DE1770050C - Process for the preparation of macromolecular polyphenylene oxides - Google Patents

Description

R.-

-R,

8. Catalyst for carrying out the process «measure claim!, Characterized in that that it consists of 0OJ to 50 moles, drawn to 100 moles of the phenol used, a manganese, Cobalt or copper compound, 0.1 to 500 moles, based on 1 mole of the manganese, cobalt or Copper compound, an alkali metal alcoholate or a single unsubstituted or ring-substituted one Alkali metal phenolate and optionally 0.01 to 5 mol, based on 100 mol of the used Phenol, a compound that produces free radicals. consists.

^{R; l}

in which R ₁ , R ₂ , R ₃ . R ₄ and R, hydrogen or halogen atoms, hydrocarbon radicals, substituted hydrocarbon radicals, cyano, alkoxy, phenoxy, nitro or mono- or disubstituted amino groups mean at least one of the radicals R ₁ , R _; , R ₃ , R ₄ u.id R _{5 is} a hydrogen atom and at least one of the radicals is a radical other than a hydrogen atom, with oxygen or a gas containing free oxygen in the presence of catalysts, characterized in that the polymerization is carried out with exclusion of water in In the presence of a catalyst, which consists of 0.05 to 50 moles, based on 100 moles of the phenol used, of a manganese, cobalt or copper compound, 0.1 to 500 moles, based on one mole of the manganese, cobalt or copper compound , an alkali metal alcoholate or an unsubstituted or nucleus-substituted alkali metal phenolate and optionally 0.01 to 5 Mo !, based on 100 mol of the phenol used, a compound which produces free radicals.

2. The method according to claim 1, characterized in that the phenol is 2,6-xylenol used.

3. The method according to claim 1, characterized in that the polymerization is carried out with a phenol according to claim 1, in which the radicals R ₁ and / or R _{2 are} alkyl, methoxy or allyl groups or chlorine atoms.

4. The method according to claim 1, characterized in that the polymerization is carried out with a phenol according to claim 1, in which the radical R _{3 is} an alkyl group.

5. The method according to claim 1 to 4, characterized in that as manganese, cobalt or Copper compound manganese chloride, potassium permanganate, barium permanganate, manganese bromide, Cobalt acetate, cobalt acetylacetonate, cobalt chloride, copper acetate, copper chloride or copper acetylacetonate used.

6. The method according to claim 1 to 5, characterized in that the alkali metal alcoholate or unsubstituted or nucleus-substituted alkali metal phenate, potassium methylate, sodium methylate, Potassium n-butoxide, sodium n-butoxide, sodium phenolate, sodium 2,6-dimethylphenolate or potassium p-tert-octylphenolate is used.

7. The method according to claim 1 to 6, characterized in that there is used as free radicals supplying compound benzoyl peroxide, azoisobutyric acid dinitrile, cumene hydroperoxide or acetyl peroxide used.

It is known to use macromolecular polyphenylene oxides dur.h oxidative polymerization of phenols Potassium hexacyanoferrate (III) (cf. J. Am. Chem. Soc, Vol. 82 [1960], p. 3632) with a copper salt-amine complex (French patent 1 234 336) or manganese (II) acetylacetonate (Abstract of the 15th Polymer Symposium, II E 15 [19. November 1966]) as a catalyst. Furthermore, this is the simultaneous use of an amine or an amine complex from Japanese patent publications 3195/67 and 4673/67 known.

These known methods have, inter alia, the disadvantage that the catalytic activity of the MangandO-acetylacetonate is so low that macromolecular polyphenylene oxides only when used of at least equimolar amounts can be obtained or that as much tertiary amine what is required for oxidative polymerization is that it is difficult to discolour the polymer impede.

The object of the invention is to provide a process for the production of macromolecular polyphenylene oxides in good yield and with the help of a cheap catalyst system in which the catalyst residues can easily be separated from the polymers.

The invention thus relates to a process for the preparation of macromolecular polyphenylene oxides by oxidative polymerization or copolymerization of phenols of the general formula I

OH

I. R4 -, - R2

in which R ₁ , R ₂ , R ₃ , R ₄ and R _{5 represent} hydrogen or halogen atoms, hydrocarbon radicals, substituted hydrocarbon radicals, cyano, alicoxy, phenoxy, nitro or mono- or disubstituted amino groups, at least one of the _{R 1} , R ₂ , R ₃ , R and R ₆ radicals are hydrogen and at least one; the radical means a radical other than a hydrogen atom, with oxygen or a gas containing free oxygen in the presence of Kataly

sators. The procedure is characterized by that the polymerization under exclusion of water carried out in the presence of a catalyst from (1.05 to 50 mol. Based on 100 mol of the Phenol, a manganese, cobalt or copper compound, 0.1 to 50G moles, based on 1 mole of the manganese. Cobalt or copper compound, one Alkali metal alcoholate or an unsubstituted one or ring-substituted alkali metal phenolate and optionally 0.01 to 5 mol, based on 100 mol of the phenol used, a compound that generates free radicals.

