JPH0670131B2 - Method for producing polyphenylene ether - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a process for producing high quality polyphenylene ether with a highly active copper catalyst having improved water resistance. More specifically, copper salt, N-phenylethanolamine,
High quality by oxidatively polymerizing a phenolic compound with oxygen in the presence of a catalyst having high water resistance, which is composed of a secondary aliphatic amine, a specific secondary diamine, and a tertiary amine, and having high continuous polymerization activity. The present invention relates to a method for producing polyphenylene ether.

[Prior Art] Conventionally, an oxidation polymer of a phenolic compound is known as polyphenylene ether, which has mechanical properties,
It has excellent electrical characteristics, heat resistance, and low water absorption,
Due to its properties such as good dimensional stability, it has recently attracted attention as a thermoplastic engineering plastic.

Many combinations of copper compounds, manganese compounds or cobalt compounds with various amines have been proposed as polymerization catalysts for producing polyphenylene ethers by the oxidative polymerization of phenolic compounds.

Among them, diamines having a specific structure, specifically N, N ′
It is known that the copper amine complex composed of a combination with -di-t-butylethylenediamine and the like has relatively high activity.

For example, a combination of a tertiary ion such as copper ion, bromide ion, N, N'-di-t-butylethylenediamine and N-methylpyrrolidine is known (Japanese Patent Publication No. 58-53012).

However, the polymer produced by using this catalyst system is not practical because it has a poor color and a low impact resistance in a composition with a styrene resin such as rubber-modified polystyrene, and a poor heat stability. Became clear, and di-
It became practical for the first time with a catalyst system in which a secondary monoamine such as n-butylamine was combined (JP-B-59-23332). Further, in this catalyst system, a production method in which the amount of bromide ion is about 1:35 or more in molar ratio to the starting phenolic compound (JP-A-59-74124), the first copper compound is used.
A method characterized by using a mixture of a copper salt and a cupric salt (Japanese Patent Publication No. 59-131627) and a catalyst system using dimethylamine as a secondary monoamine (Japanese Patent Publication No. 60-54327).
Publications) are also known.

Further, there are known examples in which these copper amine complex catalysts are applied to a continuous polymerization method (Japanese Patent Laid-Open Nos. 59-230025 and 5).
9-230026 publication).

[Problems to be Solved by the Invention] However, as a result of additional examinations by the present inventors regarding these conventional techniques, it was found that the following basic problems have not been sufficiently solved yet. That is, the water resistance of the catalyst is not sufficiently improved, and the polymerization activity in the continuous polymerization method is still low.

One of the causes is N, N'as described in JP-A-59-196318, page 3, left column, lines 28 to 31.
It may also be related that -di-t-butylethylenediamine is often very easily consumed in the polymerization process.

In any case, the catalytic components are hydrolyzed by the reaction product water produced as a by-product during the oxidative polymerization of phenols, or the metal components become hydroxides and leave the reaction system, resulting in a decrease in catalytic activity. Therefore, there has been a demand for the development of a catalyst that does not deteriorate in activity even in the presence of reaction product water due to high activation of the catalyst.

In particular, the improvement of water resistance is an important problem in continuous polymerization methods requiring a long average residence time.

Thus, from an industrial standpoint, there is a strong demand for the development of highly active catalysts with improved water resistance.

[Means for Solving Problems] As a result of earnest studies on the method for producing polyphenylene ether in the above situation, the present inventors have found that a copper compound, N-phenylethanolamine, a specific diamine, and a third compound. It was found that a catalyst system composed of a primary amine has an extremely excellent water resistance and a high continuous polymerization activity, and a patent application was previously filed (Japanese Patent Application No. 62-139032, date of application: June 4, 1987).

As a result of further investigation based on this finding, the quality of the polyphenylene ether obtained by using the catalyst system containing both the secondary aliphatic amine and N-phenylethanolamine, especially the color tone and rubber-reinforced polystyrene, etc. The inventors have found that the strength of Izod impact when used as a product is remarkably good, and completed the present invention.

That is, the present invention relates to (a) copper salt, (b) N-phenylethanolamine, (c) secondary aliphatic amine, and (d) general formula
R ₁ -HN-R-NHR ₂ [wherein R ₁ and R ₂ represent an isopropyl group, a C _{4 to} C ₈ tertiary alkyl group or a cycloalkyl group having no hydrogen on the α-carbon atom]. ] 1,2-diamine or 1,
A method for producing a polyphenylene ether by oxidatively polymerizing a phenolic compound with oxygen, which comprises using a catalyst composed of 3-diamine and (e) a tertiary amine.

