Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same

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.

What is claimed is: 
     
         1 . A storage-stable, foamable composition that has been stored for a period of at least three months, said composition comprising:
 a. a hydrohaloolefin blowing agent,   b. one or more polyols,   c. one or more surfactants, and   d. a catalyst system comprising at least a first metal and at least a second metal, and at least one amine catalyst selected from the group of amine catalysts having a pKa of not less than about 10, wherein said composition has been stored for at least three months.   
     
     
         2 . The foamable composition of  claim 1  wherein said first and second metal 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 first and second metal catalyst is each present in an amount of about 0.001 wt. % to about 5.0 wt. %, by weight of the composition. 
     
     
         4 . The foamable composition of  claim 1  further comprising a quaternary ammonium carboxylate. 
     
     
         5 . The foamable composition of  claim 4  wherein said quaternary ammonium carboxylate is (2-hydroxypropyl)trimethylammonium 2-ethylhexanoate or (2-hydroxypropyl)trimethylammonium formate. 
     
     
         6 . The foamable composition of  claim 5  wherein said quaternary ammonium carboxylate 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 . (canceled) 
     
     
         9 . The foamable composition of  claim 1  wherein said hydrohaloolefin 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 comprises in substantial proportion 1233zd(E). 
     
     
         13 . The foamable composition of  claim 1  wherein said amine catalyst comprises n-metheyldicyclohexyl-amine. 
     
     
         14 . The foamable composition of  claim 13  wherein the amine catalyst comprises methyl(n-methylamino b-sodium acetate nonylphenol) 2. 
     
     
         15 . A storage-stable polyol premix composition that has been stored for a period of at least three months, said 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 a first metal catalyst and a second metal catalyst, wherein the metal of said first metal catalyst is not the same as the metal of said second catalyst, each of said first and second metal catalysts comprise an organic salt wherein the metal is 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 each of said first and second metal catalysts comprise 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 . (canceled) 
     
     
         18 . The polyol premix composition of  claim 15  wherein said hydrohaloolefin blowing agent comprises a hydrohaloolefin selected from the group consisting of trifluoropropene, tetrafluoropropene, pentafluoropropane, chlorotrifluoropropene, chlorodifluoropropenes, chlorotrifluoropropene, chlorotetrafluoropropene, hexafluorobutene, and combinations of these. 
     
     
         19 . 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. 
     
     
         20 . 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. 
     
     
         21 . The polyol premix composition of  claim 15  wherein said hydrohaloolefin blowing agent comprises 1234ze(E), 1233zd(E), and/or 1336mzzm(Z). 
     
     
         22 . (canceled) 
     
     
         23 . A method of forming a foam comprising:
 a. forming a polyol premix composition comprising:
 i. a hydrohaloolefin blowing agent, 
   ii. one or more polyols,   iii. one or more surfactants, and   iv. a catalyst system comprising at least one amine catalyst selected from the group of amine catalysts having a pKa of not less than about 10; and   b. storing said polyol premix composition for a period of at least about 168 hours;   c. after said storage step b., forming a foam using said polol premix composition.   
     
     
         24 . The method of  claim 23  wherein said forming step has a gel time that is not substantially increased compared to the gel time of a foam formed using said polyol premix prior to said storage step b. 
     
     
         25 . A foam formed from the method of  claim 23 .