JP2010202786A - Production method of polyphenylene ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably producing with advantageous efficiency, a polyphenylene ether excellent in heat resistance and suppressing the generation of a gel while maintaining a high activity and suppressing the generation of a scale. <P>SOLUTION: This production method of a polyphenylene ether is a method for producing a polyphenylene ether by polymerizing a phenol mixture containing three types of phenol compounds (A), (B), and (C) having predetermined structures while numerically restricting the amounts to be used of these phenol compounds. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing polyphenylene ether.

Polyphenylene ether has excellent workability and productivity, and has the advantage of being able to efficiently produce products and parts of the desired shape by molding methods such as melt injection molding and melt extrusion molding. It is widely used as a material for products and parts in the fields of automobiles, automobiles, other industrial materials, and food packaging.
With the diversification of such applications, various types of polyphenylene ethers having different characteristics such as molecular weight and glass transition temperature have been demanded. Furthermore, they have high heat resistance, and have improved mechanical properties and solvent resistance. There has been a demand for polyphenylene ether exhibiting excellent characteristics.
Furthermore, there is an increasing demand for a technique for producing various kinds of polyphenylene ethers in a short time with a short polymerization time.

Conventionally, polyphenylene ether composed of 2,6-dimethylphenol and 2,3,6-trimethylphenol has been known as a highly heat-resistant polyphenylene ether, and various studies have been made on its production method.
For example, Patent Document 1 discloses a technique for producing polyphenylene ether by oxidative coupling of a phenol compound at a reaction temperature equal to or higher than the cloud point temperature.

  Further, Patent Document 2 discloses a method of performing polymerization using a good solvent and a poor solvent for polyphenylene ether in the presence of a catalyst to precipitate polyphenylene ether, which is 5 ° C. more than conventional polyphenylene ether. As described above, a technique for producing polyphenylene ether having a high glass transition temperature and excellent heat resistance has been disclosed.

Furthermore, Patent Document 3 and Patent Document 4 disclose a technique for producing polyphenylene ether by copolymerizing orthocresol and 2,6-dimethylphenol.
Patent Document 5 discloses a technique for suppressing the generation of gel and obtaining polyphenylene ether having an extremely wide molecular weight.

International Publication No. 2003/042282 Pamphlet JP-A-60-163925 Japanese Patent Laid-Open No. 52-144097 Japanese Patent Laid-Open No. 52-144098 JP 2004-51703 A

However, since the method disclosed in Patent Document 1 applies solution polymerization as a polymerization form, the concentration of the monomer compound is decreased in order to suppress an increase in viscosity accompanying the progress of the polymerization, or externally during the polymerization. From the industrial point of view, it is necessary to increase the temperature by lowering the viscosity in the system by increasing the amount of heat, and the polymerization rate tends to decrease due to the increase in viscosity accompanying the progress of polymerization. I can't say that.
Further, the method disclosed in Patent Document 2 requires an extremely large amount of metal catalyst for the monomer, and cannot be said to be an efficient method from an industrial viewpoint.
Furthermore, the methods disclosed in Patent Documents 3 and 4 have been proposed as techniques for improving the flow characteristics by the polymerization reaction, but the polyphenylene ether is cross-linked during the polymerization reaction and a gel is generated. In order to suppress crosslinking, there is a problem that coexistence with a 4-substituted phenol is essential.
Furthermore, in the method disclosed in Patent Document 5, no investigation has been made on the polymerization activity and heat resistance, and in order to obtain a polyphenylene ether having industrially good production efficiency and excellent heat resistance. Still has many issues to consider.

On the other hand, as a technique for producing many types of polyphenylene ethers, it is known that the batch polymerization method is useful. Development of a typical polyphenylene ether production technique has become an issue.
In particular, the scale to the reactor that can be generated during batch polymerization deteriorates the yield of polyphenylene ether. Therefore, in order to obtain the desired amount of polyphenylene ether, the raw material phenol compound must be used more than necessary. However, there is a risk that the cost will be increased and the load on the environment may be increased.
Further, it is known that a continuous polymerization method is useful as a method for stably producing a large amount of the same type of polyphenylene ether. However, in this method as well, in order to obtain a desired amount of polyphenylene ether as designed, a technique for reducing the scale is required.
Therefore, in view of the above-mentioned problems of the prior art, in the present invention, polyphenylene ether having high heat resistance is efficiently suppressed while suppressing the generation of gel and preventing the generation of scale to the reactor or the like. Provided is a method for stable production.

As a result of intensive studies on the above problems, the inventors of the present invention effectively suppressed gel generation by polymerizing polyphenylene ether using specific amounts of three types of phenolic compounds having specific structures. The inventors have found that high-heat-resistant polyphenylene ether can be produced efficiently and stably by preventing the generation of scale, and the present invention has been completed.
That is, the present invention is as follows.

  [1] A phenol compound (A) represented by the following formula (1),

(In Formula (1), R ₁ and R ₂ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an alkenyl. And any one selected from the group consisting of a group, an alkynyl group, and an optionally substituted alkoxy group.)

  A phenol compound (B) represented by the following formula (2),

(In formula (2), R ₃ , R ₄ and R ₅ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. And any one selected from the group consisting of an optionally substituted alkoxy group.)

And a phenol compound (C) represented by the following formula (3),

(In the formula (3), R ₆ is a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted alkoxy group. Any one selected from the group consisting of:

A process for producing polyphenylene ether comprising a step of polymerizing using a mixed phenol containing
The mixed phenol is based on 100% by mass of the total amount of the phenol compounds (A) to (C).
The phenol compound (A) is 55.0 mass% or more and 94.5 mass% or less,
The phenol compound (B) is 5.0% by mass or more and 40.0% by mass or less,
The phenol compound (C) is 0.5% by mass or more and 5.0% by mass or less,
A process for producing polyphenylene ether.

[2] The above-mentioned [1], wherein the polyphenylene ether has a reduced viscosity ηsp / c measured at 30 ° C. with a chloroform solution having a concentration of 0.5 g / dl of 0.40 (dL / g) or more. Of producing polyphenylene ether.

[3] The polymerization step of the mixed phenol compound containing the phenol compounds (A) to (C) includes a step of oxidative polymerization using a catalyst and an oxygen-containing gas, and as the catalyst, a copper compound-halogen compound, and The manufacturing method of polyphenylene ether as described in said [1] or [2] using the diamine compound represented by following formula (4).

