JPS63142029A - Production of polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain the titled high-quality ether, by oxidatively polymerizing a phenolic compound in the presence of a highly active catalyst having improved water resistance consisting of a copper compound, N-phenylethanolamine, a specific secondary amine and a tertiary amine. CONSTITUTION:A phenolic compound is polymerized with O2 in the presence of a catalyst consisting of (A) a copper compound (preferably cuprous chloride, etc.), (B) N-phenylethanolamine, (C) a 1,2-diamine shown by the formula R1- NH-R-NHR2 (R1 and R2 are isopropyl, 3-8C tertiary alkyl or cycloalkyl containing no hydrogen on alpha-CO) (preferably N,N'-d-t-butylethylendiamine, etc.) and (D) a tertiary amine. Preferably the amount of the component A is 0.03-0.05 gram atom (based on 100mol phenolic compound), the amount of the component B is 0.1-5mols and the amounts of the components C and D are 1-4mols and 10-40mols (based on 1 copper gram atom), respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a process for producing high quality polyphenylene ether with improved water resistance and using a highly active copper catalyst. More specifically, phenolic compounds are oxidatively polymerized with oxygen in the presence of a catalyst with improved water resistance and high continuous polymerization activity consisting of a copper compound, N-phenylethanolamine, specific secondary diamine, and tertiary amine. The present invention relates to a method for producing high quality polyphenylene ether.

Conventionally, oxidized polymers of phenolic compounds are known as polyphenylene ethers, which have mechanical properties,
It has excellent electrical properties and heat resistance, and has low water absorption.
Due to its properties such as good dimensional stability, it has recently attracted attention as a thermoplastic engineering plastic.

[Conventional technology]

As polymerization catalysts for producing polyphenylene ether by oxidative polymerization of phenolic compounds, many combinations of copper compounds, manganese compounds, or co-, hexa-ruto compounds and various amines have been proposed.

Among them, diamines with specific structures, specifically N,
Copper amine complexes formed in combination with N'-di-t-butylethylenediamine and the like are known to have relatively high activity.

For example, copper ion, bromide ion, N, N'-sheet t-
Combinations of tertiary amines such as butylethylenediamine and N-methylpyrrolidine are known (Japanese Patent Publication No. 1983-
53012).

However, in addition to poor color, the polymers produced using this catalyst system have low impact resistance when combined with styrenic resins such as rubber-modified polystyrene, and poor thermal stability, making them impractical. It became clear that this catalyst system had a di-
It became practical for the first time with a catalyst system combining secondary monoamines such as n-butylamine (Japanese Patent Publication No. 59-2333).
Publication No. 2).

Furthermore, in this catalyst system, a production method in which the molar ratio of bromide ions to the raw material phenolic compound is about 1:35 or more (% 74124/1983), and cuprous salts and cupric salts as copper compounds are used. A method characterized by using a mixture of
A catalyst system using dimethylamine as a class monoamine (Japanese Patent Publication No. 60-54327) is known.

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

[Problem that the invention seeks to solve]

However, when the inventors of the present invention deeply investigated these conventional techniques, it was found that the following basic problems have not yet been sufficiently solved. That is, the water resistance of the catalyst has not been sufficiently improved and the polymerization activity of the continuous polymerization method is still low.

One of the reasons for this is that KN,N'-di-t-butylethylenediamine is produced during the polymerization process, as described in JP-A-59-96318, page 3, left column, lines 28-31. It may also be relevant that they are often quite easily consumed.

In any case, the catalyst components are hydrolyzed by the reaction product water that is produced as a by-product during the oxidative polymerization of phenols, and the metal components become hydroxides and are drawn out of the reaction system, resulting in a decrease in catalytic activity. Due to this problem, there was a demand for the development of a catalyst that would not lose its activity even in the presence of reaction product water in order to achieve high catalyst activation.

Particularly in continuous polymerization methods that require long average residence times, improving water resistance is an expensive problem.

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

(Means for Solving the Problems) The present inventors have conducted intensive studies on the method for producing polyphenylene ether in the situation described in -h.
Based on this finding, we discovered that a catalyst system consisting of a compound, N-phenylethanolamine, a specific diamine, and a tertiary amine has excellent water resistance, exhibits high continuous polymerization activity, and provides a high-quality polymer. The present invention has now been completed.

