Patent GB-1404301-A (GB)
Title: Organic addition compounds which contain phosphorus and their use as catalysts for the production of foam resins which contain carbodiimide groups
IPC: C08G18/00
Filed: 1973-09-14
Abstract: 1404301 Polycarbodiimide and polyurethane foams; phospholine-silane complexes BAYER AG 14 Sept 1973 [16 Sept 1972] 43193/73 Headings C3C C3R and C3S [Also in Division C2] The invention comprises addition compounds of (a) a phospholine- or phospholane oxide or sulphide of the formulae wherein R is an alkyl, alkenyl, aryl, aralkyl, alkoxy, or aryloxy radical, which may be substituted; a, b, c, and d, which may be the same or different, each represent a hydrogen atom, a halogen atom, or an alkyl, alkenyl, cycloalkyl, aryl or aralkyl radical, which may be substituted, or any two of a, b, c, and d taken together form a polymethylene or polymethine group which forms a cycloaliphatic ring together with two adjacent carbon atoms of the heterocyclic ring; and X represents an oxygen or sulphur atom; and (b) a mono-, di- and/or polyhydricalcohol with a molecular wieght of 32 to 250, a protonic acid whose N/10 aqueous solution has a pH between 1 and 8, a metal salt or an acid chloride. The protonic acid is preferably a mono-, di,- or polycarboxylic acid having a molecular weight of 46 to 250, or a mineral acid, e.g. HCl, HBr, HI, H 2 SO 4 , boric acid, H 3 PO 4  or phosphorous acid and suitable metal salts include ZnCl 2 , ZnBr 2 , MnCl 2 , CdCl 2 , SbCl 3 , FeCl 3 , LiCl, TiCl 4 , AlCl 3 , LiI, vanadium oxychloride, magnesium chloride, SnBr 2  and SnCl 4 . Suitable acid chlorides include PCl 3 , POCl 3 , SbCl 5 , silicon (IV) chloride, methyl trichlorosilane, methane phosphonic acid dichloride, methane sulphonic acid chloride, ptoluenesulphonic acid chloride and 1-chloro-1- oxo-phospholine. The addition compounds may be obtained by mixing the components (a) and (b) preferably in a molar ratio of 1 : 5 to 5 : 1, and an inert solvent, e.g. benzene, ethyl acetate, acetone, or preferably chloroform may be present. Specified addition compounds include that of 1-methyl-1-oxo-phospholine and methyl trichlorosilane. The products are useful as catalysts for the production of polycarbodiimide type foam resins from polyisocyanates and for this purpose they may be used either alone or in conjunction with known catalysts of conventional type. They may also be used similarly in the production of polyurethanes by including in the polyisocyanate- and catalyst-containing mixture compounds which contain reactive hydrogen atoms, e.g. amino, thiol or carboxyl groups, or especially polyhydroxy compounds particularly those having a molecular weight of 1000 to 6000, e.g. polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester amides containing at least two hydroxy groups. A wide variety of conventional additives for the foam-forming mixture may also be present. The final products are flameresistant and is desired known flame retardants may also be added. Examples (32-40) are given for the production of foamed resins from (1) diphenylmethane diisocyanate, (2) tolylene diisocyanate, (3) a mixture containing (1) and (2), and (4) a prepolymer prepared from tolylene diisocyanate and a polyether containing OH groups, using various of the addition compounds as catalysts.