Patent GB-971710-A (GB)
Title: Process for the preparation of esters and polyesters
IPC: C08L67/00
Filed: 1961-11-28
Abstract: Esters and polyesters are prepared by reacting an olefinically or cyclo-olefinically unsaturated compound containing at least three carbon atoms with hydrogen peroxide and an anhydride or mixture of anhydrides derived from one or more mono- or polycarboxylic acids containing at least 4 carbon atoms, if desired in the presence of an esterification catalyst until no substantial amount of oxinane groups can be detected in the reaction mixture.  The products have a high content of ester groups derived from secondary alcoholic hydroxyl groups. Unsaturated compounds used as starting materials are listed under the headings hydrocarbons, chlorinated hydrocarbons, alcohols and phenols, ethers, esters, aldehydes and ketones, acetals, amides, imides, nitriles and unsaturated phosphoric acid esters and many anhydrides are also listed. Anhydrides of mono-carboxylic acids yield esters which may be used as plasticizers, anhydrides of unsaturated di- or poly-carboxylic acids or mixtures thereof form copolymerizable unsaturated polyesters, and mixtures of monocarboxylic acid anhydrides and anhydrides of di- or poly-carboxylic acids form alkyd resins. The reaction may be performed in an inert organic solvent or in solution in an excess of the olefinically unsaturated compound with or without an esterification catalyst and the hydrogen peroxide is in a solution of 30 to 85 per cent strength. Examples describe the reaction of an acetal of D  3-tetrahydrobenzaldehyde and 1:1-bis-(hydroxymethyl)-cyclohex-3-ene <FORM:0971710/C1/1> with a mixture of phthalic and maleic anhydrides; phenylbutane-2:3 with hexahydrophthalic and maleic anhydrides, polymeric adipic and maleic anhydrides, polymeric adipic anhydride alone, and valeric anhydride alone; styrene with maleic and phthalic anhydrides; the acetal 3-vinyl-2:4-dioxospiro(5:5)-undecene-9 of formula <FORM:0971710/C1/2> with phthalic anhydride, or hexahydrophthalic anhydride; tetrahydrobenzyl glycerol with phthalic anhydride; cyclohexene with polymeric adipic anhydride; an addition product of xylene and butadiene with C9-C11 saturated mixed aliphatic monocarboxylic anhydrides and phthalic anhydride; tetrahydrobenzal glycerol and the C9-C11, mixed anhydrides above; dicyclopentadiene and valeric anhydride; cyclohexene and valeric anhydride; and cyclohexane and C9-C11 mixed anhydrides above, together with hydrogen peroxide. The latter ester may be used as a plasticizer for polyvinyl chloride. The acetal, 3-vinyl-2:4-dioxospiro (5:5)-undecene-9 is prepared by heating 1:1-bis-[hydroxymethyl]-cyclohexene-3, acrolein, and benzene in the presence of sulphuric acid. Specifications 758,728, 790,063 and 876,489 are referred to.ALSO:Polyesters are prepared by reacting an olefinically or cyclo-olefinically unsaturated compound containing at least three carbon atoms with hydrogen peroxide and an anhydride or mixture of anhydrides derived from one or more mono- or poly-carboxylic acids containing at least 4 carbon atoms, if desired in the presence of an esterification catalyst, until no substantial amount of oxirane groups can be detected in the reaction mixture. Copolymerizable unsaturated polyesters are prepared with anhydrides of unsaturated di- or polycarboxylic acids, or mixtures thereof, and alkyd resins by reacting the unsaturated compounds with mixtures of anhydrides of mono-carboxylic acids and saturated di- or polycarboxylic acids both containing at least 4 carbon atoms.  The products have a high content of ester groups, derived from secondary, alcoholic hydroxyl groups and may be used as plasticizers. Unsaturated compounds used as starting materials are listed under headings, hydrocarbons, chlorinated hydrocarbons, alcohols, and phenols, ethers, esters, aldehydes and ketones, acetals, amides, imides, nitriles and unsaturated phosphoric acid esters and many anhydrides are also listed.  The reaction may be performed in an inert organic solvent or in solution in an excess of the olefinically unsaturated compound with or without an esterification catalyst and the hydrogen peroxide is in a solution of 30 to 85% strength. Examples describe the reaction of an acetal of D 3-tetrahydrobenzaldehyde and 1,1-bis-(hydroxymethyl)-cyclohex-3-ene <FORM:0971710/C3/1> with a mixture of phthalic and maleic anhydrides; phenylbutene-2:3 with hexahydrophthalic and maleic anhydrides, polymeric adipic and maleic anhydrides, polymeric adipic anhydride alone, and valeric anhydride alone; styrene with maleic and phthalic anhydrides; the acetal 3-vinyl-2:4-dioxospiro (5:5)-undecene-9 of formula <FORM:0971710/C3/2> with phthalic anhydride or hexahydrophthalic anhydride; tetrahydrobenzal glycerol with phthalic anhydride; cyclohexene with polymeric adipic anhydride; an addition product of xylene and butadiene with C9-C11 saturated mixed aliphatic monocarboxylic anhydrides and phthalic anhydride; tetrahydrobenzal glycerol and the C9-C11 mixed anhydrides above; dicyclopentadiene and valeric anhydride; cyclohexene and valeric anhydride; and cyclohexene and C9-C11 mixed anhydrides together with hydrogen peroxide. The latter ester may be used as a plasticizer for polyvinyl chloride. The acetal 3 vinyl-2:4-dioxospiro (5:5)-undecane-9; is prepared by heating 1:1-bis-[hydroxymethyl]-cyclohexene-3, acrolein, and benzene in the presence of sulphuric acid.  Specifications 758,728, 790,063 and 876,489 are referred to.