JPH07121952B2 - Organosilicon compound having a pyridine ring - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a novel organosilicon compound having a pyridine ring as a substituent on silicon. The compound of the present invention is particularly useful as a synthetic intermediate for producing a polyorganosiloxane having a pyridine ring at one end by utilizing living polymerization.

[Problems to be Solved by Prior Art and Invention]

Generally, a silanol compound is used as an initiator used when synthesizing a polyorganosiloxane by living polymerization.

By using a silanol compound having various substituents, it becomes possible to synthesize a polyorganosiloxane having a substituent on the silanol compound at one end. If it is possible to introduce a pyridine ring at the end of polyorganosiloxane, which has high chain mobility and gas permeability, and is highly hydrophobic, a gas / liquid separation membrane, surfactant, or transdermal absorption enhancer, etc. It can be widely applied to.

However, there has been no synthetic example of a silanol compound having a pyridine ring as a substituent, and therefore it was not possible to introduce a pyridine ring at the end of a polyorganosiloxane.

The present inventors diligently studied a novel silanol compound that can serve as an initiator for synthesizing a polyorganosiloxane having a pyridine ring at one end. As a result, they have found that it is possible to synthesize a target silanol compound by reacting a substituted pyridine derivative with a haloalkylsilane derivative as a raw material, and arrived at the present invention.

[Means for Solving the Problems]

The present invention has the general formula (In the formula, R is an alkyl group having 4 or more carbon atoms or a phenyl group, R ¹ and R ² may be the same or different, and
A substituted alkyl group, a phenyl group or a substituted phenyl group, A is a hydrogen atom or a hydroxyl group, m is an integer of 0 to 2, and p is 1.
Is an integer from 6 to 6. ) Relating to an organosilicon compound having a pyridine ring.

The compound of the present invention can be synthesized, for example, by the production method described below.

That is, the general formula (In the formula, R is an alkyl group having 4 or more carbon atoms or a phenyl group, and m is an integer of 0 to 2.) After reacting the substituted pyridine derivative with a strong base, the compound represented by the general formula (In the formula, X is a halogen atom, R ¹ and R ² may be the same or different and is an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and p is an integer of 1 to 6.)
By reacting with a haloalkylsilane compound represented by the following general formula (A) in which A in the general formula (I) is a hydrogen atom. (In the formula, R is an alkyl group having 4 or more carbon atoms or a phenyl group, R ¹ and R ² may be the same or different, and
It is a substituted alkyl group, a phenyl group or a substituted phenyl group, m is an integer of 0 to 2, and p is an integer of 1 to 6. ) The organosilicon compound of the present invention represented by the formula (1) can be synthesized. Further, a general formula in which A in the general formula (I) is a hydroxyl group, using the organosilicon compound represented by the general formula (I) ′ as a precursor (In the formula, R is an alkyl group having 4 or more carbon atoms or a phenyl group, R ¹ and R ² may be the same or different, and
It is a substituted alkyl group, a phenyl group or a substituted phenyl group, m is an integer of 0 to 2, and p is an integer of 1 to 6. ) The organosilicon compound of the present invention represented by the formula (1) can be synthesized. For example, the organosilicon compound represented by the general formula (I) ′ is reacted with sodium alcoholate and then reacted with an aqueous solution containing a base such as sodium hydroxide or potassium hydroxide to give the general formula (I) ″. An organosilicon compound represented by can be synthesized.

As the substituted pyridine derivative represented by the general formula (II) used as a raw material when producing the organosilicon compound of the present invention, it is essential to have a methyl group on the pyridine ring. The compound represented by

Further, as the strong base to be reacted with the substituted pyridine derivative represented by the general formula (II), organic lithium compounds such as methyllithium, n-butyllithium, sec-butyllithium, t-butyllithium and phenyllithium are preferable. Used for. However, m in the general formula (II) is 0.
When an alkyl-substituted pyridine derivative that is, that is, picoline is used as a raw material, it is optimal to use phenyllithium in terms of yield. Reaction is -90 ℃ to 0 ℃
It is preferable to carry out at low temperature. Further, this reaction is preferably carried out in an organic solvent, and as the solvent, tetrahydrofuran (THF), diethyl ether, benzene, toluene or the like can be used.

