Patent GB-783300-A (GB)
Title: Process for the plasticising of halogen-containing organic materials
IPC: C08K5/1515
Filed: 1955-02-21
Abstract: High-polymeric halogen-containing organic materials, e.g polyvinyl chloride and polyvinylidene chloride, are plasticised by incorporating therein an epoxy-group-containing ester prepared by epoxidizing an ester or polyester of a mono- or di-basic unsaturated cycloaliphatic carboxylic acid by means of an organic per-acid or hydrogen peroxide and a per-acid-forming organic acid, e.g. formic acid (see Group IV (b)).  Examples of suitable epoxy esters include decyl 3,4-epoxyhexahydrobenzoate, the dibutyl, di-2-ethylhexyl, di-n-octyl, dibutoxyethyl, dibenzyl, dicyclohexyl and n-octyl-methylcyclohexyl esters of 4,5-hexahydrophthalic acid, the di-2-ethylbutyl ester of 4,5-epoxy - 3,6 - endomethyl - hexahydro phthalic acid, and a polyester of D 4-tetrahydrophthalic acid, 1,6-hexanediol and capric acid.ALSO:Esters of mono- or dibasic, unsaturated, cycloaliphatic carboxylic acids are epoxidized by known methods with the aid of organic peracids or with mixtures of hydrogen peroxide and organic acids which form per-acids.  A suitable method is to treat the ester with a mixture of 30-40 per cent hydrogen peroxide and a per-acid-forming organic carboxylic acid, e.g. formic acid, while stirring at 30-60 DEG  C., preferable using 1.2-1.5 mol. of hydrogen peroxide and 0.1-0.5 mol. of the acid per mol. of ester. Unsaturated cycloaliphatic acids whose esters can be epoxidized are: D 3-tetrahydrobenzoic acid, 2-methyl- D 3-tetrahydrobenzoic acid; 2,5 - endomethylene - D 3 - tetrahydrobenzoic acid, D 4 - tetrahydrophthalic acid, 3-methyl - D 4 - tetrahydrophthalic acid, 3,6-endomethylene - D 4 - tetrahydrophthalic acid, 1 - methyl - 3,6 - endomethylene - D 4 - tetrahydrophthalic acid, 3,6 - endoethylene - D 4-tetrahydrophthalic acid, 3,6 - endo - oxo - D 4-tetrahydrophthalic acid.  These acids may be esterified with any mono- or polyvalent aliphatic, cycloaliphatic or araliphatic alcohols, and also those whose carbon chains are interruped by hetero-atoms or hetero-atom groups.  The alcohols may also be unsaturated, additional epoxy groups then being formed in the alcohol residue.  Suitable alcohols are ethanol, butanol, 2-ethylbutanol, cyclohexanol, methylcyclohexanol, n - octanol, 2 - ethylhexanol, n - decanol, n - dodecanol, n - octadecanol, oleyl alcohol, benzyl alcohol, hexahydrobenzyl alcohol, butoxyethanol, tetrahydrofurfurol, and phenoxyethanol.  Also suitable are mixtures of alcohols, obtained by catalytic reduction of fatty acids having 4-6 or 7-9 carbon atoms obtained by paraffinic oxidation, mixtures produced by the oxo process from olefines obtained by cracking processes, and branched-chain alcohols obtained from lower alcohols by the Guerbet process.  Divalent alcohols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol and diethylene glycol may also be used.  Typical of the epoxidized esters are: decyl 3,4-epoxyhexahydrobenzoate, isodecyl 2,5 - endomethylene - 3,4 - epoxyhexahydrobenzoate, dibutoxyethyl 4,5 - epoxyhexahydrophthalate, dibenzyl 4,5 - epoxyhexahydrophthalate, dicyclohexyl 4,5-epoxyhexahydrophthalate, n - octyl - methylcyclohexyl 4,5 - epoxyhexahydrophthalate, di - n - octyl 4,5 - epoxy - 3,6 - endomethylene - hexahydrophthalate, di - 9,10 - epoxyoctadecyl 4,5-epoxy - 3,6 - endomethylenehexahydro phthalate, polyesters such as those formed from 4,5-epoxyhexahydrophthalic acid and 1,6-hexanediol or from 4,5-epoxyhexahydrophthalic acid, 1,4-butanediol and a fatty acid such as capric acid.  In examples: (1) dibutyl D 4-tetrahydrophthalic acid is epoxidized by means of 40 per cent hydrogen peroxide and 85 per cent formic acid to give dibutyl 4,5-epoxyhexahydrophthalate; the following esters are produced by similar methods; (2) di - 2 - ethylhexyl 4,5 - epoxyhexahydrophthalate; (3) di - n-octyl 4,5 - epoxyhexahydrophthalate; (4) di - 2 - ethylbutyl 4,5 - epoxy - 3,6 - endomethylene - hexahydrophthalate; (5) di - 9,10-epoxyoctadecyl 4,5 - epoxyhexahydrophthalate; (6) n - decyl benzyl 4,5 - epoxyhexahydrophthalate; (7) di-3,4-epoxyhexahydrobenzoate of 1,4-butanediol; (8) a polyester obtained from D 4-tetrahydrophthalic acid, 1,6-hexanediol and capric acid in the presence of zinc chloride is similarly epoxidized with hydrogen peroxide and formic acid.  The products are useful as plasticizers for halogen-containing polymers (see Group IV (a)).ALSO:High-polymeric halogen-containing organic materials, e.g chlorinated rubber, are plasticized by incorporating therein an epoxy-group-containing ester prepared by epoxidizing an ester or polyester of a mono- or di-basic unsaturated cycloaliphatic carboxylic acid by means of an organic per-acid or hydrogen peroxide and a per-acid forming organic acid, e.g. formic acid (see Group IV(b)).  The epoxy ester may be added in quantities between 2 and 45 per cent, preferably 10 and 35 per cent by weight of the polymer. Examples of suitable epoxy esters include: decyl 3, 4-epoxyhexahydrobenzoate, the dibutyl, di-2-ethylhexyl, di-n-octyl, dibutoxyethyl, dibenzyl, dicyclohexyl and n-octyl-methylcyclohexyl esters of 4, 5-hexahydrophthalic acid, the di-2-ethylbutyl ester of 4, 5-epoxy-3, 6-endomethylhexahydrophthalic acid, and a polyester of D 4 tetrahydrophthalic acid, 1, 6-hexanediol and capric acid.