Patent GB-922747-A (GB)
Title: Improvements relating to organic film-forming compositions
Inventor: IKEDA CAROL KAZUO
IPC: C08F24/00
Filed: 1960-02-25
Abstract: An air-drying film-forming composition comprises a mixture of (1) at least one compound containing a single 2-vinyl-1,3-cyclic acetal radical of structure:-  <FORM:0922747/IV(a)/1> where R is hydrogen, alkyl, alkenyl, aryl, chlorine, fluorine, bromine, cyano, acyloxy, chloroalkyl, fluoroalkyl, cyanoalkyl, alkoxy, aryloxy or carbalkoxy, and in which the remaining oxygen valencies are satisfied by separate carbon atoms in a cyclic structure, (2) at least one compound containing at least two 2-vinyl-1,3-cyclic acetal radicals having the above structure and (3) a metallic drier compound in sufficient amount to effect the airdrying of the mixture.  Lists of the monofunctional compound which are substituted (e.g. esters of hydroxy- or carboxy-substituted, ethers of hydroxy substituted) 2-vinyl dioxolanes, dioxanes, dioxepanes, dioxocanes, dioxonanes and dioxecanes are given.  In a long list of (2) components are di and higher esters or ethers of hydroxy-substituted or of spiro or fused ring compounds of dioxolanes, dioxanes, dioxepanes, dioxocanes, dioxonanes and dioxecanes as well as acrolein and substituted acrolein cyclic acetals of tetra- and higher hydroxy-substituted carboxhydrates or of oligomers of vinyl and allyl alcohols and derivatives thereof, e.g. a benzoic acid ester or a cyanoethyl ester of mixed sorbitol-acrolein acetals.  Thus component (2) may be the bisacrolein acetal of pentaerythritol or 1:2:3:4-dio-allylidene-D-galacto-pyranose benzoate.  The metallic driers used are the well-known siccatine metal-containing compounds and complexes, e.g. cobalt and nickel and lead butyl phthalates, cobalt 2-ethyl sebacate and linoleate, and cerium naphthenate.  In examples (1) the benzoic acid monoester of 4-hydroxybutyl-2-vinyl-1,3 dioxane and the orthophthalic acid diester thereof, (2) the cyanoethyl monoether thereof and the itaconic acid diester, (3) 5-(beta-cyanoethoxy methyl)-5-methyl-2-isopropenyl-1,3 dioxane and the itaconate diester of Example (2), (4) the benzoate monoester and the fumarate diester of the dioxane of (1), and numerous others including the benzoate esters of sorbitolacrolein acetals are used. Specifications 899,065 and 915,621 are referred to.ALSO:Compounds are prepared containing one or more 2-vinyl-1,3-cyclic acetal radicals of the structure:-  <FORM:0922747/IV(a)/1> where R is hydrogen, alkyl, alkenyl, aryl, chlorine, fluorine, bromine, cyano, acyloxy, chloroalkyl, fluoroalkyl, cyanoalkyl, alkoxy, aryloxy or carbalkoxy and in which the remaining oxygen valencies are satisfied by separate carbon atoms in a cyclic structure.  In examples 4-hydroxy-butyl- 2-vinyl-1,3-dioxane, prepared by refluxing 1,2,6-hexanetriol with acrolin, is refluxed with dimethyl ortho-phthalate in toluene to give its orthophthalic acid diester, with methyl benzoate to give the benzoic acid monoester, with dimethyl itaconate to give the itaconic and diester, with acrylonitrile to give the cyanoethyl mono-ether and with diethyl fumarate to give the fumaric and diester.  In a further example 5- (betacyanoethoxymethyl)- 5-methyl-2-isopropenyl-1,3-dioxane is prepared by reacting acrylonitrile with 5-hydroxymethyl- 5-methyl- 2-isopropenyl- 1,3-dioxane which itself is prepared by treating trimethylolethane with methacrolein, while the condensation of acrolein and sorbitol produces a mixture predominantly of di and triacrolein acetals which on treatment with benzoyl chloride gives the benzoic acid ester of these mixed acetals.  Yet further examples use 4-phenyl-2-isopropenyl- 1,3-dioxolane prepared from phenyl, glycol and methacrolein, 2[41-(211-vinyl-111, 311- dioxolan-411-yl)butoxy]-tetrahydropyran from 4-hydroxylbutyl-2-vinyl-1,3-dioxolane and dihydropyran, spiro(3-vinyl-2,4-dioxane-6,61-cyclohex-21-ene) from acrolein and 3-)cyclohexene-1,1-dimethanol, and the undecylenic acid ester of the mixed acetals obtained from glycerine and acrolein.  Specifications 899,065 and 915,621 are referred to.