Patent GB-840169-A (GB)
Title: N-(vinyloxyalkyl) amidoguanamines, their polymers and copolymers and the preparationthereof
IPC: C08F16/28
Filed: 1956-11-16
Abstract: Condensation and polymerization products are made from compounds of the formul  <FORM:0840169/IV(a)/1> <FORM:0840169/IV(a)/2> where A is -CH2CH2-, -CH(CH3)CH2- or -CHR1-; R is H, C1-C18 alkyl, C6-C10 aryl (including halo-aryl), C1-C4 alkoxy, benzyloxy or alkoxyalkyl of 1-4 carbon atoms in each part; R1 is H or C1-C8 alkyl; Z is C2-C6 alkylene; and Z1 is C1-C5 alkylene; if R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively.  The monomers can be converted into watersoluble methylol or alkoxymethyl derivatives which can be used as components of resins, alone or together with other pre-condensates, e.g. urea-formaldehyde or melamine-formaldehyde.  Fillers can be included, e.g. pigments or cellulose in the form of fibres or clippings.  Condensation products can also be made by reaction with alkylene oxides.  The monomers can be polymerized or copolymerized in bulk, in solvents or in aqueous suspensions or emulsions, using as catalysts azo compounds or redox systems.  The copolymers can be insolubilized by treatment with aldehydes, preferably by heating under acid conditions.  The other components of the copolymers can be acrylic esters (methyl, ethyl, butyl, 2-ethylhexyl, 3:5:5-trimethylhexyl, dodecyl, ethoxyethyl, butoxyethyl, phenoxyethyl, cyclohexyl, benzyl), methacrylic esters (methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cetyl, ethoxyethyl, butoxyethyl, cyclohexyl, benzyl, dimethylaminoethyl), acrylamides, acrylonitrile or methacrylonitrile.  In examples: (1) a copolymer is made from acrylonitrile, methyl methacrylate and a -[N-(b -vinyloxyethyl) - N - (ethoxycarbonyl) - amino] - acetoguanamine using azo-isobutyronitrile as catalyst (added in three batches); it forms thermoplastic films, or infusible coatings by treatment with formaldehyde and ammonium chloride; (2) as in (1) using the corresponding isovalero-guanamine; (3) a copolymer is made from butyl acrylate and b -[N-(b -vinyloxyethyl)-palmitamido] - propioguanamine in emulsion form, using as catalyst ammonium persulphate and diethylenetriamine; (4) copolymers are also made from the following: butyl acrylate and b  - [N - (b  - vinyloxyethyl) - formamido] - propioguanamine; lauryl acrylate and 2-[N-(6-vinyloxyhexyl) - carbamylmethyl] - 4:6 - diaminotriazine; butyl acrylate, methyl methacrylate and a -[N-(b -vinyloxyethyl)-acetamido]-acetoguanamine; ethyl acrylate, b -[N-(b -vinyloxyethyl)-benzamido]-propioguanamine and the isovaleroguanamine of (2).ALSO:The invention comprises compounds of the formulae <FORM:0840169/IV(b)/1> where A is -CH2CH2-, -CH(CH3)CH2- or -CHR1-; R is H, C1-C18 alkyl, C6-C10 aryl, C1-C4 alkoxy, benzyloxy or alkoxyalkyl of 1-4 carbon atoms in each part; R1 is H or C1-C8 alkyl; Z is C2-C6 alkylene; and Z1 is C1-C5 alkylene; if R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively. The compounds are made by reacting dicyandiamide with nitriles CH2=CHOZN(COR)ACN and CH2=CHOZ1 CH2NHCOCH2CN at 75-120 DEG  C. in the presence of a basic catalyst, e.g. an alkali metal hydroxide or alkoxide, or a quaternary ammonium base.  The products can be reacted with formaldehyde or its revertible polymers to give methylol derivatives or (if done in the presence of lower alcohols) polyalkoxymethyl derivatives.  They also yield detergents by reaction with alkylene oxides, e.g. ethylene oxide with or without propylene oxide.  Examples are given of the preparation of compounds in which A is methylene, ethylene, ethylidene or isobutylidene, R is H, methyl, ethyl, pentadecyl, phenyl, p-tolyl, ethoxyethyl, ethoxy and benzyloxy, Z is ethylene, propylene, trimethylene and pentamethylene, and Z1 is ethylene and hexamethylene.  It is stated that R can be phenyl or naphthyl optionally substituted by alkyl, chlorine or bromine.  Nitriles of the formula CH2=CHOZ1CH2 NHCOCH2CN are made from vinyloxyalkylamines CH2=CHOZ1CH2NH2 and lower alkyl cyanoacetates in an inert solvent.  Examples are given of the reaction of methyl cyanoacetate with b -aminoethyl and 6-aminohexyl vinyl ethers.  The nitriles of the other formula are made as in Specification 840,170.ALSO:Textiles are treated with copolymers of vinyl compounds and guanamines of the formula:  <FORM:0840169/IV (c)/1> or <FORM:0840169/IV (c)/2> where A is -CH2CH2-, -CH(CH3)CH2- or -CHR1-; R is H, C1 -C18 alkyl, C6 -C10 aryl (including halo-aryl), C1-C4 alkoxy, benzyloxy or alkoxyalkyl of 1-4 carbon atoms in each part; R1 is H or C1-C8 alkyl; Z is C2-C6 alkylene; and Z1 is C1-C5 alkylene; if R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively.  In examples, wool fabrics are shrink-proofed by padding with aqueous dispersions of various copolymers, followed by optional treatment with formaldehyde and oxalic acid. The copolymers used are from (1) butyl acrylate and b -[N-(b -vinyloxyethyl)-formamido]-propioguanamine; (2) butyl acrylate, methyl methacrylate and a -[N-(b -vinyloxyethyl)-acetamido]-acetoguanamine; and (3), ethyl acrylate, b -[N-(b -vinyloxyethyl)-benzamido]-propioguanamine and a -[N-(-b vinyloxyethyl)-N-(ethoxycarbonyl) -amino]-isovaleroguanamine.  The other component of the copolymer may be an acrylic or methacrylic ester, acrylamide, acrylonitrile or methacrylonitrile.ALSO:Coating compositions are made from guanamines as defined below, either (a) by conversion into methylol or alkoxymethyl derivatives and use alone or with other pre-condensates, e.g. of the urea-formaldehyde or melamineformaldehyde type; or (b) by copolymerization with other ethylenically unsaturated compounds. The compositions are mixed with aldehydes and acid catalysts, coated on the support (e.g. wood, steel or paper) and dried with or without baking.  The guanamines used are of the formula <FORM:0840169/III/1> <FORM:0840169/III/2> where A is -CH2CH2-, -CH(CH3)CH2- or -CHR1-; R is H, C1-C18 alkyl, C6-C10 aryl (including halo-aryl), C1-C4 alkoxy, benzyloxy or alkoxyalkyl of 1-4 carbon atoms in each part; R1 is H or C1-C8 alkyl; Z is C2-C6 alkylene; and Z1 is C1-C5 alkylene; if R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively.  In examples films are cast from tertiary copolymers of acrylonitrile, methyl p  methacrylate and either a  - [N - (b  - vinyloxyethyl) - N - (ethoxycarbonyl) - amino] - acetoguanamine or the corresponding isovaleroguanamine. The compound b  - [N - (b  - vinyloxyethyl)-palmitamido]-propioguanamine is stated to produce a water-repellent finish when rubbed on shoes, boots and other leather goods.ALSO:Substituted guanamines of the formula: <FORM:0840169/II/1> <FORM:0840169/II/2> are used as corrosion inhibitors in pickling baths.  A is -CH2CH2-, -CH(CH3)CH2-or -CHR1-; R is H, C1-C18 alkyl, C6-C10 aryl (including halo-aryl), C1-C4 alkoxy, benzyloxy or alkoxyalkyl of 1-4 carbon atoms in each part; R1 is H or C1-C8- alkyl; Z is C2-C6 alkylene; and Z1 is C1-C5 alkylene; if R is H the acylated N atom must be flanked by two -CH2- groups in Z and A respectively.