Halo-functional silane, process for its preparation, rubber composition containing same and articles manufactured therefrom
View Patent ↗A halo-functional silane possesses halogen functionality and alkanedioxysilyl functionality.
1. A halo-functional silane possessing halogen functionality and alkanedioxysilyl functionality, and partial hydrolyzates thereof, selected from one of general Formulae (1) and (2):
Y 1 (—SiZ θ X 1 ) a (1), and
[Y 1 (—SiZ θ Z β ) a ] m [Y 1 (—SiZ β 3 ) a ] n (Y 1 (—SiZ β 2 X 1 ) a ] o [[Y 1 (—SiZ β X 1 2 ) a ] p (2)
wherein:
each occurrence of Y 1 is a monovalent or polyvalent halo-containing hydrocarbon group of up to 30 carbon atoms of general Formula (3):
[(Z e CR 3-e ) b Y 2 ] c G 1 d (3)
wherein
each occurrence of G 1 is independently a divalent group selected from the group consisting of —(CH 2 ) j —, where j is an integer from 18, —CH 2 (CH 2 ) i CH(CH 3 )—, where i is an integer of from 0 to 15, and —CH 2 CH(CH 3 )CH 2 —;
each occurrence of Y 2 is independently an unsaturated group selected from the group consisting of —CH═CH—, phenylene and 2-methyl phenylene;
each occurrence of Z is independently a Cl—,
each occurrence of R is hydrogen;
each occurrence of X 1 is independently selected from the group consisting of a methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, and hydroxyl;
each occurrence of Z β , which forms a bridging structure between two different silicon atoms, is [—OG 2 (OH) f-2 O—] 0.5 , wherein each occurrence of G 2 is independently selected from the group consisting of a hydrocarbylene group of from 2 to 15 carbon atoms or a divalent heterocarbylene group of from 4 to 15 carbon atoms containing one or more etheric oxygen atoms;
each occurrence of Z θ , which forms a cyclic structure with a silicon atom, is —OG 2 (OH) f-2 O—, wherein G 2 is independently selected from the group consisting of a hydrocarbylene group of from 2 to 15 carbon atoms or a divalent heterocarbylene group of from 4 to 15 carbon atoms containing one or more etheric oxygen atoms; and,
each occurrence of subscripts a, b, c, d, e, f, m, n, o and p is independently an integer where a is 1; b is 1; c is 1, d is 0 or 1; e is 1; f is 2 to 6; m is 0 to 20; n is 0 to 18; o is 0 to 20; and, p is 0 to 20, with the proviso that m+n+o+p is equal to or greater than 2.
2. The halo-functional silane of claim 1 wherein each occurrence of X 1 is independently selected from the group consisting of methyl methoxy, ethoxy, propoxy, isopropoxy, butoxy, hydroxyl, and each occurrence of G 1 is independently selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, and —CH 2 CH(CH 3 )CH 2 —.
3. The halo-functional silane of claim 1 wherein Y 2 is —CH═CH— or phenylene.
4. The halo-functional silane of claim 3 wherein Y 2 is phenylene.
5. A process for preparing the halo-functional silane of claim 1 which comprises reacting:
a) at least one halo-functional silane selected from the group consisting of general Formula (4):
[X 2 X 3 X 4 Si—] a (G 1 ) d [—Y 2 —(CR 3-e —Z e ) b ] c (4)
wherein:
each occurrence of X 2 is independently selected from a hydrolyzable group consisting of Cl—, methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy and benzyloxy;
each occurrence of X 3 and X 4 is independently selected from X 2 , methyl, ethyl, propyl, isopropyl, sec-butyl and phenyl;
each occurrence of G 1 is independently a divalent group selected from the group consisting of —(CH 2 ) j —, where j is an integer from 18, —CH 2 (CH 2 ) j CH(CH 3 )—, where i is an integer of from 0 to 15, and —CH 2 CH(CH 3 )CH 2 —;
each occurrence of Y 2 is independently an unsaturated group selected from the group consisting of —CH═CH—, phenylene and 2-methyl phenylene;
each occurrence of Z is independently a Cl—;
each occurrence of R is hydrogen; and,
each occurrence of subscripts a, b, c and d is independently an integer where a is 1; b is 1; c is 1, d is 0 or 1; and, e is 1; with
b) one or more polyhydroxyl-containing compounds of general Formula (5):
G 2 (OH) f (5)
wherein G 2 is a hydrocarbyl group of from 2 to 15 carbon atoms or a heterocarbyl group of from 4 to 15 carbon atoms containing one or more etheric oxygen atoms and f is an integer of from 2 to 6, under transesterification reaction conditions, and accompanied by removal of by-product mono-alcohol, thereby producing halo-functional silane.
