JPH0689130B2 - Polyphenylene oxide derivative and method for producing the same - Google Patents

Description

The present invention relates to a novel polyphenylene oxide derivative having an alkoxymethyl group or a phenoxymethyl group in its side chain, which is obtained by using polyphenylene oxide as a raw material, and a method for producing the same. It is about.

The polyphenylene oxide derivative of the present invention is a novel polymer which has not been published in the literature, and is useful as a polymer material excellent in mechanical strength and durability.

(Problems to be Solved by the Invention) Polyphenylene oxide is industrially used in various fields as a thermoplastic resin excellent in heat resistance, chemical resistance, mechanical properties, electrical properties and the like. However, since polyphenylene oxide alone is a rigid polymer having a high glass transition point, there is a problem that it is difficult to form a thin film by a solvent cast method or the like. Therefore, when it is desired to use polyphenylene oxide as a film, a film is formed by a melt extrusion molding method, or it is blended with a material having excellent film forming property such as polystyrene, polycarbonate, or polysiloxane copolymer, or It is usually used as a composite membrane. However, it is difficult to form a thin film having a thickness of several tens of μm or less by the extrusion molding method, or when it is used as a blend or a composite film, the excellent characteristics of polyphenylene oxide itself are often impaired, which is a problem.

The present invention improves the thin film forming property of polyphenylene oxide described above, maintains the excellent properties of polyphenylene oxide, and provides a novel polymer material capable of forming a thin film having excellent mechanical strength. It is intended to be provided.

(Means for Solving Problems) The present invention provides a general formula (In the formula, R and R ′ are groups selected from the group consisting of halogen, methyl group, alkoxy group, phenyl group, substituted phenyl group, halomethyl group and —CH ₂ OX, and R and R ′ are the same or different. At least one of them is a methyl group, a halomethyl group or -CH ₂ OX, and X is 1 selected from the group consisting of an alkyl group, a substituted alkyl group, a phenyl group and a substituted phenyl group. A polyphenylene oxide derivative consisting of a plurality of types of repeating units represented by the following formula, wherein A ¹ and A ² are each independently hydrogen or halogen, and a methyl group present in the polyphenylene oxide derivative molecule: 8 when the ratio of the halomethyl group and -CH ₂ OX is, that a methyl group, the total of the halomethyl group and -CH ₂ OX 100
5 to 40 to 34 to 0 to 60 to 2, and to a polyphenylene oxide derivative having an average molecular weight of at least 10,000.

In producing the polyphenylene oxide derivative of the present invention, the polyphenylene oxide used as a starting material has the general formula (In the formula, R ¹ and R ² are halogen, a methyl group, an alkoxy group, a phenyl group, and a nucleus-substituted phenyl group, and R ¹ and R ² may be the same or different, but either one is It is a methyl group) and is composed of a repeating unit represented by. Examples thereof include poly (2,6-dimethyl-p-phenylene oxide), poly (2-methyl-6-chloro-).
p-phenylene oxide), poly (2-methyl-6-fluoro-p-phenylene oxide), poly (2-methyl-6-methoxy-p-phenylene oxide), poly (2
-Methyl-6-ethoxy-p-phenylene oxide),
Poly (2-methyl-6-phenyl-p-phenylene oxide), poly (2-methyl-6-p-tolyl-p-phenylene oxide), poly (2-methyl-6-pentafluorophenyl-p) -Phenylene oxide) and the like. These polyphenylene oxides can be synthesized by the oxidative coupling reaction of 2,6-disubstituted phenols (see, for example, J. Am. Chem. Soc., Vol. 81, page 6335), or a part thereof. Is commercially available.

Polyphenylene oxide derivative of the present invention, general formula A polyphenylene oxide having a repeating unit represented by the following formula is treated with halogen to halogenate the nucleus-substituted methyl group, A halogenated polyphenylene oxide having a repeating unit represented by the following formula is obtained. Here, R ¹ and R ² are the same as explained above, and one of them must be methyl. R ¹¹ is the same as R ¹ or a halomethyl group when formed by a reaction, and R ²¹ is the same as R ² or a halomethyl group similarly accompanying a reaction. R ¹ , R ¹ , R ¹¹ , and R ²¹ may be different for each repeating unit. However, R ¹ , R ¹ , R ¹¹ , R in all repeating units of halogenated polyphenylene oxide
^At least 1% of the total number of ²¹ must be halomethyl group.

