JPH0245526A - Polycyanoaryl ether and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject novel polymer excellent in heat resistance, mechanical strength, moldability, etc., with a high glass transition and thermal decomposition starting temperature by reacting a dihalobenzonitrile with bis(hydroxyphenyl)fluorene. CONSTITUTION:The objective polymer, obtained by dissolving (A) a dihalobenzonitrile, such as 2,6-difluorobenzonitrile, with (B) 9,9-bis(4- hydroxyphenyl)fluorene in, e.g., a neutral polar solvent (e.g., dimethylformamide), preferably adding and reacting an alkaline metal compound (e.g., lithium carbonate) therewith and having recurring units expressed by the formula and >=0.2dl/g reduced viscosity.

Description

Detailed Description of the Invention Field of Application 1 of "Industry" 2 The Sueyori invention relates to polycyanoaryl ether and its manufacturing method. g) and polycyanoaryl ether, which has a '7RJJL structure, which is an engineering resin with excellent moldability, which has a significantly high thermal decomposition initiation temperature and excellent mechanical strength, and which has the above-mentioned excellent properties. The present invention relates to a practically advantageous method for producing polycyanoaryl ether, which allows polycyanoaryl ether to be produced easily and efficiently under mild conditions.

[Prior art and problems to be solved by the invention] In recent years, resins with various chemical structures have been used as so-called engineering resins in various industrial fields. In order to fully meet these requirements, new materials, especially super engineering resins with extremely high heat resistance, are required.

Polycyanaryl ether is one of these engineering resins, and various structures have been proposed, such as polymers consisting of repeating units shown by the following formula, or polymers consisting of repeating units shown by the following formula. (Unexamined Japanese Patent Publication No. 59-206433)
(JP-A-3, JP-A-81-162523, JP-A-82-223226, etc.).

In particular, JP-A-47-14270 proposes polymers consisting of repeating units represented by , and copolymers of this I'n position with other monomers, such as units represented by .

However, these conventional polycyanoaryl ethers each have advantages and disadvantages based on their chemical structures and the like. Although it generally has excellent mechanical strength, 1Ili# has sufficient thermal resistance.
In particular, since the glass transition temperature or thermal decomposition initiation temperature is not high enough, it is difficult to say that it still has sufficient mature properties when used as a material in the fields of FRP and electrical/electronic materials.

Therefore, the conventional polycyanoaryl ether is −
・Although it generally has the advantage of excellent mechanical strength, it has limited heat resistance and cannot meet the strict requirements of a high glass transition temperature or high thermal decomposition temperature. I had an issue.

The present invention has been made to solve the above problems.

That is, an object of the invention as set forth in claim 1 of the present application is to solve the above-mentioned problems. The object of the present invention is to provide a borine aryl ether having a novel structure, which is an engineering resin with excellent properties.

Moreover, the object 1-] of the invention recited in claim 2 of the present application is that the polycyanoarylether of the invention of item 1 of claim 1 of the present application, which has the excellent properties as described in 1. The object of the present invention is to provide a method for producing polycyanoaryl ether, which is very advantageous in practical use because it can be obtained easily and efficiently under mild conditions using raw materials that are easy to produce.

[F-dan and Sakukawa for solving the above problem] As a result of intensive research to solve the above problem, the inventors of wood have a repeating unit with a specific new chemical structure and a specific Polycyanoaryl ethers (m polymer and Kyodo polymer) having a reduced viscosity of The inventors discovered that the polycyanoaryl ether (single I As a result of various studies on a practical and advantageous method for producing 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxyphenyl)fluorene in the presence of an alkali metal compound, discovered that the method of condensation polymerization in a specific solvent is an extremely advantageous production method that can easily, efficiently, and economically produce desired polymers, and based on this knowledge, (Thus, the invention of claim 2 of the present application was completed.

That is, the reaction 11 according to claim I of the present application is an elf 0.2 g/dJ1 using the following general formula phenol as a solvent.
The reduced viscosity of the solution at a temperature of 60°C is 0.2 dm/
It is a polycyanoaryl ether characterized in that g is 2.

In addition, the invention according to claim 2 of the present application is based on the following formula (however, X in the formula represents a halogen atom, and two Xs may be the same or different). Dihalobenzonitrile represented by 9.9bis(4
-hydroxyphenyl)fluorene in a neutral polar solvent in the presence of an alkali metal.

The polycyanoaryl ether of claim 1 of the present invention will be described in detail below, having a middle point represented by p-chloro.

