JPS61252214A - Production of graft copolymer - Google Patents

Abstract

PURPOSE:To produce the titled copolymer of excellent gas permeability, by reacting a reaction product between a polyphenylene oxide and a strong base with a polyorganosiloxane having a reactive group on one end. CONSTITUTION:A reaction product is obtained by reacting polyphenylene oxide having repeating units of formula I (wherein A<1> is a halogen, methyl or alkoxy) with 0.01-4 equivalent of a strong base (e.g., n-butyllithium) at 40-150 deg.C in the presence of a diamine such as N,N,N',N'-tetramethylethylenediamine. This reaction product is reacted with a polyorganosiloxane having a reactive group on one end of formula II [wherein X is a halogen, Y is 0 or a bivalent organic group, Z is an organosiloxane chain, R<1-5> are ach (substituted) alkyl or (substituted) phenyl] at 0-150 deg.C to obtain a polyphenylene oxide/ polyorganosiloxane graft copolymer of formula III (wherein B<1-2> are each H or formula IV and A<2> is methyl or formula V wherein A<1> is methyl).

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention is directed to polyphenylene oxide t-raw materials, which are obtained by reacting polyphenylene oxide t-raw materials with polyorganosiloxane having a one-terminal reactivity, and whose main chain is a polyphenylene oxide chain and whose side chains are polyorganosiloxane. The present invention relates to a method for producing a graft copolymer comprising siloxane chains.

The graft copolymers produced by the method of the present invention are particularly useful as gas separation membrane materials.

[Background of the invention]

Gas separation methods using membranes are rapidly expanding their applications due to their energy saving, high safety, and ease of operation. Among them, technology to separate oxygen from mixed gases,
In particular, technology that separates and concentrates oxygen from air is useful.

If oxygen-rich air can be produced easily and economically, it is expected to make a significant contribution to fields such as various combustion engines, medical equipment, the food industry, and waste treatment.

Characteristics desired for a membrane used for such purposes are a high ratio of the permeability coefficients of oxygen gas to nitrogen gas and a high permeation amount of oxygen gas. In particular, the latter is extremely important for downsizing the separation device and increasing the amount of gas that can be processed. In order to obtain a large oxygen gas permeation rate, it is necessary to select a membrane material with a large oxygen gas permeability coefficient P02 and to make the membrane thickness as thin as possible. therefore,
It is important for the membrane material to have enough strength to withstand the thinning of the membrane.

Among the polymer membranes known so far, the large gas permeability coefficient P (hereinafter, unless otherwise specified, the unit of permeability coefficient is t cm' (STP) ・cm/cm2・sea
・Set as zHg. ) Polydimethylsiloxane can be cited as a representative example of a film having t-. The permeability coefficient Po2 of oxygen gas is 6 x 10-8, and the separation coefficient α between oxygen gas and nitrogen gas (permeability coefficient Po2 of oxygen gas/permeability coefficient PN2 of nitrogen gas) is 2.0. However, since polydimethylsiloxane has a low mechanical strength, it is not possible to form a film that can withstand actual use at a thickness of several tens of μm or less. For this reason, it is difficult to obtain a membrane having a sufficient amount of gas permeation. In order to improve the film-forming properties of polydimethylsiloxane, copolymers of polydimethylsiloxane and 4-limers with high mechanical strength such as polycargonate and polyα-methylstyrene have been developed (for example, as described in the U.S. patent). No. 3,980,456, No. 3,874,986,
JP-A No. 56-26.504, etc.), oxygen permeability coefficient P
The results were not necessarily satisfactory, such as a decrease in o2 and an insufficient separation coefficient α.

