WO2014084185A1 - Diamine contenant un groupe hexafluoroisopropanol, polyimide et polyamide l'utilisant, produit cyclisé à base de celle-ci et son procédé de production - Google Patents

Diamine contenant un groupe hexafluoroisopropanol, polyimide et polyamide l'utilisant, produit cyclisé à base de celle-ci et son procédé de production Download PDF

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WO2014084185A1
WO2014084185A1 PCT/JP2013/081698 JP2013081698W WO2014084185A1 WO 2014084185 A1 WO2014084185 A1 WO 2014084185A1 JP 2013081698 W JP2013081698 W JP 2013081698W WO 2014084185 A1 WO2014084185 A1 WO 2014084185A1
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group
ring
formula
independently
bond
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大樹 魚山
山中　一広
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セントラル硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/68—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/68—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C215/70—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with rings other than six-membered aromatic rings being part of the carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
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    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/37—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom

Definitions

  • the present invention relates to a diamine containing a hexafluoroisopropanol group (—C (CF 3 ) 2 OH group), a polyimide or polyamide using the diamine, a cyclized product thereof, and a production method thereof.
  • a diamine containing a hexafluoroisopropanol group (—C (CF 3 ) 2 OH group) a polyimide or polyamide using the diamine, a cyclized product thereof, and a production method thereof.
  • the polyimides and polyamides containing hexafluoroisopropanol groups of the present invention and their cyclized products are soluble in organic solvents, have heat resistance and strength, and can be used as optical materials or the like as fluorescent materials or organic light-emitting elements.
  • the film can be formed by a wet process such as a spin coating method, a dip method, or an ink jet method, and the film thickness can be easily adjusted during film formation.
  • ⁇ -conjugated polymer compounds such as poly-p-phenylene and polyphenylene vinylene are generally known.
  • a ⁇ -conjugated polymer compound is easily soluble in an organic solvent, but has a problem that long-term stability of fluorescence characteristics such as heat resistance, fluorescence intensity, and emission spectrum is not sufficient.
  • Polyimide and polyamide have excellent heat resistance, strength, and electrical properties, but unlike the light-emitting polymer compound, the fluorescence properties are low.
  • Non-Patent Document 1 it is known that polyimide emits only a small amount of fluorescence in response to ultraviolet irradiation, and its luminous efficiency is extremely low.
  • the emission quantum yield which is an index of luminous efficiency and is the ratio of the number of photons emitted by fluorescence to the number of photons absorbed by the fluorescent molecules by excitation, is 0.01% or less in wholly aromatic polyimide.
  • the very low luminous efficiency of polyimide is due to the charge transfer complex formed between the electron donating diamine moiety and the electron accepting acid anhydride moiety in the molecular structure.
  • Non-Patent Document 2 the fluorescence of polyimide obtained by condensation polymerization of pyromellitic anhydride, which is a typical polyimide, and 4,4′-diaminophenyl ether has a fluorescence quantum yield of 9.7 ⁇ 10. It is known that a normal fluorescence spectrometer of -7 % emits so weak fluorescence that it is difficult to measure.
  • Patent Document 1 and Non-Patent Document 3 disclose a fluorescent material composed of a self-supporting film or a nanofiber assembly, and an alicyclic diamine is used as a raw material to give steric hindrance, thereby providing an electron-donating diamine moiety. It is said that polyimide having a high light emission efficiency of about 10% of light emission quantum yield can be synthesized by eliminating intermolecular charge transfer between polyimides.
  • the polyimide described in Patent Document 1 and Non-Patent Document 3 is a polyimide using alicyclic diamine or alicyclic acid dianhydride as a raw material, and one is a semi-alicyclic polyimide combined with an aromatic ring.
  • alicyclic diamine or alicyclic acid dianhydride as a raw material
  • one is a semi-alicyclic polyimide combined with an aromatic ring.
  • Non-Patent Document 4 describes a polyimide that exhibits blue light emission by introducing a fluorescent furyl group into the main chain or side chain.
  • Patent Document 2 discloses an organic EL device using a polymer thin film having at least one of a light emitting layer function, a charge transport function, or a charge injection function, and polyimide is used for the polymer thin film.
  • Patent Document 3 discloses an organic light-emitting device having a light-emitting layer and a charge transport layer, in which the charge transport layer is made of a specific polymer, and polyimide is used as the polymer.
  • Patent Document 4 the fluorescence emission of polyimide described in Non-Patent Document 4, Patent Document 2 and Patent Document 3 is due to the fluorescent substituent introduced into the main chain or side chain of the polyimide, and the fluorescent substituent was introduced.
  • the light intensity of polyimide is generated by a strong charge transfer between the imide moiety and the fluorescent substituent.
  • Polyimide When polyimide is used for a device, there is a problem that it is difficult to dissolve in an organic solvent.
  • Polyimide is obtained by polymerizing tetracarboxylic dianhydride and diamine in a polar solvent to produce a polyamic acid that is soluble in the polar solvent, and subjecting the polyamic acid to heat treatment or using a dehydrating agent. It is obtained by imidization by dehydration by a mechanical dehydration treatment.
  • Polyamide acid which is a precursor, is easy to form and process, but when it is made into a polyimide after forming a film in the form of polyamic acid, the chemical change of the polyamic acid, which is a component before imidization, does not occur uniformly, and defects are There was a problem that many films were easily formed.
  • Patent Documents 4 to 6 disclose an aromatic diamine containing a hexafluoroisopropanol group having a hydroxy group as a fluorine-containing polymerizable monomer, and a polymer compound using the aromatic diamine, for example, an aromatic polyimide.
  • Group polyimides are readily soluble in organic solvents. However, there has been no report on an aromatic polyimide having excellent fluorescence, which is a property of emitting fluorescence.