Next, as the halogenated alkylsilane compound represented by the general formula (III) used as a reagent, Etc. can be illustrated. Some of these compounds are commercially available and have the general formula (In the formula, X and X ′ may be the same or different, a halogen atom, R ¹ and R ² may be the same or different, and are an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and p is 1 to 1). It is an integer of 6) and can be easily synthesized by reducing a commercially available halosilane compound.

The organosilicon compound of the present invention represented by the general formula (I) ″ obtained by the above-described production method is suitably used as an initiator used when synthesizing a polyorganosiloxane by anionic living polymerization. That is,
As will be described later in Examples of use, after reacting the organosilicon compound of the present invention represented by the general formula (I) ″ with an organolithium compound or a strong base such as sodium hydride or potassium hydride, a cyclosiloxane compound It is possible to synthesize a polyorganosiloxane having a pyridine ring at one end by reacting with a suitable terminating agent to terminate the reaction. It can be applied to various fields such as silicone-based surfactants, percutaneous absorption enhancers, intermediates for synthesizing gas or liquid separation membrane materials, cosmetics, etc. Further, it is represented by the general formula (I). When the pyridine ring is introduced into a carrier such as a polymer compound or silica by a hydrosilylation reaction or a condensation reaction, the organosilicon compound of the present invention It can also be used as a reagent to be used.

〔The invention's effect〕

Since the organosilicon compound of the present invention has a pyridine ring and also has a reactive hydrosilyl group or silanol group, by utilizing the reactive group, the end of polyorganosiloxane and other polymer compounds and Introducing a pyridine ring on the side chain or on the surface of silica or the like can be easily achieved. In particular, the polyorganosiloxane having a pyridine ring at the end obtained using the organosilicon compound of the present invention is a silicone-based surfactant, a transdermal absorption enhancer, an intermediate for synthesizing a gas or liquid separation membrane material, It can be applied to various fields such as cosmetics, and the organosilicon compound of the present invention can be widely applied as a synthetic intermediate for synthesizing various functional materials.

[Examples and usage examples]

Hereinafter, the present invention will be described in more detail by way of examples and use examples. However, it goes without saying that the present invention is not limited to these.

Example 1 4-Methyl-2,6-di-t-butylpyridine 10.0 g (49.8
(100 mmol) was dissolved in 100 ml of tetrahydrofuran and cooled to -78 ° C under an argon gas atmosphere, 100 ml (140 mmol) of sec-butyllithium (1.4 mol / ln-hexane solution) was added, and the mixture was stirred for 1.5 hours. At this time, the reaction solution turned yellow. Then add 20.0% chloromethyldimethylsilane to this solution.
When ml (164 mmol) was added and the mixture was further stirred at room temperature for 12 hours, the solution was decolored and became cloudy. The solvent in the reaction solvent was distilled off, the formed salt was filtered, washed with diethyl ether, and then purified by column to obtain 13.3 g of a colorless transparent liquid.

