DE2011711C3 - Process for the production of polyphenylene ethers - Google Patents

Description

OH

Q '

corresponds to, in which Q and Q 'are alkyl radicals with 1 to 8 Represent carbon atoms and the reaction in the presence of a catalyst complex of anhydrous Copper H salts, hydrated copper II salts or aqueous solutions of copper-1! salts and a straight-chain aliphatic amine and a low molecular weight alkyl alcohol in an amount of not more than 5% by volume of the reaction mixture composed of the monovalent phenol, the catalyst complex and the solvent.

2. The method according to claim 1, characterized in that the alcohol in the range from 0.5 to 3, OVol .-% of the total reaction mixture is present.

3. The method according to claim 1 or 2, characterized in that the alcohol is methanol.

4. The method according to any one of claims 1 to 3, characterized in that the monovalent Phenol is 2,6-dimethylphenol

5. The method according to claim 4, characterized in that that the copper (II) salt is a copper (II) halide is.

6. The method according to claim 5, characterized in that the copper (II) halide is copper (II) chloride is.

7. The method according to claim S, characterized in that that the copper (II) halide is copper (II) bromide is.

8. The method according to one or more of claims I to 7, characterized in that the Amine is di-n-butylamine.

The invention relates to a process for the preparation of high molecular weight polyphenylene ethers from a monovalent phenol by an oxidative coupling reaction in the presence of a catalyst complex of a non-basic copper-II salt and a primary or secondary amine in the presence of a solvent and optionally an activator.

Polyphenylene ethers and processes for their preparation are well known and varied Publications, for example US Patents 3) 06 874, 33 06 870 and 33 84 619 and in the simultaneously with the own patent applications DE-OS 2011710 and filed with this application DE-OS 20 11 709) described.

The process according to the aforementioned US Pat. No. 33 06 875 comprises the self-condensation of a monohydric phenol precursor using a catalyst of a tertiary amine-basic Contains copper (II) salt complex. The after this procedure polymerizable phenols have the following structural formula:

OH

wherein X is a substituent selected from the group consisting of hydrogen, chlorine, bromine and iodine, Q is a monovalent substituent selected from the group consisting of hydrogen, hydrocarbon radicals, and halogenated hydrocarbon radicals with at least 2 carbon atoms between the halogen atom and the phenol nucleus, Oxyhydrocarbon radicals and haloxyhydrocarbon radicals having at least 2 carbon atoms between the halogen atom and the phenol nucleus; Q 'and Q "have the same meaning as Q and mean additionally halogen with the proviso that Q, Q 'and Q "are all free of a tertiary are λ carbon atom. The polymers formed from the aforementioned phenols correspond to following structural formula:

Q '

Q "

• r> where the ether oxygen atom of a recurring Unit is connected to the phenylene core of the next repeating unit; Q, Q 'and Q "have the given definition and η is an integer that is at least equal to 100.

V) In the process according to the aforementioned US Patents 33 06 874 and 33 06 875, the formation of the polyphenylene ethers comprises the self-condensation of a phenol in the presence of a catalyst system which contains a tertiary amine-basic copper-H salt complex. It is disclosed therein that the copper salt used to form the complex catalyst is not critical and can be either a basic copper (II) salt or a copper (I) salt, provided that if

M) a copper · I salt is used, it is capable. to exist in the Ktipfer-Il-Ziistand. If a copper-I-Sal /. is used, the catalyst is presumably formed by a reaction of oxygen and water with an intermediate tertiary product

fi5 amine-copper-I-salt complex and forms a tertiary amine-basic copper-II salt complex. It various processes have already been described for the formation of the complex catalyst

a copper (II) salt. For example, it has been reported that a reducing agent, together with a Copper (II) salt can be used to form the copper (I) salt in place, whichever in turn forms the tertiary amine-basic copper-H salt complex when it is mixed together with the amine. On the other hand, it has already been reported that The complex between a tertiary amine and a basic copper (II) salt is formed by using copper (II) salts with an alkaline salt of a phenol can be implemented by treating a copper (II) salt with an ion exchange resin with exchangeable hydroxyl groups by converting a base to a Copper (II) salt is added or by adding copper (II) hydroxide to a copper (II) salt. the US Pat. No. 3,3 06,874 is similar to the above except that primary and secondary amines can be used in place of the tertiary amines.

The aforementioned US Pat. No. 3,384,619 also relates to a process for the self-condensation of Phenols with the formation of high molecular weight polyphenyl ethers, but it is different from the two method described above in that a catalyst is used which is a tertiary amine and contains a non-basic copper (II) salt. It is claimed therein that the reaction must be carried out in a solvent system which is at least 5% Has wt .-% alcohol, so as to obtain a high molecular weight polymer. In addition, this is Process, the catalyst concentration in the reaction mixture is extremely high, and that is omitted typically 9 parts. Amine> 1 part phenol, which makes the entire process treacherous and economically uninteresting. Finally, it is noted in this patent that attempts to prepare a polyphenylene ether in toluene, at these high Catalyst concentrations and in the absence of the alcohol were unsuccessful and no polymer was formed.

The aforementioned simultaneously filed patent application (DE-OS 20 11 709) is on an improved Process for the self-condensation of high molecular weight polyphenylene ethers directed, wherein a complex catalyst is used, which consists of a primary or secondary amine and an anhydrous non-basic copper (II) salt is formed The method according to this application is characterized by the use of the anhydrous, non-basic Copper-II-salts and represents an improvement over of US Patent 33 84 619, in which the concentration of the catalyst components in relation on the concentration of the monomer is relatively small and, accordingly, the overall cost of the process are significantly reduced. In addition, the method according to this application represents an improvement compared to the other previously known processes, namely because the molecular weight of the in Polyphenylene ether formed in a given reaction time is greater than in the case of the other way obtained or in other words, the reaction time is shorter for obtaining a polymer of comparable molecular weight.

The invention now represents a further improvement of that disclosed in its own laid-open specification 20 11 709 The invention described and it is based on the finding that the addition of a small amount an alcohol, in an amount of less than 5% by weight of the reaction ingredients, the use

of both hydrated non-basic copper (II) salts and aqueous solutions of non-basic Copper (II) salts for the manufacture of the complex In addition, allows catalysts for use in the formation of polyphenylene ethers the addition of the alcohol to the reaction system also results in the formation of higher polymers Molecular weight or the formation of the same molecular weights in a shorter reaction time when using formation of anhydrous copper (II) salts, hydrated copper (II) salts and aqueous solutions thereof. the Ability to use hydrated cupric salts or their aqueous solutions is significant there these materials are much more readily available than that anhydrous copper (II) salts and accordingly less are expensive.

The process of producing the high molecular weight Polyphenylene ether according to the invention is characterized in that the monovalent phenol of formula

corresponds to, in which Q and Q 'are alkyl radicals with 1 to 8 Represent carbon atoms and the reaction in the presence of a catalyst complex of anhydrous copper (II) salts, hydrated copper (II) salts or aqueous solutions of copper (II) salts and a straight-chain aliphatic amine and one low molecular weight alkyl alcohol in an amount of not more than 5 VoI.-% of the reaction mixture from the monovalent phenol, the catalyst complex and the solvent.

Examples of the phenols used in the present invention

include 2,6-dimethylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-allylphenol, 2-Me ethyl-6-phenylphenol, 2,6-dibutylphenol and 2-methyl-6- propyl phenol.

The primary or secondary amine component

of the catalyst complex are straight-chain aliphatic amines such as dibutylamine and diethylamine. The concentration of the amines can be in the The reaction mixture can vary within wide limits, but it is expedient to use a low concentration tioncn added. A preferred range is 2.0 to 25.0 moles per 100 moles of the monomer.

Typical examples of the copper (II) salts suitable for the process include copper (II) chloride, copper (II) bromide, copper - !! - sulfate, copper (II) azide, copper (II) te- tramine sulfate, copper (II) acetate, copper (II) butyrate Copper-II-toluate. Preferred copper (II) salts are Copper (II) halides, with copper (II) bromide am is most preferred. The concentration of the copper salts is expediently kept low and varied preferably from 0.2 to 2.5 mol per 100 mol of the Phenolic monomers.

In the patent application filed at the same time DE-OS 20 11 719 has already been recorded that the non-basic copper (II) salts that lead to the formation of the complex catalyst are used in their must be in an anhydrous form rather than in a hydrated form. In this said application is this is a requirement because a small amount of water

before the formation of the complex of the amine and the non-basic salt present in the system is very detrimental to the polymerization reaction and to the Formation of a catalyst complex with a significantly reduced catalytic activity leads. So it was found, for example, that with a complex catalyst made of copper (II) chloride dihydrate and an amine forming a polymer which has an intrinsic viscosity of less than about 50% of that of a polymer formed using an amine catalyst and an anhydrous copper (II) chloride has been.

The alcohol used in the reaction system is a lower aliphatic alcohol. Examples are methanol, ethanol, propanol and butanol. Methanol is the most preferred because this alcohol is often used as an anti-solvent to precipitate and recover the polymer from the Resection Solution is used. In a corresponding manner, the use of the ethanol does not result in any additional organic compound is introduced into the reaction system. The amount of alcohol is added preferably kept low and can be, for example, 0.2% by volume of the entire reaction system. Preferably, the alcohol content is in a range from 0.5 to 3.0% by volume of the reaction system.

