JP5196516B2 - Process for producing polyphenylene ether - Google Patents

Description

  The present invention relates to a method for efficiently producing polyphenylene ether that can stably precipitate polyphenylene ether, has a high glass transition temperature, and has a narrow molecular weight distribution.

Polyphenylene ether is excellent in processability and productivity, and can efficiently produce products and parts of the desired shape by molding methods such as the melt injection molding method and the melt extrusion molding method. It is widely used as a material for products and parts in various industrial material fields and food packaging fields. With the diversification of applications, various types of polyphenylene ethers having different characteristics such as molecular weight and glass transition temperature are required, and polyphenylene ethers having high heat resistance and excellent mechanical properties have been desired.
Batch production is useful as a production method for producing many types of polyphenylene ethers, and an efficient production method capable of designing a wide range of molecular weights is desired. Due to the deterioration of the yield, there is a problem that phenols as raw materials must be used more than necessary. Therefore, there is a demand for a batch-type manufacturing method with less generation of scale for the purpose of reducing waste and reducing the environmental load.

  Further, as a polyphenylene ether having high heat resistance in general, for example, a polyphenylene ether composed of 2,3,6-trimethylphenol and 2,6-dimethylphenol has a glass transition temperature higher than that of a conventionally known polyphenylene ether. A polyphenylene ether that is several degrees higher is disclosed (for example, see Patent Documents 1 and 2). Patent Document 1 describes that the polymerization form during production is uniform, the reaction mixture has a cloud point temperature, and the polymerization temperature is carried out at a temperature higher than the cloud point temperature. In order to polymerize in a uniform state, fine temperature control is required according to the composition and viscosity of the target product, which cannot be said to be highly efficient from an industrial viewpoint. In addition, since the polyphenylene ether described in Patent Document 2 precipitates at a low molecular weight as compared with the conventionally known polyphenylene ether, polymerization is performed in a uniform solution system in order to obtain a polyphenylene ether having a high molecular weight equivalent to the conventionally known polyphenylene ether. It is suggested that the precipitation polymerization is unsuitable.

Further, in the method for producing polyphenylene ether in a mixed solvent composed of an aromatic hydrocarbon and an aliphatic hydrocarbon (see, for example, Patent Document 3), the form of the polymerization liquid at the end of the polymerization is precipitation polymerization. However, the total of 2,6-dimethylphenol and 2,3,6-trimethylphenol with respect to the total charge is as low as less than 10% by weight, and the molecular weight distribution and the amount of scale are not disclosed. .
WO2003 / 042282 Japanese Patent Laid-Open No. 50-150798 Japanese Patent Laid-Open No. 11-12354

  The present invention relates to a method for producing polyphenylene ethers in which generation of scales in the reactor and reduction in yield are suppressed in various types of polyphenylene ethers having different characteristics such as molecular weight and glass transition temperature, that is, efficiency and productivity are excellent. Another object of the present invention is to provide a method for producing a polyphenylene ether having a high glass transition temperature and a narrow molecular weight distribution that can be expected to improve mechanical properties and the like.

As a result of intensive studies to solve the above-mentioned problems, the present inventor surprisingly found that 10% by mass with respect to the total amount of the component (A) used for polymerization when producing polyphenylene ether by precipitation precipitation polymerization. In order to obtain mechanical characteristics by suppressing the generation of scale to the reactor and the decrease in yield by sequentially adding the mixed solution (B) composed of ˜100 mass% (A) and a poor solvent during the polymerization. It was found that a polyphenylene ether having a sufficient molecular weight and a narrow molecular weight distribution can be produced, and the present invention has been completed.
That is, the present invention
[1] Oxidative coupling of phenol compound (A) using a mixed solvent composed of a good solvent of at least one polyphenylene ether and a poor solvent of at least one polyphenylene ether, using an oxygen-containing gas in the presence of a catalyst In the method for producing polyphenylene ether in which the good solvent at the end of the polymerization is 35% by mass or more of the entire polymerization system and the form of the polymerization solution at the end of the polymerization is precipitation polymerization, the component (A) used for the polymerization is A mixed solution (B) comprising 10% by mass to 100% by mass of (A) and a poor solvent is being polymerized with respect to the total amount of the component (A) used in the polymerization, which is a phenol compound represented by the formula (1). A method for producing polyphenylene ether, which is added sequentially.

... Formula (1)
(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ each represents an independent substituent, and R ₁ represents an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, and a substituted aryl group. , An alkoxy group or a substituted alkoxy group, and R ₂ , R ₃ and R ₄ may be hydrogen or halogen in addition to the same group as defined for R _1. )

[2] The phenol compound (A) used for the polymerization comprises a phenol compound (C) represented by the formula (2) and a phenol compound (D) represented by the formula (3). The manufacturing method of polyphenylene ether as described in 1 ..

... Formula (2)
(In Formula (2), R ₅ and R ₆ each represents an independent substituent, and R ₅ represents an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, or a substituted group. An alkoxy group, R ₆ may further be hydrogen or halogen in addition to the same groups defined for R ₁ )

... Formula (3)
(In the formula (3), R ₇ , R ₈ and R ₉ each represents an independent substituent, and R ₉ represents an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group. A group or a substituted alkoxy group, which may be hydrogen or halogen in addition to the same groups defined for R ₇ and R ₈ R _1. )

[3] The phenol compound (A) used for the polymerization is composed of 60% by mass to 95% by mass of the phenol compound (C) and 5% by mass to 40% by mass of the phenol compound (D). The manufacturing method of polyphenylene ether as described in 1 ..
[4] The polyphenylene according to any one of claims 1 to 3, wherein the phenol compound (C) is 2,6-dimethylphenol and the phenol compound (D) is 2,3,6-trimethylphenol. A method for producing ether.
[5] The poor solvent of polyphenylene ether is at least one kind of solvent mainly comprising an alcohol having 1 to 10 carbon atoms as a main component. The manufacturing method of the polyphenylene ether of description.