The obtained product was subjected to ¹ H-NMR, IR and Mass spectrum analysis and elemental analysis to give 4- (2-
It was confirmed to be dimethylsilylethyl) 2,6-di-t-butylpyridine. (Yield; 96%) The results are shown below. ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); 0.11 (d, 6H, proton peak of methyl group on silyl group), 0.96 (m, 2H, proton peak of ethylene chain), 1.35 (s, 18H, t-butyl group proton peak), 2.63 (m, 2H, ethylene chain proton peak), 3.93 (m, 1H, Si-H group proton peak), 6.94
(Proton peak of s, 2H, pyridine ring). IR spectrum (cm ^-1 ); 3100 (w), 2990 (s), 2900
(S), 2130 (s, characteristic absorption by Si-H bond), 1600 (s, characteristic absorption of pyridine ring), 1562 (s), 1480 (s), 1450
(S), 1415 (s, characteristic absorption by Si-C bond), 1220
(M), 1205 (m), 1165 (m), 1050 (w), 1000
(W), 925 (s, characteristic absorption by Si-C bond), 880 (s), 8
35 (s), 770 (s), 700 (w). Mass spectrum (m / e); 277 (M ⁺ ), 276 (M ⁺ -H), 262 (M
_{^{+ -CH 3), 59 (HSi}} (CH 3) 2). Elemental analysis value (%); C: 73.07, H: 11.42, N: 4.83 (calculated value; C:
73.65, H: 11.19, N: 5.05). Example 2 Dissolving catalytic amount of metallic sodium in 40 ml of ethanol,
The solution was refluxed under an argon gas atmosphere, and the solution was treated with 4- (2-dimethylsilylethyl) 2,6-di-obtained in Example 1.
10.0 g (36.0 mmol) of t-butylpyridine was slowly added dropwise, and reflux was continued for another hour. Then, the reaction solution was poured into 100 ml of a methanol solution containing 4.2 g (107 mmol) of sodium hydroxide and 10 ml of water, 100 ml of an aqueous solution containing 4.2 g of sodium hydroxide was further added, and the mixture was stirred for about 30 minutes. Next, the solution was poured into a large amount of ice water containing 36.7 g of potassium hydrogen phosphate, and the solution became cloudy. Extracted with diethyl ether, dried under reduced pressure and distilled under reduced pressure 150-155 ℃ / 0.05mmHg
7.9 g of a colorless transparent liquid was obtained in the boiling point range.

The obtained product was subjected to ¹ H-NMR, IR and Mass spectrum analysis and elemental analysis to give 4- (2-
It was confirmed to be dimethylhydroxysilylethyl) 2,6-di-t-butylpyridine. (Yield; 76%) The results are shown below. ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); 0.15 (s, 6H, proton peak of methyl group on silyl group), 1.06 (m, 2H, proton peak of ethylene chain), 1.35 (s, 18H, t-butyl group proton peak), 2.18 (s, 1H, hydroxyl group proton peak), 2.70 (m, 2H, ethylene chain proton peak), 6.95
(Proton peak of s, 2H, pyridine ring). IR spectrum (cm ^-1 ); 3300 (m, characteristic absorption by hydroxyl group), 3100 (w), 2980 (s), 2890 (s), 1600 (s, characteristic absorption of pyridine ring), 1562 (s), 1480 (S), 1450
(M), 1415 (s), 1360 (s), 1310 (w), 1255 (s, Si
-Characteristic absorption by C bond), 1220 (w), 1200 (w), 1165
(M), 1050 (s, characteristic absorption by Si-O bond), 1000
(W), 925 (m, characteristic absorption by Si-C bond), 900 (m), 8
40 (s), 790 (s), 680 (w). Mass spectrum (m / e); 293 (M ⁺ ), 292 (M ⁺ -H), 278 (M
⁺ -CH ₃ ), 218 (M ⁺ -HOSi (CH ₃ ) ₂ ), 75 (HOSi (C
H ₃ ) ₂ ). Elemental analysis value (%); C: 69.24, H: 10.11, N: 4.55 (calculated value; C:
69.55, H: 10.67, N: 4.77). Example 3 4-Methylpyridine (12.0 g, 129 mmol) was dissolved in tetrahydrofuran (200 ml), cooled to -78 ° C under an argon gas atmosphere, 97 ml (194 mmol) of phenyllithium (2.0 mol / ln-hexane solution) was added, and the mixture was stirred for 40 minutes. . At this time, the reaction solution turned red. Next, 31.4 ml (258 mmol) of chloromethyldimethylsilane was added to this solution, and the solution was further stirred for 12 hours at room temperature. The solvent in the reaction solution was distilled off, the formed salt was filtered and washed with diethyl ether, and then distilled under reduced pressure to 60-70 ° C /
17.0 g of a colorless transparent liquid was obtained in the boiling range of 0.8 mmHg.

