JPH0546845B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention is directed to a polyphenylene oxide chain whose main chain is a polyphenylene oxide chain;
The present invention relates to a novel polyphenylene oxide/polyorganosiloxane graft copolymer whose side chains are composed of polyorganosiloxane chains, and a method for separating a gas mixture formed from the copolymer.
In particular, the invention relates to a selective gas separation membrane capable of concentrating oxygen gas in the air, having a large amount of oxygen permeation, and having excellent permselectivity and membrane strength. [Background of the Invention and Prior Art] The use of gas separation methods using membranes is rapidly expanding due to their energy saving, high safety, and ease of operation. Among these, techniques for separating oxygen from mixed gases, particularly techniques for separating and concentrating oxygen from air, are useful. If we could easily and economically produce air that is richer in oxygen than air,
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 in downsizing the separation device and increasing the amount of gas that can be processed. In order to obtain a large amount of oxygen gas permeation, it is necessary to select a membrane material with a large oxygen gas permeability coefficient P O ₂ and to make the membrane thickness as thin as possible. Therefore,
It is important that the membrane material has sufficient membrane strength to withstand thinning. Among the polymer membranes known so far, the large gas permeability coefficient P (hereinafter, unless otherwise specified,
The unit of transmission coefficient is cm ³ (STP)・cm/cm ²・sec・cm
Let it be Hg. ) is polydimethylsiloxane. The oxygen gas has a high permeability coefficient P O ₂ of 6×10 ^-8 , but
The separation coefficient α between oxygen gas and nitrogen gas (oxygen gas permeability coefficient P O ₂ /nitrogen gas permeability coefficient P N ₂ ) is as low as 2.0. Furthermore, since polydimethylsiloxane has a low mechanical strength, it is impossible 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 with sufficient gas permeation. In order to improve the film-forming properties of polydimethylsiloxane, copolymers of polydimethylsiloxane and polymers with high mechanical strength such as polycarbonate and polyα-methylstyrene have been developed (for example, U.S. Pat. No. 3,980,456). , No. 3874986, Japanese Patent Application Laid-Open No. 56-26504, etc.), the oxygen permeability coefficient P O ₂ was lowered, the separation coefficient α was insufficient, etc., and these results were not necessarily satisfactory. Polyphenylene oxide, represented by poly-2,6-dimethyl-p-phenylene oxide, is known as an oxygen-enriching membrane material with a relatively high oxygen permeability coefficient and separation coefficient (for example, poly-2,6-dimethyl-p-phenylene oxide).
-Dimethyl-p-phenylene oxide P O
₂ = ^1.58 It is a material that is difficult to form into a film using methods such as methods. Therefore, when polyphenylene oxide is used as a film, it must be formed by conventional extrusion molding, or it may be blended with a material with excellent film-forming properties such as polystyrene, polycarbonate, or polysiloxane copolymer. It has been proposed to use it as a composite membrane (for example, JP-A-57-150423, JP-A-58-95538).
No., JP-A-58-223411, JP-A-59-301, JP-A-59-203604, etc.). However, it is difficult to form a thin film of several tens of micrometers or less using extrusion molding, and when used as a blend or composite film, the permeability coefficient and separation coefficient of polyphenylene oxide itself are often impaired. [Object of the Invention] The present invention solves the disadvantages of polyphenylene oxide, which has a lower gas permeability coefficient and poorer thin film forming ability than polydimethylsiloxane, by introducing polysiloxane chains into polyphenylene oxide. Membrane materials and gas mixtures with excellent film-forming properties that can form thin films with a gas permeability coefficient comparable to that of polydimethylsiloxane and sufficient film strength while maintaining high gas separation properties. This provides an extremely efficient method for separating . [Summary of the Invention] The present inventors have created a thin film that takes advantage of the high gas separation properties of polyphenylene oxide, has a gas permeability coefficient comparable to that of polydimethylsiloxane, and has sufficient film strength. We conducted extensive research to find a film material with excellent film-forming properties.
As a result, the polyphenylene oxide/polyorganosiloxane graft copolymer obtained by introducing polysiloxane chains into polyphenylene oxide shows good film-forming properties and is far superior to polydimethyl oxide. The present invention was achieved by discovering that it has a gas permeability coefficient comparable to that of siloxane, and exhibits a gas separation coefficient superior to that of polydimethylsiloxane. That is, in the present invention, the repeating unit has the general formula (In the formula, B ¹ and B ² may be the same or different,
hydrogen atom or

