JPH02133426A - Aromatic polyimide resin and production thereof - Google Patents

Abstract

PURPOSE:To prepare a polyimide resin soluble in various org. solvents and with a high glass transition temp. by reacting a specific diamine with a specific tetracarboxylic acid dianhydride or dithioanhydride. CONSTITUTION:A polyimide resin of formula I (wherein R is a tetravalent aromatic group; Ar is a divalent tetraphenylethylene group; n is an integer of 10-200 is prepd. by reacting a diamine of formula II (wherein Ar is the same as above) with a tetracarboxylic acid dianhydride of formula III (wherein R is the same as above) in an org. solvent or by reacting said diamine with a tetracarboxylic acid dithioanhydride of formula IV (wherein R is the same as above) in said org. solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an aromatic polyimide resin and a method for producing the same.

(Conventional technology) Conventionally, aromatic polyimide resins have excellent heat resistance and
It has excellent electrical and mechanical properties and has been widely used as an industrial material. However, many of these polyimide resins are
Since it is insoluble in various organic solvents and mineral acids, and is also thermally infusible, it has been extremely difficult to mold it.

(Problems to be Solved by the Invention) Almost none of the above-mentioned conventional aromatic polyimide resins have a high glass transition temperature and excellent heat resistance, as well as good solubility in organic solvents. ,
The lack of an aromatic polyimide resin that has both such heat resistance and moldability 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 first invention of the present invention is - Monna (in the formula, the rear represents a divalent tetraphenylethylene group)
By reacting the diamine represented by the formula with the tetracarboxylic dianhydride represented by the formula -Momon (in the formula, R represents a tetravalent aromatic group) in an organic solvent, the diamine represented by the formula -Momon (the formula (wherein, R is a tetravalent aromatic group, Ar is a divalent tetraphenylethylene group, and n is an integer of 10 to 200).

The second invention of the present invention is represented by the formula - Monna % (wherein R is a tetravalent aromatic group, the latter is a divalent tetraphenylethylene group, and n is an integer from 10 to 200). This is a method for producing aromatic polyimide resin.

The third invention of the present invention is a diamine represented by the general formula H2N Ar NH2 (II) (wherein, Ar represents a divalent tetraphenylethylene group) and a By reacting the dithioanhydride of tetracarboxylic acid represented by (representing an aromatic group) in an organic solvent, -reacting (in the formula, R is a tetravalent aromatic group, Ar is a divalent tetraphenyl This is a method for producing an aromatic polyimide resin represented by an ethylene group (n is an integer from 1O to 200).

The polyimide resin represented by the general formula (I) is
from a diamine represented by II) and a tetracarboxylic dianhydride represented by general formula (I), or
) and a tetracarboxylic acid dithioanhydride represented by the general formula (IV); however, as the diamine, a diamine consisting of a divalent tetraphenylethylene group can be used alone. Alternatively, a mixture of diamines comprising one or more divalent aromatic groups may be used.

The diamine consisting of a divalent tetraphenylethylene group represented by general formula (II) refers to 1,1-bis(4-aminophenyl)-2,2-diphenylethylene. This diamine can be easily produced using a two-step synthetic route using tetraphenylethylene as a starting material.

Examples of the tetracarboxylic dianhydride derivative represented by the general formula (III) used in the present invention include pyromellitic dianhydride, 2.3.6.7-naphthalenetetracarboxylic dianhydride, 3.4 .3", 4'-biphenyltetracarboxylic dianhydride, 2.3.2', 3"-
Biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methanihydride'IL 2,2-bis(3,4-dicarboxyphenyl)propanihydride, his(3,4-dicarboxyphenyl) Ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride 3.4.3', 4°-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4
-dicarboxyphenyl)hexafluoropropane dianhydride, etc.

Examples of the tetracarboxylic acid dithioanhydride derivative represented by the general formula (IV) used in the present invention include pyromellitic acid dithioanhydride, 2.3.6.7-naphthalenetetracarboxylic acid dithioanhydride, 3 .4.3', 4°-biphenyltetracarboxylic acid dithioanhydride, 2°3.2"
, 3'-biphenyltetracarboxylic acid dithioanhydride, bis(3,4-dicarboxyphenyl)methanethioanhydride, 2,2-bis(3,4-dicarboxyphenyl)propanethioanhydride, bis(3, 4-dicarboxyphenyl)ethernitioanhydride, bis<3.4-';
Carpoxyphenyl) sulfonithioanhydride, 3.4.
Examples include 3',4'-benzophenonetetracarboxylic acid dithioanhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropanethioanhydride, and the like. These tetracarboxylic dithioanhydrides can be easily synthesized by reacting the corresponding tetracarboxylic dianhydride with sodium sulfide.

