WO2014042255A1 - Composition destinée à la fabrication d'une mousse d'uréthane dure ignifugeante, et procédé de fabrication d'une mousse d'uréthane dure ignifugeante à l'aide de ladite composition - Google Patents

Composition destinée à la fabrication d'une mousse d'uréthane dure ignifugeante, et procédé de fabrication d'une mousse d'uréthane dure ignifugeante à l'aide de ladite composition Download PDF

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WO2014042255A1
WO2014042255A1 PCT/JP2013/074929 JP2013074929W WO2014042255A1 WO 2014042255 A1 WO2014042255 A1 WO 2014042255A1 JP 2013074929 W JP2013074929 W JP 2013074929W WO 2014042255 A1 WO2014042255 A1 WO 2014042255A1
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flame
acid
urethane foam
weight
composition
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PCT/JP2013/074929
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English (en)
Japanese (ja)
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WO2014042255A8 (fr
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裕志 藤原
木曾　浩之
泰道 宮川
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東ソー株式会社
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Priority to CN201380048106.2A priority Critical patent/CN104640895A/zh
Publication of WO2014042255A1 publication Critical patent/WO2014042255A1/fr
Publication of WO2014042255A8 publication Critical patent/WO2014042255A8/fr

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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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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

Definitions

  • the present invention relates to a composition for producing a flame-retardant rigid urethane foam and a method for producing a flame-retardant rigid urethane foam using the same.
  • Rigid urethane foam is used for construction, civil engineering-related thermal insulation materials and structural materials, electrical equipment-related thermal insulation materials such as refrigerators, plant and marine thermal insulation materials, vehicle-related cold storage cabinets, etc. It is widely used as a heat insulating material for refrigeration vehicles. In recent years, flame retardant technology for rigid urethane foam has been required due to strict operation of flame retardant standards and promotion of energy saving policies.
  • flame-retarding of rigid urethane foam is performed by introducing an isocyanurate ring structure by trimerization of polyisocyanate.
  • the activity of the catalyst for producing urethane foam is low in the conventional technology, sufficient flame retardancy (for example, the oxygen index, which is an indicator of flame retardancy, is 32% or more) has not been obtained.
  • the present applicant has already used a glycerin-based polyol and a phthalic acid-based polyester polyol as a polyol, and a composition for producing a flame-retardant rigid urethane foam using a quaternary ammonium salt and a tertiary amine-based catalyst as a catalyst.
  • a patent application has been filed (see Patent Document 1).
  • Patent Document 1 in order to obtain an oxygen index of 32% or more, a large amount of flame retardant is required. Therefore, the polymer physical properties of urethane foam are lowered or the cost of the flame retardant to be used is increased. There is still room for improvement in that it is not economical.
  • the present invention has been made in view of the above-mentioned background art, and the purpose thereof is a composition for producing a flame-retardant rigid urethane foam using a small amount of a flame retardant, and an oxygen index using the composition. It is providing the manufacturing method from which the flame-retardant rigid urethane foam which is 32% or more is obtained.
  • a high-isocyanate index formulation using a specific raw material composition has a flame-retardant rigid urethane foam having an oxygen index of 32% or more with a small amount of flame retardant. As a result, the present invention was completed.
  • the present invention has the following gist.
  • a polyol (A), a catalyst (B), a foaming agent (C), a foam stabilizer (D), and a flame retardant (E) are contained, and the catalyst (B) is represented by the following general formula (1).
  • a flame retardant rigid urethane foam which is an aqueous solution containing a quaternary ammonium salt in an amount exceeding 50% by weight and the amount of the flame retardant (E) used is 120 parts by weight or less with respect to 100 parts by weight of the polyol (A). Composition for manufacture.
  • R 1 to R 4 each independently represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
  • X b- represents an inorganic acid group or 1 to 8 carboxylic acid groups are represented.
  • a represents an integer in the range of 1 to 3
  • b represents an integer in the range of 1 to 3.
