JPS61247729A - Polyphenylene oxide derivative and its production - Google Patents

Abstract

PURPOSE:To produce a polyphenylene oxide derivative excellent in mechanical strength and durability, by reacting a specified halogenated polyphenylene oxide with a hydroxyl group-containing compound in the presence of a base. CONSTITUTION:A halogenated polyphenylene oxide having repeating units of formulas II and III (wherein R<11> and R<22> are each R1 or a halomethyl, A<1-2> are each H or a halogen and at least 1% of the total of R<1-2>, R<11> and R<21> in the total repeating units are halomethyl groups), and obtained by halogenating a polyphenylene oxide having repeating units of formula I [wherein R<1-2> are each a halogen, methyl, alkoxy, or (substituted) phenyl, and either of these groups is methyl] is reacted with a hydroxyl group-containing compound in the presence of a base to obtain a polyphenylene oxide derivative having repeating units of formulae I, II and V (wherein R<111> and R<211> are each R<11> or -CH2OX and at least 1% of the total of R<1-2>, R<11>, R<21>, R<111> and R<211> are -CH2OX groups) and having a weight-average MW >=10,000.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel polyphenylene oxide derivative having an alkoxymethyl group or phenoxymethyl group in the side chain, which is obtained using polyphenylene oxide as a raw material, and a method for producing the same. be.

The polyphenylene oxide derivative of the present invention is a novel aggregate that has not been described in any literature, and is useful as a polymeric material with excellent mechanical strength and durability.

(Problems to be solved by the invention) HoIJ phenylene oxide has excellent heat resistance, chemical resistance,
It is used industrially in various fields as a thermoplastic resin with excellent mechanical and electrical properties.

However, polyphenylene oxide has a problem in that it is difficult to form a thin film by a solvent casting method or the like because it is a hard polymer with a high glass transition point when used alone.

Therefore, if you want to use polyphenylene oxide as a film, you can either form the film by melt extrusion or use polystyrene.

It is usually blended with a material with excellent film-forming properties such as polycarbonate or polysiloxane copolymer, or used as a composite film. However, using extrusion molding, it is difficult to form a thin film of several tens of micrometers or less, and when used as a blend or composite film, the excellent characteristics of b and ys rifhenylene oxide itself are often impaired. .

The present invention aims to improve the thin film forming properties of polyphenylene oxide described above, maintain the excellent properties of polyphenylene oxide, and provide a novel polymeric material capable of forming a thin film with excellent mechanical strength. This is the purpose.

(Means for Solving the Problems) The present invention is based on the general formula: one of which is a methyl group.R11 is a group selected from the group consisting of
R21 is the same as R2 or a halomethyl group R111 is the same as R11 or -CH2
0X (x is a group selected from the group consisting of an alkyl group, a substituted alkyl group, a phenyl group, and a substituted phenyl group.) R211 is the same as R21, or -CH20X and one of R111 and R211 is 〇fi
20X (X is the same as above), A, A,
R, R, R%R may be arbitrarily different for each repeating unit,] R1, R2 and R11, R21, Hllll in all repeating units,
The present invention relates to a polyphenylene oxide 9 derivative in which 1% or more of the total number of R211 is -CH20X, and a method for producing the same.

In producing the polyphenylene oxide 9 derivative of the present invention, the polyphenylene oxide used as a starting material has the general formula (wherein R1 and R2 are), rogene, and a methyl group.

Alkoxy group, phenyl M, phenyl group substituted with x nucleus
*R1 and R2 may be the same or different, but one of them is a methyl group. ) is made up of repeating units. As an example, poly(2,
6-dimethyl-p-)unicine oxide), poly(2-
Methyl-6-chloro-p-phenyleneoxys), gsu(2-methyl-6-fluoro-p-)unisine oxide), poly(2-methyl-6-medoxy p-)unisine oxide 9), PoIJ (2-methyl-6-nitoxyp
-) unicine oxide), poly(2-methyl-6-phenyl-p-phenylene oxide), poly(2-methyl-
6-p-Tolyl-p-phenylene oxide 9, poly(2
-Methyl-6--! Examples include fluorophenyl p-]2 elm oxide) and the like. These polyphenylene oxides can be synthesized by oxidative coupling reaction of 26-disubstituted phenols (for example, J, A
m, ehem, Soc, Vol. 81, p. 6335), and some of them are commercially available.

