JP2012240980A - Dihydrodiester of bisnadimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a derivative of a novel bisnadimide which is useful for a raw material of an alicyclic polyamide-imide having high heat resistance and high transparency.SOLUTION: There is provided a dihydrodiester of bisnadimide represented by general formula (1) (wherein Ris a 2C-12C straight-chain or branched alkane-diyl group, and Rand Reach independently are a 1C-5C alkyl group, a 2C-5C alkenyl group or a 7C-10C aralkyl group).

Description

  The present invention relates to a novel dihydrodiester of bisnadiimide that is useful as a raw material for highly heat-resistant, highly transparent alicyclic polyamideimides and the like.

  Conventionally, epoxy resin has been widely used as a resin for optical members used in optoelectronic devices in terms of mounting process on electronic substrates, heat resistance and mechanical properties under high temperature operation, and versatility. I came. However, in recent years, the use of 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 required.

  In general, epoxy resins are highly transparent under visible light, but it is known that sufficient transparency cannot be obtained in the ultraviolet to near-ultraviolet region. In addition, 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 such as being easily colored by heat or light, and has a heat resistance and ultraviolet resistance. Improvement is required (see, for example, Patent Documents 1 to 4).

  On the other hand, 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. Widely used as surface protection films and interlayer insulation films for devices, among them, polyamides with alicyclic structures are considered as materials for optoelectronic devices and various displays because of their excellent transparency in the ultraviolet region. Although it has started, heat resistance is still not sufficient as compared with polyamideimide having the same alicyclic structure (see, for example, Patent Document 5).

  On the other hand, nadic acid anhydride (endomethylenetetrahydrophthalic anhydride) having an alicyclic structure has long been used as an acid anhydride curing agent for epoxy resins. In recent years, alkenyl-substituted nadiimide compounds derived from this nadic anhydride, such as the following general formula (4)

(In the formula, A represents a divalent organic group.)
The bis (allyl-substituted nadiimide) or derivative thereof represented by the formula is used in various fields.
Specifically, the raw material component of the photo-alignment material (for example, refer to Patent Document 6); the constituent component of the adhesive sheet for electrical / electronic parts (for example, refer to Patent Document 7); a cured product having excellent heat resistance and mechanical properties Raw material component of heat-resistant resin composition (for example, see Patent Document 8); Raw material for laminated film having high transparency and excellent antireflection ability (for example, see Patent Document 9); Ink for ink and raw material for polyimide film ( For example, it is used as Patent Document 10).

JP 2007-308683 A JP 2006-131867 A JP 2003-171439 A JP 2004-75894 A Japanese Patent No. 3091784 JP 2002-265541 A JP 2003-13033 A JP 2005-82627 A JP 2006-281731 A JP 2010-106212 A

The bis (allyl-substituted nadiimide) used in the above Patent Documents 6 to 10 has a carbon = carbon double bond in the alicyclic structure and is not an alicyclic saturated structure. Therefore, the polyamideimide obtained therefrom Such polymers are considered to be inferior in transparency and heat resistance as compared with those having an alicyclic saturated structure.
The present invention has been made under such circumstances, and an object thereof is to provide a novel bisnadiimide derivative that is useful as a raw material for a highly heat-resistant and highly transparent alicyclic polyamideimide.

  As a result of intensive studies to achieve the above object, the present inventor obtained a dihydrodiester of bisnadiimide having an alicyclic saturated structure by hydroesterifying a bisnadiimide compound having a specific structure. And found that the purpose can be achieved. The present invention has been completed based on such findings.

That is, the present invention
(1) Dihydrodiester of bisnadiimide represented by the following general formula (1):

(Wherein R ¹ is a linear or branched alkanediyl group having 2 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Or an aralkyl group having 7 to 10 carbon atoms.)
(2) The dihydrodiester of bisnadiimide according to the above (1), wherein R ² and R ³ in the general formula (1) are each independently an alkyl group having 1 to 5 carbon atoms,
(3) A method for producing a dihydrodiester of bisnadiimide according to (1), wherein the bisnadiimide compound represented by the following general formula (2) is hydroesterified:

(In the formula, R ¹ represents a linear or branched alkanediyl group having 2 to 12 carbon atoms.)
(4) Hydroesterification is carried out by the following general formula (3)
HCOOR (3)
(In the formula, R represents R ² or R ^3. )
The production method according to the above (3), which is carried out using a formate compound represented by
Is to provide.

According to the present invention, it is possible to provide a novel dihydrodiester of bisnadiimide that is useful as a raw material for highly heat-resistant and highly transparent alicyclic polyamideimide and a method for producing the same.
The alicyclic polyamide-imide made from the dihydrodiester of bisnadiimide of the present invention is excellent in heat resistance and transparency, so that it is an optical material typified by electronic components, optical fibers and optical lenses used in semiconductors and liquid crystals, Can be used as display-related materials and medical materials.

¹ H-NMR spectrum of bisnadiimide compound (NDI-1) FT-IR spectrum of bisnadiimide compound (NDI-1) ¹ H-NMR spectrum of bisnadiimide compound (NDI-2) FT-IR spectrum of bisnadiimide compound (NDI-2) ¹ H-NMR spectrum of bisnadiimide compound (NDI-3) FT-IR spectrum of bisnadiimide compound (NDI-3) ¹ H-NMR spectrum of bisnadiimide compound (NDI-4) FT-IR spectrum of bisnadiimide compound (NDI-4) ¹ H-NMR spectrum of bisnadiimide compound (NDI-5) FT-IR spectrum of bisnadiimide compound (NDI-5) ¹ H-NMR spectrum of bisnadiimide compound (NDI-6) FT-IR spectrum of bisnadiimide compound (NDI-6) ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-1) of bisnadiimide ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-2) of bisnadiimide ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-3) of bisnadiimide ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-4) of bisnadiimide ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-5) of bisnadiimide ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-6) of bisnadiimide

