WO2020166646A1 - Composition de matière première pour des polyisocyanurates et procédé de fabrication de ces derniers - Google Patents

Composition de matière première pour des polyisocyanurates et procédé de fabrication de ces derniers Download PDF

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WO2020166646A1
WO2020166646A1 PCT/JP2020/005459 JP2020005459W WO2020166646A1 WO 2020166646 A1 WO2020166646 A1 WO 2020166646A1 JP 2020005459 W JP2020005459 W JP 2020005459W WO 2020166646 A1 WO2020166646 A1 WO 2020166646A1
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group
carbon atoms
compound
polyisocyanurate
polyfunctional isocyanate
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PCT/JP2020/005459
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English (en)
Japanese (ja)
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拓樹 倉本
中西　健一
恭章 川口
尚平 西澤
好成 奥野
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昭和電工株式会社
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Priority claimed from CN201911106849.6A external-priority patent/CN111560109A/zh
Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to JP2020572298A priority Critical patent/JPWO2020166646A1/ja
Priority to KR1020217025143A priority patent/KR20210113313A/ko
Priority to CN202080013490.2A priority patent/CN113906071A/zh
Publication of WO2020166646A1 publication Critical patent/WO2020166646A1/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
    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only

Definitions

  • the present invention relates to a polyisocyanurate raw material composition and a method for producing polyisocyanurate.
  • the present invention also relates to a polyisocyanurate production kit, a cured polyisocyanurate raw material, and a catalyst for a polyisocyanurate-forming reaction.
  • the present application claims priority based on Japanese Patent Application No. 2019-024875 filed in Japan on February 14, 2019 and application number 201111106849.6 filed in China on November 13, 2019, and The contents are incorporated here.
  • Polyisocyanurate is a resin in which isocyanurate rings are arbitrarily linked. It is said that heat resistance and flame retardancy are improved by introducing an isocyanurate ring structure into polyurethane foam, but industrial use of polyisocyanurate itself has not progressed.
  • Polyisocyanurate is synthesized by the trimerization reaction of polyfunctional isocyanate.
  • a catalyst for the trimerization reaction of isocyanate a tertiary amine, a quaternary ammonium salt, a metal salt and the like have been used (for example, Patent Document 1).
  • catalysts such as tertiary amines, quaternary ammonium salts, and metal salts have high hygroscopicity, and thus cause foaming during thermosetting.
  • examples of the catalyst having low hygroscopicity include phosphorus catalysts.
  • the reaction efficiency of the polyfunctional isocyanate trimerization reaction is low, and it is not possible to generate a sufficient amount of isocyanurate ring for thermosetting.
  • the present invention has been made in view of the above circumstances, less foaming during thermosetting, a method for producing a polyisocyanurate having good curability, and a polyisocyanurate raw material composition that can be used in the production method,
  • An object of the present invention is to provide a polyisocyanurate production kit and a catalyst for polyisocyanurate production reaction.
  • Another object of the present invention is to provide a polyisocyanurate with less foaming, that is, a cured product of a polyisocyanurate raw material, which is produced by the above production method.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • the polyisocyanate according to [1], wherein the ratio (molar ratio) of the compound (I) to the polyfunctional isocyanate is polyfunctional isocyanate/compound (I) 100/0.001 to 100/5.
  • the polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof, [ 1] or the polyisocyanurate raw material composition according to [2].
  • a polyisocyanurate production kit comprising (a) a polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound, wherein (C) is a kit stored in different containers.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • a kit for producing polyisocyanurate comprising (d) a composition containing a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) an epoxy compound:
  • the kit (d) and (c) are housed in different containers.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • kits for producing polyisocyanurate comprising (e) a composition containing a polyfunctional isocyanate and an epoxy compound, and (b) a compound (I) represented by the following general formula (I):
  • the kits (e) and (b) are contained in different containers.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • R 1 and R 2 represents a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • a method for producing polyisocyanurate comprising:
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • a catalyst for a production reaction for producing polyisocyanurate from a polyfunctional isocyanate which comprises a combination of a compound (I) represented by the following general formula (I) and an epoxy compound.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • polyisocyanurate which comprises a combination of a compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a production reaction for producing polyisocyanurate from a polyfunctional isocyanate.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • thermosetting there is little foaming during thermosetting, a method for producing a polyisocyanurate having good curability, and a polyisocyanurate raw material composition usable in the production method, a polyisocyanurate producing kit, and a polyisocyanurate.
  • a catalyst for the isocyanurate production reaction is provided.
  • a polyisocyanurate or a cured product of a polyisocyanurate raw material which is produced by the above-mentioned production method and has a small amount of foaming.
  • FIG. 15 is a scatter diagram showing the relationship between the HOMO level and the average charge at the ortho position of the compounds shown in Table 14.
  • the “polyisocyanurate” refers to a compound having a structure in which a plurality of isocyanurate rings are arbitrarily linked via a divalent organic group.
  • the “polyisocyanurate raw material composition” is a composition containing a raw material of polyisocyanurate (reaction product of polyisocyanurate production reaction) and/or a catalyst of polyisocyanurate production reaction. That is, the term refers to those used for producing polyisocyanurate or a cured product of polyisocyanurate.
  • the “kit for producing polyisocyanurate” is a kit containing a raw material of polyisocyanurate and a catalyst for a polyisocyanurate forming reaction, and is used for producing polyisocyanurate or a cured product of polyisocyanurate raw material. It is what is done.
  • the “cured product of polyisocyanurate raw material” refers to a cured product containing polyisocyanurate obtained by heating the polyisocyanurate raw material composition.
  • the carbon number does not include the carbon number of a substituent.
