Ester-functional silanes and the preparation and use thereof; and use of iminium compounds as phase transfer catalysts

Patent metadata

Field	Value
Publication number	US-9518072-B2
Application number	US-201214361790-A
Country	US
Kind code	B2
Filing date	Nov 14, 2012
Priority date	Dec 2, 2011
Publication date	Dec 13, 2016
Grant date	Dec 13, 2016

Abstract

A method for producing a reaction product comprising an ester-functional silane, the method comprising: i) reacting a composition comprising: a) a haloorganosilane, b) a metal salt of a carboxy-functional compound, c) a phase transfer catalyst comprising a bicyclic amidine, an iminium compound, or a mixture thereof, provided that the iminium compound is not an acyclic guanidinium compound or pyridinium compound, and d) a co-catalyst, provided that the co-catalyst is optional when the phase transfer catalyst comprises the iminium compound.

First claim

The invention claimed is:

1. A method for producing a reaction product comprising an ester-functional silane, the method comprising: i) reacting a composition comprising:
a) a haloorganosilane,
b) a metal salt of a carboxy-functional compound, where the metal salt of a carboxy-functional compound has the formula [R 2 COO − ] c [M c+ ] (II), wherein R 2 is substituted or unsubstituted hydrocarbyl having from 2 to 20 carbon atoms, each M c+ is an alkali metal cation, alkaline earth metal cation, or ammonium cation and c is 1 or 2,
c) a phase transfer catalyst comprising a polyazabicycloalkene, an N 2 -alkyl-polyazapolycyclo-alkenium compound, or a mixture thereof, and
d) a co-catalyst, where the co-catalyst comprises a compound of formula: M c+ R 14 , where M c+ is alkali metal cation or alkaline earth metal cation, c is 1 or 2, and R 14 is a counter ion selected from the group consisting of Cl − , HSO 4 − , HCO 3 − , acetate, SO 4 2− CO 3 2− , PO 4 3 and HPO 4 2− , and provided that the co-catalyst is optional when the phase transfer catalyst comprises the N 2 -alkyl-polyazapolycyclo-alkenium compound.

2. The method of claim 1 , the method being characterizable by one or more of limitations (g), (h), (j), (k), (I), and (m):
(g) step i) is performed under substantially anhydrous conditions by heating at a reaction temperature up to 180° C. for a reaction time up to 18 h;
(h) the method further comprises step ii) removing at least a portion of a metal halide formed as a by-product in step i);
(j) the method further comprises step iii) recovering an ester-functional silane formed in step i);
(k) the method further comprises drying one or more of a), b), and c) before step i);
(l) ingredient c) comprises a 8-octyl-1,8-diazabicyclo[5.4.0]-undec-7-enium bromide; a 8-2-ethylhexyl-1,8-diazabicyclo[5.4.0]-undec-7-enium bromide; a 8-octyl-1,8-diaza-bicyclo[5.4.0]-undec-7-enium chloride; a 7-2-ethylhexyl-7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium bromide; 5-butyl-7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium bromide; 5-octyl-7-methyl-1,5,7-triazaabicyclo[4.4.0]dec-5-enium bromide; 5-dodecyl-7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium bromide; 5-octyl-1,5-diazabicyclo[4.3.0]non-5-enium bromide, 5-nonyl-1,5-diazabicyclo[4.3.0]non-5-enium bromide, 5-decyl-1,5-diazabicyclo[4.3.0]non-5-enium bromide, 5-2-ethylhexyl-1,5-diazabicyclo[4.3.0]non-5-enium bromide, 5-didecyl-1,5-diazabicyclo[4.3.0]non-5-enium bromide or a combination thereof; and
(m) the composition further comprises a metal acetate.

3. The method of claim 2 , wherein the method is characterized by limitation (I).

4. The method of claim 1 , where the composition further comprises an ingredient selected from the group consisting of e) a solvent, f) a stabilizer, and a combination thereof.

5. The method of claim 1 , where the reaction temperature ranges from 60° C. to 180° C., and the reaction time is up to 12 hours.

6. The method of claim 1 , where ingredient c) comprises an N 2 -alkyl-polyazapolycyclo-alkenium compound.

7. The method of claim 6 , wherein the N 2 -alkyl-polyazapolycyclo-alkenium compound has a counter ion selected from the group consisting of Cl − , Br − , HSO 4 − , HCO 3 − , acetate, SO 4 2− , CO 3 2− and PO 4 2− .

8. The method of claim 1 , where ingredient c) comprises a bicyclic amidine.

9. The method of claim 8 , where ingredient c) comprises 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,5-diazabicyclo[4.3.0]non-5-ene; 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene; or a combination thereof.

10. The method of claim 1 , characterizable by limitation (n):
(n) where ingredient a) has formula (I):
X a Si(Q) (4-a) , where  (I)

subscript a is 1 or 2;
each X is independently a halogenated organic group; and
each Q is independently R 1 or —OR 1 , wherein each R 1 is independently hydrocarbyl.

11. A method for producing a reaction product comprising an ester-functional silane, the method comprising: i) reacting a composition comprising:
a) a haloorganosilane,
b) a metal salt of a carboxy-functional compound,
c) a phase transfer catalyst comprising a bicyclic amidine, an iminium compound, or a mixture thereof, and
d) a co-catalyst, where the co-catalyst comprises a compound of formula: M c+ R 14 , where M c+ is alkali metal cation or alkaline earth metal cation, c is 1 or 2, and R 14 is a counter ion selected from the group consisting of Cl − , HSO 4 − , HCO 3 − , acetate, SO 4 2− , CO 3 2− , PO 4 3 and HPO 4 2− .

Assignees

• Dow Corning

Inventors

• Backer Michael Wolfgang
• Gohndrone John Michael
• Kleyer Don Lee
• Zhou Xiaobing

Classifications

• C08K5/5419 Primary

  containing at least one Si—C bond · CPC title

• C07F7/0818

  Chemistry & Metallurgy · mapped topic

• C07F7/1876

  by reactions involving the formation of Si-C linkages · CPC title

• C08K5/5425

  containing at least one C=C bond · CPC title

• B60C1/00

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title