WO2016056552A1 - Composition de polyol pour mousse rigide de polyuréthane, et procédé de fabrication de mousse rigide de polyuréthane - Google Patents

Composition de polyol pour mousse rigide de polyuréthane, et procédé de fabrication de mousse rigide de polyuréthane Download PDF

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Publication number
WO2016056552A1
WO2016056552A1 PCT/JP2015/078350 JP2015078350W WO2016056552A1 WO 2016056552 A1 WO2016056552 A1 WO 2016056552A1 JP 2015078350 W JP2015078350 W JP 2015078350W WO 2016056552 A1 WO2016056552 A1 WO 2016056552A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane foam
rigid polyurethane
polyol
polyol composition
foam
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Application number
PCT/JP2015/078350
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English (en)
Japanese (ja)
Inventor
安楽　夏子
神野　昌洋
悠人翔 吉川
裕介 玉井
Original Assignee
東洋ゴム工業株式会社
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Publication date
Priority claimed from JP2015184859A external-priority patent/JP6809685B2/ja
Application filed by 東洋ゴム工業株式会社 filed Critical 東洋ゴム工業株式会社
Priority to KR1020177007870A priority Critical patent/KR101901538B1/ko
Priority to CN201580048642.1A priority patent/CN106687491B/zh
Publication of WO2016056552A1 publication Critical patent/WO2016056552A1/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