[6] The method for producing a polyphenylene ether according to any one of [1] to [5], wherein the polyphenylene ether has a number average molecular weight of 10,000 to 40,000.
[7] The catalyst of the polyphenylene ether according to any one of claims 1 to 6, wherein the catalyst is composed of a copper compound, a halogen compound and a diamine compound represented by the general formula (4). Production method.

... Formula (4)
(Wherein R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and all are not simultaneously hydrogen. R ₁₂ has 2 carbon atoms. To 5 linear or methyl branched alkylene groups)

[8] The composition of the component (B) added sequentially during the polymerization is 25: 1 to 1:10 in a weight ratio of the component (A) to the poor solvent. The manufacturing method of polyphenylene ether as described in claim | item.
[9] The poor solvent of polyphenylene ether is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, and Tert-butanol. 1 to 8, a method for producing the polyphenylene ether according to any one of
It is.

  According to the present invention, when a polyphenylene ether is produced by precipitation polymerization by performing oxidative polymerization using a specific phenol compound, it is sufficient to obtain mechanical properties by adding a poor solvent and a specific phenol compound sequentially during the polymerization. Thus, it is possible to provide a polyphenylene ether having a low molecular weight and a narrow molecular weight distribution, and it is possible to efficiently produce many types of polyphenylene ethers having different molecular weights with high efficiency.

The present invention will be specifically described below.
The phenol compound (A) used in the present invention is a compound represented by the following general formula (1).

... Formula (1)
In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ each represents an independent substituent, and R ₁ represents an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, An alkoxy group or a substituted alkoxy group, and R ₂ , R ₃ and R ₄ may be hydrogen or halogen in addition to the same groups as defined for R ₁ .

  Examples of the phenol compound (A) represented by the general formula (1) include a phenol compound (C), a phenol compound (D), 2, 3, 5, 6-tetramethylphenol, 2, 3, 5 -Trimethylphenol, 3,5-dimethyl-4-phenylphenol, 2-chloro-3,5,6-trimethylphenol, 2,3-dichloro-5,6-dimethylphenol, 2,3-diethyl-5-methyl Phenol, 2,3,5-triethylphenol, 2-bromo-3,5,6-trimethylphenol, 2,3-dibromo-5,6-dimethylphenol, 2,3,5,6-tetraethylphenol, etc. It is done.

Among these, a phenol compound (C) and a phenol compound (D) are preferably used, and the phenol compound (A) is more preferably composed of a phenol compound (C) and a phenol compound (D).
The phenol compound (C) used in the present invention is a compound represented by the following general formula (2).

... Formula (2)
Wherein _{(2), R 5, R} 6 each independently represents a substituent, R ₅ is the same group as defined R _1, R _6, the same groups as those defined for R ₁ In addition, hydrogen or halogen may be used.

  Examples of the phenol compound (C) include o-cresol, 2,6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n-propylphenol, 2 -Ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2- Ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol 2,6-diphenylphenol, 2,6-bis- (4-fluorophenyl) phenol, - methyl-6-tolyl, 2,6-di-tolyl phenols, and the like.

  Among these phenol compounds (C), 2,6-dimethylphenol is very important industrially and is preferably used in the present invention. In addition, these phenol compounds may be used alone or in combination. For example, there are 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. When such a mixed phenol compound is used, it is possible to use a mixed phenol compound in which the ratio of 2,6-dimethylphenol is a weight ratio of 1:99 to 99: 1. In addition, the phenol compound used contains a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which are contained as by-products during production. It doesn't matter at all.

  The phenol compound (D) used in the present invention is a compound represented by the following general formula (3).

... Formula (3)
In formula (3), R ₇ , R ₈ and R ₉ each represent an independent substituent, R ₉ is the same group defined by R ₁ , and R ₇ and R ₈ are defined for R _1. In addition to the same group, hydrogen or halogen may be used.

  Examples of the phenol compound (D) include 2,5-dimethylphenol, 2,3,6-trimethylphenol, 2,5-diethylphenol, 2-methyl-5-ethylphenol, and 2-ethyl-5-methylphenol. 2-allyl-5-methylphenol, 2,5-diallylphenol, 2,3-diethyl-6-n-propylphenol, 2-methyl-5-chlorophenol, 2-methyl-5-bromophenol, 2- Methyl-5-isopropylphenol, 2-methyl-5-n-propylphenol, 2-ethyl-5-bromophenol, 2-methyl-5-n-butylphenol, 2,5-di-n-propylphenol, 2- Ethyl-5-chlorophenol, 2-methyl-5-phenylphenol, 2,5-diphenylphenol, 2,5 -Bis- (4-fluorophenyl) phenol, 2-methyl-5-tolylphenol, 2,5-ditolylphenol, 2,6-dimethyl-3-allylphenol, 2,3,6-triallylphenol, 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.

  Among these phenol compounds (D) in the present invention, 2,3,6-trimethylphenol is very important in industry and is preferably used. In addition, these phenol compounds may be used alone or in combination. For example, a method using a combination of 2,3,6-trimethylphenol and 2,5-dimethylphenol, a method using a combination of 2,3,6-trimethylphenol and 5-diphenylphenol, and the like. When such a mixed phenol compound is used, a mixed phenol compound having a weight ratio of 2,3,6-trimethylphenol of 1:99 to 99: 1 can be used. In addition, the phenol compound (D) used contains a small amount of o-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which are contained as by-products during production. It does not matter at all.

