WO2018107453A1 - 固化性化合物 - Google Patents

固化性化合物 Download PDF

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WO2018107453A1
WO2018107453A1 PCT/CN2016/110302 CN2016110302W WO2018107453A1 WO 2018107453 A1 WO2018107453 A1 WO 2018107453A1 CN 2016110302 W CN2016110302 W CN 2016110302W WO 2018107453 A1 WO2018107453 A1 WO 2018107453A1
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group
formula
curable compound
ring
curable
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English (en)
French (fr)
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杨菲
冈野善道
中谷晃司
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Daicel Corp
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Daicel Corp
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Priority to PCT/CN2016/110302 priority Critical patent/WO2018107453A1/zh
Priority to CN201780077225.9A priority patent/CN110268003B/zh
Priority to KR1020197020158A priority patent/KR102457056B1/ko
Priority to PCT/CN2017/110386 priority patent/WO2018107929A1/zh
Priority to US16/470,057 priority patent/US11021438B2/en
Priority to JP2019529618A priority patent/JP7038121B2/ja
Priority to EP17881052.9A priority patent/EP3556793A4/en
Priority to TW106143348A priority patent/TWI758371B/zh
Publication of WO2018107453A1 publication Critical patent/WO2018107453A1/zh
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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/456—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/50—Iso-indoles; Hydrogenated iso-indoles with oxygen and nitrogen atoms in positions 1 and 3
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic

Definitions

  • the present invention relates to a curable compound and a cured product thereof.
  • it relates to materials that can be used in fields requiring good workability and high heat resistance, represented by electronic information, home appliances, automobiles, and precision machinery.
  • Engineering plastics are high-performance materials that have high heat resistance and high mechanical properties, and are widely used as materials necessary for miniaturization, weight reduction, high performance, and high reliability of various components.
  • a polyimide having excellent heat resistance/environment resistance and strength properties is difficult to dissolve and difficult to melt, and thus a molding method for obtaining a molded body according to the use is limited.
  • a functional material such as a molding material, an insulating material, or a heat-resistant adhesive used for a composite material used in a severe temperature environment is required to have good solvent solubility and to form a cured product having superheat resistance.
  • Patent Document 1 The aromatic polyimide described in Patent Document 1 or the like is known to have excellent heat resistance. However, since it is difficult to dissolve in a solvent, workability is inferior, melt molding is difficult, and it is difficult to use as a matrix resin of a fiber-reinforced composite material.
  • Non-Patent Document 1 discloses that a curable compound having high melt fluidity and high heat resistance, high toughness, and moldability is obtained by using an asymmetric dianhydride.
  • a curable compound having high melt fluidity and high heat resistance, high toughness, and moldability is obtained by using an asymmetric dianhydride.
  • it is difficult to be used for forming a cured product by a casting method or the like because it is hardly soluble in a solvent.
  • Non-Patent Document 2 describes that a crosslinkable polyether ketone which is soluble in a solvent such as toluene is obtained by using a special monomer containing fluorine. However, since special raw materials are required, versatility is poor.
  • Non-Patent Document 3 discloses that a crosslinkable polyether ketone having solvent solubility is obtained by using bisphenol A, bis(4-chlorobenzoyl)benzene or 4,4'-difluorobenzophenone as a raw material.
  • bisphenol A bis(4-chlorobenzoyl)benzene
  • 4,4'-difluorobenzophenone as a raw material.
  • the molecular weight is large, workability is deteriorated, and in order to improve workability, the molecular weight is lowered.
  • the cured product obtained at the time becomes brittle.
  • Non-Patent Document 4 describes a curable compound obtained by introducing an acetylene end group into an ether ketone oligomer obtained by combining an phenylene unit and a p-phenylene unit by an ester bond.
  • the curable compound has crystallinity, and has a problem that the solvent solubility is low and the thermal decomposition initiation temperature of the obtained cured product is also low.
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 2000-219741
  • Non-Patent Document 1 "Network Polymer”, Vol. 27 (4) 221-231 (2006)
  • Non-Patent Document 2 Polymer Journal Vol 34 (3) 209-218 (2002)
  • Non-Patent Document 3 Polymer Vol. 30 978-985 (1989)
  • Non-Patent Document 4 Polymer Vol. 33 (15) 3286-3291 (1992)
  • an object of the present invention is to provide a curable compound which has good solvent solubility and can form a cured product having super heat resistance.
  • Another object of the present invention is to provide a cured product which is a cured product of the above curable compound and which has super heat resistance.
  • the inventors of the present invention have conducted intensive studies to solve the above problems, and have found that the compound represented by the following formula (1) has excellent solvent solubility and is cured by external stimuli such as heat. A hot cured product.
  • the present invention has been completed based on the above findings.
  • the present invention provides a curable compound represented by the following formula (1).
  • R 1 and R 2 are the same or different and each represents a curable functional group
  • D 1 and D 2 are the same or different and each represents a single bond or a linking group
  • L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II).
  • Ar 1 to Ar 3 are the same or different, and represent a group obtained by removing two hydrogen atoms from a structural formula of an aromatic ring or a structure in which two or more aromatic rings are bonded via a single bond or a linking group; after removing two hydrogen atoms .
  • X represents a group -CO -, - S- or -SO 2 -, Y are identical or different, represent -S -, - SO 2 -, - O -, - CO -, - COO- or -CONH-.n represents an integer greater than 0.
  • the present invention relates to the above-mentioned curable compound, wherein R 1 and R 2 in the formula (1) are the same or different and are a curable functional group having a cyclic imide structure.
  • the present invention relates to the above-mentioned curable compound, wherein R 1 and R 2 in the formula (1) are the same or different and are selected from the group represented by the following formulas (r-1) to (r-6). Group.
  • the present invention relates to the above-mentioned curable compound, wherein D 1 and D 2 in the formula (1) are the same or different and are selected from the groups represented by the following formulas (d-1) to (d-4). Group.
  • the present invention relates to the curable compound described above, wherein Ar 1 to Ar 3 in the formula (I) and the formula (II) are the same or different, and two of the structural formulas of the aromatic ring having 6 to 14 carbon atoms are removed. a group after a hydrogen atom or a group obtained by removing two hydrogen atoms from a structural formula in which two or more aromatic rings having 6 to 14 carbon atoms are bonded via a single bond or a linking group described below, a group in which a linking group is a linear or branched alkylene group having 1 to 5 carbon atoms or a linear or branched alkylene group having 1 to 5 carbon atoms substituted with a halogen atom .
  • the present invention relates to the above-mentioned curable compound, wherein the structure represented by the formula (I) is a structure derived from benzophenone.
  • the present invention relates to the curable compound described above, wherein the proportion of the structural unit derived from benzophenone is 5% by weight or more based on the total amount of the curable compound represented by the formula (1).
  • the present invention relates to the above-mentioned curable compound, wherein the structure represented by the formula (II) is a structure derived from at least one compound selected from the group consisting of hydroquinone, resorcin and bisphenol A.
  • the present invention relates to the above-mentioned curable compound, wherein the proportion of the structural unit derived from hydroquinone, resorcin and bisphenol A in the total amount of the curable compound represented by the formula (1) It is 5% by weight or more.
  • the present invention provides a curable composition containing the above curable compound.
  • the present invention provides a cured product of the above curable composition.
  • the curable compound of the present invention having the above structure (particularly having a structure comprising a structural unit derived from benzophenone and at least one compound selected from the group consisting of hydroquinone, resorcin and bisphenol A)
  • the compound having a specific curable functional group introduced at both ends of the molecular chain of the repeating unit of the unit has good solvent solubility. Further, by rapidly curing by heat treatment or the like, a cured product having super heat resistance can be formed. Therefore, the curable compound of the present invention can be applied to fields requiring good processability (or easy moldability) and high heat resistance, typified by electronic information, home appliances, automobiles, and precision machinery.
  • Fig. 1 is a chart showing the 1 H-NMR spectrum / DMSO-d6 of Diamine-F (1) and (2) obtained in Preparation Examples.
  • Fig. 5 is a graph showing the FTIR spectrum of Diamine-B (1) obtained in the Preparation Example.
  • Fig. 6 is a view showing the FTIR spectrum of Diamine-B (2) obtained in the Preparation Example.
  • Fig. 7 is a chart showing the 1 H-NMR spectrum / CDCl 3 of PEI-F (1) and (2) obtained in the examples.
  • Fig. 8 is a view showing the FTIR spectrum of PEI-F(1) obtained in the examples.
  • Fig. 9 is a view showing the FTIR spectrum of PEI-F(2) obtained in the examples.
  • Fig. 10 is a chart showing the 1 H-NMR spectrum / CDCl 3 of PEI-B (1) and (2) obtained in the examples.
  • Fig. 11 is a view showing the FTIR spectrum of PEI-B(1) obtained in the examples.
  • Fig. 12 is a view showing the FTIR spectrum of PEI-B (2) obtained in the examples.
  • Fig. 13 is a chart showing the 1 H-NMR spectrum / CDCl 3 of BMI-F(1) obtained in the examples.
  • Fig. 14 is a chart showing the 1 H-NMR spectrum / CDCl 3 of BMI-B (1) obtained in the examples.
  • Fig. 15 is a graph showing the results of DSC measurement of PEI-F (1), (2) and PEI-B (1) and (2) obtained in Examples.
  • Fig. 16 is a graph showing the results of DSC measurement of the cured products of PEI-F (1), (2) and PEI-B (1) and (2) obtained in Examples.
  • Fig. 17 is a graph showing the results of thermogravimetric analysis of the cured products of PEI-F (1), (2) and PEI-B (1) and (2) obtained in the examples.
  • the curable compound of the present invention is represented by the following formula (1).
  • R 1 and R 2 are the same or different and each represents a curable functional group
  • D 1 and D 2 are the same or different and each represents a single bond or a linking group
  • L represents a divalent group having a repeating unit containing a structure represented by the following formula (I) and a structure represented by the following formula (II).
  • Ar 1 to Ar 3 are the same or different, and represent a group obtained by removing two hydrogen atoms from a structural formula of an aromatic ring or a structure in which two or more aromatic rings are bonded via a single bond or a linking group; after removing two hydrogen atoms .
  • X represents a group -CO -, - S- or -SO 2 -, Y are identical or different, represent -S -, - SO 2 -, - O -, - CO -, - COO- or -CONH-.n represents an integer greater than 0.
  • R 1 and R 2 each represent a curable functional group.
  • R 1 and R 2 may be the same or different.
  • the curable functional group in R 1 and R 2 is preferably a curable functional group having a cyclic imide structure such as a group represented by the following formula (r).
  • Q represents C or CH.
  • n' is an integer of 0 or more (for example, 0 to 3, preferably 0 or 1).
  • R 3 to R 6 are the same or different and each represent a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group (preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon number of 2 to 10).
  • An alkynyl group, an aromatic hydrocarbon group (preferably an aryl group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group), or two or more groups bonded to the above saturated or unsaturated aliphatic hydrocarbon group and an aromatic hydrocarbon group The group formed.
  • the two groups selected from R 3 to R 6 are optionally bonded to each other to form a ring together with adjacent carbon atoms.
  • Examples of the ring in which two groups selected from R 3 to R 6 are bonded to each other and are bonded to an adjacent carbon atom include, for example, an alicyclic ring having 3 to 20 carbon atoms and a carbon number of 6 to 14; Aromatic ring.
  • the alicyclic ring having 3 to 20 carbon atoms includes, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and the like, and is preferably 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8).
  • a cyclic cycloalkene ring of about 3 to 20 members such as a cyclopentene ring or a cyclohexene ring; a perhydronaphthalene ring;
  • the aromatic ring having 6 to 14 carbon atoms includes a benzene ring, a naphthalene ring and the like.