The above general formulas (I), (11) and (III) of the present invention
A polyphenylene oxide having a polyphenylene oxidation unit consisting of a repeating unit represented by is treated with a halogen to halogenate its nuclear substituted methyl group to form a polyphenylene oxide consisting of a repeating unit having 2 R2 Al R11 Polyphenylene oxide 3 is obtained. Here, Hl and R2 are the same as described above, and one of them must be methyl. R11 is the same as R1 or is a no-romedyl group when formed by reaction, and R21 is the same as R2 or is a halomethyl group associated with the same reaction. R1, R2, R1
1, R21 may be arbitrarily different for each repeating unit. However, R, R in all the repeating units of the no-logenated polyphenylene oxide.

1% or more of the total number of R11 and R21 must be a no-romethyl group.

This halogenated polyphenyl oxide is produced by halogenating the polyphenylene oxide 9 having the general formula (Iv) in a solvent using a halogenating reagent under radical reaction conditions. (For example, see JP-A-59-66421.) That is, polyphenylene oxide is dissolved in a solvent, and under irradiation with light (visible light or ultraviolet light) or with benzoyl peroxide, lauroyl peroxide, azobisisozothyronitrile, etc. In the coexistence of radical generators such as peroxides or azo compounds,
Halogenated polyJJ phenylene oxide can be obtained by reacting with a halogenating reagent such as chlorine, bromine, sulfuryl chloride, 1-butyl hypochlorite, N-chlorosuccinimide 9% N-gromosuccinimide, etc. can.

In the above method, the solution concentration of polyphenylene oxide 9 is preferably 1 to 20% by weight. The solvent used is preferably one that does not interact with the radicals generated during the reaction, and halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, and trichloroethane are preferably used.

In addition, the amount of light irradiation is appropriately controlled depending on the degree of progress of the reaction, the amount of the no-rogenation reagent, etc., and when a radical generator is present, o, oot ~ 0.05 It is preferable to use an equivalent amount. The reaction temperature is usually in the range of room temperature to 200°C, more preferably 60 to 150°C.

Further, although the amount of the halogenating reagent used varies depending on the type thereof, υ-no-halogenation is usually achieved by using 0.01 to 2 equivalents based on the repeating unit of the polyphenylene oxide to be halogenated.

By adjusting the amount of this halogenating reagent used, a desired halogenation rate of the halogenated polyphenylene oxide can be obtained.

The polyphenylene oxide 1 derivative consisting of repeating units (I), [D and (III) of the present invention can be obtained by combining the halogenated polyphenylene oxide having the repeating units M and (VL) obtained here with the general formula XOE in the presence of a base. !
(VID is a group selected from the group consisting of an alkyl group, a substituted alkyl group, a 7-enyl group, and a substituted phenyl group) with a compound having a hydroxyl group. can.

A halogenated polyphenylene oxide consisting of repeating units of the general formulas M and (ML) is reacted with the general formula (ML) in a solvent.
React with a compound having a hydroxyl group represented by b) in the presence of a base.

The compound having a hydroxyl group in the general formula (■) may be an alcohol or a phenol, CH30f(, CH
3CH20H, CHa(CH2)20H, CHa(Of
(z)aOH.

CEi3(CH2)60J (CEi3)2CHOH
1(CH3)acOfi.

