US20050070619A1 - Blowing agent enhancers for polyurethane foam production - Google Patents

Blowing agent enhancers for polyurethane foam production Download PDF

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Publication number
US20050070619A1
US20050070619A1 US10/672,363 US67236303A US2005070619A1 US 20050070619 A1 US20050070619 A1 US 20050070619A1 US 67236303 A US67236303 A US 67236303A US 2005070619 A1 US2005070619 A1 US 2005070619A1
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ether
composition
blowing agent
group
monomethyl ether
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US10/672,363
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John Miller
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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Priority to US10/672,363 priority Critical patent/US20050070619A1/en
Assigned to AIR PRODUCTS AND CHEMICALS, INC. reassignment AIR PRODUCTS AND CHEMICALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MILLER, JOHN WILLIAM
Priority to US10/700,163 priority patent/US6921779B2/en
Priority to BR0403991-2A priority patent/BRPI0403991A/pt
Priority to EP04022538A priority patent/EP1520873A3/en
Priority to KR1020040076225A priority patent/KR100587875B1/ko
Priority to MXPA04009244A priority patent/MXPA04009244A/es
Priority to CNB2004100874736A priority patent/CN100344668C/zh
Priority to JP2004280219A priority patent/JP2005105272A/ja
Publication of US20050070619A1 publication Critical patent/US20050070619A1/en
Priority to US12/915,385 priority patent/US9321892B2/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-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
    • C08J9/14Working-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
    • C08J9/143Halogen containing compounds
    • C08J9/144Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/2815Monohydroxy compounds
    • C08G18/283Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C08G18/2835Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/487Polyethers containing cyclic groups
    • C08G18/4883Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-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
    • C08J9/14Working-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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0025Foam properties rigid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0041Foam properties having specified density
    • C08G2110/005< 50kg/m3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/12Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/10Rigid foams
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

Definitions

  • the present invention relates to compositions and processes for making polyurethane foams. More particularly, it relates to compositions and processes incorporating compounds for enhancing the effectiveness of hydrohalocarbon blowing agents in making polyurethane foams.
  • the invention is a composition for producing a polyurethane foam.
  • the composition comprises a polyol, a polyisocyanate, a blowing agent comprising a hydrohalocarbon, and a blowing agent enhancer comprising at least one compound having a molecular weight less than about 500 g/mol and a molecular formula of RO—(CH 2 CHR′′O) n —R′; wherein:
  • R is selected from the group consisting of a C1-C10 aliphatic group, a C5-C10 cycloaliphatic group, a C7-C10 araliphatic group, a C1-C10 aliphatic group comprising a nitrogen atom or oxygen atom, a C5-C10 cycloaliphatic group comprising a nitrogen atom or oxygen atom, and a C7-C10 araliphatic group comprising a nitrogen atom or oxygen atom;
  • R′ is selected from the group consisting of R, hydrogen, acetyl, propionyl, and butyryl, provided that the at least one compound has no more than one hydroxyl group per molecule;
  • the invention is a method of making a polyurethane foam.
  • the method comprises combining a polyol and a polyisocyanate in the presence of 1) a blowing agent comprising a hydrohalocarbon and 2) a blowing agent enhancer comprising at least one compound having a molecular weight less than about 500 g/mol and a molecular formula of RO—(CH 2 CHR′′O) n —R′; wherein:
  • the invention is a composition for producing a polyurethane foam.
  • the composition comprises a polyol, a polyisocyanate, a blowing agent comprising a hydrohalocarbon, and a blowing agent enhancer comprising at least one compound having a molecular weight less than about 500 g/mol and a molecular formula ROH, wherein:
  • the invention is a polyurethane composition
  • a polyurethane composition comprising a product of a reaction between a polyol and a polyisocyanate.
  • the reaction takes place in the presence of 1) a blowing agent comprising a hydrohalocarbon and 2) a blowing agent enhancer comprising at least one compound having a molecular weight less than about 500 g/mol and a molecular formula of RO—(CH 2 CHR′′O) n —R′; wherein:
  • the invention is a composition for producing a polyurethane foam.