  • a composition for producing flame retardant rigid urethane foam [5] The flame-retardant hard material according to any one of the above [1] to [4], wherein the catalyst (B) is an aqueous solution containing 60% by weight or more of the quaternary ammonium salt represented by the general formula (1). Composition for producing urethane foam. [6] The above [1] to [1], wherein the amount of the quaternary ammonium salt contained in the catalyst (B) is in the range of 0.05 to 7 parts by weight with respect to 100 parts by weight of the polyol (A). [5] The composition for producing a flame-retardant rigid urethane foam according to any one of [5]. [7] The composition for producing a flame-retardant rigid urethane foam according to any one of the above [1] to [6], wherein the flame retardant (E) is a liquid flame retardant.
  • R 1 to R 4 each independently represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
  • X b- represents an inorganic acid group or a carboxylic acid group having 1 to 8 carbon atoms.
  • a represents an integer in the range of 1 to 3
  • b represents an integer in the range of 1 to 3.
  • the flame-retardant rigid urethane foam obtained by using the composition for producing a flame-retardant rigid urethane foam of the present invention and the production method of the present invention has a high difficulty with an oxygen index of 32% or more even when a small amount of flame retardant is used. Since it has flammability, it is useful as a heat insulating material or a structural material.
  • composition for producing a flame-retardant rigid urethane foam of the present invention (hereinafter also referred to as a composition) (1) A composition containing a polyol (A), a catalyst (B), a foaming agent (C), a foam stabilizer (D), and a flame retardant (E), (2)
  • the catalyst (B) is an aqueous solution containing more than 50% by weight of the quaternary ammonium salt represented by the general formula (1), and (3) the amount of the flame retardant (E) used is It is characterized by being 120 parts by weight or less with respect to 100 parts by weight of the polyol (A).
  • flame retardant rigid urethane foam refers to a rigid urethane foam having an oxygen index of 32% or more, which is an index representing flame retardancy.
  • polyol (A) for example, conventionally known polyether polyol, polyester polyol, polymer polyol and the like can be used, and there is no particular limitation.
  • polyether polyol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, glycerin, trimethylol bropan, Polyhydric alcohols such as pentaerythritol, methyl glucoside, sorbitol, sucrose; polyhydric phenols such as pyrogallol and hydroquinone; bisphenols such as bisphenol A, bisphenol S, bisphenol F, and a low condensation product of phenol and formaldehyde; propylene Diamine, Hexamethylenediamine, Ethylenediamine, Diethylenetriamine, Triethylenetetramine, Pentamethylenehexamine, Ethanol Aliphatic amines such as ethylene, diethanolamine, triethanolamine and aminoethylethanolamine; aromatic amines such as aniline, phenyl
  • alkylene oxide added to the active hydrogen compound examples include ethylene oxide, propylene oxide, butylene oxide and the like, and two or more of these may be used in combination.
  • Preferred as the alkylene oxide is ethylene oxide, propylene oxide, or a combination thereof.
  • polyester polyols examples include polybasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, succinic acid, adipic acid, sebacic acid, maleic acid, dimer acid, trimellitic acid, and polyhydric alcohol. Condensed polyester polyols obtained by decomposition; phthalic acid-based recovered polyester polyols obtained by decomposing phthalic polyester molded articles such as polyethylene terephthalate; polylactone polyols obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone; etc. Is mentioned.
  • polymer polyol examples include a polymer polyol obtained by reacting the above-described polyether polyol with an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.
  • ethylenically unsaturated monomer for example, butadiene, acrylonitrile, styrene, etc.
  • phthalic acid-based condensed polyester polyols such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride because of its high flame retardancy.
  • an aqueous solution containing more than 50% by weight of the quaternary ammonium salt represented by the general formula (1) is used as the catalyst (B).
  • R 1 to R 4 each independently represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
  • X b- represents an acidic group
  • a represents an integer in the range of 1 to 3
  • b represents an integer in the range of 1 to 3.
  • a is preferably 1 to 2
  • b is preferably 1 to 2.
  • R 1 to R 4 are aliphatic hydrocarbon groups
  • the aliphatic hydrocarbon groups may be linear or branched, and may be either saturated or unsaturated.
  • Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl Group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethyl group,
  • R 1 to R 4 are aromatic hydrocarbon groups
  • the aromatic hydrocarbon groups may be monocyclic or polycyclic.
