Patent GB-886636-A (GB)
Title: New organic manganese complexes and their use in preparing urethanes
Inventor: O'MANT DERRICK MICHAEL
IPC: C07F13/00
Filed: 1959-06-19
Abstract: Polyurethanes are prepared by reacting mono- or polyisocyanates with mono- or di-glycerides, unsaturated oils such as castor oil, glycols such as tetramethylene glycol, or hydroxyl group-containing polymers such as polyesters, polyesteramides or polyethers, the reaction being catalyzed by basic co-ordination complexes of divalent manganese with a b -diketone and a fully 4-N-substituted 4-aminopyridine.  Specified components of the complexes are acetylacetone, benzoylacetone, dibenzoylmethane, propionylacetone, trifluoroacetone, 4-dimethylaminopyridine, 4-diethyl-aminopyridine, 4-piperidinopyridine and 4-morpholinopyridine.  Polyisocyanates mentioned are tolylene -2:4-diisocyanate, mixtures of tolylene -2:4- and -2:6- diisocyanates, arylmethane diisocyanates such as diphenylmethane diisocyanates, m- and p-phenylene diisocyanates and chlorophenylene-2:4-diisocyanate; triisocyanates may be used admixed with diisocyanates, for example 2:4:6-triisocyanatotoluene, 4:41:411-triphenylmethane triisocyanate, 2:4:41-triisocyanatodiphenyl ether and polymers of tolylene -2:4-diisocyanate.  The polyisocyanates may be partially polymerized or may be modified by treatment with polyhydric alcohols such as trimethylolpropane. Mixtures of polyisocyanates may be used, including the products obtained by phosgenating the polyamine reaction products of formaldehyde with one or more aromatic primary amines such as aniline and o-toluidine.  The polyesters or polyesteramides may be made from dicarboxylic acids and glycols and, as necessary, diamines, amino-alcohols and polyhydric alcohols.  Polyethers mentioned are linear and branched hydroxylended polymers or copolymers of cyclic oxides, especially of 1:2-alkylene oxides such as ethylene oxide propylene oxide, 1:2- and 2:3-butylene oxides, epichlorhydrin, oxacyclobutane, substituted oxacyclobutanes and tetrahydrofuran (see for example Specification 733,624).  The preparation of the polyurethanes may be carried out in the presence of additives such as fillers, plasticizers, flame-proofing agents, antioxidants, surface-active agents such as polysiloxanes and oxyethylated fatty alcohols, and gas-forming agents such as fluoroalkanes, which may be used with or without water.  The polyurethanes may be prepared in the form of shaped cellular or homogeneous elastomers, rigid and semi-rigid products, as well as surface coatings and adhesives.  In Example (2) a polyester obtained from the condensation of adipic acid, ethylene glycol and glycerol is treated with tolylene -2:4-diisocyanate in the presence of bis(2:4-pentane-diono)di(N:N-dimethyl-41-amino-pyridine) manganese (II) to give a lacquer which gels rapidly.  In a comparative experiment dimethylcyclohexylamine is used as catalyst in place of the manganese complex.ALSO:The invention comprises basic co-ordination complexes of divalent manganese with a b -diketone and one or more fully 4-N-substituted 4-aminopyridines.  Specified components of the complexes are acetylacetone, benzoylacetone, dibenzoylmethane, propionylacetone, trifluoroacetone, 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-piperidinopyridine, and 4-morpholinopyridine.  The complexes are prepared by reacting the co-ordination complex formed by divalent manganese and a b -diketone with a solution of an N-substituted 4-aminopyridine, preferably at 50 DEG C.-100 DEG C. in the presence of a liquid organic medium.  Suitable organic liquids and solvents are benzene, toluene and xylene.  The co-ordination complexes of divalent manganese with b -diketones are prepared, for example, by reacting the b -diketone with a manganese salt of a weak organic acid, such as the acetate, in an aqueous medium.  In Example (1) 4-dimethylamino-pyridine is reacted with bis(2 : 4-pentanediono) diaquo-manganese (II) in benzene yielding on cooling a crystalline complex containing two acetylacetone and two 4-dimethylaminopyridine residues; a similar complex containing one 4-dimethylaminopyridine residue is obtained by adding petroleum ether to the mother liquor. The complexes may be used to catalyse the reaction of isocyanates with hydroxyl group-containing compounds to give urethanes and in Examples (3) and (4) the complexes of (1) are used to catalyse the reaction of n-butanol with phenyl isocyanate; comparative experiments use dimethylcyclohexylamine as catalyst.  Other specified hydroxy compounds include mono- and diglycerides, unsaturated oils such as castor oil, glycols, such as tetramethylene glycol and polyesters, polyesteramides and polyethers (see Group IV (a) ).  The complexes may be mixed with other catalysts, for example, tertiary amines, or non-basic metallic compounds.ALSO:Foamed polyurethanes are prepared by reacting mono- or polyisocyanates with mono- or di-glycerides, unsaturated oils such as castor oil, glycols such as tetramethylene glycol, or hydroxyl group-containing polymers such as polyesters, polyesteramides or polyethers, the reaction being catalysed by basic co-ordination complexes of divalent manganese with a b -diketone and a fully 4-N -substituted 4-amino-pyridine.  Specified components of the complexes are acetylacetone, benzoylacetone, dibenzoylmethane, propionylacetone, trifluoroacetone, 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-piperidinopyridine and 4-monpholinopyridine.  Polyisocyanates mentioned are tolylene-2 : 4-diisocyanate, mixtures of tolylene-2 : 4- and -2 : 6-diisocyanates, arylmethane diisocyanates such as diphenylmethane diisocyanates, m- and p-phenylene diisocyanates and chlorophenylene-2 : 4-diisocyanate; triisocyanates may be used admixed with diisocyanates, for example 2 : 4: 6-trisiocyanatotoluene, 4 : 41 : 411-triphenylmethane triisocyanate, 2 : 4 : 41-triisocyanatodiphenyl ether and polymers of tolylene-2 : 4-diisocyanate.  The polyisocyanates may be partially polymerised or may be modified by treatment with polyhydric alcohols such as trimethylolpropane.  Mixtures of polyisocyanates may be used, including the products obtained by phosgenating the polyamine reaction products of formaldehyde with one or more aromatic primary amines such as aniline and o-toluidine.  The polyesters or polyesteramides may be made from dicarboxylic acids and glycols and, as necessary, diamines, amino-alcohols and polyhydric alcohols. Polyethers mentioned are linear and branched hydroxyl-ended polymers or copolymers of cyclic oxides, especially of 1 : 2-alkylene oxides such as ethylene oxide, propylene oxide, 1 : 2-and 2 : 3-butylene oxides, epichlorhydrin, oxacyclobutane, substituted oxacyclobutanes and tetrahydrofuran (see for example Specification 733,624).  The preparation of the polyurethanes may be carried out in the presence of additives such as fillers, plasticisers, flame-proofing agents, antioxidants, surface-active agents such as polysiloxanes and oxyethylated fatty alcohols, and gas-forming agents such as fluoroalkanes, which may be used with or without water.  In Example (2) a polyester obtained from the condensation of adipic acid, ethylene glycol and glycerol is treated with tolylene-2 : 4-diisocyanate in the presence of bis (2 : 4-pentanediono)-di (N - N-dimethyl-41-aminopyridine) manganese (II) to give a lacquer which gels rapidly.  In a comparative experiment dimethylcyclohexylamine is used as catalyst in place of the manganese complex.