The polymerization reaction is carried out in a solvent from the general class such as those described in US Pat aforementioned US patents 33 06 874 and 33 06 875 is carried out. Aromatic Solvents like benzene and toluene give the best results. In addition, the reaction mixture an activator, such as a diarylguanidine, as described, for example, in the simultaneously filed patent application DE-OS 20 11 710, or contain a diarylformamidine. In other respects, the method of forming the polymer as well as the Conditions such as temperature or oxygen flow rate are essentially the same, as described in the two aforementioned US patents 33 06 874 and 33 06 875, although the The reaction time for producing high molecular weight polymers is reduced. The aforementioned concentration ranges are preferred even though these ranges are in may vary to some extent depending on the oxygen flow rate or the reaction temperature. For economic Lower concentrations of copper (II) salt and amine are preferred for reasons. It's for that Inventi-ng characteristic that a reaction system using an alcohol and a catalyst complex selected from a primary or secondary Amine and a t-m non-basic copper (II) salt is formed, the production of high molecular weight polymers with lower concentrations of copper (II) salts and Amin allowed than would otherwise be allowed.

The invention is further illustrated by the following examples, examples 1 to 4 comparing processes for the formation of a polyphenylene acid. In Example I, a catalyst complex of an anhydrous non-basic copper (II) halide and amine, in Example 2 an anhydrous copper (II) halide and an amine in the presence of an alcohol, in Example 3 an aqueous solution of a copper (II) Halopenide and an Am ^: rs and in Example 4 an aqueous solution of a copper II halide and an amine in the presence of an alcohol used.

Comparative example 1

A catalyst complex was added to 100 ml of toluene produced, in which 0.42 g of anhydrous copper-II bromide, 103 g of a di-n-butylamine and 4 ml of a 55 % By weight solution of 2,6-xylenol in toluene were stirred together. The catalyst complex thus prepared was placed in a 1 liter bottle containing a cooling coil, a thermometer and gas inlet Provide guide tubes for oxygen and the monomer was. Following the preparation of the catalyst, 400 ml of toluene were added and the mixture was driven at a speed of 1500 revolutions / minute by a single 5 cm χ 0.63 cm turbine nenmischer stirred while oxygen with a Rate of 2831 / hour was passed into the reaction mixture. Then 127 g a 55% strength by weight solution of 2,6-xylenol dissolved in toluene was added within 8 minutes. the Temperature was maintained during the ftsaktionszeit to 30 ⁰ C by water was passed from a constant temperature bath through the coil in the reaction mixture. After one hour and 45 minutes, the temperature was increased to 35 ° C and after 15 30 ml of a 50% strength by weight aqueous acetic acid solution were added for minutes to stop the reaction. The mixture was centrifuged and that Polymers precipitated from the upper toluene phase by adding methanol The polymer was filtered off, washed with methanol and the poly (2,6-dimethyl-1,4-phenylene) ether was obtained dried in a yield of 90% of theoretical at 70 ⁰ C under vacuum and the polymer had an intrinsic viscosity of 0.61 deciliters per gram (dl / g), measured in

Chloroform at 30 ° C example 1

The procedure described in Comparative Example 1 was repeated, but 6 ml of methanol were added added to the components of the catalyst. The amount of methanol added corresponded to 1% by volume all of the reaction ingredients in the reaction mixture. This was followed by the addition of the 2,6-xylenol in Toluene. The polymer was obtained in a yield of 97% of theory and had an intrinsic molar mass Viscosity of 0.65 dl / g.

Comparative example 2

The procedure of Comparative Example I was repeated with the exception that 034 g of a 50 % strength by weight aqueous copper (II) bromide solution instead of the anhydrous copper (II) bromide in Comparative Example I occurred. The polymer was used in an amount of 58% of theory was obtained and had an intrinsic viscosity of 0.09 dl / g.

Example 2

The method according to Comparison 3 Example 2 was used repeated, but 6 ml of methanol were added to the components of the catalyst system. That Polymers were obtained in a yield of 96% of theory and had an intrinsic viscosity of 0.55 dl / g.

The results of the above examples are summarized again in the table below:

Copper salt / usal /

Howl

(irundmohire Viscosity

(dl / g)

Comparative example 1 CuBn (anh) _ 90 0.61 example 1 CuBr, (anh) MeOH 97 0.65 Comparative example 2 CuBn (aq) - 58 0.09 Example 2 CuBniaq) MeOH 96 0.55

Comparing Comparative Example I and Example I / cigl. because when using anhydrous Kupft_M-11-Hromitl, the addition of methanol improves both the howling and the gruiulniolarc viscosity. In comparative example 2, where an aqueous solution of copper-II-broinide was used for the formation of the catalyst, the yield was low and the intrinsic molar viscosity of ¹ unacceptable. The addition of methanol in Example 2 resulted in a substantial increase in the howling and a greenish violet viscosity. which was clearly in the acceptable range.

Comparative example 5

A catalyst complex was prepared with 100 ml of toluene by adding 0.7 g of anhydrous copper M ~ (blonde. 10.9 g of di-n-biitvlamin and 4 ml of a V ">l'cw." Uigen solution of 2.b-xylenol in The catalyst complex prepared in this way was placed in a 1 liter manufacturer, which was provided with cooling coils, a thermometer and linear tubes for the oxygen and the monomer 400 ml of toluene were added and the mixture was stirred with a simple 3 cm χ · 0.6 J cm turbine stirrer at a speed of 1500 rpm / minute, with oxygen being introduced into the reaction mixture at a rate of 28% / hour 121g of a water amount of 2.O-Xyicimi dissolved in Tiiimii iiuiei iiaib of ο minutes / ug was added. The temperature was kept at 10 C during the reaction by pouring water from a constant Tcmncratiirhad through the snakes Hi the Rcaktions mixture escorted. After one hour and 45 minutes, the I empcralur was added to J) (L'esici.L'en. And I) Minutes later, 10 ml of a 55% by weight aqueous Lssigsaurelösur were added to stop the reaction. The mixture was centrifuged and the polymer was precipitated from the upper foluene phase by adding methanol. The polymer was filtered off, washed with methanol and dried at 70 ° C. under vacuum. A yield of 65.0 g of poly (2,6-dimethyl-1.4-phenylenediamine (95 ⁰ O of theory) with an intrinsic molar viscosity of 0.46 dl / g was obtained.

Example 3

The procedure according to Comparative Example 3 was repeated. However, 6 ml of methanol (approx % By volume of the total reaction components including monomers and solvents in the reaction mixture) added to the components of the catalyst. The polymer was obtained in a yield of 92% obtained according to theory and had an intrinsic viscosity of 0.61 dl / g. A comparison of this example with comparative example 3 showed a substantial increase in the gniiidmolaren viscosity, ml (ίπιικΙ the Addition of the methanol.

Example 4

The procedure according to Example i was repeated, but the amount of methanol was increased to 12 ml, el. H. it was the DOJ) PeIIi ¹ <li ^M m example! amount used. The polymer would have a yield of 41% of theory, and had an intrinsic viscosity of Ob 1 dl / g

Example ■ ">

I), The procedure according to Example J was repeated, but isopropyl alcohol was used instead of methanol. IVis polymers were obtained in a yield of ¹ > 7 "" i. \ ^ I theory and possessed ¹ ! an intrinsic viscosity of 0.5 i dl / g.

B e '. s ρ ι e I b

The procedure according to Example 1 was repeated, but the concentration of the copper-II-chloride was reduced by 50 "Ii. The polymer was obtained in a yield of around 4% of theory, had an intrinsic viscosity of 0.4 h dl / G.

Comparative example 4

I. in raw-like reaction vessel, which is equipped with a Vibro mixer Thermometer and an oxygen inlet tube was provided. was with 120 m; Toluene. 0.71g π πι Ii yia in ι π and ύ.22 j g (u.wi ivioi) anhydrous copper-II-bromide loaded. The mixture was stirred and 10.0 g of the 2,6-xylenol dissolved in 20 ml of toluene were added added. Oxygen was bubbled through the stirred mixture for approximately 120 minutes during which time When the reaction temperature falls to 25 C. The Polymerisalionsreaklion was with T'ssigsäurc to Broke off, removed the acid layer and that Polymers precipitated with methanol. The polymer, slurried with methanol and then in vacuo had been dried, weighed 9.1 g (93% of theory) and had an intrinsic viscosity of 0.44 dl / g.

Example 9

The process according to Comparative Example 4 was repeated with the addition of 1% by volume of methanol (based on the total volume of the reaction v stems). The polymer was obtained in an amount of 91 mi of theory and cut a basal molar Viscosity number of 0.50 dl / g.

Example IO The procedure of Example 9 was repeated.

WOuCi Ü3S! ViCtiiünOi OüTCn j '/ O iSOpropyiuiKOllöl CrSCiZi became. The polymer yield was 92.8% of theory and the polymer had a fundamental molar mass Viscosity of 0.60 dl / g.

Claims (1)

Patent claims: 1. Process for the production of high molecular weight polyphenylene ethers from a monovalent phenol by an oxidative coupling reaction in the presence of a catalyst complex of a non-basic copper (II) salt and a primary or secondary amine in the presence of a solvent and optionally an activator, characterized in that the monovalent Phenol of the formula