JP2010270250A - Method for producing new polyphenylene ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve productivity per unit volume of a reactor by suppressing foaming in the early stages of oxidative polymerization. <P>SOLUTION: A polymerization solution composed of 10-25 pts.mass of a phenolic compound (M), 75-90 pts.mass of an aromatic solvent (A), 0.1-10 pts.mass of a catalyst (C), and 0.000001-0.0001 pt.mass of a defoaming agent (D) is prepared. The oxygen-containing gas (O) is passed through the polymerization solution to perform oxidative polymerization of the phenolic compound (M), thereby obtaining polyphenylene ether with ηsp/c of 0.3-1.0 dL/g. Wherein, the total pts.mass of the phenolic compound (M) and the aromatic solvent (A) is 100 pts.mass. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a catalyst containing a phenolic compound, a copper compound, a bromine compound, a diamine compound, a tertiary monoamine compound, and a secondary monoamine compound, and an oxygen-containing gas (O In the method of producing a polyphenylene ether by oxidative polymerization of a phenolic compound, the foaming generated at the initial stage of oxidative polymerization of the conventional method is suppressed, and the production is improved.

Conventionally, various methods have been disclosed for producing polyphenylene ether by oxidative polymerization of a phenolic compound.
In Patent Documents 1 to 4, as an effective catalyst for oxidative polymerization of a phenolic compound, a catalyst in which a copper compound and an amine are combined, a catalyst in which a copper compound and a halogen compound are combined, a primary amine, a secondary amine, and a tertiary Catalysts using amines, monoamines, diamines, polyamines, and catalysts using tetraalkyl type diamines such as N, N, N ′, N′-tetramethyl-1,4-butanediamine are disclosed.
In Patent Documents 5 to 6, as a catalyst effective for oxidative polymerization, a catalyst in which a copper compound, an iodine compound and a tetraalkyl type diamine are combined is proposed.

Moreover, in patent documents 7-9, the catalyst which combined tertiary compounds, such as a copper compound, a bromine compound, and N, N'-di-t-butylethylenediamine and n-butyldimethylamine, a copper compound, a bromine compound, and tertiary Catalysts in combination with amines and secondary monoamines are disclosed.
Further, Patent Document 10 includes a copper compound and a secondary aliphatic amine or secondary aliphatic amine, an aniline having a special structure, and N, N, N ′, N′-tetramethyl 1,3-diaminopropane. Catalysts with improved water resistance are disclosed.
Further, Patent Documents 11 to 13 disclose that the catalyst is highly activated and the productivity of polyphenylene ether is improved by preparing a polymerization catalyst and a phenolic compound in an inert gas atmosphere.

Moreover, in the oxidative polymerization of a phenolic compound, there is a problem that the catalyst is deactivated by water generated as a by-product. As methods for overcoming this problem, Patent Documents 14 and 15 disclose oxidative polymerization methods for efficiently removing water.
In addition, in the oxidative polymerization of a phenolic compound, ensuring the safety is an important factor because an oxygen-containing gas is passed through a solution composed of an organic solvent and a phenolic compound to perform a polymerization reaction. As a method for ensuring safety, Patent Document 16 discloses a method for suppressing static electricity in oxidative polymerization.
Further, Patent Document 17 discloses a method for suppressing ignition by controlling the oxygen partial pressure of an oxygen-containing gas used for oxidative polymerization.

In addition, in the conventional method for producing polyphenylene ether, a sufficient polymerization rate can be secured at the initial stage of oxidative polymerization, but at the end of the oxidative polymerization, there is a problem that the polymerization rate is extremely reduced, and this problem is solved. Therefore, Patent Document 18 and the like disclose a method of increasing the amount of oxygen-containing gas flowing to the polymerization solution at the end of oxidative polymerization.
In the conventional method for producing polyphenylene ether, the oxygen-containing gas is passed through the polymerization solution to oxidatively polymerize the phenolic compound. Therefore, at the initial stage of the oxidative polymerization, the volume of the polymer solution is 5% to 30% with respect to the volume of the polymerization solution. Foaming occurs.
For this reason, in the conventional method for producing polyphenylene ether, it is necessary to design the capacity of the reactor in consideration of the foamed portion in the initial stage of oxidative polymerization.