  • the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group, (2-, 3-, 4-) biphenylyl group, (1-, 2-) naphthyl group, acenaphthylene- (1-, 3- , 4-, 5-) yl group, fluorene- (1-, 2-, 3-, 4-, 9-) yl group, phenalen- (1-, 2-) yl group, (1-, 2-, 3-, 4-, 9-) phenanthryl group and the like.
  • the aliphatic hydrocarbon group having 1 to 12 carbon atoms or the aromatic hydrocarbon group having 6 to 14 carbon atoms as R 1 to R 4 further has a substituent. Also good. Examples of such a substituent include the above-described aliphatic hydrocarbon groups having 1 to 12 carbon atoms and aromatic hydrocarbon groups having 6 to 14 carbon atoms.
  • any two of R 1 to R 4 may form an alicyclic ring or a heterocyclic ring via a carbon atom, an oxygen atom or a nitrogen atom.
  • R 1 to R 4 are not particularly limited. However, the smaller the molecular weight of the quaternary ammonium salt, the greater the amount of substance per weight and the higher the activity, so that R 1 to R 4 Is preferably a methyl group.
  • the acidic group (X b ⁇ ) represents an inorganic acid group or a carboxylic acid group having 1 to 8 carbon atoms.
  • inorganic acid groups include chloric acid groups such as hydrochloric acid groups, perchloric acid groups, chloric acid groups, chlorous acid groups, and hypochlorous acid groups; hydrobromic acid groups, perbromic acid groups, bromine Bromate groups such as acid groups, bromite groups and hypobromite groups; iodate groups such as hydroiodide groups, periodate groups, iodate groups, iodate groups and hypoiodite groups; Sulfuric acid groups such as sulfuric acid group, disulfuric acid group, thiosulfuric acid group, sulfamic acid group, sulfite group, disulfite group, and thiosulfuric acid group; nitric acid such as nitric acid group, nitrite group, hyponitrite group, nitroxyl acid group Groups;
  • Examples of the carboxylic acid group having 1 to 8 carbon atoms include formic acid group, acetic acid group, propionic acid group, butanoic acid group, pentanoic acid group, hexanoic acid group, heptanoic acid group, octylic acid group, and 2-ethylhexanoic acid group.
  • Aliphatic monocarboxylic acid groups such as oxalic acid groups, malonic acid groups, succinic acid groups, glutaric acid groups, adipic acid groups, and other aliphatic polycarboxylic acid groups; benzoic acid groups, toluic acid groups, and other aromatic monocarboxylic acid groups Groups; aromatic polycarboxylic acid groups such as phthalic acid groups, isophthalic acid groups, terephthalic acid groups, nitrophthalic acid groups; and the like.
  • These acidic groups can be used as one kind or a mixture of two or more kinds.
  • an acidic group having an acid dissociation constant in water of 3.0 or more is preferable because the quaternary ammonium salt is easily dissociated and activated.
  • a carboxylic acid group having 1 to 4 carbon atoms is preferred.
  • specific examples of the inorganic acid group or the carboxylic acid having 1 to 8 carbon atoms constituting the acidic group (X b- ) include acetic acid, formic acid, 2-ethylhexanoic acid, boric acid, and carbonic acid. Acetic acid, formic acid, carbonic acid and the like are particularly preferable.
  • the method for preparing the quaternary ammonium salt represented by the general formula (1) is not particularly limited.
  • a preparation method (1) in which a quaternary ammonium hydroxide is reacted with an acidic compound a preparation method (2) in which a tertiary amine and a carbonic acid diester are reacted, and the resulting quaternary ammonium carbonate and an acidic compound are reacted.
  • a preparation method (1) in which a quaternary ammonium hydroxide is reacted with an acidic compound
  • a preparation method (2) in which a tertiary amine and a carbonic acid diester are reacted, and the resulting quaternary ammonium carbonate and an acidic compound are reacted.
  • it does not specifically limit as reaction conditions of the said preparation method (1) It is preferable to carry out at normal temperature or a heating in solvents, such as water and ethanol.
  • the quaternary ammonium hydroxide used in the preparation method (1) is a
  • R 1 to R 4 each independently represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
  • quaternary ammonium hydroxide examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, tetran-butylammonium hydroxide, tetraisobutylammonium hydroxide.
