JPS62181333A - Polymerization of polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether having excellent quality with simplified catalyst-removing process decreasing the amount of catalyst, by carrying out oxidative polymerization of a phenolic compound in the presence of a specific catalyst composed of a manganese compound, a cobalt compound, etc., and having high water-resistance and activity. CONSTITUTION:The objective polymer can be produced by the oxidative polymerization of (A) a phenolic compound having unsubstituted p-site based on phenolic group (e.g. 2,6-dimethylphenol) in the presence of (B) a catalyst composed of (B1) 0.05-5mol% manganese compound (e.g. manganese chloride) based on the component A, (B2) 0.1-10mol (based on 1mol of the component B1) of a cobalt compound [e.g. cobalt(II) chloride], (B3) 0.5-2mol (based on 1mol of B1+B2) of an alkanolamine (e.g. triethanolamine) and (B4) a basic compound (e.g. sodium hydroxide).

Description

[Detailed Description of the Invention] [Industrial Application Field] * 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 uses phenols unsubstituted at the para position relative to the hydroxyl group as raw materials to produce manganese compounds,
This 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 a cobalt compound during oxidative polymerization in the presence of a catalyst consisting of an alkanolamine and a basic compound. be.

[Conventional technology]

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

By the way, 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, as an example of using a manganese compound, a combination of a manganese salt, a basic compound, and a primary, secondary, or tertiary amine (% Kosho 45-3
0355 Publication), a combination of monoethanolamine or jetanolamine, or both, with a manganese salt and a basic compound (Japanese Unexamined Patent Application Publication No. 57-44625), a combination of a tertiary alkanolamine, a manganese salt and a basic compound (Japanese Patent Publication No. 48-17397) is known.

Examples of using a cobalt compound include a method of polymerizing phenols in the presence of a cobalt compound and a basic compound such as an alkali metal hydroxide, alkoxide, or phenoxide (% Publication No. 33432/1983); A method of polymerizing phenols in the presence of a complex consisting of an amine (% Publication No. 42-4673) has been proposed.

Another example of using a manganese compound and a cobalt compound in combination is a method in which a chelate compound containing cobalt is used as a main catalyst, and a salt of manganese, iron, cobalt, nickel, etc. is used as a co-catalyst in the presence of a basic compound (especially Kosho 48-26
392, Japanese Patent Publication No. 48-26393), combination of transition metal trinuclear complex and amine compound (Japanese Patent Publication No. 52-300)
Publication No. 39), etc. have been proposed.

(Zero problems to be solved by the invention) However, in all of these methods, the catalytic activity is low, and the amount of manganese compound or coco/ζ site compound used is extremely high at 50 molar to 50 molar relative to the phenol. It is often used in Therefore, not only does the cost of the catalyst increase, but the process of removing the residual catalyst from the produced polymer becomes complicated, and removal of the catalyst also requires a large amount of cost. Furthermore, since the catalyst in the polymer cannot be completely removed, the quality of the polymer inevitably deteriorates due to residual catalyst.

In addition, there are problems in that 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 the reaction system, resulting in a decrease in catalyst activity. Therefore, in order to increase the activity of the catalyst, 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 is a strong demand for the development of highly active catalysts with improved water resistance.

(Means for Solving the Problems) As a result of intensive studies on the polymerization method of polyphenylene ether under the above circumstances, the present inventors found that in the presence of a catalyst consisting of a manganese compound, an alkanolamine, and a basic compound, In addition, we discovered that a highly active catalyst with extremely excellent water resistance can be obtained by coexisting a cobalt compound when oxidatively polymerizing phenols5, and based on this knowledge, we have completed the present invention.

That is, the present invention provides a method for oxidatively polymerizing phenols unsubstituted at the (l-position) by contacting them with an oxygen-containing gas to hydroxyl groups in the presence of a catalyst consisting of a manganese compound, an alkanolamine, and a basic compound. The present invention provides a method for polymerizing polyphenylene ether, which is characterized by the coexistence of a compound.