It is a group represented by the formula and may be arbitrarily different for each repeating unit. However, Y is a substituted or unsubstituted polymethylene chain (with 2 or more carbon atoms), a phenylenepolymethylene group, or

A group represented by [Formula], Z is a polyorganosiloxane chain, R ¹
~ ^R5 may be the same or different and is an alkyl group,
It is a substituted alkyl group, phenyl group or substituted phenyl group. A ¹ is a methyl group or

A group represented by [Formula], which may be arbitrarily different for each repeating unit. A ² is a methyl group or

Either one of the groups represented by [Formula], a halogen atom, or an alkoxy group, provided that a methyl group or

In the case of the group represented by [Formula], each repeating unit may be arbitrarily different. ), the molar ratio of the repeating unit of polyphenylene oxide in the main chain to the repeating polyorganosiloxane in the side chain is in the range of 80/20 to 10/90, and in the repeating unit of polyphenylene oxide, A ¹ or A ²

is a group represented by [Formula], or B ¹ and B ² are

When it is a group represented by [Formula], A ¹ , A ² , B ¹ or
When B ² is a group other than the above groups, the ratio is in the range of 5/95 to 50/50, and when A ¹ or A ² is

When B ¹ or B ² is a group represented by [Formula]

A polyphenylene oxide/polyorganosiloxane graft copolymer and a polyorganosiloxane graft copolymer having a molecular weight of at least 10,000 and having a ratio of 90/10 to 50/50 and a group represented by [Formula] The present invention relates to a method for separating a gas mixture by passing the gas mixture through a gas mixture. In addition, the polyorganosiloxane chain in the above definition means that the repeating unit has the general formula (In the formula, R ⁶ and R ⁷ may be the same or different,
It is an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group, and may be arbitrarily different for each repeating unit. ) is a group represented by The polyphenylene oxide/polyorganosiloxane graft copolymer comprising repeating units represented by the general formula () of the present invention has repeating units represented by the general formula (). (In the formula, A is a halogen atom, a methyl group, or an alkoxy group.) After reacting the polyphenylene oxide represented by the formula with a strong base, the general formula (In the formula, X is a halogen atom, Y is the same as above, Z
is a polyorganosiloxane chain, R ¹ to ^{R 5} may be the same or different, and are an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group. ) It can be synthesized by reacting with a one-end reactive polyorganosiloxane. Examples of the raw material polyphenylene oxide represented by the general formula () 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) etc. can be given. These polyphenylene oxides can be synthesized by oxidative coupling reactions of 2,6-disubstituted phenols (e.g., J, Am, Chem,
Soc., Vol. 81, p. 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, Examples include Grignard compounds such as ethylmagnesium bromide and 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 to 4 equivalents based on the repeating unit of polyphenylene oxide as a raw material, and the rate of introduction of polyorganosiloxane chains can be controlled by adjusting this amount. In addition, the reaction with these bases is N, N, N',
It is preferable to carry out the reaction in the presence of a diamine such as N'-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, such as organic solvents such as toluene, benzene, tetrahydrofuran, n-hexane, chloroform, and carbon tetrachloride. I can do it. Further, although the reaction normally proceeds suitably at around room temperature, the rate of introduction of polyorganosiloxane chains can be further increased by heating to 40 to 150°C. An example of the one-end reactive polyorganosiloxane represented by the general formula () is: etc. can be exemplified. However, in the above formula, Z
is a polyorganosiloxane chain whose repeating unit is represented by the general formula (), and an example of the repeating unit is

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. can be exemplified. The one-end reactive polyorganosiloxane represented by the general formula () is, for example, a trisubstituted silanol with an equimolar amount of n-
A cyclosiloxane compound is subjected to living anionic polymerization using a silanolate anion obtained by adding BuLi as an initiator, and the reaction is terminated using a halosilane compound having a hydrosilyl group to obtain a one-terminal hydrosilylated polyorganosiloxane, and a carbon - It can be synthesized by carrying out a hydrosilylation reaction with a halosilane compound having a carbon double bond. (See reference example) (In the formula, n is an integer of 1 or more, p is an integer of 3 or more, X is a halogen atom, Y' is a group having a carbon-carbon double bond, Y is the same as above, R ¹ to R ⁷ are the same or different) may also be an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group.However, R ⁶ ,
R ⁷ may be arbitrarily different for each repeating unit. ) The halosilane compounds having a carbon-carbon double bond used here include:

