KR20120083361A - Organic-solvent-soluble polyimide comprising pmda, dade, bpda, and bcd - Google Patents

Abstract

(a) pyromellitic acid dianhydride (PMDA), (b) biphenyltetracarboxylic acid anhydride (BPDA), (c) bicyclooctentetracarboxylic acid anhydride (BCD) and (d) diaminodiphenyl A heat-resistant polyimide soluble in an organic solvent containing ether (DADE) as a component is provided. The polyimide of the present invention is synthesized by a three step addition reaction, and in the first step, a low molecular weight imide compound is produced by reaction of an acid dianhydride and an aromatic diamine, and in the second step, a low molecular weight imide compound is produced. Acidic anhydride and aromatic diamine are made to react with a molecular weight imide compound again, and a low molecular weight imide compound is produced, and a polycondensation reaction is performed at 530 degreeC? It is a heat resistant polyimide soluble in organic solvents having a pyrolysis initiation temperature in the range of 570 ° C.

Description

Polyimide Soluble in Organic Solvents Containing PDMA, DDA, GPAD, and CDD {ORGANIC-SOLVENT-SOLUBLE POLYIMIDE COMPRISING PMDA, DADE, BPDA, AND BCD}

Solvent soluble polyimides of the invention include pyromellitic acid dianhydride (PMDA), diaminodiphenylether (DADE), biphenyltetracarboxylic acid dianhydride (BPDA) and bicyclo (2,2,2) octo-7 -Nen-2,3,5,6-tetracarboxylic acid anhydride (BCD, collectively called bicyclooctene tetracarboxylic acid anhydride) is a solvent-soluble polyimide with the functionality. Solvent-soluble polyimide produced in the presence of an acid catalyst by a three step reaction.

Here, DADE contains 4,4'- diamino diphenyl ether (4,4'-DADE) or 3,4'- diamino diphenyl ether (mDADE).

The polyimide is known KAPTON manufactured and sold by DuPont in the 1960s, and consists of pyromellitic acid anhydride (called PMDA) and 4,4'-diaminodiphenyl ether (4,4'-DADE). It is.

KAPTON is a polymer having a glass transition temperature (Tg) of 420 ° C and a thermal decomposition initiation temperature (Tm) of 500 ° C or higher. It has excellent electrical insulation, mechanical strength, and chemical resistance, and is aerospace, vehicle materials, and electrical and electronic components. And as a material for semiconductors (Non-Patent Document 1; Polyimides; D. Wilson, HD Steinberger, RM Morgenrother; Blackie, New York (1990)).

In the 1980s, polyimide "Upilex" was manufactured and sold by Ube Heungsan Co., Ltd. It is a heat resistant polyimide film comprised from biphenyl tetracarboxylic-acid anhydride (called BPDA), and 1, 4- diamino benzene (called PPD), and is Tg 500 degreeC and Tm 550 degreeC.

KAPTON, known as a super heat-resistant polyimide, is a polyimide of a two-component composition composed of PMDA and 4,4'-DADE. Likewise, Upilex is a polyimide of a two-component composition composed of BPDA and PPD. It is regarded as 不 融), and both are synthesize | combined via polyamic acid.

Since then, heat-resistant polyimides corresponding to KAPTON and Upilex have not been produced. These polyimides are poorly soluble polyimides in organic solvents, and no tetracarboxylic acid dianhydrides which can replace these components PMDA and BPDA have not been developed. KAPTON, consisting of PMDA and 4,4'-DADE, is poorly soluble in solvents. This is because PMDA-4,4'-DADE-PMDA or 4,4'-DADE-PMDA-4,4'-DADE bond is generated.

KAPTON, Upilex are poorly soluble polyimide solvents, polycondensation at low temperature in anhydrous solvents (e.g., N-dimethylacetamide, N-methylpyrrolidone, etc.) to synthesize polyamic acid, and then cast It heats, is accompanied by the imidation reaction of a polyamic acid, and high temperature process (400 degreeC or more), and the polyimide film is manufactured.

The polyamic acid is cryopreserved in anhydrous solvent, easily decomposed by water, and easy to thermally decompose, and thus poor storage stability.

The polyamic acid undergoes a rapid exchange reaction in a solution and is difficult to modify because it becomes a random copolymer.

Although it is known to directly imidize various aromatic tetracarboxylic acid anhydrides and aromatic diamines in a solution of acetic anhydride and pyridine, they are not employed as a process suitable for industrial production.

Imidization reactions in solutions using acid catalysts are also known. For example, the imidation reaction is accelerated | stimulated in solution using acid catalysts, such as toluenesulfonic acid and phosphoric acid. However, since the acid catalyst remains in the solution and causes deterioration of the polyimide, it is necessary to separate and maintain the polyimide and the catalyst [Patent Document 3; A. Berger, US Pat. No. 4,011,279; US Patent No. 4,395,527].

The synthesis of a polyimide soluble in an organic solvent first required the development of a new catalyst. During the polycondensation reaction, a novel catalyst acting as an acid catalyst and disappearing at the end of the reaction was developed [Patent Document 4; Y. Oie, H. Itatani, US Patent No. 5,502,143]

It is a novel catalyst that uses the equilibrium of lactones. a mixture of γ- lactone with a lactone as pyridine or γ- ballet ballet and N- methylmorpholine is, [acid] ⁺ [chloride] in the presence of water ^- if that is, removing water from it, again with γ- lactone ballet And an equilibrium which is a mixture of pyridine or γ-valerolactone and N-methylmorpholine. (Equation 1)

A catalytic amount of γ-valerolactone and pyridine, or γ-valerolactone and N-methylmorpholine is added to the reaction system, and an appropriate amount of toluene is added thereto and heated to 160-200 ° C. to carry out imidization reaction.

By the water produced at the beginning of the reaction [acid] ^{+ [base]} it is generated, the already promote the imidization reaction. The imidation reaction advances while refluxing toluene with the toluene added in the reaction system, and the produced water is removed out of the system by azeotroping of toluene. The end point of the imidation reaction, the reaction system approaches the anhydrous state, [acid] ⁺ [base] ^- lactone and the catalyst in pyridine or γ- ballet as γ- ballet is a lactone and N- methylmorpholine is removed out of the system . In this way, high-purity polyimide is produced.

MEANS TO SOLVE THE PROBLEM This invention is biphenyl tetracarboxylic dianhydride (BPDA) and 4,4'- diamino diphenyl ether (4,4) as main invention by patent document 1 (international publication 2008/120398 pamphlet). '-DADE), a heat-resistant polyimide copolymer soluble in an organic polar solvent, consisting of four components of pyromellitic acid dianhydride (PMDA) and 2,4-diaminotoluene (DAT), DADE at both ends of BPDA Is a reaction product of a first step of producing an oligomer to which is bonded, followed by a second step of adding a PMDA-bonded imide oligomer to the both ends thereof, and a third step of polycondensation of adding DAT to both ends thereof. And the heat resistant polyimide copolymer having a glass transition temperature of 430 ° C or higher.

And this inventor is based on patent document 2 (international publication 2008/155811 pamphlet), and 1 mol equivalent of biphenyl tetracarboxylic-acid anhydride (BPDA) and 2 mol equivalent of diamino diphenyl ether (DADE) In organic polar solvents, in the presence of a catalyst 160? By adding 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of diaminotoluene (DAT) to the imide oligomer produced by heating to 200 degreeC, 6,6- both ends are imide oligomers of PMDA. The imide segment was synthesized, 1 molar equivalent of tetracarboxylic dianhydride (called A) and 2 molar equivalent of aromatic diamine (called B) were added to the solution of the 6,6-imide segment, followed by heating. The method for producing the 6,6-polyimide copolymer produced by the three-stage polymerization method is disclosed.

From Patent Literatures 1 and 2, it has been reported that polyimide having a glass transition temperature of 430 ° C or higher, which is soluble in an organic polar solvent, can be synthesized by performing the reaction in three steps.

International Publication No. 2008/120398 Brochure International Publication No. 2008/155811 Pamphlet A. Berger, US Pat. No. 4,011,279; U.S. Patent 4,395,527 Y. Oie, H. Itatani, US Patent No. 5,502,143

 Polyimides; D. Wilson, H. D. Steinberger, R. M. Morgenrother; Blackie, New York (1990)

The present invention further develops a polyimide soluble in a polar organic solvent by carrying out the reaction in three steps disclosed in Patent Literatures 1 and 2. That is, bicyclo (2,2,2) octo-7- having the following structural formula while maintaining the characteristic of being soluble in the polar organic solvent according to the reaction in three steps, which is the characteristic of the polyimide of Patent Documents 1 and 2 Solubility in an organic solvent compared with PMDA to polyimide by adding ene-2,3,5,6-tetracarboxylic acid anhydride (BCD, commonly referred to as bicyclooctene tetracarboxylic acid anhydride) This excellent, high adhesion characteristic was further provided. It is because BCD which is an essential component in this invention is excellent in solubility compared with PMDA, and shows high adhesive characteristic.

Bicyclo (2,2,2) octo -7-en-2,3,5,6- Tetracarboxylic acid Anhydride

[Formula 1]

 PMDA-DADE system polyimide, especially when the imide compound of (PMDA-DADE-PMDA) or (DADE-PMDA-DADE) which is poorly soluble in a solvent, produces | generates a polyimide. Therefore, in this invention, what examined the synthesis process which does not contain this compound is the same as that of patent documents 1 and 2.

In order to prevent this, also in the study of the four-component block copolymer polyimide, the polyimide soluble in an organic solvent is not known.

In the present invention, PMDA and DADE employ a process not used in the same reaction step.

The invention relates to (a) pyromellitic acid dianhydride (PMDA), (b) biphenyltetracarboxylic acid dianhydride (BPDA, typically 3,3 ', 4,4'-biphenyltetracarboxylic acid anhydride) In the heat-resistant polyimide soluble in an organic solvent containing (c) bicyclooctene tetracarboxylic acid anhydride (BCD) and (d) diaminodiphenyl ether (DADE) as a component, the polyimide is Synthesized by a three-step addition reaction, in a first step, a low molecular weight imide compound is produced by reaction of an acid dianhydride and an aromatic diamine; in a second step, a low molecular weight imide compound produced in a first step The acid dianhydride and the aromatic diamine are further reacted to produce a low molecular weight imide compound, and in the third step, the polycondensation reaction is carried out at 530 ° C. Heat resistant polyimide is provided that is soluble in organic solvents having a pyrolysis onset temperature in the range of 570 ° C.

