# US 9,751,960 B2 · Catalyst component for olefin polymerization, catalyst, and use thereof

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- Number: US 9,751,960 B2
- Document ID: US9751960B2
- Status: Granted
- Kind: B2
- Application number: 14/892,533
- Filed: 2014-05-21
- Published: 2016-04-28
- Granted: 2017-09-05
- Earliest claimed: 2013-05-21
- Assignees: China Petroleum & Chemical Corporation; Beijing Research Institute of Chemical Industry, China Petroleum & Chemical Corporation
- Applicants: China Petroleum & Chemical Corporation; Beijing Research Institute of Chemical Industry, China Petroleum & Chemical Corporation
- Inventors: Changxiu Li; Mingzhi Gao; Haitao Liu; Jianhua Chen; Jing Ma; Jixing Ma; Xiaoxia Cai; Jun Wang; Xiaofan Zhang; Jianjun Hu
- Web page: https://patentgrep.com/patent/US9751960B2

## CPC

- C08F 10/06: Propene
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The present disclosure provides a solid catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen, and an electron donor, wherein the electron donor is at least one selected from the group consisting of diol diester compounds as shown in Formula (I). The catalyst according to the present disclosure has significantly improved polymerization activity, hydrogen response, and stereoselectivity. According to the present disclosure, when the catalyst system containing a diol diester compound as shown in Formula (I) of the present disclosure is used in olefin polymerization, the catalyst shows good comprehensive performance, including high catalytic activity. In particular, in the presence of highly concentrated hydrogen, the catalyst has an improved hydrogen response and/or isotacticity of the polymers obtained can be significantly improved. The catalyst of the present disclosure is beneficial for obtaining polymers with a high melt index and high isotacticity, and for development of polymers of different grades.

## Claims

### Claim 1

A catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen, and an electron donor, wherein the electron donor is at least one selected from the group consisting of diol diester compounds, wherein the diol diester compounds are one or more selected from the group consisting of 2,4-hexanediol-bis(4-ethyl benzoate),
2,4-hexanediol-bis(4-n-propyl benzoate),
2,4-hexanediol-bis(4-n-butyl benzoate),
2,4-hexanediol-bis(4-iso-butyl benzoate),
2,4-hexanediol-bis(4-tert-butyl benzoate),
2,4-hexanediol-bis(4-hexyl benzoate),
3-methyl-2,4-hexanediol-bis(4-ethyl benzoate),
3-methyl-2,4-hexanediol-bis(4-n-propyl benzoate),
3-methyl-2,4-hexanediol-bis(4-n-butyl benzoate),
3-methyl-2,4-hexanediol-bis(4-iso-butyl benzoate),
3-methyl-2,4-hexanediol-bis(4-tert-butyl benzoate),
3-methyl-2,4-hexanediol-bis(4-hexyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-ethyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-n-propyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-n-butyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-iso-butyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-tert-butyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-hexyl benzoate),
3,5-heptanediol-bis(4-n-propyl benzoate),
3,5-heptanediol-bis(4-iso-propyl benzoate),
3,5-heptanediol-bis(4-iso-butyl benzoate),
3,5-heptanediol-bis(4-tert-butyl benzoate),
3,5-heptanediol-bis(4-pentyl benzoate),
3,5-heptanediol-bis(4-hexyl benzoate),
3,5-heptanediol-cinnamic acid-4-ethyl benzoate,
4-methyl-3,5-heptanediol-bis(4-ethyl benzoate),
4-methyl-3,5-heptanediol-bis(4-n-propyl benzoate),
4-methyl-3,5-heptanediol-bis(4-iso-propyl benzoate),
4-methyl-3,5-heptanediol-bis(4-n-butyl benzoate),
4-methyl-3,5-heptanediol-bis(4-iso-butyl benzoate),
4-methyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-methyl-3,5-heptanediol-bis(4-pentyl benzoate),
4-methyl-3,5-heptanediol-bis(4-hexyl benzoate),
4-methyl-3,5-heptanediol-cinnamic acid-4-ethyl benzoate,
4-ethyl-3,5-heptanediol-bis(4-ethyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-n-propyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-iso-propyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-n-butyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-iso-butyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-pentyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-hexyl benzoate),
4-ethyl-3,5-heptanediol-cinnamic acid-4-ethyl benzoate,
4-n-propyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-n-butyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4,4-dimethyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-methyl-4-ethyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-methyl-4-n-propyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
3-methyl-2,4-heptanediol-bis(4-n-propyl benzoate),
3-methyl-2,4-heptanediol-bis(4-iso-propyl benzoate),
4-methyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-ethyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-n-propyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-n-butyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4,4-dimethyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4,4-diethyl-3,5-octanediol-bis(4-n-propyl benzoate),
4,4-di-n-propyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-methyl-4-ethyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4,6-nonanediol-bis(4-ethyl benzoate),
4,6-nonanediol-bis(4-n-propyl benzoate),
4,6-nonanediol-bis(4-n-butyl benzoate),
4,6-nonanediol-bis(4-iso-butyl benzoate),
4,6-nonanediol-bis(4-tert-butyl benzoate),
4,6-nonanediol-bis(4-hexyl benzoate),
4,6-nonanediol-cinnamic acid-4-ethyl benzoate,
5-methyl-4,6-nonanediol-bis(4-ethyl benzoate),
5-methyl-4,6-nonanediol-bis(4-n-propyl benzoate),
5-methyl-4,6-nonanediol-bis(4-n-butyl benzoate),
5-methyl-4,6-nonanediol-bis(4-iso-butyl benzoate),
5-methyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5-methyl-4,6-nonanediol-bis(4-hexyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-ethyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-n-propyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-n-butyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-iso-butyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-hexyl benzoate),
5-n-propyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5-n-butyl-4,6-nonanediol-bis(4-n-butyl benzoate),
5,5-dimethyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5,5-diethyl-4,6-nonanediol-bis(4-hexyl benzoate),
5,5-di-n-propyl-4,6-nonanediol-bis(4-pentyl benzoate), and
5,5-dibutyl-4,6-nonanediol-bis(4-tert-butyl benzoate).

### Claim 2 (depends on 1)

The catalyst component according to claim 1, wherein the catalyst component is prepared by reacting magnesium compounds, titanium compounds, and the diol diester compounds.

### Claim 3 (depends on 2)

The catalyst component according to claim 2, wherein the magnesium compounds are selected from the group consisting of magnesium dihalides, alkoxy magnesium compounds, alkyl magnesium compounds, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides with halogen atoms thereof being substituted by alkoxy groups or halogenated alkoxy groups; and
wherein the titanium compounds have a general formula of TiXm(OR1)4-m, with R1 being a C1 to C20 hydrocarbyl group, X a halogen, and 1≦m≦4.

### Claim 4 (depends on 2)

The catalyst component according to claim 2, wherein based on one mole of the magnesium compounds, the dosage of the titanium compounds is in the range from 0.5 mole to 150 mole, and that of the diol diester compounds is in the range from 0.01 mole to 5 mole.

### Claim 5 (depends on 1)

A catalyst for olefin polymerization, comprising the following components: component a): the catalyst component according to claim 1; and
component b): alkylaluminum compounds.

### Claim 6 (depends on 5)

The catalyst according to claim 5, further comprising component c): an external electron donor, which is selected from the group consisting of organosilicon compounds, ethers, and esters.

### Claim 7 (depends on 6)

The catalyst according to claim 6, wherein the molar ratio of component a) to component b) based on the molar ratio of titanium to aluminum is in the range from 1:5 to 1:1,000, and/or the molar ratio of component c) to component a) is in the range from 0:1 to 500:1.

### Claim 8 (depends on 5)

A prepolymerization catalyst for olefin polymerization, comprising the catalyst according to claim 5, and a prepolymer generated by prepolymerization between said catalyst and olefins, with the prepolymerization multiples thereof being 0.1 g to 1,000 g of olefin polymers per g of the catalyst component.

### Claim 9 (depends on 1)

A method for olefin polymerization, wherein an olefin is contacted under polymerization conditions with the catalyst component according to claim 1.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the olefins have a general formula of CH2═CHR, with R being hydrogen or a C1 to C12 alkyl or aryl group.

### Claim 11 (depends on 3)

The catalyst component according to claim 3, wherein based on one mole of the magnesium compounds, the dosage of the titanium compounds is in the range from 0.5 mole to 150 mole, and that of the diol diester compounds is in the range from 0.01 mole to 5 mole.

### Claim 12 (depends on 6)

The catalyst according to claim 6, wherein the molar ratio of component a) to component b) based on the molar ratio of titanium to aluminum is in the range from 1:5 to 1:1,000, and/or the molar ratio of component c) to component a) is in the range from 0:1 to 500:1.

### Claim 13 (depends on 5)

A method for olefin polymerization, wherein an olefin is contacted under polymerization conditions with the catalyst according to claim 5.

### Claim 14 (depends on 13)

The method according to claim 13, wherein the olefins have a general formula of CH2═CHR, with R being hydrogen or a C1 to C12 alkyl or aryl group.

### Claim 15 (depends on 8)

A method for olefin polymerization, wherein an olefin is contacted under polymerization conditions with the catalyst according to claim 8.

### Claim 16 (depends on 15)

The method according to claim 15, wherein the olefins have a general formula of CH2═CHR, with R being hydrogen or a C1 to C12 alkyl or aryl group.

### Claim 17 (depends on 2)

The catalyst component according to claim 2,
wherein the magnesium compounds are selected from the group consisting of magnesium dihalides and magnesium alcoholates; or
wherein the titanium compounds have titanium tetrachloride.

### Claim 18 (depends on 9)

The method according to claim 9, wherein the olefins are selected from propylene and ethylene.

### Claim 19 (depends on 13)

The method according to claim 13, wherein the olefins are selected from propylene and ethylene.

### Claim 20 (depends on 15)

The method according to claim 15, wherein the olefins are selected from propylene and ethylene.