However, in the conventional method for producing polyphenylene ether, the foaming of the polymerization solution gradually stops as the oxidative polymerization proceeds, and the capacity considering the foamed portion is not effectively utilized at the end of the polymerization.
Further, in the conventional method for producing polyphenylene ether, there is a possibility that a polymerization solution, a catalyst component, etc. adhere to the foamed portion of the polymerization solution and become a cause of impurities.

Japanese Patent Publication No. 36-018692 US3306875 Specification US 3344116 Specification US3432466 Specification Japanese Examined Patent Publication No. 52-017075 Japanese Examined Patent Publication No. 52-017076 Japanese Patent Publication No.58-053012 Japanese Examined Patent Publication No.59-053012 Japanese Examined Patent Publication No. 59-023332 Japanese Patent Laid-Open No. 64-03131 JP 59-179620 A JP-A 61-001453 JP 2002-003596 A Japanese Patent Laid-Open No. 2000-281776 JP 2001-342251 A JP 2001-335631 A JP 2001-342250 A JP 2002-003597 A

  An object of the present invention is to improve productivity per unit volume of the reactor by suppressing foaming at the initial stage of the oxidation polymerization.

  The present inventor completed the present invention as a result of studying the problems of the conventional method for producing polyphenylene ether, that is, the effective utilization of the foamed portion of the polymerization solution at the initial stage of polymerization. It came to.

That is, the present invention
1. In the present invention, 10 to 25 parts by mass of the phenolic compound (M) and 75 to 90 parts by mass of the aromatic solvent (A), 0.1 to 10 parts by mass of the catalyst (C), and 0.000001 of the antifoaming agent (D). A polymerization solution composed of ~ 0.0001 parts by mass is prepared, and an oxygen-containing gas (O) is passed through this to oxidatively polymerize the phenolic compound (M), and ηsp / c 0.3 to 1.0 dl / g A process for producing polyphenylene ether, characterized in that polyphenylene ether is obtained. (Here, the total mass part of the phenolic compound (M) and the aromatic solvent (A) is 100 parts by mass.)
2. 2. The method for producing polyphenylene ether according to 1 above, wherein the antifoaming agent (D) is a fluorosilicone compound-based antifoaming agent.
3. 3. The production of polyphenylene ether according to 1 or 2 above, wherein the phenolic compound (M) is 2,6-dimethylphenol or a mixture of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Method.

4). 4. The polyphenylene as described in any one of 1 to 3 above, wherein the catalyst (C) is a catalyst containing a copper compound, a bromine compound, a diamine compound, a tertiary monoamine compound and a secondary monoamine compound as essential components. A method for producing ether.
5). 5. The method for producing polyphenylene ether according to any one of 1 to 4 above, wherein the aromatic solvent (A) is toluene, xylene, or ethylbenzene.
6). 6. The method for producing polyphenylene ether according to any one of 1 to 5, wherein the oxygen-containing gas (O) is an oxygen-containing gas (O) having an oxygen concentration of 5 to 25% by volume.
7). Any one of said 1-6 characterized by oxygen-containing gas (O) being oxygen-containing gas (O) which diluted air with nitrogen-containing gas and adjusted oxygen concentration to 8-12 volume%. The manufacturing method of polyphenylene ether as described in 1 ..
8). An oxygen-containing gas (O) having an oxygen partial pressure of 0.00147 MPa or more and 0.0883 MPa or less is used, and the absolute pressure in the reactor gas phase is controlled to 0.098 MPa or more and less than 0.392 MPa. 8. The method for producing polyphenylene ether according to any one of 1 to 7 above.

  According to the present invention, an oxygen-containing gas (O) is contained in a polymerization solution comprising a phenolic compound, a copper compound, a bromine compound, a diamine compound, a tertiary monoamine compound, and a secondary monoamine compound, and an aromatic solvent. In the method for producing a polyphenylene ether by oxidative polymerization of a phenolic compound, the foamed portion at the initial stage of oxidative polymerization can be effectively utilized, and the productivity per unit volume of the reactor used for production is improved.

