WO1996037540A1 - Composition expansible contenant un agent gonflant perfluorochimique insature - Google Patents

Composition expansible contenant un agent gonflant perfluorochimique insature Download PDF

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Publication number
WO1996037540A1
WO1996037540A1 PCT/US1996/007501 US9607501W WO9637540A1 WO 1996037540 A1 WO1996037540 A1 WO 1996037540A1 US 9607501 W US9607501 W US 9607501W WO 9637540 A1 WO9637540 A1 WO 9637540A1
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Prior art keywords
group
compounds
blowing agent
compound
formula
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PCT/US1996/007501
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English (en)
Inventor
Rudolf J. Dams
Rudolf V. Van San
Rik De Vos
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Minnesota Mining And Manufacturing Company
Imperial Chemical Industries, Plc
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Application filed by Minnesota Mining And Manufacturing Company, Imperial Chemical Industries, Plc filed Critical Minnesota Mining And Manufacturing Company
Publication of WO1996037540A1 publication Critical patent/WO1996037540A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
    • C08J9/148—Halogen containing compounds containing carbon and halogen atoms only perfluorinated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • This invention relates to foamable compositions comprising fluorine- containing blowing agent compounds.
  • this invention relates to a process for preparing polymeric foams, e.g., polyurethane foams, to polymeric foams prepared from the foamable compositions, and to articles comprising the foams.
  • CFCs Chlorofluoiocarbons
  • HCFCs and HFCs have lower ozone depletion potentials (that of HFCs being zero) and shorter atmospheric lifetimes than CFCs, but their performance as blowing agents is inferior to that of CFCs.
  • U.S. Pat No.5,162,384 (Owens et al.) describes a blowing agent emulsion comprising at least one low boiling, perfluorinated, N-aliphatic, cyclic 1,3- or 1,4- aminoether.
  • EP 439,283 (BP Chemicals Limited) discloses blowing agents comprising perfluoro- or partially fluorinated-(cyclo)alkanes.
  • EP 416,777 (Imperial Chemical Industries) describes a method for the preparation of a polymeric foam which comprises vaporising a fluorine-containing ether in the presence of a foamable polymer or the precursors of a foamable polymer.
  • CA 2,037,587 (Hoechst Aktiengesellschaft) describes a process for the manufacture of foams with the aid of blowing agents containing fluoroalkanes and fluorinated ethers.
  • U.S. Pat. No.4,972,003 discloses a blowing agent composition comprising one or more organic compounds, particularly halocarbons, having a boiling point of less than or equal to 272K at atmospheric pressure, which composition is substantially free of organic compounds having a boiling point of 273K or greater.
  • U.S. Pat. No. 5,205,956 discloses a process for the production of plastic foams, in which the blowing agent used is at least one vinylfluoroalkane.
  • this invention provides foamable compositions for use in preparing polymeric, e.g., polyurethane, foams.
  • the compositions comprise (a) at least one normally liquid, unsaturated perfluorochemical blowing agent compound selected from the group consisting of perfluoroolefin compounds, e.g., perfluoro(4- methylpent-2-ene), perfluoroaromatic compounds, e.g., hexafluorobenzene, and perfluorocycloolefin compounds, e.g., perfluorocyclohexene, the perfluoroolefin compounds optionally containing one or more catenary, i.e., in-chain, heteroatoms; (b) at least one precursor of a foamable polymer comprising at least one organic polyisocyanate modified with at least one substantially fluorinated isocyanate-reactive compound; and (c) at least one compound containing at least two reactive hydrogen atoms.
  • the term "normally liquid” means liquid under ambient conditions.
  • the blowing agent compound has a boiling point greater than or equal to about 20°C.
  • Reactive components which react with one another either during or after foaming to form a foamable polymer are regarded herein as precursors of a foamable polymer.
  • Perfluoroolefins and perfluorocycloolefins are preferred blowing agent compounds due to considerations of cost and availability.
  • the foamable compositions of the invention comprising an unsaturated perfluorochemical as blowing (or co-blowing) agent generally provide polymeric foams having a smaller cell size (and therefore better insulation efficiency) than foams produced using only conventional blowing agents such as CFCs, HCFCs, HFCs, hydrocarbons, hydrochlorocarbons, or water.
  • the compositions of the invention are also more "environmentally friendly" than compositions containing some conventional blowing agents, e.g., CFCs and HCFCs, as the unsaturated perfluorochemical blowing agent compounds utilized in the compositions have an ozone depletion potential of zero.
  • the compounds also advantageously have shorter atmospheric lifetimes (due to their greater reactivity) than saturated perfluorochemical blowing agents, and thus have lower global warming potentials.
