JPH0670130B2 - Method for producing polyphenylene ether - Google Patents

Description

Description: FIELD OF THE INVENTION 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, a phenolic compound is oxidized with oxygen in the presence of a catalyst having a high continuous polymerization activity, which is composed of a copper salt, N-phenylethanolamine, a specific secondary diamine and a tertiary amine and has improved water resistance. The present invention relates to a method of polymerizing to produce high quality polyphenylene ether.

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]

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

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 third ion such as copper ion, bromide ion, N, N'-di-t-butylethylenediamine and N-methylpyrrolidine.
A combination of primary amines is known (Japanese Patent Publication No. 58-5301).
No. 2 bulletin).

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-
For the first time, a catalyst system combining a secondary monoamine such as n-butylamine became practical (Japanese Patent Publication No. 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), cuprous salts and cupric salts as copper compounds And a catalyst system using dimethylamine as a secondary monoamine (JP-B-60-5432).
No. 7) is known.

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-SHO).
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 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 catalyst 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 go out of the reaction system, resulting in a decrease in catalyst activity. There is a problem, and 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,
N-phenylethanolamine, specific diamine and 3
It was found that a catalyst system composed of a primary amine has extremely excellent water resistance, exhibits a high continuous polymerization activity, and gives a high quality polymer, and based on this finding, the present invention has been completed.

That is, the present invention provides (a) a copper salt, (b) N-phenylethanolamine, and (c) a general formula R ₁ -HN-R-NHR ₂ (wherein
R ₁ and R ₂ represent an isopropyl group, a C ₄ -C ₈ tertiary alkyl group or a cycloalkyl group having no hydrogen on the α-carbon atom. 1.) A method for producing a polyphenylene ether by oxidatively polymerizing a phenolic compound with oxygen, characterized in that a catalyst comprising 1,2-diamine or 1,3-diamine and (d) tertiary amine is used.

The present invention does not disclose the combination of N-substituted alkanolamine and copper salt in the prior art, and Nn
In contrast to the combination with -butylethanolamine, the activity is markedly reduced, whereas N-phenylethanolamine is used, so it is a completely unexpected method because it shows a high specific activity.

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 a reaction system along with the progress of the reaction by selecting a polymerization solvent, it is whiter than the batch polymerization method and It is difficult to explain from the conventional knowledge that a high-quality polymer with little heat discoloration can be obtained.

In carrying out the present invention, the copper salt may be a cuprous salt, a diacid 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 the copper salt used is 0.005 gram atom to 1 gram atom of copper, preferably 0.01 to 100 mol of the phenolic compound.
The range is from gram atom to 0.5 gram atom.

The N-phenylethanolamine in the present invention includes N-unsubstituted phenylethanolamine as well as N-unsubstituted phenylethanolamine. 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) phenyl Ethanolamine, N- (o-ethyl) phenylethanolamine, N
-(M-Ethyl) phenylethanolamine and N-
(P-ethyl) phenylethanolamine and the like. Among these, N-phenylethanolamine, N- (p-
Chloro) phenylethanolamine, N- (2 ', 6'dimethyl) phenylethanolamine and N- (o-ethyl) phenylethanolamine are 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.

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, N, N'-diisopropylethylenediamine,
There are N, N'-di-t-butylpropylenediamine, N, N'-di-t-butyl-cyclohexane-1,2-diamine and the like. Of these, N, N'-di-t-butylethylenediamine is preferred. The amount of diamine used is phenolic compound 10
0.01 to 10 mol, preferably 0.05 to 5 mol, is used relative to 0 mol.

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, propyl-dimethylamine, allyldiethylamine, butyl-dimethylamine,
Examples include diethyl isopropylamine and cyclohexyl-dimethylamine.

Further, 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 these, 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-1,3-diaminopropane, N, N, N', N'-tetra Methyl-1,3diamino-1-methyl-propane is particularly preferred.

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

In carrying out the present invention, the 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, CuBl, etc. can be used.
HBr and HCl are preferred.

