초록 ▼

A process for the production of methacrylic acid is described. The process comprises the base catalysed decarboxylation of at least one or a mixture of dicarboxylic acids selected from itaconic, citraconic or mesaconic acid. The decarboxylation is carried out in the range greater than 240 and up to

A process for the production of methacrylic acid is described. The process comprises the base catalysed decarboxylation of at least one or a mixture of dicarboxylic acids selected from itaconic, citraconic or mesaconic acid. The decarboxylation is carried out in the range greater than 240 and up to 275° C. to provide high selectivity. The methacrylic acid product may be esterified to produce an ester. A method of preparing polymers or copolymers of methacrylic acid or methacrylic acid esters using the process is also described. Optionally, the process may be preceded with a decarboxylation and, if necessary, a dehydration step on a source of pre-acid such as citric acid or isocitric acid.

대표청구항 ▼

1. A continuous process for the production of methacrylic acid by the base catalysed decarboxylation of at least one dicarboxylic acid selected from itaconic, citraconic or mesaconic acid or mixtures thereof, followed by separation of the methacrylic acid product, wherein the decarboxylation is carr

1. A continuous process for the production of methacrylic acid by the base catalysed decarboxylation of at least one dicarboxylic acid selected from itaconic, citraconic or mesaconic acid or mixtures thereof, followed by separation of the methacrylic acid product, wherein the decarboxylation is carried out at greater than 240 and up to 275° C. and at pressures which will maintain the reactants in the liquid phase. 2. A process according to claim 1, wherein the decarboxylation is in the temperature range between 245 and up to 275° C. 3. A process according to claim 1, wherein the dicarboxylic acid reactants are in aqueous solution. 4. A process according to claim 1, wherein the decarboxylation reaction is carried out at suitable pressures in excess of atmospheric pressure. 5. A process according to claim 1, wherein the base catalyst comprises a metal oxide, hydroxide, carbonate, acetate (ethanoate), alkoxide, hydrogencarbonate or salt of a decomposable di- or tri-carboxylic acid, or a quaternary ammonium hydroxide, carbonate, acetate (ethanoate), alkoxide or hydrogencarbonate, or one or more amines. 6. A process according to claim 1, wherein the base catalyst is selected from one or more of the following: LiOH, NaOH, KOH, Mg(OH)2, Ca(OH)2, Ba(OH)2, CsOH, Sr(OH)2, RbOH, NH4OH, Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, BaCO3, (NH4)2CO3, LiHCO3, NaHCO3, KHCO3, RbHCO3, CsHCO3, Mg(HCO3)2, Ca(HCO3)2, Sr(HCO3)2, Ba(HCO3)2, NH4HCO3, Li2O, Na2O, K2O, Rb2O, Cs2O, MgO, CaO, SrO, BaO, Li(OR1), Na(OR1), K(OR1), Rb(OR1), Cs(OR1), Mg(OR1)2, Ca(OR1)2, Sr(OR1)2, Ba(OR1)2, NH4(OR1) where R1 is any C1 to C6 branched, unbranched or cyclic alkyl group, being optionally substituted with one or more functional groups; NH4(RCO2), Li(RCO2), Na(RCO2), K(RCO2), Rb(RCO2), Cs(RCO2), Mg(RCO2)2, Ca(RCO2)2, Sr(RCO2)2 or Ba(RCO2)2, where RCO2 is selected from citramalate, mesaconate, citraconate, itaconate, citrate, oxalate and methacrylate; (NH4)2(CO2RCO2), Li2(CO2RCO2), Na2(CO2RCO2), K2(CO2RCO2), Rb2(CO2RCO2), Cs2(CO2RCO2), Mg(CO2RCO2), Ca(CO2RCO2), Sr(CO2RCO2), Ba(CO2RCO2), (NH4)2(CO2RCO2), where CO2RCO2 is selected from citramalate, mesaconate, citraconate, itaconate and oxalate; (NH4)3(CO2R(CO2)CO2), Li3(CO2R(CO2)CO2), Na3(CO2R(CO2)CO2), K3(CO2R(CO2)CO2), Rb3(CO2R(CO2)CO2), Cs3(CO2R(CO2)CO2), Mg3(CO2R(CO2)CO2)2, Ca3(CO2R(CO2)CO2)2, Sr3(CO2R(CO2)CO2)2, Ba3(CO2R(CO2)CO2)2, (NH4)3(CO2R(CO2)CO2), where CO2R(CO2)CO2 is selected from citrate, isocitrate and aconitate; methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, and aniline; and R4NOH where R is selected from methyl, ethyl propyl, butyl. 7. A process according to claim 1, wherein the catalyst may be homogeneous or heterogeneous. 8. A process according to claim 1, wherein the effective mole ratio of base OH−:acid is between 0.001:1 and -2:1. 9. A process according to claim 1, wherein the methacrylic acid product is esterified to produce an ester thereof. 10. A process according to claim 1, wherein the concentration of the dicarboxylic acid reactant(s) is at least 0.1M. 11. A process according to claim 1, wherein the concentration of the catalyst in the reaction mixture is at least 0.1M. 12. A continuous process for the production of methacrylic acid by the base catalysed decarboxylation of at least one dicarboxylic acid selected from itaconic, citraconic or mesaconic acid or mixtures thereof followed by separation of the methacrylic acid product, wherein the decarboxylation is carried out in the temperature range between 240 and 290° C. and the dicarboxylic acid(s) reactant(s) are exposed to the reaction conditions for a time period of at least 80 seconds and at pressures which will maintain the reactants in the liquid phase. 13. A process according to claim 1, wherein the dicarboxylic acid reactants and the base catalyst are in aqueous solution.