A diamine represented by the general formula (II) and -saccharide (I)
Tetracarboxylic dianhydride represented by the general formula (
The method for producing the polyimide resin represented by 1) is to prepare a diamine represented by -Kirobatsu (II) and a tetracarboxylic dianhydride represented by -Kakkuri (III) in an organic solvent under substantially anhydrous conditions. The reaction is carried out by reacting the compound derivative at 0 to 100°C for several tens of minutes to several days, and then subjecting it to pressure [5] at 80 to 400°C for several tens of minutes to several days.

The degree of polymerization n of the polyimide resin represented by -Sakatsu (I) is determined by the diamine represented by -Sakobatsu ([>) and -Sakatsu (II)
It is limited by the amount of the tetracarboxylic dianhydride derivative represented by I), and when these reaction components are used in equimolar amounts, it is possible to produce a polyimide resin represented by the general formula (I) with a high degree of polymerization. . - The reason why n of the polyimide resin of Saburatsu (I) was limited to an integer of 10 to 200 is that when n is smaller than 10, the mechanical properties and heat resistance of the molded product formed into a film etc. are insufficient. n is 200
This is because if the amount exceeds 100%, the solubility in organic solvents and moldability will deteriorate.

Examples of organic solvents that can be used in the method of the present invention include N
, N-dimethylformamide, N,N-dimethylacetamide, amide solvents such as N-methyl-2-pyrrolidone, sulfur solvents such as dimethylsulfokind, tetramethylene sulfone, anisole, diphenylethenohenitrobenzene, benzonitrile, cresol, Examples include benzene-based solvents such as phenol. In particular, when using a solvent that can azeotrope with water, such as cresol or nitrobenzene, the latter stage reaction can be carried out at the boiling point of these solvents, and at the same time the solvent can be removed by distillation. The reaction can proceed with even higher efficiency. Moreover, at this time, there is no problem even if the reaction is carried out by adding an additive such as isoquinoline.

In the present invention, a diamine represented by ``-- ``(n)'' and a tetracarboxylic dianhydride derivative represented by ``-- ``(III)'' are reacted, 1. r is a divalent tetraphenylethylene group,
(n does not represent an integer of 10 to 200), and a conventionally used dehydration cyclization method (for example, C, E.

Sroog, Macromolecular 5yn
theses Co11ect+veVolume 1st
The polyimide resin of the present invention represented by (1) can also be produced by the method described in Vol., p. 295 (1977). The polyamic acid derivative represented by the general formula (V) is produced by reacting a diamine represented by (II) with a tetracarboxylic dianhydride derivative represented by (I) under substantially anhydrous conditions. It can be easily obtained by - The degree of polymerization of the polyamic acid derivative represented by the formula (V) is limited by the amount of the diamine represented by the general formula (II) and the tetracarboxylic dianhydride derivative represented by the general formula (iii),
When these reaction components are used in equimolar amounts, a polyamic acid derivative represented by the general formula (V) with a high degree of polymerization can be produced. - The reaction temperature when producing the polyamic acid derivative represented by saccharide (V) can be selected between 0 and 300°C, but the reactant at high temperatures may contain a polyimide structure that has undergone further reaction. sex, 60
It is preferable to control the reaction temperature to below .degree. Further, examples of organic solvents that can be used in this reaction include the same organic solvents as in the above case in which the polyimide resin is produced without going through the polyamic acid derivative represented by (V).

One of the methods for converting the polyamic acid derivative represented by the general formula (V) thus obtained into the polyimide resin represented by the general formula (I) is to convert the polyamic acid derivative represented by the -saccharide (■) into a polyamic acid derivative represented by 150 to 400 This method involves heating to a temperature of °C. This heating time varies depending on the heating temperature, but is usually between several minutes and several tens of hours. Another method is to chemically treat the polyamic acid derivative represented by (V) with an acid anhydride such as acetic acid, propionic acid, acetic acid, benzoic acid, etc. to easily form a polyimide resin. cyclization to can be achieved. Here, pyridine or the like can be used in combination as a substance that promotes the cyclization reaction.

