Process for the production of (meth)acrylic acid and derivatives and polymers produced therefrom

1. A process for the continuous production of (meth)acrylic acid comprising the steps of:

forming an aqueous medium of at least one base catalyst and at least one dicarboxylic acid and/or a precursor thereof, wherein the at least one dicarboxylic acid is selected from fumaric, maleic, malic, itaconic, citraconic, mesaconic or citramalic acid or mixtures thereof;

decarboxylating the at least one dicarboxylic acid in the presence of the at least one base catalyst under suitable conditions of temperature and pressure to produce (meth)acrylic acid and/or base salts thereof in the aqueous medium;

introducing an organic solvent to the said aqueous medium for solvent extraction of the (meth)acrylic acid into an organic phase;

wherein the dicarboxylic acid and/or pre-cursor thereof forms a first acid salt and a second acid salt thereof in the presence of the base catalyst;

characterised in that the level of base catalyst to the said at least one dicarboxylic acid and/or pre-cursor thereof is maintained at a sub-stoichiometric level in relation to the formation of the first acid salt of the at least one dicarboxylic acid and/or pre-cursor thereof during the extraction process.

2. The process according to claim 1 , wherein the concentration of (meth)acrylic acid in the aqueous phase extraction is at least 0.05 mol dm −3 .

3. The process according to claim 1 , further comprising the additional step of adding an additional amount of at least one of the dicarboxylic acids and/or a pre-cursor thereof to the aqueous reaction medium to enhance the solvent extraction of the (meth)acrylic acid into the organic phase.

4. The process according to claim 1 , wherein the dicarboxylic acid and/or a pre-cursor thereof is selected from a group consisting of citric, itaconic, citramalic, citraconic and mesaconic acid or mixtures thereof.

5. The process according to claim 4 , wherein the dicarboxylic acid and/or a pre-cursor thereof is selected from a group consisting of citric, itaconic, citramalic and citraconic acid or mixtures thereof.

6. The process according to claim 1 , wherein the dicarboxylic acid is selected from a group consisting of maleic, fumaric, and malic acid or mixtures thereof.

7. The process according to claim 1 , wherein the dicarboxylic acid is malic acid.

8. The process according to claim 1 , wherein in the case of the (meth)acrylic acid being methacrylic acid, the organic solvent is an external organic solvent with respect to the reaction medium.

9. The process according to claim 1 , wherein the dicarboxylic acid is selected from citramalic or itaconic acid.

10. The process according to claim 1 , wherein the organic solvent for (meth)acrylic acid extraction is selected from hydrocarbon solvents or oxygenated solvents.

11. The process according to claim 10 , wherein the hydrocarbon solvents are C 4 -C 20 hydrocarbon solvents.

12. The process according to claim 10 , wherein the organic solvent include toluene, benzene, ethylbenzene, xylene, trimethylbenzene, octane, heptane, hexane, pentane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclohexene, methylcyclohexane, methylethylketone, methyl methacrylate, mixtures thereof; and ionic liquids which are immiscible with water.

13. The process according to claim 1 , wherein the mixture of solvents for the extraction of (meth)acrylic acid is a C 4 -C 20 hydrocarbon solvent and methyl methacrylate.

14. The process according to claim 1 , further comprising the step of separating the organic phase from the aqueous phase after extraction followed by subsequent treatment of the organic phase to isolate the (meth)acrylic acid extracted in the extraction process from the organic solvent.

15. The process according to claim 1 , wherein the organic solvent is introduced to the aqueous medium before or after decarboxylation.

16. The process according to claim 1 , wherein the sub-stoichiometric level of base is maintained, after, if necessary, being implemented post reaction, during at least that part of the extraction process which is carried out after the decarboxylation step.

17. The process according to claim 1 , wherein the sub-stoichiometric level of base is maintained throughout the reaction and extraction.

18. A method of preparing polymers or copolymers of (meth)acrylic acid or (meth)acrylic acid esters, comprising the steps of:

(i) preparation of (meth)acrylic acid in accordance with claim 1 ;

(ii) optional esterification of the (meth)acrylic acid prepared in (i) to produce the (meth)acrylic acid ester;

(iii) polymerisation of the (meth)acrylic acid prepared in (i) and/or the ester prepared in (ii), optionally with one or more comonomers, to produce polymers or copolymers thereof.

19. Polyacrylic acid, polymethacrylic acid, polyalkylacrylate, polymethylmethacrylate (PMMA) and polybutylmethacrylate homopolymers or copolymers formed from the method of claim 18 .

20. The process for the production of methacrylic acid comprising:

providing a source of a pre-cursor acid selected from aconitic, citric and/or isocitric acid;

performing a decarboxylation and, if necessary, a dehydration step on the source of pre-cursor acid by exposing the source thereof in the presence or absence of a base catalyst to a sufficiently high temperature to provide a dicarboxylic acid selected from itaconic, mesaconic, citraconic and/or citramalic acid; and

using the dicarboxylic acid produced in a process according to claim 1 .