The obtained product was subjected to ¹ H-NMR, IR and Mass spectrum analysis and elemental analysis to give 4- (2-
It was confirmed to be dimethylsilylethyl) pyridine. (Yield; 80%) The results are shown below. ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); 0.09 (d, 6H, proton peak of methyl group on silyl group), 0.90 (m, 6H, proton peak of ethylene chain), 3.07 (m, 2H, Proton peak of ethylene chain), 3.80 (proton peak of m, 1H, Si-H group), 6.98 (dd, 2H, proton peak of pyridine ring), 8.34
(Proton peak of dd, 2H, pyridine ring). IR spectrum (cm ^-1 ); 3100 (m), 3050 (m), 2980
(S), 2950 (m), 2120 (s, characteristic absorption by Si-H bond), 1600 (s, characteristic absorption of pyridine ring), 1560 (w), 150
0 (w), 1420 (s), 1315 (w), 1255 (s, characteristic absorption by Si-C bond), 1220 (w), 1175 (w), 1120 (m), 1070
(W), 925 (m, characteristic absorption by Si-C bond), 920 (s), 8
80 (s), 840 (s), 800 (s), 765 (s), 740 (s), 7
00 (s). Mass spectrum (m / e); 165 (M ⁺ ), 164 (M ⁺ -H), 150 (M
⁺ -CH ₃ ), 106 (M ⁺ -HSi (CH ₃ ) ₂ ), 59 (HSi (C
H ₃ ) ₂ ). Elemental analysis value (%); C: 65.11, H: 8.98, N: 8.33 (calculated value; C: 6
5.39, H: 9.17, N: 8.47). Example 4 Dissolve a catalytic amount of metallic sodium in 80 ml of ethanol,
The solution was refluxed under an argon gas atmosphere, and the solution was treated with 4- (2-dimethylsilylethyl) pyridine 1 obtained in Example 3.
7.0 g (93.8 mmol) was slowly added dropwise, and reflux was continued for another hour. After that, the reaction solution was added with sodium hydroxide 11.0.
160 ml of a methanol solution containing g (280 mmol) and 16 ml of water
Then, 160 ml of an aqueous solution containing 11.0 g of sodium hydroxide was added, and the mixture was stirred for about 30 minutes. Next, the solution was poured into a large amount of ice water containing 95.7 g of potassium hydrogen phosphate to become cloudy. After extraction with diethyl ether, drying and vacuum distillation, 15.5 g of a colorless transparent liquid was obtained in the boiling range of 39-40 ° C / 0.015 mmHg.

The obtained product was subjected to ¹ H-NMR, IR and Mass spectrum analysis and elemental analysis to give 4- (2-
It was confirmed to be dimethylhydroxysilylethyl) pyridine. (Yield: 83%) The results are shown below. ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); 0.08 (s, 6H, proton peak of methyl group on silyl group), 0.85 (m, 2H, proton peak of ethylene chain), 2.30 (s, 1H, Hydroxyl proton peak), 2.61 (m, 2H, ethylene chain proton peak), 7.07 (dd, 2H, pyridine ring proton peak), 8.45
(Proton peak of dd, 2H, pyridine ring). IR spectrum (cm ^-1 ); 3400 (s, characteristic absorption by hydroxyl group), 3100 (m), 3050 (m), 2980 (s), 2950 (m), 1
600 (s, characteristic absorption of pyridine ring), 1560 (w), 1500
(W), 1420 (s), 1315 (w), 1255 (s, characteristic absorption by Si-C bond), 1220 (w), 1175 (w), 1055 (s, characteristic absorption by Si-O bond), 995 (m), 910 (m, characteristic absorption by Si-C bond), 840 (s), 800 (s), 780 (s), 740
(W), 700 (w). Mass spectrum (m / e); 181 (M ⁺ ), 180 (M ⁺ -H), 166 (M
⁺ -CH ₃ ), 106 (M ⁺ -HOSi (CH ₃ ) ₂ ), 75 (HOSi (C
H ₃ ) ₂ ). Elemental analysis value (%); C: 59.52, H: 8.16, N: 7.65 (calculated value; C: 5
9.62, H: 8.36, N: 7.72). Usage example 1 Polysulfone consisting of repeating units represented by (Aldric
(manufactured by H) (8.0 g) was dissolved in 400 ml of tetrahydrofuran, cooled to 0 ° C. under an argon gas atmosphere, added with 22.5 ml of a butyllithium hexane solution (1.6 mol / l), and stirred for 20 minutes, whereupon the reaction solution turned red. Next, 100 ml of dimethylvinylchlorosilane was added and stirred at room temperature for 30 minutes, and after confirming that the reaction solution was decolorized, reprecipitation was carried out in 5.0 l of methanol, and reprecipitation was repeated several times in the same manner to polymerize the polymer. Was purified. The yield of the obtained polymer was 8.46 g.

