Patent GB-772295-A (GB)
Title: Improvements in or relating to amides
IPC: C08F20/60
Filed: 1954-03-29
Abstract: N - Amidoalkyl - N:N1 - alkylene ureas and thioureas of the formula <FORM:0772295/IV(a)/1> and the methylol and alkoxymethyl derivatives thereof, wherein R is hydrogen or a methyl group, the A's (which need not be identical) are alkylene groups of two or three carbon atoms with at least two carbon atoms between the nitrogen atoms, and X is oxygen or sulphur, alone or admixed with one or more other vinylidene monomers, are polymerized in bulk or in aqueous or organic solution, suspension or emulsion in the presence of a polymerization catalyst. The other monomer may be acrylic, methacrylic, maleic, fumaric or itaconic acid or a salt thereof; acrylonitrile; methacrylonitrile; maleic anhydride; an ester of acrylic or methacrylic acid, e.g. methyl, ethyl, isopropyl, butyl, tert-butyl, octyl, dodecyl, octadecyl, octenyl, oleyl, vinyloxyethyl, di-methylaminoethyl, diethylaminoethyl, diethylaminopropyl, tert. - butylaminoethyl or di-methylaminopropyl acrylate or methacrylate, ethylene diacrylate or dimethacrylate or amyl methacrylate; an este of itaconic acid, e.g. methyl, ethyl, isopropyl, butyl, tert.-butyl, octyl, dodecyl, octadecyl, octenyl or oleyl itaconate; an ester of maleic or fumaric acid, e.g. dimethyl or diethyl maleate or fumarate; diethyl chloromaleate; diethyl citraconate; acrylamide; methacrylamide; N-methylacrylamide; N-butylmethacrylamide; N-hydroxyethylacrylamide; N-dodecylacrylamide; N-dodecylmethacrylamide; dimethylaminoethylacrylamide; dimethylaminoethylmethacrylamide; dimethylaminopropylacrylamide; dimethylaminopropylmethacrylamide; a vinyl ether, e.g. hydroxyethyl, octyl, dodecyl, ureidoethyl, ureidoisobutyl, ethyl, butyl or 5-hydroxypentyl vinyl ether; a vinyl ester, e.g. vinyl acetate, propionate, laurate, butyrate, 2-ethylhexoate or stearate; a vinyl sulphide, e.g. methyl, butyl, dodecyl or lauryl vinyl sulphide; a vinylpyridine, e.g. 2-vinylpyridine; vinylcarbazol; styrene; a -methylstyrene; paramethylstyrene; para-chlorostyrene; vinylnaphthalene; divinylbenzene; trivinylbenzene; an allyl ester of a monocarboxylic acid; bis-(vinyloxyethyl) urea or mixtures thereof.  Specified solvents are n-butanol and dimethylformamide.  Exemplified N-amidoalkyl-N:N1-alkylene ureas and thioureas are N-(b -acrylamidoethyl)- and N-(b -methacrylamidoethyl)-N:N1 - ethyleneureas; 1 - (b  - methacrylamidoethyl) - thioimidazolidone - 2; 1 - (g  methacrylamidopropyl) - hexahydro - 2 - pyrimidone and -thiopyrimidone and methoxymethyl - N - (b  - methacrylamidoethyl) - 2 - imidazolidone.  The catalyst may be an anionic catalyst, e.g. sodium or sodium methoxide; a free radical catalyst, e.g. benzoyl peroxide, acetyl peroxide, caproyl peroxide, butyl perbenzoate, butyl hydroperoxide, ammonium persulphate, sodium persulphate, potassium persulphate, azodiisobutyronitrile, azodiisobutyramide, dimethyl azodiisobutyrate, diethyl azodiisobutyrate, dibutyl azodiisobutyrate, azobis - (a  : g  - dimethylvaleronitrile), azobis - (a  - methylbutyronitrile), azobis - (a - methylvaleronitrile), dimethyl azobismethylvalerate or diethyl azobismethylvalerate; or a redox combination in which an organic peroxide, hydrogen peroxide or an alkali persulphate is used in combination with an alkali metal sulphite, bisulphite, metabisulphite or hydrosulphite.  The catalyst may be used in conjunction with a chain transfer agent or regulator, e.g. mercaptoethanol.  The polymers and copolymers of compounds of the above general formula may be converted to the corresponding methylol derivatives by treatment with formaldehyde under alkaline conditions.  This reaction is preferably conducted in an alcoholic medium, and subsequent acidification of the reaction mixture yields the corresponding alkoxymethyl derivatives.  The methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl derivatives are formed in this manner.  The copolymers may be spun into fibres or added to lubricating oils.  The butoxymethyl copolymers may be used as a size or stiffening agent for nylon. Monomers of the above general formula may be used for impregnating leather, in which they may be polymerized in situ.  The polymers and copolymers and their methylol derivatives may be used for shrinkproofing wool and for imparting wet strength to paper.  The copolymers may be applied to cellulose acetate fibres in a size bath containing a solution of the copolymers.  The methylol derivatives may be added to viscose dopes which are formed into films or fibres and then cured at 220-300 DEG F.  The copolymers may also be added to viscose dopes which are formed into films or fibres, which are passed through a bath containing a solution of formaldehyde and a curing catalyst or through successive baths containing formaldehyde solution and dilute hydrochloric acid respectively before curing at 275-300 DEG  F. 2 mol. of a monomer of the above general formula may be reacted with 1 mol. of hexamethylene diamine and the product incorporated with urea or melamine to form a mixture which is reacted with formaldehyde to give resinous condensates.  