  • JP 2009-149787 A Japanese Patent Laid-Open No. 03-274663 Japanese Patent Laid-Open No. 04-93389 JP 2007-119503 A JP 2007-119504 A JP 2008-150534 A
  • the object of the present invention is to make the optical device easily soluble in an organic solvent so that it can be formed by a wet process, and when used as a film, it has heat resistance and strength, and also has excellent fluorescence characteristics. It is an object to provide a functional polyimide and a fluorescent polyamide. Moreover, it aims at providing the diamine which is the raw material of the said fluorescent polyimide and fluorescent polyamide.
  • the present inventors synthesized a novel diamine containing an aromatic ring having a hexafluoroisopropanol group and an alkyl group or a halogen group.
  • diamine as a raw material compound and polymerizing with tetracarboxylic dianhydride or dicarboxylic acid and derivatives thereof, polyimide, polyamide, or amide part of the polyamide having a hexafluoroisopropanol group and an alkyl group is cyclized.
  • the polyamic acid which is the precursor of the said polyimide is also the category of this invention.
  • the resulting polyimide, polyamide, or polymer formed by cyclization of the amide moiety of the polyamide is easily soluble in an organic solvent. Furthermore, when it is used as a film, it has strength as well as heat resistance.
  • the alkyl group or halogen group which is a fluoro group (—F), a chloro group (—Cl), a bromo group (—Br) or an iodo group (—I). Since the strong electrostatic repulsion of the fluorine atom of the HFIP group can effectively suppress intermolecular charge transfer and exhibits fluorescence characteristics, it can be used as a fluorescent material or an organic light emitting element in an optical device or the like.
  • a polyimide, polyamide, or a polymer formed by cyclization of the amide portion of polyamide synthesized from the diamine as a raw material compound is usually organic because it has a bulky hexafluoroisopropanol group and an alkyl group or a halogen group.
  • action which makes the polyimide which is hardly soluble in a solvent easily soluble in an organic solvent.
  • an alkyl group and a halogen group as compared with the polyimide and polyamide using diamine containing only the hexafluoroisopropanol group disclosed in the prior art such as Patent Documents 4 to 6 as raw material compounds
  • Polyimide, polyamide, or a polymer formed by cyclization of the amide portion of polyamide using diamine containing diamine as a raw material compound has useful effects as described above.
  • the present invention includes inventions 1 to 20.
  • A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and a and b each independently represent an integer of 0 to 2. 1 ⁇ a + b ⁇ 4)).
  • Invention 5 The diamine of Invention 3 or Invention 4, wherein A is a single bond or CH 2 and R 1 is a methyl group.
  • A is independently a single bond, ether bond, sulfide bond, CO, CH 2, SO, SO 2, C (CH 3) 2, NHCO or C (CF 3) 2 or alicyclic,
  • a divalent group having a heterocyclic ring or an aromatic ring R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group
  • R 2 is an alicyclic ring, a heterocyclic ring, an aromatic ring or A tetravalent organic group containing at least one group selected from the group consisting of linear or branched aliphatic hydrocarbon groups, wherein some of the hydrogen atoms in the organic group are alkyl groups, fluoroalkyl groups , A carboxyl group, a hydroxy group, a cyano group, or a halogen group, a and b are each independently an integer of 0 to 2, and 1 ⁇ a + b ⁇ 4.
  • A is independently a single bond, ether bond, sulfide bond, CO, CH 2, SO, SO 2, C (CH 3) 2, NHCO or C (CF 3) 2 or alicyclic, , A divalent group having a heterocyclic ring or an aromatic ring, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and R 2 is an alicyclic ring, a heterocyclic ring, an aromatic ring or A tetravalent organic group containing at least one selected from the group consisting of linear or branched aliphatic hydrocarbon groups, wherein some of the hydrogen atoms in the organic group are alkyl groups, fluoroalkyl groups, carboxyls A group, a hydroxy group, a cyano group, or a halogen group, and a and b are each independently an integer of 0 to 2, and 1 ⁇ a + b ⁇ 4.
  • Invention 13 A fluorescent material containing any one of the polyimides of Inventions 10 to 12 and having a light emission quantum yield of 0.1% or more.
  • A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring, R 1 is each independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and a and b each independently represent an integer of 0 to 2.
  • R 2 is a tetravalent organic group containing at least one selected from the group consisting of an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched aliphatic hydrocarbon group, (Part of the hydrogen atoms therein may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, or a halogen group.)
  • the tetracarboxylic dianhydride represented by General formula (6) In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , or an alicyclic ring, a heterocyclic ring or an aromatic ring.
  • a divalent group having a ring each R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group
  • R 2 is an alicyclic ring, a heterocyclic ring, an aromatic ring, a straight chain or a
  • A is independently a single bond, ether bond, sulfide bond, CO, CH 2, SO, SO 2, C (CH 3) 2
  • Formula (12) (A is a single bond, ether bond, sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , or an alicyclic ring, heterocyclic ring or aromatic ring.
  • R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group
  • R 5 is an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched chain.
  • a polyamide comprising a repeating unit represented by:
  • a fluorescent material comprising the polyamide of the invention 15 and having an emission quantum yield of 0.1% or more.
  • A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and a and b each independently represent an integer of 0 to 2.
  • a diamine represented by Formula (13) (Wherein R 5 is a divalent organic group containing at least one selected from the group consisting of an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched aliphatic hydrocarbon group, A part of the hydrogen atoms therein may be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, or a halogen group, and each R 6 independently represents a hydrogen atom, a carbon number of 1 to 10 And at least one group selected from an alkyl group or a benzyl group.)
  • a dicarboxylic acid represented by Or general formula (14) (Wherein R 5 is a divalent organic group containing at least one selected from the group consisting of an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched aliphatic hydrocarbon
  • Polycondensation, Formula (12) (A is a single bond, ether bond, sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , or an alicyclic ring, heterocyclic ring or aromatic ring.
