Patent GB-1293950-A (GB)
Title: Improvements in or relating to polyurethane resin compositions
Inventor: SELLET LUCIEN
IPC: C09D175/04
Filed: 1969-12-30
Abstract: 1293950 Alkyollated polyurethanes DIAMOND SHAMROCK CORP 30 Dec 1969 [31 Dec 1968] 63367/69 Heading C3R [Also in Divisions C2, C6 and D1-D2] Alkylolated polyurethane resins are prepared by reacting: (A) a Mannich Base condensate obtained by reacting together for 2 to 10 hours at 5‹ to 110‹ C. (1) at least one amino resin base (i.e. a low molecular weight methylol derivative of an amino compound suitable as an aminoplast resin precursor) having at least one reactive hydrogen atom, (2) at least one aldehyde or substance capable of liberating an aldehyde, and (3) at least one monoalkanolamine or dialkanolamine having at least two carbon atoms per alkylene group, in the proportions of at least one mole each of (2) and (3) in equimolar amounts per mole of (1); and (B) a polyurethane prepolymer having at least one reactive isocyanate group obtained by reacting at 50‹ to 100‹ C. under anhydrous conditions an organic polyisocyanate and at least one polyoxyalkylene polyol or polyester having at least two terminal hydroxyl groups in an NCO/OH ratio of at least 1À1 to 1À0; in such proportions of (A) and (B) that an NCO/OH ratio of 1 : 2 to 1 : 1 is maintained, the reaction being carried out for ¢ to 6 hours at 25‹ to 160‹ C. under anhydrous conditions in the absence of a blowing agent to yield a product capable of forming salts with acetic acid which are at least water dispersible; and further reacting the condensation product with (C) at least one aldehyde or substance capable of liberating an aldehyde at 5‹ to 110‹ C. for 1 to 20 hours and in an amount sufficient to react with at least one of the reactive hydrogen atoms present. The above alkylolated polyurethanes may be formulated into compositions by admixture with 0 to 20% by weight of an inorganic or C 1-4  carboxylic acid, 0 to 20% by weight of a surfactant, 0 to 40% by weight of a pigment and 0 to 99% by weight of water, a hydrophilic or hydrophobic alcohol, an ester or a chlorinated or hydrocarbon solvent. In a modification of the preparation of the alkylolated polyurethane resins the Mannich Base condensate is reacted at 5‹ to 110‹ C. for 1 to 20 hours with at least one aldehyde or substance capable of liberating an aldehyde prior to reaction with the prepolymer and in an amount sufficient to react with one of the available reactive hydrogen atoms present in each of two moles of the Mannich Base condensate so as to form a mole of a bis-Mannich Base condensate. In detailed examples Mannich Base condensates are prepared from diethanolamine, formaldehyde and dicyandiamide, from N-methyl ethanolamine, formaldehyde and lauroguanamine, and from N-methyl ethanolamine, formaldehyde and guanidine carbonate; a bis-Mannich Base condensate is prepared by reacting formaldehyde with a Mannich Base condensate prepared from diethanolamine, formaldehyde and dicyandiamide; polyurethane prepolymers are prepared from polyethylene glycols, tolylene diisocyanate and, in some cases, minor amounts of N-methyl diethanolamine; the latter are reacted with the Mannich and bis-Mannich Base condensates and the products further alkylolated with formaldehyde and optionally converted into acetates. Uses.-For treatment of fibres, textiles, paper and leather. In further examples aqueous solutions of the alkylolated polyurethanes are padded on to cotton fabric and cured thereon to impart improved dyeability; aqueous solutions are admixed with acetic acid, oxalic acid, isopropanol and Pigment Blue, are padded on cotton fabric and cured thereon to give a pigmented fabric; and further aqueous solutions are used as auxiliaries in the retanning of chrome stock leather or for impregnation of bleached kraft sheets to provide after subsequent curing paper having improved burst strength and a higher affinity for dyestuffs.