US4195030A
Expired / Lapsed
US
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Preparation of monomeric organosilicon esters
Assignee: Bausch and Lomb Inc
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Filing: 1979-01-10
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Granted: 1980-03-25
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Expires: 1999-01-10
Abstract
Abstract A process is disclosed which involves the preparation of monomeric organosilicon esters in a much shorter time and at a much higher purification than previously known in the art. More specifically, the process comprises reacting a cyclosilalkoxane having the general formula: ##STR1## wherein R is a monovalent hydrocarbon radical free of aliphatic unsaturation, R' is selected from the group consisting of H and CH 3 and n is an integral of from 1 to 2 inclusive with a free radical polymerizable monocarboxylic acid. The cyclosilalkoxane is contacted with the free radical polymerizable monocarboxylic acid in the presence of a solvent. The solvent forms an azeotropic mixture with the water formed by the reaction. During the reaction, the azeotropic mixture is continuously removed from the reaction. Also present in the reaction solution is a protonating acid catalyst and a free radical polymerization preventing inhibitor. The process further comprises heating the solution to a temperature which forces the reaction to completion at an accelerated rate. During the reaction sufficient oxygen is supplied to the reaction mixture in order to convert the inhibitor present in the reaction mixture from an inactive to an active form. This process forms a substantially pure free radical polymerizable monomeric unsaturated organosilicone ester in about 3 to about 6 hours.
Inventors
- 👤 William G. Deichert
- 👤 Kai C. Su
- 👤 Martin F. VAN Buren
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 15:21
CPC Classifications
C; C07; C07F; C07F7/00; C07F7/02; C07F7/08; C07F7/0834; C07F7/0838; C07F7/0872; C07F7/0874
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
281 words
A process for producing a monomeric organosilicon ester by reacting a cyclosilalkoxane having the general formula ##STR11## wherein R is a monovalent hydrocarbon radical free of aliphatic unsaturation, R' is selected from the group consisting of H and CH 3 and n is an integral of from 1 to 2 inclusive with a free radical polymerizable monocarboxylic acid having the general formula ##STR12## wherein R 1 , R 2 and R 3 are selected from the group consisting of hydrogen, monovalent hydrocarbon containing from 1 to 6 carbon atoms and a halogenated hydrocarbon containing from 1 to 6 carbon atoms by (1) contacting at least stoichiometric amounts of the cyclosilalkoxane with at least stoichiometric amounts of the carboxylic acid in the presence of from at least about 25.0 percent by weight, based on the total weight of the solution, of a solvent which forms an azeotrope with water and from about 0.01 percent to about 1.0 percent by weight, based on the total weight of the solution, of a free radical polymerization preventing inhibitor, from about 0.1% to about 3.0% by weight, based on the total weight of the solution, of a protonating catalytic acid, (2) heating said solution of step (1) to a temperature of from about 70° C. to about 135° C. for about 3 hours to about 6 hours while supplying a sufficient amount of air to maintain inhibitor activation, and (3) during the reaction continuously removing from the solution by azeotropic distillation water which is produced by the reaction thereby forming a free radical polymerizable monomeric unsaturated organosilicon ester without polymerizing either the free radical polymerizable monocarboxylic acid or the free radical polymerizable monomeric unsaturated organosilicon ester.
Claim 2
Dependent Claim
281 words
A process for producing a monomeric organosilicon ester by reacting a cyclosilalkoxane having the general formula ##STR11## wherein R is a monovalent hydrocarbon radical free of aliphatic unsaturation, R' is selected from the group consisting of H and CH 3 and n is an integral of from 1 to 2 inclusive with a free radical polymerizable monocarboxylic acid having the general formula ##STR12## wherein R 1 , R 2 and R 3 are selected from the group consisting of hydrogen, monovalent hydrocarbon containing from 1 to 6 carbon atoms and a halogenated hydrocarbon containing from 1 to 6 carbon atoms by (1) contacting at least stoichiometric amounts of the cyclosilalkoxane with at least stoichiometric amounts of the carboxylic acid in the presence of from at least about 25.0 percent by weight, based on the total weight of the solution, of a solvent which forms an azeotrope with water and from about 0.01 percent to about 1.0 percent by weight, based on the total weight of the solution, of a free radical polymerization preventing inhibitor, from about 0.1% to about 3.0% by weight, based on the total weight of the solution, of a protonating catalytic acid, (2) heating said solution of step (1) to a temperature of from about 70° C. to about 135° C. for about 3 hours to about 6 hours while supplying a sufficient amount of air to maintain inhibitor activation, and (3) during the reaction continuously removing from the solution by azeotropic distillation water which is produced by the reaction thereby forming a free radical polymerizable monomeric unsaturated organosilicon ester without polymerizing either the free radical polymerizable monocarboxylic acid or the free radical polymerizable monomeric unsaturated organosilicon ester.
