Ziegler-Natta (pro)catalytic systems prepared with (multialkoxy)silane compounds

Abstract

A Ziegler-Natta (pro)catalyst system prepared with an external electron donor compound, a method for synthesizing the same, a method for olefin polymerization using the same, and a polyolefin polymer prepared thereby. The external electron donor compound is a (multialkoxy)silane.

Description

[Technical Field]

[0001] Ziegler-Natta (pro) catalyst systems prepared with external electron donor compounds, methods for their synthesis, methods for olefin polymerization using same, and polyolefin polymers prepared thereby.

[0002] Introduction Published patent applications and patents in or near the field include U.S. Patent Nos. 4,242,479, 4,522,930, 4,927,797, 5,869,418, 7,196,152(B2), 7,371,806(B2), 10,113,018(B2), Canadian Patent No. 2,510,679(C), Chinese Patent No. 103,304,869(B), Chinese Patent No. 108,586,640 (A), European Patent Nos. 0731114(A1), 1017493(A1), U.S. Patent Application Publication No. 20180030179(A1), International Publication Nos. 2002 / 038624(A1), 2005 / 058982, 2009 / 027270(A1), 2009 / 148487(A1), and 2014 / 102813(A1). See also Iidar ​​Salakhov et al., Polypropylene synthesis in liquid monomer with titanium-magnesium catalyst: effect of different (multi-alkoxy)silanes as external donors, Journal of Polymer Research, June 2019, 26(6). DOI: 10.1007 / s10965-019-1794-5. Summary of the Invention

[0003] We have discovered external electron donor modified Ziegler-Natta procatalyst systems, external electron donor compound modified Ziegler-Natta catalyst systems made therefrom, methods for making them, methods for polymerizing olefin monomers using the catalyst systems, and polyolefin polymers made thereby. DETAILED DESCRIPTION OF THE INVENTION

[0004] Ziegler-Natta procatalyst systems modified with external electron donors, Ziegler-Natta catalyst systems modified with external electron donor compounds made therefrom, methods for making them, methods for polymerizing olefin monomers using the catalyst systems, and polyolefin polymers made thereby.

[0005] A procatalyst system consisting essentially of a blend of a preformed solid procatalyst system and a (multialkoxy)silane. The procatalyst system is a Ziegler-Natta type procatalyst system suitable for preparing a Ziegler-Natta type olefin polymerization catalyst prepared by contacting the procatalyst system with an activator. Depending on how the (multialkoxy)silane is used and how it is combined with the preformed solid procatalyst in the procatalyst system, the (multialkoxy)silane functions as an external electron donor compound (EEDC) in the procatalyst system. The preformed solid procatalyst consists essentially of a titanium compound, magnesium chloride solid, and optionally silica. The magnesium chloride solid consists essentially of MgCl2 and at least one of a cyclic (C2-C6) ether, a (C1-C6) alcohol, or a hydroxyl-substituted cyclic (C3-C7) ether. The procatalyst system does not contain any other electron donor organic compounds. The procatalyst system becomes a catalyst system when activated with an activator.

[0006] The polymerization process may comprise a gas phase polymerization carried out under gas phase polymerization conditions in a gas phase polymerization reactor, a slurry phase polymerization carried out under slurry phase polymerization conditions in a slurry phase polymerization reactor, a liquid phase polymerization carried out under liquid phase polymerization conditions in a liquid phase polymerization reactor, or a combination of any two thereof. For example, the combination may comprise two successive gas phase polymerizations, or the combination may comprise a slurry phase polymerization followed by a gas phase polymerization.

[0007] Polyolefin polymers made by the polymerization method have at least one improved property compared to polyolefin polymers made by a comparable Ziegler-Natta catalyst system lacking a (multialkoxy)silane as an external electron donor.

[0008] Additional inventive aspects, some of which are numbered for ease of cross-referencing, are as follows:

[0009] Aspect 1. A procatalyst system suitable for making an olefin polymerization catalyst, consisting essentially of a blend of (A) a preformed solid procatalyst and (B) a (multialkoxy)silane, wherein (A) the preformed solid procatalyst consists essentially of a titanium compound, a magnesium chloride solid, and optionally silica, wherein the magnesium chloride solid consists essentially of MgCl and at least one oxa-heterocycle, and the procatalyst system is free of any other electron donor organic compounds. Depending on how the (B) (multialkoxy)silane is used and how it is combined with the preformed solid procatalyst in the (A) procatalyst system, the (B) (multialkoxy)silane functions as an external electron donor compound (EEDC) in the procatalyst system. The titanium compound is supported by or on the magnesium chloride solid, and, if silica is present, is supported by or on the silica.

[0010] Aspect 2. (B) The (multialkoxy)silane has the formula (I): R 1 m H n Si(OR 2 ) 4-m-n (I) is an aromatic (multialkoxy)silane of the formula (I), wherein subscript m is 0 and subscript n is 0, 1, or 2, or subscript m is 1 and subscript n is 0 or 1, or subscript m is 2 and subscript n is 0; and R 1 But unsubstituted (C1~C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C10 ) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, unsubstituted (C6-C 12 ) aryl group, (C1-C 10 ) Alkyl-substituted (C6-C 10 ) aryl group, or unsubstituted (C7-C 20 ) an aralkyl group, and R 2 is unsubstituted (C1 to C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C 10 ) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, or unsubstituted (C7-C 20 2. The procatalyst system of embodiment 1, wherein R is an aralkyl group.

[0011] Aspect 3. (B) The (multialkoxy)silane has the formula (Ia): R 1 m Si(OR 2 ) 4-m-n (Ia) is an aromatic (multialkoxy)silane of formula (Ia), wherein the subscript m is 0, 1, or 2; and R 1 But unsubstituted (C1~C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C 10 ) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, unsubstituted (C6-C 12 ) aryl group, (C1-C 10 ) Alkyl-substituted (C6-C 10 ) aryl group, or unsubstituted (C7-C 20 ) an aralkyl group, and R 2 is unsubstituted (C1 to C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C 10) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, or unsubstituted (C7-C 20 3. The procatalyst system of any one of the preceding claims, wherein R is an aralkyl group.

[0012] Aspect 4. The procatalyst system of any one of Aspects 1-3, wherein the magnesium chloride solid consists essentially of MgCl and an oxaheterocycle selected from the group consisting of unsubstituted cyclic (C2-C6) ether, furan, dihydrofuran, pyran, dihydropyran, tetrahydropyran, 1,4-dioxane, difuranyl-(C1-C6)alkylene, bis(tetrahydrofuranyl)-(C1-C6)alkylene, and a (C1-C3) alkyl-substituted derivative of any one of these.

[0013] Embodiment 5. The procatalyst system of any one of embodiments 1-3, wherein the magnesium chloride solid consists essentially of MgCl2 and an oxa-heterocycle selected from tetrahydrofuran.

[0014] Aspect 6. The titanium compound is at least one compound of formula (III): TiX4(III), where each X is independently Cl, Br, I, or (C1-C 12 6. The procatalyst system of any one of aspects 1-5, wherein X is (C1-C6)alkoxy or (C1-C6)alkoxy. In some aspects, each X is Cl; alternatively, each X is (C1-C6)alkoxy or (C4-C6)alkoxy.

[0015] Aspect 7. The procatalyst system of any one of Aspects 1-6, further consisting essentially of a ligand-metal complex of Formula (IV): MX4(IV), wherein M is Hf or Zr, and each X is independently Cl, Br, I, or (C1-C6)alkoxy.

[0016] Embodiment 8. A method of synthesizing a procatalyst system, the method comprising: drying a solution consisting essentially of a mixture, and optionally silica, and free of (B) a (multialkoxy)silane and any other electron donor organic compound, the solution consisting essentially of a titanium compound, magnesium chloride, and at least one oxa-heterocycle mixed in a hydrocarbon solvent, thereby removing the hydrocarbon solvent from the mixture and crystallizing the magnesium chloride to obtain (A) a pre-made solid procatalyst; and contacting the (A) pre-made solid procatalyst with (B) a (multialkoxy)silane, thereby producing the procatalyst system blend of any one of Embodiments 1-7.

[0017] Embodiment 9. A method of making a catalyst system suitable for polymerizing olefins, comprising contacting a procatalyst system according to any one of embodiments 1-7, or a procatalyst system made by the method of embodiment 8, with an effective activating amount of (C) an activator, thereby making a catalyst system, wherein the catalyst system is free of any other electron donor organic compound and is suitable for polymerizing olefins.

[0018] Aspect 10. A method of making a catalyst system suitable for polymerizing olefins, comprising simultaneously or sequentially contacting an activating effective amount of (C) an activator, (B) a (multialkoxy)silane, and (A) a pre-formed solid procatalyst, thereby making the catalyst system, wherein (A) the pre-formed solid procatalyst consists essentially of a titanium compound, magnesium chloride solids, and optionally silica, wherein the magnesium chloride solids consist essentially of MgCl and at least one oxa-heterocycle, and wherein the catalyst system is free of any other electron donor organic compounds and is suitable for polymerizing olefins.

[0019] Aspect 11. A catalytic system made by the method of aspect 9 or 10. The catalytic system is believed to have a functionally modified or attenuated active site.

[0020] Aspect 12. A method of synthesizing a polyolefin polymer, the method comprising contacting at least one olefin monomer with the catalyst system of Aspect 11 under effective polymerization conditions in a polymerization reactor, thereby making a polyolefin polymer. In some embodiments, the polyolefin polymer is a poly(ethylene-co-1-alkene) copolymer, alternatively a poly(ethylene-co-(C4-C8)1-alkene) copolymer, or alternatively a poly(ethylene-co-1-hexene) copolymer.

[0021] Aspect 13. The embodiment of any one of aspects 2-12, wherein subscript m is 0, 1, or 2, and subscript n is 0. In some aspects, subscript m is 0 and subscript n is 0; alternatively, subscript m is 1 and subscript n is 0; alternatively, subscript m is 2 and subscript n is 0.

[0022] Aspect 14. The embodiment of any one of Aspects 2 and 4-12, wherein the (B)(multialkoxy)silane is a compound of Formula (I), wherein the subscript m is 0 and the subscript n is 1; alternatively, the subscript m is 0 and the subscript n is 2; alternatively, the subscript m is 1 and the subscript n is 1. In some aspects, the subscript m is 0 and the subscript n is 1 or 2; alternatively, the subscript m is 1 and the subscript n is 1. When the subscript n is 1 or 2, the compound of Formula (I) is a silicon hydride (Si—H)-functional (multialkoxy)silane. Without being bound by theory, it is believed that the Si—H functionality can react with hydroxyl groups under catalytic and non-catalytic conditions via a dehydrogenation mechanism. The hydroxyl groups, if present, may be present in the silica gel or may be generated in situ by partial hydrolysis of the (B)(multialkoxy)silane with ambient moisture.

