Catalytic transesterification of ester compounds with groups reactive under transesterification conditions

Patent metadata

Field	Value
Publication number	US-2016229786-A1
Application number	US-201615099831-A
Country	US
Kind code	A1
Filing date	Apr 15, 2016
Priority date	Feb 4, 2015
Publication date	Aug 11, 2016
Grant date	—

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.

First claim

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.

2 . A method according to claim 1 wherein the functional group which may undergo undesired side reactions under transesterification reaction conditions can polymerize or react with other components present.

3 . A method according to claim 2 wherein the functional group which may undergo undesired side reactions under transesterification reaction conditions is an unsaturated group.

4 . A method according to claim 3 wherein 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.

5 . (canceled)

6 . 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.

7 - 20 . (canceled)

21 . A method according to claim 1 wherein the acid exhibits a pKa in a polar aprotic solvent of about −1 to about 12.

22 . A composition comprising one or more 1,1-disubstituted alkenes and one or more compounds containing two or more core units of 1,1-disubstituted alkenes linked by oxygen atoms to the hydrocarbon backbone of one or more alcohols having two or more hydroxyl groups or the hydrocarbon backbone of one or more second ester compounds having two or more ester groups wherein the concentration of and one or more compounds containing two or more core units of 1,1-disubstituted alkenes is greater than 5 percent by weight.

23 . A composition according to claim 22 wherein the 1,1-disubstituted alkenes correspond to the formulas:

and the one or more compounds containing two or more core units of 1,1-disubstituted alkenes correspond to the formulas:

wherein:
R1, R2, and R3 are separately in each occurrence hydrocarbyl groups;
R4 is separately in each occurrence an f-valent hydrocarbyl group;
R′ is separately in each occurrence hydrocarbyl or hydrogen;
c is separately in each occurrence an integer of 2 or more;
d is separately in each occurrence an integer of 2 or more and is equal to or less than c;
f is separately in each occurrence an integer of 1 or greater; and
g is an integer of 2 or greater.

24 . A composition comprising one or more 1,1-disubstituted alkenes linked by oxygen atoms to the hydrocarbon backbone of one or more second ester compounds wherein the hydrocarbon backbone of the one or more second ester compounds is bonded to one or more ester groups.

25 . A composition according to claim 24 wherein the hydrocarbon back bone is bonded to an acrylate, acetate or formate group.

26 . A composition according to claim 24 illustrated by the formula:

wherein:
R 1 , R 2 , and R 3 are separately in each occurrence hydrocarbyl groups;
R4 is separately in each occurrence an f-valent hydrocarbyl group;
R′ is separately in each occurrence hydrocarbyl or hydrogen;
f is separately in each occurrence an integer of 2 or greater; and
g is an integer of 1 or greater with the proviso that f is greater than g.

27 . A composition according to claim 26 wherein R′ is hydrogen and R 3 is hydrogen or methyl.

28 . A composition according to claim 13 which is illustrated by the formula:

wherein:
R 1 is separately in each occurrence hydrocarbyl groups;
R′ is separately in each occurrence hydrocarbyl or hydrogen;
R 6 is the residue of an alkyl acrylate;
c is separately in each occurrence an integer of 3 or more;
d is separately in each occurrence an integer of 2 or more and is less than c.

Assignees

• Sirrus Inc

Inventors

• Sullivan Jeffrey M
• Palsule Aniruddha
• Stevenson Peter Rulon
• Parab Kshitij Kishen

Classifications

• C07C67/02 Primary

  by interreacting ester groups, i.e. transesterification · CPC title

• C07C69/604

  Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups · CPC title

• C07C69/593

  Dicarboxylic acid esters having only one carbon-to-carbon double bond · CPC title

• C07C69/732

  of unsaturated hydroxy carboxylic acids · CPC title

• C07C67/03 Primary

  by reacting an ester group with a hydroxy group · CPC title