JP2001009249A - Oxygen enriching membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce thickness as well as to ensure high oxygen permeability and selectivity by forming the oxygen enriching membrane using a compound obtained by three-dimensionally crosslinking a high molecular compound represented by a specific formula. SOLUTION: The oxygen enriching membrane is formed by using a compound obtained by three-dimensionally crosslinking a high molecular compound of the formula, wherein R1-Rn are each an alkyl, an aryl, an aralkyl, or the like, S1-Sn are each H, hydroxyl, an alkoxyl, or the like, (n) is an integer of 1-10, x1-xn are each an integer of 1-50, y1-yn are each an integer of 1-50 and 11-1n each shows the molar proportion (mol%) of the corresponding component, because it is preferable that a high molecular compound used for producing a high performance material for an oxygen enriching membrane has a flexible high molecular structure, a selectively oxygen permeable component and a three-dimensionally crosslinkable reactive part in the high molecular structure and has characteristics such as high sensitivity to electron beams.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen-enriched film comprising a three-dimensionally crosslinked compound of a silicon-containing polymer compound having siloxane chains and oligooxyalkylene chains alternately.

[0002]

2. Description of the Related Art Membranes have been studied for a long time in the field of colloid science, but as the research on biomembranes progresses, the structure and functions of the membranes are gradually elucidated, and the importance of membranes is attracting attention. It was started. Since the membrane has a two-dimensionally spread structure, it is in a form most suitable for material separation by permeation, and a simple, clean, and energy-saving material separation device can be constructed. In particular, in recent years, there is a strong demand for energy saving, resource recovery, and clean processes, and from such a viewpoint, research and development of artificial membranes having special functions such as reverse osmosis membranes, ultrafiltration membranes, and ion exchange membranes have been promoted.

[0003] Similarly, in the middle of the 19th century, gas separation membranes are also used.
Until today, reports have been made on gas permeation mechanisms by JVMitchell (1831) and T. Graham (1866).
Research on gas separation membranes having various functions has been advanced. More recently, research reports on membrane separation of volatile organic compounds (VOCs) have come to be seen with increasing interest in global and living environment issues. In research and development on such gas separation membranes, research on membranes that selectively transmit oxygen, so-called oxygen-enriched membranes,
Numerous studies have been actively conducted due to the wide range of applications. For example, it is applied to an energy field related to a combustion system such as an automobile engine or a boiler, or applied to a medical field such as an artificial lung or a contact lens.

In order to construct a highly efficient and high-performance oxygen-enriched membrane, it is important to selectively permeate oxygen and to have a large permeation amount per unit time, that is, to have a so-called high permeation rate. is there. Therefore, the materials constituting the oxygen-enriched film include (a) a high oxygen permeability coefficient P (O ₂ ) and (b)
High permselectivity (separation coefficient a = P (O ₂ ) / P (N ₂ )), (c)
Mechanical strength that enables thinning is required.

As a typical example of an organic polymer having high oxygen permeability, silicone having a structure in which a polymer main chain is composed of silicon atoms and oxygen atoms is well known. This is thought to be due to the flexibility of the siloxane bond, which is the main chain of the silicone, and the high affinity for oxygen.

[0006]

However, due to this high flexibility, the permeability coefficient of gases other than oxygen, for example, nitrogen, is increased, and as a result, the separation coefficient between oxygen and nitrogen is reduced. are doing.
It is also known that silicone has a very low glass transition temperature due to the high flexibility of the siloxane bond and has poor mechanical strength. This indicates that it is difficult to secure the strength necessary for preparing a thin film, and it is extremely disadvantageous to the oxygen permeation rate which is important as an oxygen-enriched film.

[0007] In order to overcome such drawbacks of silicone, three-dimensional cross-linking with radiation or radical generators, compounding with inorganic porous materials, or alloying with other polymers has been performed. At present, a material that sufficiently satisfies all of oxygen permeability, high selectivity, and high permeation rate has not been obtained.

[0008] In view of such circumstances, an object of the present invention is to create a three-dimensionally crosslinked polymer compound for an oxygen-enriched film having high oxygen permeability and selectivity and capable of being made thin.

