Silated core polysulfides, their preparation and use in filled elastomer compositions
View Patent ↗This invention relates to novel sulfur-containing silane coupling agents, and organic polymers containing carbon-carbon double bonds. These novel silanes can be carried on organic and inorganic fillers. The invention also relates to articles of manufacture, particularly tires, made from the elastomer compositions described herein.
1. A composition comprising:
(a) silated core polysulfide of the general formula:
[Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p ;
wherein:
each occurrence of G 1 is independently selected from a polyvalent heterocarbon-containing fragment having from 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
[(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ;
each occurrence of G 2 is independently selected from a polyvalent heterocarbon-containing fragment of 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
[(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ;
each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;
each occurrence of Y 1 and Y 2 is independently selected from consisting of silyl (—SiX 1 X 2 X 3 ), carboxylic acid, hydroxyl, hydrogen and ester (—C(═O)OR 6 ) wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of R 2 is a chemical bond or straight chain hydrocarbon represented by —(CH 2 ) f —;
each occurrence of R 4 is independently a polyvalent heterocarbon fragment of 1 to about 27 carbon atoms;
each occurrence of R 5 is independently a polyvalent heterocarbon fragment of 1 to about 27 carbon atoms;
each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of X 2 and X 3 is independently selected from the group consisting of —OSi containing groups that result from the condensation of silanols, hydrogen, R 6 , and X 1 , wherein X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, and wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given by a is 1 to about 3; b is 1 to about 5; c is 1 to about 3; d is 1 to about 5; e is 1 to about 3; f is 0 to about 5; m and p are 1 to about 100; n is 1 to about 15; o is 0 to about 10; and x is 1 to 10; and
(b) a silane of the general formula:
X 1 X 2 X 3 SiR 1 S x R 3 SiX 1 X 2 X 3
wherein each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;
each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of X 2 and X 3 is independently selected from the group consisting of hydrogen, R 6 , X 1 , and —OSi containing groups that result from the condensation of silanols, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
and x is 1 to about 10.
2. The composition of claim 1 , wherein the silated core polysulfide (a) is from about 30 to about 99 weight percent and the silane (b) is from about 70 to about 1 weight percent.
3. The composition of claim 2 wherein the silane (b) is selected from the group consisting of bis-(3-triethoxysilylpropyl)disulfide; bis-(3-triethoxysilylpropyl)trisulfide; bis-(3-triethoxysilylpropyl)tetrasulfide; bis-(3-triethoxysilylpropyl)pentasulfide; bis-(3-diethoxymethylsilylpropyl)disulfide; bis-(3-ethoxydimethylsilylpropyl)disulfide; bis-(triethoxysilylmethyl)disulfide; bis-(4-triethoxysilylbenzyl)disulfide, bis-(3-triethoxysilylphenyl)disulfide, and mixtures thereof.
4. A rubber composition comprising:
(a) silated core polysulfide of the general formula:
[Y 1 R 1 S x —] m [G 1 (R 2 SiX 1 X 2 X 3 ) a ] n [G 2 ] o [R 3 Y 2 ] p ;
wherein:
each occurrence of G 1 is independently selected from a polyvalent heterocarbon-containing fragment having from 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
[(CH 2 ) b —] c R 4 [—(CH 2 ) d S x —] e ;
each occurrence of G 2 is independently selected from a polyvalent heterocarbon-containing fragment of 3 to about 30 carbon atoms containing a polysulfide group represented by the general formula:
[(CH 2 ) b —] c R 5 [—(CH 2 ) d S x —] e ;
each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;
each occurrence of Y 1 and Y 2 is independently selected from consisting of silyl (—SiX 1 X 2 X 3 ), hydroxyl, hydrogen, carboxylic acid, and ester (—C(═O)OR 6 ) wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of R 2 is a chemical bond or straight chain hydrocarbon represented by —(CH 2 ) f —;
each occurrence of R 4 is independently a polyvalent heterocarbon fragment of 1 to about 27 carbon atoms;
each occurrence of R 5 is independently a polyvalent heterocarbon fragment of 1 to about 27 carbon atoms;
each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of X 2 and X 3 is independently selected from the group consisting of —OSi containing groups that result from the condensation of silanols, hydrogen, R 6 and X 1 , wherein X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, and wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of the subscripts, a, b, c, d, e, f, m, n, o, p, and x, is independently given by a is 1 to about 3; b is 1 to about 5; c is 1 to about 3; d is 1 to about 5; e is 1 to about 3; f is 0 to about 5; m and p are 1 to about 100; n is 1 to about 15; o is 0 to about 10; and x is 1 to 10;
(b) inorganic filler; and,
(c) rubber.
5. The rubber composition of claim 4 , further comprising (d) curative and, optionally, at least one other additive selected from the group consisting of sulfur compounds, activators, retarders, accelerators, processing additives, oils, plasticizers, tackifying resins, silicas, fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents, reinforcing materials, and mixtures thereof.
6. The rubber composition of claim 5 , wherein the curative (d) is sulfur.
7. The rubber composition of claim 4 , wherein the rubber (c) is at least one sulfur vulcanizable rubber selected from the group consisting of conjugated diene homopolymers and copolymers, copolymers of at least one conjugated diene and aromatic vinyl compound and mixtures thereof.
8. The rubber composition of claim 7 , wherein the rubber (c) is styrene/butadiene rubber containing from about 5 to about 50 percent vinyl content.
9. The rubber composition of claim 8 wherein the rubber (c) is styrene/butadiene having a styrene content of about 20 to about 28 weight percent.
10. The rubber composition of claim 7 , wherein the rubber (c) is derived from a conjugated diene selected from the group consisting of isoprene, 1,3-butadiene, styrene, and alpha methyl styrene, and mixture thereof.
11. The rubber composition of claim 4 , wherein the rubber (c) is at least one natural rubber, or emulsion polymerization derived rubber, or a solvent polymerization derived rubber.
12. The rubber composition of claim 4 , wherein the rubber (c) is selected from the group consisting of cis-1,4-polyisoprene rubber, emulsion polymerization prepared styrene/butadiene copolymer rubber, organic solution polymerization prepared styrene/butadiene rubber, 3,4-polyisoprene rubber, isoprene/butadiene rubber, styrene/isoprene/butadiene terpolymer rubber, cis-1,4-polybutadiene, medium vinyl polybutadiene rubber, wherein the medium vinyl polybutadiene rubber has about 35 to 50 weight percent vinyl, high vinyl polybutadiene rubber wherein the high vinyl polybutadiene rubber has about 50 to 75 weight percent vinyl, styrene/isoprene copolymers, emulsion polymerization prepared styrene/butadiene/acrylonitrile terpolymer rubber and butadiene/acrylonitrile copolymer rubber.
13. The rubber composition of claim 4 further comprising a silane of the general formula:
X 1 X 2 X 3 SiR 1 S x R 3 SiX 1 X 2 X 3
wherein each occurrence of R 1 and R 3 is independently selected from a divalent hydrocarbon fragment having from 1 to about 20 carbon atoms;
each occurrence of X 1 is independently selected from the group consisting of —Cl, —Br, —OH, —OR 6 , and R 6 C(═O)O—, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
each occurrence of X 2 and X 3 is independently selected from the group consisting of hydrogen, R 6 , X 1 , and —OSi containing groups that result from the condensation of silanols, wherein R 6 is a monovalent hydrocarbon group having from 1 to 20 carbon atoms;
and x is 1 to about 10.
14. The rubber composition of claim 13 , wherein the silane is selected from the group consisting of bis-(3-triethoxysilylpropyl)disulfide; bis-(3-triethoxysilylpropyl)trisulfide; bis-(3-triethoxysilylpropyl)tetrasulfide; bis-(3-triethoxysilylpropyl)pentasulfide; bis-(3-diethoxymethylsilylpropyl)disulfide; bis-(3-ethoxydimethylsilylpropyl)disulfide; bis-(triethoxysilylmethyl)disulfide; bis-(4-triethoxysilylbenzyl)disulfide, bis-(3-triethoxysilylphenyl)disulfide, and mixtures thereof.
15. The rubber composition of claim 4 , wherein the filler (b) is selected from the group consisting of particulate, precipitated silica, a combination of silica and carbon black, and aluminum oxide.