Patent GB-990632-A (GB)
Title: Processes for the preparation of urethane group-containing materials
Inventor: TWITCHETT HARRY JAMES
IPC: C08G18/16
Filed: 1961-03-06
Abstract: Urethane group containing materials are produced by reacting aliphatic or aromatic isocyanates with hydroxyl group containing compounds in the presence of a tertiary amine and a zinc salt of a thio-acid of phosphorus of the formula <FORM:0990632/C2/1> or <FORM:0990632/C2/2> wherein Z is an hydrozyl or thiol radical, and wherein (a) X and X1 are substituted or unsubstituted hydrocarbon radicals, or (b) X and X1 together form an alkylene radical which may contain a hetero-atom and which together with the remainder of the thio-acid molecule forms a ring containing 4 to 8 carbon atoms, or (c) X is an hydrocarbon radical and X1 is a radical of the formula (-A-T-)nX, wherein A is an alkylene or arylene radical or an alkylene radical interrupted by hetero-atoms and T is the radical formed by the removal of the radicals X and X1 from the thio-acid concerned and n is an integer. A complex of the amine and zinc salt may be used. In examples butanol and phenyl isocyanate are reacted in the presence of the complex of 1 molecule of zinc dinonyldithiophosphate and 2 molecules of 4-dimethylaminopyridine with or without additional amine using the dimethyl ether of diethylene glycol or acetone as the solvent.  A diester of dithiophosphoric acid of the formula <FORM:0990632/C2/3> wherein R is an alkylpolyoxyalkylene radical is made by reacting phosphorus pentasulphide with the alcohol of molecular weight 350 obtained by reacting butanol (in the presence of potassium n-butoxide as catalyst) with a mixture of equal parts by weight ethylene and propylene oxide.  A zinc salt of dithiophosphoric acid diester is obtained by reacting the above described diester with zinc oxide in chloroform whilst removing the water formed by azeotropic distillation.  Specification 937,882 is referred to.ALSO:Polyurethanes are produced by reacting organic polyisocyanates with polyethers and/or polyesters and/or polyamides in the presence of a tertiary amine and a zinc salt of a thio-acid of phosphorus of the formula <FORM:0990632/C3/1> or <FORM:0990632/C3/2> wherein Z is an hydroxyl or thiol radical and wherein (a) X and X1 are substituted or unsubstituted hydrocarbon radicals, or (b) X and X1 together form an alkylene radical which may contain a hetero-atom and which together with the remainder of the thio-acid molecule forms a ring containing 4 to 8 carbon atoms, or (c) X is a hydrocarbon radical and X1 is a radical of the formula (-A-T-)nX, wherein A is an alkylene or arylene radical or an alkylene radical interrupted by hetero-atoms and T is the radical formed by the removal of the radicals X and X1 from the thio-acid concerned and n is an integer. A co-ordination complex of the zinc salt and the amine may be used in place of the separate components.  The catalysts of the invention may be used in conjunction with other catalysts such as organic compound of iron, manganese, tin, antimony and lead, the use of dibutyltin carboxylates in the preparation of foams lead to improved heat stability and stannous carboxylates to lower density.  The reaction may be performed in solution to yield lacquers or in the presence of blowing agents such as water or volatile inert liquids to yield foams.  Surfaceactive agents, flame-retardants, plasticizers, colouring matters, fillers and antioxidants may also be present. Specification 937,882 is referred to.