(In formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from the group consisting of a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms. Any one (however, all are not hydrogen at the same time), and R ₁₁ represents a linear or branched alkylene group having 2 to 5 carbon atoms.)

[4] In the formula (1) showing the phenol compound (A), R ₁ and R ₂ are methyl groups; in the formula (2) showing the phenol compound (B), R ₃ , R ₄ , The polyphenylene ether according to any one of [1] to [3], wherein R ₅ is a methyl group, and R ₆ is a methyl group in the formula (3) showing the phenol compound (C). Production method.

[5] The polymerization form of the polyphenylene ether is a precipitation form, and the polymerization is continued for 1 minute or longer from the start of the precipitation of the polyphenylene ether polymer. The manufacturing method of polyphenylene ether as described in 1 ..

[6] Any one of [1] to [5], wherein the total amount (monomer conversion) of the mixed phenol compound used for polymerization is 10% by mass or more and 50% by mass or less with respect to 100% by mass of all raw materials used for polymerization. A method for producing a polyphenylene ether according to one item.

[7] The method for producing polyphenylene ether according to [3], further including a tertiary monoamine and / or a secondary monoamine compound as the catalyst.

  According to the method for producing polyphenylene ether of the present invention, it is possible to efficiently produce polyphenylene ether having high heat resistance while effectively suppressing the generation of gel and effectively preventing the generation of scale in a reaction vessel or the like.

  Hereinafter, although the form for implementing this invention (henceforth this embodiment) is demonstrated, this invention is not limited to the form shown below.

[Production method of polyphenylene ether]
The method for producing polyphenylene ether in the present embodiment polymerizes the phenol compounds (A) to (C) described later. Preferably, the polymerization is performed using a mixed solvent of a good solvent and a poor solvent while supplying an oxygen-containing gas in the presence of a predetermined catalyst.

[Phenol compounds to be used]
In the method for producing polyphenylene ether of the present embodiment, the phenol compound (A) represented by the following formula (1),

(In Formula (1), R ₁ and R ₂ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or a substituted group. Any one selected from the group consisting of alkoxy groups which may be used.

  A phenol compound (B) represented by the following formula (2),

(In the formula (2), R ₃ , R ₄ and R ₅ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. And any one selected from the group consisting of an optionally substituted alkoxy group.)

And it superposes | polymerizes using the mixed phenol which consists of a phenolic compound (C) represented by following formula (3).

(In the formula (3), R ₆ is a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted alkoxy group. Any one selected from the group consisting of:

〔amount to use〕
Total amount of phenol compound used for polymerization: when phenol compound (A) + phenol compound (B) + phenol compound (C) = 100 mass%, phenol compound (A) is 55.0 mass% or more and 94.5 mass% The phenol compound (B) is 5.0 mass% or more and 40.0 mass% or less, and the phenol compound (C) is 0.5 mass% or more and 5.0 mass% or less.

When the phenolic compound (A) is less than 55.0% by mass, the polymerization activity after precipitation tends to be insufficient, and when it exceeds 94.5% by mass, the polyphenylene ether has sufficient heat resistance. Tend not to be obtained.
From the viewpoint of producing a polyphenylene ether having high heat resistance and good polymerization activity, the phenol compound (A) is preferably 60.0% by mass or more and 90.5% by mass or less, and 65% by mass or more and 88.5% by mass. More preferably, it is below the mass.

When the phenolic compound (B) is less than 5.0% by mass, a polyphenylene ether having sufficient heat resistance tends not to be obtained, and when it exceeds 40.0% by mass, the polymerization activity after precipitation is obtained. Tends to be insufficient.
From the viewpoint of producing a polyphenylene ether having high heat resistance and good polymerization activity, the phenol compound (B) is preferably 10.0% by mass or more and 38.0% by mass or less, and 15% by mass or more and 35% by mass. The following is more preferable.

About phenolic compound (C), there exists a tendency for sufficient polymerization activity not to be acquired as it is less than 0.5 mass%. Moreover, when it becomes 5.0 mass% or more, the generation | occurrence | production probability of a gel will become high and there exists a tendency for sufficient heat resistance not to be acquired.
From the viewpoint of producing polyphenylene ether having high heat resistance and good polymerization activity while ensuring polymerization stability, the phenol compound (C) is preferably 0.8% by mass or more and less than 4.0% by mass. More preferably, it is 1.0 mass% or more and less than 3.0 mass%.

[Phenol compound structure]
A halogen atom, an optionally substituted alkyl group, or a substituted group represented by the symbols R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ in the above formulas (1) to (3) A good aryl group, an optionally substituted aralkyl group, and an optionally substituted alkoxy group will be described.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, A chlorine atom and a bromine atom are preferable.
Examples of the “alkyl group” of the optionally substituted alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, such as methyl, ethyl, Examples include propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like. In particular, methyl and ethyl are preferable, and methyl is more preferable.
Examples of the “alkenyl group” of the alkenyl group which may be substituted include ethenyl, 1-propenyl, 2-propenyl, 3-butenyl, pentenyl, hexenyl and the like, and ethenyl and 1-propenyl are preferable.
Examples of the “alkynyl group” of the alkynyl group which may be substituted include ethynyl, 1-propynyl, 2-propynyl (propargyl), 3-butynyl, pentynyl, hexynyl and the like, and ethynyl, 1-propynyl, 2-propynyl (Propargyl) is preferred.
Examples of the “aryl group” of the aryl group which may be substituted include phenyl, naphthyl and the like, and phenyl is preferable.
Examples of the “aralkyl group” of the aralkyl group which may be substituted include benzyl, phenethyl, 2-methylbenzyl, 4-methylbenzyl, α-methylbenzyl, 2-vinylphenethyl, 4-vinylphenethyl and the like. Benzyl is preferred.
Examples of the “alkoxy group” of the optionally substituted alkoxy group include linear or branched alkoxy groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, such as methoxy, ethoxy, Examples include propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy and the like. Methoxy and ethoxy are preferred.

The alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group and alkoxy group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ have one or more substitutable positions. It may be substituted with a substituent.
As a substituent, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl) , Pentyl, hexyl), aryl groups (eg, phenyl, naphthyl), alkenyl groups (eg, ethenyl, 1-propenyl, 2-propenyl), alkynyl groups (eg, ethynyl, 1-propynyl, 2-propynyl), aralkyl groups (eg, , Benzyl, phenethyl), an alkoxy group (for example, methoxy, ethoxy) and the like.

[Specific examples of phenolic compounds (A) to (C)]
Examples of the phenol compound (A) include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6- Chlorphenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-bis- (4-fluorophenyl) phenol 2-methyl-6-tolylphenol, 2,6-ditolylphenol, and the like.
In particular, since it is inexpensive and easily available, 2,6-dimethylphenol, 2,6-diethylphenol, and 2,6-diphenylphenol are preferable, and 2,6-dimethylphenol is more preferable.
The said phenol compound (A) may be used independently, or may be used in combination of 2 or more type.
For example, a method using a combination of 2,6-dimethylphenol and 2,6-diethylphenol, a method using a combination of 2,6-dimethylphenol and 2,6-diphenylphenol, and the like, and the mixing ratio is arbitrary. You can choose.
In addition, the phenol compound (A) to be used includes a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol and the like which are by-products during production. However, when 0.2 mass% or more of what corresponds to the phenol compound (B) or the phenol compound (C) described later is contained, the phenol compound (B) and the phenol compound (C), respectively. It is converted as the mass of
Analysis by GC / MS can be applied as a method for analyzing components contained as by-products. Specifically, GC-6890 manufactured by HP was used, column: HP-WAX (L: 30 m ID: 0.25 mm Film thickness: 0.25 μm), carrier gas: helium, sample inlet temperature Can be measured by maintaining the column temperature at 250 ° C., and the separated gas can be analyzed by determining mass spectrometry with a mass detector.

Examples of the phenol compound (B) include 2,3,6-trimethylphenol, 2,3-diethyl-6-n-propylphenol, 2,6-dimethyl-3-allylphenol, 2,3,6-triphenol. Allylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-di-t-butyl-3-methylphenol, 2,6-dimethyl-3-n -Butylphenol, 2,6-dimethyl-3-t-butylphenol and the like. In particular, 2,3,6-trimethylphenol is preferable because it is inexpensive and easily available.
The said phenol compound (B) may be used independently, or may be used in combination of 2 or more type. For example, a method in which 2,3,6-trimethylphenol and 2,3-diethyl-6-n-propylphenol are used in combination. The mixing ratio at that time can be arbitrarily selected.
In addition, the phenol compound (B) used contains a small amount of o-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which are by-products during production. However, when 0.2 mass% or more of the phenol compound (A) described above or the phenol compound (C) described later is contained in an amount of 0.2% by mass or more, the phenol compound (A) and the phenol compound (C), respectively. As mass.

Examples of the phenol compound (C) include o-cresol, 2-ethylphenol, 2-n-propylphenol, 2-t-butylphenol, 2-isopropylphenol, 2-phenylphenol and the like. In particular, o-cresol is preferable because it is inexpensive and easily available.
The said phenol compound (C) may be used independently, or may be used in combination of 2 or more type.
For example, a method of using a combination of o-cresol and 2-ethylphenol can be used, and the mixing ratio can be arbitrarily selected.
Further, the phenol compound (C) used contains a small amount of o-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which are by-products during production. However, in the case where 0.2 mass% or more of the phenol compound (A) or the phenol compound (B) described above is contained, the phenol compound (A) and the phenol compound (B) respectively. It is converted as the mass of

Regarding the above-described phenol compounds (A) to (C), in the formula (1) showing the phenol compound (A), R ₁ and R ₂ are methyl groups, and the formula (2) showing the phenol compound (B). ), R ₃ , R ₄ , R ₅ are methyl groups, and in the formula (3) showing the phenol compound (C), those in which R ₆ is a methyl group are industrially easily available. It is a suitable material from the viewpoint that the manufacturing method of the present embodiment can be implemented at low cost.

[Concentration of mixed phenolic compound]
In the method for producing polyphenylene ether of the present embodiment, the concentration of the mixed phenol compound used for polymerization is not particularly limited, but is preferably 10 to 50% by mass with respect to 100% by mass of the total raw materials used for polymerization, and is 15 to 30% by mass. Is more preferable.
If it is less than 10% by mass, a solvent of about 90% by mass is required, and the production efficiency of polyphenylene ether is lowered.
On the other hand, when it exceeds 50% by mass, it is inevitable that the viscosity becomes high when it is assumed that a polyphenylene ether having a number average molecular weight of 4000 or more is produced, and the oxygen absorption efficiency tends to decrease. Further, there is a possibility that the residual polymer adhering to the inner wall surface of the reaction tank increases.
Therefore, the operation which heats more than necessary and reduces the viscosity in the system is necessary. Therefore, the concentration of the mixed phenol compound is preferably in the range of 10 to 50% by mass from the viewpoint of efficiently producing polyphenylene ether.

[Oxygen-containing gas]
The polymerization step in the polyphenylene ether production method of the present embodiment is performed while supplying an oxygen-containing gas. As the oxygen-containing gas, pure oxygen, oxygen and an inert gas such as nitrogen mixed at an arbitrary ratio, air, and further an inert gas such as air and nitrogen or a rare gas at an arbitrary ratio. A mixture or the like can be used.
The system pressure during the polymerization reaction may be ordinary pressure, but can be used under reduced pressure or increased pressure as necessary.
The supply rate of the oxygen-containing gas can be arbitrarily selected in consideration of heat removal, polymerization rate, etc., but is preferably 5 NmL / min or more, and more preferably 10 NmL / min or more, as pure oxygen per mole of phenol compound used for polymerization. .

