Patent GB-881635-A (GB)
Title: Improvements relating to elastomeric compositions and articles comprising them
IPC: C08K5/17
Filed: 1958-12-18
Abstract: The invention comprises a composition comprising a fibre-forming or film-forming ureylene-containing polyurethane elastomer and, as a stabilizing agent, at least 1% each (of the weight of the elastomer) of titanium dioxide and of an aliphatic amine or at least 1% (of the weight of the elastomer) of an aliphatic amine of M.W. at least 280. (Such polyurethanes contain a proportion, especially 1-10%, of ureylene radicals, i.e. -NH,CO,NX-, especially -Ar,NH,CO,NX, X being hydrogen or a mono-valent organic radical and Ar being a divalent aromatic nucleus).  By "aliphatic amine" is meant an amine in which the amino group or groups are not attached directly to an aromatic nucleus.  Preferred are macromolecular amines such as polyethylene imine, poly(N,N-diethyl-b -amino-methacrylate) (DEAM), the corresponding dimethyl polymer (DMAM), urea-formaldehyde resins and dihydro-abietylamine.  Some of the stabilizing amino groups may be present as part of the elastomer macromolecules.  The elastomeric component preferably contains alternating soft and hard segments. "Soft segment" denotes the radical remaining on removal of the hydroxyl groups from a hydroxyl-terminated polymer melting below 60 DEG C. and having a second order transition temperature below room temperature.  "Hard segment" means a divalent organic radical such that, if it were part of a homopolymer of fibre-forming molecular weight, the melting point of the polymer would be above 250 DEG C. The compositions of the invention can be cast into films or dry-spun from solution in N,N-dimethyl-formamide or -acetamide, N-methyl-pyrrolidone, dimethyl sulphoxide or tetramethylene sulphone. In Example (1) polytetramethylene glycol (M.W. 1000) is reacted with half a molecular proportion of 2,4-tolylene diisocyanate.  The product ("dimer") is reacted with two molecular proportions of bis-(4-isocyanatophenyl) methane, N,N-dimethylformamide is added to the resulting "capped dimer" and the latter is chain-extended with hydrazine hydrate in dimethylformamide.  The resulting polymer has an inherent viscosity of 1,3 to 1,6 in hexamethyl phosphoramide.  To the product are added slurry and solution, respectively, in dimethyl formamide, of titanium dioxide and DEAM and the solution is dry-spun as 15 filament yarn in a column heated to 250 DEG C., at the bottom of which the filaments are allowed to coalesce to a monofilament of 300-400 denier.  In other examples the stabilizers are mixtures of titanium dioxide with (3) DMAM; (4) dihydroabietyl amine; (5) polyethylene imine; (6) butylated urea-formaldehyde resin.  In further Examples (7) one mole of a "trimer" from 2 moles of 2,4-tolylene diisocyanate and 3 moles of poly(tetramethylene ether) glycol is reacted with 2 moles of 2,4,6-trimethyl-1,3-phenylene diisocyanate.  The product is chain extended with hydrozine hydrate and stabilized with DEAM alone and with titanium dioxide; (8) "dimer" of ex. (1) is reacted with methylene-bis(4-phenylisocyanate), the product is chain-extended with N,N1-diaminopiperazine, titanium dioxide and DEAM, separately and together, are added to portions of the polymer and the mixtures are spun; (9) copolyester from ethylene and propylene glycols and adipic acid, methylene-bis(4-phenylisocyanate), and hydrazine hydrate are employed to give in a similar manner polymers which are then stabilized and spun; (10) "dimer" as in (1) is capped with methylene-bis(4-phenylisocyanate) and the capped dimer is chain-extended with p,p1-methylenedianiline.  Stabilization is effected by adding titanium dioxide, DEAM and acetic acid to the solution in dimethyl-formamide before dry-spinning. Specification 849,154 is referred to.