  • the curable functional group having a cyclic imide structure is preferably a curable functional group having a cyclic unsaturated imide structure or a curable functional group having a cyclic imide structure having an arylethynyl group. Particularly preferred is a group selected from the following formulas (r-1) to (r-6), and a group represented by the following formula (r-1) or (r-5) is particularly preferable.
  • substituents are bonded to the groups represented by the above formulas (r-1) to (r-6).
  • substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.
  • alkyl group having 1 to 6 carbon atoms examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, and a hexyl group. Chain or branched alkyl.
  • the alkoxy group having 1 to 6 carbon atoms may, for example, be a linear or branched alkoxy group such as a methoxy group, an ethoxy group, a butoxy group or a t-butoxy group.
  • D 1 and D 2 are the same or different and each represents a single bond or a linking group.
  • the linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a plurality of the above-mentioned linkages. Group and so on.
  • the divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.
  • the divalent aliphatic hydrocarbon group may, for example, be a linear or branched alkylene group having 1 to 18 carbon atoms or a linear or branched alkenylene group having 2 to 18 carbon atoms.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • Examples of the linear or branched alkenylene group having 2 to 18 carbon atoms include a vinylidene group, a 1-methylvinylidene group, a propenylene group, a 1-butenylene group, and a 2-butenylene group.
  • Examples of the divalent alicyclic hydrocarbon group include a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, and examples thereof include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, and a ring.
  • a cycloalkylene group (including a cycloalkylidene group) such as a pentyl group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group or a cyclohexylidene group.
  • the divalent aromatic hydrocarbon group may, for example, be an arylene group having 6 to 14 carbon atoms, and examples thereof include a 1,4-phenylene group, a 1,3-phenylene group, and a 4,4'-linked group.
  • the hetero ring constituting the above divalent heterocyclic group includes an aromatic hetero ring and a non-aromatic hetero ring.
  • a heterocyclic ring include a 3- to 10-membered ring (preferably a 4- to 6-membered ring) having a carbon atom and at least one hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) in the atom constituting the ring. ), and the fused rings of these rings.
  • heterocyclic ring containing an oxygen atom as a hetero atom for example, a 3-membered ring such as an oxirane ring; a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, Oxazole ring, different a 5-membered ring such as an azole ring or a ⁇ -butyrolactone ring; a 6-membered ring such as a 4-oxo-4H-pyran ring, a tetrahydropyran ring or a morpholine ring; a benzofuran ring and an isobenzofuran ring; 4-oxo-4H-chromene ring, color full ring, heterochromic ring, etc.
  • a heterocyclic ring containing an oxygen atom as a hetero atom for example, a 3-membered ring such as an oxirane ring; a 4-membere
  • a ring of a 6-membered ring such as a 4-oxo-4H-thiopyran ring
  • a fused ring such as a benzothiophene ring
  • a heterocyclic ring containing a nitrogen atom as a hetero atom for example, a pyrrole ring, a pyrrolidine ring, or a pyrazole ring.
  • the divalent heterocyclic group is a group obtained by removing two hydrogen atoms from the structural formula of the above heterocyclic ring.
  • D 1 and D 2 are preferably a divalent aromatic hydrocarbon group, and particularly preferably a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms, from the viewpoint of obtaining a cured product having particularly excellent heat resistance. It is preferably a group selected from the following formulas (d-1) to (d-4), and particularly preferably a group represented by the following formula (d-1) (1,2-phenylene group, 1,3) - phenylene or 1,4-phenylene).
  • R 1 -D 1 group and the R 2 -D 2 group in the formula (1) which are the same or different, a group represented by the following formula (rd-1) or (rd-2) is particularly preferable. .
  • L in the formula (1) represents a divalent group having a repeating unit containing the structure represented by the above formula (I) and the structure represented by the above formula (II).
  • Ar 1 to Ar 3 in the formula (I) and the formula (II) are the same or different, and represent a group obtained by removing two hydrogen atoms from the structural formula of the aromatic ring or a single bond or a linking group from two or more aromatic rings. The group in which the two hydrogen atoms are removed in the structural formula in which the group is bonded.
  • X represents -CO-, -S- or -SO 2 -
  • Y is the same or different and represents -S-, -SO 2 -, -O-, -CO-, -COO- or -CONH-.
  • n represents an integer of 0 or more, and is, for example, an integer of 0 to 5, preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.
  • the above-mentioned linking group may, for example, be a group in which a divalent hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom having 1 or 5 carbon atoms having 1 to 5 carbon atoms is substituted with a halogen atom.
  • the divalent hydrocarbon group having 1 to 5 carbon atoms includes, for example, a linear chain having 1 to 5 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group or a trimethylene group.
  • a linear or branched alkynylene group having 2 to 5 carbon atoms such as a propynylene group.
  • a linear or branched alkylene group having 1 to 5 carbon atoms is preferable, and a branched alkylene group having 1 to 5 carbon atoms is particularly preferable.
  • the above Ar 1 to Ar 3 are the same or different, and are preferably a group obtained by removing two hydrogen atoms from a structural formula of an aromatic ring having 6 to 14 carbon atoms, or a group having two or more carbon atoms: 6 to a group in which the aromatic ring of 14 is bonded via a single bond or a linking group to which two hydrogen atoms are removed, and the linking group is a linear or branched alkylene group having 1 to 5 carbon atoms.
  • the group obtained by substituting one or more hydrogen atoms of a linear or branched alkylene group having 1 to 5 carbon atoms with a halogen atom is particularly preferably removed from the structural formula of an aromatic ring having 6 to 14 carbon atoms.
  • the linking group is a group in which one or more hydrogen atoms of a branched alkylene group having 1 to 5 carbon atoms or a branched alkylene group having 1 to 5 carbon atoms are substituted with a halogen atom.
  • Ar 1 to Ar 3 are the same or different, and are particularly preferably selected from the group consisting of the following formulas (a-1) to (a-5).
  • connection position of the key in the following formula is not specifically limited.
  • Ar 1 and Ar 2 are preferably a group obtained by removing two hydrogen atoms from a structural formula of an aromatic ring having 6 to 14 carbon atoms, and particularly preferably the above formula (a-1) or ( A-2) The group shown. Further, among them, as X, -CO- or -SO 2 is preferable. As the structure represented by the formula (I), it is particularly preferable to include a structure derived from benzophenone.
  • the proportion of the structural unit derived from benzophenone is, for example, 5% by weight or more, preferably 10 to 62% by weight, particularly preferably 15 to 60% by weight. %.
  • Ar 3 in the formula (II) is preferably a group selected from the group consisting of the above formulas (a-1), (a-4) and (a-5). Further, as Y, among them, -S- or -O- is preferable.
  • the structure represented by the formula (II) particularly preferably contains a structure derived from at least one compound selected from the group consisting of hydroquinone, resorcin, and bisphenol A.
  • the proportion of the structural unit derived from hydroquinone, resorcin and bisphenol A is, for example, 5% by weight or more, preferably 10 to 55 parts by weight. % is particularly preferably 15 to 53% by weight.
  • the L in the formula (1) is preferably a divalent group represented by the following formula (1-1) or (l-2) from the viewpoint of obtaining a cured product having particularly excellent heat resistance.
  • the amount is, for example, 3 to 50, preferably 4 to 30, and particularly preferably 5 to 20. It should be noted that the values of n1 and n2 can be obtained by GPC measurement.
  • the curable compound of the present invention has the above-described structure, a cured product having a highly crosslinked structure (that is, a high crosslinking density) and having super heat resistance can be obtained by a curing reaction by heat or the like.
  • the curable compound of the present invention since the curable compound of the present invention has the above structure, it exhibits excellent solubility to the following solvents.
  • Solvent for example, aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, and trifluorotoluene; And other esters; ethers such as tetrahydrofuran; N-methyl-2-pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, and mixtures thereof.
  • L in the formula (1) is a divalent group represented by the above formula (1-1) or (l-2), and n1 and n2 in the formula are 5 to 10 Since the compound is melted at 300 ° C or lower (about 250 ° C), it can be melt-molded at a low temperature compared with PEEK or the like, and the molding processability is particularly excellent.
  • the average degree of polymerization (n1, n2) of the molecular chain is less than the above range, the obtained cured product becomes brittle and tends to have reduced mechanical properties.
  • the average degree of polymerization (n1, n2) of the molecular chain is larger than the above range, there is a tendency that the moldability is lowered due to a decrease in solubility in a solvent and an increase in melt viscosity.
  • the curable compound represented by the above formula (1) can be produced, for example, by the synthesis method described in Polymer 1989p978.
  • An example of the method for producing the curable compound represented by the above formula (1) is shown below, but is not particularly limited to the production method.
  • the compound represented by the following formula (1-1) can be produced through the following steps [1] to [3].
  • Ar 1 to Ar 3 , X, Y, n, R 3 to R 6 , Q, and n' are the same as described above.
  • D represents a linking group
  • Z represents a halogen atom.
  • n 3 is an average degree of polymerization of the repeating unit, and is, for example, 3 to 50, preferably 4 to 30, particularly preferably 5 to 20.
  • compounds other than the compound represented by the following formula (1-1) can also be produced by the following method.
  • Examples of the compound represented by the above formula (2) include halogenated products such as benzophenone, 2-benzoylnaphthalene, and di(2-naphthyl) ketone, and derivatives thereof.
  • Examples of the compound represented by the above formula (3) include hydroquinone, 4,4'-dihydroxybiphenyl, resorcin, 2,6-naphthalenediol, and 1,5-naphthalenediol. , (1,1'-biphenyl)-4,4'-bisphenol, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)methanone, bisphenol A, bisphenol F, double Phenol S, (1,1'-biphenyl)-2,5-bisphenol, and derivatives thereof.
  • the above-mentioned derivative may, for example, be a compound obtained by bonding a substituent to a compound represented by the above formula (2) or an aromatic hydrocarbon group in the compound represented by the formula (3).
  • substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.
  • the compound represented by the formula (2) and the compound represented by the formula (3) are usually used in an amount of 1 mol per mol of the compound represented by the formula (3), and preferably 1 mol or more.
  • the average degree of polymerization of the molecular chain in the desired curable compound adjusts the amount of the compound represented by the formula (2).
  • the average degree of polymerization is 5
  • the average degree of polymerization is 10
  • the compound represented by the formula (2) it is preferred to use at least a halogenated product of benzophenone, a total amount (100 mol%) of the compound represented by the formula (2), and a halogenated product of benzophenone.
  • the amount used is, for example, 10% by mole or more, preferably 30% by mole or more, particularly preferably 50% by mole or more, and most preferably 80% by mole or more. It should be noted that the upper limit is 100% by mole.
  • the compound represented by the formula (3) it is preferred to use at least one compound selected from the group consisting of hydroquinone, resorcin, and bisphenol A, and the total amount of the compound represented by the formula (3) ( In 100 mol%), the total amount of hydroquinone, resorcin and bisphenol A is, for example, 10 mol% or more, preferably 30 mol% or more, particularly preferably 50 mol% or more, and most preferably 80 mol%. the above. It should be noted that the upper limit is 100% by mole.
  • the reaction of the compound represented by the above formula (2) with the compound represented by the formula (3) is carried out in a base (for example, an inorganic substance selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc.)
  • the base is carried out in the presence of at least one of an organic base such as pyridine or triethylamine.
  • the amount of the base to be used can be appropriately adjusted depending on the kind of the base. For example, when a dibasic base such as calcium hydroxide is used, the amount of the base is, for example, about 1.0 to 2.0 mol per mol of the compound represented by the formula (3).
  • reaction can be carried out in the presence of a solvent.
  • a solvent for example, an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran or toluene or a mixed solvent of two or more of the above solvents can be used.