The halogenated polyphenylene oxide is produced by halogenating the polyphenylene oxide represented by the general formula (IV) in a solvent under a radical reaction condition with a halogenating reagent. I will do it.
That is, see, for example, JP-A-59-66421. That is, polyphenylene oxide is dissolved in a solvent and irradiated with light (visible light or ultraviolet light) or benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile. In the presence of a peroxide or a radical generator such as an azo compound, chlorine, bromine, sulfuryl chloride, -t-butyl hypochlorite,
The halogenated polyphenylene oxide can be obtained by reacting with a halogenating reagent such as N-chlorosuccinimide or N-bromosuccinimide.

In the above method, the solution concentration of polyphenylene oxide is preferably 1 to 20% by weight. The solvent used is preferably one that does not interact with halogen radicals generated during the reaction, and for example, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and trichloroethane are preferably used. Further, the irradiation amount of light is appropriately controlled depending on the progress of the reaction, the amount of the halogenating reagent, etc., and when a radical generator is coexisted, it is preferable to use about 0.001 to 0.05 equivalent to 1 equivalent of polyphenylene oxide. . The reaction temperature is usually room temperature to 200 ° C, more preferably 60 to 150 ° C. Further, the amount of the halogenating reagent to be used varies depending on its type, but it is 0.01 to 2 based on the repeating unit of polyphenylene oxide which is usually halogenated.
Halogenation is achieved by using equivalent amounts. By adjusting the amount of the halogenating reagent used, a halogenated polyphenylene oxide having a desired halogenation rate can be obtained.

The polyphenylene oxide derivative of the present invention is obtained by using the halogenated polyphenylene oxide represented by the repeating units (V) and (VI) obtained in the general formula XOH (VII) (wherein X is an alkyl group) in the presence of a base. Is a group selected from the group consisting of a substituted alkyl group, a phenyl group, and a substituted phenyl group.).

A halogenated polyphenylene oxide composed of repeating units of the general formulas (V) and (VI) is reacted with a compound having a hydroxyl group represented by the general formula (VII) in a solvent in the presence of a base.

The compound having a hydroxyl group of the general formula (VII) is an alcohol or a phenol, and CH ₃ OH, CH ₃ CH ₂ OH, CH ₃ CH ₂ ) ₂ OH, CH ₃ CH ₂ ) ₃ OH, CH ₃ CH _{2 6} OH, (CH ₃ ) ₂ CHOH, (CH ₃ ) ₃ COH, (CH ₃ ) ₃ CCH ₂ OH, (CH ₃ ) ₂ CHCH ₂ OH, CH ₂ = CHCH ₂ OH, CH ₂ = CHCH ₂ CH ₂ OH, CH≡CCH ₂ OH, CH ₃ C ≡CCH ₂ OH, CCl ₃ CH ₂ OH, CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, CF ₃ CF _{2 2} CH ₂ OH, CF ₃ CF _{2 5} CH ₂ OH, CF ₃ CH _{2 2} OH, (CF ₃ ) ₂ CHOH, (CF ₃ ) ₃ COH, (CF ₃ ) ₃ CCH ₂ OH, CF ₂ HCF ₂ CH ₂ OH, CF ₂ HCF _{2 3} CH ₂ OH, NH ₂ CH ₂ CH ₂ OH, (CH ₃ ) ₂ NCH ₂ CH ₂ OH, (CH ₃ ) ₃ SiCH ₂ OH, (CH ₃ ) ₃ Si (CH ₂ ) ₂ OH, Etc. can be illustrated. Alcohols containing fluorine are particularly preferable in that they improve the mechanical strength and solvent resistance of the film formed from the polyphenylene oxide derivative obtained by this reaction.

This reaction must be carried out in the presence of base.
Examples of the base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, methyllithium, n-butyllithium, t-butyllithium,
Lithium compounds such as lithium diisopropylamide, alkali metal hydrides such as sodium hydroxide and potassium hydride, or alkaline earth metals such as lithium, potassium and sodium are preferably used. These bases are usually used in an amount equivalent to or more than that of the compound having a hydroxyl group represented by the general formula (VII). Examples of the solvent used in this reaction include benzene, toluene,
Organic solvents such as carbon tetrachloride, THF, diethyl ether, methyl ethyl ketone and the like can be mentioned.

When the above bases are insoluble in the organic solvent used in the reaction, it is preferable to add a phase transfer catalyst. As the phase transfer catalyst, tetra-n-butylammonium hydrogen sulfate, tetramethylammonium bromide, tetra-n-
Examples thereof include butylammonium bromide, tetra-n-butylammonium iodide, tetrabutylammonium p-toluenesulfonate, benzyltrimethylammonium hydrogen sulfate, and compounds having a crown ether ring. These phase transfer catalysts are usually used in an amount equivalent to or less than that of the compound having a hydroxyl group represented by the general formula (VII). Particularly when an alkali metal hydroxide is used as the base, it is preferable to carry out the reaction in an aqueous solution of the base and in a two-phase system with the above organic solvent in the presence of a phase transfer catalyst. The reaction temperature is usually room temperature,
When the reaction is difficult to proceed, heating may be performed at 40 to 150 ° C.

Through the above reaction, the nucleus-substituted halomethyl group of the halogenated polyphenylene oxide is converted into an alkoxymethyl group or a phenoxymethyl group to synthesize the polyphenylene oxide derivative of the present invention.

The weight average molecular weight of the obtained polyphenylene oxide derivative is preferably 10,000 or more, more preferably 50,000 or more, from the viewpoint of enhancing the film-forming property of the derivative and the mechanical strength of the film formed from the derivative. Is. The larger the weight average molecular weight, the better the film-forming property and mechanical strength, but it is defined by the starting material and is usually 1 million or less.

From the film-forming property of the polyphenylene oxide derivative of the present invention and the mechanical strength of the film formed from the derivative, 1% or more of the total number of R and R'in the repeating unit of the general formula (I) is used. Is -CH ₂ OX, and 10% or more is preferably a group represented by -CH ₂ OX.

The polyphenylene oxide derivative of the present invention is toluene,
Soluble in aromatic solvents such as benzene, ethylbenzene, and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and trichloroethylene, or ether solvents such as diethyl ether and tetrahydrofuran, but insoluble in alcohols and water. is there. Further, the film formed from the polyphenylene oxide derivative of the present invention is a polymer solution obtained by dissolving the derivative in the above soluble organic solvent to a concentration of 0.5 to 20% by weight, and then the solution is a metal, A strong thin film can be obtained by gradually evaporating the solvent after spreading on a glass plate, a polyethylene fluoride plate, or a water surface. Further, a method in which the porous support is dipped in the polymer solution and then pulled up, or the solution is applied to the support and dried, can be adopted.

The polyphenylene oxide derivative of the present invention is a polyphenylene oxide having an improved mechanical strength, which has been used as a conventional polyphenylene oxide, for example, as an electric insulating material and an electric device part, and also as a cast compound. It is useful as a material for various electronic materials such as an electronic circuit protective film and a resist material, or a material for a substance separation film, by taking advantage of the fact that the film can be formed.

For example, when used as a substance separation membrane, the film thickness should be 0.01-
It is preferably 100 μm, particularly preferably 0.05 to 50 μm. Further, a thin film having a thickness of 1 μm or less is preferably used together with the support. As the support, a woven or non-woven support, a microfilter, an ultrafiltration membrane, or any other porous body having sufficient strength to support the membrane can be used. The membrane thus obtained can be used as a laminated membrane laminated with another membrane, and can be used in any shape such as a flat membrane, a tubular membrane, and a hollow fiber membrane. The target to be separated and concentrated is, for example, hydrogen, helium, oxygen, nitrogen, carbon dioxide, carbon monoxide,
Examples thereof include gas mixtures such as methane, ethane, propane and ethylene, and liquid mixtures such as water, methanol, propanol, various amino acids and acetic acid.

(Effects of the Invention) As described in detail above, the present invention solves the conventional problem of poor film forming ability of polyphenylene oxide, and is excellent in heat resistance and electrical characteristics of polyphenylene oxide. It is possible to provide a material capable of forming a functional thin film having sufficient film strength while maintaining the above characteristics.

(Example) Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it goes without saying that the present invention is not limited to these.

Example 1 (1) First, brominated polyphenylene oxide was synthesized by the following method.

