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WO1998037116A1 - Procede pour produire de la mousse polyurethane rigide - Google Patents

Procede pour produire de la mousse polyurethane rigide Download PDF

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Publication number
WO1998037116A1
WO1998037116A1 PCT/JP1998/000585 JP9800585W WO9837116A1 WO 1998037116 A1 WO1998037116 A1 WO 1998037116A1 JP 9800585 W JP9800585 W JP 9800585W WO 9837116 A1 WO9837116 A1 WO 9837116A1
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WO
WIPO (PCT)
Prior art keywords
polyol
catalyst
weight
produced
aromatic
Prior art date
Application number
PCT/JP1998/000585
Other languages
English (en)
Inventor
Yasuo Inazawa
Kei Odani
Original Assignee
Sumitomo Bayer Urethane Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Bayer Urethane Co., Ltd. filed Critical Sumitomo Bayer Urethane Co., Ltd.
Priority to AU58800/98A priority Critical patent/AU5880098A/en
Priority to JP53647898A priority patent/JP3919824B2/ja
Publication of WO1998037116A1 publication Critical patent/WO1998037116A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/127—Mixtures of organic and inorganic blowing agents
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • 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
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4879—Polyethers containing cyclic groups containing aromatic 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
    • C08G18/28—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
    • C08G18/28—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
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/546—Oxyalkylated polycondensates of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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 a method for producing a rigid polyurethane foam, which is superior in initial activity and requires a small amount of raw materials .
  • the rigid polyurethane foam of the present invention can be applied by spraying in excellent workability regardless of a change in temperature throughout the four seasons.
  • a rigid polyurethane foam is produced by mixing a polyisocyanate component with, as a polyol component, a compound having at least two reactive groups capable of reacting with an isocyanate group (particularly polyol), a catalyst, a flame retardant, a diluent, a surfactant, a low-boiling point hydrochlorofluorocarbon such as HCFC-141b and water which reacts with the polyisocyanate to generate carbon dioxide, by a foaming machine.
  • a polyisocyanate component a compound having at least two reactive groups capable of reacting with an isocyanate group (particularly polyol), a catalyst, a flame retardant, a diluent, a surfactant, a low-boiling point hydrochlorofluorocarbon such as HCFC-141b and water which reacts with the polyisocyanate to generate carbon dioxide, by a foaming machine.
  • HCFC-141b low-boiling point hydroch
  • Japanese Patent Kokoku Publication No. 99533/1994 suggests use of a specific catalyst or use of a low-boiling point blowing agent in combination with the specific catalyst.
  • the foam density becomes high when the foam thickness is comparatively thin.
  • the low-boiling point blowing agent of a gas at a normal temperature under a normal pressure it is necessary to bring a cylinder into a field of foaming.
  • the density becomes too high or too low. As a result, when the density becomes too high, the used amount of the raw material is increased.
  • Japanese Patent Kokai Publication No. 133398/1976 proposes a method for producing a flame-retardant , low-fuming polyurethane foam, which comprises blending amine carbamate of a primary or secondary amino compound having a hydroxyl group, and then foaming the blend.
  • the workability e.g. instantaneous foaming and curing
  • the in-situ foaming spray
  • isocyanate TDI (toluene diisocyanate) is used (see Examples) and is unsuitable for spray foaming.
  • Japanese Patent Kokai Publication No. 220512/1987 discloses a method for producing a thermally insulating polyurethane foam for refrigerator, using a special amine/carbon dioxide adduct. However, this method is not suitable for spray because of poor reactivity (long gelling time) .
  • the present invention provides a method for producing a rigid polyurethane foam which is superior in initial activity in low-temperature atmosphere and is a low-density foam.
