Patent GB-672088-A (GB)
Title: Copolymers of diallyl phthalate and diallyl esters of dimerised unsaturated fatty acids
IPC: C08F18/08
Filed: 1950-05-18
Abstract: Diallyl phthalate and diallyl esters of dimerized olefinically unsaturated fatty acids are copolymerized, preferably by heating the reactants together at an elevated temperature and promoting the reaction either with peroxide polymerization catalysts such as benzoyl peroxide, tert-butyl hydroperoxide, di-(tert. butyl) peroxide, and lauroyl peroxide, or by bubbling air or oxygen through the reaction mixture; the peroxide catalyst and diallyl phthalate may be added intermittently during the course of the reaction. Unsaturated fatty acids specified are palmitoleic, oleic, petroselinic, vaccenic, gadoleic, cetoleic, erucic, hiragonic, linoleic, linolenic, elaeostearic, licanic, arachidonic, and dupanodonic acids, or mixtures of these acids as derived from the natural oils.  The products obtained by stopping copolymerization at a point short of gelation vary from viscous liquids to hard solids which are soluble in acetone or toluene; air drying or further heating of these copolymers in the presence of catalysts, such as benzoyl peroxide, lauroyl peroxide, acetyl benzoyl peroxide, di-(tert. butyl) peroxide, tertiary butyl hydroperoxide, di-(tert. butyl) diperphthalate, and cobalt, lead, or manganese naphthalate, linoleate or octoate, yields products which are insoluble and infusible.  Cellulose derivatives such as alpha cellulose and wood flour may be incorporated in the soluble copolymers prior to curing. The copolymers may be employed as coatings or in the manufacture of moulded articles.ALSO:Unsaturated fatty acids, such as palmitoleic, oleic, petroselinic, vaccenic, gadoleic, cetoleic, erucic, hiragonic, linoleic, linolenic, elaeostearic, licanic, arachidonic and dupanodonic acids, or mixtures of fatty acids derived from natural oils, are dimerized.  The mono-olefinic acids are dimerized by heating the free acids in the presence of a catalyst such as boron trifluoride, aluminium chloride or stannic chloride, and separating the dimer by distillation or extraction with selective solvents.  The polyolefinic fatty acids, preferably the mixture of acids derived from a natural oil, are dimerized either by heating the methyl esters of the acids at 300 DEG  C. in an inert atmosphere followed by distillation and saponification, or by heating the free acids at 330 DEG  to 360 DEG  C. under steam pressure and distilling of the unreacted material.  The dimerized acids are converted to the allyl esters either by direct esterification with allyl alcohol, or by transesterification of the dimeric methyl esters with allyl alcohol. The allyl esters are employed in copolymerization with diallyl phthalate.ALSO:Unsaturated fatty acids, such as palmitoleic, oleic, petroselinic, vaccenic, gadoleic, cetoleic, erucic, hiragoiric, linoleic, linolenic, elaeostearic, licairic, arachidonic, and clupanodonic acids, or the fatty acids or mixtures thereof derived from fatty oils such as linseed, soy bean, corn, cottonseed, hempseed, kapok seed, herring, perilla, poppyseed, pilchard, whale, menhaden, mustard, peanut, rapeseed, salmon, sardine, walnut, dehydrated castor, rubberseed, safflower, sesame, tung and oiticica oils, are dimerised.  The mono-olefinic acids are dimerized by heating the free acids in the presence of a catalyst such as boron trifluoride, aluminium chloride, or stannic chloride, and separating the dimer by distillation or extraction with selective solvents.  The polyolefinic acids, preferably the mixture of acids derived from a natural oil, are dimerized either by heating the methyl esters of the acids at 300 DEG C in an inert atmosphere, followed by distillation and saponification, or by heating the free acids at 330 DEG  to 360 DEG C. under steam pressure and distilling the unreacted material. The dimerized acids are converted to the alkyl esters which are employed in copolymerization with diallyl phthalate.