JP2013010897A - Tetrahydro pentalene type acid dianhydride, process for producing the same, and polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: polyimide in which the solubility to an organic solvent is excellent; an acid dianhydride compound that is the monomer of the same; and a process for producing the same.SOLUTION: The acid dianhydride compound represented by formula [1], the process for producing the same, and the polyimide are disclosed (in the formula, R denotes a 1-20C alkyl group). Tetraalkyl 2,5-bis(1,3-dioxo-1,3- dihydroisobenzofuran-5-carbonyloxy)-1,4,7,8- tetrahydropentalene-1,3,4,6-tetracarboxylate is represented by formula [1].

Description

  The present invention relates to a tetrahydropentalene-type acid dianhydride and a method for producing the tetrahydropentalene-type acid dianhydride, and more specifically to, for example, a polyimide suitable for an electronic material and a tetrahydropentalene-type acid dianhydride that is a raw material monomer.

  In general, polyimide resins are widely used as electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display elements and semiconductors because of their high mechanical strength, heat resistance, insulation, and solvent resistance. Yes. Recently, the use as an optical communication material such as an optical waveguide material is also expected.

In recent years, the development of this field has been remarkable, and correspondingly, higher and higher properties are required for the materials used. That is, it is expected not only to have excellent heat resistance and solvent resistance, but also to have a large number of performances depending on the application.
However, in polyimide (Kapton: trade name) produced from polyimide, particularly pyromellitic anhydride (PMDA) and 4,4′-dioxyaniline (ODA), which are widely used as representative examples of wholly aromatic polyimide resins. Since it has poor solubility and cannot be used as a solution, it is obtained by performing a dehydration reaction by heating through a precursor called polyamic acid.
In polyimides having solvent solubility (hereinafter soluble polyimides), amide-based and lactone-based organic solvents such as N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone, which have been widely used in the past, have high boiling points. Therefore, high-temperature firing was inevitable for removing the solvent.
In the field of liquid crystal display devices, research and development of flexible liquid crystal display devices using plastic substrates has been conducted in recent years. Deterioration of element constituents becomes a problem when firing at high temperatures. became.
On the other hand, polyamic acid that exhibits high solvent solubility does not provide sufficient liquid crystal display characteristics, and is susceptible to volume changes caused by imidization, and is soluble in organic solvents with low boiling points. Polyimide has become desirable.
Therefore, a polyimide that is soluble in organic solvents having a low boiling point has been desired.
On the other hand, some tetracarboxylic dianhydrides containing certain ester groups are known (for example, Patent Documents 1 and 2).

JP2008-297362 JP2008-101187

  The present invention has been made in view of such circumstances, and a tetracarboxylic dianhydride as a monomer capable of providing a polyimide having excellent solubility even in an organic solvent having a low boiling point and a method for producing the tetracarboxylic dianhydride. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors established a method for producing an acid dianhydride monomer in which a plurality of ester substituents are introduced into a bicyclooctadiene (tetrahydropentalene) ring, The polyimide manufactured using the said acid dianhydride monomer discovered that the solubility with respect to various organic solvents was improved, and completed this invention.

That is, the present invention
1. Formula [1]

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms.)
Tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7,8-tetrahydropentalene-1,3 4,6-tetracarboxylate,
2. 2. The tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7,8 according to 1, wherein R is a methyl group or an ethyl group. -Tetrahydropentalene-1,3,4,6-tetracarboxylate,
3. Formula [2]

(In the formula, R represents the same meaning as described above.)
In the presence of a base, a tetraalkyl 2,5-dihydroxy-1,4,7,8-tetrahydropentalene-1,3,4,6-tetracarboxylate represented by the formula [3]

(In the formula, X represents a halogen atom.)
Is reacted with a trimellitic anhydride halide represented by the formula [1]

(In the formula, R represents the same meaning as described above.)
Tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7,8-tetrahydropentalene-1,3 A process characterized by obtaining 4,6-tetracarboxylate,
4). The tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7,8 according to 3, wherein R is a methyl group or an ethyl group. A process characterized by obtaining tetrahydropentalene-1,3,4,6-tetracarboxylate,
5). A polyamic acid containing a repeating unit represented by the formula [4],

(In the formula, R represents the same meaning as described above, A represents a divalent organic group, and n represents an integer of 2 or more.)
6). 6. The polyamic acid according to 5, wherein R is a methyl group or an ethyl group,
7. A polyimide containing a repeating unit represented by the formula [5],

(In the formula, R, A and n represent the same meaning as described above.)
8). 8. The polyimide according to 7, wherein R is a methyl group or an ethyl group.