More specifically, the present invention (1) reacts an acid dianhydride (2 molar equivalents) with an aromatic diamine (1 molar equivalent) in the presence of a catalyst, thereby reducing the molecular weight of the amino di group to which both amino di groups of the aromatic diamine are bound. Dehydration compound, ie the first step of producing an oligomer,

(2) A second compound in which an acid dianhydride (2 molar equivalents) and an aromatic diamine (4 molar equivalents) are added to the compound and reacted to produce a low molecular weight imide compound having an aromatic diamine bonded to both terminals, that is, an oligomer. Step, then

(3) To the heat-resistant polyimide soluble in the organic solvent produced by the third step of adding an acid dianhydride (2 molar equivalents) and an aromatic diamine (1 molar equivalent) to a polycondensation reaction to produce a high molecular weight polyimide. In

The acid dianhydride contains (i) pyromellitic acid dianhydride (PMDA), (ii) biphenyltetracarboxylic acid dianhydride (BPDA) and (iii) bicyclooctentetracarboxylic acid anhydride (BCD) To an organic solvent wherein the aromatic diamine contains (i) 4,4'-diaminodiphenyl ether (4,4'-DADE) or (ii) 3,4'-diaminodiphenyl ether (mDADE). It provides the above heat resistant polyimide which is soluble.

In addition, the present invention is (1) a low molecular weight imide compound in which an acid dianhydride (2 molar equivalents) and an aromatic diamine (1 molar equivalent) are reacted in the presence of a catalyst, and an acid dianhydride is bonded to both amino groups of the aromatic diamine. , Ie the first step of producing oligomers,

(2) A second compound in which an acid dianhydride (2 molar equivalents) and an aromatic diamine (4 molar equivalents) are added to the compound and reacted to produce a low molecular weight imide compound having an aromatic diamine bonded to both terminals, that is, an oligomer. Step, then

(3) To the heat-resistant polyimide soluble in the organic solvent produced by the third step of adding an acid dianhydride (2 molar equivalents) and an aromatic diamine (1 molar equivalent) to a polycondensation reaction to produce a high molecular weight polyimide. In

As acid dianhydride, it contains (i) pyromellitic acid dianhydride (PMDA), (ii) benzophenonetetracarboxylic acid dianhydride (BTDA) and (iii) bicyclooctentetracarboxylic acid anhydride (BCD) Soluble in an organic solvent containing (i) 4,4'-diaminodiphenyl ether (4,4'-DADE) or (ii) 3,4'-diaminodiphenyl ether (mDADE) as aromatic diamine The said heat resistant polyimide which is phosphorus is provided.

In addition, the present invention is (1) reacted in the presence of a catalyst by reaction of an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalents), and the aromatic diamine is bonded to both acid anhydride groups of both acid dianhydrides A first step of producing a molecular weight imide compound, ie an oligomer,

(2) an agent that adds an acid dianhydride (4 molar equivalents) and an aromatic diamine (2 molar equivalents) to the compound and reacts to form a low molecular weight imide compound, i.e., an oligomer, having an acid dianhydride bonded to both terminals. Step 2, then

(3) To a heat-resistant polyimide soluble in an organic solvent produced by the third step of adding an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalent) to a polycondensation reaction to produce a high molecular weight polyimide. In

As acid dianhydride, it contains (i) pyromellitic acid anhydride (PMDA), (ii) biphenyltetracarboxylic acid dianhydride (BPDA) and (iii) bicyclooctentetracarboxylic acid anhydride (BCD) Soluble in an organic solvent containing (i) 4,4'-diaminodiphenyl ether (4,4'-DADE) or (ii) 3,4'-diaminodiphenyl ether (mDADE) as aromatic diamine The said heat resistant polyimide which is phosphorus is provided.

In addition, the present invention (1) reacted in the presence of a catalyst by the reaction of an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalents), wherein the aromatic diamine is bonded to both acid anhydride groups of the acid dianhydride. A first step of producing a low molecular weight imide compound, i.e. an oligomer,

(2) an agent that adds an acid dianhydride (4 molar equivalents) and an aromatic diamine (2 molar equivalents) to the compound and reacts to form a low molecular weight imide compound, i.e., an oligomer, having an acid dianhydride bonded to both terminals. Step 2, then

(3) To a heat-resistant polyimide soluble in an organic solvent produced by the third step of adding an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalent) to a polycondensation reaction to produce a high molecular weight polyimide. In

As acid dianhydride, it contains (i) pyromellitic acid dianhydride (PMDA), (ii) benzophenonetetracarboxylic acid dianhydride (BTDA) and (iii) bicyclooctentetracarboxylic acid anhydride (BCD) Soluble in an organic solvent containing (i) 4,4'-diaminodiphenyl ether (4,4'-DADE) or (ii) 3,4'-diaminodiphenyl ether (mDADE) as aromatic diamine The said heat resistant polyimide which is phosphorus is provided.

Further, according to the present invention,

(a) pyromellitic acid dianhydride (PMDA), (b) biphenyltetracarboxylic acid anhydride (BPDA) or benzophenonetetracarboxylic acid anhydride (BTDA), (c) bicyclooctentetracarboxylic acid di In the heat resistant polyimide which contains an anhydride (BCD) and (d) diaminodiphenyl ether (DADE) as a component, and is synthesize | combined by a three step addition reaction, it is soluble in an organic solvent,

In the first step, the reaction is carried out in the presence of a catalyst by the reaction of an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalents), and a low molecular weight imide having an aromatic diamine bonded to both acid anhydrides of the acid dianhydride. To produce a compound,

In the second step, an acid dianhydride (3 molar equivalents) and an aromatic diamine (1 molar equivalent) are added to the low molecular weight imide compound and reacted to form a low molecular weight imide compound having an acid dianhydride bonded to both terminals. Create it,

In the third step, an aromatic diamine (1 molar equivalent) is added to carry out the polycondensation reaction,

The heat resistant polyimide which is soluble in an organic solvent is provided.

Poly-imide of the present invention M _N (number average molecular weight) is in the range of,, M _W (weight average molecular weight), M _Z (Z average molecular weight) and shows a M _N / M _N ratio. Degree of polymerization (n) was expressed as M _W (measured value) / molecular weight (calculated value).

Of the polyimide film of the present invention, M _N is 10,000? 25,000, preferably 10,300? 24,500, More preferably, it is 10,460? 24,380, and the primary weight loss temperature is 390 ℃? 460 ° C., preferably 395 ° C.? 450 ° C., more preferably 401? It is the range of 435 degreeC.

The thermal decomposition start temperature (Tm) of the polyimide film of this invention is 530 degreeC? 570 ° C., preferably 535 ° C.? 560 ° C, more preferably 541 ° C? It is the range of 556 degreeC.

Soluble polyimide was synthesize | combined with the solvent which has the functionality containing bicyclooctene tetracarboxylic-acid anhydride (referred to as BCD) with PMDA, DADE, and BPDA. By adding BCD, the polyimide was further given a feature that was superior in solubility in an organic solvent as compared to PMDA and exhibited high adhesion properties.

Bis (3-amino-4-hydroxyphenyl) sulfone (HOAB-SO ₂ ) is an aromatic diamine which is functional in combination with PMDA and becomes a solvent soluble. And 9,9-bis (4-aminophenyl) fluorene (called FDA). Solvent solubility, functionality, ultra-heat resistance, and poly-e of PMDA-DADE-BPDA-BCD system are adopted by adopting reaction system with 1,3-bis (4-aminophenoxy) benzene (mTPE) which coexists with BCD to enhance adhesion. Mead was developed.

HOAB? SO ₂ Has the following formula.

[Formula 2]

The FDA has the formula

(3)

mTPE has the following formula.

[Formula 4]

1,3-bis (4-aminophenoxy) benzene (m-TPE)

This invention can be used as a polyimide which has functions, such as electrodeposition property, photosensitive property, and adhesiveness.

Moreover, this invention can be used as foamed polyimide apply | coated to the surface of a metal, a fiber, and a film to make a flame-retardant composite material.

The polyimide of this invention can be cast and heated and film-formed, and can be widely used for an electrical, an electronic component, a vehicle component, a semiconductor, etc. as a heat resistant film.

The present invention is a solvent-soluble polyimide having good storage stability, and is excellent in workability as compared with a conventional poor solvent polyimide. It can be used for various purposes such as building materials, high-temperature materials for home, (bottom of iron, wall interior, wall for microwave oven, flame retardant curtain), replacement of Teflon, use of expanded polyimide.

The polyimide containing PMDA, DADE, BPDA, and BCD has become possible new development by the characteristic of a functional polyimide, low temperature workability, and adhesiveness besides heat resistance property. The low temperature of around 330 degreeC of glass transition temperature is shown. As a result, it can be used as a functional polyimide as a composite material with metal glass resin.

PMDA, DADE, BPDA, BCD, FDA, and HOAB? SO ₂ The polyimide soluble in the organic solvent containing can be used as a functional polyimide with heat resistance. FDA has high pyrolysis and solubility characteristics. HOAB? SO ₂ Is a compound having an imide bond or an oxazole bond with an acid dianhydride, which imparts positive photosensitive properties, electrodeposition, and adhesiveness to the polyimide. Moreover, as an aromatic diamine component used by this invention, diamine, such as mTPE, diaminotoluene, 3, 5- diamino benzoic acid, and 3,3'- dimethylbentidine, can be contained.

The polyimide of the invention has good storage stability and can be prepared by removing the solvent by low temperature treatment.

The solvent-soluble polyimide of the present invention is a functional polyimide containing PMDA, DADE, BPDA and BCD. 4,4'-DADE can be substituted with mDADE.

In the present invention, mTPE can be added to the third step as an aromatic amine, and HOAB? SO ₂ May be added to any of the first, second, and third stages, PMDA may not be added in the third stage, DADE may not be added in the third stage, and BCD may be added in the second stage, or It can be added to the third stage, and mTPE can be added to the third stage. Polyimides soluble in organic solvents containing PMDA, DADE, BPDA and BCD have limitations in their production. PMDA produces a crosslinked polyimide in addition to the linear polyimide. Therefore, it is not preferable to use PMDA component in the 3rd step addition reaction of this invention, ie, for the 3rd step polymerization reaction. PMDA is added in the reaction of the first stage or the second stage.

Also, in the present invention, 9,9-bis (4-aminophenyl) fluorene (FDA) may be added in the first step, PMDA may not be added in the third step, and DADE may be added in the third step. It may not be added. In addition, BPDA or BTDA and 4,4'-DADE or mDADE can be added in the same step.

