Patent GB-810489-A (GB)
Title: Synthetic rubber-like materials
Inventor: WATTS JOHN THOMAS
IPC: C08G18/60
Filed: 1956-01-20
Abstract: A process for the manufacture of synthetic rubber-like materials comprises shaping a solution of a linear polyester or polyesteramide and an isocyanate adduct which on heating decomposes to form an isocyanate with at least two free isocyanate groups, removing the solvent therefrom and heating the shaped composition.  The polyester or polyesteramide may first be modified by a limited treatment with an organic diisocyanate such that it continues to be soluble in organic solvents, or be subjected to a masticating treatment such as described in Specification 572,738 to ensure its solubility.  The amount of diisocyanate used in the modifying treatment is preferably such that between 0.9 and 1.5 isocyanate groups are added for each isocyanate-reactive group and the maximum Williams Plasticity Number on heating is between 200 and 400.  The isocyanate adduct may be the reaction product (containing no free isocyanate groups) of phenols containing alkyl, cycloalkyl, aralkyl, aryl, alkoxy, nitro, cyano, carbalkoxy, acyl or alkyl sulphonyl groups or halogen atoms, or of succinimide, N-methylacetamide, isopropanol or N-ethyl-p-toluene-sulphonamide with di- or tri-isocyanates, a number of which are listed.  Suitable solvents and diluents specified are acetone, methylethyl ketone, methylisopropyl ketone, cyclohexanone, ethylene dichloride, chloroform, trichlorethylene, tetrachlorethane, dimethyl formamide, methyl and ethyl ethers of ethylene glycol, nitroethane, diacetone alcohol, ethylene glycol monoacetate ethyl ether, ethylene glycol diacetate, benzyl benzoate, mixtures of benzene or toluene with ethanol or methanol, ethyl acetate, carbon tetrachloride, ethanol, methyl acetate and xylene.  To accelerate curing an organic tertiary amine, e.g. triethylamine, dimethylcyclohexylamine, dimethyldodecylamine or quinoline may be present in the composition.  There may also be added carbon black, clay, blanc fixe, calcium silicate, silica, titanium dioxide, vulcanized vegetable oils, dibutyl phthalate, tricresyl phosphate, paraffin wax and pigments.  In producing films cellulose derivatives and the acetal of polyvinyl alcohol may be admixed by the methods described in Specifications 585,205 and 585,083, respectively.  The products can be used for coating metals, and fabrics and webs of natural and synthetic fibres.  By coating a rotating drum a sheet is obtained which yields a thread by cutting spiral-wise.  With or without admixture of phenol-formaldehyde resins or synthetic rubbers the compositions can be used as adhesives.  Examples describe solutions comprising (1) rubber-like material from polyethylene adipate and naphthylene-1 : 5-diisocyanate, a phenol/naphthylene-1 : 5-diisocyanate adduct containing no free isocyanate group, and a toluene/ethanol mixture; (2) to (5), and (8) to (10), the same rubber-like material used in Example (1) together with (2) an adduct of naphthylene-1 : 5-diisocyanate and p-chlorophenol, and acetone; (3) an adduct of naphthylene-1 : 5-diisocyanate and succinimide, and acetone; (4) an adduct of p-phenylene diisocyanate and phenol, and acetone; (5) an adduct of phenol and 2 : 4 : 41-triisocyanatodiphenyl, and acetone; (8) a phenol/naphthylene-1 : 5-diisocyanate adduct, cellulose acetate and acetone; (9) a phenol/naphthylene - 1 : 5 - diisocyanate adduct, nitrocellulose and acetone; (10) a phenol/naphthylene - 1 : 5 - diisocyanate adduct, ethylene dichloride and the acetal of polyvinyl alcohol.  In Example (7) there is prepared a solution in acetone of a polyesteramide from ethylene glycol, ethanolamine and adipic acid and an adduct of phenol with hexamethylene diisocyanate.  The products are applied to glass and cured to form films.  In Example (6) the composition of (5) is formed into a balloon.  Specifications 553,733, 579,340, 718,218, 738,883, 747,607 and 764,509, [Group XXVIII]; are also referred to.ALSO:Adducts of isocyanates for use in the preparation of polyurethanes (see Group IV (a)) are prepared by reaction with phenol, phenol containing substituents such as alkyl, cycloalkyl, aralkyl, aryl, alkoxy, halogen, nitro, cyanocarbalkoxy, acyl or sulphonyl groups or combinations thereof, or with succinimide, N-methyl-acetamide, isopropanol or N-ethyl-p, toluenesulphonamide. Specified isocyanates are hexamethylene, diphenylmethane - 4:41, 3:31 - dichlorodiphenylmethane - 4:41, diphenyl - 4,41-, diphenyl ether - 4,41, naphthylene-1:5, m- or p-phenylene, dicyclohexylmethane, xylylene, chlorophenylene, 3:31 - dimethyldiphenylene - 4,41, 3:31 - dimethoxydiphenylene - 4,41, and 3:31 - dimethyldiphenylmethane - 4:41 -, diisocyanates; benzene - 1:3:5, toluene - 2:4:6, diphenyl-2:4:41 and triphenylmethane - 4:41:411 - triisocyanates; and the diisocyanato-carbanilides obtained by reacting diisocyanates with limited amounts of water, e.g. 3,31-diisocyanato-4,41-dimethylcarbanilide or 3:31-diisocyanato-4:41-dichlorcarbanilide.  Examples describe the preparation of adducts by reacting (1) naphthylene-1:5-diisocyanate and phenol; (2) naphthylene - 1:5 - diisocyanate and p - chlorophenol; (3) diphenylene - 4:41 - diisocyanate and succinimide; (4) phenol and p-phenylenediisocyanate; (5) phenol and 2:4:41-triisocyanatodiphenyl.  Specifications 553,733, 572,738, 579,340, 585,083, 585,205, [718,218, 738,883, 747,607, [all in Group IV (a)], and 764,509, [Group XXVIII], are referred to.