  Examples of the polyphenylene ether of the present invention include a homopolymer or a copolymer having a repeating unit represented by the following formula (1).

(In the above formula (1), R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, hydrocarbon oxy. R ₂ and R ₃ are Each independently represents hydrogen, primary or secondary lower alkyl, or phenyl.)

Specific examples of the homopolymer of polyphenylene ether resin include, for example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4) -Phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6) -Hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether and the like.
Of these, poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred.

The polyphenylene ether resin copolymer is a copolymer containing a phenylene ether unit as a single unit. Specific examples thereof include, for example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, Examples thereof include a copolymer of dimethylphenol, 2,3,6-trimethylphenol, and o-cresol.
The phenolic compound used in the present invention is a compound having a structure represented by the following formula (2).

(In the above formula (2), R ₅ and R ₇ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, hydrocarbon oxy. R ₆ and R ₈ are Each independently represents hydrogen, primary or secondary lower alkyl, or phenyl.)

Examples of such compounds include 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol. 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2- Methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-bis- (4-fluorophenyl) phenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, etc. It is. These compounds may be used alone or in combination of two or more. Moreover, even if it contains a small amount of phenol, o-cresol, m-cresol, p-cresol, 2,4-dimethylphenol, 2-ethylphenol, etc., it does not interfere.
Among these phenolic compounds, 2,6-dimethylphenol or a mixture of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and 2,6-dimethylphenol is particularly preferable.

The aromatic solvent used in the present invention is not particularly limited, but dissolves a low molecular weight phenolic compound and dissolves part or all of the catalyst mixture. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and nitro compounds such as nitrobenzene. be able to.
As the aromatic solvent used in the present invention, toluene, xylene or ethylbenzene is preferable, and toluene is very preferable.
In an amount as long as the effects of the present invention are not hindered, the aromatic solvent can be mixed with a solvent having a property compatible with water. Solvents that are compatible with water include, for example, alcohols such as methanol, ethanol, and propanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and ethyl formate, amides such as dimethylformamide, and dimethyl sulfoxide. And sulfoxides such as One or more kinds of solvents can be further mixed if necessary.

The present invention can act particularly preferably as long as the solvent used is substantially incompatible with water. Examples of frequently used solvents are aromatic hydrocarbon solvents such as toluene and xylene. By selecting the ratio of good solvent and poor solvent for polyphenylene ether, which is a polymer obtained by oxidative polymerization of phenolic compounds, it can be used as a solution polymerization method, and by increasing the ratio of poor solvent, It is also a precipitation polymerization method in which the coalesced precipitate as particles in the reaction solvent.
The catalyst of the present invention is for producing a polyphenylene ether by efficiently oxidizing and polymerizing a phenolic compound by passing an oxygen-containing gas (O) through a polymerization solution comprising a phenolic compound, an aromatic solvent and a catalyst. It is an effective oxidation catalyst.
As the catalyst of the present invention, a catalyst comprising (a copper compound and a bromine compound) and (one or more selected from a diamine compound, a tertiary monoamine compound, and a secondary monoamine compound) can be used. The catalyst which has a compound, a diamine compound, a tertiary monoamine compound, and a secondary monoamine compound as an essential component can be used more preferably.

  As the copper compound used as the catalyst component of the present invention, a cuprous compound, a cupric compound or a mixture thereof can be used. Examples of the cuprous compound include cuprous oxide, cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Examples of cupric compounds include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Among these, preferred compounds are cuprous oxide, cuprous chloride, cupric chloride, cuprous bromide and cupric bromide for cuprous and cupric compounds. These copper salts may be synthesized at the time of use from the corresponding halogen or acid with oxides, carbonates, hydroxides and the like. For example, it can be obtained by mixing cuprous oxide and hydrogen bromide (solution). A particularly preferable copper compound is a cuprous compound. These copper compounds may be used alone or in combination of two or more.

