JPH0136850B2 - - Google Patents

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a polymer compound synthesized using 2,8-diaminodiphenylene oxide, in which a hetero imide ring and a furan ring are mixed in the main chain of a polymer. The present invention relates to a method for producing a heat-resistant resin having a heat-resistant resin.

The purpose of this is that the cured resin imidized by ring-closing treatment has excellent flexibility and heat resistance, and also has the abrasion resistance, chemical resistance, electrical insulation, and film-forming properties of a polyimide resin. The object of the present invention is to provide a heat-resistant resin that has excellent mechanical properties and is useful as a material for electronic devices, an electrical insulating material, a coating, an adhesive, a paint, a molded product, a laminate, a fiber, or a film material.

[Prior Art] Conventionally, polymers having a heterocycle such as imide, imidazole, thiazole, oxadiazole, triazole, quinoxaline, thiadiazole, oxazinone, quinazoline, imidazopyrrolone, isoindoquinazolone, etc. in the polymer main chain have been used. It is already known that it is an excellent heat-resistant resin.

However, these known polymers have rigid polymer main chains, and when made into films, membranes, fibers, etc., have poor flexibility, flexibility, elongation, etc., and are unsatisfactory for practical use.

From this point of view, various studies have been conducted in the past, and by using 4,4'-diaminodiphenyl ether as one of the amine components of the raw material for producing heat-resistant resins, other amines such as phenylene diamine and benzidine have been used. , diaminodiphenylmethane,
It is also known that improved polymers with better flexibility, flexibility, elongation, etc. can be obtained compared to those using diaminodiphenylsulfone or the like.

However, those using this 4,4'-diaminodiphenyl ether had a serious drawback of reduced heat resistance.

[Object of the Invention] As a result of studies to overcome these drawbacks, the present invention uses 2,8-diaminodiphenylene oxide as the amine component to provide excellent heat resistance and improved physical properties. Also flexible,
The present invention was completed after discovering that a heat-resistant resin with excellent flexibility, elongation, etc. and well-balanced practicality can be obtained.

[Structure of the Invention] The present invention involves using 2,8-diaminodiphenylene oxide as the aromatic diamine in forming an imide ring by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine. This is a unique method for producing heat-resistant resin.

The reaction formula is as follows.

2, as the aromatic diamine used in the present invention
8-diaminodiphenylene oxide has a positional relationship in which the axes of the amine positions at both ends intersect with each other, so the main chain of the final cured product (polyimide resin) has a helical shape, which makes it flexible. It is an aromatic diamine having a structure.

The aromatic tetracarboxylic dianhydride used in the present invention is pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 2,3,6,7-
naphthalenetetracarboxylic dianhydride, 3,3',
4,4′-diphenyltetracarboxylic dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxydiphenyl) Propane dianhydride, 3,4,
9,10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxydiphenyl)ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4, 5,
8-Tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- Dichloronaphthalene-1,4,
5,,8-tetracarboxylic dianhydride, 2,7-
Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,4,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,2 ,9,10-
Tetracarboxylic dianhydride, cyclopentane
1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, pyrazine 2,3,5,6-tetracarboxylic dianhydride, 2, 2-bis(2,5-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl) ) Ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride and thiophene-2,3,4,5-tetracarboxylic dianhydride.

Further, an example of how to make 2,8-diaminodiphenylene oxide, which is an aromatic diamine used in the present invention, is shown in the following reaction formula.

[Reference: University of Fukui Faculty of Engineering Research Report 16(2)238
('68)] In the present invention, the reaction between aromatic tetracarboxylic dianhydride and 2,8-diaminodiphenylene oxide is preferably carried out in equimolar amounts as much as possible, and the degree of polymerization is also increased. If the amount of either raw material increases by 5% or more, the degree of polymerization will drop significantly and a low molecular weight product with poor film-forming properties will be obtained, so care must be taken.

Usually, using 1 to 3% more of one raw material means that
This is often done to improve workability and processability.

The solvent of the reaction system in the present invention is an organic polar solvent whose functional group has a dipole moment that does not react with tetracarboxylic dianhydride or 2,8-diaminodiphenylene oxide.

In addition to being inert to the system and solvent to the product, the organic polar solvent must be solvent to at least one, preferably both, of the reaction components.

Typical solvents of this type are N, N-
Dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N
-Diethyl acetamide, N,N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethyl phosphoamide, N-methyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, etc.These solvents can be used alone or used in combination.

