JP2019070074A - Polymer having isoimide bond and production method thereof, and polymer having imide bond - Google Patents

Abstract

To provide a stable novel polymer having an isoimide bond, which is useful as a precursor of a polyimide resin, and a production method thereof, as well as a polymer having an imide bond.SOLUTION: The invention provides a polymer having an isoimide bond represented by general formula (1). [In the general formula (1), P is a C1-100 organic group, X is a tetravalent organic group, Y is a divalent organic group, and n is an integer from 1 to 100.]SELECTED DRAWING: None

Description

  The present invention is a novel polymer having an isoimide bond, which is used as a binder for a high heat resistant coating agent or a high heat resistant additive, which is useful as an electronic material for forming a film or the like having high heat resistance. It relates to a polymer having a bond.

Polyimide resins, which have high heat resistance as a polymer film, are used as protective materials and insulating materials for liquid crystal display elements and semiconductors.
With regard to polyimide resins, for example, Patent Document 1 discloses a novel polyimide and a method of producing a polyimide containing specific structural units having good transparency, heat resistance and mechanical properties. Further, Patent Document 2 describes a polyimide film obtained by a heating process at a relatively low temperature by forming a solution of a solvent-soluble polyisoimide resin into a film and evaporating and removing the solution to thermally rearrange the polyisoimide. Is disclosed.

JP-A-8-104750 Japanese Patent Application Laid-Open No. 8-3314

Since a polyimide resin generally has low solubility in a solvent (solvent), a predetermined shape is formed by a precursor of the polyimide resin before it is formed into a molded article having a predetermined shape such as a film. For example, a molded article of a polyimide resin is manufactured by applying a solution of a polyamic acid resin which is a precursor of a polyimide resin to form a film, removing the solvent, and imidizing the film. However, polyamic acid resin solutions have the problem of poor storage stability.
An object of the present invention is to provide a novel polymer having a stable isoimide bond, a method for producing the same, and a polymer having an imide bond, which are useful as a precursor of a polyimide resin.

  The inventors of the present invention obtained the finding that a polymer having a highly stable isoimide bond can be obtained by reacting the end-capped polyamic acid polymer with a condensing agent. The present invention is based on the findings and has the following configuration.

[1] A polymer having an isoimide bond represented by the general formula (1).

[In general formula (1), P is an organic group having 1 to 100 carbon atoms, X is a tetravalent organic group, Y is a divalent organic group, and n is an integer of 1 to 100] . ]

[2] The polymer according to [1], wherein P in the general formula (1) is an organic group represented by the general formula (2) or (3).

In General formula (2), _{A 1} is a carbonyl group or an amide group, ^{R 1} is a monovalent organic group having 1 to 100 carbon atoms. ]

[In the general formula (3), A ₂ is an ethylene group or a vinylene group, the ethylene group and the hydrogen in the vinylene group may be substituted with an organic group having 1 to 100 carbon atoms. ]

  [3] X in the general formula (1) is a tetravalent organic group derived from tetracarboxylic acid dianhydride having 1 to 4 aromatic rings and / or alicyclic tetracarboxylic acid dianhydride The polymer as described in [1].

  [4] The polymer according to [1], wherein Y in the general formula (1) is an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group or an organosiloxane group.

[5] One or more selected from the group consisting of an alkyl group having 1 to 40 carbon atoms, a cycloalkyl group, an alkylene group, an aryl group, a heteroaryl group and a cyclohexane group, and R ¹ in the general formula (2) is The polymer according to [2], which is a substituent of

  [6] The polymer according to [1], wherein in the general formula (3), the C = N bond is a positional isomer.

  [7] The polymer according to [2], wherein in at least one of the general formulas (1) and (3), a C = N bond is a positional isomer.

  [8] A polymer having an imide bond, which is produced by rearrangement of the polymer according to [1].

