JPH0686527B2 - New graft copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel polydisubstituted acetylene / polyorganosiloxane graft copolymer having a polydisubstituted acetylene main chain and a polyorganosiloxane side chain. Is. In particular, the present invention relates to a membrane material useful as a selective gas separation membrane having a large amount of oxygen permeation capable of concentrating oxygen gas in air and having excellent selective permeability and membrane strength.

The gas separation method using a membrane is rapidly being used for various purposes because of its energy saving property, high safety, and easy operation. Among them, the technology to separate oxygen from mixed gas,
In particular, the technology of separating and concentrating oxygen from air is useful.
If air that is richer in oxygen than air can be produced easily and economically, it is expected to make a great contribution to the fields of various combustion engines, medical equipment, food industry, waste treatment, and the like.

[Prior Art and its Problems] The characteristics desired for the film used for the above purpose are that the ratio of the permeation coefficients of oxygen gas and nitrogen gas is large and that the permeation amount of oxygen gas is large. 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 amount, it is necessary to select a material having a large oxygen gas permeation coefficient P _O2 and to make the thickness of the film as thin as possible. Therefore, it is important for the film material to have sufficient film strength to withstand thinning.

Among the polymer membranes known so far, the permeability coefficient P of a large gas (hereinafter, the unit of the permeability coefficient is cm ² (STP) · cm / cm ² · sec · cmHg unless otherwise specified). As a typical example of the film having the above, polydimethylsiloxane can be given. The permeability coefficient P _O2 of the oxygen gas is 6 × 10 ^−8, and the permeability is the other field, but the separation factor α of the oxygen gas and the nitrogen gas (oxygen gas equivalent coefficient P _O2 / nitrogen gas permeability coefficient P _N2 ) is 2.0.
And low. Furthermore, since polydimethylsiloxane has a small mechanical strength, the film cannot be used for practical use when the film thickness is several tens μm or less. Therefore, it is difficult to obtain a membrane having a sufficient gas permeation amount. U.S. Pat.No. 3980456
No. 3874986, JP-A-56-26504, and the like, in order to improve the film-forming property of polydimethylsiloxane, polydimethylsiloxane is used together with a polymer having high mechanical strength such as polycarbonate or poly α-methylstyrene. Although a polymer has been developed, it cannot be said that the oxygen permeability coefficient P _O2 is lowered or the separation coefficient α is insufficient, which is not always satisfactory.

On the other hand, polydisubstituted acetylene represented by poly (1-trimethylsilylpropyne) is known as a material having a gas permeability coefficient higher than that of polydimethylsiloxane (J. Am. Chem. Soe., 105 , 7473 (1983). ) Or J.Appl.Poly
m.Sci., 30 , 1605 (1985)). The film formed by this poly (1-trimethylsilylpropyne) has an oxygen permeability coefficient
Since P _O2 is 4 to 7 × 10 ⁻⁷ , the separation coefficient α is 1.7 to 2.0, and the film has excellent film strength, it can be formed into a thin film. However, since the separation coefficient α is small to be used as it is as an oxygen separation membrane, a sufficient oxygen concentration cannot be obtained, and further, the oxygen permeation coefficient is lowered when used for a long time. (Polymer Preprints, Japa
n, 35 , 424 (1986)) and polydisubstituted acetylenes other than poly (1-trimethylsilylpropyne), such as poly (2-octyne), poly (2-decyne), poly (1-phenylpropyne), poly (1-phenylpropyne), Membranes formed of (1-chloro-2-phenylacetylene) etc. all have sufficient membrane strength, but have an oxygen transmission coefficient P _O2 of 4 × 10 ⁻⁹ or less (Polymer Bulletin, 10 , 114). (1983)) It cannot be a practical oxygen separation membrane.

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned drawbacks of conventional gas separation membranes, in particular, the drawbacks of polydisubstituted acetylene. The present invention provides a novel membrane material having excellent gas permeability and selectivity while maintaining a sufficient membrane strength, which provides a stable gas permeability coefficient.

[Means for Solving Problems] The inventors of the present invention have earnestly sought to obtain a novel membrane material having a high gas separation coefficient and a stable gas permeation coefficient while utilizing the excellent membrane strength of polydisubstituted acetylene. investigated. As a result, a membrane composed of a polydisubstituted acetylene / polyorganosiloxane graft copolymer obtained by introducing a polysiloxane chain into polydisubstituted acetylene has a good gas separation coefficient and membrane strength, and at the same time the polydisubstituted acetylene It has been found that the present invention has a high gas permeation coefficient significantly higher than that and gives a stable gas permeation coefficient, and has completed the present invention.