This polycyanoaryl ether is described in 16J [1
A polymer having a repeating center represented by
For example, the Sino-German-Eastern merger [
Hereinafter, this will be abbreviated as homobolymer (a). A copolymer consisting of two or more repeating intermediates represented by the above formula [I] [hereinafter referred to as a copolymer (b
). ], and at least one of the repeating intermediates represented by the formula [f] and the following formula [
III] O (wherein R1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, (, or a phenyl group;
(or represents a phenyl group). ) [hereinafter abbreviated as copolymer (c)]. ], and at least one of the repeating intermediates represented by the +iii notation [I] and the linear formula [
17] (The following are blank spaces.) [TV] (However, Y in formula 1 represents -CO- or -5O2.) A copolymer consisting of at least one repeating unit represented by [Hereinafter, this will be abbreviated as copolymer (d). ], or it may be a mixture of two or more of the various polymers listed in 1.1.

However, in the copolymers (c) and (d), the 113 repeating degree represented by the formula [III] or [IV] is 1 to 99 mol%, preferably 10
It is desirable that it be 90 mol%.

In the invention of claim 1 of the present application, the formula [I
] Repetition? The first-order formula among the n-positions (however, Q in the above formula is the repeating middle represented by , and the following formula 0 formula % (however, Q in the formula is the same as Q in [1a] above,
The repeat rIi position represented by ) is preferred, especially +i
A repeating degree expressed as i+'t[Ia] is preferred.

-A in the formula [III] in the invention of claim 1 of the present application
r-15 is naftylenz. (In the case of Can be done.

Among these, 2,7-naphthylene group and the like are particularly preferred.

In the invention of claim 1, the polycyanoaryl ether has a concentration of 0 when P-chlorophenol is used as a solvent.
．． Binary viscosity [n
sp/C] is 0.2 cH1/g or more, especially 0.5 to
Preferably it is within the range of 1.5 dJ1/g.

If the reduced viscosity is less than 0.2g7d1, the mechanical strength of the polymer will be low or the heat resistance will be insufficient. On the other hand, if the reduced viscosity is too high, the moldability may be low.

The various polycyanoaryl ethers in the invention of claim 1 of the present application can be used in China, Germany,
Alternatively, two or more of them can be used as a polymer blend, and if desired, various additives such as known modifiers and other polymers can be mixed and used.

The polycyanoaryl ether in Part II of Claim A11 of the present application can be molded into the shape of 9 using a known molding method, such as an extrusion molding method, an injection molding method, a compression molding method, etc. can.

The polycyanoaryl ether in the invention of claim 1 of the present application has a particularly high glass transition temperature (Tg) and a high thermal decomposition initiation temperature (d), and has excellent thermal properties and mechanical strength etc. It is also an engineering resin that has excellent practical use.

The polycyanoaryl ether according to the invention of claim 1 of the present application is a polymer having excellent, well-balanced properties as described above, and is used in a wide range of fields including, for example, the mechanical field, electrical and electronic fields, where FRP materials are used. It can be suitably used as a material in

The polycyanoaryl ether of the invention of claim 1 of the present application is:
Although it can be manufactured by various methods, it can be manufactured particularly preferably by the manufacturing method of the invention of claim 2 of the present application.

In the invention of claim 2 of the present application, specific examples of the dihalobenzonitrile represented by the formula (II) include 2,6-cyfluorohensonitrile, 2,6-cyglolobenzonitrile, 2- Fluoro-6-chlorobenzonitrile, 2-chloro-4-fluorobenzonitrile,
Examples include 2-chloro-6=fluorobenzonitrile, 2,4-diglorobenzonitrile, 2,4-difluorobenzonitrile, and especially 2,6-cyfluorobenzonitrile, 2,6-cyclobenzonitrile. Nitro IJ and the like are preferred. Incidentally, these dihalobenzonitrile may be used singly or in combination of two or more.

Further, in the invention according to claim 2, the above 9.9-
Along with bis(4-hydroxyphenyl)fluorene, a specific compound represented by the formula [V] H-0-A r-0-H[V] (However, Ar in formula 1 has the same meaning as in +iii) dihydric phenols can be used in combination.

When this dihydric phenol is used in combination, copolymer (C)
can be manufactured.

