Patent GB-869988-A (GB)
Title: Catalytic process for the reaction of organic isocyanates with hydroxyl group-containing substances
Inventor: TWITCHETT HARRY JAMES
IPC: C08G18/22
Filed: 1958-04-25
Abstract: A process for the manufacture of urethane group-containing materials by reacting organic isocyanates with hydroxyl group-containing substances is characterized in that the reaction is performed in the presence of a complex of a b -diketone with manganese, thorium, titanium or zirconium.  The complexes may be formed by reacting an aqueous solution of a salt of the metal, with a b -diketone, such as acetyl-acetone, benzoylacetone, dibenzoylmethane, propionyl-acetone, trifluoroacetylacetone, 3-ethylacetyl-acetone, 3-cyanoacetyl-acetone and 2-thenoyl-acetone.  The catalysts may be used in admixture with p other catalysts, e.g. tertiary amines.  The process is of use in the manufacture of foamed or non-foamed polyurethanes from diisocyanates (with which may be mixed triisocyanates) and polyethers, polyesters or polyesteramides.  The polyesters can be prepared from succinic, adipic, glutaric, suberic, azelaic, sebacic, alkyladipic, citric, phthalic, isophthalic, terephthalic and trimesic acids, and the polybasic acids obtained by polymerization of unsaturated long-chain fatty acids.  Monobasic acids and ricinoleic and dihydroxystearic acids can also be used. Glycols and higher polyalcohols for the ester preparation are listed.  Ethylene diamine, hexamethylene diamine, ethanolamine, phenyldiamines and benzidine can be used in preparing the polyesteramide.  The polyethers may be those prepared by the processes described in Specification 733,624 or those obtained by adding an alkylene oxide or succession of alkylene oxides with water, diols, glycerol, trimethylolpropane, triethanolamine, polyallyl alcohol, ethylene diamine, 3-hydroxymethylcyclobutane, glycidol, ricinoleic acid, dihydroxystearic acid and carbohydrates and their partially esterified or etherified derivatives. Reaction of a polyisocyanate with a hydroxyl-containing compound from a polyisocyanate and a hydroxy-compound can also be catalysed.  In Examples (3) phenyl isocyanate and polypropylene glycol are reacted in the presence of bis-(2 : 4-pentanediono) manganese (II); (9) polypropylene glycol, water, and toluene-2, 4 and 2, 6-diisocyanates containing a small proportion of ethyl cellulose are reacted in the presence of tris-(2 : 4-pentanediono) manganese (III) to give a foamed product; (11) a polyester from glycerol, adipic acid and ethylene glycol, is mixed in cyclohexanone and methyl ethyl ketone with 2 : 4-tolylene diisocyanate.  The gelation time of the lacquer on adding the following catalysts is given: dimethylcyclohexyl amine, bis-(2 : 4-pentanediono) manganese (II), tris-(2 : 4-pentanediono) managnese (III), bis-(1 : 3-diphenyl-1 : 3-diono) manganese(II), tetra-kis-(2 : 4-pentanediono)-zirconium (IV), tetra-kis-(3-cyano-2 : 4-pentanediono)-zirconium (IV), tetrakis-(2 : 4-pentanediono) thorium (IV), and a mixture of tetrakis-2 : 4-pentanediono) zirconium (IV) and dimethylcyclohexylamine; (12) A foam is prepared by mixing a glycerol-propylene oxide reaction product, a pyridine solution of bis-(2 : 4-pentanediono) manganese (II), an octylphenol-ethylene oxide reaction product, the sodium salt of sulphonated methyl oleate and water, and adding a diphenyl-methane diisocyanate, obtained by phosgenating an aniline/formaldehyde reaction product.ALSO:A process for the manufacture of urethane group-containing materials by reacting organic isocyanates with hydroxyl group-containing substances is characterised in that the reaction is performed in the presence of a complex of a beta-diketone with manganese, thorium, titanium or zirconium.  Examples of b -diketones are acetylacetone, benzoylacetone, dibenzoylmethane, propionylacetone, trifluoroacetylacetone, 3-ethylacetylacetone, 3-cyanoacetyl acetone and 2-thenylacetone. In Example (1) an aqueous ammoniacal solution of acetylacetone is reacted in a nitrogen atmosphere with manganese acetate to give bis-(2:4-pentanediono) manganese (II).  In further examples there are reacted (4) aqueous manganese acetate and ethanolic dibenzoylmethane; (5) acetylacetone and thorium nitrate; (6) zirconyl chloride (ZrOCl2) and acetyl-acetone ;(7) titanic chloride and acetylacetone; (8) acetylacetone and tetra-isopropyl orthotitanate (to give a product diisopropoxy-bis-(2:4-pentanediono) titanium (IV).  The products are used in preparing polyurethanes (see Group IV(a) and also in accelerating the reaction between phenyl isocyanate and (1) glycol, (2) n-butanol (3) polypropylene glycol. Specification 733,624 is referred to.ALSO:A process for the manufacture of urethane group-containing materials such as polyurethane foams by reacting organic isocyanates with hydroxyl group-containing substances is characterised in that the reaction is performed in the presence of a complex of a b -diketone with manganese, thorium, titanium or zirconium.  The complexes may be formed by reacting on aqueous solution of a salt of the metal, with a b -diketone, such as acetyl-acetone, benzoylacetone, dibenzoylmethane, propionylacetone, triflouroacetylacetone, 3-ethylacetylacetone, 3-cyanoacetylacetone and 2-thenoylacetone.  The catalysts may be used in admixture with other catalysts e.g. tertiary amines.  The polyurethanes are prepared from diisocyanates (with which may be mixed triisocyanates) and polyethers, polyesters or polyesteramides.  The polyesters can be prepared from succinic, adipic, glutaric, suberic, azelaic, sebacic, alkyladipic, citric, phthalic, isophthalic, terephthalic and trimesic acids, and the polybasic acids obtained by polymerisation of unsaturated long-chain fatty acids.  Monobasic acids and ricinoleic and dihydroxystearic acids can also be used.  Glycols and higher polyalcohols for the ester preparation are listed.  Ethylene diamine, hexamethylene diamine, ethanolamine, phenyldiamines and benzidine can be used in preparing the polyesteramide.  The polyethers may be those prepared by the processes described in Specification 733,624 or those obtained by adding an alkylene oxide or succession of alkylene oxides with water, diols, glycerol, trimethylpropane, triethanolamine, polyallyl alcohol, ethylene diamine, 3-hydroxymethylcyclobutane, glycidol, ricinoleic acid, dihydroxystearic acid and carbohydrates and their partially esterified or etherified derivatives.  In Examples (9) polyproylene glycol, water, and toluene -2,4 and 2,6 diisocyanates containing a small proportion of ethyl cellulose are reacted in the presence of tris-(2: 4- pentanediono) manganese (III) to give a foamed product; (12) A foam is prepared by mixing a glycerol-propylene oxide reaction product, a pyridine solution of bis-(2: 4-pentanediono) manganese (II), an octylphenolethylene oxide reaction product, the sodium salt of sulphonated methyl oleate and water, and adding a diphenylmethane diisocyanate, obtained by phosgenating an amiline/formaldehyde reaction product.  Other catalysts mentioned are tetrakis-(2: 4-pentanediono)zirconium (IV), bis-1 : 3-diphenyl-1 : 3-diono) manganese (II), tetrakis-(3-cyano-2: 4-pentanediono) zirconium (IV), tetrakis-(2: 4-pentanediono) Thorium (IV), and a mixture of tetrakis-(2: 4-pentanediono) zirconium (IV) and dimethylcyclohexylamine.