Other solvents that can be used in combination include benzene, benzonitrile, dioxane,
Nonsolvents such as butyrolactone, xylene, toluene, and cyclohexane are used as dispersion media for raw materials, reaction regulators, volatilization regulators for solvents from products, film leveling agents, and the like.

It is generally preferred that the present invention be carried out under anhydrous conditions. This is because the tetracarboxylic dianhydride is ring-opened by water, becomes inactivated, and there is a risk of stopping the reaction.

Therefore, it is necessary to remove both the moisture in the raw materials and the moisture in the solvent.

However, water is sometimes intentionally added to adjust the progress of the reaction and control the degree of resin polymerization.

Further, the present invention is preferably carried out in an inert gas atmosphere.

This is to prevent oxidation of diamines.

Dry nitrogen gas is generally used as the inert gas.

The reaction in the present invention can be carried out in the following various ways.

(1) 2,8-diaminodiphenylene oxide and tetracarboxylic dianhydride are mixed in advance, and the mixture is added little by little to an organic solvent while stirring. This method is relatively advantageous in exothermic reactions such as those for polyimide resins.

(2) Conversely, there is also a method of adding a solvent to a mixture of 2,8-diaminodiphenylene oxide and tetracarboxylic dianhydride while stirring.

(3) A commonly used method is to dissolve only 2,8-diaminodiphenylene oxide in a solvent, and then add tetracarboxylic dianhydride to this in a proportion that allows the reaction rate to be controlled.

(4) It is also possible to dissolve 2,8-diaminophenylene oxide and tetracarboxylic dianhydride separately in a solvent and then slowly add the two solutions in a reactor.

(5) Furthermore, it is also possible to prepare in advance a polyamic acid product containing an excess of 2,8-diaminophenylene oxide and a polyamic acid product containing an excess of tetracarboxylic dianhydride, and then further react them in a reactor. .

The reaction temperature is preferably 0 to 100°C. This is because if the temperature is below 0°C, the reaction rate is slow, and if it is above 100°C, the produced polyamic acid gradually starts the ring-closing reaction.

Usually, the reaction is carried out at around 20°C. The degree of polymerization of polyamic acid can be controlled in a planned manner.

In order to control the degree of polymerization, it is also possible to end-block with phthalic anhydride or aniline, or add water to ring-open one of the acid anhydride groups to inactivate it.

When used, the polyamic acid product produced by the method of the present invention has the adhesion and adhesion properties of various silane coupling agents, borane coupling agents, titanate coupling agents, aluminum coupling agents, and other chelate coupling agents. Improvers, various solvents, and flow agents may also be added, and in addition to these, ordinary acid curing agents, amine curing agents,
Small amounts of polyamide curing agents and curing accelerators such as imidazole and tertiary amines may be added, as well as flexibility agents and viscosity modifiers such as rubbers, polysulfides, polyesters, low molecular weight epoxies, talc, clay, mica, Fillers such as feldspar powder, quartz powder, magnesium oxide, carbon black,
Small amounts of colorants such as phthalocyanine blue, flame retardants such as tetrabromophenylmethane and tributyl phosphate, and flame retardant aids such as antimony trioxide and barium metaborate may be added; This opens up many uses.

The polyamic acid product produced by the method of the present invention is imidized and cured by heating or by using a dehydrating agent.

The heating temperature for the former heating and dehydration treatment is usually 50°C or higher, particularly preferably in the range of 150°C or higher and 200 to 400°C.

Although air may be used as the atmosphere in this case, it is often preferable to use non-oxidizing conditions such as reduced pressure or inert gas.

As the latter dehydrating agent, carboxylic anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride are often used, and these are particularly effective when used in the coexistence of basic substances such as pyridine and quinoline.

[Effects of the Invention] Compared to conventionally obtained heat-resistant resins, the polymer made using 2,8-diaminodiphenylene oxide according to the method of the present invention has a good balance of heat resistance and flexibility. It is a heat-resistant resin with excellent properties.

That is, the polymer synthesized by the method of the present invention has a large number of aromatic rings and heterocycles in its molecular structure, and therefore has excellent heat resistance.

In addition, the main chain of the molecule has a helical shape, which is thought to give it excellent flexibility due to its spring-like effect.

Specifically, the uses of the present invention are as follows:
First, it is used as a coating film to protect the surfaces of various electronic equipment, and as a heat-resistant insulating film for multilayer wiring on top of it.