[Good solvent for polyphenylene ether]
The good solvent of polyphenylene ether used in the method for producing polyphenylene ether of this embodiment is a solvent that can dissolve poly (2,6-dimethylphenylene) ether obtained by a conventional method.
Moreover, the good solvent of polyphenylene ether means the solvent whose solubility in 20 degreeC of the poly (2, 6- dimethyl phenylene) ether obtained by the conventional method is 1 or more.
Here, the solubility is the mass (g) of a solute (poly (2,6-dimethylphenylene) ether) dissolved in 100 ml of a solvent.
Examples of such a solvent include benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, styrene and other aromatic hydrocarbons, chloroform, methylene chloride, and 1,2. -Halogenated hydrocarbons such as dichloroethane, chlorobenzene and dichlorobenzene, and nitro compounds such as nitrobenzene.
In addition, those classified as other good solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and cycloheptane, esters such as ethyl acetate and ethyl formate, tetrahydrofuran, diethyl ether and the like. Examples include ethers and dimethyl sulfoxide.
These good solvents may be used alone or in combination of two or more.
Among the good solvents described above, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and styrene, and halogenated hydrocarbons such as chlorobenzene and dichlorobenzene are preferable.

[Poor solvent of polyphenylene ether]
The poor solvent of polyphenylene ether used in the method for producing polyphenylene ether of this embodiment is a solvent that does not dissolve or slightly dissolves poly (2,6-dimethylphenylene) ether obtained by a conventional method. Specifically, the poor solvent for polyphenylene ether refers to a solvent having a solubility of poly (2,6-dimethylphenylene) ether obtained by a conventional method at 20 ° C. of less than 1.
Examples of such a solvent include ketones and alcohols, and alcohols having 1 to 10 carbon atoms are preferable.
Specific examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol. The poor solvent may further contain water. Particularly preferred poor solvents are methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, and tert-butanol.
These poor solvents may be used alone, or may be used in combination of two or more. A mixed solvent containing an aromatic hydrocarbon solvent such as toluene or xylene and an alcohol such as methanol or ethanol. It is widely used.

〔catalyst〕
As the catalyst used in the method for producing polyphenylene ether in the present embodiment, a known catalyst system generally used for producing polyphenylene ether can be used.
For example, there are transition metal ions having oxidation-reduction ability and amine compounds capable of complexing with the metal ions. Specifically, a catalyst system comprising a copper compound and an amine, and a catalyst system comprising a manganese compound and an amine. And a catalyst system composed of a cobalt compound and an amine.
Since the polymerization reaction proceeds efficiently under some alkaline conditions, some alkali or further amine may be added thereto.

  A suitable catalyst in the method for producing polyphenylene ether of the present embodiment is a catalyst containing a copper compound, a halogen compound, and a diamine compound represented by the following formula (4) as constituent components of the catalyst.

In said formula (4), R < ₇ >, R <_8> , R < ₉ > and R < ₁₀ > are each independently selected from the group which consists of a hydrogen atom and a C1-C6 linear or branched alkyl group. Indicates either. However, all are not hydrogen at the same time. R ₁₁ represents a linear or branched alkylene group having 2 to 5 carbon atoms.

As a copper compound which comprises a catalyst component, a cuprous compound, a cupric compound, or a mixture thereof can be used.
Examples of the cuprous compound include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate.
Examples of the cupric compound include cupric chloride, cupric bromide, cupric sulfate, cupric nitrate and the like.
Among these, particularly preferred copper compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide.
In addition, these copper salts may be synthesized from an oxide (for example, cuprous oxide), a carbonate, a hydroxide, or the like and a corresponding halogen or acid.
For example, it can be synthesized by mixing cuprous oxide and a halogen compound (for example, a solution of hydrogen halide).

Examples of the halogen compound include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, and tetramethylammonium bromide. Tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide and the like. These can be used as an aqueous solution or a solution using an appropriate solvent.
These halogen compounds may be used alone or in combination of two or more.
Preferred halogen compounds are an aqueous solution of hydrogen chloride and an aqueous solution of hydrogen bromide.
Although the usage-amount of these compounds is not specifically limited, As a halogen atom with respect to the molar amount of a copper atom, 2 times or more and 20 times or less are preferable, As a preferable usage-amount of a copper atom with respect to 100 mol of the phenolic compound used. Is preferably in the range of 0.02 mol to 0.2 mol, and more preferably in the range of 0.02 mol to 0.2 mol from the viewpoint of efficient production while reducing the amount of catalyst. The range is from 02 mol to 0.1 mol.

Examples of the diamine compound represented by the above formula (4) include N, N, N ′, N′-tetramethylethylenediamine, N, N, N′-trimethylethylenediamine, N, N′-dimethylethylenediamine, and N, N. -Dimethylethylenediamine, N-methylethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N'-triethylethylenediamine, N, N'-diethylethylenediamine, N, N-diethylethylenediamine, N-ethyl Ethylenediamine, N, N-dimethyl-N′-ethylethylenediamine, N, N′-dimethyl-N-ethylethylenediamine, Nn-propylethylenediamine, N, N′-di-n-propylethylenediamine, Ni-propylethylenediamine N, N′-Di i-propylethylene di Min, Nn-butylethylenediamine, N, N′-di-n-butylethylenediamine, Ni-butylethylenediamine, N, N′-di-butylethylenediamine, Nt-butylethylenediamine, N, N′- Di-t-butylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N′-trimethyl-1,3-diaminopropane, N, N′-dimethyl-1 , 3-diaminopropane, N-methyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,3-diamino-1-methylpropane, N, N, N ′, N ′ -Tetramethyl-1,3-diamino-2-methylpropane, N, N, N ', N'-tetramethyl-1,4-diaminobutane, N, N, N', N'-tetramethyl-1, 5-diaminopentane And the like.
Preferred diamine compounds are those in which the alkylene group (R ₁₁ ) connecting two nitrogen atoms has 2 or 3 carbon atoms.
Although the usage-amount of these diamine compounds is not specifically limited, It is used in 0.01 mol-10 mol with respect to 100 mol of phenol compounds used normally.

The other components constituting the polymerization catalyst will be described.
The polymerization catalyst used in the polymerization step may contain, for example, a tertiary monoamine compound or a secondary monoamine compound alone or in combination in addition to the above-described constituent components.
The tertiary monoamine compound is an aliphatic tertiary amine containing an alicyclic tertiary amine.
Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine and the like.
These tertiary monoamines may be used alone or in combination of two or more. The amount used is not particularly limited, but is preferably 15 mol or less per 100 mol of the phenol compound to be polymerized.
A secondary aliphatic amine can be applied as the secondary monoamine compound.
For example, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, dipentylamines, dihexylamines, dioctylamines , Didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, and cyclohexylamine.
Further, as the secondary monoamine compound, a secondary monoamine compound containing an aromatic can also be applied. For example, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N- (m-methylphenyl) ethanolamine, N- (p-methylphenyl) ethanolamine, N- (2 ′, 6 ′ -Dimethylphenyl) ethanolamine, N- (p-chlorophenyl) ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine and the like Can be mentioned. The above-mentioned secondary monoamine compounds may be used alone or in combination of two or more. Although the usage-amount of a secondary monoamine compound is not specifically limited, 15 mol or less is suitable with respect to 100 mol of phenol compounds to superpose | polymerize.