Claim 3
Dependent Claim
27 words
The process according to claim 1 wherein R in the cyclosilalkoxane is a monovalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 6 carbon atoms.
Claim 4
Dependent Claim
13 words
The process according to claim 2 wherein R in the cyclosilalkoxane is methyl.
Claim 5
Dependent Claim
13 words
The process according to claim 1 wherein R' in the cyclosilalkoxane is hydrogen.
Claim 6
Dependent Claim
13 words
The process according to claim 1 wherein n in the cyclosilalkoxane is 2.
Claim 7
Dependent Claim
11 words
The process according to claim 1 wherein the cyclosilalkoxane is ##STR13##
Claim 8
Dependent Claim
16 words
The process according to claim 1 wherein the free radical polymerizable carboxylic acid is acrylic acid.
Claim 9
Dependent Claim
16 words
The process according to claim 1 wherein the free radical polymerizable carboxylic acid is methacrylic acid.
Claim 10
Dependent Claim
23 words
The process according to claim 1 wherein the solvent of claim 1 is selected from the group consisting of cyclohexane, heptane and benzene.
Claim 11
Dependent Claim
11 words
The process according to claim 9 wherein the solvent is cyclohexane.
Claim 12
Dependent Claim
34 words
The process according to claim 9 wherein the solvent in step (1) is present in amounts from about 40.0 percent to about 60.0 percent by weight based on the total weight of the solution.
Claim 13
Dependent Claim
21 words
The process according to claim 1 wherein the temperature of step (2) is from about 80° C. to about 115° C.
Claim 14
Dependent Claim
19 words
The process according to claim 1 wherein the reaction is completed in about 3 hours to about 4 hours.
Claim 15
Dependent Claim
24 words
The process according to claim 1 wherein the free radical polymerization preventing inhibitor is selected from the group consisting of hydroquinone, p-methoxyphenol and 1,6-di-tert-butyl-p-cresol.
Claim 16
Dependent Claim
14 words
The process according to claim 14 wherein the free radical polymerization inhibitor is hydroquinone.
Claim 17
Dependent Claim
163 words
A process comprising reacting (A) a cyclosilalkoxane having the formula ##STR14## with methacrylic acid by (1) contacting at least stoichiometric amounts of said cyclosilalkoxane with at least stoichiometric amounts of said methacrylic acid in the presence of from about 40 percent to about 60 percent by weight, based on the total weight of the solution, of cyclohexane and from about 0.01 percent to about 0.1 percent by weight, based on the total weight of the solution, of hydroquinone, and from about 0.3 percent to about 0.7 percent by weight, based on the total weight of the solution, of sulfuric acid, (2) heating said solution of step (1) to a temperature of from about 80° C. to about 90° C. while supplying sufficient amount of air to the reaction to maintain inhibitor activation, and (3) during the reaction continuously removing from the solution by azeotropic distillation water which is produced by the reaction thereby forming ##STR15## in from about 3 to about 6 hours.
Claim 18
Dependent Claim
163 words
A process comprising reacting (A) a cyclosilalkoxane having the formula ##STR14## with methacrylic acid by (1) contacting at least stoichiometric amounts of said cyclosilalkoxane with at least stoichiometric amounts of said methacrylic acid in the presence of from about 40 percent to about 60 percent by weight, based on the total weight of the solution, of cyclohexane and from about 0.01 percent to about 0.1 percent by weight, based on the total weight of the solution, of hydroquinone, and from about 0.3 percent to about 0.7 percent by weight, based on the total weight of the solution, of sulfuric acid, (2) heating said solution of step (1) to a temperature of from about 80° C. to about 90° C. while supplying sufficient amount of air to the reaction to maintain inhibitor activation, and (3) during the reaction continuously removing from the solution by azeotropic distillation water which is produced by the reaction thereby forming ##STR15## in from about 3 to about 6 hours.
Claim 19
Dependent Claim
49 words
The process of claim 16 wherein additional process steps comprise (4) after step (3) purifying the product obtained in step (3) by (2) column filtration over activated alumina (b) then column filtration over silica gel and (c) then solvent evaporation thereby forming a product at least 98 percent pure.
References Cited (Backward Citations)
US2906735A
Cited
US3878263A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-03-25 | 1983-09-24 | 1984-03-25 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-03-25 | 1987-09-24 | 1988-03-25 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-03-25 | 1991-09-24 | 1992-03-25 | $7700.00 | Window Closed / Lapsed |