That is, in the present invention, the repeating unit has the general formula (I) (In the formula, A represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. X is a hydrogen atom or a general formula. Represents a group represented by. A and X may optionally be different for each repeat unit. However, Y is an oxygen atom or a divalent organic group, and Z is a general formula. A polyorganosiloxane chain represented by R ^{1 to} R ⁵ and R ⁶ ,
R ⁷ may be the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a phenyl group or a substituted phenyl group. ), The molar ratio of the repeating unit of the main chain polydisubstituted acetylene to the repeating unit of the side chain polyorganosiloxane is 99/1.
The present invention relates to a polydisubstituted acetylene / polyorganosiloxane graft copolymer having a molecular weight of at least 10,000 and a molecular weight of at least 10,000, and a separation membrane for a gas mixture comprising the copolymer. The branched chain A represented by the general formula (I) is an alkyl group having a straight chain or a branched chain such as a propyl group, an isopropyl group, a pentyl group, a heptyl group, etc. Examples thereof include a substituted alkyl group and a phenyl group, and a substituted phenyl group in which a hydrogen atom of the phenyl group is substituted with a fluorine atom or the like.

X in the general formula (I) is a hydrogen atom or Is a group represented by. Y represents an oxygen atom or a divalent organic group, for example, a substituted or unsubstituted polymethylene chain (having 2 or more carbon atoms), a phenylene polymethylene chain, Etc. can be illustrated. Also, Z is Is a polyorganosiloxane chain represented by R ¹ ~ R ⁷
Is a hydrogen atom, a chain or cyclic alkyl group having a straight chain or branched chain of C _{1 to} C ₁₀ , and some of the hydrogen atoms of these alkyl groups are a halogen atom, a trimethylsilyl group,
Phenyl group, hexafluoro phenyl group, -COF (CF _{3) 2,}
-COOCH ₂ (CF ₂ ) ₃ CF ₃ , -COOCH ₂ C ₆ H ₅ etc. substituted alkyl groups, phenyl groups, and some of the hydrogen atoms of the phenyl groups are substituted with alkyl groups, halogen atoms, etc. And substituted phenyl groups, vinyl groups and other alkenyl groups, and substituted alkenyl groups.

The polydisubstituted acetylene / polyorganosiloxane gflat copolymer having repeating units represented by the general formula (I) of the present invention has, for example, repeating units of the general formula (III) (In the formula, A represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and each repeating unit may be arbitrarily different.) After reacting a polydisubstituted acetylene with a strong base, General formula (IV) (In the formula, R ⁶ and R ⁷ are the same as those described above, and m is an integer of 3 to 6.) Further, the cyclosiloxane compound represented by the formula (V) is further reacted. (In the formula, B is a halogen atom and R ^{3 to} R ⁵ are the same as above.) The reaction can be stopped by adding a triorganohalogenosilane compound represented by the following formula. In addition to the above method, after reacting a polydisubstituted acetylene comprising a repeating unit represented by the general formula (III) with a strong base, the general formula (VI) (In the formula, B, R ^{1 to} R ⁵ , Y and Z are the same as described above.) Alternatively, they can be synthesized by reacting with a polyorganosiloxane having one end that is reactive.

The polydisubstituted acetylene composed of the repeating unit represented by the general formula (III) as a raw material is a polymer of disubstituted acetylene which is 2-alkyne, 1-phenylpropyne or a derivative thereof. Further, as the branched chain A, a linear or branched alkyl group such as a propyl group, an isopropyl group, a pentyl group, and a heptyl group, a substituted alkyl group in which these hydrogen atoms are substituted with another atom, a phenyl group, Further, a substituted phenyl group in which a hydrogen atom of the phenyl group is substituted with a fluorine atom or the like can be given. More specifically, poly (2-hexyne), poly (4-methyl-2-pentyne), poly (4-methyl-2-hexyne), poly (2-octyne), poly (5-methyl-2-octyne) ), Poly (2-decyne), poly (1-phenylpropyne), poly (1-pentafluorophenylpropyne), and the like, and copolymers comprising a combination of at least two or more repeating units of these polydisubstituted acetylenes. can do.

