JPS59179620A - Production of polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether having excellent mechanical and thermal properties, by ageing a specified phenolic compound in the presence of a catalyst under a specified condition and effecting the oxidative coupling polymerization of the phenolic compound in contact with oxygen. CONSTITUTION:A phenolic compound of the formula [wherein X is H, Cl, Br, or I, R is a monovalent substituent selected from among a hydrocarbon(oxy) group and a halohydrocarbon(oxy) group having at least two carbon atoms between the halogen and the phenol nucleus, R1 is R or a halogen, and R2 and R3 are each R1 or H] is mixed with a copper compound-amine catalyst and/or a Mn chelate catalyst, and the mixture is aged at 80 deg.C or below for 30min or shorter in an inert gas atmosphere and/or an oxygen-containing gas atmosphere to obtain a reaction mixture of an intrinsic viscosity <=0.10dl/g. While oxygen or an oxygen-containing gas is being blown into the reaction mixture, the oxidative coupling polymerization of the mixture is started at 100 deg.C or below.

Description

[Detailed description of the invention] Concerning the method of making nirene ether.

Polyphe! Ren ether is heat resistant, chemical resistant,
It is also widely known as a money-making resin with excellent mechanical and electrical properties. In addition, modified polyphenylene ether resin, which is a composition of polyphenylene ether with 7-tyrene resin that has improved impact resistance and processability, has excellent heat resistance, mechanical properties, electrical properties, processability, etc.
Widely used in automobile parts, electrical appliance parts, etc.

Polyphenylene ether is generally produced using a copper compound-amine catalyst or a manganese chelate catalyst, but the polymerization activity thereof is low and it is not economical.

As a result of intensive studies on copper compound-amine catalysts and manganese chelate catalysts, the present inventors have found that when a mixture of a phenol compound as a monomer and a catalyst is placed under an inert gas or oxygen atmosphere, substantially no polymer is formed. The present inventors have discovered that polymerization activity can be improved by initiating oxidative coupling polymerization after aging for a specific period of time under conditions where the polymer is not heated.

(In the formula, X is hydrogen, chlorine, bromine or iodine, and R is a hydrocarbon group, a hydrocarbonoxy group, a halodanized hydrocarbon group having at least two carbon atoms between the halogen atom and the phenol nucleus, and a halodanized hydrocarbon group) R1 is the same as R or is a halodane atom; R2 and R3 are each the same as R4 or hydrogen, provided that R, R1, R2 and R5 are At least one phenolic compound represented by
When performing oxidative coupling polymerization in the presence of an amine catalyst and/or a manganese chelate catalyst, the mixture containing the above phenol compound and catalyst is heated under an inert gas atmosphere and/or under an oxygen or oxygen-containing gas atmosphere, Production of a polyphenylene ether characterized by aging at a temperature of 80° C. or lower for 30 minutes or more in a state where coalescence is not substantially formed, and then substantially starting an oxidative coupling ligation reaction while contacting with oxygen. law is provided.

In the present invention, improvement in "polymerization activity" means that the molecular weight of polyphenylene ether produced in the same reaction time is greater than that of the conventional method, or that the reaction time to produce a polymer of the same molecular weight is shorter.

It has a structure represented by the formula, where each R* R1 is an alkyl group, and! l), R2, R, are each R
R is the same as 4 or hydrogen, and more preferred compounds are those in which R is an alkyl group having 1 to 8 carbon atoms, R
2r R5 is hydrogen. Specific examples of preferred phenolic compounds include 2.6-nomethylphenol, 2.6-noethylphenol, 2-methyl-6-
Nithylphenol, 2-methyl-6-arylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-sibutylphenol and 2-methyl-6-brobylphenol 2,3.6-
) +7,)'Tylphenol, 2,3-dimethyl-
Examples include 6-nitylphenol.

Particularly preferred is 2,6-dimethylphenol, known as 2,6-xylenol. These phenolic compounds are used singly or in combination of two or more. The above-mentioned phenol compound may be polymerized by being added all at once without being dissolved or dissolved in the polymerization solvent, or may be polymerized while being added in portions or continuously.

