AU2014274606B2 - Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing z-1,1,1,4,4,4-hexafluoro-2-butene and their uses in the preparation of polyisocyanate-based foams - Google Patents

Abstract

Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing cis- 1, 1,1,4,4,4-hexafluoro-2-butene are disclosed. The foam-forming composition contains (a) an azeotropic or azeotrope-like 5 mixture of cis- 1, 1,1,4,4,4-hexafluoro-2-butene with methyl formate, 1,1,1,3,3 pentafluorobutane, trans-1,2-dichloroethylene, pentane, isopentane, cyclopentane, HFC-245fa, or dimethoxymethane; and (b) an active hydrogen containing compound having two or more active hydrogens. Also disclosed is a closed-cell polyurethane or polyisocyanurate polymer foam prepared from 10 reaction of an effective amount of the foam-forming composition with a suitable polyisocyanate. Also disclosed is a process for producing a closed cell polyurethane or polyisocyanurate polymer foam by reacting an effective amount of the foam-forming composition with a suitable polyisocyanate.

Description

P/00/01I Regulation 3.2 AUSTRALIA Patents Act 1990 COMPLETE SPECIFICATION FOR A DIVISIONAL PATENT ORIGINAL Name of Applicant: E. I. DU PONT DE NEMOURS AND COMPANY Actual Inventors: LOH Gary CREAZZO Joseph Anthony Address for Service: Houlihan 2 , Level 1, 70 Doncaster Road, Balwyn North, Victoria 3104, Australia Invention Title: FOAM-FORMING COMPOSITIONS CONTAINING AZEOTROPIC OR AZEOTROPE-LIKE MIXTURES CONTAINING Z-1,1,1,4,4,4-HEXAFLUORO-2 BUTENE AND THEIR USES IN THE PREPARATION OF POLYISOCYANATE-BASED FOAMS The following statement is a full description of this invention, including the best method of performing it known to the Applicant: - 1- TITLE FOAM-FORMING COMPOSITIONS CONTAINING AZEOTROPIC OR AZEOTROPE-LIKE MIXTURES CONTAINING Z-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE AND THEIR USES IN THE PREPARATION OF 5 POLYISOCYANATE-BASED FOAMS The present application is a divisional application from Australian patent application number 2008343200. The entire disclosures of Australian patent application number 2008343200 and its corresponding International 10 application, PCT/US2008/087227, are incorporated herein by reference. FIELD OF THE INVENTION The disclosure herein relates to foam-forming compositions comprising (a) an azeotropic or azeotrope-like mixture comprising cis-1,1,1,4,4,4 15 hexafluoro-2-butene and (b) an active hydrogen-containing compounds, and using such compositions for producing polyurethane and polyisocyanurate foams. BACKGROUND OF THE INVENTION 20 Closed-cell polyisocyanate-based foams are widely used for insulation purposes, for example, in building construction and in the manufacture of energy efficient electrical appliances. In the construction industry, polyurethane/polyisocyanurate board stock is used in roofing and siding for its insulation and load-carrying capabilities. Poured and sprayed polyurethane 25 foams are widely used for a variety of applications including insulating roofs, insulating large structures such as storage tanks, insulating appliances such as refrigerators and freezers, insulating refrigerated trucks and railcars, etc. All of these various types of polyurethane/polyisocyanurate foams require blowing agents for their manufacture. Insulating foams depend on the 30 use of halocarbon blowing agents, not only to foam the polymer, but primarily - 2 for their low vapor thermal conductivity, a very important characteristic for insulation value. Historically, polyurethane foams used CFCs (chlorofluorocarbons, for example CFC-1 1, trichlorofluoromethane) and HCFCs (hydrochlorofluorocarbons, for example HCFC-1 41 b, 1,1 -dichloro-1 5 fluoroethane) as the primary blowing agent. However, due to the implication of chlorine-containing molecules such as the CFCs and HCFCs in the destruction of stratospheric ozone, the production and use of CFCs and HCFCs has been restricted by the Montreal Protocol. More recently, hydrofluorocarbons (HFCs), which do not contribute to the destruction of 10 stratospheric ozone, have been employed as blowing agents for polyurethane foams. An example of an HFC employed in this application is HFC-245fa (1,1,1,3,3-pentafluoropropane). The HFCs do not contribute to the destruction of stratospheric ozone, but are of concern due to their contribution to the "greenhouse effect", i.e., they contribute to global warming. As a result of 15 their contribution to global warming, the HFCs have come under scrutiny, and their widespread use may also be limited in the future. Hydrocarbons have also been proposed as foam blowing agents. However, these compounds are flammable, and many are photochemically reactive, and as a result contribute to the production of ground level ozone 20 (i.e., smog). Such compounds are typically referred to as volatile organic compounds (VOCs), and are subject to environmental regulations. There is need for producing foams that provide low flammability, good thermal insulation and high dimensional stability by using a blowing agent that has substantially no ozone depletion potential (ODP) and no or very low 25 global warming potential (GWP). Cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-FC 1336mzz, or Z-CF 3

CH=CHCF

3 ) is one of the good candidates. Japanese Patent No. 05179043 discloses and attempts to use cis 1,1,1,4,4,4-hexafluoro-2-butene as the blowing agent for polyurethane foams. 30 -3- SUMMARY OF THE INVENTION This application includes a foam-forming composition, comprising an azeotropic or azeotrope-like mixture of cis- 1, 1,1,4,4,4-hexafluoro-2-butene. This disclosure provides a foam-forming composition comprising: (a) 5 an azeotropic or azeotrope-like mixture of cis-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and methyl formate; and (b) an active hydrogen-containing compound having two or more active hydrogens. This disclosure also provides a closed-cell polyurethane or polyisocyanurate polymer foam prepared from the reaction of an effective 10 amount of the foam-forming composition as described herein with a suitable polyisocyanate. This disclosure also provides a process for producing a closed-cell polyurethane or polyisocyanurate polymer foam comprising: reacting an effective amount of the foam-forming composition as described herein with a 15 suitable polyisocyanate. DETAILED DESCRIPTION A blowing agent composition (also known as foam expansion agents or foam expansion compositions) often desires a pure single component or 20 an azeotropic or azeotrope-like mixture. For example, when a blowing agent composition is not a pure single component or an azeotropic or azeotrope-like mixture, the composition may change during its application in the foam forming process. Such change in composition could detrimentally affect processing or cause poor performance in the application. Accordingly, there 25 is need for producing polyurethane/polyisocyanurate foams by using azeotropic or azeotrope-like mixtures containing Z-FC-1 336mzz as the blowing agent. Before addressing details of embodiments described below, some terms are defined or clarified. 30 By "cream time", it is meant to refer to the time period starting from the mixing of the active hydrogen-containing compound with polyisocyanate, and -4ending at when the foaming starts to occur and color of the mixture starts to change. -5- By "rise time", it is meant to refer to the time period starting from the mixing of the active hydrogen-containing compound with polyisocyanate, and ending at when the foam rising stops. By "tack free time", it is meant to refer to the time period starting from 5 the mixing of the active hydrogen-containing compound with polyisocyanate, and ending at when the surface of the foam is no longer tacky. By "initial R-value", it is meant to refer to the polymer foam's insulation value (thermal resistance) measured at a mean temperature of 75 OF within 24 hours after the foam is formed and becomes tack free. 10 Z-FC-1 336mzz is a known compound, and its preparation method has been disclosed, for example, in U.S. Patent Publication No. US2008/0269532, hereby incorporated by reference in its entirety. This application includes foam-forming compositions comprising (a) an azeotropic or azeotrope-like mixture comprising Z-FC-1336mzz; and (b) an 15 active hydrogen-containing compound. In some embodiments of this invention, the foam-forming composition comprises: (a) an azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and methyl formate; and (b) an active hydrogen-containing compound having two or more active hydrogens, in the form of hydroxyl groups. In this disclosure, 20 the azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and methyl formate is used as a blowing agent. Blowing agents Z-FC-1 336mzz and methyl formate form an azeotrope-like mixture. Typically these are combined prior to mixing with the other components in the foam-forming compositions. Alternatively, one can be mixed with some or all of the other components 25 before the other is mixed in. For example, Z-FC-1336mzz can be first mixed with the other components in the foam-forming compositions before methyl formate is added in. In one embodiment, the azeotrope like mixture contains between 1-99% by weight of Z-FC-1 336mzz, and 99-1% by weight of methyl formate. In one embodiment, the azeotrope like mixture contains between 30 50-92% by weight of Z-FC-1 336mzz and 50-8% by weight of methyl formate. - 6 - In one embodiement, the azeotrope like mixture contains 90% by weight of Z FC-1 336mzz and 10% by weight of methyl formate. The azeotropic or azeotrope-like mixtures of Z-FC-1336mzz and methyl formate has been described in U.S. Patent Application No. 60/926617 5 [FL1 369 US PRV] filed April/27/2007, hereby incorporated by reference in its entirety. In some embodiments of this invention, the foam-forming composition comprises: (a) an azeotrope-like mixture of Z-FC-1336mzz and 1,1,1,3,3 pentafluorobutane; and (b) an active hydrogen-containing compound having 10 two or more active hydrogens, in the form of hydroxyl groups. In this disclosure, the azeotrope-like mixture of Z-FC-1 336mzz and 1,1,1,3,3 pentafluorobutane (HFC-365mfc, or CF 3

CH

2

CF

2

CH

3 ) is used as a blowing agent. Blowing agents Z-FC-1 336mzz and HFC-365mfc form an azeotrope like mixture. Typically these are combined prior to mixing with the other 15 components in the foam-forming compositions. Alternatively, one can be mixed with some or all of the other components before the other is mixed in. For example, Z-FC-1 336mzz can be first mixed with the other components in the foam-forming compositions before HFC-365mfc is added in. In one embodiment, the azeotrope like mixture contains between 1 -99% by weight of 20 Z-FC-1 336mzz, and 99-1% by weight of HFC-365mfc. In one embodiment, the azeotrope like mixture contains between 45-95% by weight of Z-FC 1336mzz and 55-5% by weight of HFC-365mfc. In one embodiement, the azeotrope like mixture contains 80% by weight of Z-FC-1 336mzz and 20% by weight of HFC-365mfc. 25 The azeotrope-like mixtures of Z-FC-1 336mzz and HFC-365mfc has been described in U.S. Patent Application No. 60/930383 [FL1401 US PRV] filed May/1 6/2007, hereby incorporated by reference in its entirety. In some embodiments of this invention, the foam-forming composition comprises: (a) an azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and 30 trans-1,2-dichloroethylene; and (b) an active hydrogen-containing compound having two or more active hydrogens, in the form of hydroxyl groups. In this -7 disclosure, the azeotropic or azeotrope-like mixture of Z-FC-1336mzz and trans-1,2-dichloroethylene (trans-1,2-DCE, or trans- CICH=CHCI) is used as a blowing agent. Blowing agents Z-FC-1336mzz and trans-1,2 dichloroethylene form an azeotrope-like mixture. Typically these are 5 combined prior to mixing with the other components in the foam-forming compositions. Alternatively, one can be mixed with some or all of the other components before the other is mixed in. For example, Z-FC-1336mzz can be first mixed with the other components in the foam-forming compositions before trans-1,2-dichloroethylene is added in. In one embodiment, the 10 azeotrope like mixture contains between 66-99% by weight of Z-FC-1 336mzz, and 34-1% by weight of trans-1,2-dichloroethylene. In one embodiment, the azeotrope like mixture contains between 68-95% by weight of Z-FC-1 336mzz and 32-5% by weight of trans-1,2-dichloroethylene. In one embodiement, the azeotropic mixture contains 74.7% by weight of Z-FC-1 336mzz and 25.3% by 15 weight of trans-1,2-dichloroethylene. In one embodiement, the azeotrope like mixture contains 68% by weight of Z-FC-1 336mzz and 32% by weight of trans-1,2-dichloroethylene The azeotropic or azeotrope-like mixtures of Z-FC-1336mzz and trans 1,2-dichloroethylene has been described in U.S. Patent Application No. 20 60/931960 [FL1404 US PRV] filed May/24/2007, hereby incorporated by reference in its entirety. In some embodiments of this invention, the foam-forming composition comprises: (a) an azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and pentane; and (b) an active hydrogen-containing compound having two or 25 more active hydrogens, in the form of hydroxyl groups. In this disclosure, the azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and pentane is used as a blowing agent. Blowing agents Z-FC-1336mzz and pentane form an azeotrope-like mixture. Typically these are combined prior to mixing with the other components in the foam-forming compositions. Alternatively, one can 30 be mixed with some or all of the other components before the other is mixed in. For example, Z-FC-1 336mzz can be first mixed with the other components - 8 in the foam-forming compositions before pentane is added in. In one embodiment, the azeotrope like mixture contains between 62-78% by weight of Z-FC-1 336mzz, and 38-22% by weight of pentane. In one embodiment, the azeotrope like mixture contains between 64-76% by weight of Z-FC 5 1336mzz and 36-24% by weight of pentane. In one embodiement, the azeotropic mixture contains 70.2% by weight of Z-FC-1 336mzz and 29.8% by weight of pentane. The azeotropic or azeotrope-like mixtures of Z-FC-1336mzz and pentane has been described in U.S. Patent Application No. 60/930467 10 [FL1 394 US PRV] filed May/1 6/2007, hereby incorporated by reference in its entirety. In some embodiments of this invention, the foam-forming composition comprises: (a) an azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and isopentane; and (b) an active hydrogen-containing compound having two or 15 more active hydrogens, in the form of hydroxyl groups. In this disclosure, the azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and isopentane is used as a blowing agent. Blowing agents Z-FC-1 336mzz and isopentane form an azeotrope-like mixture. Typically these are combined prior to mixing with the other components in the foam-forming compositions. Alternatively, 20 one can be mixed with some or all of the other components before the other is mixed in. For example, Z-FC-1 336mzz can be first mixed with the other components in the foam-forming compositions before isopentane is added in. In one embodiment, the azeotrope like mixture contains between 51-70% by weight of Z-FC-1 336mzz, and 49-30% by weight of isopentane. In one 25 embodiment, the azeotrope like mixture contains between 54-67% by weight of Z-FC-1 336mzz and 46-33% by weight of isopentane. In one embodiement, the azeotropic mixture contains 61.4% by weight of Z-FC 1336mzz and 38.6% by weight of isopentane. The azeotropic or azeotrope-like mixtures of Z-FC-1336mzz and 30 isopentane has been described in U.S. Patent Application No. 60/930445 - 9 - [FL1 395 US PRV] filed May/1 6/2007, hereby incorporated by reference in its entirety. In some embodiments of this invention, the foam-forming composition comprises: (a) an azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and 5 cyclopentane; and (b) an active hydrogen-containing compound having two or more active hydrogens, in the form of hydroxyl groups. In this disclosure, the azeotropic or azeotrope-like mixture of Z-FC-1 336mzz and cyclopentane is used as a blowing agent. Blowing agents Z-FC-1 336mzz and cyclopentane form an azeotrope-like mixture. Typically these are combined prior to mixing 10 with the other components in the foam-forming compositions. Alternatively, one can be mixed with some or all of the other components before the other is mixed in. For example, Z-FC-1 336mzz can be first mixed with the other components in the foam-forming compositions before cyclopentane is added in. In one embodiment, the azeotrope like mixture contains between 75-88% 15 by weight of Z-FC-1 336mzz, and 25-12% by weight of cyclopentane. In one embodiment, the azeotrope like mixture contains between 77-87% by weight of Z-FC-1 336mzz and 23-13% by weight of cyclopentane. In one embodiement, the azeotrope like mixture contains 85% by weight of Z-FC 1336mzz and 15% by weight of cyclopentane. 20 The azeotropic or azeotrope-like mixtures of Z-FC-1336mzz and cyclopentane has been described in U.S. Patent Application No. 60/999871 [FL1445 US PRV] filed October/22/2007, hereby incorporated by reference in its entirety. In some embodiments of this invention, the foam-forming composition 25 comprises: (a) an azeotrope-like mixture of Z-FC-1336mzz and HFC-245fa; and (b) an active hydrogen-containing compound having two or more active hydrogens, in the form of hydroxyl groups. In this disclosure, the azeotrope like mixture of Z-FC-1 336mzz and HFC-245fa is used as a blowing agent. Blowing agents Z-FC-1 336mzz and HFC-245fa form an azeotrope-like 30 mixture. Typically these are combined prior to mixing with the other components in the foam-forming compositions. Alternatively, one can be - 10 mixed with some or all of the other components before the other is mixed in. For example, Z-FC-1 336mzz can be first mixed with the other components in the foam-forming compositions before HFC-245fa is added in. In one embodiment, the azeotrope-like mixture contains between 1 -24% by weight of 5 Z-FC-1 336mzz, and 99-76% by weight of HFC-245fa. In one embodiment, the azeotrope like mixture contains between 3-22% by weight of Z-FC 1336mzz and 97-78% by weight of HFC-245fa. In one embodiement, the azeotrope like mixture contains 20% by weight of Z-FC-1 336mzz and 80% by weight of HFC-245fa. 10 The azeotrope-like mixtures of Z-FC-1 336mzz and HFC-245fa has been described in U.S. Patent Application No. 60/931875 [FL1 405 US PRV] filed May/24/2007, hereby incorporated by reference in its entirety. In some embodiments of this invention, the foam-forming composition comprises: (a) an azeotrope-like mixture of Z-FC-1336mzz and 15 dimethoxymethane; and (b) an active hydrogen-containing compound having two or more active hydrogens, in the form of hydroxyl groups. In this disclosure, the azeotrope-like mixture of Z-FC-1 336mzz and dimethoxymethane is used as a blowing agent. Blowing agents Z-FC 1336mzz and dimethoxymethane form an azeotrope-like mixture. Typically 20 these are combined prior to mixing with the other components in the foam forming compositions. Alternatively, one can be mixed with some or all of the other components before the other is mixed in. For example, Z-FC-1336mzz can be first mixed with the other components in the foam-forming compositions before dimethoxymethane is added in. In one embodiment, the 25 azeotrope like mixture contains between 1-99% by weight of Z-FC-1336mzz, and 99-1% by weight of dimethoxymethane. In one embodiment, the azeotrope like mixture contains between 67-97% by weight of Z-FC-1 336mzz and 33-3% by weight of dimethoxymethane. In one embodiement, the azeotrope like mixture contains 85% by weight of Z-FC-1 336mzz and 15% by 30 weight of dimethoxymethane. - 11 - The azeotrope-like mixtures of Z-FC-1 336mzz and dimethoxymethane has been described in U.S. Patent Application No. 60/967874 [FL1 427 US PRV] filed September/7/2007, hereby incorporated by reference in its entirety. As recognized in the art, an azeotropic or an azeotrope-like mixture is 5 an admixture of two or more different components which, when in liquid form under a given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower than the boiling temperatures of the individual components, and which will provide a vapor composition essentially identical to the liquid composition undergoing boiling. 10 For the purpose of this discussion, an azeotrope-like mixture means a composition that behaves like an azeotrope (i.e., has constant boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Thus, the composition of the vapor formed during boiling or evaporation is the same as or substantially the same as the original liquid composition. Hence, 15 during boiling or evaporation, the liquid composition, if it changes at all, changes only to a minimal or negligible extent. This is to be contrasted with non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree. Additionally, azeotrope-like compositions exhibit dew point pressure 20 and bubble point pressure with virtually no pressure differential. That is to say that the difference in the dew point pressure and bubble point pressure at a given temperature will be a small value. In this invention, compositions with a difference in dew point pressure and bubble point pressure of less than or equal to 3 percent (based upon the bubble point pressure) is considered to be 25 azeotrope-like. Accordingly, the essential features of an azeotropic or an azeotrope like composition are that at a given pressure, the boiling point of the liquid composition is fixed and that the composition of the vapor above the boiling composition is essentially that of the boiling liquid composition (i.e., no 30 fractionation of the components of the liquid composition takes place). It is also recognized in the art that both the boiling point and the weight - 12 percentages of each component of the azeotropic composition may change when the azeotropic or azeotrope-like liquid composition is subjected to boiling at different pressures. Thus, an azeotropic or an azeotrope-like composition may be defined in terms of the unique relationship that exists 5 among the components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure. It is also recognized in the art that various azeotropic compositions (including their boiling points at particular pressures) may be calculated (see, e.g., W. 10 Schotte Ind. Eng. Chem. Process Des. Dev. (1980) 19, 432-439). Experimental identification of azeotropic compositions involving the same components may be used to confirm the accuracy of such calculations and/or to modify the calculations at the same or other temperatures and pressures. The active hydrogen-containing compounds of this invention can 15 comprise compounds having two or more groups that contain an active hydrogen atom reactive with an isocyanate group, such as described in U.S. Patent No. 4,394,491; hereby incorporated by reference. Examples of such compounds have at least two hydroxyl groups per molecule, and more specifically comprise polyols, such as polyether or polyester polyols. 20 Examples of such polyols are those which have an equivalent weight of about 50 to about 700, normally of about 70 to about 300, more typically of about 90 to about 270, and carry at least 2 hydroxyl groups, usually 3 to 8 such groups. Examples of suitable polyols comprise polyester polyols such as aromatic polyester polyols, e.g., those made by transesterifying polyethylene 25 terephthalate (PET) scrap with a glycol such as diethylene glycol, or made by reacting phthalic anhydride with a glycol. The resulting polyester polyols may be reacted further with ethylene - and/or propylene oxide - to form an extended polyester polyol containing additional internal alkyleneoxy groups. Examples of suitable polyols also comprise polyether polyols such as 30 polyethylene oxides, polypropylene oxides, mixed polyethylene-propylene oxides with terminal hydroxyl groups, among others. Other suitable polyols - 13 can be prepared by reacting ethylene and/or propylene oxide with an initiator having 2 to 16, generally 3 to 8 hydroxyl groups as present, for example, in glycerol, pentaerythritol and carbohydrates such as sorbitol, glucose, sucrose and the like polyhydroxy compounds. Suitable polyether polyols can also 5 include alaphatic or aromatic amine-based polyols. The present invention also relates to processes for producing a closed cell polyurethane or polyisocyanurate polymer foam by reacting an effective amount of the foam-forming compositions with a suitable polyisocyanate. Typically, before reacting with a suitable polyisocyanate, the active 10 hydrogen-containing compound described hereinabove and optionally other additives are mixed with the blowing agent to form a foam-forming composition. Such foam-forming composition is typically known in the art as an isocyanate-reactive preblend, or B-side composition. The foam-forming composition of this invention can be prepared in any manner convenient to 15 one skilled in this art, including simply weighing desired quantities of each component and, thereafter, combining them in an appropriate container at appropriate temperatures and pressures. When preparing polyisocyanate-based foams, the polyisocyanate reactant is normally selected in such proportion relative to that of the active 20 hydrogen-containing compound that the ratio of the equivalents of isocyanate groups to the equivalents of active hydrogen groups, i.e., the foam index, is from about 0.9 to about 10 and in most cases from about 1 to about 4. While any suitable polyisocyanate can be employed in the instant process, examples of suitable polyisocyanates useful for making 25 polyisocyanate-based foam comprise at least one of aromatic, aliphatic and cycloaliphatic polyisocyanates, among others. Representative members of these compounds comprise diisocyanates such as meta- or paraphenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, 30 cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers), napthylene-1,5-diisocyanate, 1 -methylphenyl-2,4-phenyldiisocyanate, - 14 diphenylmethane-4,4-diisocyanate, diphenylmethane-2,4-diissocyanate, 4,4 biphenylenediisocyanate and 3,3-dimethyoxy-4,4 biphenylenediisocyanate and 3,3-dimethyldiphenylpropane-4,4-diisocyanate; triisocyanates such as toluene-2,4,6-triisocyanate and polyisocyanates such as 4,4 5 dimethyldiphenylmethane-2,2,5,5-tetraisocyanate and the diverse polymethylenepoly-phenylopolyisocyanates, mixtures thereof, among others. A crude polyisocyanate may also be used in the practice of this invention, such as the crude toluene diisocyanate obtained by the phosgenating a mixture comprising toluene diamines, or the crude 10 diphenylmethane diisocyanate obtained by the phosgenating crude diphenylmethanediamine. Specific examples of such compounds comprise methylene-bridged polyphenylpolyisocyanates, due to their ability to crosslink the polyurethane. It is often desirable to employ minor amounts of additives in preparing 15 polyisocyanate-based foams. Among these additives comprise one or more members from the group consisting of catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, filler, antistatic agents, among others well known in this art. Depending upon the composition, a surfactant can be employed to 20 stabilize the foaming reaction mixture while curing. Such surfactants normally comprise a liquid or solid organosilicone compound. The surfactants are employed in amounts sufficient to stabilize the foaming reaction mixture against collapse and to prevent the formation of large, uneven cells. In one embodiment of this invention, about 0.1% to about 5% by weight of surfactant 25 based on the total weight of all foaming ingredients (i.e. blowing agents + active hydrogen-containing compounds + polyisocyanates + additives) are used. In another embodiment of this invention, about 1.5% to about 3% by weight of surfactant based on the total weight of all foaming ingredients are used. 30 One or more catalysts for the reaction of the active hydrogen containing compounds, e.g. polyols, with the polyisocyanate may be also - 15 employed. While any suitable urethane catalyst may be employed, specific catalyst comprise tertiary amine compounds and organometallic compounds. Exemplary such catalysts are disclosed, for example, in U.S. Patent No. 5,164,419, which disclosure is incorporated herein by reference. For 5 example, a catalyst for the trimerization of polyisocyanates, such as an alkali metal alkoxide, alkali metal carboxylate, or quaternary amine compound, may also optionally be employed herein. Such catalysts are used in an amount which measurably increases the rate of reaction of the polyisocyanate. Typical amounts of catalysts are about 0.1 % to about 5% by weight based on 10 the total weight of all foaming ingredients. In the process of the invention for making a polyisocyanate-based foam, the active hydrogen-containing compound (e.g. polyol), polyisocyanate and other components are contacted, thoroughly mixed, and permitted to expand and cure into a cellular polymer. The mixing apparatus is not critical, 15 and various conventional types of mixing head and spray apparatus are used. By conventional apparatus is meant apparatus, equipment, and procedures conventionally employed in the preparation of isocyanate-based foams in which conventional isocyanate-based foam blowing agents, such as fluorotrichloromethane (CCI 3 F, CFC-1 1), are employed. Such conventional 20 apparatus are discussed by: H. Boden et al. in chapter 4 of the Polyurethane Handbook, edited by G. Oertel, Hanser Publishers, New York, 1985; a paper by H. Grunbauer et al. titled "Fine Celled CFC-Free Rigid Foam - New Machinery with Low Boiling Blowing Agents" published in Polyurethanes 92 from the Proceedings of the SPI 34th Annual Technical/Marketing 25 Conference, October 21-October 24, 1992, New Orleans, Louisiana; and a paper by M. Taverna et al. titled "Soluble or Insoluble Alternative Blowing Agents? Processing Technologies for Both Alternatives, Presented by the Equipment Manufacturer", published in Polyurethanes World Congress 1991 from the Proceedings of the SPI/ISOPA September 24-26, 1991, Acropolis, 30 Nice, France. These disclosures are hereby incorporated by reference. - 16 - In one embodiment of this invention, a preblend of certain raw materials is prepared prior to reacting the polyisocyanate and active hydrogen-containing components. For example, it is often useful to blend the polyol(s), blowing agent, surfactant(s), catalysts(s) and other foaming 5 ingredients, except for polyisocyanates, and then contact this blend with the polyisocyanate. Alternatively, all the foaming ingredients may be introduced individually to the mixing zone where the polyisocyanate and polyol(s) are contacted. It is also possible to pre-react all or a portion of the polyol(s) with the polyisocyanate to form a prepolymer. 10 The invention composition and processes are applicable to the production of all kinds of expanded polyurethane foams, including, for example, integral skin, RIM and flexible foams, and in particular rigid closed cell polymer foams useful in spray insulation, as pour-in-place appliance foams, or as rigid insulating board stock and laminates. 15 The present invention also relates to the closed-cell polyurethane or polyisocyanurate polymer foams prepared from reaction of effective amounts of the foam-forming composition of this disclosure and a suitable polyisocyanate. 20 EXAMPLES The present disclosure is further defined in the following Examples. It should be understood that these Examples, while indicating preferred embodiments, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the 25 preferred features, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt it to various uses and conditions. Polyol is a toluene diamine (o-TDA) initiated aromatic polyether polyol (VORANOL 391) purchased from Dow Chemicals Inc. at Midland, MI, 49641 30 1206. Polyol has viscosity of 4740 centerpoise at 25 C. The content of - 17 hydroxyl groups in the Polyol is equivalent to 391 mg KOH per gram of Polyol. Silicon type surfactant is a mixture of 70% polyalkyleneoxidemethylsiloxane and 30% polyalkylene oxide (Niax Silicone 5 L-5440) purchased from Momentive Performance Materials at 187 Danbury Road, Wilton, CT 06897 USA. Amine catalyst (Polycat 8) is N,N-dimethylcyclohexylamine purchased from Air Products Inc. at 7201 Hamilton Blvd, Allentown PA 18195. Co-catalyst (Curithane 52) is 2-methyl(n-methyl amino b-sodium 10 acetate nonyl phenol) purchased from Air Products Inc. at 7201 Hamilton Blvd, Allentown PA 18195. Polymethylene polyphenyl isocyanate (PAPI 27) is purchased from Dow Chemicals, Inc. at Midland, MI, 49641-1206. Initial R-value is measured by a LaserComp FOX 304 Thermal 15 Conductivity Meter at a mean temperature of 75 OF. The unit of R-value is ft 2 _ hr- F/BTU-in. EXAMPLE 1 Polyurethane Foam Made from Z-FC-1 336mzz and Methyl formate 20 Azeotrope-like Mixture Blowing agents Z-FC-1 336mzz and methyl formate were premixed to form an azeotrope -like mixture containing 90% by weight of Z-FC-1 336mzz and 10% by weight of meththyl formate. Polyol, surfactant, catalysts, water and the blowing agent (10% by 25 weight of methyl formate and 90% by weight of Z-FC-1 336mzz) were pre mixed by hand and then mixed with polyisocyanate. The resulting mixture was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 1 and 2 below. - 18 - Table 1 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (90% by weight of Z-FC-1336mzz 25.1 and 10% by weight of methyl formate) Polymethylene polyphenyl isocyanate 132 Table 2. Polyurethane foam properties Foam Index 1.22 Cream time(second) 8 Rise time (seconds) 90 Tack free time(seconds) 100 Foam density (pounds-per-cubic-feet) 2.3 Initial R-value (ft 2 -hr-OF/BTU-in) 7.3 5 COMPARATIVE EXAMPLE 2 Polyurethane Foam Made from Z-FC-1336mzz and HFC-365mfc Azeotrope like Mixture 10 Blowing agents Z-FC-1336mzz and HFC-365mfc were premixed to form an azeotrope-like mixture containing 80% by weight of Z-FC-1 336mzz and 20% by weight of HFC-365mfc. Polyol, surfactant, catalysts, water and the blowing agent (20% by weight of HFC-365mfc and 80% by weight of Z-FC-1 336mzz) were pre-mixed 15 by hand and then mixed with polyisocyanate. The resulting mixture was - 19poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 3 and 4 below. Table 3 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (80% by weight of Z-FC-1 336mzz 28.8 and 20% by weight of HFC-365mfc) Polymethylene polyphenyl isocyanate 132 5 Table 4. Polyurethane foam properties Foam Index 1.2 Cream time(second) 8 Rise time (seconds) 90 Tack free time(seconds) 100 Foam density (pounds-per-cubic-feet) 2.2 Initial R-value (ft 2 -hr-OF/BTU-in) 7.4 COMPARATIVE EXAMPLE 3 10 Polyurethane Foam Made from Z-FC-1336mzz and Trans-1,2 dichloroethylene Azeotropic Mixture Blowing agents Z-FC-1 336mzz and trans-1,2-dichloroethylene were premixed to form an azeotropic mixture containing 74.7% by weight of Z-FC 1336mzz and 25.3% by weight of trans-1,2-dichloroethylene. 15 Polyol, surfactant, catalysts, water and the blowing agent (25.3% by weight of trans-1,2-dichloroethylene and 74.7% by weight of Z-FC-1 336mzz) - 20 were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 5 and 6 below. 5 Table 5 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (74.7% by weight of Z-FC-1 336mzz 25.1 and 25.3% by weight of trans-1,2-dichloroethylene) Polymethylene polyphenyl isocyanate 132 Table 6. Polyurethane foam properties Foam Index 1.2 Cream time(second) 11 Rise time (seconds) 90 Tack free time(seconds) 100 Foam density (pounds-per-cubic-feet) 2.1 Initial R-value (ft 2 -hr-OF/BTU-in) 7.1 10 COMPARATIVE EXAMPLE 4 Polyurethane Foam Made from Z-FC-1 336mzz and Trans- 1,2 dichloroethylene Azeotrope-like Mixture -21 - Blowing agents Z-FC-1 336mzz and trans-1,2-dichloroethylene were premixed to form an azeotrope-like mixture containing 68% by weight of Z FC-1 336mzz and 32% by weight of trans-1,2-dichloroethylene. Polyol, surfactant, catalysts, water and the blowing agent (32% by 5 weight of trans-1,2-dichloroethylene and 68% by weight of Z-FC-1 336mzz) were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 7 and 8 below. 10 Table 7 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (68% by weight of Z-FC-1336mzz 24.1 and 32% by weight of trans-1,2-dichloroethylene) Polymethylene polyphenyl isocyanate 132 Table 8. Polyurethane foam properties Foam Index 1.2 Cream time(second) 9 Rise time (seconds) 88 Tack free time(seconds) 93 Foam density (pounds-per-cubic-feet) 2.3 Initial R-value (ft 2 -hr-OF/BTU-in) 7.2 15 - 22 - COMPARATIVE EXAMPLE 5 Polyurethane Foam Made from Z-FC-1336mzz and Pentane Azeotropic Mixture Blowing agents Z-FC-1 336mzz and pentane were premixed to form an 5 azeotropic mixture containing 70.2% by weight of Z-FC-1 336mzz and 29.8% by weight of pentane. Polyol, surfactant, catalysts, water and the blowing agent (29.8% by weight of pentane and 70.2% by weight of Z-FC-1 336mzz) were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was poured 10 into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 9 and 10 below. Table 9 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (70.2% by weight of Z-FC-1 336mzz 21.4 and 29.8% by weight of pentane) Polymethylene polyphenyl isocyanate 132 15 Table 10. Polyurethane foam properties Foam Index 1.2 Cream time(second) 9 Rise time (seconds) 90 Tack free time(seconds) 100 Foam density (pounds-per-cubic-feet) 2.3 Initial R-value (ft 2 -hr-OF/BTU-in) 6.9 - 23 - COMPARATIVE EXAMPLE 6 Polyurethane Foam Made from Z-FC-1336mzz and Isopentane Azeotropic Mixture Blowing agents Z-FC-1 336mzz and isopentane were premixed to form 5 an azeotropic mixture containing 61.4% by weight of Z-FC-1 336mzz and 38.6% by weight of isopentane. Polyol, surfactant, catalysts, water and the blowing agent (38.6% by weight of isopentane and 61.4% by weight of Z-FC-1336mzz) were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was 10 poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 11 and 12 below. Table 11 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (61.4% by weight of Z-FC-1 336mzz 19.7 and 38.6% by weight of isopentane) Polymethylene polyphenyl isocyanate 132 15 Table 12. Polyurethane foam properties Foam Index 1.2 Cream time(second) 7 Rise time (seconds) 80 Tack free time(seconds) 90 Foam density (pounds-per-cubic-feet) 1.8 Initial R-value (ft 2 -hr-OF/BTU-in) 6.5 - 24 - COMPARATIVE EXAMPLE 7 Polyurethane Foam Made from Z-FC-1 336mzz and Cyclopentane Azeotrope like Mixture Blowing agents Z-FC-1336mzz and cyclopentane were premixed to 5 form an azeotrope -like mixture containing 85% by weight of Z-FC-1 336mzz and 15% by weight of cyclopentane. Polyol, surfactant, catalysts, water and the blowing agent (15% by weight of cyclopentane and 85% by weight of Z-FC-1 336mzz) were pre mixed by hand and then mixed with polyisocyanate. The resulting mixture 10 was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 13 and 14 below. Table 13 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (85% by weight of Z-FC-1 336mzz 24.5 and 15% by weight of cyclopentane) Polymethylene polyphenyl isocyanate 132 15 Table 14. Polyurethane foam properties Foam Index 1.2 Cream time(second) 10 Rise time (seconds) 85 Tack free time(seconds) 95 Foam density (pounds-per-cubic-feet) 2.3 Initial R-value (ft 2 -hr-OF/BTU-in) 7.3 - 25 - COMPARATIVE EXAMPLE 8 Polyurethane Foam Made from Z-FC-1 336mzz and HFC-245fa Azeotrope like Mixture Blowing agents Z-FC-1 336mzz and HFC-245fa were premixed to form 5 an azeotrope-like mixture containing 20% by weight of Z-FC-1 336mzz and 80% by weight of HFC-245fa. Polyol, surfactant, catalysts, water and the blowing agent (80% by weight of HFC-245fa and 20% by weight of Z-FC-1 336mzz) were pre-mixed by hand and then mixed with polyisocyanate. The resulting mixture was 10 poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 15 and 16 below. Table 15 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (20% by weight of Z-FC-1 336mzz 25.0 and 80% by weight of HFC-245fa) Polymethylene polyphenyl isocyanate 132 15 Table 16. Polyurethane foam properties Foam Index 1.2 Cream time(second) 7 Rise time (seconds) 90 Tack free time(seconds) 90 Foam density (pounds-per-cubic-feet) 2.4 Initial R-value (ft 2 -hr-OF/BTU-in) 7.1 - 26 - COMPARATIVE EXAMPLE 9 Polyurethane Foam Made from Z-FC-1336mzz and Dimethoxymethane Azeotrope-like Mixture Blowing agents Z-FC-1 336mzz and dimethoxymethane were premixed 5 to form an azeotrope-like mixture containing 85% by weight of Z-FC-1 336mzz and 15% by weight of dimethoxymethane. Polyol, surfactant, catalysts, water and the blowing agent (15% by weight of dimethoxymethane and 85% by weight of Z-FC-1 336mzz) were pre mixed by hand and then mixed with polyisocyanate. The resulting mixture 10 was poured into a 8"x8"x2.5" paper box to form the polyurethane foam. The formulation and properties of the foam are shown in Tables 17 and 18 below. Table 17 Polyurethane formulation Component Parts by weight Polyol 100 Silicon type surfactant 2.0 Amine catalyst 1.5 Co-catalyst 0.5 Water 1.0 Blowing agent (85% by weight of Z-FC-1336mzz 25.1 and 15% by weight of dimethoxymethane) Polymethylene polyphenyl isocyanate 132 15 Table 18. Polyurethane foam properties Foam Index 1.2 Cream time(second) 7 Rise time (seconds) 85 Tack free time(seconds) 105 Foam density (pounds-per-cubic-feet) 2.0 Initial R-value (ft 2 hr-OF/BTU-in) 6.8 - 27 - Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, 5 integer, step, component or group thereof. Further, any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, or is to be understood as constituting, part of the common general knowledge in Australia. 10 - 28 -

Claims (6)

1. A foam-forming composition comprising: (a) an azeotropic mixture of cis-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and 5 methyl formate; and (b) an active hydrogen-containing compound having two or more active hydrogens.

2. A foam-forming composition comprising: 10 (a) an azeotrope-like mixture of cis-1,1,1,4,4,4-hexafluoro-2-butene and methyl formate; and (b) an active hydrogen-containing compound having two or more active hydrogens. 15

3. The foam-forming composition of claim 1 or claim 2, wherein said active hydrogen-containing compound is a polyether polyol.

4. A closed-cell polyurethane or polyisocyanurate polymer foam prepared from reaction of an effective amount of the foam-forming composition of 20 any one of the preceding claims with a suitable polyisocyanate.

5. The closed-cell polyurethane or polyisocyanurate polymer foam of claim 4 wherein said polymer foam has an initial R-value greater than 6.0 ft 2 _ hr- F/BTU-in. 25

6. A process for producing a closed-cell polyurethane or polyisocyanurate polymer foam comprising: reacting an effective amount of the foam forming composition of any one of claims 1 to 3 with a suitable polyisocyanate. - 29 -