Aldrich Co., number average molecular weight 1.70 × 10 ⁴ , weight average molecular weight 4.64 × 10 ⁴ poly-2,6-dimethyl-p-phenylene oxide 8.0 g (66.6 mmol) was dissolved in carbon tetrachloride 450 ml, N- 23.70 g (133.1 mmol) of bromosuccinimide was added, and the mixture was heated under reflux for 1 hour while irradiating light with an incandescent lamp of 500 W in an argon gas stream. After cooling the reaction solution, it was poured into 3 l of methanol to form a precipitate, and the precipitate was filtered and then dissolved in 500 ml of tetrahydrofuran, reprecipitated in 3 l of methanol, filtered and dried to obtain 14.00 g of a pale yellow powdery solid. It was The obtained solid was subjected to gel permeation chromatography (hereinafter abbreviated as GPC) measurement using tetrahydrofuran as a solvent. As a polystyrene conversion value, the number average molecular weight was 3.04 × 10 ⁴ , and the weight average molecular weight was 1.75 × 10 ⁵ . It was a polymer. The nuclear magnetic absorption spectrum (hereinafter abbreviated as NMR) of this polymer
As a result of measurement, the following peaks were detected.

δ (CDCl ₃ , ppm); 2.10 (s, proton peak due to nuclear-substituted methyl group), 4.35 (s, proton peak due to nuclear-substituted bromomethyl group), 6.52 (s, proton peak due to main chain phenylene ring), 6.67 (s , The proton peak due to the main chain phenylene ring) The nucleus-substituted methyl group -CH ₃ and the nucleus-substituted bromomethyl group -CH _{2 of} the polymer obtained by the integration ratio of the above proton peaks.
Atsuta in _{-CH 3 / -CH 2 Br = 41} /59 was calculated composition ratio of Br. The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 42.26, H, 2.94, Br, 47.93 From this elemental analysis value and the above composition ratio by NMR, it was found that 9% of the main chain phenylene ring of the polymer was brominated. It was

(2) 2.02 g of brominated polyphenylene oxide obtained by the above method was dissolved in 80 ml of toluene, and 4 ml of 50% aqueous sodium hydroxide solution was added to 2,2,3,3,4,4,4-heptafluorobutanol. 4.36 g (21.8 mmol) and tetra-n-butylammonium hydrogen sulfate 4.94 g (14.5 mmol) were added and the mixture was allowed to stand at room temperature for 5
After stirring for an hour, the reaction solution was poured into 1.2 l of methanol to generate a precipitate. The obtained precipitate was filtered, dissolved in 80 ml of toluene, reprecipitated in 1.5 l of methanol, filtered, and dried to obtain 1.98 g of a pale yellow polymer. The result of GPC measurement,
The polystyrene reduced values were number average molecular weight 6.90 × 10 ⁴ and weight average molecular weight 3.07 × 10 ⁵ . Further, when NMR was measured for this polymer, the following peaks were detected.

δ (CDCl ₃ , ppm); 2.10 (s, proton peak due to nucleus-substituted methyl group), 3.81 (t, proton peak due to side chain 2,2,3,3,4,4,4-pentafluorobutyl group) , 4.54 (s, proton substitution peak of 2,2,3,3,3,4,4,4-pentafluorobutoxymethyl group), 6.52 (s, proton peak of main chain phenylene ring), 6.67 (s, main chain) Proton peak due to phenylene ring) Based on the integral ratio of the above proton peaks, the nucleus-substituted methyl group-CH ₃ , the nucleus-substituted, bromomethyl group-CH ₂ of the obtained polymer
When the composition ratio of Br and nuclear-substituted 2,2,3,3,4,4,4-pentafluorobutoxymethyl group -CH ₂ OCH ₂ CF ₂ CF ₂ CF ₃ was calculated -CH ₃ / -CH ₂ Br / Atsuta in _{-CH 2 OCH 2 CF 2 CF 2} CF 3 = 40/0/60.
The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 42.02, H, 2.30 (3) 0.78 g of the obtained polymer was dissolved in 10 ml of toluene and cast on a 7 cm x 7 cm Teflon plate to remove toluene by evaporation and evaporation. It was possible to obtain a strong homogeneous film with a film thickness of 48 μm. A part of this film was attached to a tensile strength tester and subjected to a strength test at a tensile speed of 40 mm / mm. As a result, a breaking strength of 48.2 MPa, a maximum elongation of 4% and an initial elastic modulus of 1.13 GPa were obtained.

