JPH0617426B2 - Silylized product of polydisubstituted acetylene and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention uses, as a raw material, a novel silylated product of polydisubstituted acetylene having a triorganosilyl group having various substituents in its side chain and polydisubstituted acetylene. And a method for producing a silylated product of polydisubstituted acetylene.

The silylated product of polydisubstituted acetylene of the present invention is a polymer material which has excellent mechanical strength and durability and can be applied to various uses depending on the kind of the substituent on the silyl group. In particular, it is useful as a separation membrane material excellent in selective permeability of gas and liquid mixture or an intermediate thereof.

[Conventional technology and its problems]

Polydisubstituted acetylene represented by poly (1-trimethylsilylpropyne) is known as a separation membrane material which has excellent separation characteristics of gas and liquid mixture and can be formed into a thin film (J. Am. Chem. Soc). ., 105 , 7473, (19
83), J. Appl. Polym. Sci., 30 , 1605 (1985) and Makromol. Chem., Rapid Commun., 7 , 43 (19).
86)). For example, the oxygen transmission coefficient Po ₂ of a film formed of poly (1-trimethylsilylpropyne) is 4 to 7 × 1.
It is 0 ⁻⁷ cm ³ (STP) · cm / cm ² · sec / cmHg, and the separation coefficient Po ₂ / PN ₂ of oxygen and nitrogen is 1.7 to 1.8. When this membrane is used for separating a water-ethanol mixed solution by the pervaporation method, about 7% by weight ethanol aqueous solution is added.
Can be concentrated to a wt% ethanol solution, Is about 12, and the permeation rate is about 7 × 10 ⁻⁴ g · m / m ² · h
It is known to be r.

However, when the above-mentioned membrane is used as an oxygen separation membrane or an ethanol separation membrane, there is a problem that the separation coefficient is insufficient and the permeation coefficient decreases when used for a long time.

[Means for solving problems]

In order to solve the above problems, the inventors of the present invention have conducted extensive studies, and as a result, polydisubstituted acetylene having a silyl group having various substituents has sufficient film strength, and permeability and selection. We have found that it can be a membrane material with excellent properties and stability.

However, in synthesizing the polydisubstituted acetylene having a silyl group having various substituents as described above, a generally known target functional group is introduced into a monomer structural unit as a raw material of the polydisubstituted acetylene. In most cases, the method of carrying out the polymerization does not polymerize at all due to the steric hindrance of the side chain or the deactivation of the polymerization catalyst, or only a low molecular weight product having a molecular weight of about several thousand can be obtained.
It was not applicable.

Therefore, the present inventors have conducted a polymer reaction using polydisubstituted acetylene as a raw material, thereby maintaining the high molecular weight of the main chain polymer and changing the target silyl group having various substituents to polydisubstituted acetylene. The inventors have found that they can be introduced as a side chain of, and completed the present invention.

That is, the present invention, the repeating unit is represented by the general formula (I) And general formula (II) (In the formula, R ^{1 to} R ³ may be the same or different and may be a hydrogen atom, an alkyl group, an alkenyl group, a substituted alkyl group,
A substituted alkenyl group, a phenyl group or a substituted phenyl group is shown. A is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group or a general formula And may be optionally different for each repeating unit. However, R ^{4 to} R ⁶ may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. ) And the molar ratio of the repeating unit represented by the general formula (I) to the repeating unit represented by the general formula (II) is 99/1.
To 1/99, and a silylation product of polydisubstituted acetylene having a weight average molecular weight of 10,000 or more and 2 million or less and a method for producing the same.