That is, the present invention provides (a) a copper compound, (b) N-phenylethanolamine, (/→ general formula R1-HN-R-NH
1,2-diamine or 1,3-diamine of R2 (wherein R1 and R2 represent an isopropyl group, a C4 to C8 tertiary alkyl group, or a cycloalkyl group having no hydrogen on the α-carbon atom) This is a method for producing polyphenylene ether, which is characterized by oxidatively polymerizing a phenolic compound with oxygen in the presence of a catalyst consisting of a tertiary amine and a tertiary amine.

The present invention provides a combination K of an N-substituted alkanolamine and a copper compound, which has not been disclosed in the prior art (N
-When combined with n-butylethanolamine, the activity is drastically reduced, but since N-phenylethanolamine is used, it exhibits a specifically high activity, which is a totally unexpected method.

When the catalyst used in the present invention is applied to a continuous precipitation polymerization method in which a polymerization solvent is selected and the polymer is precipitated as particles in the reaction system as the reaction progresses, the color is whiter than that in the pine polymerization method. Moreover, it is difficult to explain from conventional knowledge that a high quality polymer with little heat discoloration can be obtained.

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

Although any cupric or cupric compound may be used, the particular choice is determined primarily by economics and the availability of the compound. Soluble copper salts are preferred, but
Compounds of normally insoluble copper (cupric and cuprous) may of course also be used. This is because these insoluble compounds form soluble complexes with the amine in the reaction mixture.

Cupric compounds that can be used in the catalyst of the present invention include cupric halides such as cupric chloride or cupric bromide, cupric sulfate, cupric nodate, cupric acetate, azide, etc. Examples include cupric or cupric toluate. Examples of cuprous compounds that can be used are cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, cuprous acetate, cuprous acetate, cuprous butyrate or Cupric toluate and the like. Preferred cupric and cupric compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. Further, these copper salts may be synthesized from oxides, carbonates, hydroxides, etc. and halogen or hydrogen halide at the time of use. The amount of copper compounds used is 1 phenolic compound.
The range is from 0.01 gram atom to 1 gram atom, preferably from 0.03 gram atom to 0.5 gram atom per 00 moles of copper.

N-phenylethanolamine in the present invention can be used in a wide range of 0,605 mol to 10 mol, preferably 0.1 mol to 5 mol, per 100 mol of the phenolic compound.

General formula R+ HN RNHR2 (in the formula R1+ R2
represents an isopropyl group, an 04-C8 tertiary alkyl group, or a cycloalkyl group having no hydrogen on the α-carbon. ) 1,2-diamine or ijl,3-diamine.

Specific examples of these compounds include N, N'-di-t-
Butylethylenediamine, N,N'-sheet t-amylethylenediamine and N,N'-diisopropylethylenediamine, N,N'-sheet t-7'' t-tylzolopylenediamine, N,N'-sheet t-butylenechlorohexani ), 2-diamine, etc. Of these, N, N'-
Di-t-butylethylenediamine is preferred. The amount of diamine used is generally 1 to 4 moles per gram atom of copper.

Examples of tertiary amines that can be used in the practice of the present invention are aliphatic tertiary amines, including cycloaliphatic tertiary amines. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisopropylamine, diethylmethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, and diethylinpropylamine.

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

These tertiary amines are present in amounts ranging from 5 moles to 50 moles per gram atom of copper.
It can be used preferably in a mole range of 10 to 40 moles.

In carrying out the present invention, it is preferable to coexist halogen ions other than fluorine ions, since this improves the catalytic activity. As the halogen ions, chloride ions and bromide ions are particularly preferred. Halogen ions may be used alone or in combination.

The catalyst can be prepared using a solvent such as methanol. This objective can be achieved by methods commonly known to those skilled in the art, provided that the copper compound is dissolved. It may also be prepared in the atmosphere.

