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

Abstract

Disclosed are polyol premix compositions, and foams formed therefrom, which comprise a combination of a hydrohaloolefin blowing agent, a polyol, a silicone surfactant, and a catalyst system that includes a bismuth-based metal catalyst. Such catalysts may be used alone or in combination with an amine catalyst and/or other non-amine catalysts.

What is claimed is: 
     
         1 . A method of forming a thermoset foam comprising:
 forming a polyol premix comprising: (a) from about 60 wt % to about 95 wt % of polyol; (b) from about 1 wt % to about 30 wt % of blowing agent, said blowing agent comprising from about 7 wt % to about 98 wt % by of 1-chloro-3,3,3-trifluoropropene; (c) at least one surfactant; and (d) a catalyst system comprising metal-based catalyst, wherein said metal based-catalyst consists essentially of at least one bismuth-based metal catalyst;   using said polyol premix after a storage period of at least one month to form a foamable composition,   forming a foam from said foamable composition, provided that said polyol premix is sufficiently free of non-bismuth-based catalyst such that said foam has a cream time of not greater than 10 seconds.   
     
     
         2 . The method of  claim 1  wherein said foam formed from said polyol premix has a cream time of not greater than 10 seconds when aged for 3 months at room temperature. 
     
     
         3 . The method of  claim 1  wherein said bismuth-metal catalyst comprises a catalyst represented by the formula Bi—(R) 3 , wherein each R is independently selected from the group consisting of a hydrogen, a halide, a hydroxide, a sulfate, a carbonate, a cyanate, a thiocyanate, an isocyanate, a isothiocyanate, a carboxylate, an oxalate, a C 1 -C 10  alkane, a C 1 -C 10  alkene, a C 1 -C 10  alkyne, a heteroalkyl group, an aryl group, a ketone, an aldehyde, an esters, an ether, an alcohol, an alcoholate, a phenolate, a glycolates, a thiolates, an octoate, a hexanoate, and combinations thereof, where any of the foregoing R groups may be independently substituted or unsubstituted. 
     
     
         4 . The method of  claim 1  wherein said bismuth-metal catalyst is selected from the group consisting of a bismuth carboxylate, a bismuth octoate, bismuth hexanoate, bismuth 2-ethylhexanoate, a bismuth acetylacetonate, bismuth ethoxide, bismuth propoxide, bismuth butoxide, bismuth isopropoxide, bismuth butoxide, a derivative thereof, and combinations thereof. 
     
     
         5 . The polyol premix of  claim 1  wherein said bismuth-metal catalyst comprises a bismuth carboxylate or a derivative thereof. 
     
     
         6 . The method of  claim 1  wherein said bismuth-metal catalyst comprises bismuth 2-ethylhexanoate, or a derivative thereof. 
     
     
         7 . The method of  claim 1  wherein said at least one bismuth-based metal catalyst is present in the composition in an amount to provide foam formed from said aged polyol premix with a a cream time of less than about 6 seconds after aging for 3 months at room temperature. 
     
     
         8 . The method of of  claim 1  wherein said polyol premix further comprises an aromatic amine catalyst comprising a compound of the formula [R m C 6 Hn-NH 2 ] x , where m=0, 1, 2, 3, 4, or 5, n=0, 1, 2, 3, 4, or 5, x=1, or 2, and m+n+x=6 and wherein each R may be independently selected from the group consisting of comprises a hydrogen, a halide, a hydroxide, a sulfate, a carbonate, a cyanate, a thiocyanate, an isocyanate, a isothiocyanate, a carboxylate, an oxalate, a nitrate, a substituted or unsubstituted alkyl, heteroalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and combinations thereof. 
     
     
         9 . The method of  claim 8  wherein at least one R is selected from the group consisting of aniline, fluoroaniline, chloroaniline, bromoaniline, nitroaniline, aminotoluene, fluoroaminotoluene, chloroaminotoluene, bromoaminotoluene, nitroaminotoluene, diaminobenzene, fluorodiaminobenzene, chlorodiaminobenzene, bromodiaminobenzene, nitrodiaminobenzene, diaminotoluene, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, dimethylthiotoluenediamine, benzidine, (di)fluorobenzidine, (di)chlorobenzidine, (di)bromobenzidien, (di)nitrobenzidine, (di)methylbenzidine, (di)ethylbenzidine, diaminodiphenylmethane, (di)fluorodiaminodiphenylmethane, (di)chlorodiaminodiphenylmethane, (di)bromodiaminodiphenylmethane, (di)methyldiaminodiphenylmethane, (di)ethyldiaminodiphenylmethane, diaminobenzophenone, (di)fluorodiaminobenzophenone, (di)chlorodiaminobenzophenone, (di)bromodiaminobenzophenone, (di)methyldiaminobenzophenone, (di)ethyldiaminobenzophenone, aminoimidazole, aminopyridine, bipyridinamine and combinations thereof. 
     
