JPH0377889A - Organosilicon compound having pyridine ring - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R represents >=4C alkyl or phenyl; R<1> and R<2> represent (substituted) alkyl or (substituted) phenyl; A represents H or OH; (m) is 0-2; (p) is 1-6]. EXAMPLE:4-(2-Dimethylsilylethyl)2,6-di-t-butylpyridine expressed by formula II. USE:A synthetic intermediate for producing a polyorganosiloxane having a pyridine ring at one terminus utilizing living polymerization. PREPARATION:A substituted pyridine derivative expressed by formula III is reacted with a strong base and then reacted with a haloalkylsilane compound expressed by formula IV (X represents halogen) to afford the compound expressed by formula I wherein the group A is H.

Description

Detailed Description of the Invention (Field of Application on J!Ill) The present invention relates to a novel organosilicon compound in which a pyridine ring is grown as a substituent on silicon. It is particularly useful as a synthetic intermediate for producing polyorganosiloxanes having a pyridine ring at one end.

[Prior Art and Problems to be Solved by the Invention] Generally, silanol compounds are used as initiators for synthesizing polyorganosiloxanes by living polymerization.

By using silanol compounds having various substituents, it becomes possible to synthesize polyorganosiloxanes having a substituent on one end of the silanol compound. If a pyridine ring can be introduced at the end of polyorganosiloxane, which has high chain mobility, high permeability to gases, etc., and is also highly hydrophobic, it will be possible to absorb gases and liquids! This enables a wide range of applications such as membranes, surfactants, and transdermal absorption enhancers.

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

The present inventors have intensively investigated new silanol compounds that can be used as initiators for synthesizing polyorganosiloxanes that grow a pyridine ring at one end.

As a result, the inventors discovered that it is possible to synthesize the desired silanol compound by reacting a substituted pyridine derivative with a haloalkylsilane derivative as a raw material, and the present invention was achieved.

[Means to solve the problem]

The present invention is based on the formula (wherein R is an alkyl group having 4 or more carbon atoms or a phenyl group, R1 and R1 may be the same or different and an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group,
is a hydrogen atom or a hydroxyl group, m is an integer of 0 to 2, and p is an integer of 1 to 6. ) This relates to an organosilicon compound having a pyridine ring represented by:

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

That is, after reacting a substituted pyridine derivative represented by the formula - (wherein R is an alkyl group having 4 or more carbon atoms or a phenyl group, and m is an integer of 0 to 2) with a strong base, - the formula (In the formula, X is a halogen atom, R1 and V 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 an integer of 1 to 6.

) by reacting with a haloalkylsilane compound represented by the formula (where A is a hydrogen atom), R is an alkyl group having 4 or more carbon atoms or a phenyl group, ill and P may be the same or different and are an alkyl group, 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 invention can be synthesized.Furthermore, the organosilicon compound represented by the above-mentioned formula (I)' can be used as a precursor to synthesize a compound in which A in the above-mentioned formula (1) is a water #1 group. Formula (wherein R is an alkyl group having 4 or more carbon atoms or a phenyl group, V and P may be the same or different and are an alkyl group, 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 can be synthesized by, for example, reacting the organosilicon compound represented by formula (I) with sodium alcoholade, and then reacting it with sodium hydroxide or water. The organosilicon compound represented by the above formula (R) can be synthesized by reacting with an aqueous solution containing a base such as potassium oxide.

In the substituted pyridine derivative represented by formula (II) used as a raw material in producing the organosilicon compound of the present invention, it is essential to have a methyl group on the tridine ring. Hereinafter, C(CHs)m As the strong base to be reacted with the substituted pyridine derivative represented by formula (If), methyllithium, n-
Organolithium compounds such as butyllithium, 36C-butyllithium, t-butyllithium, and phenyllithium are preferably used.