Examples of the bromine compound used as the catalyst component of the present invention include hydrogen bromide, sodium bromide, potassium bromide, tetramethylammonium bromide, tetraethylammonium bromide and the like. These can be used as an aqueous solution or a solution using an appropriate solvent. These bromine compounds may be used alone or in combination of two or more. The most preferred combination of copper compound and bromine compound is an aqueous solution of cuprous oxide and hydrogen bromide. Although the usage-amount of these compounds is not specifically limited, 2 times or more and 10 times or less are preferable as a bromine atom with respect to the molar amount of a copper atom, From 0.02 mol as a copper atom with respect to 100 mol of a phenolic compound. The range is 0.6 mol.
The diamine compound used as the catalyst component of the present invention is a diamine compound represented by the following formula (3). Of the diamine compounds having the above structure, a preferred diamine compound is N, N′-di-t-butylethylenediamine. Although the usage-amount of a diamine compound is not specifically limited, It is 0.5 times mole amount or more with respect to the number-of-moles of copper atom normally used, and an upper limit is not critical.

(In the above formula (3), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, and all are not simultaneously hydrogen. ₅ is a linear or methyl branched alkylene group having 2 to 5 carbon atoms.)

  The tertiary monoamine compound used as the catalyst component of the present invention 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. The amount of these used is not particularly limited, but a range of 0.1 mol to 15 mol is preferable with respect to 100 mol of the phenolic compound.

  Secondary monoamine compounds used as the catalyst component of the present invention are dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, Examples include dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine and the like. Examples of N- (substituted or unsubstituted phenyl) alkanolamines include N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N- (m-methylphenyl) ethanolamine, N- (p-methyl). Phenyl) ethanolamine, N- (2 ′, 6′-dimethylphenyl) ethanolamine, N- (p-chlorophenyl) ethanolamine and the like. Examples of N-hydrocarbon substituted anilines include N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine, and the like. Is not limited. These secondary monoamine compounds may be used alone or in combination of two or more. The amount used is not particularly limited, but is generally in the range of 0.05 mol to 15 mol with respect to 100 mol of the phenolic compound.

  In the present invention, the addition of a tetraalkylammonium salt compound, a polyethylene glycol group-containing alkylamine, or a polyethylene glycol group-containing alkylammonium salt compound in a range not exceeding 0.1 wt% in the entire charged mixture can achieve the effects of the present invention. Although it is preferable because it is even more effective, it is not necessary to contain it. Examples of such compounds are those having a structure represented by the following formula (4), (5) or (6).

(In the above formula (4), R ₁ , R ₂ , R ₃ and R ₄ are each independently a linear or branched alkyl group having 1 to 22 carbon atoms, X is a paired anion, preferably Cl ⁻ , Br ⁻ ).

(In the above formula (5), R ₅ represents a linear or branched alkyl group having 1 to 22 carbon atoms, and R ₆ is — (CH ₂ CH ₂ O) n—H in addition to the group defined as R _5. The group represented by [n is an integer of 1 to 40] may be used, and R ₇ is a group represented by — (CH ₂ CH ₂ O) n—H [n is an integer of 1 to 40]. .)

(In the above formula (6), R ₈ and R ₉ represent a linear or branched alkyl group having 1 to 22 carbon atoms, and R ₁₀ is in addition to the group defined as R ₈ — (CH ₂ CH ₂ O). n—H [n is an integer of 1 to 40] may be used, and R ₁₁ is represented by — (CH ₂ CH ₂ O) n—H [n is an integer of 1 to 40]. X is a pairing anion, preferably an anion selected from Cl ⁻ and Br ⁻ ).

  A representative example of such a compound that can be suitably used in the present invention is trioctylmethylammonium chloride known under the trade names of Aliquat 336 (manufactured by Henkel) and Capriquat (manufactured by Dojindo Laboratories).

Regarding the temperature of the polymerization solution of the present invention, if the temperature is too low, the reaction is difficult to proceed, and if it is too high, the catalyst may be deactivated, so that the temperature is 0 to 80 ° C., preferably 10 to 60 ° C. Is preferred. In many cases, good results are obtained when the temperature is set lower in the first half of the polymerization and higher in the second half of the polymerization.
In the method for preparing a polymerization solution of the method for producing polyphenylene ether of the present invention, a phenolic compound (M), an aromatic solvent (A), a catalyst (C), and an antifoaming agent (D) are each independently a reactor. Alternatively, the phenolic compound (M), the catalyst (C), and the antifoaming agent (D) may be previously dissolved in the aromatic solvent (A) and introduced into the reactor.