Example 2 (1) 3.03 g of the brominated polyphenylene oxide obtained in Example 1 (1) was dissolved in 150 ml of toluene, and 6 ml of 50% aqueous sodium hydroxide solution and hexafluoroisopropanol were added.
After adding 5.49 g (32.7 mmol) and tetra-n-butylammonium sulfate 7.34 g (21.6 mmol) and stirring at room temperature for 5 hours, the reaction solution was poured into 1.9 l of methanol to generate a precipitate. The obtained precipitate was separated by filtration, dissolved in 150 ml of toluene, reprecipitated in 1.8 l of methanol, separated by filtration, and dried to give 2.72 g.
To give a pale yellow polymer. As a result of GPC measurement, the number average molecular weight was 5.30 × 10 ⁴ and the weight average molecular weight was 3.39 × 10 ⁵ in terms of polystyrene. Also, for this polymer, NMR
Was measured, the following peaks were detected.

δ (CDCl ₃ , ppm); 2.10 (s, proton peak due to nuclear-substituted methyl group), 4.08 (t, proton peak due to side chain hexafluoroisopropyl group), 4.35 (s, proton peak due to nuclear-substituted bromomethyl group), 4.73 (s, proton peak due to nuclear-substituted hexafluoroisopropoxymethyl group), 6.52 (s, proton peak due to main chain phenylene ring), 6.67 (s, proton peak due to main chain phenylene ring) From the integral ratio of the above proton peaks , nuclear-substituted methyl groups -CH ₃ of the obtained polymer, nuclear-substituted bromomethyl group -CH ₂ Br, and nuclear substituted hexafluoro isopropoxymethyl group -CH ₂
When the composition ratio of OCH (CF ₃ ) ₂ was calculated, -CH ₃ / CH ₂ Br / -CH ₂ OC
H (CF ₃ ) ₂ = 41/34/25. The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 42.02, H, 2.30 (2) 0.72 g of the obtained polymer was dissolved in 10 ml of toluene and cast on a 7 cm x 7 cm Teflon plate to remove toluene by evaporation and evaporation. It was possible to obtain a strong homogeneous film with a film thickness of 45 μm. A part of this film was attached to a tensile strength tester, and a strength test was performed at a tensile speed of 40 mm / mm. As a result, a breaking strength of 34.7 MPa, a maximum elongation of 2.9%, and an initial elastic modulus of 1.22 GPa were obtained.

Example 3 1.05 g of the brominated polyphenylene oxide obtained in Example 1 (1) was dissolved in 50 ml of toluene, and 2 ml of 50% sodium hydroxide aqueous solution, 1.05 g (11.2 mmol) of phenol, and tetra-n-butyl sulfate were dissolved. After adding 3.12 g (9.19 mmol) of ammonium and stirring at room temperature for 20 hours, the reaction solution was added with methanol 1
To form a precipitate. The obtained precipitate was filtered, dissolved in 50 ml of toluene, reprecipitated in methanol 1, filtered, and dried to obtain 0.72 g of a pale yellow polymer. As a result of GPC measurement, polystyrene-equivalent number-average molecular weight 5.57 × 10
⁴ , the weight average molecular weight was 4.08 × 10 ⁵ . Further, when NMR was measured for this polymer, the following peaks were detected.

δ (CDCl ₃ , ppm): 2.10 (s, proton peak due to nuclear-substituted methyl group), 4.35 (s, proton peak due to nuclear-substituted bromomethyl group), 4.90 (s, proton peak due to nuclear-substituted phenoxymethyl group), 6.52 (s , Proton peak due to main chain phenylene ring), 6.67 (s, proton peak due to main chain phenylene ring), 7.08 (s, proton peak due to side chain phenyl group), 7.24 (s, proton peak due to side chain phenyl group) Based on the integral ratio of the proton peaks, the nucleus-substituted methyl group-CH ₃ , the nucleus-substituted bromomethyl group-CH ₂ Br and the nucleus-substituted phenoxymethyl group of the obtained polymer were determined. When the composition ratio of was calculated, It was. The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 66.61, H, 4.87, Br, 13.45 Example 4 1.00 g of the brominated polyphenylene oxide obtained in Example 1 (1) was dissolved in 50 ml of toluene, and a 50% aqueous sodium hydroxide solution was added. 2 ml, n-propanol 2.00 g (33.3 mmol), tetra-n-butylammonium sulfate 2.44 g (7.19 mmol)
Was added and stirred at room temperature for 24 hours, and then the reaction solution was poured into methanol 1 to generate a precipitate. The obtained precipitate was separated by filtration, dissolved in 50 ml of toluene, reprecipitated in methanol 1, separated by filtration, and dried to obtain 0.80 g of a pale yellow polymer. As a result of GPC measurement, the number average molecular weight was 4.08 × 10 ⁴ and the weight average molecular weight was 2.88 × 10 ⁵ in terms of polystyrene. Further, when NMR measurement was performed on this polymer, the following peaks were detected.

δ (CDCl ₃ , ppm): 0.80 (m, proton peak due to side chain propyl group), 1.50 (m, proton peak due to side chain propyl group), 2.10 (s, proton peak due to nucleus-substituted methyl group), 3.32 (m , Proton peak due to side chain propyl group), 4.40 (s, proton peak due to nuclear-substituted propoxymethyl group), 6.52 (s, proton peak due to main chain phenylene ring), 6.67 (s, proton peak due to main chain phenylene ring) than the integral ratio of the proton peaks, nuclear-substituted methyl groups -CH ₃ of the obtained polymer, the composition ratio of nuclear-substituted bromomethyl group -CH ₂ Br and nucleus-substituted n- propoxymethyl group -CH ₂ OCH ₂ CH ₂ CH ₃ When calculated, -CH ₃ / -CH ₂ Br / -CH ₂ OCH ₂ CH ₂ CH ₃ =
It was 41/0/59. The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 65.14, H, 6.44, Br, 10.45 Example 5 1.50 g of the brominated polyphenylene oxide obtained in Example 1 (1) was dissolved in 70 ml of toluene, and a 50% sodium hydroxide aqueous solution was added. 3 ml, 2-trimethylsilylethanol 1.91 g
After adding (16.2 mmol) and stirring at room temperature for 25 minutes, the reaction solution was reprecipitated in methanol 1, filtered off and dried.
37 g of a pale yellow polymer was obtained. As a result of GPC measurement, the number average molecular weight was 2.89 × 10 ⁴ and the weight average molecular weight was 1.49 × 10 ⁵ in terms of polystyrene. Also, for this polymer N
When MR was measured, the following peaks were detected.

δ (CDCl ₃ , ppm): 0.10 (s, proton peak due to side chain trimethylsilyl group), 0.95 (t, proton peak due to side chain 2-trimethylsilylethyl group), 2.10 (s, proton peak due to nuclear-substituted methyl group), 3.55 (t, proton peak due to the side chain 2-trimethylsilylethyl group), 4.35
(S, proton peak due to nuclear-substituted bromomethyl group), 4.
50 (s, proton peak due to nuclear-substituted 2-trimethylsilylethoxymethyl group), 6.52 (s, proton peak due to main chain phenylene ring), 6.67 (s, proton peak due to main chain phenylene ring) From the above integral ratio of proton peak Of the obtained polymer, nuclear-substituted methyl group-CH ₃ , nuclear-substituted bromomethyl group-CH ₂ Br and nuclear-substituted 2-trimethylsilylethoxy group-O-CH ₂ CH
_When the composition ratio of ₂ Si (CH ₃ ) ₃ was calculated, -CH ₃ / -CH ₂ Br / -O-
CH ₂ CH ₂ Si (CH ₃ ) ₂ = 40/6/54. The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 57.48, H, 6.32, Br, 16.76 Example 6 (1) Poly-2,6-dimethyl-manufactured by Aldrich, having a number average molecular weight of 1.70 × 10 ⁴ and a weight average molecular weight of 4.64 × 10 ^4. P-phenylene oxide 8.0 g (66.6 mmol) was added to carbon tetrachloride 450 ml.
Dissolved in N-bromosuccinimide 5.93g (33.1mmo
l) was added, and the mixture was heated under reflux for 1 hour while irradiating light with an incandescent lamp of 500 W in an argon gas stream. After cooling the reaction solution, it was poured into 4 l of methanol to generate a precipitate, and the precipitate was filtered and dissolved in 450 ml of tetrahydrofuran, reprecipitated in 4 l of methanol, filtered and dried to obtain 8.30 g of a pale yellow powdery solid. It was When GPC measurement was performed on the obtained solid, the polystyrene reduced value was the number average molecular weight of 1.
The polymer was 92 × 10 ⁴ and had a weight average molecular weight of 8.79 × 10 ⁴ . Moreover, when the detected similar peaks as in Example 1 was measured by NMR for the polymer was calculated composition ratio of nuclear-substituted methyl groups -CH _3, and nuclear-substituted bromomethyl group -CH ₂ Br by integration ratio, -CH ₃ / Atsuta in -CH ₂ Br = 83/17. The elemental analysis values are as follows.

Found: C, 63.50, H, 5.09, Br, 20.47 From this elemental analysis value and the composition ratio by NMR, it was found that 3% of the main chain phenylene ring of the polymer was brominated.

(2) 1.00 g of the brominated polyphenylene oxide obtained by the above method was dissolved in 50 ml of toluene, and 2.45 g of 50% aqueous sodium hydroxide solution and 1.62 g of 2,2,3,3,3-pentafluoropropanol ( After adding 2.45 g (7.21 mmol) of tetra-n-butylammonium hydrogen sulfate (10.4 mmol) and stirring at room temperature for 5 hours, the reaction solution was poured into methanol 1 to generate a precipitate. The obtained precipitate was filtered, dissolved in 80 ml of toluene, reprecipitated in methanol 1, filtered, and dried to obtain 0.86 g of a pale yellow polymer. The result of GPC measurement,
The polystyrene reduced values were number average molecular weight 3.36 × 10 ⁴ and weight average molecular weight 2.16 × 10 ⁵ . Further, when NMR was measured for this polymer, the following peaks were detected.

δ (CDCl ₃ , ppm): 2.10 (s, proton peak due to nucleus-substituted methyl group), 3.81 (t, proton peak due to side chain 2,2,3,3,3-heptafluoropropyl group), 4.54 (s , Proton-peak due to nuclear-substituted 2,2,3,3,3-heptafluoropropoxymethyl group), 6.52 (s, proton peak due to main chain phenylene ring), 6.67 (s, proton peak due to main chain phenylene ring) From the integral ratio of the proton peak, the nucleus-substituted methyl group of the obtained polymer-CH ₃ , the nucleus-substituted bromomethyl group-CH ₂ Br and the nucleus-substituted 2,2,3,3,3-heptafluoropropoxymethyl group-CH ₂ O When the composition ratio of -CH ₂ CF ₂ CF ₃ was calculated, -CH ₃ /
Atsuta in _{-CH 2 Br / -CH 2 OCH 2} CF 2 CF 3 = 85/0/15. The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 62.60, H, 4.86 Comparative Example The same poly-2, used as the raw material in Example 1,
0.75 g of 6-dimethylphenylene oxide was dissolved in 9 ml of toluene, cast on a Teflon plate and a glass plate having a size of 7 cm × 7 cm, and when toluene was slowly removed by evaporation, a crack was immediately generated. A homogeneous film could not be obtained by the method.

Claims (1)

[Claims] 1. A general formula (In the formula, R and R ′ are groups selected from the group consisting of halogen, methyl group, alkoxy group, phenyl group, substituted phenyl group, halomethyl group and —CH ₂ OX, and R and R ′ are the same or different. At least one of them is a methyl group, a halomethyl group or -CH ₂ OX, and X is 1 selected from the group consisting of an alkyl group, a substituted alkyl group, a phenyl group and a substituted phenyl group. A polyphenylene oxide derivative consisting of a plurality of types of repeating units represented by the following formula, wherein A ¹ and A ² are each independently hydrogen or halogen, and a methyl group present in the polyphenylene oxide derivative molecule: 8 when the ratio of the halomethyl group and -CH ₂ OX is, that a methyl group, the total of the halomethyl group and -CH ₂ OX 100
A polyphenylene oxide derivative having an average molecular weight of at least 10,000 of 5 to 40:34 to 0:60 to 2.