WO1999028364A1 - Mousses de polyurethane soufflees au co2 a faible densite et son procede de preparation - Google Patents

Mousses de polyurethane soufflees au co2 a faible densite et son procede de preparation Download PDF

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Publication number
WO1999028364A1
WO1999028364A1 PCT/US1998/009662 US9809662W WO9928364A1 WO 1999028364 A1 WO1999028364 A1 WO 1999028364A1 US 9809662 W US9809662 W US 9809662W WO 9928364 A1 WO9928364 A1 WO 9928364A1
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Prior art keywords
foam
polyurethane
polyurethane foam
carbonate
low density
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PCT/US1998/009662
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English (en)
Inventor
Sol M. Mirasol
Debkumar Bhattacharjee
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The Dow Chemical Company
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Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to AU73822/98A priority Critical patent/AU737063B2/en
Priority to CA002312373A priority patent/CA2312373A1/fr
Priority to BR9815152-5A priority patent/BR9815152A/pt
Priority to KR1020007006054A priority patent/KR20010032761A/ko
Priority to EP98921146A priority patent/EP1034205A1/fr
Priority to JP2000523253A priority patent/JP2001525430A/ja
Publication of WO1999028364A1 publication Critical patent/WO1999028364A1/fr
Priority to NO20002792A priority patent/NO20002792L/no

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    • 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5033—Polyethers having heteroatoms other than oxygen having nitrogen containing carbocyclic groups
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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