However, when using alkyl-substituted pyridine derivatives in which m in formula (n) is 0, that is, picolines, as a raw material, it is optimal to use phenyllithium in terms of yield. It is preferable to carry out the reaction at a low temperature from ℃ to 0℃. Also, it is preferable to carry out this reaction in an organic solvent, and the solvent is tetrahydrofuran (TH
F), diethyl ether, benzene, toluene, etc. can be used.

Next, examples of the halogenated alkylsilane compound represented by formula (If) used as a reagent include LCHs. -CIl of these compounds
s, Cl1s, and CBs moieties are commercially available, and have the general formula: They may be the same or different and may be an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group, and p is an integer of 1 to 6.) Can be easily synthesized by reducing a commercially available halosilane compound represented by can do.

The above-mentioned formula (
(2) The organosilicon compound of the present invention represented by 1 is suitably used as an initiator for synthesizing polyorganosiloxane by anionic living polymerization. That is, as described later in usage examples, after reacting the organosilicon compound of the present invention represented by formula (1) with an organolithium compound or a strong base such as sodium hydride or potassium hydride, cyclo It is possible to synthesize a polyorganosiloxane having a pyridine ring at one end by reacting it with a siloxane compound and stopping the reaction with an appropriate terminator.The polyorganosiloxane having a pyridine ring at one end obtained in this way can be applied to various fields such as silicone surfactants, transdermal absorption enhancers, intermediates for synthesizing gas or liquid separation membrane materials, and cosmetics. The organosilicon compound of the present invention can also be used as a reagent for introducing a lysine ring into a polymer compound or a carrier such as silica through a hydrosilylation reaction or a condensation reaction.

(Effect of the invention) Since the organosilicon compound of the present invention has a pyridine ring and also has a reactive hydrosilyl group or silanol group, the reactive group can be used to produce polyorganosiloxane and other It is possible to easily introduce a lysine ring into the end or side chain of a polymeric compound, or onto the surface of silica or the like. In particular, polyorganosiloxanes with pyridine rings at the ends obtained using the organosilicon compounds of the present invention are intermediates for synthesizing silicone surfactants, transdermal absorption enhancers, and gas or liquid separation membrane materials. It can be applied to various fields such as cosmetics,
The organosilicon compound of the present invention can be widely applied as a synthetic intermediate for synthesizing various functional materials.

[Examples and usage examples]

The present invention will be explained in more detail below using Examples and Usage Examples. However, it goes without saying that the present invention is not limited to these.

Example 1 L -78°C 4-methyl-2,6-di-t-butylpyridine 10.0
g (49.8 mmol) in tetrahydrofuran 10
After cooling to -78°C under an argon gas atmosphere, 30C-butyllithium (1,4 mol/In
-Hexane solution) was added with 1QQml (140 mmol) and stirred for 5 hours.

At this time, the reaction solution turned yellow. Next, 20% of chloromethyldimethylsilane was added to this solution. Oml(164mmo
1) was added and further stirred at room temperature for 12 hours, the solution lost its color 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. 13.3 g of a colorless transparent liquid was obtained.

The obtained product was subjected to 'I-NFIR, IR# and Mass spectral analysis and elemental analysis, and the target product 4-(2-dimethylsilylethyl)2.6-dit
- It was confirmed that it was butylpyridine.

(Yield: 96%) The results are shown below.

'II-NMR spectrum, δ (CDC1*, ppm)
:0.11 (d+68° proton peak of methyl group on silyl group).

0.96 (s, 2H, ethylene proton peak).

1.35 (a, 18B, proton peak of t-butyl group).

2.63 (m, 211. proton peak of ethylene)
.

3.93 (m, IB, proton peak of 5i-11 group)
, 6.94 (sl2a, proton peak of pyridine ring)
.

IR spectrum (cm-'): 3100 e+1.2
990 (1), 290G (1).

213G (s, characteristic absorption due to 5i-H bond), 1
60G (3, characteristic absorption of pyridine ring), 1562 (
1480(s), 145G(s), 1415(s,
Characteristic absorption due to 5i-C bond), 122G), 1
205 (111,11656111,1050@.