In carrying out the present invention, the copper salt may be a cuprous salt, a cupric salt, or a mixture thereof.

Virtually any cuprous or cupric salt can be used, but the particular choice is primarily determined by economics and the availability of the compound. Soluble copper salts are preferred, but usually insoluble salts of copper (cupric and cuprous) can of course be used. This is because these insoluble salts form a soluble complex with the amine in the reaction mixture.

Examples of cupric salts that can be used in the catalyst of the present invention include cupric halides such as cupric chloride or cupric bromide, cupric sulfate, cupric nitrate, cupric acetate, and azide cupric. Examples include cupric acid and cupric toluate. Examples of cuprous salts that can be used are cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, cuprous azide, cuprous acetate, cupric butyrate or toluic acid. Cuprous etc. Preferred cuprous and cupric salts are
Cuprous chloride, cupric chloride, cuprous bromide, cupric bromide. Further, these copper salts may be synthesized at the time of use from oxides, carbonates, hydroxides and the like and halogens or hydrogen halides. The amount of copper salt used is 0.005 to 1 gram atom of copper, preferably 0.01 to 100 moles of the phenolic compound.
The range is from gram atom to 0.5 gram atom.

As N-phenylethanolamine in the present invention, N-
In addition to unsubstituted phenylethanolamine, N-substituted phenylethanolamine is also included. Preferred substituents are a lower alkyl group and an alkoxy group, which may be further substituted with halogen. Preferred specific examples thereof are N-phenylethanolamine, N- (m-methyl) phenylethanolamine, N- (p-methyl) phenylethanolamine, N- (2 ', 6'-dimethyl) phenylethanolamine, N -(M-Methoxy) phenylethanolamine, N-
(P-chloro) phenylethanolamine, N- (m-chloro) phenylethanolamine, N- (o-chloro) phenylethanolamine, N- (o-ethyl) phenylethanolamine, N- (m-ethyl) phenyl Ethanolamine,
And N- (p-ethyl) phenylethanolamine. Furthermore, among these, N-phenylethanolamine, N-
(P-Chloro) phenylethanolamine, N- (2 ', 6'
-Dimethyl) phenylethanolamine and N- (o-ethyl) phenylethanolamine are particularly preferred.

The amount of N-phenylethanolamine used is not particularly limited, and can be used in a wide range of 0.05 mol to 10 mol, preferably 0.1 mol to 5 mol, per 100 mol of the phenolic compound.

The secondary aliphatic amine used in the present invention has the formula: HNR ₁ R ₂ (1) [wherein R ₁ and R ₂ are independently or both of them are acyclic and cyclic organic groups]. I have. Preferred secondary aliphatic amines are those in which R ₁ and R ₂ each have 1 to 20 carbons, more preferably 1 to 10 carbons. R ₁ and R ₂ are C _{1 ~ 8,} respectively, especially now that it may be obtained readily _{commercially,} preferably secondary aliphatic amines C _{2 ~ 6,} more preferably an alkyl group of C _{3 ~ 5} Is preferred.

Examples of secondary amines that can be used in the present invention include:

Dimethylamine, diethylamine, di-n-propylamine, di-secondary propylamine, di-n-butylamine,
Di-secondary-butylamine, di-tertiary-butylamine, dipentylamines, dihexylamines, diheptylamines, dioctylamines, dinonylamines, didecylamines, dieicosylamines, dibenzylamines, methyl Ethylamine, methylbutylamines, methylcyclohexylamine, heptylcyclohexylamines, octadecylcyclohexylamines, etc.

Further, in the present invention, the second
In addition to the primary aliphatic monoamine, a secondary aliphatic diamine represented by the following formula (2) can be used.

However, in the formula, R ₃ and R ₅ are alkyl groups or aralkyl groups having 1 to 20 carbon atoms, R ₆ is hydrogen, an aralkyl group or aralkyl group having 1 to 20 carbon atoms, and R ₄ is 3 to 20 carbon atoms. Represents an aralkyl group.