【formula】 【formula】

etc. can be exemplified. In addition, the use of a catalyst is essential for the above hydrosilylation reaction, and chloroplatinic acid is most commonly used as a catalyst, but other metal complexes containing palladium or rhodium can also be used. It is. The reaction is preferably carried out in a solvent, and hexane, benzene, toluene, acetone, trichloroethylene, carbon tetrachloride, THF, etc. can be used as the solvent. The reaction temperature is preferably in the range of 60°C to 130°C, and preferably in an atmosphere of an inert gas such as argon or nitrogen. The present invention aims at a high yield by using 0.5 to 3.0 equivalents, preferably 0.9 to 2.0 equivalents, relative to a strong base, of the one-end reactive polyorganosiloxane represented by the general formula () obtained by the above method. It is possible to obtain a graft copolymer of 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 it is around room temperature. Reaction temperature is 0℃
Below the reaction rate decreases and the reaction temperature is reduced to 150
No improvement in reaction rate can be expected even if the reaction is carried out at temperatures above ℃. When the graft copolymer of the present invention is used as a gas separation membrane, the molar ratio between the repeating units of the main chain polyphenylene oxide and the repeating units of the side chain polyorganosiloxane is in the range of 80/20 to 10/90. It is necessary that there be. In other words, if the polyorganosiloxane units are 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 large, the glass transition temperature will be too low, resulting in poor film formability. This makes it 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 above-mentioned synthesis method. Further, the 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 of the present invention is soluble in aromatic solvents such as toluene, benzene, ethylbenzene, and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and trichloroethylene, and ether solvents such as diethyl ether and tetrahydrofuran. Insoluble in alcohols or water. The method for forming a film of the graft copolymer 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 cast solution onto a metal, a glass plate, a water surface, or the like. Alternatively, the porous support can be immersed in a solution and then pulled up.
A method such as applying a solution and drying it can also be adopted. The membrane of the present invention has a thickness of 0.05 to 100μ in order to provide sufficient gas permeation and have practical strength.
In particular, those having a diameter of 0.1 to 50 μm are preferably used.
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 be used in any form, such as a flat membrane, a tubular membrane, or a hollow fiber membrane. When separating and concentrating a gas mixture using a membrane formed from the graft copolymer of the present invention, target gas mixtures include, for example, hydrogen, helium, oxygen, nitrogen, carbon dioxide, carbon monoxide, methane, Examples include gas mixtures such as ethane, propane, and ethylene. A membrane formed from the graft copolymer having a polysiloxane chain as a side chain of the present invention has significantly increased mechanical strength and gas permeation rate compared to a membrane obtained from polyphenylene oxide as a raw material. On the other hand,
The separation coefficient α between oxygen gas and nitrogen gas was approximately 2.5 or higher, indicating that it was an excellent selectively permeable membrane. [Effects of the Invention] As described above, the polyphenylene oxide/polyorganosiloxane graft copolymer of the present invention significantly improves the drawbacks of polyphenylene oxide, such as low gas permeability and poor thin film forming ability. , it can be a film material with excellent film-forming properties that can form a thin film with high gas permeability and separation properties and sufficient film strength. Therefore, membranes formed from the graft copolymers of the present invention can be used to separate various gas mixtures, such as oxygen-enriched from air;
Concentration can be performed extremely efficiently. [Examples] 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 2.16 g (14.6 mmol) of triethylsilanol was dissolved in 10 ml of dry THF, and 10.5 ml of a 1.60 mol/n-BuLi hexane solution was added under an argon gas flow.
(16.8 mmol) was added. After stirring for 10 minutes, add 13.74 g of hexamethylcyclotrisiloxane.
A solution of (185.3 mmol) dissolved in 120 ml of dry THF was added, and the mixture was stirred at room temperature for 22 hours under an argon gas stream. 4 ml (36.7 mmol) of dimethylchlorosilane was added as a terminator to this solution to terminate the living polymerization. Next, after removing the solvent under reduced pressure, the formed salts were filtered and heated at 200°C under a vacuum of 0.1 mmHg or less.
The mixture was heated for 6 hours to remove unreacted cyclosiloxane and excess terminator, yielding 15.15 g of a colorless and transparent viscous liquid. The obtained polymer was subjected to IR and NMR measurements, and its structure was determined.