[0023] Aspect 15. (B) (multialkoxy)silanes have at least one R 1 But unsubstituted (C6~C 12 ) aryl group, (C1-C 10) Alkyl-substituted (C6-C 10 ) aryl group, or unsubstituted (C7-C 20 ) an aralkyl group, and / or at least one R 2 is unsubstituted (C7~C 20 15. The embodiment of any one of aspects 2-14, wherein the group is aromatic, such as an aralkyl group.

[0024] Aspect 16. (B) (multialkoxy)silane is R 1 is unsubstituted (C6~C 12 ) aryl group, (C1-C 10 ) Alkyl-substituted (C6-C 10 ) aryl group, or unsubstituted (C7-C 20 ) an aralkyl group, and / or R 2 is unsubstituted (C7~C 20 15. The embodiment of any one of aspects 2-14, wherein the unsaturated group is an aralkyl group.

[0025] Aspect 17. The embodiment of any one of aspects 1-14, wherein the (B) (multialkoxy)silane is a tetraalkoxysilane (e.g., tetraethoxysilane), a trialkoxysilane (e.g., trimethoxysilane), an alkyltrialkoxysilane (e.g., propyltrimethoxysilane), or a dialkyldialkoxysilane (e.g., dicyclopentyldimethoxysilane).

[0026] Aspect 18. The embodiment of any one of aspects 1-14, wherein the (B) (multialkoxy)silane is selected from the group consisting of tetraethoxysilane, propyltrimethoxysilane, dicyclopentyldimethoxysilane, and methyl,cyclohexyldimethoxysilane.

[0027] Aspect 19. The embodiment of any one of aspects 1-18, wherein the oxaheterocycle is selected from the group consisting of furan, dihydrofuran, pyran, dihydropyran, tetrahydropyran, 1,4-dioxane, 2,2-difluanyl-propane, 2,2-bis(tetrahydrofuranyl)-propane, and tetrahydro-methylfuran. In some embodiments, the oxaheterocycle is furan or 2,2-difluanyl-propane. In some embodiments, the oxaheterocycle is dihydrofuran or dihydropyran. In some embodiments, the oxaheterocycle is pyran. In some embodiments, the oxaheterocycle is tetrahydropyran or 2,2-bis(tetrahydrofuranyl)-propane. In some embodiments, the oxaheterocycle is 1,4-dioxane. In some embodiments, the oxaheterocycle is tetrahydrofuran or tetrahydromethylfuran.

[0028] Aspect 20. A method of making a second catalyst system, the method comprising: a mixture of a solution of a titanium compound, magnesium chloride, and at least one oxaheterocycle mixed in a hydrocarbon solvent, the solution being free of (B) a (multi-alkoxy)silane and any other electron donor compounds; drying the mixture, thereby removing the hydrocarbon solvent from the mixture and crystallizing the magnesium chloride to obtain an (A) prefabricated solid procatalyst; contacting the (A) prefabricated solid procatalyst with an activating effective amount of (C) an activator, thereby making a first catalyst system; and contacting the first catalyst system with (B) a (multi-alkoxy)silane, thereby making a second catalyst system, the catalyst system being free of any other electron donor organic compounds.

[0029] Aspect 21. The embodiment of any one of aspects 1 to 20, wherein the optional other electron donor compound is a heteroorganic compound consisting of at least one heteroatom selected from a C atom, an H atom, an oxaheterocycle, and N, P, S, O other than the (B)(multialkoxy)silane, and a Si atom other than the (B)(multialkoxy)silane.

[0030] Aspect 22. A method of synthesizing a polyolefin polymer, comprising contacting the catalyst system of aspect 20 or 21 with at least one olefin monomer under effective polymerization conditions in a polymerization reactor, thereby producing a polyolefin polymer.

[0031] Aspect 23. A polyolefin polymer made by the method of aspect 12 or 22.

[0032] Procatalyst System. The procatalyst system is a new type of Ziegler-Natta procatalyst system. The procatalyst system consists essentially of a blend of (A) a preformed solid procatalyst and (B) a (multialkoxy)silane. In this context, "consists essentially of" (and its equivalents, such as "consisting essentially of") means that the procatalyst system does not contain a silicon-containing organic compound that is not a (multialkoxy)silane (B) and does not contain an oxygen-containing organic compound that is not an oxaheterocycle. The procatalyst system may also be free of an activator, otherwise an activator reacts with (A) the preformed solid procatalyst to form the catalyst system. Furthermore, the procatalyst system and catalyst systems made therefrom may be free of a nitrogen-containing compound that is an azaheterocycle.

[0033] Blend. A blend of (A) a preformed solid procatalyst and (B) a (multialkoxy)silane refers to a physical admixture of components (A) and (B). Similar to a procatalyst system, the blend does not contain a silicon-containing organic compound that is not a (multialkoxy)silane (B) and does not contain an oxygen-containing organic compound that is not an oxaheterocycle. The blend may also be free of an activator that would otherwise react with (A) the preformed solid procatalyst to form the catalyst system. Furthermore, the blend may be free of a nitrogen-containing compound that is an azaheterocycle. The blend is essentially prepared by preparing component (A) in the absence of component (B) and then physically mixing (A) and (B) together to obtain the blend. Therefore, because the blend is prepared after component (A) has been prepared or prepared, the blend may be referred to as a "post-preparation blend."

[0034] The blend of components (A) and (B) is compositionally and functionally different from a comparative in-situ blend prepared by mixing a titanium compound, a solution of magnesium chloride and an oxaheterocycle dissolved in a hydrocarbon solvent, and optionally silica, in the presence of (B), followed by solidifying the magnesium chloride. This is at least in part because the resulting comparative magnesium chloride solid prepared by in-situ blending essentially contains (B) (multialkoxy)silane trapped as an internal electron donor compound. However, this comparative feature is excluded by the aforementioned "consisting essentially of." Furthermore, a comparative catalyst system prepared by contacting a comparative in-situ blend with an activator will have essentially different composition and polymerization functionality than an inventive catalyst system prepared from an inventive procatalyst system consisting essentially of the inventive blend. This is at least in part because the resulting comparative catalyst system essentially contains (B) (multialkoxy)silane trapped as an internal electron donor compound.

[0035] (A) Preformed Solid Procatalyst. (A) Preformed Solid Procatalyst consists essentially of a titanium compound, magnesium chloride solids, and optionally silica, where the magnesium chloride solids consist essentially of MgCl and an oxaheterocycle. The terms "preformed" and "consist essentially of" are consistent with and reinforce the preceding description of the procatalyst systems and blends. Like the procatalyst systems and blends, component (A) does not contain (B) a silicon-containing organic compound that is not a (multialkoxy)silane and does not contain an oxygen-containing organic compound that is not an oxaheterocycle. Component (A) also does not contain an activator, or an activator would otherwise react with it to form the catalyst system. Furthermore, component (A) does not contain a nitrogen-containing compound that is an azaheterocycle. In some embodiments, component (A), the blends made therefrom, the procatalyst systems made therefrom, and the catalyst systems made therefrom, are free of (B) silicon-containing organic compounds that are not (multialkoxy)silanes, and are free of oxygen-containing organic compounds that are not oxaheterocycles, and are free of azaheterocycles.

[0036] Component (A) is prepared in the absence of (B), in the absence of other electron donor organic compounds (not including oxaheterocycles), and in the absence of activators. Component (A) is prepared by a process consisting essentially of solidifying magnesium chloride in the presence of a titanium compound and an oxaheterocycle, but in the absence of (B) a (multialkoxy)silane and any other electron donor compounds and activators. Solidifying the magnesium chloride produces a magnesium chloride solid consisting essentially of MgCl and an oxaheterocycle. The magnesium chloride solid thus produced is free of (B), any other electron donor compounds, and activators.

[0037] The solidification of magnesium chloride may involve precipitating and / or crystallizing MgCl from a solution of magnesium chloride and oxaheterocycle contained in a solvent. The solvent may be a hydrocarbon liquid, an excess of oxaheterocycle, or a combination of a hydrocarbon liquid and an excess. Alternatively, the solidification may involve evaporating the solvent from the solution, or evaporation in combination with precipitation and / or crystallization. The solidification may be carried out at a temperature below 100°C.

[0038] An embodiment of a method for making an (A) preformed solid procatalyst comprises contacting magnesium chloride (MgCl) with at least one compound of formula (III): TiX(III), where each X is independently Cl, Br, I, or (C1-C6). In some embodiments, each X is Cl. In some embodiments, each X is a (C1-C6)alkoxy or a (C4-C6)alkoxy. In some inventive embodiments of the method for making, each X is a (C1-C6)alkoxy or a (C4-C6)alkoxy (e.g., butoxy), and the (A) preformed solid procatalyst has a titanium to magnesium molar ratio (Ti / Mg (mol / mol)) that does not include at least one of a cyclic (C2-C6) ether, a (C1-C6) alcohol, or a hydroxyl-substituted cyclic (C3-C7) ether. Such an inventive embodiment can be compared to a comparative pre-made solid procatalyst that does not include at least one of a cyclic (C2-C6) ether, a (C1-C6) alcohol, or a hydroxyl-substituted cyclic (C3-C7) ether, and that has the same molar ratio of Ti / Mg (mol / mol), but that is made by a comparative preparation method that includes contacting a magnesium alkoxide (e.g., Mg((C1-C6)alkoxy)2) with at least one compound of formula (III): TiX4(III), where each X is independently Cl, Br, I, or Cl. A comparative catalyst system made from the comparative pre-made solid procatalyst and an activator should have significantly lower catalytic activity than the catalytic activity of an inventive catalyst system embodiment made from the (A) inventive embodiment (A) pre-made solid procatalyst and the same amount of activator.

[0039] Cyclic (C2-C6) ether. Formula

[0040] [ka] wherein the subscript m is an integer from 1 to 6, alternatively an integer from 2 to 5, alternatively an integer from 3 to 4, alternatively 3. In some embodiments, the cyclic (C2-C6) ether is tetrahydrofuran or tetrahydropyran, alternatively tetrahydrofuran.

[0041] Fran. Ceremony

[0042] [ka] Compound.

[0043] Dihydrofuran. Formula

[0044] [ka] Compound.

[0045] Piran. Ceremony

[0046] [ka] Compound.

[0047] Dihydropyran. Formula

[0048] [ka] Compound.

[0049] Tetrahydropyran. Formula

[0050] [ka] Compound.

[0051] 1,4-dioxane. Formula

[0052] [ka] Compound.

[0053] Difuranyl-(C1-C6) alkylene. Formula

[0054] [ka] Compound.

[0055] Bis(tetrahydrofuranyl)-(C1-C6)alkylene. Formula

[0056] [ka] Compound.

[0057] (C1-C3) alkyl-substituted derivatives of any one of them. Any one of the foregoing oxaheterocycle formulas wherein a hydrogen atom is replaced by a methyl, ethyl, 1-methylethyl, or propyl group.

