Patent GB-786109-A (GB)
Title: Amino derivatives of acrylic and methacrylic acids
IPC: C08F20/34
Filed: 1955-07-18
Abstract: Cyanoamino acrylic and methacrylic esters of the formula: <FORM:0786109/IV (a)/1> wherein R is hydrogen or a methyl group, A is a C2-C18 alkylene group interposing at least two carbon atoms between the oxygen and nitrogen atoms, and R1 is an alkyl, cycloalkyl, aryl or aralkyl group, alone or admixed with one or more other monomers, are polymerized in bulk, solution, suspension or emulsion in presence of a polymerization catalyst. Toluene is specified as a solvent. Exemplified monomers are N - cyano - N - tert. - butylaminoethyl methacrylate, N - cyano - N - tert. - butylaminoethyl acrylate, N - cyano - N - tert. - octylaminoethyl acrylate, N-cyano-N-methylaminoethyl methacrylate, b  - (N - cyano - N - methylamino) propyl methacrylate, N - cyano - N-methylaminoethyl acrylate and N - cyano - N-dodecylaminoethyl methacrylate.  Specified comonomers are methyl, butyl, octyl, oleyl, allyl, benzyl, methoxyethyl and vinyloxyethyl acrylates; methyl, hexyl, dodecyl, laurylmyristyl, dimethylaminoethyl, vinyloxypropyl, cyclohexyl and tetrahydrofurfuryl methacrylates, N - alkylacrylamides, methacrylamide, acrylonitrile, methacrylonitrile, dimethyl itaconate, diethyl itaconate, diethyl fumarate, dimethyl maleate, styrene, vinyltoluene, parachlorostyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, vinyl propionate, allyl acetate, N-allyl acetamide, ethylene diacrylate, ethylene dimethacrylate, divinylbenzene and diallyl phthalate.  The catalyst may be azodiisobutyronitrile, azobis (a : g  - dimethylvaleronitrile), azobis (a  - methylbutyronitrile), azodiisobutyramide, dimethyl, diethyl, or dibutyl azodiisobutyrate, dimethyl, diethyl, or dibutyl azobis (methylvalerate), benzoyl, methylethyl ketone, caproyl, acetyl or lauroyl peroxide, butyl perbenzoate, tert.-butyl or cumene hydroperoxide, ammonium, sodium or potassium persulphate, or hydrogen peroxide.  The inorganic peroxidic catalysts are preferably used in a redox system containing a reducing agent such as sodium sulphite, bisulphite, metabisulphite or hydrosulphite, with or without a metal as activator.  The polymers and copolymers may be formed into films or added to coating compositions and lubricating oils. Specification 776,503 is referred to.ALSO:The invention comprises compounds of the formula <FORM:0786109/IV (a)/1> wherein R is hydrogen or a methyl group, A is a C2-C18 alkylene group interposing at least two carbon atoms between the oxygen and nitrogen atoms, and R1 is an alkyl, cycloalkyl, aryl or aralkyl group.  The compounds are prepared by effecting an addition reaction at a temperature between 0 DEG  and 75 DEG  C. between cyanogen chloride or bromide and a tertiaryaminoalkyl acrylate or methacrylate of the formula <FORM:0786109/IV (a)/2> and heating the resulting addition product to between 50 DEG  and 150 DEG C. with removal of R2Cl or R2Br, R2 being a C1-C4 alkyl or benzyl group and such that it is more easily removed from the amino group than R1.  Compounds of the formula <FORM:0786109/IV (a)/3> wherein R is hydrogen or a methyl group, CnH2n is a C2-C3 alkylene group interposing at least two carbon atoms between the oxygen and nitrogen atoms, and R0 is a C4-C24-tert.-alkyl group, are also prepared by reacting cyanogen chloride or bromide with a compound of the formula CH2=C(R)COOCnH2n-NHR0 in the presence of a hydrogen halide acceptor. The monomeric products may be reacted with alcohols, mercaptans and arylamines to give isoureas, isothioureas and guanidine salts respectively. The examples describe the preparation of N-cyano-N-tert.-butylaminoethyl methacrylate, N - cyano - N - tert. - butylaminoethyl acrylate, N - cyano - N - tert. - octylaminoethyl acrylate, N - cyano - N - methylaminoethyl methacrylate, b  - (N - cyano - N - methylamino) - propyl methacrylate, N -cyano-N-methylaminoethyl acrylate and N - cyano - N - dodecylaminoethyl methacrylate.  Specification 776,503 is referred to.