Patent GB-788530-A (GB)
Title: Epoxides and method of making the same
Filed: 1955-03-18
Abstract: The invention comprises epoxy compounds having the general formula: <FORM:0788530/IV (b)/1> wherein R1 is a hydrogen atom or an alkyl group containing from 1 to 14 carbon atoms, R2 is a straight chain alkylene group containing from 1 to 15 carbon atoms and having a CH2 group adjacent to the carbonyl radical, the sum of the carbon atoms in R1 and R2 being from 7 to 15, and R represents a vinyl or an allyl group.  The compounds may be obtained by reacting peracetic acid in an inert volatile organic solvent, e.g. acetone, with an alkenyl ester of a monoethylenic fatty acid of the formula R1-CH = CH-R2-COOR, wherein R, R1, R2 and the sum of the carbon atoms in R1 and R2 are as defined above, at a temperature within the range of - 10 DEG  C. to 75 DEG  C. and recovering the epoxy compound formed. The monoethylenic fatty acids used to form the ester starting materials are those containing from 10 to 18 carbon atoms per molecule, e.g. the decenoic, undecenoic, dodecenoic and hexadecenoic acids, and the octadenoic acids, e.g. oleic acid or elaidic acid. Mixtures of fatty acids containing a monoethylenic fatty acid having 10 to 18 carbon atoms can also be employed.  The epoxidation can be carried out by charging the unsaturated ester to a reaction vessel and then adding gradually a solution of peracetic acid in a volatile organic solvent and it is preferred to maintain the reaction temperature at from 25 DEG  to 50 DEG  C.  After the reaction is complete any excess peracetic acid and acetic acid is removed from the reaction vessel, e.g. by distillation or extraction, but it is preferred to add the reaction mixture to a kettle still containing an inert volatile organic solvent, e.g. ethylbenzene, which is refluxing at a pressure of about 25 millimetres of mercury and then distill off peracetic acid, acetic acid, ethylbenzene solvent (e.g. acetone) and any low boiling material.  The residue product may then be purified by further distillation, e.g. by continuous low pressure distillation.  Examples are given for the preparation of (1) allyl 9, 10-epoxy stearate; (2) vinyl 9,10-epoxy stearate; (3) mixed allyl esters of epoxy and saturated fatty acids by epoxidation with peracetic acid in acetone of the mixed allyl esters derived from a commercial mixture of fatty acids having the approximate composition oleic acid (46 per cent), palmitic acid (25 per cent), stearic acid (17 per cent), myristic acid (3 per cent), linoleic acid (8 per cent), linolenic acid (1 per cent) and small amounts of unsaponifiable constituents; (4) allyl esters of mixed epoxy and saturated fatty acids by epoxidation of the mixed allyl esters derived from a commercial mixture of fatty acids consisting of oleic acid (41 per cent), linoleic acid (54 per cent), linolenic acid (2 per cent) and saturated acids higher than lauric acid (3 per cent); (5) allyl trans-9,10-epoxy stearate by epoxidation of allyl elaidate; and (6) allyl-10,11-epoxyundecanoate by epoxidation of the allyl ester of 10-undecylenic acid.  It is stated that vinyl 10,11-epoxyundecanoate can be obtained by epoxidation of vinyl 10-undecylenate.  The allyl esters used in examples (1), (3) and (4) are obtained by refluxing, with removal of water at the still head, the appropriate fatty acid or fatty acid mixture with allyl alcohol in the presence of toluene and concentrated sulphuric acid as catalyst.  In (5) and (6) the allyl esters are obtained similarly except that in (5) p-toluene sulphonic acid is used as catalyst whilst in (6) benzene is used instead of toluene.  The vinyl oleate used in Example (2) is obtained by reacting vinyl acetate and oleic acid in the presence of mercuric sulphate and vinyl 10,11-undecylenate may be obtained similarly.  The epoxy esters may be polymerized by themselves or may be copolymerized with other compounds (see Group IV (a)) and since they contain an epoxide group and an olefinic group they may be subjected to conditions whereby polymerization occurs through one group to the exclusion of polymerization through the second group and the resulting polymer can then be further polymerized through the unaffected second group. Specification 788,531 and U.S.A. Specification 2,559,177 are referred to.ALSO:Epoxy compounds having the general formula <FORM:0788530/IV (a)/1> wherein R1 is a hydrogen atom or an alkyl group containing 1 to 14 carbon atoms, R2 is a straight chain alkylene group containing from 1 to 15 carbon atoms and having a CH2 group adjacent to the carbonyl radical, the sum of the carbon atoms in R1 and R2 being from 7 to 15, and R represents a vinyl group or an allyl group, e.g. vinyl and allyl 9,10-epoxy-stearates and 10, 11-epoxy-undecanoates, (see Group IV (b)), may be polymerized with themselves or copolymerized with other compounds which are copolymerizable therewith by virtue of the unsaturated group.  Since the monomers contain an expoxide group and an olefinic group they may be subjected to conditions whereby polymerization occurs only through one type of group and the resulting polymer can then be further polymerized under different conditions through the second type of group to form an infusible and insoluble polymer.  The monomers are useful as plasticizers, stabilizers, and crosslinking agents for various types of synthetic resins.