  • the present invention comprises a polyisocyanurate containing a polyfunctional isocyanate, a compound represented by the following general formula (I) (hereinafter, also referred to as “compound (I)”), and an epoxy compound.
  • a raw material composition is provided.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Polyfunctional isocyanate means a compound containing two or more isocyanato groups (—N ⁇ C ⁇ O).
  • the polyfunctional isocyanate those generally used for producing polyisocyanurate can be used without particular limitation.
  • the number of isocyanato groups contained in the polyfunctional isocyanate is not particularly limited as long as it is 2 or more, but is preferably 2 to 5, more preferably 2 or 3, and even more preferably 2.
  • Examples of polyfunctional isocyanates include aliphatic isocyanates and aromatic isocyanates.
  • the aliphatic isocyanate is a polyfunctional isocyanate containing an aliphatic hydrocarbon group and two or more isocyanato groups.
  • the aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.
  • an aliphatic hydrocarbon group containing a ring in the structure an alicyclic group, a group in which an alicyclic group is bonded to the end of a linear or branched aliphatic hydrocarbon group, or an alicyclic group is directly Examples thereof include groups intervening in the chain or branched chain aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 5 to 10 carbon atoms.
  • the aromatic isocyanate is a polyfunctional isocyanate containing at least one aromatic ring and two or more isocyanato groups.
  • the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) ⁇ electrons, and may be monocyclic or polycyclic.
  • the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle.
  • the carbon number of the aromatic ring is preferably 6 to 15, and more preferably 6 to 12.
  • the number of aromatic rings contained in the aromatic isocyanate is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.
  • the aromatic isocyanate may contain an aliphatic hydrocarbon group in addition to the aromatic ring and the isocyanato group. Examples of the aliphatic hydrocarbon group are the same as those listed as the aliphatic hydrocarbon group in the aliphatic isocyanate.
  • aliphatic isocyanate examples include tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, dodecamethylene-1, 12-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5 -Isocyanatomethylcyclohexane cis-cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane trans-cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4 '-Diisocyanate, ⁇
  • aromatic isocyanate examples include tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate and naphthylene-1,5-diisocyanate.
  • the polyfunctional isocyanate is a polyphenyl polymethylene polyisocyanate of a type obtained by condensing aniline with formalin and then phosgenating, at room temperature containing a carbodiimide group or a uretonimine group as described in German Patent 1092007. It may be a liquid diphenylmethane diisocyanate, or a modified polyisocyanate containing a urethane bond, an allophanate bond, an isocyanurate ring structure, a urea bond, a biuret bond, a uretdione ring structure, or the like. Further, the polyfunctional isocyanate may be an isocyanate-based prepolymer obtained by excessively reacting the above-mentioned isocyanate with a polyol used in the urethane industry.
  • polyfunctional isocyanate diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof are preferable.
  • polyfunctional isocyanate may be used.
  • examples of commercially available polyfunctional isocyanates include Millionate (registered trademark) MT (Tosoh), Coronate (registered trademark) T-65 (Tosoh), Coronate (registered trademark) T-80 (Tosoh), and Coronate (registered trademark).
  • the polyfunctional isocyanate may be one in which the isocyanato group is blocked.
  • “Isocyanato group is blocked” means that the isocyanato group is protected by a protecting group.
  • the blocked isocyanato group can be represented by the general formula “—NC( ⁇ O)—B (B is a protecting group)”.
  • the protecting group those generally used as a protecting group for an isocyanato group can be used without particular limitation.
  • the polyfunctional isocyanate may be used alone or in combination of two or more.
  • the proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition of the present embodiment is, for example, 80 mol% or more and less than 100 mol %.
  • the proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably 85 mol% or more and 99.99 mol% or less, more preferably 90 mol% or more and 98 mol% or less, and further preferably 93 mol% or more and 97 mol% or less. ..
  • the ratio of the polyfunctional isocyanate is at least the lower limit value of the above range, good heat resistance can be realized. Further, when the proportion of the polyfunctional isocyanate is not more than the upper limit value of the above range, it becomes easy to balance with other components.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or amino.
  • the alkyl group having 1 to 10 carbon atoms in R 3 to R 5 may be linear or branched, and may have a ring in the structure.
  • the alkyl group having 1 to 10 carbon atoms in R 3 to R 5 preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 or 2 carbon atoms.
  • linear or branched alkyl group examples include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, Examples include neopentyl group, isopentyl group, sec-pentyl group and the like.
  • the linear or branched alkyl group for R 3 to R 5 may have a substituent.
  • “which may have a substituent” means that the hydrogen atom (—H) of the hydrocarbon group may be substituted with a monovalent group.
  • substituents examples include an amino group, a carboxy group, a cyano group, a halogen atom and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • linear or branched alkyl group for R 3 to R 5 those having no substituent are more preferable.
  • the alkyl group containing a ring in the structure includes a cycloalkyl group, a group in which a cycloalkane ring is bonded to the end of a linear or branched alkyl group, or a cycloalkyl group in the middle of the linear or branched alkyl group.
  • Examples thereof include groups with an alkane ring interposed.
  • the cycloalkane ring may be monocyclic or polycyclic, but is preferably monocyclic.
  • alkyl group having a ring in the structure examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a group in which a linear or branched alkyl group is bonded to the cycloalkyl group.
  • the alkyl group containing a ring in the structure of R 3 to R 5 may have a substituent. Examples of the substituent include an amino group, a carboxy group, a cyano group, a halogen atom and the like.
  • the alkoxy group having 1 to 10 carbon atoms in R 3 to R 5 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 or 2 carbon atoms.
  • the alkoxy group is a group represented by —OR (R is an alkyl group).
  • R is an alkyl group.
  • the alkyl group for R may be linear or branched, and may have a ring in the structure, but a linear or branched alkyl group is preferable. preferable.