Specific examples of the dihydric phenols represented by the formula [V] include hydroquinone, resorcinol, catechol, 2,7-hydroxynaphthalene, 4,4'-
Dihydroxydophenyl, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfite, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl) sulfone, 2,2-bis(4)
-hydroxyphenyl)propane, 2,2-bis(3-
Methyl-4-hydroxyphenyl)propane, 2.2~
Bis(3-chloro-4-hydroxyphenyl)propane, ■-Phenyl-1゜1-bis(4-hydroxyphenyl)ethane 1.1-diphenyl-1,1-bis(4-hydroxyphenyl)methane, 3,3 -bis(4-hydroxyphenyl)pentane, bis(4-hydroxyphenyl)methane, and phenolphthalein shade. Note that these dihydric phenols may be used alone or in a mixture of two or more.

Further, in the invention according to claim 2, the above 9.9-
Together with bis(4-hydroxyphenyl)fluorene, 4,4'-dihalodiphenylketone or f is 4,4'- represented by the formula [VT] (where X and Y have the same meanings as above) Dihalodiphenylsulfone can be used in combination.

Specific examples of the 4,4'-dihalodiphenyl ketone include 4.4'-difluorodiphenyl ketone;
4'-'; Chlorodiphenyl ketone.

4.4'-Short diphenyl ketone, 4-fluoro-
Examples include 4'-chlorodiphenylketone.

Further, specific examples of 4,4'-dihalodiphenylsulfone include 4,4'-difluorodiphenylsulfone, 4.
4'-dichlorodiphenyl sulfone, 4-fluro4
'-Chlorodiphenylsulfone and the like can be mentioned.

These 4,4'-dihalodiphenyl ketones and 4,4'
- When dihalodiphenylsulfone is used in combination with dihalobenzonitrile, copolymer (d) can be prepared.

Further, as the alkali metal compound used in the invention of claim 2 of the present application, 9,9-bis(4-hydroxyphenyl)fluorene or the dihydric phenols used together with it can be converted into an alkali metal salt. There is no particular restriction as long as it is suitable, and in general, alkali metal carbonates and/or heavy alkali metal salts can be used.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate. Among these, sodium carbonate and potassium carbonate are preferred.

Said alkali metal,! ]f As carbonates, for example,
Examples include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. Among these h, sodium hydrogen carbonate and potassium hydrogen carbonate are preferred.

The various alkali metal carbonates and heavy alkali metal salts are preferably anhydrous, but if desired, they can also be used in a form containing water, such as a hydrate or a concentrated aqueous solution. Note that it is desirable that water added to the reaction system and water generated by the reaction be appropriately removed from the reaction system during or prior to the condensation polymerization reaction.

The alkali metal compounds may be used alone or in combination.

As the neutral polar solvent in IJ1 of Claim 2 of the present application, known ones can be used, and specifically,
Dimethylformamide, diethylformamide, dimethyl 7cetamide, diethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethylsulfoxide, sulfolane, diphenylsulfone, dimethylimidazolidinone, and the like can be suitably used. Among these, N-methylpyrrolidone and the like are particularly preferred.

By the way, are these neutral polar solvents one type of solvent? It can be used alone, or it can be used as a mixed solvent, etc., or it can be used with other inert solvents, especially benzene, toluene, etc., which can azeotropically remove water from the reaction system. It can be used as a mixed solvent with aromatic solvents such as xylene.

Next, the synthesis of the polymer according to the invention of claim 2 of the present application will be described.

In the invention of claim 2 of the present application, the homopolymer (a) and copolymer (b) are.

■ As one of the raw material monomers, any one or two of the above-mentioned various dihalobenzonitriles.
- and 9,9-bis(4-hydroxyphenyl)fluorene as the other one of the raw materials. In the presence of salt,
It can be suitably produced by a method of condensation polymerization by heating in the above-mentioned neutral polar solvent.

Incidentally, as a modification of Section 42 (J), ■ In the above, a part of 9,9-bis(4-hydroxyphenyl)fluorene and an alkali metal compound such as an alkali metal carbonate and/or one of the alkali metal carbonates are used. (2) In the method (2) above, the total alkali metal carbonate of 9.9-bis(4-hydroxyphenyl)fluorene is substituted for 9.9-bis(4-hydroxyphenyl)fluorene. And/or it is also possible to adopt a method in which part or all of the alkali metal bicarbonate is replaced by an alkali metal of 9.9 to bis(4-hydroxyphenyl)fluorene.