It was confirmed that [Formula]. The average degree of polymerization was approximately 10.2 based on the proton ratio in NMR. 4.40 g of the polyorganosiloxane thus obtained was dissolved in 40 ml of dry toluene, and 1.2 g of vinyldimethylchlorosilane was dissolved in 40 ml of dry toluene.
ml and 7μ of a chloroplatinic acid ethanol solution (0.193 mole/) as a catalyst were added, and the mixture was heated and stirred at 80°C for 1.5 hours. When this solution was subjected to IR measurement, the absorption peak (2175 cm ^-1 ) based on the Si--H bond at the end of the polyorganosiloxane raw material had completely disappeared. The solvent and excess dimethylchlorosilane were removed by evaporation from this solution in an argon stream to obtain a polyorganosiloxane with dimethylchlorosilylation at one end. Example 1 Manufactured by Aldrich, number average molecular weight 1.70×10 ⁴ ,
1.0 g ( ^8.30 m
mol) in THF100ml, N,N,N',N'-
Tetramethylethylenediamine 0.625ml (4.20m
mol), n-butyllithium hexane solution (1.6 mol/) 2.6 ml (4.16 mmol) was added, and the mixture was stirred at room temperature under an argon atmosphere for 4 hours, and the reaction solution turned red. Further, 3.3 g of one-end dimethylchlorosilylated polyorganosiloxane obtained in Reference Example 1 was added and stirred at room temperature for 15 minutes.
After confirming that the reaction solution changed from red to white cloudy solution, pour the reaction solution into methanol 2,
A precipitate was formed. The obtained precipitate was filtered, dissolved in 50 ml of toluene, reprecipitated in methanol 2, filtered and dried to obtain 1.30 g of a white polymer. 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 determined in terms of polystyrene.
The weight average molecular weight was 4.13×10 ⁴ and the weight average molecular weight was 1.34×10 ⁵ . Furthermore, as a result of NMR and IR measurements, the following peaks were detected. δ (CDCl ₃ ppm): 0.10(s), 0.20(s), 0.63(s), 0.95
(t), 1.55(t), 2.26(s), 6.67(s). IR characteristic absorption (cm ^-1 ): 2980, 1605, 1480,
1390, 1300, 1260, 1190, 1080, 1040, 840,
800 These peaks indicate that the produced polymer contains some of the hydrogens on the nuclear substituted methyl groups of the raw material poly(2,6-dimethylphenylene oxide) and the hydrogens on the main chain phenylene rings.

It was confirmed that it was a polyphenylene oxide/polyorganosiloxane graft copolymer having a structure substituted with a group represented by the formula: Furthermore, the above
From the integral ratio of the NMR peak, it was determined that the methyl group on the phenylene ring substituted with the above polysiloxane-containing group, the phenylene ring hydrogen substituted with the above polysiloxane-containing group, and the unsubstituted methyl group and phenylene ring hydrogen. The ratio with the total was found to be 24/8/68. From this ratio, the molar ratio of main chain polyphenylene oxide monomer units to side chain polyorganosiloxane monomer units in the obtained graft copolymer was calculated to be 24/76. Also,
The elemental analysis values of the produced polymer are shown below. Elemental analysis value (%), C, 49.75, H, 7.79 Each of the graft copolymers thus obtained was dissolved in toluene and then cast on a Teflon plate, and the toluene was slowly evaporated off. A strong homogeneous film with a film thickness of 20 μm was obtained. The obtained membrane was attached to a gas permeation device, and the permeability coefficients of oxygen and nitrogen were measured by a high vacuum pressure method.
The results are shown in Table 1. Reference Example 2 2.16g (14.6mmol) of triethylsilanol was dissolved in 10ml of dry THF, and 10.1ml of a 1.60mol/n-BuLi hexane solution was added under an argon gas stream.
(16.2 mmol) was added. After stirring for 10 minutes, add 6.52 g of hexamethylcyclotrisiloxane.
A solution of (87.9 mmol) dissolved in 60 ml of dry THF was added, and the mixture was stirred at room temperature for 22 hours under an argon gas stream. 4 ml (36.7 mmol) of dimethylchlorosilane was added as a terminator to this solution to terminate the living polymerization. Next, after removing the solvent under reduced pressure, the formed salt was filtered out and
Unreacted cyclosiloxane and excess terminator were removed by heating at .degree. C. for 6 hours, yielding 9.05 g of a colorless and transparent viscous liquid. The obtained polymer was subjected to IR and NMR measurements, and its structure was determined.