In producing the silylated product of the polydisubstituted acetylene of the present invention, the polydisubstituted acetylene used as a starting material is
Repeating unit is general formula (I) (In the formula, A is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group or a general formula And may be optionally different for each repeating unit. However, R ^{4 to} R ⁶ may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. ) Is a polymer consisting of

For example, poly (2-hexyne), poly (4-methyl-2)
-Pentin), poly (4-methyl-2-hexyne), poly (2-octyne), poly (5-methyl-2-octyne), poly (2-decine), poly (1-phenylpropyne), poly ( 1-pentafluorophenylpropyne),
Poly (1-trimethylsilylpropyne), poly [1-
(Ethyldimethylsilyl) propyne], poly [1- (propyldimethylsilyl) propyne], poly [1- (triethylsilyl) propyne], poly [1- (3,3,3-)
Trifluoropropyldimethylsilyl) propyne], poly [1- (3,3,3-trifluoropropyldiethylsilyl) propyne], poly [1- (trimethylsilylmethyldimethylsilyl) propyne], poly [1- (trimethylsilylethyldimethyl) Silyl) propyne], poly [1- (phenyldimethylsilyl) propyne], poly [1- (pentafluorophenyldimethylsilyl) propyne], poly [1- (β-phenethyldimethylsilyl)]
Examples include propyne], poly [1- (phenyldimethylsilyl) propyne] and the like. Further, a copolymer composed of a combination of at least two kinds of repeating units of polydisubstituted acetylene constituting the above polymer can also be exemplified as a starting material.

As a method for obtaining a polydisubstituted acetylene composed of the repeating unit represented by the general formula (I), one or more disubstituted acetylene compounds used as raw materials are tantalum which is a group V or VI transition metal, A molybdenum, tungsten or niobium halide such as tantalum pentachloride, niobium pentachloride, molybdenum pentachloride, tungsten hexachloride, tantalum pentabromide, niobium pentabromide, etc. is used as a catalyst in an organic solvent at 30 to 100 ° C. 2-36 at the temperature of
It is obtained by polymerizing for a time. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, chloroform, and 1,2.
-A chlorine-based solvent such as dichloroethane or carbon tetrachloride can be used. Further, an organometallic compound containing aluminum, silicon, tin, antimony or the like as the second component using the above catalyst as a main catalyst, for example, trimethylaluminum, triethylaluminum, hydrosilane derivative, tetraphenyltin, tetra-n-butyltin, The target polymer can also be obtained by using triphenylantimony or the like as a cocatalyst.

The method for producing a silylated product of polydisubstituted acetylene of the present invention comprises reacting a polydisubstituted acetylene consisting of a repeating unit represented by the general formula (I) with a strong base, and then reacting with the general formula (II
I) (In the formula, X is a halogen atom, R ^{1 to} R ³ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, a substituted alkyl group, a substituted alkenyl group, a phenyl group or a substituted phenyl group.) The reaction is stopped by adding a triorganohalogenosilane compound represented by

Examples of the strong base used in the production method of the present invention include organic lithium compounds such as methyllithium, n-butyllithium, t-butyllithium, phenyllithium, lithium diisopropylamide, and alkali metal hydrogen compounds such as potassium hydride and sodium hydride. Examples thereof include Grignard compounds such as methylmagnesium iodide, ethylmagnesium bromide, phenylmagnesium bromide, and the like, and it is preferable to use an organolithium compound from the viewpoint of reaction efficiency. These strong bases are usually used in an amount of 0.1 to 4 equivalents with respect to the repeating unit of the raw material polydisubstituted acetylene, and the introduction rate of the silyl group can be controlled by this amount.

The reaction of the polydisubstituted acetylene consisting of the repeating unit represented by the general formula (I) and a strong base is preferably carried out in the presence of a solvent, and as the solvent used, the polydisubstituted acetylene is dissolved and participates in the reaction. As long as it does not exist, any one may be used, and an organic solvent such as n-pentane, n-hexane, cyclopentane, cyclohexane, tetrahydrofuran, dimethoxyethane, toluene, benzene, xylene can be used, but reaction efficiency From the viewpoint, it is preferable to use aliphatic hydrocarbons such as n-pentane, n-hexane, cyclopentane, and cyclohexane. Also,
The reaction temperature is 0 ° C to 90 ° C, and the reaction time is 10 minutes to 2
The reaction suitably proceeds in the range of 4 hours. Furthermore, it is preferable to carry out the reaction with the strong base in the presence of a diamine such as N, N, N ', N'-tetramethylethylenediamine, because the reaction proceeds smoothly.