Definitions

  • the present invention relates to a polyol composition for rigid polyurethane foam and a rigid polyurethane foam comprising 1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as HFO-1233zd) as an essential component as a blowing agent component. It relates to a manufacturing method.
  • Hard polyurethane foam is a well-known material as a heat insulating material, a lightweight structural material, and the like. Such a rigid polyurethane foam is formed by mixing a polyol composition containing a polyol compound and a foaming agent as essential components and an isocyanate component, and then foaming and curing the mixture.
  • chlorofluorocarbon compounds such as CFC-11 were used as the foaming agent, but the CFC-11 was prohibited from use because it caused the destruction of the ozone layer, and was switched to HCFC-141b.
  • HFO-1233zd has poor compatibility with the polyol compound, the polyol composition containing HFO-1233zd is likely to be separated when stored in the state of the stock solution, and the stock solution storage stability is poor.
  • HFO-1233zd is poorly compatible with the polyol compound, when the hard polyurethane foam is produced, the mixing of the raw material polyol compound and the isocyanate component is poor, resulting in a decrease in the physical properties of the resulting rigid polyurethane foam. Turned out to be. Note that “poor stock storage stability” does not mean that the reactivity deteriorates after storage.
  • the present invention has been made in view of the above circumstances, and its object is to provide a rigid polyurethane foam that has good stock solution storage stability even when HFO-1233zd is used as a foaming agent, and that can suppress a decrease in physical properties of the rigid polyurethane foam.
  • Polyol composition, and a method for producing a rigid polyurethane foam are provided.
  • the polyol composition for rigid polyurethane foam of the present invention contains at least a polyol compound, a foaming agent, and a compatibilizing agent, and is mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam.
  • the foaming agent contains HFO-1233zd
  • the compatibilizer contains ethyl diglycol acetate.
  • the method for producing a rigid polyurethane foam of the present invention is a method for producing a rigid polyurethane foam in which an isocyanate component and a polyol composition are mixed, foamed and cured to obtain a rigid polyurethane foam, and the polyol composition contains at least a polyol compound.
  • a foaming agent, and a compatibilizer wherein the foaming agent contains HFO-1233zd, and the compatibilizer contains ethyl diglycol acetate.
  • the stock solution has good storage stability and can further suppress deterioration of physical properties of the rigid polyurethane foam, and a method for producing the rigid polyurethane foam Can be provided.
  • the polyol composition for rigid polyurethane foam of this embodiment contains at least a polyol compound, a foaming agent, and a compatibilizing agent, and is mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam.
  • the foaming agent contains HFO-1233zd
  • the compatibilizer contains ethyl diglycol acetate.
  • polyol compound As the polyol compound, known polyol compounds for rigid polyurethane foam can be used without limitation. Examples of such polyol compounds include tertiary amino group-containing polyol compounds, aliphatic polyol compounds, and aromatic polyol compounds.
  • the tertiary amino group-containing polyol compound is an alkylene oxide using a primary or secondary amine as an initiator, specifically, propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran or the like. It is a polyfunctional polyol compound obtained by ring-opening addition polymerization of one or more kinds.
  • Examples of the primary or secondary amine initiator that is an initiator of the tertiary amino group-containing polyol compound include aliphatic primary and secondary monoamines such as ammonia, methylamine, and ethylamine, ethylenediamine, and hexamethylene.
  • Aliphatic primary or secondary polyamines such as diamine, N, N'-dimethylethylenediamine, aromatic primary or secondary mono- or secondary such as aniline, diphenylamine, toluenediamine, diphenylmethanediamine, N-methylaniline
  • alkanolamines such as polyamines, monoethanolamine and diethanolamine.
  • the content of the tertiary amino group-containing polyol compound is preferably 10 to 60% by weight, more preferably 20 to 50% by weight in the polyol compound.
  • Tertiary amino group-containing polyol compounds are effective in increasing reactivity and manifesting physical properties. When the amount is less than 10% by weight, no increase in reactivity is observed. When the amount exceeds 60% by weight, the reaction becomes too fast. Causes foam burns and cracks.
  • Aliphatic polyol compounds are aliphatic or alicyclic polyfunctional active hydrogen compounds as polyol initiators, alkylene oxides, specifically propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran, etc. It is a polyfunctional oligomer obtained by ring-opening addition polymerization of one or more of the above cyclic ethers, preferably PO or PO and EO.
  • polyol initiator of the aliphatic polyol compound examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, glycols such as neopentyl glycol, trimethylolpropane, Examples include triols such as glycerin, tetrafunctional alcohols such as pentaerythritol, polyfunctional alcohols such as sorbitol and sucrose, water, and the like.
  • aromatic polyol compound examples include a polyol compound obtained by the above-described method of adding an alkylene oxide to a polyfunctional active hydrogen compound having an aromatic ring in the molecule, and an ester polyol compound of an aromatic polycarboxylic acid and a polyfunctional alcohol. Is done.
  • hydroquinone, bisphenol A, Mannich or the like is added to at least one of PO, EO, SO, preferably PO or PO and EO.
  • Specific examples are compounds having ring-opening addition.
  • ester polyol compounds of aromatic polycarboxylic acids and polyfunctional alcohols include ester polyol compounds obtained by reacting hydroxyl-terminated alcohols of terephthalic acid, orthophthalic acid, isophthalic acid, etc. with ethylene glycol, diethylene glycol, etc. .
  • the polyol compound preferably has a hydroxyl value of 200 to 2000 mgKOH / g.
  • a tertiary amino group-containing polyol compound or an aliphatic polyol compound is used, an effect of reducing the viscosity of the polyol composition can be obtained.
  • the polyol compound includes ethylene glycol (EG), triethylene glycol, diethylene glycol (DEG), 1,4-butanediol, 1,6-hexanediol (1,6-HD), neopentyl glycol, diethylene glycol, dipropylene glycol. It may also contain glycols such as (DPG), triols such as glycerin and trimethylolpropane.
  • EG ethylene glycol
  • DEG diethylene glycol
  • 1,4-butanediol 1,6-hexanediol
  • 1,6-HD 1,6-hexanediol
  • neopentyl glycol diethylene glycol, dipropylene glycol. It may also contain glycols such as (DPG), triols such as glycerin and trimethylolpropane.
  • the foaming agent contains HFO-1233zd which has a low ozone depletion coefficient and a global warming coefficient and is not flammable.
  • the foaming agent preferably further contains water.
  • water By adding water, the vapor pressure of the polyol composition can be reduced.
  • the water content is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total polyol compound.
  • the foaming agent may further contain a known foaming agent for rigid polyurethane foam.