Examples of the substituents R ₁ , R.,. R ₁ . R ₄ and R ₇ are hydrogen, chlorine, bromine or iodine atoms. Methyl, ethyl, propyl, aryl, allyl, benzyl, λ-methylbenzyl, chloromethyl. Bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy, nitro, monomethylamino and dimethylamine groups.

In the Vi Jiren according to the invention, a phenol of the general formula I in which the radicals R ₁ and / or R _{2 are} alkyl, methoxy or allyl groups or chlorine atoms and / or in which R _{3 is} an alkyl group is used before /.

Specific examples of the phenols which can be used in the process according to the invention are 2-methylphenol, 2,5-dimethylphenol, 2-ethylphenol, 4 - (\ - methylbenzyD-phenol, 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6 -Diallylphenol, 2,4-dibenzylphenol, 2-chlorophenol, 4-bromophenol, 3-iodophenol, 2,3,5-trichlorophenol, 4-bromomethylphenol, 2-methyl-6-bromophenol, 2,4-dimethyl-3-i iilophenol, 3,5-dimethyl-2, ^-1 dichlorophenol, 3-methoxyphenol, 2,6-dimethoxyphenol, 4-cyanophenol, 2-f itrophenol and 2-dimethylaminophenol.The phenol can be used alone or for the production of copolymers together with another phenol be used.

If a phenol with an alkyl group is used as a substituent, a polymer with an unsaturated side chain is obtained in the oxy- dative polymerization or copolymerization. In this case, graft copolymers can be prepared by adding a reactive monomer which contains an olefinic or acetylenic bond in the oxidative polymerization, or by graft copolymerizing the reactive monomer with the macromolecular polyphenylene oxide obtained.

Examples of the manganese compounds that can be used in the process according to the invention are manganese iodide, Manganese fluoride, manganese phosphate, manganese phosphite, ammonium manganese phosphate, manganese nitrate, Manganese carbonate, manganese format, manganese acetate, manganese monochloroacetate, manganese propionate, manganese stearate, Manganese linoleate, manganese oxalate, manganese succinai, manganese phthalate, vlangan benzoate, manganese p - toluenesulfonate, manganese - ρ - hydroxybenzenesulfonate, manganese n-butylate, the complex salt of manganese bromide with acetic acid, potassium manganese chloride, calcium permanganate, Magnesium permanganate, potassium manganese fluoride, potassium manganate, manganese dioxide, the Manganese salt of salicylic acid, salicylaldehyde and ethyl acetoacetate. Particularly preferred Manganese compounds that can be used in the process according to the invention are manganese chloride, potassium permanganate, Barium permanganate and manganese bromide.

Of the cobalt compounds that can be used in the process according to the invention, the two and three are few Compounds preferred, e.g. P. cobalt bromide. Kobalt Nitrai. Cobalt phosphate. Carbonate. Cobalt toxinate. Carbon salicylate. Cobalt splithalate and cobalt stearate: cobalt acetal is particularly preferred. Cobalt acetylacetonate and cobalt chloride.

All monovalent and divalent copper bonds can be used in the process according to the invention. /. B. copper carbonate. Copper bromide. basic copper acetate. Copper oils; ¹ 1, copper oxalate.

ίο copper oxide, copper thiocyanate. Ammonium copper sulfal. Copper salicvlate and copper oxinate. Copper acetate is particularly preferred. Copper chloride and copper acetyl acetonate.

These compounds can be used alone or in admixture. The amount of the analyzer is in Range from 0.05 to 50 moles, preferably in the range from 0.1 to 10 moles, based on 100 moles of the phenol.

In the process according to the invention, the alkali acts

Alcoholic or unsubstituted or unsubstituted Alkali metal phenate apparently as a ligand for the manganese, cobalt or copper compound and increases the activity of the catalyst. The alkali metal can be in the alcoholate or phenolate in addition to sodium and potassium, it can also be lithium. Examples of alcoholates or phenates are aliphatic, alicyclic. heterocyclic and aromatic alcoholates and phenates, which are also substituted be able. Special examples for alcoholates and phenolates which can be used in the process according to the invention are the sodium, potassium and lithium alcoholates or phenolates of methanol, ethanol, n-propanol, Isopropanol, n-butanol, tert-butanol, cyclopentanone n-pentanol, tert-pentanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol. Ethylene glycol, triethanolamine, 1,1-propylene glycol, 1,3-propylene glycol, 1.6-hexamethylene glycol, ethylene glycol monomethyl ether, Cyclohexanol, benzyl alcohol, furfuryl alcohol, phenol, 4-dimethylamine kihenol, pyrocatechol. 2-methylphenol, 4-methylphenol, 2,6-dimethylphenol, 4-methoxyphenol, 4-chlorophenol and 2,5-dimethylphenol. Potassium methylate, sodium methylate, potassium n-butylate, sodium n-butylate are particularly preferred, Sodium phenolate, sodium 2,6-dimethylphenolate and potassium p-tert-octylphenolate.

Jf ₁ The alcoholate or phenolate is used in an amount of 0.1 to 500 mol, based on the manganese, cobalt or copper compound.

Oxygen or a gas containing free oxygen can be used as the oxidizing agent.

so when using air is the reaction rate low. If oxygen is used, it is blown into the reaction mixture or one works in a closed system. When using an oxygen-rich gas, the reaction mixture vigorously stirred or otherwise kept moving to maintain good contact. In this case it is not necessary to vent the residual gas from the system. Sometimes it can too be favorable, the oxidative polymerization or mixed

carry out polymerization in a closed system under pressure. Oxygen gets into the reaction mixture initiated until the heat build-up ceases or the desired amount of oxygen is absorbed is.

6g Preferably in the method according to the invention a compound which produces free radicals is also added to the reaction mixture. When using z. B. Benzoyl peroxide, azoisobutyric acid dinitrile, Cu

5 6

molar hydroperoxide or aeetyl peroxide together with compound to form a mixture of the reaction

Oxygen is the oxidative polymerization still medium and the polymerization catalyst or

further accelerated. In the inventive method by adding the catalyst to a mixture

the usual peroxide compounds can drive. ver from the diluent, the phenol and the

be turned. 5 free radical generating compound or by adding

The free radical producing compounds can be added to the free radical producing compound too

can be used alone or in admixture. You will be a mixture of the diluent, the

in an amount of 0.01 to 5 mol, in particular 0.1 phenol and the catalyst,

up to 1 mole, based on lOOMol of the phenol, is used. When the reaction has ended, the polymer becomes

The process according to the invention can in abio be carried out by adding a solvent which does not dissolve the polyeness of a diluent and, if necessary, can become a small one. Preferably, however, a dilution amount of inorganic acid is used to completely remove the agent in order to control the reaction conditions to remove catalyst residues, to control the reaction conditions more easily and to work up the polymer more easily, and the polyphenylene oxide is separated off. To be able to speak. Any diluent can be used, if a solvent which the polymer is used, provided that it does not dissolve during the polymerization, the reaction temperature of liquid phenol can be inert and the polymer can be separated off directly. No implementation with the catalyst is received when it is released. When separated, the catalyst usually remains in the solvent. Solvents that can be used are dissolved, so that in this way the branched, branched or cyclic aliphatic constituents of the polyphenylene oxide are purified at the same time. Hydrocarbons, aromatic hydrocarbons, derivatives of these hydrocarbons, such as nitro compounds, are macromolecular polyphenylene oxides with at least bonds. Halogen compounds, Hydroxyverbin- 50 monomer units obtained. It is possible through fertilizing, ethers, ketones, lactones, and sulfonates. Working under certain conditions, various special examples of diluents are hep- 25 macromolecular polyphenylene oxides with special tan, benzene, toluene, chlorobenzene, dichlorobenzene, to produce properties. The yields are satisfactorily high in nitrobenzene, methylcyclohexane, hydroxy compounds according to the invention, such as methanol, ethanol, butanol and 2-methoxy

ethanol, methylene dichloride, ethylene dichloride, di-. . ethyl ether, tetrahydrofuran, dioxane, acetone, vinegar - example! acid ethyl ester, propiolactone and acetonitrile. Methanol, 2-methoxyethanol and other hyd.oxyver- In a three-necked flask with a thermal link the alcoholate or phenolate can dissolve well meter, a reflux condenser and a gas and thus increase the catalytic effect; line pipe is provided, 100 ml of 2-Methoxysie are particularly preferred diluents with regard to the polymerization rate 35 ethanol, 3.48 g potassium methylate and 0.413 g Mandigkeit. gar. (II) chloride submitted. The mixture is at

Sometimes this dilution is used, stirred with a magnetic stirrer at 25 ° C., and oxygen is preferably introduced as a mixture, in particular a substance is introduced in an amount of 0.5 l / min. Solvent mixture of 2-methoxyethanol or Then 4.0 g of 2,6-xylenol are entered, and the ethanol with nitrobenzene or xylene. 40 reaction is used with continuous stirring and a solvent in which polyphenylene oxide is carried out for 7 hours by introducing oxygen, is readily soluble, such as nitrobenzene, together with the Then the reaction mixture is converted into a large hydroxy compound, this has the advantage that the amount Poured in methanol, which is increased a small amount of the rate of polymerization and that contains hydrochloric acid, and the precipitate obtained is filtered off with a polyphenylene oxide having a higher molecular weight. The filter: ückstanil is weighted with methanol can be obtained. The diluent is washed and then dried. 3.11 g in an amount of 1 to 100 parts by weight, preferably a white polymer powder, are obtained. The intrinsic way 5 to 20 parts by weight, per part by weight of phenol viscosity of the polymer, measured at 25 ° C in used. Preferably the diluent is chloroform, is 0.46. Virtually anhydrous based on the IR analysis. The presence of water 50 is the polymer is a polyphenylene oxide with strong in the reaction medium is in the invention absorption of the ether group at 1190 cm " ¹ and not desired, since this results in the mol- 1015 cm ^-1 and absorptions of the phenyl group at the molecular weight of the polyphenylene oxides obtained ver 1600 cm- ¹ and 1470 cm " ¹ . When the burn rings and their gel formation is effected. analysis leaves no ashes.

The reaction temperature is set to 55

Value adjusted that the reaction medium is liquid. Example 2 is. To prevent side reactions, the

Reaction temperature is usually below 150 ^c C, Gem ^s ß Example 1, 2.87 g of polymer by

preferably between 10 and 100 ° C. 4 hour response time obtained. The reaction

The inventive method in the presence of 60 batch, 0.005 g of benzoyl peroxide are added. the

of a diluent is practically as measured by the intrinsic viscosity of the polymer

led to the fact that the manganese, cobalt or copper 25 ⁰ C in chloroform is 0.44. compound or mixtures thereof, the alkali metal

alcoholate or unsubstituted or nuclear substitu- Example 3

lerte alkali metal phenate, the diluent 65

and the free radical generating compound in each In the same reaction vessel as in Example 1 any order to each other, e.g. B. by 100 ml of 2-methoxyethanol, 2.68 g of sodium addition of the phenol and the free radical-supplying methylate and 0.413 g of manganese (II) chloride are presented.

7 '8

The mixture is stirred and oxygen is passed in. of manganese (II) chloride, however, 0.58 g of cobalt

Then 4.0 g of 2,6-xylenol are introduced and the acetate is used.
The reaction mixture was stirred at 25 ° C. for 5 hours and

then with a ktcinc amount of hydrochloric acid ent- Example 11
holding methanol added, with a white 5

Polymer precipitates. The precipitate is filtered, according to Example 10, 2.43 g of polymer are with wash and dry. 2.39 g of polymer with an intrinsic viscosity of 0.41 are obtained instead receive. However, the intrinsic viscosity of this polymer, of potassium methylate, is 4.77 g of potassium at 25 ° C in chloroform, is 0.28. n-butylate used.

IO

Example 4. Example 12

According to Example 3, the polymerization is 5 hours. According to Example 3, 0.93 g of polymer are added

the carried out, obtained instead of 2-methoxyethanol, an intrinsic viscosity of 0.14, instead of sodium methylate and manganese chloride, however, 15 of manganese chloride are 0.16 g of KobaU - a mixture of 60 ml of nitrobenzene and 10 ml of 2-Mcth - acctyl octonate used,
oxyethanol, 4.77 g potassium n-butylate and 1.23 g Ba-

rium per manganate or 1.23 g of potassium permanganate Example 13

used. There are 2.11 g of polymer with a

Intrinsic viscosity of 0.25 or 3.51 g of polymer ao. According to Example 5, 2.21 g of polymer are added with an intrinsic viscosity of 0.54. an intrinsic viscosity of 0.193 instead of

of potassium methylate and manganese (II) chloride

Example 5, however, 4.77 g of sodium n-butoxide and 0.13 g of cobalt

chloride used.

According to Example 1, 2.61 g of polymer with 25

obtained an intrinsic viscosity of 0.32 instead of Example 14

however, 2,6-xylenol becomes 2,6-dimethoxyphenol

used. In the same reaction vessel as in Example 1 who

submitted to the 60 ml of nitrobenzene. Then will

Example 6 30 entered a mixture that by adding 0.124 g

Manganese (H) chloride to 10 ml of methanol containing 0.213 g

10 g of manganese (II) bromide are contained in 50 ml of water containing sodium methylate. Entered free ethanol, and the mixture is passed in oxygen with vigorous stirring, stirred overnight. The ethanol is then added under 30 ml of nitrobenzene, which contains 4.0 g of 2,6-xyl at reduced pressure and without heating, and which contains 35 mol. The residue is dried with further introduction. It is a manganese (II) - of oxygen is obtained 2 hours at 40 ⁰ C bromide Älhanol-Komplcxsalz the reaction. accomplished. With the same processing as in the case of

According to Example 1, 3.14 g of polymer are obtained with game 1, 3.71 g of polymer are obtained with an inciner intrinsic viscosity of 0.43, but a trinsic viscosity of 0.96.
instead of potassium methylate and manganese (ll) - 4 »

chloride 0.21 g of the aforementioned complex salt from Example 15

turns.

According to Example 14, 3.69 g of polymer are added

Example 7 with an intrinsic viscosity of 0.74 obtained in place of

45 of nilrobenzene and methanol, however, are chlorine- According to Example 1, 1.69 g of polymer with benzene and n-butanol are used,
an intrinsic viscosity of 0.19 instead of

of manganese (II) chloride, however, 0.2 g of copper (l) - Example 16

chloride used.

As in Example 14, 3.91 g of polymer are added

Example 8 with an intrinsic viscosity of 0.58 obtained in place of

of MangauOO-chloTid and methanol ”however earth

According to Example 3, 1.33 g of polymer with 0.364 g of barhimpermanganate and ethanol are used obtained an intrinsic viscosity of 0.19, instead of and the reaction carried out at S0 ° C, of manganese chloride, however, 1.2 g of copper 55 acetal used Example 17

B e i s ρ i e 1 9 In the same reaction vessel as in Example 1

will be 180 m! Nitrobenzene is then submitted

According to Example 4, 1.93 g of polymer with 60 mixture are introduced, which by adding 30 m! obtained an intrinsic viscosity of 0.16, instead of methanol containing 1.00 g of Nftriumphenolat with of barine permanganate, however, 1.1 g of copper 0.12 g of manganese (II) chloride has been produced, acetylacetonate used. and oxygen into the vessel while stirring well

mixed initiated. Then 4.0 g of 2,6-xylenoi

In game 10 ⁶ S entered and the reaction for 3 hours at Sv) ⁰ C

It is carried out similarly to Example 1

According to Example 1, 2.81 g of polymer are used and 3.6 g of polymer are obtained with a obtained an intrinsic viscosity of 039 instead of an intrinsic viscosity of 1.3).

Example 18

According to Example 17, 3.78 g of polymer with an intrinsic viscosity of 1.3 are obtained instead of methanol and sodium phenolate, however, 30 ml of ethanol and UOg of potassium p-tert.-octylphenolate are obtained used.

Example 19

In an autoclave 63 p, 2,6-xylcnol, 230 μ xylene, 9.0 g 22% melhanolic sodium methylate solution and presented a solution of 1.07 g of manganese (II) chloride in 18 g of methanol. While stirring oxygen is passed into the mixture and a pressure of 2 atm is maintained. After 150 minutes At 30 C, with a similar work-up as in Example 1, 60.5 g of polymer with an intrinsic viscosity are obtained of 1.05.

Example 20

According to Example 19, those in the following list are included The phenols mentioned in the table are polymerized.

table

example Monomer Sales volume.
Weight
percent Intrinsic
viscosity 20th 2,6-dichlorophenoI 91 0.51 21 2-methyl 6-chlorophynol 93 0.63 22nd 2-methyl-6-allyl phcnol 86 0.49 23 2,6-diethylphenol 91 0.71 24 2.5-dimethyl phcnol 87 0.68 25th ο-Κ resol *) 39 0.47

*) 1.3 ρ sodium o-crsolate were added to the reaction mixture of Example 19 added.

Example 21

According to Example 19, 56.3 g of polymer with an intrinsic viscosity of 0.79 are obtained instead the Metlianolischen Sodium Methylallösung be but 2.1 g of sodium 2,6-dimethylphenolate in 7 g Methanol used.

Claims (1)

Patent claims: 1. Process for the preparation of macromolecular polyphenylene oxides by oxidative polymerization or copolymerization of phenols of the general formula I. OH