  • reaction conditions for the above preparation method (2) are not particularly limited, the reaction between the tertiary amine and the carbonic acid diester is carried out in a solvent such as methanol or ethanol or in the absence of a solvent at room temperature or under heating. It is preferable. Further, the reaction between the obtained quaternary ammonium carbonate and an acidic compound is carried out in a solvent such as methanol or ethanol, or in the absence of a solvent, at room temperature or under heating, while removing appropriately generated carbon dioxide gas from the reaction system. It is preferable.
  • the tertiary amine used in the preparation method (2) is not particularly limited.
  • carbonic acid diester used by the said preparation method (2)
  • a dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate etc. are mentioned as a suitable thing.
  • an acidic compound used by the said preparation method (1) or (2) An inorganic acid compound, an organic acid compound, etc. are mentioned.
  • inorganic acid compounds include chloric acid such as hydrochloric acid, perchloric acid, chloric acid, chlorous acid, and hypochlorous acid; hydrobromic acid, perbromic acid, bromic acid, bromic acid, hypochlorous acid, and the like.
  • Brominated acid such as bromic acid; Iodic acid such as hydroiodic acid, periodic acid, iodic acid, iodic acid, hypoiodous acid; sulfuric acid, disulfuric acid, thiosulfuric acid, sulfamic acid, sulfurous acid, disulfurous acid, thiosulfuric acid
  • Nitric acid such as nitric acid, nitrous acid, hyponitrous acid, nitroxyl acid
  • Examples include phosphoric acid such as acid and metaphosphoric acid; boric acid such as orthoboric acid, metaboric acid, perboric acid, hypoboric acid, boronic acid, and borinic acid; hydrogen carbonate;
  • organic acid compound examples include carboxylic acids having 1 to 8 carbon atoms such as fatty acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octylic acid, and 2-ethylhexanoic acid.
  • carboxylic acids having 1 to 8 carbon atoms such as fatty acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octylic acid, and 2-ethylhexanoic acid.
  • Aliphatic monocarboxylic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; aromatic monocarboxylic acids such as benzoic acid and toluic acid; phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid Aromatic polycarboxylic acids such as; and the like.
  • the acidic compound can be used as one kind or a mixture of two or more kinds. Of these, preferred are acidic compounds having an acid dissociation constant in water of 3.0 or more, more preferably an acid dissociation constant in the range of 3.5 to 11.0, and carboxylic acids having 1 to 4 carbon atoms. It is.
  • the catalyst (B) is tetramethylammonium acetate, tetramethylammonium formate, tetramethylammonium 2-ethylhexanoate, tetraethylammonium acetate, trimethylmonoethylammonium acetate, trimethylmono-n. It preferably contains at least one quaternary ammonium salt selected from the group consisting of octyl ammonium acetate and trimethylmono n-dodecyl ammonium acetate. Particularly preferred is tetramethylammonium acetate, tetramethylammonium formate or trimethylmono n-dodecylammonium acetate.
  • the amount of the catalyst (B) used is not particularly limited, but is usually in the range of 0.1 to 8 parts by weight, preferably 100 parts by weight of the polyol (A), preferably The range is 0.5 to 5 parts by weight. If the amount of the catalyst (B) used is less than 0.1 parts by weight, the flame retardancy and mechanical strength of the rigid urethane foam may be insufficient. If it exceeds 8 parts by weight, the liquid flow during the production of the rigid urethane foam May decrease.
  • the catalyst (B) is characterized by being an aqueous solution containing a quaternary ammonium salt represented by the general formula (1) and having a concentration exceeding 50% by weight.
  • the quaternary ammonium salt represented by the general formula (1) can be uniformly dispersed in the composition of the present invention.
  • the conventional catalyst containing a quaternary ammonium salt uses an organic solvent solution, and its solubility is only a low concentration of less than 50% by weight. When a sufficient amount of catalyst is used, the solvent becomes a polymer physical property. There is a problem that high flame retardancy cannot be achieved.
  • the catalyst (B) by using an aqueous solution in which the concentration of the quaternary ammonium salt exceeds 50% by weight as the catalyst (B), a high concentration of the quaternary ammonium salt can be used. The influence on physical properties is reduced, and it is easy to achieve an oxygen index of 32% or more as flame retardancy.