  According to the present invention, it is possible to provide an ester group-substituted tetracarboxylic dianhydride expected to be derived into a polyimide having excellent solubility in various organic solvents and a method for producing the same.

  Hereinafter, the present invention will be described in more detail.

  Tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7,8-tetrahydropentalene represented by the above formula [1] The production method of -1,3,4,6-tetracarboxylate (hereinafter abbreviated as TAPC) is represented by the following series of reaction schemes.

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, and X represents a halogen atom.)
That is, tetraalkyl 2,5-dihydroxy-1,4,7,8-tetrahydropentalene-1,3,4,6-tetracarboxylate (hereinafter abbreviated as TAHP) in the presence of a base, TAPC can be produced by reacting with trimellitic anhydride halide (hereinafter abbreviated as TAH).
In the above formula, the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, c-propyl, n- Butyl, i-butyl, s-butyl, t-butyl, c-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1- Dimethyl-n-propyl, c-pentyl, 2-methyl-c-butyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1- Ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, c-hexyl, 1-methyl-c-pentyl, 1-ethyl-c-butyl, 1,2-dimethyl-c-butyl, n- Heptyl, n-octyl, n-no Examples of such groups include ru, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl groups. Can be mentioned.

  Here, n represents normal, i represents iso, s represents secondary, t represents tertiary, and c represents cyclo.

  Here, the raw material TAHP is synthesized by a production method represented by the following known reaction scheme when R is methyl. (Organic Syntheses, 64, 27-38 (1986); Tetrahedron Letters, 49 (2008) 3056-3059)

That is, dimethyl 1,3-acetone dicarboxylate (DMAC) and gliogizar (GO) are reacted in the presence of sodium hydroxide to give tetramethyl 2,5-disodiumoxy-1,4,7,8-tetrahydropenta. After obtaining len-1,3,4,6-tetracarboxylate (hereinafter abbreviated as TMSP), it is acidified with hydrochloric acid to give tetramethyl 2,5-dihydroxy-1,4,7,8. -Tetrahydropentalene-1,3,4,6-tetracarboxylate (hereinafter abbreviated as TMHP) is obtained.
When R is ethyl, it is synthesized by a production method represented by the following known reaction scheme. (Japanese Patent Laid-Open No. 56-127328)

That is, tetraethyl 2,5-dihydroxy-1,4,7,8-tetrahydropentalene-1,3,4,6- is produced from diethyl 1,3-acetone dicarboxylate and glyogizal by a known production method. Tetracarboxylate (hereinafter abbreviated as TEHP) is synthesized.
The other raw material is trimellitic anhydride (TAH), and X represents each atom of fluorine, chlorine, bromine and iodine. Among these, commercially available trimellitic anhydride chloride can be used as it is.
The amount used is preferably 2.0 to 3.0 moles, more preferably 2.0 to 2.5 moles, relative to TAHP.
As the base, organic bases such as triethylamine, tripropylamine and pyridine or alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate can be used, and triethylamine is particularly preferable. The amount used is preferably 2.0 to 3.0 moles, more preferably 2.0 to 2.5, and even more preferably 2.0 to 2.3 moles with respect to TAHP.

  As the reaction solvent, tetrahydrofuran (THF), 1,4-dioxane, N, N-dimethylformamide (DMF) and the like are preferable. Their use amount is preferably 3 to 50 times by mass, more preferably 5 to 30 times by mass with respect to TAHP.

  The reaction temperature is about -30 to 150 ° C, preferably 0 to 120 ° C.

After the reaction, the residue obtained by concentrating the filtrate after filtration is dissolved by adding ethyl acetate and water, and the organic layer is separated and concentrated to obtain a gum. After adding ethyl acetate to this residue and dissolving it, adding n-heptane and then allowing to stand under ice cooling causes crystals to precipitate. The crystals are filtered, washed with an ethyl acetate / n-heptane mixture, and then dried under reduced pressure to obtain the desired TAPC.
This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.

