WO2004060947A1 - Procede de production de mousse de resine synthetique - Google Patents

Procede de production de mousse de resine synthetique Download PDF

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Publication number
WO2004060947A1
WO2004060947A1 PCT/JP2003/016908 JP0316908W WO2004060947A1 WO 2004060947 A1 WO2004060947 A1 WO 2004060947A1 JP 0316908 W JP0316908 W JP 0316908W WO 2004060947 A1 WO2004060947 A1 WO 2004060947A1
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WO
WIPO (PCT)
Prior art keywords
premix
dimethoxymethane
polyol
compound
glycol
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PCT/JP2003/016908
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English (en)
Japanese (ja)
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WO2004060947A8 (fr
Inventor
Noriaki Shibata
Takashi Shibanuma
Tatsumi Tsuchiya
Yasufu Yamada
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Daikin Industries, Ltd.
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Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to AU2003296147A priority Critical patent/AU2003296147A1/en
Publication of WO2004060947A1 publication Critical patent/WO2004060947A1/fr
Publication of WO2004060947A8 publication Critical patent/WO2004060947A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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 synthetic resin foam, a foaming agent and a premix.
  • CFC-11 trichlorofluoromethane
  • 1,1-dichloro-11-fluoroethane (HCFC-141b) is used as a substitute for CFC-11 as a chlorofluorocarbon having a small effect on the ozone layer.
  • JP-A-2-29440 and JP-A-2-235982 disclose a method for producing a foam using a fluorinated hydrocarbon that does not contain chlorine and has no risk of destroying the ozone layer. Te, ru. Also, Japanese Patent Application Laid-Open No. 5-239251 discloses 1,1,1,3,3-pentafunolelov. Mouth bread (HFC-245fe) is described as being used as a blowing agent for the production of plastic foam.
  • HFC-245fa is a non-flammable compound with a boiling point of 15 ° C and is considered to have no risk of ozone layer breakage because it is a fluorinated hydrocarbon containing hydrogen atoms. Furthermore, HFC-245fa has attracted attention as a very promising candidate for a blowing agent to replace HCFC-141b because its boiling point is close to that of CFC-11 and HCFC-141b, and its force is nonflammable. Although the boiling point (15 ° C) of HFC-245fa is within the allowable range, it is slightly lower than that of CFC-11 (boiling point 24 ° C) and HCFC-141b (boiling point 32 ° C). The rapid evaporation makes foam production difficult.
  • a premix containing HFC-245fa and a polyol may cause phase separation.
  • the boiling point of the blowing agent is low, or the solubility in the polyol is low, in the case where the polyol is mixed with the isocyanate compound to produce a foam, poor mixing and residual unreacted components may occur.
  • coarse bubbles called “voids” are likely to occur, and as a result, the strength and thermal conductivity required for the rigid urethane foam are deteriorated.
  • HFC-245fa itself or a mixture with a foam material (particularly a premix that is a mixture with a polyol) has a high pressure and a high vapor pressure depending on weather conditions, and is difficult to handle. There is also a problem that the loss of the foaming agent increases in the open system state. In addition, containers that have unprecedented pressure resistance will be required for transportation and storage.
  • a main object of the present invention is to provide a premix containing the foaming agent and a method for producing a synthetic resin foam using the foaming agent.
  • the foaming agent comprises:
  • Glycol compound, fluorine-containing surfactant and amide compound power At least one compound selected
  • a method for producing a synthetic resin foam which is a mixture containing: 2.
  • the ratio power of 1,1-dimethoxymethane is less than 50% by weight based on the sum of 1,1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane. the method of.
  • a premix containing a polyol and a foaming agent having a step of preparing a premix containing a polyol and a foaming agent, wherein the total vapor pressure of the obtained premix is 1,1-dimethoxymethane and glycolide, a fluorine-containing surfactant and A premix containing the same components as the above premix except that it does not contain at least one compound selected from the group consisting of amide compounds, and the 1,1,1,3,3-pentaful
  • the vapor pressure of the premix is the same as the total molar ratio of 1,1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane to the polyol in the premix.
  • the proportion of 1,1-dimethoxymethane is 50 weight based on the sum of 1,1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane. /. 5.
  • the blowing agent according to the above item 4 which is less than the above.
  • Glycol compound, fluorine-containing surfactant and amide compound power At least one compound selected
  • a premix which is a mixture containing
  • the total vapor pressure of the premix does not include 1,1-dimethoxymethane, glycolic compounds, fluorine-containing surfactants, and amide compounds.