CHmi CCH20B%CH3CECCH2o generation CC13
Cf120s CI'3CH20s CF'3CF'2CH
20HCF'3(CF2U2CR20FormulaCF'3(C
F 2 → 5CR20 戊CF'3%C Old 2s 20s (C1
i'3) 2CHO (CI'3) 3Co8 (CF'3)
) 3CCH20E(CF'2HC1'2CH20F(
, CI'2H-(OF'2-)-3CR20s NE12
CH2CEI 20s (CH3) 2gca2ca2o (CHa) 3S1CR 20s (CHa) asi
(CHz) 20s (CHa) asi@o Kabu CH3
) SiCH2CFf<H Okishiro etc. can be exemplified. Fluorine-containing alcohols are particularly preferred in that they enhance 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 a base,
Examples of the base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, 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 the amount of the compound having a hydroxyl group represented by the above general formula.Solvents used in this reaction include, for example, benzene, toluene, carbon tetrachloride, THF, and ethyl. Examples include organic solvents such as ether and methyl ethyl ketone.

When the above-mentioned bases are insoluble in the organic solvent used for the reaction, it is preferable to carry out the reaction by adding a phase transfer catalyst. As a phase transfer catalyst, tetra-n-butylammonium hydrogen sulfate, tetramethylammonium bromide, tetra-n-
Examples include butylammonium bromide, tetra-n-butylammonium iosito', tetrabutylammonium 1)-)luenesulfonate, indyltrimethylammonium hydrogensulfate, and compounds having a crown ether ring. These phase transfer catalysts are usually used in an amount equivalent to or less than the amount of the compound having a hydroxyl group represented by the general formula (W).

Particularly when an alkali metal hydroxide is used as the base, it is preferable to prepare the base as an aqueous solution and conduct the reaction in a two-phase system with the organic solvent in the presence of a phase transfer catalyst. The reaction temperature is usually room temperature, but if the reaction is difficult to proceed, the reaction temperature is 40-
It may be carried out by heating to 150°C.

Through the above reaction, the nuclear-substituted halomethyl group of the above-mentioned halogenated polyphenylene oxide 9 is converted into an alkoxymethyl group or a phenoxymethyl group, resulting in the polyphenylene consisting of repeating units of the above-mentioned general formulas (I), (2) and (In) of the present invention. Oxide derivatives are synthesized.

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 improving the film-forming properties of the derivative and the mechanical strength of the film formed from the derivative. be. The larger the weight average molecular weight, the better the film formability and mechanical strength.
It is determined by the starting material and is usually less than 1 million.

In addition, from the film-forming properties of the polyphenylene oxide derivative of the present invention comprising repeating units of general formula (I), marks and (g), and the mechanical strength of the film formed from the derivative,
R1 in the repeating unit of the general formula CI>, I and ■,
Out of the total number of R2, Hll, R21, Hlll, and R211, at least 1 must be -CH20X, and preferably at least 10% is a group represented by -CEI20x.

The polyphenylene oxide derivative of the present invention consisting of repeating units of the general formula (I), It is soluble in hydrocarbons or ether solvents such as diethyl ether and tetrahydrofuran, and insoluble in alcohol or water. In addition, the film formed from the polyphenylene oxide derivative consisting of repeating units of general formula CI), [D and (dish) of the present invention is
The derivative was dissolved in the above-mentioned soluble organic solvent to a concentration of 0.5 to 20 tcs to form a polymer solution, and the solution was spread on a metal, glass plate, polyfluoroethylene plate, or water surface. Afterwards, a durable thin film can be obtained by gradually evaporating the solvent. Alternatively, the porous support can be immersed in a polymer solution and then pulled up.
A method such as applying a solution to a support and drying it can also be adopted.

The polyphenylene oxide derivative of the present invention is a polyphenylene oxide with improved mechanical strength, and in addition to being used for conventional polyphenylene oxide materials such as electrical insulation materials and electrical equipment parts, it can be cast into a film. Taking advantage of this, it is useful as a material for various electronic materials such as electronic circuit protective films and resist materials, or material for substance separation membranes.

For example, when used as a substance separation membrane, the membrane thickness must be α01 in order to provide a sufficient amount of substance permeation and to have practical strength.
~100 μm1, particularly preferably 0.05 to 50 pm. Further, in the case of a thin film having a thickness of 1 μm or less, it is preferable to use it together with a support.