Diamines used in the present invention include bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) and 9,9-bis (4-aminophenyl) flu, which are combined with PMDA and exhibit solvability. It is a functional heat-resistant polyimide containing 1,3-bis (4-aminophenoxy) benzene (mTPE) which improves orene (FDA) and adhesiveness. (2,2,2) octo-7-ene-2,3,5,6-tetracarboxylic acid anhydride (BCD) is a tetracarboxylic acid having a similar structure to PMDA, and has excellent solubility compared to PMDA. And high adhesion characteristics.

Benzophenonetetracarboxylic acid dianhydride (BTDA) can be used instead of BPDA.

The polyimide composition of the present invention is soluble in organic solvents, preferably polar organic solvents. Examples of such polar organic solvents include N-methylpyrrolidone, N, N'-dimethylacetamide, sulfolane and N, N'-dimethylformamide. As the catalyst used in the present invention, a mixture of γ-valerolactone and pyridine, or a mixture of γ-valerolactone and N-methylmorpholine can be used.

The specific example of the manufacturing method of the polyimide of this invention is as follows.

Example  Manufacturing method corresponding to 1

(a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) were added in a polar organic solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to generate an oligomer having PMDA at both ends,

(b) reacting the oligomer produced in the first step with 2 molar equivalents of bicyclooctentetracarboxylic acid anhydride (BCD) and 4 molar equivalents of 3,4'-diaminodiphenyl ether (mDADE) to both terminals. A second step of using this mDADE phosphorus oligomer, and

(c) 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed and soluble in polar organic solvents. It consists of a 3rd step which synthesize | combines a phosphorus polyimide copolymer.

Example  Manufacturing method corresponding to 2

(a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) were added in a polar organic solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to generate an oligomer having PMDA at both ends,

(b) reacting the oligomer produced in the first step with 2 molar equivalents of bicyclooctentetracarboxylic acid anhydride (BCD) and 4 molar equivalents of 3,4'-diaminodiphenyl ether (mDADE) to both terminals. A second step of using this mDADE phosphorus oligomer, and

(c) 2 molar equivalents of benzophenonetetracarboxylic acid dianhydride (BTDA) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed and soluble in a polar organic solvent. It consists of a 3rd step which synthesize | combines a phosphorus polyimide copolymer.

In the reaction of Examples 1 and 2, (2 PMDA+HOAB?SO ₂ ) is reacted with the reaction of the first step to generate (PMDA-HOABSO ₂ -PMDA) which is an oligomer of both terminal PMDA.

In the reaction of the second step, (2BCD + 4mDADE) is added and reacted to produce (mDADE-BCD-mDADE) (PMDA-HOAB? SO ₂ -PMDA) (mDADE-BCD-mDADE), an oligomer of both terminal mDADEs. do.

In the reaction of the third step, (i) (2BPDA + mTPE) (Example 1) or (ii) (2BTDA + mTPE) (Example 2) is added and polycondensed to produce a high molecular weight solvent-soluble polyimide. do.

The obtained polyimide is

In Example 1, a polyimide having a repeating unit [(mDADE-BCD-mDADE) (PMDA-HOAB? SO ₂ -PMDA) (mDADE-BCD-mDADE) (BPDA-mTPE-BPDA)] _n is produced.

In Example 2, the repeating units [(mDADE-BCD-mDADE) (PMDA-HOAB? SO 2 -PMDA) (mDADE-BCD-mDADE) (BTDA-mTPE-BTDA)] is a polyimide having a _n.

The composition ratio of Example 1 is

(PMDA) ₂ (mDADE) ₄ (BCD) ₂ (HOAB? SO ₂ ) ₁ (mTPE) ₁ (BPDA) ₂ .

The composition ratio of Example 2 is

(PMDA) ₂ (mDADE) ₄ (BCD) ₂ (HOAB? SO ₂ ) ₁ (mTPE) ₁ (BTDA) ₂ .

Example  Manufacturing method corresponding to 3

(a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were dissolved in a polar organic solvent in the presence of a catalyst at 160? A first step of reacting at 200 ° C. to produce oligomers that are both terminal PMDA,

(b) 2 molar equivalents of the oligomer produced in the first step, bicyclooctentetracarboxylic acid anhydride (BCD), and 4 molar equivalents of 4,4'-diaminodiphenylether (4,4'-DADE) Reaction to give a second oligomer having 4,4'-DADE at both ends, and

(c) 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) are added to react, polycondensed to form a polar organic compound. And a third step of synthesizing the polyimide copolymer soluble in the solvent.

Example  Manufacturing method corresponding to 4

(a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were dissolved in a polar organic solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to generate an oligomer having PMDA at both ends,

(b) 2 molar equivalents of the oligomer produced in the first step, bicyclooctentetracarboxylic acid anhydride (BCD), and 4 molar equivalents of 4,4'-diaminodiphenylether (4,4'-DADE) Reaction to give a second oligomer having 4,4'-DADE at both ends, and

(c) 2 molar equivalents of benzophenonetetracarboxylic acid dianhydride (BTDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) are added to react, polycondensed to form a polar organic compound. And a third step of synthesizing the polyimide copolymer soluble in the solvent.

In the reactions of Examples 3 and 4, (2 PMDA+FDA) is reacted with the reaction of the first step to produce (PMDA-FDA-PMDA), which is an oligomer having PMDA bound to both amino groups of the FDA.

In the reaction of the second step, (2BCD + 4DADE) is added to the (PMDA-FDA-PMDA) produced in the first step and reacted to form (DADE-BCD-DADE)-( Create PMDA-FDA-PMDA)-(DADE-BCD-DADE).

In the reaction of the third step, (i) (2BPDA + HOAB? SO ₂ ) (Example 3) or (ii) (2BTDA + HOAB? SO ₂ ) (Example 4) is added and polycondensed to obtain a high molecular weight. Solvent soluble polyimide is produced.

In Example 3, a polyimide having a repeating unit [(DADE-BCD-DADE)-(PMDA-FDA-PMDA)-(DADE-BCD-DADE)-(BPDA-HOAB? SO ₂ -BPDA)] _n was produced. It became.

In Example 4, a polyimide having a repeating unit [(DADE-BCD-DADE)-(PMDA-FDA-PMDA)-(DADE-BCD-DADE)-(BTDA-HOAB? SO ₂ -BTDA)] _n is produced It became.

The composition ratio of Example 3 is

(PMDA) ₂ (DADE) ₄ (BCD) ₂ (HOAB? SO ₂ ) ₁ (FDA) ₁ (BPDA) ₂ .

The composition ratio of Example 4 is

(PMDA) ₂ (DADE) ₄ (BCD) ₂ (HOAB? SO ₂ ) ₁ (FDA) ₁ (BTDA) ₂ .

Example  Manufacturing method corresponding to 5

(a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were dissolved in a polar organic solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to generate imide oligomer having PMDA bound to both amino groups of the FDA,

(b) the imide oligomer produced in the first step, 2 molar equivalents of bicyclooctentetracarboxylic acid anhydride (BCD), 4 moles of 4,4'-diaminodiphenylether (4,4'-DADE) A second step of reacting an equivalent to form an imide oligomer having 4,4′-DADE bonded to both ends of the imide oligomer produced in the first step, and

(c) 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed and soluble in an organic polar solvent. It consists of a 3rd step which synthesize | combines a phosphorus polyimide copolymer.

Example  Manufacturing method corresponding to 6

(a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were dissolved in a polar organic solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to generate oligomers having PMDA bound to both amino groups of the FDA,

(b) 2 molar equivalents of the oligomer produced in the first step, bicyclooctentetracarboxylic acid anhydride (BCD), and 4 molar equivalents of 4,4'-diaminodiphenylether (4,4'-DADE) Reacting to form an imide oligomer having DADE bonded to both ends of the oligomer, and

(c) 2 molar equivalents of benzophenonetetracarboxylic acid dianhydride (BTDA) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added, reacted, polycondensed and soluble in a polar organic solvent. It consists of a 3rd step which synthesize | combines a phosphorus polyimide copolymer.

In the reaction of Examples 5 and 6, (2 PMDA+FDA) is reacted with the reaction of the first step to produce (PMDA-FDA-PMDA), which is an imide oligomer having PMDA bound to both amino groups of the FDA.

In the reaction of the second step, (2BCD + 4DADE) is added and reacted, and DADE binds to both ends of the imide oligomer produced in the first step, thereby making it an imide oligomer (DADE-BCD-DADE) (PMDA-FDA). -PMDA) (DADE-BCD-DADE)

In the reaction of the third step, (i) (2BPDA + mTPE) (Example 5) or (ii) (2BTDA + mTPE) (Example 6) is added and polycondensed to produce a high molecular weight solvent-soluble polyimide. do.

In Example 5, a polyimide having a repeating unit [(DADE-BCD-DADE)-(PMDA-FDA-PMDA)-(DADE-BCD-DADE)-(BPDA-mTPE-BPDA)] _n was produced.

In Example 6, a polyimide having a repeating unit [(DADE-BCD-DADE)-(PMDA-FDA-PMDA)-(DADE-BCD-DADE)-(BTDA-mTPE-BTDA)] _n was produced.

The composition ratio of Example 5 is

(PMDA) ₂ (DADE) ₄ (BCD) ₂ (mTPE) ₁ (FDA) ₁ (BTDA) ₂ .

The composition ratio of Example 6 is

(PMDA) ₂ (DADE) ₄ (BCD) ₂ (mTPE) ₁ (FDA) ₁ (BTDA) ₂ .

Example  Manufacturing method corresponding to 7

(a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) were added in an organic polar solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to generate an oligomer having PMDA at both ends,

(b) reacting the oligomer produced in the first step with 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 4 molar equivalents of 3,4'-diaminodiphenylether (mDADE) to react both ends. a second step using mDADE phosphorus oligomer, and

(c) 2 molar equivalents of bicyclooctenetetracarboxylic acid anhydride (BCD) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed to a polar organic solvent. And a third step of synthesizing the soluble polyimide copolymer.

In the reaction of Example 7, (2 PMDA+HOAB?SO ₂ ) is reacted with the reaction of the first step to generate (PMDA-HOABSO ₂ -PMDA) which is an oligomer of both terminal PMDA.

In the reaction of the second step, (2BPDA + 4mDADE) is added and reacted to generate (mDADE-BPDA-mDADE) (PMDA-HOAB? SO ₂ -PMDA) (mDADE-BPDA-mDADE), an oligomer of both terminal mDADEs. do.

In the reaction of the third step, (2BCD + mTPE) is added and polycondensed to produce a high molecular weight solvent-soluble polyimide.

