Activated halo-containing aralkylsilane composition, process of preparing same and rubber compositions made therefrom
View Patent ↗The invention is directed to an activated halo-containing aralkylsilanes possessing at least one hydrolyzable group bonded to a silicon atom and at least one halo functional group bonded to a carbon atom to which both the silicon atom and an aromatic group are covalently bonded. The invention is also directed to a process for making such a silane as well as its use in rubber compositions and articles containing such rubber compositions, such as tires.
1. A halo-containing aralkylsilane of the generalized structural Formula (1):
X 1 X 2 X 3 Si—C(R 1 ) 2−a (Z 1 a )-G-(CR 3−c —Z 2 c ) b (1)
wherein:
X 1 is a hydrolyzable moiety selected from the group consisting of Cl—, Br—, I—, R 2 O—, R 2 (═O)O—, R 2 2 C═NO—, and R 2 2 NO—, wherein each R 2 is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl, alkenyl, aryl and aralkyl groups wherein each R 2 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
each X 2 and X 3 is independently selected from X 1 and R 3 groups wherein each R 3 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 3 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
R 1 is selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl wherein R 1 , other than hydrogen, contains from 1 to 10 carbon atoms, and optionally at least one heteroatom selected from the group consisting of oxygen, sulfur, fluorine, chlorine, bromine and iodine;
each Z 1 and Z 2 is independently a halogen atom selected from the group consisting of F—, Cl—, Br— and I—;
G is a monovalent or polyvalent aromatic hydrocarbon group of Formula (2):
(−) 1+b C 6 R 4 5−b (2)
wherein the six carbon atoms are part of an aromatic ring structure and each occurrence of R 4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 4 , other than hydrogen, contains from 1 to 18 carbon atoms;
each occurrence of R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl wherein each R, other than hydrogen, contains from 1 to 30 carbon atoms; and,
a, b and c are integers whereby a is 1; b is from 0 to 5; and c is from 1 to 3.
2. The halo-containing aralkylsilane of claim 1 wherein X 1 is an alkoxy group.
3. The halo-containing aralkylsilane of claim 1 wherein both Z 1 and Z 2 are halogen atom Cl.
4. The halo-containing aralkylsilane of claim 1 wherein R 1 is methyl, ethyl or propyl; each R 2 is independently methyl, ethyl or propyl; each R 3 is independently methyl; each R 4 is independently hydrogen or methyl; X 1 is ethoxy; each X 2 and X 3 is independently ethoxy or methyl; b is 0 or 1 and c is 1 to 3.
5. The halo-containing aralkylsilane of claim 4 wherein R 2 is ethyl; X 2 and X 3 are ethoxy; b is 1 and c is 1.
6. The halo-containing aralkylsilane of claim 1 selected from the group consisting of: [1-chloro-1-(4-chloromethyl-phenyl)-ethyl]-diethoxy-methyl-silane, [1-chloro-1-(4-chloromethyl-phenyl)-ethyl]-triethoxy-silane, [1-chloro-1-(4-chloromethyl-phenyl)-ethyl]-ethoxy-dimethyl-silane, [1-bromo-1-(4-bromomethyl-phenyl)-ethyl]-diethoxy-methyl-silane, [1-bromo-1-(4-bromomethyl-phenyl)-ethyl]-triethoxy-silane, [1-Chloro-1-(4-methyl-phenyl)-ethyl]-diethoxy-methyl-silane, [1-chloro-1-(4-methyl-phenyl)-ethyl]-triethoxy-silane, [1-chloro-1-(4-chloromethyl-phenyl)-propyl]-diethoxy-methyl-silane, {1-chloro-1-[4-(1-chloro-ethyl)-phenyl]-propyl}-triethoxy-silane, [1-chloro-1-(4-dichloromethyl-phenyl)-propyl]-diethoxy-methyl-silane, [1-chloro-1-(4-dichloromethyl-phenyl)-propyl]-triethoxy-silane, [1-chloro-1-(4-trichloromethyl-phenyl)-propyl]-diethoxy-methyl-silane, [1-chloro-1-(4-trichloromethyl-phenyl)-propyl]-triethoxy-silane, [1-chloro-1-(4-chloromethyl-phenyl)-ethyl]-trimethoxy-silane, [1-chloro-1-(4-chloromethyl-phenyl)-ethyl]-tripropoxy-silane, and chloro-[1-chloro-1-(4-chloromethyl-phenyl)-propyl]-dimethyl-silane.
7. A mixture comprising a partial or complete hydrolyzate of at least one halo-containing aralkylsilane of claim 1 .
8. A composition comprising: (a) at least one halo-containing aralkylsilane of the structural Formula (1):
X 1 X 2 X 3 Si—C(R 1 ) 2−a (Z 1 a )-G-(CR 3−c —Z 2 c ) b (1)
where a is 1; and (b) at least one silane of the structural Formula (1) where a is 0,
wherein X 1 is a hydrolyzable moiety selected from the group consisting of Cl—, Br—, I—, R 2 O—, R 2 (═O)O—, R 2 2 C═NO—, and R 2 2 NO—, wherein each R 2 is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl, alkenyl, aryl and aralkyl groups wherein each R 2 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
each X 2 and X 3 is independently selected from X 1 and R 3 groups wherein each R 3 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 3 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
each R 1 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl wherein each R 1 , other than hydrogen, contains from 1 to 10 carbon atoms, and optionally at least one heteroatom selected from the group consisting of oxygen, sulfur, fluorine, chlorine, bromine and iodine;
each Z 1 and Z 2 is independently a halogen atom selected from the group consisting of F—, Cl—, Br— and I—;
G is a monovalent or polyvalent aromatic hydrocarbon group of Formula (2):
(−) 1+b C 6 R 4 5−b (2)
wherein the six carbon atoms are part of an aromatic ring structure and each occurrence of R 4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 4 , other than hydrogen, contains from 1 to 18 carbon atoms;
each occurrence of R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl wherein each R, other than hydrogen, contains from 1 to 30 carbon atoms; and,
b and c are integers whereby b is from 0 to 5; and c is from 1 to 3, with the proviso that a+b is equal to or greater than 1.
9. A process for preparing a halo-containing aralkylsilane comprising the steps of:
(a) reacting a hydridosilane (i) of general Formula (3):
HSiX 4 X 5 X 6 (3)
wherein X 4 is a hydrolyzable moiety selected from the group consisting of F—, Cl—, Br— and I—; each X 5 and X 6 is independently selected from X 4 and R 3 groups wherein each R 3 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 3 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur;
with a carbon-carbon double bond-containing aralkane (ii) of Formula (4):
R 5 R 6 C═C(R 1 )—C 6 R 4 5−b (CR 3 ) b (4)
wherein each occurrence of R is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl wherein each R, other than hydrogen, contains from 1 to 30 carbon atoms; each occurrence of R 1 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl wherein each R 1 , other than hydrogen, contains from 1 to 10 carbon atoms; each occurrence of R 4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 4 , other than hydrogen, contains from 1 to 18 carbon atoms; each R 5 and R 6 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl or aralkyl wherein each R 5 and R 6 , other than hydrogen, contains from 1 to 9 carbon atoms; and b is an integer of from 0 to 5;
in the presence of an effective amount of an alpha-selective hydrosilylation catalyst (iii) to provide an aralkylsilane of Formula (5):
X 4 X 5 X 6 Si—C(R 1 ) 2 —C 6 R 4 5−b —(CR 3 ) b (5)
(b) reacting the reaction product of step (a) with halogen (iv), optionally in the presence of an effective amount of halogenation catalyst (v) to yield a halo-containing aralkylsilane of Formula (6):
X 4 X 5 X 6 Si—C(R 1 ) 2−a (Z 1 a )-G-(CR 3−c —Z 2 c ) b (6)
wherein:
each G is independently a monovalent or polyvalent aromatic hydrocarbon group of Formula (2):
(−) 1+b C 6 R 4 5−b (2)
wherein the six carbon atoms are part of an aromatic ring structure and each occurrence of R 4 is independently selected from the group consisting of hydrogen, alkyl, alkenyl, aryl and aralkyl groups wherein each R 4 , other than hydrogen, contains from 1 to 18 carbon atoms;
each occurrence of Z 1 and Z 2 is independently a halogen atom selected from the group consisting of F—, Cl—, Br— and I—; and,
a, b and c are integers whereby a is 0 or 1; b is from 0 to 5, and c is from 1 to 3, with the proviso that a+b is equal to or greater than 1; and,
(c) optionally, reacting the halo-containing aralkylsilane of step (b) with X 1 —H, wherein X 1 is a hydrolyzable moiety selected from the group consisting of Cl—, Br—, I—, R 2 O—, R 2 (═O)O—, R 2 2 C═NO—, and R 2 2 NO—, wherein each R 2 is independently selected from the group consisting of hydrogen, straight, cyclic or branched alkyl, alkenyl, aryl and aralkyl groups wherein each R 2 , other than hydrogen, contains from 1 to 18 carbon atoms and optionally at least one heteroatom selected from the group consisting of oxygen and sulfur.
10. The process of claim 9 wherein the hydridosilane (i) is selected from the group consisting of trichlorosilane, methyldichlorosilane, dimethylchlorosilane, tribromosilane, methyldibromosilane, fluorodimethylsilane, ethyldichlorosilane, phenyldichlorosilane and isopropyldichlorosilane.
11. The process of claim 9 wherein the carbon-carbon double bond-containing aralkane (ii) is selected from the group consisting of 1-methyl-4-vinyl-benzene, 1,2-dimethyl-4-vinyl-benzene, 1-isopropenyl-4-methyl-benzene, 1-methyl-4-propenyl-benzene, 1-ethyl-4-(1-methyl-propenyl)-benzene, 1-methyl-2-vinyl-benzene, 4-dimethyl-1-vinyl-benzene and 1-methyl-4-styryl-benzene.
12. A composition comprising:
(a) at least one filler; and
(b) at least one silane of claim 1 in admixture with, or chemically bonded to, the filler of component (a).
13. The composition of claim 12 wherein the filler is at least one selected from the group consisting of silica, titanium dioxide, aluminosilicate, alumina and siliceous materials, and combinations thereof.
14. A rubber composition comprising:
(a) at least one rubber component;
(b) at least one filler;
(c) optionally, at least one activating agent; and,
(d) at least one silane of claim 1 .
15. The rubber composition of claim 14 wherein the filler (b) is silane-reactive.
16. The rubber composition of claim 14 wherein component (d) is present in an amount of from about 0.2 to about 20% based on the total weight of the rubber composition.
17. A process for preparing a rubber composition comprising mixing: (a) at least one rubber component; (b) at least one filler; (c) optionally, at least one activating agent; and, (d) at least one silane of claim 1 in effective amounts.
18. The process of claim 17 wherein the effective amounts of component (a), (b) and (d) are from about 30-98%, about 2-70%, and about 0.2-2%, respectively.
19. The process of claim 17 wherein the filler (b) and the silane (d) are pre-mixed or pre-reacted prior to mixing with the rubber component (a) and optionally the activating agent (c).
20. The process of claim 17 further comprising the step of curing the rubber composition to provide a cured product.
21. An article of manufacture selected from the group consisting of tires, industrial goods, shoe soles, hoses, seals, gaskets and cable jackets, at least one component of which is the cured rubber composition of claim 14 .
22. The article of claim 21 , wherein the article is a tire.