[0009]

In order to create the above-described high-performance oxygen-enriched film material, a polymer compound having the following properties must be created.

(1) Having a polymer structure rich in flexibility (2) Having a component that selectively allows oxygen to permeate (3) Having a three-dimensionally crosslinkable reactive site in the polymer structure (4) High sensitivity to electron beam When considering a material for an oxygen-enriched film, (1) and (2) are, of course, indispensable characteristics, but three-dimensional cross-linking or compounding with another material is required. When considered, (3) and (4) are also important characteristics. In particular, in (4), it is important that three-dimensional crosslinking can be performed by an electron beam as well as visible / ultraviolet light often used as a light source of a conventional three-dimensional crosslinking reaction. The three-dimensional cross-linking using an electron beam does not require a cross-linking agent or a reaction initiator required when light is used as a light source, and also does not require a solvent used for mixing these with a polymer compound. Furthermore, electron beams are opaque to visible / ultraviolet light (such as paper and thermoplastic / thermosetting resins).
Is also transmitted, so bonding with many materials (for example, resinous porous membranes, etc.) was difficult with the conventional method using light.
Composite can be easily performed. However, what should be noted here is the sensitivity of the polymer compound to be three-dimensionally crosslinked to the electron beam. In general, the sensitivity of a polymer compound to an electron beam is low, and as a result, it takes time for three-dimensional cross-linking and compounding, and it is difficult to apply the method to mass production. Therefore, the sensitivity to the electron beam described in (4) is an important characteristic in considering the combination and mass production, and it is necessary to carry out molecular design of a polymer compound having the above four items.

Heretofore, we have found polymer compounds having alternating oligosiloxane chains and oligooxyalkylene chains. The glass transition temperature of this polymer compound was found to be between −60 and −120 ° C., and it was known that the polymer compound was rich in flexibility. The inventors have found that oxygen permeability is excellent, and have reached the present invention. That is, since the main chain of this polymer compound was composed of a siloxane chain and an oxyalkylene chain, it was found that the polymer had high oxygen permeability and high oxygen selectivity.

Further, it has been confirmed that this compound has a reactive double bond on the silicon atom of the siloxane unit, and easily forms a three-dimensional crosslinked structure by radiation such as light or electron beam. The sensitivity to electron beam is Dg ⁵⁰
(Electron beam irradiation amount at which the normalized residual film thickness becomes 50%) is as high as 1 mC / cm ² , the crosslinking reaction can be performed in a short time, and it is possible to cope with mass production.

From the above, a polymer compound having an oligosiloxane chain and an oligooxyalkylene chain alternately is most suitable as a compound constituting an oxygen-enriched film, and a three-dimensional crosslinked film of this polymer compound is prepared. The performance as an oxygen-enriched membrane was clarified.

The present invention provides an oxygen-enriched film comprising a compound obtained by three-dimensionally cross-linking a polymer compound represented by the following structural formula (1).

[0015]

Embedded image

Here, R in the structural formula (1)¹, R^Two, ...
・ RⁿIs an alkyl group having 1 to 5 carbon atoms, an aryl group or
Represents an aralkyl group, S¹, S^Two, ... SⁿIs hydrogen, water
An acid group, an alkoxyl group having 1 to 7 carbon atoms, a phenoxy group,
An alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group,
Represents a halogenated alkyl group, a halogenated aryl group, etc.
And T¹, T^Two, ... TⁿIs hydrogen, hydroxyl, carbon
Alkoxyl groups of 1 to 7, phenoxy group, 1 to 1 carbon atoms
10 alkyl groups, aryl groups, aralkyl groups, halogenated
Represents an alkyl group, a halogenated aryl group or the like. R¹,
R^Two, ... RⁿMay be the same or different. However,
S¹, S^Two, ... SⁿAnd T¹, T^Two, ... TⁿIs the same as
Some are excluded. n represents an integer of 1 to 10.
x¹, X ^Two, ... xⁿRepresents an integer from 1 to 50;
y¹, Y^Two, ... yⁿRepresents an integer of 1 to 10.
l¹, L^Two, ... lⁿIs the composition ratio of each component (mol
%). Where l¹+ L^Two+ ... + lⁿ= 100m
ol%.

