JP3010195B2 - Method for producing poly (1,4-phenylene oxide) - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to poly (1,4-) which is an engineering plastic having excellent impact resistance.
Phenylene oxide).

[0002]

2. Description of the Related Art Various methods have been reported for the production of poly (1,4-phenylene oxide), using oxygen as an oxidizing agent, and comprising a copper compound such as cuprous chloride which is a deleterious substance and amines. A method using a catalyst is typical. However, the method using oxygen as an oxidizing agent has the disadvantage that the reaction system must be pressurized in order to avoid the explosion range of the organic solvent in an oxygen atmosphere (including under air).

On the other hand, a method using a peroxide as an oxidizing agent can react even in an inert gas atmosphere, and can avoid an explosion range. Hitherto, a method has been proposed in which hydrogen peroxide is used as an oxidizing agent in the presence of a horseradish peroxidase catalyst, but the enzyme catalyst is expensive for industrial use.

[0004]

An object of the present invention is to provide a poly (1,4) using a peroxide as an oxidizing agent and using an inexpensive catalyst.
-Phenylene oxide).

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, oxidized 2,6-disubstituted phenols using an iron complex as a catalyst and a peroxide as an oxidizing agent. The inventors have found that poly (1,4-phenylene oxide) can be obtained by polymerization, and have completed the present invention. That is, the present invention uses a peroxide as an oxidizing agent in the presence of an iron complex catalyst, and uses the following general formula (1)

Embedded image (Wherein, R ₁ and R ₂ each independently represent a hydrocarbon group which may have a substituent, a halogen group, a hydrocarbon oxy group,
Represents an amino group or a substituted amino group).
An object of the present invention is to provide a method for producing poly (1,4-phenylene oxide), which comprises oxidatively polymerizing a disubstituted phenol.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The 2,6-disubstituted phenol (hereinafter, also simply referred to as phenol) used in the present invention has the general formula (1)
This phenol can be used alone or in combination of two or more.

In the general formula (1), R ₁ and R ₂ include a hydrocarbon group, and the hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Aliphatic hydrocarbon groups include linear and cyclic alkyl and alkenyl groups. The carbon number of the aliphatic hydrocarbon group is usually
It is 1-20, preferably 1-8. The aromatic hydrocarbon group may be monocyclic or polycyclic, and the aromatic hydrocarbon group includes an aryl group and an arylalkyl group. The hydrocarbon group may have a substituent such as a halogen, a hydrocarbon oxy group, an amino group, and a substituted amino group. Specific examples of the hydrocarbon group which may have a substituent include, for example, methyl, ethyl, propyl, butyl, amyl, hex, vinyl, propylene, allyl, phenyl, tolyl, benzyl, phenethyl, naphthyl, naphthyl Methyl and substituted products thereof can be mentioned.

In the general formula (1), R ₁ and R _{2 each} include a halogen group, which includes chlorine,
Bromine, iodine and fluorine are included.

In the general formula (1), R ₁ and R _{2 each} include a hydrocarbon oxy group, which includes an aliphatic hydrocarbon oxy group and an aromatic hydrocarbon oxy group. . The aliphatic hydrocarbon oxy group includes a chain or cyclic alkoxy group and an alkenyloxy group. The number of carbon atoms of the aliphatic hydrocarbon oxy group is usually 1 to
20, preferably 1 to 8. The aromatic hydrocarbonoxy group may be monocyclic or polycyclic, and the aromatic hydrocarbonoxy group includes an aryloxy group and an arylalkyloxy group. The hydrocarbon oxy group may have a substituent such as a halogen, an amino group, and a substituted amino group. Specific examples of the hydrocarbon oxy group which may have a substituent include, for example, methoxy, ethoxy, propyloxy, butoxy, amyloxy, hexoxy, vinyloxy, propyleneoxy, allyloxy, phenoxy, tolyloxy, benzyloxy, phenethyl Examples thereof include oxy, naphthyloxy, naphthylmethyloxy, and substituted products thereof.

In the general formula (1), R ₁ and R _{2 each} include an amino group or a substituted amino group. In this case, the substituted amino group can be represented by the following general formula (3). .

Embedded image In the above formula, R ₈ and R ₉ represent a hydrocarbon group which may be substituted. As the hydrocarbon group and the substituent in this case,
Mention may be made of those given for the R ₁ and R _2.