     
         10 . The method of claim of  claim 8  wherein the aromatic amine catalyst comprises a compound of the formula [R′—NH 2 ] x , wherein x=0, 1 or 2 and R′ comprises a heteroaryl ring moiety having at least one of N, O, or S, and from 2-20 carbon atoms and may be optionally substituted. 
     
     
         11 . The method of  claim 1  wherein said polyol premix 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. 
     
     
         12 . A foam formed from the method of  claim 1 . 
     
     
         13 . The method of  claim 1  wherein said step of forming a foamable composition comprises combining an isocyanate component with said aged polyol premix composition, wherein said aged polyol premix composition comprises: (a) from about 60 wt % to about 95 wt % of polyol; (b) from about 1 wt % to about 30 wt % of blowing agent, said blowing agent comprising from about 7 wt % to about 98 wt % 1-chloro-3,3,3-trifluoropropene (1233zd); (c) at least one surfactant; and (d) a catalyst system comprising metal-based catalyst, wherein said metal based-catalyst consists essentially of at least one bismuth-based metal catalyst and being sufficiently free of non-bismuth-based catalyst to provide said foamable composition with an initial cream time of less than about 10 seconds and wherein said foamable composition combined with said aged polyol premix has a cream time of not greater than 10 seconds after aging for 3 months at room temperature, said weight percentages of each of (a) through (b) being based on the total of components (a)-(d) in the polyol premix. 
     
     
         14 . The method of  claim 13  wherein said at least one bismuth-based metal catalyst is present in the aged polyol premix in an amount to provide foam formed from said foamable composition with a cream time of less than about 6 seconds after aging for 3 months at room temperature. 
     
     
         15 . The method of  claim 14  wherein said polyol comprises (a) from about 65 wt % to about 95 wt % of at least one polyol; (b) from about 3 wt % to about 30 wt % of blowing agent, said blowing agent comprising from about 10% to about 95% by of 1-chloro-3,3,3-trifluoropropene (1233zd). 
     
     
         27 . The polyol premix of  claim 1  wherein said bismuth catalyst is present in said polyol premix in an amount of from about 0.001 wt % to about 5 wt %. 
     
     
         16 . method of forming a thermoset foam comprising: 
     
     
         17 . forming a polyol premix comprising a combination of: (i) an isocyanate component and (ii) an aged polyol premix composition comprising: (a) from about 60 wt % to about 95 wt % of at least one polyol; (b) from about 1 wt % to about 30 wt % of blowing agent, said blowing agent comprising from about 7 wt % to about 98 wt % by of at least one hydrohaloolefin blowing agent selected from the group consisting of 1,3,3,3-tetrafluoropropene (1234ze); 1-chloro-3,3,3-trifluoropropene (1233zd), 1,1,4,4,4-hexafluorobut-2-ene (1336inzzin); and combinations thereof; (c) at least one surfactant; and (d) a catalyst system comprising metal-based catalyst, wherein said metal based-catalyst consists essentially of an amount of at least one bismuth-based metal catalyst and being sufficiently free of non-bismuth-based catalyst to provide said foamable composition with at least about 10% front-end reactivity improvement relative to the same foamable composition in the absence of said bismuth-based metal catalyst. 
     
     
         18 . The method of  claim 17  wherein said at least one bismuth-metal catalyst comprises a catalyst represented by the formula Bi—(R)3, wherein each R is independently selected from the group consisting of a hydrogen, a halide, a hydroxide, a sulfate, a carbonate, a cyanate, a thiocyanate, an isocyanate, a isothiocyanate, a carboxylate, an oxalate, a nitrate, a C1-C10 alkane, a C1-C10 alkene, a C1-C10 alkyne, a hetero alkyl group, an aryl group, a ketone, an aldehyde, an esters, an ether, an alcohol, an alcoholate, a phenolate, a glycolates, a thiolates, an octoate, a hexanoate, and combinations thereof, where any of the foregoing R groups may be independently substituted or unsubstituted. 
     
     
         19 . The method of  claim 18  wherein said at least one bismuth-metal catalyst is selected from the group consisting of a bismuth carboxylate, a bismuth octoate, bismuth hexanoate, bismuth 2-ethylhexanoate, a bismuth acetylacetonate, bismuth ethoxide, bismuth propoxide, bismuth butoxide, bismuth isopropoxide, bismuth butoxide, a derivative thereof, and combinations thereof. 
     
     
         20 . The method of  claim 19  wherein the amount of said at least one bismuth-based metal catalyst is effective to provide said foamable composition with at least about 20% front-end reactivity improvement relative to the same foamable composition in the absence of said bismuth-based metal catalyst.