11000(,925(s, characteristic absorption due to 5l-C bond).

880 (111,835+1), 770 (1), 70
061°Mass spectrum (s+/e) +277(
M, 276 (M”-11).

262 (M”-CL), 59 (H3l (CHs
) m).

Elemental analysis value (χ): C173.07, B: 11.42
．． N+4.83 (calculated value + C near 3.65. B:
11.19. N+5.05).

Example 2 A catalytic amount of sodium metal was dissolved in 40 ml of ethanol, refluxed under an argon gas atmosphere, and 2.6 ml of 4-(2-dimethylsilylethyl) obtained in Example 1 was added to the solution.
-d-t-butylpyridine 10.0g (36.0mm
o 1) was slowly added dropwise, and refluxing was continued for an additional hour. Thereafter, the reaction solution was mixed with 4.2 g (1
07 mmol) and 10 ml of methanol solution containing 10 ml of water, and further added 4.2 ml of sodium hydroxide.
Added 100 ml of an aqueous solution containing g and stirred for about 30 minutes.
Next, when the solution was poured into a large amount of ice water containing 36.7 g of potassium hydrogen phosphate, it became cloudy. After extraction with diethyl ether, drying and distillation under reduced pressure, the result was 150-155
7.9 g of colorless transparent liquid with boiling point range of 10.05 days ng at °C
was gotten.

The obtained product was subjected to IIll-1l, IR and Mass spectral analysis and elemental analysis, and the target product 4-(2-dimethylhydroxysilylethyl)2
．． It was confirmed that it was 6-di-t-butylpyridine.

(Yield near 6%) The results are shown below.

'H-NM11 spectrum, δ(CDC1s, 1)p-
)+0.15(s, 6B.

Proton peak of methyl group on silyl group).

1.06 (m, 2H, proton peak of ethylene).

1.35 (s, 18B, t-butyl group proto:y peel>.

2.18 (a, ltl, proton peak of hydroxyl group), 2
．． 70 (proton peak of lI12L ethylene chain"),
6.95 (sl2*, proton peak of pyridine ring).

IR spectrum (di-'): 3300 (m, characteristic absorption by hydroxyl group), 3100 m, 298G (sl, 28
9G (!1,1600(s.

Characteristic absorption of pyridine ring), 1562 (tun 1480
(you).

14506111.14I5 ($), 1360 (f
fi), 1310 tin, 1255 (s.

Characteristic absorption due to 5l-C bond), 1220←12
00gu → 11165 (110,1050(s, 51-0
Characteristic absorption due to bonding) 81000M, 925 (octopus, 5l
-Characteristic absorption due to C bond).

9001111? , 840 (Edict L790 (ml, 680
).

19ass spectrum (m/@)+293(M”), 2
9209″4).

278()l"-C11,), 21809"-[10S
l (CI, l) J, 75(Host(CB!+
)i).

Elemental analysis value (Ri + C 69.24. H: 10.11.
N: 4.55 (lf calculated value B C: 69.55. To
lo, 67, N: 4.77).

Example 3 12.0 g of 4-methylpyridine (129 mrno l
) was dissolved in 200ml of tetrahydrofuran and cooled to -78°C under an argon gas atmosphere, and then 97ml of phenyllithium (2°Qniol/in-hexane solution) was dissolved in 200ml of tetrahydrofuran.
(194 mrnol) was added and stirred for 40 minutes. At this time, the reaction solution took on a red color. Next, add 31.4 ml of black methyldimedylsilane (258 oxmo
1) was added and further stirred at room temperature for 12 hours, the solution lost color and became cloudy. The solvent in the reaction solution was distilled off, the resulting salt was filtered and washed with diethyl ether, and then distilled under reduced pressure.
7.0 g of a colorless transparent liquid was obtained. The obtained product was subjected to 'I[-NMRlIR and Msss spectral analysis and elemental analysis, and it was confirmed that it was the desired product, 4-(2-dimethylsilylethyl)pyridine. confirmed. (Yield s80%) The results are shown below.

