JPH0366728A - Electric insulation material - Google Patents

Abstract

PURPOSE:To obtain the title material which has high glass transition point and gives an electric insulation material of high heat resistance, flame retardancy, chemical resistance and mechanical strength by specifying the composition ratio of a plurality of recurring units and melt viscosity. CONSTITUTION:The subject material is composed of the recurring units of formula I and formula 11 wherein the composition ratio is 0.15 to 0.40 [the units of formula I/(units of formula I + formula II)] and has a melt viscosity of 2,000 to 100,000 poise at 400 deg.C. The subject material is preferably produced for example, by reaction between dihalogenobenzonitrile and alkali metal compound of 4,4'-biphenol in a neutral polar solvent followed by reaction of the product with a specific amount of 4,4'-dihalogenobenzophenone.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to electrical insulating materials, and more specifically, to polyether-based copolymers used for insulating coatings and insulating members for industrial equipment, consumer equipment, etc. The present invention relates to an electrically insulating material.

[Prior Art and Problems to be Solved by the Invention] Conventionally, electrical insulating materials have been used in an extremely wide range of fields, including electrical and electronic equipment, various industrial equipment, and consumer equipment.

Electrical insulating materials vary depending on the environment in which they are used and the form of equipment.
The required performance is significantly different.

In order to meet these demands, various materials are used as electrical insulating materials, such as ceramic electrical insulating materials, rubber electrical insulating materials, and plastic electrical insulating materials. Among these, plastic electrical insulating materials are beginning to be used because they have good processability and are suitable for lightweight and compact materials.

However, it cannot be said that plastic electrical insulating materials necessarily have sufficient heat resistance, flame retardancy, and mechanical strength, and therefore improvements in these properties are desired.

In addition, in recent years, olefin polymers such as polyvinyl chloride and polyethylene have been used as electrical insulating materials and common coating materials.

However, these are not suitable for use under severe conditions.

Recently, ICI's polyetheretherketone (
PEEK) is used as a wire covering material for special purposes.

However, PEEK cannot be said to have a sufficient glass transition temperature, nor can it be said that its flame retardance is perfect.

In addition, a number of polyester-based coating materials have been proposed, but they have the problem of causing hydrolysis and the like when exposed to hot water.

The present invention has been made based on the above circumstances.

The purpose of the present invention is to have a high glass transition temperature, high heat resistance,
The object of the present invention is to provide an electrical insulating material that has high flame retardancy, high chemical resistance, and excellent mechanical strength.

[Means for Solving the Problem] The configuration of the present invention for achieving the above object is expressed by the following formula (1).
; Consisting of repeating units represented by () and repeating units represented by the following formula (■); (II), the composition ratio of the repeating units represented by formula (I) [(I)/((I)+(
n))] is 0.15 to 0.40, and the temperature is 4
Melt viscosity at 00°C is 2.000 to 1009 mouths 0
This is an electrical insulating material made of a polyether copolymer characterized by zero voids.

One of the important points in the polyether copolymer according to claim 1 is that the repeating unit represented by the formula (I) and the repeating unit represented by the formula (n) and the composition ratio [(1)/((I)+(II))] of the repeating unit represented by the formula (I) is 0.15 to 0.
It must be in the range of 40.

The composition ratio of the repeating unit represented by the formula (I) is 0,
If it is less than 15, the glass transition temperature (Tg) of the polyether copolymer will be low, resulting in a decrease in heat resistance, or the melting point (Tm) will be high, leading to deterioration in moldability. On the other hand, if it exceeds 0.40, the crystallinity of the polyether copolymer will be lost and the heat resistance and solvent resistance will decrease.

In addition, in the polyether copolymer of the present invention, the melting temperature (zero shear viscosity) at a temperature of 400°C or 2,
000 to 100.000 voids is important.

This is because a low molecular weight polyether copolymer having a melt viscosity of less than 2.000 voices cannot achieve sufficient heat resistance and mechanical strength.

On the other hand, if the melt viscosity exceeds 100,000 voices, moldability will deteriorate.

The polyether copolymer in the present invention has, for example, a crystal melting point of about 330 to 400°C, has crystallinity, and has a sufficiently high molecular weight.

It exhibits sufficient heat resistance, as well as excellent solvent resistance and mechanical strength. Moreover, the volume resistivity of this polyether-based copolymer is equivalent to that of polyether sulfone, and larger than that of polyether ketone.As for the dielectric constant, the polyether-based copolymer of the present invention is similar to polyether sulfone. The dielectric constant is almost the same as that of ether ketone and is smaller than that of polyether sulfone.The dielectric loss tangent of the polyether copolymer in the present invention is equivalent to that of polyether ether ketone and polyether sulfone. It has excellent high frequency characteristics.

