Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming

Abstract

Disclosed are bowing agent compositions, foamable compositions, foams, foaming methods and/or foamed articles comprising one or more C2 to C6 fluoroalkenes, more preferably one or more C3 to C5 fluoroalkenes, and even more preferably one or more compounds having Formula I as follows: XCF z R 3-z   (I) where X is a C 1 , C 2 , C 3 , C 4 , or C 5 unsaturated, substituted or unsubstituted radical, each R is independently Cl, F, Br, I or H, and z is 1 to 3, it generally being preferred that the fluoroalkene of the present invention has at least four (4) halogen substituents, at least three of which are F and even more preferably none of which are Br.

1 . A blowing agent comprising:
 (a) trans-1,1,1,3-tetrafluoropropene (transHFO-1234ze); and   (b) at least one compound selected from the group consisting of: fluoralkenes other than transHFO-1234ze; hydrocarbons; hydrofluorocarbons (HFCs), ethers, alcohols, aldehydes, ketones, methyl formate, formic acid, water, trans-1,2-dichloroethylene, carbon dioxide and combinations of any two or more of these.   
   
   
       2 . The blowing agent of  claim 1  wherein said at least one compound comprises at least one fluoroalkene other than transHFO-1234ze. 
   
   
       3 . The blowing agent of  claim 2  wherein said at least one fluoroalkene other than transHFO-1234ze is selected from the group consisting of cis-1,1,1,3-tetrafluoropropene (cisHFO-1234ze); 1,1,1,2-tetrafluoropropene (HFO-1234yf); 1,1,1,trifluoro,3chloro-propene (HFCO-1233zd); and 1,1,1,2,3-pentafluoropropene (HFO-1225yez), and any two or more of these. 
   
   
       4 . The blowing agent of  claim 3  wherein said at least one fluoroalkene other than transHFO-1234ze is selected from the group consisting of cisHFO-1234ze; HFO-1234yf; HFO-1225yez, and any two or more of these and is present in the composition in an amount of from about 1 wt % to about 50 wt %. 
   
   
       5 . The blowing agent of  claim 3  wherein said at least one fluoroalkene other than transHFO-1234ze comprises HFO-1233zd and is present in the composition in an amount of from about 20 wt % to about 80 wt %. 
   
   
       6 . The blowing agent of  claim 1  comprising at least one HFC selected from the group consisting HFC-245fa, HFC-245eb, HFC-245ca, HFC-227ea, HFC-236ea, HFC-236fa, HFC-134a, HFC-134, HFC-152a, HFC-32, HFC-125, HFC-143a, HFC-365mfc, HFC-161, HFC-43-10mee and any two or more of these. 
   
   
       7 . The blowing agent of  claim 6  wherein said at least one HFC is selected from the group consisting HFC-245fa, HFC-32, HFC-365mfc and any two or more of these and is present in the composition in an amount of from about 1 wt % to about 25 wt %. 
   
   
       8 . The blowing agent of  claim 7  wherein said at least one HFC comprises HFC-236fa and is present in the composition in an amount of from about 1 wt % to about 5 wt %. 
   
   
       9 . The blowing agent of  claim 1  wherein said at least one compound comprises at least one hydrocarbon. 
   
   
       10 . The blowing agent of  claim 9  wherein said at least one hydrocarbon is selected from the group consisting propane, butane, isobutane, n-hexane, isohexane, heptane and any two or more of these and is present in the composition in an amount of from about 20 wt % to about 95 wt %. 
   
   
       11 . The blowing agent of  claim 1  wherein said at least one compound comprises at least one alcohol. 
   
   
       12 . The blowing agent of  claim 11  wherein said at least one alcohol is selected from the group consisting of methanol, ethanol, proponal, isopropanol, butanol, isobutanol, t-butanol. 
   
   
       13 . The blowing agent of  claim 1  wherein said at least one compound comprises at least one ether. 
   
   
       14 . The blowing agent of  claim 13  wherein said at least one ether is selected from the group consisting of dimethylether, methylethylether, diethyl ether, methylpropylether, methylisopropylether, ethylpropylether, ethylisopropylether, dipropylether, diisopropylether, dimethyloxymethane, diethoxymethane, dipropoxymethane, dibutoxymethane and any two or more of these. 
   
   
       15 . The blowing agent of  claim 14  wherein said at least one ether is selected from the group consisting of dimethylether, methylethylether, diethyl ether, methylpropylether, methylisopropylether, dimethyloxymethane, diethoxymethane and any two or more of these and is present in the composition in an amount of from about 10 wt % to about 80 wt %. 
   
   
       16 . The blowing agent of  claim 1  wherein said at least one compound comprises at least one aldehyde. 
   
   
       17 . The blowing agent of  claim 16  wherein said at least one aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propanal, butanal, isobutanal and any two or more of these. 
   
   
       18 . The blowing agent of  claim 1  wherein said at least one compound comprises at least one ketone. 
   
   
       19 . The blowing agent of  claim 18  wherein said at least one ketone is selected from the group consisting of acetone, methylethylketone, methylisobutylketone and any two or more of these. 
   
   
       20 . The blowing agent of  claim 1  wherein said at least one compound is selected from the group consisting of water, trans-1,2dichloroethylene and any two or more of these and is present in the composition in an amount of from about 1 wt % to about 30 wt %. 
   
