Free radical grafting of functionalized resins for tires

Patent metadata

Field	Value
Publication number	US-10059782-B2
Application number	US-201515118730-A
Country	US
Kind code	B2
Filing date	Mar 6, 2015
Priority date	Mar 31, 2014
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

This invention relates to a process for the preparation of a silane-functionalized resin composition comprising the steps of mixing a polymer backbone, a silane, and a free radical initiator; and producing a silane-functionalized resin composition. The polymer backbone is selected from at least one of dicyclopentadiene (DCPD)-based polymers, cyclopentadiene (CPD)-based polymers, DCPD-styrene copolymers, C 5 homopolymers and copolymer resins, C 5 -styrene copolymer resins, terpene homopolymer or copolymer resins, pinene homopolymer or copolymer resins, C 9 homopolymers and copolymer resins, C 5 /C 9 copolymer resins, alpha-methylstyrene homopolymer or copolymer resins, and combinations thereof.

First claim

The invention claimed is:

1. A process for the preparation of a silane-functionalized resin composition, comprising the steps of:
(A) mixing a polymer backbone, a silane, and a free radical initiator; and
(B) producing a silane-functionalized resin composition,
wherein the polymer backbone has a softening point from 80° C. to 150° C. and comprises:
(i) within the range from 60 to 100 wt % cyclic components;
(ii) less than or equal to 15 wt % components derived from piperylene;
(iii) less than or equal to 15 wt % components derived from amylene;
(iv) less than or equal to 15 wt % components derived from isoprene;
(v) less than or equal to 20 wt % components derived from styrene; and
(vi) less than or equal to 20 wt % components derived from indene,
and wherein the silane is (i) vinyltrimethoxysilane and/or (ii) of the formula (I) and/or (II);

where each Y is independently a nitrogen, oxygen, or sulfur atom, each Z is independently a boron, nitrogen, oxygen, silicon or sulfur atom, each R 1 is independently a hydrogen atom, or a substituted or unsubstituted alkyl or aromatic group of from 1 to 20 carbon atoms, each R 2 is independently a divalent substituted or unsubstituted alkyl or aromatic group of from 1 to 20 carbon atoms, each R 3 is independently a hydrogen atom, a halogen atom, a sulfonate group, a substituted or unsubstituted alkyl or aromatic group of from 1 to 20 carbon atoms, R 1 , R 2 , and R 3 may form single or multinuclear rings with each other, a-f are independently integers of 1, 2, or 3, with the proviso that a+b+c and d+e+f are both equal to 3, and independently for each Y and Z, if Z is a boron atom, then x=2, if Y or Z is a nitrogen atom, then x=2, if Y or Z is an oxygen or sulfur atom, then x=1, if Z is a silicon atom, then x=3.

2. The process of claim 1 , wherein the free radical initiator is selected from the group consisting of organic peroxide, azobisisbutyronitrile), 1,1′-azobis(cyclohexanecarbonitrile), 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis(2-methylbutyronitrile), 2,3-dimethyl-2,3 -diphenylbutane, 1,1-diphenyl-2,2-diethylcyclopropane, 2,2,3,3-tetraphenylbutane, sodium, potassium, or ammonium persulfate, hydroxymethanesulfinic acid monosodium salt dihydrate, acetophenone, benzil, benzoin, benzophenone, thioxanthones, and combinations thereof.

3. A tire tread composition comprising:
(i) a functionalized resin composition within the range from 5 to 100 phr;
(ii) 100 phr of a diene elastomer; and
(iii) an inorganic filler is within the range from 50 to 150 phr,
wherein the functionalized resin comprises the reaction product of a polymer backbone, a silane, and a free radical initiator, where the polymer backbone comprises:
(i) within the range from 60 to 100 wt % cyclic components;
(ii) less than or equal to 15 wt % components derived from piperylene;
(iii) less than or equal to 15 wt % components derived from amylene;
(iv) less than or equal to 15 wt % components derived from isoprene;
(v) less than or equal to 20 wt % components derived from styrene; and
(vi) less than or equal to 20 wt % components derived from indene,
and wherein the silane is (i) vinyltrimethoxysilane and/or (ii) of the formula (I) and/or (II):

where each Y is independently a nitrogen, oxygen, or sulfur atom, each Z is independently a boron, nitrogen, oxygen, silicon or sulfur atom, each R 1 is independently a hydrogen atom, or a substituted or unsubstituted alkyl or aromatic group of from 1 to 20 carbon atoms, each R 2 is independently a divalent substituted or unsubstituted alkyl or aromatic group of from 1 to 20 carbon atoms, each R 3 is independently a hydrogen atom, a halogen atom, a sulfonate group, a substituted or unsubstituted alkyl or aromatic group of from 1 to 20 carbon atoms, R 1 , R 2 , and R 3 may form single or multinuclear rings with each other, a-f are independently integers of 1, 2, or 3, with the proviso that a+b+c and d+e+f are both equal to 3, and independently for each Y and Z, if Z is a boron atom, then x=2, if Y or Z is a nitrogen atom, then x=2, if Y or Z is an oxygen or sulfur atom, then x=1, if Z is a silicon atom, then x=3.

4. The tire tread composition of claim 3 , wherein the polymer backbone is selected from at least one of dicyclopentadiene (DCPD)-based polymers, cyclopentadiene (CPD)-based polymers, DCPD-styrene copolymers, C 5 homopolymers and copolymer resins,C 5 -styrene copolymer resins, terpene homopolymer or copolymer resins, C 9 homopolymers and copolymer resins, C 5 /C 9 copolymer resins, alpha-methylstyrene homopolymer or copolymer resins, and combinations thereof.

5. The tire tread composition of claim 3 , wherein the free radical initiator is selected from the group consisting of organic peroxide, azobisisbutyronitrile), 1,1′-azobis(cyclohexanecarbonitrile), 4,4′-azobis(4-cyanovaleric acid), 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis(2-methylbutyronitrile), 2,3-dimethyl-2,3-diphenylbutane, 1,1-diphenyl-2,2-diethylcyclopropane, 2,2,3,3-tetraphenylbutane, sodium, potassium, or ammonium persulfate, hydroxymethanesulfinic acid monosodium salt dihydrate, acetophenone, benzil, benzoin, benzophenone, thioxanthones, and combinations thereof.

6. The tire tread composition of claim 3 , wherein the inorganic filler comprises silica.

7. The tire tread composition of claim 3 , wherein the diene elastomer is selected from the group consisting of natural rubber, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, high cis-polybutadiene, ethylene-propylene rubber, ethylene-propylene-diene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, branched (“star-branched”) butyl rubber, halogenated star-branched butyl rubber, poly(isobutylene-co-p-methylstyrene), brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutylene rubber, and mixtures thereof.

8. The tire tread composition of claim 7 , wherein the diene elastomer comprises a mixture of polybutadiene rubber and styrene-butadiene rubber.

9. The tire tread composition of claim 3 , further comprising a coupling agent.

10. The tire tread composition of claim 3 , wherein the composition is cured.

11. A tire comprising the tire tread composition of claim 3 .

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Blok Edward J
• Stewart Ian C
• Harris David T

Classifications

• C08L51/04

  grafted on to rubbers · CPC title

• C08L21/00

  Compositions of unspecified rubbers · CPC title

• C08L9/06

  Copolymers with styrene · CPC title

• C08L9/00

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title

• B60C1/0016

  Compositions of the tread · CPC title