WO2011121850A1 - Polyamide-imide ayant un squelette de nadimide et son procédé d'obtention - Google Patents

Polyamide-imide ayant un squelette de nadimide et son procédé d'obtention Download PDF

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Publication number
WO2011121850A1
WO2011121850A1 PCT/JP2010/071681 JP2010071681W WO2011121850A1 WO 2011121850 A1 WO2011121850 A1 WO 2011121850A1 JP 2010071681 W JP2010071681 W JP 2010071681W WO 2011121850 A1 WO2011121850 A1 WO 2011121850A1
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nadiimide
general formula
skeleton
group
polyamideimide
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PCT/JP2010/071681
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English (en)
Japanese (ja)
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広幸 川上
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日立化成工業株式会社
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Publication of WO2011121850A1 publication Critical patent/WO2011121850A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G73/14—Polyamide-imides

Definitions

  • the present invention relates to a polyamideimide having a nadiimide skeleton, which is useful as a polymer having high heat resistance and transparency.
  • the present invention also relates to a manufacturing method thereof.
  • epoxy resin has been widely used as a resin for optical members used in optoelectronic devices and the like because of its mounting process on an electronic substrate and the like, heat resistance under high temperature operation, mechanical properties, and versatility.
  • high-intensity laser light, blue light, and near-ultraviolet light has expanded in the field of optoelectronic devices, and a resin that is superior in transparency, heat resistance, and light resistance than ever has been demanded.
  • epoxy resin has high transparency in visible light, but sufficient transparency cannot be obtained in the ultraviolet to near ultraviolet region.
  • a cured product composed of an alicyclic epoxy resin and an acid anhydride has a relatively high transparency in the near-ultraviolet region, but has a problem that it is easily colored by heat or light.
  • improvement in heat resistance and UV resistance is required, and various epoxy resins have been studied (for example, see Patent Documents 1 to 4).
  • heat-resistant resins such as polyamide and polyamide-imide are excellent in heat resistance, insulation, light resistance and mechanical properties, and are soluble in various solvents and excellent in workability. It is widely used as a surface protection film of an element, an interlayer insulating film, and the like.
  • polyamides having an alicyclic structure are excellent in transparency in the ultraviolet region, and thus have been studied as materials for optoelectronic devices and various displays (for example, see Patent Document 5).
  • the present invention has been made to solve the above problems. Specifically, the present invention relates to a polyamideimide having a nadiimide skeleton, which is excellent in heat resistance and transparency, and a method for producing the same.
  • the present invention is as follows.
  • the present invention relates to a polyamideimide having a nadiimide skeleton represented by the following general formula (I).
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group
  • R 4 is a group selected from an aliphatic group, an alicyclic group and an aromatic group. Valent organic group.
  • the present invention also provides a dicarboxylic acid derivative having a nadiimide skeleton represented by the following general formula (II):
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group
  • R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms.
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • R 4 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • the present invention relates to a method for producing a polyamide-imide having a nadiimide skeleton characterized by reacting.
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton, wherein a dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II) is obtained by a method including the following step (1).
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • a dicarboxylic acid derivative having a nadiimide skeleton represented by the above general formula (II) is obtained by reacting in the presence of a catalyst system containing a ruthenium compound, a cobalt compound, and a halide salt.
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton, wherein the bisnadiimide compound represented by the general formula (V) includes the following steps (a-1) and (a-2).
  • Step (a-1) 5-norbornene-2,3-dicarboxylic acid anhydride represented by the following general formula (VI):
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton, wherein the bisnadiimide compound represented by the general formula (V) is obtained by a method including the following step (b-1).
  • Step (b-1) 5-norbornene-2,3-dicarboxylic acid anhydride represented by the above general formula (VI) and a diisocyanate compound represented by the following general formula (IX) are reacted, A bisnadiimide compound represented by the general formula (V) is obtained.
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton in which the ruthenium compound is a ruthenium complex having both a carbonyl ligand and a halogen ligand in the molecule.
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton in which the halide salt is a quaternary ammonium salt.
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton in which the catalyst system further contains a basic compound.
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton in which the basic compound is a tertiary amine.
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton in which the catalyst system further contains a phenol compound.
  • the present invention relates to a method for producing a polyamideimide in which the catalyst system further has a nadiimide skeleton containing an organic halogen compound.