  • the amount of the above solvent to be used is, for example, the total (weight) of the reaction substrate. 5 to 20 times the weight. When the amount of the solvent used is more than the above range, the concentration of the reaction substrate is lowered, and the reaction rate tends to be lowered.
  • the reaction gas atmosphere is not particularly limited as long as it does not interfere with the reaction, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, and an argon atmosphere.
  • the reaction temperature is, for example, about 100 to 200 °C.
  • the reaction time is, for example, about 5 to 24 hours. Further, the reaction can be carried out by any method such as batch type, semi-batch type, or continuous type.
  • the obtained reaction product can be isolated and purified by a separation method such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography or the like, or a combination of the above methods.
  • Examples of the compound represented by the above formula (5) include 4-aminophenol and 2-amino-6-hydroxynaphthalene, and stereoisomers and derivatives thereof.
  • the amount of the compound represented by the above formula (5) can be appropriately adjusted depending on the average degree of polymerization of the molecular chain in the desired curable compound.
  • the average degree of polymerization is 5
  • the amount of the compound represented by the formula (3) is about 0.4 to 0.6 mol
  • the average degree of polymerization is 10
  • the ratio is represented by the formula (3).
  • the compound 1 mol is an amount of about 0.2 to 0.4 mol, and when the average degree of polymerization is 20, it is about 0.1 to 0.15 mol with respect to 1 mol of the compound represented by the formula (3).
  • this reaction Since this reaction generates a hydrogen halide as the reaction proceeds, it is preferred to carry out the reaction in the presence of a base which absorbs the generated hydrogen halide from the viewpoint of obtaining an effect of promoting the progress of the reaction.
  • a base which absorbs the generated hydrogen halide from the viewpoint of obtaining an effect of promoting the progress of the reaction.
  • the base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate; and organic bases such as pyridine and triethylamine. These bases may be used alone or in combination of two or more.
  • the amount of the above base to be used can be appropriately adjusted depending on the kind of the base.
  • the amount of the base to be used is, for example, about 1.0 to 3.0 mol per mol of the compound represented by the above formula (5).
  • reaction can be carried out in the presence of a solvent.
  • a solvent the same solvent as that used in the step [1] can be used.
  • the reaction temperature is, for example, about 100 to 200 °C.
  • the reaction time is, for example, about 1 to 15 hours. Further, the reaction can be carried out by any method such as batch type, semi-batch type, or continuous type.
  • the obtained reaction product can be isolated and purified by a separation method such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography or the like, or a combination of the above methods.
  • cyclic acid anhydride examples include maleic anhydride, 2-phenylmaleic anhydride, 4-phenylethynylphthalic anhydride, and 4-(1-). Naphthylethynyl)phthalic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and derivatives thereof.
  • the amount of the above cyclic acid anhydride can be appropriately adjusted depending on the average degree of polymerization of the molecular chain in the desired curable compound. For example, when the average degree of polymerization is 5, the amount of the compound represented by the formula (3) is about 0.4 to 0.8 mol, and when the average degree of polymerization is 10, the formula is represented by the formula (3).
  • the compound 1 mol is an amount of about 0.2 to 0.4 mol, and when the average degree of polymerization is 20, it is about 0.1 to 0.15 mol with respect to 1 mol of the compound represented by the formula (3).
  • This reaction can be carried out in the presence of a solvent.
  • a solvent the same solvent as that used in the step [1] can be used.
  • the reaction is preferably carried out at room temperature (1 to 30 ° C).
  • the reaction time is, for example, about 1 to 30 hours.
  • the reaction can be carried out by any method such as batch type, semi-batch type, or continuous type.
  • the reaction be carried out by azeotropy using a solvent (for example, toluene or the like) which azeotropes with water, and by using a dehydrating agent (for example, acetic anhydride or the like) to remove the reaction.
  • a solvent for example, toluene or the like
  • a dehydrating agent for example, acetic anhydride or the like
  • Water produced by the product is preferably carried out in the presence of a basic catalyst (for example, triethylamine or the like).
  • the obtained reaction product can be isolated and purified by a separation method such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography or the like, or a combination of the above methods.
  • the exothermic peak temperature of the curable compound represented by the formula (1) depends on the kind of the curable functional group, and is, for example, 170 to 450 ° C, preferably 200 to 430 ° C, and particularly preferably 220 to 420 ° C.
  • the exothermic peak temperature can be determined by DSC measurement.
  • the exothermic peak temperature of the curable compound represented by the formula (1) is determined depending on the type of the curable functional group, it is preferred to select a curable functional group in accordance with the molding method to be employed. For example, when a solution obtained by dissolving a curable compound in a solvent by a casting method is formed into a film and cured, the curable functional group in the curable compound represented by the formula (1) is preferably selected. In the case of the group represented by the above formula (r-5), a cured product can be formed by heating at a temperature of about 250 °C.
  • the curable compound represented by the formula (1) when the group represented by the above formula (r-1) is selected as the curable functional group in the curable compound represented by the formula (1), the curable compound can be melted at a temperature of 300 ° C or lower. Molding can be carried out by heating at a temperature of about 380 ° C to form a cured product.
  • the heating may be carried out while maintaining a constant temperature within the above temperature range, or may be carried out by changing the temperature stepwise.
  • the heating temperature is preferably appropriately adjusted within the above range depending on the heating time. For example, when it is desired to shorten the heating time, it is preferable to set the heating temperature higher. Since the curable compound of the present invention has the structure represented by the above formula (1), it is possible to form a cured product (specifically, a cured product having super heat resistance) which does not decompose even when heated at a high temperature, and can pass The mixture is heated at a high temperature for a short period of time to efficiently form a cured product with excellent workability. It should be noted that the heating method is not particularly limited, and a known or usual method can be used.
  • the curing of the curable compound represented by the formula (1) may be carried out under normal pressure, or may be carried out under reduced pressure or under pressure.
  • the 5% weight loss temperature (T d5 ) measured by the cured product of the curable compound represented by the formula (1) at a temperature increase rate of 10 ° C /min (in nitrogen) is, for example, 300 ° C or higher, more preferably 400 ° C or higher, and particularly preferably It is 450 ° C or more, and most preferably 500 ° C or more.
  • the upper limit is, for example, 600 ° C, preferably 550 ° C, and particularly preferably 530 ° C.
  • the 5% weight loss temperature can be measured by, for example, TG/DTA (differential thermogravimetric weight measurement).
  • the 10% weight loss temperature (T d10 ) of the cured product of the curable compound represented by the formula (1) at a temperature increase rate of 10 ° C /min (in nitrogen) is, for example, 300 ° C or higher, more preferably 400 ° C or higher, and particularly preferably It is 500 ° C or more, and most preferably 510 ° C or more. It should be noted that the upper limit is, for example, 600 ° C, preferably 550 ° C. It should be noted that the 10% weight loss temperature can be measured by, for example, TG/DTA (differential thermogravimetric weight measurement).
  • the curable compound of the present invention has good solvent solubility. Further, by performing heat treatment to rapidly cure, a cured product having super heat resistance as described above can be formed. Therefore, it can be used as a functional material such as a molding material, an insulating material, or a heat-resistant adhesive for a composite material used in a severe heat-resistant environment such as electronic information, home appliances, automobiles, and precision machinery. Further, it can also be preferably used for a sealant, a coating agent, an adhesive, an ink, a sealant, a resist, a forming material [for example, a substrate, an electrically insulating material (insulating film, etc.), a laminated plate, a composite material).
  • the curable composition of the present invention is characterized by comprising one or more kinds of the above curable compounds.
  • the content of the curable compound (the total amount in the case of containing two or more kinds thereof) in the total amount of the curable composition of the present invention is, for example, 30% by weight or more, preferably 50% by weight or more, and particularly preferably 70% by weight.
  • the above is most preferably 90% by weight or more. It should be noted that the upper limit is 100% by weight. That is, the curable composition of the present invention also includes a composition composed only of a curable compound.
  • the curable composition of the present invention may contain other components as needed in addition to the curable compound.
  • a known or commonly used additive may be used, and examples thereof include a curable compound other than the compound represented by the above formula (1), a catalyst, a filler, and an organic resin (silicone resin, epoxy resin, fluororesin, etc.).
  • additives include solvents, stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant Additives, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, fluidity improvers, colorants (dyes, pigments, etc.) , dispersants, defoamers, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, etc. These additives may be used alone or in combination of two or more.
  • the curable composition of the present invention may contain a curable compound other than the curable compound represented by the above formula (1) as a curable compound, but all of the curable compounds contained in the curable composition are represented by the above formula (1).
  • the proportion of the curable compound is, for example, 70% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more. It should be noted that the upper limit is 100% by weight.
  • the curable composition of the present invention does not contain a crosslinking agent or a curing accelerator (for example, even if the total content of the crosslinking agent and the curing accelerator in the total amount of the curable composition of the present invention is, for example, 3% by weight or less, It is preferably less than 1% by weight), and it is also possible to form a cured product quickly. Therefore, the obtained cured product has super heat resistance.
  • the content of the unreacted curing accelerator and the decomposition product of the curing accelerator in the cured product can be suppressed to be extremely low, generation of exhaust gas from the unreacted curing accelerator and the decomposition product of the curing accelerator can be suppressed. .
  • the curable composition of the present invention contains the curable compound described above, it can be rapidly cured by performing heat treatment, and a cured product having super heat resistance can be formed.
  • the heat treatment conditions can be appropriately set within the same range as the curing conditions of the curable compound.
  • the curable composition of the present invention can be preferably used as a composite material (fiber reinforced plastic, preform) which can be used in a severe heat-resistant environment, such as electronic information, home appliances, automobiles, precision machinery, aircraft, and aerospace industrial equipment.
  • Functional materials such as molding materials, insulating materials, and heat-resistant adhesives.
  • sealant, paint, ink, sealant, resist, forming material [thrust washer, oil filter, gasket, bearing, transmission, cylinder head, rolling bearing cage, intake manifold , automotive parts such as pedals; substrates, electrical insulation materials (insulation films, etc.), laminated boards, electronic paper, touch panels, solar cell substrates, optical waveguides, light guides, holographic memories, silicon wafer carriers, IC chip carriers, Semiconductor/liquid crystal manufacturing device components such as electrolytic capacitor holders and insulating films; optical components such as lenses; compressor components such as pumps, valves, and gaskets; interior components of aircraft cabins; medical device parts such as sterilization instruments, columns, and pipes, and foods a beverage manufacturing equipment component; a casing for a personal computer, a mobile phone, etc., a material for forming an electric/electronic instrument member represented by a keyboard support that supports a keyboard inside a personal computer, etc., and particularly preferably A semiconductor device with high heat resistance/high withstand
  • Step 1 Adding 4,4'-difluorobenzophenone 6.865 g, bisphenol to a 100 mL (three-neck) flask equipped with a stirring device, a nitrogen introduction tube, and a Dean-Stark apparatus A 5.985 g, anhydrous potassium carbonate 5.427 g, N-methylpyrrolidone 50 mL, and toluene 25 mL were heated while stirring under a nitrogen atmosphere, and toluene was refluxed at 130 to 140 ° C for 4 hours. Then, the mixture was further heated, and toluene was distilled off at 170 to 180 °C. Stirring was continued at 170 to 180 ° C for 10 hours and then returned to room temperature.
  • Step 2 1.14 g of 4-aminophenol, 1.447 g of anhydrous potassium carbonate, 5 mL of N-methylpyrrolidone, and 25 mL of toluene were added to the flask containing the product obtained in the step 1, and heated while stirring under a nitrogen atmosphere. The toluene was refluxed at 130 to 140 ° C for 3 hours. Then, heating was further carried out, and toluene was distilled off at 170 to 180 ° C, and the above temperature was maintained and stirring was continued for 4 hours. Then, the mixture was cooled to room temperature, and the reaction liquid was added to 1500 mL of ethanol, followed by filtration to obtain a powdery solid.
