Ep 0398147 B1

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Europa,schesP_ MM M II II INI Ml M I M IN II I II J European Patent Office © Publication number: 0 398 147 B1 Office_„. europeen des brevets

@ Date of filing: 09.05.90

® Priority: 10.05.89 US 350184 © Proprietor: THE DOW CHEMICAL COMPANY (a Delaware corporation) @ Date of publication of application: 2030 Dow Center 22.11.90 Bulletin 90/47 Abbott Road Midland Michigan 48640 (US) © Publication of the grant of the patent: 09.11.94 Bulletin 94/45 @ Inventor: Smlts, Guldo Freddy Veldstraat 37 © Designated Contracting States: B-2110 Wljnegem (BE) AT BE CH DE DK ES FR GB GR IT LI LU NL SE Inventor: Grunbauer, Henri Jacobus Marie Schorploen 45 © References cited: NL-4501 HC Oostburg (BE) EP-A- 0 330 988 US-A- 3 583 921 US-A- 4 624 970 © Representative: Huber, Bernhard, Dlpl.-Chem. et al Patentanwalte H. Welckmann, Dr. K. Flncke F.A. Welckmann, B. Huber Dr. H. Llska, Dr. J. Prechtel, Dr. B. Bohm Postfach 86 08 20 uD-81635 \J i \J\J\J iviuMunchen ■ ■ vs ■ ■ v> ■ ■ (DE) QQ. yi^i— j

00 Oi oo Note: Within nine months from the publication of the mention of the grant of the European patent, any person ® may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition Q,. shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee LU has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services (3. 10/3.09/3.3.3) EP 0 398 147 B1

Description

This invention relates to rigid, closed-celled polyisocyanate-based foams, particularly polyurethane, polyurethane-isocyanurate and polyurethane-urea foams prepared using halocarbon blowing system com- 5 prising a first halocarbon component having a boiling point of at least 283 K and a second halocarbon component having a boiling point of less than or equal to 266 K. It is well-known to prepare such polyurethane foams by reacting an organic polyisocyanate with an active hydrogen-containing compound in the presence of a blowing agent or agents. Generally speaking, such blowing agents are volatile organic compounds which are liquids at room temperature. The poly- io merization reaction between the active hydrogen-containing compound and the polyisocyanate giving a polyurethane is exothermic as is the trimerization reaction of isocyanate giving an isocyanurate polymer. The reaction exotherm is sufficient to vaporize the blowing agent, which then becomes encapsulated in the liquid phase of the polymerizing reaction mixture resulting in the formation of cells. The formation of cells causes the reaction mixture to expand and form a foam which subsequently cures to become a rigid 75 closed-celled polyurethane foam. A problem frequently encountered is that of preventing an unacceptable degree of shrinkage of partially cured foam during the aging or curing period following manufacture. A further problem often encountered in cured foams, especially in applications where polyurethane foam may be exposed to subzero temperatures, below 0 ° C, for extended periods of time, is shrinkage or dimensional stability. 20 Such shrinkage or poor dimensional stability is frequently observed either where blowing agents used to impart the cellular structure to the foam have a high diffusion rate through the urethane polymer such as, for example, carbon dioxide. Or where the blowing agents employed have atmospheric boiling points such that when closed-celled foam containing these blowing agents are subjected for prolonged periods to low temperatures, the blowing agent condenses. The loss of, or condensation of blowing agent from the cell gas 25 leads to greatly reduced internal cell pressures and eventually resulting in shrinkage and/or poor dimensional stability of the foam. A further disadvantage of having condensed blowing agent present can be a potentially harmful effect for any polymer or other plastics material present, such as, for example, the polystyrene inner liner used in the production of some refrigeration units which can be attacked by the condensed blowing agent. 30 The shrinkage and poor dimensional stability of some polyurethane foams used for cold-insulation purposes may be controlled to an extent by for example increasing the foam density, but this leads to a more expensive product. Therefore, it is desirable to provide a process for the manufacture of polyurethane foams which have reduced susceptibility to shrinkage and improved dimensional stability. At the same time, it would be an 35 additional advantage if such a process could provide for a reduction or elimination of the commercial dependency on especially "hard" chlorofluorocarbon (CFC) blowing agents. The "hard" CFC blowing agents are those compounds in which all hydrogens of the carbon backbone have been replaced by a halogen, normally fluorine and chlorine, in contrast to "soft" CFCs which have at least one hydrogen atom remaining on the carbon backbone. Such "hard" CFCs are suspected of destroying the earth's protective 40 ozone layer by migrating up through the troposphere to the stratosphere and participating indirectly or directly in the chemical reactions of ozone. This invention accomplishes an improvement in dimensional stability of polyurethane foams. In a preferred embodiment, a significantly lower dependency on the use of "hard" CFC blowing agents can be obtained through selection of "soft" CFC blowing agents. 45 In one aspect, this invention is a process for preparing a rigid closed-celled polyisocyanate-based foam which comprises reacting an organic polyisocyanate with an active hydrogen-containing compound in the presence of water and a blowing agent characterized in that the water is present in from at least 1 .8 parts by weight per 100 parts by weight of active hydrogen-containing compound and water, and in that the blowing agent comprises: 50 (a) from 40 to 95 mole percent, based on components (a) and (b), of at least one halocarbon compound having a boiling point of at least 283K, and (b) from 5 to 60 mole percent, based on components (a) and (b), of at least one halocarbon compound having a boiling point of from 235K to 266K, and wherein the ratio of said boiling point of a component (a) to a component (b) is from 1.06:1 to 1.20:1 55 and wherein said blowing agent is free of any organic compound having a boiling point of 338K or greater. In a second aspect, this invention is an isocyanate-reactive composition comprising at least one active hydrogen-containing compound having an equivalent weight of from 50 to 700, water, and a blowing agent characterized in that the water is present in from at least 1.8 parts by weight per 100 parts by weight of

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active hydrogen-containing compound and water, and in that the blowing agent is present in an amount of from 1 to 30 weight percent of total weight of the composition and blowing agent and in that the blowing agent comprises: (a) from 40 to 95 mole percent, based on components (a) and (b), of at least one halocarbon compound 5 having a boiling point of at least 283K, and (b) from 5 to 60 mole percent, based on components (a) and (b), of at least one halocarbon compound having a boiling point of from 235K to 266K , and wherein the ratio of said boiling point of a component (a) to a component (b) is from 1.06:1 to 1.20:1 and wherein said blowing agent is free of any compound having a boiling point of 338K or greater. io In a third aspect, this invention is a rigid, closed-celled polyisocyanate-based foam prepared according to the process of this invention and characterized in that the resulting foam contains within its cells a gaseous composition comprising: (a) from 30 to 85 mole percent, based on component (a) and component (b), of a mixture comprising: (1) from 40 to 95 mole percent, based on components (1) and (2), of at least one halocarbon is compound having a boiling point of at least 283K, and (2) from 5 to 60 mole percent, based on components (1) and (2), of at least one halocarbon compound having a boiling point of from 235K to 266K, and wherein the ratio of said boiling points of component (1) to component (2) is from 1.06:1 to 1.20:1 and wherein said composition is free of any compound having a boiling point of 338 K or greater; and 20 (b) from 15 to 70 mole percent, based on component (a) and (b), of carbon dioxide. It has been found surprisingly, that this invention provides for the use of combinations of low boiling point organic compounds with high boiling point organic compounds as blowing agent to provide polyurethane foams with overall acceptable physical properties, including improved dimensional stability. The combination of a high boiling point and a low boiling point blowing agent are not normally employed for the 25 preparation of rigid, closed-celled, polyisocyanate-based foam. A further advantage is that in certain embodiments of this invention can also allow for the production of foam with good dimensional stability that contains reduced quantities of, or no "hard" CFC. In the process of this invention, a particular blowing agent composition is employed to prepare a blown, rigid, closed-celled polyisocyanate-based foam. 30 The blowing agent composition is characterized in that it comprises as a first component, at least one organic compound having a boiling point of at least 283 K at atmospheric pressure. As a second component, the blowing agent composition comprises at least one organic compound having a boiling point less than or equal to 266 K at atmospheric pressure. The first component is present in an amount of from 40 to 95 mole percent of the total moles of the first and second components and the second component is 35 present in an amount of from 5 to 60 mole percent of the total moles of the first and second components present. The blowing agent composition is further characterized in that the ratio of the atmospheric boiling points of said first component to said second component is from 1.06:1 to 1.20:1, and in that the composition is free of any organic compound having a boiling point of 338 K or greater. As stated hereinabove, the first component having an atmospheric boiling point of at least 283 K, and 40 preferably at least 288 K, comprises up to 95, preferably up to 80, more preferably up to 65 and most preferably up to 55 mole percent of the total moles present of the first and second components of the mixture. The second component of the blowing agent composition has an atmospheric boiling point less than or equal to 266 K but equal to or greater than 235 K, preferably from at least 240 K and more preferably from 45 at least 248 K. Preferably, the blowing agent composition comprises the second component in from 20, more preferably from 35 and most preferably from 45 and up to 60 mole percent of the total moles present of the first and second components. Additionally, the blowing agent composition employed in this invention is free of organic compounds having boiling points of 338 K or greater, and preferably of 333 K or greater. 50 Preferably, the ratio of atmospheric boiling points of a compound belonging to the first component with respect to a compound belonging to the second component from 1.08:1 to 1.18:1, more preferably from 1.11:1 to 1.18:1. Although blowing agent compositions wherein the boiling point ratio of the first to the second component is larger may be used, it is found advantageous for reasons of handling and processing in the manufacturing stages of the foam to remain within these limits. 55 The first and second components of the blowing agent composition are organic compounds. Organic compounds which are suitable for use in this invention are those which are essentially inert under the conditions employed when preparing a polyurethane foam, but have boiling points of such that if not gaseous at room temperature, can be readily volatilized by the reaction exotherm. Typically, such organic

3 EP 0 398 147 B1

compounds are hydrocarbons including alkanes, alkenes, cycloalkanes and cycloalkenes; alkyl alkanoates such as methyl formate; and halocarbons such as fluorocarbons, chlorofluorocarbons, bromofluorocarbons, perfluorocarbons and non-fluorine-containing compounds. Advantageously, the halocarbon compounds contain at least one hydrogen atom on their carbon backbone. The presence of such a hydrogen atom 5 renders the halocarbon more readily degradable in the environment thus preventing the large accumulation of such compounds. To provide polyurethane foam with commercially interesting insulation properties, the organic compounds when in a gaseous phase advantageously exhibit gas thermal conductivities of less than 20, preferably less than 15, more preferably less than 13 and most preferably less than 12 mW/MK at 298 K. io In the case of the first component of the blowing agent composition, preferred organic compounds are the halocarbons. Suitable first component halocarbons include the halocarbons of methane, ethane, and mixtures thereof. Exemplary of methane halocarbons are trichlorofluoromethane (R-11; b.p. 297 K), dich- lorofluoromethane (R-21; b.p. 283 K), dibromodifluoromethane (R-12B2; b.p. 297 K), bromoch- lorofluoromethane (R-21 B1 ; b.p. 31 1 K), bromofluoromethane (R-31 B1 ; b.p. 290 K) and dichloromethane (R- 15 30; b.p. 313 K); and of the ethane halocarbons are trifluorotrichloroethane (R-11 3; b.p. 320 K), dichlorotrifluoroethane (R-123; b.p. 300 K), dichlorodifluoroethane (R-132b; b.p. 320 K), trifluorochloroethane (R- 133; b.p. 290 K), fluorodichloroethane (R-141b; b.p. 305 K) and difluoroethane (R-152; b.p. 304 K). Particularly preferred halocarbons for use as the first component are the methane halocarbons R-11, R- 31 B1, and the ethane halocarbons R-123, R-133, and R-141b and with especially R-11, R-123, and R-141b 20 being preferred, due to their commercial availability and suitability for preparing polyurethanes. In the case of the second component of the blowing agent composition, preferred organic compounds are the halogenated adducts, halocarbons, of methane, ethane, propane, ethylene, propylene, or cyclic hydrocarbons; and mixtures thereof. Exemplary of suitable second component halocarbon compounds are methane halocarbons including 25 dichlorodifluoromethane (R-12; b.p. 243 K), difluorochloromethane (R-22; b.p. 232 K ), chlorofluoromethane (R-31; b.p. 264 K), methylchloride (R-40; b.p. 249 K), bromochlorodifluoromethane (R-12B1; b.p. 269 K), and bromodifluoromethane (R-22B1; b.p. 258 K); ethane halocarbons including chloropentafluoroethane (fi- ll 5; b.p. 234 K), chlorotetrafluoroethane (R-124; b.p. 261 K or isomer R-124a; b.p. 263 K), tetrafluoroethane (R-134; b.p. 253 K or isomer R-134a; b.p. 246 K), chlorodifluoroethane (R-142b; b.p. 264 K), trifluoroethane 30 (R-143a; b.p. 225 K), difluoroethane (R-152a; b.p. 248 K) and fluoroethane (R-161; b.p. 236 °K); are propane halocarbons including chloroheptafluoropropane (R-21 7; b.p. 271 K), octafluoropropane (R-21 8; b.p. 235 K), heptafluoropropane (R-227a; b.p. 256 K), hexafluoropropane (R-236; b.p. 272 K), and pentafluoropropane (R-245d; b.p. 253 K); are ethylene halocarbons including chlorotrifluoroethylene (R-11 13; b.p. 245 K), chlorodifluoroethylene (R-11 22; b.p. 255 K), trans-chlorofluoroethylene (R-11 31; b.p. 269 K), gem- 35 chlorofluoroethylene (R-11 31 a; b.p. 248 K), difluoroethylene (R-11 32; b.p. 245 K) and chloroethylene (R- 1140 b.p. 259 K); are propylene halocarbons including hexafluoropropylene (R-21 16a; b.p. 244 K), pentafluoropropylene (R-21 25a; b.p. 252 K), tetrafluoro-propylene (R-21 34a; 245 K ), and difluoropropylene (R-21 52b; b.p. 244 K); and cyclic halocarbons including hexafluorocyclopropane (C-216; b.p. 244 K) and octa-fluorocyclobutane (C-318; 268 K). Particularly preferred for the second component, component (b) of 40 the blowing agent composition are the methane halocarbons comprising R-31 and R-22B1 and the ethane halocarbons comprising R-124, R-124a and R-142b; with R-142b being the most preferred second component. Particularly preferred blowing agent compositions for use in preparing polyurethane foams are those where component (a) comprises dichlorofluoroethane (R-141b), dichlorotrifluoroethane (R-123) or mixtures 45 thereof and where component (b) is 1-chloro-1 ,1 -difluoroethane (R-142b). Especially preferred blowing agent compositions are wherein both component (a) and component (b) comprise an ethane halocarbon. When preparing polyurethane foams by the process of this invention, there is present, in addition to the blowing agent composition, a blowing agent precursor. The blowing agent precursor is water which during 50 the course of the polymerization reaction undergoes conversion and provides a gas. The so-provided gas functions as a blowing agent in addition to the blowing agent composition. The water which is present as a blowing agent precursor in the process of this invention provides carbon dioxide when reacted with an organic polyisocyanate. Theoretically, one mole of water when allowed to react with an organic polyisocyanate provides one mole of carbon dioxide. 55 Polyurethane foams are prepared by reacting at least one organic polyisocyanate with at least one active hydrogen-containing compound in the presence of the blowing agent composition described hereinabove. It is often convenient to preblend the blowing agent composition with the active hydrogen- containing compound before contacting the resulting blend with the polyisocyanate. Preferably, the blowing