The phenolic compound used in the method of the present invention is (R in the formula
3 is a hydrocarbon group having 1 to 4 carbon atoms, and R4 is a halogen or a hydrocarbon group having 1 to 4 carbon atoms.
．． 6-dimethylphenol, 2-methyl-6-ethylphenol, 2.6-ethylphenol, 2-ethylphenol
6-n-f lovirphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2
-Methyl-6-itubrobylphenol, 2-methyl-
6-n-furobylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-probylphenol, 2-ethyl-
6-chlorophenol nato is mentioned. Each of these compounds may be used alone, or 2'! ! i or more may be used together. Further, there is no practical problem even if a small amount of orthocresol, metacresol, nozorafresol, 2,4-dimethylphenol, 2-ethylphenol, etc. is included.

Among these phenolic compounds, 2.6 dimethylphenol is particularly important.

The ratio of the phenolic compound to the solvent can be selected within 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.

The medium used in the method of the present invention is one that is less likely to be oxidized than the phenolic compound to be oxidized and has no reactivity to various radicals that are thought to be generated intermediately in the reaction process. Although there are no particular limitations, it is preferable to use one that dissolves the phenolic compound and partially or completely dissolves the catalyst mixture. Examples of such substances include aromatic hydrocarbons such as benzene, toluene, and xylene;
Chloroform, 1,2-dichloroethane, trichloroethane, chlorobenzene, halogenated hydrocarbons such as dichlorobenzenato, nitro compounds such as nitrobenzene, and the like can be conveniently used as good solvents for the polymer. Examples of poor solvents for polymers include methanol, ethanol, furominol, phthanol, benzyl alcohol, cyclohexanol natono alcohols, acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and ethyl formate, tetrahydrofuran, diethyl ether, etc. and amides such as dimethylformamide. These good solvents and poor solvents can be used alone or in combination of two or more.

By tracing the combination ratio of good solvent and poor solvent for this polymer, it can also be a solution polymerization method, and if the ratio of poor solvent is increased, the polymer will precipitate as particles in the reaction system as the reaction progresses. It can also be used as a precipitation polymerization method.

The present invention can be applied to Nototsuchi polymerization method, continuous polymerization method, solution polymerization method, and precipitation polymerization method, but in particular, continuous precipitation polymerization method has not only high polymerization activity but also narrow molecular weight distribution. In addition, it is more preferable because a highly white polymer with little discoloration upon heating can be obtained.

As an example of a continuous method of precipitation polymerization, Japanese Patent Publication No. 49-2891
Publication No. 9 can be mentioned.

That is, in order to continuously obtain polyphenylene ether by applying the polymerization reaction of a phenolic compound in which polyphenylene ether is precipitated as the polymerization progresses, it is necessary to combine a complete mixing type polymerization tank having two functions. be. That is, a first polymerization tank is required to proceed with the shake polymerization in a uniform solution state, and a second polymerization tank is required to precipitate stable particles of polyphenylene ether. If necessary, a third polymerization tank is provided to control the final properties of the polymer particles through aging and to provide a final finish for subsequent processing steps. Each of these polymerization tanks can be divided into several polymerization tanks for more delicate control.

To explain in more detail, in the first polymerization tank, the oxygen gas flow rate and average residence time are controlled in order to suppress the polymerization reaction rate to 90% or less so that precipitation does not occur due to total heat, and at the same time, to prevent the viscosity of the liquid from increasing too much. A polymerization tank format is used that takes advantage of the homogeneous solution to sufficiently remove polymerization heat.

In the second polymerization tank, depending on the medium composition, that is, the combination of solvent and non-solvent and their quantitative ratio, it is possible to prevent the precipitated polymer particles from adhering to the vessel wall, stirring @, etc., and to maintain appropriate stirring conditions and oxygen gas. Control the size and hardness of polymer particles by maintaining the feed rate.

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

The operating conditions for this continuous polymerization method vary greatly depending on the catalyst species, phenolic compound type, and medium glaze, but are particularly influenced by the concentration of the phenolic compound as a monomer. Unlike the case of homogeneous solution polymerization,
The monomer concentration is 10 to 40 parts by weight in the total polymerization solution! ll
20 to 35 times is particularly preferable, and the characteristics of continuous polymerization in a precipitation system are exhibited.