A preferable method for adjusting the polymerization solution in the method for producing polyphenylene ether of the present invention is to first react the catalyst (C) dissolved in a part of the aromatic solvent (A) and the antifoaming agent (D). The phenolic compound (M) dissolved in the remaining aromatic solvent (A) is then introduced into the reactor.
In the method for producing polyphenylene ether of the present invention, the weight of the phenolic compound (M), aromatic solvent (A), catalyst (C), and antifoaming agent (D) in the polymerization solution is adjusted to the phenolic weight in the preparation of the polymerization solution. The weight when the introduction of the compound (M), the aromatic solvent (A), the catalyst (C), and the antifoaming agent (D) into the reactor is completed.
In the method for producing the polyphenylene ether of the present invention, the start of aeration of the oxygen-containing gas (O) is not particularly limited, but in preparing the polymerization solution, the phenolic compound (M), the aromatic solvent (A), the catalyst (C) After introducing any of these into the reactor, it is preferable to start aeration of the oxygen-containing gas (O).

The oxygen-containing gas (O) in the present invention is prepared by mixing and adjusting oxygen and an arbitrary inert gas so that the oxygen concentration is within the range of the present invention, using air, or combining air and an arbitrary inert gas. Mix and adjust. Any inert gas can be used as long as it has no great influence on the polymerization reaction. Typically nitrogen.
In the present invention, the oxygen-containing gas (O) is preferably an oxygen-containing gas (O) having an oxygen concentration of 5 to 25% by volume. In the present invention, the oxygen-containing gas (O) is more preferably an oxygen-containing gas (O) obtained by diluting air with a nitrogen-containing gas and adjusting the oxygen concentration to 8 to 12% by volume.
In the present invention, when the oxygen concentration of the unreacted gas after aeration of the oxygen-containing gas (O) exceeds 11.6%, an inert gas such as nitrogen is introduced into the reactor gas phase, and the oxygen concentration Is controlled to 11.6% or less.

The aeration rate of the oxygen-containing gas (O) of the present invention is not particularly limited, but a preferable aeration rate is 0.5 Nl / min to 15 Nl / min with respect to 1 kg of the phenolic compound subjected to the polymerization reaction. This amount is not critical, but if it is too small, it takes a very long time to reach the desired molecular weight and the productivity deteriorates. On the other hand, if the amount is too large, problems such as excessive equipment and an increased amount of exhaust gas occur, which impairs economic efficiency.
The cause of the foaming of the polymerization solution at the initial stage of the oxidative polymerization is not clear, but since the foaming subsides when the oxidative polymerization is continued and the phenolic compound in the polymerization solution is consumed, the phenolic compound is present in the polymerization solution. It is thought that there is some relationship between this and foaming.

The antifoaming agent (D) in the method for producing polyphenylene ether of the present invention is an antifoaming agent that effectively suppresses foaming of the polymerization solution.
Furthermore, the antifoaming agent (D) in the method for producing polyphenylene ether of the present invention is an antifoaming agent that does not lower the polymerization activity.
The antifoaming agent (D) in the method for producing polyphenylene ether of the present invention is preferably an antifoaming agent comprising a fluorosilicone compound-based antifoaming agent.
The antifoaming agent (D) in the method for producing polyphenylene ether of the present invention is preferably FA603 fluorosilicone antifoaming agent manufactured by Shin-Etsu Silicone or FQF501 fluorosilicone antifoaming agent manufactured by Toshiba Silicone.
In the method for producing polyphenylene ether of the present invention, it is preferable to add 0.000001 to 0.0001 parts by mass of an antifoaming agent (D).
In the method for producing polyphenylene ether of the present invention, it is more preferable to add 0.000003 to 0.00005 parts by mass of an antifoaming agent (D).
In the method for producing polyphenylene ether of the present invention, it is particularly preferable to add 0.000005 to 0.00003 parts by mass of an antifoaming agent (D).

In the method for producing polyphenylene ether of the present invention, the polymerization solution does not substantially foam.
The fact that the polymerization solution that occurs at the initial stage of the oxidative polymerization of the present invention does not substantially foam means a state in which the foamed portion is approximately 1 part by volume or less with respect to 100 parts by volume of the polymerization solution.
In the present invention, since the polymerization solution does not substantially foam, the capacity of the reactor designed for the foamed portion of the polymerization solution can be utilized by a conventional method.
That is, according to the present invention, when the reactor of the same capacity is used, the capacity of the reactor used for the foamed portion of the polymerization solution can be utilized as compared with the conventional method.
The method for stopping the polymerization reaction of the present invention 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 added to the reaction solution to deactivate the catalyst, and the polymerization is stopped.
After termination of the polymerization, the produced polymer is separated, washed with a solvent that does not dissolve the polymer such as methanol, and dried to recover polyphenylene ether.

  As the best mode for carrying out the present invention, 2,6-dimethylphenol is used as a phenolic compound, cuprous oxide as a copper compound, hydrogen bromide as a bromine compound (used in an aqueous solution), N, N′-di-t-butylethylenediamine (hereinafter abbreviated as Dt) as the diamine compound, N, N-di-n-butylamine (hereinafter abbreviated as DBA) as the secondary monoamine compound, N, Although N-dimethyl-n-butylamine (hereinafter abbreviated as BD) is used in combination, the present invention should not be limited at all by these examples. The viscosity (ηsp / c) of polyphenylene ether is a value measured using a Ubbelohde viscometer at 30 ° C. with a 0.5 g / 100 ml chloroform solution of the polymer. The unit is represented by dl / g.

  A general procedure in Examples and Comparative Examples is described below.

[General procedure]
In the examples and comparative examples of the present invention, as a reactor, a sparger for introducing an oxygen-containing gas (O), a stirring turbine blade, and a sampling discharge valve are provided at the bottom of a cylindrical reactor having an inner diameter of 16 cm. A baffle, temperature control device, and a viewing window for checking the internal state are provided on the side of the reactor, and a polymerization solution component inlet and a decanter for condensate separation are attached to the vent gas line at the top of the reactor. A 10 liter jacketed autoclave reactor equipped with a reflux condenser with control valve was used.
In Examples and Comparative Examples of the present invention, 2,6-dimethylphenol was used as the phenolic compound (M).
In Examples and Comparative Examples of the present invention, toluene was used as the aromatic solvent (A).

The addition amount of each component of the catalyst (C) used in all Examples and Comparative Examples of the present invention is 1.288 g of cuprous oxide and 47% aqueous solution of hydrogen bromide with respect to 1000 g of 2,6-dimethylphenol. 7.749 g, N, N′-di-t-butylethylenediamine; 3.104 g, dimethyl-n-butylamine; 38.11 g, di-n-butylamine;
In the examples of the present invention, FA603 fluorosilicone antifoaming agent manufactured by Shin-Etsu Silicone Co., Ltd. and FQF501 fluorosilicone antifoaming agent manufactured by Toshiba Silicone Co. were used as the antifoaming agent (D).
In Examples and Comparative Examples of the present invention, an oxygen-containing gas (O) having an absolute pressure of 0.108 MPa and an oxygen concentration of 9% was used as the oxygen-containing gas (O) to be vented. (The oxygen partial pressure of this oxygen-containing gas (O) is 0.108 MPa × 0.09 = 0.00972 MPa.)
In the examples and comparative examples of the present invention, the oxygen-containing gas (O) was vented at a rate of 4 Nl / min · kg with respect to 1 kg of 2,6-dimethylphenol in the polymerization solution.

