Patent GB-1030213-A (GB)
Title: Preparation of esters
IPC: C08L27/00
Filed: 1962-11-15
Abstract: Polyesters prepared by the esterification of glycol monoesters containing a secondary hydroxyl group in the presence of a neutral or basic tin compound as catalyst (see Division C2) are used in lubricating compositions. Polyesters of formula <FORM:1030213/C4-C5/1> where R and R1 are alkyl (1-4C) radicals, R11 represents a divalent hydrocarbon radical, e.g. alkylene or alkenylene (1-10C), phenylene or substituted phenylene, a divalent alicyclic radical, -R-O-R-, or -R-S-R-, oxygen or the covalent C-C bond between the two carboxyl groups of oxalic acid, n is 1 or alone, and of formula <FORM:1030213/C4-C5/2> where Ra, Rb, Rc and Rd are each an alkyl group, R1 is an isobutyryl group, R is an alkylene, alkenylene, divalent alicyclic, phenylene, -R1-O-R1- or -R1-S-R1-, where R1 is an alkylene, n is 1 to 5, X is R, HO-CO-R-CO-, or R1-CO-, R1 and R as above, and the isomers thereof are claimed.  Examples describe the preparation of polyesters from adipic acid phthalic anhydride, azelaic acid and maleic acid, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate which may be used as lubricants with a major or minor amount of conventional diesters; of a polyester from adipic acid and 2,4-dimethyl-2-ethyl-1,3-hexanediol mono-2-methyl butyrate.  Many acids and esters are listed from which the esters may be prepared.ALSO:Glycol mono-esters with a free secondary hydroxyl group, are esterified with a carboxylic acid in the presence of a neutral or basic tin compound as catalyst to yield polyesters.  Polyesters of formula <FORM:1030213/C2/1> where R and R1 are alkyl (1-4 C) radicals, R11 represents a divalent hydrocarbon radical, e.g. alkylene or alkenylene (1-10 C), phenylene or substituted phenylene, a divalent alicyclic radical, -R-O-R- or -R-S-R-, oxygen or the covalent C-C bond between the two carboxyl groups of oxalic acid, n is 1 or above, and of formula <FORM:1030213/C2/2> where Ra, Rb, Rc and Rd are each an alkyl group and R1 is an isobutyryl group, R is an alkylene, alkenylene, divalent alicyclic, phenylene or substituted phenylene, -R1-O-R1-or -R1-S-R1-, where R1 is alkylene, n is 1 to 5, X is R, HO-CO-R-CO-, or R1-CO-, R1 and R as above, and isomers thereof in which Rc(Rd)CH-is substituted in -CH2-, are claimed.  The compounds are suitable as plasticizers for polymers. The glycol monoester may include a minor amount of the isomer thereof with the acyloxy group in the 3-position and a primary hydroxyl group in the 1-position.  Tin oxides, hydroxides, alkoxides, and carboxylates may be used and the carboxylates, e.g. stannous isobutyrate, oxalate, acetate, propionate and n-butyrate are preferred. Mono-and di-carboxylic acids are listed and tall oil fatty acids are included.  Examples also describe the reaction of adipic, azelaic, thiodipropionic, benzoic, and diglycolic acids and phthalic and maleic anhydrides with 2,2,4-trimethyl - 1,3 - pentanediol monoisobutyrate; adipic acid with 2,4 - dimethyl - 2 - ethyl - 1,3 - hexane diol mono-2-methyl-butyrate; benzoic acid with 3-hydroxy-2,2,4-trimethyl pentyl isobutyrate and the use of mixed acids, e.g. adipic and isobutyric is also described.  A flow scheme for batchwise esterification with purification stages is also described.  The products are suitable as lubricants or plasticizers for polymeric material (see Divisions C3 and C5) or when containing an <FORM:1030213/C2/3> group may be copolymerized with a vinyl monomer.ALSO:Polyesters prepared by the esterification of glycol monoesters containing a secondary hydroxyl group in the presence of a neutral or basic tin compound as a catalyst (see Division C2) are used as plasticizers for polymers, e.g. vinyl resins such as polyvinyl chloride, polyvinyl acetate, and polystyrene, phenolic alkyd and arylic resins and nitrile rubber, and cellulose esters such as cellulose acetate butyrate, cellulose nitrate and ethyl cellulose, or antioxidants for polyolefines, e.g. polypropylene. Unsaturated polyesters may be copolymerized with vinyl monomers, e.g. styrene. Polyesters of formula <FORM:1030213/C3/1> where R and R1 are alkyl (1-4 C) radicals, R11 represents a divalent hydrocarbon radical, e.g. alkylene, or alkenylene (1-10 C), phenylene or substituted phenylene, a divalent alicyclic radical, -R-O-R-, n -R-S-R-, oxygen or the covalent C-C bond between the two carboxyl groups of oxalic acid, n is 1 or above, and of formula <FORM:1030213/C3/2> where Ra, Rb, Rc, and Rd are each an alkyl group, R1 is an isobutyryl group, R is an alkylene, alkenylene, divalent alicyclic, phenylene or substituted phenylene, -R1-O-R1- or R1-S-R1- where R1 is alkylene, n is 1 to 5, X is R, HO-CO-R-CO-, or R1-CO-, R1 and R as above and isomers thereof are claimed. Examples describe the preparation and use of esters from adipic, azelaic, thiodipropionic, benzoic and diglycolic acid and phthalic and maleic anhydrides with 2,2,4-tri-methyl-1,3-pentanediol mono-isobutyrate; adipic acid with 2,4 - dimethyl - 2 - ethyl - 1,3 - hexanediol mono-2-methyl butyrate; benzoic acid with 3-hydroxy-2,2,4-tri-methyl pentyl isobutyrate. Tall oil fatty acids and mixed adipic and butyric acid may also be used in the preparation of the esters.