Specifically, N-, N, N'-, N, N, N '-(mono-, di-,
And trialkyl) diaminopropanes such as N-methyl-1,3diaminopropane, N, N'-dimethyl-1,3diaminopropane, N, N, N'-trimethyl-1,3diaminopropane, N-ethyl -1,3 diaminopropane, N, N'-diethyl-1,3 diaminopropane, N, N, N'-triethyl-1,
3diaminopropane, N, N'-dimethyl-1,3diamino-1
-Methyl-propane, N, N'-dithymel-1,3diamino-2
-Methyl-propane, N, N, N'-trimethyl-1,3diamino-1-methyl-propane, N, N, N'-trimethyl-1,3diamino-2-methyl-propane, etc., N-, N , N'-, N, N, N '
-(Mono-, di-, and trialkyl) diaminobutanes, N-, N, N'-, N, N, N '-(mono-, di-, and trialkyl) diaminopentanes, N-, N, N '-, N,
N, N '-(mono-, di-, and trialkyl) diaminohexanes, N-, N, N'-, N, N'-, N, N, N'-(mono-, di-, and (Trialkyl) diaminooctanes and the like.

In the present invention, the amount of the secondary aliphatic amine used is not particularly limited, and may be 0.0 based on 100 mol of the phenolic compound.
It may be used in the range of 5 to 15 mol, preferably 0.1 to 5 mol.

The molar ratio of N-phenylethanolamine to secondary aliphatic amine may be in the range of 90/10 to 10/90.

General formula R ₁ -HN-R-NHR ₂ (wherein R ₁ and R ₂ are isopropyl groups, C ₄
It represents a tertiary alkyl group or α- cycloalkyl group having no hydrogen on the carbon atoms of -C _8. ] 1,2-diamine or 1,3-diamine.

Specific examples of these compounds include N, N'-di-t-butylethylenediamine, N, N'-di-t-amylethylenediamine and N, N'-diisopropylethylenediamine,
N, N'-di-t-butylpropylenediamine, N, N'-di-
Examples include t-butyl-cyclohexane-1,2-diamine. Of these, N, N'-di-t-butylethylenediamine is preferred. The diamine is used in an amount of 0.01 to 10 mol, preferably 0.05 to 5 mol, per 100 mol of the phenolic compound.

Examples of tertiary amines that can be used in the practice of this invention are aliphatic tertiary amines, including cycloaliphatic tertiary amines. Examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, triisopropylamine, diethylmethylamine, propyl-dimethylamine, allyldiethylamine, butyl-dimethylamine, diethylisopropylamine and cyclohexyl-dimethylamine.

Furthermore, N, N, N ′, N′-tetraalkyldiaminoethane, N, N, N ′, N′-tetraalkyldiaminopropane,
Aliphatic tertiary polyamines such as N, N, N ', N'-tetraalkyldiaminobutane can also be used. Of which N, N,
N ', N'-tetramethyl-1,3-diamino-1-methyl-propane, N, N, N', N'-tetramethyl-1,3-diamino-2
-Methyl-propane, N, N, N ', N'-tetramethyl-1,3-
Diamino-1-ethyl-propane, N, N, N ', N'-tetramethyl-1,3-diamino-2-ethyl-propane and the like are preferable, N, N, N', N'-tetramethyl-1 Particularly preferred are 3,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,3-diamino-1-methyl-propane and the like.

The amount of the tertiary amine used in the present invention is not particularly limited, but it is used in an amount of 0.1 to 10 mol, preferably 1 to 6 mol, per 100 mol of the phenolic compound.

In carrying out the present invention, coexistence of halogen ions other than fluorine ions is preferable because the catalytic activity is improved. As the halogen ion, chlorine ion and bromine ion are particularly preferable. The halogen ions may be used alone or together. As the halogen ion source, for example, HBr, HCl, NaB
r, KBr, NaCl, KCl, CuBr ₂ , CuCl ₂ , CuBr, CuCl, etc. can be used.
Particularly preferred are HBr and HCl. The amount of these used is not particularly limited, but is preferably 0.5 to 30 mol, and particularly preferably 1 to 15 mol with respect to 1 mol of copper.

The catalyst can be prepared using a solvent such as methanol. If it is noted that the copper compound is dissolved, the object can be achieved by a method generally known to those skilled in the art. It may be prepared in the atmosphere.

The phenolic compound used in the method of the present invention has the general formula [Wherein R ₃ is a hydrocarbon group having 1 to 4 carbon atoms, R ₄ is halogen or a hydrocarbon group having 1 to 4 carbon atoms], and a phenolic compound represented by the formula Is
For example, 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-
Methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-
Ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-
6-chlorophenol and the like. These compounds may be used alone or in combination of two or more kinds. In addition, even if a small amount of orthocresol, meta-cresol, para-cresol, 2,4-dimethylphenol, 2-ethylphenol, etc. is contained, there is no problem in practical use.