  The TAPC, which is the tetracarboxylic dianhydride of the present invention described above, can be converted to a polyamic acid by a polycondensation reaction with a diamine, and then led to a corresponding polyimide by a dehydration ring-closing reaction using heat or a dehydrating agent.

  TAPC, which is a tetracarboxylic dianhydride of the present invention, gives polyimides having different organic solvent solubility depending on the type of diamine, and gives polyimides having excellent solubility even in low boiling point organic solvents.

  The diamine is not particularly limited, and various diamines conventionally used for polyimide synthesis can be used. Specific examples thereof include p-phenylenediamine (hereinafter abbreviated as p-PDA), m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-methylenedianiline (hereinafter abbreviated as MDA), 4,4'- Oxydianiline (hereinafter abbreviated as ODA), 2,2′-diaminodiphenylpropane, bis (3,5-diethyl-4-aminophenyl) methane, diaminodiphenylsulfone, diaminobenzophenone, diaminonaphthalene, 1,4- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, bis (4-aminopheno) C) Pentane, 9,10-bis (4-aminophenyl) anthracene, 4,4 ′-(1,3-phenylenedioxy) dianiline (hereinafter abbreviated as PODA), 3,5-diamino-1,6 -Dimethoxybenzene, 3,5-diamino-1,6-dimethoxytoluene, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, Aromatic diamines such as 2,2′-trifluoromethyl-4,4′-diaminobiphenyl; 4,4′-methylenebis (cyclohexylamine) (hereinafter abbreviated as MBCA), 4,4′-methylenebis (2- Methylcyclohexylamine), bis (4-aminocyclohexyl) ether, bis (4-amino-3-methylcyclohexyl) ether, (4-aminocyclohexyl) sulfide, bis (4-amino-3-methylcyclohexyl) sulfide, bis (4-aminocyclohexyl) sulfone, bis (4-amino-3-methylcyclohexyl) sulfone, 2,2-bis ( Fats such as 4-aminocyclohexyl) propane, 2,2-bis (4-amino-3-methylcyclohexyl) propane, bis (4-aminocyclohexyl) dimethylsilane, bis (4-amino-3-methylcyclohexyl) dimethylsilane Cyclic diamines; aliphatic diamines such as tetramethylene diamine, hexamethylene diamine and 3,3 ′-(dimethylsilanediyl) bis (oxy) dipropan-1-amine (MSPA). These diamines can be used alone or in admixture of two or more.

  In the above formulas [4] and [5], A is a divalent organic group derived from the diamine used.

In the present invention, it is preferable that at least 10 mol% of the total number of moles of tetracarboxylic dianhydride used is TAPC of the formula [1].
Furthermore, in order to achieve high organic solvent solubility, which is the object of the present invention, it is preferable that 50 mol% or more of the tetracarboxylic dianhydride is TAPC, and more than 70 mol% is TAPC. It is preferable that 90 mol% or more is TAPC.

  In addition, as long as TAPC becomes 10 mol% or more, the tetracarboxylic acid compound and its derivative used for the synthesis | combination of a normal polyimide can also be used simultaneously.

  Specific examples thereof include 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,4-di Carboxy-1-cyclohexyl succinic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3.3.0] octane-2,4,6,8-tetra Examples thereof include alicyclic tetracarboxylic acids such as carboxylic acids and acid dianhydrides thereof, and dicarboxylic acid diacid halides thereof.

Also, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6 , 7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, Bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-di Carboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethyl Aromatic tetracarboxylic acids such as silane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine And acid dianhydrides thereof, and dicarboxylic acid diacid halides thereof. These tetracarboxylic acid compounds may be used alone or in combination of two or more. The method for obtaining the polyamic acid of the present invention is not particularly limited, and tetracarboxylic dianhydride. And its derivative and diamine may be reacted and polymerized by a known method.

  The ratio of the number of moles of all tetracarboxylic dianhydride compounds to the number of moles of all diamine compounds when synthesizing the polyamic acid is preferably carboxylic acid compound / diamine compound = 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polymer produced. If the degree of polymerization is too small, the strength at the time of forming a polyimide film becomes insufficient, and if the degree of polymerization is too large, workability in forming a polyimide coating film may be deteriorated.

  Therefore, the degree of polymerization of the product in this reaction is 0.05 to 5.0 dl / g (in N-methyl-2-pyrrolidone at 30 ° C., concentration 0.5 g / dl) in terms of reduced viscosity of the polyamic acid solution. Is preferred.

