CA1139680A - Gas separating members and a method of making the same - Google Patents
Gas separating members and a method of making the sameInfo
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- CA1139680A CA1139680A CA000354752A CA354752A CA1139680A CA 1139680 A CA1139680 A CA 1139680A CA 000354752 A CA000354752 A CA 000354752A CA 354752 A CA354752 A CA 354752A CA 1139680 A CA1139680 A CA 1139680A
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- Prior art keywords
- gas separating
- separating member
- substrate
- gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/127—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction using electrical discharge or plasma-polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Abstract of the Disclosure A gas separating member of the present invention comprises a porous substrate in the form of a film, wall or hollow fiber and a polymer film formed on a surface of the substrate by plasma polymerization. The gas separation factor (O2/N2) ranges from 2.3 to 3.9 with the corresponding gas permeability ranging from 12 to 0.16 liter/min. m2 atm. pres.-air. A modified gas separating member of the present invention, which comprises a porous substrate in the aforementioned form and two polymers films formed on a surface of the substrate by plasma polymerization, has the gas separation factor (He/H2) ranging from 14 to 45.
Description
11~3~3~;80 This invention relates to gas separating members which separate gases selectively, and a method of making them.
The use of a gas separating member in the form of a film or wall has been examined in such fields of application as separating oxygen from nitrogen in air to obtain air having a high concentration of oxygen, or discharging an excess of carbon dioxide into the water from the interior of an underwater laboratory and taking the necessary oxygen from the water. However, such known gas separating members have been of practical use only in a very limited area of applications, because they have too small a gas separation factor, or too low a gas permeability.
It would be advantageous to have a gas separating member which is very superior in a gas separation factor and a gas permeability to any known gas separating member.
It would be advantageous to have a gas separating member which has a high mechanical strength.
In particular it would be advantageous to have a gas separating member which separates oxygen from nitrogen in air.
It would also be advantageous to have a gas separating member which separates helium or hydrogen from other gases.
The present invention provides a novel gas separating member which comprises a porous substrate in the form of a film, wall or hollow fiber, and a polymer film formed on a surface of the substrate by plasma polymerization.
The apparatus of the invention may generally be defined as a gas separating member comprising a porous substrate in the form of a film, wall or hollow fiber and a plasma polymerizate polymer film including two layers formed by a plasma polymerization, the two layers being a first layer having high gas permeability formed from an organosilane formed on a surface of the substrate by plasma polymerization and a second layer having a high gas '~ ~
~39tj80 separation factor formed of a monomer other than an organosilane formed on the first layer by plasma polymerization.
The present invention includes a method of making a gas separating member which comprises the steps of setting a porous substrate in the form of a film, wall or hollow fiber in a plasma generator, activating a monomer of organosilane by plasma to form a plasma polymerized film of said organosilane as a first layer having high gas permeability on a surface of the substrate and activating a second monomer other than the organosilane by plasma to form a plasma polymerized layer as a second layer having a high gas separation factor on the organosilane first layer.
Various features and advantages of the present invention will be apparent from the following detailed description when considered in connection with the accompanying drawings, in which like reference characters or numerals designate like parts in the various views, and wherein:
Figure 1 is a sectional view of the apparatus used for plasma polymerization in the Examples of this invention.
Figure 2 is a perspective view of a supporting frame on which a substrate in the form of a hollow fiber is wound.
Figures 3 and 4 are photographs by a scanning electron microscope of the front and rear sides, respectively, of the gas separating member of this invention made in Example 1.
Figures 5 and 6 show infrared absorption spectra for the polymer films on the gas separating members of this invention prepared in Examples 1 and 10 respectively.
Figure 7 is a sectional view of a device for producing the air en-riched with oxygen which employs the gas separating member in the form of a hollow fiber according to the present invention and is found on the same page
The use of a gas separating member in the form of a film or wall has been examined in such fields of application as separating oxygen from nitrogen in air to obtain air having a high concentration of oxygen, or discharging an excess of carbon dioxide into the water from the interior of an underwater laboratory and taking the necessary oxygen from the water. However, such known gas separating members have been of practical use only in a very limited area of applications, because they have too small a gas separation factor, or too low a gas permeability.
It would be advantageous to have a gas separating member which is very superior in a gas separation factor and a gas permeability to any known gas separating member.
It would be advantageous to have a gas separating member which has a high mechanical strength.
In particular it would be advantageous to have a gas separating member which separates oxygen from nitrogen in air.
It would also be advantageous to have a gas separating member which separates helium or hydrogen from other gases.
The present invention provides a novel gas separating member which comprises a porous substrate in the form of a film, wall or hollow fiber, and a polymer film formed on a surface of the substrate by plasma polymerization.
The apparatus of the invention may generally be defined as a gas separating member comprising a porous substrate in the form of a film, wall or hollow fiber and a plasma polymerizate polymer film including two layers formed by a plasma polymerization, the two layers being a first layer having high gas permeability formed from an organosilane formed on a surface of the substrate by plasma polymerization and a second layer having a high gas '~ ~
~39tj80 separation factor formed of a monomer other than an organosilane formed on the first layer by plasma polymerization.
The present invention includes a method of making a gas separating member which comprises the steps of setting a porous substrate in the form of a film, wall or hollow fiber in a plasma generator, activating a monomer of organosilane by plasma to form a plasma polymerized film of said organosilane as a first layer having high gas permeability on a surface of the substrate and activating a second monomer other than the organosilane by plasma to form a plasma polymerized layer as a second layer having a high gas separation factor on the organosilane first layer.
Various features and advantages of the present invention will be apparent from the following detailed description when considered in connection with the accompanying drawings, in which like reference characters or numerals designate like parts in the various views, and wherein:
Figure 1 is a sectional view of the apparatus used for plasma polymerization in the Examples of this invention.
Figure 2 is a perspective view of a supporting frame on which a substrate in the form of a hollow fiber is wound.
Figures 3 and 4 are photographs by a scanning electron microscope of the front and rear sides, respectively, of the gas separating member of this invention made in Example 1.
Figures 5 and 6 show infrared absorption spectra for the polymer films on the gas separating members of this invention prepared in Examples 1 and 10 respectively.
Figure 7 is a sectional view of a device for producing the air en-riched with oxygen which employs the gas separating member in the form of a hollow fiber according to the present invention and is found on the same page
- 2 -of the drawings as Figures 1 and 2 above.
As indicated above, the gas separating member of this- invention is characterized by comprising a porous substrate in the form of a film, wall or hollow fiber, and a polymer film formed on a surface of the substrate by plasma polymerization.
The porous substrate herein serves to provide mechanical strength to a gas separating member, and can, for example be a porous film, wall or -~ hollow fiber having pores of a diameter of several tens of angstroms (A) to several micrometers. More specifically, the substrate may be a sintered pro-duct obtained by sintering metal, ceramic or polymer particles, a fibrous product formed by knitting or weaving fibers, or stacking fibers in felt form, or a porous polymer film, or a porous hollow fiber which has a diameter of several thousands of angstroms to several millimeters.
The substrate may have the form of a flat plate or a tube, or any other form. The substrate in the form of a fine tube or hollow fiber has the following merits compared with that in the form of a flat plate or film. The substrate in the form of a hollow fiber can be used under higher pressure be-cause of its superiority in pressure resistance.
Moreover, the substrate in the form of a hollow fiber has an advan-tage over that in the form of a film in that larger area for permeation can be obtained in a certain cubic volume. Therefore a gas separating device, if the gas separating member in the form of a hollow fiber is employed, becomes more compact.
The substrates in the form of a hollow fiber which can be used for the gas separating member in accordance with this invention include a porous polypropylene hollow fiber having a multiplicity of pores of a diameter of about several hundreds of angstroms, a porous glass hollow fiber and a porous cellulose acetate hollow fiber.
The method of this invention, ~hich forms a poly~er fllm by plasma polymerization, permits relatively easy formation of a polymer film on a relatively complicated surface configuration, such as a tubular surface, or uneven surface. The polymer film may be an organosilane resin or a hydro-carbon resin.
In order to form a stable polymer film over the surfaces of the pores present in the surface of the substrate, a diameter of the pores is preferably not more than several thousands of angstroms if they are circular.
If the pores are rectangular or oval, or the like, their minor side or axis is preferably not more than 1,000 angstroms in length. The substrates which can be used advantageously include a porous cellulose acetate or porous polycarbon-ate film having a multiplicity of pores having a diameter of several tens to several hundreds of angstroms uniformly formed therein, and a porous poly-propylene film in which rectangular pores having their minor side or axis of several hundreds of angstroms are formed by stretching.
The plasma polymerization by which a polymer film is formed on the substrate surface means a method for polymerization which comprises introducing organic monomers into a space filled with a plasma, whereby the organic monomers are activated and converted into radicals or ions to effect polymerization.
More specifically, an electric field is applied to a low pressure gas to energize it into a gas of high energy, whereby the gas of high energy is con-verted into a dissociated form enriched with electrons, ions and radicals, i.e., a plasma. The space occupied by the plasma is fed with organic monomers.
The organic monomers are activated like radicals or ions, and the unreacted monomers are polymerized progressively, thereby forming a polymer film on a surface of the substrate placed in the space. The internal and external electrode methods are available for the application of an electric field.
According to the internal electrode method,it is possible to apply a direct or alternating current, or high frequency electric field, while the external electrode method permits application of a high frequency electric field. The plasma polymerization for this invention can also be accomplished by a method generally known as reverse sputtering which is the same as the aforementioned internal electrode method.
The organic monomers which can be used for the formation of a polymer film according to this invention include organosilanes such as hexamethyl-disiloxane, diethoxydimethylsilane, octamethylcyclotetrasiloxane, tetraethoxy-silane, triethoxyvinylsilane and tetramethylsilane, olefins such as l-hexene, cyclohexene, toluene, styrene, divinylbenzene, 1,3-pentadiene, dicyclopenta-diene, furan, acrylic acid, benzonitrile, acetylenecarboxylic acid, acetylene, dicarboxylic acid, dimethyl ester, and other organic substances hitherto report-ed as being capable of forming a film by plasma polymerization.
In the gas separating member of this invention, the surfaces of the pores present in the surface of the substrate are covered with a polymer film formed by plasma polymerization. It is by the polymer film formed over the surfaces of the pores that gas separation can be effected. Therefore, it is important to know the nature of the polymer film formed over the surfaces of the pores, but impossible to do so by any presently available means for deter-mining physical properties, since the pore diameter is as fine as 1,000 angstroms or less. It is, however, presumed from up-to-date knowledge on plasma polymerization that polymers begin to form around the pores of the sub-strate and grow toward the centers thereof until they close the central open-ings thereof to form a continuous film. It is, therefore, supposed that the polymer film formed over the surfaces of the pores have a greater thickness _ 5 _ 113~3~80 around the pores than in the center thereof, instead of having a uniform thickness over the whole surfaces of the pores. As it is considered that various modes of reactions take place simultaneously in a plasma, it is assumed that the polymer film thereby obtained would have a different chemical composition from that of a polymer film formed by an ordinary method for poly-merization. Differences in chemical composition therebetween can be inferred, for example, from the fact that while a known silicone film composed of a dimethylpolysiloxane structure has a low mechanical strength and a gas separa-tion factor (02/N2~ of only about 2.0, the gas separating member having a silicone film obtained by plasma polymerization in accordance with this inven-tion has a high mechanical strength and a gas separation factor (02/N2) which is as high as at least 2.3.
The performance of the gas separating member according to this invention is such that its gas separation factor (02/N2) ranges from 2.3 to
As indicated above, the gas separating member of this- invention is characterized by comprising a porous substrate in the form of a film, wall or hollow fiber, and a polymer film formed on a surface of the substrate by plasma polymerization.
The porous substrate herein serves to provide mechanical strength to a gas separating member, and can, for example be a porous film, wall or -~ hollow fiber having pores of a diameter of several tens of angstroms (A) to several micrometers. More specifically, the substrate may be a sintered pro-duct obtained by sintering metal, ceramic or polymer particles, a fibrous product formed by knitting or weaving fibers, or stacking fibers in felt form, or a porous polymer film, or a porous hollow fiber which has a diameter of several thousands of angstroms to several millimeters.
The substrate may have the form of a flat plate or a tube, or any other form. The substrate in the form of a fine tube or hollow fiber has the following merits compared with that in the form of a flat plate or film. The substrate in the form of a hollow fiber can be used under higher pressure be-cause of its superiority in pressure resistance.