  In the present invention, when the phenol compound (A) comprising the phenol compound (C) and the phenol compound (D) is subjected to oxidative polymerization, the phenol compound (A) is 60% by mass to 95% by mass of the phenol compound (C), and the phenol compound. (D) It preferably consists of 40 to 5% by mass, more preferably it consists of 70% to 90% by mass of the phenolic compound (C) and 30 to 10% by mass of the phenolic compound (D), and the phenolic compound (A) Is most preferably composed of 70 to 85% by mass of the phenol compound (C) and 30 to 15% by mass of the phenol compound (D).

  In the present invention, the good solvent for polyphenylene ether is a solvent capable of dissolving polyphenylene ether. Examples of such solvents include benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, aromatic hydrocarbons such as styrene, chloroform, methylene chloride, and 1,2-dichloroethane. , Halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and nitro compounds such as nitrobenzene. In addition, although they have some poor solvent properties, those classified as good solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and cycloheptane, and esters such as ethyl acetate and ethyl formate. , Ethers such as tetrahydrofuran and diethyl ether, dimethyl sulfoxide and the like. These good solvents may be used alone or in combination of two or more. Among these, preferred good solvents are aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and styrene, and halogenated hydrocarbons such as chlorobenzene and dichlorobenzene.

  In the present invention, the poor solvent for polyphenylene ether is a solvent that does not dissolve polyphenylene ether at all or slightly dissolves it. For example, ethers, ketones, and alcohols. A method using 1 to 10 alcohols in terms of carbon number as the poor solvent is preferred. Examples of such a poor solvent include methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, and the like, and water may be further contained in such a poor solvent. These poor solvents may be used alone or in combination of two or more, and may contain a good solvent as long as the characteristics of the poor solvent are not impaired. Particularly preferred poor solvents are methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, and Tert-butanol.

Examples of frequently used solvents include aromatic hydrocarbons alone such as toluene and xylene, and mixed solvents containing alcohols such as methanol and ethanol.
By changing the ratio of good solvent and poor solvent to polyphenylene ether, which is a polymer obtained by oxidative polymerization of a phenolic compound, and increasing the ratio of the poor solvent, the polymer becomes particles in the reaction solvent as the reaction proceeds. It becomes a precipitation polymerization method to precipitate.

  When the polyphenylene ether in the present invention has a number average molecular weight of 10,000 to 40,000, the melt processability and sufficient mechanical properties of the molded product are expected, and it is more preferably 13,000 to 40,000. If the number average molecular weight is 10,000 or less, sufficient mechanical properties may not be obtained, and if the number average molecular weight exceeds 40000, the melt processability may deteriorate depending on conditions such as heating and melting. May not be obtained. Furthermore, polyphenylene ether with a narrow molecular weight distribution such that the Mw / Mn value obtained from the weight average molecular weight Mw and the number average molecular weight Mn obtained from polystyrene equivalent molecular weight is 3.0 or less is not deteriorated in melt processability. Improvement in mechanical properties is expected, and the Mw / Mn value is more preferably 2.8 or less. When the number average molecular weight is increased in the hope of improving the mechanical properties, if the Mw / Mn is 3.0 or more, the Mw is remarkably increased, and the melt processability is lowered depending on the heating and melting conditions. May not be obtained.

  In the method for producing polyphenylene ether in the present invention, after the polymer is precipitated as particles in the reaction solvent, depending on the supply amount of the oxygen-containing gas, if the polymerization is continued for 1 minute or longer, the effects of the present invention are suitably exhibited. When the polymerization is continued for 10 minutes or more, it is more preferable, and when the polymerization is continued for 30 minutes or more, it is more preferably exhibited.

In the present invention, the good solvent of polyphenylene ether at the time of terminating the polymerization is 35% by mass or more, preferably 40% by mass, more preferably 45% by mass or more, further preferably 50% by mass or more, and most preferably 55% by mass. That's it. Varying the ratio of good solvent and poor solvent for polyphenylene ether, a polymer obtained by oxidative polymerization of phenolic compounds, the higher the ratio of poor solvent, the more the polymer will precipitate in the reaction solvent as the reaction proceeds Precipitation polymerization is used, but if the good solvent is less than 35% by mass, the desired molecular weight can be obtained, or the polymerization time can be significantly prolonged to obtain the desired molecular weight. In some cases, polyphenylene ether cannot be efficiently obtained.

  The concentration of the phenol compound (A) added sequentially during the polymerization in the present invention is a scale that adheres to the reactor when arbitrarily selected within the range of 10 to 100% by mass with respect to the total amount of the mixed phenol compound (A) used in the polymerization. And a polyphenether having a narrow molecular weight distribution can be stably obtained by precipitation polymerization. The range of 40-100 mass% is preferable, the range of 60-100 mass% is more preferable, and the range of 80-95 mass% is further more preferable.

  The mixed solution (B) sequentially added during the polymerization in the present invention comprises a phenol compound (A) and a poor solvent of the polyphenylene ether, and the weight ratio of the phenol compound (A) to the poor solvent can be selected within an arbitrary range. When the ratio is 25: 1 to 1:10, polyphenylene ether having a narrow molecular weight distribution can be stably obtained by precipitation polymerization. More preferably, it is the range of 15: 1 to 1: 5, More preferably, it is the range of 10: 1 to 1: 1. The start of addition of the component (B) to be added is preferably at the same time as the start of polymerization, and is preferably started before the polyphenylene ether is precipitated.