Due to these electrical properties, the polyether copolymer is at a sufficient practical level as an electrical insulating material and is extremely suitable as an electrical insulating material.

In addition, the physical properties of the polyether copolymer mentioned above, namely heat resistance, flame retardance, chemical resistance, and mechanical strength, allow it to withstand use under more severe conditions and can be applied to a wide range of fields of use. It can be used as a possible electrical insulating material.

The polyether copolymer is used as an insulating material in communication equipment, electronic equipment, industrial instruments, and other general equipment.

Examples of usage include covering electric wires by extrusion molding, coating with a molten copolymer, and forming and pasting into a film. In addition, other commonly known methods of using this type of polymer as an insulating member, such as botting, filling, sealing, etc., can be employed.

1. Method for producing a polyether copolymer - The polyether copolymer can be produced according to various methods.

A method for producing a polyether copolymer suitable for the present invention is to react dihalogenobenzonitrile and an alkali metal compound of 4.4゛-biphenol in the presence of a neutral polar solvent, and then to form a reaction product. It can be produced by carrying out a copolymerization reaction between a compound and a specific amount of 4,4'-dihalogenobenzophenone.

Specific examples of the dihalogenobenzonitrile that can be used include 2,6-dihalogenobenzonitrile represented by the following formula; (wherein, X is a halogen atom); (However, in the formula, X has the same meaning as above.) 2,4-dihalogenobenzonitrile and the like can be mentioned.

Among these, preferred are 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and 2.4-dichlorobenzonitrile.
-dichlorobenzonitrile, 2,4-difluorobenzonitrile, and 2,6-dichlorobenzonitrile is particularly preferred.

The dihalogenobenzonitrile and 4 represented by the following formula:
, 4°-biphenol in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is
Any substance that can convert °-biphenol into an alkali metal salt is acceptable, and is not particularly limited, but alkali metal carbonates and alkali metal hydrogen carbonates are preferred.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Among these, preferred are sodium bicarbonate and potassium bicarbonate.

Among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate can be particularly preferably used.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone (NM
P), N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone,
N-n-propyl-2-pyrrolidone, N-n-butyl-
2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4
゜5-Trimethyl-2-pyrrolidone, N-methyl-2-
Piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2
-piperidone, N-methyl-3-ethylpiperitone, dimethylsulfoxide, diethylsulfoxide, 1-methyl-1-oxosulfolane, l-ethyl-1-oxosulfolane, ■-phenyl-1-oxosulfolane, N.

Examples include No-dimethyl silidinone (DM I ), diphenyl sulfone, and the like.

Preferred are NMP, DMI, sulfolane, and diphenylsulfone.

What is the usage ratio of the dihalogenobenzonitrile?

The molar ratio of the dihalogenobenzonitrile to the total amount of dihalogenobenzonitrile and 4.4°-dihalogenobenzophenone is usually 0.15 to 0.40, and the proportion of the alkali metal compound used is is the above 4
, usually 1.0 per hydroxyl group of 4°-biphenol
The proportion is between 3 and 2,50 equivalents, preferably between 1.05 and 1.25 equivalents.

There is no particular restriction on the amount of the neutral polar solvent used, but it is usually the same as the dihalogenobenzonitrile and 4.
The amount is selected in the range of 200 to 2.000 parts by weight per 100 parts by weight of the 4"-biphenol and the alkali metal compound.

the dihalogenobenzonitrile in the presence of the alkali metal compound and the neutral polar solvent and the 4.4'-
Reaction product JR obtained by reaction with biphenol,
and the 4,4'-dihalogenobenzophenone.

The 4,4°-dihalogenobenzophenone to be used is a compound represented by the following formula: (wherein, X has the same meaning as above), 4,4'-difluorobenzophenone,
4.4'-dichlorobenzophenone can be particularly preferably used.

The proportion of the 4,4"-dihalogenobenzophenone used is the molar ratio to the total amount of dihalogenobenzonitrile and 4,4'-dihalogenobenzophenone, and is the molar ratio of the 4,4"-dihalogenobenzophenone described above.
4°-dihalogenobenzophenone is usually 0.85 to
0.60, and the 4,4′-dihalogenobenzophenone has a molar ratio of the total amount of 4,4′-dihalogenobenzophenone and dihalogenobenzonitrile to the amount of 4,4′-biphenol used. , typically 0.418
~1.02. Preferably 1.00-1. Use in a proportion that makes it ol.

To obtain the polyether copolymer, for example, the dihalogenobenzonitrile, the 4,4"-biphenol, and the alkali metal compound are simultaneously added to the neutral polar solvent, and the After reacting the dihalogenobenzophenone and the 4.4°-biphenol,
Further, the 4,4'-dihalogenobenzophenone is added, usually at 150 to 380°C, preferably at 180 to 33°C.
A series of reactions is carried out at a temperature in the range of 0°C.If the zero reaction temperature is less than 150°C, the reaction rate is too slow to be practical, and if it exceeds 380°C, side reactions may occur.

