JPH01132631A - Siloxane-modified polysulfone-imide and its production - Google Patents

Abstract

PURPOSE:To obtain a polyimide excellent in mechanical properties, heat resistance, processability, etc., and good in adhesion to an inorganic substances such as glass, by reacting diphenyl sulfone tetracarboxylic acid dianhydride with a specified diamino compound and a specified aromatic diamino compound. CONSTITUTION:This siloxane-modified polysulfone-imide can be obtained by reacting the following three components A-C in a solvent and effecting ring closure of the reaction product by heating; [A]: a diphenyl sulfone tetracarboxylic acid dianhydride of formula III, [B]: a diamino compound of formula IV (wherein n is an integer >=1) and [C]: an aromatic diamino compound of formula V {wherein Ar is a group of formula VI (wherein R is H or CH3) or the like}. The siloxane-modified polysulfone-imide formed by the above reaction is composed of repeating units of formula I (wherein n is as defined above) and formula II (wherein Ar is as defined above).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to siloxane-modified polysulfonimide and its manufacturing method. In particular, it relates to techniques for improving its adhesion to inorganic materials such as glass.

[Conventional technology]

Polyimide resin has excellent heat resistance and mechanical properties, and is known as a high-performance resin.

However, on the other hand, there are some points that should be improved, such as poor workability.

Polyimide resins are generally produced by reacting an aromatic acid dianhydride with a diamine to form a polyamic acid, which is then thermally cyclized to form a polyimide.

As the aromatic acid dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride are generally used. By using carboxylic dianhydride (DSD A),
It is known that the processability of polyimide can be improved.

That is, heat resistance can be achieved by using the DSDA.

Therefore, polyimide made of DSDA and diamine is expected to be used in electrical/electronic parts, automobiles, industrial machinery parts, #thermal adhesives, coating agents, wire coatings, etc.; , metal, etc.)
It has the disadvantage of poor adhesion.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a technique that can improve the adhesion to inorganic materials without impairing the excellent performance of polyimide resins using DSDA.

[Means for solving problems]

In the present invention, in the system of DSDA and aromatic diamino compound,
Furthermore, dimethylsiloxane containing diamino groups at both ends is used as a diamino compound, and copolymerization is performed with these, - diphenylsulfone tetracarboxylic dianhydride represented by the boat formula [in the formula, n is at least 1 An integer of %] and an aromatic diamino compound represented by the general formula % (3) are reacted in a solvent, and the reaction product is heated to cyclize the molecule. A method for producing a siloxane-modified polysulfonimide having a repeating unit (A) shown in the formula (A) and a repeating unit (B) shown in Related to polymers.

Next, the configuration of the present invention will be supplemented.

-3,3',4,4'-tetracarboxylic dianhydride (D
As SDA), commercially available ones can be used.

-2diamino n in general formula (2) is at least l, but 1 to 10
Preferably, it is 0.

In this general formula (2), 1,3-bis-gamma-7minopropyltetramethyldisiloxane with n=1 is produced by, for example, reacting acrylonitrile with dimethylchlorosilane, hydrolyzing the reaction product, and reducing hydrogen. It can be obtained by

In addition, the diamino compound with n=30 can be obtained by, for example, reacting a chlorine-terminated polydimethylsiloxane represented by with lithium hydride to obtain a corresponding hydrogen-terminated polydimethylsiloxane, which is then reacted with 7-acrylonitrile, and then reacting with 7-acrylonitrile. It can be obtained by reducing the product with hydrogen.

This diamino compound (hereinafter sometimes simply referred to as siloxane) is 0.1 to 20 mol%, preferably 0.1 mol% based on the total amount of the aromatic diamino compound represented by the following general formula (3). If the amount exceeds 20 mol %, the adhesion to inorganic materials such as glass is good, but the tensile strength and softening point decrease.

-3 Diamino Specific examples of the compound include m-phenylenediamine, P-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether , 4,4'-diaminodiphenylsulfone, 4,4'-
Diaminodiphenylsulfide, 2,2'-bis-(p
-7minophenyl)propane, 4.4'-diaminobenzophenone, 3.3'-diaminobenzophenone, 4.
4'-diaminobiphenyl, 1,4-bis(4-aminophenoxy)benzene, l, 3-bis(4-7minophenoxy)benzene, bis4-(4-7minophenoxy)zerni]impropylidene, l , 4-bis(4-7
Minophenoxy) diphenyl sulfone, 4.4'-bis(4-7 minophenoxy) biphenyl, 4.4'-bis(3-7 minophenoxy) diphenyl sulfone, 2.6
-bis(4-aminophenoxy)naphthalene, 3.3'
-diaminodiphenylsulfone and the like.