  • a premix containing the same components as the premix, wherein the molar ratio of 1,1,1,3,3-pentafunolelopropane to the polyol is 1,1,1 to the polyol of the premix.
  • the present invention relates to at least one selected from the group consisting of 1,1,1,3,3-pentafluoropropane, 1,1-dimethoxymethane, a glycol compound, a fluorine-containing surfactant and an amide compound.
  • the present invention relates to a foaming agent for producing a synthetic resin foam containing one kind of compound.
  • the foaming agent of the present invention contains one or more compounds selected from the group consisting of glycol compounds, fluorine-containing surfactants and amide compounds.
  • the resulting mixture may be referred to as a "mixed foaming agent".
  • the present invention provides a premix containing a blowing agent and a polyol, wherein the blowing agent comprises (a) l, 1,1,3,3-pentafluoropropane, (b) l, and 1-dimethoxymethane.
  • the present invention relates to a premix which is a mixture containing a glycol compound, a fluorine-containing surfactant, and at least one compound selected from the group consisting of amide compounds.
  • the premix may contain a foaming catalyst, a stabilizer, a foam stabilizer, a flame retardant, and the like, in addition to the foaming agent and the polyol.
  • the present invention relates to a method for producing a synthetic resin foam by reacting a polyol and a polyisocyanate compound in the presence of a foaming agent, wherein (a) l, 1, 1, 3 At least one compound selected from the group consisting of 1,3-pentafluoropropane (HFC-245fa), (b) l, 1-dimethoxymethane and (c) glycol compounds, fluorine-containing surfactants and amide compounds
  • a foaming agent, a polyol and the like may be mixed in advance to form a premix.
  • 1,1-Dimethoxymethane used in the present invention can itself be a blowing agent. Therefore, the addition amount of the blowing agent of the present invention can be substantially the same as the addition amount when HFC-245fa is used alone as the blowing agent. That is, the ratio of HFC-245fa in the foaming agent can be reduced, and the amount of HFC-245fa scattered in the premixing power can be reduced. Also, when actually foamed, there is no concern that 1,1-dimethoxymethane itself may act as a foaming agent and remain as a condensate in the foam.
  • glycolic compound used in the present invention examples include an alkylene glycol such as an ethylene glycol compound, a propylene glycol compound, and a butylene glycol compound.
  • the alkylene glycol generally has an alkylene group having about 2 to 4 carbon atoms, and preferably has an alkylene group having about 2 to 3 carbon atoms.
  • Examples of the ethylene glycol compound include compounds represented by the following formulas (A) to (C).
  • ethylene glycol compound represented by the formula (A) include, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol alcohol monoethyl ether, ethylene glycol methyl ether ether, and the like.
  • ethylene glycol compound represented by the formula (B) include, for example, ethylene glycol monoformate, ethylene glycol diformate, and diethylene glycol monoformate. 2003/016908
  • diethylene glycol diformate triethylene glycol monoformate, triethylene glycol diformate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycolone monoacetate, diethylene glycol diacetate, triethylene glycol monoacetate, triethylene glycol monoacetate
  • Examples include ethylene glycol diacetate, ethylene glycol monopropionate, ethylene glycol dipropionate, diethylene glycol monopropionate, diethylene glycol dipropionate, triethylene glycol monopropionate, and triethylene glycol dipropionate.
  • ethylene glycol compound represented by the formula (C) include, for example, ethylene glycol methinoleate enolefonoremate, ethylene glycol enoletin oleatenolefonolemate, and ethylene glycol propinole ethere.
  • Examples of the ethylenedalcol-based compound include a diether compound in which a and c are 1 or more in Formula (A), a diester compound in which d and f are 1 or more in Formula (B), and k and i in Formula (C). Is preferably 1 or more.
  • ethylene glycol diacetate ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol mono n-butyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol olenoethyl ether acetate, diethylene glycol butyl ether acetate
  • Preferred examples of the compound include diethylene glycol dimethinole ether, diethylene glycol getyl ether, diethylene glycol di-t-butyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
  • ethylene glycol compound examples include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monopropyl n-propyl ether, ethylene glycol mono- Hexinoleatenole, diethyleneglyconele monoethynoleatene diethyleneglycol monomethynorateether, diethyleneglyconelemonoisopropylatene, diethyleneglycolonele n-propinoleateneolete, diethyleneglyconele t-ptynoleatele, diethyleneglycolatene -Butyl ether, diethylene glycolone-n-hexinolete, triethyleneglyconelemonoethyl ether, Triethylene glycol monomethyl E one ether such be suitably Yore can Rukoto.
