Patent GB-816652-A (GB)
Title: Improvements in or relating to isocyanate-based elastomeric condensation products
IPC: C08G18/10
Filed: 1956-01-25
Abstract: Curable elastomeric condensates are prepared by reacting 1 mol of a polyether glycol of molecular weight 750-2500 with 1-2 mols. of an organic diisocyanate to form a polyurethane having terminal OH groups and a molecular weight not greater than 5510, adjusting the water content of this product to 0.05-0.35 mol. of water per mol. of product and reacting the resultant mixture with an excess of an organic diisocyanate over the stoiochiometrical amount to produce a polymer with terminal isocyanate groups which is then reacted with a chain extender which is water or an organic compound containing two groups in the molecule bearing active hydrogen atoms.  The second lot of diisocyanate may be added in two stages.  The polyether glycols may be derived from ethylene oxides or glycols or heterocyclic ethers, e.g. dioxolane and preferably contain methylene, ethylene or propylene groups. Polyalkyleneether, thioether glycols as described in Specification 791,854 or polyalkylene-arylene-ethers as described in Specification 816,651, may be employed.  A list of suitable organic di-isocyanates is given in the Specification.  The two organic di-isocyanates employed in the process may be the same or different.  Suitable organic chain extenders are carboxylic or sulphonic acids, amines or amides.  Some specific substances are listed.  If water or an acid is used as chain extender, and a porous product is not required the carbon dioxide evolved is removed by mechanically working the reaction product.  The chain-extended reaction product may be stabilized against premature curing by a nitrogen-containing compound such as piperidine or ammonia.  The stabilized polymer may be cured when desired by addition of an organic compound containing at least two isocyanate groups.  In a typical example polytetramethylene ether glycol (average mol. wt. 935) is stirred with 2.4-tolylene diisocyanate at 100-105 DEG  C. Water is added to the resulting urethane in a Werner-Pfleiderer mixer at 70 DEG  C. and more 2,4-tolylene diisocyanate is added with continued mixing at 70-75 DEG  C.  Further water is then added and mixing continued. Piperidine is milled into the rubbery polymer produced.  It may be cured, e.g. in a press at 134 DEG  C., by reaction with N,N-bis(3-isocyanato-4-methylphenyl)urea.  The Specification contains many other detailed examples with comparisons of the effect on the physical properties of variations in the process details and specific nature of the reactants.  In Example 14 the preparation of a polyether-thioether glycol by splitting out water from an equimolecular mixture of thiodiglycol and 1.4-butanediol is described.  The mixture is refluxed with benzene and p-toluenesulphonic acid, the catalyst neutralized and the polymer recovered for use in the process of the invention.  The products may be used for tyres, belts, hose and tubing, wire and cable jackets, footwear, sponges, coated fabrics or coated or moulded articles. Conventional compounding ingredients, e.g. carbon black, clay, silica, talc, zinc or magnesium oxide, calcium or magnesium carbonate, titanium dioxide, plasticisers, and colouring agents may be incorporated with the products.