  • R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group
  • R 5 is an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched chain.
  • A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring, each R 1 is independently an alkyl group having 1 to 4 carbon atoms, or a halogen group, and R 5 is an alicyclic ring, a heterocyclic ring, an aromatic ring or a straight chain or A divalent organic group containing at least one selected from the group consisting of branched aliphatic hydrocarbon groups, wherein some of the hydrogen atoms in the organic group are alkyl groups, fluoroalkyl groups, carboxyl groups, hydroxy groups , May be substituted with a cyano group or a halogen group.) Including a repeating unit represented by Polymer.
  • a fluorescent material comprising the polymer of the invention 18 and having an emission quantum yield of 0.1% or more.
  • A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring, each R 1 is independently an alkyl group having 1 to 4 carbon atoms, or a halogen group, and R 5 is an alicyclic ring, a heterocyclic ring, an aromatic ring or a straight chain or A divalent organic group containing at least one selected from the group consisting of branched aliphatic hydrocarbon groups, wherein some of the hydrogen atoms in the organic group are alkyl groups, fluoroalkyl groups, carboxyl groups, hydroxy groups , A cyano group, or a halogen group, a and b each independently represents an integer of 0 to 2, and 1 ⁇
  • A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring, each R 1 is independently an alkyl group having 1 to 4 carbon atoms, or a halogen group, and R 5 is an alicyclic ring, a heterocyclic ring, an aromatic ring or a straight chain or A divalent organic group containing at least one selected from the group consisting of branched aliphatic hydrocarbon groups, wherein some of the hydrogen atoms in the organic group are alkyl groups, fluoroalkyl groups, carboxyl groups, hydroxy groups , May be substituted with a cyano group or a
  • Polyimide, polyamide, or a polymer formed by cyclization of the amide portion of the polyamide, which is obtained by polymerizing the hexafluoroisopropanol group of the present invention and a diamine containing an alkyl group or a halogen group as a raw material compound, can be used as an organic solvent. It has a heat resistance that can be used as an organic light emitting device, and has a strength that allows a free-standing film to be obtained. Further, those exhibiting fluorescence characteristics can be used as an organic light emitting element in an optical device or the like.
  • the hexafluoroisopropanol group (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl group is —C (CF 3 ) 2 OH in chemical formula.
  • a polyimide containing a hexafluoroisopropanol group may be called a HFIP group-containing polyimide
  • a polyamide containing a hexafluoroisopropanol group may be called a HFIP group-containing polyamide.
  • the halogen group is a fluoro group, a chloro group, a bromo group or an iodo group.
  • HFIP group-containing diamine [HFIP group-containing diamine represented by formula (1)]
  • the present invention is an HFIP group-containing diamine represented by the general formula (1).
  • A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or A divalent group having an aromatic ring
  • each R 1 independently represents an alkyl group having 1 to 4 carbon atoms, or a halogen group
  • a and b each independently represent an integer of 0 to 2; 1 ⁇ a + b ⁇ 4.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group (—CH 3 , hereinafter sometimes referred to as —Me), an ethyl group (—C 2 H 5 , hereinafter referred to as — Et)),
  • an HFIP group-containing diamine in which a and b are 1 is easy to synthesize, and preferably an HFIP group-containing diamine represented by the following general formula (2) is there.
  • an HFIP group-containing diamine represented by the following general formula (3) or general formula (4) is preferable because it is easy to synthesize.
  • Examples of HFIP group-containing diamines represented by general formula (3) include the following compounds.
  • an HFIP group-containing diamine in which A is a single bond or CH 2 and R 1 is a methyl group is easy to synthesize.
  • the emission quantum yield is 0.1%. It is possible to obtain the above.
  • Examples of HFIP group-containing diamines represented by the general formula (4) include the following compounds.
  • an HFIP group-containing diamine in which A is a single bond and R 1 is a methyl group is easy to synthesize.
  • the diamine represented by the general formula (1) is obtained by reacting the diamine represented by the formula (5) which is a raw material compound with hexafluoroacetone or hexafluoroacetone trihydrate. be able to.
  • the amount of hexafluoroacetone or hexafluoroacetone trihydrate used in this reaction is preferably 2 mol or more and 10 mol or less with respect to 1 mol of the diamine represented by the general formula (5) as a raw material compound, More preferably, it is 2.5 mol or more and 5 mol or less. If the amount is less than 2 mol, the yield of the diamine represented by the general formula (1), which is the target compound, is low, and the reaction proceeds even if it is used in excess of 10 mol, but it is not necessary to use it.
  • This reaction is usually carried out in the range of 20 ° C. or higher and 180 ° C. or lower, preferably 50 ° C. or higher and 150 ° C. or lower, particularly preferably 90 ° C. or higher and 140 ° C. or lower.
  • the temperature is lower than 20 ° C., the reaction hardly proceeds, which is not preferable.
  • the reaction can be carried out without using a catalyst, it is preferable to promote the reaction by using an acid catalyst.
  • the acid catalyst to be used include Lewis acids such as aluminum chloride, iron (III) chloride, boron fluoride and the like, organic sulfonic acids such as benzenesulfonic acid, camphorsulfonic acid (CAS), methanesulfonic acid, p- Examples thereof include toluenesulfonic acid (pTsOH), p-toluenesulfonic acid monohydrate (pTsOH.H 2 O), and pyridinium p-toluenesulfonic acid (PPTS).
