Patent GB-1122248-A (GB)
Title: Guanamines and polymers thereof
IPC: C08L1/00
Filed: 1966-05-05
Abstract: Polymers containing or consisting of units derived from a monomer of the formula <FORM:1122248/C3/1> wherein R is an alkenyl group having from 3 to 9 carbon atoms and a terminal group of the formula <FORM:1122248/C3/2> R0, R1, R2 and R3 may be the same or different and represent H or-R4OR5 wherein R4 and R5\h may be the same or different saturated hydrocarbon groups containing from 1 to 8 carbon atoms, or in the case of R5, hydrogen, are obtained by homopolymerizing said monomer or copolymerizing said monomer with a copolymerizable ethylenically unsaturated monomer, the resulting polymer suitably having a molecular weight of 1000-1,000,000 and containing 0.5-99.5% by weight of units derived from compounds of the above formula.  The polymerization may be effected in bulk, in solution or by employing emulsion or suspension techniques, and it may be carried out with the aid of a free radical initiator or catalyst, e.g. an organic or inorganic peroxide, peroxy catalysts such as persulphates, azo catalysts or redox catalysts.  Regulators, e.g. mercaptans, may also be used.  Polymers containing polymerized units of the N-hydrocarbylol and the N-hydrocarbyloxyhydrocarbyl derivatives of the above formula may also be obtained by reaction of a non-hydrocarbylolated monomer with a source of an appropriate aldehyde and simultaneous, concurrent or subsequent reaction with an alcohol under conventional reaction conditions.  Preferred comonomers for making the copolymers include acrylic and methacrylic acids, the nitriles thereof, the esters thereof with C1- 18 saturated aliphatic alcohols, acrylamide, methacrylamide and the N-methylol derivatives thereof, itaconic acid, vinyl acetate, vinyl chloride, vinylidene chloride and vinyl aromatic hydrocarbons, e.g. styrene and o-, m-, and p-vinyl toluene.  Polythylenically unsaturated comonomers, e.g. divinyl benzene, ethylene glycol dimethacrylate and diallyl phthalate, may also be employed in amounts of from 0.1 to 20% or more by weight. In examples, (a) 4-penteno-guanamine is homopolymerized in the presence of di-t-butyl peroxide, (10) ethyl acrylate and methylolated-4-pentenoguanamine are emulsion copolymerized, (12) 4-pentenoguanamine is copolymerized with a solution comprising methyl methacrylate, butyl acrylate, methacrylic acid and dicumyl peroxide, (15) 4-pentenoguanamine is copolymerized with a solution comprising methyl methacrylate, butyl acrylate, methacrylic acid, (17) a solution comprising methyl methacrylate, butyl acrylate, methacrylic acid, permethoxymethyl - 4 - pentenoguanamine and benzoyl peroxide is polymerized, (20) ethyl acrylate and 10-undecenoguanamine are emulsion copolymerized, (23) ethyl acrylate and 2,2-diethyl-4-pentenoguanamine are emulsion copolymerized, and (24) ethyl acrylate and 7-octenoguanamine are emulsion copolymerized. Aqueous dispersions of, solutions of or pastes containing polymers of the above type may also contain pigments, dyes, fillers, alkyd resins, curing catalysts, powdered or flaked metal, thickening agents, mild alkali or surface-active agents.  The products are suitable for coating, impregnating, and for adhesive and moulding purposes.  Examples 11, 13, 14, 16 and 18 illustrate applications in which the polymers are cured.  In Example 14, the polymer solution used is admixed with a solution of a butylated melamine-formaldehyde condensate. missing page 536ALSO:Compounds of the formula <FORM:1122248/C2/1> wherein R is an alkenyl group having from 3 to 9 carbon atoms and a terminal group of the formula CH2 = C<, R0, R1, R2 and R3 may be the same or different and represent H or -R4OR5, wherein R4 and R5 may be the same or different saturated hydrocarbon groups containing from 1 to 8 carbon atoms, or, in the case of R5, hydrogen, may be obtained (a) by reacting a nitrile of the formula RCH2CN with dicyandiamide to form a compound of the above formula, wherein R0, R1, R2 and R3 all represent H, and, optionally, (b) further hydrocarbylolating the product of (a) to form a compound of the above formula wherein R5 is hydrogen, and optionally (c) hydrocarbylating the product from (b) to form a compound of the above formula in which at least one R5 is other than hydrogen.  Reaction (a) may be carried out in the presence of a base as catalyst at a temperature of from 40 DEG  to 200 DEG  C.; reaction (b) may be carried out at a pH of 1 to 11 employing an aldehyde as the source of -R4OH groups and reaction (c) may be effected at a pH of 1 to 6.5 using a saturated alcohol as the source of R5 groups, or steps (b) and (c) may be carried out simultaneously.ALSO:Substrates may be coated with compositions comprising polymers which contain or consist of units derived from a monomer of the formula: <FORM:1122248/B1-B2/1> where R is an alkenyl group having from 3 to 9 carbon atoms and a terminal group of the formula CH2=C<, R0, R1, R2 and R3 may be the same or different and represent H or -R4OR5 wherein R4 and R5 may be the same or different saturated hydrocarbon groups containing 1 to 8 carbon atoms, or, in the case of R5, hydrogen.  The polymers, which suitably contain 0.5 to 99.5% by wt. of units derived from monomers of the above formula and which have molecular weights of from 1000 to 1,000,000, may be homopolymers containing units derived from the above monomers, or copolymers of the above monomers with other ethylenically or polyethylenically unsaturated copolymerizable monomers.  Aqueous dispersions or solutions of the polymers employed may also contain pigments, dyes, fillers, alkyd resins, curing catalysts, powdered or flaked metal, thickening agents, mild alkali or surface active agents. Substrates which may be coated include bare and primed metals, e.g. bare cold-rolled steel, aluminium and brass, glass, asbestos-cement shingles, wood, leather, paper, textiles, ceramics, stone, cement, concrete, bricks, cinder block and masonry surfaces.  The compositions may be applied as hot-melt coatings, as solutions in organic solvents or as aqueous dispersions, by spraying, brushing, roller-coating, dipping and knife-coating.  The coatings may be dried and cured, optionally in the presence of other coreactive polyfunctional reagents.ALSO:Textiles may be treated with compositions comprising polymers which contain or consist of units derived from a monomer of the formula:  <FORM:1122248/D1-D2/1> where R is an alkenyl group having from 3 to 9 carbon atoms and a terminal group of the formula CH2=C<, R0, R1, R2 and R3 may be the same or different and represent H or -R4OR5 wherein R4 and R5 may be the same or different saturated hydrocarbon groups containing 1 to 8 carbon atoms, or, in the case of R5, hydrogen.  The polymers, which suitably contain 0.5 to 99.5% by wt. of units derived from monomers of the above formula and which have molecular weights of from 1000 to 1,000,000, may be homopolymers containing units derived from the above monomers, or copolymers of the above monomers with other ethylenically or polyethylenically unsaturated copolymerizable monomers.  Aqueous dispersions or solutions of the polymers employed may also contain pigments, dyes, fillers, alkyd resins, curing catalysts, powdered or flaked metal, thickening agents, mild alkali or surface active agents.  Materials which may be treated, which may be in the form of fibres, filaments, woven or knitted fabrics or carded webs, or other fabricated structures, include cellulose, starch, cellulose esters and ethers, paper, leather, amide-containing materials such as polyamide nylons, wool, silk, casein and other proteinaceous materials.  The materials may be treated to stiffen them, to crease-proof or render wrinkle-resistant such materials, particularly cotton, rayon and nylon, to reduce shrinkage and to stabilize against shrinkage such materials as wool, cotton and rayon, or to render any of such materials water-resistant and/or water-repellant, and/or to lubricate them.  After application the compositions may be dried and cured, optionally in the presence of other coreactive polyfunctional reagents.  The textile materials may also be treated by impregnating the material with a solution of a monomer of the above general formula and subsequently polymerising or copolymerising the monomer under addition polymerization conditions.