WO2014030654A1 - Composition mélangée de matière première pour la fabrication de mousse de polyuréthane et un procédé de fabrication de mousse de polyuréthane ou de mousse de polyuréthane modifiée par isocyanurate - Google Patents

Composition mélangée de matière première pour la fabrication de mousse de polyuréthane et un procédé de fabrication de mousse de polyuréthane ou de mousse de polyuréthane modifiée par isocyanurate Download PDF

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WO2014030654A1
WO2014030654A1 PCT/JP2013/072213 JP2013072213W WO2014030654A1 WO 2014030654 A1 WO2014030654 A1 WO 2014030654A1 JP 2013072213 W JP2013072213 W JP 2013072213W WO 2014030654 A1 WO2014030654 A1 WO 2014030654A1
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acid
raw material
polyurethane foam
dimethylamino
composition according
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PCT/JP2013/072213
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English (en)
Japanese (ja)
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徳本　勝美
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東ソー株式会社
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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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/324—Polyamines aromatic containing only one aromatic ring
    • 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
    • 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
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • 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
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a raw material blend composition used in producing a polyurethane foam and a method for producing a polyurethane foam or an isocyanurate-modified polyurethane foam.
  • a polyurethane resin is generally produced by reacting a polyol and an organic polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a crosslinking agent, and the like.
  • a catalyst In the production of polyurethane resins, it is known to use many metal compounds and tertiary amine compounds as catalysts. These catalysts are widely used industrially either alone or in combination of two or more.
  • polyurethane foam the formation reaction of polyurethane foam and isocyanurate-modified polyurethane foam (hereinafter collectively referred to as “polyurethane foam”) is a urethane group formation reaction (resinification reaction) mainly by reaction of polyol and isocyanate. It consists of two reactions: urea group formation by the reaction of isocyanate with water and carbon dioxide gas generation reaction (foaming reaction).
  • the catalyst has a great influence not only on the reaction rate but also on the curing rate of the polyurethane foam, the moldability, the low density of the polyurethane foam and the physical properties.
  • fluorocarbons have been conventionally used as one of the typical physical blowing agents for polyurethane foam. Especially when used in rigid polyurethane foams, fluorocarbons not only function as blowing agents due to their volatility, but are also enclosed in the closed cell structure of rigid polyurethane foams, contributing to the low thermal conductivity characteristics of rigid polyurethane foams To do.
  • chlorofluorocarbons such as trichloromonofluoromethane and dichlorodifluoromethane
  • HCFCs hydrochlorofluorocarbons
  • hydrofluorocarbons that do not destroy the ozone layer or have a small ozone layer destruction (tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1, Many so-called HFCs such as 1,3,3-pentafluorobutane are used.
  • hydrohaloolefins including hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HFCOs) have been newly proposed as blowing agents having a lower global warming potential than the hydrofluorocarbons described above.
  • HFOs hydrofluoroolefins
  • HFCOs hydrochlorofluoroolefins
  • Examples of such HFOs include trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), 1,1,1,4,4,4-hexafluorobut-2-ene. (HFO-1336mzz) is known.
  • HFCOs for example, 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd) is known.
  • each raw material component of the polyurethane foam into a state of a raw material mixture mixed beforehand.
  • two raw material mixture components are adjusted.
  • a 1st component is comprised from the raw material compatible with polyisocyanate and arbitrary isocyanate.
  • the other second component is composed of a polyol or mixture of polyols, a surfactant, a catalyst, a blowing agent, and other isocyanate-reactive and non-reactive components.
  • a good polyurethane foam is usually obtained by mixing the first component and the second component by a method such as manual stirring or mechanical stirring to cause a foaming reaction.
  • hydrohaloolefins including trans HFO-1234ze, HFCO-1233zd, etc.
  • react with amine catalysts commonly used in polyurethane foams resulting in partial decomposition of hydrohaloolefins Has the disadvantage of shortening the shelf life.
  • the sterically hindered amine described in Patent Document 1 has various problems.
  • volatilization of the amine component becomes remarkable in the foaming process, and the working environment is significantly deteriorated. For example, when ventilation in the foaming process is insufficient, there is a problem that causes itching of the eyes.
