Process for preparing alkoxysilanes
View Patent ↗A transesterification process for preparing alkoxysilane includes removal of metal transesterification catalyst from the alkoxysilane transesterification reaction medium.
1. A process for preparing an alkoxysilane transesterification reaction product which comprises
(a) transesterifying at least one transesterifiable alkoxysilane with at least one transesterifying alcohol under transesterification reaction conditions in the presence of at least one metal transesterification catalyst accompanied by removal of byproduct and/or unreacted alcohol to produce a crude alkoxysilane transesterification reaction product; and
(b) removing at least part of the metal transesterification catalyst from the reaction product, wherein removal of at least part of the metal transesterification catalyst from the reaction product of step (a) comprises hydrolyzing the metal transesterification catalyst to form a catalyst metal oxide and removing the catalyst metal oxide from the reaction product of step (a).
2. The process of claim 1 wherein the transesterifiable alkoxysilane is a transesterifiable alkoxysilane of general formula (I):
Y—[R 1 —Si(R 2 ) 3-a (OR 3 ) a ] b (I)
wherein:
Y is hydrogen, halo or a functional group;
each R 1 independently is a divalent straight chain alkylene group of from 1 to 12 carbon atoms, a branched chain alkylene of from 2 to 12 carbon atoms, a cycloalkylene group of from 3 to 12 carbon atoms, an arylene group of from 6 to 10 carbon atoms, an aralkylene group of from 7 to 16 carbon atoms, an alkynylene group of from 2 to 12 carbon atoms, a straight, branched alkylene or cycloalkylene group containing at least one heteroatom selected from sulfur, oxygen or nitrogen and from 2 to 12 carbon atoms, or a chemical bond, with the proviso that when R 1 is a chemical bond, then Y is an organofunctional group and the silicon atom is bonded to a carbon atom of group Y;
each R 2 independently is a monovalent straight chain alkyl group containing 1 to 16 carbon atoms, a branched alkyl group containing 3 to 16 carbon atoms, a cycloalkyl group containing 3 to 12 carbon atoms, an aryl group containing 6 to 10 carbon atoms or an aralkyl group containing 7 to 16 carbon atoms;
each R 3 independently is a monovalent straight chain alkyl group of from 1 to 4 carbon atoms or a branched chain alkyl group having 3 to 4 carbon atoms;
a is an integer of from 1 to 3; and,
b is an integer of from 1 to 4.
3. The process of claim 2 wherein transesterifiable alkoxysilane (I) is at least one member selected from the group consisting of glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, (3,4-epoxycyclohexyl)ethyl trimethoxysilane and (3,4-epoxycyclohexyl)ethyl triethoxysilane.
4. The process of claim 2 wherein transesterifying alcohol is at least one member selected from the group consisting of ethanol, propanol, isopropanol and butanol.
5. The process of claim 2 wherein metal transesterification catalyst is at least one member selected from the group consisting of tetraisopropyl titanate, tetraethyl titanate, tetraethyl zirconate and tetrapropyl zirconate.
6. The process of claim 1 wherein the transesterifying alcohol is of general formula (II):
R 4 OH (II)
wherein:
R 4 is a monovalent straight chain alkyl group of from 1 to 16 carbon atoms, a branched chain alkyl group of from 3 to 16 carbon atoms, a cycloalkyl group of from 3 to 12 carbon atoms, an alkenyl group of from 2 to 16 carbon atoms, an aralkyl group of from 7 to 12 carbon atoms, an aryl group of from 6 to 10 carbon atoms, a straight chain alkyl group containing at least one heteroatom selected from oxygen, sulfur or nitrogen containing from 2 to 16 carbon atoms or a branched alkyl group containing at least one heteroatom selected from oxygen, sulfur or nitrogen containing from 3 to 16 carbon atoms, a straight or branched alkyl group of from 2 to 16 carbon atoms and substituted with at least on hydroxyl or amino group, —NR 5 R 6 where R 5 and R 6 are independently hydrogen or a straight chain alkyl group of from 1 to 16 carbon atoms, a branched chain alkyl group of from 3 to 16 carbon atoms, an aryl group of from 6 to 10 carbon atoms or an aralkyl group of from 7 to 12 carbon atoms.
7. The process of claim 1 wherein the metal transesterification catalyst is of general formula (III):
M n+ (X) n (III)
wherein:
M is a metal that is catalytically active for transesterification;
X is OR 7 , where each R 7 is independently a monovalent straight chain alkyl group of from 1 to 12 carbon atoms, a branched chain alkyl group of 3 to 12 carbon atoms, a cycloalkyl group of from 3 to 12 carbon atoms, an aryl group of from 6 to 10 carbon atoms, an aralkyl group of from 9 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, an acyl group of from 1 to 12 carbon atoms, or two OR 7 groups are bonded to each other through a carbon-carbon linkage to form a —O—R 7 —R 7 —O— group, or X is R 8 where R 8 is a monovalent straight chain alkyl group of from 1 to 16 carbon atoms, a branched chain alkyl group of from 3 to 16 carbon atoms, a cycloalkyl group of from 3 to 12 carbon atoms, an aryl group of from 6 to 10 carbon atoms or an aralkyl group of from 7 to 12 carbon atoms, with the proviso that at least one X is OR 7 ; and,
n is the valence of M.
8. The process of claim 1 wherein following removal of the catalyst, the residual level of metal in the alkoxysilane transesterification reaction product is less than about 100 ppm based on the weight of the alkoxysilane transesterification reaction product.
9. The process of claim 1 wherein following removal of the catalyst, the residual level of metal in the alkoxysilane transesterification reaction product is less than about 50 ppm.
10. The process of claim 1 wherein following removal of the catalyst, the residual level of metal in the alkoxysilane transesterification reaction product is less than about 10 ppm.
11. The process of claim 1 further comprising adding an acid to the crude alkoxysilane transesterification reaction product of step (a).
12. The process of claim 11 wherein the acid is acetic acid and/or boric acid.
13. The process of claim 1 further comprising purifying the alkoxysilane transesterification reaction product.
14. A process for preparing an alkoxysilane transesterification reaction product which comprises
(a) transesterifying at least one transesterifiable alkoxysilane with at least one transesterifying alcohol under transesterification reaction conditions in the presence of at least one metal transesterification catalyst accompanied by removal of byproduct and/or unreacted alcohol to produce a crude alkoxysilane transesterification reaction product; and
(b) removing at least part of the metal transesterification catalyst from the reaction product, wherein the metal transesterification catalyst is removed by adding an absorption medium of precipitated silica to the crude alkoxysilane transesterification reaction product of step (a) and stirring the mixture, adsorbing the metal transesterification catalyst on an adsorption medium followed by filtering the adsorption medium containing adsorbed catalyst.
15. The process of claim 14 wherein removing metal transesterification catalyst is carried out by adsorbing metal transesterification catalyst therein on adsorption medium and separating metal transesterification catalyst-containing adsorption medium from the transesterification reaction medium by filtration or decantation to provide a transesterification catalyst-depleted transesterification medium.
16. The process of claim 15 wherein alkoxysilane transesterification reaction product is recovered from the transesterification catalyst-depleted transesterification reaction medium by distillation.
17. A process for preparing an alkoxysilane transesterification reaction product comprising:
(a) adding a metal transesterification catalyst to a transesterifiable alkoxysilane in the amount of from 0.01 weight percent to 5 weight percent, based on the weight of the transesterifiable alkoxysilane, to form a mixture;
(b) heating the mixture from step (a) under conditions sufficient to effect a transesterification reaction;
(c) adding a transesterifying alcohol into the mixture during heating step (b);
(d) removing byproduct alcohol formed during the transesterification reaction;
(e) hydrolyzing the metal transesterification catalyst to form a metal oxide of said catalyst;
(g) removing the metal oxide to form a alkoxysilane transesterification reaction product; and, optionally,
(h) further purifying the alkoxysilane transesterification reaction product of step (g).
18. The process of claim 17 wherein the transesterifiable alkoxysilane is a transesterifiable alkoxysilane of general formula (I):
Y—[R 1 —Si(R 2 ) 3-a (OR 3 ) a ] b (I)
wherein:
Y is hydrogen, halo or a functional group;
each R 1 independently is a divalent straight chain alkylene group of from 1 to 12 carbon atoms, a branched chain alkylene of from 2 to 12 carbon atoms, a cycloalkylene group of from 3 to 12 carbon atoms, an arylene group of from 6 to 10 carbon atoms, an aralkyl group of from 7 to 16 carbon atoms, an alkylene group of from 2 to 12 carbon atoms, a cycloalkylene group of from 3 to 12 carbon atoms, an alkynylene group of from 2 to 12 carbon atoms, a straight, branched or cyclic alkylene group containing at least one heteroatom selected from sulfur, oxygen or nitrogen and from 2 to 12 carbon atoms, or a chemical bond, with the proviso that where R 1 is a chemical bond, Y is an organofunctional group and the silicon atom is bonded to a carbon atom of the group Y;
each R 2 independently is a monovalent straight chain alkyl group containing 1 to 16 carbon atoms, a branched alkyl group containing 3 to 16 carbon atoms, a cycloalkyl group containing 3 to 12 carbon atoms, an aryl group containing 6 to 10 carbon atoms, an aralkyl group containing 7 to 16 carbon atoms;
each R 3 independently is a monovalent straight chain alkyl group of from 1 to 4 carbon atoms or a branched chain alkyl group having 3 to 4 carbon atoms;
a is an integer of from 1 to 3; and,
b is an integer of from 1 to 4,
the alcohol is of general formula (II):
R 4 OH (II)
wherein:
R 4 is a monovalent straight chain alkyl group of from 1 to 16 carbon atoms, a branched chain alkyl group of from 3 to 16 carbon atoms, a cycloalkyl group of from 3 to 12 carbon atoms, an alkenyl group of from 2 to 16 carbon atoms, an aralkyl group of from 7 to 12 carbon atoms, an aryl group of from 6 to 10 carbon atoms, a straight chain alkyl group containing at least one heteroatom selected from oxygen, sulfur or nitrogen containing from 2 to 16 carbon atoms or a branched alkyl group containing at least one heteroatom selected from oxygen, sulfur or nitrogen containing from 3 to 16 carbon atoms, a straight or branched alkyl group of from 2 to 16 carbon atoms and substituted with at least on hydroxyl or amino group, —NR 5 R 6 where R 5 and R 6 are independently hydrogen or a straight chain alkyl group of from 1 to 16 carbon atoms, a branched chain alkyl group of from 3 to 16 carbon atoms, an aryl group of from 6 to 10 carbon atoms or an aralkyl group of from 7 to 12 carbon atoms,
and the metal transesterification catalyst is of general formula (III):
M n+ (X) n (III)
wherein:
M is a metal that is catalytically active for transesterification;
X is OR 7 , where each R 7 is independently a monovalent straight chain alkyl group of from 1 to 12 carbon atoms, a branched chain alkyl group of 3 to 12 carbon atoms, a cycloalkyl group of from 3 to 12 carbon atoms, an aryl group of from 6 to 10 carbon atoms, an aralkyl group of from 9 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, an acyl group of from 1 to 12 carbon atoms, or two OR 7 groups are bonded to each other through a carbon-carbon linkage to form a —O—R 7 —R 7 —O— group, or X is R 8 where R 8 is a monovalent straight chain alkyl group of from 1 to 16 carbon atoms, a branched chain alkyl group of from 3 to 16 carbon atoms, a cycloalkyl group of from 3 to 12 carbon atoms, an aryl group of from 6 to 10 carbon atoms or an aralkyl group of from 7 to 12 carbon atoms, with the proviso that at least one X is OR 7 ;
n is the valence of M.
19. The process of claim 17 wherein in step (e), removing metal transesterification catalyst from the transesterification reaction medium is carried out by hydrolyzing metal transesterification catalyst therein to provide metal oxide and separating metal oxide hydrolysate from the transesterification reaction medium by filtration or decantation to provide a transesterification catalyst-depleted transesterification medium.
20. The process of claim 19 wherein alkoxysilane transesterification reaction product is recovered from the transesterification catalyst-depleted transesterification reaction medium by distillation.