Catalysts For Polyurethane Foam Polyol Premixes Containing Halogenated Olefin Blowing Agents

Abstract

The invention provides polyurethane and polyisocyanurate foams and methods for the preparation thereof. More particularly, the invention relates to closed-celled, polyurethane and polyisocyanurate foams and methods for their preparation. The foams are characterized by a fine uniform cell structure and little or no foam collapse. The foams are produced with a polyol premix composition which comprises a combination of a hydrohaloolefin blowing agent, a polyol, a silicone surfactant, and a non-amine catalyst used alone or in combination with an amine catalyst.

1 . A foamable composition comprising:
 a. a hydrohaloolefin blowing agent,   b. one or more polyols,   c. one or more surfactants, and   d. a non-amine catalyst selected from the group consisting of an inorganometallic compound, an organometallic compound, a quaternary ammonium carboxylate catalyst, and combinations thereof, wherein the inorganometallic compound or organometallic compound independently comprise an organic salt selected from the group consisting of bismuth, lead, tin, zinc, chromium, cobalt, copper, iron, manganese, magnesium, potassium, sodium, titanium, mercury, zinc, antimony, uranium, cadmium, thorium, aluminum, nickel, cerium, molybdenum, vanadium, zirconium, and combinations thereof   
     
     
         2 . The foamable composition of  claim 1  wherein said non-amine catalyst is selected from the group consisting of bismuth nitrate, lead 2-ethylhexoate, lead benzoate, lead naphthanate, ferric chloride, antimony trichloride, antimony glycolate, tin salts of carboxylic acids, dialkyl tin salts of carboxylic acids, potassium acetate, potassium octoate, potassium 2-ethylhexoate, potassium salts of carboxylic acids, zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts, alkali metal carboxylic acid salts, and sodium N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate, and combinations thereof. 
     
     
         3 . The foamable composition of  claim 2  wherein said non-amine catalyst is present in an amount of about 0.25 wt. % to about 3.0 wt. %, by weight of the composition. 
     
     
         4 . The foamable composition of  claim 1  wherein said non-amine catalyst is a quaternary ammonium carboxylate. 
     
     
         5 . The foamable composition of  claim 4  wherein said non-amine catalyst is (2-hydroxypropyl)trimethylammonium 2-ethylhexanoate or (2-hydroxypropyl)trimethylammonium formate. 
     
     
         6 . The foamable composition of  claim 5  wherein said non-amine catalyst is present in an amount of about 0.25 wt. % to about 3.0 wt. %, by weight of the composition. 
     
     
         7 . The foamable composition of  claim 1  wherein said blowing agent further comprises a co-blowing agent selected from the group consisting of water, hydrocarbon, fluorocarbon, chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon, ether, ester, alcohol, aldehyde, ketone, organic acid, gas generating material, and combinations thereof. 
     
     
         8 . The foamable composition of  claim 1  wherein said blowing agent comprises 3 to 4 carbon atoms and at least one carbon-carbon double bond. 
     
     
         9 . The foamable composition of  claim 8  wherein said blowing agent comprises a hydrohaloolefin selected from the group consisting of trifluoropropene, tetrafluoropropene, pentafluoropropane, chlorotrifluoropropene, chlorodifluoropropenes, chlorotrifluoropropene, chlorotetrafluoropropene, hexafluorobutene, and combinations of these. 
     
     
         10 . The foamable composition of  claim 8  wherein said blowing agent comprises a hydrohaloolefin selected from the group consisting of tetrafluoropropene, pentafluoropropene, and chlorotrifloropropene wherein said hydrohaloolefin comprises an unsaturated terminal carbon having not more than one F or Cl substituent. 
     
     
         11 . The foamable composition of  claim 8  wherein said blowing agent is selected from the group consisting of 1,3,3,3-tetrafluoropropene (1234ze); 1,1,3,3-tetrafluoropropene; 1,2,3,3,3-pentafluoropropene (1225ye); 1,1,1-trifluoropropene; 1,1,1,3,3-pentafluoropropene (1225zc);
 1,1,2,3,3-pentafluoropropene (1225yc); (Z)-1,1,1,2,3-pentafluoropropene (1225yez); 1-chloro-3,3,3-trifluoropropene (1233zd); 1,1,1,4,4,4hexafluorobut-2-ene (1336mzzm) and combinations thereof. 
 
     
     
         12 . The foamable composition of  claim 8  wherein said blowing agent is 1234ze(E), 1233zd(E), or 1336mzzm(Z). 
     
     
         13 . The foamable composition of  claim 1  further comprising an amine catalyst. 
     