In addition, in the method for producing IJI of Claim A12 of the present application,
+ ni core copolymer) is prepared by 9. in the method 2 above. In place of p-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene and any one of the dihydric phenols represented by the above formula [V] -L can be suitably synthesized by a method using a mixture or the like.

Incidentally, as a modification of [Co.], in the method of (i) 9,9-bis(4hydroxyphenyl)fluorene, part or all of fluorene and an alkali metal compound such as an alkali metal carbonate and/or an alkali metal part of bicarbonate and 9.9-bis(4-
(11) some or all of the dihydric phenols and an alkali metal compound, e.g. is substituted with an alkali metal of the dihydric phenol, or (ii) a method in which (1) and (11) are carried out simultaneously (middle) In the method (ii) above, 9.9-bis(4-hydroxyphenyl ) All of the fluorene, all of the dihydric phenols, and a part or all of the alkali metal compound, such as an alkali metal carbonate, are combined with the alkali metal salt of 9,9-his(4-hydroxyphecol)fluorene and the alkali metal compound, such as an alkali metal carbonate. It is also possible to adopt a method in which alkali metal salts of hydric phenols are substituted.

Further, in the manufacturing method of Part II of Claim No. 12 of the present application.

Said copolymer (d) comprises: ('7) In the method (O) above, in place of dihalobenzonitrile, dihalobenzonitrile and 4°4'
-dihalodiphenylketone or 4.4') halocyphenylsulfone. Also, this dihalobenzonitrile and 4,4'-cybalon phenyl ketone or 4
．． 4'~dihalodiphenylsulfone and 9,9-bis(
It can be suitably synthesized by a method using a mixture of 4-hypoglycyphenyl)fluorene and the dihydric phenol represented by the above formula [V].

As a modification of ■, (Φ In the method of ■, (i) 9,9-bis(4
9.9- Hydroxyphenyl)fluorene and a portion of an alkali metal compound such as an alkali metal bicarbonate and/or alkali metal 'Ri&acid salt.
Alkali gold hAli of bis(4-hydroxyphenyl)fluorene! or (ii)
Part or all of the dihydric phenols and a part of the alkali metal compounds, such as alkali metal carbonate and/or alkali metal bicarbonate, are replaced by an alkali metal of the dihydric phenols, or - 1-A method of carrying out (i) and (ii) at the same time, (9) In the method of (1) above, all of the 9.9-bis(4-hydroxyphenyl)fluorene, all of the -valent phenols, and an alkali metal A method of substituting a part or all of a compound such as an alkali metal carbonate with an alkali metal salt of 9,9-bis(4-hydroxyphenyl)fluorene and an alkali metal salt of the dihydric phenols may also be adopted. Can be done.

In the method (2) above, the dihalobenzonitrile (A)
and 9.9-bis(4-hydroxyphenyl)fluorene (B); 1 (although there are no particular restrictions on the combination,
It is preferred that the total amount of 9,9-bis(4-hydroxyphenyl)fluorene used per mole and t-lucyhalopenzonitrile used be within the range of usually 1.00 to 1.03 mole.

In addition, in the method (2) above, the alkali metal carbonate (C1) and/or the alkali metal bicarbonate tf! (C
Use of 2): There is no particular restriction on $1 unit, but per 172 moles of 9,9-bis(4-hydroxyphenyl)fluorene used, the sum of the components (CI) and (C2) as described below is: It is generally suitable to be within the range of 1.00 to 1.25 gram atoms, preferably 1.05 to 1.25 gram atoms.

Use of a neutral polar solvent in the invention of claim 2; 1,
For 1 go, the type of nanatsuma used and its use-1
Although it cannot be uniformly defined because it varies depending on the reaction conditions, etc., the total monomer C degree is, for example, from 0.4 to
It is preferable to use it at a ratio within the range of 1.2 mol/1 solvent.

In IJJ of Claim 12 of the present application, when carrying out the reaction described in +iiij, there is no particular restriction on the order and method of mixing the above-mentioned components, and the reaction may be carried out by mixing each component at 1 "11 o'clock," or The reaction may be carried out by mixing in stages.

As the polymerization method, the well-known solution East method can be applied.

There are no particular limitations on the polymerization method, and it is also possible to employ a quarter-section method, a continuous method, a semi-continuous method, or a combination of one or more of these methods using stage or multi-step polymerization.

In the invention of claim 2 of the present application, the temperature at which the reaction (condensation reaction) is carried out is usually 150 to 350°C, preferably 19
The temperature is preferably within the range of 0 to 220°C.