  • propylene glycol compound examples include propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl butyl ether, tripropylene glycol monomethyl ether tripropylene glycol monobutyl ether, 2-methoxy-1-propanol, tripropylene glycol dimethyl ether, propylene Glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, tri Compounds such as Russia propylene glycol mono ethyl ether.
  • propylene glycol compound propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate. 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate and the like are preferred.
  • glycolide conjugates include, for example, butylene cholesteric compounds such as butylene glycol diacetate.
  • glycol compound a compound having high compatibility with HFC-245fa and / or polyol is preferable. For example, after a premix containing HFC-245fa, 1,1-dimethoxymethane, glycol compound, polyol, etc. is shaken for about 10 minutes, phase separation after standing at about 0-25 ° C for about 5 hours Shiny glycol compounds are preferred. Due to the compatibility with HFC-245fa and / or polyol, the compounds having specific names described above can be preferably used.
  • the glycolic compound having higher compatibility with HFC-245fa and / or polyol reduces the loss (scattering amount) of the blowing agent when the premix containing the polyol and the blowing agent is placed in an open system. be able to. Also, the vapor pressure of the premix can be reduced.
  • the boiling point of the glycolide conjugate used in the present invention is not particularly limited, but is usually about 85 to 300, preferably 120 to 250. It is about C.
  • fluorine-containing surfactant used in the present invention for example, compounds represented by the following formulas (D) to (F) can be exemplified.
  • R represents H or a lower alkyl group
  • R ° represents H or CH 3 ,
  • R 1 represents F-containing alkyl or a substituted product thereof
  • n is usually about 3 to 30, preferably about 3 to 10.
  • a is preferably 1 to 4
  • b ' is preferably 1 to 4.
  • R represents a hydrogen atom or a lower alkyl group. Lower alkynole denoted by R The carbon number of the group is usually about 1 to 4, preferably about 1 to 2.
  • m is usually about 3 to 30, preferably about 3 to 10.
  • c ' is preferably 1-4.
  • d' is preferably 1-4.
  • n is usually about 1 to 3, preferably about 1 to 2.
  • m is usually about 410 to 15, preferably about 4 to 10.
  • R 1 represents F-containing alkyl or a substituted product thereof.
  • the carbon number of the F-containing alkyl represented by R 1 is generally about 10 to 20, preferably about 12 to 18.
  • the number of fluorine atoms of the F-containing alkyl represented by R 1 is usually about 10 to 40, preferably about 12 to 34.
  • R 2 represents H or a lower alkyl group.
  • the carbon number of the lower alkyl group represented by R 2 is usually about 1 to 2.
  • Examples of the compound represented by the general formula (F) include, for example, UNIDYNE DS-401 and DS-403 manufactured by Daikin Industries, Ltd .; and Zonyl FSO and FSN manufactured by DuPont.
  • the fluorine-containing surfactant a compound having high compatibility with HFC-245fa and / or polyol is preferable. For example, after shaking a premix containing HFC-245fa, 1,1-dimethoxymethane, a fluorine-containing surfactant and a polyol for about 10 minutes, and then allowing it to stand at about 0 to 25 ° C for about 520 hours, No phase separation, and fluorine-containing surfactants are preferred.
  • the boiling point of the fluorine-containing surfactant used in the present invention is not particularly limited, but is usually about 25 to 100 ° C, preferably about 120 to 250 ° C.
  • Examples of the amide compound used in the present invention include the compounds represented by the following formulas (G) and (H).
  • Equation (G) R ⁇ ONR'R 3
  • R 1 represents a hydrogen atom, a lower alkyl group or a phenyl group
  • R 2 and R 3 are the same or different and represent a hydrogen atom or a lower alkyl group.
  • R 1 and R 2 may form a heterocycle with the carbonyl carbon atom to which R 1 is bonded and the nitrogen atom to which R 2 is bonded.
  • RR ⁇ R 6 and R 7 are the same or different and represent a hydrogen atom or a lower alkyl group.
  • R 4 and R 6 may form a heterocyclic ring with the nitrogen atom to which R 6 is bonded, the nitrogen atom to which R 4 is bonded, and a carbonyl carbon.
