JPH0542290B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polymer membrane used for separating liquid mixtures. More specifically, the present invention relates to a liquid separation membrane that is excellent in both liquid permeability and separation ability and is particularly suitable for separating liquid mixtures by pervaporation. The pervaporation method uses a non-porous polymer membrane as the border.
By supplying a liquid mixture to one side and reducing the pressure by vacuuming the other side, or by flowing a carrier gas such as an inert gas to lower the vapor pressure, components that easily permeate through the membrane are prioritized. This is a method of separation and concentration. This membrane separation method is effective for separating liquid mixtures that are difficult to perform using conventional distillation methods, such as separating azeotropic mixtures, near-boiling point mixtures, isomers, or liquid mixtures that are easily denatured by heating. Among these, it is particularly effective for separating alcohol from a low concentration alcohol aqueous solution obtained by fermenting biomass resources. [Prior Art] Research on the separation process of liquid mixtures by pervaporation using non-porous polymer membrane permeation has a long history, and much research has been conducted mainly on mixture systems that are difficult to separate using steam. For example, Binning studied separation of azeotropic mixtures using a polyvinyl alcohol membrane (US Pat. No. 2,953,502), and separation of azeotropic mixtures using a styrene/acrylic acid copolymer membrane, etc.
Separation of formaldehyde mixtures (U.S. Patent No.
4035291), but these polymer membranes have insufficient permeability and separation ability and have not yet been put to practical use. In contrast, in recent years, from the standpoint of energy conservation,
The use of pervaporation as a separation process to supplement or replace traditional distillation is gaining attention. Particularly when it is desired to extract a high concentration of organic matter from an aqueous solution containing a small amount of organic matter, such as in alcoholic fermentation of biomass, the distillation method is economically disadvantageous, and the pervaporation method is considered the most desirable method. Separation membranes using the pervaporation method of water-alcohol mixtures include cellulose acetate, cellophane, polyamide, N-vinylpyrrolidone grafts, polyvinylpyridine, or fluorine-based cation exchange membranes (Japanese Unexamined Patent Publication No. 84005/1983). Molecular membranes have been proposed. However, these polymer membranes are membranes that selectively permeate water, and are suitable for removing water from mixtures containing a small amount of water, such as azeotropes.
It is not suitable for separating alcohol from fermentation liquid that contains only about 15%. On the other hand, as polymer membranes that selectively permeate alcohol, polyethylene, polypropylene or silicone rubber membranes (Japanese Patent Laid-Open No. 57
Only a few membranes are known, such as No. 136905), but these membranes have insufficient film formability, permeability, and selectivity, and have not been put into practical use. In addition, the present inventors have discovered that a graft copolymer consisting of polystyrene as a main chain and polyfluoroalkyl acrylate as a side chain can be used as a membrane that selectively separates alcohol from a water-alcohol mixture (Polymer Preprints , Japan, 34 , No. 7,
1841 (1985)), but there is a slight problem in that the permeation rate of low-concentration alcohol aqueous solutions is rather low. In addition, in recent years, it has become possible to synthesize polydisubstituted acetylene, and it has been discovered that polytrimethylsilylpropyne, one type of polydisubstituted acetylene, can be used as a polymer membrane material that preferentially permeates alcohol, similar to silicone rubber.
(Makromol, Chem., Rapid, Commun., 7 ,
43 (1986)) It is attracting attention because it far exceeds silicone rubber in film strength. However, the liquid permeation rate and selectivity of polytrimethylsilylpropyne membranes per unit membrane thickness are approximately the same as those of silicone rubber membranes, and in terms of selectivity in particular, they are not sufficient for concentrating low-concentration alcohols. No (see comparative example). Furthermore, polydisubstituted acetylenes other than polytrimethylsilylpropyne, namely poly(2-octyne), poly(1-
Membranes formed from materials such as chloro-1-octyne), poly(1-phenylpropyne), and poly(chlorophenylacetylene) have similarly excellent membrane strength; It has been reported that the rays are preferentially transmitted. (Polymer Preprints, Japan, 35 , No.
3, 447 (1986)) [Problems to be Solved by the Invention] The present invention solves the above-mentioned drawbacks of the conventional liquid separation membrane by providing excellent permeability and separation ability for liquid mixtures.
The aim is to solve this problem by using a polymer membrane with excellent mechanical strength. The object of the present invention is to provide a separation membrane that can extremely efficiently separate a water-organic liquid mixture among liquid mixtures. [Means for Solving the Problems] The present inventors have developed a polydisubstituted acetylene that maintains the excellent membrane strength of the aforementioned polydisubstituted acetylene, has high liquid permeability, and has higher selectivity of alcohol to water. We conducted extensive research to find a new, high-quality membrane material. As a result, a membrane made of a polydisubstituted acetylene/polyorganosiloxane graft copolymer obtained by introducing polysiloxane chains into polydisubstituted acetylene has excellent membrane strength and high liquid permeability, and also has excellent membrane strength and high liquid permeability. It was discovered that, unlike disubstituted acetylene, it has very excellent alcohol selectivity, and the present invention was achieved. That is, in the present invention, the repeating unit has the general formula (wherein A is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, or

