JPH0411631A - Polyimide resin - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin being soluble in various organic solvents and having a high glass transition temperature by specifying its structural units and its intrinsic viscosity. CONSTITUTION:This polyimide resin comprises structural units of formula I (wherein R is a tetravalent aromatic group; and Ar is a bivalent triphenylamine group) and has an inherent viscosity in concentrated sulfuric acid at 30 deg.C of 0.1-5dl/g. This resin can be produced from a diamine compound and a tetracarboxylic acid dianhydride or from a diamine compound and tetracarboxyclic acid dithioanhydride. In the former process, a diamine compound is reacted with a tetracarboxylic acid dianhydride at about -20 to 50 deg.C for several min to several days in an organic solvent to obtain a polyamic acid, which is cyclized by heating or with a dehydrating agent to obtain a polyimide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to polyimide resins, and particularly to novel polyimide resins that are soluble in various organic solvents and have a high glass transition temperature.

(Prior Art) In the past, wholly aromatic polyimide resins have excellent heat resistance and mechanical properties, and have been widely used as industrial materials. However, many of these polyimide resins are insoluble in various organic solvents and mineral acids, and are also thermally infusible, making it extremely difficult to mold them.

(Problem to be solved by the invention) In the conventional aromatic polyimide resin as described above,
There are almost no aromatic polyimide resins that have a high glass transition temperature, excellent heat resistance, and good solubility in organic solvents, and that have both such heat resistance and processability. This has been a major problem in the commercial use of this resin. Therefore, an object of the present invention is to provide a novel polyimide resin that is soluble in various organic solvents and has a high glass transition temperature, and a method for producing the same.

(Means for Solving the Problems) The present inventors have worked diligently to produce a polyimide resin that is soluble in various organic solvents and mineral acids and has a high glass transition point, and have completed the present invention.

The present invention consists of a structural unit represented by the general formula (I) (wherein R is a tetravalent aromatic group and Ar is a divalent triphenylamine group), and is It is a polyimide resin having an intrinsic viscosity of 0.1 to 5 d 17 g.

The polyimide resin of the present invention is produced from a diamine compound (ff) and a tetracarboxylic dianhydride (I [I), or from a diamine compound (II) and a tetracarboxylic dithioanhydride (IV). .

The diamine in which Ar is a divalent triphenylamine group refers to 44'-diaminotriphenylamine. This diamine can be easily produced using p-halonitrohediine and aniline as starting materials.

Specifically, aniline and p-chlorohediine in glacial acetic acid,
It is obtained by reacting at 60"C, recrystallizing the obtained compound, reducing it with zinc and hydrochloric acid, and further neutralizing with a weak alkali (R, Herz Chemische
Berichte, 23253B (1890)).

Examples of the tetracarboxylic dianhydride represented by the above general formula (III) include pyromellitic dianhydride, 3°4.3',
4'-biphenyltetracarboxylic acid anhydride, 3,4.
3',4'-diphenyl ether tetracarboxylic dianhydride, 3,4.3',4'benzophenonetetracarboxylic dianhydride, 34.3',4'-diphenylsulfone tetracarboxylic dianhydride , 2,2-bis(3,4-
dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 3,4.3"4"-terphenyltetracarboxylic dianhydride, etc. I can give an example.

In addition, examples of the tetracarboxylic acid dithioanhydride represented by the above general formula (IV) include pyromellitic acid dithioanhydride, 3
, 4.3',4'-biphenyltetracarboxylic acid dithioanhydride, 3,4.3',4'diphenyl ethertetracarboxylic acid dithioanhydride, 3,4.3',4'-benzophenonetetracarboxylic acid Dithioanhydride, 3,4.3
', 4' diphenylsulfone tetracarboxylic acid dithioanhydride, 2,2-bis(3,4-dicarboxylphenyl)-1,1,1,3,3,3-hexafluoropropane dithioanhydride, 3, Examples include tetracarboxylic acid dithioanhydrides such as 4,3'', 4#-terphenyltetracarboxylic acid dithioanhydride.

An example of the first method for producing the polyimide resin of the present invention is to react a diamine compound and a tetracarboxylic dianhydride in an organic solvent at -20 to 50°C for several minutes to several days. An acid is obtained, and then a polyimide resin is obtained by heating or treatment with a dehydrating ring-closing agent. Organic solvents that can be used in the synthesis reaction of polyamic acid include amide solvents such as N,N-dimethylacetamide and N-methyl 2-pyrrolidone, aromatic solvents such as Hensen, anisole, diphenyl ether, nitrohediine, benzonitrile, and pyridine. Solvent, chloroform, dichloromethane, 1,2 dichloroethane, 1,1,2
．． Examples include halogen solvents such as 2-tetrachloroethane, ether solvents such as tetrahydrofuran, dioxane, and diglyme. In particular, when an amide solvent such as N,N-dimethylacetamide or N-methyl-2-pyrrolidone is used, a highly polymeric polyamic acid can be obtained. Then, the obtained polyamic acid is heated at 200 to 350°C to form a polyimide resin. Moreover, a polyimide resin can also be obtained by treating polyamic acid with a dehydrating cyclizing agent such as a mixed solution of acetic anhydride and pyridine.

In this method, the molecular weight of the polyimide resin of the present invention is limited by the amount of the diamine compound charged, and when equimolar amounts are used, a high molecular weight polyimide resin can be produced.

An example of the second method for producing a polyimide resin of the present invention is to produce a polyimide resin by reacting a diamine compound and a tetracarboxylic acid dithioanhydride at 20 to 200°C for several minutes to several days in an organic solvent. It's something you get.

Organic solvents that can be used in this polyimide synthesis reaction include N,N-dimethylacetamide, N-methyl-2-
Amide solvents such as pyrrolidone, benzene, anisole,
Aromatic solvents such as diphenyl ether, nitrohediine, benzonitrile, and pyridine; halogenated solvents such as chloroform, dichloromethane, 1,2-dichloroethane, and 11.22-tetrachloroethane; ethereal solvents such as tetrahydrofuran, dioxane, and diglyme; etc. can be exemplified. In particular, when an amide solvent such as N,N-dimethylacetamide or N-methyl-2-pyrrolidone is used, a high polymer polyimide can be obtained.

In this method, the molecular weight of the polyimide resin of the present invention is limited by the amount of the diamine compound charged, and when equimolar amounts are used, a high molecular weight polyimide resin can be produced.

In the polyimide resin of the present invention, the intrinsic viscosity is 0°1 to 5.
The reason for limiting it to dl/g is that the intrinsic viscosity is 06l
If the intrinsic viscosity is less than dffi/g, the mechanical properties and heat resistance of the molded product formed into a film etc. will not be sufficient, and if the intrinsic viscosity exceeds 5 dE/g, the solubility in organic solvents etc. will deteriorate. It is.

The polyimide resin of the present invention thus produced becomes soluble in mineral acids such as sulfuric acid. In addition, the solubility particularly varies depending on the production method used and the type of the tetracarboxylic dianhydride derivative represented by the general formula (nl) and the tetracarboxylic acid dithioanhydride derivative represented by the general formula (IV) used. However, in the resin of - part, N-methyl-2
- Becomes soluble in all or part of solvents such as pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, metacresol, orthochlorophenol, and pyridine. Furthermore, the polyimide resin of the present invention has a high glass transition point of 300°C or higher, is thermally stable, and does not undergo thermal decomposition even when heated to around 500°C.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Performance 11↓ 4.4'-diaminotriphenylamine 2,754 g
(10,0 mmol) for 20 m! ! of N,N-dimethylacetamide and added 2.181 g (10
, 0 mmol) of pyromellitic dianhydride was added at once as a solid. After stirring at 15°C to 25°C for 6 hours,
The viscous polymerization solution was cast on a glass plate and kept at room temperature.
It was dried for one day under reduced pressure of about 30 Torr. On the other hand, a solid polyamic acid was obtained by pouring the reaction solution into methanol at 300 rne. The polyamic acid film created on the former glass plate was heated at 100°C for 1 hour.
A polyimide film was obtained by heat treatment at 200'C for 1 hour and at 300'C for 1 hour under a nitrogen stream.The polyimide (film) had a 178
Absorption of the carbonyl group of the imide bond was observed at 0 and 1725c+n-', respectively. The intrinsic viscosity of the obtained polyimide was 0.85 dA/g (10.5 g/df in 98% concentrated sulfuric acid (hereinafter simply referred to as "concentrated sulfuric acid") at 30°C.
(measured at a concentration of ).

In addition, the intrinsic viscosity of polyamic acid is 0.99dffi/g
(in N,N-dimethylacetamide at 30 °C2
(measured at a concentration of 0.5 g/df).

Elemental analysis of polyimide: Calculated value: Carbon; 73.52%
, hydrogen; 3.31%, nitrogen, 9.19%, actual value:
Carbon; 72.71%, hydrogen; 3.12%, nitrogen; 9.
59%.

No glass transition temperature was observed by differential scanning calorimetry, thermomechanical measurement, or dynamic viscoelasticity measurement.

The temperature was 10% weight loss by thermogravimetry MWI at 570° C. in air and 600″C in nitrogen.

Mechanical properties of polyimide film include tensile strength of 108 M
P a , tensile modulus of elasticity was 14.2 G P a , and elongation at break was 17%.

The solubility in solvents is shown in Table 1.

Example 11"λ 2.754 g (10.0 mmol) of 4,4'-diaminotriphenylamine and 3.4.3',4'-benzophenonetetracarboxylic dianhydride were prepared in the same manner as in Example 1. A film of polyamic acid was obtained from 222 g (10,0 mmol), and this was added stepwise to 30
A polyimide film was obtained by heating to 0°C.

In the infrared absorption spectrum of the polyimide (film), carbonyl absorption of the imide bond was observed at 1780 and 1725 cm'-'. The intrinsic viscosity of the obtained polyimide was 1. Odf/g (in concentrated sulfuric acid, 30°C, 0
, 5 g/dj2).

In addition, the intrinsic viscosity of polyamic acid was 1.12 dj2/g (in N,N-dimethylacetamide at 30 °C, 0
, 5 g/dj2).

Elemental analysis of polyimide: Calculated value: Carbon, 74.86%
, hydrogen i 3.41%, nitrogen i 7.48%, actual values: carbon; 74.49%, hydrogen; 3.34%, nitrogen; 7.8
8%.

The glass transition point (dynamic viscoelasticity measurement method) was 316°C.

The IO% weight loss temperature measured by thermogravimetry is 5% in air.
The temperature was 595°C in nitrogen at 70°C.

Mechanical properties of polyimide film include tensile strength of 124MP
a, tensile modulus 12.9 G P a , elongation at break 14
%Met.

The solubility in solvents is shown in Table 1.

Tip sample 1 2.754 g (10.0 mmol) of 4,4'-diaminotriphenylamine was prepared in the same manner as in Example 1.
and 3.4.3',4'-diphenylsulfonetetracarboxylic dianhydride 3.583 g (10.0 mmol)
A polyamic acid film was obtained from the above, and this film was heated stepwise to 300°C to obtain a polyimide film.

The infrared absorption spectrum of the polyimide (film) showed that carbonyl absorption of the imide bond was observed at 1780 and 1725 cm-'. The intrinsic viscosity of the obtained polyimide was 0.61 dffi/g (in concentrated sulfuric acid, 30°C,
0.5g/di! (measured at a concentration of ).

In addition, the intrinsic viscosity of polyamic acid was 0.73 dj2/g (in N,N-dimethylacetamide at 30 °C, 0
,5g/djl! (measured at a concentration of ).

Elemental analysis of polyimide: Calculated value: Carbon; 68.30%,
Hydrogen; 3.20%, Nitrogen; 7.03%, Sulfur; 5.
36%, actual value: carbon; 67.00%, hydrogen; 2°8
6%, nitrogen; 7.12%, sulfur, 5.14%.

The glass transition point (dynamic viscoelasticity measurement method) was 346°C.

The 1O% weight loss temperature measured by thermogravimetry is 5% in air.
The temperature was 560°C in 60°C2 nitrogen.

The mechanical properties of the polyimide film are tensile strength of 79 MPa.
, tensile modulus of elasticity was 3.6 GPa, and elongation at break was 8%.

The solubility in solvents is shown in Table 1.

Disaster relief soil By the same method as in Example 1, 2.754 g (10.0 mmol) of 4.4'-diaminotriphenylamine and 3.4.3',4'-biphenyltetracarboxylic dianhydride were added. A film of polyamic acid was obtained from 942 g (10,0 mmol) and heated stepwise at 300°C.
A polyimide film was obtained by heat-treating to

The infrared absorption spectrum of the polyimide (film) showed that carbonyl absorption of the imide bond was observed at 1780 and 1725 cm-'. The intrinsic viscosity of the obtained polyimide was 0.84 df/g (in concentrated sulfuric acid, 30 °C, 0
, measured at a concentration of 5 g/d12).

In addition, the intrinsic viscosity of polyamic acid was 0.97 dβ/g (in N,N-dimethylacetamide at 30 °C, 0
, 5 g/di).

Elemental analysis of polyimide: Calculated value: Carbon; 76.54%
, hydrogen; 3.59%, nitrogen, 7.88%, actual value: carbon; 76.48% dihydrogen; 3.36%, nitrogen; 8.2
2%.

The glass transition point (dynamic viscoelasticity measurement method) was 347°C.

10% weight loss temperature change using thermogravimetry device, 5 in air
The temperature was 95°C and 610'C in nitrogen.

The mechanical properties of the polyimide film are tensile strength of 112MP.
a, tensile modulus 10.7 G P a , elongation at break 13
%Met.

The solubility in solvents is shown in Table 1.

2.754 g (10, Ommol) of 4.4'-diaminotriphenylamine and 3.4.3',4'-diphenyl ether tetracarboxylic dianhydride were prepared in the same manner as in Example 1. A film of polyamic acid was obtained from 102g (10, Ommol), and this was added stepwise to 30%
A polyimide film was obtained by heat treatment to 0°C.

The infrared absorption spectrum of the polyimide (film) showed that carbonyl absorption of the imide bond was observed at 1780 and 1725 cm-'. The intrinsic viscosity of the obtained polyimide was 0.44 dj2/g (in concentrated sulfuric acid, 30°C,
0.5g/dI! , measured at a concentration of ).

In addition, the intrinsic viscosity of polyamic acid was 0.58 dj2/g (N, N-dimethylacetamide at 30°C CO
, 5 g/dff).

Elemental analysis of polyimide: Calculated value: Carbon; 74.31%,
Hydrogen, 3.48%, Nitrogen, 7.65%, actual value: Carbon; 73.88%, Hydrogen, 3.24%, Nitrogen; 7.
41%.

The glass transition point (dynamic viscoelasticity measurement method) was 304°C.

10% weight loss temperature change using thermogravimetry device, 5 in air
The temperature was 60°C and 570°C in nitrogen.

The mechanical properties of the polyimide film are tensile strength of 109MP.
a, tensile modulus 10.4 G P a , elongation at break 13
%Met.

The solubility in solvents is shown in Table 1.

2.754 g (10, Ommol) of 4,4'-diaminotriphenylamine was prepared in the same manner as in Earthwork Example 1.
and 2,2-bis(3,4-dicarboxyphenyl 1.1
,1.3,3.3-hexafluoropropanihydride 4
．． A polyamic acid film was obtained from 442 g (10,0 mmol), and this film was heated stepwise to 300°C to obtain a polyimide film.

The infrared absorption spectrum of the polyimide (film) showed that carbonyl absorption of the imide bond was observed at 1780 and 1725 cm-'. The solid viscosity of the obtained polyimide was 0.41dj2/g (in concentrated sulfuric acid, 30°C,
(measured at a concentration of 0.5 g/dffi).

In addition, the intrinsic viscosity of the polyamic acid was 0.50 dj2/g (in N,N-dimethylacetamide at 30 °C, 0
, measured at a concentration of 5 g/df).

Elemental analysis of polyimide: Calculated value: Carbon; 65.01%,
Hydrogen, 2.80%, nitrogen; 6.15%, actual value: Carbon, 65.16%, hydrogen, 2.60%, nitrogen; 6.
25%.

The glass transition point (dynamic viscoelasticity measurement method) was 332°C.

10% weight loss temperature change using thermogravimetry device, 5 in air
The temperature was 20°C9 and 530°C in nitrogen.

The mechanical properties of the polyimide film are tensile strength of 71 MPa.
, tensile modulus of elasticity was 1.5 GPa, and elongation at break was 4%.

The solubility in solvents is shown in Table 1.

Performed ±1 44'-diaminotriphenylamine 0.275 g
(1, Ommol) was dissolved in 5 mff1 of N-methyl-2-pyrrolidone, and 0.390 g (1, Ommol) was dissolved in 5 mff1 of N-methyl-2-pyrrolidone.
mol) of 343'4'-diphenylsulfonetetracarboxylic acid dithioanhydride was added in solid form all at once. After stirring at 140° C. for 24 hours, the mixture was cooled to room temperature, and the viscous polymer solution was cast onto a glass plate and dried for 1 day at room temperature under reduced pressure of about 30 Torr. On the other hand, a polyimide solid was obtained by pouring the reaction solution into 300 mj2 of methanol.

The polyimide film created on the former glass plate was heated at 100°C for 12 hours and at 200°C for 1 hour.

A polyimide film was obtained by drying under reduced pressure. Polyimide (film) has an infrared absorption spectrum.
Absorption of the carbonyl group of the imide bond was observed at 1780 and 1725 cm'. Intrinsic viscosity is 0. F9dI! ,7g
(in concentrated sulfuric acid, 30゛CO, 5g/d 42
(measured at a concentration of ).

Elemental analysis of polyimide: Calculated value: Carbon; 68.30%
, hydrogen; 3.20%, nitrogen; 7.03%, sulfur; 5
．． 36%, actual value: Carbon, 67.96%, Hydrogen: 3.02%, Nitrogen: 6.93%, Sulfur: 5.40%.

The solubility in solvents is shown in Table 1.

After implementation, in the same manner as in Example 7, 0.275 g (1.0 mmol) of 4,4'-diaminotriphenylamine and 0.275 g (1.0 mmol) of 3',4'-benzophenonetetracarboxylic acid dithioanhydride were added. A polyimide film was obtained from 354 g (1.0 mmol).

In the polyimide (film), absorption of the carbonyl group of the imide bond was observed at 1780.1725 cr' according to an infrared absorption spectrum. Intrinsic viscosity is 1.14dj! /g
(in concentrated sulfuric acid, 30"C, 0°5 g/d!2
(measured at a concentration of ).

Elemental analysis of polyimide: Calculated value: Carbon, 74.86%
, hydrogen i 3.41%, nitrogen; 7.48%, actual value: carbon, 73.95%, hydrogen; 3.19%, nitrogen; 7.
34%.

The solubility in solvents is shown in Table 1.

By the same method as in Example 7, 0.551 g (2.0 mmol) of 4.4'-diaminotriphenylamine and 0.0 g (2.0 mmol) of 3.4.3',4'-biphenyltetracarboxylic acid dithioanhydride were prepared. A polyimide film was obtained from .653 g (2.0 mmol).

In the polyimide (film), absorption of the carbonyl group of the imide bond was observed at 1780.1725 cm-' according to an infrared absorption spectrum. Intrinsic viscosity is 0.54di! ,
7g (in concentrated sulfuric acid, 30°C, 10°5 g/d
f! (measured at a concentration of ).

Elemental analysis of polyimide: Calculated value: Carbon; 76.54%
, hydrogen, 3.59%, nitrogen; 7.88%, actual measurement (+
! : carbon carbon; 75. Atsushi 1 4%.

The solubility in solvents is shown in Table 1.

4,4'-diaminotriphenylamine 0.5% was prepared by the same method as in Example 7. 5 5 1 g (2.0mm
ol) and pyromellitic acid dithioanhydride 0.5 0 1 g
A polyimide film was obtained from (2.0 mmof).

In the polyimide (film), absorption of the carbonyl group of the imide bond was observed at 1780.1725 cm-' according to an infrared absorption spectrum. Intrinsic viscosity is 0.41dl! /
g (in concentrated sulfuric acid, 30°C20.

Measured at a concentration of 5 g/d1).

Elemental analysis of polyimide: Calculated value: Carbon; 7 3. 5
2%. hydrogen. 3. 3 1%, nitrogen; 9, 19%, actual value: carbon; 7 2. 70%. hydrogen. 3. 1
1%, nitrogen; 8.87%.

The solubility in solvents is shown in Table 1.

(Effects of the Invention) The present invention provides a novel polyimide resin represented by general formula (1). Most conventional polyimides have low solubility in solvents and are therefore difficult to mold, whereas the polyimide resin of the present invention is soluble in solvents, and can be molded into solution by the production method of the present invention. This solution can be easily molded into molded products such as polyimide resin films, and has excellent heat resistance, so it has great value as an industrial material.

Applicant: Yoshio Imai (1 idiot)

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a tetravalent aromatic group and Ar is a divalent triphenylamine group.) A polyimide resin having an intrinsic viscosity of 0.1 to 5 dl/g at 30°C.