WO1994012558A1

WO1994012558A1 - Process for producing polymer

Info

Publication number: WO1994012558A1
Application number: PCT/JP1993/001715
Authority: WO
Inventors: Toru Bando; Kenji Tanaka
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 1992-11-30
Filing date: 1993-11-24
Publication date: 1994-06-09

Abstract

A process for producing a polymer by transesterification at a high productivity by conducting the reaction in the presence of a nitrile either without using any transesterification catalyst or in the presence of a reduced amount of the catalyst.

Description

Description Method for producing polymer Technical field

The present invention relates to a method for producing a polymer by a transesterification reaction. More specifically, the present invention provides a high-quality polymer by performing a transesterification reaction without using a transesterification catalyst, which reduces the physical properties of the obtained polymer, or by reducing the amount of such a catalyst used. The present invention relates to a method for producing a polymer capable of obtaining a polymer.

Technology background

The transesterification reaction is a reaction that is widely used industrially, such as in the production of polymers such as polyester and polycarbonate. In particular, polycarbonate, which is an engineering resin with excellent transparency, heat resistance, and impact resistance, is currently widely used in the industrial field. However, in the manufacturing process, there was a problem that toxic phosgene gas and methylene chloride as a chlorine impurity source were used. In order to solve this problem, development of a method for producing polycarbonate by a melting method utilizing a transesterification reaction of a carbonic diester and a dihydroxy compound in a molten state has been actively performed recently.

In the transesterification reaction, basic catalysts such as alkali metal or alkaline earth metal carbonates, acetates, and hydroxides, and Lewis acids containing transition metals have been used as reaction catalysts. However, when a polymer is produced using a catalyst containing these metal ions, there is a problem in that the product characteristics of a polymer used in the electric and electronic field are particularly deteriorated due to the metal ions remaining in the final product. Has been plucked. In addition, when the above-mentioned basic catalyst is used, there is also a problem that the obtained polymer has poor hydrolysis resistance and chemical stability is reduced. Recently, research on a new catalyst system used for the production of polycarbonate by transesterification has been very active. For example, a method using a barium compound and a borate ester as a catalyst described in Japanese Patent Application Laid-Open No. 3-209392, and an electron donating method described in Japanese Patent Application Laid-Open No. 5-11445. Methods have been reported that use a reactive amine compound and a compound containing a group IIb, IVb, or Vb element as a catalyst. However, all of these reported examples use a polymerization catalyst containing metal ions, and as described above, the problem that metal ions remain in the product as impurities and degrade the product characteristics. Dots remain. In addition, these catalysts also essentially reduce the chemical stability of the carbonate bond. Therefore, if these catalysts remain in the polycarbonate, they cause a decrease in thermal stability, hydrolysis resistance, and the like. Will be.

In order to prevent the deterioration of the physical properties of these final products, there is a method of reducing the amount of the catalyst added.However, this method slows down the polymerization rate and requires a long time for the production, which lowers the productivity and consequently lowers the productivity. There is a problem that the product cost increases. Therefore, how to reduce the addition amount of a basic catalyst or a catalyst containing metal ions while maintaining productivity is an important study item of a method for producing a polymer using a transesterification reaction.

Also, Japanese Patent Application Laid-Open No. 4-2966325 describes a method using an electron-donating amine compound as a catalyst, but this method cannot be said to be a method that can be sufficiently satisfied. Disclosure of the invention

An object of the present invention is to provide a high-quality polymer by using a transesterification reaction without using a transesterification catalyst that reduces the physical properties of the obtained polymer or by reducing the amount of such a catalyst used. It is an object of the present invention to provide a method for producing a polymer by an ester exchange reaction, which can be obtained.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, by conducting a polycondensation reaction by an ester exchange reaction in the presence of a nitrile compound, The present inventors have found that a transpolymer can be efficiently obtained without using a steal exchange catalyst or reducing the amount thereof, and a polymer can be obtained. Thus, the present invention has been completed.

That is, the present invention provides a method for producing a polymer, which comprises carrying out a transesterification reaction in the presence of a toluene compound when producing a polymer by a transesterification reaction. BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the polymer produced by the production method of the present invention include polycarbonate, polyester carbonate, and polyester.

In the present invention, when a polycarbonate is produced by a transesterification reaction, the raw material is not particularly limited, and various materials used for production by a usual transesterification reaction are used.

Examples of raw materials that can be used include: (1) a dihydroxy compound as component (A) and a diester carbonate as component (B); (2) a diester of dihydroxy compound as component (A) and a diester carbonate as component (B); A) Dicarbonate dicarbonate as component, (B) Component dicarbonate, dicarbonate dicarbonate (self-condensation), and dihydroxy compound monocarbonate ester (self-esterification). No.

Among these, a raw material comprising a dihydroxy compound as the component (A) and a carbonic acid diester as the component (B) is preferably used.

Here, the dihydroxy compound of the component (A) preferably used in the transesterification reaction includes, for example, an aromatic dihydroxy compound and an aliphatic dihydroxy compound.