  • the catalyst (B) it is preferable to use an aqueous solution containing a high concentration quaternary ammonium salt.
  • the concentration of the quaternary ammonium salt represented by the general formula (1) in the aqueous solution is preferably 60% by weight or more, and more preferably 70% by weight or more.
  • the concentration is preferably 85% by weight or less.
  • the amount of the quaternary ammonium salt represented by the general formula (1) contained in the catalyst (B) is preferably about 0.1 part by weight with respect to 100 parts by weight of the polyol (A). The range is from 05 to 7 parts by weight, more preferably from 0.25 to 5 parts by weight.
  • the amount of the quaternary ammonium salt contained in the catalyst (B) is less than 0.05 parts by weight, the flame retardancy and mechanical strength of the rigid urethane foam may be insufficient, and if it exceeds 7 parts by weight There is a possibility that the liquid flow property at the time of manufacturing the rigid urethane foam is lowered.
  • catalysts such as tertiary amines and carboxylates may be used as the catalyst (B) in addition to the quaternary ammonium salt represented by the general formula (1).
  • the amount used is desirably 50% by weight or less based on the quaternary ammonium salt represented by the general formula (1).
  • Such tertiary amines are not particularly limited.
  • the carboxylate is not particularly limited, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids.
  • the carboxylic acid is not particularly limited.
  • aliphatic mono-acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono-monomers such as dicarboxylic acids, benzoic acid and phthalic acid.
  • conventionally known compounds such as dicarboxylic acids.
  • alkaline earth metals such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.
  • the foaming agent (C) in the composition of the present invention is not particularly limited, and for example, hydrogen atom-containing halogenated hydrocarbons, low-boiling hydrocarbons, water and the like are used. These may be used individually by 1 type, or may use multiple types together.
  • the hydrogen atom-containing halogenated hydrocarbon blowing agent include those of the HCFC type (for example, “HCFC-123”, “HCFC-141b”, “HCFC-22”, “HCFC-142b”, etc.), Examples of HFC type (for example, “HFC-134a”, “HFC-245fa”, “HFC-245ca”, “HFC-365mfc”, “HFC-236ea”, etc.) and mixtures of two or more of these Is done.
  • the foaming agent (C) is preferably “HCFC-141b”, “HFC-134a”, “HFC-245fa”, “HFC-365mfc”, and a mixture of two or more thereof.
  • the low boiling point hydrocarbon is a hydrocarbon having a normal boiling point of 0 to 50 ° C., and is not particularly limited. Specific examples include propane, butane, pentane, cyclopentane, and mixtures thereof.
  • the amount used is not particularly limited, but is usually in the range of 0.5 to 10 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyol (A). The range is 8 parts by weight.
  • the amount of hydrogen atom-containing halogenated hydrocarbon used is not particularly limited, but polyol (A) 100 weight Is usually in the range of 1 to 100 parts by weight, preferably in the range of 10 to 80 parts by weight, and the amount of water used is not particularly limited, but is usually in the range of 0.1 to 10 parts by weight. The preferred range is 0.5 to 8 parts by weight.
  • the amount of low-boiling hydrocarbons used is not particularly limited, but is usually 1 to 100 parts by weight of the polyol (A).
  • the amount of water used is not particularly limited, but is usually 0.1 to 10 parts by weight, preferably 100 to 10 parts by weight, preferably 100 parts by weight of polyol (A). 0.1 to 4 parts by weight.
  • examples of the foam stabilizer (D) include conventionally known organosilicon surfactants. Specific examples include, but are not limited to, nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers, and mixtures thereof.
  • the amount of the foam stabilizer (D) used is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight, and 0.3 to 5 parts by weight with respect to 100 parts by weight of the polyol (A). More preferred.
  • the flame retardant (E) is not particularly limited, and examples thereof include a flame retardant that is liquid at room temperature (liquid flame retardant), a flame retardant that is solid at room temperature (solid flame retardant), and the like.
  • liquid flame retardant include reactive flame retardants such as phosphorus-containing polyols such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, tricresyl
  • phosphate esters such as phosphate, halogen-containing phosphate esters such as trischloroethyl phosphate and trischloropropyl phosphate.
  • solid flame retardant examples include dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol A, 2,4,6-tribromophenol, 2,2 ′, 6,6′-tetrabromobisphenol— Halogen-containing organic compounds such as S, decabromodiphenyl ether, hexabromobenzene, bis (pentabromophenyl) ethane, hexabromocyclododecane; halogenated polymers such as brominated polystyrene, brominated epoxy resin, brominated carbonate resin; Examples include phosphorus alone such as red phosphorus; inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate;
  • a liquid flame retardant is preferable in terms of dispersibility of the flame retardant.
  • the liquid flame retardant is preferably a halogen-containing phosphate ester, and trischloropropyl phosphate is particularly preferable because of its good stability and high flame retardancy.
  • the usage-amount of a flame retardant (E) is 120 weight part or less with respect to 100 weight part of polyols (A). If the flame retardant (E) is used in excess of 120 parts by weight, the polymer physical properties of the urethane foam may be lowered, and it is not economical due to the cost of the flame retardant used. Particularly preferred is 50 to 120 parts by weight per 100 parts by weight of the polyol (A).
  • composition of the present invention may contain other auxiliary agents other than the above (A) to (E) as long as the effects of the present invention are obtained.
  • auxiliaries include colorants, anti-aging agents, and other conventionally known additives. The type and amount of these additives may be within the normal usage range of the additive used.
  • the method for producing a flame-retardant rigid urethane foam of the present invention is characterized by reacting the above-described composition for producing a flame-retardant rigid urethane foam with a polyisocyanate under a condition where the isocyanate index is 300 or more.
  • the polyisocyanate is not particularly limited.
  • aliphatic polyisocyanate such as aromatic polyisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetra Aromatic polyisocyanates such as methylxylylene diisocyanate and modified products thereof (for example, carbodiimide modification, allophanate modification, urea modification, burette modification, isocyanurate modification, oxazolidone modification, etc.), isocyanate group-terminated prepolymers, etc. .
  • aromatic polyisocyanates include 2,4- or 2,6-toluene diisocyanate (TDI), crude TDI, diphenylmethane 2,4'- or 4,4'-diisocyanate (MDI), polymethylene polyisocyanate.
  • TDI 2,4- or 2,6-toluene diisocyanate
  • MDI diphenylmethane 2,4'- or 4,4'-diisocyanate
  • polymethylene polyisocyanate examples include phenyl isocyanate (crude MDI).
  • aliphatic polyisocyanate include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and the like.
  • the isocyanate index [(the number of equivalents of isocyanate groups in the isocyanate component per equivalent of active hydrogen groups in the polyol component) ⁇ 100] is 300 or more.
  • the isocyanate index is preferably 300 to 500.
  • the specific method for carrying out the production method of the present invention is not particularly limited.
  • the composition for producing a flame retardant rigid urethane foam and the polyisocyanate are rapidly mixed and stirred, and then a suitable container.
  • a desired flame-retardant rigid urethane foam can be manufactured by inject
  • the specific manufacturing apparatus is not particularly limited as long as these can be uniformly mixed.
  • a low pressure or a low pressure for injection foaming used when manufacturing a small mixer or a general urethane foam is used.
  • a high-pressure foaming machine, a low-pressure or high-pressure foaming machine for slab foaming, a low-pressure or high-pressure foaming machine for continuous lines, a spray-type foaming apparatus, or the like can be used.
  • the flame-retardant rigid urethane foam obtained by the production method of the present invention has a feature that the oxygen index, which is an index of flame retardancy, is 32% or more and exhibits high flame retardancy. Due to this feature, the flame-retardant rigid urethane foam obtained by the production method of the present invention can be used for various applications. For example, heat insulation and structural materials related to construction, civil engineering, electrical equipment related, heat insulating materials such as freezer, refrigerator, freezer showcase, etc., plant and ship related, LPG, LNG tanker and pipeline heat insulating materials, vehicle related Applications such as cold storage and heat insulation for refrigerated vehicles can be mentioned.
