Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions

• US 10,501,400 B2
• Filed: 04/03/2018
• Issued: 12/10/2019
• 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., Barrett, William, Doshi, Ami
• Primary Examiner(s): Cutliff, Yate' K
• Application Number:
  US15/944,491
• Publication Number:
  US 20180222839A1
• Time in Patent Office: 616 Days
• 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

Abstract

Disclosed are methods for the heterogeneous 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 less than 8 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 catalyst is present in an amount of 0.001 molar equivalents to 0.1 molar equivalents based on the molar equivalents of the first ester compound and the reactants are contacted at a temperature of about 80°

C. to about 160°

C. wherein the functional group which may undergo undesired side reactions under transesterification reaction conditions is an unsaturated group and the unsaturated group is in the proximity of one or more electron withdrawing groups such that the electrophilicity or electron withdrawing characteristics of the unsaturated group are increased;

wherein the catalyst is heterogeneous.

2. The process of claim 1 wherein the heterogeneous catalyst comprises the acid or ester thereof supported on an inert carrier or a membrane.

3. The process according to claim 2 wherein the catalyst is supported on porous support structure.

4. The process according to claim 3 wherein the porous support structure comprises one or more of silicon oxide, aluminum oxide, zirconium oxide, tin oxide, an aluminosilicate, or mixtures thereof.

5. The process according to claim 4 wherein the aluminosilicate, is a ZSM zeolite.

6. The process according to claim 4 wherein sulfuric acid, fluorosulfonic acid or trifluoromethanesulfonic acid is loaded onto the support.

7. The process according to claim 2 wherein the catalyst is sulfated aluminum oxide, triflated aluminum oxide, sulfated silicon oxide, triflated silicon oxide, sulfated tin oxide, triflated tin oxide, triflated HZSM-5, sulfated zirconia or triflated zirconia.

11. A method according to claim 1 wherein the hydrocarbyl moiety removed from the first ester compound forms a second alcohol or a third ester compound as a byproduct and the second alcohol or third ester compound formed is removed.

12. A method according to claim 1 wherein the acid is trifluoromethanesulfonic acid, sulfated tin oxide, triflated tin oxide or fluorosulfonic acid.

13. A method according to claim 1 wherein the acid is trifluoromethanesulfonic acid or fluorosulfonic acid.

14. A method according to claim 1 the reactants are reacted at a temperature of about 80°

C. to about 140°

C.

15. A method according to claim 1 the reactants are reacted at a temperature of about 80°

C. to about 130°

C.

16. A method according to claim 1 wherein the reactants are reacted for about 1 to about 4 hours.

17. A method according to claim 1 wherein the reactants are contacted in the present of a polar aprotic solvent having a boiling point at least 15°

C. above the temperature at which the reactants are contacted.

18. A method according to claim 1 wherein the reactants are reacted with agitation.

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 less than 8 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 catalyst is present in an amount of 0.001 molar equivalents to 0.1 molar equivalents based on the molar equivalents of the first ester compound and the reactants are contacted at a temperature of about 80°

C. to about 160°

C. wherein the functional group which may undergo undesired side reactions under transesterification reaction conditions is an unsaturated group and the unsaturated group is in the proximity of one or more electron withdrawing groups such that the electrophilicity or electron withdrawing characteristics of the unsaturated group are increased;

wherein the catalyst is heterogeneous;

wherein the heterogeneous catalyst comprises the acid or ester thereof supported on an inert carrier or a membrane; and

wherein the heterogeneous catalyst is sulfated silicon oxide or triflated silicon oxide.

9. 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 less than 8 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 catalyst is present in an amount of 0.001 molar equivalents to 0.1 molar equivalents based on the molar equivalents of the first ester compound and the reactants are contacted at a temperature of about 80°

C. to about 160°

C. wherein the functional group which may undergo undesired side reactions under transesterification reaction conditions is an unsaturated group and the unsaturated group is in the proximity of one or more electron withdrawing groups such that the electrophilicity or electron withdrawing characteristics of the unsaturated group are increased;

wherein the catalyst is heterogeneous;

wherein the heterogeneous catalyst comprises the acid or ester thereof supported on a membrane.

10. The process according to claim 9 wherein the catalyst is a strong acid ion exchange resin.