  • unsaturated perfluorochemical blowing agent compounds are known to be highly reactive toward nucleophiles such as alcohols in the presence of basic catalysts such as trialkylamines (see, e.g., Organofluorine Chemicals and their Industrial Applications edited by R E. Banks, pages 29-32, Ellis Horwood Ltd., Chichester (1979); Advances in Fluorine Chemistry. Volume 4 edited by M. Stacey, J. C. Tatlow, and A. G.
  • the apparently latent reactivity of the unsaturated perfluorochemical blowing agents can potentially be utilized to advantage later in the foam-blowing process to chemically "anchor" the blowing agent in the foam to prevent its diffusion and release into the atmosphere, thereby further reducing environmental concerns.
  • this invention provides a process for preparing polymeric foams, polymeric foams prepared from the foamable compositions of the invention, and articles comprising the foams.
  • the foams can vary in texture from very soft types useful in upholstery applications to rigid foams useful as structural or insulating materials.
  • Unsaturated perfluorochemical blowing agent compounds suitable for use in the foamable compositions of the invention are normally liquid perfluoroolefin compounds, perfluoroaromatic compounds, and perfluorocycloolefin compounds.
  • the compounds can contain some residual carbon-bonded hydrogen (generally less than about 0.4 mg/g and preferably less than about 0.1 mg/g, e.g., 0.01 to 0.05 mg/g) but are preferably substantially completely fluorinated.
  • the perfluoroolefin compounds can contain one or more catenary heteroatoms, e.g., nitrogen or oxygen atoms.
  • blowing agent compounds include hexafluoropropene dimers, e.g., perfluoro(4-methylpent-2-ene) and perfluoro(2-methylpent-2-ene); hexafluoropropene trimers, e.g., perfluoro(4-methyl-3-isopropylpent-2-ene) and perfluoro(2,4-dimethyl-3-ethylpent-2-ene); tetrafluoroethylene oligomers, e.g., perfluoro(3-methylpent-2-ene),perfluoro(3,4-dimethylhex-3-ene),andperfluoro(2,4- dimethyl-4-ethylhex-2-ene);perfluoro(1-pentene);perfluoro(2-pentene);perfluoro(1- hexene); perfluoro(2-hexene); perfluoro(3-hexene); per
  • the unsaturated perfluorochemical blowing agent compounds preferably have boiling points greater than or equal to about 20°C. More preferably, the compounds have boiling points in the range of from about 30 °C to about 125°C, and most preferably about 45°C to about 125°C. Compounds having such boiling points are well-suited for foam blowing at atmospheric pressure.
  • Perfluoroolefins and perfluorocyclooleflns are preferably utilized in the compositions of the invention due to considerations of cost and availability. More preferably, perfluoroolefins are utilized because of the wide range of boiling points available.
  • Perfluoroolefin compounds (as well as catenary heteroatom-containing perfluoroolefin compounds) suitable for use in the foamable compositions of the invention can be prepared by methods such as the decarboxylation of salts of fluorocarboxylic acids (see, e.g., A. M. Lovelace, D. A. Rausch, and W. Postelnek, Aliphatic Fluorine Compounds. Chapter III (Alkenes and Alkynes), pages 107-09, Reinhold Publishing Corporation, New York (1958)) and the coupling of two or more perfluoroolefins (as described, e.g., in U.S. Pat. No.
  • Hexafluoropropene oligomers can be prepared by various gas-phase and liquid-phase methods such as those described in, e.g., U.S. Pat. No. 5,254,774 (Prokop), the descriptions of which are incorporated herein by reference. Hexafluoropropene dimer and a mixture of hexafluoropropene trimers are also commercially available (e.g., from Fluorochem Limited).
  • Tetrafluoroethylene oligomers can be prepared by methods such as those described in, e.g., U.S. Pat. Nos. 3,758,618 (Deem) and 4,016,217 (Fielding et al.), the descriptions of which are incorporated herein by reference.
  • Perfluorocycloolefin compounds suitable for use in the foamable compositions of the invention can be prepared by the electrochemical fluorination of aromatic acid derivatives followed by decarboxylation, as described for perfluorocyclohexene by G. Gambaretto and G. Troilo in Chim. Ind.52(11), 1097-102 (1970)andAnn. Chim.59.(8-9), 690-701 (1969). See also Chambers, supra. In addition, see U.S. Pat. No. 3,331,880 (Anello et al.) which describes methods for preparing polyfluorocyclohexenes, the descriptions of which are incorporated herein by reference. Perfluorocyclohexene is also commercially available (e.g., from Fluorochem Limited).
  • Perfluoroaromatic compounds suitable for use in the foamable compositions of the invention can be prepared by various methods (such as the defluorination of perfluorocycloalkanes) described, e.g., in Chambers, supra, pages 261-73. Hexafluorobenzene is commercially available (e.g., from Fluorochem Limited).
  • the unsaturated perfluorochemical blowing agents can be used alone as the sole blowing agent in the foamable composition or can be used in combination with saturated perfluorochemical blowing agents or with conventional blowing agents, e.g., CFCs, HCFCs, HFCs, hydrocarbons, hydrochlorocarbons (HCCs), or water. Mixtures of unsaturated perfluorochemical and other blowing agent(s) are generally preferred due to cost considerations.
  • suitable co-blowing agents include hydrocarbons, e.g., pentane, hexane, and cyclopentane; halohydrocarbons, e.g., 1,1- dichloro-1 -fluoroethane, 1,1-dichloro-2,2,2-trifluoroethane, 1- hydropentadecafluoroheptane, 1,1,1,2-tetrafluoroethane, chlorodifluoromethane, 1- chloro-1,1-difluoroethane, and 2-chloropropane; chlorofluorocarbons, e.g., fluorotrichloromethane; water (which reacts with isocyanate to produce carbon dioxide); saturated perfluorochemicals, e.g., perfluoropentane, perfluorohexane, and perfluoro(N-methylmorpholine); and mixtures thereof.
  • hydrocarbons e.g., pentane, he
  • co-blowing agents are normally liquid blowing agent compounds, e.g., 1,1-dichloro-1-fluoroethane, cyclopentane, pentane, hexane, water, and perfluoro(N-methylmorpholine).
  • co-blowing agent can generally be utilized in an amount in the range of from about 0.5 to about 99.5 weight percent (preferably, from about 40 to about 95 weight percent, more preferably from about 75 to about 90 weight percent) of the blowing agent mixture.
  • Foamable polymers suitable for use in the foamable compositions of the invention include polyolefins, e.g., polystyrene, poly(vinyl chloride), and polyethylene. Foams can be prepared from styrene polymers using conventional extrusion methods. The blowing agent(s) can be injected into a heat-plastified styrene polymer stream within an extruder and admixed therewith prior to extrusion to form foam.
  • Suitable styrene polymers include the solid homopolymers of styrene, ⁇ -methylstyrene, ring-alkylated styrenes, and ring-halogenated styrenes, as well as copolymers of these monomers with minor amounts of other readily copolymerizable olefinic monomers, e.g., methyl methacrylate, acrylonitrile, maleic anhydride, citraconic anhydride, itaconic anhydride, acrylic acid, N-vinylcarbazole, butadiene, and divinylbenzene.
  • Suitable vinyl chloride polymers include vinyl chloride homopolymer and copolymers of vinyl chloride with other vinyl monomers. Ethylene homopolymers and copolymers of ethylene with, e.g., 2-butene, acrylic acid, propylene, or butadiene are also useful. Mixtures of different types of polymers can be employed.
  • Precursors of foamable polymers suitable for use in the foamable compositions of the invention include precursors of phenolic polymers, silicone polymers, and isocyanate-based polymers, e.g., polyurethane, polyisocyanurate, polyurea, polycarbodiimide, and polyimide.
  • Precursors of isocyanate-based polymers are preferred, as the unsaturated perfluorochemical blowing agent compounds utilized in the foamable compositions of the invention are especially useful for preparing polyurethane or polyisocyanurate foams. More preferred are precursors of a foamable polymer comprising an isocyanate-based polymer that has been modified with at least one substantially fluorinated isocyanate-reactive compound.
  • preferred foamable compositions of the invention comprise (a) at least one normally liquid blowing agent compound selected from the group consisting of perfluoroolefin compounds, perfluoroaromatic compounds, and perfluorocycloolefin compounds, the perfluoroolefin compounds optionally containing one or more catenary heteroatoms; (b) at least one precursor of a foamable polymer comprising at least one organic polyisocyanate modified with at least one substantially fluorinated isocyanate-reactive compound; and (c) at least one compound containing at least two reactive hydrogen atoms.
  • Polyisocyanates suitable for use in the preferred compositions of the invention include aliphatic, alicyclic, arylaliphatic, aromatic, or heterocyclic polyisocyanates, or combinations thereof. Any polyisocyanate which is suitable for use in the production of polymeric foams can be utilized. Of particular importance are aromatic diisocyanates such as toluene and diphenylmethane diisocyanates in pure, modified, or crude form.
  • MDI variants diphenylmethane diisocyanate modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine, or isocyanurate residues
  • crude or polymeric MDI polymethylene polyphenylene polyisocyanates
  • suitable polyisocyanates include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane- 1,3- diisocyanate, cyclohexane- 1,3- and -1,4-diisocyanate (and mixtures of these isomers), diisocyanato-3 ,3 ,5-trimethyl-5-isocyanatomethyl cyclohexane, 2,4- and 2,6-toluene diisocyanate (and mixtures of these isomers), diphenylmethane-2,4'- and/or -4,4'- diisocyanate, naphthalene-1,5-diisocyanate, the reaction products of four equivalents of the aforementioned isocyanate-containing compounds with compounds containing two isocyanate-reactive
  • the organic polyisocyanate modified with at least one substantially fluorinated isocyanate-reactive compound is prepared by reacting a stoichiometric excess of the organic polyisocyanate with at least one substantially fluorinated isocyanate-reactive compound.
  • substantially fluorinated isocyanate-reactive compounds suitable for use in modifying the polyisocyanates are those organic compounds having at least one isocyanate-reactive functional group in which at least 50% of those hydrogen atoms bonded to carbon atoms in the corresponding unfluorinated compound are replaced by fluorine atoms.
  • Suitable substantially fluorinated isocyanate-reactive compounds for use in the process of the invention are those of formula (I):
  • n 1 to 11;
  • p is 0 or 1;
  • q is 0 or 1
  • q' is 0 or 1
  • Y is oxygen, sulphur, the group of the formula
  • R is hydrogen, C 1-12 alkyl, or C 1-12 fluorinated alkyl
  • X is oxygen, sulphur, a group of the formula
  • R' is C 1-12 alkyl, C 1-12 fluorinated alkyl, hydrogen or the group of formula -(CH 2 ) n -(Z) q -A-[(Z') q .-(CH 2 ) m -Y-H] p ;
  • Z is a group of the formula
  • R" is hydrogen, C 1-12 alkyl, C 1-12 fluorinated alkyl or a group of formula
  • Z' is a group of the formula
  • R" is hydrogen, C 1-12 alkyl, C 1-12 fluorinated alkyl or a group of formula -(CH 2 ) n -A-[-(CH 2 ) m -Y-H] p oragroupofformula-R'"-Y-H where R'" is C 1-12 alkylene; and either
  • A is a substantially fluorinated or perfluorinated straight or branched chain alkyl group containing from 2 to 10 carbon atoms;
  • A is a substantially fluorinated or perfluorinated, straight or branched chain alkylene group containing from 2 to 10 carbon atoms.
  • One group of preferred substantially fluorinated isocyanate-reactive compounds for use in the process of the invention are those of formula (I) as defined above wherein X and Y are both oxygen, and A, Z, Z', n, m, p, q and q' have any of the meanings given above.
  • substantially fluorinated isocyanate-reactive compounds for use according to the invention are those in which p and q are each 0 and X is oxygen, i.e., of formula (II):
  • A-(CH 2 ) n -OH (II) wherein A is a substantially fluorinated or perfluorinated, straight or branched chain alkyl group containing from 2 to 10 carbon atoms and n is 1 to 11. Particular mention may be made of those compounds of Formula (II) wherein n is 1 or 2 and A is perfluorinated Q. io, straight or branched chain alkyl, such as (perfluoropropyl)methanol,
  • substantially fluorinated isocyanate reactive compounds for use in the process of the invention are those in which p is 0, q is 1 , and X is oxygen, i.e., formula (III):
  • A is a substantially fluorinated or perfluorinated, straight or branched chain alkyl group containing from 2 to 10 carbon atoms, n is 1 to 11 and R" is hydrogen or a C 1-12 alkyl or aryl or R' ' '-OH wherein R" ' is C 1-12 alkylene.
  • n is 1 or 2 and A is perfluorinated C 6-8 straight or branched chain alkyl and R" is hydrogen or C 1-4 alkyl or R'''-OH wherein R"' is C 1-4 alkylene such asN-ethyl-N-2-hydroxyethylperfluorooctane sulfonamide, N-methyl-N-2- hydroxyethylperfluorooctanesulfonamide,N-propyl-N-2-hydroxyethylperfluorooctane sulfonamide, N-2-hydroxyethylperfluorooctane sulfonamide, N-ethyl-N-2- hydroxymemylperfluorooctanesulforiamide,N-memyl-N-2-hydioxyethyl-perfluorooctane sulfonamide, N-propyl
  • Reactive hydrogen-containing compounds suitable for use in the preferred foamable compositions of the invention are those having at least two isocyanate-reactive hydrogen atoms, preferably in the form of hydroxyl, primary or secondary amine, carboxylic acid, or thiol groups, or a combination thereof.
  • Polyols i.e., compounds having at least two hydroxyl groups per molecule, are especially preferred due to their desirable reactivity with polyisocyanates.
  • Preferred polyols are those having from 2 to about 50, preferably from 2 to about 8, more preferably from 2 to about 4, hydroxyl groups.
  • Such polyols can be, e.g., polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polymethacrylates, polyester amides, or hydroxyl-containing prepolymers of these compounds and a less than stoichiometric amount of polyisocyanate.
  • the reactive hydrogen-containing compounds utilized in the preferred foamable compositions of the invention have a weight average molecular weight of from about 50 to about 50,000, preferably from about 500 to about 25,000.
  • Useful polyols include ethylene glycol, 1 ,2- and 1 ,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,5-pentane diol, 1,6-hexane diol, 1,8-octane diol, neopentyl glycol, 1,4- bis(hydroxymethyl)cyclohexane, 2-methyl-1,3-propane diol, dibromobutene diol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, higher polyethylene glycols, dipropylene glycol, higher polypropplene glycols, dibutylene glycol, higher polybutylene glycols, 4,4 '-dihydroxydiphenyl propane, and
  • suitable polyols include the condensation products of polybasic acids and polyols such as polyethylene adipate and polycaprolactone-based polyols, as well as the mixtures of hydroxy aldehydes and hydroxy ketones (“formose”) and the polyhydric alcohols obtained therefrom by reduction (“formitol”) that are formed in the autocondensation of formaldehyde hydrate in the presence of metal compounds as catalysts and compounds capable of enediol formation as co-catalysts (see, e.g., U.S. Pat. Nos.
  • polymeric foams can be prepared using the foamable compositions of the invention by vaporizing at least one normally liquid, unsaturated perfluorochemical blowing agent compound selected from the group consisting of perfluoroolefin compounds, perfluoroaromatic compounds, and perfluorocycloolefin compounds, the perfluoroolefin compounds optionally containing one or more catenary heteroatoms, in the presence of at least one foamable polymer or the precursors of at least one foamable polymer.
  • the amount ofblowing agent compound (or mixture ofblowing agent compounds, which may contain co-blowing agent) utilized is preferably up to about 30% by weight of the foamable composition.
  • Polymeric foams can be prepared using the preferred foamable compositions of the invention by vaporizing (e.g., by utilizing the heat of precursor reaction) at least one normally liquid, unsaturated perfluorochemical blowing agent compound in the presence of at least one organic polyisocyanate, modified with at least one substantially fluorinated isocyanate-reactive compound, and at least one compound containing at least two reactive hydrogen atoms.
  • vaporizing e.g., by utilizing the heat of precursor reaction
  • at least one normally liquid, unsaturated perfluorochemical blowing agent compound in the presence of at least one organic polyisocyanate, modified with at least one substantially fluorinated isocyanate-reactive compound, and at least one compound containing at least two reactive hydrogen atoms.
  • at least one normally liquid, unsaturated perfluorochemical blowing agent compound in the presence of at least one organic polyisocyanate, modified with at least one substantially fluorinated isocyanate-reactive compound, and at least one compound containing at least two
  • the polyisocyanate or modified polyisocyanate, reactive hydrogen-containing compound, and blowing agent can generally be combined, thoroughly mixed (using, e.g., any of the various known types of mixing head and spray apparatus), and permitted to expand and cure into a cellular polymer. It is often convenient, but not necessary, to preblend certain of the components of the foamable composition prior to reaction of the polyisocyanate and the reactive hydrogen-containing compound. For example, it is often useful to first blend the reactive hydrogen- containing compound, blowing agent, and any other components (e.g., surfactant) except the polyisocyanate, and to then combine the resulting mixture with the polyisocyanate. Alternatively, all components of the foamable composition can be introduced separately. It is also possible to pre-react all or a portion of the reactive hydrogen-containing compound with the polyisocyanate to form a prepolymer.
  • the polyisocyanate compound is preferably pre-reacted with the substantially fluorinated isocyanate-reactive compound to form a prepolymer.
  • a fluorinated compound such as a fluorochemical alcohol, amine, acid, epoxide, or other fluorochemical compound reactive towards isocyanates can be used.
  • the fluorinated isocyanate-reactive compounds are alcohols and thiols.
  • about 0.01-50 parts by weight of the fluorinated compound, based on the weight of the isocyanate are used.
  • the fluorinated compound is used in an amount of about 0.1-20 parts, and more preferably, 0.5-5 parts, by weight based on the weight of the isocyanate.
  • foam formulations can optionally be present in the foamable compositions of the invention.
  • foam-stabilizing agents or surfactants can be utilized.
  • catalysts can be utilized.
  • blowing agents or blowing agent precursor compounds
  • Other possible components include cell regulators, fillers, colorants, fungicides, bactericides, antioxidants, reinforcing agents, antistatic agents, and other additives or processing aids known to those skilled in the art.
  • the foamable compositions of the invention include at least one surfactant.
  • Suitable surfactants include fluorochemical surfactants, organosilicone surfactants, polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonate esters, alkyl arylsulfonic acids, fatty acid alkoxylates, and mixtures thereof.
  • Surfactant is generally employed in amounts sufficient to stablilize the foaming reaction mixture against collapse and the formation of large, uneven cells. Typically, from about 0.1 to about 5 percent by weight of surfactant is sufficient for this purpose.
  • Organosilicone surfactants and fluorochemical surfactants are preferred.
  • the preferred foamable compositions of the invention which are usefiil in preparing isocyanate-based foams often advantageously contain cross-linking and/or chain-extending agents to modify the mechanical properties of the resulting foams, as well as catalysts to increase the rate of reaction of the components of the composition.
  • Suitable cross-linking or chain-extending agents include aliphatic, alicyclic, and arylaliphatic polyols and polyamines having a molecular weight of less than about 400 and preferably containing from about 2 to about 20 carbon atoms.
  • suitable polyols include ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, and p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6- hexanediol,bis(2-hydroxyethyl)hydroquinone, 1,2,4-and 1,3,5-trihydroxycyclohexane, glycerol, trimethylolpropane, low molecular weight hydroxyl group-containing polyalkylene oxides based on ethylene oxide and 1,2-propylene oxide, and mixtures thereof.
  • cross-linking or chain-extending agents include polyamines such as primary aromatic diamines, secondary aromatic diamines, and 3,3 '-di- or 3,3',5,5'- tetraalkyl-substituted diaminodiphenylmethanes.
  • the cross-linking and chain-extending agents can be used individually or as mixtures and, when used, can generally be present in amounts ranging from about 2 to about 60 weight percent of the foamable composition.
  • Catalysts suitable for use in the preferred foamable compositions of the invention include compounds which greatly accelerate the reaction of the reactive hydrogen-containing compounds (or the cross-linking or chain-extending agents) witii the polyisocyanates. When used, catalysts are generally present in amounts sufficient to be catalytically effective. Suitable catalysts include organic metal compounds (preferably, organic tin compounds), which can be used alone or, preferably, in combination with strongly basic amines. Representative examples of these and other types of suitable catalysts are described in U.S. Pat. No. 4,972,002 (Volkert), the descriptions of which are incorporated herein by reference.
  • Foams prepared from the foamable compositions of the invention can vary in texture from very soft types useful in upholstery applications to rigid foams useful as structural or insulating materials.
  • the foams can be used, for example, in the automobile, shipbuilding, aircraft, furniture, and athletic equipment industries, and are especially useful as insulation materials in the construction and refrigeration industries.
  • the thermal conductivity (lambda) values of the resulting foams were measured on a Hesto Lambda Control A50-A thermal conductivity analyzer with a reproducibility of +/- 0.1.
  • the comparative cell sizes described in the examples are designated as follows: very fine 70 - 100 micrometers
  • the thermal conductivity of a section of the foam was measured as described above and found to be 22.3 mW[m(K)] -1 initially and 30.7 mW[m(K)] -1 after two weeks of aging at 50°C.
  • a polyurethane foam was prepared essentially according to the procedure of Example 1 (the components and their amounts are given in Table 1 ) except that 3.5 pbw of an oligomeric fluorochemical surfactant (described in Example 1 of U.S. Pat. No.
  • Polyurethane foams were prepared essentially according to the procedure of Example 1, using the components and amounts listed in Table 1.
  • the C 6 F 10 (perfluorocyclohexene) utilized in Examples 7 and 8 was purchased from Fluorochem Limited (United Kingdom) and is available as F05931.
  • the tetrafluoroethylene (TFE) oligomer utilized in Examples 3 and 4 was purchased from ICI (United Kingdom) and is believed to be a mixture of tetramer, pentamer, and hexamer.
  • the density, cell size, and thermal conductivity data for the resulting foams are shown in Table 1.
  • a polyurethane foam was prepared essentially according to the procedure of Example 1 (the components and their amounts are given in Table 1) but without the addition of HFP dimer.
  • the density, cell size, and thermal conductivity data for the resulting foam are shown in Table 1.
  • a polyurethane foam was prepared essentially as in Example 2 (the components and their amounts are given in Table 1 ) but without the addition of HFP dimer.
  • the density, cell size, and thermal conductivity data for the resulting foam are shown in Table 1.
  • Polyurethane foams were prepared essentially as in Example 2, using the components and amounts listed in Table 2.
  • the polymeric polyether polyol utilized had an average molecular weight of 630, a viscosity of about 2000 cp, and a hydroxy content of about 6 hydroxyl groups per molecule.
  • the polyol can be prepared by the reaction of sorbitol with propylene oxide and is commercially available from ICI as Polyol ICI-C.
  • the isocyanate utilized (Dow Chemical Company's PAPI TM 135) was apolymeric methylene diphenyldiisocyanate having an isocyanate equivalent of 132.
  • PAPI TM 135 is no longer available from Dow and has been replaced by PAPITM 27, an equivalent product having less color.
  • the HFP trimer utilized in Example 12 was purchased from Hoechst AG and is believed to be amixture of predominately perfluoro(4-methyl-3-isopropylpent-2-ene) and perfluoro(2,4-dimethyl-3-ethylpent-2-ene).
  • the thermal conductivity data for the resulting foams is shown in Table 2.
  • Polyurethane foam was prepared essentially as in Example 2, using the components and amounts listed in Table 2 for Example 12, except that no water was added and 90 pbw of HFP trimer was utilized.
  • the thermal conductivity of a section of the foam was measured as described above and found to be 22.0 mW[m(K)] -1 initially and 25.8 mW[m(K)] -1 after one week of aging at 70°C.
  • Polyurethane foams were prepared essentially as in Examples 11 and 12 (using the components and amounts listed in Table 2) except that various conventional blowing agents were substituted for the perfluoroolefin compounds.
  • Comparative Example E was Polyol Bayer PU 1732, having a viscosity of about 1200 cp and a hydroxy equivalent weight of about 400 mg KOH/g.
  • the thermal conductivity data for the resulting foams is shown in Table 2. This data (when compared with the data for Examples 11 and 12) indicates that foamable compositions of the present invention comprising unsaturated perfluorochemical blowing agent compound can produce foams having conductivities superior or equivalent to those of foams blown with conventional blowing agents.
  • the compositions thus provide alternatives to the use ofblowing agents which deplete atmospheric ozone (such as 1,1-dichloro-2,2,2-trifluoroethane) or which are flammable (such as cyclopentane).
  • Polyurethane foams were prepared essentially according to the procedure of Example 1 , using the components and amounts listed in Table 3.
  • Polyol 1832 A/2 commercially available from Bayer AG as Baytherm TM VP-PU 1832 A/2, is a polyether polyol having a hydroxy equivalent weight of 520 mg KOH/g, a water content of about 1.9 pbw, a catalyst content of 3.7 pbw of N,N-dimethylcyclohexyl amine, and a viscosity of about 4000 cp.
  • 1,1 -Dichloro- 1 -fluoroethane available from both Atochem and Allied-Signal was used in each case as a co-blowing agent.
  • the density, cell size, and thermal conductivity data for the resulting foams are shown in Table 3.
  • a polyurethane foam was prepared essentially as in Examples 13-16 (the components and their amounts are given in Table 3) but without the addition of unsaturated perfluorochemical.
  • the density, cell size, and thermal conductivity data for the resulting foam are shown in Table 3. This data (when compared with the data for Examples 13-16) indicates that foamable compositions of the present invention comprising unsaturated perfluorochemical blowing agent compound can provide foams having a smaller average cell size than foams prepared using 1 , 1-dichloro-1-fluoroethane and water as the sole blowing agents.
  • Polyurethane foams were prepared essentially according to the procedure ofExample 1 , using the components and amounts listed in Table 4. Pentane and water were used in each case as co-blowing agents. The density and thermal conductivity data for the resulting foams are shown in Table 4.
  • a polyurethane foam was prepared essentially as in Examples 17-19 (the components and their amounts are given in Table 4) but without the addition of perfluoroolefin compound.
  • the density and thermal conductivity data for the resulting foam are shown in Table 4. This data (when compared with the data for Examples 17-19) indicates that foamable compositions of the present invention comprising unsaturated perfluorochemical blowing agent compound can provide foams having thermal conductivities superior or equivalent to those of foams prepared using pentane and water as the sole blowing agents.
  • the density and thermal conductivity data for the resulting foam are shown in Table 4.
  • foamable compositions of the present invention comprising unsaturated perfluorochemical blowing agent compound can provide foams having thermal conductivities superior to those of foam prepared using mcompletely-fluorinated, unsaturated compounds such as that taught by Volkert et al., supra.
  • a phenolic foam was prepared essentially as in Example 1 of European Pat PublicationNo.0439283 Al (BP Chemicals Limited), exceptthat HFP trimer (Hoechst AG) was substituted for the perfluoropentane.
  • HFP trimer Hoechst AG
  • the resulting foam was stable (no collapse) and had a large cell size.
  • a polymeric diisocyanate (commercially available as DesmodurTM44V20 from Bayer AG.) and 22 g of a fluorochemical al ⁇ holhaving the structure C 8 F 17 SO 2 N(C 2 H 5 )CH 2 CH 2 OH (obtained from Minnesota Mining and Manufacturing Co., St. Paul, MN) were placed.
  • the flask was equipped with a stirrer, condensor, and thermometer.
  • the polymeric diisocyanate had a an isocyanate content of 31.5% by weight and viscosity of 200+/-40 cp at 25°C.
  • the mixture was heated at 75°C under a nitrogen atmosphere for 4 hours to form a modified isocyanate, during which time no unreacted fluorochemical alcohol was detected by gas-liquid chromatography.
  • the modified isocyanate was thai added to this polyether polyol emulsion, mixed for 10 seconds at 6000 rpm, and subsequently poured into a 350 cm x 350cm x 60cm aluminum mold,the mold being preheated to 50°C.
  • the resulting foam had a density of 38.7 kg/m 3 and a uniform distribution of fine, closed cells.
  • the closed cell content was greater than 95%.
  • the thermal conductivity of a section of the foam was measured as described above and found to be 22.3 mW[m(k)] -1 initially. Comparative Example J
  • Example 21 The fluorochemical alcohol used in Example 21 was added to the polyether polyol emulsion, instead of adding the modified isocyanate prepolymer of Example 21. The results are shown below in Table 5.
  • Example 21 As can be seen in Table 5, the use of an isocyanate modified by a fluorochemical alcohol as found in Example 21 produces foams having improved thermal conductivity and smaller cell size, as compared to foams produced in the absence of a fluorochemical alcohol-modified isocyanate prepolymer shown in Comparative Example J.
  • foams were prepared using a mixture of an unsaturated perfluorochemical blowing agent and a conventional blowing agent, cyclopentane, together with a fluorochemical alcohol- modified isocyanate prepolymer.
  • the formulas of the fluorochemical alcohols are shown in Table 6.
  • the results were compared to foams prepared using the same blowing agents mixture, but without the modified isocyanate.
  • the foams were prepared using essentially the same procedure described in Example 21 , using the components and amounts shown in Table 6. The results are also shown in Table 6.
  • the foams prepared using the unsaturated perfluorochemical blowing agent and the modified isocyanate prepolymer have lower thermal conductivity and smaller cell size than the foams prepared without the modified isocyanate.

Abstract

Compositions expansibles comprenant (a) au moins un composé d'agent gonflant perfluorochimique insaturé, normalement liquide, choisi dans le groupe constitué de composés perfluorooléfiniques, tels que des composés perfluoro(4-méthylpent-2-ène), perfluoroaromatiques, tels que des composés hexafluorobenzèniques, et des composés perfluorocyclooléfiniques, tels que des composés perfluorocyclohexène, les composés perfluorooléfiniques contenant éventuellement un ou plusieurs hétéroatomes caténaires; (b) un précurseur d'un polymère expansible comprenant au moins un polyisocyanate organique modifié à l'aide d'au moins un composé réactif à l'isocyanante sensiblement fluoré; et (c) au moins un composé contenant au moins deux atomes d'hydrogène réactifs. Lesdites compositions sont utiles dans la préparation de mousses polymères telles que du polyuréthanne cellulaire.
PCT/US1996/007501 1995-05-23 1996-05-23 Composition expansible contenant un agent gonflant perfluorochimique insature WO1996037540A1 (fr)

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JP2013163814A (ja) * 2005-11-01 2013-08-22 E I Du Pont De Nemours & Co 不飽和フルオロカーボンを含む発泡体を形成するための発泡剤
WO2015095285A1 (fr) 2013-12-20 2015-06-25 3M Innovative Properties Company Oléfines fluorées à utiliser en tant que fluides de travail et leurs procédés d'utilisation
CN112175158A (zh) * 2020-09-25 2021-01-05 海信容声(广东)冰箱有限公司 冰箱及硬质聚氨酯泡沫、硬质聚氨酯泡沫的制备方法
CN113943412A (zh) * 2021-12-03 2022-01-18 红宝丽集团股份有限公司 异氰酸酯混合物、聚氨酯硬泡及其制备方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013163814A (ja) * 2005-11-01 2013-08-22 E I Du Pont De Nemours & Co 不飽和フルオロカーボンを含む発泡体を形成するための発泡剤
WO2015095285A1 (fr) 2013-12-20 2015-06-25 3M Innovative Properties Company Oléfines fluorées à utiliser en tant que fluides de travail et leurs procédés d'utilisation
US9957428B2 (en) 2013-12-20 2018-05-01 3M Innovative Properties Company Fluorinated olefins as working fluids and methods of using same
US10280351B2 (en) 2013-12-20 2019-05-07 3M Innovative Properties Company Fluorinated olefins as working fluids and methods of using same
US10557069B2 (en) 2013-12-20 2020-02-11 3M Innovative Properties Company Fluorinated olefins as working fluids and methods of using same
CN112175158A (zh) * 2020-09-25 2021-01-05 海信容声(广东)冰箱有限公司 冰箱及硬质聚氨酯泡沫、硬质聚氨酯泡沫的制备方法
CN113943412A (zh) * 2021-12-03 2022-01-18 红宝丽集团股份有限公司 异氰酸酯混合物、聚氨酯硬泡及其制备方法
CN113943412B (zh) * 2021-12-03 2023-07-11 红宝丽集团股份有限公司 异氰酸酯混合物、聚氨酯硬泡及其制备方法

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