JPH0670129B2 - Method for producing polyphenylene ether - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing high-quality polyphenylene ether with a highly active copper catalyst having improved water resistance.

More specifically, the phenolic compound is treated with oxygen in the presence of a catalyst having a high continuous polymerization activity, which is composed of a copper salt, Nt-butylethanolamine, a specific secondary diamine and a tertiary amine and has improved water resistance. The present invention relates to a method for producing high quality polyphenylene ether by oxidative polymerization.

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,
Since it has properties such as good dimensional stability, it has recently attracted attention as a thermoplastic engineering plastic.

[Conventional technology]

As a polymerization catalyst for producing polyphenylene ether by oxidative polymerization of phenolic compounds, many combinations of copper compounds, manganese compounds or cobalt compounds with various amines have been proposed so far.

Among them, diamines having a specific structure, specifically N, N ′
A copper amine complex composed of a combination with -di-t-butylethylenediamine and the like is known to have 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. 58-53).
No. 012).

However, the polymer produced by using this catalyst system is not practical because the impact resistance of the composition with a styrene resin such as rubber-modified polystyrene is low and the heat stability is poor, in addition to the poor color. It became clear that a catalyst system in which this catalyst system was combined with a secondary monoamine such as di-n-butylamine became practical for the first time (Japanese Patent Publication No. 59-23332). Furthermore, in this catalyst system, the amount of bromide ion is adjusted to a molar ratio of about 1:35 or more with respect to the starting phenolic compound (JP-A-59-74124), and the first copper compound is used.
A method using a mixture of a copper salt and a cupric salt (JP-A-59-13)
1627), and a catalyst system using dimethylamine as a secondary monoamine (Japanese Patent Publication No. 60-54327) and the like.

Further, there are known examples in which these copper amine complex catalysts are applied to a continuous polymerization method (JP-A-59-230025 and JP-A-59-230026).

[Problems to be solved by the invention]

However, the inventors of the present invention have deeply conducted additional examinations on these conventional techniques, and have found that the following basic problems have not yet been sufficiently solved. 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 water produced as a by-product during the oxidative polymerization of phenols, or the metallic components become hydroxides and leave the reaction system, which causes 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]

The present inventors have conducted extensive studies on a method for producing a polyphenylene ether in the above situation, resulting in a copper salt,
Based on this finding, it was found that a catalyst system consisting of Nt-butyl ethanolamine, a specific diamine and a tertiary amine has extremely excellent water resistance, exhibits a high continuous polymerization activity, and gives a high quality polymer. The present invention has been completed.

That is, the present invention provides (a) a copper salt, (b) Nt-butylethanolamine, and (c) a 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, which comprises oxidatively polymerizing a phenolic compound with oxygen in the presence of a catalyst composed of 1,3-diamine and a (d) tertiary amine.

The present invention does not disclose the combination of N-alkylalkanolamine and copper salt in the prior art,
In contrast to N-n-butylethanolamine, the activity is significantly reduced, whereas Nt-butylethanolamine, which is a structural isomer, is used. It's a totally unexpected method.

Further, when the catalyst used in the present invention is applied to a continuous method of a precipitation polymerization method in which a polymer is precipitated as particles in the reaction system along with the progress of the reaction by selecting a polymerization solvent, it is less than the batch polymerization method. It is difficult to explain from the conventional knowledge that not only a polymer having a high molecular weight can be obtained with a catalytic amount, but also a high-quality polymer which is white and has a low thermal discoloration property can be obtained.

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 may be used, but the particular choice is primarily determined by economics and 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 soluble complexes with amines 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 0.01 gram atom to 1 gram atom of copper, preferably 0.03 per 100 moles of the phenolic compound.
Gram atom to 0.5 gram atom.

The Nt-butylethanolamine in the present invention can be used in a wide range of 0.05 mol to 10 mol with respect to 100 mol of the phenolic compound, preferably 0.1 mol to
It is in the range of 5 mol.

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 1,3-diamine. Specific examples of these compounds include N, N'-di-t-butylethylenediamine, N, N'-di-t-amylethylenediamine and
N, N'-diisopropylethylenediamine, N, N'-ditertiarybutylpropylenediamine, N, N'-di-t-
Butylcyclohexane 1,2-diamine and the like. Of these, N, N'-di-t-butylethylenediamine is preferred. The amount of diamine used is generally 1 to 4 mol of diamine per 1 gram atom of copper.