  • the present invention provides a method for producing a rigid polyurethane foam, which comprises mixing (a) a polyisocyanate component with a polyol component comprising (b) a polyol mixture, (c) a catalyst, (d) a blowing agent and, if necessary, a flame retardant, a diluent and a surfactant, then foaming the mixture; wherein the polyisocyanate component (a) is polymethylenepolyphenyl polyisocyanate or a modified material thereof; the polyol mixture (b) comprises: (b-1) 20 to 80 parts by weight of a polyol having a hydroxyl value of 300 to 800 mg KOH/g, which is produced by adding an alkylene oxide to an aliphatic amine;
  • (b-2) 20 to 80 parts by weight of at least one aromatic polyether polyol having a hydroxyl value of 170 to 600 mg KOH/g, which is produced by using an aromatic amine, a Mannich base having an aromatic ring or a polyfunctional phenol as a starting material; and
  • a polyol which is produced by using a compound having no aliphatic amine as a starting material, or a polyether polyol having no aromatic ring and/or an aromatic polyester polyol, and a hydroxyl value of the polyol mixture (b) is from 300 to 800 mg KOH/g;
  • the catalyst (c) is at least one metallic catalyst, which is optionally used in combination with a tertiary amine compound;
  • the blowing agent (d) is an adduct of a primary or secondary amine compound with carbon dioxide, which is optionally used in combination with a low-boiling point compound and/or water.
  • the present invention also provides a polyol composition
  • a polyol composition comprising (b) a polyol mixture, (c) a catalyst, (d) a blowing agent and, if necessary, a flame retardant, a diluent and a surfactant;
  • the polyol mixture (b) comprises:
  • (b-1) 20 to 80 parts by weight of a polyol having a hydroxyl value of 300 to 800 mg KOH/g, which is produced by adding an alkylene oxide to an aliphatic amine; (b-2) 20 to 80 parts by weight of at least one aromatic polyester polyol having a hydroxyl value of 170 to 600 mg KOH/g, which is produced by using an aromatic amine, a Mannich base having an aromatic ring or a polyfunctional phenol as a starting material; and
  • a polyol which is produced by using a compound having no aliphatic amine as a starting material, or a polyether polyol having no aromatic ring and/or an aromatic polyester polyol, and a hydroxyl value of the polyol mixture (b) is from 300 to 800 mg KOH/g;
  • the catalyst (c) is at least one metallic catalyst, which is optionally used in combination with a tertiary amine compound;
  • the blowing agent (d) is an adduct of a primary or secondary amine compound with carbon dioxide, which is optionally used in combination with a low-boiling point compound and/or water.
  • the polyisocyanate component (a) used in the present invention is (i) polymethylenepolyphenyl polyisocyanate or (ii) a product prepared by modifying polymethylene- polyphenyl polyisocyanate and/or diphenylmethane diisocyanate (MDI) as a raw material according to a known method.
  • the polyisocyanate component (a) is generally polymethylenepolyphenyl polyisocyanate, but a mixture of modified polymethylenepolyphenyl polyisocyanate and polymethylenepolyphenyl polyisocyanate may be used.
  • the modification may be urethanization, carbodiimidation, trimerization and the like.
  • the carbodiimidated polymethylenepolyphenyl polyisocyanate is a compound having a carbodiimide group and/or a uretoneimine group, which is made by carbodiimidating 0.1 to 20% by weight of isocyanate groups by using a known carbodiimidating catalyst.
  • the trimerized polymethylenepolyphenyl polyisocyanate is a compound wherein isocyanate groups are trimerized in the amount of 1 to 20% by weight based on isocyanate groups of the starting material, which is made by a known trimerization technique.
  • the modified material may be a mixture thereof .
  • the polyol mixture (b) is used.
  • the polyol mixture (b) is a mixture of (b-1) a polyol which is produced by adding an alkylene oxide to an aliphatic amine, (b-2) an aromatic polyether polyol and, if necessary, (b-3) a polyether polyol having no aliphatic amine or no aromatic ring and/or an aromatic polyester polyol .
  • Examples of the polyol (b-1) which is produced by adding an alkylene oxide to an aliphatic amine include those obtained by addition-polymerizing at least one monomer such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether or phenyl glycidyl ether by a known method in the presence of at least one compound as an initiator selected from an amine compound such as ethylenediamine, propylenediamine and diethylenetriamine and/or an alkanolamine compound such as triethanolamine, diethanolamine and monoethanolamine.
  • the polyol (b-1) may be a polyether polyol .
  • a hydroxyl value of the aliphatic amine polyol (b-1) is from 300 to 800 mg KOH/g, preferably from 450 to 800 mg KOH/g. If the hydroxyl value is smaller than 300 mg KOH/g, the compression strength of the resulting foam is low. If the hydroxyl value is larger than 800 mg KOH/g, the viscosity of the polyol (b-1) rapidly increases, which results in high viscosity of the polyol mixture (b) .
  • An amount of the used polyol (b-1) which is produced by adding an alkylene oxide to an aliphatic amine is from 20 to 80 parts by weight, preferably from 30 to 60 parts by weight, based on 100 parts by weight of the polyol mixture (b) . If the amount is smaller than 20 parts by weight, a large amount of a catalyst is necessary when adjusting to the reactivity required for performing the spray foaming, which results in high cost. If the amount is larger than 80 parts by weight, the foam does not become flat at the time of spray foaming and a problem on the finishing (e.g. bump-like portion formed by partially rising the foam from the adhesive surface, etc.) is liable to arise.
  • the polyol mixture (b) contains the aromatic polyether polyol (b-2).
  • the aromatic polyether polyol (b-2) is a polyether polyol produced from an aromatic amine, a Mannich base having an aromatic ring, or a polyfunctional phenol as the starting material.
  • the polyether polyol produced by using the aromatic amine as a starting material is a polyol prepared by adding at least one alkylene oxide such as ethylene oxide and propylene oxide to at least one aromatic polyamine such as tolylenediamine and diphenylmethanediamine .
  • the polyether polyol which is produced by using a Mannich base as a starting material is a polyol prepared by adding an alkylene oxide to a Mannich reduction product obtained by phenols, alkanolamine and formaldehydes.
  • Examples thereof include DK polyol 3773 (manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.).
  • the aromatic polyether polyol (b-2) may be a polyether polyol produced by using a polyfunctional phenol as the starting material .
  • examples thereof include resol type condensate prepared by condensing phenols with excess formaldehydes in the presence of an alkaline catalyst, a benzylic ether-type initial condensate prepared by reacting in a non-aqueous system in case of synthesizing the resol type condensate, and a novolak-type condensate prepared by reacting excess phenols with formaldehydes in the presence of an acid catalyst.
  • a molecular weight of the condensate is preferably from about 200 to 10000.
  • Phenols also include those wherein substituents other than the hydroxyl group is bonded to the benzene nucleus.
  • substituents other than the hydroxyl group is bonded to the benzene nucleus.
  • examples of the phenols include phenol, cresol, bisphenol A, resorcinol and the like.
  • examples of the formaldehydes include formalin, paraformaldehyde and the like.
  • (b-2) is from 170 to 600 mg KOH/g, preferably from 170 to 450 mg KOH/g.
  • An amount of the used aromatic polyether polyol (b-2) is from 20 to 80 parts by weight, preferably from 30 to 50 parts by weight, based on 100 parts by weight of the polyol mixture (b) . If the amount is smaller than 20 parts by weight, the adhesion to the substrate is liable to be deteriorated. If the amount is larger than 80 parts by weight, the curing of the foam proceeds slowly.
  • the polyol mixture (b) may contain (b-3) a polyol which is obtained by using a compound containing no aliphatic amine as a starting material, or a polyether polyol having no aromatic ring and/or an aromatic polyester polyol.
  • the component (b-3) is optionally used for adjusting the viscosity and reactivity of the polyol mixture (b) .
  • Examples of the component (b-3) include, a polyether polyol which is obtained by adding a cyclic ether, particularly propylene oxide, ethylene oxide or butylene oxide to polyhydric alcohols, saccharides and the like.
  • the aromatic polyester polyol (b-3) is a reaction product of a polyhydric alcohol, preferably a dihydric alcohol and/or a trihydric alcohol with a polybasic, preferably dibasic polycarboxylic acid having an aromatic ring.
  • a polyhydric alcohol preferably a dihydric alcohol and/or a trihydric alcohol
  • a polybasic preferably dibasic polycarboxylic acid having an aromatic ring.
  • Phantol PL-305 manufactured by Toho Rika Kogyo Co., Ltd.
  • a corresponding polycarboxylic anhydride or a corresponding carboxylate ester of a lower alcohol or a mixture thereof can be used in place of a free polycarboxylic acid.
  • the polycarboxylic acid may have an aromatic ring and/or a heterocyclic ring, and it may be a polycarboxylic acid substituted with a halogen atom.
  • Examples of the polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, anhydrous phthalic acid and derivatives thereof .
  • the polyhydric alcohol is preferably an alcohol having 3 to 9 carbon atoms, and may be anyone of a straight-chain, branched or cyclic alcohol.
  • the polyhydric alcohol is preferably a dihydric alcohol and/or a trihydric alcohol.
  • Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol and the like.
  • Examples of the trihydric alcohol include glycerine, trimethylolpropane and the like. Those prepared by decomposing polyethylene terephthalate with various glycols may also be used.
  • An amount of the component (b-3) is less than 40 parts by weight, preferably not more than 30 parts by weight, based on 100 parts by weight of the polyol mixture (b).
  • the catalyst (c) is at least one metallic catalyst.
  • the metallic catalyst may be a metal carboxylate salt.
  • the metal carboxylate salt is represented by the general formula: R-COOX wherein R represents an alkyl, alkenyl or aryl group having 1 to 17 carbon atoms; and X represents sodium, potassium or lead.
  • the metallic catalyst is preferably potassium octanoate, lead octanoate or potassium acetate.
  • An amount of the solid material in the used metallic catalyst is from 0.1 to 7 parts by weight, preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of the polyol mixture (b) .
  • Those prepared by dissolving the metallic catalyst in a short chain diol may be preferably used.
  • the short chain diol diethylene glycol and dipropylene glycol are preferred.
  • Two or more types of metallic catalysts may be mixed.
  • the catalyst (c) may contain a tertiary amine catalyst, if necessary.
  • a tertiary amine catalyst there can be used an amine catalyst which is generally known. In view of the odor and safety/hygiene, -those having low vapor pressure are preferred.
  • tertiary amine catalyst examples include ,N,N' , ' -tetramethylhexamethylenediamine, N,N',N"- tris (dimethylaminopropyl )hexahydro-s-triazine, triethylenediamine , ,N,N' ,N' -tetramethylpropylenediamine, N,N,N' ,N'-pentamethyldiethylenetriamine, trimethyl- aminoethylpiperazine, N,N' -dimethylcyclohexylamine, bis ( 2-dimethylaminoethyl )ether, N-methylmorpholine, N-ethylmorpholine and the like.
  • N,N,N' ,N' -tetramethylhexamethylenediamine and triethylenediamine Preferred are N,N,N' ,N' -tetramethylhexamethylenediamine and triethylenediamine.
  • An amount of the tertiary amine catalyst used may be not larger than 20 parts by weight, more preferably from 0.1 to 10 parts by weight, particularly from 2 to 5 parts by weight, based on 100 parts by weight of the polyol mixture (b) .
  • the blowing agent (d) is an adduct between an amine compound having a primary or secondary amino group and carbon dioxide.
  • the amine compound include an amine compound such as butylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine and triethylenetetramine and alkanolamine such as ethanolamine, N-methylethanolamine, diethanolamine, isopropanolamine and diisopropanolamine .
  • an amine compound having a hydroxyl group is preferred.
  • An amount of the used adduct of the amine compound having a primary or secondary amino group and carbon dioxide is from 0.1 to 30 parts by weight based on 100 parts by weight of the polyol mixture (b) .
  • reaction solution of this adduct is liable to solidify at a normal temperature, it is preferred that a liquid polyol and/or water is previously added to the amine compound .
  • the blowing agent (d) may contain a low-boiling point compound and/or water, if necessary.
  • the low-boiling point compound include hydrocarbon, halogenated hydrocarbon and the like. It is possible to use a low-boiling point compound having a boiling point within the range from -50 to 100°C (under 1 atm) .
  • An amount of the used blowing agent (d) may be within the range from 0.1 to 80 parts by weight, for example 0.1 to 60 parts by weight based on 100 parts by weight of the polyol mixture (b) .
  • additives such as a flame retardant, a diluent and a surfactant may be used, in addition to the components (a) to (d).
  • an isocyanate index is preferably from 60 to 180, particularly from 80 to 150.
  • a rigid polyurethane foam by a spray method.
  • the rigid polyurethane foam may be used for thermally insulating materials in house, building, etc., for an insulated warehouse, for a bathtub, and for building interior/exterior material.
  • the reaction liquid (4.8 kg) obtained by operating in the same manner as in Reference Example 2 was mixed with previously warmed ethylene glycol (14.4 kg).
  • the resulting mixed liquid maintained a liquid form at a normal temperature and an abnormal evolution of carbon dioxide was not observed even if the reaction liquid was heated to 80°C. Therefore, it could be stored as such in a 20 L tin-plated can.
  • This mixed solution was used as the blowing agent .
  • Examples 1 to 7 and Comparative Examples 1 to 3 A polyol, a catalyst, a flame retardant, a diluent and a surfactant, a blowing agent (those obtained in Reference Examples and fluorinated hydrocarbon) and, if necessary, water were mixed to obtain a polyol component.
  • the polyol component and isocyanate were sprayed on a substrate by a spray foaming machine (PF-1600, manufactured by Higaki Machinery Co . ) equipped with a D gun manufactured by Gasmer Co. to form a rigid polyurethane foam.
  • the ingredients of the sprayed composition are shown in Table 1.
  • the spray foaming conditions were as followings. Spray foaming conditions
  • a spray liquid was instantaneously sprayed on an aluminum plate having the temperature controlled to 0°C, and then the time required for the spray liquid to turn white on the aluminum plate (cream time) was measured.
  • a releasing agent was applied and dried on a veneer plywood of 90 cm x 90 cm x 12 mm, and then a spray liquid was sprayed on the veneer plywood in the atmosphere at 0°C so that the thickness of the primary spray layer was about 2 mm. After 30 seconds, the spraying was conducted so that the final thickness of a sprayed foam layer was about 30 mm to form a sample. At that time, the situation of spraying from the gun to the veneer plywood was observed. Then, it was visually evaluated whether the spray pattern extends in a round shape (good), or does not extend or is divided into two parts (poor). Furthermore, it was visually evaluated whether the spray pattern becomes a frothy (good) or not (poor). Furthermore, it was observed whether the foam overflows the veneer plywood or not, and then the presence or absence of the lateral elongation of the foam was evaluated.
  • the upper and lower skins were removed from the resulting sample and the core density was measured.
  • the core density was measured and the sample was allowed to stand for 24 hours under the conditions of -30°C, 100°C and 70°C x 95% R.H. and the amount of deformation ( (V x - v o)/ v o x 100) (wherein V 0 represents a volume before exposing to each condition and V x represents a volume after exposing to each condition) was determined.
  • Amount of used raw materials [Test C]
  • Isocyanate Sumidur 44V10 (manufactured by Sumitomo Bayer Urethane Co . , Ltd . ) NCO content: 31.6%, viscosity: 110 mPa»s/25°C
  • Polyol A polyol having a hydroxyl value of 760 mg KOH/g and a viscosity of 50000 mPa»s/25°C, which is produced by adding propylene oxide to ethylene diamine
  • Polyol B polyol having a hydroxyl value of 470 mg KOH/g and a viscosity of 1200 mPa»s/25°C, which is produced by adding ethylene oxide and propylene oxide to ethylenediamine
  • Polyol C polyol having a hydroxyl value of 320 mg KOH/g and a viscosity of 2100 mPa «s/25°C, which is produced by adding ethylene oxide and propylene oxide to tolylenediamine
  • Polyol D DK polyol 3773 (manufactured by Dai-Ichi Kogyo Seiyaku Co . , Ltd . ) polyether polyol having a hydroxyl value of 470 mg KOH/g and a viscosity of 11000 mPa «s/25°C, which is produced by adding an alkylene oxide to a Mannich reaction product having an aromatic ring
  • Polyol E polyether polyol having a hydroxyl value of 280 mg KOH/g and a viscosity of 12000 mPa «s/25°C, which is produced by adding ethylene oxide to bisphenol A
  • Polyol F polyether polyol having a hydroxyl value of 250 mg KOH/g and a viscosity of 250 mPa»s/25°C, which is produced by adding propylene oxide to glycerine
  • Polyol G Phantol PL-305 (manufactured by Toho Rika Kogyo Co . , Ltd . ) polyester polyol having a hydroxyl value of 315 mg KOH/g and a viscosity of 2600 mPa»s/25°C, which is a product of the reaction between a polyhydric alcohol and a polybasic polycarboxylic acid having an aromatic ring
  • Catalyst A mineral spirits solution of lead octanoate (lead content: 20% by weight)
  • Catalyst B dipropylene glycol solution of triethylenediamine (TEDA) (TEDA content: 33% by weight)
  • Catalyst C UL-28 (manufactured by Witco Co. )
  • Catalyst D bis ( 2-dimethylaminoethyl )ether
  • Flame retardant tris ( ⁇ -chloropropyl )phosphate
  • Diluent dibutyl phthalate
  • Surfactant F348 manufactured by Shinetsu Kagaku
  • R-141b dichlorofluoroethane

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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)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé pour produire une mousse polyuréthane rigide, consistant à mélanger a) un constituant polyisocyanate avec un constituant polyol comprenant b) un mélange de polyols, c) un catalyseur et d) un agent de soufflage, puis à procéder au moussage du mélange. Le constituant polyisocyanate a) est du polyisocyanate de polyméthylènepolyphényle ou bien un produit modifié de celui-ci. Le mélange de polyols b) renferme (b-1) un polyol produit par addition d'un oxyde d'alkylène sur une amine aliphatique et (b-2) un polyol de polyéther aromatique produit à l'aide d'une amine aromatique, d'une base de Mannich possédant un noyau aromatique ou bien d'un phénol polyfonctionnel comme produit de départ. Le catalyseur (c) est au moins un catalyseur métallique et l'agent de soufflage (d) est un produit d'addition d'un composé d'amine primaire ou secondaire avec du dioxyde de carbone. Ce procédé permet une activité initiale supérieure et nécessite une faible quantité de matières premières.
PCT/JP1998/000585 1997-02-20 1998-02-13 Procede pour produire de la mousse polyurethane rigide WO1998037116A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU58800/98A AU5880098A (en) 1997-02-20 1998-02-13 Method for producing rigid polyurethane foam
JP53647898A JP3919824B2 (ja) 1997-02-20 1998-02-13 硬質ポリウレタンフォームの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/36520 1997-02-20
JP3652097 1997-02-20

Publications (1)

Publication Number Publication Date
WO1998037116A1 true WO1998037116A1 (fr) 1998-08-27

Family

ID=12472104

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/000585 WO1998037116A1 (fr) 1997-02-20 1998-02-13 Procede pour produire de la mousse polyurethane rigide

Country Status (3)

Country Link
JP (1) JP3919824B2 (fr)
AU (1) AU5880098A (fr)
WO (1) WO1998037116A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002028936A1 (fr) * 2000-10-05 2002-04-11 Huntsman International Llc Procede de fabrication de mousses de polyurethanne rigides
WO2002102866A3 (fr) * 2001-06-15 2003-05-22 Stepan Co Compositions a base de polyol de polyester phtalate et mousse de polyurethanne a pulveriser gonflee uniquement a l'eau, a haute stabilite dimensionnelle, derivee desdites compositions
EP1870425A1 (fr) * 2006-06-23 2007-12-26 Bayer MaterialScience LLC Processus de production de polyoxyalkylène contenant des polyols à partir de produits de condensation de phénol
EP1806374A4 (fr) * 2004-09-30 2011-06-22 Toho Chem Ind Co Ltd Procede de fabrication de mousse de polyurethane rigide
WO2012126916A2 (fr) 2011-03-22 2012-09-27 Basf Se Mousse de polyuréthane rigide à conductivité thermique faible et stabilité thermique élevée
WO2013030063A1 (fr) * 2011-08-26 2013-03-07 Bayer Intellectual Property Gmbh Émulsions stables et utilisation de celles-ci pour la production de mousses à base d'isocyanate
US20190016673A1 (en) * 2016-06-02 2019-01-17 Shandong University Of Technology Organic amine salt compounds having co2-donating anions and their use as foaming agent
CN109422894A (zh) * 2017-08-24 2019-03-05 山东理工大学 包含叔胺盐和丙醇胺盐的发泡剂及用于聚氨酯冰箱冰柜泡沫体材料的用途
CN109422895A (zh) * 2017-08-24 2019-03-05 山东理工大学 叔胺和醇胺碱性发泡剂和用于制备聚氨酯喷涂泡沫体材料的用途
CN116854934A (zh) * 2023-07-27 2023-10-10 四川大学 环氧卤丙烷扩链的多胺聚合物的二氧化碳加合物发泡剂

Families Citing this family (8)

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WO2005090431A1 (fr) * 2004-03-11 2005-09-29 Dow Global Technologies, Inc. Mousses de polyurethane rigides, adhesives, a forte reactivite
JP4706301B2 (ja) * 2004-03-31 2011-06-22 旭硝子株式会社 硬質発泡合成樹脂の製造方法
JP2009067995A (ja) * 2007-08-21 2009-04-02 Asahi Glass Co Ltd 硬質発泡合成樹脂の製造方法
EP2565213A4 (fr) * 2010-04-28 2013-10-16 Asahi Glass Co Ltd Procédé de production d'une résine de synthèse de type mousse rigide
JP2014125490A (ja) * 2012-12-25 2014-07-07 San Apro Kk ポリウレタン樹脂製造用の触媒組成物及び硬質ポリウレタンフォーム又は硬質ポリイソシアヌレートフォームの製造法
JP6921505B2 (ja) 2016-11-25 2021-08-18 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 連続気泡性硬質ポリウレタンフォームの製造方法
JP6921506B2 (ja) 2016-11-25 2021-08-18 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 連続気泡性硬質ポリウレタンフォームの製造方法
JP6917812B2 (ja) * 2017-07-10 2021-08-11 旭有機材株式会社 ポリウレタンフォーム用発泡性組成物及びそれを用いたポリウレタンフォームの製造法

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EP0121850A2 (fr) * 1983-04-05 1984-10-17 Bayer Ag Procédé pour la préparation d'un polyuréthane cellulaire
EP0236895A2 (fr) * 1986-03-11 1987-09-16 Bayer Ag Procédé pour préparer un polyuréthane cellulaire
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US5288766A (en) * 1992-02-28 1994-02-22 Basf Corporation Poyurea based dispersions, foams prepared therefrom, and a process for the preparation therein
US5391317A (en) * 1993-12-27 1995-02-21 The Dow Chemical Process for preparing a polyurethane foam in the presence of a hydrocarbon blowing agent
US5547998A (en) * 1995-11-01 1996-08-20 Basf Corporation Insulating rigid polyurethane foam compositions

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EP0121850A2 (fr) * 1983-04-05 1984-10-17 Bayer Ag Procédé pour la préparation d'un polyuréthane cellulaire
EP0236895A2 (fr) * 1986-03-11 1987-09-16 Bayer Ag Procédé pour préparer un polyuréthane cellulaire
US5225101A (en) * 1988-07-15 1993-07-06 Takeda Chemical Industries, Ltd. Polyol compositions for producing rigid polyurethane foams
US4980388A (en) * 1988-10-17 1990-12-25 The Dow Chemical Company Use of carbon dioxide adducts as blowing agents in cellular and microcellular polyureas
DE4201269A1 (de) * 1992-01-18 1993-07-22 Bitterfeld Wolfen Chemie Verfahren zur herstellung von flammwidrigen polyurethanschaumstoffen
US5288766A (en) * 1992-02-28 1994-02-22 Basf Corporation Poyurea based dispersions, foams prepared therefrom, and a process for the preparation therein
US5391317A (en) * 1993-12-27 1995-02-21 The Dow Chemical Process for preparing a polyurethane foam in the presence of a hydrocarbon blowing agent
US5547998A (en) * 1995-11-01 1996-08-20 Basf Corporation Insulating rigid polyurethane foam compositions

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002028936A1 (fr) * 2000-10-05 2002-04-11 Huntsman International Llc Procede de fabrication de mousses de polyurethanne rigides
WO2002102866A3 (fr) * 2001-06-15 2003-05-22 Stepan Co Compositions a base de polyol de polyester phtalate et mousse de polyurethanne a pulveriser gonflee uniquement a l'eau, a haute stabilite dimensionnelle, derivee desdites compositions
EP1806374A4 (fr) * 2004-09-30 2011-06-22 Toho Chem Ind Co Ltd Procede de fabrication de mousse de polyurethane rigide
EP1870425A1 (fr) * 2006-06-23 2007-12-26 Bayer MaterialScience LLC Processus de production de polyoxyalkylène contenant des polyols à partir de produits de condensation de phénol
US7538162B2 (en) 2006-06-23 2009-05-26 Bayer Materialscience Llc Process for the production of polyoxyalkylene containing polyols from phenol condensation products
WO2012126916A2 (fr) 2011-03-22 2012-09-27 Basf Se Mousse de polyuréthane rigide à conductivité thermique faible et stabilité thermique élevée
WO2013030063A1 (fr) * 2011-08-26 2013-03-07 Bayer Intellectual Property Gmbh Émulsions stables et utilisation de celles-ci pour la production de mousses à base d'isocyanate
US20190016673A1 (en) * 2016-06-02 2019-01-17 Shandong University Of Technology Organic amine salt compounds having co2-donating anions and their use as foaming agent
US11261153B2 (en) * 2016-06-02 2022-03-01 Shandong University Of Technology Organic amine salt compounds having CO2-donating anions and their use as foaming agent
CN109422894A (zh) * 2017-08-24 2019-03-05 山东理工大学 包含叔胺盐和丙醇胺盐的发泡剂及用于聚氨酯冰箱冰柜泡沫体材料的用途
CN109422895A (zh) * 2017-08-24 2019-03-05 山东理工大学 叔胺和醇胺碱性发泡剂和用于制备聚氨酯喷涂泡沫体材料的用途
CN109422894B (zh) * 2017-08-24 2021-04-13 山东理工大学 包含叔胺盐和丙醇胺盐的发泡剂及用于聚氨酯冰箱冰柜泡沫体材料的用途
CN109422895B (zh) * 2017-08-24 2021-04-13 山东理工大学 叔胺和醇胺碱性发泡剂和用于制备聚氨酯喷涂泡沫体材料的用途
CN116854934A (zh) * 2023-07-27 2023-10-10 四川大学 环氧卤丙烷扩链的多胺聚合物的二氧化碳加合物发泡剂

Also Published As

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AU5880098A (en) 1998-09-09
JP2001524995A (ja) 2001-12-04
JP3919824B2 (ja) 2007-05-30

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