4 EP 0 398 147 B1

agent composition is prepared in the active hydrogen-containing compound. It is also possible to simulta- neously blend together the polyisocyanate, active hydrogen-containing compound and blowing agent composition in one operation resulting in the production of polyurethane foam. The quantity of blowing agent composition employed when preparing a foam is sufficient to give a 5 desired density to the foam. Advantageously, sufficient blowing agent is employed to provide a polyurethane foam having a free-rise density of from 10 to 500, preferably from 15 to 200, more preferably from 18 to 100 and most preferably from 18 to 60 kg/m3. When preparing blends of isocyanate-reactive compositions comprising at least one active hydrogen- containing compound with the blowing agent composition, to achieve the desired overall density of io polyurethane foam, the blend advantageously contains from 1 to 30, preferably from 2 and up to 30, preferably up to 25 and more preferably up to 20 weight percent of the blowing agent composition by total weight of active hydrogen-containing compound and blowing agent composition. Active hydrogen-containing compounds which are useful in the preparation of polyisocyanate-based cellular polymers include those materials having two or more groups which contain an active hydrogen atom is which reacts with an isocyanate. Preferred among such compounds are materials having at least two hydroxyl, primary or secondary amine, carboxylic acid, or thiol groups per molecule. Polyols, i.e., compounds having at least two hydroxyl groups per molecule, are especially preferred due to their desirable reactivity with polyisocyanates. Suitable isocyanate reactive materials for preparing rigid polyurethanes are active hydrogen-containing 20 compounds having an equivalent weight of from 50 to 700, preferably from 70 to 300 and preferably from 70 to 150. Such isocyanate-reactive materials also advantageously have a functionality of at least 2, preferably from 3 and up to 16, preferably up to 8, active hydrogen atoms per molecule. Suitable additional isocyanate-reactive materials include polyether polyols, polyester polyols, poly- hydroxy-terminated acetal resins, hydroxyl-terminated amines and polyamines. Examples of these and other 25 suitable isocyanate-reactive materials are described more fully in U.S. Patent 4,394,491, particularly in columns 3-5 thereof. Most preferred for preparing rigid foams, on the basis of performance, availability and cost, is a polyol prepared by adding an alkylene oxide to an initiator having from 2 to 8, preferably from 3 to 8 active hydrogen atoms per molecule. Exemplary of such polyether polyols include those commercially available under the trademark VORANOL®, such as VORANOL 202, VORANOL 360, VORANOL 370, 30 VORANOL 446, VORANOL 490, VORANOL 575, VORANOL 640, VORANOL 800, all sold by The Dow Chemical Company, and PLURACOL® 824, sold by BASF Wyandotte. Other most preferred polyols include alkylene oxide derivatives of Mannich condensates, as taught, for example, in U.S. Patents 3,297,597; 4,137,265 and 4,383,102; and amino-alkylpiperazine-initiated polyethers as described in U.S. Patents 4,704,410 and 4,704,411. 35 Polyisocyanates useful in making polyurethanes include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. Representative of these types are diisocyanates such as m- or p-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6 -diisocyanate, hexamethylene-1 ,6- diisocyanate, tetramethylene-1 ,4-diisocyanate, cyclohexane-1 ,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers), naphthylene-1 ,5-diisocyanate, 1-methylphenyl-2,4-phenyldiisocyanate, diphenylmethane-4,4'- 40 diisocyanate, diphenylmethane-2,4'-diisocyanate, 4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'- biphenylenediisocyanate and 3,3'-dimethyldiphenylpropane-4,4'-diisocyanate; triisocyanates such as toluene-2,4,6-triisocyanate and polyisocyanates such as 4,4'-dimethyldiphenylmethane-2,2',5',5'- tetraisocyanate and the diverse polymethylenepolyphenylpolyisocyanates. A crude polyisocyanate may also be used in the practice of this invention, such as the crude toluene 45 diisocyanate obtained by the phosgenation of a mixture of toluene diamines or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude diphenylmethanediamine. The preferred undistilled or crude polyisocyanates are as disclosed in U.S. Patent 3,215,652. Especially preferred are methylene-bridged polyphenylpolyisocyanates, due to their ability to cross-link the polyurethane. The isocyanate index, ratio of equivalents of isocyanates to equivalents of active 50 hydrogen-containing groups, is advantageously from 0.9 to 10, preferably from 1.0 to 4.0, more preferably from 1 .0 to 2.0, and most preferably from 1 .0 to 1 .5. In addition to the foregoing critical components, it is often desirable to employ certain other ingredients in preparing cellular polymers. Among these additional ingredients are catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, and fillers. 55 A rigid closed-celled polyisocyanate-based foam is prepared by contacting and reacting an organic polyisocyanate with an active hydrogen-containing compound in the presence of the above-described blowing agent composition and blowing agent precursor. The foam when prepared advantageously contains within its closed cells a gaseous mixture comprising the above-described blowing agent composition and