(Polymerization method)
The polymerization method in the polyphenylene ether production method of the present embodiment is not particularly limited, but when producing various types of polyphenylene ethers, different types of polyphenylene ethers having different types (for example, various glass transition temperatures) can be produced. An easy batch system is preferable, and a continuous system is preferable when producing continuously and stably.

In the method for producing polyphenylene ether of the present embodiment, it is preferable to apply precipitation-precipitation polymerization in which a polymer is precipitated as particles in a reaction solvent in common with batch and continuous systems.
By applying precipitation polymerization, the concentration of the mixed phenol compound can be increased, the polymer remaining when the polymer is extracted can be reduced, and the polymer can be isolated only by filtration. Have.

In the method for producing polyphenylene ether of this embodiment, the ratio of the good solvent and the poor solvent with respect to polyphenylene ether, which is a polymer obtained by oxidative polymerization of a phenol compound, is changed, and the reaction ratio is increased by increasing the ratio of the poor solvent. It is preferable to apply a precipitation polymerization method in which the polymer precipitates as particles in the reaction solvent as it progresses.
At this time, the ratio of good solvent: poor solvent is preferably 35:65 to 95: 5, more preferably 45:55 to 85:15, and still more preferably 55:45 to 75:25.
By setting the ratio of the good solvent and the poor solvent in the above range, generation of scale in the reactor of the precipitated polyphenylene ether particles can be effectively reduced, and a polymer can be produced stably.
If the proportion of the good solvent is less than the above range, the polymerization time must be remarkably increased in order to obtain a polyphenylene ether having a desired degree of polymerization, and external heating is required during the polymerization process. It is difficult to perform efficient production.
When the proportion of the good solvent exceeds the above range, the polymer may not be precipitated as particles in the reaction solvent.
The method for observing the polymer precipitation is not particularly limited. For example, the polymer precipitation is visually observed from the observation window of the reaction vessel. The polymer solution is extracted from the sampling port into a transparent container such as glass. Methods such as visual observation can be used as appropriate. As a guideline for the start of visual observation, although depending on the amount of phenolic compound contained in the polymerization system and the amount of good or poor solvent for polyphenylene ether, it is more preferable that the polymerization rate reaches 80%. When 70% is reached, more preferably when the polymerization rate reaches 50%, observation of polymer precipitation in the polymerization system is started.

In the method for producing polyphenylene ether in the present embodiment, the phenolic compound used in the polymerization, that is, the phenolic compounds (A) to (C), may be present in the polymerization tank from the beginning of the polymerization, or added sequentially during the polymerization. You may do it.
In addition, when all the phenol compounds (A) to (C) used as monomers are completely added to the polymerization tank in a stage before starting precipitation and starting to exhibit a slurry state, a polymerization time is obtained. Can be shortened, which is preferable.
If a phenol compound is further added at the stage after precipitation starts and a slurry state starts to be exhibited, the polymerization time becomes longer because growth of the added phenol compound requires a polymerization time.

  In the method for producing polyphenylene ether of the present embodiment, although it depends on the supply amount of the oxygen-containing gas, it is preferably 1 minute or more after the polymer is precipitated, that is, from the time when the precipitation of the polymer starts. Is preferred because polyphenylene ether having a high glass transition temperature (excellent in heat resistance) tends to be obtained by continuing the polymerization for 10 minutes or more, more preferably 30 minutes or more.

As a method for producing the polyphenylene ether powder more efficiently than the batch method, there is a continuous method. In this continuous method, it is preferable to use a polymerization tank comprising at least two tanks.
In the case where precipitation precipitation polymerization is selected in the first polymerization tank and the subsequent polymerization tanks, the phenol compound dissolved in the polymerization solvent and the catalyst described later are continuously supplied to the first polymerization tank, and It is preferable to select a continuous polymerization method in which the solvent and the poor solvent are continuously supplied to the first polymerization tank.
On the other hand, when selecting solution polymerization in which the polyphenylene ether does not exhibit precipitation in the first polymerization tank, the average residence required for precipitation by selecting precipitation precipitation polymerization in the second or subsequent polymerization tank Time can be easily observed, and the amount of by-products generated can be significantly suppressed.
Furthermore, shortening the total average residence time for obtaining polyphenylene ether can be achieved by increasing the polymerization rate within a range in which precipitation does not occur in the first polymerization tank.

〔Additive〕
In the polymerization step of the method for producing polyphenylene ether in the present embodiment, a predetermined additive such as a surfactant may be added in order to improve the activity.
Examples of the surfactant include trioctylmethylammonium chloride such as Aliquat 336 and Capriquat (trade name, manufactured by Dojindo Laboratories).
The amount of the surfactant used is preferably 0.1% by mass or less based on the total amount of the polymerization reaction mixture.
An alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alkoxide, a neutral salt such as magnesium sulfate or calcium chloride, zeolite, or the like may be added to the polymerization reaction system. Thus, the polymerization activity can be controlled.

[Recovery of polyphenylene ether]
The post-treatment method after completion of the polymerization reaction is not particularly limited. Usually, an acid such as hydrochloric acid or acetic acid, ethylenediaminetetraacetic acid (EDTA) and a salt thereof, nitrilotriacetic acid and a salt thereof are used as a reaction solution. In addition, the catalyst is deactivated.
Thereafter, since the shape of the polymerization solution at the end of the polymerization is slurry, for the purpose of washing and removing the catalyst, repeated washing treatment is performed using a solution mainly composed of a solvent having low solubility of the polyphenylene ether used for the polymerization. This is true.
Thereafter, the polyphenylene ether can be recovered as a powder by performing a drying treatment using various dryers.