     
         14 . The foamable composition of  claim 13  wherein the amine catalyst is selected from the group consisting of N,N,N′,N″,N″-pentamethyldiethyltriamine, N,N-dicyclohexylmethylamine;
 N,N-ethyldiisopropylamine; N,N-dimethylcyclohexylamine; N,N-dimethylisopropylamine; 
 N-methyl-N-isopropylbenzylamine; N-methyl-N-cyclopentylbenzylamine; N-isopropyl-N-sec-butyl-trifluoroethylamine; N,N-diethyl-(α-phenylethyl)amine, N,N,N-tri-n-propylamine, dicyclohexylamine; t-butylisopropylamine ; di-t-butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di-(α-trifluoromethylethyl)amine; di-(α-phenylethyl)amine; triphenylmethylamine;  1 , 1 -diethyl-n-propylamine; 
 dimorpholinodiethylether; N-ethylmorpholine; N-methylmorpholine; 
 bis(dimethylaminoethyl) ether; imidizole; n-methylimidazole; 1,2-dimethylimidazole; dimorpholinodimethylether; N,N,N′,N′,N″,N″-pentamethyldiethylenetriamine; 
 N,N,N′,N′,N″,N″-pentaethyldiethylenetriamine; N,N,N′,N′,N″,N″-pentamethyldipropylenetriamine; bis(diethylaminoethyl) ether; bis(dimethylaminopropyl) ether; and combinations thereof. 
 
     
     
         15 . A polyol premix composition comprising:
 a. a hydrohaloolefin blowing agent,   b. one or more polyols,   c. one or more surfactants, and   d. a non-amine catalyst selected from the group consisting of an inorganometallic compound, an organometallic compound, a quaternary ammonium carboxylate catalyst, and combinations thereof, wherein the inorganometallic compound or organometallic compound independently comprise an organic salt selected from the group consisting of bismuth, lead, tin, zinc, chromium, cobalt, copper, iron, manganese, magnesium, potassium, sodium, titanium, mercury, zinc, antimony, uranium, cadmium, thorium, aluminum, nickel, cerium, molybdenum, vanadium, zirconium, and combinations thereof.   
     
     
         16 . The polyol premix composition of  claim 15  wherein said non-amine catalyst is a compound selected from the group consisting of bismuth nitrate, lead 2-ethylhexoate, lead benzoate, lead naphthanate, ferric chloride, antimony trichloride, antimony glycolate, tin salts of carboxylic acids, dialkyl tin salts of carboxylic acids, potassium acetate, potassium octoate, potassium 2-ethylhexoate, potassium salts of carboxylic acids, zinc salts of carboxylic acids, zinc 2-ethylhexanoate, glycine salts, alkali metal carboxylic acid salts, sodium N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate, and combinations thereof. 
     
     
         17 . The polyol premix composition of  claim 16  wherein said non-amine catalyst is present in an amount of about 0.25 wt. % to about 3.0 wt. %, by weight of the composition. 
     
     
         18 . The polyol premix composition of  claim 15  wherein said non-amine catalyst is a quaternary ammonium carboxylate. 
     
     
         19 . The polyol premix composition of  claim 18  wherein said non-amine catalyst is (2-hydroxypropyl)trimethylammonium 2-ethylhexanoate or (2-hydroxypropyl)trimethylammonium formate. 
     
     
         20 . The polyol premix composition of  claim 19  wherein said non-amine catalyst is present in an amount of about 0.25 wt. % to about 3.0 wt. %, by weight of the composition. 
     
     
         21 . The polyol premix composition of  claim 15  wherein said blowing agent comprises 3 to 4 carbon atoms and at least one carbon-carbon double bond. 
     
     
         22 . The polyol premix composition of  claim 15  wherein said blowing agent comprises a hydrohaloolefin selected from the group consisting of trifluoropropene, tetrafluoropropene, pentafluoropropane, chlorotrifluoropropene, chlorodifluoropropenes, chlorotrifluoropropene, chlorotetrafluoropropene, hexafluorobutene, and combinations of these. 
     
     
         23 . The polyol premix composition of  claim 15  wherein said blowing agent comprises a hydrohaloolefin selected from the group consisting of tetrafluoropropene, pentafluoropropene, and chlorotrifloropropene wherein said hydrohaloolefin comprises an unsaturated terminal carbon having not more than one F or Cl substituent. 
     
     
         24 . The polyol premix composition of  claim 15  wherein said blowing agent is selected from the group consisting of 1,3,3,3-tetrafluoropropene (1234ze); 1,1,3,3-tetrafluoropropene;
 1,2,3,3,3-pentafluoropropene (1225ye); 1,1,1-trifluoropropene; 1,1,1,3,3-pentafluoropropene (1225zc); 1,1,2,3,3-pentafluoropropene (1225yc); (Z)-1,1,1,2,3-pentafluoropropene (1225yez); 1-chloro-3,3,3-trifluoropropene (1233zd), 1,1,1,4,4,4hexafluorobut-2-ene (1336mzzm) and combinations thereof. 
 
     
     
         25 . The polyol premix composition of  claim 15  wherein said blowing agent is 1234ze(E), 1233zd(E), or 1336mzzm(Z).