Moreover, the substrate in the form of a hollow fiber has an advan-tage over that in the form of a film in that larger area for permeation can be obtained in a certain cubic volume. Therefore a gas separating device, if the gas separating member in the form of a hollow fiber is employed, becomes more compact.
The substrates in the form of a hollow fiber which can be used for the gas separating member in accordance with this invention include a porous polypropylene hollow fiber having a multiplicity of pores of a diameter of about several hundreds of angstroms, a porous glass hollow fiber and a porous cellulose acetate hollow fiber.
The method of this invention, ~hich forms a poly~er fllm by plasma polymerization, permits relatively easy formation of a polymer film on a relatively complicated surface configuration, such as a tubular surface, or uneven surface. The polymer film may be an organosilane resin or a hydro-carbon resin.
In order to form a stable polymer film over the surfaces of the pores present in the surface of the substrate, a diameter of the pores is preferably not more than several thousands of angstroms if they are circular.
If the pores are rectangular or oval, or the like, their minor side or axis is preferably not more than 1,000 angstroms in length. The substrates which can be used advantageously include a porous cellulose acetate or porous polycarbon-ate film having a multiplicity of pores having a diameter of several tens to several hundreds of angstroms uniformly formed therein, and a porous poly-propylene film in which rectangular pores having their minor side or axis of several hundreds of angstroms are formed by stretching.
The plasma polymerization by which a polymer film is formed on the substrate surface means a method for polymerization which comprises introducing organic monomers into a space filled with a plasma, whereby the organic monomers are activated and converted into radicals or ions to effect polymerization.
More specifically, an electric field is applied to a low pressure gas to energize it into a gas of high energy, whereby the gas of high energy is con-verted into a dissociated form enriched with electrons, ions and radicals, i.e., a plasma. The space occupied by the plasma is fed with organic monomers.
The organic monomers are activated like radicals or ions, and the unreacted monomers are polymerized progressively, thereby forming a polymer film on a surface of the substrate placed in the space. The internal and external electrode methods are available for the application of an electric field.
According to the internal electrode method,it is possible to apply a direct or alternating current, or high frequency electric field, while the external electrode method permits application of a high frequency electric field. The plasma polymerization for this invention can also be accomplished by a method generally known as reverse sputtering which is the same as the aforementioned internal electrode method.
The organic monomers which can be used for the formation of a polymer film according to this invention include organosilanes such as hexamethyl-disiloxane, diethoxydimethylsilane, octamethylcyclotetrasiloxane, tetraethoxy-silane, triethoxyvinylsilane and tetramethylsilane, olefins such as l-hexene, cyclohexene, toluene, styrene, divinylbenzene, 1,3-pentadiene, dicyclopenta-diene, furan, acrylic acid, benzonitrile, acetylenecarboxylic acid, acetylene, dicarboxylic acid, dimethyl ester, and other organic substances hitherto report-ed as being capable of forming a film by plasma polymerization.
In the gas separating member of this invention, the surfaces of the pores present in the surface of the substrate are covered with a polymer film formed by plasma polymerization. It is by the polymer film formed over the surfaces of the pores that gas separation can be effected. Therefore, it is important to know the nature of the polymer film formed over the surfaces of the pores, but impossible to do so by any presently available means for deter-mining physical properties, since the pore diameter is as fine as 1,000 angstroms or less. It is, however, presumed from up-to-date knowledge on plasma polymerization that polymers begin to form around the pores of the sub-strate and grow toward the centers thereof until they close the central open-ings thereof to form a continuous film. It is, therefore, supposed that the polymer film formed over the surfaces of the pores have a greater thickness _ 5 _ 113~3~80 around the pores than in the center thereof, instead of having a uniform thickness over the whole surfaces of the pores. As it is considered that various modes of reactions take place simultaneously in a plasma, it is assumed that the polymer film thereby obtained would have a different chemical composition from that of a polymer film formed by an ordinary method for poly-merization. Differences in chemical composition therebetween can be inferred, for example, from the fact that while a known silicone film composed of a dimethylpolysiloxane structure has a low mechanical strength and a gas separa-tion factor (02/N2~ of only about 2.0, the gas separating member having a silicone film obtained by plasma polymerization in accordance with this inven-tion has a high mechanical strength and a gas separation factor (02/N2) which is as high as at least 2.3.
The performance of the gas separating member according to this invention is such that its gas separation factor (02/N2) ranges from 2.3 to
3.9 with the corresponding gas permeability ranging from 12 to 0.16 liter/
min. m . atm. pres.-air. It is noted that this performance is very superior as compared with the gas separation factor of 1.9 and the gas permeability of 0.17 liter/min. m2.atm. pres.-air of a typically known gas separating member, i.e., a silicone film composed principally of a dimethylpolysiloxane structure and having a thickness of 100 micrometers. The aforementioned values showing the performance of the gas separating member according to this invention indicate the performance of the gas separating member including the substrate. However, gas separation is accomplished only by the polymer film formed over the surfaces of the pores in the surface of the substrate.
Accordingly, if only the surface area of the pores ~effective area for gas permeation~ is taken into consideration, the gas separating member of this invention ought to show a still higher value of gas permeability. Calcula-', ,;
11~39tj80 tions indicate that the gas permeability amounts to a surprisingly high value of 650 liters/min. m2.atm. pres.-air when the separation factor ~02/N2) is about 2.7. A still better gas separating member can, therefore, be obtained if there is developed a porous substrate having a multiplicity of finer pores and having a greater total area of the surfaces of the pores.
Furthermore, in the present invention, two polymer films can be formed on the substrate by plasma polymerization. A gas separating member, which comprises a porous substrate in the form of a film, wall or hollow fiber, the first polymer film of organosilane formed on a surface of the substrate by plasma polymerization and the second polymer film of hydrocarbon formed on the surface of the first polymer film by plasma polymerization, has special features. The gas separating member has the following gas permeability for each gas. The permeability of hydrogen, helium, nitrogen and oxygen are, respectively, 1.2xlO , l.OxlO , 3.9xlO 6 and 1.6xlO 5cm /sec-cm2-cmHg.
The gas separating member can be used for the enrichment of hydrogen and helium. In order to understand more easily the features of the gas separating member, two examples are shown. Suppose that the gas separating member is placed between a mixed gas chamber at one atmospheric pressure and a vacuum chamber. The surface area of the gas separating member is 1 m2 and the time for separation is one minute. When the mixed gas consists of 50 volume % of hydrogen and 50 volume % of air, the total volume of gases, which are permeated through the gas separating members, is 2.8 liters. The permeated gases consist of about 95 volume % of hydrogen, 2.5 volume % of nitrogen and 2.8 volume % of oxygen. In the case that the mixed gas consists of 50 volume % of helium and 50 volume % of air. The total volume of gases permeated are 2.5 liters and the gases consist of about 94 volume % of helium, 2.9 volume %
of nitrogen and 3.3 volume % of oxygenO
; , ;
i~39680 With regard to the gas separating member, the first polymer film is preferably composed of organosilane and the second polymer film is preferably composed of hydrocarbon. The first polymer film is considered to be con-tributed to the high permeability of gases and the second polymer film is contributed to the high separation factors of H2/air and He/air~
The polymer film which effects gas separation is rigidly united with the substrate surface by plasma polymerization, so that the gas separat-ing member of this invention has not only a high rate of performance in gas separation, but also has as high a mechanical strength as the substrate does.
Thus, the gas separating member of this invention is, from an overall stand-point, of high practical value.
According to this invention, it is possible to form a strong polymer film easily on the substrate surface, irrespective of the shape of the substrate, since it is by plasma polymerization that the polymer film is formed on the substrate surface. Therefore, gas separating members composed of hollow fibers can also be made easily by the method of this invention.
The gas permeability and séparation factor were determined by separating, detecting and measuring constituents of permeated gas in a gas chromatograph in accordance with the ASTM method (pressure method).
More specifically, a gas separating member in the form of a film was placed in a permeation cell, and after the spaces on both sides of the film were evacuated by a vacuum pump, compressed air at 1.1 kg/cm2 was intro-duced into the space on one side of the film. The gas which had permeated through the gas separating member in the form of the film within a predeter-mined length of time was temporarily trapped, and then introduced into a gas chromatograph. The gas was separated into its constituents, i.e., oxygen and nitrogen in a molecular sieve type column, and the amount of each constituent 8C~
was obtained from a working curve which had previously been prepared, whereby the separation factor (O2/N2), rate of oxygen permeation, rate of nitrogen permeation and amount of permeated gases (02+N2) were calculated.
The gas separating member of this invention is considered to have a thickness which is not more than several thousands of angstroms. Polymer films were formed on glass plates, instead of the substrate, in accordance with the same conditions of plasma polymerization as those which were employed in the method of this invention, and the thickness of each of such polymer films was determined by inspecting an interference fringe through an interference micro-scope. The thickness of any film formed by plasma polymerization in the Examples which will hereinafter be described was within the range of from 1,000 to 3,000 angstroms.
Although the foregoing description of the gas separating member according to this invention has been directed solely to the separation of air into oxygen and nitrogen, the gas separating member of this invention can also advantageously be used for the separation of hydrogen, helium, carbon monoxide, carbon dioxide, radioactive rare gas, etc.
The invention will now be described with reference to Examples.
Figure 1 shows a sectional view in outline of a plasma generator used in the present Examples. The plasma generator comprises a glass jar 1 of about 50 cm in height and about 30 cm in diameter of the bottom part thereof which has a top projection ll having a diameter of about 7 cm; a metal base 2 forming the bottom of the jar l; and a pair of electrodes 3 made of a copper strip which is wound around the top and bottom of the projection 11, respec-tively. The base 2 is provided with a passage 21 through which a monomer gas is introduced into the jar 1 alld a passage 22 through which the interior of the jar 1 is evacuated. A sample table ~ made of a metal is provided in the _ g _ 1~39~80 jar 1.
A substrate 5 in the form of a film on which a polymer film was to be formed by plasma polymerization was placed on the sample table 4 in the jar 1 ~'A' position), between the electrodes 3 on the top proj~ction 11 ('B' position), on the shoulder of the jar 1 ('C' position), on the mid-portion of the jar 1 ('D' positionl, or on the lower portion of the jar 1 ('E' posi-tion). A pair of substrates 5 having the size of 7 cm by 10 cm each were placed side by side in the same position.
A substrate in the form of a hollow fiber 5 is wound on a supporting frame 6 made of polycarbonate, as shown in Figure 2, and the substrate with the supporting frame 6 is placed on the sample table 4. The supporting frame 6 has ditches 63 spaced in a certain distance therebetween on both of the oppositely facing sides 61, 62 of the supporting frame. The substrate in the form of a hollow fiber is embedded in each of the ditches 63 and wound in a certain space on the supporting frame 6. This use of the supporting frame 6 prevents the surface of the substrate in the form of the hollow fiber from contacting each other. If the surface of the substrate in the form of the hollow fiber comes in contact with each other, a polymer film will not be formed on the contacted surface of the substrate. At the present stage, the supporting frame 6 is used for the experimental production of the gas separat-ing member. For the mass production, a lot of bobbins arranged in a line at a certain space therebetween will be used instead of the supporting frame 6.
A polymer film may be formed on the surface of the substrate while the sub-strate in the form of a hollow fiber is continuously wound by the bobbins.
Plasma polymeri~ation was performed by firstly placing the substrates in at least one of the aforementioned 'A' to 'E' positions, and evacuating the jar 1 through the passage 22 by a vacuum pump (not shown). While the ~1396~30 vacuum pump was kept operating to continue evacuation, a predetermined kind of organic monomers were introduced into the jar 1 through the passage 21, and the atmospheric pressure in the jar was maintained at about 0.1 to 0.3 Torr. A predetermined power input of high frequency voltage was applied across the electrodes 3 so as to cause plasma polymerization to take place, whereby a polymer film was formed on the surface of the substrate 5 after a predetermined length of time. The plasma polymerization in all of the follow-ing Examples were performed by the foregoing method. Therefore, the descrip-tion of each Example will be limited to the kinds of the organic monomers and the substrates used, and the conditions of plasma polymerization involved.
The following table shows the substrates in the form of a film used in the examples 1 to 19 and 23 to 36.
