Method for the preparation and use of bis (alkoxysilylorgano)-dicarboxylates
View Patent ↗A method for preparing a bis(alkoxysilylorgano)dicarboxylate includes reacting a haloorganoalkoxysilane, a dimetal salt of a dicarboxyl functional compound, and a phase transfer catalyst. A quaternary iminium compound of a polyaza, polycycloalkene is useful as the phase transfer catalyst. The product may be a bis(alkoxysilylalkyl)fumarate, which is useful as a coupling agent in rubber compositions for tire applications.
1. A method for producing a reaction product comprising a bis(alkoxysilylorgano) dicarboxylate, where the method comprises: step 1) reacting a composition comprising:
a) a haloorganoalkoxysilane,
b) a dimetal salt of a dicarboxyl functional compound, and
c) a phase transfer catalyst comprising 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, a quaternary iminium compound of a bicyclic amidine, or a combination thereof.
2. The method of claim 1 , where step 1) is performed under substantially anhydrous conditions by heating at a reaction temperature up to 180° C. for a reaction time up to 18 h.
3. The method of claim 1 , further comprising step 2): removing at least a portion of a metal halide formed as a by-product during step 1).
4. The method of claim 3 , further comprising step 3): recovering the bis(alkoxysilylorgano)dicarboxylate.
5. The method of claim 4 , where the bis(alkoxysilylorgano) dicarboxylate is a bis(alkoxysilylalkyl)fumarate.
6. The method of claim 5 , where the bis(alkoxysilylalkyl)fumarate is bis(triethoxysilylpropyl)fumarate.
7. The method of claim 1 , further comprising: drying one or more of the ingredients before step 1).
8. The method of claim 1 , where the composition further comprises an optional ingredient selected from the group consisting of d) a co-catalyst, e) a solvent, f) a stabilizer, and a combination thereof.
9. The method of claim 8 , where the co-catalyst comprises a compound of formula: M + R 9 , where M + is an alkali metal cation or alkaline earth metal cation; and R 9 is a counter ion selected from the group consisting of HSO 4 − , HCO 3 − , acetate, SO 4 2− , CO 3 2− and PO 4 3− .
10. The method of claim 2 , where the reaction temperature ranges from 130° C. to 180° C., and the reaction time is up to 12 hours.
11. The method of claim 1 , where ingredient c) comprises a quaternary iminium compound of a bicyclic amidine.
12. The method of claim 11 , where ingredient c) comprises a 1,8-diazabicyclo[5.4.0]undec-7-ene quaternary iminium salt with octyl bromine; a 1,8-diazabicyclo[5.4.0]undec-7-ene quaternary iminium salt with ethylhexyl bromine; a 1,8-diazabicyclo[5.4.0]undec-7-ene quaternary iminium salt with octyl chlorine; 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene quaternary iminium salt with ethylhexylbromine; 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene quaternary iminium salt with butyl bromine; 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene quaternary iminium salt with octyl bromine; 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene quaternary iminium salt with dodecyl bromine; or a combination thereof.
13. The method of claim 11 , where the composition further comprises a metal acetate.
14. The method of claim 1 , where ingredient a) has formula (I):
X a R 2 b Si(OR 1 ) (4-a-b) , where
subscript a is 1 or 2;
subscript b is 0, 1, or 2;
each X is independently a halogenated organic group;
each R 1 is independently a hydrocarbyl group; and
each R 2 is independently a hydrocarbyl group.
15. The method of claim 1 where, ingredient b) has formula (II):
where
M + is an alkali metal cation or alkaline earth metal cation,
subscript c is 1 or 2, and
R 3 is a divalent organic group.
16. The bis(alkoxysilylorgano) dicarboxylate prepared by the method of claim 1 .
17. A rubber composition suitable for use in tire applications, where the rubber composition comprises:
A) a diene polymer,
B) a reinforcing filler, and
C) a bis(alkoxysilylalkyl)fumarate prepared by the method of claim 5 .
18. A rubber composition suitable for use in engineered rubber goods applications, where the rubber composition comprises:
A) a diene polymer,
B) a reinforcing filler, and
C) a bis(alkoxysilylalkyl) fumarate prepared by the method of claim 5 .
19. The method of claim 1 , further comprising: using the bis(alkoxysilylorgano) dicarboxylate for an application selected from the group consisting of a coupling agent, an adhesion promoter, and a surface modifier.
20. A method for producing a reaction product comprising a bis(alkoxysilylorgano) dicarboxylate, where the method comprises: step 1) reacting a composition comprising:
a) a haloorganoalkoxysilane,
b) a dimetal salt of a dicarboxyl functional compound,
c) a phase transfer catalyst comprising a bicyclic amidine, a quaternary iminium compound of a bicyclic amidine, or a combination thereof, and
d) a co-catalyst.
21. The method of claim 20 , where the co-catalyst comprises a compound of formula: M + R 9 , where M + is alkali metal cation or alkaline earth metal cation; and R 9 is a counter ion selected from the group consisting of HSO 4 − , HCO 3 − , acetate, SO 4 2− , CO 3 2− and PO 4 3− .