It was confirmed that [Formula]. Further, the degree of polymerization m was approximately 5.1 based on the proton ratio in NMR. 9.0 g of the polyorganosiloxane thus obtained was dissolved in 60 ml of dry toluene, and 6.0 g of vinyldimethylchlorosilane was dissolved in 60 ml of dry toluene.
ml and 7μ of chloroplatinic acid ethanol solution (0.193 mole/) as a catalyst were added, and the mixture was heated and stirred at 80°C for 1.5 hours. When this solution was subjected to IR measurement, the absorption peak (2175 cm ^-1 ) based on the Si--H bond at the end of the polyorganosiloxane raw material had completely disappeared. The solvent and excess dimethylchlorosilane were removed by evaporation from this solution in an argon stream to obtain a polyorganosiloxane with dimethylchlorosilylation at one end. Example 2 Manufactured by Aldrich, number average molecular weight 1.70×10 ⁴ ,
1.0 g ( ^8.30 m
mol) in THF100ml, N,N,N',N'-
Tetramethylethylenediamine 0.63ml (4.21m
mol), n-butyllithium hexane solution (1.6 mol/) 2.6 ml (4.16 mmol) was added, and the mixture was stirred at room temperature under an argon atmosphere for 4 hours, and the reaction solution turned red. Furthermore, after adding 4.0 g of one-end dimethylchlorosilylated polyorganosiloxane 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. The solution was poured into methanol 2 to form a precipitate. The obtained precipitate was filtered, dissolved in 50 ml of toluene, reprecipitated in methanol 2, filtered and dried to obtain 1.21 g of a white polymer. The molecular weight of the obtained polymer was measured using GPC using tetrahydrofuran as a solvent. As a result, the number average molecular weight was 3.45×10 ⁴ and the weight average molecular weight was 1.11×10 ⁵ in terms of polystyrene. In addition, as a result of NMR measurement, the following peaks were detected. The characteristic absorption of IR was similar to that of Example 1. δ (CDCl ₃ ppm): 0.10(s), 0.20(s), 0.63(s), 0.95
(t), 1.55(t), 2.26(s), 6.67(s) From these peaks and the results of IR measurement, it is clear that the produced polymer is on the nuclear substituted methyl group of the raw material poly(2,6-dimethylphenylene oxide). and some of the hydrogens on the main chain phenylene ring are

It was confirmed that it was a polyphenylene oxide/polyorganosiloxane graft copolymer having a structure substituted with a group represented by the formula: Furthermore, the above
From the integral ratio of the NMR peak, it was determined that the methyl group on the phenylene ring substituted with the above polysiloxane-containing group, the phenylene ring hydrogen substituted with the above polysiloxane-containing group, and the unsubstituted methyl group and phenylene ring hydrogen. The ratio with the total was found to be 23/8/69. From this ratio, the molar ratio of the main chain polyphenylene oxide monomer units to the side chain polyorganosiloxane monomer units of the obtained graft copolymer was calculated to be 39/61. Also,
The elemental analysis values of the produced polymer are shown below. Elemental analysis value (%), C, 57.11, H, 7.56 Each of the graft copolymers thus obtained was dissolved in toluene, cast on a Teflon plate, and the toluene was slowly evaporated off. A strong homogeneous film with a film thickness of 18 μm was obtained. The obtained membrane was attached to a gas permeation device, and the permeability coefficients of oxygen and nitrogen were measured by a high vacuum pressure method.
The results are shown in Table 1. Reference Example 3 2.16 g (14.6 mmol) of triethylsilanol was dissolved in 10 ml of dry THF, and 1.60 mol/10.1 ml of n-BuLi hexane solution was added under an argon gas flow.
(16.2 mmol) was added. After stirring for 10 minutes, add 21.72 g of hexamethylcyclotrisiloxane.
(292.8 mmol) dissolved in 190 ml of dry THF was added, and the mixture was stirred at room temperature for 22 hours under a stream of argon gas. 4 ml (36.7 mmol) of dimethylchlorosilane was added as a terminator to this solution to terminate the living polymerization. Next, after removing the solvent under reduced pressure, the formed salts were filtered out, and the salts were filtered out under a vacuum of 0.1 mmHg or less.
Unreacted cyclosiloxane and excess terminator were removed by heating at 200° C. for 6 hours, yielding 21.21 g of a colorless and transparent viscous liquid. The obtained polymer was subjected to IR and NMR measurements, and its structure was determined.