  • Lewis acids such as aluminum chloride, iron (III) chloride, boron fluoride and the like
  • organic sulfonic acids such as benzenesulfonic acid, camphorsulfonic acid (CAS), methanesulfonic acid, p- Examples thereof include toluenesulfonic acid (pTs
  • the catalyst amount is expressed in mol% with respect to the diamine represented by the general formula (5) which is a raw material compound, and is preferably 1 mol% or more and 50 mol% or less, more preferably 3 mol% or more and 40 mol% or less. . When the amount is less than 1 mol%, the reaction does not proceed and it is not necessary to use more than 50 mol%.
  • This reaction can be carried out without using a solvent, but a solvent can also be used.
  • the solvent to be used is not particularly limited as long as it does not participate in the reaction, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, nitrobenzene or benzonitrile, or water can be used. There is no restriction
  • the operation differs depending on whether hexafluoroacetone or hexafluoroacetone trihydrate is used.
  • hexafluoroacetone first, an HFIP group-containing diamine represented by the general formula (5) and an acid catalyst and a solvent as necessary are charged into the reaction vessel, and then the internal pressure of the reaction vessel does not exceed a predetermined pressure. In this manner, hexafluoroacetone is successively added and reacted while the temperature is raised as described above to obtain the HFIP group-containing diamine represented by the general formula (1).
  • a HFIP group-containing diamine represented by the general formula (5) and a required amount of hexafluoroacetone trihydrate may be charged into the reactor. Further, if necessary, the reaction is carried out by adding an acid catalyst and a solvent into the reaction vessel to obtain an HFIP group-containing diamine represented by the general formula (1).
  • the reaction time of this reaction is preferably 8 hours or more and 48 hours or less, and within this range, the preferable reaction time varies depending on the temperature, the amount of solvent used, and the like. Therefore, it is preferable to carry out the reaction while confirming the progress of the reaction by means of analysis such as gas chromatography, and to terminate the reaction after confirming that the raw material compound is sufficiently consumed in the reaction.
  • the diamine represented by the general formula (1) can be obtained by means such as extraction, distillation or precipitation. Moreover, it can also refine
  • HFIP group-containing polyamic acid The HFIP group-containing polyamic acid of the present invention can be synthesized by reacting with a tetracarboxylic acid using the HFIP group-containing diamine of the present invention.
  • the present invention relates to a general formula (6) (In the formula, A is independently a single bond, ether bond, sulfide bond, CO, CH 2, SO, SO 2, C (CH 3) 2, NHCO or C (CF 3) 2 or alicyclic, , A divalent group having a heterocyclic ring or an aromatic ring, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and R 2 is an alicyclic ring, a heterocyclic ring, an aromatic ring or a direct ring A tetravalent organic group containing at least one group selected from the group consisting of a chain or branched aliphatic hydrocarbon group, wherein a part of the hydrogen atoms is an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group A group, a cyano group, or a halogen group may be substituted, and a and b are each independently an integer of 0 to
  • the present invention also provides a general formula (7) of the invention 8. (Wherein Me is a methyl group, R 3 is independently Is a divalent group. )
  • HFIP group-containing polyamic acid represented by the general formula (7) of the invention 8 include compounds containing the following repeating units.
  • the present invention provides a compound represented by the general formula (8) (Wherein Me is a methyl group, R 4 is It is. )
  • the HFIP group containing polyamic acid of the invention 9 containing the repeating unit represented by these.
  • HFIP group-containing polyamic acid (8) of the invention 9 include compounds containing the following repeating units.
  • the HFIP group-containing polyamic acid of the present invention preferably has a weight average molecular weight (Mw) of 10,000 or more and 500,000 or less in terms of polystyrene.
  • Mw weight average molecular weight
  • the strength of the obtained HFIP group-containing polyimide is low and it is difficult to form a self-supporting film, and when it is larger than 500,000, the obtained HFIP group-containing polyimide is inferior in solubility.
  • Mw weight average molecular weight
  • the HFIP group-containing polyimide of the present invention can be obtained by imidizing the HFIP group-containing polyamic acid.
  • the present invention relates to a general formula (9) (In the formula, A is independently a single bond, ether bond, sulfide bond, CO, CH 2, SO, SO 2, C (CH 3) 2, NHCO or C (CF 3) 2 or alicyclic, , A divalent group having a heterocyclic ring or an aromatic ring, R 1 is each independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and R 2 is an alicyclic ring, a heterocyclic ring, an aromatic ring or a straight chain.
  • the HFIP group containing polyimide of the invention 10 containing the repeating unit represented by these.
  • the present invention provides a compound represented by the general formula (10) (Wherein Me is a methyl group, R 2 is It is. ) It is a HFIP group containing polyimide of the invention 11 containing the repeating unit represented by these.
  • HFIP group-containing polyimide of the invention 11 include compounds containing the following repeating units.
  • the present invention also provides a compound represented by the general formula (11) (Wherein Me is a methyl group, R 2 is It is. )
  • the HFIP group containing polyimide of the invention 12 containing the repeating unit represented by these.
  • the HFIP group-containing polyimide of the invention 12 is specifically a HFIP group-containing polyimide containing the following repeating units.
  • the HFIP group-containing polyimide of the present invention preferably has a weight average molecular weight (Mw) of 10,000 or more and 500,000 or less in terms of polystyrene.
  • Mw weight average molecular weight
  • the strength of the HFIP group-containing polyimide is low and it is difficult to form a self-supporting film, and when it is more than 500,000, the HFIP group-containing polyimide is inferior in solubility.
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • Method for producing HFIP group-containing polyimide General formula (1) (In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring; R 1 is an alkyl group having 1 to 4 carbon atoms or a halogen group; a and b each independently represent an integer of 0 to 2; 1 ⁇ a + b ⁇ 4)
  • An HFIP group-containing diamine represented by: Formula (11) (In the formula, R 2 is a tetravalent organic group containing at least one selected from the group consisting of an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched aliphatic hydrocarbon group; May be substituted with an alkyl group,
  • a HFIP group-containing polyamic acid is produced and the polyamic acid is dehydrated.
  • A, R 1 and R 2 are the same as those in formula (1), formula (6), formula (11), a and b are each independently an integer of 0 to 2, and 1 ⁇ a + b ⁇ 4.
  • the HFIP group-containing polyamic acid of the inventions 7 to 9 is obtained by reacting the HFIP group-containing diamine of the inventions 1 to 5 with the tetracarboxylic dianhydride represented by the general formula (11).
  • the HFIP group-containing polyimides of Inventions 10 to 12 are obtained.
  • the HFIP group-containing polyamic acid of the present invention is obtained by reacting methane and pyromellitic anhydride in dimethylacetamide (hereinafter sometimes referred to as DMAc).
  • the tetracarboxylic dianhydride represented by the general formula (11) can be used without particular limitation as long as it is generally known as a polyamic acid or polyimide raw material compound.
  • tetracarboxylic dianhydrides examples include benzenetetracarboxylic dianhydride (pyromellitic dianhydride) (hereinafter sometimes referred to as PMDA), trifluoromethylbenzenetetracarboxylic dianhydride, bistrihydrate.
  • PMDA benzenetetracarboxylic dianhydride
  • PMDA trifluoromethylbenzenetetracarboxylic dianhydride
  • Two or more of these tetracarboxylic dianhydrides may be used in combination.
  • PMDA, BPDA, 6FDA, BTDA, ODPA, and DSDA are preferably used because they are easily available, excellent in heat resistance, and easily soluble in solvents.
  • HFIP group-containing polyamic acid can be polymerized from the HFIP group-containing diamine and the tetracarboxylic dianhydride represented by the general formula (11).
  • a method in which the HFIP group-containing diamine and tetracarboxylic dianhydride are reacted in an organic solvent at a temperature of ⁇ 20 ° C. or higher and 80 ° C. or lower can be given.
  • the organic solvent to be used is only required to dissolve the HFIP group-containing diamine and tetracarboxylic dianhydride, and amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylformamide, Hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, etc., aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene or benzonitrile, halogenated solvents such as chloroform, dichloromethane, 1,2-dichloroethane, or 1 1,2,2,2-tetrachloroethane, or lactone solvents such as ⁇ -butyllactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyllactone, and the like.
  • an acid acceptor such as pyridine or triethylamine
  • the HFIP group-containing diamine of the present invention may be a copolymer of a polyamic acid combined with another diamine having no HFIP group or dihydroxyamine.
  • Examples of the diamine compound that can be used in combination include 3,5-diaminobenzotrifluoride.
  • the HFIP group-containing polyamic acid represented by the general formula (6) described above is dehydrated within the compound by heat treatment or reaction with a dehydrating reagent, and an imide ring is formed, and is represented by the general formula (9).
  • An HFIP group-containing polyimide can be synthesized.
  • an imide ring is formed at a reaction temperature of 80 ° C. or higher and 350 ° C. or lower, and a HFIP group-containing polyimide represented by the general formula (9) can be synthesized.
  • it can.
  • it is 150 degreeC or more, More preferably, it is 200 degreeC or more.
  • the reaction temperature is less than 80 ° C.
  • the imidization ratio is insufficient, and when the polyimide is used as a coating film, the film strength may be impaired, or the water absorption may be increased.
  • the reaction temperature exceeds 350 ° C., a part of the polyimide is thermally decomposed, and when the polyimide is used as a coating film, the film strength may be lost or the film may be colored.
  • the addition amount of the dehydrating reagent is 2 mol or more and 10 mol or less and the addition amount of the base is 2 mol or more and 10 mol or less with respect to 1 mol of acid dianhydride as the raw material of the polyamic acid.
  • the HFIP group-containing polyimide of the present invention can be used in a varnish state, a powder state, a film state, or a solid state dissolved in an organic solvent.
  • an additive such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, or a sensitizer may be added to the obtained HFIP group-containing polyimide as necessary.
  • an additive such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, or a sensitizer may be added to the obtained HFIP group-containing polyimide as necessary.
  • a varnish it can be applied on a glass, silicon wafer, metal, metal oxide, ceramics or resin by a known method such as spin coating, spray coating, flow coating, impregnation coating or brush coating. .
  • the present invention relates to a HFIP group-containing polyamide and a polymerization method thereof.
  • A is a single bond, ether bond, sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , or an alicyclic ring, heterocyclic ring or aromatic ring.
  • R 1 independently represents an alkyl group having 1 to 4 carbon atoms or a halogen group
  • R 5 represents an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched chain.
  • the HFIP group-containing polyamide of the invention 15 comprising a repeating unit represented by:
  • the present invention provides a general formula (1) (In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or R 1 is a divalent group having an aromatic ring, R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and a and b each independently represent an integer of 0 to 2.
  • R 5 is a divalent organic group containing at least one selected from the group consisting of an alicyclic ring, a heterocyclic ring, an aromatic ring or a linear or branched aliphatic hydrocarbon group, May be substituted with an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, a cyano group, or a halogen group, and each R 6 independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or It is at least one group selected from benzyl groups.
  • Dicarboxylic acid or derivative thereof, or general formula (14) (Wherein R 5 is a divalent organic group containing at least one selected from the group consisting of an alicyclic ring, a heterocyclic ring, an aromatic ring, or a linear or branched aliphatic hydrocarbon group, A part
  • polyamide is obtained by polymerizing the raw material compound with the HFIP group-containing diamine of the present invention and the dicarboxylic acid represented by the general formula (13) or a derivative thereof, or the compound represented by the general formula (14). It is done.
  • dicarboxylic acid dihalide, dicarboxylic acid monoester, and dicarboxylic acid diester can be used.
  • dicarboxylic acid represented by the general formula (13) examples include aliphatic carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, An example is sebacic acid.
  • aromatic dicarboxylic acids phthalic acid, isophthalic acid, terephthalic acid, 4,4'-dicarboxybiphenyl, 3,3'-dicarboxybiphenyl, 3,3'-dicarboxyldiphenyl ether, 3,4'-dicarboxyl Diphenyl ether, 4,4′-dicarboxyldiphenyl ether, 3,3′-dicarboxyldiphenylmethane, 3,4′-dicarboxyldiphenylmethane, 4,4′-dicarboxyldiphenylmethane, 4,4′-dicarboxyldiphenylmethane, 3,3′-dicarboxyldiphenyldifluoromethane, 3, , 4′-dicarboxyldiphenyldifluoromethane, 4,4′-dicarboxyldiphenyldifluoromethane, 3,3′-dicarboxyldiphenylsulfone, 3,4
  • Polymerization reaction method and conditions are not particularly limited. For example, a method in which the component and the amide-forming derivative of the dicarboxylic acid are melted (melted) at 150 ° C. or higher and lower than 250 ° C. and reacted in a solvent-free manner, or in an organic solvent at ⁇ 20 ° C. to 80 ° C. Can be illustrated.
  • the organic solvent that can be used it is sufficient that the diamine as the raw material compound and the carboxylic acid represented by the general formula (13), its derivative, or the compound represented by the general formula (14) are dissolved together.
  • aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile
  • Halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane, or lactone solvents such as ⁇ -butyllactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone Or ⁇ -methyl- Examples thereof include ⁇ -butyl lactone.
  • the HFIP group-containing polyamide of the present invention preferably has a weight average molecular weight (Mw) of 10,000 or more and 500,000 or less in terms of polystyrene.
  • Mw weight average molecular weight
  • the strength of the obtained HFIP group-containing polyamide is low and it is difficult to form a self-supporting film, and when it is larger than 500,000, the obtained HFIP group-containing polyamide is inferior in solubility.
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • HFIP group-containing polymer and method for producing the same (In the formula, A is a single bond, an ether bond, a sulfide bond, CO, CH 2 , SO, SO 2 , C (CH 3 ) 2 , NHCO, or C (CF 3 ) 2 , an alicyclic ring, a heterocyclic ring, or A divalent group having an aromatic ring, each R 1 is independently an alkyl group having 1 to 4 carbon atoms or a halogen group, and R 5 is an alicyclic ring, heterocyclic ring, aromatic ring, linear or branched It is a divalent organic group containing at least one selected from the group consisting of branched aliphatic hydrocarbon groups, and part of the hydrogen atoms in the organic group is an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxy group, (It may be substituted with a cyano group or a halogen group.) It is
  • the polymer compound represented by the general formula (12) of the present invention can be made into a polymer compound represented by the general formula (15) by cyclization.
  • the cyclization reaction can be performed by heating, or can be performed by a method of promoting dehydration such as heating by adding an acid catalyst.
  • the HFIP group-containing polyamic acid represented by the general formula (12) described above undergoes dehydration in the compound by heat treatment or reaction with a dehydrating reagent, and a ring structure is formed.
  • a ring structure is formed.
  • a polymer represented by the general formula (15) can be synthesized. More preferably, it is 300 degreeC or more and 380 degreeC or less.
  • the reaction temperature is lower than 250 ° C.
  • the cyclization does not proceed sufficiently, and there is a possibility that the film strength is impaired or the water absorption is increased when the polymer is used as a coating film.
  • the reaction temperature exceeds 400 ° C.
  • a part of the polymer may be thermally decomposed, and when the polymer is used as a coating film, the film strength may be impaired or the film may be colored.
  • cyclization is performed by dehydrating in the polyamic acid using a dehydrating reagent, acetic anhydride is added as a dehydrating reagent, a base such as pyridine or triethylamine is further added, and the reaction is performed with the polyamic acid.
  • the polymer can be synthesized by cyclization by dehydration in an acid.
  • the polymer preferably has a weight average molecular weight (Mw) of 10,000 or more and 500,000 or less in terms of polystyrene.
  • Mw weight average molecular weight
  • the strength of the polymer is low and it is difficult to form a self-supporting film, and when it is larger than 500,000, the polymer is inferior in solubility.
  • they are 50000 or more and 150,000 or less.
  • Fluorescent material By including the HFIP group-containing polyimides of the inventions 10 to 12, the HFIP group-containing polyamide of the invention 15 and the HFIP group-containing polymer of the invention 18, a fluorescent material having an emission quantum yield of 0.1% or more can be obtained. . Fluorescence having an emission peak at a wavelength of 400 nm to 550 nm is emitted by irradiation with visible light or ultraviolet light.
  • Fluorescence emission wavelength and emission quantum yield for the HFIP group-containing polyimides of the present invention obtained in Examples 1, 3, 6, and 8, the conventional polyimides of Comparative Examples 1 to 5, and the polyimides containing only the HFIP groups of Reference Example 1. The ratio was measured, and the fluorescence characteristics were compared and evaluated.
  • Example 1 ⁇ Synthesis of HFIP group-containing diamic acid> As shown in the following formula, bis (4-amino-3- (1,1,1,3,3,3-hexafluoro-2-hydroxy-2) synthesized in ⁇ Synthesis of HFIP group-containing diamine 1> HFIP group-containing polyamic acid was synthesized by polymerization reaction of (propyl) -5-methylphenyl) methane and pyromellitic anhydride (PMDA).
  • PMDA pyromellitic anhydride
  • n represents the degree of polymerization, and the same applies hereinafter.
  • the solution was continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while gradually increasing the temperature on the glass substrate.
  • a membrane was obtained.
  • the film thickness was 21 ⁇ m.
  • IR infrared absorption
  • Example 2 ⁇ Synthesis of HFIP group-containing amic acid> As shown in the following formula, bis (4-amino-3- (1,1,1,3,3,3-hexafluoro-2-hydroxy-2) synthesized in ⁇ Synthesis of HFIP group-containing diamine 1> HFIP group-containing polyamic acid was synthesized by a polymerization reaction of (propyl) -5-methylphenyl) methane and the following carboxylic anhydride (6FDA).
  • 6FDA carboxylic anhydride
  • the solution is applied onto a glass substrate using a spin coater, and continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours with stepwise temperature increase, and a film is formed on the glass substrate.
  • the film thickness was 18 ⁇ m.
  • the film was composed of the above-mentioned HFIP group-containing polyimide having absorption specific to imide groups at 1790 cm ⁇ 1 and 1717 cm ⁇ 1 .
  • Example 3 ⁇ Synthesis of HFIP group-containing diamic acid> As shown in the following formula, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl synthesized in ⁇ Synthesis of HFIP group-containing diamine 2> ) A HFIP group-containing polyamic acid was synthesized by the polymerization reaction of -5,5'-dimethylbenzidine and pyromellitic anhydride.
  • the film is continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while gradually increasing the temperature to form a film on the glass substrate. Obtained.
  • the film thickness was 13 ⁇ m. From the IR spectrum measurement results, it was confirmed that the films were composed of the above-mentioned HFIP group-containing polyimides having absorptions specific to imide groups at 1723 cm ⁇ 1 and 1789 cm ⁇ 1 .
  • Example 4 ⁇ Synthesis of HFIP group-containing diamic acid> As shown in the following formula, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl synthesized in ⁇ Synthesis of HFIP group-containing diamine 2> ) A HFIP group-containing polyamic acid was synthesized by a polymerization reaction of -5,5'-dimethylbenzidine and tetracarboxylic dianhydride (6FDA).
  • HFIP group-containing polyamic acid is added to the above HFIP group-containing polyamic acid solution in the order of pyridine, 2.92 g and acetic anhydride 3.76 g and stirred at room temperature (20 ° C.) for 4 hours.
  • Mw was 42,000.
  • the solution After the solution is applied on a glass substrate using a spin coater, it is continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while being heated stepwise to form a film on the glass substrate. Got. The film thickness was 28 ⁇ m. From the IR spectrum measurement results, it was confirmed that 1791 cm ⁇ 1 and 1726 cm ⁇ 1 had absorptions specific to imide groups and were films made of the above HFIP group-containing polyimide.
  • Example 5 ⁇ Synthesis of HFIP group-containing diamic acid> As shown in the following formula, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl synthesized in ⁇ Synthesis of HFIP group-containing diamine 2> ) HFIP group-containing polyamic acid was synthesized by a polymerization reaction of -5,5'-dimethylbenzidine and tetracarboxylic dianhydride (BTDA).
  • BTDA tetracarboxylic dianhydride
  • reaction liquid was a solution of the HFIP group containing polyamic acid represented by said formula.
  • Mw was 48,000.
  • the HFIP group-containing polyamic acid solution is added with pyridine, 2.94 g and acetic anhydride (3.77 g) in this order, and stirred at room temperature (20 ° C.) for 4 hours, thereby containing an HFIP group-containing solution.
  • Polyamic acid was imidized to obtain a solution containing HFIP group-containing polyimide.
  • Mw was 50500.
  • the film is continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while gradually increasing the temperature to form a film on the glass substrate. Obtained.
  • the film thickness was 60 ⁇ m. From the IR spectrum measurement results, it was confirmed that the films were composed of the above HFIP group-containing polyimides, which had absorption specific to imide groups at 1723 cm ⁇ 1 and 1791 cm ⁇ 1 .
  • Example 6 ⁇ Synthesis of HFIP group-containing diamic acid> 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl) -synthesized in ⁇ Synthesis of HFIP group-containing diamine 2> shown in the following formula
  • An HFIP group-containing polyamic acid was synthesized by a polymerization reaction of 5,5′-dimethylbenzidine and tetracarboxylic dianhydride (BPDA).
  • HFIP group-containing polyamic acid is added to the HFIP group-containing polyamic acid solution in the order of 2.92 g of pyridine and acetic anhydride (3.77 g) and stirred at room temperature (20 ° C.) for 4 hours.
  • acetic anhydride 3.77 g
  • Mw 98,000.
  • the film is continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while gradually increasing the temperature to form a film on the glass substrate. Obtained.
  • the film thickness was 51 ⁇ m. From the measurement results of the IR spectrum, it was confirmed that the film was composed of the FIP group-containing polyimide, with absorption inherent to imide groups at 1717 cm ⁇ 1 and 1781 cm ⁇ 1 .
  • Example 7 ⁇ Synthesis of HFIP group-containing diamic acid> As shown in the following formula, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl synthesized in ⁇ Synthesis of HFIP group-containing diamine 2> ) HFIP group-containing polyamic acid was synthesized by a polymerization reaction of -5,5'-dimethylbenzidine and tetracarboxylic dianhydride (DSDA). Specifically, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl) as HFIP group-containing diamine was added to a 300 mL solution container.
  • DSDA tetracarboxylic dianhydride
  • a solution containing HFIP group-containing polyimide is added to the above HFIP group-containing polyamic acid solution in the order of 2.94 g of pyridine and 3.76 g of acetic anhydride and stirred at room temperature (20 ° C.) for 4 hours.
  • Mw was 26500.
  • the film is continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while gradually increasing the temperature to form a film on the glass substrate. Obtained.
  • the film thickness was 33 ⁇ m. From the IR spectrum measurement results, it was confirmed that 1731 cm ⁇ 1 and 1791 cm ⁇ 1 had absorption specific to imide groups and were films made of the above HFIP group-containing polyimide.
  • Example 8 ⁇ Synthesis of HFIP group-containing diamic acid> As shown in the following formula, 3,3′-bis (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl synthesized in ⁇ Synthesis of HFIP group-containing diamine 2> ) HFIP group-containing polyamic acid was synthesized by a polymerization reaction of -5,5'-dimethylbenzidine and tetracarboxylic dianhydride (ODPA).
  • ODPA tetracarboxylic dianhydride
  • the HFIP group-containing polyamic acid solution is added with pyridine, 2.92 g and 3.76 g of acetic anhydride in this order, and stirred at room temperature (20 ° C.) for 4 hours to contain the HFIP group-containing polyimide. A solution was obtained. As a result of GPC measurement of the solution, Mw was 47000.
  • the film is continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while gradually increasing the temperature to form a film on the glass substrate. Obtained.
  • the film thickness was 55 ⁇ m. From the IR spectrum measurement results, it was confirmed that the films were made of the above-mentioned HFIP group-containing polyimide, with absorptions specific to imide groups at 1719 cm ⁇ 1 and 1786 cm ⁇ 1 .
  • Comparative Examples 1 to 5 and Reference Example 1 Polyimides of Comparative Examples 1 to 5 and Reference Example 1 shown in Table 1 that do not belong to the category of the present invention were synthesized.
  • a polyimide shown in Table 1 was obtained by polymerizing diamine and tetracarboxylic dianhydride to synthesize polyamic acid, and then cyclizing by dehydrating in polyamic acid.
  • each diamine and tetracarboxylic dianhydride shown in Table 1 were mixed at a molar ratio of 1: 1 in a reaction vessel having a volume of 300 mL, N, N-dimethylacetamide was added as a solvent, and a nitrogen atmosphere was added. Under stirring at room temperature (20 ° C.) for 20 hours, a solution containing polyimide acid was obtained. Next, pyridine and acetic anhydride were added to the solution in this order, and the mixture was stirred at room temperature (20 ° C.) for 4 hours and dehydrated in polyamic acid to cyclize to obtain respective solutions containing the polyimides shown in the table.
  • each of the obtained solutions was applied onto a glass substrate using a spin coater, and then continuously heated at 130 ° C. for 30 minutes, 180 ° C. for 30 minutes, and 200 ° C. for 3 hours while gradually raising the temperature.
  • a film made of each polyimide was obtained. From the measurement results of IR spectrum, there is an imido group-specific absorption around 1720 cm -1 and near 1780 cm -1, it was confirmed that the film made from each of the imide shown in Table 1.
  • Example 1 Each polyimide is shown in Table 2 and Table 3.
  • the polyimide in Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 has the same polyimide skeleton.
  • Table 4 shows the measurement results of the fluorescence emission wavelength and the emission quantum yield, measured with ultraviolet light and excitation light having a wavelength of 365 nm, using a fluorescence spectrometer (trade name, FluoroMax-4, manufactured by Horiba, Ltd.).
  • the fluorescence spectrum was measured using a polyimide film formed on a quartz substrate.
  • the light emission quantum yield was measured by attaching an integrating sphere to a fluorescence spectrometer using a single polyimide film.
  • the HFIP group-containing aromatic polyimide containing methyl groups of Examples 1, 3, 6, and 8 of the present invention has fluorescence characteristics that generate fluorescence, and the emission quantum yield is 0.1% or more. Met.
  • the polyimides in Example 1, Comparative Example 1, Comparative Example 2, and Reference Example 1 have the same main polyimide skeleton. In the polyimides containing no HFIP groups in Comparative Examples 1 and 2, no luminescence could be detected regardless of the presence or absence of methyl groups. In the polyimides having HFIP groups of Example 1 and Reference Example 1, light emission was observed.
  • the polyimide of the present invention containing both the HFIP group and the methyl group of Example 1 showed an extremely high emission quantum yield that was twice or more that of the polyimide containing only the HFIP group of Reference Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne une diimine représentée par la formule générale, un polyimide et un polyamide obtenus en utilisant ladite diamine comme matière première, un produit cyclisé à base de ladite diamine et un procédé de production de ladite diamine. Dans la formule, A représente une simple liaison, une liaison éther, une liaison sulfure, CO, CH2, SO, SO2, C(CH3)2, NHCO ou C(CF3)2 ou un groupe divalent comportant un noyau alicyclique, hétérocyclique ou aromatique, R1 représente un groupe alkyle comportant de 1 à 4 atomes de carbone ou un groupe halogène, et a et b représentent indépendamment un nombre entier entre 0 et 2 et sont tels que 1 ≤ a+b ≤ 4. Le polyimide et le polyamide sont facilement solubles dans un solvant organique, cela allant jusqu'à la possibilité de formation d'un film par un procédé par voie humide lorsqu'ils sont utilisés en vue de l'obtention d'un dispositif optique. Ils se révèlent également résistants à la chaleur et solides après formation du film et constituent un polyimide fluorescent et un polyamide fluorescent combinant de remarquables propriétés en matière de fluorescence.
PCT/JP2013/081698 2012-11-28 2013-11-26 Diamine contenant un groupe hexafluoroisopropanol, polyimide et polyamide l'utilisant, produit cyclisé à base de celle-ci et son procédé de production WO2014084185A1 (fr)

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WO2022030447A1 (fr) 2020-08-05 2022-02-10 セントラル硝子株式会社 Diamine fluorée ou son sel, procédé de production d'une diamine fluorée ou d'un sel de celle-ci, polyamide, procédé de production de polyamide, solution de polyamide, polyamide cyclisé, procédé de production de polyamide cyclisé, matériau isolant pour composant électronique haute fréquence, procédé de production d'un matériau isolant pour composant électronique haute fréquence, composant électronique haute fréquence, appareil haute fréquence et matériau isolant pour produire un composant électronique haute fréquence

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