DE2160059A1 - Process for the production of polyphenylene oxides - Google Patents

Description

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68

Kanegafuchi Kagakxi-Kogyo Kabushiki-Kaisha, Osaka, Japan

Process for the production of polyphenylene oxides

Brief description of the drawings

Fig. 1 is a graph showing the proportions of oxygen absorbed at the prescribed reaction times to absorbed oxygen with a reaction time of 50 minutes (maximum amount absorbed). Fig. 2 is a graph showing the relationship between Intrinsic viscosity of the polymer obtained and the reaction time.

Description of the invention

The invention relates to a process for the preparation of polyphenylene oxides, which is characterized in ₅ that a nucleus-substituted phenol in the presence of a basic manganese chelate oxidized with oxygen.

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The polymers to be produced according to the invention have a repeating one Structure represented by the following formula (l) will:

(D

where T,

and T>. are yet to be described substituents;

they are important high molecular weight materials with good thermal, mechanical, electrical and chemical characteristics Properties.

As a known method for producing polyphenylene oxide using metal chelate compounds, there can be cited as an example a method which uses a catalyst containing a manganese, cobalt or copper salt and an alkali alcoholate or phenolate, as proposed in the description of the Belgian patent 712 845 or a method using a catalyst containing a manganese salt, an alcohol and a tertiary amine as proposed in the specification of Belgian Patent 710,263; a method using a basic copper salt as proposed in the specification of Japanese Patent Publication 18 692/61; or a method using a cobalt (II) chelate compound (trade name "Salcomine") as suggested in the specification of Japanese Patent Publication No. 22 154/70 was proposed. The "salcomine" is a chelate compound, which is composed of a condensate of two molecules of salicylaldehyde with one molecule of ethylenediamine / ~ N, N ^! -Ethylene-bis (salicyliden-imine) _7, and cobalt (II); it is known that this compound reversibly absorbs and releases oxygen.

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As shown in the comparative examples given later, the known processes have disadvantages insofar as the rate of reaction is small, the reaction must be carried out for a long time so that a polymer with a high degree of polymerization is obtained, and productivity is low from the economic point of view.

In the method using a basic copper salt, the following disadvantages are observed; a large amount of amine must be used, diphenoquinone is easily produced as a by-product, the catalyst is deactivated by the water produced by the reaction, and the amine remaining in the polymer obtained causes discoloration. Furthermore, with the ¹¹ salcomine "catalyst, it is difficult to keep the quality of the catalyst at the same level even by the same synthesis method; therefore, it is very difficult to use polymers with a method using its catalyst of constant quality, because there is a great uncertainty about the activity of the catalyst.

The invention is intended to propose a method which addresses these disadvantages overcomes by conventional procedures; it is described in detail below.

The catalyst to be used according to the invention is a basic one Manganese chelate compound represented by the following formula (2) can be:

where P stands for a bifunctional hydrocarbon group, Q, a., Aiders toff atom or a hydrocarbon group means R is a hydrogen atom, a hydrocarbon group, a carbon; ai;:; t.-r "tofi'ocy group, represents a halogen atom, an amino group

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and S for a primary amine, a secondary amine, a tertiary Amine, an amide, an alkoxy group or a phenoxy group.

It has already been reported by LH Vogt, HL Finkbeiner et | al. _i reported in Journal of Organic Chemistry j # (2), 273 (I969) that chelate compounds, which were formed by replacing the cobalt atom in the "Salcomine" by manganese, iron, nickel or copper, no activity, show under the conditions under which "Salcomine "Phenols can oxidize and condense. It is therefore utterly impossible to predict that the basic manganese chelate compound of this invention would exhibit very high activity for oxidative condensation of phenols; therefore the invention should be valued particularly highly.

In practicing the invention, it is preferred that the one to be used basic manganese chelate compound acts stable enough under the conditions for the oxidative condensation of phenols, which will be explained in more detail. In view of such a stable effect, it is not preferable that P in the above formula is a group with too long a chain (for example, a decamethylene group and the like) because of such a long chain Group reduces the stability of the catalyst »Furthermore, if R is a strongly hydrophilic atom or a group of atoms (for example, a sulfonic acid group and the like), the solubility the basic manganese CheTatverbindungen in organic solvents extremely low. Therefore it is to be avoided that R is such a strongly hydrophilic atom or group. Achieving the highly active state of the chelate compound depends on the atomic group denoted by S in the above formula. As described above, S is made up of basic atomic groups selected, however, other substances that show a basic property (e.g. alcohols and the like) are also effective. Examples of P, Q, R and S, which give particularly preferred basic manganese-Che ^ compounds, are the following: Hexamethylene and o-phenylene groups as P; Hydrogen atom and Methyl group as Q; Hydrogen atom, chlorine atom, methyl group and methoxy group as R; and amines and alkoxy groups as S. Identification

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illustrative examples of preferred chelate compounds are methylenediamine complexes, Butylamine complexes and methoxy complexes des NjN'-Ätnylen-bisisalicyliden-iminatJ-manganese, N, N'-Äthylenbis (3-methoxysalicyliden-iminat) -mangans and N, N * -o-phenylene ~ bis- (3 or 5-chlorosalicylidene iminate) manganese.

The method for the synthesis of the to be used according to the invention basic manganese chelate compounds are known from the art. For example, they are usually synthesized by reaction a manganese salt, an amine and salicylaldehyde or its Derivatives under heat with an S donor in an organic solvent or water, or by first forming a Schiff * see base by adding a diamine and salicylaldehyde or subjects its derivatives to dehydrating condensation, and then reacting them with a manganese salt and a S donor in a solvent. Through this synthesis method the basic manganese chelate compounds are obtained in the form of solids or catalytic solutions.

The amount of catalyst used varies depending on the reaction conditions (temperature, kind of solvent, solvent composition, pressure and other factors) and the intended degree of polymerization in the polymer obtained; it is impossible to determine in a simple manner the amount of catalyst used. However, good results are generally obtained when the catalyst is used in an amount of 0.1 mol # or more based on the phenol, which will be explained later. In the specification of Japanese Patent Publication 22 154/70 (a method using chelate compounds of the "salcomine" type), it is taught that, in the case of continuous polymerization, it is advantageous to use the catalyst in a higher concentration (up to 10 mol%) , whereas in the process according to the invention it is sufficient to use the catalyst in a concentration of only 1-3 mol- # for the continuous polymerization. A higher productivity is thus achieved in the process according to the invention.

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Phenols to be used in this invention are as follows Formula (3):

(3)

wherein X represents a hydrogen or alkali metal atom and T ₁ , T ₂ , T ^, T ^ and T _{5 represent} a hydrogen atom, a hydrocarbon group, a hydrocarbonoxy group, a halogen atom, a cyano group, a nitro group, an amino group or a substituted one Amino group.

In particular, X is selected from hydrogen, sodium, potassium and other alkali metals. Specific examples of T-., T ₂ , T 1, T ₂ , and Tf- include hydrogen, chlorine, bromine and iodine atoms and methyl, ethyl, propyl, propenyl, phenyl, methoxy -, ethoxy, phenoxy, cyano, nitro, amino and dimethy! Amino groups etc .. Typical examples of the phenols represented by the above sleeve can be o-cresol, 2-chlorophenol, 2-bromophenol, 2, 6-dimethylphenol, 2,6-diethylphenol, 2,6-dimethoxyphenol, 2,6-dipropenylphenol, 2,6-diphenylphenol, 2,4,6-trimethylphenol, 2,3,5-trichlorophenol, 3-methoxyphenol, 2, 4-dimethyl-j5-chlorophenol, 3-cyanophenol, 2-nitrophenol, 2-aminophenol and the like can be given. They can be used alone or in mixtures of two or more of these compounds.