The triorganohalogenosilane compound represented by the general formula (III), Etc. can be illustrated. Most of these triorganohalogenosilane compounds are commercially available and can be easily synthesized by known methods.

The desired silylation reaction is completed by adding these triorganohalogenosilane compounds to the reaction system in an amount of 1.1 to 20 equivalents with respect to the strong base used. In that case,
The time required to stop the reaction is preferably 20 minutes or more.

By the reaction described above, the polydisubstituted acetylene consisting of the repeating unit represented by the general formula (I) as a starting material, the repeating unit represented by the general formula (I) and (II) of the present invention A silylated product of polydisubstituted acetylene can be produced.

When producing a silylated product of polydisubstituted acetylene by the production method of the present invention, the repeating unit represented by the general formula (I) and the above by adjusting the amount of a strong base added to the raw material polydisubstituted acetylene The molar ratio with the repeating unit represented by the general formula (II) can be arbitrarily adjusted within the range of 99/1 to 1/99. The weight average molecular weight of the silylation product of polydisubstituted acetylene of the present invention is preferably 10,000 or more because it is desirable that the strength of the membrane obtained when used as a separation membrane material is high. More preferably, it is 100,000 or more.

Further, the silylated product of the polydisubstituted acetylene of the present invention is generally an aromatic solvent such as toluene, benzene, ethylbenzene and xylene, a halogenated hydrocarbon such as carbon tetrachloride, chloroform and trichloroethylene, n-hexane,
It is soluble in hydrocarbon solvents such as cyclohexane and cyclohexene or ether solvents such as tetrahydrofuran, but insoluble in alcohols and water.

〔The invention's effect〕

EFFECTS OF THE INVENTION According to the present invention, it is possible to form a highly thin film having excellent gas and liquid permeability and polydisubstituted acetylene, which is known as a film material, into which a triorganosilyl group having various substituents is introduced in the side chain. A molecular material can be provided. The silylated product of the polydisubstituted acetylene of the present invention is
The polydisubstituted acetylene used as the raw material retains the excellent properties such as gas and liquid permeability and thin film forming ability, and also improves the selective separation of the gas and liquid mixture compared to the raw material, thus enriching oxygen from air. A gas separation membrane used for separation of various gas mixtures such as, and a liquid separation membrane when used as a liquid separation membrane used for separation of various liquid mixtures such as water-alcohol mixtures, can be a material providing a membrane having extremely excellent separation characteristics. . Furthermore, by introducing a silyl group containing a substituent sensitive to heat, light, or radiation into the silylated product of the polydisubstituted acetylene of the present invention, a heat-sensitive material, a photosensitive material, a resist material, a thermosetting material, It can be applied to photo-curable materials, etc. In addition, various water-repellent and oil-repellent materials, various electronic materials such as insulating materials, vinyl groups, allyl groups, styryl groups, methacryloxy substrates, silyl containing acryloxy groups, etc. By introducing a group, it can be applied to various uses such as a raw material for a graft copolymer.

Further, in the reaction in the production method of the present invention, each reagent can be continuously added in the same reaction vessel, and therefore it is easy to industrially obtain polydisubstituted acetylene by the production method of the present invention.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Reference Example 1 Synthesis of poly (1-trimethylsilylpropyne) 42.6 g of 1-trimethylsilylpropyne was added to toluene 3
The mixture was dissolved in 00 ml, 2.4 g of tantalum pentachloride was added, the mixture was degassed and sealed in a stainless steel polymerization tube, and shaken at 80 ° C. for 24 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 white fibrous solid was dried under vacuum at 60 ° C. The yield was 38.8 g (yield 91.0%). The obtained polymer was subjected to IR, ¹ H-NMR, ¹³ C-NMR measurement and elemental analysis to confirm that it was the target poly (1-trimethylsilylpropyne). In addition, as a result of GPC measurement, the number average molecular weight and the weight average molecular weight were 2.01 × 10 ⁵ and 4.19 × 10 ⁵ respectively in terms of polystyrene.
Met.