Examples of the technique using the phenol compound (A) comprising the phenol compound (C) and the phenol compound (D) include the following.
1. A method in which the total amount of the phenol compound (A) used in the polymerization and a poor solvent are mixed solution (B), and polymerization is started simultaneously with the addition of component (B).
2. The phenol compound (A) total amount and poor solvent used for the polymerization are mixed solution (B), the component (B) is dropped, and 0.01 to 90% by mass with respect to the total amount of the phenol compound (A) in the polymerization tank. A method in which polymerization is started after dropwise addition and the mixed solution (B) is sequentially added.
3. A method in which the entire amount of the phenolic compound (C) is put in the initial stage of the reaction to carry out oxidative polymerization, and the total amount of the phenolic compound (D) and the poor solvent are mixed solution (B) and added sequentially during the polymerization.
4). A method in which the entire amount of the phenolic compound (D) is put in the initial stage of the reaction to carry out oxidative polymerization, and the total amount of the phenolic compound (C) and the poor solvent are mixed solution (B) and added sequentially during the polymerization.
5). The weight fraction (C) / (D) of the phenolic compound (C) and the phenolic compound (D) that are successively dropped during the polymerization is the weight fraction of the component (C) and the component (D) that are stretched in the initial stage of the polymerization ( C) A method of preparing to be equal to '/ (D)', starting polymerization and adding sequentially.
6). The weight fraction (C) / (D) of the phenolic compound (C) and the phenolic compound (D) that are successively dropped during the polymerization is the weight fraction of the component (C) and the component (D) that are stretched in the initial stage of the polymerization ( C) A method of preparing to be larger than '/ (D)', starting polymerization and sequentially adding.
7). The weight fraction (C) / (D) of the phenolic compound (C) and the phenolic compound (D) that are successively dropped during the polymerization is the weight fraction of the component (C) and the component (D) that are stretched in the initial stage of the polymerization ( C) A method of preparing to be smaller than '/ (D)', starting polymerization and adding sequentially.

The end of the addition is not particularly limited as long as it is in the middle of polymerization, but by continuing the polymerization after the end of the addition, the unreacted mixed phenol compound (A) that has just been added to the polymerization system is polymerized, and more Since the phenol compound (A) can be polymerized into a polyphenylene ether structure and polyphenylene ether can be efficiently obtained, it is preferable to continue the polymerization for 1 minute or more after the addition is completed, more preferably for 10 minutes or more, and for 30 minutes. The above is more preferable.
Like this invention, it has a desired number average molecular weight by adding the mixed solution (B) which consists of a poor solvent of a mixed phenol compound (A) and polyphenylene ether in the middle of superposition | polymerization in the middle of superposition | polymerization, and has a molecular weight Narrow distribution polyphenylene ether can be produced, and more suitably dispersed polyphenylene ether particles can be produced.

The concentration of the total amount of the phenol compound (A) in the solution used for the polymerization in the polymerization method of the present invention is not particularly limited, but is preferably 10 to 50% by weight in the total polymerization solution, and 15 to 30% by weight. The feature is exhibited and it is more preferable.
As the catalyst used in the present invention, any known catalyst system that can be generally used for production of polyphenylene ether can be used. Known catalyst systems are known to be composed of transition metal ions having redox ability and amine compounds capable of complexing with the metal ions. For example, catalyst systems consisting of copper compounds and amines, manganese compounds And a catalyst system comprising an amine, a catalyst system comprising a cobalt compound and an amine, and the like. Since the polymerization reaction proceeds efficiently under some alkaline conditions, some alkali or further amine may be added thereto.

  The catalyst suitably used in the present invention is a catalyst comprising a copper compound, a halogen compound and a diamine compound represented by the general formula (4) as constituent components of the catalyst.

... Formula (4)
(Wherein R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and all are not simultaneously hydrogen. R ₁₂ has 2 carbon atoms. To 5 linear or methyl branched alkylene groups)

  Examples of the copper compounds of the catalyst component described here are listed. As a suitable copper compound, a cuprous compound, a cupric compound or a mixture thereof can be used. Examples of the cupric compound include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Among these, particularly preferred metal compounds are cuprous chloride, cupric chloride, cuprous bromide and cupric bromide. In addition, these copper salts may be synthesized at the time of use from oxides (for example, cuprous oxide), carbonates, hydroxides, and the corresponding halogens or acids. A method often used is a method in which cuprous oxide and hydrogen halide (or a solution of hydrogen halide) exemplified above are mixed and prepared.

  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, tetramethylammonium bromide, iodine. 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 as a component 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, 2 times or more and 20 times or less are preferable as a halogen atom with respect to the molar amount of a copper atom, As a preferable usage amount of a copper atom with respect to 100 mol of the phenol used, The range is from 0.02 mol to 0.6 mol.

  Next, examples of diamine compounds as catalyst components are listed. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N′-trimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-dimethylethylenediamine, N-methylethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N'-triethylethylenediamine, N, N'-diethylethylenediamine, N, N-diethylethylenediamine, N-ethylethylenediamine, N, N-dimethyl-N'-ethylethylenediamine, N, N'-dimethyl-N-ethylethylenediamine, Nn-propylethylenediamine, N, N'-di-n-propylethylenediamine, Ni-propylethylenediamine, N, N'-di-propylethylenediamine, N- n-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- Examples include 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 for the present invention are those in which the alkylene group 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 normally used.

In the present invention, it is preferable to further include a tertiary monoamine compound or a secondary monoamine compound alone or in combination as a constituent component of the catalyst.
The tertiary monoamine compound is an aliphatic tertiary amine including 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. Although the usage-amount of these is not specifically limited, The range of 15 mol or less is preferable with respect to 100 mol of phenol normally used.

  Examples of secondary monoamine compounds include secondary aliphatic amines such as 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, cyclohexylamine. Examples of secondary monoamine compounds containing aromatics include 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 Examples include -2,6-dimethylaniline and diphenylamine, but are not limited to these examples. These secondary monoamine compounds may be used alone or in combination of two or more. Although the usage-amount is not specifically limited, The range of 15 mol or less is preferable with respect to 100 mol of the phenol normally used.

