# US 9,751,964 B2 · Processes to improve reactor stability for the preparation of ethylene-based polymers using asymmetrical polyenes

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- Number: US 9,751,964 B2
- Document ID: US9751964B2
- Status: Granted
- Kind: B2
- Application number: 15/101,347
- Filed: 2014-12-23
- Published: 2016-10-20
- Granted: 2017-09-05
- Earliest claimed: 2013-12-26
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Christopher R. Eddy; John O. Osby; Sean W. Ewart; Sarat Munjal; Stefan Hinrichs; Otto J. Berbee
- Web page: https://patentgrep.com/patent/US9751964B2

## CPC

- C08F 210/02: Ethene
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The invention provides a process to form an ethylene-based polymer, said process comprising polymerizing ethylene and at least one asymmetrical polyene, comprising an “alpha, beta unsaturated—carbonyl end” and a “C—C double bond end,” and wherein the polymerization takes place in the presence of at least one free-radical initiator, and wherein the polymerization takes place in a reactor configuration comprising at least two reaction zones, reaction zone I and reaction zone i (i>2), wherein reaction zone I is downstream from reaction zone I; and wherein at least one chain transfer agent (CTA) is added to the polymerization, and wherein the CTA is a saturated hydrocarbon or an unsaturated hydrocarbon.

## Claims

### Claim 1

A process to form an ethylene-based polymer, said process comprising polymerizing ethylene and at least one asymmetrical polyene, comprising an “alpha, beta unsaturated—carbonyl end” and a “C—C double bond end,” and
wherein the polymerization takes place in the presence of at least one free-radical initiator, and wherein the polymerization takes place in a reactor configuration comprising at least two reaction zones, reaction zone 1 and reaction zone i (i≧2), wherein reaction zone i is downstream from reaction zone 1; and
wherein at least one chain transfer agent (CTA) is added to the polymerization, and wherein the CTA is a saturated hydrocarbon or an unsaturated hydrocarbon.

### Claim 2 (depends on 1)

The process of claim 1, wherein the CTA is selected from an alkane, an alkene, or a combination thereof.

### Claim 3 (depends on 1)

The process of claim 1, wherein the polyene is subject to an “oxygen removal step” prior to being fed to a reaction zone.

### Claim 4 (depends on 1)

The process of claim 1, wherein the polyene is stored in a feed vessel, and wherein the feed vessel has a “head-space gas” comprising less than 5.0 volume percent oxygen.

### Claim 5 (depends on 1)

The process of claim 1, wherein the polyene is fed through a compression stage directly into the reaction zone or directly into the feed to the reaction zone.

### Claim 6 (depends on 1)

The process of claim 1, wherein the polyene is fed directly into the reaction zone or directly into the feed to the reaction zone.

### Claim 7 (depends on 1)

The process of claim 1, wherein the maximum temperature of the first reaction zone is greater than the maximum temperature of each consecutive reaction zone, downstream from the first reaction zone.

### Claim 8 (depends on 1)

The process of claim 1, wherein the maximum temperature of the last reaction zone is less than the maximum temperature of each prior reaction zone.

### Claim 9 (depends on 1)

The process of claim 1, wherein no polyene is fed to reaction zone 1.

### Claim 10 (depends on 1)

The process of claim 1, wherein more polyene is added to reaction zone i, as compared to the amount of polyene added to reaction zone 1.

### Claim 11 (depends on 1)

The process of claim 1, wherein the ethylene fed to the first reaction zone is from 10 to 100 percent of the total ethylene fed to the polymerization.

### Claim 12 (depends on 1)

The process of claim 1, wherein the process takes place in a reactor configuration that comprises at least one tubular reactor.

### Claim 13 (depends on 1)

The process of claim 1, wherein the asymmetrical polyene is selected from the group consisting of the following i) through x):
wherein n is from 1 to 50; Ra is selected from H or alkyl; Rb is selected from H or alkyl;
where m=1 to 20.