JPS62236825A - Polymerization of polyphenylene ether - Google Patents

Abstract

PURPOSE:To improve the water resistance of a catalyst and to decrease its amount of use, by adding a Ni compound, a Pb compound or a Ce compound to a catalyst for the oxidative polymerization of a phenol comprising a Mn compound, an alkanolamine and a basic compound. CONSTITUTION:A catalyst comprising a manganese compound (A) (e.g., manganese chloride), an alkanolamine (B) (e.g., N-methylethanolamine), a basic compound (C) (e.g., sodium hydroxide) and at least one compound (D) selected from among a nickel compound, a lead compound and a cerium compound (e.g., nickel chloride) is prepared. A phenol (e.g., 2,6-dimethylphenol)is oxidatively polymerized in the presence of a high-activity catalyst of improved water resistance to produce polyphenylene ether. In this way, the polymerization can be performed well by using a small amount of the catalyst and the amount of a solvent for removing the catalyst remaining in the polymer can be decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for polymerizing polyphenylene ether using a novel highly active catalyst with improved water resistance. More specifically, the present invention provides 6
When oxidative polymerization is performed using phenols with unsubstituted occlusions as raw materials in the presence of a catalyst consisting of a manganese compound, an alkanolamine, and a basic compound, a nickel compound,
The present invention relates to a method for polymerizing polyphenylene ether, which is characterized by using a highly active catalyst with improved water resistance due to the coexistence of one or more selected from lead compounds and cerium compounds.

[Conventional technology]

Conventionally, oxidized polymers of phenols that are unsubstituted at the para position are known as polyphenylene ethers (6J), which have excellent mechanical properties, electrical properties, heat resistance, etc., as well as low water absorption and dimensional stability. Due to its excellent properties, it has recently attracted attention as a thermoplastic engineering plastic.

Many combinations of copper salts, manganese salts, or cobalt salts and various amines have been proposed as polymerization catalysts for producing polyphenylene ether (by oxidative polymerization of phenols). . For example, examples of using manganese compounds include manganese salts, basic compounds, and primary and secondary compounds.

Combination with tertiary amine (Japanese Patent Publication No. 45-30355), combination of monoethanolamine or jetanolamine or both with manganese salt and basic compound (Japanese Patent Publication No. 57-44625), No. 3 Combinations of alkanolamines, manganese salts, and basic compounds (Japanese Patent Publication No. 17397/1983) are known.

Examples of using nickel compounds, lead compounds, or cerium compounds as catalysts for oxidative polymerization of phenols include:
Nickel peroxide (Japanese Patent Publication No. 45-1069) and lead dioxide (Japanese Patent Publication No. 44-28510)
etc. can be given.

[Problem that the invention seeks to solve]

However, in all of these methods, the catalytic activity is low, and the amount of manganese compounds, nickel compounds, or lead compounds used is usually 1 to 1 to 1% per phenol.
There are 200 moles, which is quite a lot.

Particularly in the case of nickel compounds or lead compounds, the amount used is large, and the amount is required to be 1 mole or more per mole of phenol. Therefore, not only does the cost of the catalyst increase, but the process of removing the catalyst residue from the produced polymer is complicated and time-consuming), and catalyst removal also requires a large amount of cost. Since the catalyst in the coalescence cannot be completely removed during the process, the quality of the polymer inevitably deteriorates due to the catalyst residue.

In addition, catalyst components are hydrolyzed by reaction product water that is produced as a by-product during oxidative polymerization of phenols, and metal components become hydroxides and exit from the reaction system, resulting in a decrease in catalytic activity. In order to achieve high catalyst activation, there was a need to develop a catalyst that would not lose its activity even in the presence of reaction product water.

In particular, improving water resistance is an important issue in continuous polymerization methods that require a long average residence time.

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

[Means for solving problems]

The present inventors have carried out intensive studies on the polymerization method of polyphenylene ether under the above-mentioned situation. As a result, they have found that nickel is Compound.

We have discovered that a highly active catalyst with excellent water resistance can be obtained by coexisting one or more selected from lead compounds and cerium compounds, and based on this knowledge, we have completed the present invention. It's arrived.

That is, the present invention provides oxidative polymerization of phenols in which the aR position of the hydroxyl group is unsubstituted in the presence of a catalyst consisting of a manganese compound, an alkanolamine, and a basic compound by contacting with an oxygen-containing gas, a nickel compound, The present invention provides a method for polymerizing polyphenylene ether, characterized in that one or more groups selected from lead compounds or cerium compounds coexist.

Manganese compounds are used as oxidative polymerization catalysts for phenols.
A system in which one or more selected from nickel compounds, lead compounds, and cerium compounds coexists with a system consisting of an alkanolamine and a basic compound has not been previously known, and this catalyst system It was completely unexpected that the compound showed high activity even in the presence of reaction product water.

The phenols used in the method of the present invention are unsubstituted phenol derivatives at the position above the hydroxyl group, represented by the general formula %. R(t R2# in general formula (1)
R3 and R4 are hydrogen atoms, halogen atoms, hydrocarbon groups,
It is a hydrocarbon group or a hydrocarbon oxy group, which may be the same or different, and the hydrocarbon group or hydrocarbon moiety does not have a tertiary-α-hydrocarbon. is preferable. Such phenols include
For example, 2,6-dimethylphenol, 2-methyl-6-
Nithylphenol, 2.6-dinitylphenol, 2-
Methyl-6-n-propylphenol, 2-methyl-6
-iso-propylphenol, 2-methyl-6-medoxyphenol, 2.6-simethoxyphenol, 2.
6-diphenylphenol, 2,3.6-trimethylphenol, 2,3,5.6-titramethylphenol,
Examples include 2,6-dimethyl-3-chlorophenol and 0-cresol.

These may be used alone or in combination of two or more.

Examples of the manganese compound used in the method of the present invention include manganese chloride, manganese bromide, manganese halides such as manganese iodide, and manganese nitrate.

W, 8 manganese, manganese salts of inorganic acids such as manganese carbonate, manganese formate, manganese acetate, manganese oxalate,
Examples include manganese salts of organic acids such as manganese stearate, manganese octylate, and manganese benzoate, as well as manganese acetylacetone, manganese hydroxide, and manganese oxide.

The preferred amount of these manganese salts to be used is 0.05 to 5 mol based on the phenol, more preferably 0.1
~1 molti.

If the amount is less than 0.05 mol, the effect of the present invention will not be achieved, and even if 5 mol is used, the effect will not be exhibited in proportion to the amount used.

Examples of the nickel compound, lead compound and cerium compound used in the present invention include halides.

Salts of inorganic acids such as sulfates, nitrates, acetates, phosphates, carbonates, and organic acid salts such as formates, acetates, oxalates, stearates, benzoates, salicylates.

Any one can be selected from acetylacetonate, hydrates, hydroxides, etc. thereof.

The amount of nickel compound, lead compound and cerium compound is 0.1 to 10 in molar ratio to manganese compound.
, preferably from 0.2 to 3.

If the amount is less than 0.1 (molar ratio), the effect of the present invention will not be sufficiently exhibited, and even if it is added in an amount of 10 (molar ratio), the effect will not be exhibited in proportion to the amount.

Further, each of these may be used alone, or two or more types may be used in combination.

The alkanolamines used in the method of the present invention include primary, secondary and tertiary alkanolamines.

Examples of primary alkanolamines are ethanolamine, 2-hydroxypropylamine.

Examples include 3-hydroxypropylamine, 2-phenylethanolamine, and 3-hydroxy-2-aminobutane.

Examples of secondary alkanolamines include N, methylethanolamine #N*ethylethanolamine, N-butylethanolamine, jetanolamine, di-
//' Lovanolamine, bis(2-phenyl-2-hydroxyethyl)amine, etc. are mentioned.

Examples of tertiary alkanolamines include triethanolamine, tri-1-pyropanolamine, tris(2
-phenyl-2-hydroxyethyl)amine, N,N dimethylethanolamine.

N,N diethylethanolamine, dimethylamino-2
- propatool and Nφ hydroxyethylmorpholine.

Although these alkanolamines are highly active as primary, secondary, and tertiary alkanolamines, the action and effect of secondary and tertiary alkanolamines are remarkable.

Further, each of these may be used alone or in combination of two or more.

In particular, by combining two or more types of alkanolamines, it has become easier to control the viscosity during the reaction).
Effects such as further improvement in thermal stability are expected.

The usage ratio of these alkanolamines is usually 0.5 mol to 20 mol per 1 mol of the total amount of one or more of the manganese compound, nickel compound, lead compound, and cerium compound. .

If the ratio of alkanolamine used is less than 0.5 mole, the effect of the present invention will not be fully exhibited, and if it exceeds 20 mole, the effect will not be exhibited considering the amount.

Examples of the basic compound used in the basic reaction medium in the method of the present invention include hydroxides, alkoxides, and phenoxy groups of group IA metals in the periodic table, quaternary ammonium hydroxides, and pyridinium hydroxy Ps. Examples include basic compounds. Examples of hydroxides of Group IA metals in the periodic table include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.; examples of alkoxy groups of the metals include lithium methoxide, sodium methoxide, potassium methoxide, Lithium ethoxide, sodium ethoxy P, potassium ethoxide, etc.
Further, examples of the 7-enoxides of the metal include sodium phenoxy r and the like. Furthermore, examples of quaternary ammonium hydroxy Ps and pyridinium hydroxides include tetramethylammonium hydroxide.

Examples include tetrabutylammonium hydroxide, trimethylbenclammonium hydroxide, and N-methylpyridinium hydroxide.

These bases may be used alone or in combination of two or more. Among these basic compounds, commercially available alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred.

The basic compound is preferably used in an anhydrous state, but if desired, it can be used in the form of an aqueous solution, such as an aqueous solution of 4O dihydroxide, and the amount used is as follows: It can be arbitrarily selected within the conventionally used range.

To prepare the catalyst used in the present invention, for example, after dissolving a manganese compound in an alcohol such as methanol,
After adding one or more selected from nickel compounds, lead compounds, and cerium compounds, alkanolamines may be added in a predetermined ratio, or alkanolamines may be added to alcoholic solutions of manganese compounds and then nickel compounds may be added. , lead compounds, and cerium compounds may be added.

The basic compound may be added to the catalyst solution or may be added to an organic medium in which phenols are dissolved.

Further, the preparation of the catalyst may be carried out in the presence of oxygen, such as under atmospheric pressure, or may be carried out in a nitrogen atmosphere as desired.

The reaction solvent used in the method of the present invention is preferably one that dissolves some or all of the catalyst components including phenols and manganese compounds. There is no particular restriction as long as it is inert to these compounds and is liquid at the reaction temperature. Examples of such solvents include chain and cyclic aliphatic hydrocarbons, aromatic hydrocarbons, etc. hydrogen,
Examples include halogenated hydrocarbons, alcohols, nitro compounds, ethers, ketones, lactones, ami-Ps, and sulfone compounds. Specific examples include hexane,
Hepmene, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, styrene, dichloromethane, chloroform.

Bromoform, monochlorobenzene, dichlorobenzene, methanol, ethanol, furonogol.

butanol, amyl alcohol, hexyl alcohol,
Benzyl alcohol, cyclohexyl alcohol, ethylene glycol, trimethylene glycol, butanediol, glycerin, β-chloroethanol, dibenzene, diethyl ether, tetrahydrofuran, dioxane, acetone.

Methyl ethyl ketone, methyl isobutyl ketone.

Examples include proviolactone and dimethylformamide. Among these, particularly suitable solvents include mixed solvents of lower alcohols such as methanol, ethanol, propatool, and butanol, and aromatic hydrocarbons such as benzene, toluene, and xylene. Moreover, you may combine several types of them arbitrarily. Polar solvents such as alcohols in the mixed solvent can be used in any proportion. For example, when it is desired to increase the molecular weight of the polyphenylene ether produced, it is preferable to use a lower proportion of the polar solvent, while when it is desired to lower the molecular weight of the polyphenylene ether, it is better to increase the proportion of the polar solvent.

The ratio of phenol to solvent can be selected within a wide range, but the oxidative polymerization is usually carried out in a reaction solution with a phenol concentration of 70% by weight, preferably from 5 to 40% by weight.

In the method of the invention, oxygen or oxygen diluted with an inert gas, for example air, is used as the oxidizing agent. Although the reaction rate decreases when air is used, it can be used satisfactorily. Regarding the reaction temperature, if it is too low, the reaction will be difficult to proceed, and if it is too high, the catalyst will be easily deactivated.
The temperature is selected from 80°C, preferably from 10 to 60°C. Although normal pressure is used as the reaction pressure, the reaction can also be carried out under increased pressure or reduced pressure if desired.

There are no particular restrictions on the post-treatment of the reaction finished liquid, but usually an acid such as hydrochloric acid or acetic acid is added to the reaction finished liquid to deactivate the catalyst, and then the produced polymer is separated and treated with alcohol, etc. Polyphenylene ether can be recovered by a simple procedure of washing with a solvent that does not dissolve the polymer and drying.

〔Effect of the invention〕

In the present invention, as a polymerization catalyst for polyphenylene ether, a flat active catalyst with improved water resistance is used, which is composed of one or more of manganese compounds, nickel compounds, lead compounds, and cerium compounds, an alkanolamine, and a basic compound. Because of this, the amount of catalyst used is significantly smaller than in conventional methods, and the amount of solvent used to remove the catalyst residue in one coalescence is also small, resulting in a reduction in solvent recovery costs. . In addition, the catalyst removal process is simplified, as the equipment for removing the catalyst can be reduced to a shed.

As described above, by using the method of the present invention, not only can polyphenylene ether be economically advantageously produced, but also the catalyst residue can be almost completely removed, resulting in the production of polyphenylene ether of excellent quality. has advantages.

〔Example〕

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

In addition, when measuring ηts p/c, the polymer was measured at 0.5
The test was conducted using a chloroform solution of WlV at 30°C using an Ubbelohde viscometer.

Example 1 2.6 dimethylphenol 709 (0,574 mol)
was dissolved in a mixed solvent of 378 g of toluene and 126 I of n-sitanol. To this, add manganese chloride (■) in advance to 126 g of methanol, and 0.341 g of tetrahydrate. ! i!
E, L: Nickel chloride hexahydrate 0.388. ! Add 0.862 N.methylethanolamine to the solution containing 9.
g, Sodium hydroxide, 38. A catalyst solution prepared by adding j9 while blowing oxygen was added. Then, while stirring the solution vigorously, oxygen gas was introduced at a flow rate of 300 d/min, and the reaction was carried out at 40° C. for 6 hours. After the reaction was completed, the polymerization solution was added to a 5-fold volume of hydrochloric acid methanol solution of 5 parts by weight to precipitate the polymer.

The ηs p/e of the precipitated polymer was 0.68.

The molar ratio of 2,6 xylenol: manganese chloride: nickel chloride was 333:1:1.

Example 2 The experiment was repeated by adding an amount of water equivalent to the reaction product water to the system of Example 1 in advance.

That is, 70 g of t-,2,6 dimethylphenol (0
, 574 mol) was dissolved in a mixed solvent of 378 g of toluene and 126 g of fi11 butanol. Add 0.341.9 of manganese chloride (If) tetrahydrate and 0.388 of nickel chloride hexahydrate to 126 g of methanol.
Add 0.8 of N-methylethanolamine to the solution of
62. 1.389 of sodium hydroxide was added to the reactor while blowing oxygen into the reactor. Add to the mixture an amount of water equivalent to the water produced by the reaction: 10.33. ji+ was added.

Next, oxygen gas was blown into the solution while vigorously stirring it, and the same procedure as in Example 1 was carried out to obtain a polymer. 6
The viscosity ηsp/e after time reaction was 0.62.

Example 3 and Comparative Examples 1 to 3 Example 2 with different amounts of manganese chloride and nickel chloride
Table 1 shows the results of repeated experiments under the same conditions.

Table 1 Example 4 The same procedure as in Example 2 was repeated except that N ethylethanolamine was used instead of ON methylethanolamine in Example 2. The viscosity ηsp/c of the polymer obtained was 0.
It was 65.

Example 5 The same operation as in Example 2 was repeated except that cerium chloride heptahydrate was used in place of nickel chloride in Example 2.

The obtained sf IJ mom-ηsp/c was 0.64.

Example 6 ηs p/c of a polymer obtained by repeating the same operation as in Example 2 except that lead dioxide was used in place of nickel chloride in Example 2 and jetanolamine was used in place of N-methylethanolamine. was 0.72.

Example 7 In Example 2, 0.0% lead dioxide was added as a catalyst component.
The experiment was repeated with the addition of 2069 (0.15 mo1%/monomer) and jetanolamine 0.603, lit (Imo1%/monomer). The obtained polymer had a ηsp/c of 0.78.

Claims (1)

[Claims] It is characterized by the coexistence of one or more selected from nickel compounds, lead compounds and cerium compounds when oxidatively polymerizing phenols in the presence of a catalyst consisting of a manganese compound, an alkanolamine and a basic compound. Polyphenylene ether polymerization method