That is, the oxygen-enriched film of the present invention comprises a three-dimensional cross-linking compound containing, as a main component, a polymer compound having an oligosiloxane chain and an oligooxyalkylene chain represented by the structural formula (1) alternately.

The crosslinking reaction is carried out by irradiating the polymer represented by the structural formula (1) with heat or radiation such as light or an electron beam. Further, it is also carried out by mixing a crosslinking agent having two or more functional groups or reactive sites, and a catalyst such as a radical generator that generates radicals by heat or radiation irradiation. The reaction solvent may or may not be used, and the use of the solvent is not particularly limited as long as it does not hinder the crosslinking reaction. The reaction conditions vary depending on the presence or absence of a catalyst, or the catalyst used, but when azobisisobutyronitrile well known as a thermal radical generator is used, the temperature is 40 to 80 ° C, and the time is 12 to
48 hours is desirable. When 2,2-dimethoxy-2-phenylacetophenone, which is well known as a photoradical generator, is used, 10 to 100,000 mJ /
Irradiation with ultraviolet / visible light of cm ² is desirable.

The molding can be performed by a solvent casting method or an arbitrary shape casting. Further, it can be easily formed into a composite with a polymer porous material such as polypropylene or a metal porous material.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the scope of the present invention in any way.

Example 1 In a polymerization apparatus, 4.68 g of diethylene glycol and 1,3-bis (diethylamino)-
1,1,3,3-tetramethyldisiloxane 9.77
g, bis (diethylamino) divinylsilane 1.99 g
And stirred at 60 ° C. for 72 hours to obtain a polysiloxyethylene glycol alternating copolymer (yield 9.77 g). Here, the charging ratio of the silicon monomer having a vinyl group is 20 mol%.

When this was analyzed by gel permeation chromatography, it was found that the number average molecular weight was 13,000, and the weight average molecular weight /
The number average molecular weight was 1.75.

The polymer compound obtained in this example is represented by the following formula (2).

[0024]

Embedded image

The results of ¹ H-NMR analysis of this compound are as follows. ¹ H-NMR (CDCl ₃ ) δ (pp
m): 0.1 (12H, O -Si-CH 3), 3.7
_{(52H, O-CH 2 -CH} 2), 3.7 (52H, O-
CH ₂ —CH ₂ ), 6.0 (6H, Si—CH ＝ C)
H _2). From the integrated intensity ratio of each signal of ¹ H-NMR, l ₂ / l ₁ was 0.13.

To 0.59 g of the polymer obtained here, 2,
2-dimethoxy-2-phenylacetophenone 0.00
18 g and pentaerythritol tetrakis (3-mercaptopropionate) 0.0867 g were mixed, and 0.5 ml of tetrahydrofuran was further added to prepare a solution. This solution was poured into a mold in which a Teflon frame was sandwiched between glass plates, and light from a high-pressure mercury lamp (illuminance = 3.5 mW / c)
m ² ) was irradiated for 286 seconds to allow the crosslinking reaction to proceed. The light irradiation amount at this time is about 1000 mJ / cm.
^{Was 2} . After the photocrosslinking reaction, the sample was dried under reduced pressure at room temperature for 24 hours to prepare a sample for measuring gas permeation. The thickness of the measurement sample was 680 μm.

Example 2 In a polymerization apparatus, 6.32 g of tetraethylene glycol, 7.19 g of 1,3-bis (diethylamino) -1,1,3,3-tetramethyldisiloxane, bis (diethylamino) disiloxane 1.47 g of vinyl silane was added and polymerized for 72 hours while stirring at 60 ° C. to obtain a polysiloxyethylene glycol alternating copolymer (yield 10.27 g). Here, the charging ratio of the silicon monomer having a vinyl group is 20 mol%.

When this was analyzed by gel permeation chromatography, the number average molecular weight was 20,000, and the weight average molecular weight /
The number average molecular weight was 1.93.

The polymer compound obtained in this example is represented by the following formula (3).

[0030]

Embedded image

The results of ¹ H-NMR analysis of the compound are as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm): 0.1 (12
_{H, O-Si-CH 3} ), 3.7 (52H, O-CH 2 -
_{CH 2), 3.7 (52H,} O-CH 2 -CH 2), 6.
0 (6H, Si-CH = CH 2). Further, the integrated intensity ratio of each signal of ¹ H-NMR was l ₂ / l ₁ = 0.11.

To 0.61 g of the polymer obtained here, 2,
2-dimethoxy-2-phenylacetophenone 0.00
13 g and pentaerythritol tetrakis (3-mercaptopropionate) 0.0547 g were mixed, and 0.5 ml of tetrahydrofuran was further added to prepare a solution. This solution was poured into a mold in which a Teflon frame was sandwiched between glass plates, and light from a high-pressure mercury lamp (illuminance = 3.5 mW / c)
m ² ) was irradiated for 286 seconds to allow the crosslinking reaction to proceed. The light irradiation amount at this time is about 1000 mJ / cm.
^{Was 2} . After the photocrosslinking reaction, the sample was dried under reduced pressure at room temperature for 24 hours to prepare a sample for measuring gas permeation. The thickness of the measurement sample was 550 μm.

Example 3 14.66 g of polyethylene glycol (molecular weight 300), 10.78 g of 1,3-bis (diethylamino) -1,1,3,3, -tetramethyldisiloxane, and bis ( 2.29 g of (diethylamino) divinylsilane was added and polymerized for 72 hours while stirring at 60 ° C. to obtain a polysiloxyethylene glycol alternating copolymer (yield 19.96 g). Here, the charging ratio of the silicon monomer having a vinyl group is 20 mol.
%.

When this was analyzed by gel permeation chromatography, it was found that the number average molecular weight was 8000 and the weight average molecular weight / number average molecular weight was 1.80 in terms of polystyrene standard sample.

The polymer compound obtained in this example is represented by the following formula (4).

[0036]

Embedded image

The results of ¹ H-NMR analysis of such a compound are as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm): 0.1 (12
_{H, O-Si-CH 3} ), 3.7 (52H, O-CH 2 -
_{CH 2), 3.7 (52H,} O-CH 2 -CH 2), 6.
0 (6H, Si-CH = CH 2). Also, the integrated intensity ratio of each signal of ¹ H-NMR was l ₂ / l ₁ = 0.20.

To 0.75 g of the polymer obtained here, 2,
2-dimethoxy-2-phenylacetophenone 0.00
19 g and pentaerythritol tetrakis (3-mercaptopropionate) 0.0845 g were mixed, and 0.5 ml of tetrahydrofuran was further added to prepare a solution. This solution was poured into a mold in which a Teflon frame was sandwiched between glass plates, and light from a high-pressure mercury lamp (illuminance = 4.5 mW / c)
m ² ) was irradiated for 222 seconds to advance the crosslinking reaction. The light irradiation amount at this time is about 1000 mJ / cm.
^{Was 2} . After the photocrosslinking reaction, the sample was dried under reduced pressure at room temperature for 24 hours to prepare a sample for measuring gas permeation. The thickness of the measurement sample was 475 μm.

Example 4 In a polymerization apparatus, 16.69 g of polyethylene glycol (molecular weight: 600), 6.18 g of 1,3-bis (diethylamino) -1,1,3,3, -tetramethyldisiloxane, and bis ( 1.26 g of (diethylamino) divinylsilane was added and polymerized for 72 hours while stirring at 60 ° C. to obtain a polysiloxyethylene glycol alternating copolymer (yield 19.91 g). Here, the charging ratio of the silicon monomer having a vinyl group is 20 mol%.
It is.

When this was analyzed by gel permeation chromatography, the number average molecular weight was 8,500 and the weight average molecular weight / number average molecular weight was 1.68 in terms of polystyrene standard sample.

The polymer compound obtained in this example is represented by the following formula (5).

[0042]

Embedded image

The results of ¹ H-NMR analysis of such a compound are as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm): 0.1 (12
_{H, O-Si-CH 3} ), 3.7 (52H, O-CH 2 -
_{CH 2), 3.7 (52H,} O-CH 2 -CH 2), 6.
0 (6H, Si-CH = CH 2). From the integrated intensity ratio of each signal of ¹ H-NMR, l ₂ / l ₁ was 0.17.

To 0.75 g of the polymer obtained here, 2,
2-dimethoxy-2-phenylacetophenone 0.00
31 g and pentaerythritol tetrakis (3-mercaptopropionate) 0.0322 g were mixed, and 0.5 ml of tetrahydrofuran was further added to prepare a solution. This solution was poured into a mold in which a Teflon frame was sandwiched between glass plates, and light from a high-pressure mercury lamp (illuminance = 4.5 mW / c)
m ² ) was irradiated for 222 seconds to advance the crosslinking reaction. The light irradiation amount at this time is about 1000 mJ / cm.
^{Was 2} . After the photocrosslinking reaction, the sample was dried under reduced pressure at room temperature for 24 hours to prepare a sample for measuring gas permeation. The thickness of the measurement sample was 460 μm.

Example 5 4.59 g of diethylene glycol and 1,3-bis (diethylamino)-were placed in a polymerization apparatus.
1,1,3,3-tetramethyldisiloxane 10.7
5 g, bis (diethylamino) divinylsilane 0.98
g for 72 hours while stirring at 60 ° C.
A polysiloxyethylene glycol alternating copolymer was obtained (yield 10.25 g). Here, the charging ratio of the silicon monomer having a vinyl group is 10 mol%.

When this was analyzed by gel permeation chromatography, the number average molecular weight was 12,000, and the weight average molecular weight /
The number average molecular weight was 1.90.

The polymer compound obtained in this example is represented by the following formula (6).

[0048]

Embedded image

The results of ¹ H-NMR analysis of such a compound are as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm): 0.1 (12
_{H, O-Si-CH 3} ), 3.7 (52H, O-CH 2 -
_{CH 2), 3.7 (52H,} O-CH 2 -CH 2), 6.
0 (6H, Si-CH = CH 2). From the integrated intensity ratio of each signal of ¹ H-NMR, l ₂ / l ₁ was 0.08.

To 0.60 g of the polymer obtained here, 2,
2-dimethoxy-2-phenylacetophenone 0.00
11 g and 0.0489 g of pentaerythritol tetrakis (3-mercaptopropionate) were mixed, and 0.5 ml of tetrahydrofuran was further added to prepare a solution. This solution was poured into a mold in which a Teflon frame was sandwiched between glass plates, and light from a high-pressure mercury lamp (illuminance = 4.0 mW / c)
m ² ) was irradiated for 250 seconds to allow the crosslinking reaction to proceed. The light irradiation amount at this time is about 1000 mJ / cm.
^{Was 2} . After the photocrosslinking reaction, the sample was dried under reduced pressure at room temperature for 24 hours to prepare a sample for measuring gas permeation. The thickness of the measurement sample was 495 μm.

Example 6 6.08 g of tetraethylene glycol and 1,3-bis (diethylamino) -1,1,3,3-tetramethyldisiloxane were placed in a polymerization apparatus.
83 g, bis (diethylamino) divinylsilane 0.6
9 g was added thereto and polymerized for 72 hours while stirring at 60 ° C. to obtain a polysiloxyethylene glycol alternating copolymer (yield 9.98 g). Here, the charging ratio of the silicon monomer having a vinyl group is 10 mol%.

When this was analyzed by gel permeation chromatography, the number average molecular weight = 15,000 and the weight average molecular weight /
The number average molecular weight was 1.86.

The polymer compound obtained in this example is represented by the following formula (7).

[0054]

Embedded image

The results of ¹ H-NMR analysis of such a compound are as follows. ¹ H-NMR (CDCl ₃ ) δ (ppm): 0.1 (12
_{H, O-Si-CH 3} ), 3.7 (52H, O-CH 2 -
_{CH 2), 3.7 (52H,} O-CH 2 -CH 2), 6.
0 (6H, Si-CH = CH 2). From the integrated intensity ratio of each signal of ¹ H-NMR, l ₂ / l ₁ was 0.07.