Copper compounds used as catalysts include cuprous salts and cuprous salts.
Copper salts are used. Cuprous salts include cuprous chloride, cuprous bromide, cuprous sulfate, cuprous azide, copper tetramine sulfate, cuprous acetate, cuprous lactate, cuprous tetraamine sulfate, and zolopion. Examples include cuprous acid, cuprous palmitate, cuprous toluate, etc., and preferably cuprous bromide, cuprous chloride, cuprous acetate, cuprous azide. Examples of cupric salts include cupric chloride, cupric bromide, cupric sulfate, cupric tetraamine sulfate, cupric acetate, cupric lactate, cupric thoriate, etc., and are preferred. are cupric chloride, cupric bromide, and cupric asodo. One or more of these may be used. It is also possible to use a mixture of cuprous salts and cupric salts @ the ratio can vary within the range of 10/90 to 90/10 (weight ratio), but is preferably 20/8.
0 to 80/20.

The amount of these copper salts used is preferably about 0.1 to 20 mol per 100 mol of the phenolic compound. Furthermore, when using a primary or secondary amine as a Kb medium complex, the amount of copper salt used is 0.2 per 100 moles of phenol.
The amount of copper salt used is preferably 4 to 15 moles per 100 moles of phenol when a tertiary amine is used. The amines used as the catalyst complex include primary amines, secondary amines, and tertiary amines. Examples of this are aliphatic amines in which the aliphatic group comprises a straight-chain, branched-chain hydrocarbon or alicyclic group. Preferred are aliphatic primary, secondary and tertiary monoamines and diamines. Methyl is a typical example,
Amines substituted with 7-no, no- or tri-substituted alkyl groups such as ethyl, n-propyl, ■=propyl, n-butyl, etc. N-alkyl cycloaliphatic amine, N, d-dialkylethylenediamine, N,N'-dialkylpropanediamine, N,N,N'-)realkylpentanoamine, N,
Diamines such as N,N',N'-tetraalkylethylenediamine (here, the alkyl group is an inglovir group,
Examples of cyclic amines include pyridine, α-colicin, r-picoline, etc. Particularly preferred amines include n-butylamine,
di-n-butylamine, triethylamine, pyridine,
N,N'-di-tert-butylethylenediamine,
N, N, N', N'-tetramethylbutanediamine and the like. The above amines may be used alone or in combination of two or more.

The concentration of amine in the reaction mixture varies over a wide range of I[! In the case of primary and secondary amines, the range is preferably 0.1 to 3000 mol, preferably 2 to 1500 mol, per 100 mol of the phenolic compound. Preferably, the amount is 0.1 to 100 moles, more preferably 2 to 25 moles, and in the case of tertiary amines, it is preferably 300 to 2,000 moles, and more preferably 500 to 1,500 moles.

The manganese chelate catalyst used in the present invention has the general formula Lx
It is represented by Mn(U), and examples of the Mn(IT) compound in the formula include Mn(II) halides such as Mn(U) chloride, Mn(II) bromide, and Mn(II) iodide; (II) Carbonate, Mn(It) L oxalate group, Mn(IT) sulfate, Mn(U) acetate, p/In(
II) Also included are nitrates, My(U) phosphates, etc. and hydrates of Mn(ff) compounds. In the above formula, R//// is an aqueous atom and an acyclic or cyclic hydrocarbon group, -NH2, -NHR, -N(R)2. -OH, -O
R and -00CR (where R is an alkyl group having 1 to 10 carbon atoms)] and/or an alkyl group having general formulas 1 to 5, Rb is hydrogen, alkyl, cyclo Alkyl, aryl, amino, monoalkylamide, dialkylaminohalide, alkoxy,
selected from the group consisting of alkanoates and combinations thereof, wherein Ar is at least one 10H group and at least one a-C=N-OH group directly bonded to the arene carbon atom in the ortho position; is at least a divalent arene group having a divalent arene group).

