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.

Claims

1. A foamable 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.

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. 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 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 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 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. 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.

18. 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.

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 blowing agent is 1234ze(E), 1233zd(E), or 1336mzzm(Z).

22. A foamable 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 one amine catalyst selected from the group of amine catalysts having a pKa of not less than about 10.

Description

BRIEF DESCRIPTION ON OF THE DRAWINGS

[0024] FIG. 1 is a graphical representation of the results according to the description in Table B.

[0025] FIG. 2 is a graphical representation of the results of testing regarding reaction rates as described in the specification

[0026] FIG. 3 is a graphical representation of the results according to the description in Example 1A

[0027] FIG. 4 is a graphical representation of the results according to the description in Example 3B.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0028] Although applicants do not intend to be bound by or to any particular theory of operation, it is believed that the deleterious effects observed by applicants may be occurring as a result of the reaction between the hydrohaloolefin blowing agent and the amine catalysts, one example of such a possible reaction scheme being illustrated below:

##STR00001##

[0029] It is believed that this reaction scheme or similar reaction schemes produce a halogen ion, such as a fluorine ion or chlorine ion, which leads to a decrease in the reactivity of the blowing agent. In addition, applicants believe that the deleterious effects may also be caused, either alone or in addition to the above causes, by the halogen ion, such as fluoride, produced from the above noted reaction in turn reacting with silicone surfactant present in such blowing agents and related systems to produce a lower average molecular weight surfactant, which is then a less effective than originally intended. This depletion/degradation of the surfactant is believe to tend to reduce the integrity of the cell wall and hence tends to produce a foam that is subject higher than desired levels of cell collapse.

[0030] The invention in another aspect provides a high-water content polyol premix composition which comprises a combination of a blowing agent, one or more polyols, one or more silicone surfactants, and a catalyst comprising a precipitation-resistant metal catalyst, more preferably a precipitation-resistant zinc-based catalyst, a precipitation-resistant bismuth-based catalyst, and even more preferably a combination of precipitation-resistant zinc-based catalyst and precipitation-resistant bismuth-based catalyst, including particularly preferably the zinc-based and bismuth based carboxylate catalysts described above. In certain preferred embodiments the catalyst comprising the components (a)-(c) mentioned above (preferably formed as indicated in U.S. Pat. No. 7,485,729), wherein the blowing agent comprises one or more hydrohaloolefins, and optionally a hydrocarbon, fluorocarbon, chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon, ether, ester, alcohol, aldehyde, ketone, organic acid, gas generating material, water or combinations thereof. One preferred catalyst comprising an amine catalyst and a precipitation-resistant metal catalyst comprising a combination of a zinc-based carboxylate catalyst, such as the catalyst sold under the trade designation K-Kat XK-614 by King Industries of Norwalk, Conn., and a bismuth-based metal carboxylate catalyst, such as the catalyst sold under the trade designation K-Kat XC-227 by King Industries of Norwalk, Conn. The invention provides polyol premix composition which comprises a combination of a blowing agent, one or more polyols, one or more silicone surfactants, and a catalyst in which said catalyst comprises in major proportion, and even more preferably consists essentially of a non-amine catalyst, such as an inorgano- or organo-metallic compound or quaternary ammonium carboxylate material. In certain embodiments, the non-amine catalyst can be used either alone or in combination with amine catalysts, wherein the blowing agent comprises one or more hydrohaloolefins, and optionally a hydrocarbon, fluorocarbon, chlorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, halogenated hydrocarbon, ether, ester, alcohol, aldehyde, ketone, organic acid, gas generating material, water or combinations thereof.

[0031] The invention also provides a method of preparing a polyurethane or polyisocyanurate foam comprising reacting an organic polyisocyanate with the polyol premix composition.

The Hydrohaloolefin Blowing Agent

[0032] The blowing agent component comprises a hydrohaloolefin, preferably comprising at least one or a combination of 1234ze(E), 1233zd(E), and isomer blends thereof, and/or 1336mzzm(Z), and optionally a hydrocarbon, fluorocarbon, chlorocarbon, fluorochlorocarbon, halogenated hydrocarbon, ether, fluorinated ether, ester, alcohol, aldehyde, ketone, organic acid, gas generating material, water or combinations thereof.

[0033] The hydrohaloolefin preferably comprises at least one halooalkene such as a fluoroalkene or chlorofluoroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond. Preferred hydrohaloolefins non-exclusively include trifluoropropenes, tetrafluoropropenes such as (1234), pentafluoropropenes such as (1225), chlorotrifloropropenes such as (1233), chlorodifluoropropenes, chlorotrifluoropropenes, chlorotetrafluoropropenes, hexafluorobutenes (1336) and combinations of these. More preferred for the compounds of the present invention are the tetrafluoropropene, pentafluoropropene, and chlorotrifloropropene compounds in which the unsaturated terminal carbon has not more than one F or Cl substituent. Included are 1,3,3,3-tetrafluoropropene (1234ze); 1,1,3,3-tetrafluoropropene; 1,2,3,3,3-pentafluoropropene (1225ye), 1,1,1-trifluoropropene; 1,2,3,3,3-pentafluoropropene, 1,1,1,3,3-pentafluoropropene (1225zc) and 1,1,2,3,3-pentafluoropropene (1225yc); (Z)-1,1,1,2,3-pentafluoropropene (1225yez); 1-chloro-3,3,3-trifluoropropene (1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm) or combinations thereof, and any and all stereoisomers of each of these.

[0034] Preferred hydrohaloolefins have a Global Warming Potential (GWP) of not greater than 150, more preferably not greater than 100 and even more preferably not greater than 75. As used herein, GWP is measured relative to that of carbon dioxide and over a 100-year time horizon, as defined in The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project, which is incorporated herein by reference. Preferred hydrohaloolefins also preferably have an Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more preferably about zero. As used herein, ODP is as defined in The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project, which is incorporated herein by reference.

Coblowing Agents

[0035] Preferred optional co-blowing agents non-exclusively include water, organic acids that produce CO.sub.2 and/or CO, hydrocarbons; ethers, halogenated ethers; esters, alcohols, aldehydes, ketones, pentafluorobutane; pentafluoropropane; hexafluoropropane; heptafluoropropane; trans-1,2 dichloroethylene; methylal, methyl formate; 1-chloro-1,2,2,2-tetrafluoroethane (124); 1,1-dichloro-1-fluoroethane (141b); 1,1,1,2-tetrafluoroethane (134a); 1,1,2,2-tetrafluoroethane (134); 1-chloro 1,1-difluoroethane (142b); 1,1,1,3,3-pentafluorobutane (365mfc); 1,1,1,2,3,3,3-heptafluoropropane (227ea); trichlorofluoromethane (11); dichlorodifluoromethane (12); dichlorofluoromethane (22); 1,1,1,3,3,3-hexafluoropropane (236fa); 1,1,1,2,3,3-hexafluoropropane (236ea); 1,1,1,2,3,3,3-heptafluoropropane (227ea), difluoromethane (32); 1,1-difluoroethane (152a); 1,1,1,3,3-pentafluoropropane (245fa); butane; isobutane; normal pentane; isopentane; cyclopentane, or combinations thereof. In certain embodiments the co-blowing agent(s) include one or a combination of water and/or normal pentane, isopentane or cyclopentane, which may be provided with one or a combination of the hydrohaloolefin blowing agents discussed herein. The blowing agent component is preferably present in the polyol premix composition in an amount of from about 1 wt. % to about 30 wt. %, preferably from about 3 wt. % to about 25 wt. %, and more preferably from about 5 wt. % to about 25 wt. %, by weight of the polyol premix composition. When both a hydrohaloolefin and an optional blowing agent are present, the hydrohaloolefin component is preferably present in the blowing agent component in an amount of from about 5 wt. % to about 90 wt. %, preferably from about 7 wt. % to about 80 wt. %, and more preferably from about 10 wt. % to about 70 wt. %, by weight of the blowing agent components; and the optional blowing agent is preferably present in the blowing agent component in an amount of from about 95 wt. % to about 10 wt. %, preferably from about 93 wt. % to about 20 wt. %, and more preferably from about 90 wt. % to about 30 wt. %, by weight of the blowing agent components.