Examples of tertiary amines that can be used in the practice of the present invention are aliphatic tertiary amines including alicyclic tertiary amines. Trimethylamine, triethylamine, tripropylamine, tributylamine, triisopropylamine, diethylmethylamine, dimethylpropylamine,
Allyldiethylamine, dimethyl-n-butylamine,
Diethyl isopropyl amine etc. are mentioned.

Further, aliphatic tertiary polyamines such as N, N, N ', N'-tetraalkylethylenediamine and N, N, N', N'-tetraalkylpropanediamine can also be used.

These tertiary amines can be used in the range of 5 to 50 mol, preferably 10 to 40 mol, per gram atom of copper.

In the practice of the present invention, the coexistence of halogen ions other than fluorine ion improves the catalytic activity, which is preferable. As the halogen ion, chlorine ion and bromine ion are particularly preferable.

The catalyst can be adjusted using a solvent such as methanol. If it is noted that the copper salt is dissolved, the purpose 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 (I) (In the formula, 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: 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-
Examples include chlorphenol. 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.

Among 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 medium used in the method of the present invention is not particularly limited as long as it is less oxidizable than the oxidizable phenolic compounds and does not have reactivity with various radicals 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 thereof 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 a good solvent for the polymer. Examples of the poor solvent for the polymer include alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, and cyclohexanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and ethyl formate, tetrahydrofuran, diethyl ether, etc. Examples thereof include ethers 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 a good solvent and a 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 with the progress of the reaction. It can also be a precipitation polymerization method.

The present invention is applicable to batch polymerization method, continuous polymerization method, solution polymerization method, precipitation polymerization method, but in the case of continuous precipitation polymerization method, not only high polymerization activity but also narrow molecular weight distribution,
It is more preferable because a highly white polymer with little discoloration upon heating can be obtained.

As an example of a continuous precipitation polymerization method, two functions are required to continuously obtain polyphenylene ether by applying a polymerization reaction of a phenolic compound that precipitates polyphenylene ether with the progress of polymerization. It is composed of a combination of complete mixing type polymerization tanks. That is, a first polymerization tank for allowing the polymerization to proceed in a uniform solution state and a second polymerization tank for precipitating stable particles of polyphenylene ether are required. If necessary, a third polymerization tank is installed,
Control the final properties of the polymer particles by aging,
Finishing is done so that it can be subjected to post-treatment steps.
Each of these polymerization tanks can be divided into several polymerization tanks for more delicate control.

More specifically, in the first polymerization tank, the oxygen gas flow rate and the average residence time are controlled so that the polymerization reaction rate is controlled to 90% or less and no precipitation occurs at the same time. That is, a polymerization tank type of a type that sufficiently removes the heat of polymerization is adopted. In the second polymerization tank, the medium composition, that is, the combination of the solvent-non-solvent and the amount ratio thereof, to prevent deposition of polymer particles to be deposited on the vessel wall, stirring blades, etc., and a proper stirring state, The size and hardness of the polymer particles are controlled by maintaining the oxygen gas supply rate.

The third polymerization tank as an aging tank often plays an important role in order to give the polymer particles a size and hardness suitable for filtering and drying in the post-treatment step. In this third polymerization tank, the stirring state and the residence time are strictly controlled.

The operating conditions of this continuous polymerization method vary greatly depending on the catalyst species, the phenolic compound, and the medium species,
In particular, it largely depends on the concentration of the phenolic compound which is a monomer. Unlike the case of homogeneous solution polymerization, the monomer concentration can be 10 to 40% by weight in the whole polymerization solution, and particularly 20 to 35% by weight is preferable, because the characteristics of continuous polymerization in the precipitation system are exhibited. It

In this method, the use of a complete mixing type as the polymerization tank is an oxidation polymerization reaction of the phenolic compound, which is a reaction that needs to improve the contact efficiency with oxygen gas. Because it must be done. That is, a polymerization tank that does not cause stirring in the traveling direction of the reaction solution is unsuitable for handling a reaction mixture having a viscosity as low as that of this reaction. In other words, in order to achieve this continuous polymerization method, a complete mixing type reaction vessel having an average residence time and a stirring state capable of exhibiting the functions of at least two types of reaction vessels shown above should be combined. Is necessary.

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 between 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 ℃. Oxygen is pure oxygen,
A mixture of an inert gas such as nitrogen with 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 of the reaction-terminated liquid.
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 such as methanol that does not dissolve the polymer, and then dried. Polyphenylene ether can be recovered by operation.