The catalyst used in the present invention is an iron complex catalyst. It can be liquid or solid at room temperature. Further, it is preferable that the iron complex catalyst exhibit solubility in the raw material phenol and the reaction solvent under the reaction conditions. In the iron complex catalyst used in the present invention, the ligand may be any organic compound having a structure capable of coordinating with an iron ion, such as an amino group or a hydroxyl group,
Organic compounds containing one or more carboxylic acid groups or the like in the molecule, for example, chain or cyclic amines, phenol compounds, benzoic acid and the like are included.

The iron complex catalyst preferably used in the present invention is represented by the following general formula (2).

Embedded image In the above formula, R ₃ represents a bifunctional hydrocarbon group, and R ₄ and R
₅ each independently represents hydrogen or a hydrocarbon group; R ₆ and R
₇ independently represents hydrogen, an optionally substituted hydrocarbon group, a halogen group, a hydrocarbon oxy group, an amino group or a substituted amino group.

R ₃ represents a bifunctional hydrocarbon group,
These include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups. As the divalent aliphatic group,
Examples thereof include an alkylene group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Examples of the divalent aromatic group include an arylene group such as phenylene, tolylene, and naphthylene, and phenylene dimethylene (—CH ₂ C ₆ H ₄ CH). _And phenylenedialkylene groups such as _2- ).

R ₄ and R _{5 each} represent a hydrocarbon group which may be substituted, and examples thereof include those described for R ₁ and R _{2 in} the general formula (1). be able to.

The above R ₆ and R ₇ include an optionally substituted hydrocarbon group, a halogen group, a hydrocarbonoxy group, an amino group and a substituted amino group. mention may be made of those given for R ₁ and R ₂ 1).

In the present invention, the iron complex catalyst may be used alone or
A mixture of more than one species can be used. These can be used in any amount, but are generally preferably used in an amount of about 0.001 to 50 mol%, more preferably about 0.01 to 1 mol%, based on the starting phenol.

The process according to the invention is preferably carried out in the presence of a tertiary amine. By causing a tertiary amine to be present in the reaction system, effects such as improvement in polymerization activity can be obtained. The tertiary amine is a liquid or solid at room temperature, and various types of conventionally known tertiary amines can be used as long as they are soluble in the starting phenol and the reaction solvent. The amount of the tertiary amine used is 0.01 to 1 with respect to the starting phenol.
It is preferred to use 0% by weight. Specific examples of the tertiary amine include, for example, pyridine, triethylamine, 2,6-lutidine, N, N, N, -N-tetraethylethylenediamine and the like.

As the peroxide used as the oxidizing agent, various conventionally known ones (organic peroxide, hydrogen peroxide, etc.) can be used, but hydrogen peroxide is preferably used. Hydrogen peroxide can be used at any concentration. It is preferable that the peroxide used is not more than 2 molar equivalents relative to the starting phenol.

In the present invention, the oxidative polymerization of the starting phenol is preferably carried out in the presence of a reaction solvent. The reaction solvent is inert to the catalyst, and various known organic solvents can be used as long as they dissolve the catalyst to some extent. In general, ethers such as 1,4-dioxane, tetrahydrofuran, and dimethoxyethane; hydrocarbons such as benzene and toluene; alcohols; amides; organic solvents such as nitriles; Used.

The reaction temperature may be within a range in which the reaction medium is kept in a liquid state, and is preferably from -20 ° C to 80 ° C.

[0021]

EXAMPLES The present invention will be described below in detail with reference to examples, but these examples do not limit the present invention.

Example 1 In a 50 mL round-bottomed flask equipped with a magnetic stirrer, 611 mg of 2,6-dimethylphenol and μ-oxobis @ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were used.
I)｝ [In the general formula (2), R ₃ : —C ₂ H ₄ ,
R ₄ , R ₅ , R ₆ , R ₇ : H] 3.3 mg, and
10 mL of 4-dioxane and 0.1 mL of pyridine were added,
It was dissolved by stirring. Further, 5 wt% hydrogen peroxide 3.
4 mL was added over 1 hour and then stirred for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer. This was isolated by centrifugation and vacuum dried to give 556 mg of a yellow powder. About the obtained polymer, EX-270 manufactured by JEOL Ltd.
Was used to perform NMR measurement. As a result, formation of poly (1,4-phenylene oxide) was confirmed. Further, the molecular weight was determined by using HLC-8010 gel permeation chromatography manufactured by Tosoh Corporation. As a result, the number average molecular weight was 11,300 and the molecular weight distribution was 1.39 in terms of standard polystyrene.

Example 2 In a 50 mL round-bottom flask equipped with a magnetic stirrer, 611 mg of 2.6-dimethylphenol and μ-oxobis @ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were used.
I) $ 3.3mg, 10m 1,4-dioxane
L was added and dissolved by stirring. Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, followed by stirring for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer. This is isolated by centrifugation and dried under vacuum to obtain polymer powder 477.
mg was obtained. The obtained polymer was subjected to gel permeation chromatography measurement. As a standard polystyrene-equivalent value, a number average molecular weight of 16,400, a peak of a molecular weight distribution of 1.47, a number average molecular weight of 1,300, and a peak of a molecular weight distribution of 1.20 were found. The area ratio of each peak is 5
It was 0:50.

Example 3 In a 50 mL round-bottom flask equipped with a magnetic stirrer, 611 mg of 2,6-dimethylphenol and μ-oxobis {N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were added.
I) $ 3.3 mg, and add tetrahydrofuran 10
mL and 0.1 mL of pyridine were added and dissolved by stirring. Further, the reaction solution was added to 100 mL of 5 wt% peracid to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 556 mg of a polymer powder.
When the molecular weight of the obtained polymer was determined using gel permeation chromatography, the number average molecular weight was 16400 and the molecular weight distribution was 1.36 as a standard polystyrene equivalent value.

Example 4 A 50 mL round bottom flask equipped with a magnetic stirrer was charged with 611 mg of 2,6-dimethylphenol and μ-oxobis @ N, N as a catalyst.
Di (salicylidine) ethylenediaminatoiron (III)｝ 3.
3 mg was added, and 10 mL of dimethoxyethane and 0.1 mL of pyridine were added thereto and dissolved by stirring. An additional 3.4 mL of 5% hydrogen peroxide was added over 1 hour and then stirred for 2 hours. After completion of the reaction, methanol 100m
The reaction liquid was added to L to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 556 mg of a polymer powder. When the molecular weight of the obtained polymer was determined using gel permeation chromatography, the number average molecular weight was 1 as a standard polystyrene conversion value.
8,700 and molecular weight distribution 1.38.

Example 5 In a 50 mL round bottom flask equipped with a magnetic stirrer, 611 mg of 2,6-dimethylphenol and μ-oxobis @ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were added.
I) $ 3.3mg and add 10mL of acetonitrile
And 0.1 mL of pyridine were added and dissolved by stirring.
Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, followed by stirring for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer.
This was isolated by centrifugation and vacuum dried to obtain 556 mg of a polymer powder. When the molecular weight of the obtained polymer was determined by gel permeation chromatography, the number average molecular weight was 2270 and the molecular weight distribution was 1.57 in terms of standard polystyrene.

Example 6 In a 50 mL round-bottom flask equipped with a magnetic stirrer, 611 mg of 2,6-dimethylphenol and μ-oxobis @ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were used.
I) $ 3.3mg and add 10m of isopropanol
L and 0.1 mL of pyridine were added and dissolved by stirring. Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, followed by stirring for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 428 mg of a polymer powder. When the molecular weight of the obtained polymer was determined using gel permeation chromatography, as a standard polystyrene conversion value,
The number average molecular weight was 22,10 and the molecular weight distribution was 1.36.

Example 7 A 50 mL round bottom flask equipped with a magnetic stirrer was charged with 611 mg of 2,6-dimethylphenol and μ-oxobis @ N, N as a catalyst.
Di (salicylidine) ethylenediaminatoiron (III)｝ 3.
3 mg, and N, N-dimethylformamide 1
0 mL and 0.1 mL of pyridine were added and dissolved by stirring. An additional 3.4 mL of 5% hydrogen peroxide was added over 1 hour and then stirred for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer.
This was isolated by centrifugation and vacuum dried to obtain 600 mg of a polymer powder. When the molecular weight of the obtained polymer was determined by gel permeation chromatography, the number average molecular weight was 1930 and the molecular weight distribution was 1.40 in terms of standard polystyrene.

Example 8 In a 50 mL round bottom flask equipped with a magnetic stirrer, 611 mg of 2,6-dimethylphenol and μ-oxobis オ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were added.
I) $ 3.3mg, and add 1,4-dioxane 8mL
And 2 mL of distilled water and 0.1 mL of pyridine were added and dissolved by stirring. Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, followed by stirring for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 452 mg of polymer powder. When the molecular weight of the obtained polymer was determined using gel permeation chromatography, the number average molecular weight was 3840 and the molecular weight distribution was 1.64 as a standard polystyrene equivalent value.
Met.

Example 9 In a 50 mL round-bottom flask equipped with a magnetic stirrer, 611 mg of 2,6-dimethylphenol and μ-oxobis @ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were added.
I) $ 3.3mg, 10m 1,4-dioxane
L and 0.1 mL of 2,6-lutidine were added and dissolved by stirring. Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, and then stirred for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 556 mg of a polymer powder. When the molecular weight of the obtained polymer was determined using gel permeation chromatography, the number average molecular weight was 13900 and the molecular weight distribution was 1.56 as a standard polystyrene equivalent value.
Met.

Example 10 In a 50 mL round-bottom flask equipped with a magnetic stirrer, 611 mg of 2,6-dimethylphenol and μ-oxobis @ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were used.
I) $ 3.3mg, 10m 1,4-dioxane
L and 0.1 mL of triethylamine were added and dissolved by stirring. Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, followed by stirring for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 556 mg of a polymer powder. When the molecular weight of the obtained polymer was determined using gel permeation chromatography, the number average molecular weight was 9630 and the molecular weight distribution was 1.28 as a standard polystyrene equivalent value.

Example 11 In a 50 mL round bottom flask equipped with a magnetic stirrer, 741 mg of 2-methyl-6-allylphenol and μ-oxobis {N, N-di (salicylidine) ethylenediaminatoiron (III)} 3 as a catalyst were added. 0.3 mg was added, and 10 mL of 1,4-dioxane and 0.1 mL of pyridine were added thereto and dissolved by stirring. Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, followed by stirring for 2 hours. After the reaction,
The reaction solution was added to 100 mL of methanol to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 655 mg of polymer powder. When NMR measurement was performed on the obtained polymer, poly (1,4
-Phenylene oxide) was confirmed. Further, the molecular weight of the polymer was determined by gel permeation chromatography. As a result, the number average molecular weight was 8710 and the molecular weight distribution was 3.42 in terms of standard polystyrene.

Example 12 In a 50 mL round-bottom flask equipped with a magnetic stirrer, 1.23 g of 2,6-diphenylphenol and μ-oxobis @ N, N-di (salicylidine) ethylenediaminatoiron (II) as a catalyst were used.
I) $ 3.3 mg was added, and 1,4-dioxane 10
mL and 0.1 mL of pyridine were added and dissolved by stirring. Further, 3.4 mL of 5 wt% hydrogen peroxide was added over 1 hour, and then stirred for 2 hours. After completion of the reaction, the reaction solution was added to 100 mL of methanol to precipitate a polymer. This was isolated by centrifugation and vacuum dried to obtain 721 mg of a polymer powder. When NMR measurement was performed on the obtained polymer, formation of poly (1,4-phenylene oxide) was confirmed. When the molecular weight was determined by gel permeation chromatography, the number average molecular weight was 1490 and the molecular weight distribution was 1.22 in terms of standard polystyrene.

[0034]

According to the method for producing poly (1,4-phenylene oxide) of the present invention, a 2,6-substituted phenol is used as a reaction raw material and a peroxide is used as an oxidizing agent.
This is a method using an iron complex as a catalyst, and can produce a target product in good yield and at low cost, and its industrial significance is great.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hideyuki Higashimura 2-13-1 Umezono, Tsukuba, Ibaraki Prefecture 3-201, Sumitomo Kagaku Umezono Company Housing (72) Takahisa Oguchi 3-5-5, Kasuga, Tsukuba, Ibaraki More・ Rischel Tsukuba Kasuga 101 Examiner Yoshiichi Eizawa (56) References JP-A-8-53545 (JP, A) JP-A-9-286854 (JP, A) JP-A-9-291146 (JP, A) (JP) B-3837 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 65/00-65/48 CA (STN)

Claims (3)

(57) [Claims] 1. Use of a peroxide as an oxidizing agent in the presence of an iron complex catalyst to obtain a compound represented by the following general formula (1): (Wherein R ₁ and R ₂ each independently represent a hydrocarbon group, a halogen group, a substituted hydrocarbon group, a hydrocarbonoxy group, an amino group or a substituted amino group) Poly (1,4) characterized by oxidative polymerization of phenol
-Phenylene oxide). 2. The method for producing poly (1,4-phenylene oxide) according to claim 1, wherein the peroxide is hydrogen peroxide. 3. An iron complex catalyst represented by the following general formula (2): (Wherein, R ₃ represents a bifunctional hydrocarbon group, and R 4 and R 5
Each independently represents hydrogen, a hydrocarbon group or a substituted hydrocarbon group, and R ₆ and R ₇ each independently represent hydrogen, a hydrocarbon group, a halogen group, a substituted hydrocarbon group, a hydrocarbon oxy group,
The poly (1,1) according to claim 1 or 2, which is an iron complex represented by an amino group or a substituted amino group.
4-phenylene oxide).