  [9] An end-capped amic acid in which one or more of the group consisting of a monoisocyanate, a monocarboxylic acid active substance and a compound having a monoamine react with an amic acid polymer to react with an end. The method is characterized by including an end capping step of producing a polymer, and an isoimidization step of reacting the above-mentioned end-blocked amic acid polymer and a condensing agent to produce a polymer having an isoimide bond. , The manufacturing method of the polymer as described in [1].

  [10] The method for producing a polymer according to [9], wherein the condensing agent in the isoimidization step is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.

  The polymer having an isoimide bond of the present invention is useful as a precursor of an imide resin because of its high solubility and stability in various solvents. Moreover, according to the method for producing a polymer of the present invention, the polymer having an isoimide bond of the present invention can be stably produced.

  Hereinafter, the polymer having an isoimide bond of the present invention (hereinafter, also referred to as “isoimide polymer”) and the method for producing the isoimide polymer will be described.

<Isoimide polymer>
The polymer having an isoimide bond of the present embodiment is represented by the general formula (1).

[In general formula (1), P is an organic group having 1 to 100 carbon atoms, X is a tetravalent organic group, Y is a divalent organic group, and n is an integer of 1 to 100] . ]

P in the general formula (1) is an organic group represented by the general formula (2), (3), (4) or (5).

[In the general formula (2), A ₁ represents a carbonyl group [—C (= O) or an amido group —C (= O) —NH-, and R ¹ represents a monovalent organic group having 1 to 100 carbon atoms] is there. ]

In the general formula (2), R ¹ is at least one or more substituents selected from the group consisting of an alkyl group having 1 to 40 carbon atoms, a cycloalkyl group, an alkylene group, an aryl group, a heteroaryl group and a cyclohexane group It is.

[In the general formula (3), A ₂ is an ethylene group or a vinylene group, the ethylene group and the hydrogen in the vinylene group may be substituted with an organic group having 1 to 100 carbon atoms. ]

[X in General Formula (4) is a group similar to X in General Formula (1), and R ² is an organic group having 1 to 100 carbon atoms. ]

[X in General Formula (5) is a group similar to X in General Formula (1), and R ³ is an organic group having 1 to 100 carbon atoms. ]

  In the general formula (1), X is a tetravalent organic group derived from tetracarboxylic acid dianhydride having 1 to 4 aromatic rings and / or alicyclic tetracarboxylic acid dianhydride. "Derived from tetracarboxylic acid dianhydride" means that it is part of tetracarboxylic acid dianhydride used as a raw material.

The tetracarboxylic acid dianhydride is not particularly limited, but 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid dianhydride, 2, 3,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl sulfone tetracarboxylic acid Dianhydride, 2,3,3 ', 4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2 ', 3,3' -Diphenyl ether tetracarboxylic acid dianhydride, 2,3,3 ', 4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride And aromatic tetracarboxylic acid dianhydrides such as ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.); cyclobutane tetracarboxylic acid dianhydride, methyl cyclobutane tetracarbon Mention may be made of cycloaliphatic tetracarboxylic acid dianhydrides such as acid dianhydrides, cyclopentane tetracarboxylic acid dianhydrides and cyclohexane tetracarboxylic acid dianhydrides, and compounds represented by the following formulae.


In formula (AN-4-17), m is an integer of 1-12.





In formula (AN-12), the rings A ¹¹ are each independently a cyclohexane ring or a benzene ring.

In the formula ^{(AN-13), X} 13 is alkylene of 2 to 6 carbon atoms, Ph represents phenyl.

  It is preferable that X independently be a C2-C25 tetravalent organic group from the viewpoint of becoming an isoimide polymer having good compatibility with other components, and a C2-C20 tetravalent organic group. It is more preferably a group, and still more preferably a group represented by General Formula (6).

[In the general formula (6), R ⁴ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁵ — or —COO—R ⁵ —OCO— (R ⁵ Is independently an alkyl group having 1 to 4 carbon atoms. ]

  In the general formula (1), Y is an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group or an organosiloxane group, and is a divalent organic group derived from a diamine.

