Patent GB-475132-A (GB)
Title: Improvements in or relating to the manufacture of synthetic resins
IPC: C08F20/34
Filed: 1936-05-15
Abstract: Resinous materials are prepared by polymerizing salts of esters having the general formula <FORM:0475132/IV/1> wherein R represents a hydrogen atom or an alkyl, aryl, aralkyl, cycloalkyl or heterocyclic radical and R<1> represents the radical of an aminoalcohol.  The polymerization may be effected in solution or emulsion.  The polymerized salt may be converted into the free base by heat treatment.  The aminoalcohols are amines containing primary, secondary or tertiary alcoholic hydroxyl groups in which the amino groups may be primary, secondary or tertiary.  The amino group may contain alkyl, aryl, aralkyl or cyclo-paraffin groups or be a member of a heterocyclic ring. Suitable aminoalcohols include b -diphenylaminoethanol, b  - di - n- or b  - di - iso - propylaminoethanol, b -diacrylaminoethanol, g -dibutyldiethylaminopropanol, diethylaminobutanol, dibutyl- or di - iso - butyl - aminobutanol, b -di-iso-butylaminoethanol, phenyl- or o-tolyl-aminocyclohexanol, b -ethylaminoethanol, g -ethylaminopropanol, butylaminobutanol, b -cyclohexylaminoethanol, aminocyclohexanol, the mono-, di- or tri-ethanolamines, butanolamines, propanolamines or isobutanolamines, glucamine, methylglucamine, 1 : 3 - diaminopropanol, b -ethylcyclohexylaminoethanol, dimethylaminomethanol, b -decahydroquinyl-N-ethanol, vinylalkylaminoethanols, p - hydroxyphenylmorpholine, b -thiomorpholine-N-ethanol, aminophenols, methanolamine diethers, b -hydroxy-b -dialkylaminodiethyl ether and analogous compounds from tri- and tetraethylene glycol, triethanolamine diesters, b  - piperazine - N-ethanol, b -(monoalkylpiperazine)-N-ethanols, N-alkyl-2-hydroxymorpholine, tertiary butanolamine, dimethylglucamine, octylmethylglucamine, laurylglucamine, aminooctadecanol, aminonaphthols, aminotetra- and aminodecahydronaphthols and corresponding mono- and dialkyl derivatives, primary, secondary or tertiary-3-amino alcohols such as 3-methylamino-2 : 2-dimethyl propanol-1, glycol monoesters of aminoacids, aminoalcohol esters of hydroxy acids, aminoalcohols produced by reacting camphene oxide, dipentene oxide, pinene oxide, bornylene oxide, with ammonia or amines.  Suitable acids for esterification include acrylic, methacrylic, a -butylacrylic, a -ethylacrylic, a -phenylacrylic, a -isopropylacrylic, a -hexylacrylic, a -methylphenylacrylic, a -methylcyclohexylacrylic, and a -cyclohexylacrylic acids. Acids used for preparation of the salts of the esters include sulphuric, sulphurous, carbonic, phosphoric, fluosilicic, glycollic, lactic, formic, chloracetic, p-toluenesulphonic, propionic, butyric, l vulinic, chloriso-butyric, adipic, succinic and phthalic acids.  Catalysts such as barium peroxide, sodium peroxide, hydrogen peroxide, per-acetic acid, per-acids, ultra-violet light or combinations thereof may be used. Interpolymers may be prepared by effecting the polymerization in the preparation of other polymerizable compounds such as vinyl esters, styrene, indene, coumarone, 2-chloro-1 : 3-butadiene, acrylic acid or methacrylic acid preferably in organic solvent medium.  The free base polymers are soluble in dilute acids, hydrocarbons, alcohols, ketones, esters and ethers such as dilute hydrochloric, formic and acetic acids, benzene, toluene, methanol, ethanol, acetone, diethyl ketone, ethyl acetate, butyl acetate, methyl formate and ethylene glycol monomethyl ether.  The polymeric salts may be used as dispersing agents for pigments, as emulsifying agents for oils, fats, waxes and rubber, as fixatives for pigments, waxes and oils to paper, fabrics and leather, as adhesive especially for laminated wood, as ingredients in water paints, as finishes for rubberized fabrics, as sizes for improving adhesion of lacquers to regenerated cellulose sheet, as insecticides and bactericides (especially fluosilicates and thiocyanates), in coating compositions (especially fatty acid and rosin salts).  The free base polymers may be used as adhesives especially for laminated wood, as stabilizers for gasoline and chlorine containing substances, as fixatives for pigments, oils and waxes to paper, cloth, and leather, as fixing agents for acid dyes, as ingredients of moisture proofing lacquers, as sizes for improving adhesion of lacquers to regenerated cellulose sheet, as ingredients in coating compositions especially in conjunction with nitrocellulose, ethyl cellulose, fatty oils and polyhydric alcoholpolycarboxylic acid resins.  In examples, the following solutions are polymerized in the presence of benzoyl peroxide, the free polymeric bases being liberated if desired by heating with a sodium bicarbonate solution: (1) b -dimethylaminoethyl methacrylate in dilute aqueous acetic acid; (2) b -diethylaminoethyl methacrylate in aqueous or alcoholic acetic, formic or glycollic acid; (3) b -dicyclohexylaminoethyl methacrylate or b -di-n-butylaminoethyl methacrylate in hydrochloric acid; (5) 2-aminocyclohexyl methacrylate in aqueous acetic acid; (6) triethanolamine monomethacrylate in aqueous acetic acid; (7) 2-(diethylamino) cyclohexyl methacrylate in dilute hydrochloric acid; (8) b -piperidyl-N-ethyl methacrylate in dilute acetic acid; (9) b -diethylaminoethyl methacrylate hydrochloride in water; (10) b -morpholine-N-ethyl methacrylate in dilute acetic acid; (11) b -diethylaminoethyl methacrylate carbonate in water; (12) b -dimethylaminoethyl methacrylate in aqueous fluosilicic acid.  2-Aminocyclohexyl methacrylate is prepared by reacting the sodium salt of 2-aminocyclohexanol with methacrylyl chloride.  b -Diethylaminoethyl acrylate hydrochloride is prepared by reacting b -diethylamine ethanol with acrylyl chloride in solution in dry benzene.  b -Diethylaminoethyl methacrylate carbonate is prepared by treating the base suspended in ice cold water with carbon dioxide. Specifications 358,534, 374,436, 427,494, and 475,131 are referred to.  The Specification as open to inspection under Sect. 91 refers also to the use of acrylic and methacrylic acids as salt forming acids. This subject-matter does not appear in the Specification as accepted.