Process for preparing (meth)acrylates

Patent metadata

Field	Value
Publication number	US-9688601-B2
Application number	US-201514924018-A
Country	US
Kind code	B2
Filing date	Oct 27, 2015
Priority date	Dec 19, 2007
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

Process for preparing (meth)acrylates of the formula (I)

CH 2 ═C(R 1 )—CO—O—R 2   (I)

in which R 1 is hydrogen or methyl and

R 2 is a saturated or unsaturated, linear or branched, aliphatic or cyclic alkyl radical having 6 to 22 carbon atoms, or a (C 6 -C 14 )-aryl-(C 1 -C 8 )-alkyl radical;

by reacting a (meth)acrylate of the formula II

CH 2 ═C(R 1 )—CO—OR 3   (II)

with an alcohol of the formula (III)

HO—R 2   (III)

in the presence of an amount of a suitable catalyst which catalyzes the reaction and of an amount of a phenolic polymerization inhibitor or a combination of two or more phenolic polymerization inhibitors which is sufficient to inhibit undesired polymerization;

the reaction being undertaken with input or introduction into the reaction mixture resulting from the reaction of an amount of oxygen or of an oxygenous gas mixture sufficient to inhibit undesired polymerization, and the process is characterized in that

the specific total oxygen input is less than or equal to 1.0 l/kg, measured in liters of oxygen per kilogram of (meth)acrylate of the formula (I), where the volume of oxygen introduced is calculated at a temperature of 25° C. and a pressure of 101 325 pascal.

The resulting (meth)acrylates can surprisingly be processed to particularly high molecular weight emulsion polymers which are, for example, outstandingly suitable for use as flow resistance reducers in mineral oil extraction.

First claim

The invention claimed is:

1. A process for preparing a (meth)acrylate of formula (I)
CH 2 ═C(R 1 )—CO—O—R 2   (I)

wherein R 1 is hydrogen or methyl, and
R 2 is a saturated or unsaturated, linear or branched, aliphatic or cyclic alkyl radical having 6 to 22 carbon atoms, or a (C 6 -C 14 )-aryl-(C 1 -C 8 )-alkyl radical,
the process comprising:
reacting a (meth)acrylate of formula II
CH 2 ═C(R 1 )—CO—OR 3   (II)

wherein R 1 is hydrogen or methyl and R 3 is methyl,

with an alcohol of formula (III)
HO—R 2   (III)

wherein R 2 is a saturated or unsaturated, linear, branched or cyclic alkyl radical having 6 to 22 carbon atoms, or a (C 6 -C 14 )-aryl-(C 1 -C 8 )-alkyl radical,
in the presence of an amount of a suitable catalyst which catalyses the reaction and
in the presence of an amount of a phenolic polymerization inhibitor or a combination of two or more phenolic polymerization inhibitors which is sufficient to inhibit undesired polymerization, to form a reaction mixture,
the reaction undertaken with introduction into the reaction mixture resulting from the reacting, of an amount of oxygen or of an oxygenous gas mixture sufficient to inhibit undesired polymerization,
wherein
a specific total oxygen input is less than or equal to 1.0 l/kg, measured in liters of oxygen per kilogram of (meth)acrylate of formula (I), where the volume of oxygen introduced is calculated at a temperature of 25° C. and a pressure of 101,325 pascal,
and wherein the reacting is performed continuously.

2. The process according to claim 1 , wherein the reacting of the alcohol of formula (III) to (meth)acrylate of formula (I) is carried out in a reaction vessel having a reactor volume of greater than or equal to 0.25 m 3 .

3. The process according to claim 1 , wherein the (meth)acrylate of formula (I), after the reacting has ended, is isolated by distillation.

4. The process according to claim 1 ,
wherein R 2 is a linear or branched alkyl radical having 8 to 12 carbon atoms or a (C 6 -C 12 )-aryl-(C 1 -C 4 )-alkyl radical.

5. The process according to claim 1 , wherein R 2 is a 2-ethylhexyl radical.

6. The process according to claim 1 , wherein the catalyst is tetraisopropyl titanate, tetrakis(ethylhexyl) titanate, zirconium acetylacetonate, a dialkyltin compound, a lithium compound, optionally in combination with a calcium compound, or an acid.

7. The process according to claim 1 , wherein the phenolic inhibitor is hydroquinone and/or hydroquinone monomethyl ether.

8. The process according to claim 1 ,
wherein the oxygenous gas mixture introduced into the reaction mixture is oxygenous lean air having a content of less than or equal to 5% oxygen (v/v).

9. The process according to claim 1 , wherein the specific total oxygen input is less than or equal to 0.5 liter of oxygen per kilogram of product of the formula (I).

10. The process according to claim 1 , wherein the specific total oxygen input is less than or equal to 0.3 liter of oxygen per kilogram of product of the formula (I).

11. The process according to claim 1 , wherein the specific total oxygen input is less than or equal to 0.2 liter of oxygen per kilogram of product of the formula (I).

12. The process according to claim 1 , wherein the catalyst is tetraisopropyl titanate or tetrakis(ethylhexyl) titanate.

13. The process according to claim 1 , wherein the catalyst is tetraisopropyl titanate.

14. The process according to claim 1 , wherein the catalyst is tetrakis(ethylhexyl) titanate.

15. The process according to claim 1 , wherein the catalyst is zirconium acetylacetonate.

16. The process according to claim 1 , wherein the catalyst is a dialkyltin compound.

17. The process according to claim 1 , wherein the process is performed without a further solvent.

18. The process according to claim 1 , wherein a concentration of the phenolic polymerization inhibitor is less than 50 ppm, based on the (meth)acrylate of formula (I).

19. The process according to claim 1 , wherein the alcohol of formula III and the (meth)acrylate of formula II are combined with the catalyst and polymerization inhibitor in a reaction vessel such that a weight ratio of alcohol of formula III:(meth)acrylate of formula II is in a range of from 1:1.5 to 1:10, to form the reaction mixture.

20. A process for preparing a (meth)acrylate of formula (I)
CH 2 ═C(R 1 )—CO—O—R 2   (I)

wherein R 1 is hydrogen or methyl, and
R 2 is a saturated or unsaturated, linear or branched, aliphatic or cyclic alkyl radical having 6 to 22 carbon atoms, or a (C 6 -C 14 )-aryl-(C 1 -C 8 )-alkyl radical,
the process comprising:
reacting a (meth)acrylate of formula II
CH 2 ═C(R 1 )—CO—OR 3   (II)

wherein R 1 is hydrogen or methyl and R 3 is methyl,

with an alcohol of formula (III)
HO—R 2   (III)

wherein R 2 is a saturated or unsaturated, linear, branched or cyclic alkyl radical having 6 to 22 carbon atoms, or a (C 6 -C 14 )-aryl-(C 1 -C 8 )-alkyl radical,
in the presence of an amount of a suitable catalyst which catalyses the reaction and
in the presence of an amount of a phenolic polymerization inhibitor or a combination of two or more phenolic polymerization inhibitors which is sufficient to inhibit undesired polymerization, to form a reaction mixture,
the reaction undertaken with introduction into the reaction mixture resulting from the reacting, of an amount of an oxygenous gas mixture sufficient to inhibit undesired polymerization,
wherein
a specific total oxygen input is less than or equal to 1.01/kg, measured in liters of oxygen per kilogram of (meth)acrylate of formula (I), where the volume of oxygen introduced is calculated at a temperature of 25° C. and a pressure of 101,325 pascal,
the oxygenous gas mixture introduced into the reaction mixture is oxygenous lean air having a content of less than or equal to 5% oxygen (v/v),
and wherein the reacting is performed continuously.

Assignees

• Evonik Roehm Gmbh

Inventors

• Knebel Joachim
• Merbach Ralf
• Protzmann Guido
• Gottmann Klaus
• Hirsh John
• Schmitt Gerold
• Tessmer Dieter
• Karnbrock Wilhelm
• Klesse Wolfgang
• Kerscher Volker

Classifications

• C08F120/12

  of monohydric alcohols or phenols · CPC title

• C08F20/18

  with acrylic or methacrylic acids · CPC title

• C07C67/03 Primary

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

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title