[0058] Any other electron donor compound: The expression "any other electron donor compound" means (B) an organic compound containing at least one heteroatom selected from N, O, S, and P that is not a (multialkoxy)silane or at least one oxa-heterocycle.

[0059] (B) (Multialkoxy)silane: A compound consisting essentially of, or consisting of, one silicon atom, 2 to 4 silicon-bonded and carbon-bonded oxygen atoms, at least two carbon atoms, and multiple hydrogen atoms in one molecule.

[0060] (B) (multialkoxy)silanes contain no carbon-carbon double or carbon-carbon triple bonds.

[0061] In some embodiments, the (B) (multialkoxy)silane is a tetraalkoxysilane, trialkoxysilane, alkyltrialkoxysilane, or dialkyldialkoxysilane.

[0062] Tetraalkoxysilanes are represented by the formula (IIa): Si(OR 2 ) 4(IIa), wherein each R 2 are independently defined in formula (I) or (Ia).

[0063] Trialkoxysilanes are represented by the formula (IIb): HSi(OR 2 ) 3(IIb), wherein each R 2 are independently defined in formula (I) or (Ia).

[0064] In some embodiments relating to Formula (IIa) and (IIb), each R 2 are independently unsubstituted (C1 to C 20 ) alkyl group, or an unsubstituted (C1-C5) alkyl group, or an unsubstituted (C1-C3) alkyl group (for example, methyl or ethyl).

[0065] Alkyltrialkoxysilanes are represented by the formula (IIc): R 1 Si(OR 2 ) 3(IIc), wherein R 1 is unsubstituted (C1 to C 20 ) alkyl group or unsubstituted (C3-C 12 ) cycloalkyl group, and each R 2 are independently defined in formula (I) or (Ia). In some embodiments relating to formula (IIc), each R 1 are independently unsubstituted (C1 to C 20 ) alkyl group, or an unsubstituted (C1-C5) alkyl group, or an unsubstituted (C1-C3) alkyl group (e.g., methyl or ethyl), and each R 2 are independently unsubstituted (C1 to C 20 ) alkyl group, or an unsubstituted (C1-C5) alkyl group, or an unsubstituted (C1-C3) alkyl group (for example, methyl or ethyl).

[0066] Dialkyldialkoxysilanes are represented by the formula (IId): R 1 2Si(OR 2 )2(IId), wherein each R1 are independently unsubstituted (C1 to C 20 ) alkyl group or unsubstituted (C3-C 12 ) cycloalkyl group, and each R 2 are independently defined in formula (I) or (Ia). In some embodiments relating to formula (IId), one R 1 are independently unsubstituted (C1 to C 20 ) alkyl group, or unsubstituted (C1-C5) alkyl group, or unsubstituted (C1-C3) alkyl group (e.g., methyl or ethyl), and other R 1 is unsubstituted (C3 to C 12 ) cycloalkyl group, or an unsubstituted (C5-C7) cycloalkyl group (e.g., cyclohexyl), and each R 2 are independently unsubstituted (C1 to C 20 ) alkyl group, or an unsubstituted (C1-C5) alkyl group, or an unsubstituted (C1-C3) alkyl group (e.g., methyl or ethyl). In another embodiment of Formula (IId), each R 1 are independently unsubstituted (C3 to C 12 ) cycloalkyl group, or an unsubstituted (C4-C6) cycloalkyl group (e.g., cyclopentyl), and each R 2 are independently unsubstituted (C1 to C 20 ) alkyl group, or an unsubstituted (C1-C5) alkyl group, or an unsubstituted (C1-C3) alkyl group (for example, methyl or ethyl).

[0067] Examples of suitable (B) (multialkoxy)silanes are tetraethoxysilane (i.e., Si(OCH2CH3)4), propyltrimethoxysilane (i.e., CH3CH2CH2Si(OCH3)3), dicyclopentyldimethoxysilane (i.e., (C5H9)2Si(OCH3)2), and methyl,cyclohexyldimethoxysilane (i.e., (CH3)(CH6H 11 )Si(OCH3)2).

[0068] A method for synthesizing a procatalyst system. During synthesis, the titanium compound, magnesium chloride, and oxaheterocycle can be mixed in a hydrocarbon solvent. Method embodiments can synthesize the procatalyst system in a non-polymerization reactor that does not contain olefin monomer or polyolefin polymer, and the procatalyst system can be removed from the non-polymerization reactor and optionally dried (to remove the hydrocarbon solvent) to obtain the procatalyst system in isolated or isolated and dried form (as a powder). Alternatively, method embodiments can synthesize the procatalyst system in situ in a feed tank, which can then be fed into a polymerization reactor without isolation or drying. Alternatively, a method embodiment can synthesize the procatalyst system in situ in a polymerization reactor. The in situ process in a polymerization reactor can be carried out in the absence or presence of at least one olefin monomer and / or polyolefin polymer. The polymerization reactor can be a gas-phase polymerization reactor or a floating-bed gas-phase polymerization reactor. Drying can include spray drying. The (B) (multialkoxy)silane can be as defined in any one of embodiments 1-3 and 13, or any one of the other embodiments (numbered or unnumbered) above.

[0069] Catalyst System. The catalyst system is a new type of Ziegler-Natta catalyst. The catalyst system is prepared by contacting a procatalyst system with an activator. The catalyst system advantageously has increased catalytic activity and / or a narrower molecular weight distribution (M w / M n ) and / or lower M z A polyolefin polymer having M w is the weight average molecular weight, M n is the number average molecular weight, and M z is the z-average molecular weight, all determined according to the GPC test method described herein.

[0070] Activator. Also known as a cocatalyst. The activator can be an alkylaluminum compound. Preferably, the alkylaluminum compound is a (C1-C6) alkylaluminum dichloride, a di(C1-C6) alkyl-aluminum chloride, or a tri(C1-C6) alkylaluminum. The activator may include a (C1-C4) alkyl-containing aluminum compound. The (C1-C4) alkyl-containing aluminum compound may independently contain one, two, or three (C1-C4) alkyl groups and two, one, or zero groups, each independently selected from a chlorine atom and a (C1-C4) alkoxide. Each (C1-C4) alkyl may independently be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl. Each (C1-C4) alkoxide can independently be methoxide, ethoxide, propoxide, 1-methylethoxide, butoxide, 1-methylpropoxide, 2-methylpropoxide, or 1,1-dimethylethoxide. The (C1-C4) alkyl-containing aluminum compound can be triethylaluminum (TEA), triisobutylaluminum (TIBA), diethylaluminum chloride (DEAC), diethylaluminum ethoxide (DEAE), ethylaluminum dichloride (EADC), or a combination thereof or a mixture of any two or more thereof. The activator can be triethylaluminum (TEA), triisobutylaluminum (TIBA), diethylaluminum chloride (DEAC), diethylaluminum ethoxide (DEAE), or ethylaluminum dichloride (EADC). In some embodiments, the activator is triethylaluminum (TEA).

[0071] Methods of preparing a catalyst system. In some embodiments, the procatalyst system is preformed in situ, and the method of preparing the catalyst system further comprises a preliminary step of (A) pre-contacting the preformed solid procatalyst with (B) a (multialkoxy)silane for a time period to prepare the procatalyst system in situ. The length of time for the pre-contacting step can be from 0.1 to 30 minutes (e.g., about 20 minutes) or more. In another embodiment, an activating effective amount of activator is contacted with the procatalyst system in a polymerization reactor, thereby preparing the catalyst system in situ in the polymerization reactor. The (B) (multialkoxy)silane can be as defined in any one of aspects 1-3 and 13, or any one of the other aspects (numbered or unnumbered) previously described.

[0072] In another embodiment of the method of making a catalyst system, an activating effective amount of an activator, (B) (multi-alkoxy)silane, and (A) pre-made solid procatalyst are contacted together simultaneously in a feed tank, and then the catalyst system is fed into a polymerization reactor. In another embodiment, an activating effective amount of an activator, (B) (multi-alkoxy)silane, and (A) pre-made solid procatalyst are separately fed into a polymerization reactor, and the activator, (B) (multi-alkoxy)silane, and (A) pre-made solid procatalyst are contacted together simultaneously to make the catalyst system in situ in the polymerization reactor. In another embodiment, an activating effective amount of an activator is pre-contacted with the (B) (multi-alkoxy)silane to form a pre-mixture consisting essentially of the activator and the (B) (multi-alkoxy)silane, but not the (A) pre-made solid procatalyst, and then the pre-mixture is contacted with the (A) pre-made solid procatalyst to make the catalyst system in situ (either in a feed tank or in the polymerization reactor). The length of time for the pre-contacting step can be from 0.1 to 30 minutes (eg, about 20 minutes) or more.

[0073] A method for synthesizing a polyolefin polymer. The at least one olefin monomer can be as described below. In some embodiments, there is one olefin monomer independently selected from ethylene, propylene, a (C4-C8) alpha-olefin, and 1,3-butadiene. In other embodiments, there is a combination of any two or more olefin monomers. In the combination, each olefin monomer can be independently selected from ethylene, propylene, and optionally 1,3-butadiene, or ethylene and a (C4-C8) alpha-olefin.

[0074] Olefin monomers. Each olefin monomer is independently ethylene, propylene, (C4-C 20 ) alpha-olefins or 1,3-dienes. (C4-C 20 ) Alpha-olefins are represented by the formula (III): H2C=C(H)-R * (III), wherein R * is a straight chain (C2 to C 18 ) alkyl group. * Examples of aryl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. In some embodiments, (C4-C 20 ) The alpha-olefin is 1-butene, 1-hexene, or 1-octene, alternatively 1-butene or 1-hexene, alternatively 1-butene, alternatively 1-hexene, or alternatively 1-octene.

[0075] Polyolefin polymers. Polyolefin polymers are macromolecules or aggregates of macromolecules having repeating units derived from at least one olefin monomer. Polyolefin polymers have a density of 0.89 to 0.98 grams per cubic centimeter (g / cm), as measured according to ASTM D792-08 (Method B, 2-propanol). 3). The polyolefin polymer can be linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), or high-density polyethylene (HDPE). In some embodiments, the polyolefin polymer is LLDPE. The polyolefin polymer has a unimodal molecular weight distribution M w / M n a unimodal polyolefin polymer having a polymodal molecular weight distribution M w / M n and a multimodal polyolefin polymer having M w / M n is determined by conventional gel permeation chromatography (GPC) according to the method described below, and M w is the weight average molecular weight and M n is the number average molecular weight. The multimodal polyolefin polymer may be a bimodal polyethylene polymer comprising a higher molecular weight (HMW) polyethylene component and a lower molecular weight (LMW) polyethylene component, the bimodal polyethylene polymer having a bimodal molecular weight distribution M w / M n The polyolefin polymer may be a polyethylene homopolymer, a poly(ethylene-co-propylene) copolymer, a poly(ethylene-co-propylene-1,3-butadiene) terpolymer, or a poly(ethylene-co-(C4-C 20 ) alpha-olefin) copolymer. In some embodiments, the polyolefin polymer is a poly(ethylene-co-1-alkene) copolymer, alternatively a poly(ethylene-co-(C4-C8) 1-alkene) copolymer, or alternatively a poly(ethylene-co-1-hexene) copolymer.

[0076] Beneficial Effects of Invention Embodiments: It has been discovered that (multialkoxy)silane compounds (multidentate compounds consisting of one silicon atom, at least two silicon-bonded oxygen atoms, carbon atoms, and hydrogen atoms per molecule) can be used as external electron donor compounds (EEDCs) in inventive procatalyst systems prepared from titanium compounds, magnesium chloride, and oxa-heterocyclic compounds used as internal electron donor compounds (IEDCs). Inventive catalyst systems prepared therefrom and containing (multialkoxy)silane compounds as EEDCs have improved catalyst productivity and / or MFRs, respectively, of comparative polyolefin polymers prepared using comparative catalyst systems not containing inventive (multialkoxy)silane compounds as EEDCs. w / M n and / or M z / M w Compared with 21 / I2) and / or at least one narrower molecular weight distribution (lower M w / M n and / or lower M z / M w These beneficial results are shown for many different embodiments of the inventive (pro)catalyst system and at different molar ratios of (B) to Ti, and are demonstrated for polymerization reactions carried out in a batch reactor and in a continuous fluidized bed gas phase reactor. Furthermore, in embodiments of the inventive catalyst system made from an embodiment of the inventive procatalyst system made from a titanium compound and THF-solubilized MgCl (i.e., the oxa-heterocycle is THF), the (B) (multialkoxy)silane also beneficially exhibits the ability to significantly reduce the molecular weight of the polyolefin polymer, resulting in a reduction in M z (LS) / M w (LS), Δ(M z (LS) / M w (LS)), and M w 3 / M w 3(0) is a substantial change.

[0077] In some embodiments, Mz(LS) / Mw(LS)≦10. In other embodiments, Mz(LS) / Mw(LS)≦10 and at least one of limitations (i) and (ii) is met: (i) Mz(LS) / Mw(LS) of the resulting inventive polyolefin (co)polymer is at least 50% less than the Mz(LS) / Mw(LS) of a comparative polyolefin (co)polymer obtained in the absence of (B) (multialkoxy)silane (as EEDC), and (ii) the ratio of Mw3 of the resulting inventive polyolefin (co)polymer to Mw3 of a comparative polyolefin (co)polymer obtained in the absence of (B) (multialkoxy)silane ("Mw3(0)") is less than 0.90.

[0078] In some embodiments, the titanium compound is TiCl or TiCl, or an oxaheterocycle, a complex thereof, and the MgCl is solubilized in the oxaheterocycle (e.g., THF). In such embodiments, the inventive catalyst system may have an inventive catalyst productivity or inventive catalyst activity that is less than 90% of the comparative catalyst productivity or comparative catalyst activity, respectively, and / or the inventive catalyst system may have a comparative MFR (I 21 / I2) is at least 1.2 lower, or at least 1.5 lower, or at least 1.8 lower than the MFR of the invention (I 21 / I2), the comparative properties of which are measured using a comparative catalyst system that does not contain (B) a (multialkoxy)silane as the EEDC and that is obtained under the same polymerization conditions.

[0079] In some embodiments, the titanium compound is TiX4, where each X is (C1-C 12 ) alkoxy, or oxaheterocycle, or a complex thereof, and MgCl is solubilized in the oxaheterocycle (e.g., THF). In such embodiments, the inventive catalyst system may have an inventive catalyst productivity or inventive catalyst activity that is 10% higher to 50% lower than the comparative catalyst productivity or comparative catalyst activity, respectively, and / or the inventive catalyst system may have a comparative MFR (I 21 / I2) is at least 1.2 lower, or at least 1.5 lower, or at least 1.8 lower than the MFR of the invention (I 21 / I2), the comparative properties of which are measured using a comparative catalyst system that does not contain (B) a (multialkoxy)silane as the EEDC and that is obtained under the same polymerization conditions.

[0080] Embodiments of the inventive Ziegler-Natta catalyst systems can be made by contacting a pre-formed Ziegler-Natta catalyst system that does not contain an external electron donor compound with a (multialkoxy)silane compound, thereby making such embodiments of the inventive Ziegler-Natta catalyst system. The pre-formed Ziegler-Natta catalyst systems used to make such embodiments can be pre-formed by contacting a Ziegler-Natta procatalyst system with an activator (e.g., an alkylaluminum compound), thereby making a pre-formed Ziegler-Natta catalyst system. Other embodiments of the inventive Ziegler-Natta catalyst systems can be made by contacting a Ziegler-Natta procatalyst that does not contain (i.e., is not present in) an activator with a (multialkoxy)silane compound to make embodiments of the Ziegler-Natta procatalyst system, and then contacting these embodiments with an activator, thereby making such embodiments of the inventive Ziegler-Natta catalyst system. The latter embodiment of the inventive Ziegler-Natta catalyst system advantageously has higher catalytic activity and can produce polyethylene (co)polymers with reduced MFR. The reduced MFR is beneficial for improving the impact strength and optics of the polymer. Such inventive embodiments provide a low-cost method for improving polymer properties. Furthermore, since changes in polyolefin polymer properties correspond to changes in the (multialkoxy)silane donor / Ti ratio, the inventive polymerization method can also provide tunable control for tailoring polymer properties.

[0081] The direction and extent of the benefit can be adjusted by selecting different (B)(multialkoxy)silanes in embodiments of the invention, since different embodiments of (B)(multialkoxy)silanes have different amounts and types of external electron donor effect in the catalyst systems of the invention. Without being bound by theory, it is believed that the stronger the electron donating effect of a (B)(multialkoxy)silane, the greater the extent of its external electron donor effect.

[0082] The direction and extent of the benefit of the (B)(multialkoxy)silane can also be adjusted by selecting an embodiment of the (B)(multialkoxy)silane having three oxygen atoms per molecule (e.g., a (multialkoxy)silane of formula (IIb) or (IIc)) or an embodiment of the (B)(multi-alkoxy)silane having four oxygen atoms per molecule (e.g., a (multialkoxy)silane of formula (IIa)) instead of two oxygen atoms per molecule (e.g., a (multialkoxy)silane of formula (IId)). Without being bound by theory, it is believed that the stronger the electron-donating effect of the (B)(multialkoxy)silane, the greater the extent of its external electron donor effect.

[0083] General Definitions. The general definitions of Ziegler-Natta type, electron donor compound, external electron donor compound, internal electron donor compound, film, and polyethylene polymer procatalyst compositions are as follows:

[0084] Procatalyst compositions (Ziegler-Natta type). Typically, a catalytic metal (e.g., a Group 4 element such as Ti, Zr, or Hf) is supported on a three-dimensional structure composed of magnesium halide. Typically, the process for preparing the procatalyst composition uses a reaction mixture containing a solvent and reactants including magnesium halide and titanium compounds. The preparation involves halogenating the titanium metal, titanating the magnesium halide in solution, and then solidifying the procatalyst composition.

[0085] Electron donor compound (EDC). Generally, an organic molecule containing carbon, hydrogen, and at least one heteroatom having a free electron pair capable of coordinating to a metal atom (e.g., a metal cation) in need thereof. The heteroatom may be selected from N, O, S, or P. Depending on when or to which reactant the electron donor compound is added in the process of making the procatalyst composition, the electron donor compound may function in the procatalyst composition as described herein, either as an internal electron donor compound (IEDC) if added first, or as an external electron donor compound (EEDC) if added later. Generally, the terms "internal" and "external" refer to where the electron donor compound is located and what type of effect it has in the procatalyst composition containing it, which is a direct result of when or to which reactant the electron donor compound is added in the process of making the procatalyst composition.

[0086] External electron donor compounds (EEDCs). Also known as external electron donors or external donors. The term "external" indicates that the electron donor compound is located outside or external to the three-dimensional structure composed of magnesium halide in the procatalyst composition, where it has its primary effect. These external characteristics are achieved by adding the electron donor compound to the procatalyst composition after the three-dimensional structure composed of magnesium halide is formed in the procatalyst composition. The resulting post-solidification presence of the electron donor compound allows it to donate at least one of its electron pairs to one or more of the Ti or Mg metals primarily external to the three-dimensional structure composed of magnesium halide. Therefore, without being bound by theory, it is believed that electron donor compounds, when used as external electron donor compounds, affect the following properties of polyolefin polymers made from catalyst systems made from the procatalyst compositions: The properties include the level of tacticity (i.e., xylene soluble material), molecular weight, and properties that are at least a function of molecular weight (e.g., melt flow), molecular weight distribution (MWD), melting point, and / or oligomer level.

[0087] Internal electron donor compounds (IEDCs), also known as internal electron donors or internal donors. The term "internal" indicates that the electron donor compound is located within or within the three-dimensional structure composed of magnesium halide in the procatalyst composition, where it exerts its primary effect. These internal characteristics are achieved by adding or otherwise forming the electron donor compound in the presence of the magnesium halide and titanium compound reactants during the preparation of the procatalyst composition. The resulting in-situ presence of the electron donor compound allows it to donate at least one of its electron pairs to one or more of the Ti or Mg metals within the three-dimensional structure composed of magnesium halide in the procatalyst composition. If the electron donor compound were added after the three-dimensional structure composed of magnesium halide had been formed, it would not have been able to reach the interior or interior of the three-dimensional structure composed of magnesium halide in the procatalyst composition. Thus, without being bound by theory, electron donor compounds, when used as internal electron donor compounds, can be used to (1) (A) modulate the formation of active sites in the procatalyst composition, (2) modulate the location of titanium on the magnesium-based support in the procatalyst composition, thereby enhancing the stereoselectivity of the procatalyst composition and ultimately the stereoselectivity of catalyst systems made therefrom, (3) promote the conversion of the magnesium salt and titanium compound to their respective halide compounds, and (4) modulate the size (e.g., crystallite size) of the magnesium halide solids during conversion and solidification (e.g., crystallization) of the magnesium halide solids. Thus, the provision of an internal electron donor results in a procatalyst composition with enhanced stereoselectivity.

[0088] As used herein, (B)(multialkoxy)silane is an EEDC but not an IEDC.

[0089] Film. A manufactured article that is limited to one dimension.

[0090] Low density, as applied to polyethylene herein, is 0.910 to 0.929 g / cm when measured according to ASTM D792-08 (Method B, 2-propanol). 3 It has a density of

[0091] Medium density, as applied to polyethylene herein, is 0.930 to 0.940 g / cm when measured according to ASTM D792-08 (Method B, 2-propanol). 3 It has a density of

[0092] High density, as applied to polyethylene herein, is 0.941 to 0.970 g / cm, as measured according to ASTM D792-08 (Method B, 2-propanol). 3 It has a density of

[0093] Homopolymer. A polymer derived from one type of monomer. As IUPAC teaches, that species can be actual (e.g., ethylene or 1-alkene), implicit (e.g., poly(ethylene terephthalate)), or hypothetical (e.g., poly(vinyl alcohol)).

[0094] The relative terms "higher" and "lower" in the context of the HMW polyethylene component and the LMW polyethylene component, respectively, are used relative to each other and refer simply to the weight average molecular weight (M w-HMW ) is the weight average molecular weight (M w-LMW ), i.e., M w-HMW >M w-LMW This means that

[0095] Any compound, composition, formulation, mixture, or product herein may be free of any one of the chemical elements selected from the group consisting of H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanides, and actinides, provided that required chemical elements (e.g., C and H required by polyolefins, or C, H, and O required by alcohols) are not excluded.

[0096] or precedes a different embodiment. Aspect means embodiment. ASTM means standardization organization, ASTM International, West Conshohocken, Pennsylvania, USA. Any comparative examples are used for illustrative purposes only and are not prior art. "Free of" or "lacking" means complete absence or undetectable. ISO (International Organization for Standardization) is the International Organization for Standardization, Chemist de Blandonnet 8, CP 401-1214 Vernier, Geneva, Switzerland. Terms used herein have the meaning ascribed to IUPAC unless otherwise defined. See, e.g., IUPAC's Compendium of Chemical Terminology, Gold Book, version 2.3.3, February 24, 2014. IUPAC (International Union of Pure and Applied Chemistry) is the International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina). Carolina, USA). "May" gives a permitted option, not a required one. "Operative" means functionally possible or effective. "Optional" means absent (or excluded) or present (or included). A property can be measured using standard test methods and conditions. Ranges include endpoints, subranges, and whole and / or fractional values ​​contained therein, except that integer ranges do not include decimals. In a formula, " * " indicates multiplication and " / " indicates division.

[0097] For property measurements, samples are prepared into test specimens, plaques, or sheets in accordance with ASTM D4703-10, Standard Practice for Compression Molding Thermoplastic Materials into Test Specimens, Plaques, or Sheets.

[0098] Density is measured according to ASTM D792-08, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, e.g., liquid 2-propanol). Results are reported in grams per cubic centimeter (g / cm). 3 , also written as g / cc).

[0099] Gel Permeation Chromatography (GPC) Test Method (Traditional GPC) Instrumentation and Eluents. The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) coupled to a Precision Detectors (now Agilent Technologies) two-angle laser light scattering (LS) detector model 2040. A 15-degree angle was used for all light scattering measurements. The autosampler oven compartment was set to 160 °C, and the column compartment was set to 150 °C. The columns used were three Agilent "Mixed B" 30 centimeter (cm), 20 micron (μm) linear mixed-bed columns. The nitrogen-sparged chromatography solvent "TCB" with 1,2,4 trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT) was used. The injection volume used was 200 microliters (μL) and the flow rate was 1.0 milliliters / minute (mL / min).

[0100] Calibration. The GPC column set was calibrated using at least 20 narrow molecular weight distribution polystyrene standards from Agilent Technologies, ranging in molecular weight from 580 to 8,400,000 grams per mole (g / mol). These were prepared as six "cocktail" mixtures with at least a 10-fold separation between individual molecular weights. The polystyrene standards were prepared at a concentration of 0.025 grams (g) of polystyrene in 50 mL of solvent for molecular weights of 1,000,000 or greater, and 0.05 g of polystyrene in 50 mL of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved in the solvent with gentle stirring at 80°C for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A * (M ポリスチレン ) B (EQ.1), where M ポリエチレン is the molecular weight of polyethylene, and M ポリスチレン is the molecular weight of polystyrene, A has a value of 0.4315, and B is equal to 1.0. A fifth-order polynomial was used to fit each polyethylene equivalent calibration point. NIST standard NBS1475 is M w A small adjustment (approximately 0.415 to 0.44) was made to A to correct for column resolution and band broadening effects, as obtained at 52,000 g / mol.

[0101] Total Plate Count and Symmetry. Total plate counts for the GPC column set were performed using Eicosane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). Plate count (Equation 2) and symmetry (Equation 3) were measured for a 200 microliter injection. Plate count = 5.54 * [(RV ピーク最大) ) / peak width at half height)] 2 (EQ.2), where RV ピーク最大is the retention volume in milliliters at the maximum height of the peak, peak width in milliliters, and half height is one-half (1 / 2) height of the peak maximum. Symmetry = (rear peak RV) 1 / 10高さ -RV ピーク最大 ) / (RV ピーク最大 -Anterior peak RV 1 / 10高さ ](EQ.3), where posterior peak RV 1 / 10高さ is the retention volume in milliliters at 1 / 10 peak height of the peak tail, which is the portion of the peak that elutes after the peak maximum, and RV ピーク最大 is as defined for EQ.2, and the anterior peak RV 1 / 10高さ is the retention volume in milliliters at one-tenth the peak height of the peak front, which is the portion of the peak that elutes earlier than the peak maximum. The plate count value of the chromatographic system from EQ.2 should be greater than 24,000 and its symmetry should be between 0.98 and 1.22.

[0102] Test Sample Preparation. Polyolefin polymer samples for GPC were prepared in a semi-automated fashion using PolymerChar "Instrument Control" software, with a target sample concentration of 2 milligrams per milliliter (mg / mL) by weight, and TCB solvent was added via a PolymerChar high-temperature autosampler to a septa-capped vial pre-sparged with nitrogen gas. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0103] Calculation of molecular weight. M n(GPC) , M w(GPC) , and M z(GPC) The calculation was based on GPC results obtained using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 4-6 using PolymerChar GPCOne™ software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) from EQ.1.

[0104] [ka]

[0105] M w / M n represents the width of the molecular weight distribution of the polymer. z / M w is used as an indicator of the presence of high molecular weight polymer chains. The M of the polymer obtained from using an external donor (Mz(1) / Mw(1)) z / M w and Mz(0) / Mw(0) under the same polymerization conditions without external donor. z / M w The percentage difference Δ(Mz / Mw)% between is calculated to reflect the change in high molecular weight content in the polymer in the presence of the external donor: Δ(Mz / Mw)%=(Mz(1) / Mw(1)-Mz(0) / Mw(0)) / Mz(0) / Mw(0). * 100 (EQ.7).

[0106] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow Rate (Apparent)) for each sample by RV-matching the respective decane peak in the sample (RV (FM Sample)) with that of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in the RV measurement of the flow rate marker peaks, a least-squares fitting routine is used to fit the peaks of the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) is calculated as shown in Equation 8. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne™ software. Acceptable flow correction is one where the effective flow is within + / - 2% of the apparent flow. Flow (effective) = Flow (apparent) * (RV(FM calibrated) / RV(FM sample))(EQ.8).

[0107] Hexane Extractable Content Test Method: Measured by a procedure that complies with both the Food and Drug Administration (FDA) procedure for determining the hexane extractable portion of homopolymer and copolymer polyethylene and copolymer polypropylene (Title 21 Code of Federal Regulations (CFR) § 177.1520(d)(3)(ii) Paragraphs ei) (option 2) 4-1-2001 edition) and ASTM D5227-13, Standard Test Method for Measurement of Hexane Extractable Content of Polyolefins.

[0108] High Load Melt Index (Flow Index) Test Method ("HLMI" or "FI" or "I" 21 "): ASTM D1238-10, Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Platometer, using 190°C / 21.6 kilograms (kg). Results are reported in grams dissolved per 10 minutes (g / 10 min).

[0109] Melt Index Test Method "I2": For ethylene-based (co)polymers, measured according to ASTM D1238-13 using the conditions 190°C / 2.16 kg.

[0110] Melt Index Test Method "15": For ethylene-based (co)polymers, measured according to ASTM D1238-13 using the conditions 190°C / 5.0 kg.

[0111] Melt flow ratio MFR5: (I 21 / I5) Test method: HLMI I 21 It is calculated by dividing the value from the test method by the value from the Melt Index I5 test method.

[0112] Improved Comonomer Content Distribution (iCCD) Test Method: Improved comonomer content distribution (iCCD) analysis was performed using a Crystallization Elution Fractionation (CEF) instrument (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a two-angle light scattering detector, Model 2040 (Precision Detectors, now Agilent Technologies). A 10 cm (length) x 1 / 4 in. (ID) (0.635 cm ID) guard column packed with 20-27 micron glass (MoSCi Corporation, USA) on stainless steel was installed immediately before the IR-5 detector in the detector oven. Ortho-dichlorobenzene (ODCB, 99% anhydrous grade or technical grade) was used. Silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3) was obtained from EMD Chemicals (which may be used to dry the ODCB solvent). The CEF instrument is equipped with an autosampler with N2 purge capability. ODCB was sparged with dry nitrogen (N2) for 1 hour before use. Sample preparation was performed using an autosampler at 4 mg / mL (unless otherwise specified) with shaking at 160 °C for 1 hour. The injection volume was 300 μL. The temperature profile for the iCCD was crystallization from 105 °C to 30 °C at 3 °C / min, thermal equilibration at 30 °C for 2 minutes (including setting the soluble fraction elution time to 2 minutes), and elution from 30 °C to 140 °C at 3 °C / min. The flow rate during crystallization was 0.0 milliliters per minute (mL / min). The flow rate during elution was 0.50 mL / min. Data were collected at 1 data point per second. The iCCD column was a 15 cm (length) x 0.635 cm (1 / 4 inch) (ID) stainless steel tube packed with gold-coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.). The column was packed and conditioned using a slurry method according to references (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO 2017 / 040127(A1)). The final pressure with the TCB slurry packing was 15 megapascals (Mpa, 150 bar).

[0113] Column temperature calibration was performed using a standard linear homopolymer polyethylene (zero comonomer content, melt index (I2) of 1.0, polydispersity M) of 1.0 mg / mL by conventional gel permeation chromatography. w / M n The experiment was carried out using a mixture of eicosane (2 mg / mL) in ODCB (approximately 2.6). The iCCD temperature calibration consisted of four steps: (1) calculating the delay volume, defined as the temperature offset, which is the measured peak elution temperature of eicosane minus 30.00 °C; (2) subtracting the temperature offset of the elution temperature from the iCCD raw temperature data (note that this temperature offset is a function of experimental conditions such as elution temperature and elution flow rate); (3) creating a linear calibration line converting elution temperatures over the range of 30.00 °C to 140.00 °C, such that a linear homopolymer polyethylene reference material has a peak temperature at 101.0 °C and eicosane has a peak temperature of 30.0 °C; and (4) linearly extrapolating elution temperatures below 30.0 °C for the soluble fraction measured isothermally at 30 °C by using an elution heating rate of 3 °C / min according to the literature (Cerk and Cong et al., U.S. Patent No. 9,688,795).

[0114] Comonomer content versus iCCD elution temperature was constructed using 12 reference materials (ethylene homopolymers and single-site metallocene-catalyzed ethylene-octene random copolymers with ethylene equivalent weight average molecular weights ranging from 35,000 to 128,000). All of these reference materials were analyzed at 4 mg / mL using the same methodology as previously specified.

[0115] Modeling the reported elution peak temperatures as a function of mole percent octene using linear regression yields the model in Equation 12 (EQ.12), with a statistical coefficient of determination r 2was 0.978. (Elution temperature) = -6.3515 (1-octene mole percent) + 101.000 (EQ.12).

[0116] For the whole resin, the integration window is set to integrate all chromatograms at elution temperatures ranging from 23.0° C. to 115° C. (Temperature calibration is specified above.) The elution components from a CCD analysis of an ethylene / alpha-olefin copolymer resin include the high density fraction (HDF or Wt3), copolymer fraction (Wt2), and purge fraction (PF or Wt1).

[0117] The weight percent of the high density polyolefin fraction (HDF or Wt3) of the resin is defined by the following Equation 13 (EQ.13): HDF or Wt3 = 100% * (integrated area of ​​the elution window 94.5°-115°C) / (integrated area of ​​the entire elution window 23°-115°C) (EQ.13).

[0118] The weight percent of the copolymer fraction (Wt2) of the resin is defined by Equation 14 (EQ.14): Wt2 = 100% * (integrated area in the elution window 35°-94.5°C) / (integrated area in the total elution window 23°-115°C) (EQ.14).

[0119] The weight percent of the purge fraction (PF or Wt1) of the resin is defined by Equation 15 (EQ.15): Wt1 = 100% * (integrated area in the elution window 23°-35°C) / (integrated area in the total elution window 23°-115°C) (EQ.15).

[0120] The iCCD plot has a peak temperature Tp3 for the high density fraction Wt3, a peak temperature Tp2 for the copolymer fraction Wt2, and a peak temperature Tp1 for the purge fraction Wt1. The high density fraction or Wt3 has a weight average molecular weight Mw3, the copolymer fraction Wt2 has a weight average molecular weight Mw2, and the purge fraction Wt1 has a weight average molecular weight Mw1.

[0121] The molecular weights of the polymer and polymer fractions were determined directly from the LS detector (at a 90-degree angle) and the concentration detector (IR-5) according to the Rayleigh-Gans-Debys approximation (Striegel and Yau, "Modern Size Exclusion Liquid Chromatogram," pp. 242 and 263) by assuming a form factor of 1 and all virial coefficients of zero. Baselines were subtracted from the LS and concentration detector chromatograms. An integration window was set to integrate all chromatograms over the elution temperature range of 23.0 °C to 120 °C (temperature calibration specified above).

[0122] The weight average molecular weights Mw3, Mw2, and Mw1 are calculated from the iCCD using the following steps (1) to (4). (1): Measure the inter-detector offset. The offset is defined as the geometric volume offset between the LS detector and the concentration detector. This is calculated as the difference in elution volume (mL) of the polymer peak between the concentration detector and the LS chromatogram. This is converted to a temperature offset by using the elution heat rate and elution flow rate. A linear high-density polyethylene (comonomer content zero, melt index (I2) 1.0 g / 10 min, MWD (M w / M n) is used in conventional gel permeation chromatography (approximately 2.6). The same experimental conditions as those for the conventional iCCD method described above were used, except for the following parameters: crystallization from 140°C to 137°C at 10°C / min, 1-minute thermal equilibration at 137°C as the soluble fraction elution time, 7-minute soluble fraction (SF) time, and elution from 137°C to 142°C at 3°C / min. The flow rate during crystallization was 0.0 mL / min. The flow rate during elution was 0.80 mL / min. The sample concentration was 1.0 mg / mL. (2): Each LS data point in the LS chromatogram was shifted to correct for inter-detector offset before integration. (3): The baseline-subtracted LS and concentration chromatograms were integrated over the entire elution temperature range of step (1). The MW detector constant is calculated using HDPE samples of known MW in the range of 100,000 to 140,000 MW and the area ratio between the LS and concentration integrated signals. (4) The Mw of the polymer was calculated using the ratio between the integrated light scattering detector (at a 90 degree angle) and the concentration detector and the MW detector constant. [Example]

[0123] Preparation 1 (Prep 1): Synthesis of a spray-dried granular solid consisting essentially of hydrophobic fumed silica, MgCl, and THF. Anhydrous tetrahydrofuran (14 kg) is added to a feed tank. Finely divided solid MgCl (1255 g) is then added. The mixture is heated to 60°C and mixed for 5 hours to overnight to form a solution. The solution is cooled to 40°C-45°C. Hydrophobic fumed silica (Cabosil TS-610, 1.6 kg) is then added to form a suspension. The suspension is mixed for 30 minutes to obtain a slurry of hydrophobic fumed silica in the MgCl solution in THF. The slurry is sprayed into a spray dryer using the following conditions: inlet temperature 160°C, outlet temperature 110°C, feed rate of approximately 45 kg / hr, total gas flow rate of approximately 270 kg / hr, atomizer speed: typically approximately 85% variable, to obtain Prep1 modified spray-dried granular solids with an expected d50 particle size of 18-25 micrometers.

[0124] (A) Synthesis of pre-made solid procatalyst examples PCAT-1 to PCAT-3.

[0125] PCAT-1: A spray-dried procatalyst prepared according to the method of U.S. Patent Application Publication No. 9988475(B2), column 7, line 64 to column 8, line 47, to obtain PCAT-1, which contains 2.3 wt. % Ti and 26.8 wt. % tetrahydrofuran (THF) as the internal electron donor compound.

[0126] PCAT-2: A slurry of PCAT-1 in mineral oil is charged to a vessel. Tri-n-hexylaluminum (TnHAl) is added to the vessel in a molar ratio of 0.20 mol TnHAl / 1.00 mol THF and mixed for 1 hour. Diethylaluminum chloride (DEAC) is then added to the mixture in a molar ratio of 0.45 mol DEAC / 1.00 mol THF and mixed for 1 hour to obtain PCAT-2.

[0127] Synthesis of PCAT-3: Spray-Dried Ziegler-Natta Procatalyst System. 150 g of the spray-dried particulate solids of Prep 1, 520 g of mineral oil, and 73.5 g of EADC were mixed at 30°C for 0.5 hours to obtain an intermediate mixture consisting essentially of the spray-dried particulate solids, mineral oil, and EADC, or an intermediate mixture that was a reaction product made from the spray-dried particulate solids, mineral oil, and EADC. The intermediate mixture did not contain Ti(OiPr)4. The intermediate mixture was then combined with 8.7 g of Ti(OiPr)4 for 2 hours at 30°C to obtain PCAT-3 in mineral oil. PCAT-3 contains Ti as an internal electron donor and THF. MgCl2 was solubilized in THF during procatalyst preparation.

[0128] A selection of (B) (multialkoxy)silane Examples 1-4 and 20-25 are referred to herein as External Electron Donor Compounds 1-4 (EEDC-1 to EEDC-4). These examples are listed in Table B.

[0129] All EEDC-1 to EEDC-4 are used in the working examples as 0.20 molar (M) solutions in an alkane solvent (Isopar E).

[0130] [Table 1]

[0131] Examples of the inventive and comparative procatalyst systems, and examples of the inventive and comparative catalyst systems prepared therefrom, can be implemented by using different steps or different orders of steps. Examples of these different preparation modes include Modes M-1 through M-3, described below. Modes M-1 through M-3 vary the addition of the system components (constituents or reactants) triethylaluminum (TEA), (B) one of Examples EEDC-1 through EEDC-25 (if used), and (A) one of the pre-prepared solid procatalyst Examples PCAT-1 through PCAT-4.

[0132] Addition Mode M-1: One of EEDC-1 to EEDC-4 (if used) and one of PCAT-1 to PCAT-4 are contacted with each other for about 20 minutes, and then the resulting mixture is injected into the polymerization reactor.

[0133] Addition mode M-2: TEA and one of EEDC-1 to EEDC-4 are contacted with each other for about 20 minutes, and the resulting premixture is added to the polymerization reactor. Then, one of PCAT-1 to PCAT-4 is added to the polymerization reactor.

[0134] Addition mode M-3: TEA is added to the polymerization reactor first, followed by the addition of a pre-prepared procatalyst system by contacting one of EEDC-1 to EEDC-4 with one of PCAT-1 to PCAT-4 for about 20 minutes.

[0135] In the comparative example, when no EEDC is used, addition modes M-2 and M-3 are virtually the same.

[0136] Continuous Fluidized-Bed Gas-Phase Polymerization Procedure. The procatalyst (PCAT-1 or PCAT-3) is injected into a fluidized-bed gas-phase polymerization reactor as a slurry. Triethylaluminum (TEA) cocatalyst is fed to the fluidized-bed reactor as a 2.5 wt. % solution in isopentane. When EEDC is used, it is fed to the fluidized-bed reactor as a solution in isopentane. Polymerization is conducted in a 13.25-inch internal diameter gas-phase fluidized-bed reactor. Ethylene, hydrogen, 1-hexene, and nitrogen are continuously fed to the cycle gas loop just upstream of the compressor in amounts sufficient to maintain the desired gas concentrations. Product polyethylene is removed from the reactor in a separate draw to maintain a bed weight below the desired maximum. The polymerization process is conducted according to the process conditions reported in Table C. Catalyst activity is calculated based on the amount of polymer produced and the amount of procatalyst fed. Additionally, procatalyst residual metals in the polyethylene or polyolefin can be measured, and catalyst activity can be determined using the residual metals and the known or measured metal content in the procatalyst prior to polymerization.

[0137] [Table 2]

[0138] An example number "IE" indicates that the example is an example of the invention. An example number "CE" indicates that the example is a comparative example, i.e., not an example of the invention.

[0139] [Table 3]

[0140] [Table 4]

[0141] Batch Reactor Slurry-Phase Polymerization Procedure. The slurry-phase reactor used was a 2-liter stainless steel autoclave equipped with a mechanical stirrer. The reactor was subjected to several heating and nitrogen purging steps to ensure the reactor was clean and under an inert nitrogen atmosphere. Approximately 1 L of liquid isobutane was added to the reactor at ambient temperature. The reactor agitator was turned on and set to 750 rpm. The desired amount of hydrogen (H2) and 1-hexene was charged to the reactor. The amount of H2 was measured in liters (L) at standard temperature and pressure (STP). The reactor was heated to the desired polymerization temperature. Ethylene was introduced to achieve a differential pressure of 125 psi. The amount of procatalyst (solid weight) used in the batch reactor polymerization reactions was: 10.0 mg for PCAT-1, 15.0 mg for PCAT-2, and 10.0 mg for PCAT-3. The activator (cocatalyst) TEA (triethylaluminum) or TMA (trimethylaluminum), external donor, and procatalyst are added through a shot cylinder using nitrogen pressure according to the catalyst component addition mode described above. The polymerization reaction proceeds at 85°C, and ethylene is continuously added to maintain a constant pressure. After 1 hour, the reactor is vented, cooled to ambient temperature, and opened, and the poly(ethylene-co-1-hexene) copolymer product is recovered. After drying, the polymer sample is tested.

[0142] Catalyst productivity is calculated as grams of polymer produced per gram of procatalyst per hour. The percent change in catalyst productivity, Δ(catalyst productivity) due to the inclusion of EEDC is calculated by subtracting the catalyst productivity in the absence of EEDC from the catalyst productivity, then dividing that difference by the catalyst productivity in the absence of EEDC and multiplying by 100.

[0143] Batch reactor polymerization results: Effect of (multialkoxy)silane external donors under the same polymerization conditions.

[0144] [Table 5]

[0145] In Table 1A, (B) tetraethoxysilane (EEDC-1) or n-propyltrimethoxysilane (EEDC-2), a (multialkoxy)silane, is used as an external electron donor compound in an inventive embodiment of the catalyst system, and the inventive embodiment exhibits significantly lower I 21 As the EEDC / Ti molar ratio increases, the catalyst productivity decreases and the melt index I2 of the (ethylene-co-1-hexene) copolymer product decreases (IE1-IE3 and IE4-IE6 vs. CE1 in Table 1A).

[0146] [Table 6]

[0147] Analysis by triple detector GPC was performed by detecting high molecular weight components (M from the light scattering ("LS") detector). z (LS)). The polyolefin polymers prepared from the inventive catalyst system containing (B) a (multialkoxy)silane as the external electron donor compound exhibit a substantial reduction in M z (LS) / M w The results show a significant decrease in the EEDC / Ti molar ratio (IE1-IE3 and IE4-IE6 vs. CE1 in Table 1B). The higher the EEDC / Ti molar ratio, the lower the comonomer content (SCB / 1000 TC) in the poly(ethylene-co-1-hexene) copolymer. Furthermore, the M of the poly(ethylene-co-1-hexene) copolymer w / M n The decrease in I in Table 1A 21 This is consistent with the change in poly(ethylene-co-1-hexene) copolymers in / I2.

[0148] [Table 7]

[0149] The iCCD results show that as the EEDC / Ti molar ratio increases, the comonomer content (1-hexene content) (Wt2) of the poly(ethylene-co-1-hexene) copolymer decreases, while the high-density fraction (HDF) content (Wt3) increases. The changes in the molecular weights (MW) of these two components, Wt2 and Wt3, also show opposite trends: the MW of the poly(ethylene-co-1-hexene) copolymer decreases, while the MW of the HDF decreases. The Mw3 / Mw3(0) ratio is lower than 0.90 due to the influence of EEDC-1 and EEDC-2 (IE1-IE3 and IE4-IE6 vs. CE1 in Table 1C).

[0150] [Table 8]

[0151] [Table 9]

[0152] [Table 10]

[0153] In Tables 1A-1C, poly(ethylene-co-1-hexene) copolymers are prepared by mixing together the procatalyst, TEA, and (B)(multialkoxy)silane as EEDC (if used) prior to polymerization (catalyst component addition mode M-1). Catalyst productivity is reduced compared to polymerizations in which the TEA and (B)(multialkoxy)silane are premixed and added to the reactor, followed by the procatalyst (catalyst component addition mode M-2). Minimizing contact between the procatalyst and TEA results in higher catalyst productivity (catalyst productivity results in Table 2A vs. catalyst productivity results in Table 1A). At low EEDC / Ti molar ratios, I 21 Although the decrease in I2 was not large (CE3 and CE4 in Table 2A), increasing the amount of EEDC-1 (IE7) or EEDC-2 (IE8 and IE9) 21The polymer prepared by M-2 addition mode can significantly reduce the M obtained by M-1. z (LS) / M w (LS) and Mw3 / Mw3(0) show the same tendency.

[0154] [Table 11]

[0155] When dicyclopentyldimethoxysilane (EEDC-3) was used as the EEDC in the M-1 addition mode, I 21 / I2 decreases by more than 4 units (IE10-IE12 vs. CE5 in Table 3A).

[0156] [Table 12]

[0157] [Table 13]

[0158] A decrease in Mz(LS) / Mw(LS) and Mw3 / Mw3(0) was also observed (Tables 3B and 3C), similar to EEDC-1 and EEDC-2.

[0159] [Table 14]

[0160] [Table 15]

[0161] [Table 16]

[0162] Premixing EEDC-3 with the cocatalyst TEA before contacting with the procatalyst PCAT-1 (catalyst component addition mode M-2) maintains high catalyst productivity at high EEDC / Ti molar ratios, which is beneficial for achieving high polymer MW when using addition mode M-2. 21 Although the reduction in Mw / Mn is not as great as in catalyst addition mode M-1 (CE6 and IE13-IE14 in Tables 4A-4C vs. IE10-IE12 in Tables 3A-3C), lower values ​​of Mw / Mn are achieved with addition mode M-2 at comparable I2 and SCB / 1000 TC (IE13 vs. IE11). Furthermore, EEDC-4 exhibits a lower I than EEDC-3 in addition mode M-2. 21 / I2, M w / M n , M z (LS) / M w (LS), and performed better in achieving lower values ​​of Mw3 / Mw3(0).

[0163] [Table 17]

[0164] When CE2, CE6, and IE13 were repeated using 7 L of H2 instead of 3.8 L as in Table 4A, the catalytic system productivity remained nearly the same (CE7, IE20, and IE21 in Table 5A). When the procatalyst PCAT-1 was mixed with the external donor EEDC-3 before contacting with TEA (IE18 and IE19 using catalyst component addition mode M-3 in Table 5A), the catalytic system productivity decreased compared to the catalytic system productivity obtained from addition mode M-2 (IE20 and IE21 in Table 5A), but was still higher than the catalytic system productivity obtained from addition mode M-1, which should be similar to IE10 and IE11 in Table 3A, as expected. An additional benefit of using catalyst component addition mode M-3 was the ability to achieve higher copolymer content (Mt2) and copolymer molecular weight (Mw2) while maintaining higher I (Table 5C). 21 / I2, M w / M n , and M z(LS) / M w (LS) decreased more significantly (Table 5B).

[0165] [Table 18]

[0166] [Table 19]

[0167] [Table 20]

[0168] [Table 21]

[0169] PCAT-2 was prepared by modifying PCAT-1 with tri-n-hexylaluminum and diethylaluminum chloride. When PCAT-2 was used for polymerization with trimethylaluminum as the cocatalyst and EEDC-3 as the EEDC, the productivity of the catalyst system remained high (Table 6A). At EEDC / Ti molar ratios of 5 to 10 (IE23 and IE24), a lower I of about 21 was observed. 21 / I2 was achieved. M z (LS) / M w A larger reduction in (LS) and a lower Mw3 / Mw3(0) were also achieved (IE22-IE24 vs. CE8 in Tables 6A and 6B).

[0170] [Table 22]

[0171] I 21Significant decreases in / I2, Mz(LS) / Mw(LS), and Mw3 / Mw3(0) are also obtained with another procatalyst, PCAT-3, derived from THF-solubilized MgCl2 and titanium alkoxide (IE25-IE27 vs. CE9 in Tables 7A-7C). Similar to IE4-IE6 in Tables 1A-1C, relatively low catalyst productivity is again observed for this set of experiments using catalyst component addition mode M-1.

[0172] [Table 23]

[0173] [Table 24]

[0174] [Table 25]

[0175] When the procatalyst PCAT-3 was treated with EEDC-3 before contacting with the cocatalyst TEA (catalytic component addition mode M-3), the catalyst system of the invention maintained high catalyst productivity at a high EEDC / Ti molar ratio while achieving I 21 / I2, M z (LS) / M w (LS) and Mw3 / Mw3(0) can be significantly reduced (IE28-IE30 vs. CE10 in Tables 8A-8C). The effect of the external donor EEDC-3 on the decrease in catalytic productivity of PCAT-3 is smaller than that on PCAT-1 (Table 6A). In fact, when the EEDC / Ti molar ratio is 10 or less, the catalytic productivity increases slightly (CE10-CE13 and IE28-IE30 in Table 8A). However, when the EEDC / Ti molar ratio is ≦2, the I 21 / I2, M z (LS) / M w The decrease in (LS) and Mw3 / Mw3(0) is relatively small (CE10~CE13).

[0176] [Table 26]

[0177] [Table 27]

[0178] Results from a continuous fluidized bed gas phase reactor: Effect of (multialkoxy)silane external donors on polymers with similar density and MI(I2)

[0179] [Table 28]

[0180] Three sets of poly(ethylene-co-1-hexene) copolymers are prepared. Each set contains two poly(ethylene-co-1-hexene) copolymers with similar I2 and density: one prepared in the absence of EEDC and one prepared with (multialkoxy)silane EEDC-3 (CE-P1 vs. IE-P1, CE-P2 vs. IE-P2, and CE-P2 vs. IE-P3 in Tables 9A-9C). The results show that preparing polymers with similar I2 and density results in a decrease in catalyst activity and I 21 The contribution of (B)(multialkoxy)silanes as external electron donor compounds to the reduction in I2 / I2 is confirmed (Table 9A). Because (B)(multialkoxy)silanes function as EEDCs to reduce I2 and comonomer incorporation (SCB / 1000 TC) in poly(ethylene-co-1-hexene) copolymers (Tables 1A-8A), higher H2 content and higher comonomer content (1-hexene content) can be used in the polymerization reactor to achieve similar I2 and density (CE-P1 vs. IE-P1, CE-P2 vs. IE-P2 in Table C). To produce polyethylene homopolymer, only a higher H2 content is required to achieve the same I2 (CE-P3 vs. IE-P3 in Table C).

[0181] There is no consistent trend regarding the effect of (B)(multialkoxy)silane as an EEDC (e.g., EEDC-3) on the content of hexane extractables in polyolefin polymer products. When (B)(multialkoxy)silane is present as the EEDC, the content of hexane extractables is higher for polyolefin products having an I2 of about 3.6 g / 10 min and a density of about 0.9489 g / cc (CE-P1 vs. IE-P1 in Table 9A), slightly lower for polyolefin products having an I2 of about 10.1 g / 10 min and a density of about 0.9522 g / cc (CE-P2 vs. IE-P2), and about the same for polyolefin products having an I2 of about 1.2 g / 10 min and a density of about 0.9591 g / cc (CE-P3 vs. IE-P3).

[0182] [Table 29]

[0183] Substantial reductions are also observed when using EEDC-3 to make polymers with similar I2 and density (CE-P1 vs. IE-P1, CE-P2 vs. IE-P2, and CE-P2 vs. IE-P3 in Table 9B). However, the comonomer distribution is less uniform, with the comonomer preferably present on the low molecular weight polymer chain.

[0184] [Table 30]

[0185] The external donor EEDC-3 also reduced Mw3, with Mw3 / Mw3(0)<0.80 (CE-P1 vs. IE-P1, CE-P2 vs. IE-P2, and CE-P2 vs. IE-P3 in Table 9C). The present specification includes the following aspects. Section 1. 1. A procatalyst system suitable for making an olefin polymerization catalyst, the procatalyst system consisting essentially of a blend of (A) a pre-made solid procatalyst and (B) a (multialkoxy)silane, wherein the (A) pre-made solid procatalyst consists essentially of a titanium compound, a magnesium chloride solid, and optionally silica, the magnesium chloride solid consisting essentially of MgCl and at least one oxa-heterocycle, and the procatalyst system is free of any other electron donor organic compounds. Section 2. The (B) (multialkoxy)silane is represented by the formula (I): R 1 m H n Si(OR 2 ) 4-m-n (I) is an aromatic (multialkoxy)silane of the formula (I), wherein subscript m is 0 and subscript n is 0, 1, or 2, or subscript m is 1 and subscript n is 0 or 1, or subscript m is 2 and subscript n is 0; and R 1 But unsubstituted (C1~C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C 10 ) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, unsubstituted (C6-C 12 ) aryl group, (C1-C 10 ) Alkyl-substituted (C6-C 10 ) aryl group, or unsubstituted (C7-C 20 ) an aralkyl group, and R 2 is unsubstituted (C1 to C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C 10 ) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, or unsubstituted (C7-C 20 Item 2. The procatalyst system according to item 1, wherein the aryl group is an aralkyl group. Section 3. The (B) (multialkoxy)silane is represented by the formula (Ia): R 1 m Si(OR 2 ) 4-m-n (Ia) is an aromatic (multialkoxy)silane of formula (Ia), wherein the subscript m is 0, 1, or 2; and R 1 But unsubstituted (C1~C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C 10 ) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, unsubstituted (C6-C 12 ) aryl group, (C1-C 10 ) Alkyl-substituted (C6-C 10 ) aryl group, or unsubstituted (C7-C 20 ) an aralkyl group, and R 2 is unsubstituted (C1 to C 20 ) alkyl group, unsubstituted (C3-C 12 ) cycloalkyl group, (C1-C 10 ) Alkyl-substituted (C3-C 12 ) cycloalkyl group, (C3-C 10 ) Cycloalkyl-substituted (C1-C 10 ) alkyl group, or unsubstituted (C7-C 20 Item 3. The procatalyst system according to item 1 or 2, wherein R is an aralkyl group. Section 4. 4. The procatalyst system of any one of paragraphs 1 to 3, wherein the magnesium chloride solid consists essentially of MgCl and an oxaheterocycle selected from the group consisting of unsubstituted cyclic (C2-C6) ether, furan, dihydrofuran, pyran, dihydropyran, tetrahydropyran, 1,4-dioxane, difuranyl-(C1-C6)alkylene, bis(tetrahydrofuranyl)-(C1-C6)alkylene, and a (C1-C3) alkyl-substituted derivative of any one of these. Section 5. 4. The procatalyst system of any one of paragraphs 1 to 3, wherein the magnesium chloride solid consists essentially of MgCl2 and an oxa-heterocycle selected from tetrahydrofuran. Section 6. The titanium compound is at least one compound of formula (III): TiX4(III), where each X is independently Cl, Br, I, or (C1-C 12 6. The procatalyst system according to any one of items 1 to 5, wherein the alkoxy is (C1-C6)alkoxy. Section 7. 7. The procatalyst system of any one of paragraphs 1 to 6, further consisting essentially of a ligand-metal complex of formula (IV): MX4(IV), wherein M is Hf or Zr, and each X is independently Cl, Br, I, or (C1-C6)alkoxy. Section 8. 8. A method of synthesizing a procatalyst system, the method comprising: drying a mixture consisting essentially of a solution and optionally silica, and free of (B) a (multialkoxy)silane and any other electron donor organic compound, the solution consisting essentially of a titanium compound, magnesium chloride, and at least one oxa-heterocycle mixed in a hydrocarbon solvent, thereby removing the hydrocarbon solvent from the mixture and crystallizing the magnesium chloride to obtain (A) a pre-fabricated solid procatalyst; and contacting the (A) pre-fabricated solid procatalyst with the (B) (multialkoxy)silane, thereby producing the procatalyst system blend of any one of paragraphs 1-7. Section 9. 10. A method for preparing a catalyst system suitable for polymerizing olefins, comprising contacting the procatalyst system of any one of paragraphs 1 to 7, or the procatalyst system prepared by the method of paragraph 8, with an effective activating amount of (C) an activator, thereby preparing the catalyst system, wherein the catalyst system is free of any other electron donor organic compound and is suitable for polymerizing olefins. Section 10. 1. A method for preparing a catalyst system suitable for polymerizing olefins, comprising simultaneously or sequentially contacting an activating effective amount of (C) an activator, (B) a (multialkoxy)silane, and (A) a pre-formed solid procatalyst, thereby preparing the catalyst system, wherein the (A) pre-formed solid procatalyst consists essentially of a titanium compound, magnesium chloride solids, and optionally silica, and the magnesium chloride solids consist essentially of MgCl and at least one oxa-heterocycle, and the catalyst system is free of any other electron donor organic compounds and is suitable for polymerizing olefins. Section 11. 11. A catalytic system produced by the method of claim 9 or 10, wherein the catalytic system is believed to have a functionally modified or weakened active site. Section 12. 12. A method of synthesizing a polyolefin polymer, comprising contacting at least one olefin monomer with the catalyst system of claim 11 under effective polymerization conditions in a polymerization reactor, thereby producing said polyolefin polymer.

Claims

1. A procatalyst system for making an olefin polymerization catalyst consisting essentially of a blend of (A) a pre-made solid procatalyst and (B) a (multialkoxy)silane, The (A) pre-formed solid procatalyst consists essentially of a titanium compound, a magnesium chloride solid, and optionally silica, the magnesium chloride solid being MgCl ２ and at least one oxaheterocycle; the oxaheterocycle is tetrahydrofuran; The procatalyst system does not include any other electron donor organic compounds.

2. The (B) (multialkoxy)silane is represented by the formula (I): R １ ｍ H ｎ Si(OR ２ ) ４－ｍ－ｎ (I) (multialkoxy)silane, During the ceremony, subscript m is 0 and subscript n is 0, 1, or 2, or subscript m is 1 and subscript n is 0 or 1, or subscript m is 2 and subscript n is 0; R １ is unsubstituted (C １ ~C ２０ ) alkyl group, unsubstituted (C ３ ~C １２ ) a cycloalkyl group, (C １ ~C １０ ) alkyl-substituted (C ３ ~C １２ ) a cycloalkyl group, (C ３ ~C １０ ) cycloalkyl-substituted (C １ ~C １０ ) alkyl group, unsubstituted (C ６ ~C １２ ) an aryl group, (C １ ~C １０ ) alkyl-substituted (C ６ ~C １０ ) aryl group, or unsubstituted (C ７ ~C ２０ ) an aralkyl group; R ２ is unsubstituted (C １ ~C ２０ ) alkyl group, unsubstituted (C ３ ~C １２ ) a cycloalkyl group, (C １ ~C １０ ) alkyl-substituted (C ３ ~C １２ ) a cycloalkyl group, (C ３ ~C １０ ) cycloalkyl-substituted (C １ ~C １０ ) alkyl group, or unsubstituted (C ７ ~C ２０ ) an aralkyl group; The procatalyst system of claim 1.

3. The (B) (multialkoxy)silane is represented by the formula (Ia): R １ ｍ Si(OR ２ ) ４－ｍ (Ia) (multialkoxy)silane, During the ceremony, the subscript m is 0, 1, or 2; R １ is unsubstituted (C １ ~C ２０ ) alkyl group, unsubstituted (C ３ ~C １２ ) a cycloalkyl group, (C １ ~C １０ ) alkyl-substituted (C ３ ~C １２ ) a cycloalkyl group, (C ３ ~C １０ ) cycloalkyl-substituted (C １ ~C １０ ) alkyl group, unsubstituted (C ６ ~C １２ ) an aryl group, (C １ ~C １０ ) alkyl-substituted (C ６ ~C １０ ) aryl group, or unsubstituted (C ７ ~C ２０ ) an aralkyl group; R ２ is unsubstituted (C １ ~C ２０ ) alkyl group, unsubstituted (C ３ ~C １２ ) a cycloalkyl group, (C １ ~C １０ ) alkyl-substituted (C ３ ~C １２ ) a cycloalkyl group, (C ３ ~C １０ ) cycloalkyl-substituted (C １ ~C １０ ) alkyl group, or unsubstituted (C ７ ~C ２０ ) an aralkyl group; The procatalyst system of claim 1.

4. The titanium compound is at least one compound represented by formula (III): TiX ４ (III), wherein each X is independently Cl, Br, I, or (C １ ~C １２ ) alkoxy, or (C １ ~C ６ 4. The procatalyst system of claim 1, wherein the procatalyst system is a )alkoxy.

5. 1. A method for synthesizing a procatalyst system, comprising: (B) a mixture consisting essentially of a solution and optionally silica, and free of (multialkoxy)silanes and any other electron donor organic compounds, said solution consisting essentially of a titanium compound, magnesium chloride, and at least one oxa-heterocycle mixed in a hydrocarbon solvent, drying the mixture, thereby removing the hydrocarbon solvent from the mixture and crystallizing the magnesium chloride to obtain (A) a pre-fabricated solid procatalyst; contacting the (A) pre-formed solid procatalyst with the (B) (multialkoxy)silane, thereby producing the procatalyst system blend of any one of claims 1-4; Including, The method wherein said oxaheterocycle is tetrahydrofuran.

6. 10. A method of making an olefin polymerization catalyst, comprising contacting the procatalyst system of any one of claims 1-4, or a procatalyst system made by the method of claim 5, with an effective activating amount of (C) an activator, thereby making said olefin polymerization catalyst, wherein said procatalyst system is free of any other electron donor organic compound.

7. 1. A method of making an olefin polymerization catalyst, comprising simultaneously or sequentially contacting an activating effective amount of (C) an activator, (B) a (multialkoxy)silane, and (A) a pre-formed solid procatalyst, thereby making the olefin polymerization catalyst, wherein the (A) pre-formed solid procatalyst consists essentially of a titanium compound, magnesium chloride solids, and optionally silica, and the magnesium chloride solids are selected from the group consisting of MgCl ２ and at least one oxaheterocycle, wherein the oxaheterocycle is tetrahydrofuran, and wherein the procatalyst system consisting essentially of a blend of (A) and (B) does not contain any other electron donor organic compounds.

8. 8. A method for synthesizing a polyolefin polymer, comprising contacting at least one olefin monomer with an olefin polymerization catalyst made by the method of claim 6 or 7 under effective polymerization conditions in a polymerization reactor, thereby making said polyolefin polymer.

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