Examples of the aromatic dihydroxy compound as an example of the component (A) of the raw material I include those represented by the following general formula (I). H0- ^ Z- ^ 0H (I)

[Wherein, R ¹ is independently a halogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group, an isoamyl group, A cycloalkyl group having 5 to 7 carbon atoms or an aryl group having 6 to 12 carbon atoms, m is an integer of 0 to 4, Z is a single bond, —0—, one CO—, one S-, one SO-, one S0 ₂ -, one CR ² R ³ - (wherein each R and R ³ represents a hydrogen atom, an alkyl group or a C 6 -C 1 2 of § reels 1 to 6 carbon atoms A cycloalkylene group having 5 to 15 carbon atoms, a 1,1-cycloalkylidene group having 5 to 15 carbon atoms, an ω-alkylene group having 2 to 12 carbon atoms, or a compound represented by the following formula (II) or (II ')

The bond represented by is shown. ]

Examples of such aromatic dihydroxy compounds include, for example, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxy-2,2′-dimethylbiphenyl, and 4,4′-dihydroxy-1,3,3′-dimethyl Dihydroxybiphenyls such as biphenyl, 4,4 'dihydroxy 3,3' dicyclohexylbiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl; bis (4.-hydroxy Bis (hydroxylaryl) ethers such as xyl (phenyl) ether, bis (3-fluoro-4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether; 4,4′-dihydroxybenzopheno Screws Bis (4-hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4 "-hydroxyphenyl) sulfide; bis (4-hydroxy) Bis (hydroxyphenyl) sulfoxides such as sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, bis (3-phenyl 4-hydroxydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) sulfoxides Bis (hydroxylaryl) sulfones such as sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-14-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) methane, bis (3 —Methyl-1-hydroxydroxyphenyl) Tan, bis (3-chloro-4-hydroxyphenyl) methane, bis (35-dibromo-1-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-1phenylmethane, 1,1-bis ( 4 —Hydroxyphenyl) '― 1,1 —Diphenylmethane, 1,1bis (2-tert-butyl 4-hydroxy-1-5-methylphenyl) 1 1-Phenylmethane, 1 1-bis (4-Hydroxyphen) 1,2-bis (2-tert-butyl-1-4-hydroxy-3-methylthiophenyl) ethane, 1-phenyl-1,1,1bis (4-fluoro-4-hydroxyphenyl) ethane, 1, 1 1-bis (4-hydroxyphenyl) 1 1-phenylene, 2- (3-methyl-4-hydroxyphenyl) 1 2 -— (4-hydroxyphenyl) 1-phenyl Tan, 1 1 _ bis (4 - heat Dorokishifueniru) - 2, 2, 2-triphenyl E Tan, 2 2 - bis (4 - arsenate Dorokishifuweniru) flop ⁰ emissions, 2 2 - bis (3-methyl-4 - arsenide Kishifu yl) flop ⁰ emissions, 2, 2 - bis (2-methyl-4-arsenide Dorokishifueniru) flop down, 2, 2 - bis (3, 5 - dimethyl 4 - arsenate Dorokishifueniru) propane, 1 1 one-bis (2- tert Butyl 4-hydroxy-propoxy-5-methylphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxydroxyphenyl) propane, 22-bis ( 3—Bromo-1-hydroxypropyl) propane, 2,2-bis (3,5-difluoro-4-hydrogen) Roxyphenyl) propane, 2,2-bis (3,5-dichloro-1-4-hydrazine) phenyl ^: 2¾-bis (3,5-dibromo-4-hydroxyphenyl) propane , 2,2-bis (3-promo 4-hydroxy-1-5-propanephenyl) propane, 2,2-bis (3-hydroxyphenyl) hexafluoropropane, 2,2-bis ( 3—Phenyl-1 4—Hydroxyphenyl) propane, 2,2—Bis (4-hydroxyphenyl) butane, 2,2—bis (3—Methyl-14—Hydroxyphenyl) butane, 1,1 Bis (2—butyl) 1,4-hydroxy-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-1-5-methylphenyl) butane, 1,1-bis (2-tert-butyl-4-hydroxy-5 —Methylpheny Iso) butane, 1,1-bis (2-tert-amylyl 4-hydroxyl-5-methylphenyl) butane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis ( 3,5—Jib mouth Mo 4-Hydroxyphenyl) butane, 2,2—Bis (4-hydroxyphenyl) -1-4-methylpentane, 4,4-Bis (4-hydroxyphenyl) heptane, 1,1 Bis such as 1-bis (2-tert-butyl-1-hydroxy-5-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 1,2-bis (4-hydroxyphenyl) ethane (Hydroxyaryl) alkynes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3— Tyl-1-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl-14-hydroxyphenyl) cyclohexane, etc. Bis (hydroxyaryl) cycloalkanes; 1,1'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,1'-bis (4-hydroxyphenyl) -1m-diisopropylbenzene Bis {(hydroxyaryl) methyl} benzenes. As the aromatic dihydroxy compound other than the general formula (I), the following general formula (III)

(In the formula, R ⁴ is each independently a halogen atom or an alkyl group having 1 to 8 carbon atoms, and k represents an integer of 0 to 4.)

And halogen- and alkyl-substituted dihydroxybenzenes. For example, resorcin, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-tert-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, 2,3,4,6 —Tetrafluororesorcin, 2,3,4,6-Tetrabromoresorcin, Catechol, Hydroquinone, 3-Methylhydroquinone, 3-Ethylhydroquinone, 3 ^ Propylhydroquinone, 3-Butylhydroquinone Tert-butylhydroquinone, 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-cuminolenodiloquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,4,6-tetra-tert-butylhydroquinone , 2,5-dichlorohydrin quinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetra Such as Romohai Dorokinon and the like.

Specific examples of the aliphatic dihydroxy compound which is an example of the component (A) of the raw material I include, for example, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol, hexane-1,1, 6-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, N, N-methyljetanolamine, cyclohexane-1,3,3-diol, cyclohexane-1,4 -Diol, 1,4-dimethylolcyclohexane, p-xylylene glycol, 2,2-bis (4-hydroxycyclohexyl) propane, and the like.