Definitions

  • This invention relates to C0 2 -blown polyurethane foams.
  • This invention particularly relates to low density C0 2 -blown polyureth.ane foams and a method of making same.
  • foams Polyurethane and polyisocyanurate fo.ams
  • foams can be used in a variety of applications.
  • the term "foams” will be understood to include polyurethane-modified polyisocy-anurate foams and polyisocyanurate foams.
  • Rigid polyurethane foams can provide support in applications where rigid support is desirable. Such applications include: construction materials for roofing, sheathing, building panels, pipe insulation, and vessel insulation; flotation; floral and craft foams; and lightweight structural parts for marine, aerospace and other industries, for example.
  • Rigid foams can be prepared by various methods, including block-foam, double-band lamination, discontinuous panel, and pour-in-place processes. The double- band lamination, discontinuous panel, and pour-in-place processes can each be used to prepare a rigid foam in situ in a single step.
  • a pour-in-place (PIP) process is a process wherein a polyurethane foam formulation is poured into an empty shell, mold or casing (hereinafter mold) and the foam fills the mold to form a foam-filled article.
  • the PIP process and its useful applications are well known in the .art of preparing polyurethane foams (see, for example, Reaction Polymers: Gum, W. F., Riese, W., and Ulrich, H., Eds. Hanser: New York 1992; pg. 575).
  • Articles made by the PIP method include, for example, garage doors, walk-in coolers, portable coolers, refrigerators, doors, and water heaters.
  • the foams described herein include rigid foams, molded foams and slabstock foams.
  • a polyurethane foam formulation When used in a PIP process, a polyurethane foam formulation can escape or leak from a mold if foaming does not occur during, or soon after, pouring. Leakage from a mold can result in higher costs associated with production of a foam product, due to loss of product and increased maintenance costs.
  • leakage is typically reduced by adding a low-boiling compound at ambient temperature into a foaming system to enhance pre-expansion of the foaming system, or frothing, of the foaming system at the start of the polyurethane reaction. This practice, however, normally requires modification of conventional equipment.
  • Pre-expansion refers to an increase in the volume of a foaming system, that is a polyurethane- forming reaction mixture, prior to the start of the polyurethane reaction.
  • polyurethane foams utilize blowing agents, such as halogenated alkanes, to produce the cellular structure found in a polyurethane foam.
  • C0 2 can be a useful blowing agent.
  • C0 2 can be produced as a result of a reaction between an isocyanate and water, when water is included in a polyurethane foam formulation.
  • the use of water and C0 2 can help reduce the amount of halogenated alkanes used in making a polyurethane foam. This can result in reducing the amount of halogenated alkanes released into the atmosphere, which can be desirable.
  • Polyurethane foams can be made using water or a combination thereof C0 2 exclusively as the blowing agent. Such foams (hereinafter C0 2 -blown foams) are described in U.S. Patent No. 5,013J66, for example.
  • C0 2 -blown foams can typically be high density foams, that is foams having an overall density greater than about 2.3 pounds per cubic foot (pcf).
  • C0 2 -blown foams having low density can be obtained by conventional methods, but such foams can have low closed cell content. In certain applications where a low density polyurethane foam having high closed cell content is desirable, typical C0 2 -blown foams can be undesirable.
  • the present invention is a polyurethane foam formulation comprising a polyisocyanate composition, .and a polyol composition, wherein the polyol composition includes: (a) at least one aromatic amine-initiated polyol; (b) at least one alkylene carbonate; and (c) water.
  • the present invention is a low density C0 2 -blown foam prepared from a polyurethane foam formulation comprising a polyisocyanate composition and a polyol composition wherein the polyol composition includes: (a) at least one aromatic amine-initiated polyol; (b) at least one alkylene carbonate; and (c) water.
  • the present invention is A process for preparing a polyurethane-filled article comprising the steps: (i) pouring a polyurethane foam formulation into a mold; (ii) allowing the foam to fill the mold; and (iii) demolding the foam after the foam attains cure to obtain the polyurethane-filled article, wherein the polyurethane foam formulation comprises a polyisocyanate composition and a polyol composition and wherein the polyol composition includes: (a) at least one aromatic amine-initiated polyol; (b) at least one alkylene carbonate; and (c) water.
  • a C0 2 -blown foam obtained using the process of the present invention is a low density foam which can have a 15 percent to 30 percent reduction in overall density relative to foams produced by conventional practice.
  • the present invention is a foam formulation useful for preparing a C0 2 -blown foam.
  • a foam formulation of the present invention includes a polyisocyanate composition and a polyol composition. When the polyisocyanate and polyol compositions are combined under suitable reaction conditions, a low density polyurethane foam of the present invention is obtained.
  • a polyol composition of the present invention includes isocyanate reactive material, an alkylene carbonate, and water.
  • optional components can be included in either or both components of the foam formulation.
  • Isocyanate-reactive materials suitable for use in the practice of the present invention include aromatic amine-initiated polyols (AAPs).
  • AAPs suitable for use in the practice of the present invention can be obtained commercially.
  • Voranol ® 391 ( ® Trade Designation of the Dow Chemical Co.) is a commercially available polyol suitable for the practice of the present invention.
  • Voranol ® 391 is an aromatic amine initiated polyol prepared from o-toluene diamine, ethylene oxide and propylene oxide.