Of these phenolic compounds, 2,6 dimethylphenol is particularly important.

The ratio of the phenolic compound to the solvent can be selected in a wide range, but usually the concentration of the phenolic compound in the reaction solution is 70% by weight or less, preferably 10 to 40% by weight, more preferably 20 to 35% by weight. is there.

The solvent used in the method of the present invention is not particularly limited as long as it is less oxidizable than the oxidizable phenolic compound and does not have reactivity with various radicals that are considered to be generated in the intermediate of the reaction process. However, it is preferable to dissolve the phenolic compound and to dissolve a part or all of the catalyst mixture. Examples of such substances include aromatic hydrocarbons such as benzene, toluene and xylene,
Halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, trichloroethane, chlorobenzene and dichlorobenzene, and nitro compounds such as nitrobenzene can be used as good solvents for the polymer. Examples of poor solvents for the polymer include methanol, ethanol, propanol,
Examples thereof include alcohols such as butanol, benzyl alcohol and cyclohexanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and ethyl formate, ethers such as tetrahydrofuran and diethyl ether, and amides such as dimethylformamide. These good solvents and poor solvents may be used alone or in combination of two or more.

By selecting the combination ratio of the good solvent and the poor solvent of this polymer, it also becomes a solution polymerization method, and if the ratio of the poor solvent is increased, the polymer will precipitate as particles in the reaction system as the reaction progresses. Although it can be a precipitation polymerization method, the present invention can be applied to any method.

The present invention can be applied to both batch polymerization method and continuous polymerization method.

It is difficult to explain from the conventional knowledge, but when the continuous polymerization method of the precipitation polymerization method is applied to the present invention, compared to the batch polymerization method, not only a high molecular weight polymer can be obtained with less catalyst but also a high quality polymer is obtained. The continuous polymerization method of the precipitation polymerization method is preferable because a polymer can be obtained.

A quaternary ammonium salt and a surfactant can be added to the reaction system for the purpose of improving the reaction rate, controlling the particle size of the polymer, and improving the phase separation property between the solvents.

Regarding the reaction temperature, if the reaction temperature is too low, the reaction is difficult to proceed,
If it is too high, the catalyst may be deactivated.
It is in the range of ℃, preferably 10 to 60 ℃.

As oxygen, in addition to pure oxygen, a mixture of an inert gas such as nitrogen at an arbitrary ratio and air can be used. The pressure may be normal pressure or increased pressure.

There is no particular limitation on the post-treatment method after completion of the reaction.
Usually, an acid such as hydrochloric acid or acetic acid is added to the reaction solution to deactivate the catalyst, and then the produced polymer is separated, washed with a solvent that does not dissolve the polymer such as methanol, and then dried. Polyphenylene ether can be recovered by operation.

[Effects of the Invention] In the method of the present invention, since a highly active catalyst having improved water resistance is used, the amount of the catalyst used can be small, and the catalyst is used for removal of the catalyst residue in the polymer. The amount of solvent is small and as a result the cost of solvent recovery is reduced. Further, the catalyst removing process can be simplified, for example, the equipment for removing the catalyst can be downsized. In addition, since the Izod impact strength of the composition obtained by blending the color tone of the obtained polymer and rubber-reinforced polystyrene is excellent, it is possible to obtain a polyphenylene resin and a modified polyphenylene resin of excellent quality which have never been obtained. Offering is now possible.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The measurement of ηsp / c was performed by using a 0.5 w / v% chloroform solution as a polymer and using an Ubbelohde viscosity system at 30 ° C.

<Definition of color index> 0.5 g of the obtained polymer or a polymer compression-molded at 310 ° C. was dissolved in chloroform to make 100 ml, and 480 at 25 ° C.
The absorbance at nm is measured and calculated by the following formula.

The value of the color index is used as a means for evaluating the degree of thermal oxidation of polyphenylene ether, and the lower the value, the less the polymer is colored by heating and the more stable it is to thermal oxidation.

Where Io: intensity of incident light I: intensity of transmitted light a: cell length [cm] b: solution concentration [g / cm ³ ] Example 1 Using a 100 cc glass reactor, after a certain polymerization time The catalytic activity was examined by the ultimate viscosity of.