  Examples of the solvent used for polyamic acid synthesis include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N, N-dimethylformamide (hereinafter abbreviated as DMF), N, N-dimethylacetamide ( (Hereinafter abbreviated as DMAc), m-cresol, N-methylcaptolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, γ-butyrolactone, and the like. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve a polyamic acid, you may use it in addition to the said solvent within the range in which a uniform solution is obtained.

  The temperature of the polycondensation reaction can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.

  The polyimide of the present invention can be obtained by subjecting the polyamic acid synthesized as described above to dehydration ring closure (thermal imidization) by heating. At this time, it is also possible to convert polyamic acid to imide in a solvent and use it as a solvent-soluble polyimide.

  Moreover, the method of chemically ring-closing using a well-known dehydration ring-closing agent is also employable.

  The method by heating can be performed at an arbitrary temperature of 100 to 350 ° C, preferably 120 to 300 ° C.

  The method of chemically cyclizing can be performed, for example, in the presence of pyridine, triethylamine, and the like, and acetic anhydride, and the temperature at this time can be selected from -20 to 200 ° C. .

  The polyimide solution thus obtained can be used as it is, and a polyimide is precipitated by adding a poor solvent such as methanol, ethanol and water, and this is isolated as a polyimide powder or the polyimide powder. Can be used by re-dissolving in a suitable solvent.

  The solvent for re-dissolution is not particularly limited as long as it can dissolve the obtained polyimide. For example, m-cresol, 2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, N-vinyl-2 -Pyrrolidone, DMAc, DMF, γ-butyrolactone, 1,4-dioxane, THF and the like.

  Moreover, even if it is a solvent which does not melt | dissolve a polyimide independently, if it is a range which does not impair solubility, it can be used in addition to the said solvent. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-butoxy-2-propanol. 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-Ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester and the like.

  The polyamic acid (polyimide precursor) solution prepared as described above is applied to the substrate and dehydrated and closed while the solvent is evaporated by heating, or the polyimide solution is applied to the substrate and the solvent is evaporated by heating. Thus, a polyimide film can be manufactured.

  Under the present circumstances, heating temperature is about 100-300 degreeC normally.

  An additive such as a coupling agent may be added to the polyamic acid solution or the polyimide solution for the purpose of further improving the adhesion between the polyimide film and the substrate.

  EXAMPLES Hereinafter, although a reference example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. The measuring device for each physical property in the examples is as follows.

[1] [LC-MASS]
Instrument: Agilent 1100MSD Trap (Agilent) Column: Atlantis dC18, 2.1 x 20 mm (3 mm)
Solvent: Acetonitrile / H ₂ O = 30/70 (0 min) -90/10 (0-5 min) -hold 15 min-30 / 70 (20-25 min)
Flow rate: 0.10 ml / min Temperature: 40 ° C Ionization method: ESI (-)
[2] [ ¹ H NMR]
Model: NMR System 400NB (400MHz) manufactured by Varian
Measurement solvent: CDCl ₃ , DMSO-d ₆
Standard substance: tetramethylsilane (TMS)
[3] [IR]
Equipment: Nicolet 6700 FT-IR (Thermo)
Measurement method: Diamond-ATR method Resolution: 4 cm ^-1 (Measurement range: 400 to 4000 cm ^-1 )
Sample scan: 50 times Background scan: 50 times [4] [Melting point (mp)] [Softening point (PMT)]
Model: Micro melting point measuring device (MP-S3) (manufactured by Yanaco Instrument Development Laboratory Co., Ltd.))
[5] Measurement of number average molecular weight and weight average molecular weight: GPC (Gel Permeation Chromatography) method The weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of a polymer are determined by a GPC apparatus (Shodex (registered trademark)) manufactured by JASCO Corporation. Columns KF803L and KF805L) were used, and DMF was measured as the elution solvent under conditions of a flow rate of 1 mL / min and a column temperature of 50 ° C. In addition, Mw was made into the polystyrene conversion value.

Example 1 Production of TMPC

A 500 mL four-necked reaction flask was charged with 18.5 g (50 mmol) of TMHP obtained by a known production method (Organic Syntheses, 64, 27-38 (1986)) and 185 g (10 times by mass) of THF, and dissolved at 20 ° C. 22.1 g (105 mmol) of trimellitic anhydride chloride (TAC) was added and dissolved while stirring with a magnetic stirrer at 5 ° C. on ice. Subsequently, 12.2 g (120 mmol) of triethylamine was added dropwise over 20 minutes. A precipitate started to form immediately and returned to 20 ° C. over 10 minutes, and then stirred at 45 ° C. for 7 hours to stop the reaction.
Subsequently, when the filtrate after filtration was concentrated, 45 g of a pasty solid was obtained. 150 g of ethyl acetate was added to the crude product and dissolved by stirring at 70 ° C. for 40 minutes. After cooling with ice, 100 g of water was added and washed with water, and the organic layer was concentrated to obtain 34 g of a gummy solid. 100 g of ethyl acetate was added again to dissolve, and the mixture was concentrated to 54 g, cooled on ice and allowed to stand overnight. The precipitated crystals were filtered, then washed 5 times with ethyl acetate / hexane = 1/1 (v / v) and then dried under reduced pressure to obtain 15.9 g (yield 44.3%) of light brown crystals.
This crystal was confirmed to be the target TMPC from MASS, ¹ H NMR and IR.
^{LC-MASS (MS -, m} / z (%)): 753.1 ([MH] -, 100) (M = TMPC + 2H 2 O)
¹ H NMR (DMSO-d ₆ , δppm): 2.468-2.506 (m, 3H), 6.540 (d, J = 1.2 Hz, 1H), 7.838 (s, 1H), 8.140 (s, 1H), 8.207 (t , J = 7.2 Hz, 2H), 8.478 (s, 1H), 8.528 (t, J = 8.0 Hz, 3H)
IR (cm ^-1 ): 1782.7 (cyclic acid anhydride C = O), 1865.4 (cyclic acid anhydride C = O)
m. p. (° C.): 183-185

Example 2 Production of TEPC

A 100 mL four-necked reaction flask was charged with 2.13 g (5 mmol) of TEHP obtained by a known production method (Japanese Patent Laid-Open No. Sho 56-127328) and 22 g of THF (10 times by mass), dissolved at 20 ° C., and then cooled at 5 ° C. with ice cooling. Then, 2.21 g (10.5 mmol) of trimellitic anhydride chloride (TAC) was added and dissolved while stirring with a magnetic stirrer. Subsequently, 1.22 g (120 mmol) of triethylamine was added dropwise over 20 minutes. A precipitate started to form immediately and returned to 20 ° C. over 10 minutes, and then stirred at 45 ° C. for 6 hours to stop the reaction.
Subsequently, the filtrate after filtration was concentrated to obtain a pasty solid. Ethyl acetate was added to this crude product and dissolved at 70 ° C., then ice-cooled, water was added and the mixture was washed with water, and the organic layer was concentrated to obtain a gummy solid. After dissolving again by adding ethyl acetate, n-heptane was added, and the mixture was cooled with ice and allowed to stand overnight. The precipitated crystals were filtered, then washed twice with ethyl acetate / hexane = 1/1 (v / v) and dried under reduced pressure to obtain 1.81 g (yield 46.7%) of flesh-colored crystals.
This crystal was confirmed to be the target TEPC from MASS, ¹ H NMR and IR.
^{LC-MASS (MS -, m} / z (%)): 773.0 ([MH] -, 100)
¹ H NMR (DMSO-d ₆ , δppm): 2.468-2.506 (m, 3H), 6.540 (d, J = 1.2 Hz, 1H), 7.838 (s, 1H), 8.140 (s, 1H), 8.207 (t , J = 7.2 Hz, 2H), 8.478 (s, 1H), 8.528 (t, J = 8.0 Hz, 3H)
IR (cm ^-1 ): 1781.2 (cyclic acid anhydride C = O), 1765.7 (cyclic acid anhydride C = O)
m. p. (C): 172-174

Example 3 Synthesis of TMPC-PODA polyamic acid and polyimide

In a 50 mL four-necked reaction flask equipped with a stirrer set at a room temperature of 20 ° C., 0.698 g (2.5 mmol) of 4,4 ′-(1,3-phenylenedioxy) dianiline (PODA) and 10 g of NMP were charged and dissolved. It was. Subsequently, while this solution was stirred, 1.80 g (2.5 mmol) of TMPC obtained in Example 1 was added in portions while being dissolved. Furthermore, it stirred at 20 degreeC for 24 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 20 mass% was obtained. The viscosity of this polymerization liquid was 105 mPa · s.