Example 1 4.0 g of poly (1-trimethylsilylpropyne) obtained in Reference Example 1 was dissolved in 600 ml of dry cyclohexane and heated to 60 ° C. under an argon stream, and then N, N, N ′, N ′. −
Tetramethylethylenediamine 6.0 ml (40.0 mmol),
n-Butyllithium hexane solution (1.6mol / l) 24.0ml
(38.4 mmol) was added and stirring was continued for 1 hour, and the reaction solution turned red. Next, the temperature of the reaction solution was cooled to room temperature, and trimethylchlorosilane (10.0 ml, 78.9 mm) was added.
ol) was added, the reaction solution was decolorized and at the same time white precipitation of lithium chloride was produced. Then, the mixture was left at room temperature for 30 minutes, and the reaction solution was poured into 5 l of methanol to precipitate a white polymer. The obtained polymer was again added with toluene 500
The polymer was purified by dissolving in ml and reprecipitating in 5 l of methanol, and repeating reprecipitation several times in the same manner.
The yield of the obtained polymer was 4.5 g.

When GPC measurement was performed on this polymer, the number average molecular weight and the weight average molecular weight were 2.20 × 10 ⁵ and 4.72 × 10 ⁵ , respectively, in terms of polystyrene.

The results of infrared absorption spectrum and elemental analysis were as follows.

Infrared absorption spectrum (cm ^-1 ); 2980 (s), 292
0 (s), 1565 (s), 1433 (m), 1370
(M), 1250 (s: characteristic absorption of methyl group on silyl group), 1180 (m), 1030 (m), 1006
(M), 915 (m), 840 (s), 750 (s),
685 (m), 630 (m) Elemental analysis value (%); C: 62.50, H: 10.14 From the above results, the polymer produced is a repeating unit. It was confirmed to be a trimethylsilyl compound of poly (1-trimethylsilylpropyne). Further, the molar ratio of the former repeating unit to the latter repeating unit was calculated from the carbon content of the elemental analysis value, and it was 79/21.

Example 2 The same operation as in Example 1 was conducted except that 19 ml (43.1 mmol) of (tridecafluoro-1,1,2,2-tetrahydrooctyl) dimethylchlorosilane was used in place of trimethylchlorosilane. As a result, 4.6 g of a white polymer was obtained.

The number average molecular weight and the weight average molecular weight measured by GPC are 2.11 × 10 ⁵ and 5.06 ×, respectively, in terms of polystyrene.
It was 10 ⁵ .

The infrared absorption spectrum and elemental analysis results of the obtained polymer were as follows.

Infrared absorption spectrum (cm ^-1 ); 2980 (s), 292
0 (s), 1565 (s), 1433 (m), 1370
(M), 1250 (s: characteristic absorption of methyl group on silyl group), 1210 (m: characteristic absorption of C—F bond), 118
0 (m), 1145 (m: characteristic absorption of C—F bond), 1
030 (m), 1006 (m), 915 (m), 840
(S), 750 (s), 685 (m), 630 (m) Elemental analysis value (%); C: 59.42, H: 9.64 From the above results, the polymer produced is a repeating unit. Was confirmed to be (tridecafluoro-1,1,2,2-tetrahydrooctyl) dimethylsilylated product of poly (1-trimethylsilylpropyne). Further, the molar ratio of the former repeating unit and the latter repeating unit was calculated from the carbon content of the elemental analysis value, and it was 95/5.

Example 3 The same operation as in Example 1 was carried out except that 10 ml (73.2 mmol) of vinyldimethylchlorosilane was used in place of trimethylchlorosilane, to obtain 4.9 g of a white polymer.

The number average molecular weight and the weight average molecular weight measured by GPC are 2.32 × 10 ⁵ and 4.82 ×, respectively, in terms of polystyrene.
It was 10 ⁵ .