  • step 1 the amount of 4,4'-difluorobenzophenone is changed to 6.586 g, which is double
  • the amount of phenol A used was changed to 6.264 g, and the amount of anhydrous potassium carbonate was changed to 5.680 g.
  • step 2 the amount of 4-aminophenol was changed to 0.599 g, and the amount of anhydrous potassium carbonate was changed to 0.599 g.
  • a powdery solid (Diamine-F (2) represented by the above formula (6-1), wherein n1 was 9.7, yield: 94%) was obtained. .
  • Step 1 To a 100 mL (three-neck) flask equipped with a stirring device, a nitrogen introduction tube, and a Dean-Stark apparatus, 8.905 g of 4,4'-difluorobenzophenone and 3.745 g of resorcinol were added. 7.040 g of potassium carbonate, 50 mL of N-methylpyrrolidone and 25 mL of toluene were heated while stirring under a nitrogen atmosphere, and toluene was refluxed at 130 to 140 ° C for 4 hours. Then, the mixture was further heated, and toluene was distilled off at 170 to 180 °C. Stirring was continued at 170 to 180 ° C for 10 hours and then returned to room temperature.
  • Step 2 To the flask containing the product obtained in the step 1, 1.485 g of 4-aminophenol, 1.878 g of anhydrous potassium carbonate, 5 mL of N-methylpyrrolidone, and 25 mL of toluene were added. Further, the mixture was heated while stirring under a nitrogen atmosphere, and toluene was refluxed at 130 to 140 ° C for 3 hours. Then, heating was further carried out, and toluene was distilled off at 170 to 180 ° C, and the above temperature was maintained and stirring was continued for 4 hours. Then, the mixture was cooled to room temperature, and the reaction liquid was added to 1500 mL of ethanol, followed by filtration to obtain a powdery solid.
  • the powdery solid was repeatedly washed with ethanol and water, and then dried under reduced pressure at 100 ° C for 8 hours to obtain a powdery solid (Diamine-B (1), represented by the following formula (6-2), n2 in the formula The compound was 6.1, yield: 95%).
  • step 1 the amount of 4,4'-difluorobenzophenone was changed to 9.121 g.
  • the amount of the benzenediol was changed to 4.185 g, and the amount of the anhydrous potassium carbonate was changed to 7.867 g.
  • step 2 the amount of the 4-aminophenol was changed to 0.829 g, and the amount of the anhydrous potassium carbonate was changed to 1.049 g.
  • a powdery solid (Diamine-B (2), represented by the above formula (6-2), wherein n2 was 8.8, yield: 93% was obtained. ).
  • the 1 H-NMR spectrum and the FTIR spectrum of the powdery solid obtained in the Preparation Example are shown in Figs. 1 to 6 . Further, the number average molecular weight, the weight average molecular weight, and the average polymerization degree determined by gel permeation chromatography (GPC) (converted to standard styrene) are shown in the following table.
  • GPC gel permeation chromatography
  • Diamine-F (1) 4.550 g, 4-phenylethynyl phthalic anhydride 1.395 g, N-A obtained in the preparation example were placed in a 50 mL (three-neck) flask equipped with a stirring device, a nitrogen introduction tube, and a drying tube. 33 mL of pyrrolidone was stirred under a nitrogen atmosphere at room temperature for 18 hours. Then, the drying tube was replaced with a Dean-Stark apparatus, and 25 mL of toluene was added, and then the temperature was raised to 130 to 140 ° C, and toluene was refluxed for 5 hours. Next, the mixture was heated to 170 to 180 ° C to distill off the toluene, and stirring was continued for 4 hours.
  • a powder was obtained in the same manner as in Example 1 except that Diamine-F (2) 4.599 g obtained in the Preparation Example was used instead of Diamine-F (1), and 0.766 g of 4-phenylethynylphthalic anhydride was used. Solid (PEI-F (2), yield: 91%).
  • the 1 H-NMR spectrum of the obtained powdery solid is shown in Fig. 7, and the FTIR spectrum is shown in Fig. 9.
  • a powder was obtained in the same manner as in Example 1 except that 4.51 g of Diamine-B (1) obtained in the Preparation Example was used instead of Diamine-F (1), and 1.852 g of 4-phenylethynylphthalic anhydride was used. Solid (PEI-B (1), yield: 90%). The 1 H-NMR spectrum of the obtained powdery solid is shown in Fig. 10, and the FTIR spectrum is shown in Fig. 11.
  • a powder was obtained in the same manner as in Example 1 except that Diamine-B (2) 4.607 g obtained in the Preparation Example was used instead of Diamine-F (1), and 1.046 g of 4-phenylethynylphthalic anhydride was used. Solid (PEI-B (2), yield: 92%).
  • the 1 H-NMR spectrum of the obtained powdery solid is shown in Fig. 10, and the FTIR spectrum is shown in Fig. 12.
  • a powdery solid (BMI-B (1) was obtained in the same manner as in Example 5 except that Diamine-B (1) 4.571 g was used instead of Diamine-F (1), and the amount of maleic anhydride was changed to 0.733 g. , yield: 90%).
  • the 1 H-NMR chart of the obtained powdery solid is shown in Fig. 14 .
  • the Tg and the exothermic peak temperature of the powdery solid obtained in the examples were determined by DSC measurement. The results are shown in Fig. 15.
  • the Tg of PEI-F(1) and (2) is about 140 °C
  • the Tg of PEI-B(1) and (2) is about 120 °C
  • PEI-F(1), (2), PEI-B(1) Both (2) and an exothermic peak caused by the curing reaction were observed at around 400 °C.