  • the number of carbon atoms of the lower alkyl group represented by RR 2 or is usually about! -2, preferably a methyl group.
  • R 1 is a hydrogen atom, a lower alkyl group or a phenyl group, preferably a hydrogen atom or a methyl group.
  • R 2 is a hydrogen atom or a lower alkyl group, preferably a lower alkyl group, particularly preferably a methyl group.
  • R 3 is a hydrogen atom or a lower alkyl group, preferably a lower alkyl group, and particularly preferably a methyl group.
  • R 1 and R 2 may form a heterocyclic ring with the carbonyl carbon atom to which R 1 is bonded and the nitrogen atom to which is bonded. That is, the compound represented by the formula (G) may be a cyclic amide compound. Examples of the heterocycle include a 5-membered ring. Examples of the amide compound represented by the formula (G) include N, N-dimethylformamide, N, N-dimethylacetamide, ⁇ , ⁇ -dimethylpropionamide, ⁇ -methylformamide, ⁇ -methylacetamide ⁇ - Examples of the methylamidopropionamide, ⁇ -methylbenzamide, etc.
  • Examples of the cyclic amido conjugate represented by the formula (G) include ⁇ -methylpyrrolidone, etc.
  • Formula (G) As the amide compound represented by, R, R-dimethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ , ⁇ are particularly preferred for compounds in which both R 2 and R 3 are lower alkyl go. -Dimethylpropionamide, ⁇ -methylpyrrolidone and the like are preferred.
  • the lower alkyl group represented by R 4 , R 5 , R 6 or R 7 usually has about 1 to 2 carbon atoms, and is preferably a methyl group.
  • R 4 and R 6 may form a heterocycle with the nitrogen atom to which R 6 is bonded, the nitrogen atom to which R 4 is bonded, and a carbon carbon. That is, the compound of the formula (H) may be a cyclic compound. Examples of the heterocycle include a 5-membered ring.
  • Examples of the amide compound represented by the formula (H) include, for example, tetramethylurea.
  • Examples of the cyclic conjugate represented by the formula (H) include 1,3-dimethylimidazolidinone.
  • At least one selected from the group consisting of (a) HFC-245fa and (b) l, 1-dimethoxymethane and (c) glycolide conjugate, a fluorine-containing surfactant and an amide compound in a foaming agent can be arbitrarily selected according to the application, the composition of the synthetic resin foam raw material, and the like.
  • the total vapor pressure of the premix ⁇ (a) + (b) + (c) + (d) ⁇ containing the polyol, etc. is (b) 1,1-dimethoxymethane, (c) ) Premix ((a) + (b) + (c) + (d) except that it does not contain at least one compound selected from the group consisting of glyconole compounds, fluorine-containing surfactants and amide compounds.
  • Vapor pressure of the premix which is equal to the total molar ratio of HFC-245fa and 1,1-dimethoxymethane to the total amount of ⁇ ((a) + (b) moles) Z (d) moles ⁇ 100%
  • the vapor pressure of the premix consisting of «a) + (b) + (c) + (d) ⁇ is usually about 96% or less, preferably about 70-94%.
  • the composition ratio of each component is set so as to be about 70 to 90%.
  • the value at any temperature of about 20 to 40 ° C is usually used, and the value at the same temperature is compared.
  • premix I consisting of (a) to (d) and premix II consisting of (a) and (d) (not including (b) and (c)). I do.
  • premix I content (mol)
  • the premix I containing (a) to (d) above It is preferable to set the composition ratio of each component so that the vapor pressure S is usually about 96% or less, preferably about 70 to 94% or less, more preferably about 70 to 90 ° / o or less.
  • the total molar ratio of (a) HFC-245fa and (b) 1,1-dimethoxymethane to (d) polyol in the premix I of the present invention is (A mole + B mole) / D mole
  • the molar ratio (A, / D ') of HFC-245fa to polyol in the premix II to be compared should be the same.
  • the types of the components contained in the premix II to be compared are as follows: from the premix I of the present invention, (c) a glycol compound and / or a fluorine-containing surfactant and / or an amide compound and (b) , L Dimethoxymethane is the same except that.
  • the premix of the present invention contains components such as a foaming catalyst, a stabilizer, a foam stabilizer, and a flame retardant
  • the premix to be compared also contains the same amount of the components. I do.
  • the vapor pressure ratio was measured based on (a) 100 parts by weight of polyol, (a) HFC-245fa, (b) 1,1-dimethoxymethane, and (c) glycol aldehyde compound and / or fluorine. Total amount of surfactant and / or amide compound contained
  • the boiling point of the premix containing the blowing agent of the present invention, polyol, etc. (the temperature at which the vapor pressure of the premix becomes 1 atm (about O.lMPa)) is usually about 15 ° C or more, preferably about 17 to 35 ° C. And more preferably about 18-30 ° C.
  • the mixing ratio of HFC-245fa, 1,1-dimethoxymethane, dalicol compound, fluorine-containing surfactant, amide compound and the like may be set so that the boiling point of the premix falls within the above range.
  • the vapor pressure of the premix containing the blowing agent and the polyol of the present invention is not particularly limited, but is preferably about 1 atm or less at 17 ° C, more preferably about 1 atm or less at 20 ° C, and still more preferably 24 ° C or less. It is about 1 atmosphere or less. At least one selected from the group consisting of HFC-245fa, 1,1-dimethoxymethane and glycoly conjugate, a fluorine-containing surfactant and an amide compound in such a ratio that the vapor pressure of the premix is in the above range. It is preferable to prepare one compound and mix it with a polyol or the like.
  • the mixing ratio of HFC-245fa, 1,1-dimethoxymethane, glycolide conjugate and / or fluorine-containing surfactant and / or amide compound in the foaming agent of the present invention depends on the application, the composition of the synthetic resin foam raw material.
  • the ratio can be arbitrarily selected according to the ratio, etc., but the boiling point of the blowing agent (temperature at which the vapor pressure reaches 1 atm (about O.lMPa)) is preferably about 17 to 35 ° C. A ratio of about C is more preferable.
  • the total amount of HFC-245fa and 1,1-dimethoxymethane is HFC-245fa, 1,1-dimethoxymethane and a glycol compound and / or a fluorine-containing surfactant and / or an amide-based compound. It is usually about 50% by weight or more, preferably about 65 to 99% by weight, more preferably about 75 to 98% by weight, based on the total amount of the compound.
  • the mixing ratio of HFC-245fa and 1,1-dimethoxymethane in the blowing agent of the present invention is such that when the total of HFC-245fa and 1,1-dimethoxymethane is 100% by weight, 1,1-dimethoxymethane is Usually about less than 50% by weight, preferably about 9 to 50% by weight, more preferably 13 to 45% by weight. / 0 , particularly preferably about 16 to 41% by weight.
  • the total amount of the glyconole compound and / or the fluorine-containing surfactant and / or the amide compound in the foaming agent of the present invention is usually based on 100 parts by weight of the total of HFC-245fa and 1,1-dimethoxymethane. It is about 1 to 49 parts by weight, preferably about 1 to 35 parts by weight, particularly preferably about 2 to 25 parts by weight. .
  • the blowing agent of the present invention may contain another blowing agent. That is, the mixed foaming agent may be used alone or in combination with another foaming agent.
  • the foaming agent that can be used in combination include an inert gas such as air, nitrogen, and carbon dioxide; and a low-boiling halogenated hydrocarbon.
  • Examples of low boiling halogenidani hydrocarbons include 1,1,1,2-tetrafluoroethane and 1,1,1,2,3,3,3-hexafluoropropane.
  • the low boiling point halogenated hydrocarbon is not particularly limited, and its boiling point is usually about ⁇ 30 to 0 ° C. at 1 atm (about 0.1 MPa).
  • blowing agents The amount of addition is not particularly limited as long as the effects of the present invention can be obtained, but the total power of HFC-245fa and 1,1-dimethoxymethane in all the blowing agents is usually about 20% by weight or more, preferably. Is about 40% by weight or more, more preferably about 60 to 95% by weight. These foaming agents are often used by being mixed with a premix at the time of foaming.
  • the blowing agent of the present invention may contain water. That is, the mixed foaming agent can be used in combination with water.
  • the proportion of water can be added to such an extent that water is less than 20% by weight based on the sum of HFC-245fa, 1,1-dimethoxymethane and water. By setting it in this range, a highly heat-insulating foam can be obtained more reliably.
  • the foaming agent of the present invention may optionally contain a known decomposition inhibitor.
  • a decomposition inhibitor include nitro compounds such as nitrobenzene and nitromethane; aromatic hydrocarbons such as ⁇ -methylstyrene and ⁇ -isopropenyltoluene; and aliphatic unsaturated hydrocarbons such as isoprene and 2,3-dimethylbutadiene. Hydrogen; epoxy compounds such as 1,2-butylene oxide and epichlorohydrin; phenol compounds such as ⁇ -t-butyl catechol and 2,6-di-t-butyl-1-p-tarezol; Such acetic acid ester compounds can be exemplified.
  • the mixing ratio of the decomposition inhibitor can be appropriately set according to the type of the inhibitor, etc. Usually, about 0.05 to 5 parts by weight with respect to 100 parts by weight of the total of HFC-245fa and 1,1-dimethoxymethane. is there.
  • the decomposition inhibitor may be previously mixed with the foaming agent used in the present invention, or may be separately added at the time of foaming.
  • the amount of the foaming agent of the present invention can be appropriately set according to the type of the glycol compound, the fluorine-containing surfactant and the amide compound used.
  • the total of HFC-245fa and 1,1-dimethoxymethane is usually about 1 to 70 parts by weight, preferably about 10 to 60 parts by weight, more preferably about 20 to 55 parts by weight, based on 100 parts by weight of the polyol.
  • a polyol and a polyisocyanate conjugate are reacted in the presence of a foaming agent to produce a synthetic resin foam.
  • a foaming agent for producing a synthetic resin foam.
  • the synthetic resin foam obtained by the method of the present invention include a polyurethane foam and a polyisocyanurate foam.
  • Raw materials other than foaming agents such as polyols and polyisocyanate compounds are not particularly limited, and known materials can be used. The following can be exemplified as these.
  • the polyisocyanate toy is, for example, "Keiji Iwata, polyurethane resin handpouch 71-98 Page, Nikkan Kogyo Shimbun, Inc., any of organic isocyanates such as aliphatic, alicyclic, and aromatic compounds can be used.
  • the most commonly used polyisocyanates include, for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), etc.
  • 2,4-TDI 2,4-tolylene diisocyanate
  • 2,6-TDI 2,6-tolylene diisocyanate
  • Mainly a mixture in which the weight ratio of 2,4-TDI / 2,6-TDI is about 80Z20 or about 65/35 is used, and can be suitably used in the present invention.
  • polyphenylpolymethylene polyisocyanate obtained by phosgenating a condensate of aniline and formaldehyde is
  • polyether polyols for example, polyether polyols, polyester polyols and the like described in "Keiji Iwata, Polyurethane Resin Handbook, pp. 99-117, Nikkan Kogyo Shimbun" can be used.
  • the polyether polyol can be obtained, for example, by reacting an initiator having an active hydrogen atom with an alkylene oxide.
  • an initiator for example, ethylene glycol, trimethylolpropane, glycerin, triethanolanolamine, ethylenediamine, methyldanorecodit, tolylenediamine, sorbitol, sucrose, etc. are used, and as an alkylene oxide, ethylene oxide, propylene oxide, or the like is used.
  • those having a functional group number of about 2 to 8 and a hydroxyl value of about 300 to 800 mgKOH / g obtained by reacting both can be suitably used.
  • polyester polyols examples include condensed polyester polyols obtained by dehydration condensation of adipic acid and dalicol or toluene, rataton-based polyesters obtained by ring-opening polymerization of force prolactam, polycarbonate diols, aromatic polyester polyols, and the like. Among them, those having a functional group number of about 2 to 4 and a hydroxyl value of about 250 to 500 mgKOH / g can be suitably used.
  • the mixing ratio of the polyol and the polyisocyanate compound can be determined as appropriate.
  • the active hydrogen force in the polyol is usually 1 to 3 equivalents. It mixes so that it may become a degree.
  • a catalyst in the reaction between the polyol and the polyisocyanate is used.
  • a known catalyst such as a tertiary amine, an organometallic compound, or a mixture thereof can be used.
  • the amount of the catalyst to be added can be appropriately set according to the type of the catalyst, etc., but it is usually from 01 to: LO parts by weight, preferably per 100 parts by weight of the polyol. Is about 0.1 to 5 parts by weight.
  • ⁇ , ⁇ , N ′, N′-tetramethylhexane-1,1,6-diamine can be exemplified as diamines.
  • the organic metal compound include, for example, starnazotoate, dibutyltin dilaurate, dibutyltin diacetate, and the like.
  • additives known in the art for example, a foam stabilizer
  • the foam stabilizer include silicone-based and fluorine-containing surfactants, and more specifically, surfactants based on polysiloxane-polyalkylene block copolymer, methylpolysiloxane, and the like are used. be able to.
  • the above-mentioned fluorinated surfactant include perfluoroalkylethylene oxide adduct, perfluoroalkyl sulfonate, perfluoroalkyl group-containing oligomer and the like.
  • the addition amount of the foam stabilizer is usually about 0.1 to 10 parts by weight based on 100 parts by weight of a polyol which can be appropriately set according to the kind of the foam stabilizer.
  • the production method of the present invention is not particularly limited as long as the foaming agent of the present invention is used in a method of producing a synthetic resin foam by reacting a polyol and a polyisocyanate compound in the presence of a blowing agent. .
  • a foaming agent, a polyol and the like may be mixed in advance to form a premix.
  • the manufacturing conditions may be in accordance with a conventional method.
  • any apparatus may be used as long as it can uniformly mix the raw materials. More specifically, by using a mixer, a foaming machine, etc., the raw materials such as polyol, polyisocyanate conjugate, foaming agent, catalyst, and other additives are mixed well and molded. The desired foam can be obtained.
  • the foaming agent and other additives are preliminarily dissolved in the polyol component and used as a premix, a uniform foam can be easily obtained.
  • the foaming agent and other additives are not limited to this, but may be added to the polyisocyanate compound in advance. It can also be dissolved.
  • a blowing agent having a low vapor pressure can be obtained while maintaining the performance of HFC-245fa as a blowing agent. That is, according to the present invention, the vapor pressure of the premix is HFC-245fa A synthetic resin foam having the same heat insulating properties and mechanical strength as when HFC-245fa is used alone can be obtained, though the level is lower than when HFC-245fa is used alone as a foaming agent. Since the blowing agent of the present invention does not contain chlorine, the ability to destroy the ozone layer is substantially zero. Further, in the present invention, a low-boiling halogenated hydrocarbon having a risk of destruction of the ozone layer may be used, but even in this case, the danger is higher than when the hydrocarbon is used alone. Can be greatly reduced.
  • the foaming agent of the present invention has an appropriate boiling point such that a conventional one can be used as a container for transportation or storage, it is not necessary to use a container having particularly high pressure resistance. Further, even in the case of an open system, loss due to vaporization of the premixing foaming agent can be suppressed.
  • Polyol A Aromatic polyester polyol with hydroxyl value of 300mgKOH / g
  • Polyol B Aromatic polyether polyol with hydroxyl value of 440mgKOH / g
  • a premix was prepared by mixing 100 parts by weight of polyol A and 35 parts by weight of HFC-245fa (0.26 mol AlOOg). The vapor pressure at 30 ° C. of the obtained premix was measured. Table 1 shows the results.
  • HFC-245fa, 1,1-dimethoxymethane, and diethylene glycol ethyl ether acetate were mixed at the ratio shown in Table 1 to prepare a foaming agent.
  • a premix was prepared by mixing the obtained blowing agent and 100 parts by weight of polyol A. At this time, the mixing ratio of each mixed blowing agent to the polyol was determined by the total molar amount of HFC-245fa and 1,1-dimethoxymethane in the mixed blowing agent. / Polyol A 100 g).
  • Example 1 A foaming agent was prepared in the same manner as in Example 1 except that in Example 1, ethylene glycol dimethyl ether was used instead of diethylene glycolonoethenolate / rareacetate. Using the obtained blowing agent, a premix was prepared in the same manner as in Example 1, and the vapor pressure of the premix was measured by using the same method as in Example 1.
  • the vapor pressure of the premix at 30 ° C. was 0.129 MPa, which was 16% lower than the vapor pressure of the premix of Comparative Example 1.
  • a premix was prepared by mixing the required amount for 70 seconds and the blowing agent shown in Table 5 and stirring vigorously.
  • the obtained premix was mixed with 112 parts by weight of crude polymethylene polyphenylisocyanate (manufactured by Nippon Polyurethane Industry, MR-100), and vigorously stirred to foam to obtain a rigid polyurethane foam.
  • the amount of the foaming agent was adjusted such that the core density of the foam was 25 ⁇ lkg / in 3 .
  • Table 2 shows the measurement results of the physical properties of the obtained foam after aging for one week at -20 ° C or room temperature (20 to 25 ° C) one day after foaming. In addition, the evaluation method of the foam conformed to JIS A 9514. Table 2
  • the amount of the blowing agent in the table is shown in parts by weight based on 100 parts by weight of the polyol.

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  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Emergency Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Cette invention concerne un procédé de production de mousse de résine synthétique, lequel procédé consiste à faire réagir un polyol avec un composé polyisocyanate en présence d'un agent gonflant. Cette invention se caractérise en ce que l'agent gonflant est un mélange composé (a) de 1,1,1,3,3-pentafluoropropane, (b) de 1,1-diméthoxyméthane et (c) d'au moins un composé sélectionné dans le groupe renfermant des composés glycol, des tensioactifs renfermant du fluor ainsi que des composés amide.
PCT/JP2003/016908 2002-12-27 2003-12-26 Procede de production de mousse de resine synthetique WO2004060947A1 (fr)

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JPH05505205A (ja) * 1990-03-23 1993-08-05 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 阻止剤を含有する重合体フォーム
JPH07102106A (ja) * 1993-08-11 1995-04-18 Matsushita Electric Ind Co Ltd 断熱発泡体
JPH07133368A (ja) * 1993-11-10 1995-05-23 Toho Chem Ind Co Ltd 硬質ポリウレタンフォームの製造方法
JPH10226718A (ja) * 1997-02-17 1998-08-25 Daikin Ind Ltd 硬質ポリウレタンフォームの製造法
JPH11343326A (ja) * 1998-04-20 1999-12-14 Basf Ag 低減された熱伝導性を有するポリウレタン硬質発泡体の製造方法およびその用途
WO2001068735A1 (fr) * 2000-03-16 2001-09-20 Alliedsignal Inc. Mousse hydrofluorocarbonee expansee amelioree et procede de preparation correspondant
JP2003212949A (ja) * 2001-09-20 2003-07-30 Central Glass Co Ltd 硬質ポリウレタンフォームまたはポリイソシアヌレートフォームの調製用のプレミックス、該フォームの製造方法および該フォーム
JP2004002642A (ja) * 2002-04-25 2004-01-08 Daikin Ind Ltd 合成樹脂発泡体の製造方法
JP2004002643A (ja) * 2002-04-25 2004-01-08 Daikin Ind Ltd 合成樹脂発泡体の製造方法
JP2004051671A (ja) * 2002-07-16 2004-02-19 Daikin Ind Ltd 低い蒸気圧を有する発泡剤、プレミックスおよび発泡体の製造法
JP2004083847A (ja) * 2002-06-28 2004-03-18 Central Glass Co Ltd 発泡剤組成物、硬質ポリウレタンフォームまたはポリイソシアヌレートの調製用のプレミックスおよび該フォームの製造方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05505205A (ja) * 1990-03-23 1993-08-05 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 阻止剤を含有する重合体フォーム
JPH07102106A (ja) * 1993-08-11 1995-04-18 Matsushita Electric Ind Co Ltd 断熱発泡体
JPH07133368A (ja) * 1993-11-10 1995-05-23 Toho Chem Ind Co Ltd 硬質ポリウレタンフォームの製造方法
JPH10226718A (ja) * 1997-02-17 1998-08-25 Daikin Ind Ltd 硬質ポリウレタンフォームの製造法
JPH11343326A (ja) * 1998-04-20 1999-12-14 Basf Ag 低減された熱伝導性を有するポリウレタン硬質発泡体の製造方法およびその用途
WO2001068735A1 (fr) * 2000-03-16 2001-09-20 Alliedsignal Inc. Mousse hydrofluorocarbonee expansee amelioree et procede de preparation correspondant
JP2003212949A (ja) * 2001-09-20 2003-07-30 Central Glass Co Ltd 硬質ポリウレタンフォームまたはポリイソシアヌレートフォームの調製用のプレミックス、該フォームの製造方法および該フォーム
JP2004002642A (ja) * 2002-04-25 2004-01-08 Daikin Ind Ltd 合成樹脂発泡体の製造方法
JP2004002643A (ja) * 2002-04-25 2004-01-08 Daikin Ind Ltd 合成樹脂発泡体の製造方法
JP2004083847A (ja) * 2002-06-28 2004-03-18 Central Glass Co Ltd 発泡剤組成物、硬質ポリウレタンフォームまたはポリイソシアヌレートの調製用のプレミックスおよび該フォームの製造方法
JP2004051671A (ja) * 2002-07-16 2004-02-19 Daikin Ind Ltd 低い蒸気圧を有する発泡剤、プレミックスおよび発泡体の製造法

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