Patent GB-655615-A (GB)
Title: Improvements in or relating to polymerizable compositions
IPC: C08F20/54
Filed: 1947-10-16
Abstract: A polymerizable composition comprises one or more unsaturated alkyd resins and one or more compatible monomeric substances of the general formula <FORM:0655615/IV (a)/1> where R1 is an aliphatic radical containing at least one CH2=C< group and free from conjugated carbon to carbon double bonds, R2, R3 and R4 are hydrogen atoms or alkyl, alkoxy, aryl or aralkyl radicals and X is an alkylidene radical.  The unsaturated alkyd resins contain a plurality of a -b -enal groups and may be derived from a -b -unsaturated acids. e.g. maleic, fumaric, itaconic, citraconic, mesaconic, aconitic, chlormaleic which may be partially replaced by acrylic, b -benzoyl acrylic, methacrylic, D 1-cyclohexene carboxylic, cinnamic and crotonic acids.  The acids are esterified with glycols or polyhydric alcohols, e.g. glycerol, di-pentaerythritol, polyallyl alcohols or glycidol reacted with monohydric alcohols, in solution in solvents such as benzene, toluene, xylene, chloroform, carbon tetrachloride ethylene, propylene or butylene dichlorides or trichloride, cresol or methyl cyclohexanone with an esterification catalyst such as thymol, d-camphor, naphthalene or p-toluene sulphonic acid.  Examples are ethylene or diethylene glycol fumarate, a -propylene glycol maleate, hexaethylene or decamethylene glycol maleate, octadecandiol fumarate, maleic esters of 2,2-dimethyl propanediol-1,3, glycerol maleate undecylenate, triethylene glycol chlormaleate and a terpene maleate. The alkyds may be modified with alcohols, e.g. n-butanol, 1,2-and 1,3-dichloropropanols, amyl alcohols, cyclohexanol, n-hexanol, 2-methyl hexanol, n-octanol, decanol, do-, tetra- and octadecanol, cetyl alcohol, reduced geraniol, reduced coconut or palm oil, benzyl, phenylethyl, furfuryl, or tetrahydrofurfuryl alcohol, ether alcohols, such as 1-chloro-2-hydroxy phenyl propyl ether, 1,3 - diphenyl - 2 - hydroxy - propyl ether, and 1,3-dialkyl-2-hydroxy-propyl ether, and monobutyl ethers of ethylene and diethylene glycols, ethylene cyanohydrin, terpineol, fenchyl alcohol, allyl and methallyl alcohols, oleyl and linoleyl alcohols; or with mono or dibasic or hydroxy acids, e.g. phthalic, succinic, glutaric, adipic, azelaic, sebacic, lactic, a -hydroxyisobutyric, hydracrylic, o -hydroxycaproic, o -hydroxydecanoic, o -hydroxymyristic, acetic, caproic, lauric and stearic acids and linseed oil fatty acids.  The reactive materials containing the amido group include, e.g. acrylamide, methacrylamide, ethacrylamide, methylene bis-acrylamide or methacrylamide, ethylidene-bis-acrylamide, and propylidene-bisethacrylamide, N-methyl, N,N-dimethyl, N-methylol, N-phenyl, N,N-dibenzyl acrylamides and N-ethyl, N,N-ditolyl or N-benzyl methacrylamide or mixed products such as N-methyl-N-benzyl or N-ethyl-N-tolyl acrylamide or N-phenyl-N-benzyl ethacrylamide. Polymerization is effected with the aid of heat or light in the presence of catalysts, e.g. benzoyl, phthalic, succinic, benzoyl acetic, coconut oil acid, lauric, stearic or oleic acid peroxides or tertiary butyl hydroperoxide, ascaridole, or cobalt linoleate or naphthenate, p-toluene sulphonic acid, aluminium or stannic chloride or boron trifluoride, with or without an inhibitor such as hydroquinone, benzaldehyde, ascorbic or isoascorbic acid, rescorcinol, tannin, symmetrical di-beta-naphthyl-p-phenylene diamine, phenolic resins or sulphur compounds.  The polymers when partially polymerized may be moulded or cast and then polymerized to the final hard form which may be machined.  As a liquid partial polymer or in solution they may be used as bonding agents for laminates, or as adhesives for wood, metal, glass, rubber, or phenolic or urea condensation products.  For use as a surface coating, materials such as cellulose ethers or esters, natural or artificial resins, e.g. shellac, urea, phenolic or alkyd resins, ester gum, or rubber may be incorporated, and hardening is effected by light or catalysts, e.g. cobalt salts or oxygen liberating substances.  Fillers, wood flour or fibre, paper dust or paper, clay, diatomaceous earths, zein, glass wool or fibre, steel wool, mica, granite dust, silk or cotton flock, silicon carbide, cloth, sand, silica flour, pigments, Sudan IV or nigrosine dyes or triphenyl phosphate may be included.  Specification 600,917 is referred to.ALSO:Bis-acrylamide derivatives such as methyleneor ethylidene-bis-acrylamide, methylene-bismethacrylamide and propylidene-bis-ethacrylamide are prepared by condensing a saturated lower aliphatic aldehyde with acrylamide, one of its homologues or one of its mono-N-substituted derivatives in a 1 : 2 molar proportion in the presence of a strong acid.  In examples, 2 mols. of acrylamide or methacrylamide are condensed with 1 mol. of formaldehyde in the presence of a strong acid.