  It is preferable that Y is a divalent organic group having 2 to 35 carbon atoms, and it is a divalent organic group having 2 to 30 carbon atoms from the viewpoint of becoming an isoimide polymer having good compatibility with other components. And the group represented by the general formula (7) is more preferable.

[In the general formula (7), R ⁶ is —O—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —R ⁷ — or —O-ph-R ⁸ -ph-O - a (ph is a benzene ^{ring, R} 8 _{is, -O -, - CO -,} - SO 2 -, - C (CF 3) 2 - or -R ⁷ - is a.). In addition, R < ⁷ > is a C1-C4 alkyl group independently. ]

  In the general formulas (1) and (3), the C = N bond may be a regioisomer. Here, “CCN bond is a positional isomer” means that in the general formulas (1) and (3), the position of the C = N bond bonded to X and the position of the C = O bond are Refers to a regioisomer that has been replaced.

<Polymer Having Imide Bond>
By rearranging a polymer having an isoimide bond, a polymer having an imide bond can be obtained. The polymer having an isoimide bond causes rearrangement within the molecule by heating, or an intramolecular molecule using a catalyst (acid catalyst, base catalyst) such as 1,8-diazabicyclo [5.4.0] undecene-7. Can be generated by causing dislocations. By using a polymer having an isoimide bond as a precursor of a polymer having an imide bond (imide resin), a dehydrating reaction does not occur as in the case of using a polyamic acid polymer, and therefore, a molded body involved in the dehydrating reaction Can be avoided.

  The temperature in the case of causing a rearrangement by heating may be a temperature at which a rearrangement occurs in a polymer having an isoimide bond, but it is preferably 100 to 350 ° C., and more preferably 150 to 250 ° C. The time for the rearrangement reaction (reaction time) is usually about 30 minutes to 3 hours, preferably about 1 to 2 hours.

  Rearrangements using a catalyst can be achieved at temperatures lower than those used for thermal rearrangements. The temperature of rearrangement using a catalyst is preferably 25 to 200 ° C., and more preferably 25 to 150 ° C.

  By using an isoimide polymer as a precursor, a dehydration reaction is not involved in forming a polymer having an imide bond, and therefore it is possible to suppress the shrinkage of the molded body. Therefore, it is possible to prevent the physical properties of the molded body from being lowered due to the dehydration reaction. Examples of a method of forming the isoimide polymer into a predetermined shape before rearrangement include a coating method, an extrusion molding method, a compression molding method, an injection molding method, an inflation molding method, and the like.

<Method of Producing Polymer Having Isoimide Bond>
The polymer having an isoimide bond of the present invention can be produced by a production method comprising an end capping step and an isoimidization step.

The amic acid polymer used in the end capping step is obtained by reacting an acid anhydride and a diamine.
As an acid anhydride used as a raw material of an amic acid polymer, the tetracarboxylic dianhydride mentioned as a origin of the tetravalent organic group X in General formula (1) can be used, for example.

The diamine used as a raw material of the amic acid polymer is not particularly limited, but 1,3-bis (4-aminophenoxy) benzene, 3,3'-diaminophenylsulfone, benzidine, 2,7-fluorenedamine, siloxane diamine , Paraphenyldiamine, 4,4'-methylenedianiline, 4,4'-diaminobenzophenone, 4,4'-oxydianiline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane And 4,4'-methylenebiscyclohexaneamine, 1,3-bis (4-aminophenyl) adamantane, and compounds represented by the following formula.

