# US 9,434,795 B2 · Production of vinyl terminated polyethylene using supported catalyst system

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- Number: US 9,434,795 B2
- Document ID: US9434795B2
- Status: Granted
- Kind: B2
- Application number: 14/033,636
- Filed: 2013-09-23
- Published: 2014-03-27
- Granted: 2016-09-06
- Earliest claimed: 2012-09-24
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Donna J. Crowther; Patrick Brant
- Web page: https://patentgrep.com/patent/US9434795B2

## CPC

- C08F 4/76: selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
- C08F 4/52: selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence)
- C08F 8/00: Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C)
- C08F 10/02: Ethene
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention relates to processes to produce vinyl terminated polyethylene involving contacting ethylene with a supported metallocene catalyst system; wherein the supported catalyst system comprises a support material; an alumoxane activator; and a metallocene compound. A supported metallocene catalyst system is also disclosed. Processes to produce ethylene copolymers are also disclosed.

## Claims

### Claim 1

A process to produce polyethylene comprising:
(a) contacting ethylene with a supported metallocene catalyst system;
wherein the supported catalyst system comprises:
(i) a support material;
(ii) an alumoxane activator having from about 1 wt % to about 14 wt % trimethylaluminum, based on the weight of the alumoxane activator;
(iii) a metallocene compound represented by the formula:
wherein
T is Si or Ge;
each RA is a C1 to C20 substituted or unsubstituted hydrocarbyl group;
each RB is, independently, H or a C1 to C8 substituted or unsubstituted hydrocarbyl group, or a group represented by the formula —CH2Rx;
wherein Rx is a C1 to C20 substituted or unsubstituted hydrocarbyl group provided that at least one RB is methyl or a group represented by the formula —CH2Rx;
each RC is, independently, H or a C1 to C20 substituted or unsubstituted hydrocarbyl group;
each A is independently selected from the group consisting of C1 to C20 substituted or unsubstituted hydrocarbyl groups, hydrides, amides, amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines, and ethers, and two A groups can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system;
each X is, independently, hydrogen, halogen or a substituted or unsubstituted C1 to C20 hydrocarbyl, and two X groups can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system;
further provided that any of adjacent RA, RB, and/or RC groups may form a fused ring or multicenter fused ring systems, where the rings may be substituted or unsubstituted, and may be aromatic, partially unsaturated, or unsaturated;
(b) obtaining a vinyl terminated polyethylene having:
(i) at least 60% allyl chain ends, based on total unsaturations;
(ii) a molecular weight distribution of less than or equal to 4.0;
(iii) an Mn (1HNMR) of at least 20,000 g/mol; and
(iv) wherein the polyethylene is an ethylene polymer having less than 2wt % of a C3 to C40 alphaolefin comonomer.

### Claim 2 (depends on 1)

The process of claim 1, wherein the vinyl terminated polyethylene has at least 95% allyl chain ends, based on total unsaturations.

### Claim 3 (depends on 1)

The process of claim 1, wherein the vinyl terminated polyethylene has a molecular weight distribution of less than or equal to 3.5.

### Claim 4 (depends on 1)

The process of claim 1, wherein the vinyl terminated polyethylene comprises 0 wt % of a C3 to C40 alphaolefin comonomer.

### Claim 5 (depends on 1)

The process of claim 1, wherein the vinyl terminated polyethylene having 2 to about 20 wt % of a C3 to C40 alphaolefin comonomer.

### Claim 6 (depends on 5)

The process of claim 5, wherein the vinyl terminated polyethylene has at least 75 wt % allyl chain ends, based on total unsaturations.

### Claim 7 (depends on 1)

The process of claim 1, wherein the vinyl terminated polyethylene has an Mn (GPC)/Mn (1HNMR) in the range of from about 0.8 to about 1.2.

### Claim 8 (depends on 1)

The process of claim 1, wherein the vinyl terminated polyethylene has an Mn (GPC)/Mn (1HNMR) in the range of from about 0.9 to about 1.1.

### Claim 9 (depends on 1)

The process of claim 1, wherein 0 wt % of hydrogen is used in the polymerization.

### Claim 10 (depends on 1)

The process of claim 1, wherein the group represented by the formula —CH2Rx is selected from the group consisting of ethyl, n-propyl, n-butyl, sec-butyl, and benzyl groups.

### Claim 11 (depends on 1)

The process of claim 1, wherein RA is methyl.

### Claim 12 (depends on 1)

The process of claim 1, wherein RB and/or RA or RC fuse to form a substituted or unsubstituted indene or a fluorene.

### Claim 13 (depends on 1)

The process of claim 1, wherein the catalyst is represented by the following structure:
wherein each RB is, independently, H or a C1 to C8 substituted or unsubstituted hydrocarbyl group, or a group represented by the formula —CH2Rx;
wherein Rx is a C1 to C20 substituted or unsubstituted hydrocarbyl group, provided that at least one RB is methyl or a group represented by the formula —CH2Rx.

### Claim 14 (depends on 1)

The process of claim 1, wherein the metallocene compound is represented by the following structure:

### Claim 15 (depends on 1)

The process of claim 1, wherein the metallocene compound is one or more of: Me2Si(3-n-propylCpMe3)(C13H8)ZrCl2; Me2Si(3-n-propylCpMe3)(C13H8)ZrMe2; Me2Si(3-n-butylCpMe3)(C13H8)ZrCl2; Me2Si(3-n-butylCpMe3)(C13H8)ZrMe2; Me2Si(3-benzylCpMe3)(C13H8)ZrCl2; Me2Si(3-benzylCpMe3)(C13H8)ZrMe2; Me2Si(3-CH2-cyclopropylCpMe3)(C13H8)ZrCl2; Me2Si(3-CH2-cyclopropylCpMe3)(C13H8)ZrMe2; Me2Ge(3-n-propylCpMe3)(C13H8)ZrCl2; Me2Ge(3-n-propylCpMe3)(C13H8)ZrMe2; Et2Si(3-n-propylCpMe3)(C13H8)ZrCl2; Et2Si(3-n-propylCpMe3)(C13H8)ZrMe2; (Hexyl)2Si(3-n-propylCpMe3)(C13H8)ZrCl2; (Hexyl)2Si(3-n-propylCpMe3)(C13H8)ZrMe2; [(C3H6)Si](3-n-propylCpMe3)(C13H8)ZrCl2; [(C3H6)Si](3-n-propylCpMe3)(C13H8)ZrMe2; [(C4H8)Si](3-n-propylCpMe3)(C13H8)ZrCl2; [(C4H8)Si](3-n-propylCpMe3)(C13H8)ZrMe2; Me2Si(CpMe4)(C13H8)ZrCl2; Me2Si(CpMe4)(C13H8)ZrMe2; Me2Ge(CpMe4)(C13H8)ZrCl2; Me2Ge(CpMe4)(C13H8)ZrMe2; Et2Si(CpMe4)(C13H8)ZrCl2; Et2Si(CpMe4)(C13H8)ZrMe2; (Hexyl)2Si(CpMe4)(C13H8)ZrCl2; (Hexyl)2Si(CpMe4)(C13H8)ZrMe2; [(C3H6)Si](CpMe4)(C13H8)ZrCl2; [(C3H6)Si](CpMe4)(C13H8)ZrMe2; [(C4H8)Si](CpMe4)(C13H8)ZrCl2; [(C4H8)Si](CpMe4)(C13H8)ZrMe2; Me2Si(3-n-propylCpMe3)(2,3-Me2C9H4)ZrCl2; Me2Si(3-n-butylCpMe3)(2,3-Me2C9H4)ZrCl2; Me2Si(3-benzylCpMe3)(2,3-Me2C9H4)ZrCl2; Me2Si(3-CH2-cyclopropylCpMe3)(2,3-Me2C9H4)ZrCl2; Me2Ge(3-n-propylCpMe3)(2,3-Me2C9H4)ZrCl2; Et2Si(3-n-propylCpMe3)(2,3-Me2C9H4)ZrCl2; (Hexyl)2Si(3-n-propylCpMe3)(2,3-Me2C9H4)ZrCl2; [(C3H6)Si](3-n-propylCpMe3)(2,3-Me2C9H4)ZrCl2; [(C4H8)Si](3-n-propylCpMe3)(2,3-Me2C9H4)ZrCl2; Me2Si(CpMe4)(2-methyl,3-n-propylC9H4)ZrCl2; Me2Si(CpMe4)(2-methyl,3-n-butylC9H4)ZrCl2; Me2Si(CpMe4)(2-methyl,3-benzylC9H4)ZrCl2; Me2Si(CpMe4)(2-methyl,3-sec-butylC9H4)ZrCl2; Me2Si(CpMe4)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; Me2Ge(CpMe4)(2-methyl,3-n-propylC9H4)ZrCl2; Me2Ge(CpMe4)(2-methyl,3-n-butylC9H4)ZrCl2; Me2Ge(CpMe4)(2-methyl,3-benzylC9H4)ZrCl2; Me2Ge(CpMe4)(2-methyl,3-sec-butylC9H4)ZrCl2; Me2Ge(CpMe4)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; Et2Si(CpMe4)(2-methyl,3-n-propylC9H4)ZrCl2; Et2Si(CpMe4)(2-methyl,3-n-butylC9H4)ZrCl2; Et2Si(CpMe4)(2-methyl,3-benzylC9H4)ZrCl2; Et2Si(CpMe4)(2-methyl,3-sec-butylC9H4)ZrCl2; Et2Si(CpMe4)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; (Hexyl)2Si(CpMe4)(2-methyl,3-n-propylC9H4)ZrCl2; (Hexyl)2Si(CpMe4)(2-methyl,3-n-butylC9H4)ZrCl2; (Hexyl)2Si(CpMe4)(2-methyl,3-benzylC9H4)ZrCl2; (Hexyl)2Si(CpMe4)(2-methyl,3-sec-butylC9H4)ZrCl2; (Hexyl)2Si(CpMe4)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; [(C3H6)Si](CpMe4)(2-methyl,3-n-propylC9H4)ZrCl2; [(C3H6)Si(CpMe4)(2-methyl,3-n-butylC9H4)ZrCl2; [(C3H6)Si](CpMe4)(2-methyl,3-benzylC9H4)ZrCl2; [(C3H6)Si](CpMe4)(2-methyl,3-sec-butylC9H4)ZrCl2; [(C3H6)Si](CpMe4)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; [(C4H8)Si](CpMe4)(2-methyl,3-n-propylC9H4)ZrCl2; [(C4H8)Si(CpMe4)(2-methyl,3-n-butylC9H4)ZrCl2; [(C4H8)Si](CpMe4)(2-methyl,3-benzylC9H4)ZrCl2; [(C4H8)Si](CpMe4)(2-methyl,3-sec-butylC9H4)ZrCl2; [(C4H8)Si](CpMe4)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; Me2Si(3-n-propylCpMe3)(CpMe4)ZrCl2; Me2Si(3-n-propylCpMe3)(CpMe4)ZrMe2; Me2Si(3-n-butylCpMe3)(CpMe4)ZrCl2; Me2Si(3-n-butylCpMe3)(CpMe4)ZrMe2; Me2Si(3-benzylCpMe3)(CpMe4)ZrCl2; Me2Si(3-benzylCpMe3)(CpMe4)ZrMe2; Me2Si(3-CH2-cyclopropylCpMe3)(CpMe4)ZrCl2; Me2Si(3-CH2-cyclopropylCpMe3)(CpMe4)ZrMe2; Me2Ge(3-n-propylCpMe3)(CpMe4)ZrCl2; Me2Ge(3-n-propylCpMe3)(CpMe4)ZrMe2; Et2Si(3-n-propylCpMe3)(CpMe4)ZrCl2; Et2Si(3-n-propylCpMe3)(CpMe4)ZrMe2; (Hexyl)2Si(3-n-propylCpMe3)(CpMe4)ZrCl2; (Hexyl)2Si(3-n-propylCpMe3)(CpMe4)ZrMe2; [(C3H6)Si](3-n-propylCpMe3)(CpMe4)ZrCl2; [(C3H6)Si](3-n-propylCpMe3)(CpMe4)ZrMe2; [(C4H8)Si](3-n-propylCpMe3)(CpMe4)ZrCl2; [(C4H8)Si](3-n-propylCpMe3)(CpMe4)ZrMe2; rac-Me2Si(2-Me,3-n-propylC9H4)(2,3-Me2C9H4)ZrCl2; rac-Me2Si(2-Me,3-n-propylC9H4)2ZrCl2; rac-Me2Si(2-Me,3-n-butylC9H4)(2,3-Me2C9H4)ZrCl2; rac-Me2Si(2-Me,3-n-butylC9H4)2ZrCl2; rac-Me2Si(2-Me,3-CH2-cyclopropylC9H4)(2,3-Me2C9H4)ZrCl2; rac-Me2Si(2-Me,3-CH2-cyclopropylC9H4)2ZrCl2; rac-Me2Ge(2-Me,3-n-propylC9H4)(2,3-Me2C9H4)ZrCl2; rac-Me2Ge(2-Me,3-n-propylC9H4)2ZrCl2; rac-Et2Si(2-Me,3-n-propylC9H4)(2,3-Me2C9H4)ZrCl2; Et2Si(2-Me,3-n-propylC9H4)2ZrCl2; rac-(Hexyl)2Si(2-Me,3-n-propylC9H4)(2,3-Me2C9H4)ZrCl2; rac-(Hexyl)2Si(2-Me,3-n-propylC9H4)2ZrCl2; rac-[(C3H6)Si](2-Me,3-n-propylC9H4)(2,3-Me2C9H4)ZrCl2; rac-[(C3H6)Si](2-Me,3-n-propylC9H4)2ZrCl2; rac-[(C4H8)Si](2-Me,3-n-propylC9H4)(2,3-Me2C9H4)ZrCl2; rac-[(C4H8)Si](2-Me,3-n-propylC9H4)2ZrCl2; Me2Si(C13H8)(2-methyl,3-n-propylC9H4)ZrCl2; Me2Si(C13H8)(2-methyl,3-n-butylC9H4)ZrCl2; Me2Si(C13H8)(2-methyl,3-benzylC9H4)ZrCl2; Me2Si(C13H8)(2-methyl,3-sec-butylC9H4)ZrCl2; Me2Si(C13H8)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; Me2Ge(C13H8)(2-methyl,3-n-propylC9H4)ZrCl2; Me2Ge(C13H8)(2-methyl,3-n-butylC9H4)ZrCl2; Me2Ge(C13H8)(2-methyl,3-benzylC9H4)ZrCl2; Me2Ge(C13H8)(2-methyl,3-sec-butylC9H4)ZrCl2; Me2Ge(C13H8)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; Et2Si(C13H8)(2-methyl,3-n-propylC9H4)ZrCl2; Et2Si(C13H8)(2-methyl,3-n-butylC9H4)ZrCl2; Et2Si(C13H8)(2-methyl,3-benzylC9H4)ZrCl2; Et2Si(C13H8)(2-methyl,3-sec-butylC9H4)ZrCl2; Et2Si(C13H8)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; (Hexyl)2Si(C13H8)(2-methyl,3-n-propylC9H4)ZrCl2; (Hexyl)2Si(C13H8)(2-methyl,3-n-butylC9H4)ZrCl2; (Hexyl)2Si(C13H8)(2-methyl,3-benzylC9H4)ZrCl2; (Hexyl)2Si(C13H8)(2-methyl,3-sec-butylC9H4)ZrCl2; (Hexyl)2Si(C13H8)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; [(C3H6)Si](C13H8)(2-methyl,3-n-propylC9H4)ZrCl2; [(C3H6)Si(C13H8)(2-methyl,3-n-butylC9H4)ZrCl2; [(C3H6)Si](C13H8)(2-methyl,3-benzylC9H4)ZrCl2; [(C3H6)Si](C13H8)(2-methyl,3-sec-butylC9H4)ZrCl2; [(C3H6)Si](C13H8)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; [(C4H8)Si](C13H8)(2-methyl,3-n-propylC9H4)ZrCl2; [(C4H8)Si(C13H8)(2-methyl,3-n-butylC9H4)ZrCl2; [(C4H8)Si](C13H8)(2-methyl,3-benzylC9H4)ZrCl2; [(C4H8)Si](C13H8)(2-methyl,3-sec-butylC9H4)ZrCl2; [(C4H8)Si](C13H8)(2-methyl,3-CH2-cyclopropylC9H4)ZrCl2; and the zirconium dimethyl analogs of the above dichloride metallocene compounds, wherein the Cl groups on the Zr are preplaced with CH3 groups; wherein Me is methyl, Et is ethyl, C9H4 is an indenyl group; C13H8 is a fluorenyl group, [(C3H6)Si] is silacyclobutyl bridge, and [(C4H8)Si] is silacyclopentyl bridge.

### Claim 16 (depends on 1)

The process of claim 1, wherein the support material is SiO2, Al2O3, or SiO2/Al2O3.

### Claim 17 (depends on 1)

The process of claim 1, wherein the alumoxane activator is an alkylalumoxane.

### Claim 18 (depends on 1)

The process of claim 1, wherein the alumoxane activator is methylalumoxane.

### Claim 19 (depends on 1)

The process of claim 1, wherein the alumoxane activator comprises from about 0.5 to about 13 wt % trimethylaluminum, based on total aluminum.

### Claim 20 (depends on 1)

The process of claim 1, wherein the alumoxane activator comprises from about 1.0 to about 12 wt % trimethylaluminum, based on total aluminum.

### Claim 21 (depends on 1)

The process of claim 1, wherein the polyethylene has at least 98% allyl chain ends, based on total unsaturations.

### Claim 22 (depends on 1)

The process of claim 1, wherein the contacting step (a) takes place at a temperature in the range of about 40° C. to about 150° C.

### Claim 23 (depends on 1)

The process of claim 1, wherein the contacting step (a) takes place at a pressure in the range of from about 0.55 MPa to about 2.4 MPa.

### Claim 24 (depends on 1)

The process of claim 1, wherein the polyethylene is in the form of free-flowing, discrete particles.

### Claim 25 (depends on 1)

The process of claim 1, wherein the polyethylene has a branching index, g′(vis), of greater than 0.90.

### Claim 26 (depends on 1)

The process of claim 1, wherein the polyethylene has an Mn (1H NMR) of less than 125,000 g/mol.