〔The invention's effect〕

In the method of the present invention, since a highly active catalyst having improved water resistance composed of a copper salt, Nt-butylethanolamine, a specific diamine and a tertiary amine is used as a polymerization catalyst for polyphenylene ether, The amount of the catalyst used is small, and the amount of the solvent used for removing the catalyst residue in the polymer is small. As a result, the recovery cost of the solvent is reduced. Further, the catalyst removing process can be simplified, for example, the equipment for removing the catalyst can be downsized. Further, the obtained polymer has a good color tone, and in particular, it has a great advantage that a high quality polyphenylene ether having a small change in physical properties such as a color tone due to heating can be produced.

〔Example〕

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 ηsp / c was measured using a 0.5 W / V% chloroform solution of the polymer and using an Ubbelohde viscometer at 30 ° C.

<Definition of color index> 0.5 g of the obtained polymer or a polymer molded by compression at 310 ° C.
Is dissolved in chloroform to bring the total volume to 100 ml.
The absorbance at 80 nm is measured and calculated by the following formula.

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

Where l ₀ : intensity of incident light l: intensity of transmitted light a: cell length [cm] b: solution concentration [g / cm ³ ] Example 1 Fine powdery cuprous oxide (Cu ₂ O) was added to an Erlenmeyer flask. ) 0.152gr (1.0
7 mmol) and 48% hydrogen bromide water 3.31 gr (19.6 mmol)
Was added and, after being completely dissolved, 103 gr of methanol was added. This is a copper salt solution. In another Erlenmeyer flask, add N, N ′
-Di-t-butylethylenediamine 0.732 gr (4.27 mmol), n-butyl dimethylamine 4.31 gr (42.7 mmol), Nt-butyl ethanolamine 2.37 gr (20.2
Mmol) and 103 gr of methanol were added. This is an amine solution.

The above copper salt solution and then the above amine solution were added to a 1.5 flask equipped with a stirrer to prepare a catalyst. Then toluene
260 gr (2132) of 2,6-dimethylphenol dissolved in 618 gr
206 mmol of n-butanol was added to the flask. The above operation was carried out in the atmosphere. The reaction solvent used was 1030 gr, and the composition thereof was toluene: n-butanol: methanol in a weight ratio of 60:20:20. Also, 2,
The concentration of 6-dimethylphenol is 20% by weight and copper is
It is 0.1 gram atom per 100 mol of 2,6-dimethylphenol.

The reaction was carried out at 25 ° C while supplying oxygen with stirring. On the way, the reaction solution was sampled with time, 5 times volume of methanol was added, filtration, washing and drying were performed, and the viscosity of the obtained polymer was measured, and the following results were obtained.

After the lapse of 4 hours, the increase in viscosity reached the ceiling. After 6 hours, the polymerization was terminated. That is, the yellowish white reaction liquid containing the slurry was taken out, added with methanol and then filtered. It was thoroughly purified and washed with a mixed solvent (toluene, butanol and methanol) and dilute hydrochloric acid. The polymer obtained after drying had a viscosity of 0.63 and a color index of 1.5. The color index after compression molding at 310 ° C was 7.5.

Example 2 To dissolve cuprous oxide, 35% instead of 48% hydrobromide water was used.
The experiment was repeated under the same conditions as in Example 1 except that% hydrochloric acid was used as an equimolar amount of hydrogen halide.

On the way, the reaction liquid was sampled to measure the viscosity of the produced polymer.

The increase in viscosity after 4 hours had reached the ceiling. After 6 hours, the polymerization was terminated, and the reaction solution was purified by the method of Example 1.

As a result, the viscosity of the polymer was 0.60, the color index was 1.6, and the color index after compression molding at 310 ° C. was 7.1.

Example 3 A 100 cc glass reactor was used to examine the catalytic activity by the ultimate viscosity after a certain polymerization time.

That is, fine powdery cuprous oxide 0.0041 gr (0.0287 mmol) and 48
0.089 gr (0.528 mmol) of hydrogen bromide water was added, and after completely dissolving, 6.25 gr of methanol was added. Nt-butylethanolamine 0.0638 prepared in a separate container.
gr (0.545 mmol), N, N'-di-t-butylethylenediamine 0.0197 gr (0.115 mmol), n-butyl-dimethylamine 0.116 gr (1.15 mmol) and methanol 6.2
A solution containing 5 gr was added. Then, 7.0 gr (57.4 mmol) of 2,6-dimethylphenol dissolved in 37.5 gr of toluene and 12.5 gr of n-butanol were added. The above operation was performed in the atmosphere. The reaction solvent used was 62.5 gr, and its composition was 60:20:20 by weight ratio of toluene: n-butanol: methanol. The concentration of 2,6-dimethylphenol is 10% by weight, and copper is 0.1 gram atom per 100 mol of 2,6-dimethylphenol.

