Patent GB-576153-A (GB)
Title: Condensation products and polymerization products thereof
IPC: C08G12/20
Filed: 1942-04-07
Abstract: An unsaturated alcohol having not more than six carbon atoms is esterified with a mono amide of a polycarboxylic acid and then condensed with an aldehyde.  Monoamides of citric, tartaric and tricarballylic acids may be used and also carbamic, oxamic, malonamic, succinamic, adipic and phthalamic acids.  The ester amides may be made by direct esterification, by reaction of silver or sodium salts of the acids with aliphatic halides or by reacting ammonia with a diester of the dibasic acid.  Unsaturated alcohols mentioned are: propenyl, butenyl, pentenyl, vinyl, allyl, propargyl, tiglyl, ethylallyl, furfuryl, butadienyl and crotyl alcohols and methylvinyl carbinol, ethylvinylcarbinol and methylallyl carbinol.  Unsaturated monoethers of glycols, diethylene-glycol and glycerol may also be used.  Formaldehyde and compounds yielding formaldehyde such as hexamethylenetetramine, acetaldehyde, butyraldehyde, acrolein, crotonaldehyde, methacrolein, b -ethylacrolein, furfural, benzaldehyde and glyoxal are aldehydes which may be used for the final condensation which may be effected in the presence of acid or alkaline catalysts.  The non-resinous products polymerize when heated in the presence of oxidation catalysts.  The fusible, soluble polymers are soluble in acetone, dichlorethylether, dibutylphthalate, trichlorethylene, carbon tetrachloride, benzene, xylene, toluene and dioxane and are best prepared while in solution.  They may be further polymerised to products which are infusible and insoluble, but polymerization may be stopped before the formation of gels by precipitating the fusible polymer by means of methyl or ethyl alcohol, water, petroleum ether or glycol or inhibitors such as pyrogallol, hydroquinone, aniline, phenylenediamine or sulphur may be added.  In examples: (1) allyl carbamate is condensed with formaldehyde in the presence of hydrochloric acid to give methylene bis-allylcarbamate; on heating with benzoylperoxide it gives a transparent polymer, a mouldable product is obtained by polymerizing while dissolved in dioxane and precipitating with methanol; (2) methallyl carbamate is condensed with formaldehyde and the reacting oil freed from water and other volatile matter; it gives a gel on heating in an oven and a polymer may be obtained from its solution in dioxane by heating and adding methanol; (3) methallyl carbamate is condensed with isobutyraldehyde, prepared in situ by isomerisation of methallylalcohol; the crystalline product may be polymerized in dioxane solution in the presence of benzoylperoxide; (4) formaldehyde is used to condense with allyloxamate and with allylphthalamate; the crystalline products are polymerized by means of acetoneperoxide. The monomers, syrupy polymers and fusible polymers may be used for coating and impregnating wood, paper, cloth and other fibrous material and in the production of laminated resinous products. Shaped products may be made by moulding and polymerizing the fusible polymer or by cast polymerizing the monomer or syrupy polymer. Specification 461,352 is referred to.