Preferred oxime compounds include penzoinmexime,
p-dimethylaminobenzoin oxime, 2-phenyl-2-hydroxybutane-3-oxime, salicylaldoxime, 2-hydroxy-5-chlorophenylaldoxime, 2-hydroxy-5-bromophenylaldoxime, 2-hydroxy- 5-methylacetophenone oxime, etc.

In the above general formula, X is at least 1 or more.

When preparing the LxMn(U) solution, alcohols,
Solvents such as ketones, hydrocarbons, chlorohydrocarbons, nitroaromatic hydrocarbons, ethers, sulfoxides can be used; preferably methanol, chlorobenzene, toluene and hxylene or mixtures thereof are used. Ru. In order to accelerate the polymerization reaction, a strong alkali metal base such as an alkali metal hydroxide, an alkali metal alkoxide, etc. or a mixture thereof is used as necessary. Specifically, sodium hydroxide, potassium hydroxide,
Examples include lithium hydroxide and sodium methoxide. The amount used is a molar ratio of phenol compound to alkali metal base of 1:1 to 100:1, preferably 40:1 to 5:1, and more preferably 20:1 to 1O:1. Further, the above-mentioned manganese chelate melting medium can be carried out in the presence of a primary amine, a 2R amine, or a 3M amine. The molar ratio of phenolic compound/amine is preferably from 10010.05 to 10
It is 0/3.

Examples of the above amines include n-butylamine, n-hexylamine, di-n-hexylamine, trimethylamine, methylethylamine, diethylamine, di-n-propylamine, di-n-butylamine, piperazine, 2-hydroxyethylamine, 2- methylaminoethylamine,
Amine compounds such as n-zorobylamine, isozorobylamine, tertiary-butylamine, cycloditylamine, 1,4-butanediamine, 4-hydroxybutylamine, 4-ethoxybutylamine, n-pentylamine, 1,5-bentankamine, etc. is available. In addition to these, cyclic polyamines can also be used, such as 1,3-bis(β-aminoethyl)benzene, 1,
4-bis(γ-amino-n-hexyl)benzene, 3.
3',5.5'-tetraaminobiphenyl, 1,8-bis(β-amino-n-7"thyl)naphthalene, 1,3-
7 enylene diamine, 1.4-7x nylene diamine, 4
．． 4'-Noaminodiphenylpropane, 4.4'-diaminonophenylmethane, hensisin, 4.4'-diaminodiphenylnulfite, 3,3',5,5'-
Examples include tetraamino-) phenyl sulfone, 4,4'-cyamino diphenyl ether, and 1,5-diaminonaphthalene.

The above amines may be used alone or in combination of two or more.

The amount of manganese compound to be used relative to the phenol compound is 2 to 0, preferably 0.5 to 0.02 mole, per 100 mole of the phenol compound.

The copper compound-amine catalyst and the manganese chelate catalyst used in the present invention can also be used in an appropriate mixture. The polymerization reaction is preferably carried out in a polymerization solvent, and examples of the polymerization solvent include benzene, toluene, xylene, 0-dichlorobenzene, tetrachloroethane, trichloroethane, dichloromethane, 1,2-dichloroethane, and trichloroethylene, preferably benzene, These are toluene, xylene, and 0-dichlorobenzene. The amount of the polymerization solvent to be used is not particularly limited, but the amount of phenol compound in the polymerization solvent is 2 to 50% by weight, preferably 1 to 5 to 3% by weight.
The weight ratio is adjusted to 0 weight ratio, more preferably 8 to 25 weight ratio.

An important feature of the present invention is that in order to improve the polymerization activity, a mixture of a phenolic compound monomer and a catalyst, preferably a mixed solution to which a polymerization solvent is added, is prepared under an inert gas atmosphere and/or in an oxygen or oxygen-containing atmosphere. After aging at a temperature of 80° C. or lower for 30 minutes or more in an atmosphere without substantially producing a polymer, the oxidative coupling polymerization reaction is completely initiated by contact with oxygen. Aging of the mixture is carried out with or without stirring. The time is 30 minutes or more, preferably 60 minutes to 600 minutes after the phenol compound and catalyst are completely mixed, and the temperature is 80°C or less, preferably 10°-60°C.

