WO2001012707A1 - Procedes d'amelioration des proprietes isolantes de mousses rigides de polyurethane a alveoles fermees - Google Patents

Procedes d'amelioration des proprietes isolantes de mousses rigides de polyurethane a alveoles fermees Download PDF

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Publication number
WO2001012707A1
WO2001012707A1 PCT/US2000/021860 US0021860W WO0112707A1 WO 2001012707 A1 WO2001012707 A1 WO 2001012707A1 US 0021860 W US0021860 W US 0021860W WO 0112707 A1 WO0112707 A1 WO 0112707A1
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WIPO (PCT)
Prior art keywords
foam
inert gas
isocyanate
polyisocyanate
amount
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PCT/US2000/021860
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English (en)
Inventor
Joseph S. Costa, Jr.
Rachel E. Berrier
Martyn C. Barker
Karen L. Van Der Dande
Philip L. Berthels
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Hunstman International Llc
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Priority to AU67638/00A priority Critical patent/AU6763800A/en
Publication of WO2001012707A1 publication Critical patent/WO2001012707A1/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
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • 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
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • 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

  • the present invention relates to methods of improving the insulation performance of closed celled rigid polyurethane or urethane-modified polyisocyanaurate foam (henceforth collectively referred to as PU foam).
  • the invention relates to processes used to produce such foam and the foams prepared thereby.
  • Closed celled rigid PU foams have many known uses, such as thermal insulation medium for use in the construction industry as well as in refrigerated storage devices.
  • the widespread commercial acceptance of rigid PU foam as a thermal insulation medium is based upon its ability to provide outstanding initial and long term thermal insulation, its superior structural properties and its superior flammability performance all at relatively low densities.
  • Closed celled rigid PU foams have conventionally been prepared by reacting appropriate polyisocyanate and isocyanate-reactive compositions in the presence of a suitable blowing agent.
  • CFC's chlorofluorocarbons
  • CFC-11 trichlorofiuorornethane
  • CFC-12 dichlorodifiuormethane
  • US Patent No. 5,034,424 discloses a rigid foam blown with C0 2 and proportion of a
  • insoluble blowing agent which is substantially insoluble in at least one of the raw materials.
  • insoluble blowing agents are perfluorinated and substantially fluorinated ethers and hydrocarbons. It further specifies the droplet size of the insoluble physical blowing agent, mixing requirements (high shear force) along with cell size of the final foam (less than 100 micron etc.).
  • the insoluble blowing agents defined in this patent are liquids.
  • US Patent No. 3,882,052 describes a process for making PU foam by blending a mixture of polyol/isocyanate/blowing agent/catalyst and a sufficient proportion of an inert gas to bring about nucleation of the mixture using inert gas having an atmospheric boiling point below about -80°C. Nitrogen, helium and air are specifically mentioned as the inert gas of choice.
  • the gas can be blended into the polyol component, the isocyanate component or the whole mixture with the idea of improving mixing quality (of foam forming ingredients) in low pressure (e.g., static mixer) devices to make foam.
  • Polyurethane foams with significant improvements in the insulation performance according to the present invention may be made by dispersing relatively inexpensive, inert gases such as air and/or nitrogen into the isocyanate stream containing a surfactant and reacting it with isocyanate-reactive compositions and non-CFC blowing agent.
  • the instant invention relates to a process for the production of closed celled rigid PU foams by reaction of a foamable mixture of (1) one or more organic polyisocyanates containing a surfactant, (2a) one or more non-CFC physical blowing agents. (2b) optionally water or other C0 2 evolving compounds, (3) one or more polyfunctional isocyanate-reactive compositions
  • the polyisocyanate containing a surfactant is charged with at least some, and preferably a minimum of about 0.5 volume % of inert gas, preferably the gas being finely dispersed to a maximum average gas bubble size of 100 micro-meter, said volume percent being based on the gas at standard conditions of temperature and pressure, i.e., 25°C and 1 atmosphere, respectively, so as to reduce the thermal conductivity of the foam below that of corresponding foam structures produced without the dispersed inert gas in component (1).
