Catalyst composition for production of rigid polyurethane foam and isocyanurate-modified rigid polysurethane foam and raw-material composition containing the same

Abstract

An object of the present invention is to provide a catalyst for producing a rigid polyurethane foam and an isocyanurate-modified rigid polyurethane foam excellent in storage stability in the case that water is contained as a blowing agent, and a raw material-blended composition using the same. In the present invention, a catalyst composition comprising the following amine compounds of (A) and (B) and/or (C) is used and further, a raw material-blended composition further containing a polyol component and water is used. (A) A quaternary ammonium salt represented by the following general formula (1): wherein each of R 1 to R 3 represents a hydrocarbon group having 1 to 12 carbon atoms, R 4 represents an alkyl group or an aromatic hydrocarbon group having 1 to 18 carbon atoms, and X represents an organic acid group having an acid dissociation constant (pKa) of 4.8 or less; (B) A hydrophobic amine compound; (C) A heterocyclic tertiary amine compound.

1 . A catalyst composition for producing a rigid polyurethane foam and/or an isocyanurate-modified rigid polyurethane foam comprising at least the following amine compounds of (A) and (B): 
 (A) a quaternary ammonium salt represented by the following general formula (1):                          wherein each of R 1  to R 3  represents a saturated or unsaturated hydrocarbon group having I to 12 carbon atoms, R 4  represents an alkyl group or an aromatic hydrocarbon group having 1 to 18 carbon atoms, and X represents an organic acid group having an acid dissociation constant (pKa) of 4.8 or less, provided that any two of R 1  to R 3  may together form a hetero ring through a carbon atom, an oxygen atom, or a nitrogen atom;    (B) one or two or more hydrophobic amine compounds selected from the group consisting of N-methyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine, N,N-dimethyldecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine, N,N-dimethyltridecylamine, N,N-dimethyltetradecylamine, N,N-dimethylpentadecylamine, N,N-dimethylhexadecylamine, N,N-dimethylheptadecylamine, N,N-dimethyloctadecylamine, N-methyldioctylamine, N-methyldinonylamine, N-methyldidecylamine, N-methyldiundecylamine, N-methyldidodecylamine, N-methylditridecylamine, N-methylditetradecylamine, N-methyldipentadecylamine, N-methyldihexadecylamine, N-methyldiheptadecylamine, and N-methyldioctadecylamine.    
   
   
       2 . The catalyst composition according to  claim 1 , wherein the organic acid constituting the quaternary ammonium salt represented by the general formula (1) is formic acid and/or acetic acid.  
   
   
       3 . The catalyst composition according to  claim 1 , wherein the quaternary ammonium salt represented by the general formula (1) is one or two or more salts selected from the group consisting of tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, tetrapropylammonium acetate, tetrapropylammonium formate, tetrabutylammonium acetate, tetrabutylammonium formate, methyltriethylammonium acetate, methyltriethylammonium formate, methyltripropylammonium acetate, methyltripropylammonium formate, methyltributylammonium acetate, methyltributylammonium formate, trimethyldodecylammonium formate, and trimethyldodecylammonium acetate quaternary ammonium salts.  
   
   
       4 . The catalyst composition according to  claim 1 , which further comprises the following amine compound of (C): 
 (C) one or two or more heterocyclic tertiary amine compounds selected from the group consisting of 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, 1-(2-hydroxyethyl) imidazole, N-methyl-N′-(2-hydroxyethyl)piperazine, and N-(2-hydroxyethyl)morpholine.    
   
   
       5 . A catalyst composition for producing a rigid polyurethane foam and/or an isocyanurate-modified rigid polyurethane foam comprising at least the following amine compounds of (A) and (C): 
 (A) a quaternary ammonium salt represented by the following general formula (1):                          wherein each of R 1  to R 3  represents a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, R 4  represents an alkyl group or an aromatic hydrocarbon group having 1 to 18 carbon atoms, and X represents an organic acid group having an acid dissociation constant (pKa) of 4.8 or less, provided that any two of R 1  to R 3  may together form a hetero ring through a carbon atom, an oxygen atom, or a nitrogen atom;    (C) one or two or more heterocyclic tertiary amine compounds selected from the group consisting of 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, 1-(2-hydroxyethyl) imidazole, N-methyl-N′-(2-hydroxyethyl)piperazine, and N-(2-hydroxyethyl)morpholine.    
   
   
       6 . The catalyst composition according to  claim 5 , wherein the organic acid constituting the quaternary ammonium salt represented by the general formula (1) is formic acid and/or acetic acid.  
   
   
       7 . The catalyst composition according to  claim 5 , wherein the quaternary ammonium salt represented by the general formula (1) is one or two or more salts selected from the group consisting of tetramethylammonium acetate, tetramethylammonium formate, tetraethylammonium acetate, tetraethylammonium formate, tetrapropylammonium acetate, tetrapropylammonium formate, tetrabutylammonium acetate, tetrabutylammonium formate, methyltriethylammonium acetate, methyltriethylammonium formate, methyltripropylammonium acetate, methyltripropylammonium formate, methyltributylammonium acetate, methyltributylammonium formate, trimethyldodecylammonium formate, and trimethyldodecylammonium acetate quaternary ammonium salts.  
   
   
       8 . A raw material-blended composition for producing a rigid polyurethane foam and/or an isocyanurate-modified rigid polyurethane foam comprising a polyol component, water, and the catalyst composition according to  claim 1 .  
   
   
       9 . The raw material-blended composition according to  claim 8 , which further comprises one or two or more compounds selected from the group consisting of 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoroprpane, 1,1,1,2,3,3-hexafluoroprpane, 1,1,1,4,4,4-hexafluorobutane, propane, butane, pentane, cyclopentane, and hexane, as a blowing agent.  
   
   
       10 . The raw material-blended composition according to  claim 8 , which comprises an aromatic polyester polyol as the polyol component.  
   
   
       11 . A process for producing a rigid polyurethane foam and/or an isocyanurate-modified rigid polyurethane foam, which comprises mixing a polyisocyanate with the raw material-blended composition according to  claim 8 , and reacting them.  
   
   
       12 . A raw material-blended composition for producing a rigid polyurethane foam and/or an isocyanurate-modified rigid polyurethane foam comprising a polyol component, water, and the catalyst composition according to  claim 5 .  
   
   
       13 . The raw material-blended composition according to  claim 12 , which further comprises one or two or more compounds selected from the group consisting of 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoroprpane, 1,1,1,2,3,3-hexafluoroprpane, 1,1,1,4,4,4-hexafluorobutane, propane, butane, pentane, cyclopentane, and hexane, as a blowing agent.  
   
   
       14 . The raw material-blended composition according to  claim 12 , which comprises an aromatic polyester polyol as the polyol component.  
   
   
       15 . A process for producing a rigid polyurethane foam and/or an isocyanurate-modified rigid polyurethane foam, which comprises mixing a polyisocyanate with the raw material-blended composition according to  claim 12 , and reacting them.