Method for producing (meth)acrylic acid esters

• US 7,026,503 B2
• Filed: 05/28/2002
• Issued: 04/11/2006
• Est. Priority Date: 06/08/2001
• Status: Expired due to Term

• Current Assignee: BASF AG (BASF SE), Robert Bosch GmbH
• Original Assignee: BASF AG (BASF SE)
• Inventors: Schröder, Jürgen, Nestler, Gerhard, Rauh, Ulrich
• Primary Examiner(s): Zucker, Paul A.
• Application Number:
  US10/478,695
• Publication Number:
  US 20040158096A1
• Time in Patent Office: 1,414 Days
• Field of Search: 560/217
• US Class Current: 560/217
• CPC Class Codes: C07C 213/06 from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
• CPC Class Codes: C07C 213/10 Separation; Purification; Stabilisation; Use of additives
• CPC Class Codes: C07C 219/08 having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
• CPC Class Codes: C07C 67/54 by distillation
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

Higher (meth)acrylates IV are prepared by transesterification of a lower (meth)acrylate I with a higher alcohol R²OH in the presence of a stabilizer or stabilizer mixture and of a catalyst or catalyst mixture, by a process in which the liberated lower alkanol R¹OH is separated off and is fed at least partly to the preparation of the lower (meth)acrylate I.

Claims

1. A process for the preparation of higher (meth)acrylates by transesterification of a lower (meth)acrylate with a higher alcohol R²OH which either carries, as R², C₂–

C₁₂-alkyl radical having at least one NR³₂ group in which R³ is C₁–

C₆-alkyl and N may also be a member of a five- to seven-membered ring or is R³₂N(—

CH₂CH₂—

O)y-H, R³₂N(—

CH(CH₃)—

CH—

O)_y—

H or R³₂N(—

CH₂CH(CH₃)—

O)_y—

H, where y is an integer from 1 to 4, in the presence of a stabilizer or stabilizer mixture and of a catalyst or catalyst mixture, wherein the liberated lower alkanol R¹OH, where R¹ contains at least 1 carbon atom less than R², is separated off and is fed at least partly to the preparation of a lower (meth)acrylate without further purification.

4. A process as claimed in claim 1, wherein the liberated lower alkanol R¹OH is separated off and is fed at least partly to a working-up process in the preparation of the lower (meth)acrylate.

5. A process as claimed in claim 1, wherein the lower alkanol R¹OH is separated off by distillation.

6. A process as claimed in claim 1, wherein the lower alkanol R¹OH liberated during the transesterification is separated off substantially together with lower (meth)acrylate and any higher alcohol R²OH.

7. A process as claimed in claim 1, wherein the mixture liberated during the transesterification, separated off and containing lower alkanol R¹OH is brought into contact with a (meth)acrylic acid-containing stream in a working-up process in the preparation of the lower (meth)acrylate.

8. A process as claimed in claim 7, wherein the mixture liberated during the transesterification, separated off and containing lower alkanol R¹OH is used in a working-up process in the preparation of the lower (meth)acrylate for an extraction of (meth)acrylic acid.

9. A process as claimed in claim 7, wherein the mixture liberated during the transesterification, separated off and containing lower alkanol R¹OH is used in the working-up process in the preparation of a lower (meth)acrylate for an extraction of (meth)acrylic acid from acidified washwater.

10. A process as claimed in claim 8, wherein the extraction is carried out countercurrently.

11. A process as claimed in claim 1, which is carried out continuously.

12. A process as claimed in claim 1, wherein the lower alkanol R¹OH is n-butanol and the lower (meth)acrylate is n-butyl (meth)acrylate.

13. A process as claimed in claim 1, wherein the higher alkanol R²OH is 2-(N,N-dimethylamino)ethanol and the higher (meth)acrylate is 2-(N,N-dimethylamino)ethyl (meth)acrylate.

2. A process for the preparation of higher (meth)acrylates by transesterification of a lower (meth)acrylate with a higher alcohol R²OH which is selected from 2-(dimethylamino)ethanol, 3-(dimethylamino)propanol, 4-(dimethylamino)butanol, 5-(dimethylamino)pentanol, 6-(dimethylamino)hexanol, 8-(dimethylamino)octanol, 10-(dimethylamino)decanol, 12-(dimethylamino)dodecanol, 2-(diethylamino)ethanol, 3-(diethylamino)propanol, 4-(diethylamino)butanol, 5-(diethylamino)pentanol, 6-(diethylamino)hexanol, 8-(diethylamino)octanol, 10-(diethylamino)decanol, 12-(diethylamino)dodecanol, 2-(di(isopropyl)amino)ethanol, 3-(di(isopropyl)amino)propanol, 4-(di(isopropyl)amino)-butanol, 5-(di(isopropyl)amino)pentanol, 6-(di(isopropyl)amino)hexanol, 8-(di(isopropyl)amino)octanol, 10-(di(isopropyl)amino)decanol, 12-(di(isopropyl)amino)-dodecanol, 2-(dibutylamino)ethanol, 3-(dibutylamino)propanol, 4-(dibutylamino)butanol, 5-(dibutylamino)pentanol, 6-(dibutylamino)hexanol, 8-(dibutylamino)octanol, 10-(dibutylamino)decanol, 12-(dibutylamino)dodecanol, 2-(dihexylamino)ethanol, 3-(dihexylamino)propanol, 4-(dihexylamino)butanol, 5-(dihexylamino)pentanol, 6-(dihexylamino)hexanol, 8-(dihexylamino)octanol, 10-(dihexylamino)decanol, 12-(dihexylamino)dodecanol, 2-(methylethylamino)ethanol, 2-(methylpropylamino)ethanol, 2-(methylisopropylamino)-ethanol, 2-(methylbutylamino)ethanol, 2-(methylhexylamino)ethanol, 2-(methyloctylamino)ethanol, 2-(ethylpropylamino)ethanol, 2-(ethylisopropylamino)ethanol, 2-(ethylbutylamino)ethanol, 2-(ethylhexylamino)ethanol, 2-(ethyloctylamino)ethanol, 3-(methylethylamino)propanol, 3-(methylpropylamino)propanol, 3-(methylisopropylamino)-propanol, 3-(methylbutylamino)propanol, 3-(methylhexylamino)-propanol, 3-(methyloctylamino)propanol, 3-(ethylpropylamino)-propanol, 3-ethylisopropylamino)propanol, 3-(ethylbutylamino)propanol, 3-(ethylhexylamino)propanol, 3-(ethyloctylamino)propanol, 4-(methylethylamino)butanol, 4-(methylpropylamino)butanol, 4-(methylisopropylamino)-butanol, 4-(methylbutylamino)butanol, 4-(methylhexylamino)butanol, 4-(methyloctylamino)butanol, 4-(ethylpropylamino)butanol, 4-(ethylisopropylamino)butanol, 4-(ethylbutylamino)butanol, 4-(ethylhexylamino)butanol, 4-(ethyloctylamino)butanol, 2-(N-piperidinyl)ethanol, 3-(N-piperidinyl)propanol, 4-(N-piperidinyl)butanol, 5-(N-piperidinyl)pentanol, 6-(N-piperidinyl)hexanol, 8-(N-piperidinyl)octanol, 10-(N-piperidinyl)decanol, 12-(N-piperidinyl)dodecanol, 2-(N-pyrrolidinyl)ethanol, 3-(N-pyrrolidinyl)propanol, 4-(N-pyrrolidinyl)butanol, 5-(N-pyrrolidinyl)pentanol, 6-(N-pyrrolidinyl)hexanol, 8-(N-pyrrolidinyl)octanol, 10-(N-pyrrolidinyl)decanol, 12-(N-pyrrolidinyl)dodecanol, 2-(N-morpholino)ethanol, 3-(N-morpholino)propanol, 4-(N-morpholino)butanol, 5-(N-morpholino)pentanol, 6-(N-morpholino)hexanol, 8-(N-morpholino)octanol, 10-(N-morpholino)decanol, 12-(N-morpholino)dodecanol, 2-(N′

