Polyols containing carboxyl groups and production thereof

Abstract

The present invention is directed to a low viscosity carboxyl-containing polyol composition having a viscosity in the range of about 3,000-100,000 centipoise, and having an oligomer content of less than 30 mg KOH/g. Preferably, the carboxyl-containing polyol has one ester group per molecule. The carboxyl-containing polyol is suitable for use in preparing low viscosity polyurethane prepolymers. Also disclosed is a method of producing this carboxyl-containing polyol composition by reacting a low molecular weight triol with an acid anhydride in the presence of 25-500 ppm of an inorganic or organic acid catalyst. The organic or inorganic acid is preferably selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, formic acid, proprionic acid, p-toluenesulfonic acid, oxalic acid, and combinations thereof. The present invention is also directed to methods of making the above carboxyl-containing polyols, as well as prepolymers and urethane polymers containing the above carboxyl-containing polyols.

What is claimed is:  
     
         1 . A low viscosity carboxyl-containing polyol composition having a viscosity in the range of about 3,000-100,000 centipoise, and having an oligomer content of less than 30 mg KOH/g.  
     
     
         2 . A low viscosity carboxyl-containing polyol amine salt having a viscosity in the range of about 3,000-100,000 centipoise, and having an oligomer content of less than 30 mg KOH/g, said carboxyl being neutralized with an organic amine to provide said carboxyl-containing polyol amine salt.  
     
     
         3 . A method for producing the carboxyl-containing polyol of  claim 1  comprising reacting a low molecular weight triol with an acid anhydride in the presence of 5-500 ppm of an organic or inorganic acid catalyst.  
     
     
         4 . The method of  claim 3  wherein said organic or inorganic acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, formic acid, proprionic acid, p-toluenesulfonic acid, oxalic acid, and combinations thereof.  
     
     
         5 . The carboxy-containing monomer of  claim 3 , wherein said triol compound is selected from the group consisting of glycerol, trimethylolpropane, trimethylolethane, polyether polyols, and combinations thereof.  
     
     
         6 . The carboxy-containing monomer of  claim 1 , wherein said acid anhydride is selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, and mixtures thereof.  
     
     
         7 . The carboxy-containing monomer of  claim 1 , wherein said carboxyl-containing monomer is made in the presence of 50-250 ppm of said organic or inorganic acid.  
     
     
         8 . The carboxy-containing monomer of  claim 7 , wherein said carboxyl-containing monomer is made in the presence of 100-200 ppm of said organic or inorganic acid.  
     
     
         9 . The carboxy-containing monomer of  claim 1 , wherein said viscosity of said carboxyl-containing monomer ranges from 3,000 to 50,000 cps.  
     
     
         10 . The carboxy-containing monomer of  claim 9 , wherein said viscosity of said carboxyl-containing monomer ranges from 3,000 to 20,000 cps.  
     
     
         11 . The carboxy-containing monomer of  claim 1 , wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 30 mg KOH/g.  
     
     
         12 . The carboxy-containing monomer of  claim 11 , wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 20 mg KOH/g.  
     
     
         13 . A method of preparing a carboxyl-containing monomer for use in preparation of a polyurethane polymer, comprising the step of combining a low molecular weight polyol compound and an acid anhydride, in the presence of 25-500 ppm of an organic or inorganic acid, to produce said carboxyl-containing monomer, said carboxyl-containing monomer having a viscosity in the range of about 3,000 to about 100,000 cps and having a free oligomer content of sol less than about 30 mg KOH/g.  
     
     
         14 . The method of  claim 13 , wherein said low molecular weight polyol compound comprises from two to four hydroxyl groups.  
     
     
         15 . The method of  claim 14 , wherein said low molecular weight polyol compound is a triol compound possessing three hydroxyl groups.  
     
     
         16 . The method of  claim 15 , wherein said triol compound is selected from the group consisting of glycerol, trimethylolpropane, trimethylolethane, polyether polyols, and combinations thereof.  
     
     
         17 . The method of  claim 16 , wherein said low molecular weight polyol compound is a polyether triol.  
     
     
         18 . The method of  claim 13 , wherein said acid anhydride is selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, and mixtures thereof.  
     
     
         19 . The method of  claim 13 , wherein said carboxyl-containing monomer is made in the presence of about 50-250 ppm of said organic or inorganic acid.  
     
     
         20 . The method of  claim 19 , wherein said carboxyl-containing monomer is made in the presence of an organic or inorganic acid selected from the group consisting of. hydrochloric acid, sulfuric acid, nitric acid, formic acid, propionic acid, p-toluenesulfonic acid, oxalic acid, and combinations thereof.  
     
     
         21 . The method of  claim 13 , wherein said viscosity of said carboxyl-containing monomer ranges from about 3,000 to 50,000 cps.  
     
     
         22 . The method of  claim 21 , wherein said viscosity of said carboxyl-containing monomer ranges from about 3,000 to 20,000 cps.  
     
     
         23 . The method of  claim 13 , wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 30 mg KOH/g.  
     
     
         24 . The method of  claim 23 , wherein said free oligomer content of said carboxyl-containing monomer ranges from about 2 to 20 mg KOH/g.  
     
     
         25 . A prepolymer for use in preparing a polyurethane polymer, said prepolymer being the reaction product of (1) the carboxyl-containing monomer of  claim 1 , and (2) a polyisocyanate compound, said prepolymer having a viscosity in the range of about 3,000 to about 100,000 cps.  
     
     
         26 . The prepolymer of  claim 25 , wherein said polyisocyanate is selected from the group consisting of diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4′-tetramethylene diisocyanate, 1,10-decamethylene disiocyanate, 1,12-dodecamethylene diisocyanate, tolulene-2,4- or 2,6-diisocyanate, 1,5-naphthalene diisocyanates, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4′-diisocyanatodiphenyl ether, 5,6-dimethyl-1,3-phenylate diisocyanate, 2,4-diemthyl-1,3-phenylene diisocyanate, 4,4′-diisocyanatodiphenylether, benzidene diisocyanate, 4,4′-diisocyanataodibenzyl, methylene-bis(4-phenylisocyanate), 1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,12-dodecanediisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethyl-xylylene diisocyanate, polymethylene polyphenyl isocyanate, and combinations thereof.  
     
     
         27 . A prepolymer for use in preparing a polurethane polymer, said prepolymer being the reaction product of (1) carboxyl-containing polyol amine salt of  claim 2 , and (2) a polyisocyanate compound, said prepolymer having a viscosity in the range of about 3,000 to about 100,000 cps.  
     
     
         28 . The prepolymer of  claim 27 , wherein said polyisocyanate compound is selected from the group consisting of diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4′-tetramethylene diisocyanate, 1,10-decamethylene disiocyanate, 1,12-dodecamethylene diisocyanate, tolulene-2,4- or 2,6-diisocyanate, 1,5-naphthalene diisocyanates, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4′-diisocyanatodiphenyl ether, 5,6-dimethyl-1,3-phenylate diisocyanate, 2,4-diemthyl-1,3-phenylene diisocyanate, 4,4′-diisocyanatodiphenylether, benzidene diisocyanate, 4,4′-diisocyanataodibenzyl, methylene-bis(4-phenylisocyanate), 1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,12-dodecanediisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, tetramethyl-xylylene diisocyanate, polymethylene polyphenyl isocyanate, and combinations thereof.  
     
     
         29 . A water-borne polyurethane polymer, said water-borne polyurethane polymer being the reaction product of (1) the prepolymer of  claim 25 , and (2) an amine compound.  
     
     
         30 . The water-borne polyurethane polymer of  claim 29 , wherein said amine compound is selected from the group consisting of: triethylamine, tripropylamine, ethylene diamine, n-butylamine, diethylamine, trimethylamine, monoethanol amine, dimethylethanolamine, aminoalcohols, hydrazine, hexamethylene diamine, isophorone diamine, cyclohexane diamine, dimethylcyclohexylamine, tris(3-aminopropyl)amine, 2-methylpentamethylenediamine, 1,12-dodecanediamine, and combinations thereof.  
     
     
         31 . A prepolymer combination comprising the prepolymer of  claim 25  and the prepolymer of claim  27 .