Patent GB-808633-A (GB)
Title: Improvements in or relating to the preparation of polyurethane elestomers
IPC: C08L75/08
Filed: 1956-05-18
Abstract: A process of curing a stable, uncured polyurethane elastomer and which consists essentially of structural units having the general formula -[-HN-(-B.NH.CO.OGO.OC.NH-)-n B.NH.-(-Q.NH.B.NH)m-]- (wherein -OGO-is a bivalent radical resulting from the removal of the terminal hydrogen atoms of a glycol of molecular weight at least 750 having its hydroxyl groups at the end of a chain of polymeric structure, B is a bivalent organic radical inert to isocyanate groups, Q is a carbonyl group or a non-polymeric diacyl radical, n is an integer greater than zero, and m is an integer or zero, each of the said structural units being connected with each other by a radical Q as above defined), comprises incorporating therewith from 5 to 20 per cent by weight of a compound having the general structure <FORM:0808633/IV (a)/1> wherein R is an arylene radical, R1 is a polyalkylene ether glycol residue obtained by removing the terminal hydroxyl groups from a polyalkylene ether glycol having a molecular weight of at least 500 and p is a small whole number between 1 and 5 inclusive, thereafter incorporating from 1 to 20 per cent by weight of a diisocyanate curing agent and heating the mixture until a cured elastomer is formed.  As a modification the mixture is allowed to stand at room temperature until curing has taken place.  The diisocyanate terminated polymer which is added to the polyurethane elastomer as a processing additive is prepared by reacting a polyalkylene ether glycol (preferably of molecular weight 750 to 3500) with excess of an arylene diisocyanate.  Suitable reactants are polytetramethylene, polytetraethylene and poly-1,2-dimethylethylene ether glycols and also those derived from the polymerization of cyclic ethers, and suitable diisocyanates are tolylene and 4-tertiary-butyl, 4-methoxy, 4-propyloxy, 4-chloro, 4-bromo and 4-phenoxy-m-phenylene diisocyanates.  The polyurethane elastomers which can be cured include those described in Specification 796,041, prepared by reacting a polyalkylene ether glycol, a diisocyanate and a chain-extending agent.  If the elastomer is to be stored before curing it can be stabilized by adding a primary or secondary nitrogen base, as described in Specification 791,853.  Suitable chain-extending agents are 2,4-tolylene diamine, ethylene diamine, ethylene glycol, adipamide, p-aminobenzoic acid, ethanolamine, 1,4-cyclohexane - disulphonamide, succinic acid and hydroxypropionic acid.  The polyalkylene ether glycols may also contain arylene or cycloalkylene radicals in addition to the alkylene radicals.  Other suitable glycols for the preparation of the curable elastomers are those of the formula HO(QY)rH, in which Q represents hydrocarbon radicals, at least some being alkylene, Y represents halogen atoms of which some are sulphur and the rest oxygen and r is an integer such that the glycol has a molecular weight of at least 750.  As glycols yielding the radicals -O-G-O there may also be used urethane elastomers prepared by reaction of a diisocyanate and a chain extending agent with a long chain compound having a molecular weight of at least 750 and having at each end a functional group terminating in an hydroxyl group, the functional groups being connected by a hydrocarbon or halogen-substituted-hydrocarbon chain.  Also included in the polyurethane elastomers which may be cured are those obtained by reacting a polyester, a diisocyanate and a chain-extending agent; and elastomers prepared by the process of Specification 796,042.  As diisocyanate curing agents there can be used 1,3-bis-(3-isocyanato-p-tolyl)-urea, 4,41-methylene di-o-tolylisocyanate, 2,4-tolylenediisocyanate or its dimer or m-phenylene diisocyanates having as 4-substituent a tertiary butyl, methoxy, propyloxy, chloro, bromo or phenoxy substituent. As compounding agents carbon black, clay, silica, talc, zinc, calcium and magnesium oxides, titanium dioxide, plasticisers and colouring matter are suitable.  In examples (1) to (4) the elastomer is prepared from polytetramethylene glycol and 2,4-tolylene diisocyanate, the diisocyanate additive is prepared by reacting one molar proportion of polytetramethylene ether glycol (M.Wt. 2400) with two molar proportions of tolylene 2,4-diisocyanate, and these two materials together with 1,3-bis-(3-isocyanato-p-tolyl urea are milled together and then cured in moulds.  Example 5 employs a polytetramethylene ether glycol / 2,4 - tolylene diisocyanate reaction product chain-extended with m-tolylene diamine as the initial elastomer in a similar process.