First, the dihydrodiester of bisnadiimide of the present invention will be described.
[Dihydrodiester of bisnadiimide]
The dihydrodiester of bisnadiimide of the present invention has the following general formula (1)

(Wherein R ¹ is a linear or branched alkanediyl group having 2 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Or an aralkyl group having 7 to 10 carbon atoms.)
It has the alicyclic saturated structure represented by these.
In the general formula (1), examples of the linear or branched alkanediyl group having 2 to 12 carbon atoms represented by R ¹ include ethane-1,2-diyl group, propane-1,3-diyl group, Examples include linear alkanediyl groups such as butane-1,4-diyl group, branched alkanediyl groups such as 1-methylethane-1,2-diyl group, and 1-methylpropane-1,3-diyl group. it can.

On the other hand, the alkyl group having 1 to 5 carbon atoms in R ² and R ³ may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. Groups, sec-butyl groups, tert-butyl groups and various pentyl groups.
In addition, the alkenyl group having 2 to 5 carbon atoms of R ² and R ³ may be either linear or branched, such as vinyl group, allyl group, 1-propenyl group, isopropenyl group, various types A butenyl group and various pentenyl groups can be exemplified, and examples of the aralkyl group having 7 to 10 carbon atoms of R ² and R ³ include a benzyl group and a phenethyl group. Among these, a C1-C5 alkyl group is preferable from the viewpoint of high reactivity and low cost, and a methyl group is particularly preferable.
The bonding positions of the ^two substituents in the general formula (1), that is, —COOR ² and —COOR ³ are not particularly limited, but when the imide group is considered to be bonded to the 5th and 6th positions of the norbornane ring, Is also bonded to the 2nd or 3rd position.

(Production method)
The dihydrodiester of bisnadiimide of the present invention represented by the general formula (1) can be produced by hydroesterifying a bisnadiimide compound represented by the following general formula (2).

(In the formula, R ¹ represents a linear or branched alkanediyl group having 2 to 12 carbon atoms.)
As shown in the following reaction formula (A), the bisnadiimide compound represented by the general formula (2) is a nadic acid anhydride (5-norbornene-2,3-dicarboxylic acid anhydride) represented by the formula (5). And a diamine represented by the general formula (6) to obtain a bisnadiamidic acid compound represented by the general formula (7), followed by dehydration and ring closure.

(Wherein R ¹ has the same meaning as described above.)
Hydroesterification of the bisnadiimide compound represented by the general formula (2) is not particularly limited, but the following general formula (3)
HCOOR (3)
(In the formula, R represents R ² or R ³ , and R ² and R ³ have the same meaning as described above.)
By using a formic acid ester compound represented by the following formula (hereinafter abbreviated as formic acid ester), a hydroesterification reaction takes place and the dihydro of bisnadiimide having an alicyclic saturated structure represented by the general formula (1) A diester body can be obtained.

  The reaction between the bisnadiimide compound and the formate ester is not particularly limited, and examples thereof include a hydroesterification reaction with a formate ester using a transition metal complex catalyst or the like, such as a ruthenium compound, a cobalt compound, and a halide salt. A method in which a bisnadiimide compound and a formate esterification reaction in the presence of a catalyst system containing

  As the formic acid ester as a raw material for the hydroesterification reaction, formic acid ester (HCOOR) corresponding to -C (O) OR of the target dihydrodiester of bisnadiimide is used. For example, methyl formate, ethyl formate, propyl formate, Examples include isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, vinyl formate, and benzyl formate. Among these, methyl formate is preferable from the viewpoint of cost and reactivity.

The ruthenium compound that can be used as a catalyst for the hydroesterification reaction is not particularly limited as long as it contains ruthenium. Specific examples of suitable compounds include [Ru (CO) ₃ Cl ₂ ] ₂ , [RuCl ₂ (CO) ₂ ] _n (n is an unspecified natural number), [Ru (CO) ₃ Cl ₃ ] ⁻ , Ruthenium compounds having both a carbonyl ligand and a halogen ligand in the molecule, such as [Ru ₃ (CO) ₁₁ Cl] ⁻ , [Ru ₄ (CO) ₁₃ Cl] ⁻ , and the like are mentioned. From the viewpoint of improving the reaction rate, [Ru (CO) ₃ Cl ₂ ] ₂ and [RuCl ₂ (CO) ₂ ] _n are more preferable.

Ruthenium compounds having the above ligands are 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 ), Ru (C ₈ H ₁₀ ) (C ₈ H ₁₂ ) or the like as a precursor compound, and the ruthenium compound is prepared and introduced into the reaction system before or during the hydroesterification reaction. May be.

  The ruthenium compound may be used singly or in combination of two or more, and the amount used is preferably 1/10000 to 1 equivalent, more preferably 1/100, with respect to the bisnadiimide compound as a raw material. 1000 to 1/50 equivalent. 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. Moreover, even if it exceeds 1 equivalent, the reaction rate does not increase, but only the production cost tends to increase.

The cobalt compound that can be used as a catalyst for the hydroesterification reaction is not particularly limited as long as it contains cobalt. Specific examples of suitable compounds include cobalt compounds having a carbonyl ligand such as Co ₂ (CO) ₈ , HCo (CO) ₄ , and Co ₄ (CO) ₁₂ , cobalt acetate, cobalt propionate, cobalt benzoate, and citric acid. Examples thereof include cobalt compounds having a carboxylic acid compound such as cobalt as a ligand, and cobalt phosphate. Among these, from the viewpoint of improving the reaction rate, Co ₂ (CO) ₈ , cobalt acetate, and cobalt citrate are more preferable.

