Method for producing carboxylic acid esters and the use thereof as plasticizers

Patent metadata

Field	Value
Publication number	US-10106486-B2
Application number	US-201415033296-A
Country	US
Kind code	B2
Filing date	Oct 30, 2014
Priority date	Oct 31, 2013
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

The present invention relates to a process for the production of carboxylic esters by reaction of carboxylic acids and/or carboxylic anhydrides with at least one alcohol selected from alkanols having at least 5 carbon atoms, cycloalkanols, and alkoxy-alkanols, in the presence of an acidic esterification catalyst. The invention further relates to the use of the resultant carboxylic esters as plasticizers or in a plasticizer composition for thermoplastic polymers and elastomers.

First claim

The invention claimed is:

1. A process for producing a carboxylic ester, the process comprising:
reacting a reaction mixture comprising a carboxylic acid, a carboxylic anhydride, or both, and an alcohol R 1 —OH, an alcohol R 2 —[O—X] n —OH, or both, in a reaction system comprising one or more reactors, in the presence of methanesulfonic acid wherein a sulfate content of the methanesulfonic acid is at most 50 ppm and a chlorine content of the methanesulfonic acid is at most 20 ppm, and at a reaction mixture temperature of from 150° C. to 240° C.;
introducing an inert gas into the reaction system during the reacting;
removing, from the one or more reactors, water formed during the reacting as an azeotropic mixture with the alcohol R 1 —OH, the alcohol R 2 —[O—X] n —OH, or both; and
returning at least some of the alcohol R 1 —OH, the alcohol R 2 —[O—X] n —OH, or both, removed from the one or more reactors to the reaction system,
to obtain a carboxylic ester,
wherein:
R 1 represents an unbranched or branched C 5 -C 13 -alkyl group, or a C 5 -C 6 -cycloalkyl group that is optionally substituted by at least one C 1 -C 10 -alkyl moiety;
R 2 represents an unbranched C 1 -C 13 -alkyl group or a branched C 3 -C 13 -alkyl group;
X represents an unbranched C 2 -C 5 -alkylene group or branched C 3 -C 5 -alkylene group; and
n has the value 1, 2 or 3.

2. The process according to claim 1 , where the inert gas is passed into at least one of the reactors below a liquid surface of the reaction mixture, such that the inert gas bubbles through the reaction mixture.

3. The process of claim 1 , wherein:
the reaction system comprises a cascade of at least two reactors; and
the inert gas is introduced at least into a first reactor of the cascade.

4. The process of claim 1 , wherein the reaction occurs continuously.

5. The process of claim 1 , wherein the inert gas is nitrogen.

6. The process of claim 1 , wherein R 1 is a n-octyl group, a 2-ethylhexyl group, a n-nonyl group, an isononyl group, an isodecyl group, a 2-propylheptyl group, a n-undecyl group or an isoundecyl group.

7. The process of claim 1 , wherein the alcohol R 1 —OH is 2-ethylhexanol.

8. The process of claim 1 , wherein:
R 2 is an unbranched C 1 -C 9 -alkyl group or a branched C 3 -C 9 -alkyl group;
X is an unbranched C 2 -C 3 -alkylene group or a branched C 3 -C 4 -alkylene group; and
n has the value 1 or 2.

9. The process of claim 1 , wherein the alcohol R 2 —[O—X] n —OH is 2-butoxyethanol, 2-(2-butoxyethoxy)ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, or a mixture thereof.

10. The process of claim 1 , comprising reacting an alcohol R 1 —OH, an alcohol R 2 —[O—X] n —OH, or both, with an aromatic mono-, di-, tri-, or tetracarboxylic acid or anhydride thereof, an aliphatic mono- or dicarboxylic acid or anhydride thereof, a hydroxycarboxylic acid or anhydride thereof, an alicyclic mono-, di-, tri-, or tetracarboxylic acid or anhydride thereof, a heterocyclic dicarboxylic acid or anhydride thereof, or a mixture thereof.

11. The process of claim 1 , wherein the carboxylic acid, the carboxylic anhydride, or both, is selected from the group consisting of acetic acid, acetic anhydride, benzoic acid, benzoic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, and mixtures thereof.

12. The process of claim 1 , wherein the carboxylic acid, the carboxylic anhydride, or both, is selected from the group consisting of acetic acid, acetic anhydride, benzoic acid, benzoic anhydride, terephthalic acid, trimellitic acid, trimellitic anhydride, and mixtures thereof.

13. The process of claim 1 , comprising reacting terephthalic acid with 2-ethylhexanol to produce bis(2-ethylhexyl)-terephthalate.

14. The process of claim 1 , comprising reacting 2-butoxyethanol, 2-(2-butoxyethoxy)ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, or a mixture thereof, with acetic acid or acetic anhydride to produce 2-butoxyethyl acetate, 2-(2-butoxyethoxy) ethyl acetate, I-methoxy-2-propyl acetate, 3-methoxypropyl acetate, or a mixture thereof.

15. The process of claim 1 , wherein the alcohol R 1 —OH, the alcohol R 2 —[O—X] n —OH, or both, is present in a 1.01- to 2.0-fold molar excess, based on carboxylic acid equivalents of the carboxylic acid, a carboxylic anhydride, or both.

16. The process of claim 1 , wherein a sulfate content of the methanesulfonic acid is at most 20 ppm.

17. The process of claim 1 , wherein a proportion of the catalyst is from 0.5 to 5 mol %, based on a molar amount of carboxylic acid groups reacted.

Assignees

• Basf Se

Inventors

• Kaller Martin
• Koch Michael
• Breitscheidel Boris

Classifications

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08K5/0016

  Plasticisers · CPC title

• C07C67/08 Primary

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C07C67/48

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C08K5/12

  of cyclic polycarboxylic acids · CPC title