The infrared absorption spectrum and elemental analysis results of the obtained polymer were as follows.

Infrared absorption spectrum (cm ^-1 ); 2980 (s), 292
0 (s), 1640 (w: characteristic absorption by vinyl group),
1565 (s), 1433 (m), 1370 (m), 1
250 (s: characteristic absorption of methyl group on silyl group), 11
80 (m), 1030 (m), 1006 (m), 915
(M), 840 (s), 750 (s), 685 (m),
630 (m) Elemental analysis value (%); C: 62.87, H: 10.26 From the above results, the polymer produced is a repeating unit. It was confirmed to be a vinyldimethylsilylated product of poly (1-trimethylsilylpropyne). Further, the molar ratio of the former repeating unit and the latter repeating unit was calculated from the carbon content of the elemental analysis value, and it was 69/31.

Example 4 The same operation as in Example 1 was carried out except that 12.0 ml (79.8 mmol) of allyldimethylchlorosilane was used in place of trimethylchlorosilane, to obtain 5.1 g of a white polymer.

When GPC measurement was performed on this polymer, the number average molecular weight and the weight average molecular weight were 1.90 × 10 ⁵ and 4.60 × 10 ⁵ , respectively, in terms of polystyrene.

The results of infrared absorption spectrum and elemental analysis were as follows.

Infrared absorption spectrum (cm ^-1 ); 2980 (s), 292
0 (s), 1635 (w: characteristic absorption by allyl group),
1565 (s), 1433 (m), 1370 (m), 1
250 (s: characteristic absorption of methyl group on silyl group), 11
80 (m), 1030 (m), 1006 (m), 915
(M), 840 (s), 750 (s), 685 (m),
630 (m) Elemental analysis value (%); C: 63.33, H: 10.06 From the above results, the polymer produced is a repeating unit. It was confirmed that the poly (1-trimethylsilylpropyne) was an allyldimethylsilyl compound. Further, the molar ratio of the former repeating unit to the latter repeating unit was calculated from the carbon content of the elemental analysis value, and it was 55/45.

Example 5 The procedure of Example 1 was repeated except that 13.0 ml (67.9 mmol) of (3-methacryloxypropyl) dimethylchlorosilane was used in place of trimethylchlorosilane. As a result, 4.6 g of a white polymer was obtained. was gotten.

When GPC measurement was performed on this polymer, the number average molecular weight and the weight average molecular weight were 2.22 × 10 ⁵ and 4.21 × 10 ⁵ , respectively, in terms of polystyrene.

The results of infrared absorption spectrum and elemental analysis were as follows.

Infrared absorption spectrum (cm ^-1 ); 2980 (s), 292
0 (s), 1735 (s: characteristic absorption by carbonyl group), 1630 (w: characteristic absorption by methacryloxy group), 1565 (s), 1433 (m), 1370.
(M), 1250 (s: absorption of characteristics of methyl group on silyl group), 1180 (m), 1030 (m), 1006.
(M), 915 (m), 840 (s), 750 (s),
685 (m), 630 (m) Elemental analysis value (%); C: 63.33, H: 9.99 From the above results, the polymer produced is a repeating unit. Of poly (1-trimethylsilylpropyne) (3
-Methacryloxypropyl) dimethylsilyl compound was confirmed. Further, the molar ratio of the former repeating unit to the latter repeating unit was calculated from the carbon content of the elemental analysis value, and was 89/11.

Reference Example 2 Synthesis of poly (1-phenylpropyne) 20.2 g of 1-phenylpropyne was dissolved in 200 ml of toluene, 1.3 g of tantalum pentachloride was added, and the mixture was degassed and sealed in a stainless steel polymerization tube at 80 ° C. The mixture was shaken for 6 hours to obtain a viscous gel polymer. Dissolve this polymer in toluene,
Reprecipitation was repeated several times in a large amount of methanol, and the obtained white fibrous solid was dried under vacuum at 60 ° C. Yield is 15.
It was 2 g (yield 75.2%). The obtained polymer was subjected to IR, ¹ H-NMR, ¹³ C-NMR measurement and elemental analysis to confirm that it was the target poly (1-phenylpropyne). As a result of GPC measurement, the number average molecular weight and the weight average molecular weight were 1.43 × 10 ⁵ and 5.23 × 10 ⁵ , respectively, in terms of polystyrene.