As the support, any porous material having sufficient strength to support the membrane can be used, such as a woven or nonwoven support, a microfilter, or an ultrafiltration membrane. be able to. The membrane thus obtained can be used as a laminated membrane by laminating other membranes, and can be used in any shape such as a flat membrane, a tubular membrane, or a hollow fiber membrane. Examples of targets to be separated and concentrated include hydrogen, helium,
Examples include gas mixtures such as oxygen, nitrogen, carbon dioxide, carbon oxide, methane, ethane, propane, and ethylene, and liquid mixtures such as water, methanol, propatool, various amino acids, and acetic acid.

(Effects of the Invention) As explained in detail above, the present invention solves the conventional problem of poor thin film forming ability of polyphenylene oxide, and improves the excellent properties of polyphenylene oxide 9 such as heat resistance and electrical properties. It is possible to provide a material that can form a functional thin film having sufficient film strength while maintaining the same strength.

(Examples) The present invention will be explained in more detail below using Examples and Comparative Examples. However, it goes without saying that the present invention is not limited to these.

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

Manufactured by Aldrich, number average molecular weight L70XLO.

Poly-2,6-dimethyl-p-phenylene oxide &O with a weight average molecular weight of 4.64XLO'! i' (66,
6 mmol) was dissolved in 450 d of carbon tetrachloride to obtain 23.70 ml of N-tetramosuccinimide. The mixture was heated under reflux for 1 hour while being irradiated with light from a 500 W incandescent bulb under a stream of argon gas. After cooling the reaction solution,
The precipitate was poured into 3 parts of methanol to form a precipitate, and this precipitate was filtered and then dissolved in 500 m/m of tetrahydrofuran, reprecipitated in 31 parts of methanol, filtered and dried, resulting in L4. O
A pale yellow powdery solid of Og was obtained. When the obtained solid was measured by gel permeation chromatography (hereinafter abbreviated as GPC) using 90% tetrahydrofuran as a solvent, it was found that the number average molecular weight was 3 in terms of polystyrene.
．． 04Xto' and a weight average molecular weight of 1.75XLO5. Further, as a result of measuring the nuclear magnetic absorption spectrum (hereinafter abbreviated as NMR) for this polymer, the following peaks were detected.

δ (CD (Ja, blue); 2.10 (s, proton peak due to nuclear substitution methyl group), 435 (day, proton peak due to nuclear substitution bromomethyl group), 6.52 (s, main chain)
Proton peak due to enylene ring), 6.67 (s.

Proton peak due to main chain phenylene ring) Nuclear substituted methyl group -CH3 and nuclear substituted bromomethyl group -CE (2B
When the composition ratio of r was calculated, it was -Cf(3/-CH20C
It was H41/59. The elemental analysis values of the obtained polymer were as follows.

F'ound: C, 4126, H, zci4, B
r, 47.93 Based on this elemental analysis value and the composition ratio determined by NMH, it was found that 9% of the main chain phenylene rings of the obtained polymer were brominated.

(2) Brominated polyphenylene oxide λ02,9 obtained by the above method was dissolved in toluene 80d L, 50%
Sodium hydroxide aqueous solution 4d% 2. Honsou 444-hebutafluorobutanol 4.361 (218 mmol)
.

Tetra-n-butylammonium hydrogen sulfate 4.94g (
After adding 14.5 mmol) and stirring at room temperature for 5 hours,
The reaction solution was poured into methanol 121 to generate a precipitate.

The obtained precipitate was separated by filtration, dissolved in 80 ad of toluene, reprecipitated in methanol L51, and dried on the side edge, resulting in a concentration of 1.9
8 g of pale yellow polymer was obtained. As a result of GPC measurement, the number average molecule is, 9oxto' in terms of polystyrene.
, there was a heavy average molecule i3.0 critical average molecule. Further, when NMR was measured for this polymer, the following peaks were detected.

J (CDCJ3, pu); zto (s, proton peak due to nuclear substitution methyl group), 3.81 (t, 2 of side chain
23.3,4- is a proton peak due to the tafluoropter group).