As a polymerization catalyst for phenols, manganese compounds,
The catalytic system consisting of a cytosolic compound, an alkanolamine, and a basic compound was previously unknown, and it was completely unexpected that this catalytic system would exhibit 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 para position relative to the hydroxyl group, represented by -. R1+R2+R3 and R in general formula (I) are hydrogen atoms, halogen atoms, hydrocarbon groups, halohydrocarbon groups, or hydrocarbonoxy groups, and they may be the same or different; Preferably, the group or hydrocarbon moiety is free of tertiary-α-hydrocarbons. Such phenols include, for example, 2.6
-Simethylphenol, 2-methyl-6-nitylphenol, 2,6-diethylphenol, 2-methyl-6-
n-propylphenol, 2-methyl-6-iso-propylphenol, 2-methyl-6-medoxyphenol, 2,6-simethoxyphenol, 2,6-cyphenylphenol, 213+6-t! J methylphenol,
2,3,5.6-tetramethylphenol, 2.6-)
Examples include methyl-3-chlorophenol-cresol. These may be used alone or in combination of two or more.

Manganese salts used in the method of the present invention include, for example, manganese chloride, manganese chloride, manganese iodide, manganese salts of inorganic acids such as manganese nitrate, manganese sulfate, and manganese carbonate; manganese formate, manganese acetate, Manganese salts of organic acids such as manganese oxalate, manganese stearate, manganese octylate, and manganese benzoate; further examples include manganese acetylacetone, manganese hydroxide, and manganese oxide.

The preferred usage amount of these manganese salts is 0.05 to 5 molti, more preferably 0.1 molti based on the phenols.
~1 molti. If the amount is less than 0.05 molty, the effect of the present invention will not be exhibited, and even if it is used in excess of 5 molty, the effect will not be exhibited in proportion to the amount used.

The cobalt compounds used in the method of the present invention are divalent,
Any trivalent compound can be used. Examples of divalent co-Z-cyto compounds include copal chloride (Ill), co-divalent bromide (I[), and copal iodide H
ill, (I acid cobacit + II), nitrate co-malt (
Tl), cobalt phosphate ([1, cobalt acid 62 FTl
+, Copal oxalate [111, Cobalt benzoate (■
), naphthenic acid (U), stearic acid (ml), cobalt (ITJ acetylacetonate, cobaltocene, etc.) and their hydrates, and trivalent cobalt compounds. may include cobalt (I[ll acetylacetonate, etc.) and hydrates thereof.

The amount of the cobalt compound to be used is selected from 0.1 to 10, more preferably 0.2 to 3 in molar ratio to the manganese compound.

If the amount is less than 0.+ (molar ratio), the effect of the present invention will not be sufficiently exhibited, and if it is added in an amount exceeding 10 (molar ratio), the effect will not be exhibited considering the amount.

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

Examples of primary alkanolamines include ethanolamine, 2-hydroxypropylamine, 3-hydroxypropylamine, 2-phenylethanolamine, 3-hydroxypropylamine,
Examples include hydroxy-2-aminobutane.

Examples of secondary alkanolamines include jetanolamine, di-t-, P-A-nolamine, bis(2-phenyl-2-hydroxyethyl)amine, and the like.

Examples of tertiary alkanolamines include triethanolamine, tri-pronozonelamine, tris(
2-phenyl-2-hydroxyethyl)amine, N,
Examples include N-dimethylethanolamine, NIN-diethylethanolamine, dimethylamine-2-propatol, and N-hydroxy7morpholine.

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

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

In particular, by combining two or more alkanolamines, effects such as easier control of viscosity during reaction and further improvement of thermal stability are expected.

The ratio of these alkanolamines used is usually 0.5 mol to 20 mol per 1 mol of the total amount of the manganese compound and the cobalt compound.