The polyphenylene ether powder obtained as described above preferably has a reduced viscosity (dL / g) of 0.40 or more. Thereby, polyphenylene ether having sufficient heat resistance is obtained.
The reduced viscosity means the reduced viscosity of a 0.5 g / dL chloroform solution of polyphenylene ether resin under the condition of 30 ° C.
The reduced viscosity is preferably 0.45 or more, more preferably 0.48 or more, and further preferably 0.5 or more.
The reduced viscosity is a value that varies depending on the amount of good solvent used, the amount of catalyst, the flow rate and speed of the oxygen-containing gas, the concentration of the raw material monomer, and the like. In the present embodiment, these production conditions are appropriately selected so that the reduced viscosity is obtained.
In addition, the upper limit of the reduced viscosity is, for example, less than 1.5 (dL / g) because when used for processing by extrusion molding or the like, the molding fluidity may decrease and the processability may decrease. Preferably, it is 1.3 (dL / g) or less, more preferably 1.1 (dL / g) or less.

The polyphenylene ether obtained by the production method in the present embodiment can be sampled by melt-kneading with a conventionally known thermoplastic resin and thermosetting resin.
Examples of the thermoplastic resin and the thermosetting resin include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, methacrylic resin, vinyl chloride, polyamide, polyacetal, ultrahigh molecular weight polyethylene, polybutylene terephthalate, Polymethylpentene, polycarbonate, polyphenylene sulfide, polyetheretheretherketone, liquid crystal polymer, polytetrafluoroethylene, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyamideimide, phenol, urea, melamine, unsaturated polyester, Resins such as alkyd, epoxy, and diallyl phthalate are listed.
Further, at the time of melt kneading with these, desired properties may be added by adding conventionally known additives and thermoplastic elastomers for the purpose of imparting effects such as conductivity, flame retardancy, impact resistance and the like. .

Examples of the present invention and comparative examples will be specifically described below.
First, measurement methods such as physical properties and characteristics applied to Examples and Comparative Examples are shown below.

(1) Quantification of by-products in phenolic compounds Analyzed by GC / MS.
GC-6890 manufactured by HP was used, column: HP-WAX (L: 30 m ID: 0.25 mm Film thickness: 0.25 μm), carrier gas: helium, and the temperature of the sample inlet was 250 ° C. The temperature of the column was kept at 250 ° C., detected by a flame ionization detector, and the separated gas was quantified by mass analysis of the separated gas using a mass detector.
In addition, water that could not be detected was not considered.
When 0.2 mass% or more was contained, the component was specified and it added to the phenolic compound which belongs from a structure.

(2) Measurement of reduced viscosity ηsp / c The reduced viscosity (ηsp / c) at 30 ° C. was determined using a Ubbelohde viscosity tube as a 0.5 g / dL chloroform solution. The unit is dL / g.

(3) Measurement of yield The mass ratio of the dry polyphenylene ether to the total mass of the monomers used for the polymerization was measured at 100 minutes.

(4) Measurement of glass transition temperature The glass transition temperature was measured using a differential scanning calorimeter DSC (manufactured by PerkinElmer-Pyris 1).
After heating from room temperature to 280 ° C. at a temperature rising rate of 20 ° C. in a nitrogen atmosphere, the temperature was lowered to 50 ° C. at 40 ° C. per minute, and then the glass transition temperature was measured at a temperature rising rate of 20 ° C. per minute.
A glass transition temperature of 220 ° C. or higher was determined to be preferable from the viewpoint of heat resistance.

(5) Confirmation of scale adhesion to reactor After removing the polymerization solution from the reactor, the amount of scale adhered to the reactor was visually confirmed.

(6) Gel inspection (observation of gel)
The polyphenylene ether obtained by polymerization was used as a 0.5 g / dL chloroform solution, and the occurrence of gel was visually confirmed.
In addition, after heating the polyphenylene ether obtained by polymerization at 310 ° C. and 10 MPa for 20 minutes, the occurrence of gel was visually confirmed as a 0.5 g / dL chloroform solution (see “Heating” in Table 1). After ").
When an insoluble component such as a gel was not observed, it was evaluated as ◯ (good), when a large amount was observed, it was evaluated as x (poor), and when a small amount was observed, it was evaluated as Δ (normal).

[Phenol compounds used]
Phenol compound (A): 2,6-dimethylphenol (manufactured by Wako Pure Chemical Industries): purity was 99.92%.
Phenol compound (B): 2,3,6-trimethylphenol (Honshu Chemical): purity 99.94%.
Phenolic compound (C): o-cresol (manufactured by Wako Pure Chemical Industries): purity was 99.92% by mass.
These were used as they were because the impurity concentration was less than 0.2% by mass.

[Production of polyphenylene ether]
[Example 1]
50 mL / min flow rate to a 1 liter jacketed polymerization tank equipped with a sparger for introducing oxygen-containing gas, a stirring turbine blade and a baffle at the bottom of the polymerization tank, and equipped with a reflux condenser in the vent gas line at the top of the polymerization tank 0.0871 g of cupric chloride dihydrate, 0.3730 g of 35% hydrochloric acid, 3.3272 g of N, N, N ′, N′-tetramethylpropanediamine, 3.1371 g Di-n-butylamine, 63.3 g n-butanol, 54.6 g methanol, 443.2 g xylene, 11.88 g 2,6-dimethylphenol, 3.96 g 2,3,6-trimethylphenol 0.16 g o-cresol was added. These were stirred until a uniform solution was obtained and the internal temperature of the polymerization tank reached 40 ° C.
In addition, nitrogen gas was blown into the storage tank at a flow rate of 20 mL / min into a 1-liter storage tank equipped with a sparger for introducing nitrogen gas, a stirring turbine blade and baffle, and a reflux gas cooler in the vent gas line at the top of the storage tank. However, 72 g of methanol, 106.92 g of 2,6-dimethylphenol, 35.64 g of 2,3,6-trimethylphenol and 1.44 g of o-cresol were added. They were stirred until they became a homogeneous solution, and a mixed solution was prepared.
Next, oxygen gas is started to be introduced from the sparger into the vigorously stirred polymerization tank at a rate of 200 NmL / min, and at the same time, the mixed solution in the storage tank is 4.32 g / min using a liquid feed pump. Sequentially added at a rate of
Aeration was performed for 90 minutes, and the internal temperature of the polymerization tank was controlled to 40 ° C.
In addition, after 54 minutes from the start of supply of oxygen gas, polyphenylene ether precipitated and showed a slurry form.
The addition of the mixed solution was completed before starting to show the slurry form.
The form of the polymerization solution at the end of the polymerization was precipitation polymerization.
After passing the oxygen-containing gas for 90 minutes, the oxygen-containing gas was stopped and 0.3 g of a 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture for 60 minutes. The polymerization mixture was stirred.
Next, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and stirring was continued until the slurry-like polyphenylene ether became white.
Thereafter, filtration was performed to obtain wet polyphenylene ether.
Wet polyphenylene ether and 500 g of methanol were both dispersed in a 1 L washing tank, stirred for 30 minutes, and then filtered again.
The internal temperature of the washing tank was controlled to 50 ° C.
Dispersion and filtration in the washing tank were repeated three times, and then vacuum-dried at 140 ° C. for 120 minutes to obtain dry polyphenylene ether.

[Example 2]
11.40 g of 2,6-dimethylphenol, 3.80 g of 2,3,6-trimethylphenol, and 0.80 g of o-cresol were placed in the polymerization tank.
102.60 g of 2,6-dimethylphenol, 34.20 g of 2,3,6-trimethylphenol, and 7.20 g of o-cresol were placed in the storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

Example 3
11.64 g of 2,6-dimethylphenol, 3.88 g of 2,3,6-trimethylphenol, and 0.48 g of o-cresol were placed in the polymerization tank.
104.76 g of 2,6-dimethylphenol, 34.92 g of 2,3,6-trimethylphenol, and 4.32 g of o-cresol were placed in the storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

Example 4
The amount of 2,6-dimethylphenol charged in the polymerization tank was 13.53 g, 2,3,6-trimethylphenol was 2.39 g, o-cresol was 0.08 g, xylene was 379.8 g, and butanol was 126.6 g.
121.79 g of 2,6-dimethylphenol, 21.49 g of 2,3,6-trimethylphenol, and 0.72 g of o-cresol were placed in the storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

Example 5
The amount of 2,6-dimethylphenol placed in the polymerization tank was 13.19 g, 2,3,6-trimethylphenol was 2.33 g, o-cresol was 0.48 g, xylene was 379.8 g, and butanol was 126.6 g.
118.73 g of 2,6-dimethylphenol, 20.95 g of 2,3,6-trimethylphenol, and 4.32 g of o-cresol were placed in a storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

Example 6
The amount of 2,6-dimethylphenol to be placed in the polymerization tank was 12.92 g, 2,3,6-trimethylphenol was 2.28 g, o-cresol was 0.80 g, xylene was 379.8 g, and butanol was 126.6 g.
116.28 g of 2,6-dimethylphenol, 20.52 g of 2,3,6-trimethylphenol, and 7.20 g of o-cresol were placed in the storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

Example 7
The amount of 2,6-dimethylphenol in the polymerization tank was 10.30 g, 2,3,6-trimethylphenol was 5.54 g, o-cresol was 0.16 g, xylene was 443.2 g, and butanol was 63.3 g.
92.66 g of 2,6-dimethylphenol, 49.90 g of 2,3,6-trimethylphenol, and 1.44 g of o-cresol were placed in the storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

Example 8
0.0837 g of oxidation while blowing nitrogen at a flow rate of 50 mL / min into a 1 liter jacketed SUS polymerization tank equipped with a sparger for introducing oxygen gas at the bottom of the polymerization tank, a stirring turbine blade, and a reflux condenser. Cuprous, 0.5037 g of 47 wt% aqueous hydrogen bromide solution, 0.2017 g of N, N′-di-t-butylethylenediamine, 0.9766 g of di-n-butylamine, 2.4771 g of butyldimethylamine, 0 0.1 g of trioctylmethylammonium chloride, 365.666 g of toluene was added.
Nitrogen gas is blown into a 1 liter storage tank equipped with a sparger for introducing nitrogen gas, a stirring turbine blade and baffle into the storage tank, and a reflux condenser in the vent gas line at the top of the storage tank at a flow rate of 20 mL / min. While adding 48.75 g of 2,6-dimethylphenol, 9.46 g of 2,3,6-trimethylphenol, 1.95 g of o-cresol and 65.0 g of toluene, the mixture was stirred until a homogeneous solution was obtained. A mixed solution was prepared.
Next, oxygen gas is introduced from the sparger at a rate of 80 Nml / min into the vigorously stirred polymerization tank, and at the same time, the mixed solution in the storage tank is added to 6.50 g / min using a liquid feed pump. Sequentially added at a rate of
Aeration was performed for 90 minutes, and the internal temperature of the polymerization tank was set to 40 ° C. for 60 minutes from the start of oxygen introduction to 55 ° C. from 60 minutes after the introduction of oxygen to the termination of oxygen introduction.
After completion of the polymerization, 50 g of a 1.83 wt% aqueous solution of EDTA.3 potassium salt is added to the reaction mixture, and the mixture is stirred at 70 ° C. for 150 minutes, and then 400 g of methanol is added to precipitate the polymer, followed by filtration to wet polyphenylene ether Got.
Wet polyphenylene ether and 350 g of methanol were both placed in a 1 L washing tank, dispersed, stirred for 30 minutes, and then filtered again.
The internal temperature of the washing tank was controlled to 50 ° C.
Dispersion and filtration in the washing tank were repeated twice, and then vacuum-dried at 140 ° C. for 120 minutes to obtain dry polyphenylene ether.