Polyphenylene oxide, represented by /+7-2,6-dimethyl-p-7 enylene oxide, is known as an oxygen-enriching membrane material with a relatively high oxygen permeability coefficient and separation coefficient (for example, polyphenylene oxide In the case of dimethyl-p-phenylene oxide, Po2=1, 58 X 10-9.α
= 4.2) and has a high glass transition point (approximately 210°C). Because it is a hard polymer, it is difficult to form a film using a solvent casting method or the like. Therefore, when polyphenylene oxide is used as a film, it is necessary to form the film by conventional extrusion molding, or to use a round material with excellent film formability such as polystyrene, polycargonate, or polysiloxane copolymer. It has been proposed to blend with or use as a composite membrane (for example, JP-A-57-150423, JP-A-58-95538, JP-A-58-223411,
JP-A-59-301, JP-A-59-203604, etc.). However, by 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 high permeability coefficient and separation coefficient of polyphenylene oxide itself are often impaired. However, the present inventors discovered that the repeating unit has the general formula % (wherein B' and B2 may be the same or different,
Each repeating unit may be arbitrarily different, A1 is a halodane atom, a methyl group or an alkoxy group, Y is an oxygen atom or a divalent organic group, 2 is an organosiloxane chain,
R1-R5 may be the same or different, and are an alkyl group,
It is a substituted alkyl group, phenyl group or substituted phenyl group. A2 is the same as A1, but when AI is a methyl group, the methyl group may be arbitrarily different for each repeating unit. ) can be used as a separation membrane material that exhibits good film-forming properties and superior oxygen gas permselectivity over polyphenylene oxide. (See Reference Examples 4 to 6).

As for the production method of the above-mentioned graft copolymer, when 2 is an oxygen atom, the phenylene oxide is lithiated with butyl lithium, and then reacted with hexamethylcyclotrisiloxane to carry out ring-opening polymerization, and then an appropriate lorosilane is used as a terminator. It is known how to obtain this by adding as.

[Summary of the invention]

The present invention is based on the general formula (wherein, , Y is an oxygen atom or a divalent organic group, and 2 is an organosiloxane chain R1 to R5 may be the same or different and are an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group. The repeating unit is characterized by being reacted with a polyorganosiloxane having a one-terminal reactivity (in the formula, B1 and B2 may be the same or different, 1)
May be arbitrarily different for each repeating unit, A1, Ys
Z s R' to R5 are the same as above. A2tiA
', except that when AI is a methyl group, the group may be arbitrarily different for each repeating unit. ) A method for producing a polyphenylene oxide/polyorganosiloxane graft copolymer comprising:

Examples of the divalent organic group in the above definition include a substituted or unsubstituted polymethylene chain (having 2 or more carbon atoms), a phenylenepolymethylene group, a group represented by ÷O-CM2CH2CH2-, and the like. In addition, the organosiloxane chain in the above definition means that the repeating unit has the general formula % () (in the formula, R6 and R7 may be the same or different, and are an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group). The groups may be arbitrarily different for each repeating unit.

) It is a group represented by

Examples of the raw material polyphenylene oxide represented by the general formula (III) include poly(2,6-dimethyl-p
-phenylene oxide') % Isu (2-methyl-6-chloro-p-7 enylene oxide), zsu (2-mef-6-fluoro-p-7 enylene oxide),
Examples include methyl-6-nodoxy-p-phenylene oxide), poly(2-methyl-6-nitoxy-p-phenylene oxide), and the like.

These polyphenylene oxides can be synthesized by oxidative coupling reactions of 2,6-disubstituted phenols (e.g., Js Am, Ch@m, Soc
, Volume 81, Page 6335), and some of them are commercially available.

Examples of strong bases include organic lithium compounds such as methyllithium, n-butyllithium, t-butyllithium, phenyllithium, and lithium diisopropylamide; alkali metal hydrides such as potassium hydride and sodium hydride;
Methylmagnesium iodide, ethylmagnesium bromide,
Examples include Grignard compounds such as phenylmagnesium bromide, but organic lithium compounds are preferred in terms of reaction efficiency. These strong bases are usually used in an amount of 0.01 based on the repeating unit of polyphenylene oxide as a raw material.
~4 equivalents are used, and the introduction rate of organosiloxane chains can be controlled by this amount.

In addition, the reactions with these bases are N, N, N'.

(2) It is preferable to carry out the reaction in the presence of a diamine such as tetramethylethylenediamine because the reaction proceeds smoothly.

The solvent used in this reaction may be any solvent as long as it dissolves both polyphenylene oxide and polyorganosiloxane. For example, organic solvents such as toluene, benzene, tetrahydrofuran, n-hexane, chloroform, and carbon tetrachloride can be used. .

Further, although the reaction normally proceeds suitably at around room temperature, the rate of introduction of the I-liorganosiloxane chain can be further increased by heating to 40 to 150°C.

In the method of the present invention, after reaction with a strong base, the general formula (mV) is
One-end reactivity expressed by ? It is reacted with liorganosiloxane.

Examples of the one-end reactive polyorganosiloxane represented by the general formula (IV) include the following. However, 2 in the above formula is a polyorganosiloxane chain whose repeating unit is represented by the above general formula (V), and Example 1! i-I raise F
'aH,' etc. can be exemplified.

Among the single-end reactive/IJ organosiloxanes, the compound of group (1) is, for example, an equimolar amount of n-BuLi f to trisubstituted silanol, as shown in the reaction formula below.
A cyclosiloxane compound t-IJ pin anion is polymerized using the silal anion obtained by adding the silal anion as an initiator, and the reaction is terminated using a halosilane compound having a reactive substituent (in the formula, m is 1 or more). , p is an integer of 3 or more, X and r are the same or different halodane atoms, R1-R7 may be the same or different, and are an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group. R6 and R7 may be arbitrarily different for each repeating unit.) In addition, the above silal-doanio y can be synthesized by reacting with an equimolar amount of α,ω-dichloro?liorganosiloxane. (See Reference Example 1) Furthermore! The one-end reactive polyorganosiloxane of group (2) has a general formula in place of the compound represented by x'-5t-x in the above reaction formula, Table 7 (In the formula, R3 to R7 are the same as above), which can be synthesized by the same method using a silane compound represented by (16 and R7 are the same as above). It can be synthesized by a hydrosilylation reaction between the single-end hydrosilylated polyorganosiloxane shown above and a chlorosilane compound having a double bond (see Reference Examples 2 and 3).
.

Examples of the chlorosilane compound having a double bond used here include CH3LkL5 and the like.

One-end reactive polyorganosiloxane represented by the above general formula (■) is mixed with a strong base in an amount of 0.5 to 3. By using 1 equivalent of O, preferably 0.9 to 2.0 equivalents, the desired product can be obtained in good yield.

This reaction can be carried out continuously in the same container following the reaction of the polyphenylene oxide and the strong base described above.

The reaction temperature is preferably in the range of 0 to 150°C, more preferably around room temperature. If the reaction temperature is 0°C or lower, the reaction rate will decrease, and even if the reaction temperature is 150°C or higher, no improvement in the reaction rate can be expected.

When the graft copolymer obtained by the method of the present invention is used as a total gas separation membrane, the molar ratio of the repeating units of the main chain I phenylene oxide and the repeating units of the side chain polyorganosiloxane is from 80/20 to 80/20. It is necessary to be in the range of 10/90. In other words, if the amount of cibolyorganosiloxane units is less than this range, the resulting film will not have sufficient mechanical strength and gas permeability will be too low, and if it is too much, the glass transition temperature will be too low, resulting in poor film formability. It becomes difficult to obtain a thin film. A graft copolymer having the above molar ratio range can be obtained by adjusting the amount of strong base and the amount and chain length of one-end reactive polyorganosiloxane in the present production method.

Further, the weight average molecular weight of the copolymer is desirably large from the viewpoint of membrane strength, and is usually 10,000 or more, particularly preferably 50,000 or more.

The graft copolymer obtained by the method of the present invention includes toluene,
Soluble in aromatic solvents such as benzene, ethylbenzene, and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and trichloroethylene, and ether solvents such as diethyl ether and tetrahydro7rane, and is soluble in alcohols and water. Insoluble.

