Patent GB-1256387-A (GB)
Title: Ester-containing polyols and use in preparation of urethane compositions
IPC: C07H15/06
Filed: 1969-05-09
Abstract: 1,256,387. Ester-containing polyols; polyurethane foams. MARLES-KUHLMANNWYANDOTTE S.A. 9 May, 1969 [13 May, 1968], No. 23809/69. Headings C3C and C3R. An ester-containing polyol is prepared by reacting together at temperatures not exceeding 150‹ C. a polyhydroxy-containing compound, an acid or oxide of phosphorus, a halogen-containing organic acid anhydride and an alkylene oxide in an amount such that the reaction mixture has an acid number of less than 5. Polyhydroxy starting compounds include polyhydroxy-containing polyesters obtained from polycarboxylic acids and polyhydric alcohols such as alkylene diols and triols, alpha-methylglucoside, pentaerythritol, sorbitol and Bisphenol A; polyalkylene polyether polyols such as those obtained from the above-specified polyhydric alcohols and alkylene or aralkylene oxides or block copolymers thereof, tetrahydrofuran, alkylene oxide-tetrahydrofuran copolymers, and epihalohydrins; polyhydric polythioethers such as those obtained by reacting alkylene oxides with condensation products of thioether glycols or with reaction products of thioether glycols with the above-specified polyhydric alcohols ; polyhydroxy-containing polyester amides such as those obtained by substituting aminoalcohols or a proportion of diamines for the polyhydric alcohols used for the preparation of the above polyhydroxy-containing polyesters ; polyhydroxy-containing phosphorus compounds such as those obtained from alkylene oxides and acids of phosphorus; polyhydroxycontaining polyacetals such as those obtained by condensing an alkylene oxide with reaction products of aldehydes and dihydric alcohols or alkylene oxides; polyhydroxy-terminated polyurethane polymers ; and polyhydroxy-containing adducts of alkylene oxides and aliphatic thiols or aliphatic and aromatic amines. Acids or oxides of phosphorus include ortho-, meta-, pyro- and tripoly-phosphoric acids, phosphorous acid, phenyl, hydroxymethyl and chloromethyl phosphoric acids, phenyl and methyl phosphinic acids, phosphinous acid, phosphorus pentoxide, diphosphorus trioxide, aminotri - (methylphosphonic)anhydride and mixtures thereof. Halogen-containing organic acid anhydrides include dichloromaleic, tetrabromophthalic, tetrachlorophthalic, chlorendic, 1,4,5,6,7,7-hexachloro-2-methyl-bicyclo ( 2, 2,1 )-5-heptene-2,3-dicarboxylic, 1,4,5,6,7,7-hexachlorobicyclo(2,2,1) 5 - heptene - - 2 -acetic - 2 - carboxylic, 5,6,7,8,9,9- hexachloro - 1,2,3,4,4a,5,8,8a - octahydro - 5,8- methano - 2,3 - naphthalene dicarboxylic and 1,2,3,4,5,6,7,7 - octachloro - 3,6 - methano- 1,2,3,6-tetrahydrophthalic anhydrides, or mixtures thereof. The above anhydrides may also be used in admixture with non-halogenated anhydrides such as phthalic, maleic and trimellitic anhydrides. Alkylene oxide reactants include ethylene, propylene, alkoxypropylene, butylene, hexylene, octylene, dodecene, styrene and cyclohexene oxides, epihalohydrins, 3,3-dichloropropylene oxide, 3-chloro- 1,2-epoxypropane, 3-chloro-1,2- epoxybutane, 1-chloro-2,3-epoxybutane, 3,4- dichloro - 1,2 - epoxybutane, 1,4 - dichloro - 2,3 - epoxybutane, 1 - chloro - 2,3 - epoxybutane and 3,3,3-trichloropropylene oxide. The polyhydroxyl-containing compound, phosphorus compounds and halogenated carboxylic anhydride are preferably first reacted at 25‹ C. to 150‹ C. in a ratio ranging from 1 : 0.1 : 0.1 to 1 : 3 : 12, and sufficient alkylene oxide is then added at temperatures of 75‹ to 150‹ C. to reduce the hydroxyl number of the intermediate product to five or less. The ester-containing polyols may be subsequently reacted with isocyanates to form polyurethanes, if desired in the form of a foam. In examples ester-containing polyols are prepared from (1) tetrabromophthalic anhydride, propylene oxide, .phosphorus pentoxide and a mixture of oxypropylated sucrose and a phosphate polyol derived from phosphoric acid and propylene oxide.; (2) tetrabromophthalic anhydride, propylene oxide, 115% phosphoric acid and oxypropylated sucrose; (3) tetrabromophthalic anhydride, propylene oxide, 115% phosphoric acid and oxypropylated ethylene diamine; (4) tetrachlorophthalic anhydride, propylene oxide, phosphorus pentoxide and polypropylene glycol in the presence of a tri-n-butylamine catalyst; (5) the ingredients of (4) using tetrabromophthalic anhydride in place of tetrachlorophthalic anhydride; and (6) tetrabromophthalic anhydride, propylene oxide, phosphorus pentoxide and a polyalkylene ether triol (obtained from glycerine and propylene oxide) in the presence of a tri-n-butylamine catalyst. The products of the examples are further converted into polyurethane foams, optionally after admixture with conventional polyols. Uses.-In polyurethane foams, adhesives, binders, laminates and coatings.