# US 5,350,877 A · Process for the improved production of (meth)acrylic acid esters of polyhydric alcohols (I)

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- Number: US 5,350,877 A
- Document ID: US5350877A
- Status: Granted
- Kind: A
- Application number: 07/720,443
- Filed: 1991-06-24
- Granted: 1994-09-27
- Earliest claimed: 1988-12-24
- Assignees: Henkel Kommanditgesellschaft auf Aktien
- Inventors: Wolfgang Ritter; Hans-Dieter Sitz; Ludwig Speitkamp
- Web page: https://patentgrep.com/patent/US5350877A

## CPC

- C08G 65/3322: {acyclic}
- A63C 9/088: with electronically controlled locking devices
- C07C 67/08: by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
- C08G 2650/20: Cross-linking
- C08L 2312/00: Crosslinking
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- A63C: SKATES; SKIS; ROLLER SKATES; DESIGN OR LAYOUT OF COURTS, RINKS OR THE LIKE (water skis B63B32/00, B63B34/00)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The invention relates to a process for the production of (meth)acrylic acid esters of polyhydric alcohols by reaction of the reactants in the presence of acidic esterification catalysts with addition of .alpha.-substituted phenolic compounds, more particularly di-tert.-butyl hydroquinone, as polymerization inhibitors. The new process is characterized in that the reaction mixtures used are liquid at room temperature and are at least substantially free from solvents and/or azeotropic entraining agents and in that the water of condensation formed is removed from the gas phase of the reaction zone.

## Claims

### Claim 1

In a process for the production of (meth)acrylic acid esters of polyhydric alcohols by the reaction of (meth)acrylic acid with a polyhydric alcohol in the presence of an acidic esterification catalyst and a polymerization inhibitor, the improvement wherein:
A. the reaction mixture is liquid at room temperature,
B. the reaction mixture is free from added solvents and azeotropic entraining agents, and
C. the water of condensation which forms in the reaction is removed from the reaction zone.

### Claim 2 (depends on 1)

The process of claim 1 wherein the reaction zone is purged with a gas stream containing free oxygen.

### Claim 3 (depends on 2)

The process of claim 2 wherein the gas stream is air or a mixture of nitrogen and air.

### Claim 4 (depends on 1)

The process of claim 1 wherein the polymerization inhibitor is an .alpha.-substituted phenolic compound.

### Claim 5 (depends on 4)

The process of claim 4 wherein the .alpha.-substituted phenolic compound is di-tert butyl hydroquinone.

### Claim 6 (depends on 1)

The process of claim 1 wherein the process is carried out at a temperature of from about 90.degree. to about 150.degree. C.

### Claim 7 (depends on 6)

The process of claim 6 wherein said temperature is from about 100.degree. to about 140.degree. C.

### Claim 8 (depends on 1)

The process of claim 1 wherein the reaction is carried out at subatmospheric pressure.

### Claim 9 (depends on 1)

The process of claim 1 wherein the polymerization inhibitor is present in a quantity of from about 200 to about 10,000 ppm based on the weight of the reaction mixture.

### Claim 10 (depends on 9)

The process of claim 9 wherein from about 300 to about 2,000 ppm of polymerization inhibitor is present.

### Claim 11 (depends on 1)

The process of claim 1 wherein the reaction is carried out to a yield of at least about 90% of the theoretical during a reaction time of no more than about 10 hours.

### Claim 12 (depends on 1)

The process of claim 1 wherein the crude reaction product is subjected to dry neutralization.

### Claim 13 (depends on 12)

The process of claim 12 wherein the dry neutralization is carried out with at least one of an alkali metal oxide, an alkali metal hydroxide, an alkaline earth metal oxide, an alkaline earth metal hydroxide, aluminum oxide, and aluminium hydroxide.

### Claim 14 (depends on 1)

The process of claim 1 wherein the reaction product is treated with a decolorizing agent.

### Claim 15 (depends on 1)

The process of claim 1 wherein the reaction zone is purged with a gas stream containing free oxygen, the process is carried out at a temperature of from about 90.degree. C. to about 150.degree. C., and the reaction is carried out to a yield of at least about 90% of the theoretical during a reaction time of no more than about 10 hours.

### Claim 16 (depends on 15)

The process of claim 15 wherein the polymerization inhibitor is an .alpha.-substituted phenolic compound and is present in from about 200 to about 10,000 ppm, based on the weight of the reaction mixture.

### Claim 17 (depends on 15)

The process of claim 15 wherein the reaction temperature is in the range of from about 100.degree. to about 140.degree. C.

### Claim 18 (depends on 16)

The process of claim 16 wherein from about 300 to about 2,000 ppm of polymerization inhibitor is present.

### Claim 19 (depends on 15)

The process of claim 15 wherein the crude reaction product is subjected to dry neutralization.

### Claim 20 (depends on 15)

The process of claim 15 wherein the reaction is carried out at subatmospheric pressure.

### Claim 21

A process for the production of a polyfunctional ester of (meth)acrylic acid comprising the steps of
a) forming a reaction mixture liquid at room temperature containing
i) a (meth)acrylic acid,
ii) a polyhydric alcohol,
iii) a polymerization inhibitor which is an .alpha.-substituted phenolic compound, and
iv) an acidic esterification catalyst, and wherein the reaction mixture is free from added solvents and azeotropic-entraining agents;
b) heating the above reaction mixture to a temperature in the range of from about 90.degree. to about 150.degree. C. while removing water of reaction from the reaction zone to form a crude reaction product; and
c) subjecting the crude reaction product to dry neutralization.

### Claim 22 (depends on 21)

The process of claim 21 wherein in step b) the reaction zone is purged with a gas stream containing free oxygen, and step b) is carried out using a subatmospheric pressure.