Furthermore, in the present invention, 2,2,2 ', 2'-tetrahydrodraw 3,3,3', 3'-tetramethyl-1,1,1'-spilove is used as a dihydroxy compound. Spiro compounds such as [1H-indene] -6,6'-diol can also be used.

Further, a dihydric alcohol such as a hydroxyalkyl ester of biphenyldicarboxylic acid or a hydroxyalkyl ester of bicyclohexyldicarboxylic acid may be used instead of a part of the dihydroxy compound. In this case, a polyester carbonate is obtained.

Among them, in the present invention, an aromatic dihydroxy compound is preferably used. These dihydroxy compounds may be used alone or in combination of two or more.

The diester carbonates used as component (B) in raw materials (1) and (3) include diaryl carbonate compounds, dialkyl carbonate compounds and alkylaryl carbonate compounds.

Examples of the diaryl carbonate compound as an example of the component (B) include the following general formulas (IV) and (V)

0

Ar ² 0C0Ar ² (IV)

0 0

II II

Ar ² 0C0— Ar ¹ — OCOAr ^ (V)

(Wherein, A r ¹ is shows the two a residue obtained by removing hydroxyl groups from the aromatic dihydroxy compound, A r ² represents a § re Ichiru group.)

The compound represented by these is mentioned.

Examples of the dialkyl carbonate compound as an example of the component (B) include, for example, the following general formula

(V I) and (V I I)

0

II

R ⁵ OCOR ⁵ (VI)

0 0

II II

R ⁵ 0C0— Ari-OCOR ⁵ (VII) (In the formula, R ⁵ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms, and ^ A r ¹ has the same meaning as described above.)

The compound represented by these is mentioned.

Examples of the alkylaryl compound which is an example of the component (B) include the following general formulas (VIII) and (IX)

0

Ar20C0R ⁵ (VIII)

0 0

0 II II

Ar ^ OCO-Ar ¹ — OCOR ⁵ (IX) (wherein, A r 1 "and 1 ^ ⁵ have the same meaning as above.)

The compound represented by these is mentioned.

Specific examples of diaryl carbonate compounds include difluorocarbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthylcarbonate, bis (biphenylyl) carbonate, bisphenol A Bisphenyl carbonate and the like can be mentioned.

Specific examples of the dialkyl carbonate compound include getyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like.

On the other hand, specific examples of the alkylaryl carbonate compounds include methyl phenyl carbonate, ethynolefurium carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. And so on.

Of these carbonic acid diesters, carbonic acid diaryl compounds such as diph X-nyl carbonate are preferably used.

These carbonic acid diesters may be used alone or in combination of two or more.

Diesters of dihydroxy compounds used as component (A) in raw material I Examples thereof include diphenolic acid ester of bisphenol A, dipropionic acid ester of bisphenol A, dibutanoic acid ester of bisphenol A, and dibenzoic acid ester of bisphenol A.

Examples of the (A) component of the raw material ③ and the dicarbonates of the dihydroxy compound used as the raw material 、 include bismethyl carbonate of bisphenol A, bisphenol carbonate of bisphenol A, and bisphenyl carbonate of bisphenol A. Carbonate esters and the like can be mentioned.

Examples of the monocarbonates of the dihydroxy compound used as the raw material I include, for example, monomethyl carbonate of bisphenol A, monoethyl carbonate of bisphenol A, monopropyl carbonate of bisphenol A, and monophenol of bisphenol A. And the like.

Each of these raw materials may be used alone, or two or more of them may be used in combination.

The amount of the carbonic acid diester used as the component (B) of the raw materials (1) and (3) is usually the amount of the dihydroxy compound, the diester of the dihydroxy compound, the dicarbonate of the dihydroxy compound or the monocarbonate of the dihydroxy compound. This is referred to as a dihydroxy compound). The amount is about 0.9 to 1.5 mol, preferably about 0.95 to 1.25 mol, per 1 mol.

If necessary, a dicarboxylic acid or a dicarboxylic acid ester may be used instead of a part of the carbonic acid diester. In this case, polyester carbonate is obtained. Examples of the dicarboxylic acid and dicarboxylic acid ester include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, diphenyl isophthalate, diphenyl terephthalate, dichloride isophthalate, dichloride terephthalate; succinic acid, glutaric acid, adipic acid; Aliphatic dicarboxylic acids such as pimelic acid, speric acid, azelaic acid, sebacic acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl decanniate; cyclopropanedicarboxylic acid, 1,2-cyclobutane Dicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentane Dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diphenyl cyclopropanedicarboxylate, Diphenyl 1,2-cyclobutanedicarboxylate, diphenyl 1,3-cyclobutanedicarboxylate, diphenyl 1,1,2-cyclopentanedicarboxylate, diphenyl 1,1,2-cyclohexanedicarboxylate, diphenyl 1,1,3-cyclohexanedicarboxylate, Examples include alicyclic dicarboxylic acids such as diphenyl 1,4-cyclohexanedicarboxylate. The amount of the dicarboxylic acid and the dicarboxylic acid ester used is, for example, 50 mol% or less, preferably 30 mol% or less of the ester carbonate.

Polyester carbonate can also be obtained by using a dihydric alcohol such as a hydroxyalkyl ester of biphenylcarboxylic acid or a hydroxyalkyl ester of bicyclohexylcarboxylic acid and a diester carbonate as raw materials.

For example, a polyester can be obtained by using a dicarboxylic acid ester such as a lower alkyl ester of dicarboxylic acid and a dihydric alcohol such as glycol as raw materials.

The nitrile compound used in the present invention is not particularly limited. For example, the chemical structure is not particularly limited as long as it has a sufficient electron density for the lone pair of the cyano group. Aromatic nitrile compounds represented by the general formula (X) are preferably used.

