# US 8,541,333 B2 · Catalyst component for olefin polymerization and a catalyst comprising the same

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- Number: US 8,541,333 B2
- Document ID: US8541333B2
- Status: Granted
- Kind: B2
- Application number: 12/856,175
- Filed: 2010-08-13
- Published: 2011-02-17
- Granted: 2013-09-24
- Earliest claimed: 2009-08-13
- Assignees: China Petroleum & Chemical Corporation; Beijing Research Institute of Chemical Industry, China Petroleum & Chemical Corporation
- Applicants: Lunjia Xie; Yongtai Ling; Yu Tian; Zaixing Feng; Siyuan Zhao; Qing Hu; Zhufang Sun; Yu Kang
- Inventors: Lunjia Xie; Yongtai Ling; Yu Tian; Zaixing Feng; Siyuan Zhao; Qing Hu; Zhufang Sun; Yu Kang
- Web page: https://patentgrep.com/patent/US8541333B2

## CPC

- C08F 10/06: Propene
- B01J 27/135: with titanium, zirconium, hafnium, germanium, tin or lead
- B01J 27/138: with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
- B01J 31/0201: {Oxygen-containing compounds}
- B01J 31/0255: {Phosphorus containing compounds}
- B01J 31/0272: {containing elements other than those covered by B01J31/0201 - B01J31/0255}
- B01J 31/143: {of aluminium}
- B01J 31/38: of titanium, zirconium or hafnium
- C08F 110/06: Propene
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A catalyst component for olefin polymerization comprising an α-cyanosuccinate compound as an internal electron donor, a catalyst comprising the catalyst component, and use of the catalyst in olefin polymerization. When used in propylene polymerization, the catalyst can exhibit good catalytic activity and good hydrogen response, and the resulting polymer can have a good isotacticity and a good molecular weight distribution.

## Claims

### Claim 1

A catalyst component for olefin polymerization, comprising magnesium, titanium, at least one halogen, and at least one internal electron donor, wherein the at least one internal electron donor in the catalyst component is chosen from an α-cyanosuccinate compound of formula (I):
wherein R1 and R2, which may be the same or different, are each chosen from hydrogen, C1-C14 linear alkyl, C3-C14 branched alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C7-C10 alkaryl, and C7-C10 aralkyl groups; and R3 and R4, which may be the same or different, are each chosen from C1-C10 linear alkyl, C3-C10 branched alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C7-C20 alkaryl, and C7-C20 aralkyl groups, and
a combination of at least one α-cyanosuccinate compound of formula (I) and at least one monofunctional or difunctional compound E chosen from esters other than the α-cyanosuccinate compound of formula (I), ethers, ketones, ketals, amines, and silanes.

### Claim 2 (depends on 1)

The catalyst component of claim 1, which is obtained by a process comprising
(1) dissolving at least one magnesium halide in a solvent system comprising at least one organic epoxy compound, at least one organophosphorus compound and at least one optional inert diluent, to form a solution A;
(2) combining the solution A with at least one titanium compound and at least one auxiliary precipitant, to form a mixture B;
(3) precipitating a solids C from the mixture B;
(4) separating a solids D from the product of operation (3); and
(5) treating the solids D with at least one titanium compound in at least one inert organic solvent at least once, to obtain the catalyst component,
wherein the internal electron donor is introduced at any stage before the separation of operation (4),
wherein the molar ratio of the magnesium halide to the titanium compound to the internal electron donor, used in the process, is 1-200:20-4000:1;
and wherein in the case where the at least one internal electron donor is chosen from a combination of at least one α-cyanosuccinate compound of formula (I) and at least one monofunctional or difunctional compound E, the α-cyanosuccinate compound of formula (I) is in an amount ranging from 5 mol % to 95 mol % of the combination.

### Claim 3 (depends on 2)

The catalyst component of claim 2, wherein the molar ratio of the magnesium halide to the titanium compound to the internal electron donor, used in the process, is 5-100:50-2000:1, and wherein in the case where the at least one internal electron donor is chosen from a combination of at least one α-cyanosuccinate compound of formula (I) and at least one monofunctional or difunctional compound E, the α-cyanosuccinate compound of formula (I) is in an amount ranging from 50 mol % to 95 mol % of the combination.