The reaction time when carrying out the aJk reaction cannot be unconditionally specified, as it varies depending on the type of salt and alkali metal compound used, the amount of water used, the reaction temperature, etc.
Usually, it is appropriate that the time is between 0.5 and 1011ν, preferably within the range of 2 to 7 hours.

The reaction pressure is not limited to 4 yen, and can be under reduced pressure, normal pressure, or increased pressure (+I fE), but it is usually preferable to carry out the reaction at a range from reduced pressure F to normal pressure.

The reaction atmosphere is usually preferably an inert atmosphere such as nitrogen, an inert gas stream such as an argon/helium shade, or a vacuum exhaust atmosphere.

The homopolymer (d), copolymer (b), copolymer (C), and copolymer (d) can be synthesized in the following manner.

After the condensation polymerization reaction, the synthesized polymer is left to cool to room temperature, diluted by adding chloroform, and the resulting mixture is poured into acetone, methanol, etc. to precipitate the resulting polymer (11f precipitation). After washing the produced polymer for several minutes, the produced polymer is washed with the above-mentioned acetone or methanol, etc., the washed polymer is pulverized, and the pulverized polymer is further washed with hot water (including neutralization washing), and then with methanol. Wash, then e.g.
One example is the 1L order of drying at 40°C all day and night.

The method according to claim 2 of the present application is characterized in that it is possible to produce
The polycyanoaryl ether of I, that is, the engineering resin having the above-mentioned excellent properties, can be easily, efficiently, and economically converted into polycyanoaryl ether under mild conditions. This is a method for producing aryl ether.

Further, the purity of the polycyanoaryl ether produced by the method of the invention of claim 2 of the present application can be improved by various purification and removal methods, and it can be effectively purified by the following method. Manufactured by the above method
It is preferable to acid-treat the solvent H solution containing the polycyanoaryl ether.

The solvent is not particularly limited as long as it can dissolve the polycyanoaryl ether, but specific examples include methylene chloride, chloroform, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, and N-methylpyrrolidone. , dimethyl sulfoxide, diethyl sulfoxide,
Preferred examples include dimethylimitanridinone and sulfolane.

Further, examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, chloric acid, acetic acid, propionic acid, and oxalic acid.

When performing acid treatment, the polymer concentration of the polycyanoaryl ether-containing polymer solution should be 2 to 2.
The contact treatment time is preferably about 30 ifilj:%, and preferably 1 to 60 minutes, preferably 5 to 30 minutes.

Since the above-mentioned purification method is processed as a solution, a homogeneous purified product can be obtained without consuming mechanical or thermal energy, and is an excellent practical method for purifying polycyanoaryl ether.

[Example] (Example 1) Argon gas blowing tube 1 300mM of Dean-Starck trap filled with toluene, thermocouple, and stirrer
In a separable flask, add 10.424 g (0,061 mol) of 2,6-cyclohennenitrile and 9.9-his(4-hydroquinphenyl)fluorene 2+',02
5 g (0,080 mol), sodium carbonate 7.313
(0.69 mol) and 100 layers of N-methylpyrrolidone were charged and dissolved at room temperature while flowing argon gas.The reactor was placed in an oil bath and heated to 195°C over 50 minutes. Once it's warmed up,
A small amount of toluene was added and refluxed for 1 hour, and toluene was distilled off together with the water produced. 2 This state was continued for about 1 hour. 1. After removing toluene, the mixture was reacted for 4 hours while heating to 200°C. Giseta.

After the reaction was completed, the reaction product cooled to 50°C was poured with 200 layers of chloroform, poured into two streams of methanol, the resulting polymer was precipitated, and the resulting polymer was pulverized using a pulverizer. Next, wash with oxalic acid solution, and then wash with warm water,
Washed with methanol and then dried to obtain polymer powder 2.
8.2g was obtained. The yield (A) was planted in 97 layers.

This polymer was dissolved in a solvent of p-chlorophenol, and the reduced viscosity [η sp/G] of a solution with a concentration of 0.28/d at a temperature of 60° C. was 0.90 du 1 g. The glass transition temperature of this polymer (7g
) was measured to be 283℃, and thermal decomposition initiation temperature (Td) in air was measured using the thermal stitching analysis method (temperature increase rate of 10℃)
5% decrease in temperature per minute) was measured.
It was 0°C.