4.54C8 nuclear substitution szaa<proton peak due to 44-pentafluorobutoxymethyl group), 6.52(
'+ proton peak due to main chain phenyl ring), 6.6
(Proton peak due to 7Csr main chain phenylene ring) According to the integration ratio of the above proton peak, the obtained polymer has a nuclear substituted methyl group -CH3, a nuclear substituted bromomethyl group -C
H2Br and nuclear substitution 2.2.3a444-pentafluorobutoxymethyl group -CH20CEi2CF2CF2
The composition ratio of CFa was calculated as -CH3/-CH20
CH-CH20CH2CF'20F'2CFa-401
It was 0/60. The elemental analysis values of the obtained polymer were as follows.

round (%): "t 4102, EI, Z30
(3) Obtained polymer 0.78, F toluene 1O
W11! A strong homogeneous film with a film thickness of 48 μm was obtained by dissolving the solution in water, casting it on a 7 m x 7 m Teflon plate, and slowly evaporating the toluene. When a part of this membrane was attached to a tensile strength tester and a strength test was conducted at a tensile strength tester of 40 on/-, the breaking strength was 48.2.
MP, , maximum elongation rate 4%, initial elastic modulus 1. l 3
A value of GPa was obtained.

Example 2 (1) 3.03 g of brominated polyphenylene oxide obtained in Example 1 (1) was dissolved in toluene tsoy.
0% hydroxide) IJium aqueous solution 6d, hexafluoroisopro/zono/115.49,! i' (32-
After adding 7.34 g (21.6 mmol) of tetra-n-butylammonium sulfate and stirring at room temperature for 5 hours.

The reaction solution was poured into methanol L91 to generate a precipitate.

After filtering the obtained precipitate, add 15ONl of toluene! dissolved in
After re-precipitating in methanol L81 and drying the side edges, 2.
A pale yellow polymer of 729 was obtained.

As a result of GPC measurement, the number average molecular weight is 5.30XLO' and the weight average molecular weight is 3.39x105 in terms of polystyrene.
Met. Further, when NMR was measured for this polymer, the following peaks were detected.

δ (CDC13, ll1m); LIO (51j proton peak due to nuclear substitution methyl group), tos (t, proton peak due to hexafluoroisopropyl group in side chain)
, 435 (8, proton peak due to nuclear substitution bromomethyl group), 4.73 (s, proton peak due to nuclear substitution hexafluoroisopropoxymethyl group), 6.52 (s
, proton peak due to main chain phenylene ring), 6.67
(S, proton peak due to main chain phenylene ring) According to the integration ratio of the above proton peak, the obtained polymer has a nuclear substituted methyl group -CH3, a nuclear substituted bromomethyl group -CH2B
When the composition ratio of r and the nuclear substituted hexafluoroisopropoxymethyl group -CH20CH(CF'3)2 was calculated, it was -CFi3/CH2Br/-CHzOCH(CF3
) 2-41/34/25. The elemental analysis values of the obtained polymer were as follows.

1'ound (%): C't 102. EI,
2-30 (2) The obtained polymer α72p is mixed with toluene l0III! A strong homogeneous film with a film thickness of 45 μm was obtained by dissolving the mixture in 100% and casting it on a 7c1n×7crn Teflon plate and slowly evaporating the toluene. A part of this membrane was attached to a tensile strength tester, and
When a strength test was conducted at a tensile speed of wn, /-,
A breaking strength of 34.7 MPa, a maximum elongation rate of z9, and an initial elastic modulus of L22 GPa were obtained.Example 3 Example L 10!L of the brominated polyphenylene oxide obtained in (1) was dissolved in 50au of toluene. 50% sodium hydroxide aqueous solution 2id, phenol LO59 (l
L2 mmol), tetra-n-butylammonium sulfate 3.12. After adding 1 mol of S' (9.19 mmol) and stirring at room temperature for 20 hours, the reaction solution was diluted with 1 liter of methanol.
to form a precipitate. The obtained precipitate was dissolved in 50% of toluene, reprecipitated in 1 Jl of methanol, filtered, and dried to obtain a pale yellow polymer of α721.

As a result of GPC measurement, the polystyrene equivalent number average molecular weight was 5.57×104 and the weight molecular weight was 408XL05. Further, when NMR was measured for this polymer, the following peaks were detected.

δ (CDC13, PF): 2. ．． 10 (s, proton peak due to nuclear-substituted methyl group), 4.35 (8, proton peak due to nuclear-substituted bromomethyl group), 4JO (s, proton peak due to nuclear-substituted phenoxymethyl group), 6.
52 (8, proton peak due to main chain phenylene ring),
6.67 (s, proton peak due to main chain phenylene ring), 7.08 (8, proton peak due to side chain phenyl group), 7.24 (a, proton peak due to side chain phenyl group) Integration of the above proton peaks Compared to the obtained polymer, the nuclear substituted methyl group -CH3, the nuclear substituted bromomethyl group -0
fi2Br and nuclear substituted phenoxymethyl group -CH2B
r/-CH2O@=40/9/51.

The elemental analysis values of the obtained polymer were as follows.

F'ound: C, 6a6t, El, 4.
87, Br, 13.45 Example 4 Example L Brominated polyphenylene oxide LOOg obtained in (1) was dissolved in 50 d of toluene, and 50 sodium thihydroxide aqueous solution 2-1 n-propanol 2. ．． 00
fj (33.3 mmol), tetra-n-butylammonium sulfate Z, 44. ! i' (7,19 mmol
) was added and stirred at room temperature for 24 hours, and then the reaction solution 1 was poured into methanol 11 to form a precipitate. The obtained precipitate was dissolved in 50% of toluene by filtration, reprecipitated in methanol tX, drained, and dried to obtain a pale yellow polymer of 0.80y. As a result of GPC measurement, the number average molecular weight was 4. osx104, weight average molecular weight λgsxto5.

Further, when this polymer was subjected to NMR measurement, the following peaks were detected.

δ (CDCla, ppm): 0.80 (proton peak due to propyl group on side chain) h L 50
(proton peak due to me side chain propyl group), ZIO
day C, proton peak due to nuclear substitution methyl group), 3.3
2 (m, proton peak due to side chain propyl group), 44
0 (s, proton peak due to nuclear substituted propoxymethyl group), 6.52 (proton peak due to 8+ main chain phenylene ring), 6.67 (a, proton peak due to main chain phenylene ring).

According to the integral ratio of the above proton peak, the obtained polymer has a nuclear substituted methyl group -CH3, a nuclear substituted bromomethyl group -C
H2Br and nuclear substituted n-propoxymethyl group -0f (
When the composition ratio of zOCH2CH2CH3 was calculated, -
CHa/-CH2Br/-CH20CH2CH2CH3
= 41/0159. The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 65, 14, Hp 6.44.
Br, 10.45 Example 5 150 g of the brominated polyphenylene oxide obtained in Example 1 (1) was dissolved in 70 d of toluene, and dissolved in 50 aqueous sodium hydroxide solution 34% 2-trimethylsilylethanol L9 t fi (16,2 mmox). After stirring at room temperature for 5 hours, the reaction solution was reprecipitated in 1 liter of methanol, filtered, separated, and dried to obtain a pale yellow polymer of 1.37I. As a result of GPC measurement, in polystyrene equivalent value,
Number average molecular weight zs9xto.

The weight average molecular weight was L49XLO. Further, when NMR was measured for this polymer, the following peaks were detected.

δ (CD (J 3, 4): O, LO (a, proton peak due to side chain trimethylsilyl group), 0.95 (t, proton peak due to side chain 2-trimethylsilylethyl group).

2.10 (a, proton peak due to nuclear substitution methyl group) 3.55 (t, proton peak due to side chain 2-trimethylsilylethyl group), 435 (s, proton peak due to nucleus substitution bromomethyl group), 450 (g, nucleus Proton peak due to substituted 2-trimethylsilylethoxymethyl group), 6.52 (e, proton peak due to main chain phenylene ring), 6.67 (g, proton peak due to main chain phenylene ring) , Nucleically substituted methyl group -033 of the obtained polymer, Nucleically substituted bromomethyl group -C
When the composition ratio of H2Br and the nuclear substituted 2-trimethylsilylethoxy group -0-CE12CH2Si (CH3) 3 was calculated, it was -CH3I-CH2Br/-0-
CH2Cf(zsi(CH3)2-40/6154) The elemental analysis values of the obtained polymer were as follows.

Found (%): C, 57, 48, H, C32,
Br, 16.76 Example 6 (1) Manufactured by Aldrich, number average molecular weight L70X10'
Poly-26-dimethyl-p-phenylene oxide with a weight average molecular weight of 4.64 The mixture was heated under reflux for 1 hour while being irradiated with light from a 500 W incandescent bulb under a stream of air. After cooling the reaction solution, methanol 41
This precipitate was filtered, dissolved in 450 g of tetrahydrofuran, reprecipitated in 4 g of methanol, filtered and dried to obtain 30 g of pale yellow powdery solid.

GPC measurement was performed on the obtained solid.

Number average molecular weight in terms of polystyrene: 1.92XIO.

The polymer had a weight average molecular weight of 8.79XLO'.

In addition, peaks similar to those in Example 1 were detected when NMRft was measured for this polymer, and the integral ratio revealed that the nuclear substituted methyl group -CEI3 and the nuclear substituted bromomethyl group -CH2Br
When the composition ratio of -CEI3/-CH2Br was calculated, it was found that -CEI3/-CH2Br
The single element analysis value, which was = 83/l 7, was as follows.

F'ound: C, 63, 50, kl, C09,
Br, 2α47 3 of the main chain phenylene rings of the polymer obtained from this elemental analysis value and the composition ratio by NMR
It was found that 1Z was brominated.

(2) Brominated polyphenyleneoxy) obtained by the above method was dissolved in 50 d of toluene.
0% hydroxide) Rim aqueous solution Z, 45, V,
22aa3-R phtafluoropropanol 162g (
lα4mmol) Tetra-n-butylammonium hydrogen sulfate! 45,! i' (7.2 L mmol) was added and stirred at room temperature for 5 hours, and then the reaction solution was poured into 1 liter of methanol to form a precipitate. The obtained precipitate was filtered, dissolved in 80Rt of toluene, reprecipitated in 12% methanol, and dried separately. ! A pale yellow polymer of i' was obtained. As a result of GPC measurement, number average molecular weight a, 36XlO', weight average molecular weight jLl16x in terms of polystyrene.
It was to'. In addition, when NMR was measured for this polymer, the following peaks were detected.

δ (CDC13, pp): ZIO (s, nuclear substitution me?A4
proton peak due to 1C), &8t(t, side chain 0ZZa
a3-hebutafluoropropyl group), 4.54 (a, nuclear substitution 2.2333-hebutafluoropropoxymethyl group proton peak), C52
(s, proton peak due to main chain phenylene ring), 6.
67 (s, proton peak due to main chain phenylene ring) According to the integration ratio of the above proton peak, the obtained polymer has a nuclear substituted methyl group -CH3, a nuclear substituted promomethyl group -
CH2Br Nuclear Substitution 22. C3,3-heptafluoropropoxymethyl group -CH20-C112CF'2
When the composition ratio of 0F3 was calculated, -CH3I-CH2
Br/-CH2oca2cr2era-85/ O/
It was l5. The elemental analysis values of the obtained polymer were as follows.

Found (%): c, 6λ60. H, 4, 86 Comparative Example The same poly-2 used as the raw material in Example 1
, 6-) Methylphenylene Oxide) 0.75g was dissolved in toluene 9- and cast on a 7cm x 7cm Teflon plate and glass plate, and the toluene was removed by evaporation. Cracks occurred in the film, and a homogeneous film could not be obtained using this method.

Patented Tanfu Sumo Central Chemical Research Institute (4 others)

Claims (3)

[Claims] (1) General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 in the formula,
R^2 is a group selected from the group consisting of halogen, methyl group, alkoxy group, phenyl group, and substituted phenyl group, and R^1 and R^2 may be the same or different. , at least one of which is a methyl group, R^1^
1 is the same as R^1 or a halomethyl group, R^2^1 is R^
is the same as 2 or is a halomethyl group, and R^1^1^1 is R
^1^1 is the same as or -CH_2OX, R^2^1^1 is the same as R^2^1 or -CH_2OX, R^1^
At least one of 1^1 and R^2^1^1 is -C
H_2OX, X is one group selected from the group consisting of an alkyl group, a substituted alkyl group, a phenyl group, and a substituted phenyl group, and A^1 and A^2 are each hydrogen or halogen, A^1, A in repeating unit
^2, R^1^1, R^2^1, R^1^1^1, R^
2^1^1 may be arbitrarily different for each repeating unit. ), R in all repeating units
^1, R^2, R^1^1, R^2^1, R^1^1^
1, more than 1% of the total number of R^2^1^1 is -CH_2
A polyphenylene oxide derivative having a weight average molecular weight of at least 10,000, which is OX. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 are groups selected from the group consisting of halogen, methyl group, alkoxy group, phenyl group, and substituted phenyl group, and R^1 and R^2 may be the same or different, but at least one of them shall be a methyl group, and R^1^1 is the same as R^1 or a halomethyl group, R^2^1 is the same as R^2 or is a halomethyl group, and A^1 and A^2 each consist of hydrogen or halogen.) R^1 and R in all repeating units ^2, R^1^1
, halogenated polyphenylene oxide in which 1% or more of the total number of R^2^1 is a halomethyl group, is prepared with the general formula General formulas ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas, tables, etc., which are characterized by reacting with a compound having a hydroxyl group, which is one group selected from the group consisting of substituted phenyl groups. There are ▼ and ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2, R^1^1, R^2^1, A
^1 and A^2 are as described above, and R^1^1^1 is the same as R^1^1 or -CH_2OX, R^2^1^1
is the same as R^2^1 or -CH_2OX, and R^1
At least one of ^1^1 and R^2^1^1 is -
CH_2OX, where X is as described above, and A^1, A^2, R^1^1, R^2 in the repeating unit
^1, R^1^1^1, R^2^1^1 may be arbitrarily different for each repeating unit), and R^ in all repeating units. 1, R^2,
R^1^1, R^2^1, R^1^1^1, R^2^1
A method for producing a polyphenylene oxide derivative having a weight average molecular weight of at least 10.000, in which 1% or more of the total number of ^1 is -CH_2OX. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are halogen, methyl group, alkoxy group,
A group selected from the group consisting of a phenyl group and a substituted phenyl group, and R^1 and R^2 may be the same or different, and at least R^1 and R^2 One of the polyphenylene oxides is a methyl group, and the polyphenylene oxide consisting of repeating units is halogenated and the general formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ (In the formula, R^1 and R^2 are as described above, and R^1^
1 is the same as R^1 or a halomethyl group, R^2^1 is R^
2 or a halomethyl group, A^1, A
^2 each consists of hydrogen or halogen,
), R^ in all repeating units.
1, R^2, R^1^1, 1% of the total number of R^2^1
The above gives a halogenated polyphenylene oxide having a halomethyl group, and converts this halogenated polyphenylene oxide into a compound having the general formula There are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1, R^2, R^1^1, R^2^1, A^
1, A^2 is as mentioned above, and R^1^1^1 is R
^1^1 is the same as or -CH_2OX, R^2^1^1 is the same as R^2^1 or -CH_2OX, R^1^
At least one of 1^1 and R^2^1^1 is -C
H_2OX, where X is as described above,
A^1, A^2, R^1^1, R^2^ in repeat unit
1, R^1^1^1, R^2^1^1 may be arbitrarily different for each repeating unit), and R^1 in all repeating units, R^2, R^
1^1, R^2^1, R^1^1^1, R^2^1^1
A method for producing a polyphenylene oxide derivative having a weight average molecular weight of at least 10,000, in which 1% or more of the total number of -CH_2OX is -CH_2OX.