The group represented by [Formula], X is a hydrogen atom or

It is a group represented by the formula: A and X may be arbitrarily different for each repeating unit. However, Y is an oxygen atom or a divalent organic group, Z is a polyorganosiloxane chain, and ^R1 to ^R8 may be the same or different and are an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group. ), the molar ratio of the polydisubstituted acetylene repeating unit in the main chain to the polyorganosiloxane repeating unit in the side chain is in the range of 99/1 to 5/95, and the molecular weight is at least 10,000 or more. The present invention relates to a polymer membrane for separating liquid mixtures, characterized in that it is formed from a disubstituted acetylene/polyorganosiloxane graft copolymer. The divalent organic group in the above definition of Y includes a substituted or unsubstituted polymethylene chain (having 2 or more carbon atoms), a phenylenepolymethylene group, or

Examples include groups represented by [Formula]. In addition, the polyorganosiloxane chain of Z means that the repeating unit has the general formula (In the formula, R ⁹ and R ¹⁰ may be the same or different and are an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group, and may be arbitrarily different for each repeating unit.) It's a chain. The general formula () forming the polymer membrane of the present invention
A polydisubstituted acetylene/polyorganosiloxane graft copolymer consisting of a repeating unit represented by, for example, a repeating unit having the general formula (In the formula, A is an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, or

It is a group represented by the formula and may be arbitrarily different for each repeating unit. ) After reacting the polydisubstituted acetylene consisting of the general formula (In the formula, R ⁹ and R ¹⁰ are the same as above, and m is 3
It is an integer of ~6. ) is reacted with a cyclosiloxane compound represented by
More general formula (In the formula, B is a halogen atom, and R ⁶ to R ⁸ are the same as above.) It can be synthesized by adding a triorganohalogenosilane compound represented by the following to stop the reaction. In addition to the above method, after reacting polydisubstituted acetylene consisting of repeating units represented by the general formula () with a strong base, the general formula (In the formula, B is a halogen atom, and R ⁴ to R ⁸ , Y and Z are the same as described above.) It can also be synthesized by reacting with a polyorganosiloxane having a one-end reactivity. The raw material polydisubstituted acetylene consisting of a repeating unit represented by the general formula () includes 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(phenyldimethylsilylpropyne), poly(β-phene) poly(1-pentafluorophenylpropyne), poly(3,3,3-trifluoropropyldiethylsilylpropyne), poly(1-trimethylsilylpropyne), poly[1-( butyldimethylsilyl)propyne] or a copolymer consisting of a combination of at least two or more repeating units of these polydisubstituted acetylenes. As a method for obtaining these polydisubstituted acetylenes, one or more disubstituted acetylene compounds as raw materials are mixed with a group or group transition metal such as tantalum, molybdenum, tungsten, or a niobium halide (for example, tantalum pentachloride). , niobium pentachloride, molybdenum pentachloride, tungsten hexachloride, tantalum pentabromide, niobium pentabromide, etc.) as a catalyst, usually at 30 to 100°C in an organic solvent.
It is obtained by polymerizing at a temperature of 2 to 36 hours. As the solvent, aromatic hydrocarbons such as benzene, toluene, and xylene, alicyclic hydrocarbons such as cyclohexane, chlorine solvents such as chloroform, 1,2-dichloroethane, and carbon tetrachloride, etc. can be used. In addition, the above catalyst is used as the main catalyst, and the second component is aluminum, silicon, tin,
The desired polymer can also be obtained using an organometallic compound containing antimony (for example, trimethylaluminum, triethylaluminum, hydrosilane derivatives, tetraphenyltin, tetra-n-butyltin, triphenylantimony, etc.) as a promoter. . A polydisubstituted acetylene consisting of a repeating unit represented by the general formula () is reacted with a cyclosiloxane compound represented by the general formula () or a one-end reactive polyorganosiloxane represented by the general formula (). The strong base used in this case is
Organolithium compounds such as methyllithium, n-butyllithium, t-butyllithium, phenyllithium, lithium diisopropylamide, alkali metal hydride compounds such as potassium hydride and sodium hydride, methylmagnesium iodide, ethylmagnesium bromide, Examples include Grignard compounds such as phenylmagnesium bromide, but organic lithium compounds are preferred in terms of reaction efficiency. These strong bases are usually used in an amount of 0.1 to 4 equivalents based on the repeating unit of the polydisubstituted acetylene as a raw material, and the introduction rate of the polyorganosiloxane component can be controlled by this amount. It is preferable to use a solvent in the reaction between the polydisubstituted acetylene represented by the general formula () and a strong base, and any solvent may be used as long as it dissolves the polydisubstituted acetylene and does not participate in the reaction. , e.g. n-pentane, n-hexane,
Cyclopentane, cyclohexane, tetrahydrofuran (THF), dimethoxyethane, toluene,
Organic solvents such as benzene and xylene can be used. However, in terms of reaction efficiency, THF, n-pentane, n-hexane, cyclopentane,
Preferably, aliphatic hydrocarbons such as cyclohexane are used. In addition, the reaction temperature is usually 0℃~
The reaction proceeds suitably within a temperature range of 90°C. 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, since the reaction proceeds smoothly. As the cyclosiloxane compound represented by the general formula (), (However, m is an integer of 3 to 6). Furthermore, a mixture of two or more of these cyclosiloxane compounds may be used. When adding the cyclosiloxane compound represented by the general formula () to the reaction system, it is preferable to dissolve the cyclosiloxane compound in a solvent beforehand. In this case, the solvent used is tetrahydrofuran, n-pentane, n- -Organic solvents such as hexane, cyclopentane, and cyclohexane can be mentioned. In addition, when reacting with a cyclohexane compound, the reaction progresses suitably at a reaction temperature usually around room temperature, and the reaction time is 2 hours or more, preferably 10 hours or more, so that the ring-opening polymerization of the cyclokiloxane compound is completed. do. The triorganohalogenosilane compound represented by the general formula () used to stop the above reaction includes: etc. can be exemplified. 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 excess of 2 to 20 equivalents relative to the strong base used. In that case, the reaction time is preferably 20 minutes or more. In addition, as an example of the one-end reactive polyorganosiloxane represented by the general formula (), (1) (2) 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 is:

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

etc. can be exemplified. Among the single-end reactive polyorganosiloxanes, the compound of group (1) is, for example, as shown in the reaction formula below, in which an equimolar amount of n-
It can be synthesized by living anionic polymerization of a cyclosiloxane compound using a silanolate anion obtained by adding BuLi as an initiator, and stopping the reaction using a halogenosilane compound having a reactive substituent. (In the formula, P is 1 or more, m is an integer of 3 to 6, B and B' are the same or different halogen atoms,
R ⁴ to ^{R 10} may be the same or different and are an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group. However, R ⁹ and R ¹⁰ may be different for each repeating unit. ) In addition, it can also be synthesized by reacting the above-mentioned silanolate anion with an equimolar amount of α,ω-dichloropolyorganosiloxane. Furthermore, the single-end reactive polyorganosiloxane of group (2) is expressed in the above reaction formula.

Represented by [formula] General formula instead of compound,

[Formula] () (In the formula, R ⁹ and R ¹⁰ are the same as above.) A general formula that can be synthesized by the same method using a silane compound represented by (In the formula, R ⁶ to ^{R 10} , m and p are the same as above.) It can be synthesized by a hydrosilylation reaction between a one-end hydrosilylated polyorganosiloxane represented by the formula and a chlorosilane compound having a double bond. can. As the chlorosilane compound having a double bond used here, etc. can be exemplified. One end reactive polyorganosiloxane represented by the above general formula () is mixed with a strong base at a concentration of 0.5 to 3.0.
By using an equivalent amount, preferably 0.9 to 2.0 equivalents, the desired product can be obtained in good yield. The strong graft polymers of the present invention are aromatic solvents such as toluene, benzene, ethylbenzene, and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and trichloroethyln, and hydrocarbons such as n-hexane, cyclohexane, and cyclohexene. It is soluble in solvents or ether solvents such as tetrahydrofuran, and insoluble in alcohols or water. The general formula () forming the polymer membrane of the present invention
A polydisubstituted acetylene/polyorganosiloxane graft copolymer consisting of repeating units represented by has a molar ratio of polydisubstituted acetylene repeating units in the main chain and polyorganosiloxane repeating units in the side chain from 99/1 to 99/1. It must be within the range of 5/95. In other words, if the organosiloxane units are less than this range, the liquid separation properties of the resulting membrane will be almost the same as those of the raw material polydisubstituted acetylene, and if it is too large, the glass transition point of the graft copolymer will be too low. Therefore, film forming properties tend to deteriorate and it is difficult to form a thin film. In particular, A in the general formula () is