  • the closed celled rigid foams of the invention are useful in, for example, the construction and appliance insulation industries. Additional application areas include, for example, any application where the thermal insulation performance is a considered factor, such as boardstock, panel, appliances, water heaters, etc.
  • Production of closed celled rigid polyurethane or urethane-modified polyisocyanaurate foams with improved insulation performance properties may be achieved by reaction of a foamable mixture of (1) one or more organic polyisocyanates containing a surfactant, (2a) one or more non-CFC physical blowing agents, (2b) optionally water or other CO, evolving compounds, (3) one or more
  • polyfunctional isocyanate-reactive compositions and (4) one or more other auxiliaries or additives, wherein the polyisocyanate containing a surfactant, is charged with an inert gas such as air and/or nitrogen and preferably with a minimum of 0.5 volume % of inert gas, the gas preferably being finely dispersed to a maximum average gas bubble size of 100 micrometer, said volume percent being based on the gas at standard conditions of temperature and pressure, i.e., 25°C and 1 atmosphere respectively so as to reduce the thermal conductivity of
  • the process in accordance with the present invention is economical and odes not suffer from the drawbacks usually accosted with production of PU foams that use CFC-blowing agents.
  • the organic polyisocyanates that may be use in the present invention include any of the polyisocyanates, including aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates, known in the art for the production of rigid polyurethane or urethane- modified polyisocyanurate foams.
  • aromatic polyisocyanates such as tolylene diisocyanate (TDI) and methylene diphenylene diisocyanate (MDI).
  • useful MDI include those having a functionality equal to or greater than 2.0 such as diphenylmethane diisocyanate in the form of its 2,4'- and 4,4'-isomers and mixtures thereof, mixtures of diphenylmethane diisocyanate and oligomers thereof (known as "crude” MDI) and polymeric MDI (i.e., polymethylene polyphenylene polyisocyanates).
  • Polyisocyanates modified with various groups containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups, uretdione groups, oxazolidone groups and urethane groups may also be used in the process of the present invention. Such modified isocyanates and methods for the preparation are known in the art.
  • Suitable surfactant that may be employed in the production of the foams of this invention could be inorganic or organic surfactants.
  • Suitable inorganic surfactants include siloxane-oxyalkylene copolymers and other organopolysiloxanes.
  • examples of inorganic surfactants useful in the present invention include, among others, polydimethylsiloxane- polyoxyalkylene block copolymer which are non-reactive with isocyanate and available from the Witco corporation under the trade name.
  • Suitable organic surfactants include oxyalkylated alkylphenols, oxyalkylated fatty alcohols, paraffin oils, castor oil esters, vegetable oils etc.
  • organic surfactants useful in the present invention include, among others, tradenames "Lk-221 " and “Lk-443” from Air-Products and tradenames "Vorasurf 504" and “Vorasurf 704" from Dow Chemicals, as well as those described in US Patent No. 5,600,019, to Dow Chemicals.
  • organic surfactants are those which are non-reactive with isocyanate, e.g. "Vorasurf 704" from Dow Chemicals.
  • the surfactant comprises from about 0.05 to 5, and preferably 0.1 to 3 weight percent of the organic polyisocyanate.
  • the organic polyisocyanate containing surfactant should be used in an amount from about 25 % to about 75% by weight, preferably about 30 % to about 70 % by weight and more preferable 40-65 % by weight of the entire reaction system.
  • Blowing agents may be selected from, for example, hydrocarbons, hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), dialkyl ethers, and fluorine containing ethers. Suitable blowing agents exclude CFC-blowing agents.
  • hydrocarbon which is vaporizable under foam forming conditions can be used as a blowing agent.
  • Suitable hydrocarbons include butane, isobutane, isopentane, n-pentane, cyclopentane, 1 -pentene, n-hexane, iso-hexane, 1 -hexane, n-heptane, isoheptane, and mixtures thereof.
  • the hydrocarbon blowing agent is selected from isopentane, n- pentane, cyclopentane and mixtures thereof.
  • Suitable HFCs blowing agents include 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2-tetrafluorethane (HFC- 134a), 1 , 1 -difluoroethane (HFC- 152a), difluoromethane (HFC- 32).