In the above formula (DI-1), G ²⁰ is —CH ₂ —, and at least one —CH ₂ — may be replaced by —NH— or —O—, and m is an integer of 1 to 12 And at least one hydrogen of alkylene may be replaced by -OH. In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ independently represents a single bond, -NH-, -NCH _3- , -O-, -S-, -S _{-S -, - SO 2 -,} - CO -, - COO -, - CONCH 3 -, - CONH -, - C (CH 3) 2 -, - C (CF 3) 2 -, - (CH 2) m _{-, - O- (CH 2)} m -O -, - N (CH 3) - (CH 2) k -N (CH 3) -, - (O-C 2 H 4) m -O -, - O -CH ₂ -C (CF ₃ ) ₂ -CH ₂ -O-, -O-CO- (CH ₂ ) _m -CO-O-, -CO-O- (CH ₂ ) _m -O-CO-,- _{(CH 2) m -NH- (CH} 2) m -, - CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH -, - CO -C ₃ H _{6 - (NH-C 3 H 6} ) n -CO-, or -S- _{(CH 2)} a m -S-, m is an integer from 1 to 12 independently, k is an integer from 1 to 5 Yes, n is 1 or 2. In formula (DI-4), s is independently an integer of 0-2. In Formula (DI-6) and Formula (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF _{3 2} )-, -NH-, or alkylene having 1 to 10 carbon atoms. In the formulas (DI-2) to (DI-7), at least one hydrogen of a cyclohexane ring and a benzene ring is —F, —Cl, an alkyl having 1 to 3 carbon atoms, —OCH ₃ , —OH, —CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and additionally in formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring is It may be substituted by one selected from the group of groups represented by the following formulas (DI-4-a) to (DI-4-e). The group whose bonding position is not fixed to the carbon atom which comprises a ring shows that the bonding position in the ring is arbitrary. The bonding position of -NH ₂ to cyclohexane ring or benzene ring ^is any position except the bonding position of the ^{G 21} or ^{G 22.}

The diamine which does not have a side chain represented by the following formula.

In Formula (DI-1-7) and Formula (DI-1-8), k is each independently an integer of 1 to 3.






In formula (DI-5-1), m is an integer of 1 to 12.

In formula (DI-5-12) and formula (DI-5-13), m is an integer of 1-12.

In formula (DI-5-16), v is an integer of 1 to 6.

In formula (DI-5-30), k is an integer of 1 to 5.

In formulas (DI-5-35) to (DI-5-37) and formula (DI-5-39), m is an integer of 1 to 12, and formula (DI-5-38) and formula (DI-5-38) In DI-5-39), k is an integer of 1 to 5, and in the formula (DI-5-40), n is an integer of 1 or 2.


In Formula (DI-7-3) and Formula (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2.



In formula (DI-7-12), m is an integer of 1-12.

[In general formula (8), m is 0-200. ]
Among these, 1,3-bis (4-aminophenoxybenzene) is particularly preferable.

In order to allow the reaction for producing the amic acid polymer described above to proceed smoothly, it is preferable to carry out the reaction in a reaction solvent. Although the reaction solvent is not particularly limited, specific examples thereof include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Examples thereof include methyl methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide and tetrahydroxyfuran.
The above reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours.

In the end capping step, one or more of the group consisting of a monoisocyanate, a monocarboxylic acid active substance and a monoamine compound are reacted with an amic acid polymer to form an end-capped end-capped amic It is a process of producing an acid polymer. The monocarboxylic acid active substance refers to a compound having an acid anhydride structure, an acid chloride structure, or a thionyl chloride structure, represented by the following structural formula.

  The end capping component used in the end capping step reacts with a group remaining at the end of the polymer and does not act as a dehydrating condensing agent. Examples of the monoisocyanate used as the end capping component in the end capping step include methyl isocyanate, phenyl isocyanate and naphthyl isocyanate, and as the monocarboxylic acid active substance, for example, maleic anhydride, phthalic anhydride, phenyl Chloride is mentioned, and as a monoamine compound, aniline is mentioned, for example.

The end capping component used in the end capping step is one that reacts with the group remaining at the end of the polymer. Therefore, from the viewpoint of improving the stability of the end-capped amic acid polymer, the number of moles of the end-capping component added in the end-capping step is equal to or more than the number of moles of the group remaining at the end of the polymer. Is preferred. [(The number of moles of reactive functional groups of diamine-the number of moles of reactive functional groups of acid anhydride)]: the number of moles of reactive functional groups of the end capping component is 1: 1 to 1: 3. Is preferred, and more preferably 1: 1 to 1: 1.2.