Furthermore, as an alternative method to the method for producing the polyimide resin represented by -Sakuhatsu (I), the reaction is proceeded by the same method as the method for producing the polyamic acid derivative represented by the general formula (V), and in the latter stage, the There is a method in which an additive such as acetic anhydride is added without isolating the polyamic acid derivative represented by formula (V), and the reaction is further carried out at a temperature of 0 to 300° C. for several minutes to several tens of hours. As additives used in this reaction, the same additives as those used in producing the polyimide resin represented by the general formula (I) by chemical treatment of the polyamic acid derivative represented by -saccharide (V) can be used. can.

A method for producing a polyimide resin represented by the general formula (I) from a diamine represented by the general formula (n) and a tetracarboxylic dithioanhydride represented by the general formula (TV) is a method for producing a polyimide resin represented by the general formula (I) from a diamine represented by the general formula (n) and a tetracarboxylic acid dithioanhydride represented by the general formula (TV). It is carried out by reacting a diamine represented by -carboxylic acid (n) and a tetracarboxylic acid dithioanhydride derivative represented by the general formula (rV) at 0 to 200°C for several tens of minutes to several days under the following conditions: . Since this reaction accompanies the generation of hydrogen sulfide, the reaction can be considered to have ended when the generation of hydrogen sulfide is no longer observed. In this method, the degree of polymerization n of the polyimide resin represented by the formula (I) is determined by the amount of the diamine represented by -carboxylic acid (I[)] and the tetracarboxylic acid dithioanhydride derivative represented by -carboxylic acid (rV). When these reaction components are used in equimolar amounts, it is possible to produce a polyimide resin represented by the general formula (I) with a high degree of polymerization. -n of the polyimide resin of killing (I) is 10
If n is smaller, the mechanical properties and heat resistance of the molded product, such as a film, will not be sufficient, and if n exceeds 200, the solubility in organic solvents and moldability will deteriorate.

Examples of organic solvents that can be used in this method include N,
Amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone,
Examples include sulfur-based solvents such as dimethyl sulfoxide and tetramethylene sulfone, and benzene-based solvents such as anisole, diphenyl ether, nitrobenzene, and benzonitrinobecrezonopephenol.

The amount of organic solvent used may be 1, which is sufficient to dissolve one of the reaction components. Usually, the reaction component is 0.05-50%
If used to the extent that it is included, polyimide with a high degree of polymerization can be obtained.

The polymerization reaction may proceed in a solution state, or the polymer may precipitate from the reaction system. Molded articles such as polyimide resin films can be directly formed from this polymerization solution.

The polyimide resin represented by the general formula (I) produced in this way is based on the manufacturing method used and the general formula (III) used.
) and the type of tetracarboxylic dithioanhydride derivative represented by (TV), the solubility varies depending on the type of tetracarboxylic dianhydride derivative represented by (TV), but many polyimide resins are Soluble in mineral acids such as Further, the polyimide resin in Part 2 is soluble in all or part of a solvent such as N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, metacresonopeorthochlorophenol, or pyridine. −Slaughter (
Many of the polyimide resins represented by I) have a high glass transition point of 300°C or higher, are thermally stable, and do 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.

Example 1 1.1-bis(4-aminophenyl)-2,2-diphenylethylene 0.362 g (1 mmol) 0.4
g of isoquinoline was dissolved in 5 mβ of purified metacresol and heated to 40° C. under a nitrogen stream. This solution contains 0
．． 322 g (1 mmol) of 3.4.3°, 4'benzophenonetetracarboxylic dianhydride was added. This solution was reacted at 45°C for 3 hours and at 150°C for 3 hours with stirring. A distillation device was attached to the reaction apparatus, and the solvent metacresol was distilled off under a nitrogen stream at an oil bath temperature of 240°C. At this time, metacresol K containing 0.5% inquinoline was added to keep the liquid volume in the reactor at about 4 mj2.
added. After performing this operation for 5 hours, the mixture was cooled to room temperature under a nitrogen stream to obtain a yellow polyimide resin solution. A portion of this solution was heated to 300 m, i! of methanol to obtain a polyimide resin precipitate, which was filtered and dried under vacuum at 100°C.

Cast the remaining polymerization solution on a glass plate, and
A polyimide film was obtained by vacuum drying at 00°C and then at 180°C.

Intrinsic viscosity: 0.54 dn/g (measured in N-methylpyrrolidone, concentration 0.5 g/dβ, 30°C) Infrared absorption spectrum (film): 1780.1720.
1365.720 Cm-+ (Both are characteristic absorptions of imide bonds) Elemental analysis value Carbon Hydrogen Nitrogen Calculated value (%) 79.62 3.73 4
．． 32 Actual value (%) 78.60 3.54
4.28 Glass transition temperature; 300°C 10% weight loss 535°C in air, 56°C in nitrogen
It was 0°C.