'1I-N111 spectrum, δ(CDC1il+1'
concave); 0009 (d, 6m.

proton beak of the methyl group on the silyl group).

0°90 (proverb, 6B. Proton beak of ethylene chain).

3.07 (m, 211.Proton beak of ethylene protection)
, 3.80 (■, 111.5i-B group proton beak''), 6.98 (dd, 2H, proton beak of pyridine ring), 8.34 (dd, zl[, proton beak of pyridine ring) 6IR Spectrum O'li ;3XOOm,3
05011116.2980 (s), 2950 (m,
2120 (characteristic absorption due to s, sl-[1 bond), 16
00 (s, characteristic absorption of pyridine ring), 1560
f@, 15004 m, 1420 (s), 1315 m
, 1255 (s, characteristic absorption due to 5l-C bond), 12
204m, 1175 f@, 1120m, 1070M
, 925 (Peng, Characteristic absorption by 5i-c bond), 920
(ri, 880 (ml), 840 (1), 800 (s)
), Flo5 (Il11+74O(1), 700(#
).

Mass spectrum (m/@): 165 (M'),
164 (M”-H).

15001"-CI!s), 106(1'1th-R3
i(CHs)J, 59(H5i(C!Is)m).

Elemental analysis value α) 8 C: 65° 11.8 = 8.98.
N+8.33 (calculated value HC: 65-3L 89.1?
, N: 8.47).

Example 4 Dissolve the metal sodium J- of the catalyst in 80 ml of ethanol, let it flow under an argon gas atmosphere, and add 17.0 g of 4-(2-dimethylsilylethyl)pyridine obtained in Example G43 to the solution. 93.11 mmol) was slowly added dropwise, and refluxing was continued for an additional hour.

Thereafter, the reaction solution was mixed with 11.0 g (28 g) of sodium hydroxide.
0 mmol) and water (1.6 rn 1) were poured into 160 ml of methanol solution, and then 15 Q ml of an aqueous solution containing 11.0 g of sodium hydroxide was added and stirred for about 30 minutes.
When poured into a large amount of ice water containing g, it became cloudy. After extraction with diethyl ether, drying and vacuum MW, 39-
15.5 g of a colorless and transparent liquid with a boiling point range of 10.015 mH1 at 40° C. was obtained.

For the obtained product, 'H-NMR%IR and M
Ass spectrum analysis and elemental analysis were performed, and it was confirmed that the product was the target product, 4-(2-dimethylhydroxysilylethyl)pyridine. (Yield: 83%) The results are shown below.

'H-NMR spectrum, δ (CDC1s, ppm)
;0.08(s, 6B.

Proton peak of methyl group on silyl group).

0.85 (■, 211. Proton peak of ethylene chain)
.

2.30 (m, 111. proton peak of hydroxyl group), 2
．． 61 (+b2B+proton peak of ethylene chain), 7
．． 07 (dd, 2H, proton peak of pyridine ring),
8.45 (dd, 211. Proton peak of pyridine ring).

■2 spectrum (cs+-') +3400 (s, characteristic absorption by hydroxyl group), 3100 (111, 3050 (1
11,2980 (scold 29501m.

1600 (s, characteristic absorption of pyridine ring), 1560 (1
1).

1500-. 142G (s), 1315 (we, 1
255 (m, characteristic absorption due to 5i-C bond), 1220
I@, 1175 M, 1055 (a.

Characteristic absorption due to 5t-O bond), 995 m, 910 (
haze.

Characteristic absorption due to 5t-C bond), 840 (s)
, 800(a).

780 (1), 740M, 700-.

Maas spectrum (w/e); 181 (M”), 18
G(M"-H).

166 (M”-CR2), 106 (M”-H0
3l (CIll) l), 75(11081(C
[5)t).

Elemental analysis value α)+C+59.52. H: 8.16
．． N near, 65 (calculated value, C+59.62.H:
8.36. Nia, 72).

Use example 1 Polysulfone (Ald
(manufactured by rlch) 8.0g in 400ml of tetrahydrofuran
and cooled to 0°C under argon gas atmosphere to add 22.5 ml of butyllithium hexane solution (1.5 mol).
was added and stirred for 20 minutes. The reaction solution turned red. Next, 100 ml of dimethylvinylchlorosilane was added and stirred at room temperature for 30 minutes. After confirming that the reaction solution was discolored, it was reconstituted with 5.0 ml of methanol. The polymer was purified by performing precipitation and repeating reprecipitation several times in the same manner. The yield of the obtained polymer was 8.46 g.

'B-N' of this polymer? It was confirmed from the IR spectrum and the IR spectrum that the produced polymer was a vinyldimethylsilylated polysulfone in which some of the hydrogens on the main chain phenylene rings of the raw material polysulfone were substituted with vinyldimethylsilyl groups. 'II-N again? The proton peak of the methyl group on the silyl group (0,5
Based on the ratio of the integrated value of the proton peak (1,76 ppm) of the methyl group of the main chain polysulfone (09 pm) and the proton peak (1,76 ppm) of the main chain polysulfone, the average loss of vinyldimethylsilyl groups per one repeating unit of the polysulfone 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. , 0.2 ml of isopropanol chloroplatinic acid solution (0.1 mo 1/1) was added, and the mixture was stirred at 80° C. for 48 hours. When this solution was reprecipitated in 300 ml of methanol, 0.35 g of white polymer was obtained. 'I-NNR spectrum and IR
From the spectrum, it was confirmed that the produced polymer was a silyl-substituted polysulfone in which a part of the main chain phenylene ring of the raw material polysulfone was substituted with a substituent represented by the following. Also, the average number of silyl groups per polysulfone fiber unit is 1°7011"?
? there were.

Thus obtained silyl i-substituted polysulfone 100
When the solution was cast horizontally on a Teflon plate held still and the solvent was slowly evaporated off, a strong homogeneous film with a thickness of 25 μm was obtained. This membrane was attached to a gas permeation device 12, and the permeability coefficients (Pea, PM++s PC9+1) of nitrogen, oxygen, and carbon dioxide at 25° C. were measured using a high vacuum pressure method. The results are shown below.

Pun=3.80X10-'! (d + csl o4
・see ・aillg)Pol! =2.16XiO
-”(d ” csl aa ・sec ・ash)P
cn* w-8,93X 10-”(cd-csl c
sl ・sac ・asHz) Psi/Pb+g+=5
．． 68. When a product was made in the same manner from the polysulfone used as the Pco*/Pun-23,5 raw material and a similar permeation experiment was conducted, the following results were obtained.

P, a-2, 58) gu10-' ” (eJ -e
a/oA・sec・aillg)P
ea”1.18X10-”(aft *cs/ ejt
1ac sorrow 1@)Pc+5n=7.06X10-”(
cd ・csl d ・see ・aillg) Psa
/I'ull=4.57. Pcei noh*=2
Comparing the values of 7.4 and 2, it can be seen that the oxygen permeability and selectivity of the polymer were improved by introducing a pyridine ring into the polymer using the silicon-containing compound of the present invention.

Usage example 2 2.0 g of polytrimethylsilylpropyne consisting of a repeating unit represented by C1's 1 + C trout C → - 51 (CHs) s was dissolved in 400 ml of tetrahydrofuran and heated under an argon gas cloud at 0'C! Cool to butyllithium hexane flI solution (1,6yno 1/1)
When 11.2 ml was added and stirred for 2 hours, the reaction solution turned red. Next, dimethylvinylchlorosilane 6.
After adding 8 ml and pressing at room temperature for 30 minutes and confirming that the reaction solution was discolored, reprecipitation was performed in methanol 3601, and the polymer was purified by repeating the reprecipitation several times in the same manner. The yield of the obtained polymer was 1.96g.
It was.

From the 1-NMR spectrum and the 1-cost spectrum of this polymer, the produced polymer is vinyldimethylsilylated polytrimethylsilyl in which part of the water purple color on the side chain methyl group of the raw material polytrimethylsilylpropyne is converted to vinyldimethylsilyl group. It was confirmed that it was propyne. Also, from the carbon content of elemental analysis, vinyl = S for i repeating units of polytrimethylsilylpropyne.
The number of /dimethylsilyl groups was 0.05 on average.

0.3 g of vinyldimethylsilylated polytrimethylsilylpropyne thus obtained and 4-(2-dimethylsilylethyl) 2.6-dit obtained in Example 1.
-Dissolve 1.0 g of butylpyridine in 20 ml of toluene and
1/1) was added thereto, and the mixture was stirred at 80°C for 48 hours. When this solution was reprecipitated in 400 vnl of methanol, 36 g of a white polymer was obtained. '
From the I-N) 911 spectrum and 1 spectrum, the produced polymer was C■.

It was confirmed that it was a silyl-substituted polytrimethylsilylpropyne consisting of repeating units represented by 1 +C, C→-5l(CHs)s and Sl(CHi)s.

Further, in the above structure, the composition ratio of the former repeating unit and the latter repeating unit was 9515 from the results of elemental analysis.

100 μl of the silyl-substituted polytrimethylsilylpropyne thus obtained was dissolved in g ml of toluene, the solution was cast onto a Teflon plate placed horizontally, and the solvent was slowly evaporated to remove the film thickness. A durable uniform film with a diameter of 36 μm was obtained. This membrane was attached to a gas permeation device, and the permeability coefficients (Po%P□, PCIl) of nitrogen, oxygen, and carbon dioxide at 25° C. were measured using a high vacuum pressure method. The results are shown below.

h*”7.11X1G-@(aJ-cs/ d ・se
c ・ails) Pot-1,81X10-' (d
・ts/d ・ssc ・cmHg) Peas-5,
41X 10-' (d -cm/ d ・see ・
cm [1g) Pot/Pw snow-2,55, Pa5s/P
A membrane was prepared in the same manner from the polytrimethylsilylpropyne used as the m5-7.61 raw material, and a similar permeation experiment was conducted, and the following results were obtained.

P, m-1, 51X10-” (aj ・cm/d
・sec-cmlg)Pot"2.51X10-',
(aj ・cs/ d ・l@C・as!Ig)Pea
s-9,35X+10-' (j ・cs/ aj ・
see ・csllg>Pet/P+t-1,66,P
eas/PIIm-6,19 A comparison of the above values shows that the oxygen selectivity of the polymer was improved by introducing a pyridine ring into the polymer using the silicon-containing compound of the present invention.

From the IR spectrum and IR spectrum, this product was found to be 1.5 g of 4-(2-dimethylhydroxysilylethyl)2.6-di-t-butylpyridine obtained in Example 2.
(5,1 mm o 1) was dissolved in 5 ml of tetrahydrofuran under an argon gas atmosphere, and after cooling to -10°C, n-butyllithium hexane solution (1,6 no 1/
1) 3.2 ml (5.1 mmol 1) was added and stirred for 1 hour. A solution of 2.27 g (10.2 mmol) of hexamethylcyclotrisiloxane dissolved in 15 ml of tetrahydrofuran was added to this solution, and the mixture was further stirred at room temperature for 12 hours. Next, dimethylchlorosilane 6.
The reaction was stopped by adding 0 ml (55 mmol). After distilling off the solvent, the resulting salt was filtered off, and the mixture was further heated and stirred at 160° C. for 2 hours under reduced pressure to obtain 3.30 g of a colorless and transparent viscous oil. 'II-NMR
It was found that it is a polydimethylsiloxane having a pyridine ring at one end with the structure shown in the spectrum.

1.3 g of the polymer thus obtained and 0.25 g of the vinyldimethylsilylated polysulfone obtained in Use Example 1.
Dissolve g in 10 ml of tetrahydrofuran, and add 0.2 ml of isopropanol chloroplatinic acid solution (0.1no 1/1).
1 was added and stirred at 80°C for 48 hours. When this solution was reprecipitated in 300 ml of methanol, 0.55 g of white polymer was obtained. 'II-NMR spectrum and II! From the spectrum, it was confirmed that the produced polymer was a siloxane-containing polysulfone in which some of the hydrogens on the main chain phenylene rings of the raw material polysulfone were substituted with substituents represented by (i-7,2). In addition, the average loss of siloxane chains for one unit bond of polysulfone is 1.2 (
[It was 1.

Silyl W obtained in this way, converted polysulfone 10
When 0w was dissolved in 8 ml of chloroform, the solution was cast on a horizontally etched Teflon plate, and the solvent was slowly evaporated off, a strong uniform 1F film with a film thickness of 25 μm was obtained. This membrane was attached to a gas permeation device, and the permeability coefficients (Poo-Pl, Peol) of nitrogen, oxygen, and carbon dioxide at 25° C. were each measured by a high vacuum pressure method. The results are shown below.

Pm5-3.41 X 10-” (aff-csi
ad ・sec ・cellg) Psm-1, 34X1
0-” (all = csi d ・see ・i
sHg) Fces-7, [E4XXO'-'' (csi
・csi d ・see ・allg)Poe/l
'u*=3.93. Pco*/Pu*=22.4
Therefore, it is possible to synthesize polydimethylsiloxane having a pyridine ring at one end using the silicon-containing compound of the present invention, and furthermore, by introducing the obtained polydimethylsiloxane into the side chain of another polymer, oxygen selection is possible. A membrane material with high properties was obtained.

Usage Example 4 1°10 g of 4-(2-dimethylhydroxysilylethyl)pyridine obtained in Example @4 (6,0TmmoX)
was dissolved in 301 Tll of tetrahydrofuran and hydrogenated at room temperature in an argon gas atmosphere] 0.26 g of lithium
(66,62nxrno 1) was added and stirred for 2 hours.

Add 3°69 hexamethylcyclotrisiloxane to this solution.
A solution of g (16,6ammo 1) dissolved in 20 ml of tetrahydrofuran was added, and the mixture was further stirred at room temperature for 12 hours. Next, 1.54 m of trimethylchlorosilane
1 (12,2Inmo 1) was added to stop the reaction. After removing the solvent, the resulting salt was filtered, heated and stirred under reduced pressure at 120° C. for 2 hours, and further purified by column to obtain 3.80 g of a colorless and transparent viscous oil. 'B-NWR spectrum and page spectrum,
This product is CBs C11, (i-10,5)
It was found that it is a polydimethylsiloxane having a pyridine ring at one end with the structure represented by:

Polydimethylsiloxane thus obtained 0.3
2 g was dissolved in 5 rn 1 of dimethylformamide, 0.03 ail of methyl iodide was added, and the mixture was heated and stirred at 50° C. for 7 hours, and the solvent was distilled off to obtain 0.33 g of a brown viscous liquid. 'l(-[82 spectrum and 1! spectrum show that this product is a polydimethylsiloxane having a pyridinium group at one end with a structure of I would like to confirm that it has properties as an activator. Therefore, it is possible to synthesize polydimethylsiloxane having a pyridine ring at one end using the silicon-containing compound of the present invention, and furthermore, it is possible to synthesize polydimethylsiloxane having a pyridine ring at one end. It was found that new silicone surfactants can be synthesized by grading.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. group, substituted alkyl group, phenyl group or substituted phenyl group, A is a hydrogen atom or a hydroxyl group, m is an integer of 0 to 2,
p is an integer from 1 to 6. ) Organosilicon compound having a pyridine ring.