Patent GB-814199-A (GB)
Title: New di- and tri-epoxy esters and process for making the same
Filed: 1955-10-05
Abstract: Synthetic resins such as polyvinyl chloride are plasticized and stabilized by means of epoxy esters having the general formula <FORM:0814199/IV (a)/1> wherein Z represents <FORM:0814199/IV (a)/2> or <FORM:0814199/IV (a)/3> and R1-R6 each represent a hydrogen atom or an alkyl radical, R7 is a C1-15 alkylene radical, R8 represents an hydrogen atom or an alkyl or hydroxyalkyl radical containing 1-14 carbon atoms, R9 is a C1-7 alkylene radical and R10 is a C1-7 alkyl radical, the total number of carbon atoms in R7 plus R8 being from 7 to 19 and the total number of carbon atoms in R7 plus R9 plus R10 being from 7 to 18.  The following epoxy esters are mentioned: 3 : 4-epoxy cyclohexyl methyl alcohol esters of 9 : 10-epoxy myristic acid, 9 : 10-epoxy palmitic acid, 9 : 10-epoxystearic acid and 9 : 10 : 12 : 13-diepoxystearic acid; 3 : 4 - epoxy - 6 - methyl cyclohexyl methyl alcohol esters of 9 : 10-epoxystearic acid, 5 : 6-epoxylauric acid and 9 : 10 : 12 : 13 - diepoxystearic acid; and 3 : 4-epoxy - 1- methyl - cyclohexyl methyl alcohol esters of 9 : 10 - epoxystearic acid and 9 : 10 : 12 : 13-diepoxystearic acid.  Numerous unsaturated esters from which other suitable epoxy esters may be obtained are also mentioned (see Group IV (b)).ALSO:The invention comprises di- and tri-epoxides of substituted aliphatic esters of mono- and di-ethylenically unsaturated fatty acids, respectively, having the general formula <FORM:0814199/IV (b)/1> wherein Z represents <FORM:0814199/IV (b)/2> and R1 to R6 each represent hydrogen or an alkyl radical containing preferably 1-4 carbon atoms, R7 is a C1-15 alkylene chain, R8 represents hydrogen or an alkyl or hydroxyalkyl radical containing 1-14 carbon atoms, R9 is a C1-7 alkylene radical and R10 is a C1-7 alkyl radical, the total number of carbon atoms in R7 plus R8 being from 7 to 19 and in R7 plus R9 plus R10 being from 7 to 18; the total number of carbon atoms in R1-R6 preferably does not exceed 10. The epoxy esters are prepared by reacting the corresponding 3-cyclohexenylmethyl esters of appropriate unsaturated acids having the general formula <FORM:0814199/IV (b)/3> wherein X represents a -CH = CH-R8 or a -CH = CH-R9-CH = CH-R10 group, R1 to R10 being as defined above, with at least one mol. of peracetic acid per ethylenic bond in the unsaturated ester, and preferably at - 25 DEG  to 150 DEG  C.  Suitably, the peracetic acid, preferably dissolved in an inert organic volatile solvent such as acetone, is gradually added to the unsaturated ester.  The epoxy esters may be used as plasticizers and stabilizers for synthetic resins, e.g. polyvinyl resins.  The epoxy group in the cyclohexyl residue of the esters is more reactive than the other epoxy groups and reacts preferentially with active hydrogen compounds such as alcohols, phenols and carboxylic acids.  The unsaturated esters used as starting materials may be obtained by esterifying appropriate unsaturated fatty acids and 3-cyclohexenyl methyl alcohols, the latter being obtainable by reduction of the corresponding aldehydes which may be prepared by a Diels-Alder reaction of an appropriate butadiene such as butadiene, piperylene, isoprene or 2,3-dimethyl-1,3-pentadiene with acrolein, methacrolein, croton aldehyde or other like unsaturated aldehyde.  Suitable unsaturated acids include decenoic, undecenoic, dodecenoic, hexadecenoic and octadecenoic acids and especially oleic, elaidic, myristoleic, palmitoleic, ricinoleic and erucic acids or mixtures thereof, and linoleic acid.  In examples: (1) 6-methyl-3-cyclohexenyl methyl oleate is reacted with excess peracetic acid in acetone, the reacted mixture then being added dropwise to refluxing ethyl benzene whereby unchanged per-acetic acid, acetic acid and acetone are distilled off and the residue is stripped of ethyl benzene in vacuo to provide the desired di-epoxide as a viscous liquid; 3,4-epoxy - 6 - methyl - cyclohexyl methyl 5,6-epoxy laurate; 3,4-epoxy cyclohexyl methyl 9,10-epoxy myristate; 3,4-epoxy cyclohexyl methyl 9,10-epoxypalmitate; 3,4-epoxy cyclohexyl methyl 9,10-epoxy stearate and 3,4-epoxy-1-methyl cyclohexyl methyl 9,10-epoxystearate may be prepared similarly; (2) 3-cyclohexenyl methyl linoleate is likewise reacted with excess peracetic acid in acetone to yield the corresponding tri-epoxy ester and 3,4-epoxy 1-methyl cyclohexyl methyl- and 3,4-epoxy - 6 - methyl cyclohexyl methyl - 9,10, 12,13-diepoxy stearates may be prepared similarly.  The preparation of 6-methyl-3-cyclohexyl methyl oleate used in (1) by reaction of the acid and alcohol using sulphuric acid as catalyst with removal of water of esterification by means of toluene is described in detail; the lauroleate, palmitoleate and decenoate, 1-methyl-3-cyclohexyl methyl ricinoleate and the lauroleate, myristoleate, palmitoleate and ricinoleate of 3-methyl cyclohexenyl methyl alcohol can be prepared similarly.