That is, fine powdery cuprous oxide 0.00205 gr (0.0144 mmol)
Then, 0.0275 gr (0.264 mmol) of 35% hydrochloric acid was added, and after completely dissolving, 6.3 gr of methanol was added. Di-n-butylamine 0.0325 gr (0.273 mmol), N-phenylethanolamine 0.0374 gr (0.273 mmol), N, N'-di-t-butyl-ethylenediamine 0.0
A liquid consisting of 099 gr (0.057 mmol), N, N, N ', N'-tetramethyl-1,3-diaminopropane 0.15 gr (1.15 mmol) and methanol 6.3 gr was added. Then toluene 3
7.0 gr (57.4 mmol) of 2,6-dimethylphenol dissolved in 7.8 gr and 12.6 gr of n-butanol were added. The reaction solvent used was 63 gr, and the composition thereof was toluene: n-butanol: methanol in a weight ratio of 60:20:20. Also 2,6-
The concentration of dimethylphenol is 10% by weight and copper is 2,6-
It is 0.05 gram atom per 100 moles of dimethylphenol. Then, after adding 1.0 gr of water corresponding to the water produced by the reaction, the reaction was carried out at 30 ° C. for 3.5 hours while supplying oxygen while stirring. The reaction liquid had changed to a yellowish white liquid containing the slurry. The polymer obtained by adding 5 times the volume of methanol to the reaction solution, filtering, washing and drying had a viscosity of 0.69.

Examples 2,3,4,5 The same procedure as in Example 1 was repeated except that the amounts of di-n-butylamine and N-phenylethanolamine in Example 1 were changed, and the results shown in Table 1 were obtained.

Example 6,7,8,9 N- (o-
Ethyl) phenylethanolamine, N- (2'6'-dimethyl) phenylethanolamine, N- (2 ', 4', 6 '
-Trimethyl) phenylethanolamine and N- (P-chloro) phenylethanolamine were used, respectively, and the same results as in Example 1 were obtained.

Examples 10, 11, 12, 13, 14 In place of di-n-butylamine in Example 1, diethylamine, di-n-propylamine, di-n-octylamine, di-cyclohexylamine, di-benzylamine were used. The results of Table 1 were obtained in the same manner as in Example 1 except that each was used.

Example 15 The amount of copper salt in Example 1 was changed, and 35% hydrochloric acid was added to 48%.
The results of Table 1 were obtained in the same manner as in Example 1 except that the amount of hydrogen bromide was changed.

Comparative Example 1 The results of Table 1 were obtained in the same manner as in Example 1 except that the di-n-butylamine in Example 1 was not added.

Comparative Example 2 The results of Table 1 were obtained in the same manner as in Example 1 except that N-phenylethanolamine in Example 1 was not added.

Examples 16,17,18,19 Instead of N, N, N ', N'-tetramethyl-1,3-diaminopropane in Example 1, N-butyl-dimethylamine, cyclohexyl-dimethylamine, isopropyl-
Dimethyl-amine, N, N, N ', N'-tetramethyl-1,3-
The same procedure as in Example 1 was carried out except that diamino-1-methyl-propane was used and the amounts thereof and the amounts of the copper salt and hydrogen halide used were changed.

The results are shown in Table-2.

Examples 20 to 26 Mixed xylene, ethylbenzene, and chlorobenzene were used in place of toluene in Example 16, and the temperature and time were set to 25.
Example 16 was repeated except that the temperature was changed to 6 hours.

That is, cuprous oxide 0.000328 gr (0.023 mmol), 35% hydrochloric acid 0.044 gr (0.422 mmol), methanol is 50% of the amount used.
% Was added. N-phenylethanolamine 0.0374 gr (0.273 mmol), di-n-butylamine 0.352 gr (0.273 mmol), N, N'-di-t-
Butylethylenediamine 0.0158 gr (0.0914 mmol),
A catalyst solution was prepared by adding 0.0923 gr (0.914 mmol) of n-butyl-dimethylamine and the remaining 50% of the used amount of methanol.

Further, solvent species such as toluene and mixed xylene, and a predetermined amount of n-butanol and 7.0 gr (57.4 mmol) of 2,6-dimethylphenol were added.

The composition ratios of the solvent species used and n-butanol and methanol are shown in Table-3. The total amount of those used is 63 gr in each example.

Furthermore, 1.03 gr of water equivalent to the water produced by the reaction is added to the reaction system,
The reaction was performed at 25 ° C. for 6 hours while supplying oxygen while stirring. The viscosities (ηsp / c) of the polymers are summarized in Table-3.

