# US 11,028,195 B2 · Hydroxyaryl functionalized polymers

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- Number: US 11,028,195 B2
- Document ID: US11028195B2
- Status: Granted
- Kind: B2
- Application number: 16/297,689
- Filed: 2019-03-10
- Published: 2019-08-01
- Granted: 2021-06-08
- Earliest claimed: 2007-12-28
- Assignees: Bridgestone Corporation
- Applicants: Bridgestone Corporation
- Inventors: Xiao-Dong Pan; Zengquan Qin; Yuan-Yong Yan; Dennis R. Brumbaugh; Jason T. Poulton
- Web page: https://patentgrep.com/patent/US11028195B2

## CPC

- C08F 212/24: {Phenols or alcohols}
- C07D 339/08: Six-membered rings
- C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton
- C08F 36/04: conjugated
- C08F 36/06: Butadiene
- C08F 290/06: Polymers provided for in subclass C08G
- C08F 290/14: Polymers provided for in subclass C08G
- C08F 297/02: using a catalyst of the anionic type
- C08F 297/04: polymerising vinyl aromatic monomers and conjugated dienes
- C08K 3/013: Fillers, pigments or reinforcing additives
- C08L 53/02: of vinyl-aromatic monomers and conjugated dienes
- C08F 236/10: with vinyl-aromatic monomers
- Y02P 20/55: Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Vulcanizates with desirable properties can be obtained from compounds incorporating polymers that include hydroxyl group-containing aryl functionalities. The functionalities can be incorporated by using any or all of appropriate initiators, monomers and terminating compounds. Such polymers exhibit excellent interactivity with both conventional and non-conventional fillers.

## Claims

### Claim 1

A method of making a functionalized polymer that comprises polyene mer and a terminal functional group, said method comprising
a) providing a solution that comprises a catalyst system and one or more types of ethylenically unsaturated monomers which include at least one type of polyene;
b) allowing said one or more types of ethylenically unsaturated monomers to polymerize, thereby providing a terminally active polymer;
c) reacting said terminally active polymer with a functionalizing compound that comprises
(1) a functional group that is reactive toward a terminally active polymer, and
(2) an aryl group having at least two directly bonded OR groups where each R is a hydrolyzable t-butyldimethylsilyl protecting group,
thereby providing said functionalized polymer.

### Claim 2 (depends on 1)

The method of claim 1 wherein said catalyst system comprises a lanthanide compound and a cocatalyst, said terminally active polymer being pseudo-living.

### Claim 3 (depends on 2)

The method of claim 2 wherein said cocatalyst comprises an alkylating agent.

### Claim 4 (depends on 3)

The method of claim 3 wherein said cocatalyst further comprises a halogen-containing compound.

### Claim 5 (depends on 3)

The method of claim 3 wherein said cocatalyst further comprises a non-coordinating anion or precursor thereof.

### Claim 6 (depends on 2)

The method of claim 2 wherein said cocatalyst comprises aluminoxane.

### Claim 7 (depends on 1)

The method of claim 1 wherein each of said one or more types of ethylenically unsaturated monomers is a polyene.

### Claim 8 (depends on 7)

The method of claim 7 wherein said functionalized polymer has a cis-1,4-linkage content of at least about 95%.

### Claim 9 (depends on 7)

The method of claim 7 wherein said functionalized polymer has a 1,2-linkage content of less than about 2%.

### Claim 10 (depends on 1)

The method of claim 1 wherein said at least two directly bonded OR groups are on adjacent ring C atoms of said aryl group.

### Claim 11 (depends on 10)

The method of claim 10 wherein said aryl group is a phenyl group.

### Claim 12 (depends on 11)

The method of claim 11 wherein said functional group reactive toward a terminally active polymer is an aldehyde.

### Claim 13 (depends on 12)

The method of claim 12 wherein said functionalizing compound is defined by the general formula
wherein each R5 independently is a hydrogen atom, an alkoxy group, or a hydrocarbyl group.

### Claim 14 (depends on 11)

The method of claim 11 wherein said functional group reactive toward a terminally active polymer is a ketone.

### Claim 15 (depends on 14)

The method of claim 14 wherein said functionalizing compound is defined by one of the following general formulae,
wherein each R5 independently is a hydrogen atom, an alkoxy group, or a hydrocarbyl group.

### Claim 16 (depends on 1)

The method of claim 1 further comprising introducing to said functionalized polymer an active hydrogen atom-containing compound, thereby hydrolyzing each of said OR groups.