# US 9,751,965 B2 · Methods for preparation of propylene polymers

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- Number: US 9,751,965 B2
- Document ID: US9751965B2
- Status: Granted
- Kind: B2
- Application number: 14/067,289
- Filed: 2013-10-30
- Published: 2014-05-01
- Granted: 2017-09-05
- Earliest claimed: 2012-10-30
- 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: Luqiang Yu; Zhichao Yang; Jiangbo Chen; Jianxin Zhang; Yafeng Du; Qinyu Tong; Kang Sun; Yang Liu; Jie Zou; Lusheng Wang; Zengyue Dai; Zhong Tan
- Web page: https://patentgrep.com/patent/US9751965B2

## CPC

- C08F 210/06: Propene
- C08F 10/06: Propene
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Disclosed herein is a polymerization method of propylene, which can prepare a propylene homopolymer with both high fluidity and high rigidity as well as a propylene/α-define copolymer having both high fluidity and a good rigidity-toughness balance by, for example, control of polymerization steps and elevation of polymerization temperature, while the catalyst still maintains a relatively high polymerization activity.

## Claims

### Claim 1

A method for polymerization of propylene, comprising:
(1) performing pre-polymerization of propylene or an olefin mixture containing propylene and at least one another α-olefin comonomer in a gas phase or a liquid phase in the presence of a Ziegler-Natta catalyst at a temperature ranging from −10° C. to 50° C. and under a pressure ranging from 0.1 MPa to 10.0 MPa to obtain a propylene prepolymer, wherein the pre-polymerization multiplication is controlled within the scope ranging from 2 to 3000 g polymer/g catalyst; wherein the Ziegler-Natta catalyst comprises a reaction product of the following components:
(i) at least one titanium-containing solid catalyst component;
(ii) at least one alkyl aluminum compound; and
(iii) optionally, at least one external electron donor component,
and wherein the at least one titanium-containing solid catalyst component of the component (i) is a reaction product of contacting at least one alkoxy magnesium compound, at least one titanium compound and at least one internal electron donor compound,
wherein
the at least one titanium compound is selected from compounds of formula: Ti(OR)4-nXn, in which R is selected from C1-C14 aliphatic or aromatic hydrocarbonyl group, X is a halogen atom, n is an integer from 0 to 4 and in case of n being equal to or less than 2, the existing R groups can be same or different;
the at least one internal electron donor compound is selected from alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers and aliphatic ketones; and
the at least one alkoxy magnesium compound is selected from the compounds of formula Mg(OR1)2-m(OR2)m, wherein R1 is ethyl, R2 is (2-ethyl)hexyl, and 0.001≦m≦0.5;
(2) performing a homopolymerization of propylene or copolymerization of propylene and at least one another α-olefin comonomer in a gas phase in the presence of the propylene prepolymer as obtained in step (1) under conditions of 91-150° C. and 1-6 MPa to obtain a propylene polymer, wherein the polymerization time ranges from 0.5 h to 4 h;
(3) continuing the homopolymerization or copolymerization of propylene in a gas phase or a liquid phase in the presence of the product as obtained in step (2) under conditions of 50-150° C. and 1-6 MPa.

### Claim 2 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the pre-polymerization multiplication is controlled within the scope ranging from 3 to 2000 g polymer/g catalyst.

### Claim 3 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein, in step (2), the temperature ranges from 91 to 130° C.

### Claim 4 (depends on 3)

The method for polymerization of propylene according to claim 3, wherein, in step (2), the temperature ranges from 91 to 110° C.

### Claim 5 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the individual steps are performed in one reactor for the batch polymerization operation, or performed in different reactors for continuation polymerization operation.

### Claim 6 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein in step (1), the pre-polymerization temperature ranges from 0 to 30° C. and the pre-polymerization pressure ranges from 1.0 to 6.0 MPa.

### Claim 7 (depends on 6)

The method for polymerization of propylene according to claim 6, wherein, in step (1), the pre-polymerization temperature ranges from 10 to 25° C.

### Claim 8 (depends on 6)

The method for polymerization of propylene according to claim 6, wherein, in step (1), the pre-polymerization pressure ranges from 1.5 to 5.5 MPa.

### Claim 9 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the at least another α-olefin comonomer has the carbon atom number of 2 to 6 but not 3.

### Claim 10 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the gas phase polymerization of propylene in step (2) is performed in a horizontal reaction kettle having a horizontal agitating shaft and a stirring speed of 10-150 rpm, in which the agitating blade is selected from T-shape, rectangle shape, inclined paddle, door shape, wedge-shape and any combination thereof, and the reaction kettle uses a quench liquid to remove heat.

### Claim 11 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the polymer obtained in step (2) has a melt flow rate MFR of 20-1000 g/10 min, as measured according to ISO1133 under 230° C. and 2.16 kg load.

### Claim 12 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the gas phase homopolymerization or copolymerization of propylene in step (3) is performed at the polymerization temperature of 55-110° C., and the polymer obtained in step (3) has a melt flow rate MFR of 1-500g/10min, as measured according to ISO1133 under 230° C. and 2.16 kg load.

### Claim 13 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein a liquid phase bulk pre-polymerization of propylene is performed at 0-30° C. in step (1); a gas phase homopolymerization of propylene is performed at 91-110° C. in step (2); and the gas phase homopolymerization or copolymerization of propylene is continued in the presence of the product as obtained in step (2) at 55-110° C. in step (3), wherein the weight ratio of the polymers obtained in steps (2) and (3) ranges from 0.3:1 to 3:1.

### Claim 14 (depends on 13)

The method for polymerization of propylene according to claim 13, wherein the weight ratio of the polymers obtained in steps (2) and (3) ranges from 1.0:1 to 2.0:1.

### Claim 15 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein a homopolymerization of propylene is performed in steps (1) and (2), while a copolymerization of propylene and at least one another α-olefin comonomer is performed in step (3).

### Claim 16 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the at least one another α-olefin comonomer is selected from ethylene, butylene and hexylene.

### Claim 17 (depends on 15)

The method for polymerization of propylene according to claim 15, wherein in step (3) the copolymerization is performed using ethylene in an amount ranging from 4 to 40 wt % relative to the weight of propylene homopolymer as obtained in step (2).

### Claim 18 (depends on 17)

The method for polymerization of propylene according to claim 17, wherein in step (3) the copolymerization is performed using ethylene in an amount ranging from 6 to 30 wt % relative to the weight of propylene homopolymer as obtained in step (2).

### Claim 19 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein 0.001≦m≦0.25.

### Claim 20 (depends on 19)

The method for polymerization of propylene according to claim 19, wherein 0.001≦m≦0.1.

### Claim 21 (depends on 1)

The method for polymerization of propylene according to claim 1, wherein the at least one internal electron donor compound is selected from alkyl esters of C1-C4 saturated aliphatic carboxylic acids, alkyl esters of C7-C8 aromatic carboxylic acids, C2-C6 aliphatic esters, C3-C4 cyclic ethers, C3-C6 saturated aliphatic ketones, and 1,3-diether compounds.