The reason why a complete mixing type polymerization tank is used in this method is that the oxidative polymerization reaction of phenolic compounds requires high contact efficiency with oxygen gas, so sufficient stirring is required in all reaction tanks. Because it must be done. That is, a single tank in which stirring in the direction of movement of the reaction solution does not occur is inappropriate when handling a reaction mixture as low in viscosity as this reaction. In other words, in order to achieve this slow-crack polymerization method, it is necessary to combine a complete mixing type reactor with an average residence time and agitation state that can perform the functions of at least the two types of reactors shown above. γL is necessary.

A quaternary ammonium salt or a surfactant may be added to the reaction system during the reaction, or for the purpose of controlling the particle size of the polymer or improving phase separation between solvents.

Regarding the reaction temperature, if it is too low, the reaction will not proceed.
Also, the catalyst may become deactivated if the temperature rises too high, so
It is in the range of 80°C, preferably 10-60°C.

As oxygen, a mixture of oxygen, nitrogen, or other inert gas in any proportion, or air can be used. The pressure can be normal pressure or increased pressure.

There are no particular restrictions on the method for post-processing the reaction-completed edge.

Usually, the catalyst is activated by adding an acid such as hydrochloric acid or acetic acid to the reaction solution, then the resulting polymer is separated, washed with a solvent that does not dissolve the polymer such as methanol, and then dried. Phenylene ether recovered by operation is recovered.

〔Effect of the invention〕

In the method of the present invention, a highly active catalyst with improved water resistance consisting of a copper compound, N-phenylethanolamine, a specific diamine, and a tertiary amine is used as a polymerization catalyst for polyphenylene ether, so the amount of catalyst used is In addition, the amount of solvent used to remove the catalyst residue in the polymer is small, and as a result, the cost of recovering the solvent is eliminated.Also, the equipment for removing the catalyst can be made smaller. The process for removing the catalyst is simplified.Furthermore, the obtained polymer has a good color tone, and high quality polyphenylene ether polymers with little heat discoloration can be produced, which is a great advantage.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, η9p/e? tllll N is 0.5 for the polymer
The test was conducted using a W/Vt% chloroform solution at 30°C using an Ubbelohde viscometer.

Definition of color index> Obtained polymer or polymer compression molded at 310°C 0.
Dissolve 5g in chloroform, make the total concentration 100t/,
The absorbance at 480 nm is measured at 25C and calculated using the following formula.

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

Here 10: Intensity of incident light l: Intensity of transmitted light a: Cell length [leap] b = Solution concentration Cg/crri'] Example 1 Finely powdered cuprous oxide (Cu20) 0, 10 was placed in an Erlenmeyer flask.
6gr (0,749mmol) and 48% Beautiful Hydrogen Water Z32gr (117mmol) were added, and after completely dissolving, 103gr of methanol was added. This is used as a liquid preparation.

In another Erlenmeyer flask, 0.512 gr (199 mmol) of N,N'-di-t-butylethylenediamine, n-
Butyl-dimethylamine 3.02 gr (29.9 mmol), N-phenylethanolamine 277 gr (20
, 2 mmol) and 3 gr of methanol IQ were added. This is a total amine solution.

A catalyst was prepared by adding the above liquid preparation and then the above amine liquid to a 1,52-column flask equipped with a circulation pump.

Thereafter, 260 gr (2132 mmol) of 2,6-dimethylphenol and 206 gr of n-butanol dissolved in 618 gr of toluene were added to the flask. The above operations were performed in the atmosphere. The reaction solvent used was 10103O
The composition is toluene:n-butanol:methanol in a weight ratio of 60:20:20. The concentration of 2,6-dimethylphenol is 20% by weight, and the concentration of 2,6-dimethylphenol is 2.
0.07 gram atoms were used per 100 moles of 6-dimethylphenol. The color of the prepared plate was initially grayish black, but later changed from green to evening yellow.

2$00 without supplying oxygen while stirring with a circulation pump
The reaction was carried out.

During the course of the reaction, reaction g was sampled over time, 5 times the volume of methanol was added, filtered, washed and dried, and the viscosity of the obtained polymer was measured, and the following results were obtained.