Polyol Component

[0036] The polyol component, which includes mixtures of polyols, can be any polyol or polyol mixture which reacts in a known fashion with an isocyanate in preparing a polyurethane or polyisocyanurate foam. Useful polyols comprise one or more of a sucrose containing polyol; phenol, a phenol formaldehyde containing polyol; a glucose containing polyol; a sorbitol containing polyol; a methylglucoside containing polyol; an aromatic polyester polyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol; graft copolymers of polyether polyols with a vinyl polymer; a copolymer of a polyether polyol with a polyurea; one or more of (a) condensed with one or more of (b), wherein (a) is selected from glycerine, ethylene glycol, diethylene glycol, trimethylolpropane, ethylene diamine, pentaerythritol, soy oil, lecithin, tall oil, palm oil, and castor oil; and (b) is selected from ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide; and combinations thereof. The polyol component is usually present in the polyol premix composition in an amount of from about 60 wt. % to about 95 wt. %, preferably from about 65 wt. % to about 95 wt. %, and more preferably from about 70 wt. % to about 90 wt. %, by weight of the polyol premix composition.

Surfactant

[0037] The polyol premix composition preferably also contains a silicone surfactant. The silicone surfactant is preferably used to form a foam from the mixture, as well as to control the size of the bubbles of the foam so that a foam of a desired cell structure is obtained. Preferably, a foam with small bubbles or cells therein of uniform size is desired since it has the most desirable physical properties such as compressive strength and thermal conductivity. Also, it is critical to have a foam with stable cells which do not collapse prior to forming or during foam rise.

[0038] Silicone surfactants for use in the preparation of polyurethane or polyisocyanurate foams are available under a number of trade names known to those skilled in this art. Such materials have been found to be applicable over a wide range of formulations allowing uniform cell formation and maximum gas entrapment to achieve very low density foam structures. The preferred silicone surfactant comprises a polysiloxane polyoxyalkylene block co-polymer. Some representative silicone surfactants useful for this invention are Momentive's L-5130, L-5180, L-5340, L-5440, L-6100, L-6900, L-6980 and L-6988; Air Products DC-193, DC-197, DC-5582, and DC-5598; and B-8404, B-8407, B-8409 and B-8462 from Evonik Industries AG of Essen, Germany. Others are disclosed in U.S. Pat. Nos. 2,834,748; 2,917,480; 2,846,458 and 4,147,847. The silicone surfactant component is usually present in the polyol premix composition in an amount of from about 0.5 wt. % to about 5.0 wt. %, preferably from about 1.0 wt. % to about 4.0 wt. %, and more preferably from about 1.5 wt. % to about 3.0 wt. %, by weight of the polyol premix composition.

[0039] The polyol premix composition may optionally contain a non-silicone surfactant, such as a non-silicone, non-ionic surfactant. Such may include oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, turkey red oil, groundnut oil, paraffins, and fatty alcohols. A preferred non-silicone non-ionic surfactant is LK-443 which is commercially available from Air Products Corporation. When a non-silicone, non-ionic surfactant used, it is usually present in the polyol premix composition in an amount of from about 0.25 wt. % to about 3.0 wt. %, preferably from about 0.5 wt. % to about 2.5 wt. %, and more preferably from about 0.75 wt. % to about 2.0 wt. %, by weight of the polyol premix composition.

The Catalyst System

[0040] Applicants have generally found that it is difficult to identify amine catalysts which generate relatively low levels of halogen ions, such as fluoride and chloride, when in contact with hydrohaloolefins while at the same time possessing sufficient activity characteristics to be acceptable for use in producing foams when used alone. In other words, applicants have found that a large number of amine catalysts can be identified which are relatively stable when in the presence of hydrdohaloolefins, but that such catalysts are generally not sufficiently active to provide the necessary foam reactivity. On the other hand, applicants have also found that a relatively large number of amine catalysts can be identified which are sufficiently active to produce acceptable foam reactivity but that such catalysts are generally not sufficiently stable for use in combination with hydrdohaloolefins, as measured by the generation of fluoride.

[0041] Applicants have tested a large number of amine catalyst to determine the physical and/or chemical interaction with certain hydrohaloolefins, and to identify and assess the stability of same. Some of the catalysts tested are identified in Table A below:

TABLE-US-00001 TABLE A % Amine in Trade name Chemical name Formula MW Catalyst* Curithane? 52 Methyl(n-methyl amino b- sodium acetate nonyl phenol) 2- [00002] 343 50 Dabco? TMR-30 Tris- 2,4,6- (dimethylamonomethyl)- phenol [00003] 265 90 Bis(dimethylamino- methyl)phenol [00004] 151 15 Dabco? DEOA-LF Cross linker Diethanol amine Water [00005] 105 85 15 Ethacure? 100 curing agent (DETDA) Diethyltoluenediamine [00006] 178 100 Ethacure? 300 Curative 1,3,benzenediamine 4- methyl-2,6-bis (methylthio) 1,3-benzenediamine-2 methyl-4,6-bis (methylthio) [00007] 214 NS NS 1-methyl- imidazole 1-Methylimidazole [00008] 82 100 Jeffcat? ZR 70 Dimethylaminoethoxy- ethanol [00009] 133 99 Ethylene glycol 1 Jeffamine? D 230 Polyoxpropylene- diamine [00010] 230 100 Jeffamine? T 5000 Glycerol poly(oxypropylene) triamine [00011] 5000 100 Polycat? 5 Pentamethyldiethylene- triamine [00012] 173 NS Polycat? 12 N-Methyldicyclohexyl- amine [00013] 195 NS Dabco? Unidentified amine 24 H-1010 salt in water (50%) *wt % of the indicated molecule in the total catalyst, with the remainder being a carrier such as water, glycol and the like.

[0042] Applicants tested the compatibility of the catalyst with the gaseous and/or liquid blowing agent by use of a pressure reaction vessel. Three grams of catalyst is added to a tarred vessel and it is sealed. After sealing, 3 grams of the blowing agent, such as 1234ze(E), is added through a gas port into the vessel. The contents are mixed and the final weight is recorded. The vapor pressure is taken of the initial solution and a picture is taken to document the color and consistency of the solution and catalyst. The tube is then placed in a 54? C. oven for 24 hours. Twice during the 24 hours the vapor pressure of the solution is measured at the elevated temperature. The solution is removed from the oven and allowed to cool. The vapor pressure is measured and a picture of the solution is taken. The pressure is released from the pressure reaction vessel. The remaining solution is dissolved in de-ionized water to a final volume of 100 ml. The fluoride and chloride concentration is determined by Ion Chromatography.

[0043] Applicants measured fluoride generation when each catalysts is exposed to 1234ze(E) for 24 hours at 54? C. The results are reported in Table B below:

TABLE-US-00002 TABLE B F ppm after Catalyst ID Chemical Identification Structure pka 24 hours Ethacure? 300 Curative 1,3,benzenediamine-4- methyl-2,6-bis (methylthio) [00014] 11 3 1,3-benzenediamine-2 methyl-4,6-bis (methylthio) [00015] 2 Ethacure? 100 curing agent (DETDA) Diethyltoluenediamine [00016] 11-10 11 [00017] 7 Polycat? 12 N-Methyldicyclohexyl- amine [00018] 10 20 18 Jeffamine? T 5000 Glycerol poly(oxypropylene) triamine [00019] 263 166 Curithane? 52 Methyl(n-methyl amino b- sodium acetate nonyl phenol) 2- [00020] 10-11 468 448 Dabco? Amine salt in solvent 634 H-1010 24% amine remainder 663 water Dabco? DEOA-LF Cross linker Diethanol amine [00021] 8.9 1378 1367 Polycat? 5 Pentamethyldiethylene- triamine [00022] 9.1 8.0 2.4 2942 3078 Jeffamine? D 230 polyoxpropylenediamine [00023] 9.5 3751 3174 1-methyl- imidazole 1-Methylimidazole [00024] 7.4 4372 4407 Jeffcat? ZR 70 Diamethylamino ethoxyethanol Ethylene glycol [00025] 9.1 6015 6025 Dabco? TMR-30 Tris-2,4,6- (dimethylamino- methyl)-phenol [00026] 5.8 6790 Bis(dimethylamino- methyl)-phenol [00027] 7577

[0044] Applicants plotted the results of this experimentation, as illustrated in FIG. 1.

[0045] Applicants have also tested the compatibility of the catalyst with the gaseous blowing agent by us of a pressure reaction vessel as described above containing a 50/50 solution of blowing agent, such as 1234ze(E), and catalyst. The tube is then placed in a 54? C. oven for an extended period of time and the fluoride concentration is determined by Ion Chromatography after increasing periods of time according to the procedure describe above. The results, which are depicted in FIG. 2 hereof, show that tertiary amine catalysts react at various rates with the hydrohalofin blowing agents, with the rate being generally inversely correlated with the extent of steric crowding around the amine nitrogen.

[0046] Based on the above noted experimental results, applicants have found that the stability of a particular amine catalyst is related partially to steric hinderance of the amine group and also to the pKa of the amine. In particular, applicants have found that it is highly desirable to select an amine catalyst, if such a catalyst is to be used, that has a pKa of not less than about 10.

[0047] Applicants also analyzed the relationship between fluoride ion generation and the vapor pressure of the solution containing the blowing agent and the catalyst after time. These results are reported in Table C below:

TABLE-US-00003 TABLE C F.sup.? ppm after 24 Vapor Pressure @ RT, psig Catalyst ID hours Initial 24 hours Delta Ethacure? 300 Curative 3 52 53 +1 Ethacure? 300 Curative 2 46 41 ?5 Ethacure? 100 curing agent 11 38 44 +6 (DETDA) Ethacure? 100 curing agent 7 48 49 +1 (DETDA) Polycat? 12 20 62 63 +1 Polycat? 12 18 62 64 +2 Jeffamine? T 5000 263 53 52 ?1 Jeffamine? T 5000 166 58 55 ?3 Curithane? 52 468 72 66 ?6 Curithane? 52 448 66 60 ?6 Dabco? H-1010 634 62 69 +7 Dabco? H-1010 663 62 69 +7 Dabco? DEOA-LF Cross linker 1378 73 66 ?7 Dabco? DEOA-LF Cross linker 1367 74 66 ?8 Polycat? 5 2942 29 22 ?7 Polycat? 5 3078 33 36 +3 Jeffamine? D 230 3751 43 57 +14 Jeffamine? D 230 3714 45 60 +15 1-methylimidazole 4372 38 17 ?21 1-methylimidazole 4407 37 15 ?22 Jeffcat? ZR 70 6015 42 24 ?18 Jeffcat? ZR 70 6025 40 24 ?16 Dabco? TMR-30 6790 43 12 ?21 Dabco? TMR-30 7577 48 9 ?39

[0048] Based on the results obtained as reported in Table C, applicants have found that there is a strong correlation between decrease in vapor pressure (an indication of a decrease in blowing effectiveness) and the increase in generation of F- in the catalyst/hydrohalogen blowing agent (such as 1234ze(E)) test solutions at room temperature. At a fluoride concentration of >4000 ppm there is a consistent loss in vapor pressure. However, applicants have found a surprising and unexpected results with regard to the interrelationship between the catalyst Jeffamine D 230 and 1234ze(E), and in particular that this combination actually results in an increase in vapor pressure over time even though the levels of fluoride generation are significant and nearly at a level of approximately 4000 ppm.

[0049] Based on testing performed by applicants, the following catalysts have been found to have the relative fluoride generation as indicated below in the presence of 1234ze(E).

TABLE-US-00004 TABLE 1 1234ze(E) CATALYST NO. CATALYST PPM, F- 1 diazabicyclo undecane 226,944 2 Diazabicyclooctane (triethylenediamine) 99,000 3 Tris-2,4,6-(dimehtylamino-methyl)- 7184 phnol/Bis(dimehtylaminomethyl)-phenol 4 Dimethylaminoethoxyethanol/ethylene 6020 glycol 5 1-methylimidazole 4390 6 polyoxypropylenediamine 3732 7 Pentamethyldiethylene-triamine 3242 8 Diethylcyclohexl 1970 9 diethanolamine 1372 10 N-mtheyldicyclohexyl-amine 480 11 Methyl(n-methylamino b-sodium acetate 458 nonylphenol) 2- 12 Glycerol poly(oxypropylene) triamine 216 13 Diisopropylethylamine 67 14 Diethyltoluenediamine 10 15 1,3,benzenediamine 4-methyl-2,6- 3 bis(mehtylthio)/1,3-benzenediamine 2- methyl-4,6-bis (mehtylthio)

[0050] In addition to the above, applicants have tested the reactivity of several of the above-noted catalysts, as measured by Gel Time in seconds in a typical panel foam formulation with the blowing agent consisting of 1234ze(E). The results are reported in Tables 2A and 2B provided below:

TABLE-US-00005 TABLE 2B GEL TIMES, SEC CATALYSTS (FROM CHART ABOVE) INITIAL 2.5 DAYS 14 DAYS CHANGE % PMDETA -Std 78 PMDETA/Acid Block 270 PMDETA/Scavenger 75 88 +17 DMCHA 140 145 +3.5 Dicyclohexylmethyl 225 280 290 +29 Dicyclohexylmethyl/ 55 65 72 +31 Dibutyltin Dilaurate Diisopropylethyl 310 370 375 21

[0051] Based upon the testing done by applicants, applicants have found that for blowing agents comprising, and preferably consisting essentially of 1234ze(E), the catalysts numbered 1-9 in Table 1 above are not generally preferred because of stability problems, as indicated by the high level of fluoride concentration. On the other hand, applicants have found that the catalysts numbered 12-15, while demonstrating a high level of stability, are generally not preferred because they are believed to be of not sufficient activity to produce acceptable foam reactivity. Unexpectedly and surprisingly, applicants have found that the catalysts numbered 10 and 11, namely, n-metheyldicyclohexyl-amine and methyl(n-methylamino b-sodium acetate nonylphenol) 2- are preferred in accordance with the present invention because they exhibit a highly desirable but difficult to achieve combination of stability and activity when used in combination with hydrohaloolefins.

[0052] Applicants have also surprisingly and unexpectedly found that from among hydrohaloolefins, 1233zd(E) is substantially less reactive with amine-catalysts in comparison to other hydrohaloolefins, and in particular hydrohalogenated propenes. More specifically, applicants have found as a result of testing that the following catalysts have the relative fluoride generation as indicated below in the presence of 1233zd(E) as reported in Table 3 below.

TABLE-US-00006 TABLE 3 1233zd(E) CATALYST NO./Tradename CATALYST PPM, F- 1 Polycat DBU DBU 26,994 (estimated) 2. Dabco 33LV Diazabicyclooctane (triethylenediamine) 9900 (estimated) 2A Jeffamine D 230 Polyoxypropylenediamine (Jeffamine D 2157 230) 3 Dabco TMR-30 Tris-2,4,6-(dimehtylamino-methyl)- 1521 phnol/Bis(dimehtylaminomethyl)-phenol 4 Jeffcat ZR 70 Dimethylaminoethoxyethanol/ethylene 1753 glycol Toyocat RX5 Bis(dimehtylaminoethyl) ether (Toyocat 1002 RX5) Polycat 9 Bis(dimehtylaminopropyl)-n (Polycat 9) 754 Polycat 30 Tertiary amine (10-30%), gelling catalyst 548 (30-60%) fatty amine (10-30%) 5 Lupragen 1-methyl 1-methylimidazole 221 imidazole 6 polyoxypropylenediamine 1919 7 Polycat 5 Pentamethyldiethylene-triamine 429 Polycat 41 Dimethylaminopropylhexahydrotriuazine, 392 N,N,N 8 Diethylcyclohexl NT 9 Dabco DEOA-LF diethanolamine 343 Lupragen 1-methyl imidazole 1-methylimidazole 221 Dabco H1010 50/50 blend water + amine salt 171 Toyocat DM70 70% 1,2 dimethylimidazole, 30% 170 ethyleneglycol Toyocat TRX Trimerized catalyst 129 N-Methylmorpholine N-methylmorpholine 102 DIPEA Diisopropylethylamine 67 10 Polycat 12 n-methyldicyclohexyl-amine 15 11 Curithane 52 Methyl(n-methylamino b-sodium acetate 190 nonylphenol) 2- 12 Jeffamine T5000 Glycerol poly(oxypropylene) triamine 49 K-Kat x614 Zinc Zinc catalyst complex 36 Jeffcat DMDEE 2,2-dimorpholineodiethylether 24 Polycat 12 N-methyldicycohexyl-amine 15-22 Firstcure N,N- N,N-dimethylparatoluuidine 20 Dimethylparatoluidine Ethacure 300 Curative 3,5-dimethythio-2,4-toluenediamine 9-16 Tyzor TE Titanium Titanium complex 10 Dabco MB20 Bismuth carboxylate catalyst 6 Borchi Oxycoat 1101 Iron catalyst 2 PUCAT 25 Bismuth 2-ethylhexzanoate (25%) 1 13 Diisopropylethylamine NT 14 Ethacure 100 curing agent Diethyltoluenediamine 24 15 Ethacure 300 Curative 1,3,benzenediamine 4-methyl-2,6- 16 bis(mehtylthio)/1,3-benzenediamine 2- methyl-4,6-bis (mehtylthio) NTnot tested

[0053] As can be seen from the results reported above, applicants have found that 1233zd(E) is many times more stable, as measured by fluoride ion generation, in the presence of amine catalysts than are other halogenated olefins, and particularly the tetra-fluorinated propenes such as 1234ze. Moreover, an even more unexpectedly, applicants have found that 1-methylimidazole exhibits an exceptionally high level of stability while retaining a relatively high level of foam reactivity when used in combination with 1233zd(E). Similarly, applicants have unexpectedly found that n-methyldicyclohexyl-amine exhibits an exceptionally high level of stability while retaining a relatively high level of foam reactivity when used in combination with 1233zd(E).

[0054] Notwithstanding the unexpected and advantageous results described above regarding combinations of halogenated olefins and certain amine catalysts, applicants have found that even the best of such combinations is not fully satisfactory for many embodiments, and that further substantial and unexpected improvement can be achieved by replacing all or a substantial portion of the amine catalyst(s) with one or more metal catalysts, and even more preferably two or more catalysts wherein at least a first and a second of said catalysts is based upon a different metal. In general, applicants have found that metal catalysts are relatively nonreactive with halogenated olefins that are adaptable for use as blowing agents and therefore appear to produce a relatively stable system, and that with a judicious selection of at least a first and second metal catalyst surprisingly effective and stable compositions, systems and methods can be obtained.

[0055] Applicants have found that the use of a catalyst system based upon a single metal in many embodiments is not capable of fully satisfying the desired reactivity profile for the foamable composition and/or method. Applicants have found that surprising and highly beneficial results can be achieved in certain embodiments by the selection of catalyst systems comprising a first metal catalyst wherein said first metal is selected from a metal catalysts exhibiting relatively high activity at low temperatures and a second metal catalyst wherein said second metal is selected from the catalytic metals tending to exhibit relatively high activity at higher temperatures. In certain preferred embodiments, the metal of the first metal catalyst is selected from the group consisting of kin, zinc, cobalt, lead and combinations of these, with catalyst comprising and even more preferably consisting essentially of zinc-based metal catalysts (and even more preferably organozinc-metal-based catalysts) being especially preferred. In certain preferred embodiments, the metal of the second metal catalyst is selected from the group consisting of bismuth, sodium, calcium and combinations of these, with catalyst comprising and even more preferably consisting essentially of bismuth-based metal catalysts (and even more preferably organobismuth-metal-based catalysts) being especially preferred. In highly preferred embodiments of the present invention, the catalyst system comprises a first metal catalyst and a second metal catalyst according to the broad and preferred aspects of the present invention but but contains less than 50% by weight, based on the total weight of catalyst, of amine-based catalyst, and in certain preferred embodiments is substantially free of amine catalyst.

[0056] Furthermore, applicants have found that blowing agents and foamable systems that are highly desirable in certain embodiments can be obtained by utilizing one or more of the preferred amine catalysts of the present invention in combination with at least one, and preferably at least two, metal catalysts according to the invention as described above.

[0057] In certain embodiments, the non-amine catalysts are inorgano- or organo-metallic compounds. Useful inorgano- or organo-metallic compounds include, but are not limited to, organic salts, Lewis acid halides, or the like, of any metal, including, but not limited to, transition metals, post-transition (poor) metals, rare earth metals (e.g. lanthanides), metalloids, alkali metals, alkaline earth metals, or the like. According to certain broad aspects of the present invention, the metals may include, but are not limited to, 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, or combinations thereof. Non-exclusive examples of such inorgano- or organo-metallic catalysts include, but are not limited to, 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, or combinations thereof. In certain preferred embodiments the catalysts are present in the polyol premix composition in an amount of from about 0.001 wt. % to about 5.0 wt. %, 0.01 wt. % to about 3.0 wt. %, preferably from about 0.3 wt. % to about 2.5 wt. %, and more preferably from about 0.35 wt. % to about 2.0 wt. %, by weight of the polyol premix composition. While these are usual amounts, the quantity amount of the foregoing catalyst can vary widely, and the appropriate amount can be easily be determined by those skilled in the art.

[0058] Furthermore, as mentioned above, applicants have found that it is desirable to use certain metal-based catalysts in foamable and foaming systems having relatively high levels of water, and particularly high-water poyol pre-mix compostions. More specifically, applicants have found that certain catalysts based on zinc, tin, bismuth and potassium are preferred in such systems because of their ability to retain their reactivity and avoid stability problems in such high water systems. Furthermore, applicants have found that catalysts based upon zinc and bismuth generally have a acceptable performance in systems having relatively low water content but that not all of such catalyst are able to produce the most desirably results in high-water content systems and compositions. Applicants have found that the class of metal catalysts described above, and preferably zinc-based catalysts and/or bismuth-based catalysts, and even more preferably in certain embodiments amine/zinc-based/bismuth based catalyst blends are capable of performing effectively in high-water content systems and compositions wherein the metal catalyst comprises a precipitation-resistant metal-based catalyst(s) as that term is defined herein. In other or additional embodiments, applicants have found that it is preferred in certain systems that the metal catalysts comprise at least a first catalysts based upon tin and/or zinc, and a second catalyst based upon potassium and/or bismuth, and preferably the first and second metal catalysts comprise and preferably consist essentially of precipitation-resistant metal-based catalyst(s).

[0059] In another embodiment of the invention, the non-amine catalyst is a quaternary ammonium carboxylate. Useful quaternary ammonium carboxylates include, but are not limited to: (2-hydroxypropyl)trimethylammonium 2-ethylhexanoate (TMR? sold by Air Products and Chemicals) and (2-hydroxypropyl)trimethylammonium formate (TMR-2? sold by Air Products and Chemicals). These quaternary ammonium carboxylate catalysts are usually present in the polyol premix composition in an amount of from about 0.25 wt. % to about 3.0 wt. %, preferably from about 0.3 wt. % to about 2.5 wt. %, and more preferably from about 0.35 wt. % to about 2.0 wt. %, by weight of the polyol premix composition. While these are usual amounts, the quantity amount of catalyst can vary widely, and the appropriate amount can be easily be determined by those skilled in the art.

[0060] In another embodiment, as mentioned above, the non-amine catalyst is used in combination with an amine catalyst. Such amine catalysts may include any compound containing an amino group and exhibiting the catalytic activity provided herein. Such compounds may be straight chain or cyclic non-aromatic or aromatic in nature. Useful, non-limiting, amines include primary amines, secondary amines or tertiary amines. Useful tertiary amine catalysts non-exclusively include 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-(?-phenylethyl)amine, N,N,N-tri-n-propylamine, or combinations thereof. Useful secondary amine catalysts non-exclusively include dicyclohexylamine; t-butylisopropylamine; di-t-butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di-(?-trifluoromethylethyl)amine; di-(?-phenylethyl)amine; or combinations thereof. Useful primary amine catalysts non-exclusively include: triphenylmethylamine and 1,1-diethyl-n-propylamine.

[0061] Other useful amines includes morpholines, imidazoles, ether containing compounds, and the like. These include:

dimorpholinodiethylether

N-ethylmorpholine

N-methylmorpholine

[0062] 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.

[0063] In embodiments where an amine catalyst is provided, the catalyst may be provided in any amount to achieve the function of the instant invention without affecting the foam forming or storage stability of the composition, as characterized herein. To this end, the amine catalyst may be provided in amounts less than or greater than the non-amine catalyst.

[0064] The preparation of polyurethane or polyisocyanurate foams using the compositions described herein may follow any of the methods well known in the art can be employed, see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology, 1962, John Wiley and Sons, New York, N.Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, N.Y. or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, Ohio. In general, polyurethane or polyisocyanurate foams are prepared by combining an isocyanate, the polyol premix composition, and other materials such as optional flame retardants, colorants, or other additives. These foams can be rigid, flexible, or semi-rigid, and can have a closed cell structure, an open cell structure or a mixture of open and closed cells.

[0065] It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foams in pre-blended formulations. Most typically, the foam formulation is pre-blended into two components. The isocyanate and optionally other isocyanate compatible raw materials, including but not limited to blowing agents and certain silicone surfactants, comprise the first component, commonly referred to as the A component. The polyol mixture composition, including surfactant, catalysts, blowing agents, and optional other ingredients comprise the second component, commonly referred to as the B component. In any given application, the B component may not contain all the above listed components, for example some formulations omit the flame retardant if flame retardancy is not a required foam property. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like. Optionally, other ingredients such as fire retardants, colorants, auxiliary blowing agents, water, and even other polyols can be added as a stream to the mix head or reaction site. Most conveniently, however, they are all incorporated into one B component as described above.

[0066] A foamable composition suitable for forming a polyurethane or polyisocyanurate foam may be formed by reacting an organic polyisocyanate and the polyol premix composition described above. Any organic polyisocyanate can be employed in polyurethane or polyisocyanurate foam synthesis inclusive of aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates which are well known in the field of polyurethane chemistry. These are described in, for example, U.S. Pat. Nos. 4,868,224; 3,401,190; 3,454,606; 3,277,138; 3,492,330; 3,001,973; 3,394,164; 3,124.605; and 3,201,372. Preferred as a class are the aromatic polyisocyanates.

[0067] Representative organic polyisocyanates correspond to the formula:

R(NCO)z

wherein R is a polyvalent organic radical which is either aliphatic, aralkyl, aromatic or mixtures thereof, and z is an integer which corresponds to the valence of R and is at least two. Representative of the organic polyisocyanates contemplated herein includes, for example, the aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate and the like; the aromatic triisocyanates such as 4,4,4-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates; the aromatic tetraisocyanates such as 4,4-dimethyldiphenylmethane-2,25,5-tetraisocyanate, and the like; arylalkyl polyisocyanates such as xylylene diisocyanate; aliphatic polyisocyanate such as hexamethylene-1,6-diisocyanate, lysine diisocyanate methylester and the like; and mixtures thereof. Other organic polyisocyanates include polymethylene polyphenylisocyanate, hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 4,4-biphenylene diisocyanate, 3,3-dimethoxy-4,4-biphenyl diisocyanate, 3,3-dimethyl-4,4-biphenyl diisocyanate, and 3,3-dimethyldiphenylmethane-4,4-diisocyanate; Typical aliphatic polyisocyanates are alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, isophorene diisocyanate, 4, 4-methylenebis(cyclohexyl isocyanate), and the like; typical aromatic polyisocyanates include m-, and p-phenylene disocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6-toluenediisocyanate, dianisidine diisocyanate, bitoylene isocyanate, naphthylene 1,4-diisocyanate, bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane, and the like. Preferred polyisocyanates are the polymethylene polyphenyl isocyanates, Particularly the mixtures containing from about 30 to about 85 percent by weight of methylenebis(phenyl isocyanate) with the remainder of the mixture comprising the polymethylene polyphenyl polyisocyanates of functionality higher than 2. These polyisocyanates are prepared by conventional methods known in the art. In the present invention, the polyisocyanate and the polyol are employed in amounts which will yield an NCO/OH stoichiometric ratio in a range of from about 0.9 to about 5.0. In the present invention, the NCO/OH equivalent ratio is, preferably, about 1.0 or more and about 3.0 or less, with the ideal range being from about 1.1 to about 2.5. Especially suitable organic polyisocyanate include polymethylene polyphenyl isocyanate, methylenebis(phenyl isocyanate), toluene diisocyanates, or combinations thereof.

[0068] In the preparation of polyisocyanurate foams, trimerization catalysts are used for the purpose of converting the blends in conjunction with excess A component to polyisocyanurate-polyurethane foams. The trimerization catalysts employed can be any catalyst known to one skilled in the art, including, but not limited to, glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, and alkali metal carboxylic acid salts and mixtures of the various types of catalysts. Preferred species within the classes are potassium acetate, potassium octoate, and sodium N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

[0069] Conventional flame retardants can also be incorporated, preferably in amount of not more than about 20 percent by weight of the reactants. Optional flame retardants include tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tris(1,3-dichloropropyl)phosphate, tri(2-chloroisopropyl)phosphate, tricresyl phosphate, tri(2,2-dichloroisopropyl)phosphate, diethyl N,N-bis(2-hydroxyethyl) aminomethylphosphonate, dimethyl methylphosphonate, tri(2,3-dibromopropyl)phosphate, tri(1,3-dichloropropyl)phosphate, and tetra-kis-(2-chloroethyl)ethylene diphosphate, triethylphosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, melamine, and the like. Other optional ingredients can include from 0 to about 7 percent water, which chemically reacts with the isocyanate to produce carbon dioxide. This carbon dioxide acts as an auxiliary blowing agent. Formic acid is also used to produce carbon dioxide by reacting with the isocyanate and is optionally added to the B component.