The obtained polyimide is

In Example 7, a polyimide having a repeating unit [(mDADE-BPDA-mDADE)-(PMDA-HOAB? SO ₂ -PMDA)-(mDADE-BPDA-mDADE)-(BCD-mTPE-BCD)] _n was produced. do.

The composition ratio of Example 7 is

(PMDA) ₂ (mDADE) ₄ (BCD) ₂ (mTPE) ₁ (HOAB? SO ₂ ) ₁ (BPDA) ₂ .

Example  Manufacturing method corresponding to 8

(a) 2 molar equivalents of 4,4'-diaminodiphenylether (4,4'-DADE) and 1 molar equivalent of biphenyltetracarboxylic acid dianhydride (BPDA) in a polar organic solvent in the presence of a catalyst ? Reacting at 200 ° C. to produce an oligomer having 4,4′-DADE at both ends,

(b) reacting the oligomer produced in the first step with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ); A second step of using an oligomer whose both ends are PMDA, and

(c) 1 molar equivalent of bicyclooctentetracarboxylic acid anhydride (BCD) and 2 molar equivalents of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed to a polar organic solvent. And a third step of synthesizing the soluble polyimide copolymer.

In the reaction of Example 8, (BPDA + 2DADE) is reacted with the reaction of the first step to generate (DADE-BPDA-DADE) which is an oligomer of both terminal DADEs.

In the reaction of the second step, (2HOAB? SO ₂ + 4PMDA) is added and reacted to form (PMDA-HOAB? SO ₂ -PMDA) (DADE-BPDA-DADE) (PMDA-HOAB? SO), which is an oligomer of both terminal PMDA. ₂ -PMDA).

In the reaction of the third step, (BCD + 2mTPE) is added and polycondensed to produce a high molecular weight solvent-soluble polyimide.

The obtained polyimide is

In Example 8, polys having a repeating unit [(PMDA-HOAB? SO ₂ -PMDA)-(DADE-BPDA-DADE)-(PMDA-HOAB? SO ₂ -PMDA)-(mTPE-BCD-mTPE)] _n Produce a mead.

The composition ratio of Example 8 is

(PMDA) ₄ (DADE) ₂ (BCD) ₁ (mTPE) ₂ (HOAB? SO ₂ ) ₂ (BPDA) ₁ .

Example  Manufacturing Method corresponding to 9

(a) 2 molar equivalents of 4,4'-diaminodiphenyl ether (4,4'-DADE) and 1 molar equivalent of benzophenonetetracarboxylic acid dianhydride (BTDA) in a polar organic solvent in the presence of a catalyst ? Reacting at 200 ° C. to produce an oligomer having 4,4′-DADE at both ends,

(b) reacting the oligomer produced in the first step with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ); A second step of using an oligomer whose both ends are PMDA, and

(c) 1 molar equivalent of bicyclooctene tetracarboxylic acid anhydride (BCD) and 2 molar equivalents of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed to an organic polar solvent. And a third step of synthesizing the soluble polyimide copolymer.

In the reaction of Example 9, (BTDA + 2DADE) is reacted with the reaction of the first step to generate ([DADE]-[BTDA]-[DADE]), which are oligomers of both terminals of DADE.

In the reaction of the second step, (2HOAB? SO ₂ + 4PMDA) is added and reacted to obtain ([PMDA]-[HOAB? SO ₂ ]-[PMDA]), which is an oligomer of both terminal PMDA, [[DADE]-[BTDA ]-[DADE]) ([PMDA]-[HOAB? SO ₂ ]-[PMDA]).

In the reaction of the third step, (BCD + 2mTPE) is added and polycondensed to produce a high molecular weight solvent-soluble polyimide.

The obtained polyimide is

In Example 9, the repeating unit [([PMDA]-[HOAB? SO ₂ ]-[PMDA]) ([DADE]-[BTDA]-[DADE]) ([PMDA]-[HOAB? SO ₂ ]-[ PMDA]) ([mTPE]-[BCD]-[mTPE])] to produce a polyimide with _n .

[PMDA] is a residue of PMDA, [BCD] is a residue of BCD, [HOAB? SO ₂ ] is a residue of HOAB? SO ₂ , [DADE] is a residue of DADE, and [BTDA] is a residue of BTDA. It is a residue and [mTPE] is a residue of mTPE, It can also be expressed as

The composition ratio of Example 9 is

(PMDA) ₄ (DADE) ₂ (BCD) ₁ (mTPE) ₂ (HOAB? SO ₂ ) ₂ (BTDA) ₁ .

Example  Manufacturing Method corresponding to 10

(a) 2 molar equivalents of 4,4'-diaminodiphenylether (4,4'-DADE) and 1 molar equivalent of biphenyltetracarboxylic acid dianhydride (BPDA) in a polar organic solvent in the presence of a catalyst ? Reacting at 200 ° C to produce an imide oligomer having 4,4'-DADE bound to both acid anhydride groups of BPDA,

(b) the oligomer produced in the first step, 2 molar equivalents of pyromellitic acid dianhydride (PMDA), 1 molar equivalent of bicyclooctene tetracarboxylic acid anhydride (BCD) and bis (3-amino-4-hydride A second step of reacting 1 molar equivalent of oxyphenyl) sulfone (HOAB? SO ₂ ) with an imide oligomer wherein PMDA is bonded to one end of the oligomer produced in the first step and BCD is bonded to the other end. , And

(c) by reacting the oligomer produced in the second step with 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) and polycondensing to form a polyimide copolymer soluble in an organic polar solvent. The third step is to synthesize.

In the reaction of Example 10, (BPDA + 2DADE) is reacted with the reaction of the first step to generate (DADE-BPDA-DADE) which is an oligomer of both terminal DADEs.

In the two-step reaction, (2 PMDA+HOAB?SO ₂ + BCD) to the reaction was added and, both ends of the (PMDA) (DADE-BPDA- DADE) (PMDA-HOAB? SO 2 -BCD) oligomers of PMDA Create

In the reaction of the third step, (mTPE) is added and polycondensed to produce a high molecular weight solvent-soluble polyimide.

The polyimide obtained in Example 10 was a polyimide having a repeating unit [(PMDA)-(DADE-BPDA-DADE)-(PMDA-HOAB? SO ₂ -BCD)-(mTPE)] _n .

The composition ratio of Example 10 is

(PMDA) ₂ (DADE) ₂ (BCD) ₁ (mTPE) ₁ (HOAB? SO ₂ ) ₁ (BPDA) ₁ .

Example 1 of the present invention? The reaction of 10 is shown in Table 1 and Table 2 below.

In the examples, the molecular weight of the product was measured. The reaction solution was diluted with NMP and measured by high performance liquid chromatography (TOSO GPC: HL8 320) to determine M _N (number average molecular weight), M _W (weight average molecular weight), M _Z (Z average molecular weight) and M _N / M _N ratio. Degree of polymerization (n) was expressed as M _W (measured value) / molecular weight (calculated value).

The thermal decomposition initiation temperature (Tm) and the glass transition temperature (Tg) of the polyimide film were measured. Using a TG-DTA analyzer manufactured by MacScience, the temperature increase rate was 10 ° C / min, and room temperature? To 600 ℃ was measured in the N ₂ stream.

Example 1

Reaction product of (2 PMDA + HOAB ? SO ₂ ) (2 BCD +4 mDADE ) (2 BPDA + mTPE )

A 500-mL glass three-necked glass flask equipped with a stainless anchored stirrer was fitted with a tubular cooler equipped with a water separation trap. The flask was immersed in a silicon bath, heated and stirred while flowing nitrogen gas. A small amount of toluene added in the reaction liquid is refluxed and the resulting water remains in a water separation trap.

(1) 4.36 g (20 mmol) pyromellitic acid dianhydride (hereinafter referred to as PMDA) in a 500-neck three-necked flask made of glass, bis (3-amino-4-hydroxyphenyl) sulfone (hereinafter HOAB-SO ₂₎ 2.80 g (10 mmol), γ-valerolactone 1.2 g (12 mmol), pyridine (MW79) 2.4 g (14 mmol), N-methylpyrrolidone (hereinafter referred to as NMP) 80 g, toluene It was added in 15 g of solution. The reactor was immersed in a silicone oil bath and heated and stirred for 50 minutes at a silicone oil bath temperature of 180 ° C. and a rotation speed / minute (hereinafter abbreviated as rpm) 180 for 50 minutes while flowing nitrogen. Then, the reactor was removed from the silicon bath and air cooled for 20 minutes.

(2) 8.00 g (40 mmol) of 3,4'-diaminodiphenylether (mDADE), followed by 4.96 g (20 mmol) of bicyclooctentetracarboxylic acid anhydride (hereinafter referred to as BCD) 60 g of NMP Together, and again, the reactor was immersed in a silicone oil bath, 180 ° C., 180 rpm The reaction was carried out for 30 minutes, followed by air cooling for 20 minutes.

(3) 5.88 g (20 mmol) of BPDA were added, followed by 2.92 g (10 mmol) of mTPE together with 50 g of NMP. After stirring for 20 minutes at room temperature, the reactor was immersed in a silicone oil bath and 180 ° C, 180 r.p.m. Heated and stirred to initiate the polymerization reaction. Since the viscosity rose after reaction for 3 hours, NMP100g was added and it was made to react for 30 minutes again. A polyimide solution of 10% concentration was obtained. The part after reaction was diluted with NMP, and molecular weight and molecular distribution were measured by the high performance liquid chromatograph (GPC: HL8 320 by Toso Corporation).

Number average molecular weight (Mn) 23,200

Weight average molecular weight (Mw) 63,500

Z Average Molecular Weight (Mz) 130,640

Mw / Mn ratio 2.90

Single molecular weight (calculated) 2694

Degree of Polymerization (n) 24

After apply | coating a polyimide solution on the glass plate and stirring at 150 degreeC for 30 minutes, the polyimide film was peeled off from the glass plate, it fixed to the metal frame, it heated and stirred at 280 degreeC for 1 hour, and it was set as the sample.

Thermal analysis was performed using a TG-GTA apparatus manufactured by McScience. The primary weight loss temperatures were 405 ° C, Tm 545 ° C and Tg 330 ° C. By Example 1, a polyimide having a repeating unit [(mDADE-BCD-mDADE) (PMDA-HOAB? SO ₂ -PMDA) (mDADE-BCD-mDADE) (BPDA-mTPE-BPDA)] _n was produced.