The inert gas may include nitrogen, helium, neon, argon, krypton, xenon, radon, etc., with nitrogen being preferred. In this case, if the polymer is not substantially produced, the oxidative polymerization reaction due to oxygen is not occurring at all, or even if it is occurring, the intrinsic viscosity of the reaction product (
Measured in chloroform at 30℃) is 0.1 Odl111
Preferably 0.05 di/f! The following must be met. In such a system, oxygen or an oxygen-containing gas is blown into a mixture of a phenolic compound and a catalyst, more preferably a polymerization solvent is present, or oxygen pressure is applied for a short time, and then the mixture is blown or pressurized. This can be achieved by stopping and holding it. A short time varies depending on the scale or type of polymerization system, but is 15 minutes or less, preferably 10 minutes or less, and more preferably 5 minutes or less.

When ripening the above mixture or mixture, the phenolic compound and the catalyst may be mixed in their respective amounts in their entirety at once, or at least 10% by weight, preferably 20% by weight, of the total amount of each. Uesara KiEt
L< may be mixed with a weight factor of 30 or more. The phenolic compound and/or catalyst remaining after aging may be added all at once at the start of polymerization, or may be added in portions or continuously before and/or during polymerization.

The polymerization reaction of the present invention is carried out in the presence of oxygen.

The polymerization may be carried out while blowing oxygen or an oxygen-containing gas into the polymerization system, or the polymerization may be carried out under the pressure of oxygen or an oxygen-containing gas. In the present invention, this is the point at which the polymerization reaction starts and oxygen or an oxygen-containing gas is blown into the polymerization system to completely start, or the point at which specie is poured. The reaction temperature according to the present invention is a maximum temperature of 100
℃, preferably not exceeding 80℃. More preferably, the temperature is 10°C to 50°C. Furthermore, in order to improve the polymerization activity, 0.02 guanidine such as diphenylguanidine, ditolylguanidine, tetramethylguanidine, triphenylguanidine, etc.
It is also possible to use 5 to 3.0 moles.

In addition, 1 is used for all reaction systems of lower alcohols such as methanol, ethanol, solonol, butanol, and allyl alcohol.
It is also possible to have an awn that is less than 0 weight.

In addition, alkali metal bromides and alkaline earth metal bromides such as lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, calcium bromide, strontium bromide, and barium bromide are combined with copper compounds and manganese compounds 1 0.5 to 2.5 moles may be used per mole, and a quaternary ammonium salt such as methyltri-n-octylammonium chloride may be used in an amount of 5 to 0.2 mole of O,OO per 100 moles of the phenol compound. Alternatively, a binuphenol type or trinuphenol type antioxidant may be used in an amount of 0.01 to 10% by weight of the hexaphenol compound. Alkanolamines such as ethanolamine, 0-aminophenol, 2-(2-aminoethylamine)ethanol, 1-phenyl-2-aminoethanol and 1-methyl-2-aminoethanol can also be used.

In addition, known methods can be used to terminate the polymerization reaction, such as using a non-solvent for the polymer such as methanol, hydrochloric acid, acetic acid,
The polymerization reaction can be stopped by adding carbon dioxide, a known chelating agent, or other known terminal capping agent to obtain a polymer of a desired molecular weight.

The polyphenylene ether produced by the method of the present invention has excellent mechanical properties and thermal properties, so it can be used for various purposes, and it can be produced into various molded products by ordinary molding methods. . Further, antioxidants, ultraviolet rays, absorbers, lubricants, flame retardants, antistatic agents, fillers, plus fibers, etc. that are commonly used in use can be added. Furthermore, depending on the required performance, other known polymers such as polystyrene, styrene-acrylonitrile copolymer, rubber modification, [linutylene (rubber polymer: polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene) may be used. Polymer, EPDM), A
BS &&, styrene-butadiene block polymer, nutylene-butazoene-nutyrene block polymer, nutylene-butadiene-styrene radial teleblock polymer, polyzolopyrene, polybutanoene, butadiene-styrene copolymer, butadiene-acrylonitrile Copolymer, acrylic rubber, ethylene-zolopyrene M combination, E
PDM.

