Abstract: A novel bidentate ligand of general formula (I) is described together with a process for the carbonylation of ethylenically unsaturated compounds. The group X1 may be defined as a univalent hydrocarbyl radical of up to 30 atoms containing at least one nitrogen atom having a pKb in dilute aqueous solution at 18° C. of between 4 and 14 wherein the said at least one nitrogen atom is separated from the Q2 atom by between 1 and 3 carbon atoms. The group X2 is defined as X1, X3 or X4 or represents a univalent radical of up to 30 atoms having at least one primary, secondary or aromatic ring carbon atom wherein each said univalent radical is joined via said at least one primary, secondary or aromatic ring carbon atom(s) respectively to the respective atom Q2. Q1 and Q2 each independently represent phosphorus, arsenic or antimony.

Abstract: A continuous process for the production of an alkyl ester product is described. The process includes the steps of carbonylating ethylene with carbon monoxide in the presence of C1-6 alkanol co-reactant to form the alkyl ester product. The carbonylation takes place in the presence of a catalyst system that includes (a) a bidentate ligand, (b) a catalytic metal selected from a group 8, 9 or 10 metal or a compound thereof, and (c) a sulphonic acid capable of forming an acid alkyl ester with the C1-6 alkanol. The process includes the step of separating the alkyl ester product from a carbonylated crude product stream by treatment effective to vaporizing the alkyl ester product in a single stage flash distillation column and providing a purified alkyl ester product stream separated from the bidentate ligand and catalytic metal.

Abstract: A process for the carbonylation of ethylenically unsaturated compounds including vinyl esters and a process for the production of 3-hydroxy propanoate esters or acids. The process comprises reacting said compound with carbon monoxide in the presence of a source of hydroxyl groups and of a catalyst system. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a compound thereof: and (b) a bidentate ligand of general formula (I): X1(X2)-Q2-A-R—B-Q1-X3(X4).

Abstract: A method of extracting (meth)acrylic acid from an aqueous reaction medium into an organic phase in contact therewith is described. The aqueous reaction medium is formed from at least one base catalyst and at least one dicarboxylic acid selected from maleic, fumaric, malic, itaconic, citraconic, mesaconic, and citramalic acid or mixtures thereof in aqueous solution and contains the base catalysed decarboxylation products of the base catalysed reaction. The method includes either the addition of at least one of the said 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 solvent or maintaining the level of base catalyst to dicarboxylic acid and/or pre-cursor at a sub-stoichiometric level during the extraction process. The method extends to a process of producing (meth)acrylic acid, its esters and polymers and copolymers thereof.

Abstract: 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.

Abstract: A method of extracting (meth)acrylic acid from an aqueous reaction medium into an organic phase in contact therewith is described. The aqueous reaction medium is formed from at least one base catalyst and at least one dicarboxylic acid selected from maleic, fumaric, malic, itaconic, citraconic, mesaconic, and citramalic acid or mixtures thereof in aqueous solution and contains the base catalysed decarboxylation products of the base catalysed reaction. The method includes either the addition of at least one of the said 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 solvent or maintaining the level of base catalyst to dicarboxylic acid and/or pre-cursor at a sub-stoichiometric level during the extraction process. The method extends to a process of producing (meth)acrylic acid, its esters and polymers and copolymers thereof.

Abstract: A process for the production of an alkyl methacrylate, particularly methyl methacrylate, is provided, in which a Baeyer-Villiger Monooxygenase enzyme is used to convert an alkylisopropenylketone substrate to the relevant alkyl methacrylate by abnormal asymmetric oxygen insertion. The invention provides a biobased route to key industrial monomers in particular for the generation of polymers such as poly methyl methacrylate.

Abstract: A process for the production of methacrylic acid or esters thereof by the base catalysed decarboxylation of at least one dicarboxylic acid selected from itaconic, citraconic or mesaconic acid or mixtures thereof in an aqueous reaction medium is described. The decarboxylation is carried out at a temperature in the range from 200° C. and up to 239° C. The methacrylic acid is isolated from the aqueous reaction medium by a purification process which does not include introducing an organic solvent to the aqueous reaction medium for solvent extraction of the methacrylic acid into an organic phase. A method of preparing polymers or copolymers of methacrylic acid or methacrylic acid esters is also described.

Abstract: The invention includes a process of producing methyl methacrylate or derivatives thereof is described. The process includes the steps of converting 2-butanone to methyl propionate using a Baeyer-Villiger monooxygenase, and treating the methyl propionate produced to obtain methyl methacrylate or derivatives thereof. A method of preparing polymers or copolymers of methyl methacrylate or its derivatives is also described.

Abstract: A continuous process for the production of an alkyl ester product is described. The process includes the steps of carbonylating ethylene with carbon monoxide in the presence of C1-6 alkanol co-reactant to form the alkyl ester product. The carbonylation takes place in the presence of a catalyst system that includes (a) a bidentate ligand, (b) a catalytic metal selected from a group 8, 9 or 10 metal or a compound thereof, and (c) a sulphonic acid capable of forming an acid alkyl ester with the C1-6 alkanol. The process includes the step of separating the alkyl ester product from a carbonylated crude product stream by treatment effective to vaporizing the alkyl ester product in a single stage flash distillation column and providing a purified alkyl ester product stream separated from the bidentate ligand and catalytic metal.

Abstract: A 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 is described. The decarboxylation is carried out at a temperature in the range from 100 to 199° C. A method of preparing polymers or copolymers of methacrylic acid or methacrylic acid esters is also described.

