Catalytic transesterification of ester compounds with groups reactive under transesterification conditions

• US 9,416,091 B1
• Filed: 07/31/2015
• Issued: 08/16/2016
• Est. Priority Date: 02/04/2015
• Status: Active Grant

• Current Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Sullivan, Jeffrey M., Palsule, Aniruddha Sudhir, Stevenson, Peter Rulon, Parab, Kshitij Kishen
• Primary Examiner(s): Zucker, Paul A
• Assistant Examiner(s): LUDERER, MARK R
• Application Number:
  US14/814,961
• Publication Number:
  US 20160221922A1
• Time in Patent Office: 382 Days
• US Class Current: 1/1
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 2602/42 the bicyclo ring system containing seven carbon atoms
• CPC Class Codes: C07C 67/02 by interreacting ester groups, i.e. transesterification
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07C 69/604 Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
• CPC Class Codes: C07C 69/732 of unsaturated hydroxy carboxylic acids

Abstract

Disclosed are methods for the catalytic transesterification of compounds having one or more ester groups and groups reactive under transesterification conditions, such as 1,1-disubstituted alkene compounds, with alcohols or esters and novel compositions prepared therefrom. Further disclosed are novel compounds and compositions prepared as a result of the methods.

Claims

1. A method comprising:

contacting a first ester compound having one or more ester groups with hydrocarbyl moieties as part of each of the ester groups and a functional group which may undergo undesired side reactions under transesterification reaction conditions, with one or more alcohols having a hydrocarbon backbone and one or more hydroxyl groups or one or more second ester compounds having one or more ester groups with hydrocarbyl moieties different from the hydrocarbyl moieties on the first ester compounds, in the presence of one or more acids having a pKa in a polar aprotic solvent of about −

5 to about 14 or esters of the acid under conditions that at least one of the hydrocarbyl moieties on the first ester compound is replaced by the alcohol hydrocarbon backbone or hydrocarbyl moieties from the second ester compounds;

wherein the alcohols comprise a mixture of alcohols or the second ester compounds comprise a mixture of ester compounds.

2. A method according to claim 1 wherein the mixture of alcohols comprise at least one alcohol having one hydroxyl group and at least one alcohol having more than one hydroxyl group or the mixture of second ester compounds comprise at least one ester compound having one ester group and at least one ester compound having more than one ester group.

3. A method according to claim 1 wherein the acid or the ester of a the acid is present in a sufficient amount to catalyze the replacement of one or more hydrocarbon moieties of the first compound having one or more ester groups with the hydrocarbon backbone of the one or more alcohols or a hydrocarbyl moiety from the one or more second compounds having one or more ester groups, wherein the acid or the ester of the acid is present in an amount of about 0.1 molar equivalents or less of the acid or the ester of acid per molar equivalent of the first compound having one or more ester groups.

4. A method according to claim 1 wherein the method is performed at a temperature of about 50°

C. to about 160°

C.

5. A method according to claim 1 wherein the first ester compound comprises one or more 1,1-disubstituted alkenes, cyanoacrylates. or methacrylates.

6. A method according to claim 5 wherein the first ester compound comprises one or more 1,1-disubstituted alkenes.

7. A method of according to claim 5 wherein the first ester compound is contacted with the one or more alcohols or one of more second ester compounds in the presence of a free radical polymerization stabilizer.

8. A method comprising:

contacting a first ester compound having one or more ester groups with hydrocarbyl moieties as part of each of the ester groups and a functional group which may undergo undesired side reactions under transesterification reaction conditions, with one or more alcohols having a hydrocarbon backbone and one or more hydroxyl groups or one or more second ester compounds having one or more ester groups with hydrocarbyl moieties different from the hydrocarbyl moieties on the first ester compounds, in the presence of one or more acids having a pKa in a polar aprotic solvent of about −

5 to about 14 or esters of the acid under conditions that at least one of the hydrocarbyl moieties on the first ester compound is replaced by the alcohol hydrocarbon backbone or hydrocarbyl moieties from the second ester compounds;

wherein the method is performed at a temperature of about 50°

C. to about 160°

C.

9. A method according to claim 8 wherein the acid or the ester of the acid is present in a sufficient amount to catalyze the replacement of one or more hydrocarbon moieties of the first compound having one or more ester groups with the hydrocarbon backbone of the one or more alcohols or a hydrocarbyl moiety from the one or more second compounds having one or more ester groups, wherein the acid or the ester of the acid is present in an amount of about 0.1 molar equivalents or less of the acid or the ester of acid per molar equivalent of the first compound having one or more ester groups.