To this solution, 29 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 6,009 and the weight average molecular weight (Mw) was 11,783. Yes, Mw / Mn was 1.96.
Subsequently, 2.6 g (25 mmol) of acetic anhydride and 1.2 g (15 mmol) of acetic anhydride were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 4 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 165 ml of water, and the mixture was further stirred for 1 hour to precipitate an orange solid. This was filtered, washed with 50 ml of water three times, and dried under reduced pressure at 80 ° C. for 2 hours to obtain 1.41 g (yield 59%) of TMPC-PODA polyimide orange powder.
PMT: 240-250 ° C

Example 4 Synthesis of TMPC-p-PDA polyamic acid and polyimide

In a 50 ml four-necked reaction flask equipped with a stirrer placed at a room temperature of 20 ° C., 0.270 g (2.5 mmol) of p-phenylenediamine (p-PDA) and 8.28 g of NMP were charged and dissolved. Subsequently, while this solution was stirred, 1.80 g (2.5 mmol) of TMPC obtained in Example 1 was added in portions while being dissolved. Furthermore, it stirred at 20 degreeC for 21 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 20 mass% was obtained. The viscosity of this polymerization liquid was 77 mPa · s.

To this solution, 24 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 4,115, and the weight average molecular weight (Mw) was 7,023. Yes, Mw / Mn was 1.71.
Subsequently, 2.6 g (25 mmol) of acetic anhydride and 1.2 g (15 mmol) of acetic anhydride were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 4 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 140 ml of methanol, and further stirred for 2 hours to precipitate a gray solid. This was filtered, washed three times with 50 ml of methanol, and then dried under reduced pressure at 80 ° C. for 2 hours to obtain 0.98 g (yield 50%) of TMPC-p-PDA polyimide gray powder.
PMT:> 300 ° C

Example 5 Synthesis of TMPC-MDA polyamic acid and polyimide

In a 50 ml four-necked reaction flask equipped with a stirrer set at a room temperature of 20 ° C., 0.397 g (2.0 mmol) of 4,4′-methylenedianiline (MDA) and 7.35 g of NMP were charged and dissolved. Subsequently, while stirring this solution, TMPC1.44 g (2.0 mmol) obtained in Example 1 was added in portions while being dissolved. Furthermore, it stirred at 20 degreeC for 23 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 20 mass% was obtained. The polymerization solution had a viscosity of 111 mPa · s.

To this solution, 22 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 5,896, and the weight average molecular weight (Mw) was 11,052. Yes, Mw / Mn was 1.87.
Subsequently, 2.1 g (20 mmol) of acetic anhydride and 0.96 g (12 mmol) of acetic anhydride were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 4 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 125 ml of water, and further stirred for 1 hour to precipitate a gray solid. This was filtered, washed with 50 ml of water three times, and dried under reduced pressure at 80 ° C. for 2 hours to obtain 1.10 g (yield 63%) of TMPC-MDA polyimide gray powder.
PMT: 240-245 ° C

Example 6 Synthesis of TMPC-ODA polyamic acid and polyimide

In a 50 mL four-neck reaction flask equipped with a stirrer placed at a room temperature of 20 ° C., 1.44 g (2.0 mmol) of TMPC obtained in Example 1 and 4.27 g of NMP were charged and dissolved. Subsequently, while the solution was stirred, 0.400 g (2.0 mmol) of 4,4′-oxydianiline (ODA) was added in portions while being dissolved. Furthermore, it stirred at 20 degreeC for 26 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 30 mass% was obtained. The polymerization solution had a viscosity of 399 mPa · s.

To this solution, 25 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 3,849, and the weight average molecular weight (Mw) was 6,276. Yes, Mw / Mn was 1.63.
Subsequently, 2.1 g (20 mmol) of acetic anhydride and 1.0 g (12 mol) of pyridine were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 3 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 125 ml of water, and further stirred for 1 hour to precipitate an ocherous solid. This was filtered, washed with 50 ml of water three times, and then dried under reduced pressure at 80 ° C. for 2 hours to obtain 1.07 g (yield 61%) of TMPC-ODA polyimide ocher powder.
PMT: 230-240 ° C

Example 7 Synthesis of TMPC-MSPA polyamic acid and polyimide

In a 50 mL four-necked reaction flask equipped with a stirrer at room temperature of 20 ° C., 0.413 g (2.0 mmol) of 3,3 ′-(dimethylsilanediyl) bis (oxy) dipropan-1-amine (MSPA) and NMP5. 6 g was charged and dissolved. Subsequently, while stirring this solution, TMPC1.44 g (2.0 mmol) obtained in Example 1 was added in portions while being dissolved. Furthermore, it stirred at 20 degreeC for 22 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 25 mass% was obtained. The polymerization solution had a viscosity of 40 mPa · s.

To this solution, 23 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 2,216, and the weight average molecular weight (Mw) was 3,459. Yes, Mw / Mn was 1.56.
Subsequently, 2.1 g (20 mmol) of acetic anhydride and 0.96 g (12 mmol) of acetic anhydride were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 5 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 125 ml of water, and further stirred for 1 hour to precipitate a brown solid. This was filtered, washed with 50 ml of water three times, and then dried under reduced pressure at 80 ° C. for 2 hours to obtain 0.25 g (yield 14%) of TMPC-MSPA polyimide brown powder.
PMT: 65-70 ° C

Example 8 Synthesis of TEPC-MDA polyamic acid and polyimide

In a 50 ml four-necked reaction flask equipped with a stirrer placed at a room temperature of 20 ° C., 1.79 g (2.3 mmol) of TEPC obtained in Example 2 and 6.67 g of NMP were charged and dissolved. Subsequently, while the solution was stirred, 0.436 g (2.2 mmol) of 4,4′-methylenedianiline (MDA) was added in portions while being dissolved. Furthermore, it stirred at 20 degreeC for 22 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 25 mass% was obtained. The polymerization solution had a viscosity of 162 mPa · s.

To this solution, 28 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 4,729, and the weight average molecular weight (Mw) was 8,643. Yes, Mw / Mn was 1.83.
Subsequently, 2.3 g (22 mmol) of acetic anhydride and 1.04 g (13 mmol) of pyridine were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 5 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 145 ml of water, and further stirred for 2 hours to precipitate a flesh-colored solid. This was filtered, washed with 50 ml of water three times, and then dried under reduced pressure at 80 ° C. for 2 hours to obtain 1.25 g of TEPC-MDA polyimide skin color powder (yield 61%).
PMT: 240-250 ° C

Example 9 Synthesis of TEPC-ODA polyamic acid and polyimide

In a 50 mL four-necked reaction flask equipped with a stirrer placed at a room temperature of 20 ° C., 1.79 g (2.3 mmol) of TEPC obtained in Example 2 and 5.1 g of NMP were charged and dissolved. Subsequently, while the solution was stirred, 0.400 g (2.0 mmol) of 4,4′-oxydianiline (ODA) was added in portions while being dissolved. Furthermore, it stirred at 50 degreeC for 22 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 30 mass% was obtained. The polymerization solution had a viscosity of 134 mPa · s.

To this solution, 29 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 2,694 and the weight average molecular weight (Mw) was 4,052. Yes, Mw / Mn was 1.50.
Subsequently, 2.3 g (22 mmol) of acetic anhydride and 1.1 g (13 mol) of pyridine were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 5 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 140 ml of water, and the mixture was further stirred for 1 hour to precipitate an ocherous solid. This was filtered, washed with 50 ml of water three times, and then dried under reduced pressure at 80 ° C. for 2 hours to obtain 1.63 g (yield 87%) of an ocher powder of TEPC-ODA polyimide.

Example 10 Synthesis of TEPC-PODA polyamic acid and polyimide

In a 50 mL four-necked reaction flask equipped with a stirrer placed at a room temperature of 20 ° C., 1.79 g (2.3 mmol) of TEPC obtained in Example 2 and 5.6 g of NMP were charged and dissolved. Subsequently, while stirring the solution, 0.643 g (2.2 mmol) of 4,4 ′-(1,3-phenylenedioxy) dianiline (PODA) was dissolved and added in portions. Furthermore, it stirred at 30 degreeC for 23 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 30 mass% was obtained. The polymerization solution had a viscosity of 142 mPa · s.

To this solution, 33 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 2,529 and the weight average molecular weight (Mw) was 3,810. Yes, Mw / Mn was 1.51.
Subsequently, 2.3 g (22 mmol) of acetic anhydride and 1.1 g (13 mol) of pyridine were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 5 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 160 ml of water, and the mixture was further stirred for 1 hour to precipitate a gray solid. This was filtered, washed with 50 ml of water three times, and then dried under reduced pressure at 80 ° C. for 2 hours to obtain 1.86 g (yield 82%) of TEPC-PODA polyimide gray powder.

[Comparative Example 1] Synthesis of PMDA-ODA polyamic acid and polyimide

ODA (1.00 g, 5.0 mmol) and NMP (18.2 g) were charged and dissolved in a 50 mL four-necked reaction flask equipped with a stirrer at a room temperature of 22 ° C. Subsequently, while the solution was stirred, 1.03 g (4.75 mmol) of pyromellitic dianhydride (PMDA) was added in portions while being dissolved. Furthermore, it stirred at 20 degreeC for 23 hours, the polymerization reaction was performed, and the polyamic acid solution with a solid content of 10 mass% was obtained. To this solution, 14 g of NMP was added and diluted to a polyamic acid solution having a solid content of 6% by mass. As a result of GPC measurement, the number average molecular weight (Mn) was 2,173, and the weight average molecular weight (Mw) was 4,310. Yes, Mw / Mn was 1.98.
Subsequently, 5.1 g (50 mmol) of acetic anhydride and 2.37 g (30 mmol) of pyridine were added to the polyamic acid solution having a solid content of 6% by mass and stirred at 100 ° C. for 4 hours. After returning to room temperature, the reaction solution was added dropwise while stirring 147 ml of methanol, and the mixture was further stirred for 1 hour to precipitate an orange solid. This was filtered, washed with 50 ml of methanol three times, and dried under reduced pressure at 80 ° C. for 2 hours to obtain 1.55 g of PMDA-ODA polyimide orange powder (yield 86%).
PMT:> 300 ° C

Organic solvent solubility of TMPC-each diamine polyimide obtained in Examples 3-7, TEPC-each diamine polyimide obtained in Examples 8-10, and PMDA-ODA polyimide obtained in Comparative Examples 1 and 2. Was evaluated by the following method. The results are shown in Table 1.
(Measurement method)
5 mg of each polyimide was added to 100 mg of an organic solvent and stirred at a predetermined temperature to confirm its solubility.
A: dissolved at 20 ° C., ○: dissolved by heating, Δ: partially dissolved by heating, −: insoluble by heating (warming: 60-80 ° C.)

(Solubility result)
[Table 1]

TMPC-each diamine polyimide and TEPC-each diamine polyimide showed higher solubility than the known PMDA-ODA polyimide. The polyimide of the present invention was also dissolved in a low boiling point solvent such as dioxane or THF.

  The polyimide obtained by using the tetrahydropentalene type acid dianhydride of the present invention as one raw material is suitable, for example, as an electronic material such as a protective material in a liquid crystal display element or a semiconductor, an insulating material, and an optical communication material such as an optical waveguide It is expected to be used.

Claims (8)

Formula [1]

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms.)
Tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7,8-tetrahydropentalene-1,3 4,6-tetracarboxylate.   The tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7 according to claim 1, wherein R is a methyl group or an ethyl group. , 8-tetrahydropentalene-1,3,4,6-tetracarboxylate. Formula [2]

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms.)
In the presence of a base, a tetraalkyl 2,5-dihydro-1,4,7,8-tetrahydropentalene-1,3,4,6-tetracarboxylate represented by the formula [3]

(In the formula, X represents a halogen atom.)
Is reacted with a trimellitic anhydride halide represented by the formula [1]

(In the formula, R represents the same meaning as described above.)
Tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7,8-tetrahydropentalene-1,3 A method for producing 4,6-tetracarboxylate. The tetraalkyl 2,5-bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyloxy) -1,4,7 according to claim 3, wherein R is a methyl group or an ethyl group. , 8-tetrahydropentalene-1,3,4,6-tetracarboxylate is obtained. A polyamic acid containing a repeating unit represented by the formula [4].

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, A represents a divalent organic group, and n represents an integer of 2 or more.) The polyamic acid according to claim 5, wherein R is a methyl group or an ethyl group. A polyimide containing a repeating unit represented by the formula [5].

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, A represents a divalent organic group, and n represents an integer of 2 or more.) The polyimide according to claim 7, wherein R is a methyl group or an ethyl group.