Patent GB-889204-A (GB)
Title: Synthetic elastomers
IPC: C08G18/68
Filed: 1958-10-31
Abstract: The invention comprises an elastomeric reaction product resulting from the reaction of approximately equal molecular parts of (A) an organic diisocyanate and (B) at least one linear polymer prepared from at least one dicarboxylic acid containing at least three carbon atoms and at least one complementary reactant selected from glycols, amino alcohols, primary diamines, secondary diamines and dithiols, the linear polymer having an acid number not greater than 5 and an average molecular weight of from 900 to 5,000, at least one linear polymer and/or the diisocyanate containing a radical having a pendant group which exhibits ethylenic unsaturation attached thereto, the total number of said groups in the elastomeric reaction product being at least one for each 6,000 units of molecular weight of the elastomeric reaction product.  "Pendant group" means a group which is extra-linear in the sense of not being located within the main polymer chain but rather located in a position pendant from the main polymer chain. The elastomer can be prepared by heating the mixture of (A) and (B), pouring the reaction mixture in a container and heating it while protecting it from contact with the atmosphere. There can also be employed a process in which the reaction mixture includes a third component (C) (added at the same time as, or subsequent to the partial reaction of (A) and (B)) of the formula X-R(Z)-Y in which R is an organic radical inert with respect to the isocyanate groups X and Y are selected from -NH2; -NH; =NH; -OH; -COOH and -SH and Z is -CH2=CH2, -(CH2)n-CH=CH2 in which n is a whole number from 3 to 10, -OCH2-CH=CH2, -CH2-O-CH2-CH=CH2, -CH2-O-CH2-C(CH3)=CH2, -S-CH2-CH=CH2 or -CH2-S-CH2-CH=CH2, the third ingredient being employed in an amount to provide all or part of the pendant groups present in the elastomeric product.  As a further modification the hydroxyl-terminated polyester from (A) and (B) is reacted with an acid anhydride containing the unsaturation and the acid-terminated polyester thus formed is reacted with ethylene oxide to produce a hydroxyl terminated polyester containing the desired unsaturation which is reacted with an approximately equal molecular amount of diisocyanate.  The products can be stabilized with ethyl p-aminobenzoate or phenyl betanaphthylamine. Catalysts for the esterification and chain-extension reactions are magnesium oxide and compounds obtained by the reaction of titanic acid esters with polyhydroxy, polycarboxylic and hydroxy carboxylic compounds.  The products can be cured by sulphur vulcanization or with peroxides. Carbon black is a suitable reinforcing agent for the cured material. In typical Examples (1), (13) and (14) a hydroxypolyester (M.W. 1,870) prepared from adipic acid, ethylene glycol and glycerol-alpha-allyl ether is reacted with 4,41-tolidine diisocyanate, phenyl-beta-naphthylamine is added and the product is baked to give a rubber.  This is mixed on a rubber mill with mercaptobenzthiozyl disulphide, mercaptobenzthiazole, sulphur and furnace black, and the mixture is heated to effect vulcanization; (2) an unvulcanized product is prepared by reacting an adipic acid/glycol polyester-tolylene diisocyanate prepolymer with glycerol-alpha-allyl ether and is cured as in (1); (3) a glycol/propylene glycol/adipic acid polyester, tolidine diisocyanate and erythrol are employed in a similar process; (5) a similar prepolymer is further reacted with bis-hydroxyethyl allyloxy succinate; (7) bishydroxyethyl n-octenyl succinate; (8) allyl ethylene glycol; (11) pentaerythritol diallyl ether; (12) vinyl-cyclohexane-diol are employed similarly; unsaturation is introduced into the elastomer, similarly to (1), by the reaction of polyester, polyisocyanate and (9) bis(hydroxyethyl)allylamine; (10) N,N-diallyl melamine.  Other unsaturated compounds including thiols are listed.  Diisocyanates containing pendant unsaturation can be prepared from such amines as 4-allyloxy-m-phenylene diamine.  In preparing the initial polyesters amino-alcohols and diamines may replace part of the glycols.  The products can be used for tyres, belts, hose, packing, gaskets, mouldings, floor-mats, tank-lining, soles, heels and covered rolls.