  The cobalt compound may be used singly or in combination of two or more, and the amount used is preferably 1/100 to 10 equivalents, more preferably 1/10 to 1 equivalent of the ruthenium compound. ~ 5 equivalents. Even if the ratio of the cobalt compound to the ruthenium compound is lower than 1/100 equivalent or higher than 10 equivalent, the production amount of the ester compound tends to be remarkably reduced.

  The halide salt that can be used as a catalyst for the hydroesterification reaction is not particularly limited as long as it is a compound composed of a halogen ion such as a chloride ion, a bromide ion, and an 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 ion constituting the halide salt may be one metal ion selected from alkali metals and alkaline earth metals. Specific examples include lithium, sodium, potassium, rubidium, cesium, calcium, and strontium.

  The organic ion may be a monovalent or higher organic group derived from an organic compound. Examples include ammonium, phosphonium, pyrrolidinium, pyridium, imidazolium, and iminium, and the hydrogen atom of these ions may be substituted with a hydrocarbon group such as alkyl and aryl. Although not particularly limited, specific examples of suitable organic ions include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium, and trioctyl. Examples include methylammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, tetramethylphosphonium, tetraethylphosphonium, tetraphenylphosphonium, benzyltriphenylphosphonium, butylmethylpyrrolidinium, and bis (triphenylphosphine) iminium. Of these, quaternary ammonium salts such as butylmethylpyrrolidinium chloride, bis (triphenylphosphine) iminium iodide and trioctylmethylammonium chloride are more preferable from the viewpoint of improving the reaction rate.

  The halide salt that can be 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. Specific examples of cations used in such 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, 1-ethyl-2,3-dimethylimidazolium, 1-butyl -2,3-dimethylimidazolium, 1-hexyl-2,3-dimethylimidazole Zorium, 1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecene, 8-ethyl-1,8-diazabicyclo [5. 4.0] -7-undecene, 8-propyl-1,8-diazabicyclo [5.4.0] -7-undecene, 8-butyl-1,8-diazabicyclo [5.4.0] -7-undecene , 8-pentyl-1,8-diazabicyclo [5.4.0] -7-undecene, 8-hexyl-1,8-diazabicyclo [5.4.0] -7-undecene, 8-heptyl-1,8 Organic organic ions such as -diazabicyclo [5.4.0] -7-undecene and 8-octyl-1,8-diazabicyclo [5.4.0] -7-undecene. In the present invention, the above halide salts may be used alone or in combination.

  Among the above-mentioned halide salts, preferred halide salts are chloride salts, bromide salts, and iodide salts, and the cation is an organic ion. Although not particularly limited, 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, preferably 1 to 1000 equivalents, more preferably 2 to 50 equivalents per 1 equivalent of the ruthenium compound. By setting the addition amount to 1 equivalent or more, the reaction rate can be effectively increased. On the other hand, when 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.

  In hydroesterification by the reaction of the bisnadiimide compound and formate, a basic compound, a phenol compound, or an organic halogen compound is added to a specific catalyst system including a ruthenium compound, a cobalt compound, and a halide salt as necessary. By doing so, it is possible to further enhance the effect of promoting the reaction by the catalyst system.

  The basic compound 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. Among the above basic compounds, a tertiary amine compound is preferable from the viewpoint of the reaction promoting effect. Specific examples of suitable tertiary amines that can be used in the present invention include trialkylamines, N-alkylpyrrolidines, quinuclidine, and triethylenediamine.

  One kind of the basic compound may be used, or two or more kinds may be used in combination. The amount of the basic compound is not particularly limited, but for example, preferably 1 with respect to 1 equivalent of the ruthenium compound. -1000 equivalent, More preferably, it is 2-200 equivalent. By making the addition amount 1 equivalent or more, the reaction promoting effect tends to be more pronounced. Moreover, when 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 is not particularly limited. Specific examples of usable phenol compounds include phenol, cresol, alkylphenol, methoxyphenol, phenoxyphenol, chlorophenol, trifluoromethylphenol, hydroquinone and catechol.

  The above phenol compounds may be used singly or in combination of two or more, and the amount added is not particularly limited, but for example, preferably 1 to 1 equivalent of ruthenium compound. 1000 equivalents, more preferably 2 to 200 equivalents. By making the addition amount 1 equivalent or more, the reaction promoting effect tends to be more pronounced. Moreover, when 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 is not particularly limited. Specific examples of usable organic halogen compounds include monohalogenated methane, dihalogenated methane, dihalogenated ethane, trihalogenated methane, tetrahalogenated methane, halogen Benzene or the like.

  One kind of the organic halogen compound may be used, or two or more kinds thereof may be used in combination. The amount of the organic halogen compound is not particularly limited, but is preferably 1 with respect to 1 equivalent of the ruthenium compound, for example. -1000 equivalent, More preferably, it is 2-200 equivalent. By making the addition amount 1 equivalent or more, the reaction promoting effect tends to be more pronounced. Moreover, when 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.

Hydroesterification by the reaction of the bisnadiimide compound and formic acid ester can proceed without using any solvent. However, if necessary, a solvent may be used. The solvent that can be used is not particularly limited as long as the compound used as a raw material can be dissolved. Specific examples of 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, and the like.
The said solvent may be used 1 type and may be used in combination of 2 or more type.