The copolymers described above may be used as modifiers for aqueous urea-formaldehyde condensates and the copolymer formed from vinyl acetate and N - (b  - methacrylamidoethyl)-N:N1-ethyleneurea is exemplified for this purpose.ALSO:The invention comprises (1) compounds of the formula <FORM:0772295/IV(b)/1> wherein R is hydrogen or a methyl group, the A's (which need not be identical) are alkylene groups of two or three carbon atoms with at least two carbon atoms between the nitrogen atoms, and X is oxygen or sulphur; (2) methylol derivatives of (1) obtainable therefrom by treatment with formaldehyde under alkaline conditions; and (3) alkoxymethyl derivatives of (1) obtainable by treatment of the corresponding methylol derivatives with an alcohol under acid conditions.  Compounds of the above formula are prepared by reacting a compound of formula <FORM:0772295/IV(b)/2> with acrylic or methacrylic anhydride, or with a compound of formula CH2=C(R)COY (wherein Y is chlorine or bromine) at a temperature between - 20 DEG C. and 50 DEG  C. in presence of an acceptor for hydrogen halides (e.g. an alkali metal base, a tertiary amine or a molar excess of amine reactant) and preferably in the presence of an inert solvent. The reaction is preferably conducted in presence of a polymerization inhibitor.  Specified cyclic urea starting materials are 1-(2-aminoethyl)-2- and 1-(2-aminopropyl)-4-(or 5)-methyl-2-imidazolidones; 1-(2-aminoethyl)-2-imidazolidinethione; 1 - (3 - aminopropyl) - hexahydro - 2 - pyrimidone and -thiopyrimidone. The examples describe the preparation of N-(b -acrylamidoethyl)- and N - (b  - methacrylamidoethyl) - N : N1 - ethylene - ureas; 1-(b -methacrylamidoethyl)-thioimidazolidone - 2; 1 - (g  - methacrylamidopropyl) - hexa - hydro - 2 - pyrimidone and -thiopyrimidone and methoxymethyl N - (b  - methacrylamido - ethyl)-2-imidazolidone.  1 - (3 - Aminopropyl) - hexahydro - 2 - pyrimidone and -thiopyrimidone are prepared by reacting 3 : 31-iminobispropylamine with urea and carbon disulphide respectively. Compounds of the first general formula may be reacted with an equimolecular amount of tetradecyl mercaptan in presence of an alkaline catalyst to yield the corresponding alkylthio derivative. Two moles. of a compound of the above general formula also form a reaction product with 1 mole. of hexamethylenediamine.ALSO:N - amidoalkyl - N : N1 - alkylene ureas and thioureas of the formula <FORM:0772295/IV(b)/1> wherein R is hydrogen or a methyl group, the A's (which need not be identical) are alkylene groups of two or three carbon atoms with at least two carbon atoms between the nitrogen atoms, and X is oxygen or sulphur, are reacted with tetradecylmercaptan to give alkylthio derivatives which may be used for imparting waterrepellency to fabrics, or are polymerized or copolymerized to form products which may be used, as such or in the form of their methylol or alkoxymethyl derivatives, to impart shrink resistance to wool and for stiffening or sizing textiles e.g. nylon, cellulose acetate fibres or regenerated cellulose fibres. Exemplified urea and thiourea monomers are N - (b  - acrylamidoethyl) - and N - (b  - methacrylamidoethyl) - N : N1 - ethyleneureas, 1 - (b  - methacrylamidoethyl) - thioimidazolidone - 2, 1 (g  - methacrylamidopropyl) - hexahydro - 2 - pyrimidone and - thiopyrimidone and methoxymethyl N - (b  - methacrylamidoethyl) - 2 - imidazolidone.  The comonomer(s) may be acrylic, methacrylic, maleic, fumaric or itaconic acid or a salt thereof; acrylonitrile; methacrylontrile; maleic anhydride; an ester of acrylic or methacrylic acid, e.g. methyl, ethyl, isopropyl, butyl, tert-butyl, octyl, dodecyl, octadecyl, octenyl, oleyl, vinyloxyethyl, dimethylaminoethyl, diethylaminoethyl, diethylaminopropyl, tert.-butylaminoethyl or dimethylaminopropyl acrylate or methacrylate, ethylene diacrylate or dimethacrylate or amyl methacrylate; an ester of itaconic acid, e.g. methyl, ethyl, isopropyl, butyl, tert.-butyl, octyl didecyl, octadecyl, octenyl, or oleyl itaconate; an ester of maleic or fumaric acid, e.g. dimethyl or diethyl maleate or fumarate; diethyl chloromaleate; diethyl citraconate; acrylamide; methacrylamide; N-methylacrylamide; N butylmethacrylamide; N - hydroxyethylacrylamide; N - dodecylacrylamide; N dodecylmethacrylamide; dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide; dimethylaminopropylacrylamide; dimethylaminopropylmethacrylamide, a vinyl ether, e.g. hydroxyethyl, lamide, a vinyl ether, e.g. hydroxyethyl, octyl, dodecyl, ureidoethyl, ureidoisobutyl, ethyl, butyl or 5 - hydroxypentyl vinyl ether; a vinyl ester, e.g. vinyl acetate, propionate, laurate, butyrate, 2 - ethylhexoate or stearate; a vinyl sulphide, e.g. methyl, butyl, dodecyl or lauryl vinyl sulphide; a vinylpyridine, e.g. 2 - vinylpyridine; vinylcarbazol; styrene, a  - methylstyrene;