The reaction temperature and reaction time in the end capping step differ depending on the end capping component used. When using the compound which has a monocarboxylic acid active body or a monoamine as an end capping component, it can carry out on the conditions similar to the reaction which makes an acid anhydride and diamine react, and it makes an amic acid polymer. On the other hand, when monoisocyanate is used as the end capping component, the reaction may proceed under the same conditions as the reaction to form the amic acid polymer, or it may be necessary to set a higher reaction temperature. Although the reaction temperature and the reaction time vary depending on the end-capping component to be used, they are generally about 20 to 200 ° C. and about 0.2 to 20 hours.

The isoimidization step is a step of reacting an end-capping amic acid polymer with a condensing agent to form a polymer having an isoimide bond. As the condensing agent, for example, 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide, which is a carbodiimide type condensing agent, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-Dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide; N, N'-carbonyldiimidazole which is an imidazole condensing agent, 1,1'-carbonyldi (1,2,4 triazole); a triazine condensing agent 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium = chloride n hydrate, trifluoromethanesulfonic acid (4,6-dimethoxy-1, 3,5-Triazin-2-yl)-(2-octoxy-2-oxoethyl) dimethyl ammonium; phosphonium system 1H-benzotriazol-1-yloxy tris (dimethylamino) phosphonium hexafluorophosphate which is a condensing agent, 1H-benzotriazol-1-yloxytripyrrolidinophosphodiium hexafluorophosphate, (7- Azabenzotriazol-1-yloxy) tripyrrolidinophosphonium hexafluorophosphate, chlorotripyrrolidinophosphodiium hexafluorophosphate, bromotris (dimethylamino) phosphonium hexafluorophosphate, 3- (diethoxyphosphoryloxy) O)-(benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium which is a uronium-based condensing agent))-1,2,3-benzotriazine-4 (3H) -one; Hexafluorophosphate, O- (7-azabenzotriazole) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, O- (N-succinimidyl) -N, N, N', N'-tetramethyluronium tetrafluoroborate Salt, O- (N-succinimidyl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, O- (3,4-dihydro-4-oxo-1,2,3-benzo Triazin-3-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, S- (1-oxido-2-pyridyl) -N, N, N', N'-tetramethyl Thiuronium tetrafluoroborate, O- [2-oxo-1 (2H) -pyridyl] -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, {{[(1-cyano-) 2-Ethoxy-2-oxoethylidene) Amino] oxy} -4-morpholinomethylene} dimethyl ammonium hexafluorophosphate; 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate which is a halouronium condensing agent, 1- (chloro-1-pylori Dinyl methylene) pyrrolidinium hexafluorophosphate, 2-fluoro-1,3-dimethylimidazolinium hexafluorophosphate, fluoro-N, N, N ', N'-tetramethylformamidinium hexafluoro Phosphate etc. are mentioned. In addition, additives may be used in combination with the condensing agent. As the additive, 1-hydroxybenzotriazole, 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, N, N'-disuccinimidyl carbonate and the like can be mentioned.
Among the condensing agents exemplified, a carbodiimide-based condensing agent is preferred because a stable and isolatable isoimide polymer can be obtained, and in particular, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (1-ethyl chloride) Preferred is -3- (3-dimethylaminopropyl) carbodiimide hydrochloride).

  The reaction temperature and reaction time in the isoimidization step vary depending on the type of condensing agent to be used, the structure of the resulting polymer having an isoimide bond, and the like, but are generally about 20 to 200 ° C. and about 0.2 to 20 hours.

  Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. The names of compounds and the like used in the examples and the abbreviations thereof are shown. This abbreviation is used in the following description.

THF: Tetrahydrofuran PSt: Polystyrene PMMA: Polymethyl methacrylate NMP: N-Methyl-2-pyrrolidone IPA: 2-Propanol 6FDA: 2, 2-Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride PMDA: Pyromellitic anhydride (pyromellitic anhydride)
TPE-R: 1,3-bis (4-aminophenoxy) benzene DDS: 3,3'-diaminophenylsulfone FDA: 2,7-fluorened amine PDA: paraphenyldiamine MDA: 4,4'-methylenedianiline MODA : 4,4'-diaminobenzophenone ODA: 4,4'-oxydianiline 4-BDAF: 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane EDC.HCl: 1-ethyl-3 -(3-Dimethylaminopropyl) carbodiimide hydrochloride Mw: weight average molecular weight Mn: number average molecular weight

Next, analysis conditions in the examples are shown.
<GPC>
Device: Waters ACQUTY APC system (detector: differential refractometer)
Solvent: THF
Flow rate: 0.8 ml / min
Column temperature: 40 ° C
Use column: Connect ACQUITY APC XT 45 and ACQUITY APC XT 45 to use standard for calibration curve: PSt
Solvent: NMP
Flow rate: 0.4 ml / min
Column temperature: 60 ° C
Use column: Connect ACQUITY APC XT 45 and ACQUITY APC XT 45 and use standard for calibration curve: PMMA

<DSC>
Device: Diamond-DSC (manufactured by Perkin Elmer)
Heating rate: 100 ° C / min
Measurement temperature: 20 to 350 ° C
Analysis: intermediate glass transition _temperature; T g (JIS K 7121-compliant)

<TG / DTA>
Device: TG / DTA 6200 (made by Hitachi High-Tech Science)
Heating rate: 10 ° C / min
Measurement temperature: 40 to 700 ° C
Analysis: 5% weight loss temperature; T _d5

<Spinner>
Device: Mikasa MS-A150

Example 1 Synthesis of Polymer (1) TPE-R (11.99 g, 0.041 mol) as a diamine component is added to a 500 mL four-necked flask equipped with a stirrer, thermometer, and reflux condenser. Further, 222.00 g of NMP was added and stirred well until the diamine was dissolved. After the diamine component is dissolved, the solution is heated to 50 ° C. using an oil bath, 6FDA (12.15 g, 0.027 mol) as an acid anhydride component is added to the system and maintained at 50 ° C. 3 Stirring was performed for a time. Subsequently, the solution was heated to 80 ° C., phenyl isocyanate (3.26 g, 0.027 mol) was added as an end capping component, and stirring was performed for 2 hours while maintaining 80 ° C. Subsequently, the solution temperature was lowered to 50 ° C., EDC.HCl (11.54 g, 0.060 mol) was added, and stirring was carried out for 4 hours while maintaining 50 ° C. The obtained polymer solution was dropped into a mixed solution of IPA / heptane = 2/1 (volume ratio) to carry out reprecipitation. After filtration through a Kiriyama funnel, vacuum drying was performed at 40 ° C. for 8 hours to obtain 23.18 g of the polymer (1) represented by the general formula (9). As a result of measuring molecular weight using GPC, it was _Mw = 5,300 and _Mw / _Mn = 1.2. Results of measurement of the glass transition point by using _DSC, was T g = 292 ℃. As a result of measuring 5% weight reduction temperature using TG / DTA, it was _Td5 = 320 _degreeC .

Example 2 Synthesis of Polymer (2) In the same manner as in Example 1 except that DDS (0.041 mol) was used instead of TPE-R, the polymer (2) represented by the general formula (10) was It can be synthesized.

Example 3 Synthesis of Polymer (3) In the same manner as in Example 1 except that Benzidine (0.041 mol) was used instead of TPE-R, the polymer (3) represented by the general formula (11) was obtained It can be synthesized.

Example 4 Synthesis of Polymer (4) In the same manner as in Example 1 except that FDA (0.041 mol) was used instead of TPE-R, the polymer (4) represented by the general formula (12) was It can be synthesized.

Example 5 Synthesis of Polymer (5) A polymer (5) represented by the general formula (13) in the same manner as in Example 1 except that siloxane diamine (0.041 mol) was used instead of TPE-R. Can be synthesized.

Example 6 Synthesis of Polymer (6) In the same manner as in Example 1 except that PDA (0.041 mol) was used instead of TPE-R, the polymer (6) represented by the general formula (14) was It can be synthesized.

Example 7 Synthesis of Polymer (7) In the same manner as in Example 1 except that MDA (0.041 mol) was used instead of TPE-R, the polymer (7) represented by the general formula (15) was It can be synthesized.

Example 8 Synthesis of Polymer (8) In the same manner as in Example 1 except that MODA (0.041 mol) was used instead of TPE-R, the polymer (8) represented by the general formula (16) was It can be synthesized.

Example 9 Synthesis of Polymer (9) In the same manner as in Example 1 except that ODA (0.041 mol) was used instead of TPE-R, a polymer (9) represented by General Formula (17) was obtained It can be synthesized.

Example 10 Synthesis of Polymer (10) A polymer (10) represented by the general formula (18) was prepared in the same manner as in Example 1, except that 4-BDAF (0.041 mol) was used instead of TPE-R. Can be synthesized.

Example 11 Synthesis of Polymer (11) In the same manner as in Example 1, except that 4,4′-methylenebiscyclohexaneamine (0.041 mol) was used instead of TPE-R, a compound represented by general formula (19) The polymer (11) shown in the above can be synthesized.

Example 12 Synthesis of Polymer (12) The general formula was the same as in Example 1 except that 1,3-bis (4-aminophenyl) adamantane (0.041 mol) was used instead of TPE-R. The polymer (12) represented by (20) can be synthesized.

Example 13 Synthesis of Polymer (13) In the same manner as in Example 1, except that dicyclohexyl-3,4,3,4-tetracarboxylic acid dianhydride (0.041 mol) was used instead of 6FDA, The polymer (13) represented by the general formula (21) can be synthesized.

Example 14 Synthesis of Polymer (14) A polymer (14) represented by the general formula (22) is synthesized in the same manner as in Example 4 except that PMDA (0.027 mol) is used instead of 6FDA. be able to.

Example 15 Synthesis of Polymer (15) A polymer (15) represented by the general formula (23) is synthesized in the same manner as in Example 6 except that PMDA (0.027 mol) is used instead of 6FDA. be able to.

Example 16 Synthesis of Polymer (16) To a 500 mL four-necked flask equipped with a stirrer, thermometer, and reflux condenser, add ODA (8.204 g, 0.041 mol) as a diamine component, and further add 156.00 g of NMP was added and stirred well until the diamine was dissolved. After the diamine component is dissolved, the solution is heated to 50 ° C. using an oil bath, PMDA (5.919 g, 0.027 mol) as an acid anhydride component is added to the system, and after the addition is completed, 50 ° C. Stirring was performed for 3 hours while keeping the Subsequently, the solution is heated to 80 ° C. using an oil bath, and phenyl isocyanate (3.26 g, 0.027 mol) is added as an end-capping component, and stirring is performed for 2 hours while maintaining 80 ° C. Did. Subsequently, the solution temperature was lowered to 50 ° C., EDC.HCl (11.54 g, 0.0602 mol) was added, and stirring was carried out for 4 hours while maintaining 50 ° C. The obtained polymer solution was added dropwise to a mixed solution of IPA / heptane = 2/1 (volume ratio) to carry out reprecipitation. After filtration through a Kiriyama funnel, vacuum drying was performed at 40 ° C. for 8 hours to obtain 13.65 g of a polymer (16) represented by the general formula (24). As a result of measuring molecular weight using GPC, it was _Mw = 14,000 and _Mw / _Mn = 1.2. The glass transition temperature was measured using DSC but was not observed. As a result of measuring 5% weight reduction temperature using TG / DTA, it was _Td5 = 310.degree.

Example 17 Synthesis of Polymer (17) In the same manner as in Example 1, except that PMDA (0.027 mol) was used instead of 6FDA, and phthalic anhydride (0.027 mol) was used instead of phenyl isocyanate. The polymer (17) represented by the general formula (25) can be synthesized.

Example 18 Synthesis of Polymer (18) In the same manner as in Example 6, except that PDA (0.027 mol) and 6FDA (0.041 mol) were used, a polymer (18) represented by the general formula (26) Can be synthesized.

Example 19 Synthesis of Polymer (19) In the same manner as in Example 15 except that aniline (0.027 mol) was used instead of phenylisocyanate, a polymer (19) represented by the general formula (27) was synthesized can do.

[Example 20]
Preparation and Evaluation of Film of Polymer Containing Imide Bond by Thermal Rearrangement of Isoimide The isoimide polymer (1) obtained in Example 1 was dissolved in THF to prepare a 15% solution. The prepared solution was coated on a glass substrate using a spin coater at a rotation number of 600 rpm, and dried at 120 ° C. for 10 minutes to obtain a coating film of an isoimide polymer.
The obtained coated film was heat-treated in an oven at 300 ° C. for 1 hour. By this heat treatment, the isoimide polymer in the coating film was rearranged to obtain a polymer having an imide bond (imide resin). No change in film thickness was observed before and after heat treatment, and the film of the polymer having an imide bond showed good heat resistance.

Comparative Example 1 Synthesis of Polymer (20) TPE-R (2.899 g, 0.0099 mol) was added as a diamine component to a 200 mL four-necked flask equipped with a stirrer, thermometer, and reflux condenser. Further, 65.700 g of NMP was added and stirred well until the diamine was dissolved. After the diamine component is dissolved, the solution is heated to 50 ° C. using an oil bath, 6FDA (4.3212 g, 0.0097 mol) as an acid anhydride component is added to the system, and after the addition is completed, 50 ° C. Stirring was performed for 3 hours while keeping the Subsequently, EDC.HCl (7.438 g, 0.0602 mol) is added, and stirring is performed while maintaining 50 ° C., gelation occurs, and the polymer (20) represented by the general formula (28) can be obtained. It was not.

The polymer having an isoimide bond of the present invention can be used as a precursor of an imide resin.

Claims (10)

The polymer which has an isoimide bond represented by General formula (1).

[In general formula (1), P is an organic group having 1 to 100 carbon atoms, X is a tetravalent organic group, Y is a divalent organic group, and n is an integer of 1 to 100] . ] The polymer according to claim 1, wherein P in the general formula (1) is an organic group represented by the general formula (2) or (3).

In General formula (2), _{A 1} is a carbonyl group or an amide group, ^{R 1} is a monovalent organic group having 1 to 100 carbon atoms. ]

[In the general formula (3), A ₂ is an ethylene group or a vinylene group, the ethylene group and the hydrogen in the vinylene group may be substituted with an organic group having 1 to 100 carbon atoms. ]   The X in the general formula (1) is a tetravalent organic group derived from tetracarboxylic acid dianhydride having 1 to 4 aromatic rings and / or alicyclic tetracarboxylic acid dianhydride The polymer according to Item 1.   The polymer according to claim 1, wherein Y in the general formula (1) is an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group or an organosiloxane group. R ¹ in the general formula (2) is an alkyl group having 1 to 40 carbon atoms, a cycloalkyl group, an alkylene group, an aryl group, a heteroaryl group, one or more substituents selected from the group consisting of cyclohexane group The polymer according to claim 2, which is   The polymer according to claim 1, wherein in the general formula (1), the C = N bond is a regioisomer.   The polymer according to claim 2, wherein in at least one of the general formulas (1) and (3), the C = N bond is a positional isomer.   A polymer having an imide bond, which is produced by rearrangement of the polymer according to claim 1. An end-capped amic acid polymer whose end is capped by reacting one or more of the group consisting of a monoisocyanate, a monocarboxylic acid active substance, and a compound having a monoamine with an amic acid polymer. End-capping process to produce
An isoimidization step of reacting the end-capping amic acid polymer with a condensing agent to form a polymer having an isoimide bond,
The method for producing a polymer according to claim 1, comprising: The method for producing a polymer according to claim 9, wherein the condensing agent in the isoimidization step is 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.