2.5 o'clock lit! A portion of the reaction solution during columnar filtration was extracted and treated. A portion of the yellowish-white reaction solution containing the slurry was taken out, methanol was added thereto, and the mixture was filtered. It was thoroughly purified and washed using a mixed solvent (toluene, butanol and methanol) and diluted hydrochloric acid. The viscosity of the 1t polymer obtained after drying is 0.6
0 and its color index was 1.3. Further, the color index after pressure path 1 molding at 310° C. was 7.3.

Example 2 Example except that when discussing cuprous oxide, equimolar amounts of 35% hydrochloric acid as hydrogen halide were used instead of 48% hydrogen bromide water! I changed my experience with IP = i building 5r.

During the process, the reaction solution was sampled and the viscosity of the produced polymer was measured.

After 3 hours had elapsed, a portion of the reaction solution was extracted, and the reaction solution was purified by the method of Example 1 to obtain a polymer.

As a result, the viscosity of the polymer was 0.60 and its color index was 1.4.3 after compression molding at 10 DEG C. Color index #-i was 6.9.

Example 3 Using a 100 cc glass reactor, the catalytic activity was examined based on the viscosity reached after a certain polymerization time.

That is, finely powdered cuprous oxide 0.0041 gr (0,0287
0.089 gr (0.5 mmol) and 48
After completely dissolving 28 mmol), 6.25 g of methanol was added. This was combined with N, prepared in a separate container.
-Phenylethanolamine 0.0748gr (0,5
45 mmol), N, N') ti-methylethylenediamine 0.0197 gr (0,1159 rimole), n-butyl-dimethylamine 0.116 gr (1,
A solution containing 15 mmol) and 6.25 g of methanol was added. Thereafter, 7.0 gr (57.4 mmol) of 2,6-dimethylphenol and 115 gr of n-butanol dissolved in 37.5 g of toluene were added. The reaction bath used was 615 gr, and its composition was toluene:n-butanol:methanol in a weight ratio of 6.
It was 0:20:20. The concentration of 2,6-dimethylphenol is 10% by weight, and the amount of copper is 0.1 gram atom per 100 moles of 2,6-dimethylphenol.

The reaction was carried out at 30C for 3.5 hours while stirring and without supplying oxygen. The reaction liquid had changed to a yellow-white liquid containing slurry. The viscosity of the polymer obtained by adding methanol 5 times the volume of the reaction solution, filtering, washing and drying was 0.98.

Comparative Examples 1 to 4 Instead of N-phenylethanolamine, N shown in Table 2)
- Example 3 except using alkylethanolamine
The experiment was repeated under the same conditions.

The results are shown in Table D). N-phenylethanolamine was specifically highly active.

Table d) *Polymer was not obtained. Example 4 The experiment was repeated in the same manner as in Example 3, except that 35-thihydrochloric acid was used in place of the 48-thiobromide water in Example 3 in an equimolar amount as the hydrogen halide.

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

Example 5.6 In order to test the water resistance of the catalyst, an experiment was conducted by adding an amount of water equivalent to the reaction product water into the reaction system in advance.

That is, in Examples 5 and 6, reaction solutions were prepared in the same manner as in Examples 3 and 4 under the atmosphere. Thereafter, 1.03 g of water equivalent to the water produced by the reaction was added under stirring, and then oxygen was introduced to start the polymerization reaction. The polymerization conditions and reaction solution treatment method were the same as in Examples 3 and 4.

The results are summarized in Table-2.

Comparative Examples 5-7 The experiments were repeated in the same manner as Examples 4-6, except that 0.0703 gr (0,545 mmol) of di-n-butylamine was used in place of N-phenylethanolamine.

The results are summarized in Table-2.

Table 2 Examples 7 to 9 The types and amounts of copper compounds, hydrogen halides, and amines used are as shown in Table 3. The experiment was repeated in the same manner as in Examples 5 and 6. The results are shown in Table-3.

Examples 10 to 16 Mixed xylene, ethylbenzene, and cyclohexane were used in place of toluene in Example 5, and the amount of copper used was 0.6-dimethylphenol per 100 moles of 2.6-dimethylphenol.
Changed from 1 gram atom to 0.07 gram atom, 25℃
The mixture was allowed to react for 6 hours.