  • the measurement method for each measurement item is as follows. ⁇ Reactivity measurement items> Cream time: The rising start time of the foamed foam was measured visually. Gel time: The time required for the reaction to proceed to change from a liquid material to a resinous material was measured.
  • ⁇ Core density of foam> The center part of the foam which was free-foamed in a 5 L (liter) mold was cut into a size of 25 cm ⁇ 25 cm ⁇ 8 cm, and the core density was calculated by accurately measuring the size and weight.
  • ⁇ Oxygen index of foam> A sample in which the core density of the foam was measured was measured according to JIS K7201.
  • Example 1 Production of flame retardant rigid urethane foam.
  • Mannich polyether polyol manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name
  • Examples 4 to 10 Production of flame retardant rigid urethane foam.
  • a flame retardant rigid urethane foam was produced by changing the catalyst type in the same manner as in Example 1.
  • the reactivity, foam core density, oxygen index, and compressive strength were measured in the same manner as in Example 1. These results are also shown in Table 1.
  • the flame-retardant rigid urethane foam of the present invention has an isocyanate index of 300 or more and a quaternary ammonium salt as a catalyst. It was possible to achieve high flame retardance with an oxygen index of 32% or more.
  • Comparative Example 1 manufactured using a 50% by weight ethylene glycol solution of tetramethylammonium acetate as a catalyst and having the same composition as Patent Document 1, a large amount was achieved to achieve an oxygen index of 32% or more. Of flame retardant was required.
  • the oxygen index was less than 32%. Therefore, when manufacturing a flame-retardant rigid urethane foam using the composition for manufacturing a flame-retardant rigid urethane foam of the present invention in which the amount of flame retardant used is small, the isocyanate index may be set to 300 or more. It is understood that it is preferable. Further, in Reference Example 2 produced under the condition that the amount of the flame retardant used was 150 parts by weight, although the oxygen index was 32% or more, the compressive strength was lower than that in Example 1. Therefore, it is understood that when the flame retardant rigid urethane foam is produced using the catalyst solution for producing the flame retardant rigid urethane foam of the present invention, it is not necessary to increase the amount of the flame retardant used.
  • Examples 11-12 Production of flame retardant rigid urethane foam.
  • a flame-retardant rigid urethane foam was produced by the same method as in Example 1 under the conditions in which the catalyst amount of a 75% by weight aqueous solution of tetramethylammonium acetate was changed.
  • the reactivity, foam core density, oxygen index, and compressive strength were measured in the same manner as in Example 1. These results are also shown in Table 2.
  • the flame-retardant rigid urethane foam of the present invention was able to improve the oxygen index by increasing the amount of catalyst.
  • Comparative Examples 2 to 4 using a 50 wt% ethylene glycol solution of tetramethylammonium acetate the oxygen index did not reach 32% or more even when the catalyst amount was increased.
  • Comparative Examples 5 to 7 using a 30% by weight aqueous solution of tetramethylammonium acetate the oxygen index did not reach 32% or more even when the catalyst amount was increased.
  • Examples 13 to 15 Production of flame retardant rigid urethane foam.
  • flame retardant rigid urethane foams having an isocyanate index of 300 to 400 were produced in the same manner as in Example 1 under the conditions where the polyol was changed.
  • the reactivity, foam core density, oxygen index, and compressive strength were measured in the same manner as in Example 1. These results are also shown in Table 2.
  • the flame-retardant rigid urethane foam of the present invention has a high oxygen index of 32% or more with a small amount of flame retardant of 120 parts by weight or less even in a system in which the polyol is changed. Flame retardancy could be achieved.
  • the flame retardant rigid urethane foam produced using the composition for producing the flame retardant rigid urethane foam of the present invention is a building, civil engineering related heat insulating material or structural material, an electric equipment related freezer, refrigerator, freezer showcase, etc. It is useful as a heat insulating material for plants, heat insulating materials for plant and ship-related LPG, LNG tanker, etc., a heat insulating material for vehicles, a heat insulating material for refrigerator trucks, and the like.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une composition destinée à la fabrication d'une mousse d'uréthane dure ignifugeante qui utilise une faible quantité d'agent ignifugeant, et un procédé de fabrication d'une mousse d'uréthane dure ignifugeante présentant un indice limite d'oxygène supérieur ou égal à 32 % utilisant ladite composition. La présente invention contient un polyol (A), un catalyseur (B), un agent d'expansion (C), un stabilisant de mousse (D), et un agent ignifugeant (E). Le catalyseur (B) est une solution aqueuse contenant plus de 50 % en poids d'un sel d'ammonium quaternaire représenté par la formule générale (1) ; et la teneur en agent ignifugeant (E) est inférieure ou égale à 120 parties en poids pour 100 parties en poids du polyol (A) (les R1 à R4 représentent un groupe hydrocarbure aliphatique en C1 à C12 ou un groupe hydrocarbure aromatique en C6 à C14 ; Xb- représente un groupe acide ; a représente un entier de 1 à 3 ; et b représente un entier de 1 à 3).
PCT/JP2013/074929 2012-09-14 2013-09-13 Composition destinée à la fabrication d'une mousse d'uréthane dure ignifugeante, et procédé de fabrication d'une mousse d'uréthane dure ignifugeante à l'aide de ladite composition WO2014042255A1 (fr)

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JP6993238B2 (ja) * 2016-12-08 2022-01-13 積水化学工業株式会社 ウレタン樹脂組成物

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US5308393A (en) * 1988-12-14 1994-05-03 Haettich Thomas Aqueous release agent and the use thereof
JP2004292582A (ja) * 2003-03-26 2004-10-21 Tosoh Corp 硬質ポリウレタンフォーム及び／又は硬質ポリイソシアヌレートフォームの製造用触媒、並びにそれを用いた硬質ポリウレタンフォーム及び／又は硬質ポリイソシアヌレートフォームの製造方法
JP2005126695A (ja) * 2003-09-29 2005-05-19 Tosoh Corp 硬質ポリウレタンフォーム及びイソシアヌレート変性硬質ポリウレタンフォーム製造用触媒組成物及びそれを用いた原料配合組成物
WO2008018601A1 (fr) * 2006-08-11 2008-02-14 Tosoh Corporation Composition de catalyseur pour la production d'une résine de polyuréthane et procédé de production de la résine de polyuréthane
JP2008280410A (ja) * 2007-05-09 2008-11-20 Sumika Bayer Urethane Kk ポリウレタン樹脂の製造法およびそのポリウレタン成形品
JP2013119584A (ja) * 2011-12-07 2013-06-17 Tosoh Corp 硬質ポリウレタンフォーム製造用触媒、及びそれを用いた硬質ポリウレタンフォームの製造方法

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ES2525116T3 (es) * 2003-09-29 2014-12-17 Tosoh Corporation Composición de catalizador para la producción de espuma rígida de poliuretano y espuma rígida de poliuretano modificado con isocianurato, y composición de materias primas que contiene la misma

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Publication number Priority date Publication date Assignee Title
US5308393A (en) * 1988-12-14 1994-05-03 Haettich Thomas Aqueous release agent and the use thereof
JP2004292582A (ja) * 2003-03-26 2004-10-21 Tosoh Corp 硬質ポリウレタンフォーム及び／又は硬質ポリイソシアヌレートフォームの製造用触媒、並びにそれを用いた硬質ポリウレタンフォーム及び／又は硬質ポリイソシアヌレートフォームの製造方法
JP2005126695A (ja) * 2003-09-29 2005-05-19 Tosoh Corp 硬質ポリウレタンフォーム及びイソシアヌレート変性硬質ポリウレタンフォーム製造用触媒組成物及びそれを用いた原料配合組成物
WO2008018601A1 (fr) * 2006-08-11 2008-02-14 Tosoh Corporation Composition de catalyseur pour la production d'une résine de polyuréthane et procédé de production de la résine de polyuréthane
JP2008280410A (ja) * 2007-05-09 2008-11-20 Sumika Bayer Urethane Kk ポリウレタン樹脂の製造法およびそのポリウレタン成形品
JP2013119584A (ja) * 2011-12-07 2013-06-17 Tosoh Corp 硬質ポリウレタンフォーム製造用触媒、及びそれを用いた硬質ポリウレタンフォームの製造方法

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CN104640895A (zh) 2015-05-20
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JP6213083B2 (ja) 2017-10-18

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