In the present invention, the catalyst is preferably included in the mixed solution (B) sequentially added during the polymerization for the purpose of improving the polymerization activity.
In the present invention, there is no limitation on adding a surfactant which has been conventionally known to have an effect of improving activity. For example, trioctylmethylammonium chloride known under the trade names of Aliquat 336 and Capriquat. The amount used is preferably within a range not exceeding 0.1% by mass relative to the total amount of the polymerization reaction mixture.

The oxygen-containing gas in the polymerization of the present invention is pure oxygen, oxygen and an inert gas such as nitrogen mixed at an arbitrary ratio, air, and optionally an inert gas such as air and nitrogen or a rare gas. The thing etc. which were mixed in the ratio of can be used. The system pressure during the polymerization reaction is normal pressure, but it 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 it is preferably 5 Nml / min or more, and more preferably 10 Nml / min or more, as pure oxygen per mole of phenol mixture used for polymerization. .
The temperature of the polymerization is not particularly limited, but if it is too low, the reaction is difficult to proceed, and if it is too high, the selectivity of the reaction may be lowered, and therefore it is in the range of 0 to 100 ° C, preferably 10 to 80 ° C.

Alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, neutral salts such as magnesium sulfate and calcium chloride, zeolite, and the like can also be added to the polymerization reaction system of the present invention.
There is no particular limitation on the post-treatment method after completion of the polymerization reaction. Usually, an acid such as hydrochloric acid or acetic acid, ethylenediaminetetraacetic acid (EDTA) and its salt, nitrilotriacetic acid and its salt or the like is added to the reaction solution to deactivate the catalyst. Since the shape of the polymerization solution at the end of the polymerization is a slurry after that, for the purpose of washing and removing the catalyst, repeated washing with a solution mainly composed of a solvent having low solubility of polyphenylene ether used for polymerization is performed. Is more preferable. Thereafter, polyphenylene ether can be recovered by an operation of drying in a drying process using various dryers.

The polyphenylene ether obtained by the method of the present invention can be melt-kneaded with conventionally known thermoplastic resins and thermosetting resins. Next, examples of the thermoplastic resin and the thermosetting resin are listed.
For example, 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, polyether Examples include ether ether ketone, liquid crystal polymer, polytetrafluoroethylene, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyamideimide, phenol, urea, melamine, unsaturated polyester, alkyd, epoxy, diallyl phthalate, etc. It is done. Moreover, it is more preferable to add conventionally known additives and thermoplastic elastomers for the purpose of imparting effects such as conductivity, flame retardancy and impact resistance during melt kneading.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention should not be limited at all by these examples.
The measurement was performed according to the following method.
(1) Measuring method of molecular weight A standard curve is created and measured with gel permeation chromatography System 21 manufactured by Showa Denko K.K. The molecular weight of standard polystyrene is 365, 2170000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550. Two columns, K-805L manufactured by Showa Denko KK, are connected in series. The solvent is chloroform, the solvent flow rate is 1.0 ml / min, and the column temperature is 40 ° C. A 0.1% by weight chloroform solution of polyphenylene ether is prepared and measured. The UV wavelength of the detection unit is 254 nm for standard polystyrene and 283 nm for polyphenylene ether.
(2) Yield The mass ratio of the dry polyphenylene ether to the mass of the monomer subjected to polymerization was measured at 100 fractions.

(3) Glass transition temperature measurement The glass transition temperature of the obtained polyphenylene ether was measured using a differential scanning calorimeter DSC (manufactured by PerkinElmer-Pyris 1). After heating from room temperature to 280 ° C. in a nitrogen atmosphere at a rate of 10 ° C./min, the temperature was lowered to 50 ° C. at 40 ° C./min, and then the glass transition temperature was measured at a rate of 10 ° C./min.
(4) Confirmation of scale adhesion to reactor After the polymerization solution was extracted from the reactor, the amount of scale adhered in the reactor was visually confirmed.

[Example 1]
Nitrogen gas at a flow rate of 500 ml / min is supplied to a 10-liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank. 1.099 g cupric chloride dihydrate, 4.705 g 35% hydrochloric acid, 41.971 g N, N, N ′, N′-tetramethylpropanediamine, 31.658 g di-n while blowing. -Butylamine, 1264 g of n-butanol, 544 g of methanol, 3792 g of xylene, 136 g of 2,6-dimethylphenol, 24 g of 2,3,6-trimethylphenol were put into a homogeneous solution, and the internal temperature of the reactor was Stir until 40 ° C.

  Nitrogen gas was blown into a 5 liter storage tank equipped with a sparger for introducing nitrogen gas, a stirring turbine blade and baffle in the storage tank, and a reflux condenser in the vent gas line at the top of the storage tank at a flow rate of 200 ml / min. While adding 720 g of methanol, 1224 g of 2,6-dimethylphenol and 216 g of 2,3,6-trimethylphenol, the mixture was stirred until it became a homogeneous solution, and (B) a mixed solution was prepared.

  Subsequently, oxygen gas was started to be introduced into the polymerization tank from the sparger at a rate of 1000 Nml / min into the vigorously stirred polymerization tank, and at the same time using the liquid feed pump from the storage tank, (B) the mixed solution was 17.4 g / min. Sequentially added at a rate of Aeration was performed for 280 minutes, and the internal temperature of the reactor was controlled to 40 ° C. In addition, polyphenylene ether deposited 140 minutes after the start of supply of oxygen gas, showing a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization.

Stop the ventilation of the oxygen-containing gas, add 11.5 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white.
The internal temperature of the reactor was controlled to 40 ° C.
Thereafter, the wet polyphenylene ether remaining after filtration was placed in a 10 L washing tank and dispersed together with 6400 g of methanol, stirred for 30 minutes, and then filtered again to obtain wet polyphenylene ether. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 150 minutes to obtain dry polyphenylene ether.