  • the powdery solid (0.5 g) obtained in the Example was mixed with the following solvent (10 g), and stirred at room temperature for 8 hours, and when the powdery solid was completely dissolved, it was evaluated that the solvent solubility was good ( ⁇ ), and it was insoluble. Or the case of partial insolubility was evaluated as poor solvent solubility (x). The results are shown in the table below.
  • the powdery solid obtained in the examples was placed on a glass plate to have a thickness of about 0.5 mm and uniform, and heated in a muffle furnace to be solidified.
  • the muffle furnace was heated from 25 ° C to 371 ° C at 10 ° C / min and then held at 371 ° C for 2 hours.
  • the DSC results of the obtained cured product are shown in Fig. 16, the results of the thermogravimetric analysis are shown in Fig. 17, and the 5% weight loss temperature ( Td5 ) and the 10% weight loss temperature ( Td10 ) are shown in Table 3.
  • T d5 (°C) T d10 (°C) Cured PEI-F (1) 505 517 Cured PEI-F (2) 504 517 Cured PEI-B (1) 539 553 Cured PEI-B (2) 519 529 BMI-F after curing (1) 501 525 BMI-B after curing (1) 512 528
  • T d5 is 500 ° C or more.
  • the curable compound of the present invention has good solvent solubility. Further, it can be quickly cured by performing heat treatment, and a cured product having super heat resistance can be formed. Therefore, it can be suitably used as a sealant or the like for a semiconductor device.

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Abstract

本发明提供具有良好的溶剂溶解性、且能够形成具有超耐热性的固化物的固化性化合物。本发明的固化性化合物用下述式(1)表示。式(1)中，R1、R2表示固化性官能团，D1、D2表示单键或连接基团。L表示具有重复单元的2价基团，所述重复单元包含下述式(I)所示的结构和下述式(II)所示的结构(式中，Ar1～Ar3表示从芳香环的结构式中去除2个氢原子后的基团、或者从2个以上芳香环经由单键或连接基团键合而成的结构式中去除2个氢原子后的基团。X表示-CO-、-S-或-SO2-，Y表示-S-、-SO2-、-O-、-CO-、-COO-或-CONH-。N表示0以上的整数)。

Description

固化性化合物 技术领域
本发明涉及固化性化合物及其固化物。特别是涉及以电子信息、家电、汽车、精密机械为代表的、能够在要求良好的加工性和高耐热性的领域使用的材料。
背景技术
工程塑料是兼具高耐热性和高机械特性的高性能材料，作为各种部件的小型化、轻质化、高性能化、高可靠性化所必需的材料而被广泛使用。但是，例如、具有优异的耐热/耐环境性和强度特性的聚酰亚胺由于难溶解、难熔融，因此用于得到与用途相应的成型体的成型法受到限制。因此，广泛进行了克服难成型性的研究开发，要求兼具工程塑料所具有的高机械特性、电特性、耐药品性、耐水性、高耐热性与良好加工性的材料，即，作为在严苛的温度环境下使用的复合材料的成型材料、绝缘材料、耐热性粘接剂等功能材料，要求具有良好的溶剂溶解性、且能够形成具有超耐热性的固化物的固化性化合物。
已知专利文献1等记载的芳香族聚酰亚胺的耐热性优异。但是由于难以溶解于溶剂而使加工性较差，难以进行熔融成型，难以用作纤维强化复合材料的基体树脂。
非专利文献1中记载了通过使用非对称的二酐而得到具有高熔融流动性、且兼具高耐热、高韧性、易成型性的固化性化合物。但是，存在由于难溶于溶剂而无法用于通过浇注法等形成固化物的用途的问题。
非专利文献2中记载了通过使用含有氟的特殊单体而得到对甲苯等溶剂具有可溶性的交联性聚醚酮。但是，由于需要特殊的原料，因此通用性差。
非专利文献3中记载了将双酚A与二(4-氯苯甲酰基)苯或4,4’-二氟二苯甲酮作为原料而得到具有溶剂溶解性的交联性聚醚酮。但是，存在分子量大时加工性变差，为了改善加工性而使其低分子量化 时得到的固化物变脆的问题。
非专利文献4中记载了通过酯键向由间亚苯基单元与对亚苯基单元组合而成的醚酮低聚物中导入了乙炔端基而得到的固化性化合物。但是，上述固化性化合物具有结晶性，存在溶剂溶解性低，得到的固化物的热分解起始温度也低的问题。
现有技术文献
专利文献
专利文献1：日本特开2000-219741号公报
非专利文献
非专利文献1：“网状聚合物(network polymer)”,Vol.27(4)221-231(2006)
非专利文献2：Polymer Journal Vol34(3)209-218(2002)
非专利文献3：Polymer Vol.30 978-985(1989)
非专利文献4：Polymer Vol.33(15)3286-3291(1992)
发明内容
发明要解决的课题
因此，本发明的目的在于提供一种具有良好的溶剂溶解性、且能够形成具有超耐热性的固化物的固化性化合物。
本发明的其它目的是提供一种固化物，其是上述固化性化合物的固化物，其具有超耐热性。
解决课题的方法
本发明人等为了解决上述课题而进行了深入研究，结果发现，下述式(1)所示的化合物具有良好的溶剂溶解性，且通过赋予热等外部刺激来进行固化，从而形成具有超耐热性的固化物。本发明是基于上述见解而完成的。
即，本发明提供下述式(1)所示的固化性化合物。
[化学式1]
Figure PCTCN2016110302-appb-000001
[式中，R1、R2相同或不同，表示固化性官能团，D1、D2相同或不同，表示单键或连接基团。L表示具有包含下述式(I)所示的结构和下述式(II)所示的结构的重复单元的2价基团。
[化学式2]
Figure PCTCN2016110302-appb-000002
(式中，Ar1～Ar3相同或不同，表示从芳香环的结构式中去除2个氢原子后的基团、或者从2个以上芳香环经由单键或连接基团键合而成的结构式中去除2个氢原子后的基团。X表示-CO-、-S-或-SO2-，Y相同或不同，表示-S-、-SO2-、-O-、-CO-、-COO-或-CONH-。n表示0以上的整数。)]
另外，本发明涉及上述的固化性化合物，其中，式(1)中的R1、R2相同或不同，是具有环状酰亚胺结构的固化性官能团。
另外，本发明涉及上述的固化性化合物，其中，式(1)中的R1、R2相同或不同，是选自下述式(r-1)～(r-6)所示基团的基团。
[化学式3]
Figure PCTCN2016110302-appb-000003
(式中从氮原子伸出的键与D1或D2键合)
另外，本发明涉及上述的固化性化合物，其中，式(1)中的D1、D2相同或不同，是选自下述式(d-1)～(d-4)所示基团的基团。
[化学式4]
Figure PCTCN2016110302-appb-000004
另外，本发明涉及上述的固化性化合物，其中，式(I)及式(II)中的Ar1～Ar3相同或不同，是从碳原子数6～14的芳香环的结构式中去除2个氢原子后的基团、或者是从2个以上碳原子数6～14的芳香环经由单键或下述连接基团键合而成的结构式中去除2个氢原子后的基团，所述连接基团为碳原子数1～5的直链或支链亚烷基、或碳原子数1～5的直链或支链亚烷基的1个以上氢原子被卤原子取代后的基团。
另外，本发明涉及上述的固化性化合物，其中，式(I)所示的结构是来自于二苯甲酮的结构。
另外，本发明涉及上述的固化性化合物，其中，在式(1)所示的固化性化合物总量中，来自于二苯甲酮的结构单元所占的比例为5重量％以上。
另外，本发明涉及上述的固化性化合物，其中，式(II)所示的结构是来自于选自对苯二酚、间苯二酚及双酚A中的至少1种化合物的结构。
另外，本发明涉及上述的固化性化合物，其中，在式(1)所示的固化性化合物总量中，来自于对苯二酚、间苯二酚及双酚A的结构单元所占的比例为5重量％以上。
另外，本发明提供含有上述固化性化合物的固化性组合物。
另外，本发明提供上述固化性组合物的固化物。
发明的效果
具有上述结构的本发明的固化性化合物(特别是在具有包含来自于二苯甲酮的结构单元和来自于选自对苯二酚、间苯二酚及双酚A中至少1种化合物的结构单元的重复单元的分子链的两个末端导入了特定的固化性官能团的化合物)具有良好的溶剂溶解性。而且，通过实施加热处理等快速地固化，可以形成具有超耐热性的固化物。因此，本发明的固化性化合物能够适用于以电子信息、家电、汽车、精密机械为代表的、要求良好的加工性(或易成型性)和高耐热性的领域。
附图说明
图1是示出制备例中得到的Diamine-F(1)、(2)的1H-NMR图谱/DMSO-d6的图。
图2是示出制备例中得到的Diamine-F(1)的FTIR图谱的图。
图3是示出制备例中得到的Diamine-F(2)的FTIR图谱的图。
图4是示出制备例中得到的Diamine-B(1)、(2)的1H-NMR图谱/DMSO-d6的图。
图5是示出制备例中得到的Diamine-B(1)的FTIR图谱的图。
图6是示出制备例中得到的Diamine-B(2)的FTIR图谱的图。
图7是示出实施例中得到的PEI-F(1)、(2)的1H-NMR图谱/CDCl3的图。
图8是示出实施例中得到的PEI-F(1)的FTIR图谱的图。
图9是示出实施例中得到的PEI-F(2)的FTIR图谱的图。
图10是示出实施例中得到的PEI-B(1)、(2)的1H-NMR图谱/CDCl3的图。
图11是示出实施例中得到的PEI-B(1)的FTIR图谱的图。
图12是示出实施例中得到的PEI-B(2)的FTIR图谱的图。
图13是示出实施例中得到的BMI-F(1)的1H-NMR图谱/CDCl3的图。
图14是示出实施例中得到的BMI-B(1)的1H-NMR图谱/CDCl3的图。
图15是示出实施例中得到的PEI-F(1)、(2)及PEI-B(1)、(2)的DSC测定结果的图。
图16是示出实施例中得到的PEI-F(1)、(2)及PEI-B(1)、(2)的固化物的DSC测定结果的图。
图17是示出实施例中得到的PEI-F(1)、(2)及PEI-B(1)、(2)的固化物的热失重分析结果的图。
具体实施方式
[固化性化合物]
本发明的固化性化合物以下述式(1)表示。
[化学式5]
Figure PCTCN2016110302-appb-000005
式(1)中，R1、R2相同或不同，表示固化性官能团，D1、D2相同或不同，表示单键或连接基团。L表示具有包含下述式(I)所示的结构和下述式(II)所示的结构的重复单元的2价基团。
[化学式6]
Figure PCTCN2016110302-appb-000006
(式中，Ar1～Ar3相同或不同，表示从芳香环的结构式中去除2个氢原子后的基团、或者从2个以上芳香环经由单键或连接基团键合而 成的结构式中去除2个氢原子后的基团。X表示-CO-、-S-或-SO2-，Y相同或不同，表示-S-、-SO2-、-O-、-CO-、-COO-或-CONH-。n表示0以上的整数。)]
式中，R1、R2表示固化性官能团。R1、R2可以相同，也可以各自不同。作为R1、R2中的固化性官能团，优选例如下述式(r)所示的基团等具有环状酰亚胺结构的固化性官能团。
[化学式7]
Figure PCTCN2016110302-appb-000007
(式中从氮原子伸出的键与D1或D2键合)