Polyethylene, polyvinyl chloride, polycargonate, P
ET% PBT, polyacetal, polyamide,
Epoxy resin, polyvinylidene heptadide, polynulfone,
Ethylene-vinyl acetate copolymer, polyisoprene, natural rubber, nutylene-methyl methacrylate copolymer, nutylene-maleic anhydride copolymer, chlorinated butyl rubber, chlorinated polyethylene, PPS resin, polyether ether ketone, etc. as appropriate. They may be used in a blended manner. Next, the present invention will be explained in more detail with reference to Examples.

Example-1 After the inside of a glass reaction vessel equipped with an oxygen blowing device, a cooling coil, and a stirrer at the bottom of the reactor was sufficiently replaced with nitrogen,
Cupric bromide 0.672y, non-n-butylamide y13.
95') was dissolved in 2.6-xylenol 18354 and added to 1400 ml of 2.6-xylenol.

The reaction mixture was allowed to stand at 30° C. under nitrogen pressure for 60 minutes with stirring, and then polymerization was carried out for 120 minutes while rapidly blowing oxygen into the reactor. During polymerization, water is circulated through the cooling coil to maintain the internal temperature f:
The temperature was maintained at 30°C. After the polymerization was completed, the reaction mixture was stirred with a 50% acetic acid aqueous solution, centrifuged, the polymer solution phase was removed, and the polymer was recovered using methanol. This was filtered, thoroughly washed with methanol, and then dried under vacuum. The intrinsic viscosity of the obtained polymer was 0.55 dl when measured in a chloroform solution at 30°C! /P.

Example-2 All the conditions of Example-1 were omitted except that the standing time was changed from 60 minutes to 120 minutes in Example-1. The intrinsic viscosity of the obtained polymer was 0.64 #/g.

Example-3 All the conditions were as in Example-1 except that the standing temperature in Example-1 was changed from 30°C to 60°C. The intrinsic viscosity of the obtained polymer was 0.52 dll'i.

Example 4 After sufficiently purging the inside of a glass reaction vessel equipped with an oxygen blowing device, a cooling coil, and a stirrer at the bottom of the reactor with nitrogen,
2,6-xylenol 175y was dissolved in 500 ml toluene and charged into the reactor. Sibutylamine 175
9-1R4nCtzo, 120], ff, α-
Ben/inoxime 0.4347? '＜Methanol? 0
A homogeneous solution in which 400 rnl f of toluene was added was added to the reactor. Furthermore, 50qI) methanol 70ml1f to 7.15P of zutorium hydroxide aqueous solution
After the added homogeneous solution was added to the reactor, it was allowed to stand at 30° C. for 60 minutes with stirring under nitrogen pressure, and then polymerization was carried out for 120 minutes while rapidly blowing in oxygen.

During this time, water was circulated through the cooling coil to maintain the internal temperature at 30°C. After the polymerization was completed, the reaction was stopped in the same manner as in Example-1, and the polymer was recovered. The intrinsic viscosity of the resulting polymer was 0.62 dl/g.

Example-5 In Example-4, 4.4' was used instead of butylamine.
- Diaminodiphenylmethane 2.84 S''k was used, but all the conditions were as in Example 4. The intrinsic viscosity of the obtained polymer was 1.2 di/f.

Example-6 Toluene when left under nitrogen in Example-1, 2
．． Amount of 6-xylenol: 1400 rnl of toluene,
2r 6-xylenol 1831 to toluene 70
0TrLl, changed to 2,6-xylenol 91.5s', left for 60 minutes, then added 700 ml of toluene, 2.
．． All polymerization was carried out under the conditions of Example 1, except that the 6-xylenol 9157 solution was added to the entire polymerization system and then polymerized. The ultimate viscosity of the obtained polymer was 0.55 de/g.

Comparative Example-1 All the conditions were as in Example-1, except that in Example-1, the polymerization reaction was carried out without standing under nitrogen for 60 minutes.

The intrinsic viscosity of the obtained polymer was 0.25d11! /f Comparative Example-2 All conditions were as in Example-1 except that in Example-1, the polymerization reaction was carried out by standing under nitrogen for 15 minutes. The intrinsic viscosity of the resulting 1-coalescence was 0.25 di/'if. Comparative Example-3 The temperature at which the mixture was left to stand in Example-1 was changed from 30°C to 10°C.
All the conditions were as in Example 1 except that the temperature was changed to 0°C. The intrinsic viscosity of the resulting single coalescence was 0.26 de/g.

Comparative Example 4 All of the polymerization reactions were carried out under the same conditions as in Example 4, except that the polymerization reaction was carried out without being left under nitrogen. The intrinsic viscosity of the obtained polymer was 0.50 dlVfl.

Comparative Example 5 All of the polymerization reactions were carried out under the same conditions as in Example 5, except that the polymerization reaction was carried out without standing under nitrogen for 60 minutes.

The intrinsic viscosity of the obtained polymer was 0.85 di/fi'.Comparative Example-6 All polymerization was carried out under the conditions of Comparative Example-1, except that the polymerization time was 180 minutes in Comparative Example-1. The intrinsic viscosity of the obtained polymer was 0.28 dlVP.

Comparative Example-7 All polymerization was carried out under the conditions of Comparative Example-1, except that the polymerization time was 240 minutes in Comparative Example-1. The intrinsic viscosity of the obtained polymer was 0.36 dllP.

Example-7 Oxygen blowing device, cooling coil, and stirring a! at the bottom of the reactor.
! After fully replacing the interior of the reaction vessel with nitrogen, cupric bromide 0.67254, non-n-butylamine 13.9P, ) #-T-7'l 400nLl 2.6
-Xylenol 183 It was dissolved in P' and added.

Oxygen was blown into the mixture for 0.5 minutes at 30° C. while stirring, and then the oxygen injection was stopped and the mixture was left for 60 minutes.

At this point, a small amount of the mixture was removed and added to methanol, but no polymer formation was observed. After standing for 60 minutes, polymerization was carried out for 120 minutes while rapidly blowing oxygen into the reactor. During polymerization, water was circulated through a cooling coil to maintain the internal temperature at 30°C. After completion of polymerization, reaction mixture total 50
The mixture was stirred with an aqueous acetic acid solution, centrifuged, the polymer solution phase was taken out, and the entire polymer was recovered using methanol. This was filtered, thoroughly washed with methanol, and then dried under vacuum. The intrinsic viscosity of the obtained polymer was 0.64 dVf when measured in a chloroform solution at 30°C.Example-8 In Example-7, the standing time was changed from 60 minutes to 120 minutes. All conditions except 1 were carried out under the conditions of Example 7. The intrinsic viscosity of the polymer thus prepared was 0.71 dVy-.

Example-9 In Example-7, the leaving temperature 'f! :30℃ to 60℃
All conditions were as in Example 7 except for the following changes. The intrinsic viscosity of the obtained polymer was 0.58 dlQ.
All the conditions were as in Example 7 except that the time was changed to 1 minute. The intrinsic viscosity of the obtained polymer is 0.62 dll fit
Met.

Example-11 Oxygen blowing device, cooling coil, stirring ia at the bottom of the reactor
After the interior of the reaction vessel containing all the gold was subjected to optical nitrogen exchange with nitrogen, 2,6-xylenol (1757i5001nl) was dissolved in toluene and charged into the reactor. Di-butylamine 1.7
5 fI, MnC42o, i 201 P.

0.4347P' of α-benzoin oxime was dissolved in 70ml of methanol and then 400mA of toluene! The homogeneous solution added was placed in the reactor. Furthermore, a homogeneous solution of 7.15 fl of a 50% aqueous sodium hydroxide solution and 70 ntlf of methanol was added to the reactor, and then heated at 30°C with stirring.
Oxygen was blown in for a total of 1 minute, and then the oxygen injection was stopped and left for 60 minutes. At this point, a small amount of the mixture was removed and added to methanol, but no polymer was formed.

After standing for 60 minutes, polymerization was carried out for 120 minutes while rapidly blowing oxygen into the reactor. During this time, water was circulated through the cooling coil to maintain the internal temperature at 30°C. After the polymerization was completed, the reaction was completely stopped in the same manner as in Example 7, and the polymer was recovered. The intrinsic viscosity of the obtained polymer was 0.74 d&/g@Example-12 In Example-11, 4,4
All procedures were carried out under the conditions of Example 11 except that 2.845'-diaminodiphenylmethane was used.

The intrinsic viscosity of the obtained polymer was 1.35 delg.

Example-13 Toluene when left under oxygen in Example-7, 2
, 6-xylenol amount Wotoluene 1400-, 2,6-
xylenol 183 fI to toluene 700 vol., 2,6
- Changed to xylenol 91.5y, left for 60 minutes, then toluene 700d, 2.6-xylenol 91.51
All polymerization was carried out under the conditions of Example 7, except that the 7' solution was added to the entire polymerization system and then polymerized. The intrinsic viscosity of the obtained polymer was 0.64 d&/! Comparative Example 8 The polymerization reaction was carried out under the same conditions as in Example 7, except that the polymerization reaction was carried out without standing for 60 minutes. The intrinsic viscosity of the obtained polymer was 0.25 dlQ.Comparative Example-9 All the conditions were as in Example-7 except that the standing time was changed from 60 minutes to 15 dlQ in Example-7. The intrinsic viscosity of the obtained polymer was 0.25 dl,/fF.
All the conditions were as in Example 7 except that the temperature was changed to 0°C. The intrinsic viscosity of the obtained polymer was 0.28 dl! /f
Met.

Comparative Example-11 In Example-7, oxygen injection time ranged from 0.5 minutes to 60 minutes.
(The intrinsic viscosity at this point was 0.14 til/7). The intrinsic viscosity of the obtained polymer was 0.32d7/1.

Comparative Example-12 All the conditions were as in Example-11 except that the polymerization reaction was carried out without standing for 60 minutes in Example-11. The intrinsic viscosity of the obtained 1-coalescence was 0.50 dllfl. Comparative Example-13 All the polymerization reactions were carried out under the conditions of Example-12 except that the polymerization reaction was carried out without standing for 60 minutes in Example-12. The intrinsic viscosity of the obtained polymer is 0.85 d/y? Met.

Comparative Example-14 All polymerization was carried out under the conditions of Comparative Example-8, except that in Comparative Example-8, the polymerization time was 180 minutes. The intrinsic viscosity of the obtained polymer was 0.28.11/7.

Comparative Example-15 All polymerization was carried out under the conditions of Comparative Example-8, except that in Comparative Example-8, the polymerization time was 240 minutes. The intrinsic viscosity of the polymer tested was 0.3.6 dl/f.

Claims (1)

[Scope of Claims] (In the formula, A monovalent substituent selected from a hydrogenated hydrocarbon group and a halogenated backhydrogenated oxy group; R4 is the same as R or is a halodane atom; R2 and R5 are each the same as R1 or hydrogen, provided that Rr R1* R2 and R
When performing oxidative coupling polymerization of at least one phenol compound represented by (3) (none of which has a tertiary carbon atom) in the presence of a copper compound-amine catalyst and/or a manganese chelate catalyst, The mixture containing the above phenol compound and catalyst was aged for 30 minutes or more at a temperature of 80° C. or lower under a total inert gas atmosphere and/or under an oxygen or oxygen-containing gas atmosphere, but without substantially forming a polymer. A method for creating polyphenylene ether, which comprises substantially starting an oxidative coupling polymerization reaction while contacting the polyphenylene ether with oxygen. (2) The manufacturing method according to item 1, wherein the aging temperature is 10° to 60°C. (3) The first stage in which a mixed solution obtained by adding a polymerization solvent to the mixture containing the phenol compound and the catalyst is subjected to the above-mentioned aging.
Creation method described in section.