  • the content of the foaming agent is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the total polyol compound.
  • the compatibilizing agent contains ethyl diglycol acetate.
  • HFO-1233zd and ethyl diglycol acetate in combination, the stock solution storage stability such as the suppression of the separation of the polyol composition can be improved. Further, by using HFO-1233zd and ethyl diglycol acetate in combination, it is possible to suppress deterioration of physical properties of the rigid polyurethane foam. The reason is not clear, but is considered as follows.
  • HFO-1233zd is poorly compatible with hydrophilic polyol compounds, when the isocyanate component undergoes foam curing reaction with the polyol compound in a foamed stock solution composition in which a hydrophobic isocyanate component and a hydrophilic polyol composition are mixed. HFO-1233zd is considered to bloom. As a result, it is presumed that HFO-1233zd in the foaming stock solution composition inhibits the foaming and curing reaction of the isocyanate component and the polyol compound, and as a result, the physical properties of the foam are lowered.
  • Ethyl diglycol acetate has the effect of improving the compatibility between HFO-1233zd and the polyol compound, so that the foam curing reaction of the isocyanate component and the polyol compound proceeds better, improving the physical properties of the produced rigid polyurethane foam. It is considered possible.
  • the weight ratio of HFO-1233zd to ethyl diglycol acetate in the polyol composition is 99 from the viewpoint of storage stability of the stock solution and the deterioration of physical properties of the rigid polyurethane foam. 5: 0.5 to 70:30 is preferable, and 99: 1 to 80:20 is more preferable.
  • the polyol composition may contain a known catalyst for rigid polyurethane foam, a foam stabilizer, a flame retardant, a plasticizer, a colorant, an antioxidant, and the like.
  • the catalyst examples include tertiary amines such as triethylenediamine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine and DBU.
  • Metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate and tin octylate can be exemplified as the urethanization reaction catalyst. It is also preferable to use a catalyst that forms an isocyanurate bond that contributes to an improvement in flame retardancy in the structure of the polyurethane molecule.
  • Examples of the catalyst for forming an isocyanurate bond include potassium acetate and potassium octylate. Some of the tertiary amine catalysts promote the formation of isocyanurate bonds. A catalyst that promotes the formation of isocyanurate bonds and a catalyst that promotes the formation of urethane bonds may be used in combination. Metal catalysts, quaternary ammonium salt catalysts, acid block catalysts, and imidazole catalysts can also be used.
  • foam stabilizer a known foam stabilizer for rigid polyurethane foam can be used without limitation.
  • foam stabilizer polydimethylsiloxane and a graft copolymer or block copolymer of polydimethylsiloxane and polyalkylene oxide are usually used.
  • polyalkylene oxide polyethylene oxide, polypropylene oxide, a random copolymer or block copolymer of ethylene oxide and propylene oxide having an average molecular weight of 5000 to 8000 is used.
  • a non-silicone foam stabilizer may be used.
  • the flame retardant examples include metal compounds such as halogen-containing compounds, organic phosphate esters, antimony trioxide, and aluminum hydroxide. These flame retardants, for example, may reduce the physical properties of the rigid polyurethane foam obtained by adding an excessive amount of organophosphate, and if adding an excessive amount of metal compound powder such as antimony trioxide, it may affect the foaming behavior of the foam. May occur, and the amount of addition is limited to a range that does not cause such a problem.
  • plasticizer examples include halogenated alkyl esters of phosphoric acid, alkyl phosphoric acid esters, aryl phosphoric acid esters, phosphonic acid esters, and the like. Specifically, tris (2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical Co., Ltd.) ), Tris ( ⁇ -chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical Co., Ltd.), tributoxyethyl phosphate (TBEP, manufactured by Rhodia), tributyl phosphate, triethyl phosphate, cresyl phenyl phosphate, dimethylmethylphosphonate, etc. N, one or more of these can be used.
  • CLP tris (2-chloroethyl) phosphate
  • TCPP Tris ( ⁇ -chloropropyl) phosphate
  • TEP tributoxyethyl phosphate
  • tributyl phosphate
  • the addition amount of the plasticizer is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polyol compound. If it exceeds this range, the plasticizing effect cannot be sufficiently obtained, and problems such as deterioration of the physical properties of the foam may occur.
  • the polyol composition of this embodiment can be used for the production of continuously produced rigid polyurethane foams such as slabstock foams and sandwich panels, injection-injected rigid polyurethane foam sandwich panels, in-situ foamed rigid urethane foams, and the like.
  • the manufacturing method of the rigid polyurethane foam of this embodiment is a manufacturing method of the rigid polyurethane foam which mixes an isocyanate component and the said polyol composition, is foamed and hardened to make a rigid polyurethane foam.
  • liquid MDI is used because it is easy to handle, the reaction speed is excellent, the physical properties of the resulting rigid polyurethane foam are excellent, and the cost is low.
  • crude (crude) MDI c-MDI
  • uretonimine-containing MDI Millionate MTL; manufactured by Nippon Polyurethane Industry Co., Ltd.
  • the use of crude (crude) MDI is particularly preferred in that the formed rigid polyurethane foam has excellent physical properties such as mechanical strength and is inexpensive.
  • liquid MDI In addition to liquid MDI, other isocyanate components may be used in combination.
  • Di- or polyisocyanate compounds and isocyanate components well known in the technical field of rigid polyurethane can be used without limitation.
  • Prepolymers can also be used without limitation.
  • the isocyanate group / active hydrogen group equivalent ratio (NCO index) in the mixing of the polyol composition and the isocyanate component is 50 to 500, more preferably 110 to 400.
  • the foam curing reaction is promoted, and a urethane, urea bond, and isocyanurate bond are formed in the resin constituting the rigid polyurethane foam, and the physical properties, particularly compressive strength and physical properties of thermal conductivity are further improved.
  • Polyurethane foam can be produced.
  • the manufacturing method of the rigid polyurethane foam of this embodiment can be used for manufacturing a rigid polyurethane foam continuously produced such as a slab stock foam and a sandwich panel, a rigid polyurethane foam sandwich panel to be injected and injected, an in-situ foamed rigid urethane foam and the like. is there.
  • the foam density was determined according to JIS K 7222.
  • Table 1 shows the constituent materials of the polyol composition.
  • the polyol compositions according to Examples 1 to 7 are excellent in stock solution storage stability such as separation suppression even when HFO-1233zd is contained as a foaming agent.
  • the results in Table 2 show that the rigid polyurethane foams produced using the polyol compositions according to Examples 1 to 7 can suppress deterioration of physical properties even when HFO-1233zd is used as the foaming agent.

