Patent GB-968849-A (GB)
Title: Mixed esters of naphthenic and acyclic carboxylic acids
IPC: C07D303/40
Filed: 1960-10-26
Abstract: The invention comprises mixed esters of formula: <FORM:0968849/C1/1> in which X is hydrogen or an -OR3 group, G is a residue of a polyhydric alcohol having 2 hydroxyl groups when X is hydrogen and 3 hydroxyl groups when X is -OR3, and R1 and R2 and R3 are each residues of a naphthenic acid or an acyclic aliphatic monocarboxylic acid, at least one of R1, R2 and R3 being a naphthenic acid residue and at least one an acyclic aliphatic monocarboxylic acid residue.  A mixture of esters may be prepared in which 20 to 80% of the R1, R2 and R3 residues are naphthenic acid residues and the balance is composed of acyclic aliphatic carboxylic acid residues.  The acyclic acid residues each contain more than 4 carbon atoms, or, when a mixture of acids is used in the esterification, an average of more than 4 carbon atoms.  The esters are prepared by esterification of the polyhydric alcohol, naphthenic acid and acyclic acid at 100 DEG to 300 DEG C. in the presence of a catalyst e.g. toluene sulphonic acid, benzene sulphonic acid, alkanesulphonic acid, alkali metal hydrogen sulphate, hydrochloric acid, sulphuric acid, zinc chloride, metallic zinc and boron fluoride, and a solvent, e.g. toluene, xylene, heptane, octane, kerosene and mineral oil. Esters in which unsaturated acid residues are present may be epoxidized by contact at 25 DEG  to 50 DEG C. with a peracid e.g. perbenzoic or peracetic acid in a solvent; or with hydrogen peroxide in acetic acid.  The mixed esters may be used to plasticize polyvinyl halide homopolymers and copolymers. In examples 4-(2-methylvaleroxy) butyl naphthenate is prepared from tetramethylene glycol, naphthenic acid and 2-methylpentanoic acid; 4-isovaleroxylbutyl naphthenate is prepared from tetramethylene glycol and naphthenic and isovaleric acids; 3-caproyloxypropyl naphthenate is prepared from trimethylene glycol and naphthenic and caprylic acids; 2-naphthenoxymethyl - 2 - heptanoyloxymethyl propyloleate is prepared from oleic acid, naphthenic acid, heptanoic acid and trimethylolethane and is epoxidized to naphthenoxymethyl-2-heptanoyloxymethyl-propyl 9, 10-epoxystearate, and substituting linoleic acid for oleic acid 2 - naphthenoxymethyl - 2 - heptanoyloxymethylpropyl 7, 8, 10, 11-diepoxystearate is obtained; naphthenoxypentyl oleate is obtained from oleic acid, naphthenic acid and 1, 5-pentanediol and epoxidized to naphthenoxypentyl 9, 10-epoxystearate. Other esters mentioned are 3-stearyloxypropyl naphthenate, 2(2-methylbutyroxymethyl)-2-methylpropyl naphthenate, 3-isobutyroxyethoxyethyl naphthenate and 2, 2-diethyl-3-valeroxypropyl naphthenate.  Lists of suitable dihydric and trihydric alcohols and of acyclic monocarboxylic acids are given.ALSO:Plasticizers for polyvinyl halide polymers and copolymers comprise esters of formula: <FORM:0968849/C3/1> in which X is hydrogen or an -OR3 group, G is a residue of a polyhydric alcohol having 2 hydroxyl groups when X is hydrogen and 3 hydroxyl groups when X is -OR3, and R1 and R2 and R3 are each residue of a naphthenic acid or an acyclic aliphatic monocarboxylic acid, at least one of R1, R2 and R3 being a naphthenic acid residue and at least one an acyclic aliphatic monocarboxylic acid residues.  A mixture of esters may be used in which 20 to 80% of the R1, R2 and R3 residues are naphthenic acid residues and the balance is composed of acyclic aliphatic carboxylic acid residues.  The acyclic acid residues each contain more than 4 carbon atoms, or, when a mixture of acids is used in the esterification, an average of more than 4 carbon atoms.  Esters prepared from unsaturated acids may be epoxidized.  The mixed esters are used to plasticize polyvinyl halide homopolymers and copolymers in amounts of 5 to 100 parts by weight of polymer.  The ester is mixed with powdered resin and then heated at 150 DEG  to 200 DEG C. In examples 4-(2-methyl-valeroxy) butyl naphthenate, 4-isovaleroxylbutyl naphthenate, 3-caproyloxypropyl naphthenate, 2-naphthenoxymethyl-2-heptanoyloxymethyl-propyl 9, 10-epoxystearate, 2-naphthenoxymethyl-2-heptanoyloxymethyl-propyl 7, 8, 10, 11-diepoxystearate, and naphthenoxypentyl 9, 10-epoxystearate are used to plasticize polyvinyl chloride and polyvinyl chloride-polyvinyl acetate copolymers. Other esters mentioned are 3-stearyloxypropyl naphthenate, 2(2-methylbutyroxymethyl)-2-methyl-propyl naphthenate, 3-isobutyroxy-ethoxyethyl naphthenate and 2, 2-diethyl-3-valeroxypropyl naphthenate.  Other copolymers mentioned are prepared from vinyl chloride with vinylidene chloride, methyl acrylate, vinyl isobutyl ether, vinyl propionate, vinyl butyrate, vinyl benzoate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylamide, acrylonitrile, styrene, chlorostyrene, ethyl styrene, vinyl naphthalene, alkyl esters of maleic, crotonic, itaconic and fumaric acids, vinyl alkyl ketones, vinyl pyridine, and isobutylene. Lists of suitable dihydric and trihydric alcohols and of acyclic monocarboxylic acids are given.