5 EP 0 398 147 B1

gas derived from a blowing agent precursor. As already stated hereinabove, the blowing agent precursor is water, which provides carbon dioxide when reacted with an organic polyisocyanate. The quantity of water used in addition to the blowing agent composition is sufficient to provide a rigid closed-celled polyisocyanate-based foam containing in its cells a 5 gaseous mixture comprising, as calculated from quantities of blowing agent and precurser present in the process of this invention, (a) from about 30 to about 85 mole percent, based on component (a) and component (b), of a mixture itself comprising; (1) from 40 to 95 mole percent, based on components (1) and (2), of at least a halocarbon compound io having a boiling point of at least 283 K, and (2) from 5 to 60 mole percent based, on components (1) and (2), of a halocarbon compound having a boiling point of from 235 K to 266 K, and wherein the ratio of said boiling point of a component (1) to a component (2) is from 1.06:1 to 1.20:1 and wherein said composition is free of any compound having a boiling point of 338 K or greater, and is (b) from 15 to 70 mold percent, based on components (a) and (b), of carbon dioxide. Preferably component (a) of the cell gas mixture is present in an amount of from 40, more preferably from 50, and most preferably from 55, and up to 85, preferably up to 80 and more preferably up to 75 mole percent based on components (a) and (b) of the mixture. Component (b) is present preferably in an amount of from 20, more preferably from 25, and up to 70, 20 preferably up to 60, more preferably up to 50 and most preferably up to 45 mole percent based on components (a) and (b) of the mixture. Although foams can be prepared with cell gas compositions outside these limits, the resulting foams may not exhibit commercially desirable physical properties. Other auxiliaries useful in producing polyurethanes include surfactants, pigments, colorants, fillers, fibers, antioxidants, catalysts, flame retardants, and stabilizers. In making polyurethane foam, it is generally 25 highly preferred to employ a minor amount of a surfactant to stabilize the foaming reaction mixture until it cures. Such surfactants advantageously comprise a liquid or solid organosilicone surfactant. Other, less preferred surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or al- kanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonic esters and alkyl arylsulfonic acids. Such surfactants are employed in amounts sufficient to stabilize the foaming reaction mixture against 30 collapse and the formation of large, uneven cells. Typically, from 0.2 to 5 parts of the surfactant per 100 parts by weight polyol are sufficient for this purpose. One or more catalysts for the reaction of the polyol with the polyisocyanate are advantageously used. Any suitable urethane catalyst may be used, including tertiary amine compounds and organometallic compounds. Exemplary tertiary amine compounds include triethylenediamine. N-methyl morpholine, pen- 35 tamethyldiethylenetriamine, tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, 3- methoxy-N-dimethylpropylamine, N-ethyl morpholine, diethylethanolamine, N-coco morpholine, N,N- dimethyl-N'.N'-dimethyl isopropylpropylenediamine, N,N-diethyl-3-diethylaminopropylamine, and dimethyl- benzylamine. Exemplary organometallic catalysts include organomercury, organolead, organoferric and organotin catalysts, with organotin catalysts being preferred among these. Suitable tin catalysts include 40 stannous chloride, tin salts of carboxylic acids such as dibutyltin di-2-ethyl hexanoate, as well as other organometallic compounds such as are disclosed in U.S. Patent 2,846,408. 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 are from 0.001 to 2 parts of catalyst per 100 45 parts by weight of polyol. In making a polyurethane foam, the polyol(s), polyisocyanate and other components are contacted, thoroughly mixed and permitted to expand and cure into a cellular polymer. The particular mixing apparatus is not critical, and various types of mixing head and spray apparatus are conveniently used. It is often convenient, but not necessary, to preblend certain of the raw materials prior to reacting the polyisocyanate 50 and active hydrogen-containing components. For example, it is often useful to blend the polyol(s), blowing agent, surfactants, catalysts and other components except for polyisocyanates, and then contact this mixture with the polyisocyanate. Alternatively, all components can 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, although such is not preferred. 55 The polyurethane foam of this invention is useful in a wide range of applications, such as in spray insulation, appliance foam, rigid insulating boardstock, laminates, and many other types of rigid foam. The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are given by weight.

6 EP 0 398 147 B1

Examples 1 to 7

Rigid polyurethane foams according to the invention are prepared from the formulations described below in Table I. The foams are prepared using a low pressure foaming machine equipped with a high shear mixer set to 7000 rpm. B.A. - I (Blowing Agent - I) is trichlorofluoromethane (R - 11) boiling point 296.8 K B.A. - II is 1-chloro-1,1 -difluoroethane boiling point 263.8 K (R-142b) Boiling point ratio 296.8 ° K/263.8 K is equal to 1.125 The properties of the resulting foams are shown in Table II. tO T3 O O 2 ^ 00 re^ > * co t- n 1 1 ' Q' - ? o a <*•«>» 3 £ o^1 -=T C j-> re >> —I -H >> Q, 4J L H i —1 c\i m _ on -h oicor-ico ^'co'-zrotn'^r oo to >» o ~i - O bO*J S~ CO ■H O CO £ cm oo _ m -c Ei) * • . • i00?" • CJ CO 3 E Oloo'vO 1 ■ ^ go C KHh O M OA CM 00 *~ OvJ 3 O O C t^, 0) — < O MO C C\J .— ^ m CO -r QJ 3 rt r-H -H _... • in . in 00 ' . to co t. xi re ^' CO 1 t-LO 0 3- ' ^ J "J OJCflJJ > -u rO O

£3; cS2 ^: «^ ?«J ^cm » o^.2m*>.»«« o2 njre a,o, re >»>. — q-) . ™0^ reres-reorecou s. re o re co u * • i • ' >> o. o --h an a) "SI i . vnS ^ a -JEXJn cr> ro cmvviVVi r- o hOT3 iflre Oo iflre Ee n00 cC cC .-1<-< oO j->J-> 3 . —t-h —-h < <0re 3 Cc cm m-^ vo^ „ 10 in >, c E >—h i goco ^.i . -in • in 03 * • <-h —i jj s. re -h r-i 'M| oo 1 >ot '° *x>*o o recoox:>,re c o o x: >» o-\C7\ ^^_-^^.'~"-:r'~ ,0 a.Q, *i*l a viVi hH *> xX C j-> E O C CB O OH 0) C S.!- ^ CMcm m ^ —, _^ ^r—- OCoc Ooreox:-<-a « O £ h tj , • .in o> 03CO . coCO «-. >>o >, ""1'"Ico't-C-'CM*0 CO 1, "CM * ° ->->-^-h Cc^h>,x: i, H >, x: 5n C-C- - ^ vOvo^ C >> 0 3 0 3 ^H •—^- ^iy cocox: x: —i «in aoa o »Hi «- cm ^ in cccore-coreo a> re - co re o , l^ GO —< S £ CO S- -i » 3^Hx;re-o S m ^-=r gogihEOHQ. h E O H Q. jCJC anQ.0O oh • >,« a)CO i— «m O O X>J3 j-ij-> r-i t3 re C'^^ oocx:o>,hjj>, °? , a>bo>>cs-orex U rv~n- COX:—COX!— »2Q.reEOT30 >,2 O. aj E O T3 o £j ^_ Q^"5o -H3UDCt. *- v*.^ —i o reoj-sre-oc^r—iQ.reo-^re-oc-T—iQ. aQ. cou*CJ-> Sco S h^cocooc co i-h I . 2 OJ^-iO) c-ore 1 ^._ 0) ^^►-.cOhhM re 3 L QJ h OOl^l^r-i^-o-n^ 1-1 a >,>,-l>,>,•!. -t.reooj3a s<:qT0s<:ci0o a- « ° Er-H^-f> >> reoo-Q.-Q.otoreoo.Q..Q.oto core* r~l 1—1 n a. a, j, * o o H hlw * a. cua.

8 EP 0 398 147 B1

o o c— in O OO • on o on o oo • in i i ,_' ' OO C- CM O oo

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The height/weight measurements and density distribution data are obtained using a 200 x 4 x 6 cm 55 mold preheated to 45 °C. The larger the height/weight value the better the flow of the reacting system. The density distribution is a statistical analysis of the foam density obtained when the mold has been overpacked by 10 percent; the lower the value the smaller the deviation in foam density overall.

9 EP 0 398 147 B1

Post Demold expansion is measured in millimeters in the parallel-to-rise direction on 20 x 20 x 20 cm cube foam, molded to an overall density of about 30 kg/m3. The expansion is observed after a curing time of 10 minutes and then 24 hours, with one face of the mold having initially been opened after 3 or 4 minutes curing. Lower values of expansion indicate improved demold performance. Compressive strengths 5 are measured in the parallel-to-rise and perpendicular-to-rise directions using 5 x 5 x 5 cm cubes obtained from the core of the larger molded cubes. K-factor is measured on molded foam, having an overall density of about 30 kg/m3, cut to approximately 2.5 x 18 x 18 cm. K-factor performance is observed in both perpendicular and parallel-to-rise directions. An Anacon Model 88, Thermal Conductivity Analyzer with cold and hot plate temperatures of 10.2 and 37.8 °C io was employed.

Examples 8 and 9

Rigid polyurethane foams which contain no "hard" CFCs are prepared as in Examples 1 to 7 according is to the formulations given in Table III. Foam properties are reported in Table IV. B.A. - III is dichlorotrifluoroethane (R-123) boiling point 300.1 K B.A. - IV is dichlorofluoroethane (R-141b) boiling point 305 K 20 B.A. - II as for Examples 1-6 Boiling point ratio: B.A. - lll/B.A. - II is 1.138 B.A. - IV/B.A. - II is 1.156

Table III

(Examples 8 and 9) 8 9 Polyol A* (parts) 98.2 98.2 B.A. - III parts (mole %) 20.5 (50%) B.A. -IV - 15.2(50%) B.A. -II 13.4(50%) 13.1(50%) Total Water (parts) 1 .8 1 .8 Isocyanate** (parts) 142.1 142.1 % R-1 1 reduction over Sample A 100% 100% Polyol A* - a polyol formulation containing propoxylated sucrose, glycerine and ethylene diamine polyols; average functionality 4.0, hydroxyl number 460. The polyol formulation is available commercially as VORANOL RST 460 sold by The Dow Chemical Company containing the 1 .8 parts water indicated separately in this table. ** A Crude polyphenyl polymethylene polyisocyanate, average functionality, 2.7 average NCO equivalent weight 137