Solubility: Soluble in sulfuric acid, metacresol, orthochlorophenol, pyridine, dimethylimidazolidinone, N-methylpyrrolidone, etc.

Example 2 0.217 g (0.6 mmol) of 1.1-bis(4-aminophenyl)-2,2-diphenylethylene was added to 3
, dissolved in 5 ml of purified N,N-dimethylacetamide. Add 0.131 g (0.6 μIJ) to this solution
mol) of pyromellitic anhydride was added under a nitrogen stream and heated at 20°C.
The mixture was allowed to react for 3 hours. A portion of the obtained polymerization solution was
ml of methanol to precipitate polyamic acid, which was filtered and then vacuum dried at room temperature (intrinsic viscosity: 0.51 dβ/
g, in dimethylacetamide, concentration 0.5 g/dc30
(measured in °C). On the other hand, the remaining polymer solution was cast into a glass plate shape and dried at 80°C to obtain a polyamic acid film. This film was heated at 100°C, 200°C, and 280°C.
A polyimide film was obtained by sequentially heat-treating at ℃ for 1 hour each.

Infrared absorption spectrum (film): 1780.1730
．． 1355.720 am, (both characteristic absorption of imide bond) Intrinsic viscosity: 0.45 dl/g (in sulfuric acid,
Concentration 0.5g/+jjl', measured at 30℃) Elemental analysis values Carbon Hydrogen Nitrogen Calculated values (%
) 79.40 3.70 5.14 Actual value (%) 78.60 3.50 4.9
5 Glass transition temperature; 396°C 10% weight loss 550°C in air, 56°C in nitrogen
It was 0°C.

Solubility: Soluble only in sulfuric acid.

Example 3 0.217 g (0.6 mmol) of 1.1-bis(4-aminophenyl i2,2-diphenylethylene) was
5m f! was dissolved in purified N,N-dimethylacetamide. Add 0.193 g (0.6 mi + J
mol) of 3.4.3'',4''-benzophenonetetracarboxylic dianhydride was added under a nitrogen stream, and the mixture was reacted at 20°C for 3 hours. A part of the obtained polymerization solution was poured into 300 mβ methanol to precipitate the polyamic acid, and after filtration, it was dried under vacuum at room temperature.Intrinsic viscosity 0.50 i/g, concentration 0.5 g/dρ in dimethylacetamide, 30 (measured in °C). Meanwhile, cast the remaining polymerization solution into a glass plate shape,
This was dried at 80°C to obtain a film of polyamic acid. This film was heat treated at 100°C, 200°C and 280°C for 1 hour each to obtain a polyimide film.

Intrinsic viscosity: 0.45 dl/g (measured in N-methyl-2-pyrrolidone at a concentration of 0.5 g/d at 1.30°C) Glass transition temperature: 300°C 10% weight reduction temperature: 535°C in air; 56 in nitrogen
The temperature was 0°C.

Solubility: Soluble in sulfuric acid and N-methyl-2-pyrrolidone.

Example 4 1. 0.217 g (0.6 mmol) of 1-bis(4-aminophenyl)-22-diphenylethylene was added to 3.
5 mβ of purified N,N-dimethylacetamide. To this solution was added 0.177 g (0.6 mmol) of 3.4.3°, 4′-biphenyltetracarboxylic dianhydride under a nitrogen stream, and the mixture was reacted at 20° C. for 3 hours. A portion of the obtained polymerization solution was poured into 300 ml of methanol to precipitate polyamic acid, and after filtration, it was dried under vacuum at room temperature.Intrinsic viscosity 0.93 dβ/g, concentration range 5 g/dβ in dimethylacetamide, 30°C. ).

On the other hand, the remaining polymer solution was cast into a glass plate shape and dried at 80°C to obtain a polyamic acid film. This film was heated sequentially at 100°C, 200°C, and 280°C.
A polyimide film was obtained by heat treatment for different times.

Intrinsic viscosity: 0.88 dR/g (in sulfuric acid, concentration 0.5
g/dβ, measured at 30°C) Glass transition temperature: 295°C 10% weight loss 540°C in air, 56°C in nitrogen
It was 0°C.

Solubility: Soluble in sulfuric acid and orthochlorophenol.