From the ¹ H-NMR spectrum and IR spectrum of this polymer, it was confirmed that the polymer produced was vinyldimethylsilylated polysulfone in which some of the hydrogen atoms on the main chain phenylene ring of the starting polysulfone were substituted with vinyldimethylsilyl groups. In addition, from the ratio of the integral value of the proton peak of the methyl group on the silyl group (0.50 ppm) and the proton peak of the methyl group of the main chain polysulfone (1.76 ppm) in the ¹ H-NMR spectrum, it is possible to determine the vinyldimethyl The average number of silyl groups was 1.70.

0.3 g of the vinyldimethylsilylated polysulfone thus obtained and 2.0 g of 4- (2-dimethylsilylethyl) 2.6-di-t-butylpyridine obtained in Example 1 were dissolved in 10 ml of toluene to obtain platinum chloride. 0.2 ml of acid isopropanol solution (0.1 mol / l) was added and stirred at 80 ° C. for 48 hours.
When this solution was reprecipitated in 300 ml of methanol, 0.35 g of a white polymer was obtained. ^{From the 1} H-NMR spectrum and the IR spectrum, the produced polymer shows that a part of hydrogen on the main chain phenylene ring of the raw material polysulfone is It was confirmed to be a silyl-substituted polysulfone substituted with the substituent represented by. The average number of silyl groups per polysulfone repeating unit was 1.70.

100 mg of silyl-substituted polysulfone thus obtained
Was dissolved in 8 ml of chloroform, and the solution was cast on a Teflon plate which was left standing horizontally, and the solvent was slowly removed by evaporation, and a strong homogeneous film having a film thickness of 25 μm was obtained. This membrane was attached to a gas permeation apparatus, and the permeation coefficients (P _O2 , P _N2 , Pc _O2 ) of nitrogen, oxygen, and carbon dioxide at 25 ° C. were measured by the high vacuum pressure method. The results are shown below.

P _N2 ＝ 3.80 × 10 ^-11 (cm ³・ cm / cm ²・ sec ・ cmHg) P _O2 ＝ 2.16 × 10 ^-10 (cm ³・ cm / cm ²・ sec ・ cmHg) Pc _O2 ＝ 8.93 × 10 ^-10 (Cm ³ · cm / cm ² · sec · cmHg) P _O2 / P _N2 = 5.68, Pc _O2 / P _N2 = 23.5 A membrane was prepared in the same way from the polysulfone used as the raw material, and the same permeation experiment was conducted. The following results were obtained.

P _N2 ＝ 2.58 × 10 ^-11 (cm ³・ cm / cm ²・ sec ・ cmHg) P _O2 = 1.18 × 10 ^-10 (cm ³・ cm / cm ²・ sec ・ cmHg) Pc _O2 ＝ 7.06 × 10 ^-10 (Cm ³ · cm / cm ² · sec · cmHg) P _O2 / P _N2 = 4.57, Pc _O2 / P _N2 = 27.4 Comparing the above values, the pyridine ring was introduced into the polymer using the silicon-containing compound of the present invention. By doing so, it can be seen that the oxygen permeability and selectivity of the polymer were improved.

Usage example 2 When 2.0 g of polytrimethylsilylpropyne consisting of the repeating unit represented by is dissolved in 400 ml of tetrahydrofuran, cooled to 0 ° C. under an argon gas atmosphere, 11.2 ml of butyl lithium hexane solution (1.6 mol / 1) is added, and the mixture is stirred for 2 hours. The reaction solution turned red. Next, 6.8 ml of dimethylbutylchlorosilane was added and stirred at room temperature for 30 minutes, after confirming that the reaction solution was decolorized, reprecipitation was carried out in 3.0 l of methanol, and reprecipitation was repeated several times in the same manner. The polymer was purified. The yield of the obtained polymer was 1.96 g.