Polysulfonamide I and the siloxane-modified polysulfonimide of the present invention generally have the general formula (1
), a siloxane represented by the general formula (2), and an aromatic diamino compound represented by the general formula (3) in the presence of a solvent at a temperature of, for example, 50°C or lower, preferably at room temperature, for preferably 10 minutes. It is synthesized by reacting for ~20 hours to obtain polyamide carboxylic acid, followed by dehydration and imide cyclization of the polyamide carboxylic acid.

The polyamide carboxylic acid consists of the following repeating unit (A)' and repeating unit (B)'.

...-(B)' The intrinsic viscosity of the polyamide carboxylic acid (30"0 dimethyl 77-doamide solvent) is 0.1 to 5. fldl/g.

The solvent used when preparing poly-7midecarboxylic acid is dimethyl-7cet-7mide (DMA(:).

Tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), sulfolane, dimethylformamide (D
MF), N-methylpyrrolidone (NMP), etc., and it is preferable to use a mixed solvent of THF and a polar solvent other than THF.
MAc/THF mixed solvent is recommended.

During the above reaction, it is also possible to add phthalic anhydride or a monoamine compound such as aniline, ethylamine, propylamine, butylamine, etc. as a molecular weight regulator.

The method for dehydrating and converting polyamide carboxylic acid into a polyamide carboxylic acid is to prepare a polyamide carboxylic acid solution or solid at a concentration of preferably about 150 to
This is achieved by heat treatment at a temperature of 300° C. for an appropriate time.

In addition, solid polyamide carboxylic acid is obtained by adding polyamide carboxylic acid solution to a poor solvent such as methanol, ethanol, water, etc. to precipitate polyamide, and then
It can be obtained by drying at a temperature below °C.

In addition, in some cases, a method of adding a dehydrating agent such as acetic anhydride to a solution or solid of polyamide carboxylic acid and heating it to 100 to 200°C, or heating it in a solvent such as toluene, xylene, chlorobenzene, etc., and azeotropically Polyamide carbo five depending on the method of dehydration! It is also possible to dehydrate and imide acid. In these cases, a tertiary amine compound such as triethylamine or tributylamine or pyridine may be added as a catalyst in an arbitrary proportion. A siloxane represented by general formula (2) and an aromatic diamino compound represented by general formula (3) were added to a solvent, and in the first step, they were reacted at a temperature of 5°C or less for 10 minutes to 20 hours to obtain a polyamide carboxylic acid. After that, it can also be produced by reacting at a temperature of 100 to 250° C. while removing reaction water.

Solvents that can be used at this time include phenol, 0-lm-
and P-cresol, or a mixture thereof.The reaction water can be removed azeotropically by adding a solvent such as toluene, xylene, or chlorobenzene.

The polysulfonimide according to the present invention can be produced as described above, and a polyamide carboxylic acid solution is film cast onto a base material such as a glass plate, and the solvent is removed and the polysulfonimide is dehydrated and imidized. can do.

The polysulfonimide of the present invention consists of the following repeating units.

However, n is an integer of at least 1, preferably 1 to 20/
99.9~80, preferably 0.3~10/99.7~
It is 90.

〔Example〕

Next, an example of the present invention will be shown.

Example 1゜4.4'-diaminodiphenyl ether 1.003゜(
5,91m @ole,) OJ: and molecular weight 100 (l
0.15 g of polydimethylsiloxane having aminopropyl groups at both ends of [-in ship formula (2), n = 11] (
0,15■■ole,) was dissolved in 20d of a mixed solvent of dimethylacetamide/tetrahydrofuran (50150voQ,
After stirring the reaction mixture to which 10% of the reaction mixture had been added, a portion of the reaction mixture was taken out and purified by reprecipitation in isopropyl alcohol.

The intrinsic viscosity of this product is 0.59 dl/g (30°C
.

dimethylacetamide solvent (the same applies hereinafter).

The IR spectrum of the product was as follows.

-COOH, 3700~2400".s-' and (/1
7LOcm-'-CON H-; 1840cm-
'Benzene ring; 1480c■-1 -S O2-; 1310cm-'-O-; 1000cm-5CH 5i-0-; 800Cm' ■ CH From the above results, the product obtained above is It consists of the following repeating unit (A)' and repeating unit (B)', (A'')' / (B) ' C molar ratio) -3/
It is a polyamide carboxylic acid having a siloxane chain of 97.

・・・－・・・（A）゛ ・・・－・・・(B).

Next, the remaining reaction solution was cast on a glass plate, and after drying at 70°C for 30 minutes, the film-like product was peeled off from the glass plate, and the film-like product was peeled off from the glass plate.
It was dried at 00°C for 30 minutes and at 300°C for 2 hours.

A several-colored transparent film-like product was obtained.

As a result of IR analysis, the product was 3700-24'00
The absorption of 1000H at cm-5 and the absorption of 100NH- at 1840cm-' disappear, and a new 1770.1?
lOc■-5 is Isan.

The physical properties of the obtained film are shown in Table 1, and it shows good values for both heat resistance and mechanical properties, and is compatible with glass. Adhesive properties also showed good results.

Example 2゜In Example 1, 4,4'-diaminodiphenyl ether was added to 0.
．． 830g (4, θ4 mole,) 1 both terminal aminoprodiphenyl sulfone tetracarboxylic dianhydride 1.
7? A film-like product was obtained by the same manufacturing method as in Example 1 except that Og (4,94 g+ mole) was used.

Polyamide carbon @ [same repeating unit as Example 1,
However, A) ' / (B) ' = 8/94]
The intrinsic viscosity of the polyimide film was 0.52 dM/g, and the physical properties of the obtained polyimide film [same repeating unit as in Example 1, where A)/(B) = 8/94] are shown in Table 1. Although the mechanical properties were slightly lower than those in Example 1, the adhesion to glass was extremely good.Example 3
1.044g (5,21m moJe,), 0.040g (0,18mm o
A film-like product was obtained in the same manner as in Example 1, except that 1.922 g (5.37 mmole, ) of diphenylsulfone tetracarboxylic dianhydride was used.

The intrinsic viscosity of the polyamide carboxylic acid [repeating unit (A)'H3 S H3 same as Example 1] is O/73 dl/g, and the obtained polyimide film [same as Example 1 except that repeating unit H3 H3 ] The physical property values are shown in Table 1, and the heat resistance and mechanical properties were both good, and the adhesion to glass was also good.

Example 4゜In Example 1, 4,4'-diaminodiphenyl ether
0.92E1g (4,84m mo(le,), siloxane having aminopropyl groups at both ends (molecular weight 250
〇-In ship formula (2), n=31) is 0.359g (0,
14m mole, ), diphenylsulfone tetracarboxylic dianhydride 1.712g (4,78 oJe,
) A film-like product was obtained by the same manufacturing method as in Example 1, except that the following was used.

The physical properties of the polyamide carboxylic acid [having the repeating unit (A)'H3 and the obtained polyimide film [same as Example 1 except that it is a repeating unit H3 H3] are shown in Table 1, heat resistance and mechanical properties. Both results were good, and the adhesion to glass was also good.

Comparative Example 1゜Execution (1.078 g of 4,4'-diaminodiphenyl ace 9-hontyl (5,37 layer ole,) in M1,
Difemitoda 1 lacarponic dianhydride 1.924g
(5.37m mole) was manufactured using a similar manufacturing method. The intrinsic viscosity of the polyamide carboxylic acid is 0.95+HL/g, and the physical properties of the polyimide film obtained are shown in Table 1. The adhesion to glass of the polyimide film obtained without using siloxane was extremely poor. Ta.

(Effects of the Invention) According to the present invention, the mechanical properties, heat resistance, processability, etc., which are the valuable performances of the polysulfonimide resin using diphenylsulfonetetracarboxylic dianhydride as the acid component, can be maintained. At the same time, it was also possible to improve the adhesion to inorganic substances such as glass.

Patent applicant: Tonen Petrochemical Co., Ltd. New Japan Chemical Co., Ltd.

Claims (1)

[Claims] 1. One molecule contains a repeating unit (A) represented by ▲ a mathematical formula, a chemical formula, a table, etc. [in the formula, n is an integer of at least 1] and a ▲ a mathematical formula, a chemical formula, a table, etc. ▼ [In the formula, Ar is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where R is a hydrogen atom or CH_3 group, X is a bond, oxygen atom, sulfur atom, SO_2, CH_2 Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Ar' is▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, respectively. ] A siloxane-modified polysulfonimide having a repeating unit (B) represented by the following. 2. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼………………(1) Diphenylsulfone tetracarboxylic dianhydride and general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(2) [In the formula, n is an integer of at least 1] A diamino compound represented by the following and the general formula H_2N-Ar-NH_2………………………………(3)
[Ar in the formula is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where R is a hydrogen atom or CH_3 group, X is a bond, oxygen atom, sulfur atom, SO_2, CH_2 Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Ar' is▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, respectively. ] The aromatic diamino compound shown by is reacted in a solvent, and the reaction product is heated to cyclize.There are ▲mathematical formulas, chemical formulas, tables, etc. in one molecule▼ [In the formula, n is the same as the general formula (2)] The repeating unit (A) represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Ar is the same as the general formula (3)] The repeating unit (B) ) A method for producing a siloxane-modified polysulfonimide.