It was confirmed that [Formula]. Further, the degree of polymerization m was about 17.6 based on the proton ratio in NMR. 15.2 g of the polyorganosiloxane thus obtained was dissolved in 60 ml of dry toluene, and 2.4 g of vinyldimethylchlorosilane was dissolved in 60 ml of dry toluene.
ml and 10μ of a chloroplatinic acid ethanol solution (0.193 mole/) as a catalyst were added, and the mixture was heated and stirred at 80°C for 1.5 hours. When this solution was subjected to IR measurement, the absorption peak (2175 cm ^-1 ) based on the Si--H bond at the end of the polyorganosiloxane raw material had completely disappeared. The solvent and excess dimethylchlorosilane were removed by evaporation from this solution in an argon stream to obtain a polyorganosiloxane with dimethylchlorosilylation at one end. Example 3 Manufactured by Aldrich, number average molecular weight 1.70×10 ⁴ ,
1.0 g ( ^8.30 m
mol) in THF100ml, N,N,N',N'-
Tetramethylethylenediamine 0.63ml (4.21m
mol), n-butyllithium hexane solution (1.6 mol/) 2.6 ml (4.16 mmol) was added, and the mixture was stirred at room temperature under an argon atmosphere for 4 hours, and the reaction solution turned red. Furthermore, after adding 10.2 g of one-end dimethylchlorosilylated polyorganosiloxane obtained in Reference Example 3 and stirring at room temperature for 15 minutes, it was confirmed that the reaction solution changed from red to white cloudy solution. The solution was poured into methanol 2 to form a precipitate. The obtained precipitate was filtered, dissolved in 50 ml of toluene, reprecipitated in methanol 2, filtered and dried to obtain 2.78 g of a white polymer. The molecular weight of the obtained polymer was measured using GPC using tetrahydrofuran as a solvent. As a result, the number average molecular weight was 5.85×10 ⁴ and the weight average molecular weight was 1.95×10 ⁵ in terms of polystyrene. In addition, as a result of NMR measurement, the following peaks were detected. The characteristic absorption of IR was similar to that of Example 1. δ (CDCl ₃ , ppm): 0.10(s), 0.20(s), 0.63(s), 0.95
(t), 1.55(t), 2.26(s), 6.67(s). These peaks and the results of IR measurements show that the produced polymer contains hydrogen on the nuclear substituted methyl group of the raw material poly(2,6-dimethylphenylene oxide) and some of the hydrogen on the main chain phenylene ring.

It was confirmed that it was a polyphenylene oxide/polyorganosiloxane graft copolymer having a structure substituted with a group represented by the formula: Furthermore, the above
From the integral ratio of the NMR peak, it was determined that the methyl group on the phenylene ring substituted with the above polysiloxane-containing group, the phenylene ring hydrogen substituted with the above polysiloxane-containing group, and the unsubstituted methyl group and phenylene ring hydrogen. The ratio with the total was found to be 13/5/82. From this ratio, the molar ratio of main chain polyphenylene oxide monomer units to side chain polyorganosiloxane monomer units in the obtained graft copolymer was calculated to be 24/76. Also,
The elemental analysis values of the produced polymer are shown below. Elemental analysis value (%), C, 46.11, H, 7.51 Each of the graft copolymers obtained in this way was dissolved in toluene and cast on a Teflon plate, and the toluene was slowly evaporated off. A strong homogeneous film with a film thickness of 12 μm was obtained. The obtained membrane was attached to a gas permeation device, and the permeability coefficients of oxygen and nitrogen were measured by a high vacuum pressure method.
The results are shown in Table 1. Reference Example 4 Dissolve 1.61 g (17.8 mmol) of trimethylsilanol in 10 ml of dry THF, and add 1.60 mol/hexane solution of 1.60 mol/n-BuLi to 13.4 ml of hexane solution under an argon gas flow.
(21.4 mmol) was added. After stirring for 10 minutes, add 7.96 g of hexamethylcyclotrisiloxane.
(107 mmol) and tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane 11.17 g (71.5 mmol) dissolved in 150 ml of dry THF were added, and the mixture was heated at room temperature under an argon gas stream.
Stirred for 20 hours. 4 ml (36.7 mmol) of dimethylchlorosilane was added as a terminator to this solution to terminate 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 0.1 mmHg or less to remove unreacted cyclosiloxane and excess terminator. 18.50 g of clear viscous liquid was given. The obtained polymer was subjected to IR and NMR measurements, and its structure was determined.

[Formula] and Z is

[expression] and

It was confirmed that it was a polyorganosiloxane chain consisting of repeating units of [Formula]. Also, based on the proton ratio in NMR, the repeating unit

[expression] and

The molar ratio of [Formula] was 7:3, and the average degree of polymerization was about 10.9. 9.55 g of the polyorganosiloxane thus obtained was dissolved in 60 ml of dry toluene, and 1.7 g of vinyldimethylchlorosilane was dissolved in 60 ml of dry toluene.
ml and 10μ of a chloroplatinic acid ethanol solution (0.193 mole/) as a catalyst were added, and the mixture was heated and stirred at 80°C for 1.5 hours. When this solution was subjected to IR measurement, the absorption peak (2175 cm ^-1 ) based on the Si--H bond at the end of the polyorganosiloxane raw material had completely disappeared. The solvent and excess dimethylchlorosilane were removed by evaporation from this solution in an argon stream to obtain a polyorganosiloxane with dimethylchlorosilylation at one end. Example 4 Manufactured by Aldrich, number average molecular weight 1.70×10 ⁴ ,
1.0 g ( ^8.30 m
mol) in THF100ml, N,N,N',N'-
Tetramethylethylenediamine 0.625ml (4.20m
mol), n-butyllithium hexane solution (1.6 mol/) 2.6 ml (4.16 mmol) was added, and the mixture was stirred at room temperature under an argon atmosphere for 4 hours, and the reaction solution turned red. Furthermore, 8.3 g of one-end dimethylchlorosilylated polyorganosiloxane obtained in Reference Example 4 was added and stirred at room temperature for 15 minutes.
After confirming that the reaction solution changed from red to white cloudy solution, pour the reaction solution into methanol 2,
A precipitate was formed. The obtained precipitate was filtered, dissolved in 50 ml of toluene, reprecipitated in methanol 2, filtered and dried to obtain 1.58 g of a white polymer. 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 determined in terms of polystyrene.
The molecular weight was 3.78×10 ⁴ and the weight average molecular weight was 1.38×10 ⁵ . Furthermore, as a result of NMR and IR measurements, the following peaks were detected. δ (CDCl ₃ ppm): 0.10(s), 0.20(s), 0.63(s), 0.75
(t), 1.25(t), 2.26(s), 6.67(s). IR characteristic absorption (cm ^-1 ): 2980, 1605, 1480,
1390, 1300, 1260, 1210, 1190, 1080, 1020,
900, 840, 800. These peaks indicate that the produced polymer contains some of the hydrogens on the nuclear substituted methyl groups of the raw material poly(2,6-dimethylphenylene oxide) and the hydrogens on the main chain phenylene rings.

[Formula] (In the formula, Z is

[expression] and

A polyorganosiloxane consisting of repeating units of [formula],
repeat unit

[expression] and

The molar ratio of [Formula] is 7:3, and the average degree of polymerization is about 10.9. ) was confirmed to be a polyphenylene oxide/polyorganosiloxane graft copolymer having a structure substituted with a group represented by the following. Furthermore, from the integral ratio of the above NMR peaks, it was found that the methyl group on the phenylene ring substituted with the above polysiloxane-containing group, the phenylene ring hydrogen substituted with the above polysiloxane-containing group, the unsubstituted methyl group and The ratio of phenylene ring hydrogen to the total was found to be 10/3/87.
From this ratio, the molar ratio of the main chain polyphenylene oxide monomer units to the side chain polyorganosiloxane monomer units of the obtained graft copolymer was calculated to be 41/59. In addition, the elemental analysis values of the produced polymer are shown below. Elemental analysis value (%), C, 42.21, H, 7.01 Each of the graft copolymers obtained in this way was dissolved in toluene, then cast on a Teflon plate, and the toluene was slowly evaporated off. A strong homogeneous film with a film thickness of 15 μm was obtained. The obtained membrane was attached to a gas permeation device, and the permeability coefficients of oxygen and nitrogen were measured by a high vacuum pressure method.
The results are shown in Table 1.

【table】

Claims (1)

[Claims] 1. The repeating unit is a general formula (In the formula, B ¹ and B ² may be the same or different,
It is a hydrogen atom or a group represented by the formula, and may be arbitrarily different for each repeating unit. However, Y is a substituted or unsubstituted polymethylene chain (having 2 or more carbon atoms), a phenylenepolymethylene group, or a group represented by [Formula], Z is a polyorganosiloxane chain, and R ¹
~ ^R5 may be the same or different and is an alkyl group,
It is a substituted alkyl group, phenyl group or substituted phenyl group. A ¹ is a methyl group or a group represented by the formula, and may be arbitrarily different for each repeating unit. A ² is either a methyl group or a group represented by [Formula], a halogen atom, or an alkoxy group; however, in the case of a methyl group or a group represented by [Formula], it may be arbitrarily different for each repeating unit. Good too. ), the molar ratio of the repeating unit of polyphenylene oxide in the main chain to the repeating polyorganosiloxane in the side chain is in the range of 80/20 to 10/90, and in the repeating unit of polyphenylene oxide, A ¹ or A ² is a group represented by [Formula], or B ¹ or B ² is a group represented by [Formula], and A ¹ , A ² , B ¹ or B ² is The ratio between the case where A ¹ or A 2 is a group represented by [Formula] and the case where B ¹ or ^{B 2} is a group represented by [Formula] is in the range of 5/95 to 50/50. ] A polyphenylene oxide/polyorganosiloxane graft copolymer having a ratio of 90/10 to 50/50 and a molecular weight of at least 10,000. 2 The repeating unit is (In the formula, B ¹ and B ² may be the same or different,
It is a hydrogen atom or a group represented by the formula, and may be arbitrarily different for each repeating unit. However, Y is a substituted or unsubstituted polymethylene chain (having 2 or more carbon atoms), a phenylenepolymethylene group, or a group represented by [Formula], Z is a polyorganosiloxane chain, and R ¹
~ ^R5 may be the same or different and is an alkyl group,
It is a substituted alkyl group, phenyl group or substituted phenyl group. A ¹ is a methyl group or a group represented by the formula, and may be arbitrarily different for each repeating unit. A ² is either a methyl group or a group represented by [Formula], a halogen atom, or an alkoxy group; however, in the case of a methyl group or a group represented by [Formula], it may be arbitrarily different for each repeating unit. Good too. ), the molar ratio of the repeating unit of polyphenylene oxide in the main chain to the repeating polyorganosiloxane in the side chain is in the range of 80/20 to 10/90, and in the repeating unit of polyphenylene oxide, A ¹ or A ² is a group represented by [Formula], or B ¹ or B ² is a group represented by [Formula], and A ¹ , A ² , B ¹ or B ² is The ratio between the case where A ¹ or A 2 is a group represented by [Formula] and the case where B ¹ or ^{B 2} is a group represented by [Formula] is in the range of 5/95 to 50/50. The ratio with the group represented by the formula is in the range of 90/10 to 50/50, and the gas mixture is permeated through the polyphenylene oxide/polyorganosiloxane graft copolymer having a molecular weight of at least 10,000. A method for separating a gas mixture, characterized by: