Foams And Foamable Compositions Containing Halogenated Olefin Blowing Agents

Abstract

The invention provides foam forming methods that comprise: (a) preparing a foamable system comprising at least one hydrohaloolefin; and (b) ensuring either (i) the substantial absence of long-term decomposition-inducing contact between said hydrofluoroolefin and an amine-containing catalyst; (ii) that an effective amount of surfactant is available in the system under conditions which prevent long term exposure of the surfactant to a long-term decomposition reaction environment; or (iii) a combination of (i) and (ii). Related methods, foamable systems and foams are also disclosed. Preferred embodiments provide polyurethane and polyisocyanurate foams and methods for the preparation thereof, including closed-celled, polyurethane and polyisocyanurate foams and methods for their preparation. The preferred foams are characterized by a fine uniform cell structure and little or no foam collapse. The foams are preferably produced with a polyol premix composition which comprises a combination of a hydrohaloolefin blowing agent, a polyol, a silicone surfactant, a catalyst and is further characterized by being substantially free of added water.

1 . A foam forming method comprising:
 (a) preparing a foamable system comprising at least one hydrohaloolefin; and   (b) ensuring (i) substantial absence of long-term decomposition-inducing contact between said hydrofluoroolefin and an amine-containing catalyst; or (ii) that an effective amount of surfactant is available in the system under conditions to prevent long term exposure of the surfactant to a long-term decomposition reaction environment; or (iii) a combination of (i) and (ii).   
     
     
         2 . The method of  claim 1  wherein said foamable system comprises an A side comprising a polyisocyanate and a B side comprising a polyol that is reactive with said polyisocyanate. 
     
     
         3 . The method of  claim 2  wherein said B side further comprises a catalytically effective amount of the amine-containing catalyst and hydrohaloolefin, which is generally decomposition reactive with said amine-containing catalyst. 
     
     
         4 . The method of  claim 3  wherein said ensuring step comprises ensuring that said B side contains a sufficient absence of a polar solvent to ensure that there is no substantial decomposition reaction between said hydrofluoroolefin and said amine after about two months of storage under ambient temperature conditions. 
     
     
         5 . The method of  claim 3  wherein said ensuring step comprises ensuring that said B side contains a sufficient absence of a polar solvent to ensure that there is no substantial decomposition reaction between said hydrofluoroolefin and said amine after about three months of storage under ambient temperature conditions. 
     
     
         6 . The method of  claim 3  wherein said ensuring step comprises ensuring that said B side contains a sufficient absence of a polar solvent to ensure that there is no substantial decomposition reaction between said hydrofluoroolefin and said amine after about six months of storage under ambient temperature conditions. 
     
     
         7 . The method of  claim 1  wherein said decomposition reactive hydrofluoroolefin comprises trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)). 
     
     
         8 . (canceled) 
     
     
         9 . The method of  claim 3  wherein said ensuring step comprises ensuring that said B side contains a sufficient absence of water to ensure that there is no substantial decomposition reaction between said hydrofluoroolefin and said amine after about three months of storage under ambient temperature conditions. 
     
     
         10 . The method of  claim 3  wherein said ensuring step comprises ensuring that said B side contains not more than about 1 weight % water. 
     
     
         11 . The method of  claim 3  wherein said ensuring step comprises ensuring that said B side contains not more than about 0.75 weight % water. 
     
     
         12 . The method of  claim 3  wherein said ensuring step comprises ensuring that said B side contains not more than about 0.5 weight % water. 
     
     
         13 . A foam forming method comprising:
 (a) providing a foamable system comprising an A side and a B side, said B side comprising a catalytically effective amount of an amine-containing catalyst and at least one hydrohaloolefin that is generally decomposition reactive with said amine-containing catalyst; and   (b) ensuring that said A side contains an effective amount of surfactant, optionally silicon-containing surfactant, to ensure the formation of insulating effective cells in the foam.   
     
     
         14 . (canceled) 
     
     
         15 . The foam forming method system of  claim 13  wherein said B side is storage stable for a period of at least about 6 months. 
     
     
         16 . (canceled) 
     
     
         17 . (canceled) 
     
     
         18 . (canceled) 
     
     
         19 . The foam forming method of  claim 13  wherein said B side is substantially free of polar solvents. 
     
     
         20 . The foam forming method of  claim 13  wherein a gas-generating co-blowing agent other than water is included in said A side, said B side, or both. 
     
     
         21 . The foam forming method of  claim 20  wherein said gas-generating co-blowing agent comprises formic acid. 
     
     
         22 . A foam forming system comprising: at least a first composition and a second composition, and means for storing said first composition separate from said second composition, said first composition comprising at least one polyol and said second composition comprising at least one isocyanate reactive with said polyol, said system further comprising a decomposition reactive hydrohalocarbon and an amine-containing catalyst, each of said decomposition reactive hydrohalocarbon and said an amine-containing catalyst being independently contained in said first composition, said second composition, or in both of said compositions, provided that if a substantial portion of each of said reactive hydrohalocarbon and said amine-containing catalyst are contained in the same composition then that composition does not contain more than about 1 wt % of a polar solvent. 
     
     
         23 . The foam forming method of  claim 13  wherein if a substantial portion of each of said reactive hydrohalocarbon and said amine-containing catalyst are contained in the same composition then that composition does not contain more than about 1 wt % of water. 
     
     
         24 . (canceled) 
     
     
         25 . (canceled) 
     
     
         26 . The foam forming method of  claim 13  wherein said B side is storage stable for a period of at least about 2 months. 
     
     
         27 . A foam formed from the method of  claim 1 . 
     
     
         28 . A foam formed from the method of  claim 13 . 
     
     
         29 . (canceled)