CN

X

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryloxy group having 6 to 13 carbon atoms.) Aromatic nitrilation ^ "Specific examples of the product include 2-methoxybenzonitrile, 3-methoxybenzonitrile, 4-methoxybenzonitrile, and 2-ethoxybenzonitrile. Tolyl, 3-ethoxybenzonitrile, 4-ethoxybenzonitrile, 2,6-dimethoxybenzonitrile, 2, 6-diethoxyquinbenzonitrile, 2, 6-diphenoxybenzonitrile, 2,4,6 Limethoxybenzonitrile, 2,4,6-triethoxybenzonitrile, 2,4,6-tritrifluorobenzonitrile, benzonitrile, 2,6-dichlorobenzonitrile, 2,6-difluo Zonnitrile, 2-chlorbenzonitrile, 4-chlorbenzonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, 2-cyanotoluene, 3-cyanotoluene, 4-cyanotoluene, 2,5-dimethylbenzoyl Nitriles, 2—Cyanophenols, 3—Cyanophenols, 4 Cyanophenols, 2—Cyanobenzaldehyde, 3— Cyanobenzaldehyde, 4-cyanobenzaldehyde, 1-cyanonaphthalene, 2-cyanonaphthalene, 1-naphthylacetonitrile, 2-naphthylacetonitrile, 9-cyananthracene, 2-methylbenzide Lucyanide, 3-methylbenzyl cyanide, 2-ethylbenzyl cyanide, 3-ethylbenzyl cyanide and the like.

Among them, aromatic ditolyl compounds substituted with an electron donating group, such as 2-methoxybenzonitrile, 3-methoxybenzonitrile, 4-methoxybenzonitrile, 2-ethoxybenzonitrile, and 3-ethoxybenzonitrile in the above specific examples. —Ethoxybenzonitrile, 4-Ethoxybenzonitrile, 2, 6 —Dimethoxybenzonitrile, 2,6 —Jetoxybenzonitrile, 2,6 —Diphenyloxybenzonitrile, 2,4,6— Trimethoxybenzonitrile, 2,4,6—triethoxyquinbenzotril, 2,4,6—triphenoxybenzonitrile and the like are preferred.

Further, the nitrile compound used in the present invention does not need to be a low molecular compound, and for example, a polycyanaryl ether represented by the following general formula (XI) can also be preferably used. CN

J—

: (XI) [where A r 'is

(Wherein, Q is an alkylene group having 1 to 3 carbon atoms, 6 to 1 3 of Ariren group carbon, chromatography 0-, -S-, one S 0 ₂ - CO- represents a - or.) Represent, n represents a number from 1 to 500. ]

One of these nitrile compounds may be used alone, or two or more thereof may be used in combination.

When only the above nitrile compound is used without using a transesterification catalyst in the transesterification reaction, the amount of the nitrile compound used is calculated as the equivalent of a cyano group to 1 mol of the dihydroxy compound present in the reaction system (equivalent). in normal, 1 0 one ⁶ mol to 1 0 one ¹ molar, preferably from 1 0 _ ⁴ mol to 1 0 ² mol. If the amount is less than 10 to ¹⁶ mol, the polymerization rate may be slow. If the amount exceeds 10 ^_1 mol, the quality of the polymer as a final product may be degraded, for example, coloring and heat resistance may be reduced.

In the present invention, a nitrile compound and a transesterification catalyst can be used in combination. In this case, the amount of the transesterification catalyst used can be reduced as compared with a case where the transesterification reaction is performed using only the transesterification catalyst, and the deterioration of the physical properties of the polymer can be prevented.

A basic compound is preferably used as the transesterification catalyst. In particular, an alkali metal compound, an alkaline earth metal compound, a nitrogen-containing basic compound and the like are preferably used. Specific examples of the alkali metal compound and the alkaline earth metal compound include organic metal salts, inorganic acid salts, oxides, hydroxides, hydrides, and alcoholates of alkali metals and alkaline earth metals. Are preferred.

More specifically, the alkali metal compounds include sodium hydroxide, hydroxide hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, carbon dioxide lime, and carbon dioxide. Lithium, sodium acetate, acetate acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium 7-borohydride, sodium borohydride, sodium benzoate, benzoate Potassium, Lithium Benzoate, Ninatrium Hydrogen Phosphate, Dilithium Hydrogen Phosphate, Dilithium Hydrogen Phosphate, Ninatridium Salt of Bisphenol, Double Lime Salt, Dilithium Salt, Sodium Salt of Phenol, Potassium Salts, lithium salts and the like.

Examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, Examples include barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

Examples of the nitrogen-containing basic compound include an amine compound such as R. N (wherein R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and tolyl, etc.), represented by trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, Tertiary amine compounds such as dorihexylamine, dimethylbenzylamine and triphenylamine, and dimethylamine, getylamine and dipropylamine represented by R ₂ NH (where R is the same as above) , Dibutylamine, dipentylamine, dihexylamine, methylbenzylamine, diphenylamine and other secondary amine compounds, RNH ₂ (where R is Same as above. A) primary amine compounds such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, benzylamine, phenylamine, etc .;

N, N-Dimethyl 4-amino pyridine, 4-ethylpyramino pyridine, 4-pyrrolidino pyridine, 4-amino pyridine, 2-amino pyridine, 2-hydroxy pyridine, 4-hydroxy pyridine, 2-methoxy pyridine, 4 -Methoxy pyridine, imidazole, 2-methylimidazole, 4-methylimidazole, 2-dimethylaminoimidazole, 2-methoxyimidazole, 2-phenylimidazole, 2, mercaptoimidazole, aminoquinoline, diamine Nitrogen-containing heterocyclic compounds such as zabicyclooctane (DAB CO);

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (EtNOH), tetrabutylammonium hydroxide (Bu ^ NOH), trimethylbenzylammonium hydroxide [C „H _r CH ₂ (Me) NOH] alkyl group such as, Ariru group, § Nmoniumuhi Dorokishido acids having like Aruariru group;

Tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutyl ammonium borohydride (BU NBH, tetrabutylammonium phenylporate (Bi ^ NBPh), tetramethyl ammonium borohydride And basic salts such as nyl borate (Me ₄ NB Ph ₄ ).