  • Furthermore, as a result of the use in large quantities there have been a problem of leaving a bad odor in the polyurethane foam product itself and a problem of scattering from the product to the outside and contaminating other materials.
  • the present invention has been made in view of the above-mentioned problems, and an object thereof is to improve the storage stability of a raw material blend composition for producing polyurethane foam containing hydrohaloolefins as a foaming agent. Furthermore, it is providing the manufacturing method of the polyurethane foam using this raw material compounding composition.
  • a raw material blend composition containing a combination of a specific tertiary amine and an acid is an amine catalyst composition.
  • the inventors have found that the decomposition is remarkably improved and the storage stability is increased, and the present invention has been completed. That is, this invention relates to the raw material compounding composition for polyurethane foam manufacture as shown below.
  • a raw material blend composition for producing polyurethane foam comprising an amine catalyst composition (A) containing tertiary amines and acids, a blowing agent (B) containing hydrohaloolefins, and a polyol (C) .
  • the hydrohaloolefin used in the blowing agent (B) is at least selected from the group consisting of trifluoropropene, tetrafluoropropene, pentafluoropropene, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene.
  • Hydrohaloolefins used in the blowing agent (B) are 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,1,3,3-tetra Fluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,1-trifluoropropene, 3,3,3-trifluoropropene, 1,1,1,3-tetrafluoropropene, 1 , 1,1,3,3-pentafluoropropene, 1,1,2,3,3-pentafluoropropene, 1,1,1,2-tetrafluoropropene, 1,1,1,2,3-penta Fluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluorobut-2-ene, and their structural isomers, geometric isomers, and stereo From the group consisting of isomers At least one type of the above [1] or the
  • Tertiary amines used in the amine catalyst composition (A) are N, N, N ′, N′-tetramethylhexamethylenediamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 2,5,8,11-tetramethyl-2,5,8,11-tetraazadodecane, 1,8-diazabicyclo [5.4.0] undec-7-ene, triethylenediamine, hydroxymethyltriethylenediamine, 1 -Methyl-4- [2- (dimethylamino) ethyl] piperazine, N, N-dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, 1,2-dimethylimidazole, N, N-dimethyloctylamine N, N-dimethyldodecylamine, N, N-dimethylaminoethanol, 2- [2- (dimethylamino) ethoxy] Tanol,
  • Acids used in the amine catalyst composition (A) are phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, formic acid, acetic acid, 2-ethylhexanoic acid, glycolic acid, chloroacetic acid, cyanoacetic acid, dichloroacetic acid, trichloroacetic acid, Fluoroacetic acid, trifluoroacetic acid, bromoacetic acid, methoxyacetic acid, mercaptoacetic acid, iodoacetic acid, lactic acid, pyruvic acid, 2-chloropropionic acid, 3-chloropropionic acid, oxaloacetic acid, citric acid, tartaric acid, suberic acid, fumaric acid, Maleic acid, aminobenzoic acid, chlorobenzoic acid, dichlorobenzoic acid, nitrobenzoic acid, dinitrobenzoic acid, trinitrobenzoic acid, salicylic acid, fluorobenzoic acid, bromobenzoic
  • the ratio of acids and tertiary amines contained in the amine catalyst composition (A) is [valence of acids x number of moles of acids] / [valence of tertiary amines x tertiary amine]
  • the raw material-blended composition according to any one of [1] to [6] above, which is in the range of 0.1 to 2.
  • the amine catalyst composition (A) contains a carboxylic acid as an acid and [number of moles of carboxyl groups in the carboxylic acid] / [number of moles of amino groups in the tertiary amine] (molar ratio)
  • the raw material-blended composition according to any one of [1] to [6], wherein is in the range of 0.1 to 2.
  • Polyamines (D) are 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 3,5-bis (methylthio) -2,6-toluene
  • a raw material blend composition for producing polyurethane foam containing hydrohaloolefins as a foaming agent is improved.
  • a raw material compounding composition can be provided as a raw material compounding solution in which a highly active catalyst composition having a reduced required amount is uniformly mixed.