[0070] In addition to the previously described ingredients, other ingredients such as, dyes, fillers, pigments and the like can be included in the preparation of the foams. Dispersing agents and cell stabilizers can be incorporated into the present blends. Conventional fillers for use herein include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fibers, carbon black and silica. The filler, if used, is normally present in an amount by weight ranging from about 5 parts to 100 parts per 100 parts of polyol. A pigment which can be used herein can be any conventional pigment such as titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron blue siennas, molybdate oranges and organic pigments such as para reds, benzidine yellow, toluidine red, toners and phthalocyanines.

[0071] The polyurethane or polyisocyanurate foams produced can vary in density from about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably from about 1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6.0 pounds per cubic foot. The density obtained is a function of how much of the blowing agent or blowing agent mixture disclosed in this invention plus the amount of auxiliary blowing agent, such as water or other co-blowing agents is present in the A and/or B components, or alternatively added at the time the foam is prepared. These foams can be rigid, flexible, or semi-rigid foams, and can have a closed cell structure, an open cell structure or a mixture of open and closed cells. These foams are used in a variety of well known applications, including but not limited to thermal insulation, cushioning, flotation, packaging, adhesives, void filling, crafts and decorative, and shock absorption.

[0072] The following non-limiting examples serve to illustrate the invention.

Example 1ASpray Foam

[0073] Two typical commercial polyol spray-foam formulations are formed in accordance with Table E1A below:

TABLE-US-00007 TABLE E1A Components php Polyol Blend, 50? F. (10? C.) Voranol? 470X 40.0 40.0 Terate? 4020 60.0 60.0 Dabco? DC193 2.0 2.0 Dabco? K-15 1.4 1.4 Polycat? 5 1.4 1.4 Dabco 33LV 0.7 1.2 Antiblaze AB80 20 1.5 Water 2 2.0 245fa 20 1233zd(E) 20 Isocyanate, 70? F. (21? C.) Lupranate? M20S Iso Index = 150

[0074] After testing for stability, the results reported in FIG. 3 are obtained.

[0075] The formulations are maintained for up to 168 hours at about 52 C according to the procedure described above. Three different foams are formed from each formulation: one essentially upon initial formulation; one after about 62 hours of aging; and one after 168 hours of aging. Gel time is observed for each of the foams thus formed and the results are provided in FIG. 3. As can be seen from the above example and the data illustrated in FIG. 3, the gel time for a typical foam formulation, particularly a spray foam formulation, increases substantially as the foamable composition is aged when a typical catalyst formulation is used, especially in comparison to the level of increase which is observed for saturated blowing agent materials such as HFC-245fa. Those skilled in the art would appreciate that such performance is generally considered not acceptable for many commercial embodiments.

Example 1BSpray Foam

[0076] Two typical commercial polyol spray-foam formulations are formed in accordance with Table E1BA below:

TABLE-US-00008 TABLE E1BA Sample LW Sample HW Components php php Polyol Blend, 50? F. (10? C.) Mannich polyether polyol having 40 40 an OH# 470 (Voranol 470X) Aromatic polyester polyol (Terate 60 60 4020) Silicone surfactant (Dabco DC193) 2.0 2.0 Potassium octoate in diethylene 1.4 1.4 glycol solution - 15% (Dabco K-15 Dicyclohexylmethylamine 2.0 2.0 zinc 2-ethlyhexanoate* 2.0 2.0 Bismuth Carboxylate Catalyst 0.7 0.7 (Dabco MB-20) TCPP (tris(2-chloroisopropyl) 20 20 phosphate Water 0.5 2 1233zd(E) 20 20 Isocyanate, 70? F. (21? C.) Polymethyldiisocyanate (PMDI) ISO Index = ISO Index = 150 150 Test results for precipitation Negative Positive resistance (according to test (no substantial (substantial described herein) precipitation precipitation observed based observed after on High Temper- Both High ature Test and Temperture and Low Temperature Low Temperature Test) Tests) *The MSDS for this material is attached as Attachment C and incorporated herein by reference.

[0077] The table above indicates that while the zinc-based catalyst and the bismuth-based catalyst used in this system does not produce a precipitate in low water systems (Sample LW), when tested under either High Temperature test or the Low Temperature test, but that a precipitate is formed in both tests when the composition is otherwise identical except that the system is a high water content system (Sample HW).

[0078] For comparison purposes, the zinc catalyst used in Sample HW above is replaced with a catalyst that is a zinc-based precipitation resistant catalyst according to the present invention, as illustrated by Sample HW-PR in Table E1BB below:

TABLE-US-00009 TABLE E1BB SAMPLE HW-PR Components php Polyol Blend, 50? F. (10? C.) Mannich polyether polyol having 40.0 an OH# of 470 Aromatic polyester polyol 60.0 Silicone surfactant 2.0 Potassium octoate solution - 15% 1.4 Dicyclohexylmethylamine 2.0 K-Kat XK-614 2.0 MB-20 Bismuth Catalyst 0.7 TCPP 20 Water 2 1233zd(E) 20 Isocyanate, 70? F. (21? C.) Lupranate? M20S Iso Index = 150 Test results for precipitation Negative/Postitive resistance (according to test (no substantial described herein) precipitation observed after the High Temperature test but bismuth salt precipitation is observed after three months of the Low Temperature test)

[0079] In the above formulation, the K-Kat XK-614 is blended with the polyol blend (resins) first and the water component is then added, and applicants have found that this the preferred order of addition of the components in the system.

[0080] After testing for stability using the same procedure as described in Example 1 above, the stability is greatly improved for the Sample HW in Table E1BB, showing no increase in gel time even when the formulation is stored before use for 168 hours at 52 C.

Example 2Spray Foam without Catalyst

[0081] A typical commercial polyol spray-foam formulations, except with no catalyst present, is formed in accordance with Table E2A below:

TABLE-US-00010 TABLE E2A Components php Polyol Blend, 50? F. (10? C.) Voranol? 470X 40 Terate 4020? 60 Dabco? DC193 2 Water 2 Antiblaze? AB80 20 1233zd(E) 20 Isocyanate, 70? F. (21? C.) Lupranate? M20S ISO Index = 150

[0082] After testing for stability, results consistent with those illustrated in FIG. 1 are obtained, indicating that 1233zd(E) is acceptable as a blowing agent for use in combination with typical commercially used polyol compounds, including particularly polyal compounds used in typical commercial spray foam applications.

Example 3Spray Foam with Catalyst

[0083] A polyol spray-foam formulations according to the present invention is formed using the preferred blowing agent 1233zd(E) but with a less-preferred catalyst system consisting of a single bismuth metal catalyst and a non-preferred amine-based catalyst in accordance with Table E3A below:

TABLE-US-00011 TABLE E3A Components php Polyol Blend, 50? F. (10? C.) Voranol? 470X 40.0 Terate? 4020 60.0 Dabco? DC193 2.0 Dabco? K-15 1.4 Polycat 5 1.4 MB-20 Bismuth Catalyst 0.7 Antiblaze AB80 20 Water 2 1233zd(E) 20 Isocyanate, 70? F. (21? C.) Lupranate? M20S Iso Index = 150

[0084] The same formulation as illustrated in Table E3A is formed, except the catalyst is replaced with a more preferred catalyst system of the present invention consisting of a first metal (zinc), precipitation resistant catalyst and second metal (bismuth) catalyst and a preferred amine-based catalyst in accordance with Table E3B below:

TABLE-US-00012 TABLE E3B Components php Polyol Blend, 50? F. (10? C.) Voranol? 470X 40.0 Terate? 4020 50.0 Dabco? DC193 2.0 Dabco? K-15 1.4 Polycat? 12 2.0 Zinc Catalyst 2.0 Bismuth Catalyst 0.7 Antiblaze AB80 20 Water 2 1233zd(E) 20 Isocyanate, 70? F. (21? C.) Lupranate? M20S Iso Index = 150 * The Zinc Catalyst is K-Kat XK-614 described herein and the Bismuth catalyst is MB-20 described herein.