  The hydroesterification by the reaction of the bisnadiimide compound and formate is preferably performed in a temperature range of 80 ° C to 200 ° C, and more preferably in a temperature range of 100 ° C to 160 ° C. By carrying out the reaction at a temperature of 80 ° C. or higher, the reaction rate is increased and the reaction is facilitated efficiently. On the other hand, by controlling the reaction temperature to 200 ° C. or lower, decomposition of the formate used as a raw material can be suppressed. A reaction temperature that is too high is undesirable because when the formate is decomposed, the addition of ester groups to the bisnadiimide compound cannot be achieved. When the reaction temperature exceeds the boiling point of either the bisnadiimide compound or formate used as the 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 reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

<Synthesis of a bisnadiimide compound represented by the general formula (2)>
The bisnadiimide compound represented by the general formula (2) can be obtained by the synthesis method (a) shown below.
The synthesis method (a) for obtaining the bisnadiimide compound represented by the general formula (2) includes the following steps (a-1) and (a-2).
Step (a-1) In step (a-1), nadic acid anhydride (5-norbornene-2,3-dicarboxylic acid anhydride) represented by the following formula (5);

Reaction with a diamine represented by the following general formula (6),
H ₂ N—R ¹ —NH ₂ (6)
A bisnadiamidic acid compound represented by the following general formula (7) is obtained.

(R ^{1 in} formula (6) and formula (7) has the same meaning as described above.)

The diamine represented by the general formula (6) is not particularly limited, and R ¹ is a linear alkanediyl group such as an ethylene group, a propane-1,3-diyl group, or a butane-1,4-diyl group; Any alkanediyl group having 2 to 12 carbon atoms such as a branched alkanediyl group such as 1-methylethane-1,2-diyl group and 1-methylpropane-1,3-diyl group may be used. For example, ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,4-butanediamine, 1,3-butanediamine, 1,2-butanediamine, 2,3-butanediamine, 1,5- Pentanediamine, neopentyldiamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1, 12-dodecanediamine and the like can be used.

  (A-1) The reaction of the nadic acid anhydride represented by the formula (5) and the diamine represented by the general formula (6) in the step is the reaction of the nadic acid anhydride represented by the formula (5). The ratio of the number of moles of the amino group of the diamine represented by the general formula (6) to the number of moles of the acid anhydride group is preferably 0.7 to 1.5, and is preferably 0.8 to 1.3. More preferably, it is 0.9 to 1.2, more preferably 0.95 to 1.05. When it is less than 0.7 or exceeds 1.5, impurities in the bisnadiamidic acid compound represented by the general formula (7) 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.
In this way, the bisnadiamic acid compound obtained in the step (a-1) may be isolated by filtration under reduced pressure or the like, but considering the production cost and the like, the next step (a-2) with the reaction solution remaining It is more preferable to use it.

-Step (a-2) In step (a-2), the bisnadiamidic acid compound is dehydrated and cyclized to obtain the bisnadiimide compound represented by the above formula (2).
There is no particular limitation on the reaction to form a bisnadiimide compound represented by the above general formula (2) by dehydrating and ring-closing the bisnadiamic acid compound represented by the above general formula (7). For example, acetic anhydride or phosphorus pentoxide Can be used, such as a chemical ring closure method using a dehydrating agent, etc., a thermal ring closure method in which heating is refluxed in the presence of a solvent, etc., but considering the production cost and residual ionic impurity concentration in the resulting polyamideimide, etc. Is preferred.
The thermal ring closure method is preferably carried out at 50 to 250 ° C., and can be a reduced pressure reaction to facilitate dehydration ring closure.

Reaction for obtaining a bisnadiamidic acid compound represented by the above general formula (7) (step a-1) and reaction for dehydrating and ring-closing the bisnadiamidic acid compound to form a bisnadiimide compound represented by the general formula (2) (a- Step 2) can be performed stepwise or continuously, but it is preferably performed continuously in consideration of cost.
Reaction for obtaining a bisnadiamidic acid compound represented by the above general formula (7) (step a-1) and reaction for dehydrating and ring-closing the bisnadiamidic acid compound to form a bisnadiimide compound represented by the general formula (2) (a- Step 2) can be carried out without a solvent, but a solvent can be used if necessary.

  Examples of the organic solvent that can be used include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and γ-butyrolactone; diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol, and the like. Ether solvents such as ethylene 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-tetrahydronaphthalene Tetrahydrofuran, dioxane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl; Sulfoxide, sulfolane, and the like. These may be used alone or in combination of two or more, but considering the solubility, boiling point, and cost, a polyamideimide having a subsequent norbornane skeleton It is preferable to use a polar solvent used in the production of the resin, and it is more preferable to carry out the reaction without a solvent.

  The amount of the solvent used is preferably 50 to 300 parts by mass and more preferably 70 to 200 parts by mass with respect to 100 parts by mass of the bisnadiamidic acid compound represented by the general formula (7). When the amount used is less than 50 parts by mass, the raw materials are not sufficiently dissolved, and the reaction rate tends to be slow. Even if the amount exceeds 300 parts by mass, only the yield of the bisnadiimide compound per batch is reduced. There is no advantage.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
<Synthesis of a bisnadiimide compound represented by the general formula (2)>
(Synthesis Example 1) [Synthesis of bisnadiimide compound (NDI-1)]
A reaction formula (A-1) for synthesizing the bisnadiimide compound (NDI-1) is shown below.

After charging 246.00 g of 5-norbornene-2,3-dicarboxylic acid anhydride (5) and 301.50 g of toluene in a 1 liter flask equipped with a stirrer, thermometer, nitrogen introduction tube and cooling tube, While taking care to maintain the temperature at 30 to 40 ° C., 55.50 g of 1,3-propanediamine (6-1) (acid anhydride / amine (equivalent ratio) = 1.00 / 1.00) ) Is dripped. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Then, it heated up to the reflux temperature of toluene, and it heated and refluxed for 2 hours, and obtained 273 g of bisnadiimide compounds (NDI-1) (2-1). When the obtained bisnadiimide compound (NDI-1) was analyzed by high performance liquid chromatography, the purity was 100%. The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI
NDI-1 was analyzed by ¹ H-NMR and FT-IR. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 1 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Each proton was assigned as follows.

Proton a: Peak near 3.3 ppm Proton b: Peak near 3.4 ppm Proton c: Peak near 3.4 ppm Proton d: Peak near 3.3 ppm Proton e: Peak near 6.1 ppm Proton f: 6. Peak near 1 ppm Proton g: Peak near 1.6 ppm Proton h: Peak near 3.1 ppm Proton i: Peak near 1.4 ppm

Further, the integrated intensity ratio of each proton is ad / bc / ef / g / h / i = 4.08 / 4.007 / 4.00 / 4.007 / 4.06 / 2.06 (theoretical value: 4/4/4/4/4/2).
Further, as a result of the FT-IR analysis (FIG. 2), the characteristic absorption of the amide group near 1540 cm ⁻¹ disappeared, and the characteristic absorption of the imide group was confirmed near 1780 cm ⁻¹ .
In the reaction formula (A-1), (7-1) is a bisnadiamidic acid compound.

(Synthesis Example 2) [Synthesis of bisnadiimide compound (NDI-2)]
A reaction formula (A-2) for synthesizing the bisnadiimide compound (NDI-2) is shown below.

After charging 246.00 g of 5-norbornene-2,3-dicarboxylic acid anhydride (5) and 301.50 g of toluene in a 1 liter flask equipped with a stirrer, thermometer, nitrogen introduction tube and cooling tube, While taking care to maintain the temperature at 30 to 40 ° C., 55.50 g of 1,2-propanediamine (6-2) (acid anhydride / amine (equivalent ratio) = 1.00 / 1.00) ) Is dripped. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Then, it heated up to the reflux temperature of toluene, and it heated and refluxed for 2 hours, and obtained 270 g of bisnadiimide compounds (NDI-2) (2-2). When the obtained bisnadiimide compound (NDI-2) was analyzed by high performance liquid chromatography, the purity was 100%. The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI
NDI-2 was analyzed by ¹ H-NMR and FT-IR. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 3 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Each proton was assigned as follows.

Proton a: Peak near 3.3 ppm Proton b: Peak near 3.4 ppm Proton c: Peak near 3.4 ppm Proton d: Peak near 3.3 ppm Proton e: Peak near 5.9 ppm Proton f: 6. Peak near 0 ppm Proton g: Peak near 1.6 ppm Proton h: Peak near 3.3 ppm Proton i: Peak near 1.5 ppm Proton j: Peak near 1.1 ppm

The integral intensity ratio of each proton is ad / bc / e / f / g / h / i / j = 4.25 / 4.38 / 1.81 / 2.00 / 4.08 / 1.86. /0.90/2.86 (theoretical value: 4/4/2/2/4/2/1/3).
As a result of the FT-IR analysis (FIG. 4), the characteristic absorption of amide group near 1540 cm ⁻¹ disappeared, and the characteristic absorption of imide group was confirmed near 1780 cm ⁻¹ .
In the reaction formula (A-2), (7-2) is a bisnadiamidic acid compound.

(Synthesis Example 3) [Synthesis of bisnadiimide compound (NDI-3)]
A reaction formula (A-3) for synthesizing the bisnadiimide compound (NDI-3) is shown below.

After charging 229.60 g of 5-norbornene-2,3-dicarboxylic acid anhydride (5) and 291.20 g of toluene in a 1 liter flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube, 61.60 g of 1,4-butanediamine (6-3) (acid anhydride / amine (equivalent ratio) = 1.00 / 1.00) while being careful to keep the temperature at 30 to 40 ° C. ) Is dripped. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Then, it heated up to the reflux temperature of toluene, and heated and refluxed for 2 hours, and 270 g of bisnadiimide compounds (NDI-3) (2-3) were obtained. When the obtained bisnadiimide compound (NDI-3) was analyzed by high performance liquid chromatography, the purity was 100%. The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI
NDI-3 was analyzed by ¹ H-NMR and FT-IR. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 5 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Each proton was assigned as shown below.

Proton a: Peak near 3.1 and 3.25 ppm Proton b: Peak near 2.7 and 3.3 ppm Proton c: Peak near 2.7 and 3.3 ppm Proton d: Near 3.1 and 3.25 ppm Proton e: Peak in the vicinity of 6.0 to 6.3 ppm Proton f: Peak in the vicinity of 6.0 to 6.3 ppm Proton g: Peaks in the vicinity of 1.1, 1.4 and 1.55 ppm Proton h: 3. Peaks near 2 and 3.35 ppm Proton i: Peak near 1.2 to 1.35 ppm Also, the integrated intensity ratio of each proton is ad / bc / ef / g / h / i = 4.11 / 4. 03 / 3.86 / 4.00 / 4.09 / 3.86 (theoretical value: 4/4/4/4/4/4).
As a result of the FT-IR analysis (FIG. 6), the characteristic absorption of the amide group near 1540 cm ⁻¹ disappeared and the characteristic absorption of the imide group was confirmed near 1780 cm ⁻¹ .
In the reaction formula (A-3), (7-3) is a bisnadiamidic acid compound.

(Synthesis Example 4) [Synthesis of bisnadiimide compound (NDI-4)]
A reaction formula (A-4) for synthesizing the bisnadiimide compound (NDI-4) is shown below.

In a 1 liter flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube, 223.04 g of 5-norbornene-2,3-dicarboxylic acid anhydride (5) and 78.88 g of hexamethylenediamine (6-4) ( Acid anhydride / amine (equivalent ratio) = 1.00 / 1.00), heated to 80 ° C. and stirred for 30 minutes. Thereafter, the temperature was raised to 160 ° C., and the mixture was stirred under reduced pressure conditions (pressure in the flask: about 8.8 × 10 ⁴ Pa) for 2 hours to obtain 276 g of a bisnadiimide compound (NDI-4) (2-4). When the obtained bisnadiimide compound (NDI-4) was analyzed by high performance liquid chromatography, the purity was 100%. The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI
NDI-4 was analyzed by ¹ H-NMR and FT-IR. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 7 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Each proton was assigned as shown below.

Proton a: Peak near 3.2 ppm Proton b: Peak near 3.3 ppm Proton c: Peak near 3.3 ppm Proton d: Peak near 3.2 ppm Proton e: Peak near 6.0 ppm Proton f: 6. Peak near 0 ppm Proton g: Peak near 1.6 ppm Proton h: Peak near 3.1 ppm Proton i: Peak near 1.3 ppm Proton j: Peak near 1.1 ppm

Moreover, the integral intensity ratio of each proton is ad / bc / ef / g / h / i / j = 4.09 / 4.00 / 4.00 / 4.04 / 4.04 / 4.13 / 4. .22 (theoretical value: 4/4/4/4/4/4/4).
Further, as a result of FT-IR analysis (FIG. 8), the characteristic absorption of amide group near 1540 cm ⁻¹ disappeared, and the characteristic absorption of imide group was confirmed near 1780 cm ⁻¹ .
In the reaction formula (A-4), (7-4) is a bisnadiamidic acid compound.

(Synthesis Example 5) [Synthesis of bisnadiimide compound (NDI-5)]
The reaction formula (A-5) for synthesizing the bisnadiimide compound (NDI-5) is shown below.

After charging 196.80 g of 5-norbornene-2,3-dicarboxylic acid anhydride (5) and 320.40 g of toluene in a 1 liter flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube, While taking care to maintain the temperature at 30 to 40 ° C., 123.60 g of 1,12-dodecanediamine (6-5) (acid anhydride / amine (equivalent ratio) = 1.00 / 1.00) ) Is dripped. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Then, it heated up to the reflux temperature of toluene, and heated and refluxed for 2 hours, and 290 g of bisnadiimide compounds (NDI-5) (2-5) were obtained. When the obtained bisnadiimide compound (NDI-5) was analyzed by high performance liquid chromatography, the purity was 100%. The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI
NDI-5 was analyzed by ¹ H-NMR and FT-IR. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 9 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Each proton was assigned as shown below.

Proton a: Peak near 3.2 ppm Proton b: Peak near 3.3 ppm Proton c: Peak near 3.3 ppm Proton d: Peak near 3.2 ppm Proton e: Peak near 6.0 ppm Proton f: 6. Peak near 0 ppm Proton g: Peak near 1.5 ppm Proton h: Peak near 3.1 ppm Proton i: Peak near 1.1-1.3 ppm Proton j: Peak near 1.1-1.3 ppm Proton k : Peak near 1.1 to 1.3 ppm Proton l: Peak near 1.1 to 1.3 ppm Proton m: Peak near 1.1 to 1.3 ppm

Further, the integral intensity ratio of each proton is ad / bc / ef / g / h / ijklm = 4.11 / 4.19 / 4.00 / 4.09 / 4.07 / 20.39 (theoretical value: 4/4/4/4/4/20).
As a result of the FT-IR analysis (FIG. 10), the characteristic absorption of amide group near 1540 cm ⁻¹ disappeared, and the characteristic absorption of imide group was confirmed near 1780 cm ⁻¹ .

(Synthesis Example 6) [Synthesis of bisnadiimide compound (NDI-6)]
A reaction formula (A-6) for synthesizing the bisnadiimide compound (NDI-6) is shown below.

After charging 229.60 g of 5-norbornene-2,3-dicarboxylic acid anhydride (5) and 313.60 g of toluene in a 1 liter flask equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube, 84.00 g (acid anhydride / amine (equivalent ratio) = 1.00 / 1.00) of ethylenediamine (6-6) is added dropwise while taking care to maintain the temperature at 30 to 40 ° C. After completion of dropping, the mixture is stirred at room temperature for 1 hour. Then, it heated up to the reflux temperature of toluene, and it heated and refluxed for 2 hours, and obtained 285 g of bisnadiimide compounds (NDI-6) (2-6). When the obtained bisnadiimide compound (NDI-6) was analyzed by high performance liquid chromatography, the purity was 100%. The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI
NDI-6 was analyzed by ¹ H-NMR and FT-IR. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 11 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Each proton was assigned as shown below.

Proton a: Peak near 3.2 ppm Proton b: Peak near 3.27 ppm Proton c: Peak near 3.27 ppm Proton d: Peak near 3.3 ppm Proton e: Peak near 6.0 ppm Proton f: 6. Peak near 0 ppm Proton g: Peak near 1.5 ppm Proton h: Peak near 3.3 ppm

Moreover, the integrated intensity ratio of each proton is ad / bc / ef / g / h = 4.08 / 4.04 / 4.00 / 4.09 / 4.073.96 (theoretical value: 4/4 / 4/4/4).
Further, as a result of FT-IR analysis (FIG. 12), the characteristic absorption of amide group near 1540 cm ⁻¹ disappeared, and the characteristic absorption of imide group was confirmed near 1780 cm ⁻¹ .

<Synthesis of Dihydrodiester of Bisnadiimide Represented by General Formula (1)>
Example 1 [Synthesis of Bisnadiimide Compound (NDI-1) Dihydrodicarboxylate Dimethyl Compound (NDIDAC-1)]
Reaction formula (B-1) for synthesis of dimethyl dihydrodicarboxylate (NDIDAC-1) of bisnadiimide compound (NDI-1) is shown below.

In a stainless steel pressure reactor with an internal volume of 50 ml at room temperature, 0.025 mmol of [Ru (CO) ₃ Cl ₂ ] ₂ as a ruthenium compound, 0.025 mmol of Co ₂ (CO) ₈ as a cobalt compound, halide 0.5 mmol of trioctylmethylammonium chloride as a salt, 0.5 mmol of tripropylamine as a basic compound, and 0.5 mmol of p-cresol as a phenol compound were added and mixed to obtain a catalyst system. To this catalyst system, 10.0 mmol of the bisnadiimide compound (NDI-1) obtained in Synthesis Example 1 and 5.0 mL of methyl formate (9-1) were added, and then the reaction vessel was purged with nitrogen gas of 0.5 MPa, Hold at 120 ° C. for 15 hours. Thereafter, the reaction apparatus was cooled to room temperature, released, a part of the remaining organic phase was extracted, and the components of the reaction mixture were analyzed using high performance liquid chromatography. According to the analysis results, the dimethyl dihydrodicarboxylate of bisnadiimide produced by the reaction was 8.00 mmol (yield 80.0% based on the bisnadiimide compound). The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI

FIG. 13 shows the ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-1) of bisnadiimide obtained as a product. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 13 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Data: ppm: Methyl group at the methyl ester site

Example 2 [Synthesis of Dimethyl Dihydrodicarboxylate (NDIDAC-2) of Bisnadiimide Compound (NDI-2)]
A reaction formula (B-2) for synthesizing the dimethyl dihydrodicarboxylate (NDIDAC-2) of the bisnadiimide compound (NDI-2) is shown below.

In Example 1, the same operation as in Example was performed except that the bisnadiimide compound (NDI-1) obtained in Synthesis Example 1 was changed to the bisnadiimide compound (NDI-2) obtained in Synthesis Example 2. The components of the reaction mixture were analyzed using high performance liquid chromatography. According to the analysis results, the dimethyl dihydrodicarboxylate of bisnadiimide produced by the reaction was 7.88 mmol (yield 78.8% based on the bisnadiimide compound). The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI

FIG. 14 shows the ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-2) of bisnadiimide obtained as a product. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 14 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Data: ppm: Methyl group at the methyl ester moiety

(Example 3) [Synthesis of dimethyl dihydrodicarboxylate (NDIDAC-3) of bisnadiimide compound (NDI-3)]
A reaction formula (B-3) for synthesizing dimethyl dihydrodicarboxylate (NDIDAC-3) of a bisnadiimide compound (NDI-3) is shown below.

In Example 1, the same operation as Example 1 was carried out except that the bisnadiimide compound (NDI-1) obtained in Synthesis Example 1 was changed to the bisnadiimide compound (NDI-3) obtained in Synthesis Example 3. The components of the reaction mixture were analyzed using high performance liquid chromatography. According to the analysis results, the dimethyl dihydrodicarboxylate of bisnadiimide produced by the reaction was 8.24 mmol (yield 82.4% based on the bisnadiimide compound). The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI

FIG. 15 shows the ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-3) of bisnadiimide obtained as a product. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 15 are as follows.
Conditions: Solvent DMSO-d6, apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Data: ppm: Methyl group at the methyl ester moiety

(Example 4) [Synthesis of dimethyl dihydrodicarboxylate (NDIDAC-4) of bisnadiimide compound (NDI-4)]
Reaction formula (B-4) for synthesizing dimethyl dihydrodicarboxylate (NDIDAC-4) of bisnadiimide compound (NDI-4) is shown below.

In Example 1, the same operation as Example 1 was carried out except that the bisnadiimide compound (NDI-1) obtained in Synthesis Example 1 was changed to the bisnadiimide compound (NDI-4) obtained in Synthesis Example 4. The components of the reaction mixture were analyzed using high performance liquid chromatography. According to the analysis results, the dimethyl dihydrodicarboxylate of bisnadiimide produced by the reaction was 9.10 mmol (yield 91.0% based on the bisnadiimide compound). The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI

FIG. 16 shows the ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-4) of bisnadiimide obtained as a product. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 16 are as follows.
Conditions: Solvent CDCl ₃ , apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Data: Near 3.6 ppm: Methyl group at the methyl ester site

(Example 5) [Synthesis of dimethyl dihydrodicarboxylate (NDIDAC-5) of bisnadiimide compound (NDI-5)]
A reaction formula (B-5) for synthesizing a dimethyl dihydrodicarboxylate (NDIDAC-5) of a bisnadiimide compound (NDI-5) is shown below.

In Example 1, except that the bisnadiimide compound (NDI-1) obtained in Synthesis Example 1 was changed to the bisnadiimide compound (NDI-5) obtained in Synthesis Example 5, the same operation as in Example 1 was performed. The components of the reaction mixture were analyzed using high performance liquid chromatography. According to the analysis results, the dimethyl dihydrodicarboxylate of bisnadiimide produced by the reaction was 8.88 mmol (yield 88.8% based on the bisnadiimide compound). The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI

FIG. 17 shows the ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-5) of bisnadiimide obtained as a product. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 17 are as follows.
Conditions: Solvent CDCl ₃ , apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Data: Near 3.6 ppm: Methyl group at the methyl ester site

Example 6 Synthesis of Dimethyl Dihydrodicarboxylate (NDIDAC-6) of Bisnadiimide Compound (NDI-6)
A reaction formula (B-6) for synthesizing a dimethyl dihydrodicarboxylate (NDIDAC-6) of a bisnadiimide compound (NDI-6) is shown below.

In Example 1, the same operation as in Example 1 was performed except that the bisnadiimide compound (NDI-1) obtained in Synthesis Example 1 was changed to the bisnadiimide compound (NDI-6) obtained in Synthesis Example 6. The components of the reaction mixture were analyzed using high performance liquid chromatography. According to the analysis results, the dimethyl dihydrodicarboxylate of bisnadiimide produced by the reaction was 9.48 mmol (94.8% yield based on the bisnadiimide compound). The measurement conditions for high performance liquid chromatography are as follows.
Column: Nakarai Cosmo Seal 5C18-AR-II 4.6 mmφ × 250 mm
Mobile phase: MeOH / H ₂ O = 1/1
Flow rate: 1.0 mL / min
Detector: RI

FIG. 18 shows the ¹ H-NMR spectrum of dimethyl dihydrodicarboxylate (NDIDAC-6) of bisnadiimide obtained as a product. The measurement conditions and identification data of the ¹ H-NMR spectrum shown in FIG. 18 are as follows.
Conditions: Solvent CDCl ₃ , apparatus “AV400M” manufactured by BRUKER (proton fundamental frequency: 400.13 MHz).
Data: Near 3.6 ppm: Methyl group at the methyl ester site

(Reference Example 1) [Synthesis of polyamideimide having norbornane skeleton]
Into a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a cooling tube, 216.48 g (0.410 mol) of bisnadiimide dimethyl dihydrodicarboxylate (NDIDAC-4) obtained in Example 4 was charged, and the flask was charged. After adjusting the temperature to 60 ° C., 86.10 g (0.410 mol) of 4,4′-diaminocyclohexylmethane (dimethyl dihydrodicarboxylate of bisnadiimide / diamine (molar ratio) = 1.00 / 1.00) ) Is added over 2 hours. After raising the temperature to 160 ° C., the mixture was reacted for 3 hours and further reacted at 190 ° C. for 2 hours to obtain a polyamideimide (PAI-6) having a norbornane skeleton having a number average molecular weight of 70,000.

The obtained polyamideimide (PAI-6) having a norbornane skeleton was applied on a Teflon (registered trademark) substrate, heated at 250 ° C., and the organic solvent was dried to form a coating film having a thickness of 30 μm. The glass transition temperature (Tg) and thermal decomposition onset temperature (5% mass reduction temperature, Td ₅ ) of this coating film were measured under the following conditions.
The results are shown in Table 1.
(1) Glass transition temperature (Tg)
It measured with the thermomechanical analyzer (Seiko Electronics Co., Ltd. product 5200 type TMA).
Measurement mode: Extension Measurement span: 10 mm
Load: 10g (98mN)
Temperature increase rate: 5 ° C / min
Atmosphere: Air (2) Thermal decomposition start temperature (5% mass reduction temperature, Td ₅
It measured with the differential thermal balance (Seiko Electronics Co., Ltd. product 5200 type TG-DTA).
Temperature increase rate: 5 ° C / min
Atmosphere: Air

  Moreover, the light transmittance in each wavelength of the obtained polyamideimide (PAI-6) which has a norbornane skeleton was measured with JASCO Corporation V-570 type UV / VIS spectrophotometer. The evaluation results are summarized in Table 1.

(Reference Example 2) [Synthesis of aromatic polyamideimide]
In a 500 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a condenser tube, 51.84 g (0.270 mol) of trimellitic anhydride, 68.85 g (0.275 mol) of 4,4′-diphenylmethane diisocyanate ( Tricarboxylic acid anhydride / diisocyanate (molar ratio) = 1.00 / 1.02) and 181.04 g of N-methylpyrrolidone, heated to 120 ° C. and reacted for 5 hours to give a number average molecular weight of 110, 000 aromatic polyamideimide was obtained.

  The characteristics of the obtained aromatic polyamideimide were evaluated in the same manner as in Reference Example 1. The results are summarized in Table 1.

(Reference Example 3) [Synthesis of polyamideimide]
In a 500 ml flask equipped with a stirrer, thermometer, nitrogen introduction tube and cooling tube, 49.92 g (0.260 mol) trimellitic anhydride and 69.48 g (0.265 mol) 4,4'-dicyclohexylmethane diisocyanate (Tricarboxylic acid anhydride / diisocyanate (molar ratio) = 1.00 / 1.02) and 179.10 g of N-methylpyrrolidone were charged, heated to 120 ° C., reacted for 5 hours, and the number average molecular weight was 76. 1,000 polyamideimides were obtained.

  The properties of the obtained polyamideimide were evaluated in the same manner as in Example 1. The results are summarized in Table 1.

As can be seen from Table 1, the polyamideimide (PAI-6) having a norbornane skeleton according to the present invention obtained in Reference Example 1 is a reference example with respect to glass transition temperature, thermal decomposition start temperature, tensile strength and breaking elongation. 3 is almost the same as the polyamideimide having a cyclohexyl ring obtained in 3, but the light transmittance is 100% in the wavelength regions of 400 nm, 500 nm, and 600 nm, much more than that of Reference Example 3. good.
On the other hand, the aromatic polyamideimide obtained in Reference Example 2 has a light transmittance of 0% in any of the wavelength ranges of 400 nm, 500 nm, and 600 nm.

  The dihydrodiester of bisnadiimide of the present invention is useful as a raw material for alicyclic polyamideimide having high heat resistance and high transparency.

Claims (4)

A dihydrodiester of bisnadiimide represented by the following general formula (1).

(Wherein R ¹ is a linear or branched alkanediyl group having 2 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Or an aralkyl group having 7 to 10 carbon atoms.) The dihydrodiester of bisnadiimide according to claim 1, wherein R ² and R ³ in the general formula (1) are each independently an alkyl group having 1 to 5 carbon atoms. The method for producing a dihydrodiester of bisnadiimide according to claim 1, wherein the bisnadiimide compound represented by the following general formula (2) is hydroesterified.

(In the formula, R ¹ represents a linear or branched alkanediyl group having 2 to 12 carbon atoms.) Hydroesterification is carried out according to the following general formula (3)
HCOOR (3)
(In the formula, R represents R ² or R ^3. )
The manufacturing method of Claim 3 performed using the formate compound represented by these.

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