Abstract: A novel bidentate ligand of general formula (I) is described together with a process for the carbonylation of ethylenically unsaturated compounds. The group X1 may be defined as a univalent hydrocarbyl radical of up to 30 atoms containing at least one nitrogen atom having a pKb in dilute aqueous solution at 18° C. of between 4 and 14 wherein the said at least one nitrogen atom is separated from the Q2 atom by between 1 and 3 carbon atoms. The group X2 is defined as X1, X3 or X4 or represents a univalent radical of up to 30 atoms having at least one primary, secondary or aromatic ring carbon atom wherein each said univalent radical is joined via said at least one primary, secondary or aromatic ring carbon atom(s) respectively to the respective atom Q2. Q1 and Q2 each independently represent phosphorus, arsenic or antimony.

Abstract: A method of producing a compound of formula (i): wherein R=H or CH3 the method comprising exposing a source of a compound of formula (ii) to reaction conditions of temperature and pressure: formula (ii) wherein R is defined as above wherein, when R=CH3, the source of a compound of formula (ii) is exposed to reaction conditions of temperature and pressure while being in a liquid phase.

Abstract: A novel bidentate ligand of general formula (I) is described together with a process for the carbonylation of ethylenically unsaturated compounds. The group X1 may be defined as a univalent hydrocarbyl radical of up to 30 atoms containing at least one nitrogen atom having a pKb in dilute aqueous solution at 18° C. of between 4 and 14 wherein the said at least one nitrogen atom is separated from the Q2 atom by between 1 and 3 carbon atoms. The group X2 is defined as X1, X3 or X4 or represents a univalent radical of up to 30 atoms having at least one primary, secondary or aromatic ring carbon atom wherein each said univalent radical is joined via said at least one primary, secondary or aromatic ring carbon atom(s) respectively to the respective atom Q2. Q1 and Q2 each independently represent phosphorus, arsenic or antimony.

Abstract: A novel bidentate catalytic ligand of general formula (I) is described. R represents a hydrocarbyl aromatic structure having at least one aromatic ring to which Q1 and Q2 are each linked, via the respective linking group, if present, on available adjacent atoms of the at least one aromatic ring. The groups X3 and X4 represent radicals joined via tertiary carbon atoms to the respective atom Q1 and the groups X1 and X2 represent radicals joined via primary, or substituted aromatic ring carbon atom(s) to the respective atom Q2. A and B represent an optional lower alkylene linking group. Q1 and Q2 each represent phosphorus, arsenic or antimony. A process for the carbonylation of ethylenically unsaturated compounds comprising reacting the compound with carbon monoxide in the presence of a source of hydroxyl groups, optionally, a source of anions and catalyst system obtainable by combining a metal of Group 8, 9 or 10 or a compound thereof and the bidentate ligand of general formula (I) is also described.

Abstract: A method of extracting (meth)acrylic acid from an aqueous reaction medium into an organic phase in contact therewith is described. The aqueous reaction medium is formed from at least one base catalyst and at least one dicarboxylic acid selected from maleic, fumaric, malic, itaconic, citraconic, mesaconic, and citramalic acid or mixtures thereof in aqueous solution and contains the base catalysed decarboxylation products of the base catalysed reaction. The method includes either the addition of at least one of the said 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 solvent or maintaining the level of base catalyst to dicarboxylic acid and/or pre-cursor at a sub-stoichiometric level during the extraction process. The method extends to a process of producing (meth)acrylic acid, its esters and polymers and copolymers thereof.

Abstract: 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.

Abstract: The invention concerns metal complexes and their preparation, in particular a metal complex MLnXm, where M is a metal of group 8, 9 or 10 and X is a halide, HCO3-, NO3-, CO32- or carboxylate. n is a number equal to or less than the coordination number of the metal and m is 1 or 2 and is equal to the oxidation state of the metal. The ligand L may be a bidentate phosphine of formula (I), (II), (III) or (IV) as set out herein. The process of production comprises reacting an ammine compound of metal M with a complexing compound, which is preferably a phosphine.

Abstract: A novel bidentate ligand of general formula (I) is described together with a process for the carbonylation of ethylenically unsaturated compounds. The group X1 may be defined as a univalent hydrocarbyl radical of up to 30 atoms containing at least one nitrogen atom having a pKb in dilute aqueous solution at 18° C. of between 4 and 14 wherein the said at least one nitrogen atom is separated from the Q2 atom by between 1 and 3 carbon atoms. The group X2 is defined as X1, X3 or X4 or represents a univalent radical of up to 30 atoms having at least one primary, secondary or aromatic ring carbon atom wherein each said univalent radical is joined via said at least one primary, secondary or aromatic ring carbon atom(s) respectively to the respective atom Q2. Q1 and Q2 each independently represent phosphorus, arsenic or antimony.

Abstract: A method of increasing the TON of a catalyst system for the monocarbonylation of ethylenically unsaturated compounds using carbon monoxide in the presence of a co-reactant, other than water or a source thereof, having a mobile hydrogen atom is described. The catalyst system is obtainable by combining: (a) a metal of Group (8, 9) or (10) or a suitable compound thereof; (b) a ligand of general formula (I) wherein the groups X3 and X4 independently represent univalent radicals of up to 30 atoms or X3 and X4 together form a bivalent radical of up to 40 atoms and X5 has up to 400 atoms; Q1 represents phosphorus, arsenic or antimony; and c) optionally, a source of anions. The method includes the step of adding water or a source thereof to the catalyst system. The method is preferably carried out in the presence of an electropositive metal.