In practicing the invention there is the use of a solvent not always necessary. However, in the absence of a solvent, the viscosity of the reaction mixture decreases as it proceeds the reaction and therefore the diffusion of oxygen as an oxidizing agent, which will be explained in more detail, is prevented, with the result that a polymer having a high degree of polymerization cannot be obtained. Furthermore, re-solution

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and precipitation steps required to recover the catalyst from the polymer obtained. For these reasons, the method which does not use a solvent is under economical Aspect of no importance, and it is preferred that the invention Procedure to be carried out using a solvent. Almost all organic solvents can be used for the invention be used-. In detail, aromatic and substituted aromatic hydrocarbons such as benzene, toluene, Xylene, anisole, chlorobenzene, dichlorobenzene, bromobenzene, nitrobenzene and benzonitrile; Ketones such as acetone and methyl ethyl ketone Esters such as ethyl acetate and amyl acetate; Alcohols such as methanol, ethanol, propanol, isopropanol and butanolj halogenated hydrocarbons such as chloroform, methylene chloride, 1,2-dichloroethane, methyl chloroform, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane Ethers such as tetrahydrofuran and dioxane; and amides such as dimethylformamide, dimethylac & amide and hexamethylphosphoamide can be used. Some of these solvents dissolve the basic manganese chelate compound used as a catalyst or the obtained polyphenylene oxide not good. In this case, the reaction is allowed to proceed up to a catalyst concentration that is determined by the Solvent is determined, or up to a polymer which reaches a degree of polymerization determined by the solvent and forms a separate phase in the reaction mixture. For example, although the catalyst in benzene is insufficient is dissolved, the reaction mixture is homogeneous when the starting phenol is added, and the catalyst falls into Form a solid with continued reaction from while the polymer is obtained in a dissolved state in benzene. Accordingly, in such a case, it is possible to use the catalyst to win by filtering the reaction mixture and to convert the catalyst back to its original state. However such procedures are generally associated with complications and are not preferred. That is why it is particularly important to use different solvents in the form of mixtures.

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Good results are achieved by using a combination of an aromatic or substituted aromatic hydrocarbon or halogenated hydrocarbons, which are good solvents for the polymer, with an alcohol or other solvent which is a good solvent for the catalyst and also as a diluent for the reaction formed water can serve. When such a combination is used, as an alcohol, the polymer does not form that Polymers dissolves when it reaches a degree of polymerization determined by the composition of the mixed solvent, a separate phase and precipitates in the form of particles. if such a separate phase is formed, the degree of polymerization does not or hardly decreases in the known catalyst systems to. For example, the degree of polymerisation increases in the case of a Copper-amine complex, even if an alcohol is used in combination with a good solvent for the polymer, the degree of polymerization of the precipitated polymer no longer if it is left to stand still for a long time in the reaction system (see Comparative Example 7) above description, which is a catalyst of the "Saleomine" -Type discloses that a polymer with a certain degree of polymerization can be obtained by forming a separate phase is, and one can easily imagine that the degree of polymerization in the polymer having such a separate phase has formed, is hardly changed.

In contrast, and to my own surprise, it was now unexpected found that in the case of the catalyst according to the invention the polymer, which has already formed a separate phase, continues an oxidizing coupling reaction and is readily converted into a high molecular weight polymer. In view of the fact daas the degree of increase in the degree of polymerization is very noticeable, it is assumed that in the above state the oxidizing Coupling reaction at the head of the polymer (phenol end) and at the tail of the polymer (phenyl end) via the quinol-ether equations

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weight reaction dominates. This phenomenon makes it possible to din To obtain polymer of very high degree of polymerization in a short time using a small amount of the catalyst, and this is the most salient feature of the present invention.

Although the polymer obtained contains very small amounts of catalyst, Since the catalyst is very easily soluble in alcohol, it can easily be removed from the polymer. As a result the polymer thus obtained is essentially free from impurities.

The reaction liquid from which the polymer is separated is drawn with fresh catalyst corresponding to the catalyst that accompanied the polymer was incorporated and then treated with a dehydrating agent Means subjected to what will be described, after which the starting phenol is added and the polymerization again is carried out.

Addition of a basic substance such as amines, diamines, amides, alkalis, Alkoxides and phenoxides, acts in the direction of an increase in the reaction rate, furthermore an increase in the molecular weight of the polymer and increasing the selectivity of the oxidation reaction. Among these basic substances, there is one alkaline substance, particularly preferred results when a component of the reaction solvent is an alcohol. The usage such a basic substance is not always necessary because the catalyst of the invention is highly active and has a high Shows selectivity of the oxidation reaction. Where such a basic Substance is used, it is preferable to use it in an amount of at least 1/2 mole per mole of the catalyst. The usage too large an amount (for example, in an amount similar to the amount of the reaction solvent) is not preferable, because a decrease in activity can occur due to the fact that the basic substance has a higher coordination for the manganese chelate compound shows than for the starting phenol.

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The reaction temperature should depend on the reaction rate and the selectivity of the reaction are determined; generally it is preferred to run the reaction at a temperature not exceeding 100 ° C Temperature. At higher temperatures, the reaction rate can be increased, but it can side reactions, such as the formation of quinones, can easily occur. Then it must be avoided the reaction at temperatures perform that are above the boiling point under the reaction conditions of the solvent used, because the boiling of the solvent prevents the dissolution of oxygen in the reaction liquid, which will be described later.

The use of a dehydrating agent inhibits deactivation of the catalyst (oxidation to ma ^ and conversion to an inactive chelate) and brings good results emerged. Generally, as the dehydrating agent, a molecular sieve, alumina, silica gel and the like can be used.

Oxygen, air and diluted oxygen are used as oxidizing agents used with an inert gas. In general, the use of oxygen makes the reaction system maximal Shows reaction rate; however, where simple sailing is intended it is preferable to use diluted oxygen to use. Although the reacting oxygen under high pressure helps to increase the rate of the reaction, it is High pressure reaction not actually necessary because of the inventive Catalyst is sufficiently active. The termination of the reaction can be due to the substantial cessation of oxygen consumption or heat generation can be detected.

In the present invention, the intended polymer may have a high degree of polymerization can be obtained in a short time, the use of a large amount of amine is unnecessary and it occurs no deactivation of the catalyst dn.

The invention will now be explained in detail by means of the examples.

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Comparative example 1

2.0 grams (0.05 moles) of sodium hydroxide were hot in 122 grams Dissolved (1.0 mole) 2,6-dimethylphenol and the mixture at 2,200 g 1,2-dichloroethane given. After ^ 2.5 g (0.1 mol) of "Salcomine" was added to the mixture became oxygen at 50 ° C initiated.

When the reaction started, the temperature was increased. The temperature increase was controlled by cooling so that the temperature of the reaction system was kept at 30 ° C. After oxygen was introduced for 1 hour, the reaction mixture was filtered and the filtrate was poured into hydrochloric acid containing 20 liters of methanol to precipitate the polymer. The precipitated polymer was collected by filtration, washed with methanol and dried at 110 ° C. in a vacuum. The amount of polymer obtained was 55.9 g (yield: 45.8 %) , and the intrinsic viscosity of the polymer was 0.18 (calculated from the viscosity measured at 25 ° C. in chloroform, the same applies to the following examples).

When the above reaction was repeated while increasing the amount of sodium hydroxide to 4.0 g, 49 * 7 g of a polymer having an intrinsic viscosity of 0.18 was obtained (yield: 40.7 %).

From the foregoing it can be seen that increasing the amount of sodium hydroxide used does not improve leads.

Comparative example 2

Comparative example 1 was repeated on a scale of 1/122, using a reaction vessel equipped with an oxygen-filled gas burette and the rate of oxygen absorption (reaction rate) was measured.

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The change in the ratio of the amount of oxygen absorbed to the maximum amount of oxygen absorbed (see attached Fig. 1) is listed below.

Response time Amount of absorbed ratio to the maximum amount (min.) oxygen (ml) of absorbed oxygen

£ 1}

0 0.0 0.0

1 21.5 15 * 7 2.5 68.5 50.0 5 107.2 78.3

10 128.6 94.0

20 13 ^, 0 98.6

50 137.0 100.0

In the case where polyphenylene oxide is formed by the oxidative coupling of a phenol, the necessary and sufficient amount of oxygen for the reaction is 1/2 mole of the phenol. In this comparative example, however, oxygen was absorbed in an amount of 136%, based on the theoretical amount, during a reaction time of 30 minutes. This shows that side reactions have taken place in this comparative example.

Comparative example 3

The reaction was carried out in the same manner as in Comparative Example 1 without using sodium hydroxide. Specifically, after 122 g (1.0 mol) of 2,6-dimethylphenol was dissolved in 2,200 g of 1,2-dichloroethane and 32.5 g (0.1 mol) of "Salcomine" was added to the solution, oxygen was added 30 ° C passed into the mixture. The temperature of the reaction system was gradually raised but kept at 30 ° C by cooling. 3.3 *, 5.5 ^f -tetramethyldiphenoquinone was formed during the above procedure. After 5 hours, the reaction mixture was filtered and the filtrate in 20 liters of methanol, the 2 liters of salt

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acid was poured, but no precipitation of polymers was observed. The obtained amount of diphenochin was 12.3 g (10.1 % yield).

Comparative example 4

Instead of the 1,2-dichloroethane solvent, a mixture of 1,2-dichloroethane and methanol was used. in the each was 2.0 g (0.05 mol) of sodium hydroxide in 610 ml of methanol dissolved and added to the solution 1,220 ml of 1,2-dichloroethane and 122 g (1.0 mol) of 2,6-dimethylphenol. After adding 32.5 g Oxygen (0.1 mole) "Salcomine" was bubbled into the mixture. The catalyst was homogeneously dissolved in the reaction mixture. After the reaction continued for about 18 minutes, a polymer began to settle to be eliminated from the reaction liquid. After 1 hour Reaction, the reaction product was collected by filtration.

The amount of the precipitated polymer was 20.5 g (16.8 % yield) and the intrinsic viscosity of the polymer was 0.56. The filtrate was poured into 10 liters of hydrochloric acid-methanol to precipitate a low molecular weight polymer which is soluble in the filtrate. The amount of the low molecular weight polymer thus obtained was 6.2 g (5 * 1 % yield), and the intrinsic viscosity of the polymer was 0.07.

Comparative example 5

Comparative Example 4 was repeated on a scale of 1/122 using a reaction vessel which was filled with one containing oxygen filled gas burette, and the rate of oxygen absorption was measured (see Fig. 1).

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Response time amount of "absorbed ratio to the maximum

(min) oxygen (ml) amount absorbed {%)

0 0 0. '

1 14.5 7.8 2.5 34.0 18.3 5 81.2 43.6

10 131.0 70.3

15 167.6 89.9

20 180.1 96.8

30 186.2 100.0

In this comparative example, too, oxygen was absorbed in an amount corresponding to 183.4% of the theoretical amount; this indicates that side reactions have taken place.

Comparative example 6

7 * 0 g (0.07 moles) of copper chloride were in 554 g (7.0 moles) of pyridine dissolved and then added 91.5 ml of benzene and 915 ml of methanol to the solution. After adding 122 g (1.0 mol) of 2,6-dimethylphenol oxygen was passed into the mixture at 30 ° C. After 5 minutes a polymer began to precipitate. There were small amounts of the polymer precipitated at a reaction time of 20, 40, 60 and 120 minutes was collected into samples. the Intrinsic viscosity of each polymer sample was determined from the viscosity measured at 25 ° C in chloroform. The viscosity of each of the polymers removed at the above reaction times 0.143 and no increase in molecular weight was observed.

Comparative example 7

32.1 g of N, N ^f ethylene bis (salicylidene iminate) manganese were added to 2.5 liters of 1,2-dichloroethane and 122 g of 2,6-dimethyl

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phenol added. Oxygen was bubbled into the mixture with stirring while maintaining the temperature at J> 0 ° C. After 3 hours had elapsed, the introduction of oxygen was interrupted and the reaction mixture was poured into methanol containing hydrochloric acid, but no polymer was obtained.

The above experimental result shows that when a compound of the formula (2), as it is given in the present description, does not have a group S, and this does not have a catalyst for the oxidative condensation of phenols, and this agrees with that in Journal of Organic Chemistry j &, (2) 273 (1969) reported the result.

Comparative example 8

In a liquid mixture of 500 ml of methanol and 500 ml of pyridine 12.5 g of manganese chloride tetrahydrate were dissolved; 50 grams of 2,6-dimethylphenol were also admitted. Oxygen was introduced into the mixture at 50 ° C. with stirring. After expiration of 10 hours, the reaction mixture was dissolved in 2 liters of methanol poured containing 20 ml of hydrochloric acid, but no precipitation of a polymer was observed.

Comparative example 9

10 ml of methanol containing 0.124 g of manganese chloride and 0.213 g of sodium methoxide was added to 60 ml of nitrobenzene, and the mixture was stirred for 5 minutes while oxygen was bubbled through. 30 ml of nitrobenzene containing 40 g of 2,6-dimethylphenol was was added to the above solution, and oxygen was bubbled through the mixture with stirring at 40 ° C. After about 130 minutes of the addition of the 2,6-dimethylphenol was an equivalent amount Oxygen has been absorbed. If an additional three hours was passed, no further absorption of oxygen could occur to be established. The reaction mixture was poured into methanol containing a small amount of hydrochloric acid. The received Precipitation was separated off by filtration, washed and dried

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net to obtain a white polymer having an intrinsic viscosity of 0.35 in a yield of 86.4 % .

example 1

J8, lg (0.1 mol, 10 mol $, based on the monomer) of a complex compound of N, N ^f -ethylene bis (salieylidene iminate) with ethylenediamine were added to 2.5 liters of benzene and the mixture was heated, so that the temperature was kept at J> 0 ° C. Then 122 g (1 mole) of 2,6-dimethylphenol was added to the mixture and oxygen was bubbled through the mixture with stirring. Since Wihne is generated, it was filled to keep the temperature at 30 ° C. After 15 minutes, the introduction of oxygen was interrupted and the reaction mixture was immediately filtered. The benzene solution was poured into 5 × 0 liters of a methanol solution containing 2 liters of hydrochloric acid to precipitate a white polymer. The precipitated polymer was washed with methanol and dried to give a polymer having an intrinsic viscosity of 0.4-80 (in chloroform at 25 ° C) in a yield of 94.8 %.

Example 2

Example 1 was made on a 1/122 scale using a reaction vessel which was equipped with a gas burette filled with oxygen, and the oxygen absorption rate was measured (see Fig. 1).

Response time Amount of absorbed ratio to the maximum (min.) Oxygen (ml) amount absorbed (#)

0 0 0

1 24.0 23.5

2 49.8 48.8 3 74.6 73.0

4 89.5 87.7

5 99.7 97.6 10 101.3 99.5

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Response time Amount of absorbed ratio to the maximum

(min) oxygen (ml) amount absorbed {%)

(Continuation)

15 102.0 99.8

20 102.2 100.0

30 102.2 100.0

In this example, unlike in comparative example 2 or 5>, oxygen was absorbed in an amount which corresponded to 101% of the theoretical amount, namely almost the equivalent amount. This shows that there was hardly any side reaction in this example.

Example 3

The reaction was carried out under the same conditions as in Example 1 using an equal amount of nitrobenzene in place of the benzene in Example 1. As a result, a polymer having an intrinsic viscosity of 0.598 was obtained in a yield of 90.5 % .

Example 4

The reaction was carried out under the same conditions as in Example 1, with an equal amount of 1,2-dichloroethane being used in place of the benzene in Example 1. As a result, a polymer having an intrinsic viscosity of Ο.5β5 was obtained in a yield of 92.1 % .

Example 5

38.1 g (0.1 mol - 10 mol #, based on the monomer) of a complex compound of N, N ^l -ethylene bis (salicylidene iminate) manganese with ethylenediamine were dissolved in 10 liters of methanol, and 1, 5

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Liters of benzene were added. After 122 g of 2,6-dimethylphenol (1 mol) was added to the mixture while maintaining the temperature at 30 ° C, oxygen was introduced into the mixture while the reaction vessel was cooled so as to keep the temperature at 30 ° C stayed. After 1 minute from the beginning of the oxygen introduction, the polymer began to precipitate. Since hardly any further evolution of heat could be observed after 10 minutes had elapsed since the start of the introduction of oxygen, the flow of oxygen was stopped and the reaction mixture was filtered. The obtained crude polymer was washed with methanol containing hydrochloric acid and then with methanol, followed by drying. A polymer having an intrinsic viscosity of 0.860 was obtained in a yield of 90.0 % .

In this example, although the reaction time was shorter than that in Comparative Example 5 *, a polymer having a higher intrinsic viscosity could can be obtained and also in higher yield.

Example 6

7 g (0.018 mol - 1.8 mol $, based on the monomer) of a complex compound of N, N ^f -ethylene-bis (salicylidene-iminate) -manganese with ethylenediamine were dissolved in 0.6 liters of methanol and with 1.2 liters of benzene added. The following operations were carried out as in Example 5, and ^S 8in polymer with an intrinsic viscosity of 0.785 was obtained in a yield of 93 * 6 $.

Example XL 7

7 g (0.02 mol - 2 mol $ in terms of the monomer) of a complex compound of N, N ¹ -ethylene bis (salicylidene iminate) manganese with methoxide was used and the reaction was carried out in the same manner as in Example 6 to obtain a polymer having an intrinsic viscosity of 0.876 in a yield of 96.1 % .

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Example 3

Example 6 was repeated, using 8 g (0.18 mol - 1.8 Wol-ytf based on the monomer) of a complex compound of N, N'-hexamethylene-bis-salicylidene-iminate) manganese with ethylenediamine as the analyzer. A polymer having an intrinsic viscosity of 0.713 and a yield of 92.3 % was obtained.

Example 9

Example 6 was repeated, using 8 g (0.019 mol -1.9 mol, based on the monomer) of a complex compound of N, N'-o-phenylene-bis (salicylidene-iminate) manganese with ethoxide as the catalyst . A polymer with an intrinsic viscosity of 0.665 and a yield of 91 * 6 % was obtained.

Example 10

Example 6 was repeated using as a catalyst 8.8 g (0.02 mol - 2 ^ MOI, based on the monomers) of a complex compound of N, N ^{t i} -Äthylen -bis (3-methoxysaliGyliden-iminat) -manganese with Ethylenediamine were used. A polymer with an intrinsic viscosity of 0.860 was obtained in a yield of 96.9 % .

Example 11

Example 6 was repeated, using 9 g (0.02 mol - 2 mol, based on the monomer) of a complex compound of N, N ¹ -ethylene bis (5-chlorosalicylidene iminate) manganese with ethylene diamine as the catalyst . A polymer with an intrinsic viscosity of 0.792 was obtained in a yield of 93.2 % .

Example 12

In 0.6 liter of methanol, 3.7 g (0.015 mol - 1.5 mol #, based on the monomer) Manganese acetate tetrahydrate, 4.0 g (0.015 mol)

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Dissolved N, N'-ethylene-bis (salicylidene-imine) and 0.9 g (0.015 mol) of ethylenediamine. 1.8 g (0.045 mol) of sodium hydroxide were then dissolved in the resulting solution and 122 g (1 mol) of 2,6-dimethylphenol were also added. Oxygen was bubbled through the mixture while maintaining the temperature at 30 ° C. After 20 minutes had elapsed after the start of the introduction of oxygen, the supply of oxygen was stopped. The following operations were carried out as in Example 6. A polymer with an intrinsic viscosity of 0.996 was obtained in a yield of 94.6 % .

Example I3

In 0.6 liter of methanol 3 * 7 g (0.015 mol - 1.5 mol #, based on the monomer) of manganese acetate tetrahydrate, 4.0 g (0.015 mol) of N, N ^! -Ethylene-bis (salicylidene-imine) dissolved, Then 1.2 g (0.03 mol) of sodium hydroxide were dissolved and 0.3 liter of methanol containing 0.8 g (0.015 mol) of sodium methoxide was added to the resulting solution and 1.2 liters of benzene were added, after which 122 g (1 mol) of 2,6-dimethylphenol were added. Oxygen was bubbled through the Gemisca while the temperature was held at 30 ° C. The following operations were carried out as in Example 6. A polymer with an intrinsic viscosity of 1.12 was obtained in a yield of 91 * 8 % .

Example 14

7 g (0.018 mol - 1.8 mol $, based on the monomer) of a complex compound of N, N'-ethylene bis (salicylidene iminate) manganese with ethylene diamine were converted into a solvent mixture of 1.2 liters of benzene and 0 , 6 liters of methanol were added, followed by the addition of 4.2 g (0.03 mol) of tetramethylenediamine. Thereafter, 122 g (1 mol) of 2,6-dimethylphenol were added to the mixture, and oxygen was passed through the mixture with stirring while the temperature was maintained at 30.degree. The following operations were carried out as in Example 6. A polymer with an intrinsic viscosity of 0.631 was obtained in a yield of QQ 2 % .

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Example 15

In 0.6 liters of methanol there were 3.35 g (0.0125 mol - 1.25 based on the monomer) of N, N * -ethylene-bis (salicylidene-imine) and 304 g (0.0125 mol) of manganese acetate tetrahydrate solved. Then, 1.52 g (0.038 mol) of sodium hydroxide and 0.75 g (0.0125 mol) of ethylenediamine were dissolved in the solution, after which 122 g (1 mol) of 2,6-dimethylphenol were added to the solution and oxygen was passed through the resulting mixture was passed while the temperature was kept at 30 ⁰ C. Samples were taken during the reaction and the intrinsic viscosity of the polymer sample was measured for each sampling time / time. In this example, it was found that, unlike Comparative Example 6, the degree of increase in the intrinsic viscosity of the polymer was very conspicuous in spite of the very small amount of the manganese catalyst, namely 1.25 mol # based on 2,6-dimethylphenol (see Fig. 2).

Reaction time (min.) Intrinsic viscosity (dl / g)

23 0.33

25 0.53

29 0.72

33 0.92

40 1.13

Examples 16-19

3.81 g (0.01 mol - 10 mol $, based on the monomer) of a complex compound of N, N ¹ -ethylene bis (salicylidene iminate) manganese with ethylenediamine were dissolved in 0.1 liter of methanol and mixed with 0.15 liters of benzene were added and the resulting reaction mixture was stirred. 0.1 mol of a phenol in the following table was then added to the mixture, after which oxygen was bubbled through the mixture from a gas burette while the temperature was at

209824/0991

2160053

K 977

30 C was held. When no further oxygen absorption was observed, the reaction was interrupted and the reaction mixture was poured into oxygen-containing methanol to obtain the To completely precipitate pests. The resulting precipitate was washed with methanol and dried. The results of the polymerization the phenols are summarized in the following table.

Tabel :

Example phenols Art Amount (mole) Polymers Border visco
sity No. 2,6-diethylphenol
o-cresol
/ 2,6-dimethylphenol
£ _o-cresol 0.1
0.1
0.08
0.02 yield
(*) 0.76
0.44
0.95 16
18th
19th 91
80
92

- patent claims -

209824/0991

Claims (1)

Claims 1. A process for the preparation of polyphenylene-oxides, characterized in that a phenol of general formula (1) in the presence of a basic manganese chelate compound of the general formula (2) in an organic solvent like oxidized and condensed. y Process for the preparation of polyphenylene oxides, characterized in that a phenol, of the general formula (I) in the presence of a basic manganese chelate compound of the general formula (2) and a basic compound from the group of primary amines, secondary amines, tertiary amines, diamines, amides, alkalis, alkoxides and phenoxides, oxidized and condensed in an organic solvent,, where formula (l) and formula (2) are as follows Formula (l): wherein X stands for a hydrogen or alkali metal atom and T _{1 , T 2} , T 1, T 1. and Tj, represents a hydrogen atom, a hydrocarbon group, a hydrocarbonoxy group, a halogen atom, a cyano group, a nitro group, an amino group or a substituted amino group. K 977 Formula (2); where P stands for a bifunctional hydrocarbon group, Q represents a hydrogen atom or a hydrocarbon group, R is a hydrogen atom, a hydrocarbon group, a hydrocarbon tof ^ group, a halogen atom, an amino group, a substituted Amino group, a nitro group or a hydroxyl group and S for a primary amine, secondary amine, tertiary Amine, an amide, an alkoxy group or a phenoxy group. Dr. Pa. / Br. 209824/0991