  • the raw material blend composition of the present invention includes an amine catalyst composition (A) containing tertiary amines and acids, a blowing agent (B) containing hydrohaloolefins, and a polyol (C).
  • the tertiary amine used in the amine catalyst composition (A) includes, for example, a tertiary amine compound for producing a polyurethane resin, and is not particularly limited. Specifically, N, N , N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, N, N, N ′, N′-tetramethylhexamethylenediamine, 1,1 , 4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,7-pentaethyldiethylenetriamine, 1,1,4,7,7-pentamethyldipropylenetriamine, 2,5,8,11-tetra Methyl-2,5,8,11-tetraazadodecane, N, N, N′-trimethyl-N ′-[3- (dimethylamino) propyl] -1,2-ethanediamine, N, N, N ′,
  • tertiary amines having a primary amino group, a secondary amino group, or a hydroxyalkyl group in the molecule react with isocyanate and are incorporated into the foam. It is possible to reduce the amount.
  • N, N, N ′, N′-tetramethylhexamethylenediamine, 1,1,4,7,7-pentamethyldiethylenetriamine is used because of its high catalytic activity.
  • 2,5,8,11-tetramethyl-2,5,8,11-tetraazadodecane, 1,8-diazabicyclo [5.4.0] undec-7-ene triethylenediamine, hydroxymethyltriethylenediamine, 1-methyl-4- [2- (dimethylamino) ethyl] piperazine, N, N-dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, 1,2-dimethylimidazole, N, N-dimethyloctyl Amine, N, N-dimethyldodecylamine, N, N-dimethylaminoethanol, 2- [2- (dimethylamino) eth Si] ethanol, 2-[[2-[2-
  • the tertiary amines used in the amine catalyst composition (A) can be easily produced by methods known in the literature. Examples thereof include a method by reductive methylation of monoamine and amination of alcohol, a reductive methylation of amino alcohols, a method by reaction of alkyl halide and dialkylamine, and the like.
  • acids used for an amine catalyst composition (A) For example, an inorganic acid, phenols, a sulfonic acid, carboxylic acid, hydroxycarboxylic acid, vinylic carboxylic acid etc. are mentioned. Of these, one or a combination of two or more can be used.
  • Acids used in the amine catalyst composition (A) are not particularly limited, and specifically, phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, formic acid, glycolic acid, chloroacetic acid, cyanoacetic acid, dichloroacetic acid, Trichloroacetic acid, fluoroacetic acid, trifluoroacetic acid, bromoacetic acid, methoxyacetic acid, mercaptoacetic acid, iodoacetic acid, lactic acid, pyruvic acid, 2-chloropropionic acid, 3-chloropropionic acid, oxaloacetic acid, citric acid, tartaric acid, suberic acid, Fumaric acid, maleic acid, aminobenzoic acid, chlorobenzoic acid, dichlorobenzoic acid, nitrobenzoic acid, dinitrobenzoic acid, trinitrobenzoic acid, salicylic acid, fluorobenzoic acid, bromobenzoic acid, iodobenzoic acid, 1-
  • the mixing ratio of acids and tertiary amines is not particularly limited.
  • Valence ⁇ number of moles of tertiary amine preferably in the range of 0.1 to 2, more preferably in the range of 0.75 to 2.
  • the curability and moldability of the resulting urethane foam are good when the [valence of acid x number of moles of acid] / [valence of tertiary amine x number of moles of tertiary amine] is 2 or less. It becomes.
  • the progress of decomposition of the hydrofluoroolefin is achieved by setting [valence of acid x number of moles of acid] / [valence of tertiary amine x number of moles of tertiary amine] to 0.1 or more.
  • the storage stability of the raw material composition is improved.
  • carboxylic acid as an example, [number of moles of carboxyl group in carboxylic acid] / [number of moles of amino group in tertiary amine] (molar ratio), preferably in the range of 0.1-2. More preferably, it is in the range of 0.75 to 1.
  • the content of the amine catalyst composition (A) is not particularly limited.
  • the content is preferably 0.8.
  • the range is from 01 to 15 parts by weight, and more preferably from 0.05 to 10 parts by weight.
  • the amine catalyst composition (A) is used in excess of 15 parts by weight, although the curability and productivity of the resulting urethane foam are improved, the amount of volatile amine may be increased.
  • the catalyst used in the raw material blend composition of the present invention is the amine catalyst composition (A), and it is not necessary to dare to use other catalysts, but other catalysts can be used without departing from the spirit of the present invention. It does not prevent you from using it together.
  • examples of such other catalysts include organometallic catalysts and quaternary ammonium salt catalysts.
  • organometallic catalysts include, but are not limited to, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride. , Dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate and the like.
  • the quaternary ammonium salt catalysts are not particularly limited.
  • tetraalkylammonium halides such as tetramethylammonium chloride
  • tetraalkylammonium hydroxides such as tetramethylammonium hydroxide
  • tetramethylammonium Tetraalkylammonium organic acid salts such as acetate, tetramethylammonium 2-ethylhexanoate, hydroxyalkylammonium organic acid salts such as 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanoate Is mentioned.
  • the amount of the other catalyst described above is not particularly limited, but is usually in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyol (C).
  • the amine catalyst composition (A) and another catalyst when used in combination, dipropylene glycol, ethylene glycol, 1,4-butane can be used as a solvent, if necessary, in preparing the mixture.
  • Diols and water can be used.
  • the amount of the solvent is not particularly limited, but is preferably 70% by weight or less with respect to the total amount of the catalyst.
  • the catalyst prepared as described above may be used by adding to the polyol (C), or each catalyst component may be added separately to the polyol (C) and used. is not.
  • the hydrohaloolefins used in the blowing agent (B) are not particularly limited, and examples thereof include trifluoropropene, tetrafluoropropene such as HFO-1234, and pentafluoropropene such as HFO-1225. , Chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, chlorotetrafluoropropene, and combinations thereof. Of these, tetrafluoropropene, pentafluoropropene, and chlorotrifluoropropene compounds in which the unsaturated terminal carbon has one or less F or Cl substituents are preferred.
  • a foaming agent other than hydrohaloolefins can be used in combination as the foaming agent (B) without departing from the spirit of the present invention.
  • blowing agents include, but are not limited to, hydrocarbons, fluorocarbons, chlorocarbons, fluorochlorocarbons, halogenated hydrocarbons, ethers, fluorinated ethers, esters, aldehydes, and ketones. And CO 2 generating material. Of these, one or a combination of two or more can be used.
  • the foaming agent other than hydrohaloolefins used in the foaming agent (B) is not particularly limited.
  • the organic acid and hydrocarbon generate CO 2 when reacted with water, formic acid, and isocyanate.
  • the content of the foaming agent (B) in the raw material blend composition is not particularly limited, but is preferably in the range of 1 to 30% by weight of the total weight of the raw material blend composition, for example, 3 to 25% by weight. The range of 5 to 25% by weight is more preferable.
  • the hydrohaloolefins are preferably in the range of 5 to 90% by weight of the total weight of the blowing agent (B), The range of 7 to 80% by weight is more preferable, and the range of 10 to 70% by weight is more preferable.
  • the foaming agent other than hydrohaloolefins is preferably in the range of 95 to 10% by weight, more preferably in the range of 93 to 20% by weight, and in the range of 90 to 30% by weight of the total weight of the foaming agent (B). Further preferred.
  • polystyrene resin examples include polyether polyols, polyester polyols, polymer polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. These polyols can be used alone or in combination as appropriate.
  • the polyether polyol is not particularly limited.
  • a compound having at least two active hydrogen groups polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine
  • alkanolamines such as ethanolamine and diethanolamine
  • alkylene oxides such as ethylene oxide and propylene oxide
  • the polyester polyol is not particularly limited.
  • polyester polyol obtained from the reaction of dibasic acid and glycol, waste from the production of nylon, trimethylolpropane, pentaerythrole waste, phthalic polyester And polyester polyols obtained by treating and inducing waste [for example, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun, p. See description of 117. ].
  • the polymer polyol is not particularly limited.
  • the polyether polyol and an ethylenically unsaturated monomer for example, butadiene, acrylonitrile, styrene, etc.
  • a radical polymerization catalyst for example, butadiene, acrylonitrile, styrene, etc.
  • the flame retardant polyol is not particularly limited.
  • a polyol, a phenol polyol, etc. are mentioned.
  • polyether polyols and polyester polyols are particularly preferred in the production of rigid polyurethane foams.
  • the average functionality of the polyol is 4 to 8, and the average hydroxyl value is preferably in the range of 200 to 800 mgKOH / g, more preferably in the range of 300 to 700 mgKOH / g.
  • the raw material-blended composition of the present invention further contains a polyamine (D) in order to improve initial reactivity and storage stability.
  • polyamines (D) used in the raw material blend composition of the present invention for example, aliphatic polyamines such as ethylenediamine can be used, but aromatic polyamines are more preferable.
  • aromatic polyamines used in the polyamines (D) include phenylenediamine, xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, methylenebisol chloraniline, 1,2-bis (2-amino).
  • Phenylthio) ethane 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 3,5-bis (methylthio) -2,6-toluenediamine and 3,5 -Bis (methylthio) -2,4-toluenediamine and the like are exemplified.
  • 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, 3,5-bis (methylthio) -2,6-toluenediamine and 3,5- Bis (methylthio) -2,4-toluenediamine is particularly preferred.
  • These polyamines can be used alone, or can be used in combination as appropriate.
  • the raw material-blended composition of the present invention can be used for producing a polyurethane foam, but is particularly preferably used for producing a rigid polyurethane foam and an isocyanurate-modified rigid polyurethane foam.
  • a rigid polyurethane foam is a foam that has a highly crosslinked closed cell structure and cannot be reversibly deformed, and has completely different properties from flexible and semi-rigid foams [for example, Gunter Oeltel “Polyurethane”. Handbook "(1985 edition) Hanser Publishers (Germany), p. 234-313, Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. 224-283 etc.].
  • the physical properties of the rigid polyurethane foam are not particularly limited, but are generally in the range of a density of 20 to 100 kg / m 3 and a compressive strength of 0.5 to 10 kgf / cm 2 (50 to 1000 kPa).
  • the method for producing a polyurethane foam of the present invention is characterized by reacting the above-described raw material-blended composition of the present invention with an organic polyisocyanate.
  • the organic polyisocyanate is not particularly limited.
  • toluene diisocyanate hereinafter sometimes referred to as “TDI”
  • MDI diphenylmethane diisocyanate
  • TDI and its derivatives examples include aromatic polyisocyanates such as isocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and mixtures thereof.
  • aromatic polyisocyanates such as isocyanate and xylylene diisocyanate
  • aliphatic polyisocyanates such as hexamethylene diisocyanate
  • alicyclic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate
  • mixtures thereof examples thereof include aromatic polyisocyanates such as isocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate
  • MDI and its derivatives examples include a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate, and a diphenylmethane diisocyanate derivative having a terminal isocyanate group.
  • MDI or a derivative of MDI is preferable, and these may be mixed and used.
  • a foam stabilizer can be used if necessary.
  • the foam stabilizer include known foam stabilizers, and specifically, nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers, silicone-grease copolymers, or the like. A mixture etc. are illustrated.
  • the amount used is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of polyol.
  • a crosslinking agent or a chain extender can be used if necessary.
  • crosslinking agent or chain extender examples include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine. And polyamines such as xylylenediamine and methylenebisol chloroaniline.
  • a colorant, a flame retardant, an anti-aging agent, and other known additives may be used as necessary. The types and amounts of these additives can be used as long as they are usually used.
  • the polyurethane foam product produced using the raw material blend composition of the present invention can be used for various applications. For example, in a rigid polyurethane foam, a heat insulating building material, a freezer, a refrigerator, etc. are mentioned.
  • the raw material mixture having the composition shown in Table 1 was determined.
  • a rigid polyurethane foam was produced by stirring and mixing for 5 seconds to cause foaming reaction.
  • the cream time (CT) at this time was measured visually to obtain initial reactivity.
  • CT is defined as the time when the reaction started after stirring and mixing, and the liquid level rise was visually confirmed.
  • the external appearance was confirmed and the state of a cell and the presence or absence of collapse were recorded.
  • polyamines (D) a mixture of aromatic polyamines 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine, or 3,5-bis (methylthio) )
  • the decrease in reactivity after storage was extremely small.
  • the CT change rate was 0%.
  • the obtained rigid polyurethane foam also has a curing rate and an appearance that are sufficiently suitable.
  • the reaction start time (cream time) is as fast as 15 seconds or less, and the curing speed and appearance are also sufficiently suitable.
  • Comparative Examples 1 and 2 which deviated from the amine catalyst composition (A) contained in the raw material blend composition of the present invention and did not use a combination of tertiary amines and acids, there was a marked decrease in reactivity after storage. It became bigger. Further, the obtained rigid polyurethane foam was severe in cell roughness or collapsed during the foaming reaction, so that it was not practically usable.
  • the raw material-blended composition of the present invention is used for producing a polyurethane foam, and is particularly suitably used for producing a rigid polyurethane foam and an isocyanurate-modified rigid polyurethane foam.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention améliore la stabilité de stockage d'une composition mélangée de matière première pour fabriquer une mousse de polyuréthane, la composition comprenant une hydrohalogénooléfine comme agent moussant. L'invention concerne l'utilisation d'une composition mélangée de matière première pour la fabrication d'une mousse de polyuréthane, la composition comprenant une composition de catalyseur d'amine (A) comprenant une amine tertiaire et un acide, un agent moussant (B) comprenant une hydrohalogénooléfine et un polyol (C).
PCT/JP2013/072213 2012-08-21 2013-08-20 Composition mélangée de matière première pour la fabrication de mousse de polyuréthane et un procédé de fabrication de mousse de polyuréthane ou de mousse de polyuréthane modifiée par isocyanurate WO2014030654A1 (fr)

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WO2016149001A1 (fr) * 2015-03-13 2016-09-22 Basf Se Procédé de formation d'un article en mousse de polyuréthane
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WO2019067572A1 (fr) * 2017-09-28 2019-04-04 Dow Global Technologies Llc Système de mousse rigide de polyuréthane présentant une durée de conservation et une stabilité de conservation de polyol améliorées
CN112898523A (zh) * 2021-01-25 2021-06-04 惠彩材料科技(苏州)有限公司 一种聚氨酯泡棉及其制备方法和应用
JP2022160687A (ja) * 2016-07-25 2022-10-19 ハネウェル・インターナショナル・インコーポレーテッド Ｈｆ０－１３３６ｍｚｚｍ（ｚ）を含有するポリエステルポリオール組成物
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WO2019022077A1 (fr) * 2017-07-25 2019-01-31 積水ソフランウイズ株式会社 Composition de polyol pour mousse de polyuréthane rigide, composition pour mousse de polyuréthane rigide, et procédé de production de mousse de polyuréthane rigide

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WO2015012267A1 (fr) * 2013-07-24 2015-01-29 花王株式会社 Mélange de polyols pour la production de mousse de polyuréthane dure
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JP2017206598A (ja) * 2016-05-17 2017-11-24 東ソー株式会社 ハロアルケン発泡ポリウレタン製造用のポリオール系配合液組成物
JP2022160687A (ja) * 2016-07-25 2022-10-19 ハネウェル・インターナショナル・インコーポレーテッド Ｈｆ０－１３３６ｍｚｚｍ（ｚ）を含有するポリエステルポリオール組成物
JP7474290B2 (ja) 2016-07-25 2024-04-24 ハネウェル・インターナショナル・インコーポレーテッド Ｈｆ０－１３３６ｍｚｚｍ（ｚ）を含有するポリエステルポリオール組成物
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CN112898523B (zh) * 2021-01-25 2022-05-31 惠彩材料科技(苏州)有限公司 一种聚氨酯泡棉及其制备方法和应用
CN112898523A (zh) * 2021-01-25 2021-06-04 惠彩材料科技(苏州)有限公司 一种聚氨酯泡棉及其制备方法和应用
WO2023221693A1 (fr) * 2022-05-20 2023-11-23 海信容声(广东)冰箱有限公司 Mousse de polyuréthane rigide, procédé de préparation et matériau de conservation de chaleur, réfrigérateur et congélateur comprenant une mousse de polyuréthane

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