From the ¹ H-NMR spectrum and IR spectrum of this polymer, the produced polymer was found to be vinyldimethylsilylated polytrimethylsilylpropyne in which part of the hydrogen on the side chain methyl group of the raw material polytrimethylsilylpropyne was replaced by vinyldimethylsilyl groups. Was confirmed. From the carbon content of elemental analysis, the average number of vinyldimethylsilyl groups per repeating unit of polytrimethylsilylpropyne was 0.05.

0.3 g of the vinyldimethylsilylated polytrimethylsilylpropyne thus obtained and 1.0 g of 4- (2-dimethylsilylethyl) 2,6-di-t-butylpyridine obtained in Example 1 in 20 ml of toluene. After dissolution, 0.2 ml of isopropanolic chloroplatinate solution (0.1 mol / l) was added, and the mixture was stirred at 80 ° C. for 48 hours. When this solution was reprecipitated in 400 ml of methanol, 0.36 g of a white polymer was obtained. ¹ H-NMR
From the spectrum and IR spectrum, the resulting polymer and It was confirmed to be a silyl-substituted polytrimethylsilylpropyne consisting of a repeating unit represented by In the above structure, the composition ratio of the former repeating unit and the latter repeating unit was 95/5 based on the result of elemental analysis.

100 mg of the silyl-substituted polytrimethylsilylpropyne obtained in this way was dissolved in 8 ml of toluene, and the solution was cast on a Teflon plate that was left standing horizontally, and when the solvent was slowly removed by evaporation, the film thickness was 36 μm. A strong homogeneous film was obtained. This membrane was attached to a gas permeation apparatus, and the permeation coefficients (P _O2 , P _N2 , Pc _O2 ) of nitrogen, oxygen, and carbon dioxide at 25 ° C. were measured by the high vacuum pressure method. The results are shown below.

P _N2 = 7.11 × 10 ^-8 (cm ³ · cm / cm ² · sec · cmHg) P _O2 = 1.81 × 10 ^-7 (cm ³ · cm / cm ² · sec · cmHg) Pc _O2 = 5.41 × 10 ^-7 (Cm ³ · cm / cm ² · sec · cmHg) P _O2 / P _N2 = 2.55, Pc _O2 / P _N2 = 7.61 A film was similarly prepared from the polytrimethylsilylpropyne used as the raw material, and the same permeation experiment was conducted. As a result, the following results were obtained.

P _N2 = 1.51 × 10 ^-7 (cm ³・ cm / cm ²・ sec ・ cmHg) P _{O 2} ＝ 2.51 × 10 ^-7 (cm ³・ cm / cm ²・ sec ・ cmHg) Pc _O2 ＝ 9.35 × 10 ^-7 (Cm ³ · cm / cm ² · sec · cmHg) P _O2 / P _N2 = 1.66, Pc _O2 / P _N2 = 6.19 By comparing the above values, the pyridine ring is introduced into the polymer using the silicon-containing compound of the present invention. By doing so, it is understood that the oxygen selectivity of the polymer was improved.

Use Example 3 1.5 g of 4- (2-dimethylhydroxysilylethyl) 2,6-di-t-butylpyridine obtained in Example 2 (5.1 mmo
l) was dissolved in 5 ml of tetrahydrofuran under an argon gas atmosphere, cooled to -10 ° C, 3.2 ml (5.1 mmol) of n-butyllithium hexane solution (1.6 mol / l) was added, and the mixture was stirred for 1 hour. Hexamethylcyclotrisiloxane 2.
A solution prepared by dissolving 27 g (10.2 mmol) in 15 ml of tetrahydrofuran was added, and the mixture was further stirred at room temperature for 12 hours. Next, 6.0 ml (55 mmol) of dimethylchlorosilane was added to stop the reaction. After distilling off the solvent, the salt formed was filtered off and further heated and stirred under reduced pressure at 160 ° C. for 2 hours to obtain 3.30 g of a colorless and transparent viscous oil. ^{From the 1} H-NMR spectrum and IR spectrum, this product was It was found to be a polydimethylsiloxane having a pyridine ring having a structure represented by