〔Effect of the invention〕

As described above, the separation membrane of the present invention has superior membrane strength compared to conventional silicone rubber membranes, so it can be made thinner, and it also has extremely superior liquid permselectivity. The membrane of the present invention can be used to very efficiently separate or concentrate various liquid mixtures, such as water-alcohol mixtures. [Examples and Reference Examples] The present invention will be explained in more detail below using Reference Examples, Examples, and Comparative Examples. However, it goes without saying that the present invention is not limited to these. Reference example 1 [Synthesis of poly(1-phenylpropyne)] 44.3g of 1-phenylpropyne was added to 500ml of toluene.
2.7 g of tantalum pentachloride was added, the tube was degassed and sealed in a stainless steel polymerization tube, and the mixture was shaken at 80° C. for 6 hours to obtain a viscous gel-like polymer. This polymer was dissolved in toluene and reprecipitated several times in a large amount of methanol, and the obtained yellow fibrous solid was dried under vacuum at 60°C. The yield is 38.2g (yield 86.2
%). For the obtained polymer, IR, ^1H
−NMR, ¹³ C−NMR measurements and elemental analysis were performed.
It was confirmed that it was the desired poly(1-phenylpropyne). Furthermore, as a result of GPC measurement, the number average molecular weight and weight average molecular weight were 2.15×10 ⁵ and 5.53×10 ⁵ , respectively, in terms of polystyrene. Example 1 3.8 g of poly(1-phenylpropyne) obtained in Reference Example 1 was dissolved in 450 ml of dry cyclohexane,
After heating to 60℃ under argon gas flow,
N′,N′-tetramethylethylenediamine 4.90ml
(32.7 mmol) and n-butyllithium hexane solution (1.6 mol/) 20.4 ml (32.7 mmol) were added and stirring was continued for an additional hour, and the reaction solution turned black-red. Next, the temperature of the reaction solution was cooled to room temperature, and 36.4 g of hexamethylcyclotrisiloxane was added.
(163.6 mmol) dissolved in 250 ml of dry THF was added all at once, and the reaction solution changed from black-red to black-purple, and then gradually changed to pale yellow. Stirring was further continued at room temperature for 24 hours, and 18 ml (142 mmol) of trimethylchlorosilane was added to stop the reaction, followed by further stirring for 2 hours. lastly,
A white polymer was obtained by pouring the above reaction solution into methanol 5. The obtained polymer was dissolved again in 300 ml of toluene and reprecipitated in a mixed solvent of methanol/diethyl ether (80/20 vol.%) 4, and the contaminating polydimethylsiloxane was removed by repeating the reprecipitation several times in the same manner. The polymer was purified. The yield of produced polymer is 6.8
It was hot at g. When the obtained polymer was subjected to GPC measurement, the number average molecular weight and weight average molecular weight were 2.37×10 ⁵ and 5.61×, respectively, in terms of polystyrene.
It was 10 ⁵ . Furthermore, the results of the IR spectrum, ¹ H-NMR spectrum, and elemental analysis were as follows. IR spectrum (cm ^-1 ); 3100(m), 3070(s), 3040
(m), 2980(s), 2860(m), 1950(w), 1890(w), 1800(w),
1600 (s, characteristic absorption of phenyl group in main chain poly(1-phenylpropyne)), 1500(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: 57.01, H: 7.54 From the above results, the produced polymer is based on the methyl group of the raw material poly(1-phenylpropyne). Some of the hydrogen in

[Formula] (p is an integer of 1 or more) Poly(1
-phenylpropyne)/polydimethylsiloxane graft copolymer. Also,
The mole of the poly(1-phenylpropyne) repeating unit in the main chain and the polydimethylsiloxane repeating unit in the side chain of this graft copolymer was determined from the proton peak area ratio of 0.10ppm and 6.90ppm in the ¹ H-NMR spectrum. The ratio was 30/70. The graft copolymer thus obtained was dissolved in toluene and cast onto a Teflon plate, and the toluene was slowly evaporated to reduce the film thickness.
A uniform, transparent, and strong film of 28 μm was created. The obtained membrane was inserted into a stainless steel cell for pervaporation, and the permeation side was reduced to 0.5 mgHg to allow the water-ethanol mixture to permeate. The composition of the mixture passing through the membrane is TCD
- Detected by gas chromatography, permeation rate P (g·m/m ² ·hr) and selectivity α were determined by the following formula. P=permeate weight x membrane pressure/membrane area x time (g・m/m ²・
hr) α ^A _B = (weight fraction of component A in permeate/weight fraction of component B in permeate)/(weight fraction of component A in feed solution/weight of component B in feed solution) Fraction) The permeation experiment as described above was conducted several times with different feed liquid compositions, and P and α were measured in each case. The results are shown in Table 1.

【table】

[Table] Example 2 The same procedure as in Example 1 was carried out except that the amount of hexamethylcyclotrisiloxane was changed to 54.6 g (245 mmol) to obtain 8.7 g of a white polymer. The number average molecular weight and weight average molecular weight measured by GPC are 2.44 x polystyrene equivalent values, respectively.
10 ⁵ , 5.65×10 ⁵ . IR spectrum and ¹ H− of the obtained polymer
The NMR spectrum was similar to the results of Example 1, and the elemental analysis values were as follows. Elemental analysis value (%); C: 49.98, H: 7.65 Therefore, the produced polymer is a poly(1-phenylpropyne)/polydimethylsiloxane graft copolymer having a structure similar to that of the polymer obtained in Example 1. Yes, the molar ratio of the repeating unit of poly(1-phenylpropyne) in the main chain and the repeating unit of polydimethylsiloxane in the side chain, determined from the proton peak area ratio of the ¹ H-NMR spectrum, is
It was 20/80. A uniform, transparent, and strong film having a thickness of 25 μm was prepared from the obtained graft copolymer by the same method as in Example 1. The permeation characteristics of this membrane for a water-ethanol mixture were measured in the same manner as in Example 1 while varying the feed liquid composition. The results are shown in Table 2.