That is, 0.000287 gr (0.02 mmol) of cuprous oxide, 0°0623 gr (0.370 mmol) of 48 thihydrobromide
mmol), and methanol was added in the amount used (50 g). To this, 70.0748 gr (0,545 mmol) of N-phenylethanolamine, N, N, prepared in a separate container.
'-di-t-butylethylenediamine 0.0138gr
(0.080 mmol), 0.0138 gr (0.8 mmol) of n-butyl-dimethylamine, and the remaining 50 g of methanol used to prepare a catalyst solution.

Furthermore, a solvent line such as toluene or mixed xylene, a predetermined amount of -n-butanol and 2,6-dimethylphenol 7,0
gr (57.4 mmol) was added.

Table 4 shows the composition ratios of at, n-butanol, and methanol in the solvent used. The total amount used in each example was 62. ．． It is 5gr.

In addition, 1.03 g of water equivalent to the reaction product hydration was added to the reaction system.
After adding r, the reaction was carried out at 25° C. for 6 hours while stirring and supplying oxygen. The reaction solution was treated according to the method of Example 5 to obtain a polymer. The viscosity (ηsp/c) of the polymer is shown in Table 4 with 1 being set.

(Leaving space below) Table 4 Band 1 N-Butanol 2 Methanol Example 17 In order to examine the influence of the reaction solvent, a mixed solvent of toluene-methanol (80/20 in heavy leaf ratio) was used at 62°C and 5gr. The procedure was as in Example 10.

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

Examples 18-21 In order to investigate the influence of the 3-mounted amine rod, cyclohexyl-dimethylamine, isopropyl-dimethylamine,
N,N,N',N'-tetramethyldi),3-'yaminobutane is used, and the amount of copper used is 100 mol l'lJ of 2,6-dimethylphenol, from 0.1 gram atom to 0.08 gram atom. The temperature was changed to 30° C. and the reaction was carried out for 3.5 hours.

That is, 0.00329 gr (0,023 mmol) of oxidized No. 1 steel 0.0443 gr (0,425 mmol) of 35% hydrochloric acid and 6.25 gr of methanol were added. 074
8 gr (0,545 mmol), N,N'-di-t-butylethylenediamine 0. O158gr (0,091
8 mmol), 0.918 mmol of tertiary amine and 6.25 gr of methanol were added. Furthermore, n-butanol 1
After preparing a reaction solution by adding λ5gr, 37.5gr of toluene and 7.0gr (57.4mm IJmol) of 2,6-dimethylphenol, add 1.03gr of water equivalent to the produced water.
The same procedure as in Example 6 was carried out by adding .

Table 5 summarizes the tertiary amine used and the viscosity of the obtained polymer.

Table - <= Example 22 Polymerization was carried out using a continuous polymerization reactor consisting of three complete mixing tanks for continuous polymerization activity and polymer quality evaluation. The first reactor has a capacity i, sβ and is equipped with a circulation pump. Second
The reactor and the third reactor are equipped with stirrers and have capacities of 3.7A and 1.5J, respectively! It is.

The catalyst solution was prepared by dissolving cuprous oxide in 35% hydrochloric acid, adding methanol, and then adding N-phenylethanolamine, N, N'
-di-t-butylethylenediamine, n-butyl-dimethylamine and methanol were added. A monomer solution was prepared by dissolving 2,6-dimethylphenol in toluene and n-butanol.

Each was prepared under air.

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

Based on the amounts of the catalyst solution and monomer solution sent, the composition of the reaction raw material solution is as follows.52.6-Dimethylphenol concentration is 20% by weight and the solvent ratio is toluene:n -Butanol:methanol=60:20:
It is 20.

2.6-For every 100 moles of xylenol, steel is 009 gram atoms, C2 ion is 0.83 gram atoms, N-phenylethanolamine is 0.95 mol, N,N'-)-
The ratio of t-7'' methylethylenediamine UO, t8 mol, and n-butyl-dimethylamine was 1.8 mol.

Also, 2,6-dimetherphenol is 240 g/Hr
It was supplied at a rate of n.