[Example 2]

(2 PMDA + HOAB ? SO ₂ )(2 BCD +4 mDADE )(2 BTDA + mTPE )

(1) In a 500 ml glass three-necked flask, 6.48 g (30 mmol) of PMDA, 4.2 g (15 mmol) of HOAB-SO ₂ and 1.0 g of γ-valerolactone, 1.5 g of pyridine, 100 g of NMP, and toluene 30 g was added. After heating and stirring at 180 degreeC for 50 minutes, distribute | circulating nitrogen, after 30 minutes of air cooling,

(2) 12.0 g (60 mmol) of 3,4'-diaminodiphenyl ether (referred to as mDADE) were added, followed by 7.44 g (30 mmol) of BCD and 100 g of NMP, which were stirred at room temperature for 20 minutes. after,

(3) 8.82 g (30 mmol) of BTDA, then 4.38 g (10 mmol) of mTPE were added together with 86 g of NMP, and 180 r.p.m. It stirred for 20 minutes. The reactor was immersed in a silicon bath, 180 ° C., 180 r.p.m. Heated and stirred. After reaction for 3 hours, the mixture was cooled. The reaction solution obtained 15% concentration polyimide solution.

A part after reaction was taken, diluted with NMP, and the molecular weight by GPC was measured.

Mn (Number Average Molecular Weight) 14,300

Mw (weight average molecular weight) 80,410

Mz (Z average molecular weight) 195,800

Mw / Mn ratio 5.36

Single molecular weight (calculated) 2750

Degree of Polymerization (n) 29

The polyimide solution was apply | coated on the glass plate, it was set as 150 degreeC, it was made into a film, it was removed from the glass plate, fixed to the metal frame, and it heated and stirred at 280 degreeC for 1 hour. Thermal analysis was performed using a TG-GTA apparatus manufactured by McScience, and the primary weight loss temperature was 401 ° C, Tm 548 ° C, and Tg 330 ° C.

By Example 2, a polyimide having a repeating unit [(mDADE-BCD-mDADE) (PMDA-HOAB? SO ₂ -PMDA) (mDADE-BCD-mDADE) (BTDA-mTPE-BTDA)] _n was produced.

[Example 3]

(2 PMDA + FDA )(2 BCD +4 DADE )(2 BPDA + HOAB ? SO ₂ )

The operation was performed in the same manner as in Example 1. The sample was introduced into a three-necked flask equipped with a nitrogen inlet and a reflux reactor of toluene, and the nitrogen was passed through at 180 ° C and 180 r.p.m. The resulting water was removed out of the system while heating and stirring to reflux the toluene.

(1) To a glass container (500 ml capacity), 4.36 g (20 mmol) of PMDA, 3.49 g (10 mmol) of FDA, 1.2 g of gamma-valerolactone, 2.0 g of pyridine, 85 g of NMP, and 25 g of toluene are added. . 180 ° C., 180 r.p.m. In the nitrogen stream, it heated for 40 minutes, stirred, and air-cooled for 30 minutes.

(2) 8.00 g (40 mmol) of 4,4'-DADE, followed by 4.96 g (20 mmol) of BCD were added together with 81 g of NMP, followed by 180 r.p.m. Stirred for 30 minutes. Dipping in an oil bath, 180 ° C, 150 r.p.m. The mixture was heated for 30 minutes, stirred, and air cooled for 20 minutes.

(3) 5.88 g (20 mmol) of BPDA, 2.80 g (10 mmol) of HOAB? SO ₂ , and 80 g of NMP were added, followed by stirring for 20 minutes, followed by heating and stirring at 180 ° C. and 180 rpm to conduct a polymerization reaction. It was. The reaction was carried out for 3 hours 10 minutes. The polyimide concentration was 12%.

The polyimide solution was measured for GPC to determine the molecular weight.

Number average molecular weight (Mn) 13,800

Weight average molecular weight (Mw) 58,240

Z Average Molecular Weight (Mz) 211,400

Mw / Mn 4.22

Single molecular weight (calculated) 2941

Degree of Polymerization (n) 20

Thermal analysis of the polyimide film was performed.

The primary weight loss temperature was 418 ° C, Tm 546 ° C, and Tg 377 ° C.

By Example 3, a polyimide having a repeating unit [(DADE-BCD-DADE) (PMDA-FDA-PMDA) (DADE-BCD-DADE) (BPDA-HOAB? SO ₂ -BPDA)] _n was produced.

Example 4

(2 PMDA + FDA )(2 BCD +4 DADE )(2 BTDA + HOAB ? SO ₂ )

The operation was performed in the same manner as in Example 1.

(1) In a glass reactor, 4.36 g (20 mmol) of PMDA, 3.49 g (10 mmol) of FDA, 1.2 g of gamma-valerolactone, 2.0 g of pyridine, 85 g of NMP, and 25 g of toluene were added to give 180 r.p.m. Stirred at 180 ° C. and 180 r.p.m. Heated for 40 minutes, stirred, and then air cooled for 30 minutes,

(2) 8.00 g (40 mmol) of 4,4'-DADE, followed by 4.96 g (20 mmol) of BCD were added together with 85 g of NMP to give 180 r.p.m. The mixture was stirred for 30 minutes, and then 180 ° C and 150 r.p.m. After heating and stirring for 30 minutes, the mixture was air cooled for 20 minutes.

(3) 6.44 g (20 mmol) of BTDA, 2.80 g (10 mmol) of HOAB? SO ₂ , and 80 g of NMP were added, the mixture was stirred at 180 rpm at room temperature for 20 minutes, heated up, and heated at 180 ° C. and 180 rpm, Stirring accelerated the polymerization. The reaction was stopped at 3 hours 10 minutes. A polyimide solution having a concentration of 12% was obtained.

The molecular weight by GPC was measured.

Number average molecular weight (Mn) 13,800

Weight average molecular weight (Mw) 58,240

Z Average Molecular Weight (Mz) 211,400

Mw / Mn 4.23

Single molecular weight (calculated) 2969

Degree of polymerization (n) 19

Thermal analysis of the film was performed.

The primary weight loss temperature was 418 ° C, Tm 546 ° C, and Tg 377 ° C.

By Example 4, a polyimide having a repeating unit [(DADE-BCD-DADE) (PMDA-FDA-PMDA) (DADE-BCD-DADE) (BTDA-HOAB? SO ₂ -BTDA)] _n was produced.

[Example 5]

(2 PMDA + FDA )(2 BCD +4 DADE )(2 BPDA + mTPE )

The operation was performed in the same manner as in Example 1.

(1) In a glass three-necked flask, 5.88 g (20 mmol) of PMDA, 3.49 g (10 mmol) of FDA, 1.2 g of gamma -valerolactone, 2.0 g of pyridine, 80 g of NMP, and 25 g of toluene were added. 180 ° C., 180 r.p.m. After air heating and stirring for 40 minutes, air cooling was carried out for 20 minutes.

(2) 4,4'-DADE 8.00 g (40 mmol) was added and stirred and spaced apart, BCD 4.96g (20 mmol) was added together with NMP60g, and after stirring for 20 minutes, 180 degreeC, 180 degreeC rpm Heating and stirring were performed for 20 minutes and air cooled.

(3) 5.88 g (20 mmol) of BPDA were added, followed by addition of 2.92 g (10 mmol) of mTPE and 80 g of NMP, followed by stirring at room temperature for 40 minutes. The reactor was immersed in a silicon bath, 180 ° C., 180 r.p.m. Heated and stirred. The reaction was stopped at 5 hours. A polyimide solution having a concentration of 14% was obtained.

The molecular weight of the product was measured by GPC.

Number average molecular weight (Mn) 32,300

Weight average molecular weight (Mw) 77,740

Z Average Molecular Weight (Mz) 243,300

Mw / Mn 2.43

Single molecular weight (calculated) 3023

Degree of Polymerization (n) 26

Thermal analysis of the film was performed.

The primary weight loss temperature was 435 ° C and Tm 556 ° C, and Tg was recognized at 322 ° C and 459 ° C.

By Example 5, the polyimide having the repeating unit [([DADE]-[BCD]-[DADE]) (PMDA-FDA-PMDA) (DADE-BCD-DADE) (BPDA-mTPE-BPDA)] _n Generated.

[Example 6]

(2 PMDA + FDA )(2 BCD +4 DADE )(2 BTDA + mTPE )

The operation was performed in the same manner as in Example 1.

(1) 8.72 g (40 mmol) of PMDA, 6.98 g (20 mmol) of FDA, 2.0 g of γ-valerolactone, 4.0 g of pyridine, 140 g of NMP, and 50 g of toluene were added, and 180 ° C and 180 r.p.m. Then, it heated and stirred for 40 minutes in nitrogen stream, and air-cooled for 20 minutes.

(2) 16.00 g (80 mmol) of 4,4'-DADE were added, and then 9.92 g (40 mmol) of BCD was added with 80 g of NMP, and it stirred and dissolved. Then, 20 minutes, 180 degreeC, 180 r.p.m. Heated, stirred, and air-cooled for 20 minutes.

(3) 12.88 g (40 mmol) of BTDA were added, followed by 5.84 g (20 mmol) of mTPE was added together with 82 g of NMP. After stirring at room temperature for 20 minutes, 180 ° C., 180 r.p.m. The mixture was heated and stirred to carry out the reaction for 2 hours 30 minutes. The viscosity in the bubble viscometer was 17.6. A polyimide solution of 20% concentration was obtained. This solution has a high viscosity, and if left overnight, it becomes gelled. Therefore, it was preserved by diluting with a solvent.

The molecular weight by GPC was measured.

Number average molecular weight (Mn) 24,380

Weight average molecular weight (Mw) 84,460

Z Average Molecular Weight (Mz) 244,300

Mw / Mn 3.46

Single molecular weight (calculated) 3019

Degree of polymerization (n) 28

Thermal analysis was performed.

The primary weight loss temperatures were 431 ° C and Tm 541 ° C, and Tg was found to be 425 ° C and 455 ° C.

By Example 6, a polyimide having a repeating unit [(DADE-BCD-DADE) (PMDA-FDA-PMDA) (DADE-BCD-DADE) (BTDA-mTPE-BTDA)] _n was produced.

[Example 7]

(2 PMDA + HOAB ? SO ₂ )(2 BPDA +4 mDADE )(2 BCD + mTPE )

(1) A 500-mL glass three-necked flask equipped with an anchor stirrer made of stainless steel is used. Equipped with a tubular cooler with a water separation trap. Nitrogen is introduced from one inlet to reflux the toluene, and the produced water is removed by azeotroping with toluene to collect the water generated in the water separation trap.

In the reactor, HOSO ₂ AB 2.85 g (10 mmol) was added together with a solution of 4.36 g (20 mmol) PMDA and 1.2 g of gamma -valerolactone, 2.0 g pyridine, 80 g NMP, 25 g toluene, Dissolve in stirring.

180 ° C., 180 r.p.m. while circulating nitrogen. Heated and stirred. Heated for 50 minutes, after 20 minutes of air cooling,

(2) 8.00 g (40 mmol) of 3,4'-diaminodiphenyl ether (mDADE) are added, followed by 5.88 g (20 mmol) of BPDA together with 60 g of NMP. After stirring for 10 minutes, 180 ° C., 180 r.p.m. Heat for 30 minutes. After 20 minutes of air cooling,

(3) 4.96 g (20 mmol) of BCD were added, followed by 2.92 g (10 mmol) of mTPE together with 50 g of NMP. After stirring for 10 minutes, 180 ° C., 180 r.p.m. Heated and stirred. Since the viscosity improved after reaction for 3 hours, 100 g of NMP was added. Again, for 30 minutes, 180 ° C., 180 r.p.m. Reaction was stopped and the reaction was stopped. It is a polyimide solution of 10% concentration.

The molecular weight by GPC was measured.

Number average molecular weight (Mn) 10,460

Weight average molecular weight (Mw) 24,260

Z Average Molecular Weight (Mz) 43,900

Mw / Mn 2.32

Single molecular weight (calculated) 2694

Degree of Polymerization (n) 9

The thermal reduction analysis showed a primary weight loss temperature of 409 ° C, Tm 549 ° C and Tg 236 ° C.

By Example 7, a polyimide with a repeating unit [(mDADE-BPDA-mDADE) (PMDA-HOAB? SO ₂ -PMDA) (mDADE-BPDA-mDADE) (BCD-mTPE-BCD)] _n was produced.

[Example 8]

( BPDA +2 DADE )(4 PMDA +2 HOAB ? SO ₂ ) ( BCD +2 mTPE )

It operated in the same manner as in Example 7.

(1) In a glass container (500 mL capacity), 2.94 g (10 mmol) of BPDA, 4.00 g (20 mmol) of 4,4'-DADE were added thereto, 1.2 g of gamma -valerolactone, 2.0 g of pyridine, 83 g of NMP and 25 g of toluene were added, and it stirred and dissolved. Then, 180 ° C., 180 r.p.m. After heating and stirring for 40 minutes, the mixture was air cooled for 20 minutes.

(2) Next, 8.72 g (40 mmol) PMDA was added, and then 5.64 g (10 mmol) of HOAB-SO ₂ was added together with NMP 80 g, followed by stirring at 180 rpm for 20 minutes, 180 ° C., 180 It heats and stirred for 30 minutes at rpm. Then air cooled for 20 minutes,

(3) 5.84 g (20 mmol) of mTPE and 2.48 g (10 mmol) of BCD were added together with 80 g of NMP, followed by stirring for 10 minutes, followed by 180 ° C and 180 r.p.m. Heated and stirred. After 3 hours, stirring was carried out at 130 r.p.m. Drop at 180 ° C. for 130 minutes and 130 r.p.m. Heated and stirred. A polyimide varnish having a concentration of 12% was obtained.

The molecular weight was measured by GPC.

Number average molecular weight (Mn) 16,110

Weight average molecular weight (Mw) 123,990

Z Average Molecular Weight (Mz) 214,450

Mw / Mn 6.46

Single molecular weight (calculated) 2960

Degree of Polymerization (n) 42

Thermal analysis of the film was performed.

It was primary weight loss temperature 411 degreeC, Tm 542 degreeC, and Tg 361 degreeC.

[Example 9]

( BTDA +2 DADE )(4 PMDA +2 HOAB ? SO ₂ ) ( BCD +2 mTPE )

It operated in the same manner as in Example 7.

(1) 3.22 g (10 mmol) of BTDA, 4.00 g (20 mmol) of 4,4'-DADE were added, and 1.2 g of gamma-valerolactone, 2.0 g of pyridine, 85 g of NMP, and 24 g of toluene were added thereto. 180 ° C., 180 rpm The reaction was carried out while stirring. Then, 180 ° C., 180 r.p.m. The mixture was cooled with air for 20 minutes in a nitrogen stream for 40 minutes, after heating and stirring.

(2) Next, 8.72 g (40 mmol) of PMDA was added, and then 5.64 g (20 mmol) of HOAB-SO ₂ were added together with NMP 80 g and stirred for 20 minutes.

(3) 5.84 g (20 mmol) of mTPE, followed by 2.48 g (10 mmol) of BCD and NMP 80 g were added together, stirred at room temperature for 20 minutes, and 180 ° C, 180 r.p.m. The mixture was heated and stirred to carry out a polymerization reaction. An increase in viscosity was recognized at 2 hours 55 minutes. Rotation speed 180 r.p.m. At 130 r.p.m. It was dropped to and heated and stirred for 35 minutes again. A polyimide varnish having a concentration of 12% was obtained.

The molecular weight was measured by GPC.

Number average molecular weight (Mn) 15,250

Weight average molecular weight (Mw) 98,000

Z Average Molecular Weight (Mz) 244,970

Mw / Mn 6.42

Single molecular weight (calculated) 2932

Degree of polymerization (n) 33

Thermal analysis of the film was performed.

The primary weight loss temperature was 408 ° C, Tm 544 ° C, and Tg 332 ° C.

According to Example 9, the polyimide having the repeating unit [(PMDA-HOAB? SO ₂ -PMDA) (DADE-BTDA-DADE) (PMDA-HOAB? SO ₂ -PMDA) (mTPE-BCD-mTPE)] _n Generated.

[Example 10]

( BPDA +2 DADE )(2 PMDA + BCD + HOAB ? SO ₂ ) ( mTPE )

It operated in the same manner as in Example 7.

(1) In a 500 ml glass reactor, 2.94 g (10 mmol) of BPDA, 4.0 g (20 mmol) of 4,4'-DADE and 1.2 g of γ-valerolactone, 2.0 g of pyridine, 80 g of NMP, toluene 25 g is added and stirred, 180 ° C., 180 rpm The mixture was heated for 40 minutes, stirred and air-cooled for 20 minutes while flowing nitrogen.

(2) Then, 4.36 g (20 mmol) of PMDA, followed by 2.48 g (10 mmol) of BCD and 2.80 g (10 mmol) of HOSO ₂ AB were added together with 60 g of NMP, followed by stirring at room temperature for 20 minutes, followed by 180 It heated and stirred at 20 degreeC and 180 rpm for 20 minutes. After 10 minutes of air cooling,

(3) 2.92 g (10 mmol) and NMP30 g of mTPE were added, and after stirring for 10 minutes, it was 180 degreeC and 180 r.p.m. Then, it heated and stirred in nitrogen and performed the polymerization reaction. The reaction was stopped at 4 hours 40 minutes. A 11% polyimide solution was obtained.

The molecular weight of the varnish by GPC was measured.

Number average molecular weight (Mn) 24,030

Weight average molecular weight (Mw) 71,120

Z Average Molecular Weight (Mz) 158,880

Mw / Mn 3.17

Single molecular weight (calculated) 1695

Degree of Polymerization (n) 42

Thermal analysis of the film was performed.

The primary weight loss temperature was 413 ° C, Tm 552 ° C, Tg 354 ° C and 418 ° C.

In Example 10, a polyimide having a repeating unit [(PMDA) (DADE-BPDA-DADE) (PMDA-HOAB? SO ₂ -BCD) (mTPE)] _n was produced.

[Referential Example 1]

(2BPDA + HOAB? SO ₂ ) (2BCD + 4DADE) (2BTDA + mTPE)

(1) It operated similarly to Example 1. The glass reactor, and the BPDA 5.88 g (20 _{mmol), HOAB? SO 2 2.80 g} (10 mmol) was added to 78 g NMP, adding an additional lactone 1.2 g, 2.0 g pyridine in a ballet γ-. 25 g of toluene was added to this and it was set as the solution.

180 ° C., 180 r.p.m. while circulating nitrogen. Heating and stirring were performed for 50 minutes, and air cooled for 20 minutes.

(2) Next, 8.00 g (40 mmol) of 4,4'-DADE was added, 4.96 g (20 mmol) of BCD was further added with 66 g of NMP, and it stirred at room temperature for 20 minutes, and set it as the solution. next,

(3) 6.44 g (20 mmol) of BTDA are added, and 2.92 g (10 mmol) of mTPE are added with NMP80g, and it is set as a homogeneous liquid for 20 minutes of stirring at room temperature. 180 ° C., 180 r.p.m. Heated and stirred. The reaction was carried out for 3 hours. A polyimide solution of 15% concentration was obtained.

The molecular weight of the polyimide solution was measured by GPC.

Number average molecular weight (Mn) 9,620

Weight average molecular weight (Mw) 51,740

Z Average Molecular Weight (Mz) 121,190

Mw / Mn 5.38

Single molecular weight (calculated) 3103

Degree of Polymerization (n) 17

Thermal analysis of the film was performed.

Primary weight loss temperature was 402 degreeC, Tm 551 degreeC, and Tg 284 degreeC.

By Reference Example 1, a polyimide having a repeating unit [(DADE-BCD-DADE) (BPDA-HOAB? SO ₂ -BPDA) (DADE-BCD-DADE) (BTDA-mTPE-BTDA)] _n was produced.

[Reference Example 2]

(2 BPDA + HOAB ? SO ₂ )(2 BCD +4 DADE )(2 BPDA + FDA )

Synthesis was carried out in the same manner as in Example 1.

(1) Into a 500 ml glass reactor, 5.88 g (20 mmol) of BPDA, 2.80 g (10 mmol) of HOAB-SO ₂ , 1.2 g of γ-valerolactone, 2.0 g of pyridine, 80 g of NMP, and 25 g of toluene were added. do.

In an oil bath, 180 ° C., 180 r.p.m. The mixture was heated for 40 minutes, stirred, and air cooled for 20 minutes.

(2) 8.00 g (40 mmol) of 4,4'-DADE was added, followed by 4.96 g (20 mmol) of BCD was added together with 60 g of NMP. After stirring for 20 minutes, 180 ° C., 180 r.p.m. Heating and stirring were performed for 20 minutes. Then, air cooling was performed for 20 minutes.

(3) 5.88 g (20 mmol) BPDA and 3.49 g (10 mmol) FDA were added along with 80 g of NMP. After stirring the homogeneous reaction solution for 20 minutes, 180 degreeC, 180 r.p.m. The mixture was heated and stirred in a nitrogen stream. The reaction was stopped at 5 hours. A polyimide solution having a concentration of 14% was obtained.

By thermal analysis of GPC

Number Average Molecular Weight (Mn) 34,990

Weight average molecular weight (Mw) 109,200

Z Average Molecular Weight (Mz) 202,312

Mw / Mn 3.12

Single molecular weight (calculated) 3103

Degree of polymerization (n) 35

Thermal analysis of the film was performed.

The primary weight loss temperature was 435 ° C and Tm 556 ° C, and Tg was found to be 322 ° C and 459 ° C.

By Reference Example 2, a polyimide having a repeating unit [(DADE-BCD-DADE) (BPDA-HOAB? SO ₂ -BPDA) (DADE-BCD-DADE) (BPDA-mTPE-BPDA)] _n was produced.

Claims (28)

(a) pyromellitic acid dianhydride (PMDA), (b) biphenyltetracarboxylic acid anhydride (BPDA), (c) bicyclooctentetracarboxylic acid anhydride (BCD) and (d) diaminodiphenyl In a heat-resistant polyimide soluble in an organic solvent containing ether (DADE) as a component, the polyimide is synthesized by a three step addition reaction, and in the first step, low polyimide is reacted with an acid dianhydride and an aromatic diamine. A molecular weight imide compound is produced, and in the second step, an acid dianhydride and an aromatic diamine are further reacted with the low molecular weight imide compound generated in the first step to produce a low molecular weight imide compound. 530 degreeC which consists of performing a sum reaction? Heat resistant polyimide soluble in organic solvents having a pyrolysis initiation temperature in the range of 570 ° C. The method of claim 1,
The aromatic diamines are bis (3-amino-4-hydroxyphenyl) sulfone (HOAB-SO ₂ ), 9,9-bis (4-aminophenyl) fluorene (FDA) and 1,3-bis (4-amino The said heat resistant polyimide which further contains the component chosen from the group which consists of phenoxy) benzene (mTPE). The method of claim 1,
In the first step, PMDA is used as the acid dianhydride, BCD is used as the acid dianhydride in the second step, DADE is used as the aromatic diamine, and BPDA is used as the acid dianhydride in the third step. Heat resistant polyimide. (a) pyromellitic acid dianhydride (PMDA), (b) benzophenonetetracarboxylic acid dianhydride (BTDA), (c) bicyclooctentetracarboxylic acid anhydride (BCD) and (d) diaminodiphenyl In a heat-resistant polyimide soluble in an organic solvent containing ether (DADE) as a component, the polyimide is synthesized by a three step addition reaction, and in the first step, low polyimide is reacted with an acid dianhydride and an aromatic diamine. A molecular weight imide compound is produced, and in the second step, an acid dianhydride and an aromatic diamine are further reacted with the low molecular weight imide compound generated in the first step to produce a low molecular weight imide compound. 530 degreeC which consists of performing a sum reaction? Heat resistant polyimide soluble in organic solvents having a pyrolysis initiation temperature in the range of 570 ° C. The method of claim 4, wherein
The aromatic diamines are bis (3-amino-4-hydroxyphenyl) sulfone (HOAB-SO ₂ ), 9,9-bis (4-aminophenyl) fluorene (FDA) and 1,3-bis (4-amino The said heat resistant polyimide which further contains the component chosen from the group which consists of phenoxy) benzene (mTPE). The method of claim 4, wherein
In the first step, PMDA is used as the acid dianhydride, BCD is used as the acid dianhydride in the second step, DADE is used as the aromatic diamine, and BTDA is used as the acid dianhydride in the third step. Heat resistant polyimide. (1) a first step of reacting an acid dianhydride (2 molar equivalents) with an aromatic diamine (1 molar equivalent) in the presence of a catalyst to produce a low molecular weight imide compound having an acid dianhydride bonded to both amino groups of the aromatic diamine; ,
(2) a second step of adding an acid dianhydride (2 molar equivalents) and an aromatic diamine (4 molar equivalents) to the compound and reacting to produce a low molecular weight imide compound having aromatic diamines bonded to both ends thereof, and then ,
(3) By the third step of adding an acid dianhydride (2 molar equivalents) and an aromatic diamine (1 molar equivalent) to the imide compound produced in (2) and polycondensing to produce a high molecular weight polyimide. In the heat resistant polyimide soluble in the resulting organic solvent,
The acid dianhydride contains pyromellitic acid dianhydride (PMDA), biphenyltetracarboxylic acid dianhydride (BPDA) and bicyclooctene tetracarboxylic acid anhydride (BCD), and the aromatic diamine is diaminodiphenyl It contains ether (DADE), and is 530 degreeC? The heat resistant polyimide soluble in organic solvents having a pyrolysis onset temperature in the range of 570 ° C. The method of claim 1,
The aromatic diamines are bis (3-amino-4-hydroxyphenyl) sulfone (HOAB-SO ₂ ), 9,9-bis (4-aminophenyl) fluorene (FDA) and 1,3-bis (4-amino The said heat resistant polyimide which further contains the component chosen from the group which consists of phenoxy) benzene (mTPE). The method of claim 1,
In the first step, PMDA is used as the acid dianhydride, BCD is used as the acid dianhydride in the second step, DADE is used as the aromatic diamine, and BPDA is used as the acid dianhydride in the third step. Heat resistant polyimide. (1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) were added in an organic polar solvent in the presence of a catalyst at 160? A first step of reacting at 200 ° C. to produce a low molecular weight imide compound having PMDA bound to both amino groups of HOAB? SO ₂ ,
(2) To the low molecular weight imide compound produced in the first step, 2 molar equivalents of bicyclooctentetracarboxylic acid anhydride (BCD) and 4 molar equivalents of 3,4'-diaminodiphenyl ether (mDADE) were added. Reacting to obtain a low molecular weight imide compound having mDADE bonded to both ends thereof, and
(3) 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 1 mole of 1,3-bis (4-aminophenoxy) benzene (mTPE) to the low molecular weight imide compound produced in the second step The reaction is carried out by the addition of an equivalent, followed by polycondensation to synthesize a polyimide copolymer soluble in an organic polar solvent.
Formula (I):
[(mDADE-BCD-mDADE)-(PMDA-HOAB? SO ₂ -PMDA)-(mDADE-BCD-mDADE)-(BPDA-mTPE-BPDA)] _n
Wherein the bond between the compounds is an imide bond
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by. (1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) were added in an organic polar solvent in the presence of a catalyst at 160? A first step of reacting at 200 ° C. to produce a low molecular weight imide compound having PMDA bound to both amino groups of HOAB? SO ₂ ,
(2) To the low molecular weight imide compound produced in the first step, 2 molar equivalents of bicyclooctentetracarboxylic acid anhydride (BCD) and 4 molar equivalents of 3,4'-diaminodiphenyl ether (mDADE) were added. Reacting to obtain a low molecular weight imide compound having mDADE bonded to both ends thereof, and
(3) 2 molar equivalents of benzophenonetetracarboxylic acid dianhydride (BTDA) and 1 mole of 1,3-bis (4-aminophenoxy) benzene (mTPE) to the low molecular weight imide compound produced in the second step The reaction is carried out by the addition of an equivalent, followed by polycondensation to synthesize a polyimide copolymer soluble in an organic polar solvent.
Formula (II) below:
[(mDADE-BCD-mDADE)-(PMDA-HOAB? SO ₂ -PMDA)-(mDADE-BCD-mDADE)-(BTDA-mTPE-BTDA)] _n
Wherein the bond between the compounds is an imide bond
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by. (a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were added in an organic polar solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to produce a low molecular weight imide compound having PMDA bound to both amino groups of the FDA,
(b) 2 molar equivalents of bicyclooctaentetetracarboxylic acid dianhydride (BCD), 4,4'-diaminodiphenyl ether (4,4'-DADE) to the low molecular weight imide compound produced in the first step ) A second step of reacting 4 molar equivalents to form a low molecular weight imide compound having 4,4′-DADE bound to both ends thereof, and
(c) 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) are added to react, polycondensed to give an organic polarity. The following formula (III) comprising the third step of synthesizing a polyimide copolymer soluble in a solvent:
[(DADE-BCD-DADE)-(PMDA-FDA-PMDA) (DADE-BCD-DADE) (BPDA-HOAB? SO ₂ -BPDA)] _n
Wherein the bond between the compounds is an imide bond
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by. (a) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were added in an organic polar solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to produce a low molecular weight imide compound having PMDA bound to both amino groups of the FDA,
(b) 2 molar equivalents of bicyclooctenetetracarboxylic acid dianhydride (BCD), 4,4'-diaminodiphenyl ether (4,4'-DADE), to the low molecular weight imide compound produced in the first step A second step of reacting 4 molar equivalents to form a low molecular weight imide compound having 4,4′-DADE bound to both ends thereof, and
(c) 2 molar equivalents of benzophenonetetracarboxylic acid dianhydride (BTDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) are added to react, polycondensed to give an organic polarity. Formula (IV) consisting of the third step of synthesizing a polyimide copolymer soluble in a solvent:
[(DADE-BCD-DADE)-(PMDA-FDA-PMDA)-(DADE-BCD-DADE)-(BTDA-HOAB? SO ₂ -BTDA)] _n
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by (wherein the bond between the compounds is an imide bond). (1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were added in an organic polar solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to produce a low molecular weight imide compound having PMDA bound to both amino groups of the FDA,
(2) Low molecular weight imide compound produced in the first step, 2 molar equivalents of bicyclooctentetracarboxylic acid anhydride (BCD), 4,4'-diaminodiphenyl ether (4,4'-DADE) A second step of reacting 4 molar equivalents to form a low molecular weight imide compound having 4,4′-DADE bound to both ends thereof, and
(3) 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) to the low molecular weight imide compound produced in the second step The reaction is carried out by addition, polycondensation, and a third step of synthesizing a polyimide copolymer soluble in an organic polar solvent.
Formula (V):
[(DADE-BCD-DADE)-(PMDA-FDA-PMDA)-(DADE-BCD-DADE)-(BPDA-mTPE-BPDA)] _n
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by (wherein the bond between the compounds is an imide bond). (1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of 9,9-bis (4-aminophenyl) fluorene (FDA) were added in an organic polar solvent in the presence of a catalyst at 160? Reacting at 200 ° C. to produce a low molecular weight imide compound having PMDA bonded to both amino groups of fluorene,
(2) 2 molar equivalents of the oligomer produced in the first step and bicyclooctentetracarboxylic acid anhydride (BCD) and 4 molar equivalents of 4,4'-diaminodiphenylether (4,4'-DADE) Reacting to obtain a low molecular weight imide compound having 4,4'-DADE bonded to both ends thereof, and
(3) 2 molar equivalents of benzophenonetetracarboxylic acid dianhydride (BTDA) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed and soluble in an organic polar solvent. It consists of the 3rd step which synthesize | combines phosphorus polyimide copolymer
Formula (VI):
[(DADE-BCD-DADE)-(PMDA-FDA-PMDA)-(DADE-BCD-DADE)-(BTDA-mTPE-BTDA)] _n
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by (wherein the bond between the compounds is an imide bond). (1) 2 molar equivalents of pyromellitic acid dianhydride (PMDA) and 1 molar equivalent of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ) were added in an organic polar solvent in the presence of a catalyst at 160? A first step of reacting at 200 ° C. to produce a low molecular weight imide compound having PMDA bound to both amino groups of HOAB? SO ₂ ,
(2) The oligomer produced in the first step is reacted with 2 molar equivalents of biphenyltetracarboxylic acid dianhydride (BPDA) and 4 molar equivalents of 3,4'-diaminodiphenyl ether (mDADE) to each terminal. a second step of forming a low molecular weight imide compound bonded with mDADE, and
(3) 2 molar equivalents of bicyclooctenetetracarboxylic acid dianhydride (BCD) and 1 molar equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed to an organic polar solvent. And a third step of synthesizing the soluble polyimide copolymer.
Formula (i):
[(mDADE-BPDA-mDADE)-(PMDA-HOAB? SO ₂ -PMDA)-(mDADE-BPDA-mDADE)-(BCD-mTPE-BCD)] _n
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by (wherein the bond between the compounds is an imide bond). (1) a first step of reacting an acid dianhydride (2 molar equivalents) with an aromatic diamine (1 molar equivalent) in the presence of a catalyst to produce a low molecular weight imide compound having an acid dianhydride bonded to both amino groups of the aromatic diamine; ,
(2) a second step of adding an acid dianhydride (2 molar equivalents) and an aromatic diamine (4 molar equivalents) to the compound and reacting to produce a low molecular weight imide compound having aromatic diamines bonded to both ends thereof, and then ,
(3) To the heat-resistant polyimide soluble in the organic solvent produced by the third step of adding an acid dianhydride (2 molar equivalents) and an aromatic diamine (1 molar equivalent) to a polycondensation reaction to produce a high molecular weight polyimide. In
As the acid dianhydride, pyromellitic acid dianhydride (PMDA), benzophenonetetracarboxylic acid dianhydride (BTDA) and bicyclooctene tetracarboxylic acid anhydride (BCD) are contained, and diaminodiphenyl ether as aromatic diamine The said heat resistant polyimide soluble in the organic solvent containing (DADE). The method of claim 8,
The heat-resistant polyimide in which the aromatic diamine contains ingredients selected from the group consisting of HOAB? SO _2, FDA and mTPE. The method of claim 8,
In the first step, PMDA is used as the acid dianhydride, BCD is used as the acid dianhydride in the second step, DADE is used as the aromatic diamine, and BTDA is used as the acid dianhydride in the third step. Heat resistant polyimide. (1) by reacting acid dianhydride (1 molar equivalent) with aromatic diamine (2 molar equivalents) in the presence of a catalyst, a low molecular weight imide compound having an aromatic diamine bonded to both acid anhydride groups of an acid dianhydride The first step of producing,
(2) a second step of adding a acid dianhydride (4 molar equivalents) and an aromatic diamine (2 molar equivalents) to the compound and reacting to produce a low molecular weight imide compound having an acid dianhydride bonded to both terminals; next,
(3) a third step of adding a polyimide of an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalents) to produce a high molecular weight polyimide;
In the heat-resistant polyimide soluble in the organic solvent produced by
The acid dianhydride contains pyromellitic acid dianhydride (PMDA), biphenyltetracarboxylic acid dianhydride (BPDA) and bicyclooctentetracarboxylic acid anhydride (BCD), and the aromatic diamine is diaminodiphenyl ether The said heat resistant polyimide soluble in the organic solvent containing (DADE). 21. The method of claim 20,
The diamine is mTPE, or bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂₎ adding a heat resistant polyimide containing as the. (1) Reacting in the presence of a catalyst by reaction of an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalent), a low molecular weight imide compound having an aromatic diamine bonded to both acid anhydride groups of an acid dianhydride The first step of producing,
(2) a second step of adding a acid dianhydride (4 molar equivalents) and an aromatic diamine (2 molar equivalents) to the compound and reacting to produce a low molecular weight imide compound having an acid dianhydride bonded to both terminals; next,
(3) To a heat-resistant polyimide soluble in an organic solvent produced by the third step of adding an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalent) to a polycondensation reaction to produce a high molecular weight polyimide. In
As the acid dianhydride, pyromellitic acid dianhydride (PMDA), benzophenonetetracarboxylic acid dianhydride (BTDA) and bicyclooctene tetracarboxylic acid anhydride (BCD) are contained, and diaminodiphenyl ether as aromatic diamine The said heat resistant polyimide soluble in the organic solvent containing (DADE). The method of claim 1,
A heat resistant polyimide wherein said diamine is also mTPE, or bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ). (1) 2 molar equivalents of 4,4'-diaminodiphenyl ether (4,4'-DADE) and 1 molar equivalent of biphenyltetracarboxylic acid dianhydride (BPDA) were added in an organic polar solvent in the presence of a catalyst. ? Reacting at 200 ° C to produce a low molecular weight imide compound having 4,4'-DADE bound to both acid anhydride groups of BPDA;
(2) The oligomer produced in the first step is reacted with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ), A second step of forming a low molecular weight imide compound having PMDA bonded to both ends thereof, and
(3) 1 molar equivalent of bicyclooctene tetracarboxylic acid anhydride (BCD) and 2 molar equivalents of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed to an organic polar solvent. Consisting of a third step of synthesizing a soluble polyimide copolymer,
Formula (VI):
[(PMDA-HOAB? SO ₂ -PMDA)-(DADE-BPDA-DADE)-(PMDA-HOAB? SO ₂ -PMDA)-(mTPE-BCD-mTPE)] _n
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by (wherein the bond between the compounds is an imide bond). (a) 2 molar equivalents of 4,4'-diaminodiphenylether (4,4'-DADE) and 1 molar equivalent of benzophenonetetracarboxylic acid dianhydride (BTDA) in an organic polar solvent in the presence of a catalyst ? A first step of reacting at 200 ° C. to produce a low molecular weight imide compound having 4,4′-DADE bound to both acid anhydride groups of BTDA,
(b) reacting the oligomer produced in the first step with 4 molar equivalents of pyromellitic acid dianhydride (PMDA) and 2 molar equivalents of bis (3-amino-4-hydroxyphenyl) sulfone (HOAB? SO ₂ ); A second step of forming a low molecular weight imide compound having PMDA bonded to both ends thereof, and
(c) 1 molar equivalent of bicyclooctene tetracarboxylic acid anhydride (BCD) and 2 molar equivalents of 1,3-bis (4-aminophenoxy) benzene (mTPE) are added to react, polycondensed to an organic polar solvent. And a third step of synthesizing the soluble polyimide copolymer.
Formula (VI):
[(PMDA-HOAB? SO ₂ -PMDA)-(DADE-BTDA-DADE)-(PMDA-HOAB? SO ₂ -PMDA)-(mTPE-BCD-mTPE)] _n
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by (wherein the bond between the compounds is an imide bond). (a) pyromellitic acid dianhydride (PMDA), (b) biphenyltetracarboxylic acid anhydride (BPDA), (c) bicyclooctentetracarboxylic acid anhydride (BCD) and (d) diaminodiphenyl In the heat-resistant polyimide which contains an ether (DADE) as a component and is soluble in the organic solvent synthesize | combined by a three step addition reaction,
In the first step, the reaction is carried out in the presence of a catalyst by the reaction of an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalents), and a low molecular weight imide having an aromatic diamine bonded to both acid anhydrides of the acid dianhydride. To produce a compound,
In the second step, an acid dianhydride (3 molar equivalents) and an aromatic diamine (1 molar equivalent) are added to the low molecular weight imide compound and reacted to form a low molecular weight imide compound having an acid dianhydride bonded to both terminals. Create it,
The heat resistant polyimide soluble in an organic solvent which adds aromatic diamine (1 mol equivalent) and performs a polycondensation reaction in a 3rd step. (a) pyromellitic acid dianhydride (PMDA), (b) benzophenonetetracarboxylic acid dianhydride (BTDA), (c) bicyclooctentetracarboxylic acid anhydride (BCD) and (d) diaminodiphenyl In the heat-resistant polyimide which contains an ether (DADE) as a component and is soluble in the organic solvent synthesize | combined by a three step addition reaction,
In the first step, the reaction is carried out in the presence of a catalyst by the reaction of an acid dianhydride (1 molar equivalent) and an aromatic diamine (2 molar equivalents), and a low molecular weight imide having an aromatic diamine bonded to both acid anhydrides of the acid dianhydride. To produce a compound,
In the second step, an acid dianhydride (3 molar equivalents) and an aromatic diamine (1 molar equivalent) are added to the low molecular weight imide compound and reacted to form a low molecular weight imide compound having an acid dianhydride bonded to both terminals. Create it,
The heat resistant polyimide soluble in an organic solvent which adds aromatic diamine (1 mol equivalent) and performs a polycondensation reaction in a 3rd step. (1) 2 molar equivalents of 4,4'-diaminodiphenyl ether (4,4'-DADE) and 1 molar equivalent of biphenyltetracarboxylic acid dianhydride (BPDA) were added in an organic polar solvent in the presence of a catalyst. ? Reacting at 200 ° C to produce a low molecular weight imide compound having 4,4'-DADE bound to both acid anhydride groups of BPDA;
(2) the oligomer produced in the first step, 2 molar equivalents of pyromellitic acid dianhydride (PMDA), 1 molar equivalent of bicyclooctene tetracarboxylic acid anhydride (BCD) and bis (3-amino-4-hydride A _{second step} of reacting 1 molar equivalent of oxyphenyl) sulfone (HOAB? SO ₂ ) to form a low molecular weight imide compound in which PMDA is bonded to one terminal and BCD is bonded to the other terminal; and
(3) The oligomer produced in the second step is reacted with 1 mole equivalent of 1,3-bis (4-aminophenoxy) benzene (mTPE), and polycondensation yields a polyimide copolymer soluble in an organic polar solvent. Formula (VI) consisting of the third step of synthesis:
[(PMDA)-(DADE-BPDA-DADE)-(PMDA-HOAB? SO ₂ -BCD)-(mTPE)] _n
A heat resistant polyimide soluble in an organic solvent having a repeating unit represented by (wherein the bond between the compounds is an imide bond).