Example 27 Polymerization was carried out using a continuous polymerization reactor consisting of three complete mixing tanks for continuous polymerization activity and quality evaluation of the polymer. The first reactor has a capacity of 1.5 and is equipped with a circulation pump. The second and third reactors have a stirrer and the capacity is 3.
It is 7,1.5.

The catalyst solution was prepared by dissolving cuprous oxide in 35% hydrochloric acid and adding methanol, and then N-phenylethanolamine, di-n-butylamine, N, N, N ', N'-tetramethyl-1,3-diaminopropane. , N, N'-di-t-butylethylenediamine and methanol were added. The monomer solution was prepared by dissolving 2,6-dimethylphenol in mixed xylene and n-butanol. Each was prepared under air.

The catalyst liquid and the monomer liquid were fed to the first reactor at a constant rate.

The composition of the reaction raw material liquid obtained by combining the catalyst liquid and the monomer liquid is as follows.

2,6-Dimethylphenol concentration 20% by weight The weight ratio of the solvent used is mixed xylene: n-butanol: methanol = 60: 20: 2
It is 0.

Copper is 0.06 g atom per 100 mol of 2,6-xylenol, C
l ion is 0.55 gram atom, N-phenylethanolamine is 0.5 mol, di-n-butylamine is 0.5 mol, N, N, N ',
N'-tetramethyl-1,3-diaminopropane was in a proportion of 2 mol.

Also, 2,6-dimethylphenol was supplied at a rate of 216 g / Hr.

In the first reactor, a circulation pump was used to circulate the reaction solution violently while allowing oxygen to flow. The internal temperature was controlled to 30 ° C. The reaction liquid sent from the first reactor to the second reactor by head pressure was uniform.

The second reactor is a stirrer and vigorously stirs the oxygen gas.
Flowed at a rate of 500 ml / min and kept at 25 ° C. A polymer is deposited, but it is uniformly distributed throughout the reactor by stirring. The reaction liquid containing polymer particles enters the third reactor by overflow from the second reactor.

While controlling the third reactor at 25 ° C., oxygen gas was caused to flow at a rate of 200 ml / min while stirring with a stirrer.

The reaction liquid containing the polymer was continuously taken out from the third reactor by overflow.

After adding methanol to the yellowish white reaction liquid containing the slurry, the reaction liquid was filtered. It was thoroughly purified and washed with a mixed solvent (mixed xylene, butanol, and methanol) and dilute hydrochloric acid. The viscosity (ηsp / c) of the polymer obtained after drying was in the range of 0.63 ± 0.03, and stable operation was possible for a long time.

The color index of the obtained polymer was 0.3.
The color index after compression molding at 310 ° C was 2.9.

55 parts by weight of this polymer, 45 parts by weight of rubber-reinforced polystyrene (manufactured by Asahi Kasei Corporation, trade name; Styron 492), 4 parts by weight of triphenyl phosphate, octadecyl-3- (3,5-
9 parts by weight of styrene was added to a composition of 0.5 parts by weight of ditertiary butyl-4-hydroxyphenyl) propionate (Irganox 1076), and the mixture was melt-kneaded at 290 ° C. to measure the Izod impact strength of the resulting composition. The result was 12 (kg-cm / cm). The test method is ASTM D-2
According to 56.

The above results are summarized in Table-4.

Comparative Example 5 Example 17 was repeated except that the amounts of copper salt and hydrochloric acid were changed, di-n-butylamine was not added, and the amount of 2,6-xylenol fed was changed. The results shown in Table 4 were obtained.

Comparative Example 6 The procedure of Example 17 was repeated except that N-phenylethanolamine was not added and the amount of di-n-butylamine and the amount of 2,6-xylenol fed were changed. I got the result.

From these results, N-phenylethanolamine and di-
It can be seen that the quality (color and Izod impact strength) of the polymer obtained with the catalyst system containing n-butylamine is excellent.

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Claims (1)

[Claims] 1. A copper salt, (b) N-phenylethanolamine, (c) a secondary aliphatic amine, and (d) a general formula R ₁ —HN—R—NHR ₂ [wherein R ₁ , R ₂ represents an isopropyl group, a C ₄ -C ₈ tertiary alkyl group, or a cycloalkyl group having no hydrogen on the α-carbon atom. ] The manufacturing method of the polyphenylene ether which oxidatively polymerizes the phenolic compound with oxygen characterized by using the catalyst consisting of 1,2-diamine or 1,3-diamine and (e) tertiary amine.