[0085] After testing for stability, the results reported in FIG. 4 are obtained, with the data represented by the white column and labeled 1233zd(E) corresponding to the results from formulation in Table E3A and the data represented by the green column and labeled 1233zd(E)+modified catalyst corresponding to the results from formulation in Table E3B, illustrating no increase in gel time after 62 hours and only an 8% increase in gel time after 168 hours.

[0086] The formulation shows a negative result for precipitation resistance under High Temperature conditions (no substantial precipitation observed after the High Temperature test) but a positive result with respect to bismuth (bismuth salt precipitation is observed after three months of the Low Temperature test).

[0087] The results reported in this example illustrates the surprising and highly beneficial advantages associated with use of blowing agents, foamable compositions, foams and foaming methods using the preferred catalyst systems of the present invention.

Example 3CSpray Foam with Catalyst

[0088] A polyol spray-foam formulation the same as the formulation used in Example 3A is formed, except that the bismuth catalyst that is not Precipitation Resistant according to the Low Temperature test is replaced by a bismuth catalyst that is Precipitation Resistant according to both the Low Temperature test and the High Temperature test.

TABLE-US-00013 TABLE E3C Components php Polyol Blend, 50? F. (10? C.) Voranol? 470X 40.0 Terate? 4020 50.0 Dabco? DC193 2.0 Dabco? K-15 1.4 Polycat? 12 2.0 Zinc Catalyst 2.0 Bismuth Catalyst 0.7 Antiblaze AB80 20 Water 2 1233zd(E) 20 Isocyanate, 70? F. (21? C.) Lupranate? M20S Iso Index = 150 * The Zinc Catalyst is K-Kat XK-614 described herein and the Bismuth Catalyst is K-Kat XC-227 described herein.

[0089] The gel time for this typical foam formulation, particularly a spray foam formulation, did not increase after three months storage at room temperature when the blowing agent consists of 1233zd and the preferred catalyst of the present invention is used as per Table 3C. Those skilled in the art will appreciate that such performance is generally considered acceptable for many commercial embodiments and would appreciate that such an improvement in gel time performance is substantial, significant and surprising. Furthermore, the formulation shows a negative result for precipitation resistance under High Temperature conditions (no substantial precipitation observed after the High Temperature test) and a negative result with respect to bismuth (bismuth salt precipitation is not observed after three months of the Low Temperature test). According, both metal catalysts in this system are Precipitation Resistant under both the High Temperature and the Low Temperature tests.

Example 3DSpray Foam with Catalyst

[0090] A polyol spray-foam formulation different than the formulation used in Example 3C is formed using the preferred blowing agent 1233zd(E) and the preferred catalyst system of Example 3C, as indicated in Table E3D below.

TABLE-US-00014 TABLE E3D Components Php Polyol Blend, 40? F. (4.4? C.) Polyether polyol EDA-PO, EDA- 70 PO/EO (50/50) Mannich polyol (OH 350) 30.0 Dabco?1 DC193 (Silicone 1.5 surfactant) Lead (20%) (optional) 0.5 Dabco K-15 1.5 Polycat 12 2.0 K-Kat?11 XK-614 Zinc Catalyst 2.0 K-Kat XK-227 Bismuth Catalyst 0.7 Antiblaze?13 AB80 20 Water 1.5 1233zd(E) 30 Isocyanate, 70? F. (21? C.) Lupranate?3 M20S Iso Index = 150

[0091] As can be seen from the table above, the type and amounts of the various components are changed, but a catalyst consisting of a first metal (zinc) Precipitation Resistant catalyst and second metal (bismuth) Precipitation Resistant catalyst, and a preferred amine-based catalyst is used. Furthermore, the formulation shows Precipitation Resistance under High Temperature conditions (no substantial precipitation observed after the High Temperature test) and Precipitation Resistance under Low Temperature conditions (bismuth salt precipitation is not observed after three months of the Low Temperature test). According, both metal catalysts in this system are Precipitation Resistant under both the High Temperature and the Low Temperature tests.

Example 3ESpray Foam with Catalyst

[0092] A polyol spray-foam formulation different than the formulation used in Example 3C is formed using the preferred blowing agent 1233zd(E) and a preferred catalyst system as indicated in Table E3E below.

TABLE-US-00015 TABLE E3E Components Php Polyol Blend, 40? F. (4.4? C.) Polyether polyol EDA-PO, EDA- 70 PO/EO (50/50) Mannich polyol (OH 350) 30.0 Dabco?1 DC193 (Silicone 1.5 surfactant) Lead (20%) (optional) 0.5 Dabco K-15 1.5 Polycat 12 2.0 potassium acetate 2.7 Antiblaze?13 AB80 20 Water 1.5 1233zd(E) 30 Isocyanate, 70? F. (21? C.) Lupranate?3 M20S Iso Index = 150

[0093] The formulation shows a negative result for precipitation resistance under High Temperature conditions (no substantial precipitation observed after the High Temperature test) and precipitation resistance under Low Temperature conditions (no substantial precipitation is observed after three months of the Low Temperature test). Accordingly the metal catalysts in this system is Precipitation Resistant under both the High Temperature and the Low Temperature tests.

Example 3FSpray Foam with Catalyst

[0094] A polyol spray-foam formulation different than the formulation used in Example 3C is formed using the preferred blowing agent 1233zd(E) and a preferred catalyst system as indicated in Table E3F below.

TABLE-US-00016 TABLE E3F Components Php Polyol Blend, 40? F. (4.4? C.) Polyether polyol EDA-PO, EDA- 70 PO/EO (50/50) Mannich polyol (OH 350) 30.0 Dabco?1 DC193 (Silicone 1.5 surfactant) Lead (20%) (optional) 0.5 Dabco K-15 1.5 Polycat 12 2.0 potassium octoate 2.7 Antiblaze?13 AB80 20 Water 1.5 1233zd(E) 30 Isocyanate, 70? F. (21? C.) Lupranate?3 M20S Iso Index = 150

[0095] The formulation shows a negative result for precipitation resistance under High Temperature conditions (no substantial precipitation observed after the High Temperature test) and precipitation resistance under Low Temperature conditions (no substantial precipitation is observed after three months of the Low Temperature test). Accordingly the metal catalysts in this system is Precipitation Resistant under both the High Temperature and the Low Temperature tests.

Example 3GSpray Foam with Catalyst

[0096] A polyol spray-foam formulation different than the formulation used in Example 3C is formed using the preferred blowing agent 1233zd(E) and a preferred catalyst system as indicated in Table E3G below.

TABLE-US-00017 TABLE E3G Components php Polyol Blend, 40? F. (4.4? C.) Polyether polyol EDA-PO, EDA- 70 PO/EO (50/50) Mannich polyol (OH 350) 30.0 Dabco?1 DC193 (Silicone 1.5 surfactant) Lead (20%) (optional) 0.5 Dabco K-15 1.5 Polycat 12 2.0 sodium N-(2-hydroxy-5- 2.7 nonylphenol)methyl-N- methylglycinate Antiblaze?13 AB80 20 Water 1.5 1233zd(E) 30 Isocyanate, 70? F. (21? C.) Lupranate?3 M20S Iso Index = 150

[0097] The formulation shows a negative result for precipitation resistance under High Temperature conditions (no substantial precipitation observed after the High Temperature test) and precipitation resistance under Low Temperature conditions (no substantial precipitation is observed after three months of the Low Temperature test). Accordingly the metal catalysts in this system is Precipitation Resistant under both the High Temperature and the Low Temperature tests.

Example 4 (Comparative Example)

[0098] A polyol (B Component) formulation was made up of 100 parts by weight of a polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5 parts by weight water, 1.2 parts by weight pentamethyldiethylenetriamine (sold as Polycat 5 by Air Products and Chemicals) catalyst, and 8 parts by weight trans-1,3,3,3-tetrafluoropropene blowing agent. The total B component composition, when freshly prepared and combined with 120.0 parts by weight of Lupranate M20S polymeric isocyanate yielded a good quality foam with a fine and regular cell structure. Foam reactivity was typical for a pour in place foam. The total B-side composition (112.2 parts) was then aged at 130? F. for 62 hours, and then combined with 120.0 parts of M20S polymeric isocyanate to make a foam. The foam was very poor in appearance with significant cell collapse. Significant yellowing of the polyol premix was noted during aging.

Example 5 (Comparative Example)

[0099] A polyol (B Component) formulation was made up of 100 parts by weight of a polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5 parts by weight water, 1.2 parts by weight pentamethyldiethylenetriamine (sold as Polycat 5 by Air Products and Chemicals) catalyst and 8 parts by weight blowing agent trans-1-chloro-3,3,3-trifluoropropene. The total B component composition, when freshly prepared and combined with 120.0 parts by weight of Lupranate M20S polymeric isocyanate yielded a good quality foam with a fine and regular cell structure. Foam reactivity was typical for a pour in place foam. The total B-side composition (112.2 parts) was then aged at 130? F. for 168 hours, and then combined with 120.0 parts of M20S polymeric isocyanate to make a foam. The foam was very poor in appearance with significant cell collapse. Significant yellowing of the polyol premix was noted during aging.

Example 6 (Foam Test)

[0100] A polyol (B Component) formulation was made up of 100 parts by weight of a polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.5 parts by weight water, 2.0 parts by weight N,N-dicyclohexylmethylamine (sold as Polycat 12 by Air Products and Chemicals) catalyst (a different amine was used such that both this foam and the comparative example had the same initial reactivity), 1.75 parts by weight a bismuth based catalyst (sold as Dabco MB-20 by Air Products and Chemicals) and 8 parts by weight trans-1,3,3,3-tetrafluoropropene blowing agent. The total B component composition, when freshly prepared and combined with 120.0 parts by weight of Lupranate M20S polymeric isocyanate yielded a good quality foam with a fine and regular cell structure. Foam reactivity was typical for a pour in place foam. The total B-side composition (114.75 parts) was then aged at 130? F. for 336 hours, and then combined with 120.0 parts of M20S polymeric isocyanate to make a foam. The foam was excellent in appearance with no evidence of cell collapse. There was no yellowing of the polyol premix noted during aging.

Example 7 (Foam Test)

[0101] A polyol (B Component) formulation was made up of 100 parts by weight of a polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 0.5 parts by weight water, 2.0 parts by weight N,N-dicyclohexylmethylamine (sold as Polycat 12 by Air Products and Chemicals) catalyst (a different amine was used such that both this foam and the comparative example had the same initial reactivity), 1.75 parts by weight of zinc 2-ethylhexanoate (sold as 30-3038 by Strem Chemicals) and 8 parts by weight trans-1-chloro-3,3,3-trifluoropropene blowing agent. The total B component composition, when freshly prepared and combined with 103.0 parts by weight of Lupranate M20S polymeric isocyanate yielded a good quality foam with a fine and regular cell structure. Foam reactivity was typical for a pour in place foam. The total B-side composition (113.75 parts) was then aged at 130? F. for 336 hours, and then combined with 103.0 parts of M20S polymeric isocyanate to make a foam. The foam was excellent in appearance with no evidence of cell collapse. There was no yellowing of the polyol premix noted during aging

Example 8 (Foam Test)

[0102] A polyol (B Component) formulation was made up of 100 parts by weight of a polyol blend, 1.5 parts by weight Niax L6900 silicone surfactant, 1.0 parts by weight water, 2.0 parts by weight N,N-dicyclohexylmethylamine (sold as Polycat 12 by Air Products and Chemicals) catalyst (a different amine was used such that both this foam and the comparative example had the same initial reactivity), 1.75 parts by weight a Potassium based catalyst (sold as Dabco K15 by Air Products and Chemicals) and 8 parts by weight trans-1-chloro-3,3,3-trifluoropropene blowing agent. The total B component composition, when freshly prepared and combined with 112.0 parts by weight of Lupranate M20S polymeric isocyanate yielded a good quality foam with a fine and regular cell structure. Foam reactivity was typical for a pour in place foam. The total B-side composition (114.75 parts) was then aged at 130? F. for 504 hours, and then combined with 112.0 parts of M20S polymeric isocyanate to make a foam. The foam was good in appearance with only slight evidence of cell collapse. There was very slight yellowing of the polyol premix noted during aging.

Example 9Panel Foam

[0103] Two typical commercial polyol panel-foam formulations are formed in accordance with Table E9A below:

TABLE-US-00018 TABLE E9A Sample Sample 9-LW 9-HW Components php php Polyol Blend, 50? F. (10? C.) Sucrose/glycerine initiated polyether 50 50 polyol having OH # 490 (Veranol 490) Glycerine initiated triol polyether 50 50 polyol having OH# 290 (Veranol 270) Dicyclohexylmethylamine (Polycat 12) 2.00 2.00 zinc 2-ethlyhexanoate manufactured 1.75 1.75 by Strem Chemicals, product number 30-3038 (attachment C) Non-hydrolizable silicone copolymer 1.5 1.5 (Niax L6900) Water 0.5 1.5 1233zd(E) 8 8 Isocyanate, 70? F. (21? C.) Lupranate? M20S ISO Index = ISO Index = 110 110 Test results for Negative (no Positive precipitation resistance substantial (substantial precipitation precipitation observed) observed)

[0104] The table above indicates that while the zinc-based catalyst does not produce a precipitate in low water systems (Sample LW), that a precipitate is formed when the composition is otherwise identical except that the system is a high water content system (Sample HW). The zinc catalyst used in Sample HW above is replaced with a catalyst that is a precipitation resistant catalyst according to the present invention as illustrated by Sample HW-PR in Table E9B below:

TABLE-US-00019 TABLE E9B Sample HW - PR Components php Polyol Blend, 50? F. (10? C.) Voranol? 490 (Sucrose/glycerine initiated polyether 50 polyol) Voranol? 270 (Glycerine initiated triol polyether 50 polyol) Dicyclohexylmethylamine (Polycat? 12) 2.00 K-Kat XK-614 1.75 Niax? L6900 (Non-hydrolizable silicone copolymer) 1.5 Water 1.5 1233zd(E) 8 Isocyanate, 70? F. (21? C.) Lupranate? M20S ISO Index = 110 Test results for precipitation resistance (according to Negative (no test described herein) substantial precipitation observed)

[0105] In the above formulation, the K-Kat XK-614 is blended with the polyol blend (resins) first and the water component is then added, and applicants have found that this the preferred order of addition of the components in the system.

[0106] After testing for stability, the Sample HW had performance in terms of gel time that is substantially inferior to the performance of the Sample HW-PR as measured by gel time.