O Total Pore Thickness Substrate Material Pore Size (A) Area ~%) Micrometers) Others PP Polypro- 200 x 2,000 Approx. 25 Rectan-Pylene 3 gular pores PC-l Polycar- 1,000 dia. 2.4 5 Cir-bonate cular pores PC-2 " 500 dia. 1.2 5 '~
PC-3 " 300 dia. 0.4 5 "
PC-4 " 150 dia. 0.1 5 "
AC-l Cellulose 500 dia. 3 150 "
acetate AC-2 " 250 dia. 2 150 "
Example 1:
A PP substrate was placed in the sample position 'A' (Figure 1), and hexamethyldisiloxane was used as organic monomers. They were reacted for 30 minutes at a monomer pressure of 0,2 Torr and a power lnput of 50 watts across the electrodes, so that a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
11:3~80 Figure 3 is a photograph ~10,000 magnifications) by a scanning electron microscope of the surface of the polymer film formed on the substrate which constitutes the thus-obtained gas separating member. Figure 4 is a photograph (10,000 magnifications) by a scanning electron microscope of the surface of the substrate side of the gas separating member. These photographs show that the rectangular pores in the substrate are completely covered with the polymer film. For further reference, Figure 5 shows an infrared absorp-tion spectrum for the polymer film obtained in the present Example. The results of Electron Spectroscopy for Chemical Analysis (ESCA) indicated that the polymer film was composed of 70 atomic % of carbon, 12 atomic % of oxygen and 18 atomic % of silicon.
The gas permeability and separation factor of the gas separating member were measured by the ASTM method.
The results were as follows;
Separation factor (02/N2) : 2.5 Rate of oxygen permeation : 2.0 x 10 4 cm3/sec.-cm cmHg Rate of nitrogen permeation : 8.0 x 10 5 cm3/sec. cm2 cmHg Amount of oxygen and nitrogen permeated:
min. m . atm. pres.-air. It is noted that this performance is very superior as compared with the gas separation factor of 1.9 and the gas permeability of 0.17 liter/min. m2.atm. pres.-air of a typically known gas separating member, i.e., a silicone film composed principally of a dimethylpolysiloxane structure and having a thickness of 100 micrometers. The aforementioned values showing the performance of the gas separating member according to this invention indicate the performance of the gas separating member including the substrate. However, gas separation is accomplished only by the polymer film formed over the surfaces of the pores in the surface of the substrate.
Accordingly, if only the surface area of the pores ~effective area for gas permeation~ is taken into consideration, the gas separating member of this invention ought to show a still higher value of gas permeability. Calcula-', ,;
11~39tj80 tions indicate that the gas permeability amounts to a surprisingly high value of 650 liters/min. m2.atm. pres.-air when the separation factor ~02/N2) is about 2.7. A still better gas separating member can, therefore, be obtained if there is developed a porous substrate having a multiplicity of finer pores and having a greater total area of the surfaces of the pores.
Furthermore, in the present invention, two polymer films can be formed on the substrate by plasma polymerization. A gas separating member, which comprises a porous substrate in the form of a film, wall or hollow fiber, the first polymer film of organosilane formed on a surface of the substrate by plasma polymerization and the second polymer film of hydrocarbon formed on the surface of the first polymer film by plasma polymerization, has special features. The gas separating member has the following gas permeability for each gas. The permeability of hydrogen, helium, nitrogen and oxygen are, respectively, 1.2xlO , l.OxlO , 3.9xlO 6 and 1.6xlO 5cm /sec-cm2-cmHg.
The gas separating member can be used for the enrichment of hydrogen and helium. In order to understand more easily the features of the gas separating member, two examples are shown. Suppose that the gas separating member is placed between a mixed gas chamber at one atmospheric pressure and a vacuum chamber. The surface area of the gas separating member is 1 m2 and the time for separation is one minute. When the mixed gas consists of 50 volume % of hydrogen and 50 volume % of air, the total volume of gases, which are permeated through the gas separating members, is 2.8 liters. The permeated gases consist of about 95 volume % of hydrogen, 2.5 volume % of nitrogen and 2.8 volume % of oxygen. In the case that the mixed gas consists of 50 volume % of helium and 50 volume % of air. The total volume of gases permeated are 2.5 liters and the gases consist of about 94 volume % of helium, 2.9 volume %
of nitrogen and 3.3 volume % of oxygenO
; , ;
i~39680 With regard to the gas separating member, the first polymer film is preferably composed of organosilane and the second polymer film is preferably composed of hydrocarbon. The first polymer film is considered to be con-tributed to the high permeability of gases and the second polymer film is contributed to the high separation factors of H2/air and He/air~
The polymer film which effects gas separation is rigidly united with the substrate surface by plasma polymerization, so that the gas separat-ing member of this invention has not only a high rate of performance in gas separation, but also has as high a mechanical strength as the substrate does.
Thus, the gas separating member of this invention is, from an overall stand-point, of high practical value.
According to this invention, it is possible to form a strong polymer film easily on the substrate surface, irrespective of the shape of the substrate, since it is by plasma polymerization that the polymer film is formed on the substrate surface. Therefore, gas separating members composed of hollow fibers can also be made easily by the method of this invention.
The gas permeability and séparation factor were determined by separating, detecting and measuring constituents of permeated gas in a gas chromatograph in accordance with the ASTM method (pressure method).
More specifically, a gas separating member in the form of a film was placed in a permeation cell, and after the spaces on both sides of the film were evacuated by a vacuum pump, compressed air at 1.1 kg/cm2 was intro-duced into the space on one side of the film. The gas which had permeated through the gas separating member in the form of the film within a predeter-mined length of time was temporarily trapped, and then introduced into a gas chromatograph. The gas was separated into its constituents, i.e., oxygen and nitrogen in a molecular sieve type column, and the amount of each constituent 8C~
was obtained from a working curve which had previously been prepared, whereby the separation factor (O2/N2), rate of oxygen permeation, rate of nitrogen permeation and amount of permeated gases (02+N2) were calculated.
The gas separating member of this invention is considered to have a thickness which is not more than several thousands of angstroms. Polymer films were formed on glass plates, instead of the substrate, in accordance with the same conditions of plasma polymerization as those which were employed in the method of this invention, and the thickness of each of such polymer films was determined by inspecting an interference fringe through an interference micro-scope. The thickness of any film formed by plasma polymerization in the Examples which will hereinafter be described was within the range of from 1,000 to 3,000 angstroms.
Although the foregoing description of the gas separating member according to this invention has been directed solely to the separation of air into oxygen and nitrogen, the gas separating member of this invention can also advantageously be used for the separation of hydrogen, helium, carbon monoxide, carbon dioxide, radioactive rare gas, etc.
The invention will now be described with reference to Examples.
Figure 1 shows a sectional view in outline of a plasma generator used in the present Examples. The plasma generator comprises a glass jar 1 of about 50 cm in height and about 30 cm in diameter of the bottom part thereof which has a top projection ll having a diameter of about 7 cm; a metal base 2 forming the bottom of the jar l; and a pair of electrodes 3 made of a copper strip which is wound around the top and bottom of the projection 11, respec-tively. The base 2 is provided with a passage 21 through which a monomer gas is introduced into the jar 1 alld a passage 22 through which the interior of the jar 1 is evacuated. A sample table ~ made of a metal is provided in the _ g _ 1~39~80 jar 1.
A substrate 5 in the form of a film on which a polymer film was to be formed by plasma polymerization was placed on the sample table 4 in the jar 1 ~'A' position), between the electrodes 3 on the top proj~ction 11 ('B' position), on the shoulder of the jar 1 ('C' position), on the mid-portion of the jar 1 ('D' positionl, or on the lower portion of the jar 1 ('E' posi-tion). A pair of substrates 5 having the size of 7 cm by 10 cm each were placed side by side in the same position.
A substrate in the form of a hollow fiber 5 is wound on a supporting frame 6 made of polycarbonate, as shown in Figure 2, and the substrate with the supporting frame 6 is placed on the sample table 4. The supporting frame 6 has ditches 63 spaced in a certain distance therebetween on both of the oppositely facing sides 61, 62 of the supporting frame. The substrate in the form of a hollow fiber is embedded in each of the ditches 63 and wound in a certain space on the supporting frame 6. This use of the supporting frame 6 prevents the surface of the substrate in the form of the hollow fiber from contacting each other. If the surface of the substrate in the form of the hollow fiber comes in contact with each other, a polymer film will not be formed on the contacted surface of the substrate. At the present stage, the supporting frame 6 is used for the experimental production of the gas separat-ing member. For the mass production, a lot of bobbins arranged in a line at a certain space therebetween will be used instead of the supporting frame 6.
A polymer film may be formed on the surface of the substrate while the sub-strate in the form of a hollow fiber is continuously wound by the bobbins.
Plasma polymeri~ation was performed by firstly placing the substrates in at least one of the aforementioned 'A' to 'E' positions, and evacuating the jar 1 through the passage 22 by a vacuum pump (not shown). While the ~1396~30 vacuum pump was kept operating to continue evacuation, a predetermined kind of organic monomers were introduced into the jar 1 through the passage 21, and the atmospheric pressure in the jar was maintained at about 0.1 to 0.3 Torr. A predetermined power input of high frequency voltage was applied across the electrodes 3 so as to cause plasma polymerization to take place, whereby a polymer film was formed on the surface of the substrate 5 after a predetermined length of time. The plasma polymerization in all of the follow-ing Examples were performed by the foregoing method. Therefore, the descrip-tion of each Example will be limited to the kinds of the organic monomers and the substrates used, and the conditions of plasma polymerization involved.
The following table shows the substrates in the form of a film used in the examples 1 to 19 and 23 to 36.
O Total Pore Thickness Substrate Material Pore Size (A) Area ~%) Micrometers) Others PP Polypro- 200 x 2,000 Approx. 25 Rectan-Pylene 3 gular pores PC-l Polycar- 1,000 dia. 2.4 5 Cir-bonate cular pores PC-2 " 500 dia. 1.2 5 '~
PC-3 " 300 dia. 0.4 5 "
PC-4 " 150 dia. 0.1 5 "
AC-l Cellulose 500 dia. 3 150 "
acetate AC-2 " 250 dia. 2 150 "
Example 1:
A PP substrate was placed in the sample position 'A' (Figure 1), and hexamethyldisiloxane was used as organic monomers. They were reacted for 30 minutes at a monomer pressure of 0,2 Torr and a power lnput of 50 watts across the electrodes, so that a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
11:3~80 Figure 3 is a photograph ~10,000 magnifications) by a scanning electron microscope of the surface of the polymer film formed on the substrate which constitutes the thus-obtained gas separating member. Figure 4 is a photograph (10,000 magnifications) by a scanning electron microscope of the surface of the substrate side of the gas separating member. These photographs show that the rectangular pores in the substrate are completely covered with the polymer film. For further reference, Figure 5 shows an infrared absorp-tion spectrum for the polymer film obtained in the present Example. The results of Electron Spectroscopy for Chemical Analysis (ESCA) indicated that the polymer film was composed of 70 atomic % of carbon, 12 atomic % of oxygen and 18 atomic % of silicon.
The gas permeability and separation factor of the gas separating member were measured by the ASTM method.
The results were as follows;
Separation factor (02/N2) : 2.5 Rate of oxygen permeation : 2.0 x 10 4 cm3/sec.-cm cmHg Rate of nitrogen permeation : 8.0 x 10 5 cm3/sec. cm2 cmHg Amount of oxygen and nitrogen permeated:
4.7 liters/min.-m2-atm. pres.-air Example 2 The same substrate and organic monomers as used in Example 1 were ùsed, and reacted in the sample position 'B' for 30 minutes at a monomer pressure of 0.3 Torr and a power input of 80 watts across the electrodes, whereby a polymer film was formed on the substrate to prepare a gas separating member.