  • Examples of the alkyl group include the same groups as those mentioned above for the alkyl group having 1 to 10 carbon atoms.
  • the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group and the like.
  • the alkoxy group having 1 to 10 carbon atoms in R 3 to R 5 is preferably a methoxy group or an ethoxy group, more preferably a methoxy group.
  • the aryl group having 6 to 12 carbon atoms in R 3 to R 5 preferably has 6 to 10 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a tolyl group, an o-xylyl group, a naphthyl group and a biphenyl group.
  • the aryl group having 6 to 12 carbon atoms in R 3 to R 5 may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an amino group, a carboxy group, a cyano group, a halogen atom and the like.
  • the fluorinated alkyl group having 1 to 10 carbon atoms in R 3 to R 5 preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 or 2 carbon atoms.
  • Specific examples of the fluorinated alkyl group having 1 to 10 carbon atoms in R 3 to R 5 include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, and alkyl groups exemplified as the alkyl group having 1 to 10 carbon atoms. And a group in which some or all of the hydrogen atoms of are substituted with fluorine atoms.
  • halogen atom in R 3 to R 5 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the halogen atom for R 3 to R 5 is preferably a fluorine atom.
  • Each alkyl group of the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms in R 3 to R 5 preferably has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, The number 1 to 3 is more preferable, and the number 1 or 2 is more preferable.
  • the alkyl group may be linear or branched, and may have a ring in the structure.
  • Specific examples of the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms in R 1 and R 2 include a methylamino group, a dimethylamino group, and a hydrogen atom of an amino group. Examples thereof include groups in which one or two are substituted with the alkyl group exemplified as the alkyl group having 1 to 10 carbon atoms.
  • R 3 to R 5 are preferably hydrogen atoms or electron donating groups from the viewpoint of reactivity. More specifically, R 3 to R 5 are preferably a hydrogen atom, an alkoxy group, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms, and a hydrogen atom or an alkoxy group. A group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms is more preferable.
  • R 3 to R 5 include a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkylamino group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms, a hydrogen atom, A methoxy group, a monomethylamino group, or a dimethylamino group is particularly preferable.
  • the three R 3 to R 5 may be the same or different.
  • Three R 3 s may be different from each other, 2 out of 3 may be the same and 1 may be different from each other, or all 3 may be the same, but all 3 R 3 are the same.
  • Three R 4 s may be different from each other, two out of three may be the same and one may be different from each other, or all three may be the same, but all three R 4 are the same.
  • Three R 5 s may be different from each other, two out of three may be the same and one may be different, and all three may be the same, but all three R 5 are the same.
  • at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • the compound (I) include phosphorus catalyst Nos. Compounds 13 to 59 and DMAPDPP (phosphorus catalyst No. 12) described later can be mentioned.
  • the phosphorus catalyst No. Compounds 12 to 59 are compounds that satisfy the following formula (1).
  • the average charge of the HOMO level and the ortho position can be calculated by the method described in Examples.
  • the phosphorus catalyst having an activation energy of 32.17 kcal/mol or less is phosphorus catalyst No. 11 (TOAP: see Tables 1 to 3) is preferable because it can be expected to show catalytic activity equal to or higher than that.
  • the activation energy can be calculated by the method described in the examples. y ⁇ 28.5x+5.644 (1)
  • the proportion of the compound (I) in the polyisocyanurate raw material composition of the present embodiment is, for example, more than 0 mol% and 10 mol% or less.
  • the proportion of compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 5 mol% or less, more preferably 0.01 mol% or more and 2 mol% or less, and 0.05 mol% or more 2 mol % Or less is more preferable.
  • the ratio of the compound (I) is at least the lower limit value of the above range, good reaction efficiency can be realized. Further, when the ratio of the compound (I) is at most the upper limit value of the above range, it becomes easy to balance with other components.
  • the epoxy compound in this embodiment is a compound containing one or more epoxy groups.
  • the epoxy compound those generally used in the trimerization reaction of isocyanate can be used without particular limitation.
  • the epoxy equivalent of the epoxy compound is not particularly limited, but is preferably 50 g/mol to 1000 g/mol, more preferably 100 g/mol to 500 g/mol, and further preferably 100 g/mol to 300 g/mol.
  • epoxy compounds include monoepoxides such as allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butylene oxide, propylene oxide, octylene oxide, styrene oxide, glycidol, and glycidyl ester of versatic acid;
  • epoxy compound phenyl glycidyl ether, styrene oxide, diglycidyl 1,2-cyclohexanedicarboxylic acid, diglycidyl ether of bisphenol A, triglycidyl isocyanurate, polyglycidyl ether of phenol novolac, polyglycidyl ether of cresol novolac. And the like are industrially easily available, which is preferable.
  • the epoxy compounds may be used alone or in combination of two or more.
  • the ratio of the epoxy compound in the polyisocyanurate raw material composition of the present embodiment is, for example, more than 0 mol% and 20 mol% or less.
  • the proportion of compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 15 mol% or less, more preferably 0.005 mol% or more and 10 mol% or less, and 0.1 mol% or more 7 mol. % Or less is more preferable.
  • the ratio of the compound (I) is at least the lower limit value of the above range, good reaction efficiency can be realized. Further, when the ratio of the compound (I) is at most the upper limit value of the above range, it becomes easy to balance with other components.
  • the ratio (molar ratio) of the epoxy compound to the polyfunctional isocyanate is preferably 100/0.001 to 100/15 of polyfunctional isocyanate/epoxy compound, more preferably 100/0.005 to 100/10, and 100/0. 1 to 100/7 is more preferable.
  • the polyisocyanurate raw material composition of the present embodiment may contain other components in addition to the polyfunctional isocyanate, the compound (I) and the epoxy compound.