  • the composition comprises 1) one but not both of a polyol and a polyisocyanate, 2) a blowing agent comprising a hydrohalocarbon and 3) a blowing agent enhancer comprising at least one compound having a molecular weight less than about 500 g/mol and a molecular formula of RO—(CH 2 CHR′′O) n —R′; wherein:
  • the present invention involves the use of low molecular weight ethers and alcohols as blowing agent enhancers for improving the efficiency of hydrohalocarbon blowing agents in the preparation of rigid polyurethane and/or polyisocyanurate foam.
  • polyurethane is intended to mean polyurethane and/or polyisocyanurate, as is understood in the art.
  • a rigid polyurethane foam can be a rigid polyurethane and/or polyisocyanurate foam.
  • hydrohalocarbon is used herein to mean a compound consisting of carbon, hydrogen, and one or both of fluorine and chlorine, and no other elements.
  • enhancers are provided that are useful in the reaction of a polyisocyanate and a polyol in the presence of a blowing agent comprising a hydrohalocarbon.
  • the reaction is performed in the presence of a urethane catalyst, and typically in the presence of a surfactant.
  • the enhancer comprises a low molecular weight alcohol or ether, for example di(ethylene glycol) methyl ether.
  • the process according to the invention can easily be carried out by conventional means for making rigid polyurethane foam, excepting that the general preparation of rigid polyurethane foam using a hydrohalocarbon blowing agent, preferably a C1-C4 hydrofluorocarbon, is carried out using the blowing agent enhancer according to the invention to improve the blowing agent efficiency.
  • a hydrohalocarbon blowing agent preferably a C1-C4 hydrofluorocarbon
  • Rigid polyurethane products made in accordance with the invention may be prepared using any suitable organic polyisocyanates well known in the art for making rigid polyurethane foam including, for example, hexamethylene diisocyanates, isophorone diisocyanates, phenylene diisocyanates, toluene diisocyanates (TDI) and 4,4′-diphenylmethane diisocyanates (MDI).
  • TDI toluene diisocyanates
  • MDI 4,4′-diphenylmethane diisocyanates
  • Especially suitable are mixtures of diisocyanates known commercially as “crude MDI”, marketed as PAPI by Dow Chemical, which contain about 60% of 4,4′-diphenylmethane diisocyanates along with other isomeric and analogous higher polyisocyanates.
  • isocyanates are the 2,4- and 2,6-TDl's individually or together as their commercially available mixtures. Also suitable are “prepolymers” of these polyisocyanates comprising a partially pre-reacted mixture of a polyisocyanate and a polyether or polyester polyol. Typically, the above polyisocyanates are used in an amount relative to the polyol to establish an isocyanate index in the range of 80 to 400.
  • Suitable polyols are those typically used in the art for making rigid polyurethane foam, including for example polyalkylene ether and polyester polyols.
  • Polyalkylene ether polyols include poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, for example diols and/or triols.
  • Such diols and triols include, as non-limiting examples, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, sugars such as sucrose, and other low molecular weight polyols.
  • amine polyether polyols which can be prepared by reacting an amine, such ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, triethanolamine or the like, with ethylene oxide or propylene oxide.
  • a single high molecular weight polyether polyol such as described above may be used.
  • mixtures of such high molecular weight polyether polyols for example mixtures of different multifunctional materials and/or of compounds having different molecular weights or different chemical compositions, may be used.
  • Useful polyester polyols include those produced by reacting a dicarboxylic acid with an excess of a diol, for example, adipic acid or phthalic acid anhydride with ethylene glycol or butanediol, or reacting a lactone such as caprolactone with an excess of a diol such as propylene glycol.
  • hydrohalocarbon blowing agents used in the present invention for making rigid foams include, as nonlimiting examples, HCFC (hydrochlorofluorocarbon) compounds, HFC (hydrofluorocarbon) compounds, and mixtures of these.
  • Hydrochlorofluorocarbon compounds comprise at least one atom of each of hydrogen, chlorine, and fluorine per molecule.
  • Hydrofluorocarbon compounds comprise at least one atom of each of hydrogen and fluorine per molecule, and no chlorine atoms.
  • Nonlimiting examples of suitable HCFC's include HCFC-123, HCFC-141b, HCFC-22, HCFC-142b, and mixtures of any of these.
  • suitable HFC compounds include HFC-134a, HFC-245fa, HFC-245ca, HFC-236ea, HFC-365mfc, and mixtures of any of these.
  • Preferred blowing agents include HCFC-141b, HFC-134a, HFC-245fa, and mixtures of two or more of these.
  • third generation C1 —C4 HFC blowing agents with a molecular weight of 50 to 170 g/mole, a boiling point of ⁇ 60 to 50 C and preferably an Ozone Depletion Potential (ODP) of ⁇ 0.10, ODP as described by: Synthesis of the Reports of the Ozone Scientific Assessment Panel, Environmental Effect Assessment Panel Technology and Economic Assessment Panel, prepared by the Assessment Chairs for the Parties to the Montreal Protocol, November, 1991.
  • HFC's meeting these criteria include HFC-134a, HFC-236ea, HFC-365mfc and most preferably HFC-245fa. Mixtures of these may also be used. Water may be included in the formulation at 0 to 4 pphp (parts per hundred parts of polyol).
  • blowing agents which may optionally be used in combination with HFC blowing agents according to the invention include HCFC's, CFC's (chlorofluorocarbons), hydrocarbons such as pentanes, and the like.
  • the blowing agent consists essentially of one or more hydrohalocarbons comprising at least one fluorine atom per molecule, either alone or in combination with one or more CFC.
  • Blowing agent enhancers include compounds having a molecular weight less than about 500 g/mol and a molecular formula according to Structure I: RO—(CH 2 CHR′′O) n —R′ I wherein R is selected from the group consisting of a C1-C10 aliphatic group, a C5-C10 cycloaliphatic group, a C7-C10 araliphatic group, a C1-C10 aliphatic group comprising a nitrogen atom or oxygen atom, a C5-C10 cycloaliphatic group comprising a nitrogen atom or oxygen atom, and a C7-C10 araliphatic group comprising a nitrogen atom or oxygen atom;
  • R′ is R, hydrogen, acetyl, propionyl, or butyryl, provided that the at least one compound has no more than one hydroxyl group per molecule;
  • R′′ is hydrogen or C1-C5 alkyl group; and n is an integer greater than or equal to
  • Suitable C1-C5 alkyl groups useful for R′′ include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, n-pentyl, 2-methylbutyl, and 3-methylbutyl.
  • Suitable C1-C10 aliphatic groups comprising a nitrogen atom or oxygen atom, and C5-C10 cycloaliphatic groups comprising a nitrogen atom or oxygen atom include groups wherein a nitrogen atom is incorporated in the form of an amine group and groups where an oxygen atom is incorporated as an ether group, a hydroxyl group, or a carbonyl group.
  • Suitable C7-C10 araliphatic groups comprising a nitrogen atom or oxygen atom include groups wherein a nitrogen atom is incorporated in the form of an amine group or as a member of a heterocyclic ring, and groups where an oxygen atom is incorporated as an ether group, a hydroxyl group, a carbonyl group, or as a member of a heterocyclic ring.
  • Exemplary compounds according to Structure I include those with two terminal ether groups, compounds with one terminal ether group and one terminal hydroxyl group, and acetyl, propionyl, or butyryl esters of the latter compounds.
  • Preferred enhancers comprise oxyethylene —(CH 2 CH 2 O)— and/or oxypropylene —(CH 2 CH(CH 3 )O)—groups.
  • Blowing agent enhancers according to Structure I containing two terminal ether groups include, in one exemplary embodiment, dipropylene glycol dimethyl ether.
  • Blowing agent enhancers according to Structure I containing one terminal ether group and one terminal hydroxyl group include, for example, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol monobutyl ether.
  • propylene glycol monomethyl ether propylene glycol monopropyl ether and propylene glycol monobutyl ether.
  • One preferred blowing agent enhancer is diethylene glycol monomethyl ether.
  • Blowing agent enhancers according to Structure I containing one terminal ether group and a terminal ester group include acetyl, propionyl, or butyryl esters of compounds containing one terminal ether group and a terminal hydroxyl group, for example propylene glycol monomethyl ether acetate.
  • Suitable blowing agent enhancers according to the invention also include compounds having a molecular weight less than about 500 g/mol and a molecular formula ROH, wherein R is as defined above.
  • Suitable exemplary compounds in this category include methanol, ethanol, and any isomer of propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol.
  • blowing agent enhancer or mixture of blowing agent enhancers, constitutes at least 2 pphp of the composition, typically at least 4 pphp, and even more typically at least 5 pphp. Typically, it constitutes at most 12 pphp, more typically at most 7 pphp, and even more typically at most 6 pphp.
  • a catalyst may be used to promote the reactions forming polyurethane foams according to the invention.
  • the catalyst composition may be any catalyst well known in the urethane art such as tertiary amines, organotin compounds, and carboxylate urethane catalysts (gelling and/or blowing).
  • Typical examples of useful catalysts are amine catalysts such as triethylenediamine, dimethylcyclohexylamine, tetramethylhexanediamine, bis(dimethylaminoethyl) ether, tri(dimethylaminopropyl)hexahydrotriazine, 1-isobutyl-2-methylimidazole, 1,2-dimethylimidazole, dimethylaminoethanol, diethylaminoethanol, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, methylmorpholine, ethylmorpholine, quaternary ammonium salts, salts of an organic acid and tin catalysts such as dibutyltin dilaurate and the like.
  • amine catalysts such as triethylenediamine, dimethylcyclohexylamine, tetramethylhexanediamine, bis(dimethylaminoethyl) ether, tri(dimethylaminoprop
  • a catalytically effective amount of the catalyst composition is used in the polyurethane formulation. More specifically, suitable amounts of the catalyst composition typically ranges from about 0.01 to 10 parts by weight per 100 parts polyol (0.01 to 10 pphp) in the polyurethane formulation, preferably 0.5 to 4 pphp.
  • a surfactant may be used in polyurethane foam compositions and processes according to the invention.
  • a number of surfactants suitable for use in controlling foam properties in polyurethane production are known in the art.
  • Exemplary surfactants include silicone-based surfactants such as are disclosed in U.S. Pat. No. 5,883,142 to Chojnacki et al.
  • Typical agents that may be used in the polyurethane rigid foam formulations include flame retardants and chain extenders such as ethylene glycol and butanediol.
  • NCO Index means isocyanate index, as that term is commonly used in the polyurethane art. Use of this term in a table of formulations indicates that the appropriate amount of polyisocyanate should be used in order to achieve a formulation having the indicated NCO index.
  • Foam flow was determined by measuring the % fill of the L mold when a constant amount of foam formulation (475 grams) was introduced into the mold, with a higher % fill indicating better flow for samples of equal mass. In addition to comparing flow and density, foam from each of the formulas was evaluated to determine k-factor and compression strength. The top 12 inches of the foams were cut into three sections then stored at ⁇ 30° C. for 72 hours to measure volume change, to verify that there was less than two percent change, indicating sufficient dimensional stability according to commonly accepted industry standards. The next section of the foam was used to cut a core sample to measure the k-factor or heat flow in a Lasercomp Fox 200 heat flow meter.
  • Table 4 is a summary of foam performance data for a number of blowing agent enhancers according to the invention. For each enhancer, the corresponding % fill in the L-mold and k-factor were recorded. TABLE 4 Performance of Blowing Agent Enhancers K-Factor ID Compound % Fill (W/mK) 1 Control 92.5 0.0206 (No enhancer) 2 Diethylene glycol monomethyl ether 99.2 0.0206 3 Tripropylene glycol monobutyl ether 95.6 0.0206 4 Propylene glycol monobutyl ether 97.7 0.0209 5 Dipropylene glycol monopropyl ether 94.8 0.0212 6 Propylene glycol monomethyl ether 98.0 0.0208 acetate 7 Propylene glycol monomethyl ether 99.0 0.0212 8 Ethylene glycol monobutyl ether 96.1 0.0221 9 Dipropylene glycol dimethyl ether 97.2 0.0222 10 Dipropylene glycol monobutyl ether 96.1 0.0215 11 Dipropylene glycol mono
  • blowing agent enhancers 2-14 all showed improved flow (higher value for % fill), with comparable to only slightly worse (higher numerical value) k factors.
  • the blowing agent enhancer that yielded the best flow and k-factor was (2), or di(ethylene glycol) methyl ether.
  • Table 5 collects foam performance data using di(ethylene glycol) methyl ether at 6 pbw in the formula from Table 3.
  • the objective of this example was to match the density and foam performance of the control while maximizing HFC-245fa reduction.
  • the table clearly shows that the di(ethylene glycol) methyl ether blowing agent enhancer allows for lower HFC-245fa concentrations, with no significant penalties to foam thermal properties and an improvement to the compression strengths.
  • Compression strength values are a measure of the force needed to physically crush the foam until failure. Higher force relates to improved foam mechanical properties, giving the final product (e.g. a refrigerator) structural integrity.
  • Table 5 illustrates that a 19% reduction of HFC-245fa is attainable by use of di(ethylene glycol) methyl ether as a blowing agent enhancer to achieve foams of equivalent k-factor, while maintaining equal or even improved compression strength.
  • KPa Blowing Agent Use Level Compression Minimum Strength Fill
  • Enhancer HFC-245fa Density K-Factor Perp./ Formula (pphp) (pphp) Kg/m 3 ) (W/mK) Parallel 1 None 35.2 32.84 0.0195 138/159 2 6.0 28.5 32.68 0.0195 165/193 3 6.0 28.5 32.04 0.0198 159/200 4 6.0 28.5 33.00 0.0196 152/186
  • blowing agent enhancers in the production of rigid polyurethane foams using a hydrohalocarbon blowing agent, particularly HFC-245fa, use of blowing agent enhancers according to the invention allows the production of foams with a reduced amount of blowing agent, while retaining at least equal physical properties to a reference foam with a higher level of blowing agent and none of the enhancer. In some cases, compression strength is improved with use of the enhancer.

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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)
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US10/672,363 2003-09-26 2003-09-26 Blowing agent enhancers for polyurethane foam production Abandoned US20050070619A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US10/672,363 US20050070619A1 (en) 2003-09-26 2003-09-26 Blowing agent enhancers for polyurethane foam production
US10/700,163 US6921779B2 (en) 2003-09-26 2003-11-03 Blowing agent enhancers for polyurethane foam production
BR0403991-2A BRPI0403991A (pt) 2003-09-26 2004-09-22 Composição útil para a produção de uma espuma de poliuretano
EP04022538A EP1520873A3 (en) 2003-09-26 2004-09-22 Blowing agent enhancers for polyurethane foam production
MXPA04009244A MXPA04009244A (es) 2003-09-26 2004-09-23 Mejoradores de agentes de soplado para la produccion de espuma de poliuretano.
KR1020040076225A KR100587875B1 (ko) 2003-09-26 2004-09-23 폴리우레탄 폼 제조용 발포제 강화제
CNB2004100874736A CN100344668C (zh) 2003-09-26 2004-09-24 用于聚氨酯泡沫生产的发泡剂增强剂
JP2004280219A JP2005105272A (ja) 2003-09-26 2004-09-27 ポリウレタンフォームを製造するための発泡剤用エンハンサー
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US20090305876A1 (en) * 2006-06-26 2009-12-10 Honeywell International, Inc. Compositions and Methods Containing Fluorine Substituted Olefins
US20130035021A1 (en) * 2010-03-26 2013-02-07 Toyo Tire & Rubber Co., Ltd. Polishing pad, manufacturing method therefor, and method for manufacturing a semiconductor device
US20130072594A1 (en) * 2010-05-27 2013-03-21 The Yokohama Rubber Co., Ltd. Liquid coagulant and tire puncture sealing material set
US9079289B2 (en) 2011-09-22 2015-07-14 Toyo Tire & Rubber Co., Ltd. Polishing pad
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CN101704937B (zh) * 2009-11-10 2011-12-28 航天材料及工艺研究所 低温绝热用低氟聚氨酯泡沫塑料
US20130217797A1 (en) * 2011-08-23 2013-08-22 Basf Se Microemulsions
CN102863602B (zh) * 2012-10-22 2014-06-11 株洲时代新材料科技股份有限公司 一种发泡型聚氨酯减振垫的产品及制造方法
DE102013226575B4 (de) 2013-12-19 2021-06-24 Evonik Operations Gmbh Zusammensetzung, geeignet zur Herstellung von Polyurethanschäumen, enthaltend mindestens einen ungesättigten Fluorkohlenwasserstoff oder ungesättigten Fluorkohlenwasserstoff als Treibmittel, Polyurethanschäume, Verfahren zu deren Herstellung und deren Verwendung
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KR20050030568A (ko) 2005-03-30
KR100587875B1 (ko) 2006-06-12
US20050070618A1 (en) 2005-03-31
EP1520873A3 (en) 2007-07-04
MXPA04009244A (es) 2005-03-31
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US6921779B2 (en) 2005-07-26
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US9321892B2 (en) 2016-04-26

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