  Molecular weight and glass transition temperature were measured using dry polyphenylene ether. Moreover, the scale to a reactor etc. was not confirmed. Further, 1 g of polyphenylene ether was sandwiched between cut aluminum plates and heated for 10 minutes under conditions of 330 ° C. and 10 MPa to produce a film sample of polyphenylene ether, and the transparency of the film sample was visually confirmed. The transparency of the film was evaluated as “◯” when the film was placed between the fluorescent lamp and the naked eye and the light source could be confirmed, and “X” when the light source could not be confirmed. The results are shown in Table 1.

[Example 2]
Nitrogen gas at a flow rate of 500 ml / min is supplied to a 10-liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank. While blowing, 1.093 g of cupric chloride dihydrate, 4.681 g of 35% hydrochloric acid, 41.751 g of N, N, N ′, N′-tetramethylpropanediamine, 31.493 g of di-n -Butylamine, 1264 g of n-butanol, 544 g of methanol, 3792 g of xylene, 136 g of 2,6-dimethylphenol, 24 g of 2,3,6-trimethylphenol were put into a homogeneous solution, and the internal temperature of the reactor was Stir until 40 ° C.

Nitrogen gas was blown into a 5 liter storage tank equipped with a sparger for introducing nitrogen gas, a stirring turbine blade and baffle in the storage tank, and a reflux condenser in the vent gas line at the top of the storage tank at a flow rate of 200 ml / min. While adding 720 g of methanol, 1152 g of 2,6-dimethylphenol and 288 g of 2,3,6-trimethylphenol, the mixture was stirred until it became a homogeneous solution, and (B) a mixed solution was prepared.
Subsequently, oxygen gas was started to be introduced into the polymerization tank from the sparger at a rate of 1000 Nml / min into the vigorously stirred polymerization tank, and at the same time using the liquid feed pump from the storage tank, (B) the mixed solution was 17.4 g / min. Sequentially added at a rate of Aeration was performed for 280 minutes, and the internal temperature of the reactor was controlled to 40 ° C. In addition, polyphenylene ether deposited 140 minutes after the start of supply of oxygen gas, showing a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization.

Stop the ventilation of the oxygen-containing gas, add 11.4g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white.
The internal temperature of the reactor was controlled to 40 ° C.
Thereafter, the wet polyphenylene ether remaining after filtration was placed in a 10 L washing tank and dispersed together with 6400 g of methanol, stirred for 30 minutes, and then filtered again to obtain wet polyphenylene ether. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 150 minutes to obtain dry polyphenylene ether.
Measurement of molecular weight, measurement of glass transition temperature, etc. were performed using dry polyphenylene ether. Moreover, the scale to a reactor etc. was not confirmed. The results are shown in Table 1.

[Example 3]
Nitrogen gas at a flow rate of 500 ml / min is supplied to a 10-liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank. 1.087 g cupric chloride dihydrate, 4.656 g 35% hydrochloric acid, 41.533 g N, N, N ′, N′-tetramethylpropanediamine, 31.328 g di-n while blowing. -Put butylamine, 632 g of n-butanol, 544 g of methanol, 4425 g of xylene, 140 g of 2,6-dimethylphenol, 40 g of 2,3,6-trimethylphenol into a homogeneous solution, and the internal temperature of the reactor is Stir until 40 ° C.

Nitrogen gas was blown into a 5 liter storage tank equipped with a sparger for introducing nitrogen gas, a stirring turbine blade and baffle in the storage tank, and a reflux condenser in the vent gas line at the top of the storage tank at a flow rate of 200 ml / min. While adding 720 g of methanol, 1080 g of 2,6-dimethylphenol, 360 g of 2,3,6-trimethylphenol, the mixture was stirred until it became a homogeneous solution, and (B) a mixed solution was prepared.
Next, oxygen gas was introduced from the sparger into the polymerization tank at a rate of 1000 Nml / min into the vigorously stirred polymerization tank, and at the same time, using the liquid feed pump from the storage tank, (B) the mixed solution was 17.5 g / min. Sequentially added at a rate of Aeration was performed for 280 minutes, and the internal temperature of the reactor was controlled to 40 ° C. In addition, polyphenylene ether deposited 140 minutes after the start of supply of oxygen gas, showing a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization.

Stop the ventilation of the oxygen-containing gas, add 11.5 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white.
The internal temperature of the reactor was controlled to 40 ° C.
Thereafter, the wet polyphenylene ether remaining after filtration was placed in a 10 L washing tank and dispersed together with 6400 g of methanol, stirred for 30 minutes, and then filtered again to obtain wet polyphenylene ether. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 150 minutes to obtain dry polyphenylene ether.
Measurement of molecular weight, measurement of glass transition temperature, etc. were performed using dry polyphenylene ether. Moreover, the scale to a reactor etc. was not confirmed. The results are shown in Table 1.

[Example 4]
2.747 g of cupric chloride dihydrate to be placed in the polymerization tank, 7.712 g of 35% hydrochloric acid, 63.796 g of N, N, N ′, N′-tetramethylpropanediamine, di-n-butylamine 31.658, n-butanol 441 g, methanol 413 g, xylene 4721 g, 2,6-dimethylphenol amount 136 g, 2,3,6-trimethylphenol amount 24 g The same procedure as in Example 3 was performed except that the amount of 6-dimethylphenol was 1224 g, the amount of 2,3,6-trimethylphenol was 216 g, and the oxygen aeration time was 380 minutes. Note that polyphenylene ether was deposited 155 minutes after the start of the supply of oxygen gas, indicating a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 1.

