Patent GB-802127-A (GB)
Title: Improvements in or relating to process for the epoxidation of organic compounds
IPC: B01J31/08
Filed: 1956-04-06
Abstract: Alkyd resins which are essentially mixed esters of dibasic acids and unsaturated acids of 18 to 22 carbon atoms with polyhydric alcohols such as glycerol and pentaerythritol, and polyesters of tetrahydrophthalic acid with glycols, are epoxidized by reacting with a peracid prepared by the reaction of hydrogen peroxide and an organic acid in the presence of a dehydrated acid cation exchange resin catalyst.  The peracid may be formed in situ with said organic compounds or a concentrated peracid solution may be preformed and the resin removed prior to the epoxidation.  The preferred cation exchange resin is of the sulphonated styrene-divinyl benzene copolymer type, usually obtained in the form of an alkali salt and converted to the wet form by washing with a mineral acid, such as hydrochloric acid, and then washing with water.  The resin is dehydrated by placing in a vacuum oven for several hours at 75-110 DEG  C.  After use in the epoxidation process the resin may be dehydrated again and re-used.  Suitable acids from which the peracid may be prepared are formic acid, acetic acid and benzoic acid.  In examples: (2) an alkyd resin is prepared by mixing, in a nitrogen atmosphere, soyabean oil, litharge and pentaerythritol maintaining at 238 DEG  C. for about 15 minutes, and then adding phthalic anhydride and raising the temperature to about 250 DEG  C. until the acid value reaches 10.5, and thinning with xylene.  This alkyd resin is then epoxidized by adding with xylene to a mixture of a dehydrated cation exchange resin and glacial acetic acid, and then adding hydrogen peroxide dropwise and holding at 60 DEG  C. until the reaction is complete; (3) a polyester of tetrahydrophthalic acid and a glycol is prepared by melting tetrahydrophthalic acid in the presence of n-butanol, adding pentamethylene glycol, heating gradually with agitation to 225 DEG  C. and adding sufficient xylene to give refluxing at temperatures of 225-235 DEG  C.; this polyester is epoxidized by dissolving in xylene and adding to a mixture of a dehydrated acid cation exchange resin and glacial acetic acid, and holding at 60 DEG  C. until reaction is complete.  Comparative examples are given in which the wet acid form of the cation exchange resin is used.ALSO:Epoxidation of ethylenically unsaturated organic compounds is effected by reacting said compounds with a peracid prepared by the reaction of hydrogen peroxide and an organic acid in the presence of a dehydrated acid cation exchange resin catalyst. The peracid may be formed in situ with said organic compounds or a concentrated peracid solution may be preformed and the dehydrated resin removed prior to the epoxidation.  The preferred cation exchange resin is of the sulphonated styrene-divinyl benzene copolymer type, usually obtained in the form of an alkali salt and converted to the wet acid form by washing with a mineral acid, such as hydrochloric acid, and then washing with water.  The resin is dehydrated by placing in a vacuum oven for several hours at 75-110 DEG  C.  After use in the epoxidation process the resin may be dehydrated again.  Suitable organic acids are formic acid, acetic acid and benzoic acid.  The process may be used to epoxidize hydrophobic materials such as the drying oils, unsaturated glycerides and aliphatic esters of unsaturated 18 carbon acids, such as ethyl or butyl oleate, but is particularly suitable for hydrophilic materials such as ethylenically unsaturated alkyd resins, and ethylenically unsaturated polyesters of tetrahydrophthalic acid with glycols.  In examples: (1) the wet acid form of a sulphonated styrene divinylbenzene copolymer resin is dehydrated in a vacuum oven at 85 DEG  C. for 16 hours and then mixed with glacial acetic acid and allowed to stand until the resin has completely taken up the acid; butyl oleate in xylene is then added and to the continuously agitated mixture hydrogen peroxide is added and the mixture is held at 60 DEG C. until the oxidation is complete.  A comparative example using the wet acid form of the resin is also described.  Other examples describe the epoxidation of an alkyd resin and a polyester of tetrahydrophthalic acid with a glycol (see Group IV (a)).