To 0.55 g of the polymer obtained here, 2
2-dimethoxy-2-phenylacetophenone 0.00
07 g and pentaerythritol tetrakis (3-mercaptopropionate) 0.0296 g were mixed, and 0.5 ml of tetrahydrofuran was further added to prepare a solution. This solution was poured into a mold in which a Teflon frame was sandwiched between glass plates, and light from a high-pressure mercury lamp (illuminance = 4.0 mW / c)
m ² ) was irradiated for 250 seconds to allow the crosslinking reaction to proceed. The light irradiation amount at this time is about 1000 mJ / cm.
^{Was 2} . After the photocrosslinking reaction, the sample was dried under reduced pressure at room temperature for 24 hours to prepare a sample for measuring gas permeation. The thickness of the measurement sample was 450 μm.

<Test Example> The samples prepared in Examples 1 to 6 were examined for gas permeability when using oxygen and nitrogen. The measuring method is as follows.

FIGS. 1 and 2 show schematic diagrams of the measuring cell and the gas permeation measuring device, respectively. First, the prepared crosslinked membrane sample is set in the measurement cell. FIG. 1 shows an outline of the measurement cell set as described above. As shown in FIG. 1, the measurement cell 10 has a gas-permeation-side cell 11 and a gas-introduction-side cell 12 each having a through hole.
1, a metal perforated plate 13 is provided. The crosslinked membrane sample 15 is placed on the metal porous plate 13, and is held down by the gas introduction side cell 12 via the rubber packing 17.

The measuring cell 10 is set in the apparatus, the stopcocks 1 to 9 are opened, and the stopcocks 1 to 9 are opened by a vacuum pump not shown.
Evacuated for more than 2 hours. After the evacuation, the stopcocks 6, 7 and 8 are opened after the stopcocks 1 to 9 are all closed, and a gas for measurement (oxygen or nitrogen) is led to the mercury manometer 21. When the pressure difference becomes approximately 200 mmHg, the stopcocks 6 and 7 are stopped. , 8 was closed. Next, the stopcocks 2, 4, 5, 6, and 8 are opened and gas is measured in the cell 1
0 and lead to the pressure gauge 22 to change the pressure per unit time
(ΔP / Δt) was recorded on the recorder 23.

The gas permeability coefficient (P) was calculated from ΔP / Δt obtained by the above measurement according to the following equation (1).

[0061]

[Number 1] P = (ΔP / Δt) × (V 0/76) × (L / P 0 A) × (273.2 / T) ······ (1)

Here, the symbols in the formula are as follows. V ₀ : Internal volume on low pressure side (100.966 mL) L: Film thickness (cm) P ₀ : Pressure on high pressure side (cmHg) A: Permeation area (1 cm ² ) T: Cell temperature (K) Diffusion coefficient (D) Was obtained by the Time-Lag method, and was calculated from the following equation (2).

[0063]

[Equation 2] D = L ² / 6q (2)

Here, θ is as follows. q: Delay time (sec) Solubility coefficient (S) was calculated from the following equation (3).

[0065]

[Formula 3] S = P / D ···

The separation coefficient (a) was calculated by the following (4).

[0067]

## EQU4 ## a = P (O ₂ ) / P (N ₂ ) (4)

Here, the gas permeability coefficient is as follows.

[0069]

P (O ₂ ): oxygen permeability coefficient (cm ³ (STP) cm / cm ² seccmHg) P (N ₂ ): nitrogen permeability coefficient (cm ³ (STP) cm / cm ² seccmHg)

Table 1 shows the measurement results of oxygen and nitrogen permeation of the crosslinked films prepared in Examples 1 to 6.

For comparison, gas permeability data of a silicone membrane (polydimethylsiloxane) (CERogers,
J. Polym. Sci., Part C, Vol. 10, 93 (1965) is also shown as a comparative example.