In addition, the reaction time of this series of reactions is usually 0.1 to 1
0 hours, preferably 1 hour to 5 hours.

After the reaction is completed, the polyether copolymer is separated and purified from the resulting neutral polar solvent solution containing the polyether copolymer according to three known methods. Obtainable.

In this way, the polyether copolymer according to claim 1 can be efficiently produced in a simple process.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) A polybiphenylene ether ketone copolymer, which is a polyether copolymer, was produced as follows.

32.34 g of 2,6-cyclobenzonitrile was added to a 5-liter reactor equipped with a Dean-Starck trap filled with toluene, a stirrer, and an argon gas suction tube.
(0,188 mol), 4,4'-biphenol 13
9.66 g (0.75 mol), potassium carbonate 124.
39 g (0.9 mol) and N-methylpyrrolidone 1.
51 was added, and the temperature was raised from room temperature to 195°C over 1 hour while blowing argon gas.

After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy.

Next, after carrying out the reaction at 195°C for 30 minutes, 122-85g of 4.4°-difluorobenzophenone was added.
A solution of (0,553 mol) dissolved in 1.5 ml of N-methylpyrrolidone was added, and the reaction was further carried out for 1 hour.

After the reaction is complete, the product is pulverized using a blender (manufactured by Warning Co., Ltd.), washed with acetone, methanol, water, and acetone in that order, and dried to form a white powder with a bulk density of 0.12 g/c1. 259.36 g of polymer (yield;
98%).

When the properties of this polyether copolymer were measured, the melt viscosity (zero shear viscosity) at a temperature of 400°C
The glass transition temperature was 182°C, the crystal melting point was 379°C, and the starting temperature of thermal decomposition was 562°C (5% weight loss in air).

The results are shown in Table 1.

A test piece was prepared by injection molding the polyether copolymer, and its electrical properties were measured.

The results are shown in Table 2.

In addition, mechanical strength and flame retardancy were measured.

The results are shown in Table 3.

In addition, the measurement of each evaluation item was performed as follows.

Tensile Strength, Tensile Modulus and Elongation According to ASTM D-618 Flexural Strength and Flexural Modulus According to ASTM D-790 Heat Distortion Temperature According to ASTM D-1448 Limiting Oxygen Index ASTM D- Based on Rockwell hardness ASTM D-785 Dynamic friction coefficient 345C is used as the mating material, speed of 0.6 m/see,
Coefficient of kinetic friction (#L) at a load of 20 kg/cm'' Also, chemical stability was measured and found that with regard to acid and alkali resistance, it swells when immersed in concentrated sulfuric acid for a long time, but hydrochloric acid, nitric acid, dichloroacetic acid, It was stable without being affected by trifluoroacetic acid, and was also stable against caustic soda and caustic potassium.

In addition, regarding solvent resistance, it was stable and was not attacked by acetone, dimethyl ether, methyl ethyl ketone, benzene, toluene, ethyl acetate, dimethyl elminate, N-methylpyrrolidone, methylene chloride, and p-chlorophenol.

(Comparative Examples 1 to 2) In order to compare the electrical properties of the polyether copolymer of Example 1, polyether ether ketone [manufactured by ICI: PEEK 4SOG] and polyether sulfone [manufactured by ICI: PE54100G] were used. The electrical characteristics were also measured in the same way.

The results are shown in Table 2.

(Examples 2 to 4) Copolymers having the physical properties shown in Table 1 were produced in the same manner as in Example 1, except that the raw material charging ratio and polymerization conditions were changed.

The properties of these copolymers are shown in Table 1.

Mechanical strength and flame retardancy were measured in the same manner as in Example 2 using the polymers of Examples 2 to 4.

The results are shown in Table 3.

(Comparative Example 3) Mechanical strength and flame retardance were measured in the same manner as in Example 1 using PEEK450G manufactured by IC1.

The results are shown in Table 3.

Further, when chemical stability was examined, it was found that acid resistance was affected by concentrated sulfuric acid and dichloroacetic acid, and solvent resistance was also affected by p-chlorophenol.

[Effects of the Invention] According to the present invention, an electrical insulating material having a high glass transition temperature, high heat resistance, super flame retardancy, chemical resistance, and excellent mechanical strength can be obtained.

Claims (1)

[Claims] (1) The following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ Consisting of repeating units represented by (II), and the composition ratio of the repeating units represented by formula (I) above [(I)/{(I)+(II))] is 0.15 ~0.4
0, and the melt viscosity at a temperature of 400°C is 2.
,000 to 100,000 poise.