  • Suitable HCFCs include chlorodifluoromethane (HCFC-22), and 2-chloropropane. Examples of additional suitable blowing agents are disclosed in US Patent No. 5,604,265, the subject matter of which is incorporated by reference in its entirety.
  • the blowing agents may be mixed into the isocyanate-reactive component, the isocyanate component and/or as a separate stream to the reaction system.
  • the blowing agent preferably can be used in an amount of from about 2 % to about 20
  • Water should preferably be used in an amount of less than about 4 % by weight and more preferably less than 2 % by weight of the entire reaction system.
  • the isocyanate-reactive compositions useful in the present invention include any of those known to those skilled in the art to be useful for the preparation of rigid polyurethane or urethane-modified polyisocyanurate foams.
  • suitable isocyanate-reactive compositions having a plurality of isocyanate-reactive groups include polyester polyols, polyether polyols and mixtures thereof having average hydroxyl numbers of from about 20 to about 1000 and preferably about 50 to 700 mg KOH/g and hydroxyl functionalities of about 2 to about 8 and preferably about 2 to about 6.
  • isocyanate-reactive materials which can be used in the present invention include hydrogen terminated polythioethers, polyamides, polyester amides, polycarbonates, polyacetals, polyolefins, polysiloxanes, and polymer polyols.
  • aromatic polyester polyols include those prepared by reacting a polycarboxylic acid and/or a derivative thereof or an anhydride with a polyhydric alcohol, wherein at least one of these reactants is aromatic.
  • the polycarboxylic acids may be any of the known aliphatic, cycloaliphatic, aromatic, and/or heterocyclic polycarboxylic acids and may be substituted, (e.g., with halogen atoms) and/or unsaturated.
  • Suitable polycarboxylic acids and anhydrides include oxalic acid, malonic acid, glutaric acid, pimelic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid anhydride, pyromellitic dianhydride.
  • phthalic acid anhydride tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride acid, maleic acid, maleic acid anhydride, fumaric acid, and dimeric and trimeric fatty acids, such as those of oleic acid which may be in admixture with monomeric fatty acids.
  • Simple esters of polycarboxylic acids may also be used such as terephthalic acid dimethylester, terephthalic acid bisglycol and extracts thereof.
  • Suitable aromatic polycarboxylic acids are: phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid.
  • Suitable aromatic polycarboxylic acid derivatives are: dimethyl or diethyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid.
  • suitable aromatic anhydrides are phthalic anhydride, tetrahydrophthalic anhydride, and pyromellitic anhydride.
  • polyester polyols can be prepared from substantially pure reactant materials as listed above, more complex ingredients may be advantageously used, such as the side- streams, waste or scrap residues from the manufacture of phthalic acid, phthalic anhydride, terephthalic acid, dimethyl terephthalate, polyethylene terephthalate, and the like.
  • the polyhydric alcohols suitable for the preparation of polyester polyols may be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic.
  • the polyhydric alcohols optionally may include substituents which are inert in the reaction, for example, chlorine and bromine substituents, and/or may be unsaturated.
  • Suitable amino alcohols such as monoethanolamine, diethanolamine or the like may also be used.
  • suitable polyhydric alcohols include ethylene glycol, propylene glycol, polyoxyalkylene glycols (such as diethylene glycol, polyethylene glycol, dipropylene glycol and polypropylene glycol), glycerol and trimethylolpropane.
  • suitable aromatic polyhydric alcohols are 1,4, benzene diol, hydroquinone di (2-hydroxyethyl) ether, bis (hydroxyethyl) terephthalate, and resorcinol.
  • polyester polyols commercially available. Stepanpol ® PS-2352, PS-
  • PS-3152 are some such polyols manufactured by the Stepan Company.
  • Terate ® 2541, 254, 403, 203 are some such polyols, manufactured by Hoechst-Celanese Corporation.
  • Terol ® 235, 235N, 250 are some such polyols manufactured by Oxid, Inc.
  • Suitable polyether polyols include reaction products of alkylene oxides, e.g., ethylene oxide and/or propylene oxide, with imtiators containing from 2 to 8 active hydrogen atoms per molecule.
  • Suitable imtiators include polyols, e.g., diethylene glycol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, methyl glucoside, mannitol and sucrose; polyhydric phenols, e.g., bisphenols, catechol, as well as phenol-formaldehyde condensation products (novolaks); polyamines, e.g., ethylene diamine, toluene diamine, diaminodiphenylmethane and polymethylene polyphenylene polyamines; amino alcohols, e.g., ethanolamine and diethanolamine; and mixtures thereof.
  • Preferred initiators include polyols and polyamine
  • Additional useful isocyanate-reactive materials include primary and secondary diamines (Unilink 4200), enamines, cyclic ureas, cyclic carbonate, and polycarboxylic acid. Some of these compounds react with isocyanate to evolve carbon dioxide and contribute to
  • the isocyanate-reactive material may, preferably, be used in an amount of about 20% to about 70% by weight and more preferably about 30% to about 60% by weight of the total
  • Additives are conventional to formulations for the production of rigid polyurethane and urethane-modified polyisocyanurate foams.
  • Such optional additives include, but are not limited to: crosslinking agents, foam-stablilising agents or surfactants, catalysts, reactive viscosity reducers, infra-red opacifiers, cell size reducing compounds, reinforcing agents, mold release agents, antioxidants. pigments, reactive, non-reactive fire retardants, compatibility agents, etc.
  • additives examples include: crosslinking agents, such as triethanolamine and glycerol; foam stabilizing agents or surfactants, such as siloxane-oxyalkylene copolymers; oxyethylene-oxyalkylene copolymer; catalysts, such as tertiary amines, (e.g., dimethylcyclohexylarnine, pentamethyldiethylenetriamine, 2,4,6-tris(dimethylaminomethyl) phenol, triethylenediamine); organometallic compounds (e.g., potassium octoate, potassium acetate, dibutyl tin dilaurate), quaternary ammonium salts (e.g., 2-hydroxypropyl trimethylammonium formate) and n-substituted triazines (N, N', N"- dimethylaminopropylhexahydrotriazine); viscosity reducers such as propylene carbonate, 1- methyl-2-pyrroli
  • Amount of such additives are generally from about 0.1 to about 20%, preferably from about 0.3 to about 15% and most preferably from about 0.5 to about 10%, by weight based on the total reaction system.
  • Suitable inert gas which is employed in the present invention includes any gaseous element, compound or mixture thereof which is in the gaseous state under standard conditions of temperature and pressure, i.e., 25°C and 1 atmosphere, including for example carbon dioxide, nitrogen, oxygen, noble gases or mixture thereof such as air, provided such does not react with the organic polyisocyanate and other urethane forming component.
  • the gas used has an atmospheric boiling point below about -50°C, preferably below about -80°C,
  • the gas is selected from nitrogen, air and helium. Due to the low cost and common availability, dry nitrogen and dry air are the most preferred gases.
  • k-factor 1 R, where R is a measure of the material's thermal resistance.
  • a proportion of the gas in excess of 1%, such as from about 2 to about 30% by volume may be used, although, of course, higher as well as lower concentrations may suitably be employed.
  • Any suitable procedure may be used to bring about the dispersion of the inert gas with the foam forming ingredients.
  • Both static & dynamic mixing devices can be used. It is preferred that a dynamic mixer is used as the dispersing device which is operated at a high speed of rotation, so that effective mixing of the quantities of isocyanate and gas metered into the device takes place with high shearing forces which ensure that the gas bubbles are effectively dispersed.
  • Rotor/stator mixers are one such type of dynamic mixer which may be used in the invention. Many types and sizes of rotor/stator mixers are commercially available, among others, from Silverson Machines Inc., East Longmeadow, MA and Charles Ross & Son Company. Hauppauge, NY.
  • Such a dynamic mixer can be arranged as a "batch” mixer or an "in-line” mixer with the isocyanate side of the foam mixing equipment.
  • the gas bubbles of the resulting dispersion it is desirable for the gas bubbles of the resulting dispersion to have an average diameter of less than about 150 micro-meter, preferably less than about 100 micro-meter.
  • the process for making closed celled rigid foams according to this invention employes the known one-shot, prepolymer or semi-prepolymer techniques may be used together with conventional mixing methods including impingement mixing.
  • the rigid foam may be produced in the form of slabstock, moldings, cavity filling, sprayed foam, frothed foam or laminates with other material such as paper, metal, plastics, or wood-board.
  • Such rigid foam are useful in any insulating surfaces or enclosures such as houses, roofing, buildings, refrigerators, freezers, appliances, piping, vehicles and the likes.
  • the foams obtained according to the process of the present invention exhibit lower thermal conductivity as compared to the foams obtained from a similar reactive mixture and by the same process, exclusive of the inert gas.
  • Foams according to the present invention exhibit k-factor reduced of by at least 0.003, preferably at least 0.004, more preferably at least 0.007 BTU-in/lb-ft 2 -°F.
  • Terate ® 2541L An aromatic polyester polyol of hydroxyl value 236 mg KOH/g, average functionality of about 2 and viscosity of 4,500 cPs @ 25°C available from Kosa (previously Hoechst Celanese Corporation).
  • Terate ® 254 An aromatic polyester polyol of hydroxyl value 235 mg KOH/g, average functionality of about 2 and viscosity of 2,500 cPs @ 25°C available from Kosa.
  • Pelron ® 9540A Potassium octoate in diethylene glycol available from Pelron Corp.
  • Pelron ® 9649 Organomettalic catalyst available from Pelron Corp.
  • Polycat ® TMR-2 N-(2-hydroxypropyl)-N-trimethylammonium formate in dipropylene glycol available from Air Products.
  • Polycat ® 5 Pentamethyldiethylenetriamine available from Air Products.
  • Tegostab ® B84PI A silicone surfactant available from Goldschmidt Corporation.
  • Tegostab ® B8469 A silicone surfactant available from Goldschmidt Corporation.
  • Surfactant SR-234 A silicone surfactant available from Witco Corporation.
  • HCFC-141b Dichlorofluroethane blowing agent available from Elf-Atochem North America.
  • Cyclopentane Available from Exxon Chemical Company and having purity >95%.
  • Isopentane Available from Phillips Chemical Company and having purity >97%.
  • a polyol blend "A” was made by mixing together 100 parts of Terate 254 IL with 2.3 parts of Pelron 9540A, 2.3 parts of Pelron 9649, 0.35 parts of Polycat 5, 2.5 parts of Tegostab B84PI, 0.4 parts of water and 37 parts of HCFC-141b using a high speed mixer at room temperature.
  • the polyol blend was added to the "polyol side” tank of an Edge-Sweets® high pressure impingement mix dispense machine.
  • Isocyanate was added to the "Isocyanate side” tank attached to the dispense machine.
  • Surfactant SR-234 was mixed with the isocyanate using a high speed mixer prior to charging in the isocyanate tank whenever required per Table 1. The machine parameters were set as shown in Table 2.
  • the foaming ingredients were shot from the dispense machine into a 2" x 14" x 14"
  • Foam Samples #1-4 were prepared using the formulations shown in Table 1 and tested in the manner discussed above.
  • the isocyanate stream was dispersed with air using a batch high shear rotor/stator mixer from Silverson Machines, Inc., Model L4RT.
  • the amount of air dispersed was calculated by measuring the specific gravity of the isocyanate.
  • the gas bubble size was measured using an optical microscope and was in the range of 20-60 micro-meter.
  • Process used to make Foam Sample #3 represents the inventive step whereas those used to make Sample #1 & #2 represents comparative process.
  • Foam Sample #4 air was dispersed in the polyol stream using an in-line high shear rotor/stator mixer from IKA Maschinenbau, Model “DISPAX reactor.” While dispersing air into the polyol stream it was noticed that by the time the gas bubble size was between 30-60 micrometer, the temperature of the polyol stream went up to 60-70°C due to viscous heating by the high shear mixer. This temperature is significantly above the boiling point of the physical blowing agent used, HCFC-141b. This led to loss of HCFC-141b from the system which would lead to increase in foam density.
  • Foam Sample #4 i.e., dispersing air into the polyol stream represents a comparative process taught in prior art. Foam properties are listed in Table 1. In thermal property evaluations, the lower the initial and aged k-factor, the better is the insulation performance of the foam.
  • Foam sample #3 gives a polyurethane foam which is superior in thermal insulation performance as compared to the foams made using known processes in the art (Foam Sample #1, #2, #4).
  • the relative improvement in k-factor is larger as the foam samples are aged suggesting that in applications such as insulation for buildings, roofing, appliances, etc. where use life is years, relative benefits from the instant invention is even more significant.
  • Example 2 A number of rigid polyurethane foam laminate boards were prepared using the formulations shown in Table 3.
  • the polyol blend "B” was made by mixing together 100 parts of Terate 254 with 15.5 parts of TCPP, 2.1 parts of Pelron 9540A, 3.6 parts of Polycat TMR- 2, 0.10 parts of Polycat 5, 2.15 parts of Tegostab B8469, and 26 parts of a blend of cyclopentane with isopentane in the ratio of 60:40 using a high speed mixer at room temperature.
  • Laminate board samples were made on an OMS laminator at the ICI Polyurethanes
  • the laminator is 24.3 feet (7.4 meters) long and can produce boards up to 39 inches (1 meter) wide and 7.9 inches (20 centimeters) thick.
  • the conveyor can be heated to 158°F and the laydown table to 122°F.
  • the output is 16-33 pounds per minute. All laminates were made to a thickness of 1.5 inches and 39 inches wide, using typical black glass facer from GAF Corporation.
  • the polyol blend was added to the "polyol Side” tank of the OMS laminator high pressure impingement mix dispense machine.
  • Isocyanate was added to the "Isocyanate side” tank attached to the dispense machine.
  • Surfactant SR-234 was mixed with Rubinate ® 1850 isocyanate using a high speed mixer prior to charging in the isocyante tank whenever required per Table 3.
  • the processing conditions for making the laminates are shown in the following Table 4.
  • Foam Sample #6 the isocyanate stream was dispersed with air using a batch high shear rotor/stator mixer from Silverson Machines, Inc., Model L4RT. The amount of air dispersed was calculated by measuring the specific gravity of the isocyanate. The gas bubble size was measured using an optical microscope and was in the range of 20-60 micro-meter. Process used to make Foam Sample #6 represents the inventive step whereas those used to make Sample #5 represents comparative process. Foam Sample #7 was made by keeping the isocyanate stream same as in Sample #6 and dispersing air into polyol stream too.
  • Thermal properties of the foam laminates were measured according to the procedures set forth in ASTM C 518. Thermal aging was performed at room temperature on the full thickness laminate. In thermal property evaluations, the lower the k-factor, the better the insulation performance of the foam laminate.
  • the structural performance of the foam was measured on foams taken from the core of the laminates.
  • the low temperature dimensional stability was measured after 7 days of exposure at -25°C following the "Dimvac method” described in "Techniques to Assess the Various Factors Affecting the Long Term Dimensional Stability of Rigid Polyurethane Foam, "Proceedings of the Polyurethane 1995 Conference, Page 11 (1995).
  • the dimensional stability of the foam was measured after 14 days exposure at 158°F / 97% RH following ASTM D2126. In dimensional stability test, the closer the % linear change is to zero, the better the dimensional performance of the foam.
  • Foam sample #6 gives a polyurethane foam which is superior in thermal insulation performance as compared to the foams made using known processes in the art (Foam Sample #5).
  • Foam Sample #5 Like in Example 1, the relative improvement in k-factor is larger as the foam laminate samples are aged.
  • the initial thermal performance of Foam Sample #7 is slightly better than that for Sample #6 but the difference is reduced/eliminated as foam is aged.
  • the dimensional stabilities of all foam samples in Table 3 are good.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne des mousses rigides de polyuréthane à alvéoles fermées ou des mousses de polyisocyanurate à modification uréthannique. Ces mousses sont préparées selon un procédé consistant à mélanger (1) au moins un polyisocyanate avec un surfactant chargé au moins avec du gaz inerte, (2) au moins un agent d'expansion physique exempt de CFC, et (3) au moins une composition polyfonctionnelle réagissant aux isocyanates. Les gaz inertes comprennent de l'azote, des gaz nobles ou de l'air sec. Ce procédé permet de produire des mousses à moindre coût sans utilisation d'agents d'expansion contenant des CFC.
PCT/US2000/021860 1999-08-17 2000-08-11 Procedes d'amelioration des proprietes isolantes de mousses rigides de polyurethane a alveoles fermees WO2001012707A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU67638/00A AU6763800A (en) 1999-08-17 2000-08-11 Methods for improving the insulating properties of closed celled rigid polyurethane foams

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14926699P 1999-08-17 1999-08-17
US60/149,266 1999-08-17

Publications (1)

Publication Number Publication Date
WO2001012707A1 true WO2001012707A1 (fr) 2001-02-22

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AU (1) AU6763800A (fr)
WO (1) WO2001012707A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003035731A1 (fr) * 2001-10-24 2003-05-01 Hennecke Gmbh Procede de fabrication de mousse polyurethanne
US20130212951A1 (en) * 2012-02-20 2013-08-22 Samsung Electronics Co., Ltd. Polishing pad and method of manufacturing the same
CN103998498A (zh) * 2011-12-19 2014-08-20 陶氏环球技术有限责任公司 含溴化聚合阻燃剂的热固性聚氨酯泡沫

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252625A (en) * 1990-03-19 1993-10-12 Atlas Roofing Corporation Method for producing rigid foams and products produced therefrom
US5328938A (en) * 1993-03-01 1994-07-12 Basf Corporation On-site generation of polyurethane foam using an HCFC as a sole blowing agent
US5409961A (en) * 1994-07-08 1995-04-25 Basf Corporation Rigid closed cell polyisocyanate based foams for use as positive flotation materials in watercraft
WO1997047453A1 (fr) * 1996-06-07 1997-12-18 Bayer Aktiengesellschaft Procede pour la production de mousse a l'aide de dioxyde de carbone dissous sous pression
EP0904916A2 (fr) * 1997-09-26 1999-03-31 Basf Aktiengesellschaft Procédé pour la préparation de mousse rigide à cellules fines à base d'isocyanate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252625A (en) * 1990-03-19 1993-10-12 Atlas Roofing Corporation Method for producing rigid foams and products produced therefrom
US5328938A (en) * 1993-03-01 1994-07-12 Basf Corporation On-site generation of polyurethane foam using an HCFC as a sole blowing agent
US5409961A (en) * 1994-07-08 1995-04-25 Basf Corporation Rigid closed cell polyisocyanate based foams for use as positive flotation materials in watercraft
WO1997047453A1 (fr) * 1996-06-07 1997-12-18 Bayer Aktiengesellschaft Procede pour la production de mousse a l'aide de dioxyde de carbone dissous sous pression
EP0904916A2 (fr) * 1997-09-26 1999-03-31 Basf Aktiengesellschaft Procédé pour la préparation de mousse rigide à cellules fines à base d'isocyanate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003035731A1 (fr) * 2001-10-24 2003-05-01 Hennecke Gmbh Procede de fabrication de mousse polyurethanne
CN103998498A (zh) * 2011-12-19 2014-08-20 陶氏环球技术有限责任公司 含溴化聚合阻燃剂的热固性聚氨酯泡沫
US20140343180A1 (en) * 2011-12-19 2014-11-20 Steven P. Crain Thermoset polyurethane foam containing brominated polymeric flame retardant
US9441108B2 (en) 2011-12-19 2016-09-13 Dow Global Technologies Llc Thermoset polyurethane foam containing brominated polymeric flame retardant
US20130212951A1 (en) * 2012-02-20 2013-08-22 Samsung Electronics Co., Ltd. Polishing pad and method of manufacturing the same

Also Published As

Publication number Publication date
AU6763800A (en) 2001-03-13

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