Among these nitrogen-containing basic compounds, trihexylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and dimethylaminoviridine are preferably used.

These basic compounds can be used alone or in combination. When these basic compounds are used in combination with a nitrile compound, the amount of the nitrile compound used is usually 10 to ⁷ mol in terms of cyano group (equivalent) per mol of the dihydroxy compound present in the reaction system. ~ 10- ² mol, preferably 10 ^J mol ^~ 1 0 ύ mol. If the amount is less than 10 to ¹⁷ mol, the polymerization rate may be reduced, and the amount exceeds 10 mol. In addition, the quality of the polymer as the final product may be degraded, for example, coloring and heat resistance may be degraded. The amount of the basic compound used is usually from 10 to ⁸ mol to 10 to ¹ mol, preferably from 2 to 10 to 5 mol to 1 mol, per 1 mol of the dihydroxy compound present in the reaction system. 0 - ¹ is the mole.

Although the reaction temperature of the transesterification is not particularly limited, it is usually 100 to 300 ° C, preferably 130 to 280 ° C, and more preferably, the temperature is gradually increased in accordance with the progress of the reaction. The method of raising is desirable. If the transesterification temperature is lower than 100 ° C, the progress of the reaction is slow and the production time is long, which is not economical. If the temperature exceeds 300 ° C., a side reaction may occur or the polymer may be thermally degraded, and a good product may not be obtained.

The pressure during the transesterification reaction is set according to the reaction temperature according to the vapor pressure of the monomer used. This is not limited, provided that it is set so that the reaction is performed efficiently. Normally, at the initial stage of the reaction, the atmospheric pressure or the pressure is increased to 1 to 50 atm (760 to 380,000 torr), and the pressure is reduced at the late stage of the reaction, preferably finally. It is desirable to reduce the pressure to 0.01 to 100 torr and distill off alcohols and phenols generated by the ester exchange reaction.

Further, the reaction time of the transesterification reaction may be performed until a polymer having a target molecular weight is obtained, and is usually about 0.2 to 10 hours.

The transesterification reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon.If necessary, a branching agent, a terminal terminator, an antioxidant, etc. may be added, or an inert solvent may be used. May be.

As a branching agent that can be used in the present invention, a polyfunctional compound having three or more functional groups in one molecule is used. Examples of such a polyfunctional compound include phloroglucin, pyrogallol, and 1 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxyphenyl) propane, 1,1,1 1, 1— Lis (3-methyl-4-hydroxyphenyl) ethane, 4,6-dimethyl-2 ', 4,6-tris (4-hydroxyphenyl) 1-2-heptene, 4,6-dimethyl-2,4,6-tris 4-Hydroxyphenyl) heptane, 2,6-dimethyl-1,2,4,6-tris (4-hydroxyphenyl) -13-heptene, 1,3,5—Tris (2-hydroxyphenyl) benzene, 1,3,3 5-tris (4-hydroxyphenyl) benzene, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] pro ⁰ 2,4-bis [na- (4-hydroxyphenyl) isopropyl] phenol, 2,6-bis (2'-hydroxy-5'-methylbenzyl) 1,4-methylphenol, 2- (4-hydroxy Droxyphenyl) 2- (2, 4 dihydric Dorokishi phenyl) flop ⁰ down, shed, a ', a "over preparative squirrel (4-arsenate Dorokishifuweniru) one 1, 3, 5-triisopropylbenzene, shed one methyl one shed, a' , A '— Tris (4-hydroxyphenyl) 1-1,4-diethylbenzene, hexakis [4- {a- (4-hydroxyphenyl) isopropyl} phenyl] mono-terephthalate, tetrakis (4- (Hydroxyphenyl) methane, tetrakis [4- {-(4-hydroxyphenyl) isopropyl] phenoxy] methane, 1,4-bis [(4 ', 4 "dihydroxytriphenyl) methyl] benzene, 2, 4-dihydroxybenzoic acid , Trimellitic acid, trimesic acid, pyromellitic acid, cyanuric chloride, 3,3-bis (3-methyl-4-hydroxyphenyl: r-2-oxo-2-, 3-dihydroind And 3,3-bis (4-hydroxyaryl) oxyindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin phloroglyside, and the like.

Examples of the terminating agent that can be used in the present invention include o-n-butylphenol, mn-butylphenol, p_n-butylphenol, o-isobutylphenol, m-isobutylphenol, and p-isobutyl. Phenol, o-t-butylphenol, m-t-butylphenol, p-t-butylphenol, o-n-pentinophenol, mn-pentinophenol, pn-pen Chinolepheno, o—n—hexinolephenol, m—n—hexinolephenol, p—n—hexenolephenol, o—cyclohexenophene, m—cyclohexene , P-cyclohexylphenol, o-phenylphenol, m-phenylenophenol, p-phenylenophenol, o-n-noninophenol, mn-nonylphenol, pn-nonylphenol, o-cuminolephenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,6-di-tert-butylphenol, 2, 5—di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5—dicumylphenol, 3,5 Dicumylphenol, 1-benzyl-benzene (hydroxybenzyl) benzene, dibenzyl-4-1 (4-hydroxybenzyl) benzene, and 2,2,4-trimethyl-4-1 (4—hydroxyphenyl) chroman, Monovalent phenols such as chroman derivatives such as 2,4,4—trimethyl-1-41- (4-hydroxyphenyl) chroman.

