JPS61241119A - Forming of polycyanoaryl ether film - Google Patents

Abstract

PURPOSE:To obtain a film excellent in transparency, mechanical strength and heat resistance by a method wherein polycyanoaryl ether with specified configuration is employed. CONSTITUTION:Polycyanoaryl ether, which contains 50 mole-percent or more of a repeated base unit represented by the formula I and at the same time the reduced viscosity of which is 0.3-2.0 dl/g in the solution with the concentration of 0.2g/dl by p-chlorophenold as solvent at 60 deg.C, is formed by extrusion within the temperature range of 370-460 deg.C and, after that cooled in order to obtain polycyanoaryl ether film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for forming a polycyanoaryl ether film having excellent heat resistance, mechanical strength, and transparency.

[Technical background of the invention and its problems] Patent No. 14270 discloses devices having various structures. The polycyanoaryl ether disclosed in this publication is a polymer or copolymer synthesized from 2,2-bis(4-hydroxyphenyl)propane and dinitrobenzonitrile.

However, the polycyanoaryl ether obtained by this method cannot be said to have sufficient heat resistance or mechanical strength for practical use.

Therefore, the present inventors conducted various studies and proposed a method for producing polycyanoaryl ether with excellent heat resistance and mechanical strength (Patent Application No. Sho Go-1403). This is a method for producing polycyanoaryl ether from naphthalene and dihalogenobenzonitrile.

By the way, in general, films with heat resistance, mechanical strength, and transparency are expected to have a wide range of uses in various industrial fields, and mass production thereof is desired. Therefore, the above-mentioned polycyanoaryl ether having excellent heat resistance and mechanical strength is available for purchase.

[Object of the invention] The present invention meets the above-mentioned demands, and has a heat resistance of 9.
The purpose of the present invention is to provide a method for forming a polycyanoaryl ether film having excellent mechanical strength and transparency.

[Summary of the Invention] The method for forming the polycyanoaryl ether film of the present invention is as follows.

Reduced viscosity at 60°C of a solution containing 50 mol% or more of repeating units represented by the following formula and using P-chlorophenol as a solvent at a concentration of 0.2 g/di [ηsp/cl is 0.3 to 2] ．． It is characterized in that a polycyanoaryl ether having an OeU of 1 g is extruded at 370-460°C and then cooled.

First, polycyanoaryl ether having the above-mentioned characteristics is used as a material for the film in the present invention.

In such a polycyanoaryl ether, (1
) If the content of the repeating unit represented by the formula is less than 50 mol%, heat resistance and mechanical strength will decrease.
Preferably it is 80 to 100 mol%.

In addition to the repeating unit represented by formula (I), the polycyanoaryl ether used as the film material contains at least one repeating unit represented by the following group in an amount of 50 mol%.
A copolymer containing less than

As At in the formula (II), for example, the polycyanoaryl ether in the present invention is dissolved in p-chlorophenol to give a concentration of 0.2 g/dsL. 60 of solution
Reduced viscosity at °C (ηsp/cl is 0.3 to 2.Od
i has a molecular weight of 1 g.

If the reduced viscosity is less than 0.3di/1g, it is heat resistant.

Mechanical strength is insufficient, and 2.0dl 1g
If the reduced viscosity exceeds 0.7, the melt viscosity will increase and a uniform transparent film cannot be obtained.
1.2dl 1g.

The molecular weight (reduced viscosity) is adjusted by setting the reaction conditions (temperature for 1 hour) during the polymerization reaction to a predetermined value or by adding a predetermined amount of a molecular weight regulator.

As a molecular weight regulator in the latter case.

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
Monohydric phenols represented by ) representing any of aryl group, aralkyl group, and cyano group are preferably used, such as cumylphenol and phenylphenol.

Examples include p-tert-butylphenol and cyanophenol.

In the polycyanoaryl ether having the above-mentioned characteristics, the repeating units represented by the formula (I) are linear, or both the repeating units represented by the formulas (I) and (■) are mutually disordered. Alternatively, it is structured in an ordered, linear, connected manner, and is blocked by M 1 to 10 alkyl groups, aryl groups, or aralkyl groups, and X represents a halogen atom.

The above-mentioned polycyanoaryl ether can be produced, for example, as follows. That is, dihalogenobenzonitrile is reacted with an alkali metal salt of dihydroxynaphthalene represented by (in the formula, 1M represents an alkali metal) and, if necessary, an alkali metal salt of another dihydric phenol in the presence of a solvent. This method is followed by treatment with water or alcohol.

As a compound represented by the formula (1'V), for example, 1.5
Examples include alkali metal salts of -dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene, and it is preferable to use one or more of these compounds in the reaction.

The film forming method of the present invention is carried out as follows using the above-mentioned polycyanoaryl ether.

That is, first, the polycyanoaryl ether described above is supplied to a melt extruder and subjected to melt treatment. Then, a film is extruded from the extruder's guide and cooled. When the T-die method (casting method) is applied as the extrusion method, the extruder extrudes the molten polycyanoaryl ether into a film, and the extruded film is guided onto the surface of a cooling roll or into water. Cooling. Furthermore, an inflated molding method may be applied as the extrusion molding method.

In the present invention, in the extrusion molding described above, the extrusion temperature is 37
It is necessary that the temperature is 0 to 460°C.

If the temperature is less than 370°C, film forming properties are poor and a homogeneous film cannot be obtained, and if it exceeds 460°C, a foaming phenomenon occurs in the extruder, resulting in cloudiness and wrinkles in the obtained film.

Preferably it is 390-420°C.

Furthermore, as for the cooling treatment, a transparent film can be obtained no matter which method is applied, a rapid cooling method or a slow cooling method.

From the viewpoint of productivity, it is preferable to apply the rapid cooling method.

[Embodiments of the Invention] Example 1 In an autoclave with an internal volume of 5 cubic meters equipped with a stirring device, 2.
397 g (2,48 mol) of 7-dihydroxynaphthalene and 430 g (2,48 mol) of 2,8-diglorobenzonitrile.
5 mol), potassium carbonate 414 g (3.0 mol), sulfolane 2.51. ) Lunin 1.5 hours were prepared at 180°C in an argon atmosphere for 1.5 hours, then 2 hours.
After the 0-polymerization reaction was completed at 00°C for 1.5 hours, a large amount of water was injected to precipitate and recover particulate polymer.

After washing three times with three portions of hot water and once with three portions of methanol, 618 g (yield: 96%) of polycyanoaryl nityl having 100 mol % of repeating units represented by the following were obtained.

Reduced viscosity at 60°C of a solution of the obtained polymer with a concentration of 0.2 gId using P-chlorophenol as a solvent
[ηsp/cl was measured and the results are shown in the table.

In addition, when we investigated the thermal properties of this polymer, we found that the glass transition temperature was 215°C, the melting point was 345°C, and thermal decomposition started. It was confirmed that it has.

Next, we talked about the solvent resistance of this polymer.
It was insoluble in the following solvents: acetone, ethanol, toluene, methylene chloride, and chloroform.

Furthermore, after exposing this polymer to the flame of a lighter for 10 seconds, when the flame was moved away, the flame quickly extinguished, and no melt dripping was observed, indicating good flame retardancy.

Next, this polymer powder was applied to a cylinder with a diameter of 30 cm and a ratio of the total length (L) to the diameter (D) of the cylinder L/D = 25.
It was supplied to a melt extruder with a screw rotation speed of 80 rpm, melted and kneaded at a cylinder temperature of 410°C, and the length was 300°.
mm, has a linear lip with a gap of 0.2I, and has a Gui temperature (
Extrusion temperature) Extruded from a T-die at 400℃, surface temperature 70℃
A transparent film with a wall thickness of 100° C. was obtained by electrostatically casting the film onto a cooling drum at a temperature of 100° C.

The transparency of the film was determined by measuring the light transmittance at a wavelength of 480 nl for a film having a wall thickness of 100 μm.

The mechanical properties of the obtained film, ie, breaking strength, elongation, and modulus of elasticity were measured, and the results are shown in the table.

Examples 2 to 5 Same as Example 1 except that polycyanoaryl ethers having reduced viscosities as shown in the table were produced in the same manner as in Example 1 by extending the reaction time at 200°C. A film was formed. The heat resistance, flame retardance, and solvent resistance of the obtained polymer were as good as in Example 1.

Example 6 2,7-dihydroxynaphthalene 38 in Example 1
Chemically processed to 7g, 1,5-dihydroxynaphthalene 238
．． 3g (1,49 mol) and 4,4-biphenol 1
Except that 84.5 g (0.9 g mol) of the mixture was used.
In the same manner as in Example 1, polycyano 7 aryl niter was obtained. This polycyanoaryl ether contained 40 mol% of the following formula.

When the thermal properties of the obtained copolymer were examined, the glass transition temperature was 221°C, the melting point was 302°C, and the thermal decomposition onset temperature (in air) was 519°C, indicating that it had sufficient heat resistance for practical use. This was confirmed.

Next, this copolymer was extrusion molded in the same manner as in Example 1, and the properties of the obtained film were measured in the same manner as in Example 1. Solvent resistant.

Regarding the difficulty ff1t=, it was as good as in Example 1.

Comparative Example 1 By shortening the polymerization reaction time at 200° C. in Example 1, a polycyanoaryl ether with a reduced viscosity of 0.28 dl/g was obtained. The obtained polymer was extruded and formed into a film in the same manner as in Example 1, but it was too brittle to measure its physical properties.

Comparative Example 2 A polycyanoaryl ether having a reduced viscosity of 2.1 di/g was obtained by extending the polymerization reaction time at 200° C. in Example 1 further than in the example. Similar to Example 1,
I tried extrusion molding the obtained polymer, but with extrusion molding:!
It wasn't there.

Comparative Examples 3 and 4 The extrusion temperature was 360°C in Comparative Example 3 and 470°C in Comparative Example 4.
Extrusion molding was carried out in the same manner as in Example 1, except that.

The film obtained in Comparative Example 3 had uneven film thickness, and a homogeneous film could not be obtained.

The film obtained in Comparative Example 4 contained bubbles and gel and was not practical.

The above results are shown in the table.

I. Effects of the Invention] As is clear from the above nine examples of the invention, if a polycyanoaryl ether film is produced using the present invention, a film with excellent transparency, mechanical strength, and heat resistance can be obtained. can get.

Therefore, the film obtained by the method of the present invention can be used in various industries where transparency, heat resistance, and mechanical strength are required (e.g.
Electronic/electrical equipment, 4I! It is acceptable as a film for machines and household use.

Claims (1)

[Scope of Claims] Contains 50 mol% or more of repeating units represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and
The reduced viscosity [ηsp/c] at 60°C of a solution with a concentration of 0.2 g/dl using p-chlorophenol as a solvent is 0.
A method for forming a polycyanoaryl ether film, which comprises extruding a polycyanoaryl ether having a concentration of 3 to 2.0 dl/g at a temperature of 370 to 460°C, and then cooling it.