Patent GB-1080590-A (GB)
Title: Polyurethanes
Inventor: DIETERICH DIETER
IPC: C08G18/08
Filed: 1965-12-20
Abstract: Elastic resins containing sulphonium groups are prepared by reacting polyhydroxy compounds with polyisocyanates and, optionally, chain lengthening agents, to give uncrosslinked products which either (a) contain sulphide sulphur atoms which are reacted with monofunctional alkylating agents, or (b) contain ternating halogen atoms or groups R-SO2-O (wherein R is an alkyl or aryl radical) which are reacted with monofunctional sulphides, the ternation taking place during or after the polyisocyanate addition reaction, and the product polyurethane containing more than 1 wt. per cent sulphonium sulphur. Suitable polyhydroxy compounds have M.W. of 400-10,000 and may be e.g. polyethers, polyesters, polyacetals, polyeteramides or polythioethers.  Suitable polyethers are polymerized tetrahydrofuran, ethylene oxide or propylene oxide, or polymers of hexane-diol and/or methylhexanediol and/or heptanediol and/or octanediol which may contain 10-30 wt. per cent of lower glycol residues, or ethoxylated or propoxylated glycols.  Suitable polyacetals may be obtained from 4:41-dihydroxyethoxy - diphenyl - dimethylmethane and formaldehyde or from hexanediol and formaldehyde or divinyl ether.  Polyhydroxy compounds containing sulphur may be obtained by reaction of thiodiglycols with themselves and/or other glycols, or dicarboxylic acids, formaldehydes, aminocarboxylic acids or aminoalcohols. The polyhydroxy compounds may also contain nitrogen, e.g. alkoxylated primary amines or polyesters or polythioethers containing diethanolalkylamine residues, or reactive halogen, e.g. from epichlorhydrin, and may already contain urethane or urea groups. Suitable diisocyanates are 1:5-naphthane-, 4:41-diphenylmethane-, 4:41-diphenylethane-, m or p-phenylene-, 4:41-tetraalkyldiphenyl-methane-, toluylene-, 4:41-dicyclohexylmethane-, tetramethylene-, hexamethylene-, chloromethyl - 2:4 - phenylene-, bromoethyl - 2:4-phenylene- and 3:31-bischloromethyl-4:41- di-phenylene-diisocyanates, or masked diisocyanates, e.g. TDI dimer, or 2:1 products from hexamethylene diisocyanate and thiodiglycol or dihexylolsulphide. Chain lengthening agents may be alkylene glycols, dihydroxyethyl ether of hydroquinone, cyclohexane dimethanol, alkylene and arylene diamines and ethanolamine (lists given) or thiodiglycol, diisopropanol-(2)-sulphide, dihexylol sulphide, bis(b -hydroxy b -phenylethyl) sulphide, S-methylthioglycerol, thiodiglycollic acid, thio-b -dipropionic acid, thio-a -dibutyric acid and bis(hydroxyalkylthio)-hydrocarbons, or N-diethanol-cyclohexylamine, -aniline, -toluidine, or -piperazine. Ternating chain-lentheners may be glycerol-a -chlorohydrin, glycerol monotosylate, pentaerythritol bis - benzenesulphonate and glycerol monomethanesulphonate. The preferred NCO : OH ratio is 0.8-1.4:1.  The reaction may be conducted in e.g. benzene, chlorobenzene, tetrachloroethane, acetone, methylethylketone, dioxane, tetrahydrofuran or ethyl acetate. Suitable monofunctional alkylating agents are MeCl, MeBr, BuBr, Me2SO4, Et2SO4, benzyl chloride, p-nitrobenzyl chloride, benzyl bromide, ethylene chlorohydrin or bromohydrin, epichlorhydrin and p-toluenesulphonic acid esters. When halides are used, e.g. ZnCl2, SnCl4, FeCl3, SbCl5 may be present.  Haloalkyl carboxylates or sulphonates may be used. Monofunctional sulphides include Me2S, Et2S Bu2S, i-Am2S, thiodiglycol, thiodiglycollic acid, dioctyl sulphide, diallyl sulphide, diacetalyl sulphide, diisobutenylsulphide and thio-b -di-propionic acid.  The ternation preferably occurs in a polar solvent, e.g. ethanol, isopropanol, acetone, methylethylketone, dioxan, tetrahydrofuran or acetonitrile.  The monofunctional reactant may comprise up to 50 wt. per cent of the total of polyfunctional reactant of the same type.  After preparation the organic solvent may be completely replaced by water.  There may also be added fillers, e.g. C-black, precipitated silicic acid sols or Al(OH)3 dispersions or clay or asbestos, and plasticizers, e.g. phthalates, and pigments, and cross-linking agents, e.g. sulphur or formaldehyde. In examples polyurethanes from (1) polypropylene glycol/TDI/thiodiglycol, or (2) thiodiglycol/hexamethylene glycol/TDI/diethanolamine are treated with dimethyl sulphate.  Uses.-Pigment binders, sizing and impregnating, e.g. leather and rawhide, adhesives, coatings, films, filaments, moulding, plasticizers, antistatic agents, emulsifiers and dispersants, hair-dressing and wound-sealing agents.