  • the present invention is characterized in that the dicarboxylic acid having a nadiimide skeleton represented by the general formula (III) is obtained by hydrolysis of a dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II).
  • the present invention relates to a method for producing a polyamideimide having a nadiimide skeleton.
  • Polyamideimide having a nadiimide skeleton obtained by the present invention is excellent in heat resistance and transparency. Therefore, optical materials represented by electronic parts, optical fibers, optical lenses, etc. used in semiconductors and liquid crystals, and display-related materials, It can be used as a medical material. Moreover, the polyamideimide having a nadiimide skeleton can be easily produced by the production method of the present invention.
  • Polyamideimide having nadiimide skeleton of the present invention relates to a polyamideimide having a nadiimide skeleton represented by the following general formula (I).
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group
  • R 4 is a group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • Valent organic group. R 1 in the above formula is the same as R 1 in the compounds represented by the following general formulas (II), (III), (V), (VII), (VIII), (IX). is there.
  • R 4 in the above formula is the same as R 4 in the diamine compound represented by the following general formula (IV). Details will be described in ⁇ 2> below.
  • n 2 to 800.
  • the polyamideimide having a nadiimide skeleton of the present invention preferably has a number average molecular weight of 2,000 to 250,000, more preferably 3,000 to 220,000.
  • a number average molecular weight is less than 2,000, heat resistance and the like tend to decrease, and when it exceeds 250,000, solubility in a solvent tends to decrease.
  • the polyamideimide having a nadiimide skeleton In order to make the number average molecular weight of the polyamideimide having a nadiimide skeleton within the above range, it may be produced by the production method of the present application.
  • the number average molecular weight is measured under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC), and is calculated using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • One embodiment of the present invention is a dicarboxylic acid derivative having a nadiimide skeleton represented by the following general formula (II):
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group
  • R 2 and R 3 are each independently an alkyl group having 1 to 4 carbon atoms.
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • R 4 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • the present invention relates to a method for producing a polyamide-imide having a nadiimide skeleton characterized by reacting.
  • R 4 in the general formula (IV) is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • 1,2-diaminoethane 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 3,9-bis (3-amino Propyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, methylpentamethylenediamine, trimethylhexamethylenediamine and other aliphatic diamine compounds; Alicyclic diamine compounds such as 1,2-diaminocyclohexane, methylenediaminocyclohexamine, norbornanediamine; 2,2-diaminoethane, 1,
  • the dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II) is preferably obtained by a method including the following step (1).
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • the reaction is carried out in the presence of a catalyst system comprising a ruthenium compound, a cobalt compound, and a halide salt.
  • the formic acid ester that can be used as a raw material when reacting with the bisnadiimide compound represented by the general formula (V) to obtain a dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II) is particularly limited.
  • methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, allyl formate, vinyl formate, benzyl formate and the like can be used.
  • linear alkyl formate such as methyl formate and ethyl formate is preferred, and methyl formate is more preferred.
  • ester moiety of the formic acid ester corresponds to R 2 and R 3 in the general formula (II).
  • the catalyst system for the reaction between the bisnadiimide compound represented by the general formula (V) and the formate ester includes a ruthenium compound, a cobalt compound, and a halide salt.
  • the “catalyst system” includes not only the catalyst itself, but also additives, sensitizers, and the like that assist the action of the catalyst.
  • the ruthenium compound is not particularly limited as long as it contains ruthenium.
  • suitable ruthenium compounds include [Ru (CO) 3 Cl 2 ] 2 , [Ru (CO) 2 Cl 2 ] n , [Ru (CO) 3 Cl 3 ] ⁇ , [Ru 3 (CO) 11 Cl ] -, [Ru 4 (CO ) 13 Cl] - , such as, ruthenium compounds having both a carbonyl ligand and halogen ligands in the molecule. of these, from the viewpoint of the reaction rate increase, [ Ru (CO) 3 Cl 2 ] 2 , [Ru (CO) 2 Cl 2 ] n and the like are more preferable.
  • the ruthenium compounds include RuCl 3 , Ru 3 (CO) 12 , RuCl 2 (C 8 H 12 ), Ru (CO) 3 (C 8 H 8 ), Ru (CO) 3 (C 8 H 12 ), and Ru.
  • the ruthenium compound is converted to the precursor compound before or during the reaction to obtain the bisnadiimide compound represented by the general formula (V) using (C 8 H 10 ) (C 8 H 12 ) or the like as a precursor compound. And may be introduced into the reaction system.
  • the amount of the ruthenium compound used is preferably 1/10000 to 1 equivalent, more preferably 1/1000 to 1/50 equivalent relative to the bisnadiimide compound represented by the general formula (V) as the raw material. Considering the production cost, it is preferable that the amount of the ruthenium compound used is smaller, but if it is less than 1/10000 equivalent, the reaction tends to become extremely slow.
  • the cobalt compound is not particularly limited as long as it contains cobalt.
  • suitable cobalt compounds include cobalt compounds having a carbonyl ligand such as Co 2 (CO) 8 , Co (CO) 4 , Co 4 (CO) 12 ; cobalt acetate, cobalt propionate, cobalt benzoate, Cobalt compounds having a carboxylic acid compound such as cobalt acid as a ligand; Examples include cobalt phosphate.
  • Co 2 (CO) 8 cobalt acetate, cobalt citrate and the like are more preferable from the viewpoint of improving the reaction rate.
  • the amount of the cobalt compound used is 1/100 to 10 equivalents, preferably 1/10 to 5 equivalents, relative to the ruthenium compound. Even if the ratio of the cobalt compound to the ruthenium compound is lower than 1/100 or higher than 10, the dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II) (hereinafter referred to as “ester compound”) The production amount of) tends to decrease significantly.
  • the halide salt is not particularly limited as long as it is a compound composed of a halogen ion such as chloride ion, bromide ion and iodide ion and a cation.
  • the cation may be either an inorganic ion or an organic ion.
  • the halide salt may contain one or more halogen ions in the molecule.
  • the inorganic ions constituting the halide salt may be one metal ion selected from alkali metals and alkaline earth metals. Specific examples include ions of lithium, sodium, potassium, rubidium, cesium, calcium, strontium and the like.
  • the organic ion may be a monovalent or higher valent organic group derived from an organic compound.
  • examples include ions such as ammonium, phosphonium, pyrrolidinium, pyridium, imidazolium, and iminium, and the hydrogen atom of these ions may be substituted with a hydrocarbon group such as an alkyl group and an aryl group.
  • suitable organic ions include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium, and trioctyl.
  • ions of quaternary ammonium salts such as butylmethylpyrrolidinium chloride, bis (triphenylphosphine) iminium iodide, riooctylmethylammonium chloride are more preferable.
  • the halide salt used in the present invention does not need to be a solid salt, and an ionic liquid containing halide ions that becomes liquid near room temperature or in a temperature range of 100 ° C. or less may be used.
  • ionic liquids include 1-ethyl 3-methylimidazolium, 1-propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-pentyl-3- Methylimidazolium, 1-hexyl-3-methylimidazolium, 1-heptyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, 1-dodecyl-3- Methylimidazolium, 1-tetradecyl-3-methylimidazolium, 1-hexadecyl-3-methylimidazolium, 1-octadecyl-3-methylimidazolium,
  • the above-described halide salts may be used alone or in combination.
  • halide salts are chloride salts, bromide salts, and iodide salts, and the cation is an organic ion.
  • specific examples of the halide salt suitable in the present invention include butylmethylpyrrolidinium chloride, bis (triphenylphosphine) iminium iodide, trioctylmethylammonium chloride and the like.
  • the added amount of the halide salt is, for example, 1 to 1000 equivalents, preferably 2 to 50 equivalents, relative to the ruthenium compound.
  • the addition amount is, for example, 1 to 1000 equivalents, preferably 2 to 50 equivalents, relative to the ruthenium compound.
  • the reaction between the bisnadiimide compound represented by the general formula (V) and the formate ester is carried out by adding a basic compound, phenol, and a catalyst system containing the ruthenium compound, cobalt compound and halide salt as necessary.
  • a basic compound phenol
  • a catalyst system containing the ruthenium compound, cobalt compound and halide salt as necessary.
  • the basic compound used in the present invention may be an inorganic compound or an organic compound.
  • Specific examples of the basic inorganic compound include alkali metal and alkaline earth metal carbonates, hydrogen carbonates, hydroxide salts, alkoxides, and the like.
  • Specific examples of the basic organic compound include primary amine compounds, secondary amine compounds, tertiary amine compounds, pyridine compounds, imidazole compounds, quinoline compounds, and the like.
  • tertiary amine compounds are preferred from the viewpoint of the reaction promoting effect.
  • suitable tertiary amine compounds include trialkylamine, N-alkylpyrrolidine, quinuclidine, and triethylenediamine.
  • the amount of the basic compound added is not particularly limited, but is, for example, 1 to 1000 equivalents, preferably 2 to 200 equivalents, relative to the ruthenium compound.
  • the addition amount 1 equivalent or more By making the addition amount 1 equivalent or more, the expression of the promoting effect tends to become more prominent.
  • the addition amount exceeds 1000 equivalents even if the addition amount is further increased, there is a tendency that a further improvement effect of reaction promotion cannot be obtained.
  • the phenol compound used in the present invention is not particularly limited. Specific examples of usable phenol compounds include phenol, cresol, alkylphenol, methoxyphenol, phenoxyphenol, chlorophenol, trifluoromethylphenol, hydroquinone and catechol.
  • the amount of the phenol compound added is not particularly limited, but is, for example, 1 to 1000 equivalents, preferably 2 to 200 equivalents, relative to the ruthenium compound.
  • the addition amount 1 equivalent or more By making the addition amount 1 equivalent or more, the expression of the promoting effect tends to become more prominent.
  • the addition amount exceeds 1000 equivalents even if the addition amount is further increased, there is a tendency that a further improvement effect of reaction promotion cannot be obtained.
  • the organic halogen compound used in the present invention is not particularly limited, and specific examples of usable organic halogen compounds include methyl halide, dihalogen methane, dihalogen ethane, trihalogen methane, tetrahalogen carbon, halogenated benzene and the like. It is done.
  • the amount of the organic halogen compound added is not particularly limited, but is, for example, 1 to 1000 equivalents, preferably 2 to 200 equivalents, relative to the ruthenium compound.
  • the addition amount 1 equivalent or more By making the addition amount 1 equivalent or more, the expression of the promoting effect tends to become more prominent.
  • the addition amount exceeds 1000 equivalents even if the addition amount is further increased, there is a tendency that a further improvement effect of reaction promotion cannot be obtained.
  • the reaction can proceed without using any solvent.
  • a solvent may be used.
  • the usable solvent is not particularly limited as long as it can dissolve a compound used as a raw material, that is, a bisnadiimide compound represented by the general formula (V), a formic acid ester, and the like.
  • solvents that can be suitably used include n-pentane, n-hexane, n-heptane, cyclohexane, benzene, toluene, o-xylene, p-xylene, m-xylene, ethylbenzene, cumene, tetrahydrofuran, and N-methylpyrrolidone.
  • Dimethylformamide, dimethylacetamide, dimethylimidazolidinone ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetralin and the like.
  • the reaction between the bisnadiimide compound represented by the general formula (V) and the formate ester is preferably carried out in a temperature range of 80 ° C to 200 ° C.
  • the above reaction is more preferably carried out in the temperature range of 100 ° C to 160 ° C.
  • the reaction rate is increased and the reaction is facilitated efficiently.
  • the reaction temperature is controlled to 200 ° C. or lower, decomposition of the formate used as a raw material can be suppressed.
  • addition of an ester group to the bisnadiimide compound represented by the general formula (V) cannot be achieved, so that a reaction temperature that is too high is undesirable.
  • reaction temperature exceeds the boiling point of either the bisnadiimide compound or formate ester represented by the general formula (V) used as a raw material, it is necessary to carry out the reaction in a pressure resistant vessel.
  • the completion of the reaction can be confirmed using a well-known analytical technique such as gas chromatography or NMR.
  • the dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II) obtained by the above method can be used as it is for the production of polyamideimide, but preferably by distillation under reduced pressure or the like. Use isolated.
  • the bisnadiimide compound represented by the general formula (V) can be obtained by the synthesis method (a) or the synthesis method (b) shown below.
  • the synthesis method (a) for obtaining the bisnadiimide compound represented by the general formula (V) includes the following steps (a-1) and (a-2).
  • Step (a-1) In step (a-1), 5-norbornene-2,3-dicarboxylic acid anhydride represented by the following general formula (VI):
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • the diamine compound represented by the general formula (VII) is not particularly limited as long as R 1 in the formula is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • the reaction of the 5-norbornene-2,3-dicarboxylic acid anhydride represented by the general formula (VI) and the diamine compound represented by the general formula (VII) in the step (a-1) The number of moles of the amino group of the diamine represented by the general formula (VII) is 0.7 to 1 with respect to the number of moles of the acid anhydride group of the 5-norbornene-2,3-dicarboxylic anhydride represented by formula (VII). 5, more preferably 0.8 to 1.3, still more preferably 0.9 to 1.2, and particularly preferably 0.95 to 1.05. When it is less than 0.7 or exceeds 1.5, impurities in the nadiamic acid compound represented by the general formula (VIII) to be obtained increase, which may hinder subsequent reaction.
  • the reaction temperature is preferably 0 to 150 ° C., and the reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.
  • the nadiamic acid compound obtained in the step (a-1) can be used in the next step (a-2) as the reaction solution.
  • Step (a-2) In step (a-2), the nadiamic acid compound is dehydrated and cyclized to obtain a bisnadiimide compound represented by the general formula (V).
  • the above thermal ring closure method is preferably carried out at 50 to 250 ° C., and can be carried out under reduced pressure in order to facilitate dehydration ring closure.
  • a process can be performed stepwise or continuously, it is preferably performed continuously in consideration of cost.
  • a solvent can be used if necessary.
  • organic solvents examples include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and ⁇ -butyrolactone; diethylene glycol dimethyl ether, triethylene glycol dimethyl ether diethylene glycol diethyl ether, and triethylene Ether solvents such as glycol diethyl ether; cellosolv solvents such as butyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve acetate; aromatic solvents such as toluene, xylene, p-cymene, 1,2,3,4-tetrahydroxynaphthalene Tetrahydrofuran, dioxane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Examples include methyl ketone solvents
  • the preferable amount of the solvent used is 50 to 300% by mass with respect to the total amount of the nadiamic acid compound.
  • the synthesis method (b) for obtaining the bisnadiimide compound represented by the general formula (V) includes the step (b-1).
  • step (B-1) the 5-norbornene-2,3-dicarboxylic acid anhydride represented by the general formula (VI) is reacted with the diisocyanate compound represented by the following general formula (IX).
  • the bisnadiimide compound represented by the general formula (V) is obtained.
  • R 1 is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • the diisocyanate compound represented by the general formula (IX) is not particularly limited as long as R 1 in the above formula is a divalent organic group selected from an aliphatic group, an alicyclic group and an aromatic group.
  • aliphatic isocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate; Cycloaliphatic isocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate; 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate, biphenyl-4,4 '-Diisocyanate, biphenyl-3,3'-diisocyanate, biphenyl-3,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate,
  • the reaction between the 5-norbornene-2,3-dicarboxylic acid anhydride represented by the general formula (VI) and the diisocyanate compound represented by the general formula (IX) in the step (b-1) The number of equivalents of the isocyanate group of the diisocyanate compound represented by the general formula (IX) is 1.0 to 2 with respect to the number of equivalents of the acid anhydride group of the 5-norbornene-2,3-dicarboxylic acid anhydride represented by formula (IX). 0.0, more preferably 1.0 to 1.7, still more preferably 1.0 to 1.5, and particularly preferably 1.0 to 1.3.
  • the reaction temperature in the step (b-1) is preferably 80 to 200 ° C., more preferably 90 to 190 ° C., and particularly preferably 100 to 180 ° C.
  • the reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.
  • step (b-1) the reaction between the 5-norbornene-2,3-dicarboxylic acid anhydride represented by the general formula (VI) and the diisocyanate compound represented by the above general formula (IX) Can be used.
  • the usable solvent only needs to dissolve the compounds used as the raw material (5-norbornene-2,3-dicarboxylic acid anhydride represented by the general formula (VI) and diisocyanate compound represented by the general formula (IX)). There is no particular limitation.
  • solvents that can be suitably used include N-methylpyrrolidone, N, N′-dimethylacetamide, N, N′-dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H ) -Nitrogen-containing solvents such as pyrimidinone; Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; Sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane; ester solvents such as ⁇ -butyrolactone and cellosolve acetate; And ketone solvents such as cyclohexanone and methyl ethyl ketone.
  • the amount of the solvent used is based on 100 parts by mass of the total amount of the 5-norbornene-2,3-dicarboxylic acid anhydride represented by the general formula (VI) and the diisocyanate compound represented by the general formula (IX). 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and particularly preferably 50 to 200 parts by mass.
  • the amount used is less than 20 parts by mass, the raw materials are not sufficiently dissolved and the reaction rate tends to be slow. On the other hand, even if it exceeds 500 parts by mass, the yield of the bisnadiimide compound per batch is reduced, and there is no particular advantage.
  • the amount of the dicarboxylic acid derivative having the nadiimide skeleton represented by the general formula (II) and the diamine compound represented by the general formula (IV) is the number of moles of the alkoxy group of the dicarboxylic acid derivative having the nadiimide skeleton.
  • the number of moles of the amino group relative to is preferably 0.7 to 2.0, more preferably 0.8 to 1.7, still more preferably 0.9 to 1.5, and It is particularly preferably 95 to 1.3. If it is less than 0.7 or exceeds 2.0, it will be difficult to increase the molecular weight of the polyamideimide having a nadiimide skeleton, and mechanical properties, heat resistance and the like will tend to be reduced.
  • a nadiimide skeleton represented by the following general formula (III) is used instead of the dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II). It is also possible to use the dicarboxylic acid it has as a raw material.
  • the amount of the dicarboxylic acid having a nadiimide skeleton represented by the general formula (III) and the diamine compound represented by the general formula (IV) is an amino acid based on the number of moles of the carboxyl group of the dicarboxylic acid having the nadiimide skeleton.
  • the number of moles of the group is preferably 0.7 to 2.0, more preferably 0.8 to 1.7, still more preferably 0.9 to 1.5, and 0.95 to Particularly preferred is 1.3.
  • the dicarboxylic acid having a nadiimide skeleton represented by general formula (III) in the present invention can be obtained by hydrolyzing a dicarboxylic acid derivative having a nadiimide skeleton represented by general formula (II).
  • the method for hydrolyzing the dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II) to obtain a dicarboxylic acid having a nadiimide skeleton represented by the general formula (III) is not particularly limited. Acid hydrolysis, alkali hydrolysis and the like described in Japanese Patent No. 2591492 or Japanese Patent Application Laid-Open No. 2008-31406 can be used. Alternatively, it can be hydrolyzed by heating at a high temperature of 140 ° C. or higher in the presence of moisture in a heat-resistant container without adding an acid component or an alkali component.
  • the completion of the reaction by the above method can be confirmed using a well-known analytical technique such as gas chromatography, liquid chromatography, or NMR.
  • the obtained dicarboxylic acid having a nadiimide skeleton represented by the general formula (III) can be isolated by distillation, recrystallization, reprecipitation or the like and used as a raw material for polyamideimide.
  • the reaction conditions are not particularly limited, and the method introduced in Japanese Patent No. 3091784 can be used.
  • a solution polycondensation method in which a polycondensation reaction is performed in a liquid phase homogeneous system by heating and melting at a temperature higher than the melting point of the raw material
  • a low temperature polycondensation method in which a polycondensation reaction is performed at a temperature of room temperature to 100 ° C.
  • the solid phase polycondensation method in which a polycondensation reaction is carried out by heating in the solid phase in the crystalline state at a temperature near 20 to 30 ° C. below the melting point of the polyamideimide to be obtained.
  • a method such as a solution polycondensation method for condensation can be used.
  • a compound used as a raw material a dicarboxylic acid derivative having a nadiimide skeleton represented by the general formula (II) or a nadiimide skeleton represented by the general formula (III) is used.
  • the dicarboxylic acid and the diamine compound represented by the general formula (IV) may be dissolved, and are not particularly limited.
  • solvents that can be suitably used include N-methylpyrrolidone, N, N′-dimethylacetamide, N, N′-dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H ) -Nitrogen-containing solvents such as pyrimidinone; Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; Sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane; ester solvents such as ⁇ -butyrolactone and cellosolve acetate; Ketone solvents such as cyclohexanone and methyl ethyl ketone; and the like can be used.
  • Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene
  • the amount of the organic solvent used in the solution polycondensation method is represented by a compound used as a raw material (a dicarboxylic acid derivative having a nadiimide skeleton represented by the above general formula (II) or a general formula (III)
  • the total amount of the dicarboxylic acid having a nadiimide skeleton and the diamine compound represented by the general formula (IV) is preferably 50 to 200 parts by mass with respect to 100 parts by mass.
  • the reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed.
  • reaction liquid containing the polyamideimide having a nadiimide skeleton obtained by the above method is a polymer solution
  • the polyamideimide can be isolated by heating in a normal pressure or reduced pressure environment.
  • the polyamideimide having a nadiimide skeleton have a number average molecular weight of 2,000 to 250,000, it may be produced by the production method of the present application.
  • R 1 (CH 2 ) 6
  • NDI-1 bisnadiimide compound
  • NDI-3 a bisnadiimide compound
  • the obtained bisnadiimide compound (NDI-3) was analyzed by liquid chromatography. The purity was 100%. Further, when the FT-IR spectrum of NDI-3 was measured, characteristic absorption of an imide group was confirmed in the vicinity of 1780 cm ⁇ 1 .
  • methyl dicarboxylate having a nadiimide skeleton produced by the reaction was 93.0 mmol (yield 93.0% based on methyl dicarboxylate having a nadiimide skeleton).
  • the obtained methyl dicarboxylate (II-a) having a nadiimide skeleton was isolated by distillation under reduced pressure.
  • the reaction apparatus was cooled to room temperature, released, and a part of the remaining organic phase was extracted and analyzed using a gas chromatograph. According to the analysis results, the methyl dicarboxylate having a nadiimide skeleton produced by the reaction was 92.8 mmol (yield 92.8% based on methyl dicarboxylate having a nadiimide skeleton).
  • the obtained methyl dicarboxylate (II-b) having a nadiimide skeleton was isolated by distillation under reduced pressure.
  • the reaction apparatus was cooled to room temperature, released, and a part of the remaining organic phase was extracted and analyzed using a gas chromatograph. According to the analysis results, the methyl dicarboxylate having a nadiimide skeleton produced by the reaction was 90.9 mmol (yield 90.9% based on methyl dicarboxylate having a nadiimide skeleton).
  • the obtained methyl dicarboxylate (II-c) having a nadiimide skeleton was isolated by distillation under reduced pressure.
  • the reaction apparatus was cooled to room temperature, released, and a part of the remaining organic phase was extracted and analyzed using a gas chromatograph. According to the analysis results, the methyl dicarboxylate having a nadiimide skeleton produced by the reaction was 90.1 mmol (yield 90.1% based on methyl dicarboxylate having a nadiimide skeleton).
  • the obtained methyl dicarboxylate (II-d) having a nadiimide skeleton was isolated by distillation under reduced pressure.
  • the reaction apparatus was cooled to room temperature, released, and a part of the remaining organic phase was extracted and analyzed using a gas chromatograph. According to the analysis results, the methyl dicarboxylate having a nadiimide skeleton produced by the reaction was 88.8 mmol (yield 88.8% based on methyl dicarboxylate having a nadiimide skeleton).
  • the obtained methyl dicarboxylate (II-e) having a nadiimide skeleton was isolated by distillation under reduced pressure.
  • a 1 liter eggplant-shaped flask equipped with a condenser tube was charged with 30 g of methyl dicarboxylate (II-a) having a nadiimide skeleton obtained in Synthesis Example 6 and 200 g of methanol to obtain a homogeneous solution, and then 10% sodium hydroxide. 200 g of the solution was charged, put into an oil bath at 100 ° C., and heated to reflux for 6 hours. Thereafter, methanol was distilled off until the amount of the reaction solution reached 140 g, and 48 ml of 36% hydrochloric acid was added thereto to adjust the pH to 1, whereby a white powder was precipitated. This white powder was filtered, washed with water and dried to obtain 28 g of a dicarboxylic acid (III-a) having a nadiimide skeleton.
  • III-a dicarboxylic acid
  • Synthesis Example 12 [Synthesis of dicarboxylic acid (III-b) having nadiimide skeleton]
  • Synthesis Example 11 except that methyl dicarboxylate (II-a) having a nadiimide skeleton obtained in Synthesis Example 6 was changed to methyl dicarboxylate (II-b) having a nadiimide skeleton obtained in Synthesis Example 7.
  • the same operation as in Synthesis Example 11 was performed to obtain 28 g of a dicarboxylic acid (III-b) having a nadiimide skeleton.
  • Synthesis Example 14 [Synthesis of dicarboxylic acid (III-d) having nadiimide skeleton]
  • Synthesis Example 11 except that methyl dicarboxylate (II-a) having a nadiimide skeleton obtained in Synthesis Example 6 was changed to methyl dicarboxylate (II-d) having a nadiimide skeleton obtained in Synthesis Example 9.
  • the same operation as in Synthesis Example 11 was performed to obtain 29 g of a dicarboxylic acid (III-d) having a nadiimide skeleton.
  • the obtained polyamideimide (PAI-1) having a nadiimide skeleton was once dissolved in N-methylpyrrolidone, and then applied onto a Teflon (registered trademark) substrate, heated at 250 ° C., and the organic solvent was dried. A coating film having a thickness of 30 ⁇ m was formed.
  • the glass transition temperature (Tg), thermal decomposition starting temperature (5% mass reduction temperature, Td 5 ), tensile strength and elongation at break of this coating film were measured under the following conditions. The results are shown in Table 1.
  • Tg Glass transition temperature
  • Measurement mode Extension measurement span: 10 mm Load: 10g Temperature increase rate: 5 ° C / min Atmosphere: Air (2) Thermal decomposition start temperature (5% mass loss temperature, Td 5 ) It was measured with a differential thermal balance (Seiko Electronics Co., Ltd., Model 5200 TG-DTA).
  • Example 2 [Synthesis of polyamideimide (PAI-2) having nadiimide skeleton]
  • Example 1 except that the dicarboxylic acid (III-a) having a nadiimide skeleton obtained in Synthesis Example 11 was changed to the dicarboxylic acid (III-b) having a nadiimide skeleton obtained in Synthesis Example 12.
  • the same operation as in Example 1 was performed to obtain a polyamideimide (PAI-2) having a nadiimide skeleton having a number average molecular weight of 88,000.
  • Example 4 Synthesis of Polyamideimide (PAI-4) Having Nadiimide Skeleton] To a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube was charged 244.80 g (0.30 mol) of dicarboxylic acid (III-d) having a nadiimide skeleton obtained in Synthesis Example 14, and 240 The temperature is raised to ° C.
  • Example 5 Synthesis of Polyamideimide (NAI-5) Having Nadiimide Skeleton] To a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube, 284.28 g (0.12 mol) of dicarboxylic acid (III-e) having a nadiimide skeleton obtained in Synthesis Example 15 was added, and 240 The temperature is raised to ° C.
  • PAI-6 polyamideimide having a nadiimide skeleton having a number average molecular weight of 70,000.
  • the polyamideimide having a nadiimide skeleton obtained in Examples 1 to 6 has good heat resistance and high light transmittance, whereas the polyamideimide obtained in Comparative Examples 1 and 2 is The light transmittance was inferior.
  • a polyamideimide having a nadiimide skeleton excellent in heat resistance and transparency can be obtained. Therefore, it can be used as an electronic material used for semiconductors and liquid crystals, an optical material typified by an optical fiber, an optical lens, and the like, a display-related material, and a medical material.

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Abstract

Polyamide-imide ayant un squelette de nadimide et qui est représenté par la formule générale (I). Ainsi, le polyamide-imide de l'invention possède d'excellentes caractéristiques de résistance à la chaleur et de transparence, et a un squelette de nadimide. (Dans la formule, R1 est un groupe organique divalent pris parmi un groupe aliphatique, un groupe alicyclique et un groupe aromatique, et R4 est un groupe organique divalent pris parmi un groupe aliphatique, un groupe alicyclique et un groupe aromatique.)
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WO2016163417A1 (fr) * 2015-04-07 2016-10-13 ユニチカ株式会社 Polyamide-imide, sel de matière première pour polyamide-imide et procédés de production correspondant
JP2017508747A (ja) * 2014-03-05 2017-03-30 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 水素移動反応のためのルテニウム−フェノール触媒
US10501415B2 (en) 2015-04-07 2019-12-10 Unitika Ltd. Method for producing bisimide dicarboxylic acid

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