  • Other components include, for example, solvents, curing accelerators, silane coupling agents, antioxidants, release agents, defoamers, emulsifiers, thixotropic agents, leveling agents, flame retardants, pigments, fillers, shrinkage agents. Examples include emollients and the like.
  • the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate is produced.
  • the compound (I) and the epoxy compound mainly function as a catalyst for the trimerization reaction of the polyfunctional isocyanate.
  • Phosphorus catalysts generally have low hygroscopicity and suppress foaming during heating, but when used as a catalyst for polyisocyanurate-forming reaction, reactivity is low and sufficient curability (yield) cannot be obtained. There was a problem.
  • the compound (I) has a specific structure represented by the general formula (I) as shown in Examples described later, it exhibits high reactivity when used as a catalyst for the polyisocyanurate production reaction. It is possible to realize sufficient curability (yield). That is, since the compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming can be suppressed and sufficient curability can be obtained when thermally cured.
  • the present invention provides a polyisocyanurate raw material composition comprising a polyfunctional isocyanate and compound (I).
  • the polyfunctional isocyanate is the same as that described in the description of the first embodiment.
  • Preferable examples of the polyfunctional isocyanate also include the same as those described in the first embodiment.
  • the polyfunctional isocyanate is preferably diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof.
  • the proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition of the present embodiment is, for example, 90 mol% or more and less than 100 mol %.
  • the proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably 95 mol% or more and 99.99 mol% or less, more preferably 98 mol% or more and 99.99 mol% or less, and 98 mol% or more 99.95 mol%. The following is more preferable.
  • the proportion of polyfunctional isocyanate is at least the lower limit value of the above range, good heat resistance can be realized. Further, when the proportion of the polyfunctional isocyanate is not more than the upper limit value of the above range, it becomes easy to balance with other components.
  • the compound (I) is the same as that described in the description of the first embodiment. Preferred examples of the compound (I) also include the same as those mentioned in the first embodiment.
  • R 3 to R 5 in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, or a monoalkylamino group having 1 to 4 carbon atoms. Or a compound having a dialkylamino group having 2 to 8 carbon atoms is preferable.
  • the compound (I) is preferably a compound represented by the general formula (I-1), wherein R 3 to R 5 in the general formula (I-1) are each independently a hydrogen atom or a carbon atom.
  • a compound which is an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a dialkylamino group having 2 to 8 carbon atoms is more preferable.
  • the alkoxy group having 1 to 4 carbon atoms an alkoxy group having 1 to 3 carbon atoms is preferable, an ethoxy group or a methoxy group is more preferable, and a methoxy group is further preferable.
  • each alkyl group of the monoalkylamino group having 1 to 4 carbon atoms or the dialkylamino group having 2 to 8 carbon atoms an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • Methylamino group or dimethylamino group is more preferred.
  • Specific examples of the compound (I) include phosphorus catalyst Nos. shown in Tables 14 to 16 below. 12 to 59 compounds can be mentioned.
  • the proportion of the compound (I) in the polyisocyanurate raw material composition of the present embodiment is, for example, more than 0 mol% and 10 mol% or less.
  • the proportion of compound (I) in the polyisocyanurate raw material composition is preferably 0.001 mol% or more and 5 mol% or less, more preferably 0.01 mol% or more and 2 mol% or less, and 0.05 mol% or more 2 mol % Or less is more preferable.
  • the ratio of the compound (I) is at least the lower limit value of the above range, good reaction efficiency can be realized. Further, when the ratio of the compound (I) is at most the upper limit value of the above range, it becomes easy to balance with other components.
  • the polyisocyanurate raw material composition of the present embodiment may contain other components in addition to the polyfunctional isocyanate and the compound (I). As other components, the same components as those mentioned in the first embodiment can be mentioned.
  • the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate is produced.
  • the epoxy compound the same compounds as those described in the description of the first embodiment can be used.
  • the compound (I) and the epoxy compound mainly function as a catalyst for the trimerization reaction of the polyfunctional isocyanate. Since the compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming is suppressed and sufficient curability (yield) can be obtained when heated.
  • the polyisocyanurate production kit of the present embodiment contains a polyfunctional isocyanate, compound (I), and an epoxy compound.
  • the kit of the present embodiment includes (a) polyfunctional isocyanate, (b) compound (I), (c) epoxy compound, (d) composition containing polyfunctional isocyanate and compound (I), and (e).
  • An example is one in which a composition containing a polyfunctional isocyanate and an epoxy compound is housed in different containers and combined appropriately.
  • the respective amounts of the polyfunctional isocyanate, the compound (I), and the epoxy compound contained in each container are not particularly limited, but a mixing ratio for mixing the respective components during the production of polyisocyanurate.
  • the amount according to is set according to.
  • the container is not particularly limited and may be any container.
  • the material of the container may be any one that does not corrode depending on the contents, and examples thereof include glass, resin, and metal.
  • the present invention is a kit for producing polyisocyanurate, which comprises (a) a polyfunctional isocyanate, (b) compound (I), and (c) an epoxy compound. c) provides the kit, which is housed in different containers.
  • polyfunctional isocyanate The polyfunctional isocyanate is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”.
  • the compound (I) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the compound (I) are also the same as those mentioned in the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”.
  • the compound (I) is preferably contained in a container in a state of being dissolved in a solvent.
  • the solvent is not particularly limited as long as it can dissolve the compound (I), and known organic solvents and the like can be used.
  • epoxy compound The epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferable examples of the epoxy compound also include the same ones as those described in the first embodiment of the above-mentioned "[polyisocyanurate raw material composition]”.
  • the (a) polyfunctional isocyanate, (b) compound (I), and (c) epoxy compound contained in the kit of the present embodiment may be mixed.
  • the trimerization reaction of the polyfunctional isocyanate proceeds and polyisocyanurate can be obtained.
  • the present invention provides a polyisocyanurate production kit comprising (d) a composition containing a polyfunctional isocyanate and a compound (I), and (c) an epoxy compound, wherein And (c) provide a kit, which is housed in different containers.
  • composition (d) The kit of the present embodiment includes a composition containing polyfunctional isocyanate and compound (I) (hereinafter referred to as “composition (d)”).
  • composition (d) is the same as the polyisocyanurate raw material composition according to the second embodiment described in the section "[Polyisocyanurate raw material composition]”.
  • epoxy compound The epoxy compound is the same as the kit according to the first embodiment.
  • compositions (d) and (c) the epoxy compound contained in the kit of this embodiment may be mixed. By heating the mixture, the trimerization reaction of the polyfunctional isocyanate proceeds and polyisocyanurate can be obtained.
  • the present invention provides a polyisocyanurate comprising (d) a composition comprising a polyfunctional isocyanate and a compound (I), and (e) a composition comprising a polyfunctional isocyanate and an epoxy compound.
  • composition (d) The composition (d) is the same as the kit according to the second embodiment.
  • composition (e) The kit of the present embodiment includes a composition containing a polyfunctional isocyanate and an epoxy compound (hereinafter referred to as "composition (e)").
  • the polyfunctional isocyanate contained in the composition (e) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”.
  • Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”.
  • the polyfunctional isocyanate may be the same as or different from the polyfunctional isocyanate contained in the composition (d).
  • the epoxy compound contained in the composition (e) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”.
  • Preferable examples of the epoxy compound also include the same ones as those described in the first embodiment of the above-mentioned "[polyisocyanurate raw material composition]”.
  • the composition (d) and the composition (e) contained in the kit of this embodiment may be mixed. By heating the mixture, the trimerization reaction of the polyfunctional isocyanate proceeds and polyisocyanurate can be obtained.
  • kits including (b) and (e) are kits including (b) and (e)
  • the present invention is a kit for producing a polyisocyanurate, which comprises (e) a composition containing a polyfunctional isocyanate and an epoxy compound, and (b) compound (I). And (b) provide a kit, which is housed in different containers.
  • composition (e) The composition (e) is the same as the kit according to the third embodiment.
  • the composition (e) and (b) compound (I) contained in the kit of the present embodiment may be mixed. By heating the mixture, the trimerization reaction of the polyfunctional isocyanate proceeds and polyisocyanurate can be obtained.
  • kits of the above first to fourth embodiments can include any configuration in addition to the components listed above.
  • examples of the optional configuration include instructions for producing polyisocyanurate, a mold for casting the polyisocyanurate raw material composition, and the like.
  • the (a) polyfunctional isocyanate contained in the kit of the first embodiment or the polyfunctional isocyanate contained in the composition (d) or the composition (e) contained in the kit of the second to fourth embodiments is In the case of a blocked polyfunctional isocyanate, the kits of the above-described first to fourth embodiments may optionally include a reagent for deprotecting the blocked polyfunctional isocyanate.
  • the present invention provides a polyisocyanurate raw material cured product obtained by heating a polyisocyanurate raw material composition containing a polyfunctional isocyanate, compound (I), and an epoxy compound.
  • the cured product of the polyisocyanurate raw material contains polyisocyanurate produced from a polyfunctional isocyanate, unreacted polyfunctional isocyanate, a dimer, a catalyst, a modified product of the catalyst, and other impurities.
  • the polyisocyanurate is not particularly limited as long as it has a structure in which a plurality of isocyanurate rings are arbitrarily linked via a divalent organic group.
  • the structure of polyisocyanurate can be represented by, for example, the following general formula (II).
  • R represents a divalent organic group
  • n represents an integer of 2 or more.
  • a plurality of Rs may be the same or different.
  • R is a divalent organic group derived from a polyfunctional isocyanate.
  • R is an aliphatic hydrocarbon group (for example, an alkylene group).
  • R is an aromatic hydrocarbon group (for example, an arylene group).
  • the cured polyisocyanurate raw material of the present embodiment may contain a plurality of types of polyisocyanurates having different structures and different molecular weights. Further, the cured product of the polyisocyanurate raw material of the present embodiment may contain the compound (I) and the epoxy compound as described below, and their reaction products (modified products) and the like.
  • the polyfunctional isocyanate is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]” above. Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”.
  • the compound (I) is the same as that described in the description of the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”. Preferred examples of the compound (I) are also the same as those mentioned in the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”.
  • the epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]” above.
  • Preferable examples of the epoxy compound also include the same ones as those described in the first embodiment of the above-mentioned "[polyisocyanurate raw material composition]”.
  • the cured product of the polyisocyanurate raw material of the present embodiment can be obtained by mixing the polyfunctional isocyanate, the compound (I), and the epoxy compound and heating the mixture.
  • the “heating” can be performed in the same manner as the heating step described in the section “[Method for producing polyisocyanurate]” below.
  • the cured product of the polyisocyanurate raw material of the present embodiment comprises polyisocyanurate and the compound (I) and a compound represented by the following general formula (I′) (hereinafter, also referred to as “compound (I′)”). And at least one compound selected from the group consisting of:
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • the proportion of polyisocyanurate in the cured polyisocyanurate raw material of the present embodiment is, for example, preferably 70% by mass or more and less than 100% by mass, and more preferably 80 to 99% by mass.
  • the compound (I′) is an oxide of the compound (I).
  • R 1 ⁇ R 5 in the general formula (I ') is the same as R 1 ⁇ R 5 in the general formula (I).
  • Preferable examples of R 3 to R 5 in the general formula (I′) are the same as those listed as preferable examples of R 3 to R 5 in the general formula (I).
  • oxides of the compounds listed as the specific examples of the compound (I) are preferable.
  • the compound (I′) contained in the cured product of the polyisocyanurate raw material of the present embodiment may be one type or two or more types.
  • the cured product of the polyisocyanurate raw material according to the present embodiment may contain only the compound (I) or only the compound (I′), and may contain both the compound (I) and the compound (I′). May be included.
  • the compound (I′) is an oxide of the compound (I).
  • the total ratio of the compound (I) and the compound (I′) in the cured polyisocyanurate raw material of the present embodiment is, for example, preferably 0.001 to 5 mass %, and 0.001 to 1 mass %. More preferably.
  • the polyisocyanurate raw material cured product of the present embodiment contains other components in addition to the polyisocyanurate and at least one compound selected from the group consisting of the compound (I) and the compound (I′). Good.
  • other components for example, (i) epoxy compound, (ii) reaction product of epoxy compound and polyfunctional isocyanate, (iii) reaction product of epoxy compound with the above compound (I), and (iv) epoxy compound And the epoxy compound (hereinafter, (i) to (iv) may be collectively referred to as “epoxy compound etc.”).
  • epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]” above.
  • Preferable examples of the epoxy compound also include the same ones as those described in the first embodiment of the above-mentioned "[polyisocyanurate raw material composition]”.
  • reaction product of epoxy compound and polyfunctional isocyanate is a compound generated by the reaction of the polyfunctional isocyanate and the epoxy compound during the heating reaction.
  • the reaction product of the epoxy compound and the polyfunctional isocyanate is not particularly limited as long as it is a compound generated by the reaction of the epoxy compound and the polyfunctional isocyanate. Examples of the reaction product include a compound containing an oxazolidone ring.
  • reaction product of epoxy compound and compound (I) is a compound generated by the reaction of the epoxy compound and the compound (I) during the heating reaction.
  • the reaction product of the epoxy compound and the compound (I) is not particularly limited as long as it is a compound generated by the reaction of the epoxy compound and the compound (I).
  • the epoxy compound is a compound represented by the following general formula (E)
  • the reaction product of the epoxy compound and the compound (I) is exemplified by the compound represented by the following general formula (E-1). It
  • R 1 ⁇ R 5 are the same as R 1 ⁇ R 5 in the general formula (I).
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Re 1 is an organic group.
  • Re 1 in the general formulas (E) and (E-1) is a phenoxymethyl group.
  • reaction product of epoxy compound and epoxy compound A reaction product of an epoxy compound and an epoxy compound (a reaction product of epoxy compounds) is a compound generated by the reaction of two or more epoxy compounds during a heating reaction.
  • the reaction product of the epoxy compounds is not particularly limited as long as it is a compound formed by the reaction of two or more epoxy compounds.
  • the epoxy compound is the compound represented by the general formula (E)
  • the reaction product of the epoxy compound and the epoxy compound is a polymer having a repeating unit represented by the following general formula (E-2). Is exemplified.
  • Re 1 is an organic group.
  • Re 1 in the general formula (E-2) is a phenoxymethyl group.
  • the total proportion of epoxy compounds and the like in the cured product of the polyisocyanurate raw material of the present embodiment is, for example, preferably 0.001 to 30% by mass, and more preferably 0.01 to 20% by mass.
  • Examples of the cured polyisocyanurate raw material of the present embodiment include, for example, 70% by mass or more and less than 100% by mass (preferably 79% by mass to 99.98% by mass) of polyisocyanurate; compound (I) and compound (I′). ) As a total amount of more than 0% by mass and 5% by mass or less (preferably 0.001 to 1% by mass); 20% by mass), those contained, and the like.
  • the cured product of the polyisocyanurate raw material of the present embodiment is produced by using the compound (I) as a catalyst, so that it has little foaming and has sufficient hardness. Therefore, the cured polyisocyanurate raw material of the present embodiment can be used for various applications such as paints, adhesives, encapsulants, and optical parts.
  • the present invention provides a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the general formula (I), and an epoxy compound, and a mixture obtained in the mixing step.
  • a method for producing polyisocyanurate which comprises a heating step of heating.
  • the mixing step is a step of mixing the polyfunctional isocyanate, the compound (I), and the epoxy compound.
  • polyfunctional isocyanate The polyfunctional isocyanate is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”.
  • epoxy compound The epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferable examples of the epoxy compound also include the same ones as those described in the first embodiment of the above-mentioned "[polyisocyanurate raw material composition]”.
  • the order of mixing the polyfunctional isocyanate, the compound (I) and the epoxy compound is not particularly limited, but the compound (I) and the epoxy compound are preceded from the viewpoint of suppressing unintentional progress of the reaction. It is preferable not to mix with.
  • the mixing step may be, for example, a step of mixing the epoxy compound with the mixture (d) of the polyfunctional isocyanate and the compound (I).
  • the mixture (d) the polyisocyanurate raw material composition according to the second embodiment described in the above section “[Polyisocyanurate raw material composition]” can be used.
  • the mixing step may be, for example, a step of mixing the compound (I) with the mixture (e) of the polyfunctional isocyanate and the epoxy compound.
  • the mixture (e) the same one as the composition (e) contained in the polyisocyanurate production kit according to the fourth embodiment described in the section “[Polyisocyanurate production kit]” is used. You can
  • the mixing step may be, for example, a step of mixing the mixture (d) of the polyfunctional isocyanate and the compound (I) with the mixture (e) of the polyfunctional isocyanate and the epoxy compound.
  • the mixture (d) the same one as the composition (d) included in the polyisocyanurate production kit according to the third embodiment described in the above section “[Polyisocyanurate production kit]” is used.
  • the mixture (e) the same composition (e) as the composition (e) contained in the polyisocyanurate production kit according to the third embodiment described in the section "[Polyisocyanurate production kit]” is described. Can be used.
  • the deprotection reaction of the blocked isocyanato group may be performed before the mixing step, after the mixing step, or during the mixing step.
  • the deprotection reaction can be appropriately selected depending on the type of the protecting group that blocks the isocyanato group.
  • the heating step is a step of heating the mixture obtained in the mixing step.
  • the heating temperature may be a temperature that is sufficient for the polyisocyanurate forming reaction to proceed, and for example, it can be 40 to 240° C., and 60 to 200° C. is preferable.
  • the heating time may be any time that is sufficient for the production of polyisocyanurate, and examples thereof include 1 to 360 minutes, and 30 to 180 minutes are preferable.
  • ⁇ Heating may be performed in two stages. For example, heating may be performed at a relatively low temperature in the first stage, and heating may be performed at a higher temperature than in the first stage in the second stage.
  • the heating temperature in the first step is, for example, 60 to 120° C., preferably 70 to 110° C.
  • the heating time for the first step is 1 to 180 minutes, and preferably 30 to 150 minutes.
  • the heating temperature in the second stage is, for example, 120 to 240° C., preferably 150 to 210° C.
  • the heating time for the second stage is, for example, 1 to 180 minutes, and more preferably 30 to 150 minutes.
  • a polyisocyanurate or a cured product of polyisocyanurate raw material can be produced.
  • the polyfunctional isocyanate trimerization reaction proceeds efficiently using the compound (I) and the epoxy compound as catalysts. Further, since the compound (I) has low hygroscopicity, it is possible to obtain a polyisocyanurate or a cured polyisocyanurate raw material with less foaming.
  • the present invention provides a catalyst for polyisocyanurate production reaction, which comprises a combination of the compound (I) represented by the general formula (I) and an epoxy compound.
  • this invention is a polyisocyanurate manufacture which contains the combination of the compound (I) represented by the said General formula (I), and an epoxy compound as a catalyst for polyisocyanurate production reaction.
  • a kit for use is provided.
  • the compound (I) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the compound (I) are also the same as those mentioned in the first embodiment in the above-mentioned “[polyisocyanurate raw material composition]”.
  • the epoxy compound is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferable examples of the epoxy compound also include the same ones as those described in the first embodiment of the above-mentioned "[polyisocyanurate raw material composition]”.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • the polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof,
  • the polyisocyanurate raw material composition according to any one of 1] to [3].
  • R 3 to R 5 in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or 2 to 5 carbon atoms.
  • a polyisocyanurate production kit comprising (a) a polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound, which comprises: (C) is a kit stored in different containers.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • kits for producing polyisocyanurate comprising (d) a composition containing a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) an epoxy compound:
  • the kits (d) and (c) are contained in different containers.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • kits for producing polyisocyanurate comprising (e) a composition containing a polyfunctional isocyanate and an epoxy compound, and (b) a compound (I) represented by the following general formula (I):
  • the kits (e) and (b) are contained in different containers.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • the polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof, The kit for producing polyisocyanurate according to any one of 6] to [10].
  • R 3 to R 5 in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or 2 to 5 carbon atoms.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • R 3 to R 5 in the general formulas (I) and (I′) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms,
  • the cured product of the polyisocyanurate raw material according to [14] or [15] which is a dialkylamino group having 2 to 8 carbon atoms.
  • a method for producing polyisocyanurate comprising:
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • the polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and modified polyisocyanates thereof, 17] A method for producing polyisocyanurate according to any one of [21].
  • R 3 to R 5 in the general formula (I) are each independently a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or 2 to 5 carbon atoms.
  • a catalyst for polyisocyanurate production reaction which comprises a combination of a compound (I) represented by the following general formula (I) and an epoxy compound.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • a polyisocyanurate production kit containing a combination of a compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a polyisocyanurate production reaction.
  • R 1 and R 2 represent a hydrogen atom.
  • R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 10 carbon atoms. It represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
  • Each of the three R 3 to R 5 may be the same or different. However, at least one of the three R 3 to R 5 is an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
  • Hexamethylene diisocyanate, catalysts (catalyst Nos. 1 to 11) and phenylglycidyl ether were mixed in a molar ratio of 100:0.1:5, and the gel time was evaluated by the above method.
  • Phosphorus catalyst with good gel time No. 9 to 11 have a HOMO level of -0.190a. u. That was all.
  • phosphorus catalyst No. Gel time is shorter than No. 11. 9 to 10
  • the HOMO level is also No. It was even higher than 11.
  • the phosphorus catalyst No. HOMO levels of -0.190a. u. Was lower. Therefore, it was found that the HOMO level is the first index for screening the catalyst for polyisocyanurate production reaction, which has a high reaction rate.
  • Phosphorus catalyst No. 5 and phosphorus catalyst No. 11 is a phosphorus catalyst in which a methoxy group as a substituent is bonded to the para position and the ortho position of the benzene ring, respectively.
  • the HOMO level was the same for both, a large difference was observed in the reaction time.
  • a transition state calculation is performed based on the density functional theory B3LYP/6-31+G* method, and the phosphorus catalyst nucleophilically attacks the cocatalyst 1,2-ethyloxirane (epoxy compound). The activation barrier at that time was calculated.
  • Phosphorus catalyst No. 5 and phosphorus catalyst No. As a result of observing the structure in the above transition state calculation with 11, the hydrogen atom of 1,2-ethyloxirane and the oxygen atom at the para-position or ortho-position of the phosphorus catalyst were hydrogen-bonded, and 1,2-oxirane was converted to the phosphorus catalyst molecule. It was found that the distance between the phosphorus atom, which is the reaction point, and the carbon of 1,2-ethyloxirane was shortened as a result.
  • the fact that the atom directly bonded to the carbon in the ortho position of the phosphorus atom has a low degree of electropositiveness can be a second index for screening a catalyst for polyisocyanurate production reaction with a fast reaction rate. all right.
  • the average charge at the ortho position is the average value of the Mullliken charges of the atoms directly bonded to the carbon atom among the atoms bonded to the ortho position of the three cyclic molecules directly bonded to the phosphorus atom.
  • the phosphorus catalyst No. In 1 TPP
  • the hydrogen atoms bonded to the carbon atoms on both sides of the carbon atom bonded to the phosphorus atom correspond to that.
  • the benzene ring is bonded to three phosphorus atoms, there are six applicable atoms.
  • the average of the Mullliken charges of these six atoms is defined as the “average charge at the ortho position”.
  • the phosphorus catalyst No. shown in Table 15 is used.
  • the activation energy of 15 was calculated to be 20.64 kcal/mol, and the phosphorus catalyst satisfying the condition of the formula (1) had a smaller activation barrier when the phosphorus catalyst nucleophilically attacked the cocatalyst, and the reaction proceeded. It was shown to be easy.
  • a phosphorus catalyst having at least one amino group at the meta or para position, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms has a phosphorus catalyst due to the presence of the electron donating group.
  • the HOMO level on the atoms rises, and a phosphorus catalyst satisfying the condition of formula (1) is obtained.
  • the phosphorus catalyst having an activation energy of 32.17 kcal/mol or less is phosphorus catalyst No. It is preferable because it can be expected to exhibit activity equal to or higher than that of 11.
  • R 1 ⁇ R 5, R 11 ⁇ R 15, and R 21 ⁇ R 25 is a R 1 ⁇ R 5, R 11 ⁇ R 15, and R 21 ⁇ R 25 in the following general formula Represented substituents are respectively shown, "H” is a hydrogen atom, "OMe” is a methoxy group, “NHMe” is a monomethylamino group, and “NMe2" is a dimethylamino group.
  • a method for producing a polyisocyanurate having good curability, a polyisocyanurate raw material composition that can be used in the production method, and a polyisocyanurate production kit are provided.
  • a polyisocyanurate or a polyisocyanurate composition having less foaming produced by the above-mentioned production method can be used for various purposes such as paints, adhesives, encapsulants, and various molded products.

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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 de matières premières pour des polyisocyanurates, qui comprend un isocyanate polyfonctionnel, un composé (I) représenté par la formule (I), et un composé époxy. Dans la formule (I), R1 et R2 représentent des atomes d'hydrogène. R3 à R5 représentent chacun indépendamment un atome d'hydrogène, un groupe alcoxy en C1-10, un groupe amino, un groupe amino monoalkyle en C1-10, ou un groupe amino dialkyle en C2-20. Chacun des trois R3 à R5 peut être identique ou différent. Cependant, au moins l'un de chacun des trois R3 à R5 est un groupe amino, un groupe amino monoalkyle en C1-10, ou un groupe amino dialkyle en C2-20.
PCT/JP2020/005459 2019-02-14 2020-02-13 Composition de matière première pour des polyisocyanurates et procédé de fabrication de ces derniers WO2020166646A1 (fr)

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KR1020217025143A KR20210113313A (ko) 2019-02-14 2020-02-13 폴리이소시아누레이트 원료 조성물, 및 폴리이소시아누레이트의 제조 방법
CN202080013490.2A CN113906071A (zh) 2019-02-14 2020-02-13 聚异氰脲酸酯原料组合物及聚异氰脲酸酯的制造方法

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Publication number Priority date Publication date Assignee Title
WO2023112538A1 (fr) * 2021-12-15 2023-06-22 株式会社レゾナック Composition de résine, film en résine durci, et dispositif d'affichage d'image
JP7540337B2 (ja) 2018-08-13 2024-08-27 株式会社レゾナック ポリイソシアヌレート原料組成物、及びポリイソシアヌレートの製造方法

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JP2016169362A (ja) * 2015-03-13 2016-09-23 新日鉄住金化学株式会社 オキサゾリドン環含有エポキシ樹脂、その製造方法、エポキシ樹脂組成物及びその硬化物
WO2017077928A1 (fr) * 2015-11-04 2017-05-11 三菱レイヨン株式会社 Composition durcissable, adhésif, article possédant une couche de revêtement, matériau composite renforcé par des fibres, agent d'empotage, et kit pour composition durcissable
WO2020036023A1 (fr) * 2018-08-13 2020-02-20 昭和電工株式会社 Composition de matières premières pour polyisocyanurate et son procédé de production

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Publication number Priority date Publication date Assignee Title
JP2016169362A (ja) * 2015-03-13 2016-09-23 新日鉄住金化学株式会社 オキサゾリドン環含有エポキシ樹脂、その製造方法、エポキシ樹脂組成物及びその硬化物
WO2017077928A1 (fr) * 2015-11-04 2017-05-11 三菱レイヨン株式会社 Composition durcissable, adhésif, article possédant une couche de revêtement, matériau composite renforcé par des fibres, agent d'empotage, et kit pour composition durcissable
WO2020036023A1 (fr) * 2018-08-13 2020-02-20 昭和電工株式会社 Composition de matières premières pour polyisocyanurate et son procédé de production

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7540337B2 (ja) 2018-08-13 2024-08-27 株式会社レゾナック ポリイソシアヌレート原料組成物、及びポリイソシアヌレートの製造方法
WO2023112538A1 (fr) * 2021-12-15 2023-06-22 株式会社レゾナック Composition de résine, film en résine durci, et dispositif d'affichage d'image

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