6. A rubber composition comprising:
(a) at least one rubber component;
(b) at least one silane-reactive filler;
(c) at least one silane halo-functional silane possessing halogen functionality and alkanedioxysilyl functionality, and partial hydrolyzates thereof, selected from one of general Formulae (1) and (2):
Y 1 (—SiZ θ X 1 ) n (1), and
[Y 1 (—SiZ θ Z β ) a ] m [Y 1 (—SiZ β 3 ) a ] n [Y 1 (—SiZ β 2 X 1 ) a ] o [[Y 1 (—SiZ β 3 X 1 2 ) a ] p (2)
wherein:
each occurrence of Y 1 is a monovalent or polyvalent halo-containing hydrocarbon group of up to 30 carbon atoms of general Formula (3):
[(Z e CR 3-e ) b Y 2 ] c G 1 d (3)
wherein
each occurrence of G 1 is independently a divalent group selected from the group consisting of —(CH 2 ) j —, where j is an integer from 18, —CH 2 (CH 2 ) i CH(CH 3 )—, where i is an integer of from 0 to 15, and —CH 2 CH(CH 3 )CH 2 —;
each occurrence of Y 2 is independently an unsaturated group selected from the group consisting of —CH═CH—, —C≡C—, phenylene and 2-methyl phenylene;
each occurrence of Z is independently a Cl—; and,
each occurrence of R is hydrogen;
each occurrence of X 1 is independently selected from the group consisting of a methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, and hydroxyl;
each occurrence of Z β , which forms a bridging structure between two different silicon atoms, is [—OG 2 (OH) f-2 O—] 0.5 , wherein each occurrence of G 2 is independently selected from the group consisting of a hydrocarbylene group of from 2 to 15 carbon atoms or a divalent heterocarbylene group of from 4 to 15 carbon atoms containing one or more etheric oxygen atoms;
each occurrence of Z θ , which forms a cyclic structure with a silicon atom, is —OG 2 (OH) f-2 O—, wherein G 2 is independently selected from the group consisting of a hydrocarbylene group of from 2 to 15 carbon atoms or a divalent heterocarbylene group of from 4 to 15 carbon atoms containing one or more etheric oxygen atoms; and,
each occurrence of subscripts a, b, c, d, e, f, m, n, o and p is independently an integer where a is 1; b is 1; c is 1, d is 0 or 1; e is 1; f is 2 to 6; m is 0 to 20; n is 0 to 18; o is 0 to 20; and, p is 0 to 20, with the proviso that m+n+o+p is equal to or greater than 2, and,
(d) optionally, at least one activating agent.
7. The rubber composition of claim 6 , wherein Y 2 is —CH═CH— or phenylene that is bonded to the —CR 3-e Z e fragment or at least one carbon-carbon triple bond that is bonded to the —CR 3-e Z e fragment.
8. The cured rubber composition of claim 6 .
9. The cured rubber composition of claim 8 which is a tire, a tire component, a shoe sole, a hose, a seal, a cable jacket, a gasket or an industrial good.
10. A composition comprising:
(a) a silane-reactive filler; and
(b) at least one halo-functional silane possessing halogen functionality and alkanedioxysilyl functionality, and partial hydrolyzates thereof, selected from one of general Formulae (1) and (2):
Y 1 (—SiZ θ X 1 ) a (1), and
[Y 1 (—SiZ θ Z β ) a ] m m[Y 1 (—SiZ β 3 ) a ] n [Y 1 (—SiZ β 2 X 1 ) a ] o [[Y 1 (—SiZ β X 1 2 ) a ] p (2)
wherein:
each occurrence of Y 1 is a monovalent or polyvalent halo-containing hydrocarbon group of up to 30 carbon atoms of general Formula (3):
[(Z e CR 3-e ) b Y 2 ] c G 1 d (3)
wherein
each occurrence of G 1 is independently a divalent group selected from the group consisting of —(CH 2 ) j —, where j is an integer from 18, —CH 2 (CH 2 ) i CH(CH 3 )—, where i is an integer of from 0 to 15, and —CH 2 CH(CH 3 )CH 2 —;
each occurrence of Y 2 is independently an unsaturated group selected from the group consisting of —CH═CH—, —C≡C—, phenylene and 2-methyl phenylene;
each occurrence of Z is independently a Cl—; and,
each occurrence of R is hydrogen;
each occurrence of X 1 is independently selected from the group consisting of a methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, and a hydroxyl;
each occurrence of Z β , which forms a bridging structure between two different silicon atoms, is [—OG 2 (OH) f-2 O—] 0.5 , wherein each occurrence of G 2 is independently selected from the group consisting of a hydrocarbylene group of from 2 to 15 carbon atoms or a divalent heterocarbylene group of from 4 to 15 carbon atoms containing one or more etheric oxygen atoms;
each occurrence of Z θ , which forms a cyclic structure with a silicon atom, is —OG 2 (OH) f-2 O—, wherein G 2 is independently selected from the group consisting of a hydrocarbylene group of from 2 to 15 carbon atoms or a divalent heterocarbylene group of from 4 to 15 carbon atoms containing one or more etheric oxygen atoms; and,
each occurrence of subscripts a, b, c, d, e, f, m, n, o and p is independently an integer where a is 1; b is 1; c is 1, d is 0 or 1; e is 1; f is 2 to 6; m is 0 to 20; n is 0 to 18; o is 0 to 20; and, p is 0 to 20, with the proviso that m+n+o+p is equal to or greater than 2.
11. The composition of claim 10 , wherein the silane-reactive filler (a) is at least one selected from the group consisting of silica, titanium dioxide, aluminosilicate, alumina and siliceous materials, and combination thereof.