[Table] Example 3 In Example 1, the amount of hexamethylcyclotrisiloxane was 36.1g (162mmol), and tris(3,3,3-trifluoropropyl) was added to this.
Trimethylcyclotrisiloxane 38.0g (80.9m
mol) was added, and the operation was exactly the same as in Example 1 except for that, to obtain 11.5 g of a white polymer. The number average molecular weight and weight average molecular weight measured by GPC are 2.44 x polystyrene equivalent values, respectively.
10 ⁵ , 5.29×10 ⁵ . Furthermore, the results of the 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(s, 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),
1070(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 group of 3,3,3-trifluoropropylsilyl group), 1.60 (proton peak of methyl group on main chain poly(1-phenylpropyne)) proton peak of methyl group), 2.12
(Proton peak of methylene group on the trifluoromethyl side of 3,3,3-trifluoropropylsilyl group), 6.90 (main chain poly(1-phenylpropyne)
Proton peak of phenyl group) Elemental analysis value (%); C: 46.32, H: 5.99 From the above results, the produced polymer has a part of the hydrogen on the methyl group of the raw material poly(1-phenylpropyne). (In the formula, Z′ is

[expression] and

It is a polyorganosiloxane consisting of repeating units represented by the formula: ) Poly(1) having a structure substituted with a group represented by
-phenylpropyne)/polyorganosiloxane graft copolymer. Also,
¹ H-NMR spectrum 0.10ppm, 0.85ppm,
of the side chain polyorganosiloxane determined from the proton peak area ratio of 6.90 ppm.

[expression] and

The molar ratio of the repeating units represented by [Formula] is 63/37, and the molar ratio of the repeating units of poly(1-phenylpropyne in the main chain and the repeating units of polyorganosiloxane in the side chain) is 22/78. A uniform, transparent, and strong membrane with a thickness of 22 μm was prepared from the obtained graft copolymer by the same method as in Example 1. The permeation characteristics of the water-ethanol mixture of this membrane were investigated by varying the feed liquid composition. The measurements were carried out in the same manner as in Example 1 with some changes.The results are shown in Table 3.

[Table] Reference Example 2 (Synthesis of poly(1-trimethylsilylpropyne)) 42.6g of 1-trimethylsilylpropyne was dissolved in 300ml of toluene, 2.4g of tantalum pentachloride was added, and the mixture was degassed and sealed in a stainless steel polymerization tube. Afterwards, it was shaken at 80°C for 24 hours to obtain a viscous gel-like polymer. This polymer was dissolved in toluene and reprecipitated several times in a large amount of methanol, and the obtained white fibrous mass was dried at 60° C. under vacuum. The yield was 38.5g (yield 90.3%). Regarding the obtained polymer,
IR, ¹ H-NMR, ¹³ C-NMR measurements, and elemental analysis were performed, and it was confirmed that it was the desired poly(1-trimethylsilylpropyne). Further, as a result of GPC measurement, the number average molecular weight and weight average molecular weight were 5.36×10 ⁵ and 2.26×10 ⁵ , respectively, in terms of polystyrene. Reference Example 3 (Synthesis of one-end reactive polysiloxane 1) 14.2 g (0.157 mol) of trimethylsilanol was dissolved in 200 ml of dry THF, and n-butyllithium hexane solution (1.6 mol/) was added under an argon gas stream.
100ml (0.16mol) was added. After stirring for 10 minutes,
Additionally, 35.6g of hexamethylcyclotrisiloxane
(0.479 mol) dissolved in 200 ml of dry THF was added, and the mixture was stirred at room temperature for 21 hours under a stream of argon gas. 60 ml (0.551 mol) 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 150°C for 3 hours under a vacuum of 0.1 mmHg or less to remove unreacted cyclosiloxane and excess terminator. It gave 51.6 g of clear viscous liquid. About the obtained polymer
IR and NMR measurements were performed to determine the structure.

It was confirmed that [Formula]. Moreover, the average degree of polymerization m was about 4.2 based on the proton ratio in NMR. 25.0 g (approximately 0.067 mol) of the polydimethylsiloxane thus obtained was dissolved in 50 ml of dry toluene, and under a stream of argon gas, 30 ml (0.22 mol) of vinyldimethylchlorosilane and an ethanol solution of chloroplatinic acid (0.193 mol) were added as a catalyst. /) 14μ
was added, and the mixture was heated and stirred at 80°C for 2 hours. This solution
IR measurement revealed an absorption peak (2175 cm
^-1 ) had completely disappeared. The solvent and excess dimethylchlorosilane were removed by evaporation from this solution in an argon stream to obtain about 26 g of one-end dimethylchlorosilyl polydimethylsiloxane. Example 4 1.0g (8.90mmol) of poly[1-(trimethylsilyl)propyne] obtained in Reference Example 2 was added to THF200
ml of n-butyllithium hexane solution (1.6 mol/) at 0°C under an argon atmosphere.
(9.60 mmol) and stirred for 3 hours, the reaction solution turned red. Furthermore, 14 g (approximately 24 mmol) of the one-end dimethylchlorosilyl polydimethylsiloxane obtained in Reference Example 3 was added and stirred for an additional 15 minutes at 0°C, and it was confirmed that the reaction solution changed from red to a colorless transparent solution. Thereafter, the reaction solution was poured into methanol 2 to form a precipitate. The obtained precipitate was filtered, dissolved in 200 ml of toluene, and poured into 2 methanol to form a precipitate. Thereafter, reprecipitation was performed several times in the same manner for purification. The resulting precipitate was filtered and dried to obtain 1.09 g of a white polymer. When this polymer was measured by GPC, the number average molecular weight and weight average molecular weight were 4.26×10 ⁵ and 1.90×, respectively, in terms of polystyrene.
It was 10 ⁶ . In addition, the IR spectrum and elemental analysis values were as follows. IR spectrum (cm ^-1 ): 2980(s), 2920(s), 1565
(s), 1433(m), 1370 (m, characteristic absorption of methyl groups on main chain polytrimethylsilylpropyne), 1260 (s,
Characteristic absorption of the methyl group on the side chain polydimethylsiloxane), 1250 (s, characteristic absorption of the trimethylisilyl group on the main chain polytrimethylsilylpropyne), 1180
(m), 1100 (s, characteristic absorption of siloxane bond), 1020
(s), 915(m), 840(s), 800(s), 750(s), 685(m), 630(m)
) Elemental analysis values (%): C: 63.59, H: 10.48 From the above results, the produced polymer contains one of the hydrogen atoms on the methyl group directly connected to the main chain double bond of the raw material poly[1-(trimethylsilyl)propyne]. The department It was confirmed that the copolymer was a poly(1-trimethylsilylpropyne)/polydimethylsiloxane graft copolymer having a structure substituted with a group represented by the following. Furthermore, the molar ratio of the main chain poly(1-trimethylsilylpropyne) monomer unit to the side chain polydimethylsiloxane monomer unit was calculated from the carbon content of the elemental analysis value, and was found to be 96/4. 100 mg of the obtained graft copolymer was dissolved in 2 ml of m-xylene and cast on a Teflon plate with an area of 25 cm ² .The solvent was distilled off at 40°C and thoroughly dried under vacuum to obtain a uniform, transparent film thickness. A 12.6 μm membrane was obtained. The permeation characteristics of the water-ethanol mixture of the obtained membrane were measured in the same manner as in Example 1 while varying the feed liquid composition. The results are shown in Table 4.

[Table] Reference Example 4 (Synthesis of one-end reactive polysiloxane 2) In Reference Example 3, trimethylsilanol was
7.2g (0.0798mol), n-butyllithium hexane solution 50ml (0.080mol), dimethylchlorosilane
The same procedure as in Reference Example 2 was performed except that the amount was changed to 30 ml (0.275 mol), and the structure was Polydimethylsiloxane was obtained. Furthermore, by carrying out a hydrosilylation reaction of 22.0 g of this polydimethylsiloxane with vinyldimethylchlorosilane in the same manner as in Reference Example 3, one-end dimethylchlorosilyl polydimethylsiloxane with a
I got g. Example 5 In Example 4, 10 g (approximately 16 m
The operation was exactly the same as in Example 4 except that mol) was used, and some of the hydrogens on the methyl groups directly connected to the main chain double bonds of poly[1-(trimethylsilyl)propyne] were 1.08 g of a poly(1-trimethylsilylpropyne)/polydimethylsiloxane graft copolymer having a structure substituted with the group represented by was obtained. IR
The spectrum was exactly the same as in Example 1, but the absorption intensity of the methyl group on the side chain polydimethylsiloxane at 1260 cm ^-1 and the characteristic absorption of the siloxane bond at 1100 cm ^-1 were stronger. The elemental analysis values are as follows. Elemental analysis value (%): C: 61.60, H: 9.69 Calculate the molar ratio of the main chain poly[1-(trimethylsilyl)propyne] monomer unit and the side chain polydimethylsiloxane monomer unit from the above carbon content. When I did that, it was 88/12. Further, the number average molecular weight and weight average molecular weight determined by GPC measurement were 4.13×10 ⁵ and 1.77×10 ⁶ , respectively, in terms of polystyrene. A uniform, transparent, and strong film having a thickness of 18.8 μm was prepared from the obtained graft copolymer by the same method as in Example 4. The permeation characteristics of this membrane for a water-ethanol mixture were measured in the same manner as in Example 1 while varying the feed liquid composition. The results are shown in Table 5. Furthermore, using the same membrane, the permeation characteristics of a water-acetone mixture were measured in a similar manner, and the results are shown in Table 6.

【table】

[Table] Reference Example 5 (Synthesis of one-end reactive polysiloxane 3) In Reference Example 3, trimethylsilanol was
5.4g (0.060mol), n-butyllithium hexane solution 38ml (0.061mol) dimethylchlorosilane 20
ml (0.184 mol) was carried out in exactly the same manner as in Reference Example 3, and the structure was Polydimethylsiloxane was obtained. Further, 24.0 g of this polydimethylsiloxane was subjected to a hydrosilylation reaction with vinylchlorosilane in the same manner as in Reference Example 3, to obtain about 25 g of one-end dimethylchlorosilyl polydimethylsiloxane. Example 6 In Example 4, 20 g (approximately 27 m
The operation was exactly the same as in Example 4 except that mol) was used, and some of the hydrogens on the methyl groups directly connected to the main chain double bonds of poly(1-trimethylsilylpropyne) were 1.33 g of a poly(1-trimethylsilylpropyne)/polydimethylsiloxane graft copolymer having a structure substituted with the group represented by was obtained. IR
The spectrum was exactly the same as in Example 4, but the absorption intensity of the methyl group on the side chain polydimethylsiloxane at 1260 cm ^-1 and the characteristic absorption of the siloxane bond at 1100 cm ^-1 were even stronger than in Example 5. was. The elemental analysis values are as follows. Elemental analysis value (%): C.60.23, H.10.27 From the above carbon content, the molar ratio of the main chain poly(1-trimethylsilylpropyne) monomer unit and the side chain polydimethylsiloxane monomer unit was calculated. By the way, it was 82/18. Further, the number average molecular weight and weight average molecular weight determined by GPC measurement were 5.71×10 ⁵ and 1.77×10 ⁶ , respectively, in terms of polystyrene. A uniform, transparent, and strong film having a thickness of 15.4 μm was prepared from the obtained graft copolymer by the same method as in Example 4. The permeation characteristics of this membrane for a water-ethanol mixture were measured in the same manner as in Example 1 while varying the feed liquid composition. The results are shown in Table 7.

[Table] Reference Example 6 (Synthesis of one-end reactive polysiloxane 4) In Reference Example 3, trimethylsilanol was
3.6g (0.0399mol), n-butyllithium hexane solution 25ml (0.040mol), dimethylchlorosilane
The same procedure as in Reference Example 3 was performed except that the amount was changed to 15 ml (0.138 mol), and the structure was Polydimethylsiloxane was obtained. Furthermore, by carrying out a hydrosilylation reaction of 27.2 g of this polydimethylsiloxane with vinyldimethylchlorosilane in the same manner as in Reference Example 3, about 28 g of one-end dimethylchlorosilyl polydimethylsiloxane was added.
I got g. Example 7 In Example 4, 20 g (approximately 20 m
The operation was exactly the same as in Example 4 except that mol) was used, and some of the hydrogens on the methyl groups directly connected to the main chain double bonds of poly(1-trimethylsilylpropyne) were 1.38 g of a poly(1-trimethylsilylpropyne)/polydimethylsiloxane graft copolymer having a structure substituted with the group represented by was obtained. IR
The spectrum was exactly the same as in Example 4, but the absorption intensity of the methyl group on the side chain polydimethylsiloxane at 1260 cm ^-1 and the characteristic absorption of the siloxane bond at 1100 cm ^-1 were stronger than in Example 6. was. The elemental analysis values are as follows. Elemental analysis value (%): C: 55.21, H: 9.85 From the above carbon content, the molar ratio of the main chain poly(1-trimethylsilylpropyne) monomer unit and the side chain polydimethylsiloxane monomer unit was calculated. However, it was 63/37. Further, the number average molecular weight and weight average molecular weight determined by GPC measurement were 5.05×10 ⁵ and 2.18×10 ⁶ , respectively, in terms of polystyrene. A uniform, transparent, and strong film having a thickness of 14.8 μm was prepared from the obtained graft copolymer by the same method as in Example 4. The permeation characteristics of this membrane for a water-ethanol mixture were measured in the same manner as in Example 1 while varying the feed liquid composition. The results are shown in Table 8.

[Table] Reference Example 7 (Synthesis of one-end reactive polysiloxane 5) 3.90 g (0.0432 mol) of trimethylsilanol was dissolved in 200 ml of dry THF, and an n-butyllithium hexane solution (1.6 mol/min) was added under an argon gas flow.
), 29 ml (0.046 mol) was added. After stirring for 10 minutes, 36.2 g of hexamethylcyclotrisiloxane
(0.488 mol) and 50.9 g (0.326 mol) of tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane dissolved in 150 ml of dry THF were added, and the mixture was heated at room temperature for 20 minutes under an argon gas stream.
Stir for hours. 40 ml (0.367 mol) 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.
When heated at 150°C for 3 hours to remove unreacted cyclosiloxane and excess terminator, 78.3 g of a colorless and transparent viscous liquid was obtained. IR and NMR measurements were performed on the resulting polymer to determine its structure. but

[Formula] and Z is

[expression] and

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

[expression] and

The molar ratio of [Formula] was 63/37, and the average degree of polymerization was 23.4. Furthermore, 50.0 g of this polyorganosiloxane was subjected to a hydrosilylation reaction with vinyldimethylchlorosilane in the same manner as in Reference Example 3, resulting in approximately 51 g of one-terminated dimethylchlorosilyl polyorganosiloxane.
I got it. Example 8 In Example 4, 45 g (approximately 16 m
The same procedure as in Example 4 was performed except that mol) was used, and some of the hydrogens on the methyl groups directly connected to the main chain double bonds of poly[1-(trimethylsilyl)propyne] were (In the formula, Z is

[expression] and

It is a polyorganosiloxane consisting of the repeating unit of [Formula], and the repeating unit

[expression] and

The molar ratio of [Formula] is 63/37, and the average degree of polymerization is about 23.4. ) 1.41 g of a poly[1-(trimethylsilyl)propyne]/polydimethylsiloxane graft copolymer having a structure substituted with a group represented by the following was obtained.
The IR spectrum and elemental analysis values were as follows. IR spectrum (cm ^-1 ): 2980(s), 2920(s), 1565
(s), 1433(m), 1370 (m, characteristic absorption of methyl groups on main chain polytrimethylsilylpropyne), 1260 (s,
Characteristic absorption of methyl groups on side chain polysiloxane),
1250 (s, characteristic absorption of trimethylsilyl group on main chain polytrimethylsilylpropyne), 1210 (s, characteristic absorption of trifluoromethyl group), 1180 (m), 1130
(s, characteristic absorption of trifluoromethyl group), 1100
(s, characteristic absorption of siloxane bonds), 1020(s), 915
(m), 840(s), 800(s), 750(s), 740(s), 685(m), 635(m)
) Elemental analysis value (%): C, 44.44, H, 8.52 Based on the carbon content of the elemental analysis value, the molar ratio of the main chain poly[1-(trimethylsilyl)propyne] monomer unit and the side chain polyorganosiloxane monomer unit When calculated, it was 40/60. In addition, the number average molecular weight and weight average molecular weight measured by GPC are 4.83×10 ⁵ and 2.11×10 ⁶ , respectively, in terms of polystyrene.
It was hot. A uniform, transparent, and strong film having a thickness of 16.2 μm was prepared from the obtained graft copolymer by the same method as in Example 4. The permeation characteristics of this membrane for a water-ethanol mixture were measured in the same manner as in Example 1 while varying the feed liquid composition. The results are shown in Table 9.

[Table] Example 9 1.0 g (8.90 mmol) of poly[1-(trimethylsilyl)propyne obtained in Reference Example 2 was added to 200 ml of THF.
6.0 ml (9.60
mmol) and stirred for 1 hour, then 2.1g (28.3mmol) of hexamethylcyclotrisiloxane was added.
Add the solution dissolved in 15 ml of THF and add 0 for 3 hours.
Stirring was continued at ℃. Next, 6 ml (47.6 mmol) of trimethylchlorosilane was added to stop the reaction, and then the reaction solution was poured into methanol 2 to form a precipitate. The obtained precipitate was filtered, dissolved in 200 ml of toluene, and poured into 2 methanol to form a precipitate.
Thereafter, reprecipitation was performed several times in the same manner for purification. The resulting precipitate was filtered and dried to obtain 1.20 g of a white polymer. When we performed GPC measurements on this polymer, the number average molecular weight and weight average molecular weight were each 4.42 x polystyrene equivalent values.
10 ⁵ , 1.79×10 ⁶ . Further, the IR spectrum was almost the same as in Example 4, and the elemental analysis values were as follows. Elemental analysis value (%): C: 63.26, H: 10.68 From the above results, the produced polymer has a part of the hydrogen on the methyl group directly connected to the main chain double bond of the raw material poly(1-trimethylsilylpropyne). It was confirmed to be a poly[1-(trimethylsilyl)propyne]/polydimethylsiloxane graft copolymer having a structure substituted with a group represented by the following.
Furthermore, based on the carbon content of the elemental analysis value, the main chain poly[1
The molar ratio of the -(trimethylsilyl)propyne] monomer unit and the side chain polydimethylsiloxane monomer unit was calculated to be 94/6. A uniform, transparent, and strong film having a thickness of 12.4 μm was prepared from the obtained graft copolymer by the same method as in Example 4. The permeation characteristics of this membrane for a water-ethanol mixture were measured in the same manner as in Example 1 while varying the feed liquid composition. The results are shown in Table 10.

[Comparative example]

Using the poly[1-(trimethylsilyl)propyne] obtained in Reference Example 2, a uniform, transparent, and strong film with a thickness of 17.3 μm was prepared in the same manner as in Example 4. Example 1 The permeation characteristics of this membrane for a water-ethanol mixture were investigated by varying the feed liquid composition.
It was measured in the same manner as. The results are shown in Table 11.

【table】

Claims (1)

[Claims] 1. The repeating unit is a general formula (In the formula, A is an alkyl group, substituted alkyl group, phenyl group, substituted phenyl group, or a group represented by [formula], X is a hydrogen atom or a group represented by [formula], and A and X are each repeating unit. However, Y is an oxygen atom or a divalent organic group, Z is a polyorganosiloxane chain, and R ¹ to ^{R 8} may be the same or different and are an alkyl group, a substituted alkyl group, a phenyl group, or (substituted phenyl group), the molar ratio of the polydisubstituted acetylene repeating unit in the main chain to the polyorganosiloxane repeating unit in the side chain is in the range of 99/1 to 5/95, and the molecular weight is at least A polymer membrane for separating liquid mixtures, characterized in that it is formed from a polydisubstituted acetylene/polyorganosiloxane graft copolymer having a molecular weight of 10,000 or more.