Patent GB-785386-A (GB)
Title: Guanamines
IPC: C08G12/30
Filed: 1955-08-16
Abstract: The invention comprises polymers of guanamines of the formula <FORM:0785386/IV (a)/1> alone or with other monovinylidene compounds, salts of such polymers with strong mineral acids, and methylol derivatives obtained by reacting the polymers with formaldehyde. Polymerization is effected by the action of free radical initiators such as caproyl or benzoyl peroxide, dimethyl or diethyl azo-di-isobutyrate, azo-di-isobutyronitrile or azo-bis-(a -methylbutyronitrile).  Copolymers may be obtained with the nitriles, amides, N-substituted amides, alkyl esters, methoxyethyl esters or t-aminoalkyl esters of acrylic and methacrylic acids, vinyl acetate, vinyl propionate, vinyl pyridine, vinyl pyrrole or ureidoethyl vinyl ether.  The guanamine may be present to the extent of 1-50 per cent or may be the chief monomer.  In the examples: (1) a -methacrylamido-isobutyroguanamine is polymerized with benzoyl peroxide in methanol; (2) N-methacryl-N-octylamido-propioguanamine is polymerized with dimethyl azo-di-isobutyrate in dimethylformamide; (3) methacrylamido-isobutyroguanamine is copolymerized with methyl methacrylate using benzoyl peroxide in ethoxyethyl acetate, and the polymer made into a film with butyl hemiformal in butanol and butyl acid phthalate as catalyst; (4) a copolymer is made from methacrylamido - isobutyroguanamine, methyl methacrylate and ethyl acrylate using benzoyl peroxide; films from this can be hardened with formaldehyde; (5) an inhomogeneous product is obtained from N-methyl-methacrylamido-propioguanamine and methyl methacrylate using azo-di-isobutyronitrile in ethoxyethyl acetate; (6) an aqueous solution of the hydrochloride of the monomer of Example (4) or (5) is heated with ammonium persulphate and the polymer precipitated with caustic soda; (7) a -methacrylamido-isobutyroguanamine is polymerized with dimethyl azo-di-isobutyrate in methanol; the polymer is dissolved in hydrochloric acid, reprecipitated on a fabric with alkali and hardened with formaldehyde.  Other suitable guanamine monomers are specified.ALSO:The invention comprises compounds of the formula <FORM:0785386/IV (a)/1> where R is hydrogen, alkyl, alkenyl, aralkyl or cycloalkyl and A is alkylene of 1-8 carbon atoms, and their salts with strong inorganic acids.  There are made by condensing methacrylamido-nitriles of the formula CH2:C(CH3).CO.NR.A.CN with dicyandiamide in the presence of a strong base as catalyst and an alcohol as solvent. Products mentioned in the examples are a -methacrylamido-isobutyroguanamine and its N-methyl and N-benzyl derivatives, b -methacrylamido-propioguanamine and its N-methyl and N-cyclohexyl derivatives, and N-cyclohexyl - methacrylamido - acetoguanamine.  Other suitable starting materials are listed. The products form salts with strong inorganic acids such as hydrochloric, hydrobromic, sulphuric and phosphoric.  The hydrochlorides of a -methacrylamido-isobutyroguanamine and N-methyl-b -methacrylamido-propioguanamine are mentioned.  The products can be reacted at the unsaturated linkage with compounds having a reactive hydrogen atom or at the amino groups with formaldehyde. N-methacrylyl-aminonitriles are made by reacting the appropriate aminonitrile with methacrylyl chloride or bromide.  The reactions of b -aminopropionitrile, a -amino-isobutyronitrile, N - cyclohexyl - aminoacetonitrile, N - cyclohexyl - b  - aminopropionitrile and N - methyl -b -amino-propionitrile and analogous N-benzyl and N-allyl compounds are described.  Many other aminonitriles are mentioned.