[Example 5]
The amount of 2,6-dimethylphenol placed in the polymerization tank was 96 g, the amount of 2,3,6-trimethylphenol was 64 g, and the amount of 2,6-dimethylphenol placed in the storage tank was 864 g, The same operation as in Example 3 was conducted except that the amount of 6-trimethylphenol was changed to 576 g. Incidentally, after 130 minutes from the start of the supply of oxygen gas, polyphenylene ether was deposited to show a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 1.

[Example 6]
1.110 g of cupric chloride dihydrate placed in the polymerization tank, 4.754 g of 35% hydrochloric acid, 42.409 g of N, N, N ′, N′-tetramethylpropanediamine, di-n-butylamine 15.994 g, 1267 g of n-butanol, 1181 g of methanol, 3168 g of xylene, 152 g of 2,6-dimethylphenol, 8 g of 2,3,6-trimethylphenol, and 1368 g of 2,6-dimethylphenol put in the storage tank This was carried out in the same manner as in Example 1 except that 72 g of 2,3,6-trimethylphenol was used. After 150 minutes from the start of the oxygen gas supply, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 1.

[Example 7]
1.105 g of cupric chloride dihydrate put into the polymerization tank, 4.730 g of 35% hydrochloric acid, 42.190 g of N, N, N ′, N′-tetramethylpropanediamine, di-n-butylamine 31.823 g, 1264 g of n-butanol, 544 g of methanol, 3792 g of xylene, 144 g of 2,6-dimethylphenol, 16 g of 2,3,6-trimethylphenol, and 1296 g of 2,6-dimethylphenol put in the storage tank This was carried out in the same manner as in Example 1 except that 144 g of 2,3,6-trimethylphenol was used. After 150 minutes from the start of the oxygen gas supply, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 1.

[Example 8]
1.082 g of cupric chloride dihydrate put into the polymerization tank, 4.632 g of 35% hydrochloric acid, 41.314 g of N, N, N ′, N′-tetramethylpropanediamine, di-n-butylamine 31.162 g, 1267 g of n-butanol, 544 g of methanol, 3793 g of xylene, 112 g of 2,6-dimethylphenol, 48 g of 2,3,6-trimethylphenol, and 1008 g of 2,6-dimethylphenol put into the storage tank This was carried out in the same manner as in Example 1 except that 432 g of 2,3,6-trimethylphenol was used. After 150 minutes from the start of the oxygen gas supply, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 1.

[Example 9]
The amount of 2,6-dimethylphenol placed in the polymerization tank was 360 g, the amount of 2,3,6-trimethylphenol was 120 g, the amount of 2,6-dimethylphenol placed in the storage tank was 840 g, and the amount of 2,3,6-trimethylphenol was 280 g. Except for this, the same procedure as in Example 3 was performed. After 130 minutes from the start of the oxygen gas supply, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 1.

[ Example 10 ]
The same procedure as in Example 1 was conducted except that 160 g of 2,6-dimethylphenol placed in the polymerization tank and 1440 g of 2,6-dimethylphenol placed in the storage tank were used. After 130 minutes from the start of the oxygen gas supply, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. Scale to the reactor and the like were not confirmed. The results are shown in Table 2 .

[Comparative Example 2]
Nitrogen gas at a flow rate of 500 ml / min is supplied to a 10-liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank. 1.099 g cupric chloride dihydrate, 4.705 g 35% hydrochloric acid, 41.971 g N, N, N ′, N′-tetramethylpropanediamine, 31.658 g di-n while blowing. -Butylamine, 1264 g of n-butanol, 1264 g of methanol, 3792 g of xylene, 1360 g of 2,6-dimethylphenol, 240 g of 2,3,6-trimethylphenol were put into a homogeneous solution and the internal temperature of the reactor was Stir until 40 ° C.

Next, oxygen gas was passed through the polymerization tank at a rate of 1000 Nml / min through the sparger for 280 minutes, and the internal temperature of the reactor was controlled to 40 ° C. In addition, polyphenylene ether deposited 140 minutes after the start of supply of oxygen gas, showing a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization.
Stop the ventilation of the oxygen-containing gas, add 11.5 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white.

The internal temperature of the reactor was controlled to 40 ° C.
Thereafter, the wet polyphenylene ether remaining after filtration was placed in a 10 L washing tank and dispersed together with 6400 g of methanol, stirred for 30 minutes, and then filtered again to obtain wet polyphenylene ether. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 150 minutes to obtain dry polyphenylene ether.
Molecular weight and glass transition temperature were measured using dry polyphenylene ether. Moreover, the scale to a reactor etc. was not confirmed. The results are shown in Table 2 .

[ Example 11 ]
72 g of 2,6-dimethylphenol put into the polymerization tank and 88 g of 2,3,6-trimethylphenol, 648 g of 2,6-dimethylphenol put into the storage tank, and 792 g of 2,3,6-trimethylphenol, The same operation as in Example 1 was performed except that the oxygen gas aeration time was 200 minutes. After 100 minutes from the start of the oxygen gas supply, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 2 .

[Comparative Example 5]
1.110 g of cupric chloride dihydrate placed in the polymerization tank, 4.754 g of 35% hydrochloric acid, 42.409 g of N, N, N ′, N′-tetramethylpropanediamine, di-n-butylamine The same procedure as in Example 1 was carried out except that 15.994 g, 1267 g of n-butanol, 1901 g of methanol, 3168 g of xylene, 1520 g of 2,6-dimethylphenol, and 80 g of 2,3,6-trimethylphenol were used. After 140 minutes from the start of the supply of oxygen gas, polyphenylene ether was precipitated and showed a slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization. The results are shown in Table 2.

[Comparative Example 7]
Nitrogen gas at a flow rate of 500 ml / min is supplied to a 10-liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank. While blowing, 1.649 g cupric oxide, 12.399 g 47% aqueous hydrogen bromide solution, 3.9725 g di-t-butylethylenediamine, 19.232 g di-n-butylamine, 58.535 g butyldimethylamine 5962 g of toluene, 108.8 g of 2,6-dimethylphenol, and 19.2 g of 2,3,6-trimethylphenol were added and stirred until a uniform solution was obtained and the internal temperature of the reactor reached 40 ° C.

In addition, nitrogen gas was blown into the storage tank at a flow rate of 200 ml / min. While adding 640 g of toluene, 979.2 g of 2,6-dimethylphenol and 172.8 g of 2,3,6-trimethylphenol, the mixture was stirred until it became a homogeneous solution, and a mixed solution (B) was prepared.
Next, oxygen gas was started to be introduced into the polymerization tank from the sparger at a rate of 800 Nml / min into the vigorously stirred polymerization tank, and at the same time using the liquid feed pump from the storage tank, (B) the mixed solution was 17.4 g / min. Sequentially added at a rate of Aeration was performed for 280 minutes, and the internal temperature of the reactor was controlled to 40 ° C. The polymerization solution at the end of the polymerization was in a solution state.

Stop the ventilation of the oxygen-containing gas, add 800g of 2.5% aqueous solution of ethylenediaminetetraacetic acid tetrasodium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 100 minutes, and leave it to stand for liquid-liquid separation. Separated the organic and aqueous phases. Methanol was added to the obtained organic phase in an excessive amount to precipitate polyphenylene ether, followed by filtration. The polyphenylene ether remaining in the filter was dispersed in 5120 g of methanol.
Subsequently, 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.
The internal temperature of the reactor was controlled to 40 ° C.

Thereafter, the wet polyphenylene ether remaining after filtration was placed in a 10 L washing tank and dispersed together with 5120 g of methanol, stirred for 30 minutes, and then filtered again to obtain wet polyphenylene ether. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 150 minutes to obtain dry polyphenylene ether.
Molecular weight and glass transition temperature were measured using dry polyphenylene ether. Moreover, the scale to a reactor etc. was not confirmed. The results are shown in Table 2 .

  A reduction in yield can be suppressed, and a wide range of molecular weight designs can be made of polyphenylene ether having a sufficient molecular weight and a narrow molecular weight distribution.

Claims (9)

The phenol compound (A) is subjected to oxidative coupling using a mixed solvent composed of a good solvent of at least one polyphenylene ether and a poor solvent of at least one polyphenylene ether in the presence of a catalyst, using an oxygen-containing gas, and polymerized. In the method for producing polyphenylene ether in which the good solvent at the end of the polymerization is 35% by mass or more of the entire polymerization system and the form of the polymerization solution at the end of the polymerization is precipitation polymerization, the component (A) used for the polymerization is represented by the formula (1 ) And a mixed solution (B) composed of 10% by mass to 100% by mass of (A) and a poor solvent is sequentially added during the polymerization with respect to the total amount of the component (A) used in the polymerization. A process for producing polyphenylene ether, comprising:

... Formula (1)
(In the formula (1), R ₁ , R ₂ , R ₃ and R ₄ each represents an independent substituent, and R ₁ represents an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, and a substituted aryl group. , An alkoxy group or a substituted alkoxy group, and R ₂ , R ₃ and R ₄ may be hydrogen or halogen in addition to the same group as defined for R ₁ . The phenol compound (A) used for polymerization consists of the phenol compound (C) represented by the formula (2) and the phenol compound (D) represented by the formula (3). A method for producing polyphenylene ether.

... Formula (2)
(In the formula (2), R ₅ and R ₆ each represents an independent substituent, and R ₅ represents an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group or a substituted group. An alkoxy group, R ₆ may be hydrogen or halogen in addition to the same groups defined for R ₁ )

... Formula (3)
(In the formula (3), R ₇ , R ₈ and R ₉ each represents an independent substituent, and R ₉ represents an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group. A group or a substituted alkoxy group, which may be hydrogen or halogen in addition to the same groups defined for R ₇ and R ₈ R _1. )   The polyphenylene ether according to claim 2, wherein the phenol compound (A) used for the polymerization is composed of 60% by mass to 95% by mass of the phenol compound (C) and 5% by mass to 40% by mass of the phenol compound (D). Manufacturing method.   4. The method for producing polyphenylene ether according to claim 2, wherein the phenol compound (C) is 2,6-dimethylphenol and the phenol compound (D) is 2,3,6-trimethylphenol.   The polyphenylene ether according to any one of claims 1 to 4, wherein the poor solvent of the polyphenylene ether is at least one kind of solvent mainly comprising an alcohol having 1 to 10 carbon atoms. A method for producing ether.   The number average molecular weight of this polyphenylene ether is 10,000-40000, The manufacturing method of the polyphenylene ether of any one of Claims 1-5 characterized by the above-mentioned. The method for producing a polyphenylene ether according to any one of claims 1 to 6, wherein the catalyst comprises a catalyst comprising a copper compound, a halogen compound, and a diamine compound represented by the general formula (4).

... Formula (4)
(Wherein R ₁₀ , R ₁₁ , R ₁₃ , and R ₁₄ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and all are not hydrogen at the same time. R ₁₂ is 2 carbon atoms. To 5 linear or methyl branched alkylene groups)   The composition of the component (B) added sequentially during the polymerization is 25: 1 to 1:10 in a weight ratio of the component (A) to the poor solvent, according to any one of claims 1 to 7. Of producing polyphenylene ether.   9. The poor solvent for polyphenylene ether is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, and Tert-butanol. The manufacturing method of the polyphenylene ether of any one of Claims 1.