Among such monovalent phenols, p-t-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferable, although not particularly limited in the present invention.

Other optional terminating agents include certain carbonic acid diester compounds. Specific examples of such a specific carbonic acid diester compound as a terminal terminator include carboxybutenylphenylphenyl carbonate, methylphenylbutylphenylphenylcarbonate, ethylphenylbutylphenylcarbonate, and the like. Dibutyl diphenyl carbonate, biphenyl phenyl carbonate, cumyl phenyl carbonate, dicumyl phenyl carbonate, naphthyl phenyl carbonate, dinaphthyl phenyl carbonate, carboxypropoxy phenyl Phenyl carbonate, carboheptoxyphenyl phenyl carbonate, carboxy methoxy t-butyl phenyl phenyl carbonate, carboxypropoxy phenyl methyl phenyl carbonate, chromanyl phenyl carbonate , Dichroma Bonate and the like. Also, C ₇ — _{3 ()} —alkylcarbonyloxybenzene, 'C 7

_. () Monoaliphatic alcohols, phenyl (C ₉ -alkoxy) benzoate, phenyl di (c ^ ₁₂ -alkoxy) benzoate, phenyl tri (c ^ ₁₂ -alkoxy) benzoate, phenyl (c _M2 -alkoxy) Sulfonate and the like.

The amount of the terminal terminating agent used is preferably 0.05 to 10 mol% based on 1 mol of the dihydroxy compound. Of course, the amount of the terminal terminator used can be changed according to the molecular weight of the target polymer and the like, but usually, by using the amount in the above range, the hydroxyl terminal of the obtained polymer is sufficiently sealed. Since it is stopped, a polymer sufficiently excellent in heat resistance and water resistance is obtained, which is preferable.

The above-mentioned monohydric phenol or carbonic acid diester compound as a terminal terminator may be partially added to the reaction system of the ester exchange reaction, and the remainder may be added as the ester exchange reaction proceeds. Further, in some cases, the whole amount may be added to the reaction system after the transesterification reaction has progressed to some extent.

Antioxidants that can be used in the present invention include tris (nonylphenyl) phosphite, trisphenyl phosphite, 2-ethylhexyldiphenyl phosphite, trimethyl phosphite, triethyl phosphite, and triethyl phosphite. Phosphorus antioxidants such as cresyl phosphite and triaryl phosphite are preferably used.

Examples of the inert solvent that can be used in the present invention include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, diphenyl sulfone, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; carbon dioxide; Gases such as nitrous oxide and nitrogen, chlorofluorocarbons, alkanes such as ethane and propane, cyclohexane, tricyclo (5,2,10) —cycloalkanes such as decane, cyclooctane and cyclododecane , Ethylene, argen such as probe, or hexafluoride.

In addition, the polymer obtained by the present invention further includes a plasticizer, a pigment, Well-known additives such as agents, release agents, stabilizers, inorganic fillers and the like can be blended and used. - The polymer obtained by the present invention, Poriorefui down, it can be blended with other polymers such as polystyrene, in particular 0H group, COOH group, polyunsaturated We two ethers having like end NH ₂ group, poly It is effective to use ether nitrile, terminal-modified polysiloxane compound, modified polypropylene, modified polystyrene, etc. in combination.

Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples. In each of the examples and comparative examples, reagents were used as compounds such as raw materials, except for the polycyanoaryl ether synthesized in Example 1.

Example 1

① Synthesis of nitrile compound

In a 1.5 liter separable flask equipped with a stirrer, an argon gas injection tube and a Dean-Stark trap filled with toluene, 11.25 g of 2,6-dichlorobenzonitrile, 15.25 g of resorcinol g, 2,2-bis (4-hydroxyphenyl) propane (30..55 g), 100.84 g of potassium carbonate, and 1 liter of N-methylpyrrolidone were added, and the mixture was heated at 200 ° C under a stream of argon gas. The reaction was performed for 2 hours. Thereafter, the content was poured into a large amount of water to precipitate and recover a polymer. The collected product was pulverized with a blender, washed with water and methanol, and dried under reduced pressure to obtain a polymer (polycyano aryl ether). The yield was 139 g (95% yield). The resulting polymer had a reduced viscosity of 0.2 dl Zg at 60 ° C in a solution having a concentration of 0.2 gZd 1 using p-chlorophenol as a solvent.

② Melt polymerization of polycarbonate

2,2-bis (4-hydroxyphenyl) propane 22.8 g (0. lmol), diphenyl carbonate 21.4 (0. lmol) g in a 500 ml separable flask equipped with a stirring device and a distillation device And then the policy 0.46 g [1.7 x 10 " ³ mo 1 (in terms of CN group)"] was added to the mixture. After that, the mixture was reacted at 180 ° C for 1 hour under a stream of argon gas. Further, the reaction was carried out at 50 mmHg, 240 for 1 hour and lmmHg, 270 ° C for 2 hours, and the resulting phenol was distilled off to obtain polycarbonate.The glass transition point (Tg ) Was 151 ° C. The reduced viscosity of a 0.2 g Zd 1 solution in methylene chloride as a solvent at 20 ° C. was 0.5 dl / g, and the viscosity average molecular weight calculated from this value was 0.5 dl / g. Was 22,000.

