Patent GB-816651-A (GB)
Title: Improvements in or relating to polymeric polyether-polyurethanes
IPC: C08G18/48
Filed: 1955-12-20
Abstract: The invention comprises a polymeric product comprised essentially of a plurality of structural units having the formula -[-HN-(-B-NH-CO-O-G-O-OC-NH-)-nB-NH-(-Q-HN-B-NH-) -]-wherein -O-G-O- is a bivalent radical resulting from the removal of the terminal hydrogen atoms from a polymeric glycol having a molecular weight of at least 750, the chain G of which consists of a plurality of smaller bivalent hydrocarbon radicals linked to one another by oxygen or sulphur atoms, the majority of said hydrocarbon radicals being alkylene radicals and at least one of the said hydrocarbon radicals containing a carbocyclic ring structure with the proviso that there be at least one alkylene ether segment having a formula weight of at least 500 for each hydrocarbon radical containing a carbocyclic ring structure; B is a bivalent organic radical inert towards isocyanate groups; Q is a carbonyl group or a non-polymeric diacyl radical as defined below; n is an integer greater than zero; and m is an integer including zero; each of the said structural units being connected to the next by a radical Q, and at least 35 per cent of the total weight of the polymer being the bivalent radicals O-G-O.  By a diacyl group is meant the connecting radical between the imino groups of the divalent radical produced when chain extenders (other than water or hydrogen sulphide) react with two free isocyanate groups. Products of the above formula are made reacting a molar excess of an organic diisocyanate with the appropriate glycol to give a product (referred to as an "intermediate polymer") of the formula OCN-B(NH-CO-O-G-O-CO-NH-B)n-NCO which is reacted with a chain extending agent, preferably water or an amine, to give the final product which can be cured with polyisocyanates to give vulcanized elastomers.  Preferably the polymeric glycols have a molecular weight between 1100 and 10,000. The intermediate products can also be prepared by converting the polyether glycols to bis-chloroformates by reaction with phosgene and treating the bis-chloroformates with a primary diamine in water in the presence of an acid acceptor and more phosgene.  Lists of representative polyether glycols and diisocyanates are given.  As chain extending agents (i.e. compounds containing two active hydrogen atoms capable of reacting with isocyanates) water, hydrogen sulphide and compounds with the groups OH, SH, NH, NH2, COOH, CONH2, CONHR, where R represents an organic radical, SO2OH, SO2NH2 and CSNH2 groups are referred to.  If any free isocyanate groups are still left in the final product, it can be stabilized by adding a primary or secondary monoamine.  In this case it may not be necessary to make the addition of further diisocyanate which is usual in effecting curing of the final product.  Films may be prepared from solutions in, e.g. methyl ethyl ketone or tetrahydrofuran, and these, when containing -NCO groups are cured by atmospheric moisture.  In examples polymers are prepared according to the above general methods from polymeric glycols obtained by reacting (1) polytetramethylene ether glycol and 2,21-p-bromo-p-xylene; (2) polytetramethylene ether glycol and hexahydroterephthalyl di-p-toluene sulphonate; (3) tetrahydrofuran and phenylethylene oxide in the presence of fluosulphonic acid; (7) polytetramethylene ether glycol and 1,4 - bis - bromomethyl naphthalene; (8) resorcinol and ethylene oxide; (9) di-(b -hydroxyethyl) thioresorcinol and polytetramethylene ether glycol; (10) polytetramethylene chlorohydrin (obtained by treating tetrahydrofuran with anhydrous hydrogen chloride in the presence of ferric chloride) and 2,21-diphenylolpropane; (11) polytetramethylene ether glycol, butane - 1,4 - diol - ditosyl ester and diphenylolpropane; (12) polytetramethylene chlorhydrin and 4,41-biphenyl dithiol.  Cellular products can be prepared by reacting intermediate polymers containing isocyanate groups and free diisocyanate with water, preferably in the presence of amines such as triethylamine and pyridine.  The products are useful as adhesives, films, sponges, cushions, tyres, tubes, belts, hose, wire covering, footwear and coated fabrics.  Suitable compounding agents are carbon black, clay, silica, talc, zinc and magnesium oxides, calcium and magnesium carbonates, titanium dioxide, plasticisers and inorganic and organic colouring agents.ALSO:1,4-Bis-bromomethyl naphthalene is prepared by reacting naphthalene with HBr and formaldehyde.  Di-(b -hydroxyethyl) thioresorcinol is prepared by reacting thioresorcinol with ethylene chlorohydrin in the presence of sodium ethoxide.