Abstract

La composition de polyol pour mousse rigide de polyuréthane de l'invention comprend au moins un composé polyol, un agent moussant et un agent de compatibilité, et est destinée à former une mousse rigide de polyuréthane en la mélangeant à un composant isocyanate contenant un composé polyisocyanate, puis en la faisant mousser et durcir. Ledit agent moussant comprend un 1-chloro-3,3,3-trifluoropropène, et ledit agent de compatibilité comprend un éthyldiglycolacétate. Ainsi, il est possible de fournir une composition de polyol pour mousse rigide de polyuréthane qui présente une stabilité de conservation de liquide de départ, telle qu'une inhibition de séparation, ou similaire, satisfaisante, y compris dans le cas où le 1-chloro-3,3,3-trifluoropropène est mis en œuvre en tant qu'agent moussant, et qui permet d'inhiber une baisse des propriétés physiques de la mousse rigide de polyuréthane.
PCT/JP2015/078350 2014-10-08 2015-10-06 Composition de polyol pour mousse rigide de polyuréthane, et procédé de fabrication de mousse rigide de polyuréthane WO2016056552A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020177007870A KR101901538B1 (ko) 2014-10-08 2015-10-06 경질 폴리우레탄폼용 폴리올 조성물 및 경질 폴리우레탄폼의 제조 방법
CN201580048642.1A CN106687491B (zh) 2014-10-08 2015-10-06 硬质聚氨酯泡沫用多元醇组合物、及硬质聚氨酯泡沫的制造方法

Applications Claiming Priority (4)

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JP2014206898 2014-10-08
JP2014-206898 2014-10-08
JP2015-184859 2015-09-18
JP2015184859A JP6809685B2 (ja) 2014-10-08 2015-09-18 硬質ポリウレタンフォーム用ポリオール組成物、及び硬質ポリウレタンフォームの製造方法

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005350555A (ja) * 2004-06-10 2005-12-22 Kao Corp ポリウレタンフォームの製造法
JP2012506944A (ja) * 2008-10-28 2012-03-22 ハネウェル・インターナショナル・インコーポレーテッド １−クロロ−３，３，３−トリフルオロプロペンを含む共沸混合物様組成物
JP2013521397A (ja) * 2010-03-09 2013-06-10 アルケマ フランス ヒドロクロロフルオロオレフィン発泡剤組成物
JP2013525574A (ja) * 2010-04-28 2013-06-20 アーケマ・インコーポレイテッド ハロゲン化オレフィン発泡剤を含むポリウレタンポリオールブレンド物の安定性を改良する方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005350555A (ja) * 2004-06-10 2005-12-22 Kao Corp ポリウレタンフォームの製造法
JP2012506944A (ja) * 2008-10-28 2012-03-22 ハネウェル・インターナショナル・インコーポレーテッド １−クロロ−３，３，３−トリフルオロプロペンを含む共沸混合物様組成物
JP2013521397A (ja) * 2010-03-09 2013-06-10 アルケマ フランス ヒドロクロロフルオロオレフィン発泡剤組成物
JP2013525574A (ja) * 2010-04-28 2013-06-20 アーケマ・インコーポレイテッド ハロゲン化オレフィン発泡剤を含むポリウレタンポリオールブレンド物の安定性を改良する方法

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