The amount of these used is not particularly limited, but to 1 mol of copper
0.5 to 30 mol is preferable, and 1 to 15 mol is particularly preferably used.

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 (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-methylphenol, 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 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 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 can be applied to both batch polymerization method and continuous polymerization method.

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.

The post-treatment method after the reaction is not particularly limited.
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.

〔The invention's effect〕

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 amount of the solvent used for removing the catalyst residue in the polymer is small. As a result, solvent recovery costs are reduced. Further, the catalyst removing process can be simplified, for example, the equipment for removing the catalyst can be downsized.

(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 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> The obtained polymer or the polymer which was compression molded at 310 ° C. was dissolved in 0.5 g of chloroform, and the total amount was 100 ml, and 480 nm at 25 ° C.
Absorbance 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. ) 0.106gr (0.7
49 mmol) and 48% hydrogen bromide water 2.32 gr (13.7 mmol)
Was added and, after being completely dissolved, 103 gr of methanol was added. This is a copper salt solution.

In another Erlenmeyer flask, N, N'-di-t-butylethylenediamine 0.512 gr (2.99 mmol), n-butyl-dimethylamine 3.02 gr (29.9 mmol), N-phenylethanolamine 2.778 (20.2 mmol) and methanol. 103
Added gr. This is an amine solution.

In a 1.5 tower flask with a circulation pump, the above copper solution,
Next, the above amine solution was added to prepare a catalyst. After that, 260gr of 2,6-dimethylphenol dissolved in 618gr of toluene
(2132 mmol), 206 gr of n-butanol were added to the flask. The above operation was carried out in the atmosphere. The reaction solvent used was 1030 gr, and its composition was 60:20:20 by weight ratio of toluene: n-butanol: methanol. Again 2,6
-Concentration of dimethylphenol is 20% by weight, copper is 2,
0.07 gram atom was used per 100 mol of 6-dimethylphenol. The color of the adjusted liquid was initially gray black, but later changed from green to blue.

While stirring with a circulation pump, the reaction was carried out at 25 ° C while supplying oxygen.

On the way, the reaction solution was sampled with time, 5 times volume of methanol was added, filtered, washed and dried, and the viscosity of the obtained polymer was measured to obtain the following results.

A part of the reaction solution after 2.5 hours was extracted and treated. That is, a part of 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 0.06 and a color index of 1.3. The color index after compression molding at 310 ° C was 7.3.

Example 2 To dissolve cuprous oxide, instead of 48% hydrobromide water,
The experiment was repeated under the same conditions as in Example 1 except that 35% 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.

After a lapse of 3 hours, a part of the reaction liquid was extracted and the reaction liquid was purified by the method of Example 1 to obtain a polymer.

As a result, the viscosity of the polymer was 0.60, the color index was 1.4, and the color index after compression molding at 310 ° C. was 6.9.

Example 3 Using a 100 cc. Glass reactor, the catalytic activity was examined by the arrival 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, 6.3 gr of methanol was added. N-phenylethanolamine 0.0748 gr prepared in another container
(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 6.3 gr
Was added. Then, it was dissolved in toluene 37.8 gr.
2,6-Dimethylphenol 7.0 gr (57.4 mmol) and n-
Butanol 12.6 gr was 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. 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 times the volume of methanol to the reaction mixture, filtering, washing and drying had a viscosity of 0.98.

Comparative Examples 1 to 4 Instead of N-phenylethanolamine, N shown in Table 1 was used.
-Example 3 except that an alkyl ethanolamine is used.
The experiment was repeated under the same conditions as. The results are shown in Table-1. N-phenylethanolamine was specifically highly active.

Example 4 Instead of the 48% hydrobromide water in Example 3, 35% hydrochloric acid was used.
The experiment was repeated as in Example 3, except that equimolar amounts of hydrogen halide were used.

As a result, the viscosity of the obtained polymer was 0.82.

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 Examples 5 and 6, the reaction solutions were prepared under the atmosphere in the same manner as in Examples 3 and 4. 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 Examples 3 and 4.

The results are summarized in Table-1.

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 N-phenylethanolamine.

The results are summarized in Table-1.

Examples 7 to 10 Instead of N-phenylethanolamine in Example 6, N- (2 ', 6'-dimethyl) phenylethanolamine, N- (2', 4 ', 6'-trimethyl) phenyl The same procedure as in Example 6 was performed except that ethanolamine, N- (p-chloro) phenylethanolamine and N- (o-ethyl) phenylethanolamine were used. The results are shown in Table-2.

Examples 11 to 16 The types of copper compounds, hydrogen halides and amines and their amounts used are shown in Table 2, and the same as Example 6 except for the types of copper compounds, hydrogen halides and amines and their amounts used. The experiment was repeated in the same manner. The results are shown in Table-2.

Examples 17 to 23 Mixed xylene, ethylbenzene, and chlorobenzene were used in place of toluene in Example 5, and the amount of copper was changed from 0.1 gram atom to 0.07 gram atom per 100 moles of 2,6-dimethylphenol. The reaction time was changed to 6 hours at 25 ° C.

That is, cuprous oxide 0.000287 gr (0.02 mmol), 48% hydrogen bromide water 0.0623 gr (0.370 mmol), and methanol were added at 50% of the used amount. N-phenylethanolamine 0.0748 gr (0.545 mmol) prepared in another container,
N, N'-di-t-butylethylenediamine 0.0138 gr (0.0
80 mmol), 6-butyl-dimethylamine 0.0138 gr
(0.8 mmol), and the remaining 50% of the used amount of methanol was added to prepare a catalyst solution.

Further, solvent species such as toluene and mixed xylene, and a predetermined amount of -n-butanol and 2,6-dimethylphenol 7.0 gr (5
7.4 mmol) was added.

The composition ratios of the solvent species used, 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 carried out at 25 ° C. for 6 hours while supplying oxygen while stirring. The reaction solution was treated according to the method of Example 5 to obtain a polymer. The viscosity (ηsp / c) of the polymer is summarized in Table-3.

Example 24 In order to examine the influence of the reaction solvent, the same procedure as in Example 17 was carried out using 63 gr of a toluene-methanol mixed solvent (80/20 in weight ratio).

The viscosity (ηsp / c) of the obtained polymer was 0.98.

Example 25 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.
7 and 1.5.

The catalyst solution was prepared by dissolving cuprous oxide in 35% hydrochloric acid, adding methanol, and further adding N-phenylethanolamine, N, N'-di-t-butylethylenediamine, n-butyl-dimethylamine and methanol. . Monomer liquid is 2,6
-Dimethylphenol was dissolved and prepared in toluene and n-butanol.

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.

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-dimethylphenol, 0.09 gram atom of copper, 0.83 gram atom of Cl ion, 0.95 mol of N-phenylethanolamine, 0.18 mol of N, N'-di-t-butylethylenediamine, and n- Butyl-dimethylamine
The ratio was 1.8 mol.

Also, 2,6-dimethylphenol was fed at a rate of 240 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 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 0.61 ± 0.03, and stable operation was possible for a long time.

The obtained polymer had a particle size of 50 to 80 μm and a color index of 0.7. The color index after compression molding at 310 ° C was 3.6.

It can be seen that the polymer obtained in the case of the continuous polymerization method is superior to the batch polymerization method of Example 2 in the color tone, and in particular, a high-quality polymer with little heat discoloration can be obtained.

Example 26 Example 25 was carried out in the same manner as Example 25 except that 48% hydrobromide water was used in place of 35% hydrochloric acid in Example 25, and the catalyst usage amount and the 2,6-dimethylphenol supply amount were changed.

That is, the composition of the reaction raw material liquid was 2,6-dimethylphenol concentration 20% by weight, the weight ratio of the solvent used was toluene: n-butanol: methanol = 60: 20: 20, and 2,6-dimethylphenol 100 was used. Per mole, copper is 0.08 gram atom, bromide ion is 0.74 gram atom, N-phenylethanolamine is 0.95 mole, N, N'-di-t-butylethylenediamine is 0.16 mole, and n-butyl-dimethylamine is 1.6 mole. It was a percentage. The amount of 2,6 dimethylphenol supplied to the first reactor was 208 gr / Hr.

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 3.7.

Comparative Example 8 Instead of N-phenylethanolamine, di-n-butylamine was used, and a mixed solvent of toluene and methanol was used.
Continuous polymerization was carried out with the apparatus of Example 25.

That is, the concentration of 2,6-dimethylphenol was 10% by weight, and the weight ratio of the dissolved solvent 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 2.0 mol, n-butyl-dimethylamine 4.0 mol, di-n-butylamine 0.95 mol. Further, 2,6 dimethylphenol was fed to the first reactor at a rate of 80 gr / Hr. Example in which the temperature of the first reactor, the second reactor and the third reactor was controlled at 40 ° C
It carried out like 26.

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 26 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, 310
The color index after compression molding at ℃ was 19.8.

With the known copper-chelate catalyst system, 2.5 compared to Example 26
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 27 Trioctylmethylammonium chloride was added to the reaction system of Example 26, and the effect was examined.

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 208 gr / Hr to 224 gr / Hr. The same procedure as in Example 26 was performed except for the above changes.

As a result, the viscosity of the obtained polymer is 0.61, the particle size is 20 ~
The color index was 50μ and 0.7. The color index after compression molding at 310 ° C was 3.8.

Example 28 The procedure of Example 26 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 0.58, a color index of 0.5, and a particle size of 30 to 60 μm. The color index after compression molding at 310 ° C is 3.6.
It was.

Example 29 The procedure of Example 27 was repeated except that mixed xylene was used instead of toluene which was one of the reaction solvents.

As a result, the viscosity of the obtained polymer (ηsp / c) is 0.59,
The particle size was 20-40 μm and the color index was 0.6. The color index after compression molding at 310 ° C is 3.9.
It was.

Example 30 Example 30 was carried out under the same conditions 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 0.60, a particle size of 20 to 50 μm, and a color index of 0.6. Also, the color index after compression molding at 310 ° C is 3.5.
It was.

Example 31 N, N, N ', N'-tetramethyl-1,3-diaminopropane was used in place of n-butyl-dimethylamine in Example 25, and the amount and cuprous oxide, hydrochloric acid, N , N'-di-t-
Example 25 was carried out in the same manner as in Example 25 except that the amount of butylethylenediamine was changed, and the temperature of the first reactor and the supply amount of 2,6-dimethylphenol were changed.

That is, the composition of the reaction raw material liquid was 2,6-dimethylphenol concentration 20% by weight, the weight ratio of the solvent used was toluene: n-butanol: methanol = 60: 20: 20, and 2,6-dimethylphenol 100 was used. Per mole, copper is 0.05 g atom, chlorine ion is 0.46 g atom, N-phenylethanolamine is 0.95 mol, N, N'-di-t-butylethylenediamine is 0.10 mol, and N, N, N ', N'-. The content was 2.0 mol of tetramethyl-1.3 diaminopropane. The temperature of the first reactor was 30 ° C, and the amount of 2,6-dimethylphenol supplied was 224 gr / H.
It was r.

As a result, the viscosity of the obtained polymer is 0.65, the particle size is 40 ~
The color index was 50μ and 0.6. The color index after compression molding at 310 ° C was 3.9.

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Claims (1)

[Claims] 1. A copper salt, (b) N-phenylethanolamine, and (c) a general formula R ₁ —HN—R—NHR ₂ (wherein R ₁ and R ₂ are isopropyl groups, C ₄ and 1,2-diamine or 1,3-diamine on a tertiary alkyl group or α- carbon atom of the -C ₈ cycloalkyl group having no hydrogen.), and (d) a tertiary amine, A method for producing a polyphenylene ether by oxidatively polymerizing a phenolic compound with oxygen, which comprises using a catalyst comprising