Inhibitor combination for lithium salt-catalyzed transesterification process and method for removing lithium salt

Patent metadata

Field	Value
Publication number	US-9796650-B2
Application number	US-201415100759-A
Country	US
Kind code	B2
Filing date	Nov 21, 2014
Priority date	Dec 26, 2013
Publication date	Oct 24, 2017
Grant date	Oct 24, 2017

Abstract

A process to form a composition comprising an asymmetrical polyene, the asymmetrical polyene comprising an “α,β unsaturated-carbonyl end” and a “C—C double bond end,” the process comprising: reacting an alkene- or polyene-containing alcohol with an alkyl ester of an α,β unsaturated carboxylic acid in the presence of at least the following components A) through C) to form a solution comprising an asymmetrical polyene: A) a lithium salt; B) a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, a substituted alkyl-substituted phenol, an alkyl-substituted hydroquinone, a substituted alkyl-substituted hydroquinone, and combinations thereof; and C) an N-oxyl-containing compound; wherein the “α,β unsaturated-carbonyl end” of the asymmetrical polyene is selected from the group consisting of structures a) through c), as described herein, and wherein the “C—C double bond end” of the asymmetrical polyene is selected from the group consisting of structures 1) through 17), as described herein.

First claim

The invention claimed is:

1. A process to form a composition comprising an asymmetrical polyene, the asymmetrical polyene comprising an “α,β unsaturated-carbonyl end” and a “C—C double bond end,” the process comprising:
reacting an alkene- or polyene-containing alcohol with an alkyl ester of an α,β unsaturated carboxylic acid in the presence of at least the following components A) through C) to form a solution comprising the asymmetrical polyene:
A) a lithium salt;
B) a component selected from the group consisting of hydroquinone, an alkyl-substituted phenol, a substituted alkyl-substituted phenol, an alkyl-substituted hydroquinone, a substituted alkyl-substituted hydroquinone, and combinations thereof; and
C) an N-oxyl-containing compound;
wherein the “α,β unsaturated-carbonyl end” of the asymmetrical polyene is selected from the group consisting of the following:

wherein R 1 is selected from H or a C 1 -C 6 alkyl;

wherein R 2 is selected from H or a C 1 -C 6 alkyl; R 3 is selected from H, CH 3 , or CH 2 CH 3 ; R 4 is selected from H, CH 3 , or CH 2 CH 3 ; and n is from 1 to 50; and

and
wherein the “C—C double bond end” of the asymmetrical polyene is selected from the group consisting of the following:

wherein R5 is selected from H or C1-C6 alkyl;

wherein R6 is selected from H or C1-C6 alkyl;

wherein R7 is selected from H or C1-C6 alkyl;

wherein m=1 to 20.

2. The process of claim 1 , wherein the lithium salt has the structure Li n X, wherein n is 1 or 2; and X is selected from the group consisting of hydroxide, oxide, halide, carbonate, bicarbonate, alkoxide, alkonate, alkenoate, phenoxide, sulfate, bisulfate, sulfonate, phosphate, phosphonate, perchlorate, and nitrate.

3. The process of claim 1 , wherein component A) has the structure Li n X, wherein n is 1 or 2; and X is selected from the group consisting of OH − , O −2 , a halide, OR − , CO 3 −2 , HCO 3 − , and R′CO 2 − ; wherein R is selected from a C1-C8 straight chain or branched alkyl group or from an aryl group; wherein R′ is selected from either a C1-C8 straight chain or branched alkyl group, or an aryl group, or a C1-C3 alkene group.

4. The process of claim 1 , wherein component B) is selected from the group consisting of MeHQ, derivatives thereof, and HQ.

5. The process of claim 1 , wherein component C) is selected from 4-HT or a derivative thereof.

6. The process of claim 1 , wherein the alkyl ester of the α,β unsaturated carboxylic acid is methyl methacrylate.

7. The process of claim 1 , wherein the alkene- or polyene-containing alcohol is polypropylene glycol allyl ether.

8. The process of claim 1 , wherein the asymmetrical polyene is a polypropylene glycol allyl ether methacrylate.

9. The process of claim 1 , wherein component A) is anhydrous lithium hydroxide.

10. The process of claim 1 , further comprising the step of filtering the solution comprising the asymmetrical polyene at a temperature of less than or equal to 5° C., using a 10 micron or less filter.

11. The process of claim 10 , wherein the solution comprising the asymmetrical polyene is filtered at a temperature of less than or equal to 2° C.

Assignees

• Dow Global Technologies Llc
• Rohm & Haas
• Rohm & Haas

Inventors

• Wilczynski Robert
• Eddy Christopher R
• Osby John O
• Nguyen Lan T P Hoang

Classifications

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F210/02

  Ethene · CPC title

• C07C69/587

  Monocarboxylic acid esters having at least two carbon-to-carbon double bonds · CPC title

• C07C67/02 Primary

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

• C08F220/68

  Esters · CPC title