For example, semiconductors, transistors, linear ICs,
Hybrid IC, light emitting diode, LSI, super LSI
It is a wiring structure for electronic circuits such as.

Furthermore, it is also used to impart heat resistance to various materials, to prevent microwaves, and to prevent radiation.

Examples include waveguides for computers, atomic equipment, and interior materials for X-ray equipment.

Next, it is used as a coating varnish for high temperatures, such as electric wire coating, magnet wire, dip coating for various electrical parts, and protective coating for metal parts.It is also used as an impregnation varnish for glass cloth, fused silica cloth, graphite fiber, boron, etc. Used for fiber impregnation, radar domes, printed circuit boards, radioactive waste containers, turbine blades, spacecraft requiring high temperature performance and excellent electrical properties,
It is used in other structural parts, and as an interior material for waveguides in computers, atomic equipment, and X-ray equipment to prevent microwaves and radiation.

It is also used as a molding material to produce self-lubricating driving surfaces by adding graphite powder, graphite fiber, molybdenum disulfide, and polytetrafluoroethylene, and is used for piston rings, valve seats, bearings, seals, etc. It is also used to make jet engine parts, high-strength structural molded parts, etc. by adding glass fiber, graphite fiber, or boron fiber.

It is also used as a high-temperature adhesive for bonding electrical circuit parts and structural parts of spacecraft.

The heat-resistant resin according to the present invention can be used in many other applications.

[Example] The present invention will be explained below with reference to Examples.

Example 1 Purified anhydrous 2,8-diaminodiphenylene oxide (melting point 213-214
℃) Take 1 mol of anhydrous N-methyl-2
- A mixed solvent of 95% pyrrolidone and 5% toluene,
An amount sufficient to make the solid content of all raw materials 15% was added and dissolved.

Dry nitrogen gas is allowed to flow throughout the entire process from the beginning to the end of the reaction.

Next, 1 mol of purified anhydrous pyromellitic dianhydride is added little by little while stirring.
Because it generated heat, cold water at approximately 15°C was circulated in an external water tank to cool it. After addition, the internal temperature was then increased to 20°C.
The reaction was completed by stirring continuously for 10 hours.

The obtained product is a yellow transparent extremely viscous polyamic acid, and the intrinsic viscosity of NMP 0.5% is 0.81.
(30℃).

Next, drop this polyamic acid onto a glass plate and use a spinner at 200 rpm/min for 10 seconds.
It was rotated for 30 seconds at 1500 rpm/min to form a film. This was heated to 80℃ under reduced pressure, then 150℃, 250℃,
Heat at 350℃ for 30 minutes each to dehydrate and close the ring.
A 20 μm yellow-brown transparent and tough polyimide resin film was obtained.

Taking the infrared absorption spectrum of this film,
Strong absorption based on the imide ring was observed at 1780 cm ^-1 and 730 cm ^-1 and strong absorption based on the furan ring was observed at 1200 cm ^-1 .

This film has great flexibility and excellent heat resistance, and the temperature at which the film starts to decompose when heated in air at a heating rate of 5°C/min using a differential thermal balance analyzer is
It was 500℃.

Example 2 Using the same apparatus and method as in Example 1, 1 mol of 2,8-diaminodiphenylene oxide and 3,3',
One mole of 4,4'-benzophenonetetracarboxylic dianhydride was reacted.

The obtained product was a colorless and transparent extremely viscous polyamic acid with an intrinsic viscosity of 0.52.

The obtained film was a transparent yellow polyimide resin film with extremely high flexibility and excellent heat resistance, with a thermal decomposition onset temperature of 440°C.

Comparative Example 1 A reaction was carried out using the same apparatus and method as in Example 1, using 4,4'-diaminodiphenyl ether instead of 2,8-diaminodiphenylene oxide.

The obtained film had extremely high flexibility, but the thermal decomposition onset temperature was only 360°C.

Comparative Example 2 A reaction was carried out using the same apparatus and method as in Example 1, using p-phenylene diamine instead of 2,8-diaminodiphenylene oxide.

The resulting cured product had an extremely high thermal decomposition temperature of 550°C, but was too rigid to be made into a film.

Claims (1)

[Claims] 1. Production of a heat-resistant resin characterized by using 2,8-diaminodiphenylene oxide as an aromatic diamine component when reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine to form an imide ring Method.