The separation factor and gas permeability of this gas separating member were as follows:
~1~9~80 Separation factor (02/N2) : 3.2 Rate of oxygen permeation : 2.2 x lO 5 cm /sec.-cm cmHg Rate of nitrogen permeation : 6. 8 x lO 6 cm3/sec.-cm cmHg Amount of oxygen and nitrogen permeated :
0.45 liter/min. m2-atm. pres.-air Example 3:
A PC-2 substrate was placed in the sample position 'C', and hexa -methyldîsiloxane was used as organic monomers. They were reacted for 30 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The results of ESCA ~Electron Spectroscopy for Chemical Analysis) for this polymer film indicated that it was composed of 6g atomic % of carbon, 13 atomic % of oxygen and l9 atomic % of silicon. The gas separating per-formance of this gas separating member was as follows:
Separation factor (Q2/N2) : 2.3 Rate of oxygen permeation : 3.1 x 10 5cm3/sec. cm2-cmHg Rate of nitrogen permeation : 1.3 x 10 5 cm3/sec. cm2-cmHg Amount of oxygen and nitrogen permeated :
0.77 liter/min. m2.atm. pres.-air Example 4:
A PC-3 substrate was placed in the sample position 'A', and hexa-methyldisiloxane was used as organic monomers. They were reacted for 60 m~nutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The gas separating performance of this gas separating member was as follows:
~3~3t;80 Separation factor (02/N2~ : 3.6 Rate of oxygen permeation : 9.5 x 10 cm3/sec. cm2-cmHg Rate of nitrogen permeation: 2.6 x 10 6 cm3/sec.-cm2-cmHg Amount of oxygen and nitrogen permeated :
Q.l9 liter/min..m2.atm. pres.-air Example 5:
The procedures of Example 4 were repeated, except that a PC-4 sub-strate was used, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The gas separating per-formance of this gas separating member was as follows:
Separation factor (Q2/N2) : 3.5 Rate of oxygen permeation : 1.2 x 10 5 cm3/sec.-cm2-cmHg Rate of nitrogen permeation : 3.3 x 10 6 cm3/sec.-cm2 cmllg Amount of oxygen and nitrogen permeated :
0.23 liter/min.-m2-atm. pres.-air Example 6:
The procedures of Example 4 were repeated, except that a PC-2 sub-strate was used, whereby polymer film was formed on the substrate to prepare a gas separating member according to this invention. The gas separating per-formance of this gas separating member was as follows:
Separation factor (02/N2) : 2.7 Rate of oxygen permeation : 2.4 x 10 5 cm3/sec.cm cmHg Rate of nitrogen permeation : 9.0 x 10 6 cm3/sec.cm2.cmHg Amount of oxygen and nitrogen permeated :
0.55 liter/min.m2-atm. pres.-air Example 7:
The procedures of Example 1 were repeated, except that diethoxy-1139~0 dimethylsilane as organic monomers was used, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this inven-tion. The results of ESCA for this polymer film indicated that it was composed of 60 atomic % of carbon, 22 atomic % of oxygen and 17 atomic ~
of silicon. The gas separating performance of this gas separating member was as follows:
Separation factor ~02/N2) : 2.7 Rate of oxygen permeation : 9.5 x 10 5 cm /sec. cm2-cmHg Rate of nitrogan permeation : 3.5 x 10 cm3/sec.-cm cmHg la Amount of oxygen and nitrogen permeated:
2.2 liters/min.m2-atm. pres.-air Example 8:
The procedures of Example 7 were r~peated, except that the substrate was placed in the sample position '~', and that the reaction was continued for 20 minutes, whereby a polymer ilm was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor (02/N2) : 3.5 Rate of oxygen permeation : 7.7 x 10 6 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 2.2 x 10 6 cm3/sec. cm2-cmHg Amount of oxygen and nitrogen permeated :
0.15 liter/min.m2.atm. pres.-air Example 9:
The procedures of Example 1 were repeated, except that tetraethoxy-silane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The results of ESCA for this polymer film indicated that it was composed of 3~3~i8~
70 atomic % of carbon, 22 atomic % of oxygen and 8 atomic % of silicon. The performance of this gas separating member was follows:
Separation factor C02/N2~ : 2.0 Rate of oxygen permeation : 5.3 x 10 cm /sec.cm2.cmHg Rate of nitrogen permeation: 2.7 x 10 5 cm3/sec.cm cmHg Amount of oxygen and nitrogen permeated :
1.5 liters/min.m2-atm. pres.-air Example 10:
The procedures of Example l were repeated, except that octamethyl-cyclotetrasiloxane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. For the purpose of reference, Figure 6 shows an infrared absorp-tion spectrum for the polymer film formed in the present Example. The results of ESCA of the polymer film indicated that it is composed of 81 atomic%ofcarbon,11 atomic % of oxygen and 8 atomic % of silicon. The performance of this gas separating member was as follows:
Separation factor (02/N2~ : 2.7 Rate of oxygen permeation : 1.3 x 10 4 cm3/sec.cm2-cmHg Rate of nitrogen permeation : 4.9 x 10 cm /sec.cm cmHg Amount of oxygen and nitrogen permeated :
3.0 liters/min.m2.atm. pres.-air Example 11:
The procedures of Example 10 were repeated, except that the substrate was placed in the sample position 'E', whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor tQ2/N2) : 2.3 1139~0 Rate of oxygen permeation : 4. 8 x lO cm /sec.cm cmHg Rate of nitrogen permeation : 2.1 x lO 4cm3/sec.cm2-cmHg Amount of oxygen and nitrogen permeated :
12 liters/min.m2-atm. pres.-air Example 12 The procedures of Example 1 were repeated, except that a PC-2 sub-strate, and octamethylcyclotetrasiloxane as organic monomers were used, where-by a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas sepa~ating member was as follows:
Separation factor (02/N2) : 2.7 Rate of oxygen permeation : 3.6 x lQ cm3/sec.cm2-cmHg Rate of nitrogen permeation: 1.3 x lO 5 cm3/sec.cm .cmHg Amount of oxygen and nitrogen permeated :
0.82 liter/min.m2-atm. pres.-air Example 13:
The proceduresof Example 12 were repeated, except that a PC-l sub-strate was placed in the sample position 'C', whereby a polymer film was form-ed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor ~02/N2) : 2.0 Rate of oxygen permeation : 1.6 x 10 cm /sec.cm .cmHg Rate of nitrogen permeation : 7.8 x 10-5 cm3/sec.cm2-cmHg Amount of oxygen and nitrogen permeated :
4.3 liters/min.m2 atm. pres.-air Example 14:
~he procedures of Example 12 were repeated, except that a PC-3 sub-1~3~3~i80 strate was placed in the sample position 'C' and that the reaction was con-tinued for 20 minutes, whereby a polymer ilm was formed on the su~strate to prepare a gas separating member according to this invention. The performance of this gas separating memher was as follows:
Separation factor (02/N2) : 3.5 Rate of oxygen permeation : 2.0 x 10 5 cm3/sec.cm2-cmHg Rate of nitrogen permeation : 5.7 x 10 6 cm3/sec.cm2-cmHg Amount of oxygen and nitrogen permeated 0.39 liter/min.m2atm. pres.-air Ex le 15:
amp The procedures of Example 12 were repeated, except that a PC-4 sub-strate was placed in the sample position 'C' and that the reaction was continu-ed for 20 minutes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows;
Separation factor (02/N2) : 3.1 Rate of oxygen permeation : 2.2 x 10 5 cm3/sec.cm2-cn~lg Rate of nitrogen permeation : 7.2 x 10 6 cm3/sec.cm2 cmHg Amount of oxygen and nitrogen permeated :
0.47 liter/min.m2-atm. pres.-air Example 16:
The procedures of Example 12 were repeated, except that an AC-l sub-strate was used and that the reaction was continued for 50 minutes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows:
Separation factor (02/N2) : 2.0 Rate of oxygen permeation : 1.1 x 10 4 cm3/sec.cm2-cmHg 1139tj80 Rate of nitrogen permeation : 5.4 x 10 cm /sec.cm cmHg Amount of oxygen and nitrogen permeated :
3.0 liters/min.m2-atm. pres.-air Example 17:
The procedures of Example 16 were repeated, except that an AC-2 sub-strate was used, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows:
Separation factor (02/N2~ : 2.3 Rate of oxygen permeation : 1.5 x 10 cm /sec.cm cmHg Rate of nitrogen permeation : 6.8 x 10 cm /sec.cm cmHg Amount o~ oxygen and nitrogen permeated :
3.9 liters/min.m2-atm. pres.-air Example 18:
The procedures of Example 1 were repeated, except that the substrate was placed in the sample position 'D' and that triethoxyvinylsilane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows:
Separation factor (02/N2) : 2.6 Rate of oxygen permeation : 7.0 x 10 5 cm3/sec.cm2-cm~lg Rate of nitrogen permeation : 2.8 x 10 cm /sec.cm cmHg Amount of oxygen and nitrogen permeated :
1.7 liters/min.m2-atm. pres.-air Example 19:
The procedures of Example 1 were repeated, except that l-hexene was used as organic monomers and that the reaction was continued for 60 minutes 8C~
in the sample position 'C', whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its perfor-mance was as follows:
Separation factor (Q2/N2) : 3.9 Rate of oxygen permeation : 8.7 x 10 cm3/sec.-cm2-cmHg Rate of nitrogen permeation : 2.2 x 10 6 cm3/sec. cm2-cmHg Amount of oxygen and nitrogen permeated :
0.16 liter/min.m2-atm. pres.-air Example 20;
As a substrate was used a porous polypropylene hollow fiber having the outer diameter of 250 micrometers and the inner diameter of 200 micro-meters with the pores of 200 angstroms in their miner axis and 3000 angstroms in their longer axis in the wall surface of the substrate. The substrate was wound on the supporting frame 6 as shown in ~igure 2 and placed in the sample position 'A' (Figure 1~. Hexamethyldisiloxane was used as organic monomers.
They were reacted for 3a minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, so that a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The gas permeability and separation factor of the gas separating member were measured by the ASTM method. The results were as follows:
Separation factor (2l~2) : 2.3 Rate of oxygen permeation : 3.7 x 10 5 cm3/sec. cm2.cmHg Rate of nitrogen permeation : 1.6 x 10 5 cm /sec. cm cmHg Amount of oxygen and nitrogen permeated :
0.93 liter/min..m2.atm. pres.-air A device for producing the air enriched with oxygen the sectional view of which was shown in Figure 7 was made by using the gas separating member obtained in this Example. This device comprises a pressure vessel 7 in the form of a pipe of 20 mm in diameter and 200 mm in length and a gas sep-arating body 8 placed inside the pressure vessel 7. The gas separating body 8 was made by inserting one end portion of the bundle of about 500 hollow fibers of the gas separating members 81 of 200 mm in length into an outlet pipe 84 of 16 mm in diameter and 30 mm in length and pouring thereinto epoxy resin to be hardened in the sealed condition, In this stepJ the end portion of the bundle of the hollow fibers of the gas separating members 81 was kept projecting a little out of the opening of the outlet pipe 84. After the epoxy resin was hardened, the outlet pipe 84 together with the projecting end portion of the bundle was cut into round slices near the opening of the outlet pipe 84, so that the end portion 82 of the hollow fibers of the gas separating members 81 come out on the resulting cut section. The other end portion 83 of the'bundle of the hollow fibers of the gas separating member 81 was embedded in the small bulk of epoxy resin and hardened. Therefore the hollow fiber of the gas separating members 81 result-ed to have the opening on only one end portion 82 thereof. The gas separating body 8 was placed inside the pressure vessel 7 as shown in Figure 7 and the pressure vessel 7 and the outlet pipe 84 were sealed up.
Next, a mixed gas consist,ing of 9.4 Yolume % of carbon dioxide and 90.6 volume % of nitrogen and having a pressure of 3.5 kg/cm2 was introduced into the pressure vessel 7 of the device for producing the air enriched with oxygen at the opening end 71. Then, part of the mixed gas was gradually discharged at the opening 72 provided on the side wall near the opposite opening end of the opening end 71 of the pressure vessel 7 while the gas pres-sure in the pressure vessel 7 was kept at 3.5 kg/cm2. In this way, the gas enriched with 20 volume % of carbon dioxide was obtained from the outlet pipe 113~ 30 84 at the rate of 0.1 liter per minute at 1 atm. pres. (1 kg/cm ).
Example 21:
The procedures of Example 2Q were repeated, except that octamethyl-cyclotetrasiloxane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor (02/N2) : 2.0 Rate of oxygen permeation : 6.8 x 10 5 cm /sec. cm cmHg Rate of nitrogen permeation: 3.4 x 10 cm /sec.-cm cmHg Amount of oxygen and nitrogen permeated :
1.9 liters/min.m2-atm. pres.-air Example 22:
The procedures of Example 2a were repeated, except that the reaction was continued for 15 minutes instead of 30 minutes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor (p2/N2) : 2.0 Rate of oxygen permeation : 8.6 x 10 5 cm3/sec. cm2 cmHg Rate of nitrogen permeation : 4.4 x 10 5 cm3/sec. cm2 cmHg Amount of oxygen and nitrogen permeated :
2.4 liters/min-m2-atm. pres.-air Example 23:
A PP substrate shown in the table was placed in the sample position 'A' (Figure 1), and hexamethyldisiloxane was used as organic monomers. They were reacted for 20 minutes at a monomer pressure of 0.2 Torr and a power input of S0 watts across the electrodes, so that the first polymer film was formed on the substrate. Next, cyclohexene was used instead of hexamethyldisiloxane ., 1~L3~80 as organic monomers and the reaction was continued for 20 minutes at a mono-mer pressure of 0.2 Torr and a power input of 50 watts across the-electrodes.
Thus, the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 4.1 x 10 cm3/sec. cm2 cmHg Rate of helium permeation : 3.7 x 10 cm /sec.-cm2-cmHg Rate of oxygen permeation : 2-.9 x 10 cm ~sec.-cm cmHg Rate of nitrogen permeation : 8.4 x 10 cm3/sec. cm2-cmHg Rate of methyl permeation : 9.7 x 10 cm3/sec.-cm cmHg Separation factor (H2/N2) : 49 Separation factor (He/N2) : 44 Separation factor (02/N2) : 3.5 Separation factor (CH4/N2) : 1.2 Example 24:
A PC-2 substrate shown in the table were placed in the sample position 'C', and octamethylcyclotetrasiloxane was used as organic monomers.
They were reacted for 30 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby the first polymer film was formed on the substrate. Next, cyclohexene was used instead of octamethyl-cyclotetrasiloxane as organic monomers and the reaction was continued for 5 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
i~3~ 0 Rate of hydrogen permeation : 1.1 x 10 4 cm /sec.-cm cmHg Rate of helium permeation : 9.4 x 10 cm3/sec.-cm cmHg Rate of oxygen permeation : 1.4 x lQ cm /sec.-cm cmHg Rate of nitrogen permeation : 4.3 x 10 6 cm3/sec. cm2-cmHg Rate of methyl permeation : 5.6 x 10 6 cm3/sec. cm2-cmHg Separation factor (H2/N2) : 27 Separation factor (He/N2) : 22 Separation ~actor (02/N2) : 3.2 Separation factor (CH4/N2~ : 1.3 Example 25:
The procedures of Example 23 were repeated, except that the substrate was placed in the sample position 'C' instead of 'A' and that l-hexene was used instead of cyclohexene as organic monomers of the second polymer film.
Thus, two polymer films were formed on the substrate to prepare a gas separat-ing member according to the present invention. The performance of this gas separating member was as follows:
~ate o~ hydrogen permeation : 1.2 x 10 4 cm3/sec.-cm2-cmHg Rate of helium permeation : 1.0 x 10 4 cm3/sec.-cm2 cmHg Rate of oxygen permeation : 1.6 x 10 5 cm /sec.-cm cm~lg Rate of nitrogen permeation : 3.9 x 10 6 cm3/sec. cm2 cmHg Rate of methyl permeation : 4.7 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 31 Separation factor (He/N2) : 26 Separation factor (02/N2) : 4.2 Separation factor (CH4/N2) : 1.2 Example 26:
A PC-3 ,substrate was placed in the sample position 'D', and hexa-i~39~8(~
methyldisiloxane was used as organic monomers. They were reacted for 30 minutes at a monomer pressure of 0.2 Torr, and a power input of 50 watts across the electrodes, so that the first polymer film was ormed on the substrate.
Next, for the second polymer film, toluene was used as organic monomers and the reaction was continued for fi~e minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes. Thus, the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.0 x 10 4 cm3/sec.-cm2-cmHg Rate of helium permeation : 9.0 x 10 5 cm3/sec.-cm2.cmHg Rate of oxygen permeation ; 1.1 x 10 5 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 3.9 x 10 6 cm3/sec.-cm cmHg Rate of methyl permeation : 5.7 x 10 6 cm3/sec.-cm2-cmHg Separation factor ~H2/N2~ : 26 Separation factor (He/N2) : 23 Separation factor (02/N2) : 2.7 ~eparation factor (CH4/N2) : 1.5 Example 27:
The procedures of Example 26 were repeated, except that the substrate was placed in the sample position 'C' instead of 'D' and that styrene was used instead of toluene as organic monomers of the second polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 3.3 x 10 5 cm3/sec. cm2.cmHg Rate of helium permeatlon : 3.1 x 10 5 cm3/sec. cm2 cmHg Rate of oxygen permeation : 3.2 x 10 6 cm3/sec. cm2~cmHg Rate of nitrogen permeation : 1.5 x 10 6 cm3/sec.~cm cmHg Rate of methyl permeation ; 2.2 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 22 Separation factor ~He/N2) : 20 Separation factor (02/N2) : 2.1 Separation factor (CH4/N2) : 1.4 Example 28:
The procedures of Example 27 were repeated, except that the substrate was placed in the sample position 'D' instead of 'C'. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 4.1 x 10 5 cm3/sec. cm2-cmHg Rate of helium permeation : 4.0 x 10 5 cm3/sec. cm2-cmHg Rate of oxygen permeation : 3.6 x 10 6 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 9.4 x 10 7 cm3/sec. cm2 cmHg Rate of methyl permeation : 1.7 x 10 6 cm3/sec. cm2-cmHg Separation factor (H2/N2~ : 43 Separation factor ~He/N2) : 43 Separation factor (02/N2) : 3.9 Separation factor (CH4/N2) : 1.8 Example 29:
The procedures of Example 27 were repeated to form the first polymer film on the substrate. Then, divin~lbenzene was used as organic monomers of the second polymer fil~n and the reaction was continued for one minute at a monomer pressure of 0.2 Torr and a power input of 50 watts across the elec-trodes. Tllus, two polymer films were formed on the substrate to prepare a gas i ,, ~3968~
separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.4 x 10 4 cm3/sec. cm2-cmHg Rate of helium permeation : 1.3 x 10 4 cm3/sec. cm2-cmHg Rate of oxygen permeation : 1.4 x 10 5 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 4.2 x 10 6 cm3/sec. cm2-cmHg Rate of methyl permeation : 5.4 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 35 Separation factor (He/N2) : 32 Separation factor (02/N2) : 3.3 Separation factor (CH4/N2~ : 1.3 Fxample 30:
The procedures of Example 28 were repeated to form the first poly-mer film on the substrate. Next, 1,3-pentadiene was used as organic monomers of the second polymer film and the reaction was continued for 10 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the elec-trodes. Thus, the second polymer film was formed on the:~urface of the first polymer ilm to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.7 x 10-4 cm3/sec. cm2-cmHg Rate of helium permeation : 1.4 x 10 4 cm3/sec.-cm2-cmHg Rate of oxygen permeation : 2.5 x 10 cm /sec.-cm cmHg Rate of nitrogen permeation : 6.0 x 10 cm /sec.-cm cmHg Rate of methyl permeation : 8.S x 10 6 cm3/sec.-cm2-cmrlg Separation factor (H2/N2) : 28 Separation factor (He/N2) : 23 Separation factor ~02/N2) : 4.2 Separation factor (CH4/N2) : 1.4 Example 31:
The procedures of Example 29 were repeated, except that dicyclo-pentadiene was used i~stead of divinylbenzene as organic monomers of the sec-ond polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.2 x 10 4 cm3/sec. cm cmHg Rate of helium permeation : 1.1 x 10 4 cm3/sec. cm2-cmHg Rate of oxygen permeation : 1.1 x 10 5 cm3/sec. cm2 cmHg Rate of nitrogen permeation : 4.6 x 10 6 cm3/sec. cm cmHg Rate of methyl permeation : 5.8 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 26 Separation factor (He/N2) : 24 Separation factor (02/N2) : 2.4 Separation factor (CH4/N2) : 1.3 Example 32:
The procedures of Example 27 were repeated, except that the sub-strate was placed in the sample position 'A' instead of 'C', so that the first polymer film was formed on the substrate. Next, furan was used as organic monomers of the second polymer film and the reaction was continued for 20 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes. Thus, the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.1 x 10 4 cm3/sec. cm2-cmllg Rate of helium permeation : 9.5 x 10 5 cm3/sec. cm2-cmHg Rate of oxygen permeation : 9.8 x 10 6 cm3/sec.-cm2-cmHg 1~39~80 Rate of nitrogen permeation : 2.5 x 10 6 cm3/sec.-cm2-cmHK
Rate of methyl permeation : 2.3 x 10 6 cm3/sec. cm .cmHg Separation factor ~H2/N2) : 44 Separation factor (He/N2) : 39 Separation factor ~02/N2) : 3.9 Separation factor (CH4/N2) : 0.9 Example 33:
The procedures of Example 32 were repeated, except that acrylic acid was used instead of furan as organic monomers of the second polymer film.
Thus, two polymer films were formed on the substrate to prepare a gas separat-ing member according to this invention. The performance of this gas separat-ing member was as follows:
Rate of hydrogen permeation : 2.6 x 10 4 cm3/sec. cm2-cmHg Rate of helium permeation : 1.7 x 10 4 cm3/sec.-cm2 cmHg Rate of oxygen permeation : 3.6 x 10 5 cm3/sec.-cm2-cmHg Rate of nitrogen permeation : 1.2 x 10 cm /sec. cm cmHg Rate of methyl permeation : 1.7 x 10 5 cm3/sec. cm2-cmHg Separation factor (H2/N2) : 22 Separation factor ~He/N2) : 14 Separation factor (02/N2) : 3.0 Separation factor (CH4/N2) : 1.4 Example 34:
The procedures of Example-31 were repeated, except that the substrate was placed in thesampleposition 'D' instead of 'C', and that benzonitrile was used as organic monomers of the second polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separatlng member were as follows:
11;~9~
Rate of hydrogen permeation : 5.8 x 10 5 cm3/sec. cm cmHg Rate of helium permeation : 6.9 x 10 cm /sec.-cm cmHg Rate of oxygen permeation : 3.6 x 10 6 cm3/sec.-cm cmHg Rate of nitrogen permeation : 1.5 x 10 6 cm /sec. cm2 cmHg Rate of methyl permeation : 1.9 x 10 6 cm3/sec. cm2-cmHg Separation factor ~H2/N2) : 38 Separatlon factor ~He/N2) : 45 Separation factor (02/N2~ : 2.3 Separation factor (CH4/N2) : 1.3 Example 35:
The procedures of Example 28 were repeated, except that the sub-strate was placed in the sample position 'A' instead of ID' and that acetylene-carboxylic acid was used as organic monomers of the second polymer film, whereby two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 7.3 x lC 5 cm3/sec.-cm2-cmHg Rate of helium permeation : 7.4 x 10 5 cm3/sec. cm2-cmHg Rate of oxygen permeation : 6.2 x 10 6 cm3/sec. cm cmHg Rate of nitrogen permeation : 4.2 x 10 6 cm3/sec. cm2 cmHg Rate of methyl permeation : 4.6 x 10 6 cm3/sec. cm2-cmHg Separation factor (H2/N2) : 17 Separation factor (He/N2) : 18 Separation factor (02/N2) : 1.5 Separation factor (CH4/N2) : 1.1 Example 36:
The procedures of Example 35 were repeated, except that the substrate was placed in the sample position 'C' instead of 'A' and that acetylene dicarboxylicacid dimethylester was used instead of ace~ylenecarboxylic acid as organic monomers of the second polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.6 x 10 4 cm3/sec.-cm2-cmHg Rate of helium permeation : 1.6 x 10 4 cm3/sec. cm2-cmHg Rate of oxygen permeation : 1.4 x 10 cm /sec. cm cmHg Rate of nitrogen permeation : 7.1 x 10 cm /sec. cm2-cmHg Rate of methyl permeation : 8.0 x 10 6 cm3/sec. cm2-cn~g Separation factor ~H2~N2) : 22 Separation factor (He/N2) : 22 Separation factor (02/N2) : 2.0 Separation factor ~CH4/N2) : 1.1
The separation factor and gas permeability of this gas separating member were as follows:
~1~9~80 Separation factor (02/N2) : 3.2 Rate of oxygen permeation : 2.2 x lO 5 cm /sec.-cm cmHg Rate of nitrogen permeation : 6. 8 x lO 6 cm3/sec.-cm cmHg Amount of oxygen and nitrogen permeated :
0.45 liter/min. m2-atm. pres.-air Example 3:
A PC-2 substrate was placed in the sample position 'C', and hexa -methyldîsiloxane was used as organic monomers. They were reacted for 30 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The results of ESCA ~Electron Spectroscopy for Chemical Analysis) for this polymer film indicated that it was composed of 6g atomic % of carbon, 13 atomic % of oxygen and l9 atomic % of silicon. The gas separating per-formance of this gas separating member was as follows:
Separation factor (Q2/N2) : 2.3 Rate of oxygen permeation : 3.1 x 10 5cm3/sec. cm2-cmHg Rate of nitrogen permeation : 1.3 x 10 5 cm3/sec. cm2-cmHg Amount of oxygen and nitrogen permeated :
0.77 liter/min. m2.atm. pres.-air Example 4:
A PC-3 substrate was placed in the sample position 'A', and hexa-methyldisiloxane was used as organic monomers. They were reacted for 60 m~nutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The gas separating performance of this gas separating member was as follows:
~3~3t;80 Separation factor (02/N2~ : 3.6 Rate of oxygen permeation : 9.5 x 10 cm3/sec. cm2-cmHg Rate of nitrogen permeation: 2.6 x 10 6 cm3/sec.-cm2-cmHg Amount of oxygen and nitrogen permeated :
Q.l9 liter/min..m2.atm. pres.-air Example 5:
The procedures of Example 4 were repeated, except that a PC-4 sub-strate was used, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The gas separating per-formance of this gas separating member was as follows:
Separation factor (Q2/N2) : 3.5 Rate of oxygen permeation : 1.2 x 10 5 cm3/sec.-cm2-cmHg Rate of nitrogen permeation : 3.3 x 10 6 cm3/sec.-cm2 cmllg Amount of oxygen and nitrogen permeated :
0.23 liter/min.-m2-atm. pres.-air Example 6:
The procedures of Example 4 were repeated, except that a PC-2 sub-strate was used, whereby polymer film was formed on the substrate to prepare a gas separating member according to this invention. The gas separating per-formance of this gas separating member was as follows:
Separation factor (02/N2) : 2.7 Rate of oxygen permeation : 2.4 x 10 5 cm3/sec.cm cmHg Rate of nitrogen permeation : 9.0 x 10 6 cm3/sec.cm2.cmHg Amount of oxygen and nitrogen permeated :
0.55 liter/min.m2-atm. pres.-air Example 7:
The procedures of Example 1 were repeated, except that diethoxy-1139~0 dimethylsilane as organic monomers was used, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this inven-tion. The results of ESCA for this polymer film indicated that it was composed of 60 atomic % of carbon, 22 atomic % of oxygen and 17 atomic ~
of silicon. The gas separating performance of this gas separating member was as follows:
Separation factor ~02/N2) : 2.7 Rate of oxygen permeation : 9.5 x 10 5 cm /sec. cm2-cmHg Rate of nitrogan permeation : 3.5 x 10 cm3/sec.-cm cmHg la Amount of oxygen and nitrogen permeated:
2.2 liters/min.m2-atm. pres.-air Example 8:
The procedures of Example 7 were r~peated, except that the substrate was placed in the sample position '~', and that the reaction was continued for 20 minutes, whereby a polymer ilm was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor (02/N2) : 3.5 Rate of oxygen permeation : 7.7 x 10 6 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 2.2 x 10 6 cm3/sec. cm2-cmHg Amount of oxygen and nitrogen permeated :
0.15 liter/min.m2.atm. pres.-air Example 9:
The procedures of Example 1 were repeated, except that tetraethoxy-silane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The results of ESCA for this polymer film indicated that it was composed of 3~3~i8~
70 atomic % of carbon, 22 atomic % of oxygen and 8 atomic % of silicon. The performance of this gas separating member was follows:
Separation factor C02/N2~ : 2.0 Rate of oxygen permeation : 5.3 x 10 cm /sec.cm2.cmHg Rate of nitrogen permeation: 2.7 x 10 5 cm3/sec.cm cmHg Amount of oxygen and nitrogen permeated :
1.5 liters/min.m2-atm. pres.-air Example 10:
The procedures of Example l were repeated, except that octamethyl-cyclotetrasiloxane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. For the purpose of reference, Figure 6 shows an infrared absorp-tion spectrum for the polymer film formed in the present Example. The results of ESCA of the polymer film indicated that it is composed of 81 atomic%ofcarbon,11 atomic % of oxygen and 8 atomic % of silicon. The performance of this gas separating member was as follows:
Separation factor (02/N2~ : 2.7 Rate of oxygen permeation : 1.3 x 10 4 cm3/sec.cm2-cmHg Rate of nitrogen permeation : 4.9 x 10 cm /sec.cm cmHg Amount of oxygen and nitrogen permeated :
3.0 liters/min.m2.atm. pres.-air Example 11:
The procedures of Example 10 were repeated, except that the substrate was placed in the sample position 'E', whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor tQ2/N2) : 2.3 1139~0 Rate of oxygen permeation : 4. 8 x lO cm /sec.cm cmHg Rate of nitrogen permeation : 2.1 x lO 4cm3/sec.cm2-cmHg Amount of oxygen and nitrogen permeated :
12 liters/min.m2-atm. pres.-air Example 12 The procedures of Example 1 were repeated, except that a PC-2 sub-strate, and octamethylcyclotetrasiloxane as organic monomers were used, where-by a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas sepa~ating member was as follows:
Separation factor (02/N2) : 2.7 Rate of oxygen permeation : 3.6 x lQ cm3/sec.cm2-cmHg Rate of nitrogen permeation: 1.3 x lO 5 cm3/sec.cm .cmHg Amount of oxygen and nitrogen permeated :
0.82 liter/min.m2-atm. pres.-air Example 13:
The proceduresof Example 12 were repeated, except that a PC-l sub-strate was placed in the sample position 'C', whereby a polymer film was form-ed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor ~02/N2) : 2.0 Rate of oxygen permeation : 1.6 x 10 cm /sec.cm .cmHg Rate of nitrogen permeation : 7.8 x 10-5 cm3/sec.cm2-cmHg Amount of oxygen and nitrogen permeated :
4.3 liters/min.m2 atm. pres.-air Example 14:
~he procedures of Example 12 were repeated, except that a PC-3 sub-1~3~3~i80 strate was placed in the sample position 'C' and that the reaction was con-tinued for 20 minutes, whereby a polymer ilm was formed on the su~strate to prepare a gas separating member according to this invention. The performance of this gas separating memher was as follows:
Separation factor (02/N2) : 3.5 Rate of oxygen permeation : 2.0 x 10 5 cm3/sec.cm2-cmHg Rate of nitrogen permeation : 5.7 x 10 6 cm3/sec.cm2-cmHg Amount of oxygen and nitrogen permeated 0.39 liter/min.m2atm. pres.-air Ex le 15:
amp The procedures of Example 12 were repeated, except that a PC-4 sub-strate was placed in the sample position 'C' and that the reaction was continu-ed for 20 minutes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows;
Separation factor (02/N2) : 3.1 Rate of oxygen permeation : 2.2 x 10 5 cm3/sec.cm2-cn~lg Rate of nitrogen permeation : 7.2 x 10 6 cm3/sec.cm2 cmHg Amount of oxygen and nitrogen permeated :
0.47 liter/min.m2-atm. pres.-air Example 16:
The procedures of Example 12 were repeated, except that an AC-l sub-strate was used and that the reaction was continued for 50 minutes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows:
Separation factor (02/N2) : 2.0 Rate of oxygen permeation : 1.1 x 10 4 cm3/sec.cm2-cmHg 1139tj80 Rate of nitrogen permeation : 5.4 x 10 cm /sec.cm cmHg Amount of oxygen and nitrogen permeated :
3.0 liters/min.m2-atm. pres.-air Example 17:
The procedures of Example 16 were repeated, except that an AC-2 sub-strate was used, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows:
Separation factor (02/N2~ : 2.3 Rate of oxygen permeation : 1.5 x 10 cm /sec.cm cmHg Rate of nitrogen permeation : 6.8 x 10 cm /sec.cm cmHg Amount o~ oxygen and nitrogen permeated :
3.9 liters/min.m2-atm. pres.-air Example 18:
The procedures of Example 1 were repeated, except that the substrate was placed in the sample position 'D' and that triethoxyvinylsilane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its performance was as follows:
Separation factor (02/N2) : 2.6 Rate of oxygen permeation : 7.0 x 10 5 cm3/sec.cm2-cm~lg Rate of nitrogen permeation : 2.8 x 10 cm /sec.cm cmHg Amount of oxygen and nitrogen permeated :
1.7 liters/min.m2-atm. pres.-air Example 19:
The procedures of Example 1 were repeated, except that l-hexene was used as organic monomers and that the reaction was continued for 60 minutes 8C~
in the sample position 'C', whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. Its perfor-mance was as follows:
Separation factor (Q2/N2) : 3.9 Rate of oxygen permeation : 8.7 x 10 cm3/sec.-cm2-cmHg Rate of nitrogen permeation : 2.2 x 10 6 cm3/sec. cm2-cmHg Amount of oxygen and nitrogen permeated :
0.16 liter/min.m2-atm. pres.-air Example 20;
As a substrate was used a porous polypropylene hollow fiber having the outer diameter of 250 micrometers and the inner diameter of 200 micro-meters with the pores of 200 angstroms in their miner axis and 3000 angstroms in their longer axis in the wall surface of the substrate. The substrate was wound on the supporting frame 6 as shown in ~igure 2 and placed in the sample position 'A' (Figure 1~. Hexamethyldisiloxane was used as organic monomers.
They were reacted for 3a minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, so that a polymer film was formed on the substrate to prepare a gas separating member according to this invention.
The gas permeability and separation factor of the gas separating member were measured by the ASTM method. The results were as follows:
Separation factor (2l~2) : 2.3 Rate of oxygen permeation : 3.7 x 10 5 cm3/sec. cm2.cmHg Rate of nitrogen permeation : 1.6 x 10 5 cm /sec. cm cmHg Amount of oxygen and nitrogen permeated :
0.93 liter/min..m2.atm. pres.-air A device for producing the air enriched with oxygen the sectional view of which was shown in Figure 7 was made by using the gas separating member obtained in this Example. This device comprises a pressure vessel 7 in the form of a pipe of 20 mm in diameter and 200 mm in length and a gas sep-arating body 8 placed inside the pressure vessel 7. The gas separating body 8 was made by inserting one end portion of the bundle of about 500 hollow fibers of the gas separating members 81 of 200 mm in length into an outlet pipe 84 of 16 mm in diameter and 30 mm in length and pouring thereinto epoxy resin to be hardened in the sealed condition, In this stepJ the end portion of the bundle of the hollow fibers of the gas separating members 81 was kept projecting a little out of the opening of the outlet pipe 84. After the epoxy resin was hardened, the outlet pipe 84 together with the projecting end portion of the bundle was cut into round slices near the opening of the outlet pipe 84, so that the end portion 82 of the hollow fibers of the gas separating members 81 come out on the resulting cut section. The other end portion 83 of the'bundle of the hollow fibers of the gas separating member 81 was embedded in the small bulk of epoxy resin and hardened. Therefore the hollow fiber of the gas separating members 81 result-ed to have the opening on only one end portion 82 thereof. The gas separating body 8 was placed inside the pressure vessel 7 as shown in Figure 7 and the pressure vessel 7 and the outlet pipe 84 were sealed up.
Next, a mixed gas consist,ing of 9.4 Yolume % of carbon dioxide and 90.6 volume % of nitrogen and having a pressure of 3.5 kg/cm2 was introduced into the pressure vessel 7 of the device for producing the air enriched with oxygen at the opening end 71. Then, part of the mixed gas was gradually discharged at the opening 72 provided on the side wall near the opposite opening end of the opening end 71 of the pressure vessel 7 while the gas pres-sure in the pressure vessel 7 was kept at 3.5 kg/cm2. In this way, the gas enriched with 20 volume % of carbon dioxide was obtained from the outlet pipe 113~ 30 84 at the rate of 0.1 liter per minute at 1 atm. pres. (1 kg/cm ).
Example 21:
The procedures of Example 2Q were repeated, except that octamethyl-cyclotetrasiloxane was used as organic monomers, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor (02/N2) : 2.0 Rate of oxygen permeation : 6.8 x 10 5 cm /sec. cm cmHg Rate of nitrogen permeation: 3.4 x 10 cm /sec.-cm cmHg Amount of oxygen and nitrogen permeated :
1.9 liters/min.m2-atm. pres.-air Example 22:
The procedures of Example 2a were repeated, except that the reaction was continued for 15 minutes instead of 30 minutes, whereby a polymer film was formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Separation factor (p2/N2) : 2.0 Rate of oxygen permeation : 8.6 x 10 5 cm3/sec. cm2 cmHg Rate of nitrogen permeation : 4.4 x 10 5 cm3/sec. cm2 cmHg Amount of oxygen and nitrogen permeated :
2.4 liters/min-m2-atm. pres.-air Example 23:
A PP substrate shown in the table was placed in the sample position 'A' (Figure 1), and hexamethyldisiloxane was used as organic monomers. They were reacted for 20 minutes at a monomer pressure of 0.2 Torr and a power input of S0 watts across the electrodes, so that the first polymer film was formed on the substrate. Next, cyclohexene was used instead of hexamethyldisiloxane ., 1~L3~80 as organic monomers and the reaction was continued for 20 minutes at a mono-mer pressure of 0.2 Torr and a power input of 50 watts across the-electrodes.
Thus, the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 4.1 x 10 cm3/sec. cm2 cmHg Rate of helium permeation : 3.7 x 10 cm /sec.-cm2-cmHg Rate of oxygen permeation : 2-.9 x 10 cm ~sec.-cm cmHg Rate of nitrogen permeation : 8.4 x 10 cm3/sec. cm2-cmHg Rate of methyl permeation : 9.7 x 10 cm3/sec.-cm cmHg Separation factor (H2/N2) : 49 Separation factor (He/N2) : 44 Separation factor (02/N2) : 3.5 Separation factor (CH4/N2) : 1.2 Example 24:
A PC-2 substrate shown in the table were placed in the sample position 'C', and octamethylcyclotetrasiloxane was used as organic monomers.
They were reacted for 30 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby the first polymer film was formed on the substrate. Next, cyclohexene was used instead of octamethyl-cyclotetrasiloxane as organic monomers and the reaction was continued for 5 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes, whereby the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
i~3~ 0 Rate of hydrogen permeation : 1.1 x 10 4 cm /sec.-cm cmHg Rate of helium permeation : 9.4 x 10 cm3/sec.-cm cmHg Rate of oxygen permeation : 1.4 x lQ cm /sec.-cm cmHg Rate of nitrogen permeation : 4.3 x 10 6 cm3/sec. cm2-cmHg Rate of methyl permeation : 5.6 x 10 6 cm3/sec. cm2-cmHg Separation factor (H2/N2) : 27 Separation factor (He/N2) : 22 Separation ~actor (02/N2) : 3.2 Separation factor (CH4/N2~ : 1.3 Example 25:
The procedures of Example 23 were repeated, except that the substrate was placed in the sample position 'C' instead of 'A' and that l-hexene was used instead of cyclohexene as organic monomers of the second polymer film.
Thus, two polymer films were formed on the substrate to prepare a gas separat-ing member according to the present invention. The performance of this gas separating member was as follows:
~ate o~ hydrogen permeation : 1.2 x 10 4 cm3/sec.-cm2-cmHg Rate of helium permeation : 1.0 x 10 4 cm3/sec.-cm2 cmHg Rate of oxygen permeation : 1.6 x 10 5 cm /sec.-cm cm~lg Rate of nitrogen permeation : 3.9 x 10 6 cm3/sec. cm2 cmHg Rate of methyl permeation : 4.7 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 31 Separation factor (He/N2) : 26 Separation factor (02/N2) : 4.2 Separation factor (CH4/N2) : 1.2 Example 26:
A PC-3 ,substrate was placed in the sample position 'D', and hexa-i~39~8(~
methyldisiloxane was used as organic monomers. They were reacted for 30 minutes at a monomer pressure of 0.2 Torr, and a power input of 50 watts across the electrodes, so that the first polymer film was ormed on the substrate.
Next, for the second polymer film, toluene was used as organic monomers and the reaction was continued for fi~e minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes. Thus, the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.0 x 10 4 cm3/sec.-cm2-cmHg Rate of helium permeation : 9.0 x 10 5 cm3/sec.-cm2.cmHg Rate of oxygen permeation ; 1.1 x 10 5 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 3.9 x 10 6 cm3/sec.-cm cmHg Rate of methyl permeation : 5.7 x 10 6 cm3/sec.-cm2-cmHg Separation factor ~H2/N2~ : 26 Separation factor (He/N2) : 23 Separation factor (02/N2) : 2.7 ~eparation factor (CH4/N2) : 1.5 Example 27:
The procedures of Example 26 were repeated, except that the substrate was placed in the sample position 'C' instead of 'D' and that styrene was used instead of toluene as organic monomers of the second polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 3.3 x 10 5 cm3/sec. cm2.cmHg Rate of helium permeatlon : 3.1 x 10 5 cm3/sec. cm2 cmHg Rate of oxygen permeation : 3.2 x 10 6 cm3/sec. cm2~cmHg Rate of nitrogen permeation : 1.5 x 10 6 cm3/sec.~cm cmHg Rate of methyl permeation ; 2.2 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 22 Separation factor ~He/N2) : 20 Separation factor (02/N2) : 2.1 Separation factor (CH4/N2) : 1.4 Example 28:
The procedures of Example 27 were repeated, except that the substrate was placed in the sample position 'D' instead of 'C'. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 4.1 x 10 5 cm3/sec. cm2-cmHg Rate of helium permeation : 4.0 x 10 5 cm3/sec. cm2-cmHg Rate of oxygen permeation : 3.6 x 10 6 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 9.4 x 10 7 cm3/sec. cm2 cmHg Rate of methyl permeation : 1.7 x 10 6 cm3/sec. cm2-cmHg Separation factor (H2/N2~ : 43 Separation factor ~He/N2) : 43 Separation factor (02/N2) : 3.9 Separation factor (CH4/N2) : 1.8 Example 29:
The procedures of Example 27 were repeated to form the first polymer film on the substrate. Then, divin~lbenzene was used as organic monomers of the second polymer fil~n and the reaction was continued for one minute at a monomer pressure of 0.2 Torr and a power input of 50 watts across the elec-trodes. Tllus, two polymer films were formed on the substrate to prepare a gas i ,, ~3968~
separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.4 x 10 4 cm3/sec. cm2-cmHg Rate of helium permeation : 1.3 x 10 4 cm3/sec. cm2-cmHg Rate of oxygen permeation : 1.4 x 10 5 cm3/sec. cm2-cmHg Rate of nitrogen permeation : 4.2 x 10 6 cm3/sec. cm2-cmHg Rate of methyl permeation : 5.4 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 35 Separation factor (He/N2) : 32 Separation factor (02/N2) : 3.3 Separation factor (CH4/N2~ : 1.3 Fxample 30:
The procedures of Example 28 were repeated to form the first poly-mer film on the substrate. Next, 1,3-pentadiene was used as organic monomers of the second polymer film and the reaction was continued for 10 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the elec-trodes. Thus, the second polymer film was formed on the:~urface of the first polymer ilm to prepare a gas separating member according to this invention.
The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.7 x 10-4 cm3/sec. cm2-cmHg Rate of helium permeation : 1.4 x 10 4 cm3/sec.-cm2-cmHg Rate of oxygen permeation : 2.5 x 10 cm /sec.-cm cmHg Rate of nitrogen permeation : 6.0 x 10 cm /sec.-cm cmHg Rate of methyl permeation : 8.S x 10 6 cm3/sec.-cm2-cmrlg Separation factor (H2/N2) : 28 Separation factor (He/N2) : 23 Separation factor ~02/N2) : 4.2 Separation factor (CH4/N2) : 1.4 Example 31:
The procedures of Example 29 were repeated, except that dicyclo-pentadiene was used i~stead of divinylbenzene as organic monomers of the sec-ond polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.2 x 10 4 cm3/sec. cm cmHg Rate of helium permeation : 1.1 x 10 4 cm3/sec. cm2-cmHg Rate of oxygen permeation : 1.1 x 10 5 cm3/sec. cm2 cmHg Rate of nitrogen permeation : 4.6 x 10 6 cm3/sec. cm cmHg Rate of methyl permeation : 5.8 x 10 6 cm3/sec. cm2 cmHg Separation factor (H2/N2) : 26 Separation factor (He/N2) : 24 Separation factor (02/N2) : 2.4 Separation factor (CH4/N2) : 1.3 Example 32:
The procedures of Example 27 were repeated, except that the sub-strate was placed in the sample position 'A' instead of 'C', so that the first polymer film was formed on the substrate. Next, furan was used as organic monomers of the second polymer film and the reaction was continued for 20 minutes at a monomer pressure of 0.2 Torr and a power input of 50 watts across the electrodes. Thus, the second polymer film was formed on the surface of the first polymer film to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.1 x 10 4 cm3/sec. cm2-cmllg Rate of helium permeation : 9.5 x 10 5 cm3/sec. cm2-cmHg Rate of oxygen permeation : 9.8 x 10 6 cm3/sec.-cm2-cmHg 1~39~80 Rate of nitrogen permeation : 2.5 x 10 6 cm3/sec.-cm2-cmHK
Rate of methyl permeation : 2.3 x 10 6 cm3/sec. cm .cmHg Separation factor ~H2/N2) : 44 Separation factor (He/N2) : 39 Separation factor ~02/N2) : 3.9 Separation factor (CH4/N2) : 0.9 Example 33:
The procedures of Example 32 were repeated, except that acrylic acid was used instead of furan as organic monomers of the second polymer film.
Thus, two polymer films were formed on the substrate to prepare a gas separat-ing member according to this invention. The performance of this gas separat-ing member was as follows:
Rate of hydrogen permeation : 2.6 x 10 4 cm3/sec. cm2-cmHg Rate of helium permeation : 1.7 x 10 4 cm3/sec.-cm2 cmHg Rate of oxygen permeation : 3.6 x 10 5 cm3/sec.-cm2-cmHg Rate of nitrogen permeation : 1.2 x 10 cm /sec. cm cmHg Rate of methyl permeation : 1.7 x 10 5 cm3/sec. cm2-cmHg Separation factor (H2/N2) : 22 Separation factor ~He/N2) : 14 Separation factor (02/N2) : 3.0 Separation factor (CH4/N2) : 1.4 Example 34:
The procedures of Example-31 were repeated, except that the substrate was placed in thesampleposition 'D' instead of 'C', and that benzonitrile was used as organic monomers of the second polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separatlng member were as follows:
11;~9~
Rate of hydrogen permeation : 5.8 x 10 5 cm3/sec. cm cmHg Rate of helium permeation : 6.9 x 10 cm /sec.-cm cmHg Rate of oxygen permeation : 3.6 x 10 6 cm3/sec.-cm cmHg Rate of nitrogen permeation : 1.5 x 10 6 cm /sec. cm2 cmHg Rate of methyl permeation : 1.9 x 10 6 cm3/sec. cm2-cmHg Separation factor ~H2/N2) : 38 Separatlon factor ~He/N2) : 45 Separation factor (02/N2~ : 2.3 Separation factor (CH4/N2) : 1.3 Example 35:
The procedures of Example 28 were repeated, except that the sub-strate was placed in the sample position 'A' instead of ID' and that acetylene-carboxylic acid was used as organic monomers of the second polymer film, whereby two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 7.3 x lC 5 cm3/sec.-cm2-cmHg Rate of helium permeation : 7.4 x 10 5 cm3/sec. cm2-cmHg Rate of oxygen permeation : 6.2 x 10 6 cm3/sec. cm cmHg Rate of nitrogen permeation : 4.2 x 10 6 cm3/sec. cm2 cmHg Rate of methyl permeation : 4.6 x 10 6 cm3/sec. cm2-cmHg Separation factor (H2/N2) : 17 Separation factor (He/N2) : 18 Separation factor (02/N2) : 1.5 Separation factor (CH4/N2) : 1.1 Example 36:
The procedures of Example 35 were repeated, except that the substrate was placed in the sample position 'C' instead of 'A' and that acetylene dicarboxylicacid dimethylester was used instead of ace~ylenecarboxylic acid as organic monomers of the second polymer film. Thus, two polymer films were formed on the substrate to prepare a gas separating member according to this invention. The performance of this gas separating member was as follows:
Rate of hydrogen permeation : 1.6 x 10 4 cm3/sec.-cm2-cmHg Rate of helium permeation : 1.6 x 10 4 cm3/sec. cm2-cmHg Rate of oxygen permeation : 1.4 x 10 cm /sec. cm cmHg Rate of nitrogen permeation : 7.1 x 10 cm /sec. cm2-cmHg Rate of methyl permeation : 8.0 x 10 6 cm3/sec. cm2-cn~g Separation factor ~H2~N2) : 22 Separation factor (He/N2) : 22 Separation factor (02/N2) : 2.0 Separation factor ~CH4/N2) : 1.1
Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A gas separating member comprising a porous substrate in the form of a film, wall or hollow fiber and a plasma polymerizate polymer film including two layers formed by a plasma polymerization, the two layers being a first layer having high gas permeability formed from an organosilane formed on a surface of the substrate by plasma polymerization and a second layer having a high gas separation factor formed of a monomer other than an organosilane formed on the first layer by plasma polymerization.
2. The gas separating member according to claim 1, wherein the organosilane is a member selected from the group consisting of hexamethyl-disiloxane, diethoxydimethylsilane, octamethylcyclotetrasiloxane, tetraethoxy-silane, triethoxyvinylsilane and tetramethylsilane.
3. The gas separating member according to claim 1, wherein the monomer other than the organosilane is a hydrocarbon.
4. The gas separating member according to claim 3, wherein the hydrocarbon is a member selected from the group consisting of 1-hexene, cyclohexene, toluene, styrene, divinylbenzene, 1,3-pentadiene, dicyclopentadiene, furan, acrylic acid, benzonitrile, acetylenecarboxylic acid and acetylene dicarboxylic acid dimethylester.
5. The gas separating member according to claim 1, wherein the substrate is a porous glass hollow fiber.
6. The gas separating member according to claim 1, wherein the substrate has pores having a diameter of several tens of angstroms to several micrometers.
7. The gas separating member according to claim 6, wherein the substrate has circular pores having a diameter which is not more than several thousands of angstroms.
8. The gas separating member according to claim 6 wherein the substrate has rectangular or oval pores having a minor side or axis which is not more than 1,000 angstroms.
9. The gas separating member according to claim 1, wherein the substrate is a sintered product of metal, ceramic or polymer particles.
10. The gas separating member according to claim 1, wherein the substrate is a fibrous product formed by knitting, weaving or stacking fibers in felt forms.
11. The gas separating member according to claim 1, wherein the substrate is a porous polymer film.
12. The gas separating member according to claim 11, wherein the porous polymer film is a member selected from the group consisting of a porous cellulose acetate film, a porous polycarbonate film and a porous polypropylene film.
13. The gas separating member according to claim 1, wherein the substrate is a porous polymer hollow fiber which has a diameter of several thousands of angstroms to several millimeters.
14. The gas separating member according to claim 13, wherein the porous polymer hollow fiber is a member selected from the group consisting of a porous polypropylene hollow fiber and a porous cellulose acetate hollow fiber.
15. A gas separating member according to claim 1, wherein said first layer has a thickness ranging from 1,000 to 3,000 angstroms.
16. A method of making a gas separating member which comprises the steps of setting a porous substrate in the form of a film, wall or hollow fiber in a plasma generator, activating a monomer of organosilane by plasma to form a plasma polymerized film of said organosilane as a first layer having high gas permeability on a surface of the substrate and activating a second monomer other than the organosilane by plasma to form a plasma polymerized layer as a second layer having a high gas separation factor on the organosilane first layer.
17. The method according to claim 16, wherein the organosilane is a member selected from the group consisting of hexamethyldisiloxane, diethoxy-methylsilane, octamethylcyclotetrasiloxane, tetraexthoxysilane, triethoxyvinyl-silane and tetramethylsilane.
18. The method according to claim 16, wherein the second monomer other than the organosilane is a hydrocarbon.
19. The method according to claim 18, wherein the hydrocarbon is a member selected from the group consisting of 1-hexene, cyclohexene, toluene, styrene, divinylbenzene, 1,3-pentadiene, dicyclopentadiene, furan, acrylic acid, benzonitrile, acetylenecarboxylic acid and acetylene dicarboxylic acid dimethylester.
20. The method according to claim 16, wherein the substrate is a porous glass hollow fiber.
21. A method of making a gas separating member according to claim 16, wherein said first layer has a thickness ranging from 1,000 to 3,000 angstroms.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7995279A JPS5624018A (en) | 1979-06-25 | 1979-06-25 | Gas separating member and production thereof |
| JP79952/1979 | 1979-06-25 | ||
| JP134466/1979 | 1979-10-17 | ||
| JP13446679A JPS5658518A (en) | 1979-10-17 | 1979-10-17 | Fine-tubelike gas separating member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139680A true CA1139680A (en) | 1983-01-18 |
Family
ID=26420932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354752A Expired CA1139680A (en) | 1979-06-25 | 1980-06-25 | Gas separating members and a method of making the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4410338A (en) |
| EP (1) | EP0021422B1 (en) |
| CA (1) | CA1139680A (en) |
| DE (1) | DE3066085D1 (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5895541A (en) * | 1981-11-30 | 1983-06-07 | Mitsubishi Chem Ind Ltd | Gas separating membrane |
| JPS58180205A (en) * | 1982-04-16 | 1983-10-21 | Sumitomo Electric Ind Ltd | Composite membrane having selective permeability to gas and its production |
| DE3217047A1 (en) * | 1982-05-06 | 1983-11-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V., 8000 München | MEMBRANES ON THE BASIS OF SILICA ACID THEROPOLYCONDENSATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE3220037A1 (en) * | 1982-05-27 | 1983-12-01 | Sumitomo Electric Industries, Ltd., Osaka | Selectively gas-permeable composite membranes and process for the production thereof |
| FR2527468B1 (en) * | 1982-05-27 | 1988-07-01 | Sumitomo Electric Industries | SELECTIVELY GAS PERMEABLE COMPOSITE MEMBRANES AND PROCESS FOR PRODUCING THE SAME |
| US4533369A (en) * | 1982-05-28 | 1985-08-06 | Sumitomo Electric Industries, Ltd. | Gas-permselective composite membranes and process for the production thereof |
| GB2121314B (en) * | 1982-05-28 | 1985-10-02 | Sumitomo Electric Industries | Selectively gas-permeable composite membranes and process for the production thereof |
| JPS58221338A (en) * | 1982-06-18 | 1983-12-23 | Toyota Central Res & Dev Lab Inc | Oxygen-rich air supplying device |
| JPS59196706A (en) * | 1983-04-22 | 1984-11-08 | Dainippon Ink & Chem Inc | Heterogenous membrane and preparation thereof |
| US4484935A (en) * | 1983-06-30 | 1984-11-27 | Monsanto Company | Permeation modified membrane |
| GB2144344B (en) * | 1983-08-02 | 1986-11-26 | Shell Int Research | Composite dense membrane |
| JPS60137417A (en) * | 1983-12-23 | 1985-07-22 | Toyota Central Res & Dev Lab Inc | Gas separating member and its preparation |
| US4568327A (en) * | 1984-02-27 | 1986-02-04 | Universite De Sherbrooke | Method and apparatus for the removal of gases physically dissolved by dialysis in the blood |
| JPS61153122A (en) * | 1984-12-27 | 1986-07-11 | Nippon Denso Co Ltd | Oxygen separating member and its manufacture |
| US4824444A (en) * | 1986-04-11 | 1989-04-25 | Applied Membrane Technology, Inc. | Gas permselective composite membrane prepared by plasma polymerization coating techniques |
| DE3880652T2 (en) * | 1987-12-28 | 1993-11-18 | Idemitsu Kosan Co | Selective gas permeation membranes and process for their manufacture. |
| US4919856A (en) * | 1988-02-23 | 1990-04-24 | Dainippon Ink And Chemicals, Inc. | Process for producing membranes for use in gas separation |
| GB8805992D0 (en) * | 1988-03-14 | 1988-04-13 | Shell Int Research | Process for preparing non-porous membrane layers |
| GB8806674D0 (en) * | 1988-03-21 | 1988-04-20 | Shell Int Research | Process for preparing non-porous selective membrane layers |
| US5342693A (en) * | 1988-06-08 | 1994-08-30 | Cardiopulmonics, Inc. | Multifunctional thrombo-resistant coating and methods of manufacture |
| US5262451A (en) * | 1988-06-08 | 1993-11-16 | Cardiopulmonics, Inc. | Multifunctional thrombo-resistant coatings and methods of manufacture |
| US5182317A (en) * | 1988-06-08 | 1993-01-26 | Cardiopulmonics, Inc. | Multifunctional thrombo-resistant coatings and methods of manufacture |
| US5013338A (en) * | 1989-09-01 | 1991-05-07 | Air Products And Chemicals, Inc. | Plasma-assisted polymerization of monomers onto polymers and gas separation membranes produced thereby |
| AU5914994A (en) * | 1993-04-21 | 1994-10-27 | Bend Research, Inc. | Plasma polymerization and surface modification inside hollow micro-substrates |
| US5354469A (en) * | 1993-06-14 | 1994-10-11 | Bend Research, Inc. | Layered plasma polymer composite membranes |
| US5439736A (en) * | 1994-01-21 | 1995-08-08 | Neomecs Incorporated | Gas plasma polymerized permselective membrane |
| GB9726807D0 (en) * | 1997-12-18 | 1998-02-18 | Mupor Ltd | Hydrophobic/Oleophobic surfaces and a method of manufacture |
| AU2003263761A1 (en) * | 2002-06-28 | 2004-01-19 | University Of Wyoming | Device and method for the measurement of gas permeability through membranes |
| US20070031311A1 (en) * | 2003-06-23 | 2007-02-08 | Anthony Edward J | Regeneration of calcium oxide or calcium carbonate from waste calcium sulphide |
| US7088106B2 (en) * | 2003-06-27 | 2006-08-08 | University Of Wyoming | Device and method for the measurement of gas permeability through membranes |
| US7393391B2 (en) * | 2003-10-24 | 2008-07-01 | Stc.Unm | Fabrication of an anisotropic super hydrophobic/hydrophilic nanoporous membranes |
| JP5546241B2 (en) * | 2006-05-31 | 2014-07-09 | ザ シャーウィン−ウィリアムズ カンパニー | Dispersion polymer |
| US8619255B2 (en) * | 2011-04-15 | 2013-12-31 | Rhm Technologies, Inc. | Laser induced breakdown spectroscopy |
| US20220176326A1 (en) * | 2019-05-27 | 2022-06-09 | Conopco, Inc., D/B/A Unilever | Fibre comprising organosilane for purification of liquids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB860099A (en) * | 1958-01-10 | 1961-02-01 | Atomenergi Ab | Method of producing permeable membranes |
| US2966235A (en) * | 1958-09-24 | 1960-12-27 | Selas Corp Of America | Separation of gases by diffusion through silicone rubber |
| DE1648367A1 (en) * | 1967-06-05 | 1971-04-15 | Varian Mat Gmbh | Diffusion membrane arrangement, especially for leak detection tubes |
| US3657113A (en) * | 1970-02-03 | 1972-04-18 | Mobil Oil Corp | Separating fluids with selective membranes |
| US3846521A (en) * | 1971-02-03 | 1974-11-05 | Union Carbide Corp | Low energy electron beam treatment of polymeric films, and apparatus therefore |
| US3775308A (en) * | 1972-05-18 | 1973-11-27 | Interior | Method for preparation of composite semipermeable membrane |
| US3894166A (en) * | 1972-08-21 | 1975-07-08 | Eastman Kodak Co | Integral reverse osmosis membrane with highly pressed woven fabric support member |
| US3847652A (en) * | 1972-12-08 | 1974-11-12 | Nasa | Method of preparing water purification membranes |
| JPS534020B2 (en) * | 1974-09-05 | 1978-02-13 | ||
| US3980456A (en) * | 1975-03-31 | 1976-09-14 | General Electric Company | Method for sealing breaches in multi-layer ultrathin membrane composites |
| US4032440A (en) * | 1975-11-18 | 1977-06-28 | The United States Of America As Represented By The Secretary Of The Interior | Semipermeable membrane |
| CA1077787A (en) * | 1975-11-21 | 1980-05-20 | National Aeronautics And Space Administration | Abrasion resistant coatings for plastic surfaces |
| US4199448A (en) * | 1976-06-09 | 1980-04-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Reverse osmosis membrane of high urea rejection properties |
| US4230463A (en) * | 1977-09-13 | 1980-10-28 | Monsanto Company | Multicomponent membranes for gas separations |
| US4096315A (en) * | 1976-12-15 | 1978-06-20 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Process for producing a well-adhered durable optical coating on an optical plastic substrate |
| US4260647A (en) * | 1979-06-13 | 1981-04-07 | Rca Corporation | Method of depositing an abrasive layer |
-
1980
- 1980-06-25 CA CA000354752A patent/CA1139680A/en not_active Expired
- 1980-06-25 EP EP80103599A patent/EP0021422B1/en not_active Expired
- 1980-06-25 DE DE8080103599T patent/DE3066085D1/en not_active Expired
-
1982
- 1982-06-15 US US06/388,577 patent/US4410338A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0021422B1 (en) | 1984-01-11 |
| US4410338A (en) | 1983-10-18 |
| EP0021422A1 (en) | 1981-01-07 |
| DE3066085D1 (en) | 1984-02-16 |
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