If the ratio of alkanolamine used is less than 0.5 mol, the effect of the present invention will not be fully exhibited, and if it exceeds 20 mol, 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 phenoxides of metals in Group IA of the periodic table, quaternary ammonium hydroxides, and pyridinium hydroxides. can be mentioned.

Examples of hydroxide compounds of Group IA metals in the periodic table include lithium hydroxide, sodium hydroxide, and potassium hydroxide; examples of alkoxides of these metals include lithium methoxide, sodium methoxide, potassium methoxide, and lithium. Ethoxide, sodium ethoxide, potassium ethoxide, etc., and phenoxides of the metal include, for example, sodium phenoxide. Furthermore, examples of quaternary ammonium hydroxides and pyridinium hydroxides include tetramethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and N-methylpyridinium hydroxide. These basic compounds 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 also be used in the form of an aqueous solution, such as a 40% aqueous sodium hydroxide solution, and the amount used is determined according to conventional methods. You can choose any value within the range provided.

The catalyst used in the present invention can be prepared by, for example, dissolving a manganese compound and a cobalt compound in an alcohol such as methanol in advance, and then adding an alkanolamine in a predetermined ratio, or adding an alkanolamine to an alcoholic solution of a manganese compound. The cobalt compound may be added after the addition at a predetermined ratio.

The basic compound may be added to this catalyst solution, or may be added to an organic medium in which phenols are dissolved. Also,
The catalyst may be prepared in the presence of oxygen, such as at atmospheric pressure, or in a nitrogen atmosphere, if desired.

Regarding the reaction solvent used in the method of the present invention, as long as it dissolves the phenols, the catalyst manganese compound, cobalt compound, and alkanolamine, is inert to these compounds, and is liquid at the reaction temperature, There are no particular limitations, and such solvents include, for example, chain and cyclic aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, nitro compounds, ethers, ketones, lactones, and amides. , sulfone compounds, etc. Specific examples include hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, styrene, dichloromethane, chloroform, bromoform, monochlorobenzene, dichlorobenzene, methanol, ethanol, propatool, butanol, amyl alcohol. , hexyl alcohol, benzyl alcohol, cyclohexyl alcohol, ethylene glycol, trimethylene glycol, butanediol, chrycerin, β-chloroethanol, nitrobenzene, diethyl ether, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, propiolactone, dimethyl formamide Examples include. Particularly suitable solvents among these solvents include mixed solvents of lower alcohols such as methanol, ethanol, pronozonol, 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 trying to increase the molecular weight of the polyphenylene ether produced,
When using a lower proportion of the polar solvent and, on the other hand, wishing to lower the molecular t of 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 oxidative polymerization is usually carried out when the phenol concentration in the reaction solution is 70% by weight or less, preferably 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. Further, 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.

(Effects of the invention) In the present invention, a highly active catalyst with improved water resistance consisting of a manganese compound, a cobalt compound, an alkanolamine, and a basic compound is used as a polymerization catalyst for polyphenylene ether, so it is more effective than conventional methods. Significantly less catalyst is used, resulting in less solvent being used in removing catalyst residues in the polymer and reducing solvent recovery costs. In addition, the catalyst removal process is simplified, such as by significantly downsizing the equipment for removing the catalyst.

As described above, the method of the present invention not only enables polyphenylene ether to be produced economically (2), but also allows the catalyst residue to be almost completely removed, so that polyphenylene ether of excellent quality can be obtained (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, the measurement of ηap/c was performed using a polymer of 0.5 W/V%.
The test was conducted using an Ubbelohde viscometer at 30°C.

Example 1 70 g (0,574 mol) of 2.6-dimethylphenol was dissolved in a mixed solvent of 378 g of toluene and 126 g of n-butanol. This was mixed with 126 g of methanol, 0.227 g of manganese (It) chloride, tetrahydrate, and 0.273 g of cochloride (III) hexahydrate.
A catalyst solution prepared by adding 1.71 g of triethanolamine and 1.38 g of sodium hydroxide while blowing oxygen into the syneresis solution was added. Then, while stirring the solution vigorously, oxygen gas was introduced at a flow rate of 360 d/min, and the reaction was carried out at 30° C. for 3.5 hours. After the reaction was completed, the polymerization solution was added to 5 times the volume of a 5% by weight hydrochloric acid methanol solution to precipitate the polymer.

The precipitated polymer had a ηsp/c of 0.94.

Note that the molar ratio of z6 xylenol: manganese chloride: cobalt chloride was 500:1:1.

Comparative Example 1 70 g (0,574 mol) of 2.6 dimethylphenol was dissolved in a mixed solvent of 378 g of toluene and 126 g of n-butanol. In this solution, 126 g of methanol and 0.227 g of manganese chloride tetrahydrate were dissolved in advance, 71 g of triethanolamine L, and 1 g of sodium hydroxide.
．． 38 g of the solution was added while blowing oxygen. Then, while stirring the solution vigorously, oxygen gas was added for 3 minutes.
The mixture was introduced at a flow rate of 00 at/min and reacted at 30° C. for 15 hours. After the reaction was completed, the polymerization solution was added to a 5x f1% hydrochloric acid methanol solution using a 5x needle to precipitate the polymer.

The precipitated polymer had a ηSp/c of 0.08.

In addition, the molar ratio of 2.6 xylenol:manganese chloride is 5
The ratio was 00:1.

Comparative Example 2 Comparative Example 1 was repeated by doubling the amount of manganese chloride in Comparative Example 1.

The obtained polymer had a ηsp/c of 0.06.

Comparative Example 3 Copal chloride instead of manganese chloride in Comparative Example 1)
A similar reaction was carried out using (II) hexahydrate, 0.273[, to obtain a polymer.

The precipitated polymer had a ηsp/c of 0.15.

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

That is, 70 g of 2,6 dimeterphenol (0,5
74 mol), 378 g of toluene and 126 g of n-butanol
It was dissolved in a mixed solvent with g. Add to this 126g of methanol
K pre-manganese chloride (n) tetrahydrate 0.227
A catalyst solution prepared by adding 1.71 g of triethanolamine and 138 g of sodium hydroxide while blowing oxygen was added to a solution containing 0.273 g of cobalt chloride hexahydrate and 0.273 g of cobalt chloride hexahydrate. Add 10 ml of water equivalent to the amount of reaction product to the mixture.
．． 33 g was added.

Then, while stirring the solution vigorously,
? A precipitated polymer was obtained by repeating the same operation as ff1.

The ηs p/c of the polymer after 2.0 hours of reaction is 0.15
．． The ηsp/c of the polymer after 3.5 hours of reaction is 0.39.
．． After reaction for 5.0 hours, ηSp/c was 0.7.6 hours, ηSp/e was 0.85.

Comparative Examples 4 to 6 In the same manner as in Example 2, the experiments were repeated in Comparative Examples 1 to 3 by adding an amount of water equivalent to the reaction product water in advance.

The results are shown in Cloth-1.

(Margin below) Table-1 Spicy TEA:) Reethanolamine I couldn't.

Examples 3 to 5 and Comparative Examples 7 to 8 Table 2 shows the molar ratio of manganese to cobalt in Example 2.
The effect on polymerization activity (viscosity) was examined by changing the composition as shown in the figure below.

The results are shown in Table-2.

Table 2 Viscosity after reaction at 30°C for 3.5 hours Examples 6 to 9 In Example 2, the amount of triethanolamine was adjusted so that the molar ratio of metal component (Mn+Co):amine was 1:1 to 1:20. Example 2 was repeated with the following changes. Table 3 shows the viscosity of the polymer obtained after 6 hours of reaction.

Table 3 Umbrella Viscosity after reaction at 30°C for 6 hours Examples 10 to 13 Triisopronozonolamine, N-methylethanolamine, N-ethylethanolamine, cumethanolamine-N, N-dimethylethanolamine and N instead of triethanolamine Example 2 was repeated except that hydroxyethylmorpholine was used, and the effect of the type of amine was examined. The results are shown in Table 4.

Examples 16 to 19 In Example 2, the effect of mixing triethanolamine with other alkanolamines instead of using it alone was examined. The results are shown in Table-5.

By appropriately selecting the combination with alkanolamine, the viscosity can be easily controlled and a polymer having a desired viscosity can be easily obtained.

FIG. 1 shows an example in which a combination of triethanolamine and N-methylethanolamine resulted in a gradual increase in viscosity versus reaction time.

(Leaving space below) Table 5 Viscosity after reaction at 130°C for 6 hours Examples 20 to 24 In Example 2, instead of chlorochloride, chloride bromide, sulfate chloride, acetate chloride, Poly7- was obtained in exactly the same manner as in Example 2, except that the same number of moles of benzoic acid, cobalt acetylacetonate, and acetylacetonate were used, and the reaction was carried out at 30'C for 6 hours. p/c is shown in Table-6.

Table 6 ◆ Viscosity after reaction at 30°C for 6 hours Example 25 378 g of toluene used to dissolve 70 g of 2,6 dimethyl ester in Example 2 and 12 n-butanol
Example 2 was repeated except that 504 g of toluene was used instead of 6 g of the mixed solvent.

The ηs p/c of the obtained precipitated calimer was O,SO.

Example 26 The experiment in Example 2 was repeated by changing the method of adding quartz chloride when synthesizing the methanol solution of the catalyst.

That is, 0.227 g of manganese chloride tut tetrahydrate was dissolved in 126 g of methanol in advance, and 71 g of triethanolamine L and 1.0 g of sodium hydroxide were added thereto.
After adding 38g while blowing oxygen,
4 g of methanol [dissolved chloride] (Ill.6
0.273 g of hydrate was added to obtain a catalyst liquid. Using this, the viscosity of a polymer obtained in the same manner as in Example 2 (ηsp
/c) is 0 at 3.5 hours and 0 at 38.6 hours after the start of the reaction.
．． It was 84.

Comparative Example 9 When polymerization was carried out in Example 2 without using triethanolamine, no polymer was obtained. This shows how remarkable the effect of adding triethanolamine is.

Comparative Example 10 In Example 2, when polymerization was carried out without using sodium hydroxide, no polymer was obtained. This shows that sodium hydroxide is an essential component.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between reaction time and viscosity in Example 2 and Example 16 of the present invention. Patent Applicant: Asahi Kasei Kogyo Co., Ltd. Figure 1 Reaction Fj'l thr) Procedural Amendment (Voluntary) March 18, 1985 Director General of the Patent Office Mr. Michibu Uga 1, Indication of Case Patent Application No. 22026 of 1988 No. 2,
Name of the invention Polyphenylene ether polymerization method 3, Relationship to the case of the person making the amendment Patent applicant 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka (003)
Asahi Kasei Kogyo Co., Ltd. 4, “Detailed Description of the Invention” column 5 of the specification to be amended, contents of the amendment (1) “N-hydroxymorpholine, etc.” on page 9, lines 16-17 of the specification. should be corrected to "N-hydroxyethylmorpholine, etc.". (2) "Table 1" on page 20 of the same page is corrected to the attached "Table 1". (3) "Table 4" on page 23 of the same page is corrected to the attached "Table 4." Table 1 above: *TEA nitriethanolamine** Viscosity after reaction at 30°C for 3.5 hours *** Even when added to the hydrochloric acid methanol solution, the liquid only became cloudy and no precipitated polymer was obtained.

Claims (1)

[Claims] A method for polymerizing polyphenylene ether, which comprises coexisting a cobalt compound during oxidative polymerization of phenols in the presence of a catalyst consisting of a manganese compound, an alkanolamine, and a basic compound.