Example 5 0.181 g (0.5 mmol) of 1.1-bis(4-aminophenyl)-2,2-diphenylethylene and 4
0.100 g (0.5 mmol) of 4'-oxydianiline was dissolved in 3.5 ml of purified N,N-dimethylacetamide. Add 0.294 g (1
,0 mm + J moles) (7) 3-, 4.3°, 4''-biphenyltetracarboxylic dianhydride was added under a nitrogen stream,
The reaction was carried out at 20°C for 3 hours. A part of the obtained polymerization solution was poured into 300mρ methanol to precipitate polyamic acid, which was filtered and vacuum dried at room temperature (intrinsic viscosity: 1.47d).
j7/g, concentration 0.5 g/d in dimethylacetamide
β, measured at 30°C).

On the other hand, the remaining polymer solution was cast into a glass plate shape and dried at 80°C to obtain a polyamic acid film. This film was heated sequentially at 100°C, 200°C, and 280°C.
A polyimide film was obtained by heat treatment for different times.

Intrinsic viscosity: 1.03d! /g (measured in orthochlorophenol at a concentration of 0.5 g/dC at 30°C) Glass transition temperature = 293°C 10% weight loss 550°C in air, 56°C in nitrogen
It was 0°C.

Solubility: Soluble in sulfuric acid, metacresonoborthochlorophenol, dimethylimidazolidinone, and N-methylpyrrolidone.

The mechanical properties of the film were a tensile strength of 64 MPa, an elongation at break of 3%, and a tensile modulus of elasticity of 2.4 GPa.

Example 6 1.1-bis(4-aminophenyl l-2,2-diphenylethylene 0.725 g (2 mmol) 10
ml of N-methylpyrrolidone. To this, 0.709 g (2 mmol) of 3°4.3″,4′-benzophenonetetracarboxylic acid dithioanhydride was added,
The reaction was carried out at 120° C. for 10 hours under a nitrogen stream. A portion of the polymerization solution was cast onto a glass plate at 100°C and then at 18°C.
A polyimide film was obtained by vacuum drying at 0°C. The remaining polymerization solution was poured into 300 ml of methanol to precipitate the polyimide, which was filtered and dried under reduced pressure at 100° C. to obtain polyimide.

Infrared absorption spectrum: 1780.1720.1360
．． 720Cm-1 (both characteristic absorption of imide bonds) Intrinsic viscosity: 0.60 df/g (measured in N-methylpyrrolidone, concentration 0.5g/dβ, 30°C) Elemental analysis value
Carbon Hydrogen Nitrogen calculation value (%) 79
．． 62 3.73 4.32 Actual value (%)
79.02 3.51 4.11 Glass transition temperature: 300℃ 10% weight minimum reduction temperature: 535℃ in air, 56 in nitrogen
It was 0°C.

Solubility: Soluble in sulfuric acid, metacresol, orthochlorophenol, pyridine, dimethylimidazolidinone, N-methylpyrrolidone, etc.

(Effects of the Invention) The present invention provides a polyimide resin represented by -Sakuburu (I) and an advantageous method for producing the same. Most conventional polyimide resins have low solubility in organic solvents and are therefore difficult to mold, whereas the polyimide resin of the present invention is soluble in organic solvents, and the production method of the present invention It has the characteristics that it can be obtained as an organic solvent solution by a method, and molded products such as polyimide resin films can be easily formed from this solution. Moreover, it has excellent heat resistance, so it is extremely valuable as an industrial material. .

Although the present invention has been described above with reference to specific examples and numerical values, the present invention is not limited thereto, and various changes and modifications can be made without departing from the broad spirit and scope of the present invention. Of course.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) In the formula, R is a tetravalent aromatic group, Ar is a divalent tetraphenylethylene group, (n is an integer from 10 to 200). 2. General formula H_2N-Ar-NH_2...(II) (in the formula, A
(r represents a divalent tetraphenylethylene group) and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・(III) (In the formula, R represents a tetravalent aromatic group There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting a tetracarboxylic dianhydride represented by R is a tetravalent aromatic group, Ar is a divalent tetraphenylethylene group, and n is an integer of 10 to 200). 3. General formula H_2N-Ar-NH_2...(II) (in the formula, A
(r represents a divalent tetraphenylethylene group) and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・(IV) (In the formula, R represents a tetravalent aromatic group There are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼・・・(I) (formula (wherein, R is a tetravalent aromatic group, Ar is a divalent tetraphenylfuran group, and n is an integer of 10 to 200).