  • AAPs can be obtained by reaction of an aromatic amine with an alkylene oxide under suitable reaction conditions of, for example, temperature, pH, and catalyst.
  • suitable temperature range for preparing an AAP of the present invention can be from 100°C to 135°C.
  • the temperature is in the range of from 110°C to 130°C. More preferably, the temperature is the range of from 120°C to 130°C, most preferably from 125°C to 130°C.
  • An AAP of the present invention can be obtained at a pH in the range of from
  • the pH is from 8 to 11.5. More preferably, the pH is from 8.5 to 11 , most preferably from 9 to 11.
  • a catalyst can be included to obtain an AAP of the present invention.
  • Catalysts suitable for preparing polyols of the present invention include, for example, dimethylcyclohexlamine, dimethylethanolamine, and diethylethanolamine, like compounds, and mixtures thereof; Group I and Group II metal hydroxides such as sodium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, like compounds and mixtures thereof.
  • An AAP suitable for the practice of the present invention can have a molecular weight of from 425 to 900.
  • the molecular weight of an AAP is from 520 to 825. More preferably, the molecular weight of an AAP is from 560 to 640. Most preferably, the molecular weight of an AAP is from 560 to 590.
  • the hydroxyl number of an AAP of the present invention can range from 250 to 530. Preferably the hydroxyl number is in the range of from 325 to 465. More preferably the hydroxyl number is in the range of from 350 to 450, most preferably from 380 to 430.
  • the average functionality of an AAP of the present invention is preferably not less than 2. More preferably, the average functionality of an AAP is from 3 to 5. Most preferably, the average functionality is from 3.2 to 4.1.
  • Aromatic amines suitable for preparing an AAP of the present invention can include any di-, or poly-functional aromatic amine.
  • Suitable aromatic amines include: the isomers of toluene diamine (TDA), which include 2,6-TDA, and 2,4-TDA, for example; isomers of methylene diamine (MDA) which include, for example, 2,2'-MDA, 2,4'-MDA, and 4,4'-MDA; oligomers of MDA which include, for example, mixtures of isomeric compounds having from 3 to 6 aromatic rings; alkyl derivatives of aromatic amines such as 4-methyl-2,6-TDA and isomers of dimethyl- MDA; halogenated derivatives of TDA such as 3-chloro-2,4-TDA; like compounds and mixtures of .any of these.
  • Alkylene oxides suitable for use in the present invention include oxides having from 2 to 8 carbon atoms, preferably from 2 to 4 carbon atoms.
  • suitable alkylene oxides can be ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3- butylene oxide, styrene oxide, epichlorohydrin, 3 -methyl- 1,2-butylene oxide, like compounds .and mixtures thereof.
  • polymers and copolymers of propylene oxide are preferred.
  • an AAP can be present as the only polyol component in a polyol composition or, optionally, other polyols can be included in the composition. If included, other polyols can be present in an amount of from 1 to 50 percent, by weight, of total polyol. Preferably from 0 to 10 percent, by weight, of another polyol is included.
  • Water is included in a polyol composition of the present invention in an amount of from 1 to 12 parts per 100 parts of AAP, by weight. Preferably, water is included in an amount of from 3 to 9 parts. More preferably, water is included in an amount of from 5 to 8, most preferably water is included in an amount of from 6.5 to 7.5 parts per 100 parts of AAP, by weight.
  • alkylene carbonate is included in a foam formulation of the present invention.
  • An alkylene carbonate useful in the practice of the present invention is described by either of structures I or II:
  • R,, R 2 , R 3 , .and R, . are each independently hydrogen or a combination thereof alkyl substituents of I, and wherein R 5 and R ⁇ are each independently alkyl substituents of II.
  • Alkyl substituents of I or II can be alkyl groups having from 1 to 8 carbon atoms. Suitable alkyl substituents can be aliphatic, aromatic, cyclic or acyclic, substituted or unsubstituted.
  • alkyl substituents include: methyl, ethyl , n-propyl, iso-propyl, n-butyl, isobutyl, pentyl, hexyl, cyclohexyl, phenyl, hydroxyphenyl, phenylmethyl, methylphenyl, bromophenyl, chloromethyl, like compounds, .and mixtures thereof.
  • suitable alkylene carbonates can include: ethylene carbonate; propylene carbonate; butylene carbonate; styrene carbonate (or 1- phenylethylene carbonate); isobutylene carbonate; dimethyl carbonate; diethyl carbonate; di-t-butyl carbonate; dibenzyl carbonate; diphenyl carbonate; phenyl, ethyl carbonate; like compounds, and mixtures thereof.
  • Alkylene carbonates suitable for use in the practice of the present invention are known and can be obtained commercially. The purity of an alkylene carbonate is not believed to be critical to the practice of the present invention.
  • propylene carbonate is commercially available as Arconate 1000TM from the Arco Chemical Co.
  • An alkylene carbonate of the present invention can be included in an amount of from 1 to 20 parts per 100 parts of AAP, by weight.
  • an alkylene oxide is included in an amount of from 3 to 15 parts of alkylene carbonate per 100 parts of AAP, by weight.
  • an alkylene carbonate is included in an amount of from 5 to 12 parts of alkylene carbonate per 100 parts of AAP, by weight.
  • an alkylene carbonate is include in an amount of from 7 to 10 parts of alkylene carbonate per 100 parts of AAP, by weight.
  • an alkylene carbonate can be included with either the polyol composition or the isocyanate composition.
  • the alkylene carbonate can be included as part of both the polyol and isocyanate compositions.
  • the alkylene carbonate is included in the polyol composition.
  • a polyol composition of the present invention can optionally include copolymer polyols, polyester polyols, catalysts, fillers, crosslinkers, surfactants, cell openers, mold release agents, and flame retardants, for example.
  • polyurethane catalysts suitable for preparing a polyurethane foam of the present invention are tertiary amine catalysts such as: triethylenediamine; N- methyl morpholine; dimethylethanolamine; pentamethyldimethylenetriamine; N-ethyl morpholine; diethylethanolamine; N-coco morpholine; l-methyl-4-dimethylaminoethyl piperazine; bis(N,N-dimethylaminoethyl)ether; similar compounds, and mixtures of any of these.
  • Suitable catalysts for use with the present invention also include those which catalyze the formation of isocyanurates such as those mentioned in Saunders and Frisch, Polyurethanes.
  • Such catalysts are referred to as trimerization catalysts.
  • these catalysts include aliphatic and aromatic tertiary amine compounds, organometallic compounds, alkali metal salts of carboxylic acids, phenols and symmetrical triazine derivatives.
  • Preferred catalysts are potassium salts of carboxylic acids such as potassium octoate and the potassium salt of 2-ethylhexanoic acid and tertiary amines such as, for instance, 2,4,6-tris(dimethyl aminomethyl) phenol.
  • Amine catalysts are usually used in an amount of from 0.1 to 5, preferably from 0.2 to 3 parts per 100 parts of polyol composition, by weight.
  • Organometallic catalysts are also suitable, and examples include organolead, organoiron, organomercury, organobismuth, and preferably organotin compounds. Most preferred are organotin compounds such as dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, stannous chloride and similar compounds.
  • Organometallic compounds are usually used in an amount from 0.05 to 0.2 parts per 100 parts, by weight, of polyol composition.
  • surfactants examples include silicone surfactants, most of which are block copolymers containing at least one polyoxyalkylene segment and one poly(dimethylsiloxane) segment.
  • Other surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl sulfate esters, alkyl sulfonic esters and alkylaryl sulfonic acids. When used, 0.1 to 3, preferably 0.3 to about 1 part by weight of surfactant to 100 parts of polyol by weight is normally adequate.
  • Surfact.ants prep.ared from ethylene oxide .and butylene oxide, as described in U.S. Appl. Ser. No.
  • crosslinkers are diethanolamine and methylene bis(o-chloroaniline) and similar compounds.
  • cell openers, mold release agents, flame retardants, fillers, and other additives are known in the art to modify the properties and aid in the processability of the foam, and can be desirable depending on the end-use application.
  • a polyisocyanate composition includes a polyisocyanate. Any polyisocyanate or polyisocyanate mixture known in the art is suitable for the practice of the present invention. Useful polyisocyanates are described in U.S. Patent No. 4,785,027, for example.
  • the polyisocyanate can be aliphatic or aromatic.
  • Aromatic polyisocyanates suitable for use herein include: phenyl diisocyanate; 2,4-toluene diisocyanate; 2,6- toluene diisocyanate; ditoluene diisocyanate; naphthalene 1,4-diisocyanate; 2,4'- or a combination thereof 4,4'-diphenylmethane diisocyanate (MDI); polymethylene polyphenylenepolyisocyanates (polymeric MDI); like compounds, .and mixtures thereof.
  • MDI 4,4'-diphenylmethane diisocyanate
  • MDI polymethylene polyphenylenepolyisocyanates
  • Suitable aliphatic polyisocyanates include: 1 ,6-hexamethylene diisocyanate; isophorone diisocyanate; 1,4-cyclohexyl diisocyanate; like compounds and mixtures thereof.
  • Prepolymers prepared by reacting a polyol or chain extender with a polyisocyanate are suitable, as well.
  • the polyisocyanate can be used in an amount suitable to prepare a polyurethane-forming composition with an isocyanate index of from 90 to 500.
  • the index is from 100 to 130. More preferably the isocyanate index is from 105 to 115. Most preferably, the isocyanate index is from 105 to 110.
  • the isocyanate index is determined by dividing the number of equivalents of isocyanate by the number of equivalents of isocyanate-reactive material, and multiplying the ratio obtained by 100.
  • a polyisocyanate of the present invention can have an average functionality of from 2.0 to 3.5. Preferably, the average functionality is from 2.5 to 3.3. More preferably, the average functionality is from 2.6 to 3.2. Most preferably, the average functionality is from 2.6 to 3.0.
  • the present invention is a method for preparing a polyurethane-filled .article by the PIP procedure, using a foam formulation described herein.
  • foaming is typically delayed until the start of the reaction inside of a mold cavity.
  • a pre- expansion occurs as a foam formulation is initially poured into a mold, due to the presence of the alkylene carbonate.
  • the alkylene carbonate present in a foam formulation of the present invention generates C0 2 during storage at controlled temperatures. The initial frothing prevents the foam from leaking from an unsealed mold, and the subsequent foaming enhances the mold-filling process.
  • a polyurethane-filled article is obtained according to the steps: mixing a polyisocyanate composition and a polyol composition at a suitable isocyanate index as described herein; pouring the polyurethane-forming mixture into a mold; allowing the foam mixture to fill the mold to obtain a molded rigid foam; and, demolding the foam after the foam attains cure to obtain the polyurethane-filled article.
  • a polyol composition that includes an alkylene carbonate can be stored at a temperature of from 10°C to 60°C.
  • an alkylene carbonate-containing composition is stored at a temperature of from 16°C to 32°C, more preferably at a temperature of from 18°C to 27°C, and most preferably at a temperature of from 21°C to 24°C.
  • the present invention is a low density C0 2 -blown foam prepared from a foam formulation described herein.
  • a foam of the present invention has properties that are at least equivalent to foams made according conventional processes.
  • One property of a foam that can be improved by using the process of present invention is the overall density of a foam, while maintaining foam dimensional stability.
  • the overall density is the density of the entire molded rigid foam part.
  • a foam made according to the process of the present invention can have an overall density of not greater than 10 pcf.
  • a foam of the present invention can have a density not greater than 5.0 pcf, more preferably 3.0 pcf.
  • a foam of the present invention has a density of not greater than about 2.2 pcf.
  • a foam obtained using the process of the present invention can have a closed cell content of not less than 80 percent.
  • a foam of the present invention has a closed cell content of not less than 85 percent. More preferably the closed cell content is not less than 90 percent, most preferably not less than 92 percent.
  • a foam prepared according to the process of the present invention can have low density, suitable dimensional stability, and high closed cell content.
  • Suitable dimensional stability for a foam of the present invention is from 0 to ⁇ 8 percent volume change, for example.
  • the dimensional stability is from 0 to ⁇ 6 percent volume change, most preferably from 0 to ⁇ 4 percent volume change.
  • a foam of the present invention additionally provides excellent adhesion to various substrates, for example plastic liner materials such as high impact polystyrene and high density polyethylene, as well as steel facers.
  • a foam of the present invention maintains excellent dimensional stability at a density of not less than 1.80 pcf under cold age, dry age, and humid age conditions.
  • a foam of the present invention exhibits finer and more uniform cell structure than a conventionally prepared foam.
  • foam attributable to the process of the present invention are: low free rise density of less than about 1.10 pcf, preferably from 0.95 to 1.10, more preferably from 0.95 to 1.07, most preferably from 0.95 to 1.05 pcf; low core foam friability of not greater than about 3.0 percent, preferably from 1.0 percent to 3.0 percent, more preferably from 1.0 percent to 2.5 percent, most preferably from 1.0 percent to 2.0 percent; and fast demold.
  • a foam prepared according to the process of the present invention generally can be demolded in less than about 8 minutes.
  • a foam of the present invention is demolded in from 3 minutes to 8 minutes, more preferably in from 3 minutes to 7 minutes. Most preferably, a foam of the present invention is demolded in from 3 minutes to 6.5 minutes. Demold time is dependent on the thickness of the foam obtained, and the ranges described herein are given for a foam thickness of about 1.75 inches.
  • a polyol composition was prepared by admixing polyol, propylene carbonate, and water with optional components in the amounts listed in Table 1.
  • a polyol composition was prepared by admixing polyol, propylene carbonate, and water with optional components in the amounts listed in Table 1.
  • a polyol composition was prepared by admixing polyol and water with optional components in the amounts listed in Table 1.
  • a polyol composition was prepared by admixing polyol and water with optional components in the amounts listed in Table 1.
  • Example 5 Comparative Example A polyol composition was prepared by admixing polyol and water with optional components in the amounts listed in Table 1.
  • a polyol composition was prepared by admixing polyol and water with optional components in the amounts listed in Table 1.
  • Example 1 The polyol composition of Example 1 was combined with 215 parts of P API ® 27 isocyanate to an isocyanate index of 105.
  • the polyurethane-forming mixture thus produced was poured into a mold heated to a temperature of 130°F. The foam was removed from the mold after 4.5 minutes. Some physical properties of the foam was tabulated in Table 2. The foam reactivity profile was shown in Table 3.
  • k-Factor was determined according to ASTM C-518.
  • Compression Strength was determined by according to ASTM D-1621.
  • Friability was determined according to ASTM D-421.
  • Dimensional stability was determined according to ASTM D-2126.
  • Closed cell content was determined according to ASTM D-2856.
  • Example 3 The polyol composition of Example 3 was combined with 173 parts of PAPI ® 27 isocyanate to an isocyanate index of 110.
  • the polyurethane-forming mixture thus produced was poured into a mold heated to a temperature of 130°F. The foam was removed from the mold after 4.5 minutes. Some physical properties of the foam was tabulated in Table 2. The foam reactivity profile was shown in Table 3.
  • Example 9 Comparative Example The polyol composition of Example 4 was combined with 214 parts of PAPI ®
  • Example 5 The polyol composition of Example 5 was combined with 173 parts of PAPI ® 27 isocyanate to an isocyanate index of 110.
  • the polyurethane-forming mixture thus produced was poured into a mold heated to a temperature of 130°F.
  • the foam was removed from the mold after 4.5 minutes.
  • Some physical properties of the foam was tabulated in Table 2.
  • the fo.am reactivity profile was shown in Table 3.
  • Example 6 The polyol composition of Example 6 was combined with 214 parts of PAPI ® 27 isocyanate to an isocyanate index of 110.
  • the polyurethane-forming mixture thus produced was poured into a mold heated to a temperature of 130°F. The foam was removed from the mold after 4.5 minutes. Some physical properties of the foam was tabulated in Table 2. The foam reactivity profile was shown in Table 3.
  • Example 1 The polyol composition of Example 1 was combined at 84°F with 215 parts of PAPI ® 27 isocyanate to an isocyanate index of 105.
  • the polyurethane-forming mixture thus produced was poured into a mold heated to a temperature of 130°F.
  • the foam was removed from the mold after 4.5 minutes.
  • Some physical properties of the foam was tabulated in Table 2.
  • the foam reactivity profile was shown in Table 3.
  • Example 3 The polyol composition of Example 3 was combined with 173 parts of PAPI ® 27 isocyanate to an isocyanate index of 110.
  • the polyurethane-forming mixture thus produced was poured into a mold heated to a temperature of 130°F. The foam was removed from the mold after 4.5 minutes. Some physical properties of the foam was tabulated in Table 2. The foam reactivity profile was shown in Table 3.

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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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de préparation d'une mousse soufflée au CO2 à faible densité qui présente une teneur élevée en alvéoles fermées. Les mousses préparées selon ce procédé sont utiles dans des applications de coulée sur place, comme par exemple des portes de garage, des portes, des chambres froides, des réfrigérateurs portables, des réfrigérateurs et des chauffe-eau. On peut ainsi réduire les fuites de mousse d'un moule pendant la coulée sur place et réduire de ce fait les déchets et les coûts associés à la production d'articles remplis de mousse fabriqués par coulée sur place.
PCT/US1998/009662 1997-12-04 1998-05-11 Mousses de polyurethane soufflees au co2 a faible densite et son procede de preparation WO1999028364A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU73822/98A AU737063B2 (en) 1997-12-04 1998-05-11 Low density CO2-blown polyurethane foams and a process of preparing same
CA002312373A CA2312373A1 (fr) 1997-12-04 1998-05-11 Mousses de polyurethane soufflees au co2 a faible densite et son procede de preparation
BR9815152-5A BR9815152A (pt) 1997-12-04 1998-05-11 Espumas de poliuretano de baixa densidade sopradas com co2, processo para sua obtenção e artigo obtido
KR1020007006054A KR20010032761A (ko) 1997-12-04 1998-05-11 저밀도 ｃｏ2-취입된 폴리우레탄 발포체 및 이의 제조 방법
EP98921146A EP1034205A1 (fr) 1997-12-04 1998-05-11 Mousses de polyurethane soufflees au co 2? a faible densite et son procede de preparation
JP2000523253A JP2001525430A (ja) 1997-12-04 1998-05-11 低密度二酸化炭素発泡ポリウレタンフォーム及びその製造方法
NO20002792A NO20002792L (no) 1997-12-04 2000-05-31 Lavdensitets CO2-eset polyuretanskum og fremgangsmÕte for fremstilling derav

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ARP970105703 1997-12-04
AR9705703 1997-12-04

Publications (1)

Publication Number Publication Date
WO1999028364A1 true WO1999028364A1 (fr) 1999-06-10

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Country Status (9)

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EP (1) EP1034205A1 (fr)
JP (1) JP2001525430A (fr)
KR (1) KR20010032761A (fr)
CN (1) CN1283208A (fr)
AU (1) AU737063B2 (fr)
BR (1) BR9815152A (fr)
CA (1) CA2312373A1 (fr)
PL (1) PL341111A1 (fr)
WO (1) WO1999028364A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2475803A4 (fr) * 2009-09-09 2017-05-24 Arkema Inc. Procédés améliorés de moussage de polyuréthane et propriétés de mousse utilisant un agent gonflant à base d oléfine halogénée
JP2019007256A (ja) * 2017-06-27 2019-01-17 アキレス株式会社 嵩上げ構造

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101541188B1 (ko) 2008-11-06 2015-08-03 삼성전자주식회사 폴리우레탄 발포체 조성물 및 이를 사용하여 제조된 폴리우레탄 발포체
KR101023219B1 (ko) * 2010-12-08 2011-03-18 신이철강주식회사 내열성이 우수한 이중보온관용 우레탄 조성물 및 이를 이용한 이중보온관 제조방법
KR101909047B1 (ko) * 2018-06-29 2018-10-17 주식회사 대동피에이치 창틀 하부 사춤용 폴리우레탄 조성물 및 이를 이용한 폴리우레탄 시공방법
KR102130698B1 (ko) * 2020-03-12 2020-07-07 신백범 이액형 폴리우레탄계 조성물을 포함하는 pvc 창호 프레임

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4568702A (en) * 1985-04-15 1986-02-04 Atlantic Richfield Company Method for the preparation of semi-rigid polyurethane modified polyurea foam compositions
EP0408048A2 (fr) * 1989-07-14 1991-01-16 Takeda Chemical Industries, Ltd. Procédé de préparation de mousse d'uréthane rigide
US5258418A (en) * 1992-12-04 1993-11-02 Basf Corporation Low density, water-blown, rigid polyurethane foams having good physical properties and improved initial surface friability
US5648019A (en) * 1995-11-01 1997-07-15 Basf Corporation Three component polyol blend for use in insulating rigid polyurethane foams

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4568702A (en) * 1985-04-15 1986-02-04 Atlantic Richfield Company Method for the preparation of semi-rigid polyurethane modified polyurea foam compositions
EP0408048A2 (fr) * 1989-07-14 1991-01-16 Takeda Chemical Industries, Ltd. Procédé de préparation de mousse d'uréthane rigide
US5258418A (en) * 1992-12-04 1993-11-02 Basf Corporation Low density, water-blown, rigid polyurethane foams having good physical properties and improved initial surface friability
US5648019A (en) * 1995-11-01 1997-07-15 Basf Corporation Three component polyol blend for use in insulating rigid polyurethane foams

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2475803A4 (fr) * 2009-09-09 2017-05-24 Arkema Inc. Procédés améliorés de moussage de polyuréthane et propriétés de mousse utilisant un agent gonflant à base d oléfine halogénée
JP2019007256A (ja) * 2017-06-27 2019-01-17 アキレス株式会社 嵩上げ構造

Also Published As

Publication number Publication date
CA2312373A1 (fr) 1999-06-10
CN1283208A (zh) 2001-02-07
AU7382298A (en) 1999-06-16
AU737063B2 (en) 2001-08-09
PL341111A1 (en) 2001-03-26
EP1034205A1 (fr) 2000-09-13
KR20010032761A (ko) 2001-04-25
BR9815152A (pt) 2000-10-10
JP2001525430A (ja) 2001-12-11

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