10. A method according to claim 8 wherein the first ester compound is contacted with the one or more second ester compounds to prepare a transesterification product and a third ester;

wherein the first ester corresponds to the formula

11. A method according to claim 8 wherein the one or more first ester compounds are contacted with one or more alcohols to prepare a transesterification product and an alcohol byproduct;

wherein the first ester compounds correspond to the formula;

12. A method according to claim 8 wherein the acid or the ester of the acid is present in a sufficient amount to catalyze the replacement of one or more hydrocarbon moieties of the first compound having one or more ester groups with the hydrocarbon backbone of the one or more alcohols or a hydrocarbyl moiety from the one or more second compounds having one or more ester groups, wherein the acid or the ester of the acid is present in an amount of about 0.1 molar equivalents or less of the acid or the ester of acid per molar equivalent of the first compound having one or more ester groups.

13. A method of according to claim 8 wherein the first ester compound comprises one or more 1,1-disubstituted alkenes and is contacted with the one or more alcohols or one of more second ester compounds in the presence of a free radical polymerization stabilizer.

14. A method comprising:

contacting a first ester compound having one or more ester groups with hydrocarbyl moieties as part of each of the ester groups and a functional group which may undergo undesired side reactions under transesterification reaction conditions, with one or more alcohols having a hydrocarbon backbone and one or more hydroxyl groups or one or more second ester compounds having one or more ester groups with hydrocarbyl moieties different from the hydrocarbyl moieties on the first ester compounds, in the presence of one or more acids having a pKa in a polar aprotic solvent of about −

5 to about 14 or esters of the acid under conditions that at least one of the hydrocarbyl moieties on the first ester compound is replaced by the alcohol hydrocarbon backbone or hydrocarbyl moieties from the second ester compounds;

wherein the one or more second compounds having one or more ester moieties is an acetate ester or a formate ester.

15. A method according to claim 14 wherein the transesterified first ester compound contains Michael addition products of the alkene with water of about 1 mole percent or less.

16. A method according to claim 15 wherein the acid or the ester of the acid is present in a sufficient amount to catalyze the replacement of one or more hydrocarbon moieties of the first compound having one or more ester groups with the hydrocarbon backbone of the one or more alcohols or a hydrocarbyl moiety from the one or more second compounds having one or more ester groups, wherein the acid or the ester of the acid is present in an amount of about 0.1 molar equivalents or less of the acid or the ester of acid per molar equivalent of the first compound having one or more ester groups.

17. A method according to claim 15 wherein the method is performed at a temperature of about 50°

C. to about 160°

C.

18. A method of according to claim 15 wherein the first ester compound is contacted with the one or more alcohols or one of more second ester compounds in the presence of a free radical polymerization stabilizer.

19. A method comprising:

contacting a first ester compound having one or more ester groups with hydrocarbyl moieties as part of each of the ester groups and a functional group which may undergo undesired side reactions under transesterification reaction conditions, with one or more alcohols having a hydrocarbon backbone and one or more hydroxyl groups or one or more second ester compounds having one or more ester groups with hydrocarbyl moieties different from the hydrocarbyl moieties on the first ester compounds, in the presence of one or more acids having a pKa in a polar aprotic solvent of about −

5 to about 14 or esters of the acid under conditions that at least one of the hydrocarbyl moieties on the first ester compound is replaced by the alcohol hydrocarbon backbone or hydrocarbyl moieties from the second ester compounds;

wherein the first ester compound is one or more 1,1-disubstituted alkene compounds which are contacted with one or more alcohols having two or more hydroxyl groups or one or more second ester compounds having two or more ester groups wherein the resulting product contains the core unit of two or more 1,1-disubstituted alkene compounds linked by the hydrocarbon backbone of the alcohols or the second ester compounds.

20. A method of according to claim 19 wherein the first ester compound is contacted with the one or more alcohols or one of more second ester compounds in the presence of a free radical polymerization stabilizer.

21. A method according to claim 19 wherein the method is performed at a temperature of about 50°

C. to about 160°

C.

22. A composition comprising a 1,1-disubstituted alkenes bonded to through an oxygen bond to the alkyl group which is further bonded to a hydroxyl alkyl acrylate which is illustrated by the formula: