Synthesis of alpha,beta-unsaturated carboxylic acid (meth)acrylates from olefins and co2

Patent metadata

Field	Value
Publication number	US-2016130208-A1
Application number	US-201414890298-A
Country	US
Kind code	A1
Filing date	May 12, 2014
Priority date	Jun 11, 2013
Publication date	May 12, 2016
Grant date	—

Abstract

The invention relates to a method for producing α,β-unsaturated carboxylic acids or salts thereof, comprising a step in which a metallalactone is reacted in a solvent in the presence of a halide; to a composition that comprises α,β-unsaturated carboxylic acids or salts thereof and halide ions; and to the use of said composition for the production of superabsorbent materials or as a monomer composition for producing polymers.

First claim

1 . A process for preparing α,β-unsaturated carboxylic acids or salts thereof, wherein it has a process step in which a substance of the formula (I)

where
E=element of group 4, 6, 7, 8, 9 or 10 of the Periodic Table of the Elements,
L=nitrogen- or phosphorus-containing ligand,
n=1 to 4,
R=H or an aryl or alkyl radical,
is reacted in a solvent in the presence of a halide.

2 . The process according to claim 1 , wherein R in formula (I) is H or an alkyl radical having from 1 to 10 carbon atoms.

3 . The process according to claim 1 , wherein R in formula (I) is H or a methyl radical.

4 . The process according to claim 1 , wherein E in formula (I) is nickel.

5 . The process according to claim 1 , wherein L is a bidentate ligand.

6 . The process according to claim 1 , wherein L is a bisphosphane or bisphosphonate ligand, preferably selected from among trialkylbisphosphane, dialkylarylbisphosphane, alkyldiarylbisphosphane, triarylbisphosphane ligands.

7 . The process according to claim 1 , wherein L is a ligand selected from among bis(di-tert-butylphosphino)ethane, bis(dicyclohexylphosphino)ethane or bis(diphenylphosphino)ethane.

8 . The process according to claim 1 , wherein the halide is an iodide.

9 . The process according to claim 1 , wherein the halide is selected from among NaI, LiI and (nBu) 4 NI.

10 . The process according to claim 1 , wherein the solvent is selected from among cyclic ethers, chlorinated aromatics and aliphatic chlorinated hydrocarbons, particularly preferably chloroform, chlorobenzene and dichloromethane.

11 . The process according to claim 1 , wherein the compound of the formula (I) is obtained by reaction of a complex of the formula (II)
EL n   (II)
with an olefin and carbon dioxide.

12 . The process according to claim 11 , characterized in that the process is carried out without isolation of the compound of the formula (I).

13 . The process according to claim 10 , wherein propene or ethene, preferably ethene, is used as olefin.

14 . The composition containing E, an α,β-unsaturated carboxylic acid or a salt thereof, wherein it comprises halide ions, with E as defined in claim 1 .

15 . The composition according to claim 14 , wherein the α,β-unsaturated carboxylic acid or salt thereof is acrylic acid or methacrylic acid or a salt thereof.

16 . The composition according to claim 14 , wherein the proportion of iodide ions is from 20 to 1000 mol %, based on 100 mol % of E.

17 . The composition according to claim 14 , wherein the proportion of the α,β-unsaturated carboxylic acid or salt thereof is from 2 to 100% by weight based on the composition minus the amount of halide ions, solvent, E and L, with L.

18 . The use of a composition according to claim 14 for producing superabsorbent materials or as monomer composition for preparing polymers.

Assignees

• Evonik Degussa Gmbh

Inventors

• Schäffner Benjamin
• Blug Matthias
• Vogt Dieter
• Hendriksen Coen
• Pidko Evgeny

Classifications

• C07C51/15 Primary

  by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis · CPC title