In the examples and comparative examples of the present invention, 1 Nl / min nitrogen was introduced into the gas phase part of the reactor for safety. In addition, the control valve downstream of the reflux condenser was adjusted to control the absolute pressure in the reactor gas phase to 0.108 MPa.
In the examples and comparative examples of the present invention, first, a polymerization solution composed of toluene, 2,6-dimethylphenol and the catalyst (C) in the amounts specified in the examples and comparative examples was prepared, and this was added to the reactor It introduce | transduced into the inlet and the temperature of the polymerization solution was adjusted to 40 degreeC. Until the completion of oxidative polymerization, the temperature of the polymerization solution was adjusted to 40 ° C.
In Examples and Comparative Examples of the present invention, the polymerization solution was stirred, and oxygen-containing gas (O) was introduced from a sparger to perform oxidative polymerization. The time when the introduction of the oxygen-containing gas (O) was started was taken as the polymerization start time.
In the examples and comparative examples of the present invention, after separating the aqueous phase from the polymerization solution, the polymerization solution was dropped into an equal volume of methanol to precipitate polyphenylene ether.
The precipitated polyphenylene ether was further washed three times with an equal volume of methanol, filtered, and then vacuum dried at 145 ° C. to obtain a measurement polyphenylene ether.
In Examples and Comparative Examples of the present invention, a chloroform solution having a concentration of 0.5 g / dl of polyphenylene ether for measurement was prepared, and ηsp / c was measured using an Ubbelohde viscometer.

[Example 1]
2,6-dimethylphenol; 1.51 kg and toluene; 6.89 kg, a specified amount of catalyst (C) defined in the above general procedure, and FA603 fluorosilicone antifoaming agent (D) manufactured by Shin-Etsu Silicone Co., Ltd. A polymerization solution composed of 1 mg was prepared, introduced into a reactor, the liquid temperature was adjusted to 40 ° C., and then oxygen-containing gas (O) was passed through a sparger to oxidize 2,6-dimethylphenol. Polymerized. Substantially no foaming of the polymerization solution was observed during oxidative polymerization. The height from the bottom of the reactor to the polymerization solution liquid level was 44 cm. Oxidation polymerization was stopped 150 minutes after the start of oxidative polymerization, and polyphenylene ether for measurement was obtained according to the above general procedure.
The amount of polyphenylene ether for measurement obtained was 1.40 kg.
The polyphenylene ether for measurement had a ηsp / c of 0.75.

[Example 2]
2,6-dimethylphenol; 1.51 kg and toluene; 6.89 kg, a specified amount of catalyst (C) defined in the above general procedure, and FQF501 fluorosilicone antifoaming agent (D) manufactured by Toshiba Silicone A polymerization solution composed of 3 mg was prepared, introduced into the reactor, the liquid temperature was adjusted to 40 ° C., and oxygen-containing gas (O) was passed through a sparger to oxidize 2,6-dimethylphenol. Polymerized. Substantially no foaming of the polymerization solution was observed during oxidative polymerization. The height from the bottom of the reactor to the polymerization solution liquid level was 43 cm. Oxidation polymerization was stopped 150 minutes after the start of oxidative polymerization, and polyphenylene ether for measurement was obtained according to the above general procedure.
The amount of polyphenylene ether for measurement obtained was 1.42 kg.
The polyphenylene ether for measurement had a ηsp / c of 0.76.

[Comparative Example 1]
2,6-dimethylphenol; 1.26 kg and toluene; 5.74 kg, a polymerization solution composed of a specified amount of catalyst (C) defined in the above general procedure was prepared, and this was introduced into the reactor. After adjusting the liquid temperature to 40 ° C., oxygen-containing gas (O) was passed through a sparger to oxidatively polymerize 2,6-dimethylphenol. When oxidative polymerization was started, foaming of the polymerization solution was observed. The height from the liquid level to the upper part of the foamed part was 13 cm at the maximum, and the height from the lower end of the reactor was 47 cm. After 54 minutes of polymerization, the foaming stopped. In the foamed portion, deposition of a polymerization solution and a catalyst component was observed. Oxygen-containing gas (O) was continuously vented, but no bubbling was observed. Oxidation polymerization was stopped 150 minutes after the start of oxidative polymerization, and polyphenylene ether for measurement was obtained according to the above general procedure.
The amount of polyphenylene ether for measurement obtained was 1.18 kg.
The polyphenylene ether for measurement had a ηsp / c of 0.74.

[Comparative Example 2]
2,6-dimethylphenol; 1.51 kg and toluene; 6.89 kg, a polymerization solution composed of a specified amount of catalyst (C) defined in the above general procedure was prepared, and this was introduced into the reactor. After adjusting the liquid temperature to 40 ° C., oxygen-containing gas (O) was passed through a sparger to oxidatively polymerize 2,6-dimethylphenol. When oxidative polymerization was started, foaming of the polymerization solution was observed. The foamed polymerization solution entered the vent gas line at the top of the reactor and was ejected from the gas line outlet. Since oxidative polymerization could not be continued, it was interrupted.
No polyphenylene ether for measurement was obtained.

[Comparative Example 3]
2,6-dimethylphenol: 1.51 kg and toluene: 5.49 kg, a polymerization solution composed of a specified amount of catalyst (C) defined in the above general procedure was prepared, and this was introduced into the reactor. After adjusting the liquid temperature to 40 ° C., oxygen-containing gas (O) was passed through a sparger to oxidatively polymerize 2,6-dimethylphenol. When oxidative polymerization was started, foaming of the polymerization solution was observed. The height from the liquid level to the top of the foamed part was 14 cm at the maximum, and the height from the lower end of the reactor was 48 cm. After the start of polymerization, foaming was cured in 55 minutes. In the foamed portion, deposition of a polymerization solution and a catalyst component was observed. Oxygen-containing gas (O) was continuously vented, but no bubbling was observed. Since the viscosity of the polymerization solution increased 145 minutes after the start of oxidative polymerization and stirring could not be continued sufficiently, the oxidative polymerization was stopped.
The amount of polyphenylene ether for measurement obtained was 1.17 kg.
The polyphenylene ether for measurement had a ηsp / c of 0.70.
After discharging the polyphenylene ether, a large amount of polymerization solution and deposits of catalyst components were observed inside the reactor.

  The present invention relates to a phenolic compound, a copper compound, a bromine compound, a diamine compound, a tertiary monoamine compound, a catalyst composed of a secondary monoamine compound, and a polymerization solution comprising an aromatic solvent. The productivity of the method for producing polyphenylene ether by oxidative polymerization is improved.

Claims (8)

  In the present invention, the phenolic compound (M) is 10 to 25 parts by mass, the aromatic solvent (A) is 75 to 90 parts by mass, the catalyst (C) is 0.1 to 10 parts by mass, and the antifoaming agent (D) is 0.000001. A polymerization solution composed of ~ 0.0001 parts by mass is prepared, and an oxygen-containing gas (O) is passed through this to oxidatively polymerize the phenolic compound (M), and ηsp / c 0.3 to 1.0 dl / g A process for producing polyphenylene ether, characterized in that polyphenylene ether is obtained. (Here, the total mass part of the phenolic compound (M) and the aromatic solvent (A) is 100 parts by mass.)   The method for producing a polyphenylene ether according to claim 1, wherein the antifoaming agent (D) is a fluorosilicone compound-based antifoaming agent.   The polyphenylene ether according to claim 1 or 2, wherein the phenolic compound (M) is 2,6-dimethylphenol or a mixture of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Production method.   The catalyst (C) is a catalyst containing a copper compound, a bromine compound, a diamine compound, a tertiary monoamine compound, and a secondary monoamine compound as essential components. A method for producing polyphenylene ether.   The method for producing a polyphenylene ether according to any one of claims 1 to 4, wherein the aromatic solvent (A) is toluene, xylene, or ethylbenzene.   The method for producing polyphenylene ether according to any one of claims 1 to 5, wherein the oxygen-containing gas (O) is an oxygen-containing gas (O) having an oxygen concentration of 5 to 25% by volume.   The oxygen-containing gas (O) is an oxygen-containing gas (O) prepared by diluting air with a nitrogen-containing gas and adjusting the oxygen concentration to 8 to 12% by volume. The manufacturing method of polyphenylene ether as described in claim | item.   An oxygen-containing gas (O) having an oxygen partial pressure of 0.00147 MPa or more and 0.0883 MPa or less is used, and the absolute pressure in the gas phase part of the reactor is controlled to 0.098 MPa or more and less than 0.392 MPa. The manufacturing method of the polyphenylene ether of any one of Claims 1-7.