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 volumes of methanol to the reaction solution, filtering, washing and drying had a viscosity of 0.63.

Example 4 An experiment was conducted under the same conditions as in Example 3 except that an equimolar amount was used as 35% hydrochloric acid hydrogen halide water instead of 48% hydrogen bromide water. The results are shown in Table-2.

Comparative Examples 1 to 4 Example 3 except that N-alkylethanolamine shown in Table 1 was used instead of Nt-butylethanolamine.
The experiment was repeated under the same conditions as. The results are shown in Table-1. Nt-butyl ethanolamine was specifically highly active.

Examples 5 and 6 In order to test the water resistance of the catalyst, an experiment was conducted by adding water in an amount equivalent to the water produced by the reaction in advance into the reaction system.

That is, in Example 5, the reaction liquid was prepared under the atmosphere in the same manner as in Example 3. Then, 1.03 gr of water equivalent to the water produced by the reaction was added with stirring, and then oxygen was flown to initiate the polymerization reaction. The polymerization conditions and the method of treating the reaction solution were the same as in Example 3.

In addition, in Example 6, a reaction solution was prepared under the atmosphere in the same manner as in Example 4. After that, an amount of water equivalent to the reaction product water
After adding 1.03 gr under stirring, oxygen was flown to initiate the polymerization reaction. The polymerization conditions and the method of treating the reaction solution were the same as in Example 4. The results are shown in Table-2.

Comparative Examples 5 to 7 The experiment was repeated in the same manner as in Examples 4 to 6 except that 0.0703 gr (0.545 mmol) of di-n-butylamine was used instead of Nt-butylethanolamine.

The results are shown in Table-2.

Examples 7 to 9 Tables showing types and amounts of copper salts, halides and amines
As shown in FIG. 3, an experiment was conducted under the same conditions as in Examples 5 and 6.
The results are shown in Table-3.

Examples 10 to 16 The same procedure as in Example 5 was carried out at 25 ° C. for 6 hours, except that the solvent species and the composition ratio of the reaction solvent were changed as shown in Table 4 in place of toluene. The results are shown in Table-4. The total amount of reaction solvent used was 63.5 gr.

Example 17 In order to examine the influence of the reaction solvent, 62.5 gr of a mixed solvent of toluene-ethanol (80/20 in weight ratio) was used, and the same procedure as in Example 5 was carried out at 25 ° C. for 6 hours.

The viscosity of the obtained polymer was 0.79.

Example 18 Polymerization was carried out using a continuous polymerization reactor composed of three complete mixing tanks for continuous polymerization activity and evaluation of polymer quality. 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, adding methanol, and adding Nt-butylethanolamine and N, N'-.
It was prepared by adding di-t-butylethylenediamine, dimethyl-n-butylamine and toluene. Monomer liquid is 2,6
-Dimethylphenol was dissolved and prepared in toluene 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 liquid obtained by combining the catalyst liquid and the monomer liquid is as follows.

The concentration of 2,6-dimethylphenol was 20% by weight, and the weight ratio of the solvent used was toluene: n-butanol: methanol = 60: 20:
Twenty. For 100 mol of 2,6-xylenol, 0.09 gram atom of copper, 0.83 gram atom of Cl ion, 0.95 mol of Nt-butylethanolamine, 0.18 mol of N, N'-di-t-butylethylenediamine, and n- Butyl-dimethylamine was present at a rate of 1.8 mol.

Also, 2,6-xylenol was supplied at a rate of 160 gr / 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 25 ° C.
The reaction liquid sent from the first reactor to the second reactor at a head pressure was uniform.

The second reactor is a stirrer and the oxygen gas is 50% with vigorous stirring.
Flow at a rate of 0 ml / min and keep at 25 ° C. The polymer precipitates, but it is evenly 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 and acidified with hydrochloric acid to deactivate the catalyst.

Viscosity (ηsp / c) of polymer obtained by purification by the method of Example 1
Was within the range of 0.62 ± 0.03, and stable operation was possible for a long time.