As a method for obtaining these polydisubstituted acetylenes, one or more disubstituted acetylene compounds used as raw materials are prepared by using a halide of a group V or VI transition metal such as tantalum, molybdenum, tungsten or niobium, for example, Tantalum chloride, niobium pentachloride, molybdenum pentachloride, tungsten hexachloride, tantalum pentabromide, niobium pentabromide, etc. as a catalyst, usually obtained by polymerizing in an organic solvent at a temperature of 30 to 100 ° C for 2 to 36 hours. To be As the solvent, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, chlorine-based solvents such as chloroform, 1,2-dichloroethane and carbon tetrachloride can be used. Organometallic compounds containing the above catalyst as the main catalyst and containing aluminum, silicon, tin, antimony, etc. as the second component, such as trimethylaluminum, triethylaluminum, hydrosilane derivatives, tetraphenyltin, tetra-n-butyltin,
The target polymer can also be obtained by using triphenylantimony or the like as a cocatalyst.

The polydisubstituted acetylene composed of the repeating unit represented by the general formula (III) is a cyclosiloxane compound represented by the general formula (IV) or the one-end-reactive polyorganosiloxane represented by the general formula (VI). Examples of the strong base used in the reaction with methyl lithium, n-butyl lithium, t-butyl lithium, phenyl lithium, lithium diisopropylamide and other organic lithium compounds, potassium hydride, sodium hydride and other alkali metal hydrogen compounds, Examples thereof include Grignard compounds such as methylmagnesium iodide, ethylmagnesium bromide, phenylmagnesium bromide, and the like, and organic lithium compounds are preferable in terms of reaction efficiency. These strong bases are usually used in an amount of 0.1 to 4 with respect to the repeating unit of the raw material polydisubstituted acetylene
An equivalent amount is used, and the introduction ratio of the polyorganosiloxane component can be controlled by this amount.

A solvent is preferably used in the reaction between the polydisubstituted acetylene represented by the general formula (III) and a strong base. As the solvent, any solvent which dissolves the polydisubstituted acetylene and does not participate in the reaction is used. Can be n,
Examples of the organic solvent include -pentane, -n-hexane, cyclopentane, cyclohexane, tetrahydrofuran, dimethoxyethane, toluene, benzene, and xylene. In terms of reaction efficiency, n-pentane, n-hexane, cyclopentane, It is preferable to use an aliphatic hydrocarbon such as cyclohexane. The reaction is preferably carried out in the temperature range of 0 ° C to 90 ° C for 20 minutes or longer. Furthermore, it is preferable to carry out the reaction with this strong base in the presence of a diamine such as N, N, N ', N'-tetramethylethylenediamine, because the reaction proceeds smoothly.

The cyclosiloxane compound represented by the general formula (IV), (However, m is an integer of 3 to 6) and the like. Also, a mixture of two or more of these cyclosiloxane compounds may be used.

By using the cyclosiloxane compound represented by the general formula (IV) in an amount of 0.5 to 50 equivalents relative to the strong base, the target product can be obtained in good yield. When the cyclosiloxane compound is added to the reaction system, it is preferable to dissolve the cyclosiloxane compound in a solvent in advance, and the solvent used in this case is tetrahydrofuran, n-pentane, n-hexane, cyclopentane, cyclohexane or the like. Mention may be made of organic solvents. Further, the reaction temperature at the time of reacting with the cyclosiloxane compound is preferably around room temperature. The reaction time is preferably 2 hours or more, more preferably 10 hours or more, and the reaction proceeds to complete the ring-opening polymerization of the cyclosiloxane compound.

The above general formula (V) used for stopping the above reaction
In a tri organohalogenosilanes compound _{represented, ClSi (CH 3) 3,} ClSi (C 2 H 5) 3, Etc. can be illustrated. Most of these triorganohalogenosilane compounds are commercially available and can be easily synthesized by known methods. The reaction is completely stopped by adding these triorganohalogenosilane compounds to the reaction system in an amount of 2 to 20 equivalents relative to the strong base used. In that case, the time required to stop the reaction is 20
It is preferably at least minutes.

Further, as the one-end reactive polyorganosiloxane represented by the general formula (VI), Etc. can be illustrated. However, in the above formula, Z is a polyorganosiloxane chain in which the repeating unit is represented by the general formula (II), and examples thereof are shown below.

Among the above-mentioned one-end-reactive polyorganosiloxanes, the compound of the group (1) is, for example, a silanolate obtained by adding an equimolar amount of n-BuLi to trisubstituted silanol as shown in the following reaction formula. It can be synthesized by subjecting a cyclosiloxane compound to living anionic polymerization using an anion as an initiator and using a halogenosilane compound having a reactive substituent to terminate the reaction.

(In the formula, p represents an integer of 1 or more, and m represents an integer of 3 to 6.
B and B ′ are the same or different halogen atoms, R ^{1 to} R ⁷ may be the same or different, and are a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a phenyl group or a substituted phenyl group. Indicates. However, R ⁶ and R ⁷ may be different for each repeating unit. ) Alternatively, the above silanolate anion can be synthesized by reacting it with an equimolar amount of α, ω-dichloropolyorganosiloxane.

Further, the one-end reactive polyorganosiloxane of the group (2) is represented by the above reaction formula. Instead of the compound represented by the general formula, (Wherein R ⁶ and R ⁷ are the same as above), a general formula that can be synthesized by a similar method using a silane compound represented by (Wherein R ^{3 to} R ⁷ , m and p are the same as above), and can be synthesized by a hydrosilylation reaction between a hydrosilylated polyorganosiloxane having one terminal and a chlorosilane compound having a double bond. it can.

As the chlorosilane compound having a double bond used here, Etc. can be illustrated.

The one-end-reactive polyorganosiloxane represented by the general formula (VI) is used in an amount of 0.5 to 3.0 equivalents relative to the strong base, preferably
The desired product can be obtained in good yield by adding 0.9 to 2.0 equivalents and conducting the reaction at room temperature for 5 minutes or more.

The graft copolymer of the present invention comprises an aromatic solvent such as toluene, benzene, ethylbenzene and xylene, carbon tetrachloride,
It is soluble in halogenated hydrocarbons such as chloroform and trichloroethylene, hydrocarbon solvents such as n-hexane, cyclohexane and cyclohexane, or ether solvents such as tetrahydrofuran, and insoluble in alcohols and water.

When the graft copolymer of the present invention is used as a gas separation membrane, the molar ratio of the repeating unit of the main chain polydisubstituted acetylene to the repeating unit of the side chain polyorganosiloxane is
It is desirable that it is in the range of 99/1 to 5/95, and more preferably in the range of 60/40 to 10/90. When the content of the organosiloxane unit is less than this range, the gas permeability coefficient of the obtained membrane is almost the same as that of the gas separation membrane of polydisubstituted acetylene as a raw material. It becomes worse and it becomes difficult to form a thin film. The graft copolymer in this molar ratio range has an amount of the strong base or the amount of the cyclosiloxane compound represented by the general formula (IV) or one end represented by the general formula (VI) in the above-mentioned production method. It can be obtained by adjusting the amount and chain length of the reactive polyorganosiloxane.

The molecular weight of the graft copolymer of the present invention is preferably large from the viewpoint of film strength, and is usually 10,000 or more, particularly preferably 100,000 or more.

The method for forming the graft copolymer film of the present invention is not particularly limited, and known or known means can be used. For example, a method of forming a film by evaporating a solvent from a cast solution on a metal, a glass plate, a water surface, or the like. Further, a method in which the porous support is immersed in the polymer solution and then pulled up, or the solution is applied and dried can also be employed.

The film of the present invention has a thickness of 0.01 to 100 μm, particularly 0.01 to 50 μm.
Those having a thickness of μm are preferably used. As a result, if the film thickness is large, a sufficient amount of gas permeation cannot be provided. If it is thin, it does not have practical strength. A thin film having a thickness of 1 μm or less is preferably used together with the support. As the support, a woven support, a non-woven support, a microfilter, an ultrafiltration membrane or the like can be used as long as it is a porous body having sufficient strength to support the membrane.

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

When the membrane formed from the graft copolymer of the present invention is used to separate and concentrate a gas mixture as an example of its application, examples of the gas mixture to be used include hydrogen, helium, oxygen, nitrogen, carbon dioxide, and Examples include gas mixtures of carbon oxide, methane, ethane, propane, ethylene and the like.

The membrane formed from the graft copolymer having a polysiloxane chain in the side chain of the present invention is a practical gas separation membrane which can be thinned to about 0.01 to 0.1 μm because it is particularly excellent in membrane strength. .

[Advantages of the Invention] The polydisubstituted acetylene / polyorganosiloxane graft copolymer of the present invention is an improvement over the disadvantage of the conventional polydisubstituted acetylene that the gas permeability coefficient is low, and is formed from the copolymer. The membrane becomes a practical gas separation membrane.

That is, a film formed of the graft copolymer having a polysiloxane chain of the present invention as a side chain has a good separation coefficient (for example, a film formed of polydisubstituted acetylene as a raw material).
The separation factor for oxygen and nitrogen is 2.0 or more. ) Is maintained, it becomes an excellent selective gas separation membrane with higher gas permeability, so it can be used to extremely efficiently separate and concentrate various gas mixtures such as oxygen enrichment from air. You can Further, since the membrane is particularly excellent in mechanical strength, it can be thinned to about 0.01 to 0.1 μm, and can be used in any form such as a flat membrane, a tubular membrane, and a hollow fiber membrane.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

Reference Example 1 Synthesis of poly (1-phenylpropyne) Dissolve 55.4 g of 1-phenylpropyne in 500 ml of toluene,
Tantalum pentachloride (3.4 g) was added, the mixture was degassed and sealed in a stainless steel polymerization tube, and shaken at 80 ° C. for 6 hours to obtain a viscous gel polymer. This polymer was dissolved in toluene, and reprecipitation was repeated several times in a large amount of methanol, and the obtained yellowish white fibrous solid was dried under vacuum at 60 ° C. The yield was 44.2 g (79.
8%). For the obtained polymer, IR, ¹ H-NMR,
^{By 13} C-NMR measurement and elemental analysis, it was confirmed to be the target poly (1-phenylpropyne). As a result of GPC measurement, the number average molecular weight and the weight average molecular weight were 1.55 × 10 ⁵ and 5.47, respectively, in terms of polyethylene.
It was × 10 ⁵ .

Example 1 5.0 g of poly (1-phenylpropyne) obtained in Reference Example 1
Was dissolved in 600 ml of dry cyclohexane and heated to 60 ° C. under an argon gas stream, and then 6.45 ml (43.0 mmol) of N, N, N ′, N′-tetramethylethylenediamine and a n-butyllithium hexane solution (16 mol / l) When 26.9 ml (43.0 mmol) was added and stirring was continued for another 1 hour, the reaction solution turned black red. Next, the temperature of the reaction solution was cooled to room temperature, and 47.5 g (213 mmol) of hexamethylcyclotrisiloxane was dried.
When a solution dissolved in 350 ml of THF was added at once, the reaction solution changed from black red to black purple, and then gradually changed to pale yellow. Furthermore, stirring was continued at room temperature for 17 hours, 25 ml (197 mmol) of trimethylchlorosilane was added, and stirring was continued for 2 hours to stop the reaction. At that time, white precipitation of lithium chloride was generated in the reaction solution. Finally, the above reaction solution was poured into 5 l of methanol to obtain a white polymer. The obtained polymer was dissolved again in 500 ml of toluene and 5 l of a mixed solvent of methanol / diethyl ether (80/20 vol%) was added.
Was reprecipitated, and the reprecipitation was repeated several times in the same manner to remove the contaminated polydimethylsiloxane and to purify the polymer. The yield of the produced polymer was 7.0 g.

When GPC measurement was performed on the obtained polymer, the number average molecular weight and the weight average molecular weight were 1.37 × 10 ⁵ and 4.58 × 10 ⁵ , respectively, in terms of polystyrene.

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3100 (m), 3070 (s), 3040
(M), 2980 (s), 2920 (s), 2860 (m), 1950
(W), 1890 (w), 1800 (w), 1600 (s, characteristic absorption of phenyl group of main chain poly (1-phenylpropyne)), 1
500 (s), 1440 (s), 1415 (m), 1370 (s), 1260
(S, characteristic absorption of methyl group of side-chain polydimethylsiloxane), 1100 (s, characteristic absorption of siloxane bond), 1020
(S, characteristic absorption of siloxane bond), 910 (w), 860
(S), 800 (s), 770 (s), 695 (s) ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); 0.10 (proton peak of methyl group of side chain polydimethylsiloxane), 1.60
(Proton peak of methyl group of main chain poly (1-phenylpropyne)), 6.90 (Proton peak of phenyl group of main chain poly (1-phenylpropyne)) Elemental analysis value (%); C: 65.61, H: 7.46 From the above results, in the produced polymer, part of the hydrogen on the methyl group of the raw material poly (1-phenylpropyne) It was confirmed to be a poly (1-phenylpropyne) / polydimethylsiloxane graft copolymer having a structure substituted with a group represented by (p is an integer of 1 or more). In addition, ¹ H-NMR spectrum
The molar ratio of the repeating unit of poly (1-phenylpropyne) in the main chain of the graft copolymer to the repeating unit of polydimethylsiloxane in the side chain was 44/56, which was determined from the proton peak area ratio of 0.10 ppm and 6.90 ppm. Met.

The obtained graft copolymer was dissolved in toluene and then cast on a glass plate to slowly remove the toluene by evaporation, whereby a strong homogeneous film having a film thickness of 71 μm was obtained.
The membrane was attached to a gas permeation apparatus and the oxygen and nitrogen permeation coefficients at 25 ° C were measured. The results are shown in Table 1.

Furthermore, a 0.5 wt% toluene solution of this graft copolymer was prepared and spread on the water surface to obtain a thin film having a filter thickness of about 250Å. Two layers of this thin film are laminated on Gelaguard,
It was attached to a gas permeation apparatus and the permeation rates of oxygen and nitrogen at 25 ° C were measured. The results are shown in Table 2. The permeation rate did not change even after re-measurement after 30 days.

Example 2 The same operation as in Example 1 was carried out except that the amount of hexamethylcyclotrisiloxane in Example 1 was changed to 71.3 g (320 mmol), to obtain 7.9 g of a white polymer.

The number average molecular weight and the weight average molecular weight measured by GPC were 1.57 × 10 ⁵ and 4.83 × 10 ⁵ , respectively, in terms of polystyrene.

The IR spectrum and ¹ H-NMR spectrum of the obtained polymer were almost the same as the measurement results of Example 1, and the elemental analysis values were as follows. Elemental analysis value (%); C: 62.57, H:
7.65 Accordingly, the polymer produced is poly (1-phenylpropyne) having a structure similar to that of the polymer obtained in Example 1.
/ Polydimethylsiloxane graft copolymer, ¹ H
-The molar ratio of the repeating unit of main chain poly (1-felpropyne) and the repeating unit of side chain polydimethylsiloxane calculated from the proton peak area ratio of NMR spectrum is 39/6.
Was 1.

The obtained graft copolymer was dissolved in toluene, then cast on a glass plate and the toluene was slowly removed by evaporation to obtain a strong homogeneous film having a film thickness of 69 μm.
The membrane was attached to a gas permeation apparatus and the oxygen and nitrogen permeation coefficients at 25 ° C were measured. The results are shown in Table 1.

Further, a 0.5 wt% toluene solution of this graft copolymer was prepared and spread on the water surface to obtain a thin film having a film thickness of about 260Å. Two layers of this thin film were laminated on Gelaguard, which was attached to a gas permeation apparatus, and the permeation rates of oxygen and nitrogen at 25 ° C were measured. The results are shown in Table 2. The permeation rate did not change even after re-measurement after 30 days.

Example 3 The same operation as in Example 1 was carried out except that the amount of hexamethylcyclotrisiloxane in Example 1 was changed to 95.0 g (427 mmol), to obtain 9.0 g of a white polymer.

The number average molecular weight and weight average molecular weight measured by GPC were 1.67 × 10 ⁵ and 4.73 × 10 ⁵ , respectively, in terms of polystyrene.

The IR spectrum and ¹ H-NMR spectrum of the obtained polymer were almost the same as the measurement results of Example 1, and the elemental analysis values were as follows. Elemental analysis value (%); C: 56.26, H:
7.65 Accordingly, the polymer produced is poly (1-phenylpropyne) having a structure similar to that of the polymer obtained in Example 1.
/ Polydimethylsiloxane graft copolymer, ¹ H
-Molar ratio of repeating unit of main chain poly (1-phenylpropyne) and side chain of polydimethylsiloxane calculated from proton peak area ratio of NMR spectrum is 29/7
Was 1.

The obtained graft copolymer was dissolved in toluene and then cast on a glass plate to slowly evaporate and remove the toluene to obtain a strong homogeneous film having a thickness of 60 μm. The membrane was attached to a gas permeation apparatus and the oxygen and nitrogen permeation coefficients at 25 ° C were measured. The results are shown in Table 1.

Further, a 0.5 wt% toluene solution of this graft copolymer was prepared and spread on the water surface to obtain a thin film having a film thickness of about 230Å. Two layers of this thin film were laminated on Gelaguard, which was attached to a gas permeation apparatus, and the permeation rates of oxygen and nitrogen at 25 ° C were measured. The results are shown in Table 2. The permeation rate did not change at all even after re-measurement after 30 days.

Example 4 The same operation as in Example 1 was carried out except that the amount of hexamethylcyclotrisiloxane in Example 1 was changed to 142.5 g (640 mmol), to obtain 11.4 g of a white polymer.

The number average molecular weight and weight average molecular weight measured by GPC were 1.42 × 10 ⁵ and 4.95 × 10 ⁵ , respectively, in terms of polystyrene.

The IR spectrum and ¹ H-NMR spectrum of the obtained polymer were almost the same as the measurement results of Example 1, and the elemental analysis values were as follows. Elemental analysis value (%); C: 50.06, H,
7.74 Accordingly, the polymer produced is poly (1-phenylpropyne) having a structure similar to that of the polymer obtained in Example 1.
/ Polydimethylsiloxane graft copolymer, ¹ H
-The molar ratio between the main chain poly (1-phenylpropyne) repeating unit and the side chain polydimethylsiloxane repeating unit determined from the proton peak area ratio of the NMR spectrum is 21/7.
It was 9.

The graft copolymer thus obtained was dissolved in toluene and then cast on a glass plate to slowly evaporate and remove toluene to obtain a strong homogeneous film having a film thickness of 64 μm. The membrane was mounted on a gas permeation apparatus and the oxygen and nitrogen permeation coefficients at 25 were measured. The results are shown in Table 1.

Further, a 0.5 wt% toluene solution of this graft copolymer was prepared and spread on the water surface to obtain a thin film having a film thickness of about 250Å. Two layers of this thin film were laminated on Gelaguard, which was attached to a gas permeation apparatus, and the permeation rates of oxygen and nitrogen at 25 ° C were measured. The results are shown in Table 2. The permeation rate did not change even after re-measurement after 30 days.

Example 5 The amount of hexamethylcyclotrisiloxane in Example 1 was 47.5 g (213 mmol), and tris (3,3,3-
The same operation as in Example 1 was carried out except that 100 g (213 mmol) of trifluoropropyl) trimethylcyclotrisiloxane was added to obtain 13.6 g of a white polymer.

The number average molecular weight and the weight average molecular weight measured by GPC were 2.26 × 10 ⁵ and 5.95 × 10 ⁵ , respectively, in terms of polystyrene.

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3100 (m), 3070 (m), 3040
(M), 2980 (s), 2920 (m), 1950 (w), 1600 (m,
Characteristic absorption of phenyl group of main chain poly (1-phenylpropyne)), 1500 (m), 1440 (m), 1370 (m), 1318
(M), 1260 (s, characteristic absorption of methyl group of side chain polyorganosiloxane), 1210 (s, characteristic absorption of C—F bond),
1130 (s), 1100 (s, characteristic absorption of siloxane bond), 10
70 (s), 1020 (s, characteristic absorption of siloxane bond), 900
(S), 840 (s), 800 (s), 770 (s), 695 (s), 550
(M) ¹ H-NMR spectrum, δ (CDCl ³ , ppm); 0.10 (proton peak of methyl group of side chain polyorganosiloxane), 0.85
(Proton peak of methylene group on silyl side of 3,3,3-trifluoropropylsilyl group), 1.60 (main chain poly (1-
(Phenylpropyne) methyl group proton peak), 2.1
2 (Proton peak of methylene group on trifluoromethyl side of 3,3,3-trifluoropropylsilyl group), 6.90 (Proton peak of phenyl group of main chain poly (1-phenylpropyne)) Elemental analysis value (%) C: 52.31, H: 6.53 From the above results, it is clear that in the produced polymer, part of the hydrogen on the methyl group of the raw material poly (1-phenylpropyne) (In the formula, Z ′ is Is a polyorganosiloxane having a repeating unit represented by: It was confirmed to be a poly (1-phenylpropyne) / polyorganosiloxane graft copolymer having a structure substituted with a group represented by In addition, ¹ H-NMR spectrum
Of the side chain polyorganosiloxane obtained from the proton peak area ratios of 0.10 ppm, 0.85 ppm, and 6.90 ppm. The molar ratio of the repeating unit represented by is 51/49, and the molar ratio of the repeating unit of main chain poly (1-phenylpropyne) and the repeating unit of side chain polyorganosiloxane is 33/67.
Met.

The graft copolymer thus obtained was dissolved in toluene and then cast on a glass plate to slowly remove the toluene by evaporation to obtain a strong homogeneous film having a thickness of 58 μm. The membrane was attached to a gas permeation apparatus and the oxygen and nitrogen permeation coefficients at 25 ° C were measured. The results are shown in Table 1.

Example 6 In Example 1, the amount of hexamethylcyclotrisiloxane was 95.0 g (427 mmol), and tris (3,3,3-
100 g (213 mmol) of trifluoropropyl) trimethylcyclotrisiloxane was added, and otherwise the same operation as in Example 1 was carried out to obtain 15.2 g of a white polymer.

The number average molecular weight and weight average molecular weight measured by GPC were 2.14 × 10 ⁵ and 4.19 × 10 ⁵ , respectively, in terms of polystyrene.

The IR spectrum and ¹ H-NMR spectrum of the obtained polymer were the same as the results of Example 5, and the elemental analysis values were as follows.

Elemental analysis value (%); C: 45.21, H: 6.54 Therefore, the produced polymer is a poly (1-phenylpropyne / polyorganosiloxane graft copolymer) having a structure similar to that of the polymer obtained in Example 5. ¹ H-NMR
Of the side chain polyorganosiloxane obtained from the proton peak area ratio of the spectrum The molar ratio of the repeating unit represented by is 62/38, and the molar ratio of the repeating unit of main chain poly (1-phenylpropyne) and the repeating unit of side chain polydimethylsiloxane is 21/79.
Met.

The graft copolymer thus obtained was dissolved in toluene, cast on a glass plate, and the toluene was slowly evaporated to remove a strong homogeneous film having a thickness of 54 μm. The membrane was attached to a gas permeation apparatus and the oxygen and nitrogen permeation coefficients at 25 ° C were measured. The results are shown in Table 1.

Further, a 0.5 wt% toluene solution of this graft copolymer was prepared and spread on the water surface to obtain a thin film having a thickness of about 220Å. Two layers of this thin film were laminated on Gelaguard, which was attached to a gas permeation apparatus, and the permeation rates of oxygen and nitrogen at 25 ° C were measured. The results are shown in Table 2. The permeation rate did not change even after re-measurement after 30 days.

Comparative Example The poly (1-phenylpropyne) obtained in Reference Example 1 was dissolved in toluene and then cast on a glass plate, and toluene was slowly removed by evaporation to obtain a uniform film having a thickness of 76 μm. This was attached to a gas permeation apparatus and the oxygen and nitrogen permeation coefficients at 25 ° C were measured. As a result, the oxygen permeability coefficient P _O2 is 1.12 × 10 ^-9 cm ³ (STP) · cm / cm ² · sec · cmHg,
Nitrogen permeability coefficient P _N2 is 3.59 × 10 ^-10 cm ³ (STP) ・ cm / cm ²・ se
The c · cmHg and the separation coefficient P _O2 / P _N2 were 3.12.

Therefore, comparing this result with the result shown in Table 1,
It is clear that the graft copolymers obtained in Examples 1 to 6 have a greatly increased oxygen permeability coefficient of about 5 to 17 times or more as compared with poly (1-phenylpropyne) as a raw material.

Claims (1)

[Claims] 1. The repeating unit is a general formula. (In the formula, A represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. X is a hydrogen atom or a general formula. Represents a group represented by. A and X may optionally be different for each repeat unit. However, Y is an oxygen atom or 2
Valent organic groups, Z is A polyorganosiloxane chain represented by R ^{1 to} R ⁵ and R ⁶ ,
R ⁷ may be the same or different and represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a phenyl group or a substituted phenyl group. ), Wherein the molar ratio of the repeating unit of the main chain and the polydisubstituted acetylene to the repeating unit of the side chain polyorganosiloxane is in the range of 99/1 to 5/95, and the molecular weight is at least 10,000 or more. Disubstituted acetylene / polyorganosiloxane graft copolymer.