# US 11,028,208 B2 · Terminal-functionalized polymer, rubber composition containing same and related processes

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- Number: US 11,028,208 B2
- Document ID: US11028208B2
- Status: Granted
- Kind: B2
- Application number: 16/094,808
- Filed: 2017-04-20
- Published: 2019-04-25
- Granted: 2021-06-08
- Earliest claimed: 2016-04-21
- Assignees: Bridgestone Corporation
- Applicants: Bridgestone Corporation
- Inventors: Yuan-Yong Yan
- Web page: https://patentgrep.com/patent/US11028208B2

## CPC

- C08F 257/02: on to polymers of styrene or alkyl-substituted styrenes
- C08C 19/25: Incorporating silicon atoms into the molecule
- C08C 19/28: Reaction with compounds containing carbon-to-carbon unsaturated bonds (graft polymers C08F279/00)
- C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton
- C08F 236/06: Butadiene
- C08F 236/08: Isoprene
- C08F 236/10: with vinyl-aromatic monomers
- C08F 279/02: on to polymers of conjugated dienes
- C08K 3/04: Carbon
- C08K 3/06: Sulfur
- C08K 3/22: of metals
- C08K 3/36: Silica
- C08K 5/09: Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K 5/18: with aromatically bound amino groups
- C08K 5/31: Guanidine; Derivatives thereof
- C08K 5/47: Thiazoles
- C08K 5/5419: containing at least one Si—C bond
- C08K 5/5425: containing at least one C=C bond
- C08L 7/00: Compositions of natural rubber
- C08L 9/06: Copolymers with styrene
- C08L 15/00: Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence)
- C08L 25/06: Polystyrene
- C08L 47/00: Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers (C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00)
- C08L 91/00: Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L 91/06: Waxes
- C08L 101/10: containing hydrolysable silane groups
- B60C 1/0016: {Compositions of the tread}
- C08F 2810/40: taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
- C08L 2205/02: containing two or more polymers of the same C08L -group
- C08L 2310/00: Masterbatches
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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)
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES

## Abstract

Disclosed herein are a terminal-functionalized polymer, rubber compositions containing the polymer, and related processes for preparing the polymer. The functionalizing compound used to prepare the terminal-functionalized polymer has a specified formula which includes a silicon atom and a moiety containing at least two carbon-carbon double bonds in a conjugated configuration.

## Claims

### Claim 1

A terminal-functionalized polymer having a structure according to formula I
(P)nSi(R)k(OR)m—SP—U (I)
wherein P is a polymer chain comprising at least one type of conjugated diene monomer and optionally at least one type of vinyl aromatic monomer,
n is an integer of 1-3, m is an integer of 0-2, k is an integer of 0 or 1, m+n+k=3,
each R is independently selected from: (i) an alkyl group having 1 to 20 carbons, (ii) a cycloalkyl group having 3 to 20 carbons, (iii) an aryl group having 6 to 20 carbons, (iv) an alkylaryl group having 7 to 20 carbons, or (v) SiR1R2R3 where each of R1, R2
and R3 is independently selected from H, (i), (ii), (iii), or (iv)
SP is a spacer group having at least two carbon atoms and is optionally substituted with at least one heteroatom selected from S, O, or NR, and
U is a moiety containing at least two carbon-carbon double bonds in a conjugated configuration.

### Claim 2 (depends on 1)

The terminal-functionalized polymer of claim 1, wherein U comprises a conjugated bond-containing cyclic moiety.

### Claim 3 (depends on 1)

The terminal-functionalized polymer of claim 1, wherein U comprises a moiety selected from
a. conjugated aromatics having at least one vinyl substituent,
b. conjugated non-aromatic cyclics, and
c. conjugated aliphatics.

### Claim 4 (depends on 3)

The terminal-functionalized polymer of claim 3, wherein U comprises (a) having 8-22 carbon atoms.

### Claim 5 (depends on 3)

The terminal-functionalized polymer of claim 3, wherein U comprises (b) having 5-20 carbon atoms.

### Claim 6 (depends on 4)

The terminal-functionalized polymer of claim 4, wherein U comprises vinylbenzene.

### Claim 7 (depends on 5)

The terminal-functionalized polymer of claim 5, wherein U comprises cyclopentadiene.

### Claim 8 (depends on 1)

The terminal-functionalized polymer of claim 1, wherein the at least one type of conjugated diene monomer is present and comprises 1,3-butadiene.

### Claim 9

A process for preparing a terminal-functionalized polymer, the process comprising reacting the live end of a polymer chain with a functionalizing compound having formula II, wherein the polymer chain comprises at least one type of conjugated diene monomer and optionally at least one type of vinyl aromatic monomer,
(OR)oSi(R)p—SP—U (II)
wherein o is an integer of 2-3, p is an integer of 0-1, o+p=3,
each R is independently selected from: (i) an alkyl group having 1 to 20 carbons, (ii) a cycloalkyl group having 3 to 20 carbons, (iii) an aryl group having 6 to 20 carbons, (iv) an alkylaryl group having 7 to 20 carbons, or (v) SiR1R2R3 where each of R1, R2 and R3 is independently selected from H, (i), (ii), (iii), or (iv),
SP is a spacer group having at least two carbon atoms and is optionally substituted with at least one heteroatom selected from S, O, or NR, and
U is a moiety containing at least two carbon-carbon double bonds in a conjugated configuration.

### Claim 10 (depends on 9)

The process of claim 9, wherein U comprises a conjugated bond-containing cyclic moiety.

### Claim 11 (depends on 9)

The process of claim 9, wherein U comprises a moiety selected from:
a. conjugated aromatics having at least one vinyl substituent,
b. conjugated non-aromatic cyclics, and
c. conjugated aliphatics.

### Claim 12 (depends on 11)

The process of claim 11, wherein U comprises (a) having 8-22 carbon atoms.

### Claim 13 (depends on 11)

The process of claim 11, wherein U comprises (b) having 5-20 carbon atoms.

### Claim 14 (depends on 12)

The process of claim 12, wherein U comprises vinylbenzene.

### Claim 15 (depends on 13)

The process of claim 13, wherein U comprises cyclopentadiene.

### Claim 16 (depends on 9)

The process of claim 9, wherein the at least one type of conjugated diene monomer is present and comprises 1,3-butadiene.

### Claim 17 (depends on 9)

A terminal-functionalized polymer prepared according to the process of claim 9.

### Claim 18 (depends on 3)

The terminal-functionalized polymer of claim 3, wherein U is a moiety selected from (a).

### Claim 19 (depends on 3)

The terminal-functionalized polymer of claim 3, wherein U is a moiety selected from (b).

### Claim 20 (depends on 3)

The terminal-functionalized polymer of claim 3, wherein U is a moiety selected from (c).