The polymer obtained had a particle size of 50 to 80 μm and a color index of 0.9. The color index after compression molding at 310 ° C was 4.5.

It can be seen that in the case of the continuous polymerization method as compared with the batch polymerization method of Example 2, a high viscosity polymer can be obtained with a smaller amount of catalyst. Further, it can be seen that the obtained polymer has an excellent color tone, and in particular, a high quality polymer with little discoloration by heating can be obtained.

Example 19 In Example 18, instead of 35% hydrochloric acid, 48% hydrobromide water was used as an equimolar amount of halogen, and the feed amount of 2,6-dimethylphenol to the first reactor was changed from 160 gr / Hr to 192 gr / Hr. It carried out similarly except having changed into.

As a result, the viscosity of the obtained polymer is 0.60, the particle size is 40 ~
The color index was 70μ and the color index was 0.5. The color index after compression molding at 310 ° C was 4.3.

Comparative Example 8 Di-n-butylamine was used instead of Nt-butylethanolamine, and continuous polymerization was carried out in the apparatus of Example 18 using a mixed solvent of toluene and methanol.

That is, the concentration of 2,6-dimethylphenol was 10% by weight, and the weight ratio of the solvent used was toluene: methanol 90:10.
For 100 moles of 2,6-dimethylphenol, 0.2 g atom of copper, 1.84 g atom of bromide ion, and N, N'-di-t
-Butylethylenediamine 0.4 mol, n-butyl-dimethylamine 4.0 mol, di-n-butylamine 0.95 mol. Also, 2,6-dimethylphenol is 80 g / Hr
Was fed to the first reactor at a rate of. The temperature of the 1st reactor, the 2nd reactor, and the 3rd reactor was controlled to 40 degreeC, and it implemented like Example 19.

Since the reaction liquid obtained from the outlet of the third reactor had a viscous consistency, 25 parts by weight of toluene was added to 100 parts by weight of the reaction liquid for dilution. Furthermore, after extracting the catalyst component using 25 parts by weight of hydrochloric acid containing hydrogen chloride in a molar ratio 10 times the total molar amount of copper and amine in the reaction solution, 200 parts by weight of methanol was added little by little while stirring, and the polymer was added. It was deposited. Then, the same treatment as in Example 19 was carried out to obtain a polymer. Viscosity of the obtained polymer (ηsp / c)
Was 0.46 and the color index was 1.2.

Also, the color index after compression molding at 310 ° C is 19.8.
It was.

In the known copper-chelate catalyst system, compared with Example 19, 2.
Even when a double amount of the catalyst was used, the viscosity of the obtained polymer was low and the heat discoloration was large.

Example 20 Trioctylmethylammonium chloride was added to the reaction system of Example 19 and its effect was investigated. That is, trioctyl ammonium chloride in an amount corresponding to 0.02% by weight with respect to the reaction liquid was added to the catalyst liquid and supplied to the first reactor. The amount of 2,6-dimethylphenol supplied was 192 gr / Hr.
It was supplied at a rate of 208 gr / Hr. The same procedure as in Example 19 was performed except for the above changes.

As a result, the viscosity of the obtained polymer is 0.60, the particle size is 20 ~
The color index was 50μ, and the color index was 0.5. The color index after compression molding at 310 ° C was 4.2.

Example 21 The procedure of Example 19 was repeated except that mixed xylene was used instead of toluene which was one of the reaction solvents.

As a result, the polymer obtained had a viscosity (ηsp / c) of 0.57, a color index of 0.5, and a particle size of 30 to 60 μm. Also, the color index after compression molding at 310 ° C is
It was 4.6.

Continuation of front page (56) Reference JP-A-50-110498 (JP, A) JP-A-53-29400 (JP, A) JP-A-59-131627 (JP, A) JP-A-53-30698 (JP , A)

Claims (1)

[Claims] 1. A copper salt, (b) Nt-butylethanolamine, and (c) a general formula R ₁ —HN—R—NHR ₂ (wherein R ₁ and R ₂ are isopropyl groups, It represents a tertiary alkyl group or α- cycloalkyl group on the carbon atom no hydrogen C ₄ -C _8.) and 1,2-diamine or 1,3-diamine, and (d) a tertiary amine A method for producing a polyphenylene ether, which comprises oxidatively polymerizing a phenolic compound with oxygen in the presence of a catalyst comprising