-methyl-N-piperazinyl)-ethanol, 3-(N′

-methyl-N-piperazinyl)propanol, 4-(N′

-methyl-N-piperazinyl)butanol, 5-(N′

-methyl-N-piperazinyl)pentanol, 6-(N′

-methyl-N-piperazinyl)hexanol, 8-(N′

-methyl-N-piperazinyl)octanol, 10-(N′

-methyl-N-piperazinyl)decanol 12-(N′

-methyl-N-piperazinyl)-dodecanol, 2-(N′

-ethyl-N-piperazinyl)ethanol, 3(N′

-ethyl-N-piperazinyl)propanol, 4-(N′

-ethyl-N-piperazinyl)butanol, 5-(N′

-ethyl-N-piperazinyl)pentanol, 6-(N′

-ethyl-N-piperazinyl)hexanol, 8-(N′

-ethyl-N-piperazinyl)octanol, 10-(N′

-ethyl-N-piperazinyl)decanol, 12-(N′

-ethyl-N-piperazinyl)dodecanol, 2-(N′

-isopropyl-N-piperazinyl)ethanol, 3-(N′

-isopropyl-N-piperazinyl)-propanol, 4-(N′

-isopropyl-N-piperazinyl)butanol, 5-(N′

-isopropyl-N-piperazinyl)pentanol, 6-(N′

-isopropyl-N-piperazinyl)hexanol, 8-(N′

-isopropyl-N-piperazinyl)octanol, 10-(N′

-isopropyl-N-piperazinyl)decanol, 12-(N′

-isopropyl-N-piperazinyl)dodecanol or ethoxylated and/or propoxylated alcohols and mixed ethoxylated/propoxylated amino alcohols, R³₂N(—

CH₂CH₂—

O)_y—

H or R³₂N(—

CH(CH₃)—

CH₂—

O)_y—

H or R³₂N(—

CH₂—

CH(CH₃)—

O—

)_y—

H, where y is an integer from 1 to 4, in the presence of a stabilizer or stabilizer mixture and of a catalyst or catalyst mixture, wherein the liberated lower alkanol R¹OH, which is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol and tert-butanol, is separated off and is fed at least partly to the preparation of a lower (meth)acrylate without further purification.

3. A process as claimed in claim 2, wherein the higher alcohol is selected from dimethylaminoethanol, diethylaminoethanol, di-n-butylaminoethanol, 3-dimethylaminopropanol, 3-diethylaminopropanol and 3-di-n-butylaminopropanol.

14. A process as claimed in claim 2, wherein the liberated lower alkanol R¹OH is separated off and is fed at least partly to a working-up process in the preparation of the lower (meth)acrylate.

15. A process as claimed in claim 2, wherein the lower alkanol R¹OH is separated off by distillation.

16. A process as claimed in claim 2, wherein the lower alkanol R¹OH liberated during the transesterification is separated off substantially together with lower (meth)acrylate and any higher alcohol R²OH.

17. A process as claimed in claim 2, wherein the mixture liberated during the transesterification, separated off and containing lower alkanol R¹OH is brought into contact with a (meth)acrylic acid-containing stream in a working-up process in the preparation of the lower (meth)acrylate.

18. A process as claimed in claim 17, wherein the mixture liberated during the transesterification, separated off and containing lower alkanol R¹OH is used in a working-up process in the preparation of the lower (meth)acrylate for an extraction of (meth)acrylic acid.

19. A process as claimed in claim 17, wherein the mixture liberated during the transesterification, separated off and containing lower alkanol R¹OH is used in a working-up process in the preparation of the lower (meth)acrylate for an extraction of (meth)acrylic acid from acidified washwater.

20. A process as claimed in claim 18, wherein the extraction is carried out countercurrently.

21. A process as claimed in claim 2, which is carried out continuously.

22. A process as claimed in claim 2, wherein the lower alkanol R¹OH is n-butanol and the lower (meth)acrylate is n-butyl (meth)acrylate.

23. A process as claimed in claim 2, wherein the higher alkanol R²OH is 2-(N,N-dimethylamino)ethanol and the higher (meth)acrylate is 2-(N,N-dimethylamino)ethyl (meth)acrylate.

24. A process for the preparation of higher (meth)acrylates by transesterification of a lower (meth)acrylate with a higher alcohol R²OH which either carries, as R², a C₂–

C₁₂-alkyl radical having at least one NR³₂ group in which R³ is C₁–

C₆-alkyl and N may also be a member of a five- to seven-membered ring or is R³₂N(—

CH₂CH₂—

O)y-H, R³₂N(-CH(CH₃)—

CH—

O)_y—

H or R³₂N(—

CH₁₂CH(CH₃)—

O)_y13 H, where y is an integer from 1 to 4, in the presence of a stabilizer or stabilizer mixture and of a catalyst or catalyst mixture, wherein the liberated lower alkanol R¹OH, where R¹ contains at least 1 carbon atom less than R², is separated off and is fed at least partly to the preparation of a lower (meth)acrylate without further purification over ion-exchange resin.