In the first reactor, the reaction solution was vigorously circulated using a circulation pump, and oxygen was passed through the reactor. The internal temperature was controlled to be 25°C. The reaction liquid sent from the first reactor to the second reactor under head pressure was homogeneous.

In the second reactor, 55% of oxygen gas is added while vigorously stirring with a stirrer.
00m! It was flowed at a rate of +J and kept at 25°C. The polymer precipitates out, but is evenly distributed throughout the reactor by stirring. From the second reactor, the reaction solution containing the polymer particles enters the third reactor at an autocooled flow rate.

While controlling the temperature of the third reactor at 25°C and flowing oxygen gas at a rate of 20,011/min while stirring with a stirrer, the reaction solution containing the polymer was continuously fed from the third reactor at 270°C. The catalyst was removed and acidified with hydrochloric acid to remove the catalyst.

The viscosity (ηsp/
c) rJ O was within the range of 61±0.03, and stable operation was possible for a long period of time.

The resulting 111 aggregate had a particle size of 50 to 80 μm and a color index of 07. The color index after compression molding at 310°C was 36.

It can be seen that the color tone of the polymer obtained using the continuous polymerization method is better than that of the Z-polymerization method of Example 2, and that a high-quality polymer with less discoloration upon heating can be obtained.

Example 23 The same procedure as in Example 22 was carried out except that 48% aqueous hydrogen bromide was used instead of 35-dihydrochloric acid in Example 22, and the amount of catalyst used and the amount of 2,6-dimethylphenol supplied were changed. .

That is, reaction 1fi4. The composition of the solution was 2.6-dimethylphenol + 13:20% by weight, and the ratio of the solvents used was toluene = 11-butanol: methanol = 60:
20:20, per 100 moles of 2,6-xylenol, copper is 0.08 gram atom, bromide ion Vi0.7
4 grams atom, N-phenylethanolamine is 0.
95 moles, N, N'+, di-t-butylethylenediamine is 0,167 moles, n-butyl-dimethylamine 1.6
It was a molar ratio. Further, the amount of 2.6-dimethylphenol fed to the first reactor was 208 g/Hr.

As a result, the viscosity of the obtained polymer was 0.60, and the particle size was F.
i40-70μ, color index 0.5. The color index after compression molding at 310°C was 17.

Comparative Example 8 Using C-n-butylamine instead of N-phenylethanolamine, with a mixed solvent of toluene and methanol,
Continuous polymerization was carried out using the apparatus and apparatus of Example 18.

That is, the concentration of 2.6-dimethylphenol was 10% by weight, and the weight ratio of the solvent used was 90:10 toluene:methanol.
It is. 2.6-dimethylphenol per 100 moles,
Copper is 0.2 gram atom, bromine ion is 1,84 gram atom, N, N'-di-t-butylethylenediamine 2
-0 mol, n-butyl-dimethylamine 4.0 mol, l
-n-butylamine was 0.95 mole. or,
2.6-dimethylphenol was fed to the first reactor at a rate of 80 g/Hr. Example 2 by controlling the temperatures of the first reactor, second reactor and third reactor to 40°C.
It was carried out in the same manner as in 3.

Third Reaction From Masudaguchi: Since the obtained reaction solution was viscous, 25 parts by weight of toluene was added to 100 parts by weight of the reaction solution to dilute it. Furthermore, 1 of the total molar amount of copper and amine in the reaction solution
After extracting the catalyst component using 25 parts by weight of Kanakura's hydrochloric acid containing 0 times the molar amount of hydrogen chloride, 200 parts by weight of methanol was added little by little while stirring to precipitate a polymer. Then Example 2
A polymer was obtained by treatment in the same manner as in 3. The viscosity (ηsp/c) of the obtained polymer was 0.46, and the color index was F.
i1.2. The color index after compression molding at 310° C. was 198.

In the known copper-chelate catalyst system, compared to Example 23, 2
Even when -5 times the amount of catalyst was used, the viscosity of the obtained polymer was low and the discoloration on heating was severe.

Example 24 Trioctylmethylammonium chloride was added to the reaction system of Example 23, and its effect was investigated.