When the infrared absorption spectrum of this 1E combination was measured, as shown in Figure 1, nitrile and ether were detected at 2.240 cm-l (CN stretching vibration) and 1,240 cm-l (-0-stretching vibration), respectively. Absorption was observed.

Furthermore, structural analysis from measurements such as infrared absorption spectra and lH-NMR spectra confirmed that the polymer was a polycyanoaryl ether with a novel structure consisting of a repeating center represented by F [11]. It was done. It was clear that the obtained polymer had particularly high glass transition temperature (Tg) and thermal decomposition onset temperature (Td), and had excellent jk# thermal properties.

N (Example 2) Use of 9.9-bis(4-hydroxyphenyl)fluorene iri was 18.820 g (0,048 mol), and resorcinol was 1.321 g (
The same procedure as in Example 1 was carried out except that 0,012 mol) was added.

The yield of the obtained copolymer was 23.4g (yield +97%)
and the reduced viscosity [ηsp/G] is 0-75 db/g
(pchlorophenol, 0.2g/d, 60°C).

Further, the glass transition temperature of this copolymer was 270°C, and the thermal decomposition onset temperature was 501'C.

(Example 3) Use of 2,6-cyclopenzonitrile jIX of 8.3
597 g (0,049 mol), and 2.618 g (0,049 mol) of 4.4゛-difluorobenzophenone as a comonomer.
The same procedure as in Example 1 was carried out except that g (0,012 mol) was added.

The yield of the obtained copolymer was 27.1 g (Yield +97%)
), and the reduced viscosity [ηsp/C:] is 0.70 dl
/g (P chlorophenol, 0.2g/d, 60
'C).

Further, the glass transition temperature of this copolymer was 27+'C, and the thermal decomposition onset temperature was 502C.

(Example 4) 5 g of the polymer obtained in Example 1 was dissolved in 50 m of N-methylpyrrolidone, and 3 m of hydrochloric acid of normal ejB was added to this solution. Immediately after adding hydrochloric acid, a portion of the polymer precipitated, but soon became a homogeneous solution.

This solution was poured into methanol to precipitate a single polymer, which was pulverized, washed with water, and dried.

The purified polymer was heated to a thermal decomposition initiation temperature of 508°C.

(Comparative Example 1) 2,6-cyclobenzonitrile and 2,2-bis(4
The polymer obtained in the same manner as in Example 1 using approximately equivalent amount of -hydroxyphenyl)propane had a reduced viscosity [ηSp/C] of 0.82 dl1g and a glass transition temperature (Tg) of 178 °C, thermal decomposition onset temperature (Td) (
5% qt loss in air) was 435°C. Furthermore, from the infrared absorption spectrum, IH-NMR absorption spectrum, etc., it was confirmed that this polymer is a polycyanoarylether having a structure consisting of the above repeating unit, N.1 Compared to the polymer of the present invention, Glass-transition temperature(
Tg) and thermal decomposition onset temperature (Td) were both low, and the heat resistance was poor.

[Effects of the Invention] According to the invention of Claim 1 of the present application, a highly heat-resistant engineering resin that has excellent mechanical properties, excellent heat resistance, and especially extremely high glass transition temperature and thermal decomposition temperature, and is extremely useful for practical use. A polycyanoaryl ether having a novel chemical structure can be provided.

The undeveloped polycyanoaryl ether is highly prized as a material for a wide range of fields, including the mechanical field, which is used as a material for FRP, and the gas/electronics field, and its industrial value is extremely large.

Furthermore, according to Hikari IJJK in Claim 2, the polycyanoaryl ether having the above-mentioned pickled property is produced under mild conditions using manufacturing materials that are easy and inexpensive in terms of labor. It is possible to provide a method for producing a polycyanoaryl ether which can be easily, efficiently and economically obtained and is highly advantageous for practical use.

[Brief explanation of the drawing]

FIG. 1 is an rR chart showing the results of infrared spectroscopic analysis of the polycyanoaryl ether obtained in Example 1.

Claims (2)

[Claims] (1) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A solution with a repeating unit represented by [I] and a concentration of 0.2 g/dl using p-chlorophenol as a solvent at a temperature of 60°C A polycyanoaryl ether having a reduced viscosity of 0.2 dl/g or more. (2) The following general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X in the formula represents a halogen atom, and two X
may be the same or different. ) and dihalobenzonitrile represented by 9,9-bis(
4-Hydroxyphenyl)fluorene in a neutral polar solvent in the presence of an alkali metal.