Example 6 Poly (1-phenylpropyne) 4.0 obtained in Reference Example 2
g was dissolved in 500 ml of dry cyclohexane and heated to 60 ° C. under a stream of argon, and then 5.2 ml (34.7 mmol) of N, N, N ′, N′-tetramethylethylenediamine and a n-butyllithium hexane solution ( 1.6 mol / l) 22.0 ml (35.
(2 mmol) was added and stirring was continued for another hour, and the reaction solution turned black red. Next, the temperature of the reaction solution was cooled to room temperature and trimethylchlorosilane (10.0 ml, 78.9 mmol) was added.
Then, the reaction solution was decolorized and at the same time a white precipitate of lithium chloride was produced. Then, the reaction was continued at room temperature for 30 minutes, and the reaction solution was poured into methanol 5 to precipitate a white polymer. The obtained polymer was added with toluene 50 again.
The polymer was purified by dissolving in 0 ml, reprecipitating in methanol 5 and repeating the reprecipitation several times in the same manner. The yield of the obtained polymer was 4.3 g.

When GPC measurement was performed on this polymer, the number average molecular weight and the weight average molecular weight were 1.59 × 10 ⁵ and 5.16 × 10 ⁵ , respectively, in terms of polystyrene.

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

Infrared absorption spectrum (cm ^-1 ); 3070 (s), 304
0 (s), 2970 (s), 2910 (s), 2860
(M), 1950 (w), 1880 (w), 1800
(W), 1600 (m), 1495 (s), 1438
(S), 1366 (s), 1250 (s: characteristic absorption of methyl group on silyl group), 1178 (w), 1155.
(W), 1110 (w), 1090 (m), 1070
(M), 1030 (s), 905 (m), 838
(S), 760 (s), 698 (s), 620 (w) ¹ H-NMR spectrum δ (CDCl ₃ , ppm); 0.10 (proton peak of methyl group on trimethylsilyl group), 1.50 ( Poly (1-phenylpropyne) side chain methyl group proton peak), 6.95 (poly (1-phenylpropyne side chain phenyl group proton peak) Elemental analysis value (%); C: 89.92, H : 7.18 From the above results, the polymer produced was a repeating unit. Was confirmed to be a trimethylsilyl compound of poly (1-phenylpropyne). Further, the molar ratio of the former repeating unit to the latter repeating unit was calculated from the carbon content of the elemental analysis value, and was 87/13.

Reference Example 3 The polymers obtained in Examples 1, 2 and 6 were each dissolved in toluene and then cast on a glass plate, and toluene was slowly evaporated and removed.
A tough, homogeneous film of 0 μm was obtained. These membranes were attached to a gas permeation apparatus, and oxygen and nitrogen permeation coefficients at 25 ° C. were measured. The results are shown in Table 1.

Comparative Example 1 Poly (1-trimethylsilylpropyne) and poly (1-phenylpropyne) obtained in Reference Examples 1 and 2 were dissolved in toluene and then cast on a glass plate, and toluene was slowly removed by evaporation. , The film thickness is 20 to 3 respectively
A tough, homogeneous film of 0 μm was obtained. These membranes were attached to a gas permeation apparatus, and oxygen and nitrogen permeation coefficients at 25 ° C. were measured. The results are shown in Table 2.

Comparing the results of Table 2 with Table 1, the membranes formed from the products of Examples 1 and 2 produced using the poly (1-trimethylsilylpropyne) obtained in Reference Example 1 as a raw material had a separation coefficient higher than that of the raw material. And the membrane formed from the product of Example 6 produced from the poly (1-phenylpropyne) obtained in Reference Example 2 as a raw material has both an oxygen permeability coefficient and a separation coefficient increased as compared with the raw material. You can see that Thus, the gas separation characteristics of the membrane formed from polydisubstituted acetylene are improved by carrying out the silylation reaction of the present invention.

Reference Example 4 The polymer obtained in Example 2 was dissolved in toluene and then cast on a Teflon plate to slowly remove the toluene by evaporation to obtain a strong homogeneous film having a film thickness of 18.5 μm. The obtained membrane was inserted into a stainless pervaporation cell (pervaporation cell) and the permeation side was 0.5 mmHg.
The permeation experiment was carried out using the water-ethanol mixture having an ethanol concentration of 10% by weight as the feed liquid.

The composition of the mixed solution passing through the membrane was detected by TCD-gas chromatography, and the permeation rate P (g · m / m ² · hr) and the selectivity α
^Ethanol _water was calculated by the following formula.

As a result, the ethanol concentration in the permeate was 73.3%, and the values of P and α ^ethanol _water calculated from the above formula were 1.23 × 10 ^-3 (g · m / m ² · h) and ^{2 4} respectively. It was 0.7.

Comparative Example 2 The poly (1-trimethylsilylpropyne) obtained in Reference Example 1 was dissolved in toluene and then cast on a Teflon plate to slowly evaporate and remove the toluene to give a film thickness of 2
A sturdy homogeneous film of 0.4 μm was obtained. A permeation experiment of a water-ethanol mixture having an ethanol concentration of 10% by weight was conducted on the obtained membrane in the same manner as in Reference Example 4. as a result,
The ethanol concentration in the permeate was 52.7%, and the permeation rate P and the selectivity α ^ethanol _water value were 1.15 ×, respectively.
It was 10 ⁻³ (g · m / m ² · h) and 11.6.

Comparing this result with the result of Example 2, the film formed from the product of Example 2 produced from the poly (1-trimethylsilylpropyne) obtained in Reference Example 1 as a raw material was
It can be seen that the separation characteristics of the ethanol mixture are also significantly improved in terms of selectivity, in comparison with the membrane formed from the raw materials.

Reference Example 5 The polymers obtained in Examples 3 to 5 were dissolved in toluene and then cast on a glass plate to slowly remove toluene by evaporation to obtain a strong homogeneous film having a thickness of 20 to 30 μm. It was When the obtained film was heated in an oven at 100 ° C. for 2 hours, a tough film completely insoluble in an organic solvent could be formed.

Claims (2)

[Claims] 1. The repeating unit is represented by the general formula (I). And general formula (II) (In the formula, R ^{1 to} R ³ may be the same or different,
A hydrogen atom, an alkyl group, an alkenyl group, a substituted alkyl group, a substituted alkenyl group, a phenyl group or a substituted phenyl group is shown. A is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group or a general formula And may be optionally different for each repeating unit. However, R ^{4 to} R ⁶ may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. ) And the molar ratio of the repeating unit represented by the general formula (I) to the repeating unit represented by the general formula (II) is 99/1.
To 1/99 and the weight average molecular weight of 10,000 or more is 2
Silylized products of polydisubstituted acetylene of not more than 1,000,000. 2. The repeating unit is represented by the general formula (I). (In the formula, A is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group or a formula And may be optionally different for each repeating unit. However, R ^{4 to} R ⁶ may be the same or different and each represents an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group. After reacting a polydisubstituted acetylene consisting of (In the formula, X is a halogen atom, R ^{1 to} R ³ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, a substituted alkyl group, a substituted alkenyl group, a phenyl group or a substituted phenyl group.) A repeating unit characterized by adding a triorganohalogenosilane compound represented by the following general formula (I) And general formula (II) (In the formula, R ^{1 to} R ³ and A are the same as above.), And the mole of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II). Ratio is 99/1
To 1/99, and a method for producing a silylated product of polydisubstituted acetylene having a weight average molecular weight of 10,000 or more and 2 million or less.