### Claim 4 (depends on 1)

The catalyst component of claim 1, comprising a reaction product of at least one magnesium halide-alcohol adduct, at least one titanium compound and the at least one internal electron donor, wherein the magnesium halide-alcohol adduct is of formula (II):
MgX2.(ROH)m (II)
wherein X is chlorine or bromine, R, which may be the same or different, is each chosen from C1-C12 alkyl, C3-C10 cycloalkyl and C6-C10 aryl groups, and m is from 1 to 5.

### Claim 5 (depends on 4)

The catalyst component of claim 4, wherein in the formula (II), R is chosen from C1-C4 alkyl groups, X is chlorine, and m is from 1.5 to 3.5.

### Claim 6 (depends on 4)

The catalyst component of claim 4, wherein the molar ratio of the magnesium halide-alcohol adduct to the titanium compound to the internal electron donor, used in the reaction to form the solid catalyst component, in terms of Mg:Ti:internal electron donor is 1-200:20-4000:1; and wherein in the case where the at least one internal electron donor is chosen from a combination of at least one α-cyanosuccinate compound of formula (I) and at least one monofunctional or difunctional compound E, the α-cyanosuccinate compound of formula (I) is in an amount ranging from 5 mol % to 95 mol % of the combination.

### Claim 7 (depends on 6)

The catalyst component of claim 6, wherein the molar ratio of the magnesium halide-alcohol adduct to the titanium compound to the internal electron donor, used in the reaction to form the solid catalyst component, in terms of Mg:Ti:internal electron donor is 5-100:50-2000:1; and wherein in the case where the internal electron donor is chosen from a combination of the at least one α-cyanosuccinate compound of formula (I) and at least one monofunctional or difunctional compound E, the α-cyanosuccinate compound of formula (I) is in an amount ranging from 50 mol % to 95 mol % of the combination.

### Claim 8 (depends on 1)

The catalyst component of claim 1, wherein the at least one titanium compound is chosen from compounds of formula Ti(OR5)4-nXn, wherein R5, which may be the same or different, is each chosen from C1-C20 hydrocarbyl groups, X, which may be the same or different, is each chosen from F, Cl and Br, and n is an integer ranging from 1 to 4.

### Claim 9 (depends on 8)

The catalyst component of claim 8, wherein in the formula Ti(OR5)4-nXn, R5 is chosen from C1-C14 aliphatic hydrocarbyl groups.

### Claim 10 (depends on 1)

The catalyst component of claim 1, wherein in the formula (I), R1 to R4 are each chosen from C1-C4 linear alkyl, C3-C4 branched alkyl and C3-C6 cycloalkyl groups.

### Claim 11 (depends on 1)

The catalyst component of claim 1, wherein in the formula (I), R1 and R2 are each chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, cyclopentyl, cyclohexyl, phenyl, benzyl, p-methylphenylmethyl, and phenylethyl groups; and R3 and R4 are each chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, phenyl, p-methylphenyl, o-methylphenyl, m-methyl phenyl, and benzyl groups.

### Claim 12 (depends on 1)

The catalyst component of claim 1, wherein the α-cyanosuccinate compound of formula (I) is chosen from diethyl 2,3-diisopropyl-2-cyanosuccinate, di-n-butyl 2,3-diisopropyl-2-cyanosuccinate, diisobutyl 2,3-diisopropyl-2-cyanosuccinate, diethyl 2,3-dicyclopentyl-2-cyanosuccinate, di-n-butyl 2,3-dicyclopentyl-2-cyanosuccinate, diisobutyl 2,3-dicyclopentyl-2-cyanosuccinate, diethyl 2,3-dicyclohexyl-2-cyanosuccinate, di-n-butyl 2,3-dicyclohexyl-2-cyanosuccinate, diisobutyl 2,3-dicyclohexyl-2-cyanosuccinate, diethyl 2-cyclopentyl-3-isopropyl-2-cyanosuccinate, 2,3-diisopropyl-2-cyanosuccinic acid 1-isobutyl ester 4-ethyl ester, 2,3-diisopropyl-2-cyanosuccinic acid 1-n-butyl ester 4-ethyl ester, diethyl 2-isopropyl-3-methyl-2-cyanosuccinate, diethyl 3-ethyl-2-isopropyl-2-cyanosuccinate, diethyl 2-isopropyl-3-propyl-2-cyanosuccinate, diethyl 3-butyl-2-isopropyl-2-cyanosuccinate, diethyl 2-isopropyl-3-phenyl-2-cyanosuccinate, diethyl 2-cyclohexyl-3-isopropyl-2-cyanosuccinate, and 2-isopropyl-3-phenyl-2-cyanosuccinic acid 1-ethyl ester 4-isobutyl ester.

### Claim 13 (depends on 1)

The catalyst component of claim 1, wherein the compound E is chosen from esters of mono- and poly-carboxylic acids, diether compounds, and difunctional compounds comprising both an ether group and an ester group.

### Claim 14 (depends on 13)

The catalyst component of claim 13, wherein the compound E is chosen from 2,2-dihydrocarbyl malonates, 2,3-dihydrocarbyl succinates, glutarates, phthalates, and 1,3-diether compounds of formula (IV):
wherein RI, RII, RIII, RIV, RV, and RVI, which may be the same or different, are each chosen from hydrogen, halogens, linear C1-C20 alkyl groups and branched C3-C20 alkyl groups, C3-C20 cycloalkyl groups, C6-C20 aryl groups, C7-C20 alkaryl groups, and C7-C20 aralkyl groups, RIII and RIV are optionally linked to each other to form a ring; and RVII and RVIII, which may be the same or different, are each chosen from linear C1-C20 alkyl groups, C3-C20 branched alkyl groups, and C3-C20 cycloalkyl groups.

### Claim 15 (depends on 14)

The catalyst component of claim 14, wherein the 1,3-diether compound is chosen from 9,9-bis(methoxymethyl)fluorene and 2-isopentyl-2-isopropyl-1,3-dimethoxypropane.

### Claim 16 (depends on 1)

The catalyst component of claim 1, wherein the compound E is ethyl o-methoxybenzoate.

### Claim 17 (depends on 1)

The catalyst component of claim 1, wherein said component has an IR spectrum having a characteristic absorption peak T in a range of from 2240 cm−1 to 2345 cm−1.

### Claim 18 (depends on 1)

The catalyst component of claim 1, wherein said component has an IR spectrum having a characteristic absorption peak T in a range of from 2240 cm−1 to 2295 cm−1.

### Claim 19 (depends on 1)

A catalyst for the polymerization of at least one olefin of formula CH2═CHR, wherein R is chosen from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms, comprising a reaction product of:
(1) at least one catalyst component of claim 1;
(2) at least one alkyl aluminum compound; and
(3) optionally, at least one external electron donor compound, wherein said reaction product is said catalyst.

### Claim 20 (depends on 19)

The catalyst of claim 19, having at least one of the following:
the at least one alkyl aluminum compound is of formula AlR73-aX1a, wherein R7, which may be the same or different, is each chosen from hydrogen and C1-C20 hydrocarbyl groups; X1, which may be the same or different, is chosen from halogens; and a has a value ranging from 0 to 2;
the at least one alkyl aluminum compound is used in such an amount that a molar ratio of aluminum therein to titanium in the catalyst component ranges from 5:1 to 5000:1;
the at least one external electron donor compound is chosen from carboxylic anhydrides, carboxylic esters, ketones, ethers, lactones, organophosphorus compounds, and organic silicon compounds of formula R8aR9bSi(OR10)c, wherein a and b, which may be the same or different, are each an integer ranging from 0 to 2, c is an integer ranging from 1 to 3, and the sum of (a+b+c) is 4; R8, R9 and R19, which may be the same or different, are each chosen from C1-C18 hydrocarbyl groups, optionally comprising at least one heteroatom;
the at least one external electron donor compound is used in an amount ranging from 0.005 to 0.5 moles, relative to one mole of the at least one alkyl aluminum compound; or
the at least one alkyl aluminum compound and the optional at least one external electron donor compound contact and/or react with the solid catalyst component separately or as a mixture.

### Claim 21 (depends on 19)

A process for polymerizing at least one olefin, comprising contacting at least one olefin of formula CH2═CHR, wherein R is chosen from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms, optionally at least one other olefin as a comonomer, and optionally at least one diene as a second comonomer, with the catalyst of claim 19 under polymerization conditions; and recovering the resulting polymer.