   
       21 . A blowing agent comprising:
 (a) 1,1,1,trifluoro,3-chloro-propene (HFCO-1233zd); and   (b) at least one compound selected from the group consisting of: fluoralkenes other than HFCO-1233zd; hydrocarbons; hydrofluorocarbons (HFCs), ethers, alcohols, aldehydes, ketones, methyl formate, formic acid, water, trans-1,2-dichloroethylene, carbon dioxide and combinations of any two or more of these.   
   
   
       22 . The blowing agent of  claim 21  wherein said at least one compound comprises at least one fluoroalkene other than HFCO-1233zd. 
   
   
       23 . The blowing agent of  claim 21  wherein said at least one compound comprises at least one HFC. 
   
   
       24 . The blowing agent of  claim 23  wherein said at least one HFC is selected from the group consisting HFC-245fa, HFC-245eb, HFC-245ca, HFC-227ea, HFC-236ea, HFC-236fa, HFC-134a, HFC-134, HFC-152a, HFC-32, HFC-125, HFC-143a, HFC-365mfc, HFC-161, HFC-43-10mee and any two or more of these. 
   
   
       25 . The blowing agent of  claim 21  wherein said at least one compound comprises at least one hydrocarbon. 
   
   
       26 . The blowing agent of  claim 25  wherein said at least one hydrocarbon is selected from the group consisting of propane, butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, cyclopentane, n-hexane, isohexane, heptane and combinations of two or more of these. 
   
   
       27 . The blowing agent of  claim 21  wherein said at least one compound comprises at least one alcohol. 
   
   
       28 . The blowing agent of  claim 27  wherein said at least one alcohol is selected from the group consisting of methanol, ethanol, proponal, isopropanol, butanol, isobutanol, t-butanol. 
   
   
       29 . The blowing agent of  claim 21  wherein said at least one compound comprises at least one ether. 
   
   
       30 . The blowing agent of  claim 29  wherein said at least one ether is selected from the group consisting of dimethylether, methylethylether, diethyl ether, methylpropylether, methylisopropylether, ethylpropylether, ethylisopropylether, dipropylether, diisopropylether, dimethyloxymethane, diethoxymethane, dipropoxymethane, dibutoxymethane and any two or more of these. 
   
   
       31 . The blowing agent of  claim 21  wherein said at least one compound comprises at least one aldehyde. 
   
   
       32 . The blowing agent of  claim 31  wherein said at least one aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propanal, butanal, isobutanal and any two or more of these. 
   
   
       33 . The blowing agent of  claim 21  wherein said at least one compound comprises at least one ketone. 
   
   
       32 . The blowing agent of  claim 33  wherein said at least one ketone is selected from the group consisting of acetone, methylethylketone, methylisobutylketone and any two or more of these. 
   
   
       33 . The blowing agent of  claim 21  wherein said at least one compound is selected from the group consisting of methyl formate, formic acid, water, trans-1,2dichloroethylene, carbon dioxide and any two or more of these. 
   
   
       34 . A foamable composition comprising a foam forming agent and a blowing agent in accordance with  claim 1 . 
   
   
       35 . A foamable composition comprising a foam forming agent and a blowing agent in accordance with  claim 21 . 
   
   
       36 . The foamable composition of  claim 34  wherein said foam forming agent comprises at least one thermoset foam component selected from components capable of forming polyurethane foam, polyisocyanurate foam, phenolic foam, and two or more of these 
   
   
       37 . The foamable composition of  claim 34  wherein said foam forming agent comprises at least one thermoplastic foam component is selected from monovinyl aromatic compounds, ethylene-based compounds, propylene-based polymers, and combinations of these. 
   
   
       38 . The foamable composition of  claim 35  wherein said foam forming agent comprises at least one thermoset foam component selected from components capable of forming polyurethane foam, polyisocyanurate foam, phenolic foam, and two or more of these 
   
   
       39 . The foamable composition of  claim 35  wherein said foam forming agent comprises at least one thermoplastic foam component is selected from monovinyl aromatic compounds, ethylene-based compounds, propylene-based polymers, and combinations of these. 
   
   
       40 . A foam premix composition comprising polyol and a blowing agent in accordance with  claim 1 . 
   
   
       41 . A foam premix composition comprising polyol and a blowing agent in accordance with  claim 21 . 
   
   
       42 . A method of forming a foam comprising adding to a foamable and/or foaming composition a blowing agent in accordance with  claim 1 . 
   
   
       42 . A method of forming a foam comprising adding to a foamable and/or foaming composition a blowing agent in accordance with  claim 21 . 
   
   
       43 . A foam comprising a plurality of polymeric cells and a composition contained in at least one of said cells, said composition comprising at least one blowing agent in accordance with  claim 1 . 
   
   
       44 . A foam comprising a plurality of polymeric cells and a composition contained in at least one of said cells, said composition comprising at least one blowing agent in accordance with  claim 21 . 
   
   
       45 . The foam of  claim 43  in the form of one or more of a block, a slab, a laminate, a rigid foam, an open cell foam, a closed cell foam, a flexible foam, an integeral skin foam, refrigerator foam, and a freezer foam. 
   
   
       46 . The foam of  claim 43  having a k-factor K-factor (BTU in/hr ft 2  ° F.) at 40° F. of not greater than about 0.14. 
   
   
       47 . The foam of  claim 44  in the form of one or more of a block, a slab, a laminate, a rigid foam, an open cell foam, a closed cell foam, a flexible foam, an integeral skin foam, refrigerator foam, and a freezer foam. 
   
   
       48 . The foam of  claim 44  having a k-factor K-factor (BTU in/hr ft 2  ° F.) at 40° F. of not greater than about 0.14.