1.3 g of the polymer thus obtained and 0.25 g of vinyldimethylsilylated polysulfone obtained in Use Example 1 were dissolved in 10 ml of tetrahydrofuran, and 0.2 ml of isochlorochloroplatinate solution (0.1 mol / l) was added to 80 ° C. And stirred for 48 hours. Reprecipitation of this solution in 300 ml of methanol
0.55 g of white polymer was obtained. ^{From the 1} H-NMR spectrum and the IR spectrum, the produced polymer shows that a part of hydrogen on the main chain phenylene ring of the raw material polysulfone is It was confirmed that the siloxane-containing polysulfone was substituted with the substituent represented by. The average number of siloxane chains per repeating unit of polysulfone was 1.20.

100 mg of silyl-substituted polysulfone thus obtained
Was dissolved in 8 ml of chloroform, and the solution was cast on a Teflon plate which was left standing horizontally, and the solvent was slowly removed by evaporation, and a strong homogeneous film having a film thickness of 25 μm was obtained. This membrane was attached to a gas permeation apparatus, and the permeation coefficients (P _O2 , P _N2 , Pc _O2 ) of nitrogen, oxygen, and carbon dioxide at 25 ° C. were measured by the high vacuum pressure method. The results are shown below.

P _N2 ＝ 3.41 × 10 ^-10 (cm ³・ cm / cm ²・ sec ・ cmHg) P _O2 = 1.34 × 10 ^-9 (cm ³・ cm / cm ²・ sec ・ cmHg) Pc _O2 ＝ 7.64 × 10 ^-9 (Cm ³ · cm / cm ² · sec · cmHg) P _O2 / P _N2 = 3.93, Pc _O2 / P _N2 = 22.4 Therefore, using the silicon-containing compound of the present invention, a polydimethylsiloxane having a pyridine ring at one end can be prepared. By introducing the obtained polydimethylsiloxane into the side chain of another polymer, which is synthesizable, a membrane material having high oxygen selectivity was obtained.

Use Example 4 1.10 g (6.07 mmol) of 4- (2-dimethylhydroxysilylethyl) pyridine obtained in Example 4 was dissolved in 30 ml of tetrahydrofuran, and 0.26 g (10.8 mmol) of sodium hydride was added at room temperature under an argon gas atmosphere. The mixture was stirred for 2 hours. Hexamethylcyclotrisiloxane 3.69 was added to this solution.
A solution of g (16.6 mmol) dissolved in 20 ml of tetrahydrofuran was added, and the mixture was further stirred at room temperature for 12 hours. Then, the reaction was stopped by adding 1.54 ml (12.2 mmol) of trimethylchlorosilane. After the solvent was distilled off, the salt formed was filtered off, heated and stirred at 120 ° C. for 2 hours under reduced pressure, and further column purified to obtain 3.80 g of a colorless transparent viscous oil. ¹
From the H-NMR spectrum and IR spectrum, this product It was found to be a polydimethylsiloxane having a pyridine ring having a structure represented by

0.32 g of polydimethylsiloxane obtained in this way
Was dissolved in 5 ml of dimethylformamide, and methyl iodide 0.0
When 3 ml was added and the mixture was heated with stirring at 50 ° C. for 7 hours and the solvent was distilled off, 0.33 g of a brown viscous liquid was obtained. ^{From the 1} H-NMR spectrum and IR spectrum, this product was It was found to be a polydimethylsiloxane having a pyridinium group having a structure represented by It was confirmed that this polymer was dissolved in water and had a property as a surfactant.

Therefore, it is possible to synthesize a polydimethylsiloxane having a pyridine ring at one end using the silicon-containing compound of the present invention, and further to obtain a novel silicone-based surfactant by quaternizing the obtained polydimethylsiloxane. It was found that can be synthesized.

Claims (1)

[Claims] 1. A general formula (In the formula, R is an alkyl group having 4 or more carbon atoms or a phenyl group, R ¹ and R ² may be the same or different, and
A substituted alkyl group, a phenyl group or a substituted phenyl group, A is a hydrogen atom or a hydroxyl group, m is an integer of 0 to 2, and p is 1.
Is an integer from 6 to 6. ) An organosilicon compound having a pyridine ring represented by: