62.5 ml) and chloro benzene (62.5 ml) was added. Then di-n-butyl phthalate (DBP) (mole ratio DBP/Mg = 0.15) in 3 mL of chlorobenzene was added to the reactor and the reaction mixture temperature was increased to 115 °C. The reaction mixture was kept at 115oC for 30 minutes. After which the stirring was stopped and the solid substance was allowed to settle. The supernatant was removed by decantation, after which a mixture of titanium tetrachloride (62.5 ml) and chloro benzene (62.5 ml) was added. The reaction mixture was kept at 115oC for 30 minutes, after which the solid substance was allowed to settle. The supernatant was decanted off and the solid was washed five times using 150 ml of heptane at 600°C, after which the procatalyst, suspended in heptane, was obtained. Batch Propylene Polymerization Experiments
[00402] Propylene polymerization experiments (Table 1) were performed using procatalysts I, II and III described above. Triethyl aluminum was used as a cocatalyst, and several external electron donors (ED) were employed. Experiments were carried out at different molar ratios of H2/C3. Examples represented with CE are comparative examples which are not in accordance with the present invention.
[00403] The copolymerization of propylene and ethylene was carried out in a stainless steel reactor with a volume of 1800 mL. Under a nitrogen atmosphere, the cocatalyst (TEAL) and procatalyst synthesized according to the procedure described above and the external electron donor were dosed into the reactor as solutions or pastes in heptane. 10-15 mg of procatalyst were used. The molar ratio of cocatalyst to titanium (from procatalyst) was set to 160, and the Si/Ti ratio was set to 9. During this dosing, the reactor temperature was kept below 30°C. Subsequently, the reactor was pressurized using a fixed ratio of propylene and hydrogen, and the temperature and pressure were raised to their set points (70oC and 20 barg). After the pressure set point was reached, polymerization was continued for 60 minutes. During the polymerization reaction the cap composition of propylene and hydrogen gas was controlled using mass flow meters and in-line GC control. After reaching the polymerization time, the reactor was depressurized and cooled to ambient conditions. The propylene polymer thus obtained was removed from the reactor and stored in aluminum bags. Polymer powders were pre-mixed with the additives (end product amounts: 2000 ppm thermal stabilizer, 2000 ppm process stabilizer and 900 ppm Ca stearate) and extruded into ribbons using a mini-composer. Abbreviations and measurement processes:
[00404] With C-donor is intended: cyclohexyl methyl dimethyl silane
[00405] With D-donor is intended: dicyclopentyl dimethyl silane.
[00406] - PP yield, kg/g is the amount of polypropylene obtained per gram of catalyst system.
[00407] - H2/C3 is the molar ratio of hydrogen to propylene in the reactor gas cap, measured by in-line gas chromatography.
[00408] - Oligomer content refers to the amount in ppm in a polymer sample of the C6-C33 hydrocarbon oligomers, which typically originate from the low molecular weight material in the polymer composition. Thermal desorption of these oligomers from polymer samples was performed using a Markes TD100. A 50-100 mg weighed sample of the produced polymer tape was loaded into an inert metal tube. This tube was briefly purged at room temperature using helium. The tube was heated to 200oC and a carrier gas was passed over the molten polymer sample for 30 minutes. Upon exiting the tube, the carrier gas was passed through a cold siphon, condensing the volatile components released from the polymer. Subsequently, the cold siphon was quickly heated to 250oC and volatiles were injected into an Agilent GC, using a CP-SIL5 GC column (25 meters) to separate the individual components. Component identification was performed using an MS detector and quantification was performed using an FID detector. Table 1. Analysis and polymerization data

[00409] From figures 1 and 2, and the data in Table 1 above, it is clear that with catalysts and ll, the use of nPTES as an external donor results in materials with lower oligomer content compared to materials with similar MFR values , manufactured using other donors. Also for Catalyst II, material produced using nPTMS shows higher oligomer content than a material with similar range for MFR value produced using nPTES as external donor. This can be seen when comparing CE12 with Example 6 and when comparing CE10 with Example 5.
Therefore, with the external donor of Formula IV: nPTES, it is possible to obtain polypropylene (homopolymers) having lower emissions (as shown by the lower oligomer content) than polypropylene having similar MFR values with a different external donor.
[00411] Therefore in another aspect, the invention relates to a polymer based on propylene, such as homopolymer of propylene or copolymer of propylene - olefin, for example, copolymer of propylene - ethylene, for example, having a content of ethylene based on propylene-ethylene copolymer in the range of 1 to 10% by weight, for example in the range of 1 to 8, for example in the range of 1 to 5% by weight; or heterophasic propylene copolymers,
[00412] - having a melt flow index in the range of 30 to 1000, for example 40 to 500 as determined in accordance with the process discussed above;
[00413] - a ratio of the oligomer content in ppm to the log(melt flow index) of less than 1650, e.g. less than 1550, where the oligomer content is measured according to the process discussed above;
[00414] - where in log (MFR) = 2.1, the oligomer content is less than 1850 ppm, where this is determined as discussed above.

权利要求:
Claims (11)
[0001]
1. Process for the preparation of a catalyst system suitable for olefin polymerization, said process characterized by the fact that it comprises the steps of: providing a support based on magnesium; optionally activate said magnesium-based support; contacting said magnesium-based support with a Ziegler-Natta type catalytic species, and one or more internal electron donors to obtain a procatalyst, and contacting said procatalyst with a cocatalyst and at least one external donor; wherein the at least one outer electron donor is n-propyl triethoxy silane and wherein the inner donor is selected from amino benzoates represented by Formula XI:
[0002]
2. Process according to claim 1, characterized in that it comprises the steps of: (i) preparing a magnesium-based support by heating a carbonated magnesium compound of the formula MgR'R"xCO2 in which R' is an alkoxide or aryloxide group, R" is an alkoxide group, aryloxide or halogen group, and has a value between about 0.1 and 2.0 at a temperature above 100oC for a period of time sufficient to cause completeness loss of CO2; (ii) contacting the resulting product with a tetravalent titanium halide such as the Ziegler-Natta type catalytic species in the presence of a hydrocarbon halo and an internal electron donor; and (iii) contacting the resulting halogenated product with a tetravalent titanium halide; and contacting said product obtained with a cocatalyst and at least one external donor; wherein the at least one external electron donor is n-propyl triethoxy silane.
[0003]
3. Process according to claim 1, characterized in that it comprises the step of preparing a magnesium-based support through halogenation of a magnesium compound of the formula MgR'R", in which R' and R" are alkoxide groups containing 1 to 8 carbon atoms, with titanium tetrachloride, in the presence of: (1) an aromatic hydrocarbon halo containing 6 to 12 carbon atoms and 1 to 2 halogen atoms and; (2) a polycarboxylic acid ester derived from a branched or unbranched monohydric alcohol containing 1 to 12 carbon atoms, and a monocyclic or polycyclic aromatic compound containing 8 to 20 carbon atoms and two carboxyl groups which are bonded to atoms of carbon ortho from the ring structure and contacting the product obtained with a cocatalyst and at least one external donor; wherein the at least one external electron donor is n-propyl triethoxy silane.
[0004]
4. Process according to claim 1, characterized in that it comprises the steps of: preparing the magnesium-based support by forming a solution of a species containing magnesium from a magnesium carbonate or a magnesium carboxylate , precipitating solid particles from such a magnesium-containing solution by treatment with a transition metal halide and an organo silane having the formula: RnSiR'4-n, where n = 0 to 4 and where R is hydrogen or an alkyl, a haloalkyl or an aryl radical containing one to about ten carbon atoms or a halo silyl radical or a halalkyl silyl radical containing one to about eight carbon atoms, and R' is OR or a halogen reprecipitating such solid particles of a mixture containing a cyclic ether and contacting the product obtained with a cocatalyst and at least one external donor; wherein the at least one external electron donor is n-propyl triethoxy silane.
[0005]
5. Process according to claim 1, characterized in that it comprises the steps of: (A) providing said pro-catalyst obtainable via a process comprising the steps of: (i) contacting a compound R4zMgX42- z with an alkoxy- or aryloxy-containing silane compound to yield a first intermediate reaction product, being a solid Mg(OR1)xX12-x, wherein: R4 is the same as R1 being a linear, branched, or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxy carbonyl, or alkyl aryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms and preferably has between 1 and 20 carbon atoms; X4 and X1 are each independently selected from the group consisting of fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-), preferably chloride; z is in a range greater than 0 and less than 2, where 0 < z < 2; (ii) optionally contacting Mg(OR1)xX2-x solid obtained in step (i) with at least one activation compound selected from the group consisting of activation electron donors and metal alkoxide compounds of formula M1(OR2)vw(OR3 )w or M2(OR2)vw(R3)w, to obtain a second intermediate product; wherein M1 is a metal selected from the group consisting of Ti, Zr, Hf, Al or Si; M2 is a metal being Si; v is the valence of M1 or M2; R2 and R3 are each a linear, branched or cyclic hydrocarbyl group independently selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof; wherein said hydrocarbyl group may be substituted or unsubstituted, may contain one or more heteroatoms, and preferably has between 1 and 20 carbon atoms; (iii) contacting the first or second intermediate reaction product, obtained respectively in step (i) or (ii), with a Ti-compound containing halogen and optionally an internal electron donor to obtain said procatalyst; (B) contacting said procatalyst with a cocatalyst and at least one external electron donor being n-propyl triethoxy silane.
[0006]
6. Process according to any one of claims 1 to 5, characterized in that it is essentially phthalate-free.
[0007]
7. Process according to any one of claims 1 to 6, characterized in that the internal electron donor is selected from the group consisting of: 4-[benzoyl(methyl)amino]pentan-2yl benzoate; 2,2,6,6-tetramethyl-5-(methylamino)heptan-3-ol dibenzoate; 4-[benzoyl(ethyl)amino]pentan-2-yl benzoate; 4-(methylamino)pentan-2-yl bis-(4-methoxy)benzoate; 3-[benzoyl(cyclohexyl)amino]-1-phenylbutyl benzoate; 3-[benzoyl(propan-2-yl)amino]-1-phenylbutyl; 4-[benzoyl(methyl)amino]-1,1,1-trifluoropentan-2-yl; 3-(methylamino)-1,3-diphenyl-propan-1-ol dibenzoate; 3-(methyl)aminopropane-1-ol dibenzoate; 3-(methyl)amino-2,2,-dimethyl propane-1-ol dibenzoate, and 4-(methylamino)pentan-2-yl bis-(4-methoxy)benzoate.
[0008]
8. Process according to any one of claims 1 to 7, characterized in that the internal electron donor is activated by an activator, preferably in which the activator is a benzamide according to formula X,
[0009]
9. Catalyst system, characterized in that it is obtained or obtainable through the process, as defined in any one of claims 1 to 8.
[0010]
10. Process for preparing a polyolefin, characterized in that it contacts at least one olefin, preferably polypropylene or a mixture of propylene and ethylene with the catalyst system, as defined in claim 9.
[0011]
11. Polyolefin, characterized in that it is obtained or obtainable through a process as defined in claim 10.

类似技术:

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BR112016014175B1|2021-06-22|CATALYST SYSTEM FOR POLYMERIZATION OF AN OLEFIN, ITS PREPARATION PROCESS, POLYOLEFIN AND PREPARATION PROCESS

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BR112016014183B1|2021-10-05|POLYOLEFIN, CATALYST SYSTEM FOR POLYMERIZATION OF AN OLEFIN, PROCESSES FOR THE PREPARATION OF THE SAME AND MOLDED ARTICLE FROM POLYOLEFIN

同族专利:

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公开号 | 公开日

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EP3083723B1|2022-01-19|

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US20160333121A1|2016-11-17|

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WO2015091982A1|2015-06-25|

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法律状态:
2019-12-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-15| B06J| Correction of requirement [chapter 6.10 patent gazette]|Free format text: REFERENTE A PUBLICACAO 6.1 - RPI 2603 - 24.11.2020 |

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2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-22| 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 19/12/2014, 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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EP13199165.5|2013-12-20|

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EP13199165|2013-12-20|

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EP14170829.7|2014-06-02|

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EP14170829|2014-06-02|

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