[0072]

[Table 1]

Description in the table * 1: 10 ^-10 cm ³ (STP) · cm / cm ² · sec · cmHg * 2: 10 ^-7 cm ² / sec * 3: 10 ^-3 cm ³ / cmHg The number in parentheses after the parentheses represents the number of units of the siloxane chain and oxyethylene, and the number in parentheses after V is the mol
%.

The oxygen permeability coefficient P (O ₂ ) of each sample was 10 ^-8
It showed a very high value of 1010 ⁻⁹ cm ³ (STP) cm / cm ² seccmHg. It was also found that the separation coefficient (a) had a high selective permeability of 2.88 to 3.41. From the above measurement results, it was confirmed that the crosslinked membrane of PSEG-V polymer was excellent in oxygen permeability and permselectivity.

[0075]

As described above, the silicon-containing polymer prepared according to the present invention has a structure in which a siloxane chain and an oxyethylene chain are alternately connected to each other, so that it is very excellent in flexibility and very useful for material separation. It is convenient. In addition, it was confirmed that a crosslinked membrane having an arbitrary thickness can be easily formed by using heat or radiation and the reactive site introduced into the polymer chain, and application as an industrial material for the purpose of gas separation. Turned out to be possible. Furthermore, since the three-dimensionally crosslinked membrane of the polymer compound has very high oxygen permeability and nitrogen selective permeability, it can be a new material for an oxygen-enriched membrane that can be freely formed and thinned.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a measurement cell used in a test example of the present invention.

FIG. 2 is a schematic view showing an apparatus used in a test example of the present invention.

[Explanation of symbols]

 10 Measurement cell 15 Crosslinked membrane sample

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hidetoshi Aoki 2-3-6 Shirite, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture Inside of Hokushin Kogyo Co., Ltd. (72) Naoki Hirakawa 2-3-3 Shirite, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture No. 6 Inside Hokushin Kogyo Co., Ltd. (72) Inventor Takashi Tokuda 2-3-6 Shirite, Tsurumi-ku, Yokohama-shi, Kanagawa F-term inside Hokushin Kogyo Co., Ltd. 2H006 BB05 BB06 4D006 GA41 MA03 MA31 MB03 MB04 MC65X MC84 MC88 NA01 NA42 NA44 PA02 PB17 PB19 PB62 PB63 PC41 PC71 4F071 AA65 AF08 AG05 AH02 BA02 BB02 BC01 4J030 CA02 CC16 CD11 CE02 CF02 CG10 CG19 CG29 4J035 BA01 CA022 CA052 CA062 CA132 CA14N CA141 CA152 FB05 FB07 GA08

Claims (1)

[Claims] 1. A polymer compound represented by the following structural formula (1)
Characterized by a three-dimensionally cross-linked compound
Oxygen enriched membrane. Embedded imageHere, R in the structural formula (1)¹, R^Two, ... RⁿIs carbon
An alkyl group, an aryl group or an aralkyl group of the formulas 1 to 5
And S¹, S^Two, ... SⁿIs hydrogen, hydroxyl group, carbon number
1-7 alkoxyl group, phenoxy group, carbon number 1-1
0 alkyl group, aryl group, aralkyl group, halogenated
Alkyl group, halogenated aryl group, etc.
¹, T^Two, ... TⁿRepresents hydrogen, a hydroxyl group, an alkyl group having 1 to 7 carbon atoms.
Lucoxyl group, phenoxy group, alkyl having 1 to 10 carbon atoms
Group, aryl group, aralkyl group, halogenated alkyl group,
Represents a halogenated aryl group or the like. R¹, R^Two, ... R
ⁿMay be the same or different. Where S¹, S^Two,
..SⁿAnd T¹, T^Two, ... TⁿExcept if is the same as
I will n represents an integer of 1 to 10. x¹, X ^Two,
.. xⁿRepresents an integer from 1 to 50;¹, Y^Two, ...
・ YⁿRepresents an integer of 1 to 10. l¹, L^Two...
lⁿRepresents the composition ratio (mol%) of each component. However,
l¹+ L^Two+ ... + lⁿ= 100 mol%.