[Comparative Example 1]
The amount of 2,6-dimethylphenol charged in the polymerization tank was 10.80 g, 2,3,6-trimethylphenol was 3.60 g, and o-cresol was 1.60 g.
97.20 g of 2,6-dimethylphenol, 32.40 g of 2,3,6-trimethylphenol, and 14.40 g of o-cresol were placed in the storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

[Comparative Example 2]
The amount of 2,6-dimethylphenol placed in the polymerization tank was 12.24 g, 2,3,6-trimethylphenol was 2.16 g, o-cresol was 1.60 g, xylene was 379.8 g, and butanol was 126.6 g.
110.16 g of 2,6-dimethylphenol, 19.44 g of 2,3,6-trimethylphenol, and 14.40 g of o-cresol were placed in a storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

[Comparative Example 3]
9.36 g of 2,6-dimethylphenol, 5.04 g of 2,3,6-trimethylphenol, 1.60 g of o-cresol, 443.1 g of xylene, and 63.3 g of butanol were placed in the polymerization tank.
84.24 g of 2,6-dimethylphenol, 45.36 g of 2,3,6-trimethylphenol, and 14.40 g of o-cresol were placed in a storage tank.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

[Comparative Example 4]
2.60 g of 2,6-dimethylphenol, 2.40 g of 2,3,6-trimethylphenol, and o-cresol were not used, 379.8 g of xylene, and 126.6 g of butanol were placed in the polymerization tank. .
122-40 g of 2,6-dimethylphenol and 21.60 g of 2,3,6-trimethylphenol put in the storage tank were used, and o-cresol was not used.
Other conditions were the same as in Example 1 to obtain dry polyphenylene ether.

[Comparative Example 5]
63.05 g of 2,6-dimethylphenol put in the storage tank, 2,3,6-trimethylphenol were not used, and 1.95 g of o-cresol was used.
Other conditions were the same as in Example 8, and dry polyphenylene ether was obtained.
In this example, bubbling was confirmed on the liquid surface during the polymerization process.

  Regarding Examples 1 to 8 and Comparative Examples 1 to 5, the reduced viscosity of the produced polyphenylene ether, the yield of polyphenylene ether, the glass transition temperature, the presence or absence of scale on the reaction vessel wall, and the insoluble component (gel) test results (before heating) And after heating) are shown in Table 1, respectively.

As shown in Table 1, in Examples 1 to 8, a good polymerization reaction rate can be maintained and a suitable degree of polymerization can be achieved. Finally, polyphenylene having a high molecular weight, a high glass transition temperature, and excellent heat resistance. Ether could be produced efficiently.
In the precipitation polymerization performed in Examples 1 to 7, the scale to the reactor was not confirmed. Further, no gel was observed in the polyphenylene ether obtained by polymerization, and no gel was generated after heating.
In Example 8, no gel was generated in the polyphenylene ether obtained by polymerization, but a slight gel was generated after heating. This is because the molecular weight distribution became wide regardless of precipitation polymerization, but it was not a problem in practical use.
The polyphenylene ether obtained in Comparative Examples 1 to 3 was a polyphenylene ether having a high glass transition temperature and excellent heat resistance, but a large amount of gel was generated, and a large amount of gel was confirmed even after heating. Further, the copolymerization was carried out in a state where the amount of o-cresol was excessive, so that a crosslinking reaction occurred and became insoluble in the solvent, and the viscosity could not be measured. Furthermore, the yield also decreased.
In Comparative Example 4, no scale was generated and the yield was high. However, since o-cresol corresponding to the phenol compound (C) was not used, the polymerization rate was insufficient with respect to the amount of oxygen blown, and the obtained polyphenylene ether was lower in ηsp / c than that obtained in Examples. became. That is, the degree of polymerization was low.
In Comparative Example 5, since 2,3,6-trimethylphenol corresponding to the phenol compound (B) was not used, the glass transition point was low and the heat resistance was insufficient.

  The polyphenylene ether produced by the production method of the present invention has industrial applicability as mechanical parts, automobile parts, electrical and electronic parts, particularly electronic parts, films, sheets and the like.

Claims (7)

A phenol compound (A) represented by the following formula (1),

(In Formula (1), R ₁ and R ₂ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an alkenyl. And any one selected from the group consisting of a group, an alkynyl group, and an optionally substituted alkoxy group.)
A phenol compound (B) represented by the following formula (2),

(In formula (2), R ₃ , R ₄ and R ₅ are each independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. And any one selected from the group consisting of an optionally substituted alkoxy group.)
as well as,
A phenol compound (C) represented by the following formula (3),

(In the formula (3), R ₆ is a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted alkoxy group. Any one selected from the group consisting of:
A process for producing polyphenylene ether comprising a step of polymerizing using a mixed phenol containing
The mixed phenol is based on 100% by mass of the total amount of the phenol compounds (A) to (C).
The phenol compound (A) is 55.0 mass% or more and 94.5 mass% or less,
The phenol compound (B) is 5.0% by mass or more and 40.0% by mass or less,
The phenol compound (C) is 0.5% by mass or more and 5.0% by mass or less,
A process for producing polyphenylene ether.   2. The production of polyphenylene ether according to claim 1, wherein the reduced viscosity ηsp / c of the polyphenylene ether measured at 30 ° C. with a chloroform solution having a concentration of 0.5 g / dl is 0.40 (dL / g) or more. Method. In the polymerization step of the mixed phenol compound containing the phenol compounds (A) to (C), a step of oxidative polymerization using a catalyst and an oxygen-containing gas is included.
As the catalyst,
The manufacturing method of the polyphenylene ether of Claim 1 or 2 using the copper compound-halogen compound and the diamine compound represented by following formula (4).

(In formula (4), R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from the group consisting of a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms. Any one (however, all are not hydrogen at the same time), and R ₁₁ represents a linear or branched alkylene group having 2 to 5 carbon atoms.) In said formula (1) which shows the said phenol compound (A), R < ₁ >, R < ₂ > is a methyl group,
In the formula (2) showing the phenol compound (B), R ₃ , R ₄ and R ₅ are methyl groups,
The manufacturing method of the polyphenylene ether as described in any one of Claims 1 thru | or 3 whose R < ₆ > is a methyl group in the said Formula (3) which shows the said phenol compound (C).   The polymerization form of the polyphenylene ether according to any one of claims 1 to 4, wherein the polymerization form of the polyphenylene ether is a precipitation form, and the polymerization is continued for 1 minute or more from the time when the precipitation of the polyphenylene ether polymer starts. Production method.   The polyphenylene according to any one of claims 1 to 5, wherein a total amount (monomer conversion) of the mixed phenol compound used for polymerization is 10% by mass or more and 50% by mass or less with respect to 100% by mass of all raw materials used for polymerization. A method for producing ether.   The method for producing a polyphenylene ether according to claim 3, further comprising a tertiary monoamine and / or a secondary monoamine compound as the catalyst.