# US 9,518,072 B2 · Ester-functional silanes and the preparation and use thereof; and use of iminium compounds as phase transfer catalysts > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,518,072 B2 - Document ID: US9518072B2 - Status: Granted - Kind: B2 - Application number: 14/361,790 - Filed: 2012-11-14 - Published: 2015-05-07 - Granted: 2016-12-13 - Earliest claimed: 2011-12-02 - Assignees: Dow Corning Corporation - Applicants: Dow Corning Corporation - Inventors: Michael Wolfgang Backer; John Michael Gohndrone; Don Lee Kleyer; Xiaobing Zhou - Web page: https://patentgrep.com/patent/US9518072B2 ## CPC - C07F 7/1892: {by reactions not provided for in C07F7/1876 - C07F7/1888} - B60C 1/00: Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition - B60C 1/0016: {Compositions of the tread} - C07F 7/1804: {Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896)} - C08K 5/5419: containing at least one Si—C bond - C08K 5/5425: containing at least one C=C bond - C07F 7/081: {comprising at least one atom selected from the elements N, O, halogen, S, Se or Te} - C07F 7/1876: {by reactions involving the formation of Si-C linkages} - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## 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. ## Claims ### Claim 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 [R2COO−]c[Mc+] (II), wherein R2 is substituted or unsubstituted hydrocarbyl having from 2 to 20 carbon atoms, each Mc+ 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 N2-alkyl-polyazapolycyclo-alkenium compound, or a mixture thereof, and d) a co-catalyst, where the co-catalyst comprises a compound of formula: Mc+R14, where Mc+ is alkali metal cation or alkaline earth metal cation, c is 1 or 2, and R14 is a counter ion selected from the group consisting of Cl−, HSO4−, HCO3−, acetate, SO42−CO32−, PO43 and HPO42−, and provided that the co-catalyst is optional when the phase transfer catalyst comprises the N2-alkyl-polyazapolycyclo-alkenium compound. ### Claim 2 (depends on 1) 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. ### Claim 3 (depends on 2) The method of claim 2, wherein the method is characterized by limitation (I). ### Claim 4 (depends on 1) 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. ### Claim 5 (depends on 1) 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. ### Claim 6 (depends on 1) The method of claim 1, where ingredient c) comprises an N2-alkyl-polyazapolycyclo-alkenium compound. ### Claim 7 (depends on 6) The method of claim 6, wherein the N2-alkyl-polyazapolycyclo-alkenium compound has a counter ion selected from the group consisting of Cl−, Br−, HSO4−, HCO3−, acetate, SO42−, CO32− and PO42−. ### Claim 8 (depends on 1) The method of claim 1, where ingredient c) comprises a bicyclic amidine. ### Claim 9 (depends on 8) 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. ### Claim 10 (depends on 1) The method of claim 1, characterizable by limitation (n): (n) where ingredient a) has formula (I): XaSi(Q)(4-a), where (I) subscript a is 1 or 2; each X is independently a halogenated organic group; and each Q is independently R1 or —OR1, wherein each R1 is independently hydrocarbyl. ### Claim 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: Mc+R14, where Mc+ is alkali metal cation or alkaline earth metal cation, c is 1 or 2, and R14 is a counter ion selected from the group consisting of Cl−, HSO4−, HCO3−, acetate, SO42−, CO32−, PO43 and HPO42−.