The method for forming a film of the graft copolymer obtained by the method of the present invention is not particularly limited, and any known or well-known means can be used. For example, a film can be formed by evaporating the solvent from a casting solution onto a metal, a glass plate, a water surface, or the like. Alternatively, methods such as immersing a porous support in a solution, pulling it up, applying the solution, and drying can be employed.

The membrane of the present invention preferably has a thickness of 0.05 to 100 .mu.m, particularly 0.1 to 50 .mu.m, in order to provide a sufficient gas permeation rate and a practical strength. For thin films with a thickness of 1 μm or less, it is preferable to use them together with a support. As the support, any porous material having sufficient strength to support the membrane can be used, such as a woven support, a nonwoven support, a microfilter, and an ultrafiltration membrane.

The membrane of the present invention can also be used in various forms such as a flat membrane, a tubular membrane, and a hollow fiber membrane.

When separating and concentrating a gas mixture using a membrane formed from the graft copolymer obtained by the method of the present invention, examples of the target gas mixture include hydrogen, helium,
Oxygen, nitrogen, carbon dioxide.

- Gas mixtures such as carbon oxide, methane, ethane, propane, ethylene, etc.

The membrane formed from the graft copolymer having side chains of polysiloxane chains obtained by the method of the present invention has significantly greater mechanical strength and gas permeation rate than membranes obtained from raw phenylene oxide. increases to On the other hand, it was found that the separation coefficient α between nitrogen gas and nitrogen gas was approximately 2.5 or more, indicating that the membrane was an excellent selectively permeable membrane.

〔Effect of the invention〕

As described above, by using the method of the present invention, it is possible to easily produce a 4-refined nylene oxide/polyorganosiloxane graft copolymer that has good surface film-forming properties and can exhibit high gas permeability. can do. The method of the present invention also has the feature that it is possible to produce the above-mentioned graft copolymer having any polyorganocycloxane chain length and content.

〔Example〕

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

Reference example 1 Trimethylsilanol 6°09f (67.5mmo
J) was dissolved in tetrahydro 7ran 7Q+a/, and a hexane solution of n-butyllithium (1,61 mol/l
) 42m (67.6 mmol) was added and stirred for 15 minutes at 0°C under an alden stream, and then the solution t-1,7-cyclooctamethyltetrasiloxane 25? (71
, 1 mmoJ) in 100 ml of tetrahydrofuran was added dropwise over about 30 minutes at room temperature under an argon atmosphere, and stirred for an additional 3 hours. From this reaction solution, alco
When the solvent was removed by evaporation in an air stream and distilled under reduced pressure, 75
~b Cycloxane 14.21F was obtained. Its structure was confirmed by gas chromatography, mass spectroscopy, and infrared absorption spectroscopy (hereinafter abbreviated as IR). mask(
According to Kutle, its molecular weight was 404.

Example 1 Poly(2,6-dimethyl-p-phenylene oxide) 1.0f (8,30 mm) manufactured by Aldrich, having a number average molecular weight of 1.70 x 10' and a weight average molecular weight of 4.64 x 10'.
oj) in THF 100 m/, N, N, N'
, N'-tetramethylethylenediamine 2.5m (16
, 6 mmol), n-butyllithium hexane solution (1
,6 mol/l) 10.4 tnl (16,6 m
When the reaction solution was stirred at room temperature for 4 hours under an argon stream, the reaction solution turned red. Furthermore, 13 t (32
, 2rrmol) f and stirred at room temperature for 15 minutes.

After confirming that the reaction solution changed from red to cloudy, the reaction solution was poured into methanol 21 to form a precipitate. The obtained precipitate was filtered, dissolved in 5 Qrnl of toluene, reprecipitated in 2 Qrnl of methanol, filtered and dried to obtain a white polymer of 1.25 f.

The molecular weight of the obtained 9L remer was measured using Darno 9-Miecin chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a solvent.
/IJ styrene equivalent value, number average molecular weight 2.87
10', and the weight average molecular weight was 9.27×104. Further, as a result of nuclear magnetic resonance spectrum (hereinafter abbreviated as "Oji") and IRt-measurement, the following peaks were detected.

δ (CDC25, ppm): 0.10 (s),
0.20(s), 0.63(s), 2.26(s
), 6.67(s) IR characteristic absorption (cln-1):
29B0,1605,1480゜1390.130
0,1260°1190.1080,1040°840.800 These peaks indicate that the produced polymer is the raw material? (2I
It was confirmed that the copolymer was a polyphenylene oxide/polyorganosiloxane graft copolymer having hydrogen on the nuclear substituted methyl group of 6-sitatylphenylene oxide) and a hydrogenated structure on the main chain phenylene ring. Furthermore, what is the integral ratio of the above-mentioned peak and the main chain of the obtained graft copolymer? When the molar ratio of the liphenylene oxide monomer unit and the side chain polyorganosiloxane monomer unit was calculated, it was found to be 45
It was 155. In addition, the elemental analysis values of the produced polymer are shown below.

Elemental analysis value (%), C, 59,37, H, 7,83 Reference example 2 Triethylsilanol 2.16 f! (14.6mm
ol) in dry THF 10 m/l and 10°5 yttl (16.8 mmoJ) of 1.60 mol/l n-BuL1 hexane solution under an argon gas stream.
added. After stirring for 10 minutes, hexamethylcyclotrisiloxane 13.749 (185.3 rran
A solution dissolved in 120 rnl of dry THF was added, and the mixture was stirred at room temperature for 22 hours under a stream of arco gas. Dimethylchlorosilane 41R1 (36.7 mmo)) was added as a terminator to this solution to terminate the living polymerization. Next, the solvent was removed under reduced pressure, and the salt formed was filtered off. When unreacted cyclosiloxane and excess terminator were removed by heating at 200°C for 6 hours under a vacuum of less than lmmHg, a colorless and transparent viscous liquid 15.1
5 f was given. The obtained polymer was subjected to cold positive IR measurement and confirmed. Further, the average degree of polymerization was about 10.2 based on the proton ratio in NMR.

Polyorganosiloxane thus obtained 4.4
0f'? : Dissolved in 40 d of dry toluene and heated under a stream of argon gas with 1.2 ml of vinyldimethylchlorosilane and a chloroplatinic acid ethanol solution (0,193 mol) as a catalyst.
le/J) 7 fil was added, and the mixture was heated and stirred at 80°C for 1.5 hours. When this solution was subjected to engineering R measurement, the absorption peak (2175an-') based on the 5i-H bond at the terminal end of the raw polyorganosiloxane had completely disappeared. The solvent and excess zomethylchlorosilane were removed by evaporation from this solution in an alden gas stream to obtain a polyorganosiloxane with dimethylchlorosilylation at one end.

Example 2 Poly(2,6-dimethyl-p-phenylene oxide) 1.0f (8,30 mm) manufactured by Altri, Chi Co., Ltd., number average molecular weight 1.70 x 10', weight average molecular weight 4.64 x 10'
oj) Dissolved in t-THF 100 tut, N,
N,N',N'-tetramethylethylenediamine 0.6
25mA! (4,20 ftmol), n-butyllithium hexane solution (1,6 mol/l) 2.6 m
1 (4.16 mxnol) was added thereto and stirred at room temperature under an argon stream for 4 hours, and the reaction solution turned red. Furthermore, after adding 3.3 ft of the polyorganosiloxane with one terminal end methylchlorosilylated obtained in Reference Example 2 and stirring at room temperature for 15 minutes, it was confirmed that the reaction solution changed from red to white cloudy solution. Then, the reaction solution was poured into two volumes of methanol to form a precipitate. The resulting precipitate was filtered off, dissolved in 50 rrLl of toluene, reprecipitated in 21 methanol, filtered off and dried to obtain a white polymer weighing 1.30 f. As a result of measuring the molecular weight of the obtained 7j&rimer using GPC using tetrahydro 7ran as a solvent, the number average molecular weight was 4.13 in terms of polystyrene.
X10', and the weight average molecular weight was 1.34X105.

In addition, as a result of measuring ■, the following peaks were detected.

The characteristic absorption of IR was the same as in Example 1. δ (CDCJ5.ppm): 0.10 (s)
, 0.20 (s).

0.63 (@), 0.95 (t).

1.55 (t), 2.26 (8).

6.67 (s) According to these peaks and the IR measurement results, the produced polymer contains hydrogen on the nuclear substituted methyl group of the raw material poly(2,6-sitatylphenylene oxide) and hydrogen on the main chain phenylene ring. It was confirmed that this is a polyphenylene oxide/polyorganosiloxane graft copolymer having a structure in which a portion of is substituted with the following groups. Furthermore, ``What is the main chain polyphenylene oxide monomer unit and side chain of the graft copolymer obtained from the above integral ratio of heat? The calculated molar ratio of the liorganosiloxane monomer units was 24/76. In addition, the elemental analysis values of the produced polymer are shown below.

Elemental analysis value (H), C, 49,75, H, 7,79 Reference example 3 Triethylsilanol 2.16 f (14,6 mmo
1) was dissolved in 10 m of dry THF, and 10.1 rtl (16.2 mmoj) of a 1.60 mol/l n-BuLi hexane solution was added under an argon gas flow. After stirring for 10 minutes, hexamethylcyclotrisiloxane 6,521 (87,9 mmoj) was added to dry TH.
A solution dissolved in F 60 m was added and stirred at room temperature for 22 hours under an argon gas stream. Dimethylchlorosilane (36.7 mmo/) was added to this solution as a stopper.
f was added to stop the living polymerization. Next, after removing the solvent under reduced pressure, the formed salt was filtered and heated at 200°C for 6 hours under a vacuum of less than 1 mmHg to remove unreacted cyclosiloxane and excess terminator. Provided 9.05 ft. of clear viscous liquid. The obtained polymer was subjected to 70 IR measurements, and it was confirmed that the structure was as follows. Further, the degree of polymerization m was about 5.1 based on the proton ratio in NMR.

Polyorganosiloxane thus obtained 9.0
5P'i dissolved in 60 d of dry toluene and 6.0 mA of vinyldimethylchlorosilane under a stream of argon gas! and chloroplatinic acid ethanol solution (0,193
mol@/l) 7 fit was added, and the mixture was heated and stirred at 80°C for 1.5 hours. When this solution was measured by IR measurement, the absorption peak (2175 crn-') based on the Si-H bond at the end of the polyorganosiloxane raw material had completely disappeared. From this solution, the solvent and excess dimethylchlorosilane were removed by evaporation in an argon stream, and one terminal was converted to dimethylchlorosilylation. Liorganosiloxane was obtained.

Example 3 Manufactured by Aldrich, number average molecular weight 1.70 x 104, weight average molecular weight 4.64
mmoA f Dissolved in THF 100 d, N, N
, N', N'-tetramethylethylenediamine 0.63
mJ (4,21rnmol), n-butyllithium hexane solution (1,6mol//l) 2.6d (4
, 16rnmoj) k was added and stirred for 4 hours at room temperature under an argon stream, and the reaction solution turned red. Furthermore, one-end dimethylchlorosilylated I-liorganosiloxane obtained in Reference Example 3 4. Add Ori and 15 at room temperature
After stirring for a minute, it was confirmed that the reaction solution changed from red to a cloudy white solution, and then the reaction solution was poured into methanol 21 to form a precipitate. The obtained precipitate was filtered, dissolved in 50 ml of toluene, reprecipitated in 21 methanol, filtered and dried to obtain a white polymer of 1.21 f. As a result of measuring the molecular weight of the obtained polymer using GPC using tetrahydrofuran as a solvent, the number average molecular weight was 3°45 x 10' in terms of polystyrene.
The weight average molecular weight was 1.11×105. Also,
As a result of measuring m', the following peaks were detected. I
The characteristic absorption of H was the same as in Example 1.

δ (CDCl2.ppm): 0.10 (a),
0.20 (s).

0.63 (a), 0.95 (t).

1.55 (t), 2.26 (s).

6, 67 (s) From these peaks and the IR measurement results, the produced polymer contains hydrogen on the nuclear substituted methyl group of the raw material poly(2,6-sitatylphenylene oxide) and hydrogen on the main chain phenylene ring. It was confirmed that this was a I diphenylene oxide/polyorganosiloxane graft copolymer having a structure partially substituted with a group. Furthermore, when the molar ratio of the main chain polyphenylene oxide monomer unit and the side chain polyorganosiloxane monomer unit of the graft copolymer obtained from the integral ratio of the above-mentioned Ran peak was calculated, it was 39/61. . In addition, the elemental analysis values of the produced polymer are shown below.

Elemental analysis values (%) %C, 57,11, H, 7,56 Reference Examples 4 to 6 The graft copolymers obtained in Examples 1 to 3 were each dissolved in toluene and then cast on a Teflon plate. , by slowly evaporating toluene, the film thickness was reduced to 4.
Sturdy homogeneous films of 3 μm, 40 μm, and 45 μm were obtained. The obtained membrane was installed in a gas permeation device, and the permeability coefficients of oxygen and nitrogen were measured by a high vacuum pressure method. As the results are shown in Table 1, the graft copolymer obtained by the method of the present invention has a higher oxygen selection than the film formed from the raw material poIJ (2,6-dimethyl-p-phenylene oxide). It had excellent permeability.

Procedural amendments filed on September 29, 1939, Showa 6υ years, application number '? 33 to 5 Name It! 'l = #m Junior high school 8th grade, 4th grade, 3rd grade, 1st year old≦)Tun agent゛Address: 2-6-2 Marunouchi, Chiyoda-ku, Tokyo
Shigesu Building 330 Amendment to Marunouchi We will amend the following articles in the specification of this application.

Record 1. The scope of claims is amended as shown in the attached sheet.

On page 8, line 12, the phrase ``a holifuenilene+sito represented by'' is corrected to ``a holifuenylene oxide + sito consisting of a repeating unit represented by.''

3. 4 in the reaction formula on the bottom line of page 16, and ``The membrane of the present invention'' on page 21, line 12, has been replaced with ``The membrane formed from the kraft copolymer obtained by the method of the present invention is ” he corrected.

5. On the bottom line of page 21, the phrase "The membrane of the present invention is a flat membrane" is corrected to read "The membrane formed from the graft copolymer obtained by the method of the present invention is a flat membrane."

ClaimsA polyphenylene compound consisting of repeating units represented by the general formula (wherein A is a halogen atom, a methyl group, or an alkoxyl group) is reacted with a strong base, and then where, It is a phenyl group or a substituted) engineering group. ) One-end reactive polyorganosynthesis. The repeating unit is characterized by being reacted with beef starch and has a general formula (wherein B1 and B2 are the same or different groups and may be arbitrarily different for each repeating unit, A1, Y,
Z, R1 to R5 C above FJ-teal.

A is the same as A, except that A is a group represented by a methyl group, and may be an arbitrary fitting for each repeating unit. ) Consisting of unsufuenile υoshito/boliorganoshi 0+
Method for producing Hunkraft copolymer.

Claims (1)

[Claims] Polyphenylene oxide represented by the general formula ▲ includes numerical formulas, chemical formulas, tables, etc. ▼ (in the formula, A^1 is a halogen atom, methyl group, or alkoxy group) is reacted with a strong base. After that, there are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, The repeating unit is characterized by being reacted with a single-end reactive polyorganosiloxane represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, B^1 and B^2 may be the same or different,
A hydrogen atom or a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, which may be arbitrarily different for each repeating unit, A^1, Y
, Z, and R^1 to R^5 are the same as above. A^2 is A
It is the same as ^1, but if A^1 is a methyl group, it is a methyl group or a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, even if it is arbitrarily different for each repeating unit. good. ) A method for producing a polyphenylene oxide/polyorganosiloxane graft copolymer.