That is, trioctyl ammonium chloride in an amount corresponding to 0.02 weight tqb of the reaction solution was added to the catalyst solution and supplied to the first reactor. Father, the supply amount of 2,6-zinthylxylenol was increased from 208 g r / Hr to 2 zag
It was supplied at a ratio of r/Hr. Example 2 except for the above changes
It was carried out in the same manner as in 3.

As a result, the obtained polymer had a viscosity of 0.61, a particle size of 20 to 50 μm, and a color index Fi of 0.7.

The color index after compression molding at 310°C is 3.
It was 8.

Example 25 Example 23 was carried out under the same conditions except that mixed xylene was used instead of toluene, one of the reaction solvents.

As a result, the viscosity (ηsp/c) of the obtained polymer was 0.
58, color index is o, 5, particle size is 30~
It was 60μ. The color index after compression molding at 310°C was 16.

Example 26 A reaction was carried out under the same conditions as in Example 24 except that mixed xylene was used instead of toluene, one of the reaction solvents.

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

Example 27 A reaction was carried out under the same conditions as in Example 22 except that mixed xylene was used instead of toluene, one of the reaction solvents.

As a result, the viscosity (ηsp/c) of the obtained polymer was 0.
60, particle size 20-50μ, color index O26. The color index after compression molding at 310°C was 3.5.

Park Heo-su A Tribute Jeongdan Ihiwei Industrial Shosha Proceedings Amendment (Spontaneous) February 4, 1986 Director General of the Patent Office Kunio Ogawa 1, Indication of Case Patent Application No. 2/22 of 1986!
No. 2, Name of the invention Process for producing polyphenylene ether 3, Relationship with the case of the person making the amendment Patent applicant 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka (003)
Asahi Kasei Industries, Ltd. President and Representative Director Masaomi Seiko (N'□-Mon) 4
, Get the "Detailed Description of the Invention" of the specification to be amended Contents of the amendment (1) Specification ratio 2 True 1st line l'-N, N''-G-t
-butylethylenediamine, etc." to l'-N,N'-di-t-butylethylenediamine, etc." (: Correct.

(2) In the same page, page 3, line 77, [(JP-A-Sho J9-/3/6-7] is corrected to "(JP-KOKAI J-9-/3/lλ2").

(8) r-t-promophenol in the second line from the bottom of page 70, J is r-4-bromophenol” (
Make two corrections.

(4) In the second line of page 73, "solution type method" is amended to "solution polymerization method."

(5) On page 16, line 5 of the same page, ``Oxygen is pure oxygen in any proportion with an inert gas such as nitrogen.'' [Oxygen is pure oxygen.

Inert gas such as nitrogen and any ratio].

(6) [Processing method after reaction completion] on page 1, line ♂:
"For information on processing methods after the reaction is complete,"
Correct to.

(7) In line 7 of page 77, the phrase "The amount is small, and as a result, the cost of recovering the solvent is reduced" is corrected to "The amount is small, and as a result, the cost of recovering the solvent is reduced."

(8) The "Table" on page 20 of the same document shall be amended.

(9) “Table 2” of the same No. 25
Correct to −.

"Table 3" on page λ♂ of αO is amended to the attached "Table 3".

I Amend "while using -7,3-diaminobutane" on page 30, line λ of the same to "while using -7,3-diaminobutane."

0 Same 3rd! In the seventh line of the page, "Continuous polymerization was carried out using the apparatus of Example/Female" was corrected to "Continuous polymerization was carried out using the apparatus of Example 2".

0 In the same page 35, page 74, the line "Tyle diamine λ, θ moles" is corrected to "Tyle diamine θ, 4 t moles."

aφ Correct "amount of tylxylenol supplied" in line 37 of the same page to "amount of t-ruphenol supplied".

that's all

Claims (1)

[Scope of Claims] (a) Copper compound, (b) N-phenylethanolamine, and (c) general formula R_1-HN-R-NHR_2 (in the formula R_
1, R_2 represents an isopropyl group, a C_4 to C_8 tertiary alkyl group, or a cycloalkyl group having no hydrogen on the α-carbon atom. ) of 1,2-diamine or 1,
A method for producing polyphenylene ether, which comprises oxidatively polymerizing a phenolic compound with oxygen in the presence of a catalyst consisting of a 3-diamine and a (d)tertiary amine.