# US 2022/0033548 A1 · Process of polymerizing tetra-functional long-chain branched polyolefin resins

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- Number: US 2022/0033548 A1
- Document ID: US20220033548A1
- Status: Published application
- Kind: A1
- Application number: 17/280,301
- Filed: 2019-09-27
- Published: 2022-02-03
- Earliest claimed: 2018-09-28
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Robert D.J. Froese; Daniel J. Arriola; Bryan D. Stubbert
- Web page: https://patentgrep.com/patent/US20220033548A1

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 210/18: with non-conjugated dienes, e.g. EPT rubbers
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The present process embodiments for synthesizing long-chain branched copolymers include contacting together one or more C2-C14 alkene monomers, at least one diene or polyene, optionally a solvent, and a multi-chain catalyst. The multi-chain catalyst includes a plurality of polymerization sites and produces at least two polymer chains of the C2-C14 alkene monomers, each polymer chain polymerizing at one of the polymerization sites. The process synthesizes the long-chain branched polymers by connecting the two polymer chains with the diene or polyene, the joining of the two polymer chains being performed in a concerted manner during the polymerization.

## Claims

### Claim 1

A process of synthesizing long-chain branched copolymers, the process comprising:
contacting together one or more C2-C14 alkene monomers, at least one diene or polyene, optionally a solvent, and a multi-chain catalyst, wherein the multi-chain catalyst comprises multiple polymerization sites;
producing at least two polymer chains of the C2-C14 alkene monomers, each polymer chain polymerizing at one of the polymerization sites; and
synthesizing the long-chain branched polymers by connecting the two polymer chains with the diene or polyene, the connecting of the two polymer chains being performed in a concerted manner during the polymerization.

### Claim 2 (depends on 1)

The process of claim 1, wherein ethylene is added to such an extent that the resulting copolymer content is greater than 50 mol % ethylene.

### Claim 3 (depends on 1)

The process of claim 1, wherein the diene and polyene comonomer is incorporated at such level to achieve at least one bridging juncture per 100 copolymer chains.

### Claim 4 (depends on 1)

The process of claim 1, wherein the diene is unconjugated or the polyene has at least two unconjugated bonds per molecule.

### Claim 5 (depends on 1)

The process of claim 1, wherein the multi-chain catalyst is a heterogeneous catalyst with surface concentration of metal atoms greater than or equal to 0.3 metal atoms per nanometer squared (metal/nm2).

### Claim 6 (depends on 1)

The process of claim 1, wherein the multi-chain catalyst has two ligated transition metals linked by a dianionic activator where the distance between the metal atoms is less than or equal to 18.5 Å.

### Claim 7 (depends on 1)

The process of claim 1, wherein the multi-chain catalyst consists of two or more transition metals covalently tethered, where the distance between the metal atoms is less than or equal to 18.5 Å.

### Claim 8 (depends on 1)

The process of claim 1, wherein the multi-chain catalyst has two or more polymer chains on the same metal.

### Claim 9 (depends on 1)

The process of claim 1, wherein the multi-chain catalyst has a monoanionic ligand, is a Group IV Metal (Ti, Zr, Hf, and has two polymer chains on the same metal.

### Claim 10 (depends on 1)

The process of claim 1, wherein the long-chain branched copolymer Mw is at least 20% greater than the Mw of the polymer synthesized without the diene or polyene or wherein the long-chain branched copolymer Mp is at least 20% greater than the Mp of the polymer synthesized without the diene or polyene.

### Claim 11 (depends on 1)

The process of claim 1, wherein the polydisperse long-chain branched polymer has from 0.01 to 0.5 diene junctures per number average copolymer chain or 0.02 to 1.0 diene junctures per weight average copolymer chain.

### Claim 12 (depends on 1)

The process of claim 1, wherein the polymerization occurs in a solution polymerization reactor or a particle forming polymerization reactor such as a slurry reactor or a gas phase reactor, wherein the molecular or solid-supported catalyst is delivered to the reaction media or developed in the reaction media, wherein the reactor system is batch or continuous or a hybrid such as semi-batch, wherein the reactor residence time distribution is narrow such as in non-backmixed reactors or broad such as in backmixed reactor and series and recycle reactors.

### Claim 13 (depends on 1)

The process of claim 1, wherein the diene is linear.

### Claim 14 (depends on 1)

The process of any one of claim 1, wherein the diene is selected from 2-methyl-1,4-pentadiene, 3-methyl-1,4-pentadiene, 1,3-divinylcyclopentane, 2-methyl-1,5-hexadiene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, and 1,15-hexadecadiene.