上述式(r)中，Q表示C或CH，在Q为C时，式中的2个Q通过双键键合，在Q为CH时，式中的2个Q通过单键键合。n’为0以上的整数(例如0～3，优选为0或1)。R3～R6相同或不同，表示氢原子、饱和或不饱和脂肪族烃基(优选为碳原子数1～10的烷基、碳原子数2～10的烯基、碳原子数2～10的炔基)、芳香族烃基(优选为苯基、萘基等碳原子数6～10的芳基)、或者选自上述饱和或不饱和脂肪族烃基和芳香族烃基的2个以上基团键合而成的基团。选自R3～R6的2个基团任选相互键合而与邻接的碳原子共同形成环。
作为选自R3～R6的2个基团任选相互键合而与邻接的碳原子共同形成的环，可以列举例如：碳原子数3～20的脂环及碳原子数6～14的芳环。上述碳原子数3～20的脂环包括例如：环丙烷环、环丁烷环、环戊烷环、环己烷环等3～20元(优选为3～15元、特别优选为5～8元)左右的环烷烃环；环戊烯环、环己烯环等3～20元(优选为3～15元、特别优选为5～8元)左右的环烯烃环；全氢萘环、降冰片烷环、降冰片烯环、金刚烷环、三环[5.2.1.02,6]癸烷环、四环[4.4.0.12,5.17,10]十二烷环等桥环烃基等。上述碳原子数6～14的芳香环包括苯环、萘环等。
作为上述具有环状酰亚胺结构的固化性官能团，其中，优选具有环状不饱和酰亚胺结构的固化性官能团、或具有带芳基乙炔基的环状酰亚胺结构的固化性官能团，特别优选选自下述式(r-1)～(r-6)所示的基团，尤其优选下述式(r-1)或(r-5)所示的基团。
[化学式8]
Figure PCTCN2016110302-appb-000008
(式中从氮原子伸出的键与D1或D2键合)
任选在上述式(r-1)～(r-6)所示的基团中键合1种或2种以上的取代基。作为上述取代基，可以列举例如：碳原子数1～6的烷基、碳原子数1～6的烷氧基及卤原子等。
作为上述碳原子数1～6的烷基，可以列举例如：甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、己基等直链或支链烷基。
作为上述碳原子数1～6的烷氧基，可以列举例如：甲氧基、乙氧基、丁氧基、叔丁氧基等直链或支链烷氧基。
式(1)中，D1、D2相同或不同，表示单键或连接基团。作为上述连接基团，可以列举例如：2价的烃基、2价的杂环基、羰基、醚键、酯键、碳酸酯键、酰胺键、酰亚胺键、以及上述多个连接而成的基团等。
上述2价烃基包括2价脂肪族烃基、2价脂环族烃基及2价芳香族烃基。
作为上述2价脂肪族烃基，可以列举例如：碳原子数1～18的直链或支链亚烷基、以及碳原子数2～18的直链或支链的亚烯基等。作为碳原子数1～18的直链或支链亚烷基，可以列举例如：亚甲基、甲基亚甲基、二甲基亚甲基、亚乙基、亚丙基、三亚甲基等。作为碳原子数2～18的直链或支链亚烯基，可以列举例如：亚乙烯基、1-甲基亚乙烯基、亚丙烯基、1-亚丁烯基、2-亚丁烯基等。
作为上述2价脂环族烃基，可以举出碳原子数3～18的2价脂环族烃基等，可以列举例如：1,2-亚环戊基、1,3-亚环戊基、环戊叉基、1,2-亚环己基、1,3-亚环己基、1,4-亚环己基、环己叉基等亚环烷基(包括环烷叉基)等。
作为上述2价芳香族烃基，可以举出例如碳原子数6～14的亚芳基等，可以列举例如：1,4-亚苯基、1,3-亚苯基、4,4’-联苯撑基、3,3’-联苯撑基、2,6-亚萘基、2,7-亚萘基、1,8-亚萘基、亚蒽基等。
构成上述2价杂环基的杂环包括芳香族杂环及非芳香族杂环。作为这样的杂环，可以列举：构成环的原子中具有碳原子和至少1种杂原子(例如，氧原子、硫原子、氮原子等)的3～10元环(优选为4～6元环)、以及这些环的稠环。具体而言，可以列举：含有氧原子作为杂原子的杂环(例如，环氧乙烷环等3元环；氧杂环丁烷环等4元环；呋喃环、四氢呋喃环、
Figure PCTCN2016110302-appb-000009
唑环、异
Figure PCTCN2016110302-appb-000010
唑环、γ-丁内酯环等5元环；4-氧代-4H-吡喃环、四氢吡喃环、吗啉环等6元环；苯并呋喃环、异苯并呋喃环、4-氧代-4H-色烯环、色满环、异色满环等稠环；3-氧杂三环[4.3.1.14,8]十一烷-2-酮环、3-氧杂三环[4.2.1.04,8]壬烷-2-酮环等桥环)、含有硫原子作为杂原子的杂环(例如，噻吩环、噻唑环、异噻唑环、噻二唑环等5元环；4-氧代-4H-噻喃环等6元环；苯并噻吩环等稠环等)、含有氮原子作为杂原子的杂环(例如，吡咯环、吡咯烷环、吡唑环、咪唑环、三唑环等5元环；三聚异氰酸环、吡啶环、哒嗪环、嘧啶环、吡嗪环、哌啶环、哌嗪环等6元环；吲哚环、吲哚啉环、喹啉环、吖啶环、萘啶环、喹唑啉环、嘌呤环等稠环等)等。2价杂环基是从上述杂环的结构式中去除2个氢原子后的基团。
作为上述D1、D2，其中，从可以得到具有特别优异的耐热性的 固化物的观点考虑，优选2价芳香族烃基，特别优选碳原子数6～14的2价芳香族烃基，最优选选自下述式(d-1)～(d-4)所示的基团，尤其优选下述式(d-1)所示的基团(1,2-亚苯基、1,3-亚苯基或1,4-亚苯基)。
[化学式9]
Figure PCTCN2016110302-appb-000011
因此，作为式(1)中的R1-D1基及R2-D2基，其相同或不同，特别优选为下述式(rd-1)或(rd-2)所示的基团。
[化学式10]
Figure PCTCN2016110302-appb-000012
(从式中的亚苯基伸出的键与L键合)
式(1)中的L表示具有重复单元的2价基团，所述重复单元包含上述式(I)所示的结构和上述式(II)所示的结构。式(I)及式(II)中的Ar1～Ar3相同或不同，表示从芳香环的结构式中去除2个氢原子后的基团、或者从2个以上芳香环经由单键或连接基团键合而成的结构式中去除2个氢原子后的基团。X表示-CO-、-S-或-SO2-，Y相同或不同，表示-S-、-SO2-、-O-、-CO-、-COO-或-CONH-。n表示0以上的整数，例如为0～5的整数，优选为1～5的整数，特别优选为1～3的整 数。
作为上述芳香环(＝芳香族烃环)，可以列举例如：苯、萘、蒽、菲等碳原子数6～14的芳香环。在本发明中，其中，优选苯、萘等碳原子数6～10的芳香环。
作为上述连接基团，可以列举例如：碳原子数1～5的2价烃基或碳原子数1～5的2价烃基的1个以上氢原子被卤原子取代后的基团等。
上述碳原子数1～5的2价烃基包括例如：亚甲基、甲基亚甲基、二甲基亚甲基、二亚甲基、三亚甲基等碳原子数1～5的直链或支链亚烷基；亚乙烯基、1-甲基乙烯基、亚丙烯基等碳原子数2～5的直链或支链亚烯基；亚乙炔基、亚丙炔基、1-甲基亚丙炔基等碳原子数2～5的直链或支链亚炔基等。在本发明中，其中，优选碳原子数1～5的直链或支链亚烷基，特别优选碳原子数1～5的支链亚烷基。
因此，作为上述Ar1～Ar3，其相同或不同，优选从碳原子数6～14的芳香环的结构式中去除2个氢原子后的基团、或者是从2个以上碳原子数6～14的芳香环经由单键或下述连接基团键合而成的结构式中去除2个氢原子后的基团，所述连接基团为碳原子数1～5的直链或支链亚烷基、或碳原子数1～5的直链或支链亚烷基的1个以上氢原子被卤原子取代后的基团，特别优选为从碳原子数6～14的芳香环的结构式中去除2个氢原子后的基团、或者是从2个以上碳原子数6～14的芳香环经由单键或下述连接基团键合而成的结构式中去除2个氢原子后的基团，所述连接基团为碳原子数1～5的支链亚烷基、或碳原子数1～5的支链亚烷基的1个以上氢原子被卤原子取代后的基团。
作为上述Ar1～Ar3，其相同或不同，特别优选为选自下述式(a-1)～(a-5)所示的基团。需要说明的是，下述式中的键的连接位置没有特别限制。
[化学式11]
Figure PCTCN2016110302-appb-000013
作为式(I)中的Ar1、Ar2，其中，优选从碳原子数6～14的芳香环的结构式中去除2个氢原子后的基团，特别优选上述式(a-1)或(a-2)所示的基团。另外，其中，作为X，优选-CO-或-SO2。作为式(I)所示的结构，特别优选包含来自于二苯甲酮的结构。
在式(1)所示的固化性化合物总量中，来自于二苯甲酮的结构单元所占的比例为例如5重量％以上，优选为10～62重量％，特别优选为15～60重量％。
作为式(II)中的Ar3，其中优选为选自上述式(a-1)、(a-4)及(a-5)所示的基团。另外，作为Y，其中优选-S-或-O-。作为式(II)所示的结构，特别优选包含来自于选自对苯二酚、间苯二酚及双酚A中至少1种化合物的结构。
在式(1)所示的固化性化合物总量中，来自于对苯二酚、间苯二酚及双酚A的结构单元所占的比例为例如5重量％以上，优选为10～55重量％，特别优选为15～53重量％。
作为式(1)中的L，其中，从可以得到耐热性特别优异的固化物的观点考虑，优选下述式(l-1)或(l-2)所示的2价基团。
[化学式12]
Figure PCTCN2016110302-appb-000014
上述式中的n1、n2是平均聚合度，即，分子链(＝上述式(l-1)或(l-2)所示的2价基团)中含有的圆括号内所示的重复单元的数量，例如为3～50，优选为4～30，特别优选为5～20。需要说明的是，n1、n2的值可以通过GPC测定来求出。
本发明的固化性化合物具有上述结构，因此通过利用热等进行的固化反应而获得具有高度交联结构(即，交联密度高)、且具有超耐热性的固化物。
另外，本发明的固化性化合物具有上述结构，因此对下述溶剂显示出优异的溶解性。
溶剂：可以列举例如苯、甲苯、二甲苯等芳香烃类；二氯甲烷、氯仿、1,2-二氯乙烷、氯苯、二氯苯、三氟甲苯等卤代烃类；乙酸乙酯等酯类；四氢呋喃等醚类；N-甲基-2-吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜及它们的混合物等。
另外，在本发明的固化性化合物中，式(1)中的L为上述式(l-1)或(l-2)所示的2价基团，式中的n1、n2为5～10的化合物在300℃以下(250℃左右)熔融，因此，与PEEK等相比，能够在低温下进行熔融成型，成型加工性特别优异。
另一方面，分子链的平均聚合度(n1、n2)低于上述范围时，得到的固化物变脆，具有力学特性降低的倾向。另外，分子链的平均聚合度(n1、n2)大于上述范围时，存在由于对溶剂的溶解性降低、熔融粘度增高等而导致成型加工性降低的倾向。
上述式(1)所示的固化性化合物例如可以利用Polymer 1989p978中记载的合成方法来制造。下面示出上述式(1)所示的固化性化合物的制造方法的一个例子，但并不特别限定于该制造方法。
下述式(1-1)所示的化合物可以经由下述工序[1]～[3]来制造。下述式中，Ar1～Ar3、X、Y、n、R3～R6、Q、n’与上述相同。D表示连接基团，Z表示卤原子。n3为重复单元的平均聚合度，例如为3～50，优选为4～30，特别优选为5～20。在上述式(1)所示的固化性化合物中，下述式(1-1)所示的化合物以外的化合物也可以按照下述方法来制造。
工序[1]：在碱存在下使作为反应基质的下述式(2)所示的化合物与下述式(3)所示的化合物发生反应，由此得到下述式(4)所示的化合物
工序[2]：使氨基醇(下述式(5)所示的化合物)与下述式(4)所示的化合物反应，由此得到下述式(6)所示的二胺。
工序[3]：使环状酸酐(下述式(7)所示的化合物)与下述式(6)所示的二胺反应，由此得到下述式(1-1)所示的化合物。
[化学式13]
Figure PCTCN2016110302-appb-000015
(工序[1])
作为上述式(2)所示的化合物，可以列举例如：二苯甲酮、2-苯甲酰萘及二(2-萘基)酮等的卤代物及它们的衍生物等。
作为上述式(3)所示的化合物，可以列举例如：对苯二酚、4,4’-二羟基联苯、间苯二酚、2,6-萘二酚、1,5-萘二酚、(1,1’-联苯)-4,4’-双酚、4,4’-二羟基二苯醚、二(4-羟基苯基)甲酮、双酚A、双酚F、双酚S、(1,1’-联苯)-2,5-双酚、以及它们的衍生物等。
作为上述衍生物，可以列举例如：取代基键合于上述式(2)所示的化合物、式(3)所示的化合物中的芳香族烃基而得到的化合物等。 作为上述取代基，可以列举例如：碳原子数1～6的烷基、碳原子数1～6的烷氧基及卤原子等。
作为式(2)所示的化合物和式(3)所示的化合物的用量，通常相对于式(3)所示的化合物1摩尔，式(2)所示的化合物为1摩尔以上，优选根据希望的固化性化合物中的分子链的平均聚合度来调整式(2)所示的化合物的用量。例如，在平均聚合度为5的情况下，相对于式(3)所示的化合物1摩尔，优选使用式(2)所示的化合物1.2(1.18～1.22)摩尔，在平均聚合度为10的情况下，优选使用式(2)所示的化合物1.1(1.08～1.12)摩尔，在平均聚合度为20的情况下，优选使用式(2)所示的化合物1.05(1.04～1.06)摩尔左右。
特别是，作为式(2)所示的化合物，优选至少使用二苯甲酮的卤代物，式(2)所示的化合物的总用量(100摩尔％)中，二苯甲酮的卤代物的用量为例如10摩尔％以上，优选为30摩尔％以上，特别优选为50摩尔以上，最优选为80摩尔以上。需要说明的是，其上限为100摩尔％。
特别是，作为式(3)所示的化合物，优选至少使用选自对苯二酚、间苯二酚及双酚A中的至少1种化合物，式(3)所示的化合物的总用量(100摩尔％)中，对苯二酚、间苯二酚及双酚A的用量总计为例如10摩尔％以上，优选为30摩尔％以上，特别优选为50摩尔％以上，最优选为80摩尔％以上。需要说明的是，其上限为100摩尔％。
上述式(2)所示的化合物与式(3)所示的化合物的反应在碱(例如：选自氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠等无机碱；吡啶、三乙胺等有机碱中的至少1种)的存在下进行。碱的用量可以根据碱的种类而适当调整。例如，在使用氢氧化钙等二元碱的情况下，相对于式(3)所示的化合物1摩尔，碱的用量为例如1.0～2.0摩尔左右。
另外，该反应可以在溶剂的存在下进行。作为上述溶剂，可以使用例如N-甲基-2-吡咯烷酮、二甲基甲酰胺、二甲基亚砜、丙酮、四氢呋喃、甲苯等有机溶剂、或者2种以上上述溶剂的混合溶剂。
作为上述溶剂的用量，相对于反应基质的总计(重量)，例如为 5～20重量倍左右。溶剂的用量高于上述范围时，反应基质的浓度降低，存在反应速度降低的倾向。
作为反应气体氛围，只要不妨碍反应即可，没有特别限定，例如，可以是空气氛围、氮气氛围、氩气氛围等中的任一种。
反应温度为例如100～200℃左右。反应时间为例如5～24小时左右。另外，该反应可以用间歇式、半间歇式、连续式等任意方法来进行。
该反应结束后，得到的反应产物可以通过例如过滤、浓缩、蒸馏、提取、晶析、吸附、重结晶、柱色谱等分离方法、上述方法组合而成的分离方法来进行分离纯化。
(工序[2])
作为上述式(5)所示的化合物，可以列举例如：4-氨基苯酚、2-氨基-6-羟基萘、以及它们的立体异构体、衍生物等。
上述式(5)所示的化合物的用量可以根据希望的固化性化合物中分子链的平均聚合度而适当调整。例如，在平均聚合度5的情况下，相对于式(3)所示的化合物1摩尔为0.4～0.6摩尔左右的量，在平均聚合度10的情况下，相对于式(3)所示的化合物1摩尔为0.2～0.4摩尔左右的量，在平均聚合度20的情况下，相对于式(3)所示的化合物1摩尔为0.1～0.15摩尔左右的量。
该反应随反应进行而生成卤化氢，因此，从获得促进反应进行的效果的观点考虑，优选在吸收所生成的卤化氢的碱的存在下进行反应。作为上述碱，可以列举例如：氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠等无机碱；吡啶、三乙胺等有机碱。这些碱可以单独使用1种，或者组合使用2种以上。
上述碱的用量可以根据碱的种类而适当调整。例如，在使用氢氧化钠等一元碱的情况下，相对于上述式(5)所示的化合物1摩尔，碱的用量为例如1.0～3.0摩尔左右。
另外，该反应可以在溶剂的存在下进行。作为溶剂，可以使用与工序[1]中使用的溶剂相同的溶剂。
反应温度为例如100～200℃左右。反应时间为例如1～15小时左右。另外，该反应可以用间歇式、半间歇式、连续式等任意方法来进行。
该反应结束后，得到的反应产物可以通过例如过滤、浓缩、蒸馏、提取、晶析、吸附、重结晶、柱色谱等分离方法、上述方法组合而成的分离方法来进行分离纯化。
(工序[3])
作为上述环状酸酐(上述式(7)所示的化合物)，可以列举例如：马来酸酐、2-苯基马来酸酐、4-苯基乙炔基邻苯二甲酸酐、4-(1-萘基乙炔基)邻苯二甲酸酐、双环[2.2.1]庚-5-烯-2,3-二甲酸酐、以及它们的衍生物等。
上述环状酸酐的用量可以根据希望的固化性化合物中的分子链的平均聚合度而适当调整。例如，在平均聚合度5的情况下，相对于式(3)所示的化合物1摩尔为0.4～0.8摩尔左右的量，在平均聚合度10的情况下，相对于式(3)所示的化合物1摩尔为0.2～0.4摩尔左右的量，在平均聚合度20的情况下，相对于式(3)所示的化合物1摩尔为0.1～0.15摩尔左右的量。
该反应可以在溶剂的存在下进行。作为溶剂，可以使用与工序[1]中使用的溶剂相同的溶剂。
该反应优选在室温(1～30℃)下进行。反应时间为例如1～30小时左右。另外，该反应可以用间歇式、半间歇式、连续式等任意方法来进行。
另外，从能够促进反应进行的观点考虑，优选该反应通过使用了与水共沸的溶剂(例如，甲苯等)的共沸、通过使用脱水剂(例如，乙酸酐等)来去除反应时作为副产物而生成的水。另外，利用脱水剂进行的生成水除去优选在碱性催化剂(例如，三乙胺等)的存在下进行。
该反应结束后，得到的反应产物可以通过例如过滤、浓缩、蒸馏、提取、晶析、吸附、重结晶、柱色谱等分离方法、上述方法组合而成的分离方法来进行分离纯化。
式(1)所示的固化性化合物的放热峰值温度依赖于固化性官能团的种类，例如为170～450℃，优选为200～430℃，特别优选为220～420℃。放热峰值温度可以通过DSC测定求出。
式(1)所示的固化性化合物的放热峰值温度根据固化性官能团的种类而确定，因此，优选根据采用的成型法来选择固化性官能团。例如，在通过浇注法由将固化性化合物溶解在溶剂中而得到的溶液成型为膜状并使其固化的情况下，作为式(1)所示的固化性化合物中的固化性官能团，优选选择上述式(r-5)所示的基团，在该情况下，可以通过在250℃左右的温度下加热来形成固化物。另一方面，作为式(1)所示的固化性化合物中的固化性官能团，在选择上述式(r-1)所示的基团时，该固化性化合物可以在300℃以下的温度熔融而成型，可以通过在380℃左右的温度下加热而形成固化物。
需要说明的是，加热可以在上述温度范围内保持恒定温度的状态下进行，也可以阶段性地改变温度来进行。加热温度优选根据加热时间而在上述范围中适当调整，例如，在希望缩短加热时间的情况下，优选较高地设定加热温度。由于本发明的固化性化合物具有上述式(1)所示的结构，因此，能够形成即使在高温下加热也不分解的固化物(具体而言，有超耐热性的固化物)，可以通过高温下短时间加热而以优异的操作性高效地形成固化物。需要说明的是，加热方式没有特别限制，可以使用公知或常用的方法。
式(1)所示的固化性化合物的固化可以在常压下进行，也可以在减压下或加压下进行。
式(1)所示的固化性化合物的固化物在升温速度10℃/分(氮中)下测定的5％失重温度(Td5)为例如300℃以上，更优选为400℃以上，特别优选为450℃以上，最优选为500℃以上。需要说明的是，其上限为例如600℃，优选为550℃，特别优选为530℃。需要说明的是，5％失重温度可以通过例如TG/DTA(示差热热重量同时测定)来测定。
式(1)所示的固化性化合物的固化物在升温速度10℃/分(氮中)下测定的10％失重温度(Td10)为例如300℃以上，更优选为400℃以上，特别优选为500℃以上，最优选为510℃以上。需要说明的是，其上 限为例如600℃，优选为550℃。需要说明的是，10％失重温度可以通过例如TG/DTA(示差热热重量同时测定)来测定。
本发明的固化性化合物具有良好的溶剂溶解性。另外，通过实施加热处理而快速固化，可以形成如上所述具有超耐热性的固化物。因此，可以用作例如在电子信息、家电、汽车、精密机械等严苛耐热环境下使用的复合材料的成型材料、绝缘材料、耐热性粘接剂等功能材料。另外，还可以优选用于密封剂、涂敷剂、粘接剂、油墨、密封胶、抗蚀剂、形成材料[例如，基材、电绝缘材料(绝缘膜等)、叠层板、复合材料(纤维强化塑料、预成型料等)、光学元件(透镜等)、光固化造型、电子纸、触摸面板、太阳能电池基板、光波导、导光板、全息存储器等的形成材料]等，特别是可以优选用于目前的树脂材料难以应对的、在高耐热/高耐电压的半导体装置(电力半导体(power semiconductor)等)中包覆半导体元件的密封剂用途。
[固化性组合物]
本发明的固化性组合物的特征在于包含1种或2种以上的上述固化性化合物。本发明的固化性组合物总量中上述固化性化合物的含量(在含有2种以上的情况下为其总量)为例如30重量％以上，优选为50重量％以上，特别优选为70重量％以上，最优选为90重量％以上。需要说明的是，其上限为100重量％。即，本发明的固化性组合物也包括仅由固化性化合物构成的组合物。
本发明的固化性组合物除了上述固化性化合物以外还可以根据需要含有其它成分。作为其它成分，可以使用公知或常用的添加剂，可以列举例如：上述式(1)所示的化合物以外的固化性化合物、催化剂、填料、有机树脂(有机硅树脂、环氧树脂、氟树脂等)、溶剂、稳定剂(抗氧剂、紫外线吸收剂、耐光稳定剂、热稳定剂等)、阻燃剂(磷系阻燃剂、卤系阻燃剂、无机系阻燃剂等)、阻燃助剂、增强材料、成核剂、偶联剂、润滑剂、蜡、增塑剂、脱模剂、耐冲击性改良剂、色相改良剂、流动性改良剂、着色剂(染料、颜料等)、分散剂、消泡剂、脱泡剂、抗菌剂、防腐剂、粘度调节剂、增稠剂等。这些添加剂可以单独使用1种，或组合使用2种以上。
本发明的固化性组合物可以含有上述式(1)所示的固化性化合物以外的固化性化合物作为固化性化合物，但固化性组合物中含有的全部固化性化合物中上述式(1)所示的固化性化合物所占的比例为例如70重量％以上，优选为80重量％以上，特别优选为90重量％以上。需要说明的是，其上限为100重量％。
另外，本发明的固化性组合物即使不含交联剂、固化促进剂(例如，即使本发明的固化性组合物总量中交联剂及固化促进剂的总含量为例如3重量％以下，优选为小于1重量％)，也能够快速地形成固化物。因此，得到的固化物具有超耐热性。另外，可以将固化物中未反应的固化促进剂、固化促进剂的分解物的含量抑制得极低，因此能够抑制来自于未反应的固化促进剂、固化促进剂的分解物的排气的产生。
本发明的固化性组合物含有上述固化性化合物，因此通过实施加热处理可以快速地固化，能够形成具有超耐热性的固化物。需要说明的是，加热处理条件可以在与上述固化性化合物的固化条件相同的范围内适当设定。
本发明的固化性组合物可以优选用作例如：电子信息、家电、汽车、精密机械、飞机、航天工业用机器等能够在严苛的耐热环境下使用的复合材料(纤维强化塑料、预成型料等)的成型材料、绝缘材料、耐热性粘接剂等功能材料。另外，可以优选用于：密封剂、涂料、油墨、密封胶、抗蚀剂、形成材料[推力垫圈、滤油器、密封垫、轴承、传动装置、汽缸盖、滚动轴承保持架、进气歧管、踏板等汽车部件；基材、电绝缘材(绝缘膜等)、叠层板、电子纸、触摸面板、太阳能电池基板、光波导、导光板、全息存储器、硅晶片载体、IC芯片托架、电解电容器托架、绝缘膜等半导体/液晶制造装置部件；透镜等光学部件；泵、阀门、密封垫等压缩机部件；飞机机舱的内装部件；灭菌器具、柱、管道等医疗器具部件、食品/饮料制造设备部件；用于个人电脑、手机等的框体、以个人电脑内部支撑键盘的构材的键盘支撑体为代表的电气/电子仪器用构材等形成材料]等，特别是可以优选用于目前的树脂材料难以应对的、在高耐热/高耐电压的半导体装置(电 力半导体等)中包覆半导体元件的密封剂用途。
实施例
以下，通过实施例更具体地对本发明进行说明，但本发明并不限定于这些实施例。
需要说明的是，测定在下述条件下进行。
＜NMR测定＞
测定装置：BRUKER 400MHz/54mm
测定溶剂：DMSO、氯仿
化学位移：以TMS作为基准
＜GPC测定＞
装置：泵“LC-20AD”(株式会社岛津制作所制造)
检测器：RID-10A(株式会社岛津制作所制造)
溶剂：THF
柱：shodex GPC KF-801+KF-801+KF-803+KF-806M
流速：1.0mL/分
温度：40℃
样品浓度：0.1％(重量/体积)
换算为标准苯乙烯
＜DSC测定＞
装置：TA Q20
升温速度：10℃/分
气体氛围：氮气氛围
＜TGA测定＞
装置：NETZSCH TG209F3
升温速度：10℃/分
气体氛围：氮气氛围
＜IR测定＞
装置：Perkin Elmer Spectrum RX1(ATR法)
制备例1(Diamine-F(1)的合成)
工序1：向具有搅拌装置、氮导入管及迪安-斯塔克(Dean-Stark apparatus)装置的100mL(三颈)烧瓶中加入4,4’-二氟二苯甲酮6.865g、双酚A 5.985g、无水碳酸钾5.427g、N-甲基吡咯烷酮50mL及甲苯25mL，一边在氮气氛围下搅拌一边加热，在130～140℃下使甲苯回流4小时。然后，进一步加热，在170～180℃下馏去甲苯。继续在170～180℃下搅拌10小时，然后恢复至室温。
工序2：向装有经过工序1得到的产物的烧瓶添加4-氨基苯酚1.144g、无水碳酸钾1.447g、N-甲基吡咯烷酮5mL及甲苯25mL，再一边在氮气氛围下搅拌一边加热，在130～140℃下使甲苯回流3小时。然后，再进行加热，在170～180℃下馏去甲苯，再保持上述温度并继续搅拌4小时。然后，冷却至室温，将反应液添加于1500mL的乙醇中，并进行过滤，由此得到了粉末状固体。将该粉末状固体用乙醇和水反复清洗，然后在100℃下减压干燥8小时，得到了粉末状固体(Diamine-F(1)，以下述式(6-1)表示，式中的n1为6.8的化合物，产率：95％)。
[化学式14]
Figure PCTCN2016110302-appb-000016
制备例2(Diamine-F(2)的合成)
在工序1中，将4,4’-二氟二苯甲酮的用量变更为6.586g，将双 酚A的用量变更为6.264g，将无水碳酸钾的用量变更为5.680g，在工序2中，将4-氨基苯酚的用量变更为0.599g，将无水碳酸钾的用量变更为0.599g，除此以外，与制备例1同样地进行，得到了粉末状固体(Diamine-F(2)，以上述式(6-1)表示，式中的n1为9.7的化合物，产率：94％)。
制备例3(Diamine-B(1)的合成)
工序1：向具有搅拌装置、氮导入管及迪安-斯塔克装置的100mL(三颈)烧瓶中加入4,4’-二氟二苯甲酮8.905g、间苯二酚3.745g、无水碳酸钾7.040g、N-甲基吡咯烷酮50mL及甲苯25mL，一边在氮气氛围下搅拌一边加热，在130～140℃下使甲苯回流4小时。然后，进一步加热，在170～180℃下馏去甲苯。在170～180℃下继续搅拌10小时，然后恢复至室温。
工序2：向装有经过工序1得到的产物的烧瓶添加4-氨基苯酚1.485g、无水碳酸钾1.878g、N-甲基吡咯烷酮5mL、甲苯25mL。再一边在氮气氛围下搅拌一边加热，在130～140℃下使甲苯回流3小时。然后，再进行加热，在170～180℃下馏去甲苯，再保持上述温度并继续搅拌4小时。然后，冷却至室温，将反应液添加于1500mL的乙醇中，并进行过滤，由此得到了粉末状固体。将该粉末状固体用乙醇和水反复清洗，然后在100℃下减压干燥8小时，得到了粉末状固体(Diamine-B(1)，以下述式(6-2)表示，式中的n2为6.1的化合物，产率：95％)。
[化学式15]
Figure PCTCN2016110302-appb-000017
制备例4(Diamine-B(2)的合成)
在工序1中，将4,4’-二氟二苯甲酮的用量变更为9.121g、将间 苯二酚的用量变更为4.185g、将无水碳酸钾的用量变更为7.867g，在工序2中，将4-氨基苯酚的用量变更为0.829g，将无水碳酸钾的用量变更为1.049g，除此以外，与制备例3同样地进行，得到了粉末状固体(Diamine-B(2)，以上述式(6-2)表示，式中的n2为8.8的化合物，产率：93％)。
将制备例中得到的粉末状固体的1H-NMR图谱和FTIR图谱示于图1～6。另外，将通过凝胶渗透色谱(GPC)测定(换算为标准苯乙烯)求得的数均分子量、重平均分子量及平均聚合度示于下表。
表1
Figure PCTCN2016110302-appb-000018
实施例1(PEI-F(1)的合成)
向具有搅拌装置、氮导入管及干燥管的50mL(三颈)烧瓶加入制备例中得到的Diamine-F(1)4.550g、4-苯基乙炔基邻苯二甲酸酐1.395g、N-甲基吡咯烷酮33mL，在氮气氛围、室温下搅拌18小时。然后，将干燥管更换为迪安-斯塔克装置，加入甲苯25mL，然后升温至130～140℃，使甲苯回流5小时。接着，加热至170～180℃使甲苯馏去，并继续搅拌4小时。然后，冷却至室温，将反应液加入1500mL的乙醇，并过滤，由此得到了粉末状固体。将该粉末状固体用乙醇和水反复清洗，然后在100℃下减压干燥8小时，得到了粉末状固体(PEI-F(1)、产率：90％)。将得到的粉末状固体的1H-NMR图谱示于图7，将FTIR图谱示于图8。
[化学式16]
Figure PCTCN2016110302-appb-000019
1H-NMR(CDCl3)δ：1.71(s),7.02(m),7.11(d,J＝8.8Hz),7.21(d,J＝8.8Hz),7.27(m),7.41(m),7.48(d,J＝8.8Hz),7.58(m),7.81(m),7.93(m),8.08(s)
实施例2(PEI-F(2)的合成)
除了使用制备例中得到的Diamine-F(2)4.599g来代替Diamine-F(1)，并使用4-苯基乙炔基邻苯二甲酸酐0.766g以外，与实施例1同样地得到了粉末状固体(PEI-F(2)、产率：91％)。将得到的粉末状固体的1H-NMR图谱示于图7，将FTIR图谱示于图9。
1H-NMR(CDCl3)δ：1.71(s),7.02(m),7.11(d,J＝8.8Hz),7.21(d,J＝8.8Hz),7.26(m),7.40(m),7.48(d,J＝8.8Hz),7.58(m),7.80(m),7.93(m),8.08(s)
实施例3(PEI-B(1)的合成)
除了使用制备例中得到的Diamine-B(1)4.571g来代替Diamine-F(1)，并使用4-苯基乙炔基邻苯二甲酸酐1.852g以外，与实施例1同样地得到了粉末状固体(PEI-B(1)、产率：90％)。将得到的粉末状固体的1H-NMR图谱示于图10，将FTIR图谱示于图11。
[化学式17]
Figure PCTCN2016110302-appb-000020
1H-NMR(CDCl3)δ：6.83(m),6.90(m),7.09(m),7.21(d,J＝8.8Hz),7.39(m),7.48(d,J＝8.8Hz),7.58(m),7.81(m),7.92(m),8.08(s)
实施例4(PEI-B(2)的合成)
除了使用制备例中得到的Diamine-B(2)4.607g来替代Diamine-F(1)，并使用4-苯基乙炔基邻苯二甲酸酐1.046g以外，与实施例1同样地得到了粉末状固体(PEI-B(2)、产率：92％)。将得到的粉末状固体的1H-NMR图谱示于图10，将FTIR图谱示于图12。
1H-NMR(CDCl3)δ：6.83(m),6.90(m),7.09(m),7.21(d,J＝8.8Hz),7.39(m),7.48(d,J＝8.8Hz),7.58(m),7.81(m),7.92(m),8.07(s)
实施例5(BMI-F(1)的合成)
向具有搅拌装置、氮导入管及干燥管的50mL(三颈)烧瓶加入制备例中得到的Diamine-F(1)4.550g、马来酸酐0.551g、N-甲基吡咯烷酮33mL，在氮气氛围、室温下搅拌24小时。然后，添加乙酸酐4.215g、三乙胺1.405g，并在60℃下搅拌6小时。将反应液恢复至室温，然后将反应液加入1500mL的乙醇中，并进行过滤，由此得到了粉末状固体。将该粉末状固体用乙醇和水反复清洗，然后在100℃下减压干燥8小时，得到了粉末状固体(BMI-F(1)、产率：90％)。将得到的粉末状固体的1H-NMR图谱示于图13。
1H-NMR(CDCl3)δ：1.71(s),6.87(s),7.02(m),7.09(m),7.17(d,J＝8.8Hz),7.26(m),7.37(d,J＝8.8Hz),7.80(m)
[化学式18]
Figure PCTCN2016110302-appb-000021
实施例6(BMI-B(1)的合成)
除了使用Diamine-B(1)4.571g来代替Diamine-F(1)，并将马来酸酐的用量变更为0.733g以外，与实施例5同样地得到了粉末状固体(BMI-B(1)、产率：90％)。将得到的粉末状固体的1H-NMR图谱示于图14。
1H-NMR(CDCl3)δ：6.88(m),7.08(d,J＝8.0Hz),7.17(d,J＝8.0Hz),7.39(m),7.81(d,J＝8.0Hz)
[化学式19]
Figure PCTCN2016110302-appb-000022
评价
通过DSC测定求出实施例中得到的粉末状固体的Tg及放热峰值温度。将结果示于图15。PEI-F(1)、(2)的Tg为140℃左右，PEI-B(1)、(2)的Tg为120℃左右，PEI-F(1)、(2)、PEI-B(1)、(2)均在400℃附近观察到了由固化反应引起的放热峰。
将实施例中得到的粉末状固体(0.5g)与下述溶剂(10g)混合，并在室温下搅拌8小时，将粉末状固体完全溶解的情况评价为溶剂溶解性良好(○)，将不溶或部分不溶的情况评价为溶剂溶解性不良(×)。将结果示于下表。
表2
  NMP DMSO 氯仿 THF
PEI-F(1) ○ ○ ○ ○
PEI-F(2) ○ ○ ○ ○
PEI-B(1) ○ ○ ○ ○
PEI-B(2) ○ ○ ○ ○
BMI-F(1) ○ ○ ○ ○
BMI-B(1) ○ ○ ○ ○
NMP：N-甲基-2-吡咯烷酮
DMSO：二甲基亚砜
THF：四氢呋喃
将实施例中得到的粉末状固体放置于玻璃板上，使其为厚度0.5mm左右且均匀，用马弗炉进行加热使其固化。马弗炉以10℃/分从25℃升温至371℃，然后在371℃下保持2小时。将得到的固化物的DSC结果示于图16，将热失重分析结果示于图17，将5％失重温 度(Td5)和10％失重温度(Td10)示于表3。
表3
  Td5(℃) Td10(℃)
固化后的PEI-F(1) 505 517
固化后的PEI-F(2) 504 517
固化后的PEI-B(1) 539 553
固化后的PEI-B(2) 519 529
固化后的BMI-F(1) 501 525
固化后的BMI-B(1) 512 528
由图16的DSC图中未观察到放热峰可知，得到的固化物的固化性优异(通过固化而失去了全部固化性官能团)。由图17可知Td5均为500℃以上。
工业实用性
本发明的固化性化合物具有良好的溶剂溶解性。另外，可以通过实施加热处理来快速地固化，能够形成具有超耐热性的固化物。因此，可以适于用作半导体器件的密封剂等。

Claims (11)

  1. 一种固化性化合物，其是下述式(1)所示的固化性化合物，
    Figure PCTCN2016110302-appb-100001
    式中，R1、R2相同或不同，表示固化性官能团，D1、D2相同或不同，表示单键或连接基团，L表示具有包含下述式(I)所示的结构和下述式(II)所示的结构的重复单元的2价基团，
    Figure PCTCN2016110302-appb-100002
    式中，Ar1～Ar3相同或不同，表示从芳香环的结构式中去除2个氢原子后的基团、或者从2个以上芳香环经由单键或连接基团键合而成的结构式中去除2个氢原子后的基团，X表示-CO-、-S-或-SO2-，Y相同或不同，表示-S-、-SO2-、-O-、-CO-、-COO-或-CONH-，n表示0以上的整数。
  2. 根据权利要求1所述的固化性化合物，其中，式(1)中的R1、R2相同或不同，是具有环状酰亚胺结构的固化性官能团。
  3. 根据权利要求1所述的固化性化合物，其中，式(1)中的R1、R2相同或不同，是选自下述式(r-1)～(r-6)所示基团的基团，
    Figure PCTCN2016110302-appb-100003
    式中从氮原子伸出的键与D1或D2键合。
  4. 根据权利要求1～3中任一项所述的固化性化合物，其中，式(1)中的D1、D2相同或不同，是选自下述式(d-1)～(d-4)所示基团的基团，
    Figure PCTCN2016110302-appb-100004
  5. 根据权利要求1～4中任一项所述的固化性化合物，其中，式(I)及式(II)中的Ar1～Ar3相同或不同，是从碳原子数6～14的芳香环的结构式中去除2个氢原子后的基团、或者是从2个以上碳原子数6～14的芳香环经由单键或下述连接基团键合而成的结构式中去除2个氢原子后的基团，所述连接基团为碳原子数1～5的直链或支链亚烷基、或碳原子数1～5的直链或支链亚烷基的1个以上氢原子被卤原子取代后的基团。
  6. 根据权利要求1～5中任一项所述的固化性化合物，其中，式(I)所示的结构是来自于二苯甲酮的结构。
  7. 根据权利要求6所述的固化性化合物，其中，在式(1)所示的固化性化合物总量中，来自于二苯甲酮的结构单元所占的比例为5重量％以上。
  8. 根据权利要求1～7中任一项所述的固化性化合物，其中，式(II)所示的结构是来自于选自对苯二酚、间苯二酚及双酚A中至少1种化合物的结构。
  9. 根据权利要求8所述的固化性化合物，其中，在式(1)所示的固化性化合物总量中，来自于对苯二酚、间苯二酚及双酚A的结构单元所占的比例为5重量％以上。
  10. 一种固化性组合物，其含有权利要求1～9中任一项所述的固化性化合物。
  11. 一种固化物，其是权利要求10所述的固化性组合物的固化物。
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