Comparative Example 1

■ Polycarbonate was obtained in exactly the same manner as in Example 1 except that only 2,2-bis (4-hydroxyphenyl) propane and diphenyl carbonate were used. The glass transition temperature of this product was measured and found to be 104 ° C. The reduced viscosity at 20 ° C. of a solution of 0.2 g Zd 1 using methylene chloride as a solvent is 0.11 d 1 / g, and the viscosity average molecular weight calculated from this value is 3400.

/ o

Example 2 Melt polymerization of polycarbonate

2,2-bis (4-hydroxyphenyl) propane 22.8 g (0.1mol), diphenyl carbonate 21.4 g (0.1 l) in a 500 ml separable flask equipped with a stirrer and distillation apparatus mo l) was charged, 2, 6-dimethyl Tokishibenzo nitrile 0. 082 g (5 X 1 0- 4 mo 1) was added. Thereafter, the mixture was reacted at 180 ° C for 1 hour under an argon gas stream, and further reacted at 50 mmHg, 240 for 1 hour and lmmHg, 270 ° C for 1 hour. I got Thermal analysis of this product showed a glass transition point (Tg) of 154 ° C. The reduced viscosity at 20 ° C of a 0.2 g / d 1 solution using methylene chloride as a solvent was 0.6 dl Zg, and the viscosity average molecular weight calculated from this value was 26,000.

Comparative Example 2

2,2-bis (4-hydroxyphenyl) propane and diphenyl carbonate Except for using only, the same operation as in Example 2 was performed to obtain a polycarbonate ′. The glass transition temperature of this product was measured and found to be 65 ° C. The reduced viscosity at 20 ° C of a solution of 0.2 gZd1 using methylene chloride as a solvent was 0.051 d1 / g, and the viscosity average molecular weight calculated from this value was 1800.

2,2-bis (4-hydroxyphenyl) propane 22.8 g (0.1 mol), diphenyl carbonate 21.4 g (0.1) in a 500 ml separable flask equipped with a stirrer and distillation apparatus mo 1), sodium hydroxide ^{04mg (1 xl O- O mo l} ), 2, 6- diphenyl Nokishibenzonito drill ^{28. 7 mg (1 x 10- 4} mo 1) was charged. Thereafter, the reaction was carried out under an argon stream at 180 ° C for 1 hour, then at 50mmHg, 240 ° C for 1 hour, and further at lmmHg at 270 ° C for 2 hours. Was. Thermal analysis of this product showed a glass transition point (Tg) of 145 ° C. The reduced viscosity at 20 ° C of a solution having a concentration of 0.2 gZd1 using methylene chloride as a solvent was 0.36 d1 Zg, and the viscosity average molecular weight calculated from this value was 14,300.

Example 4

Instead of sodium hydroxide used as a catalyst in Example 3, 0.13 mg of calcium acetate (1 ^× 10 ^{-1 omo} 1), and ^{2,6-dimethoxybenzonitrile} instead of 2,6-diphenoxybenzonitrile Nitrile (16.3 m, 5 x 10 "° mo 1) was charged, and the same procedure as in Example 3 was carried out to obtain polycarbonate. A thermal analysis measurement of the product showed a glass transition point. (Tg) was 150 ° C, and the reduced viscosity at 20 ° C of a 0.2 g / d1 solution using methylene chloride as the solvent was 0.47 d1 Zg. The calculated viscosity average molecular weight was 19,200.

Comparative Example 3 A polycarbonate was obtained in the same manner as in Example 3 except that 2,6-diphenyloxybenzonitrile was not added. When a thermal analysis measurement of this product was performed, the glass transition point (T g) was 110 ° C. The reduced viscosity at 0.20 ° C of a 0.2 g Zd 1 concentration solution using methylene chloride as the solvent was 0.12 d 1, and the viscosity average molecular weight calculated from this value was 3,700.

Comparative Example 4

A polycarbonate was obtained in the same manner as in Example 4 except that 2,6-dimethoxybenzonitrile was not added in Example 4. Thermal analysis of this product showed a glass transition point (Tg) of 104 ° C. The reduced viscosity at 20 ° C of a 0.2 g / d1 concentration solution using methylene chloride as the solvent is 0.09 d1 Zg, and the viscosity average molecular weight calculated from this value is 2,600. o

Comparative Example 5

Example 3 was repeated except that 1,3-diphenoxybenzene 26.2 mg (1 X 10 " ⁴ mo 1) was used in place of 2,6-diphenoxybenzonitrile. A polycarbonate was obtained in exactly the same manner as in Example 3. The glass transition point (Tg) of this product was determined to be 112 ° C by thermal analysis, and methylene chloride was used as the solvent. The reduced viscosity at 20 ° C of the 0.2 gZd 1 concentration solution was 0.14 d 1 / g, and the viscosity average molecular weight calculated from this value was 4,500.

In Examples and Comparative Examples, the viscosity average molecular weight (Mv)

[eta = 1. was calculated by ^{^{1 1 X 10- 4 Μν 0 ·}} 82.

Industrial applicability

According to the present invention, when a polymer is produced by a transesterification reaction, the reaction can be carried out without using a transesterification catalyst or even when the amount of the transesterification catalyst added is reduced. The process can proceed promptly, and the polymer can be obtained with high productivity. In addition, since the residual amount of the polymer of the ester exchange catalyst is also reduced, a high quality polymer having a low metal ion content and excellent chemical stability such as hydrolysis resistance is obtained. Can be The polymer obtained in this way is suitably used as a material in the fields of electricity and electronics, automobiles, and machinery.

Claims

The scope of the claims

1. A method for producing a polymer, which comprises conducting a transesterification reaction in the presence of a nitrile compound when producing a polymer by a transesterification reaction.

2. The nitrile compound has the following general formula

CN

OJ X Ύ χ

X

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 110 carbon atoms, or an aryloxy group having 6 to 13 carbon atoms.) An aromatic nitrile compound represented by the following formula: And the following general formula

CN

, Ar'— 0-

[Where A r 'is

O; or 〇 Q 〇

(Wherein, Q is an alkylene group, having 6 to 1 3 of § Li one alkylene group having a carbon carbon atoms ί~1 3, - 0-, -S-, - S0 2 - or represents one CO-.) The And n represents a number from 1 to 500. ]

2. The method for producing a polymer according to claim 1, which is selected from the group consisting of polyanoaryl ether represented by

3. The method for producing a polymer according to claim 2, wherein the polymer produced by the transesterification reaction is a polycarbonate.

4. The method for producing a polymer according to claim 3, wherein a dihydroxy compound and a carbonic acid diester are used as raw materials for the transesterification reaction.

5. preparation of the polymer in the range 4 wherein claims for performing transesterification dihydric Dorokishi based on 1 mol of the compound in the presence of a nitrile compound 10 mol to ^10-1 mol.

6. The dihydroxy compound has the following general formula (I)

H0- ^ -Z- (¾ -0H (I)

Wherein R ¹ is independently a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms or an aryl group having 6 to 12 carbon atoms, and m is 0 to 4 is an integer, Z is a single bond, one 0-, one CO-, one S -, - SO -, - S0 2 -, - CR 2 R 3 - ( provided that R ² and R ³ represents a hydrogen atom, An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.), A cycloalkylene group having 5 to 15 carbon atoms, a 1,1-cycloalkylidene group having 5 to 15 carbon atoms, and 2 carbon atoms -12, ω-alkylene group or the following formula (II) or (II ')

)

The bond represented by is shown. ] 'And an aromatic dihydroxy compound represented by the following general formula (III):

Five

(In the formula, R is each independently a halogen atom or an alkyl group having 1 to 8 carbon atoms, and k represents an integer of 0 to 4.)

6. The method for producing a polymer according to claim 5, which is an aromatic dihydroxy compound selected from the group consisting of aromatic dihydroxy compounds represented by the formula:

Ten

7. The dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane, the carbonic acid diester is diphenyl carbonate, and the ditolyl compound is 2,6-dimethoxybenzonitrile, 2,6. —Diphenyloxybenzonitrile or the following formula

Fifteen

7. The method for producing a polymer according to claim 6, which is a polyaryl ether having a repeating unit represented by the formula:

20

8. The method for producing a polymer according to claim 1, wherein the transesterification reaction is carried out in the presence of a nitrile compound and a transesterification catalyst.

9. The nitrile compound has the following general formula

twenty five CN

X (wherein, X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 110 carbon atoms, or an aryloxy group having 6 to 13 carbon atoms.) Compound and the following general formula

CN

υ ヽ

Ar-0--〇 n

[Where A r 'is

, ^ Or 〇 Q 〇

(Wherein, Q is an alkylene group, Ariren group having 6 to 13 carbon atoms of 1 to 13 carbon atoms, -0-, One S-, one S 0 ₂ - or -. Which CO- represents a) represents, n represents Represents a number from 1 to 500. ]

9. The method for producing a polymer according to claim 8, wherein the method is selected from the group consisting of polyaryl ether represented by the formula:

10. The method for producing a polymer according to claim 9, wherein the transesterification catalyst is a basic compound selected from the group consisting of an alkaline metal compound, an alkaline earth metal compound and a nitrogen-containing basic compound.

1 1. Check that the polymer produced by transesterification is polycarbonate. 13. The method for producing a polymer according to claim 10. '

12. The process for producing a polymer according to claim 11, wherein a dihydroxy compound and a carbonic acid diester are used as raw materials for the transesterification reaction.

13. transesterification, a dihydroxy compound 1 mole two Bok Lil compound ^10-7 mol to 10 ^_2 moles and transesterification catalyst 10- ⁸ moles to 10 ¹ mol of claims 12, wherein the carried out in the presence relative to A method for producing a polymer.

14. A dihydroxy compound represented by the following general formula (I)

Wherein R ¹ is independently a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms or an aryl group having 6 to 12 carbon atoms, and m is 0 to 4 Where Z is a single bond, one 0—, one CO—, —S—, —SO—, one S0. —, — CR ² R ³ — (where R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms), and 5 to 15 carbon atoms A cycloalkylene group having from 5 to 15 carbon atoms, a 1,1-cycloalkylidene group having from 2 to 12 carbon atoms, an ω-alkylene group or the following formula (II) or (I))

The bond represented by is shown. ] An aromatic dihydroxy compound represented by the following general formula (IΓI) ′

14. The method for producing a polymer according to claim 13, which is an aromatic dihydroxy compound selected from the group consisting of aromatic dihydroxy compounds represented by the formula:

1 5. The dihydroxy compound is 2,2-bis (4-hydroxyphenyl) propane, the carbonic acid diester is diphenylcarbonyl, and the nitrile compound is 2,6-dimethoxybenzonitrile, 2,6. —Diphenoxybenzonitrile or the following formula

CN

15. The method for producing a polymer according to claim 14, which is a polycyanoaryl ether having a repeating unit represented by the formula: wherein the transesterification catalyst is sodium hydroxide or calcium acetate.

16. The nitrile compound is 2,6-dimethoxybenzonitrile, 2,6-diphenoxybenzonitrile or the following formula

3. The method for producing a polymer according to claim 2, which is a polycyanaryl ether having a repeating unit represented by the formula: