JPS60114323A - Film for separating and enriching oxygen - Google Patents

Abstract

PURPOSE:To obtain an oxygen separating and enriching film having excellent oxygen permeability coefficient, permeability coefficient ratio, and permeation velocity by using a bilayer film consisting of an amphipatic compd. having a long-chain alkyl group contg. a fluorocarbon group. CONSTITUTION:As a method for forming a bilayer film from an amphipatic compd. having a long-chain alkyl group contg. a fluorocarbon group, the compd. is added into water and dispersed by the irradiation of an ultrasonic wave, or the compd. is dissolved in a solvent, and the water or the solvent is evaporated. A mixture obtained by mixing an amphipatic compd. having a long-chain group contg. a fluorocarbon group with an amphipatic compd. contg. an alkyl group having a structure corresponding to said compd. in 1:(0.1-10) molar ratio or the mixture further added with a polar polymer is used for manufacturing the bilayer film which is used for separating and enriching oxygen.

Description

[Detailed description of the invention] The present invention relates to oxygen separation and concentration films.

Conventionally, the practical application of oxygen separation using polymer thin films has been widely studied. The ability to separate oxygen and nitrogen in the air is evaluated using a, oxygen permeability coefficient P02 (unit: am' (STP
) -an/an5- sea -crrtHg)
, b, permeability coefficient ratio P02/PN2, C1 permeation rate Po2
/7 (l is film thickness), and research is being conducted to obtain films with as large these values as possible.

Recently developed ones include a, polyphenylene oxide, b, polydimethylsiloxane-polycarbonate block copolymer, ○, poly(4-methylpentene-1
).

However, a, polyphenylene oxide is Po2/
Although it has an excellent PN2 of 4.3 and can be easily made into a thin film of 1 μm or less, it has a small drawback of Po2 of 1.6 x 10'-'.

b. The polydimethylsiloxane-polycarbonate block copolymer has a large Po7 of .2×10 and about 0.
It is possible to make the film as thin as 0.03μm, but PO2/PN2=2
There is a small drawback of ~2.3.

a-Bo! j (4-1 chillpentene-1) has a slightly larger Po2/PN2=2°5 than silicone-based polymers, but it has the disadvantage of being inferior in Po2=3.4 x 10. Currently, there is nothing that satisfies the evaluation.

The present invention aims to solve these problems,
The purpose is to provide an oxygen separation/concentration film made of a polymer membrane that satisfies all three evaluations.

In 1977, the present inventors were the first in the world to discover that when an ammonium salt with two long alkyl chains was dispersed in water, a bilayer membrane similar to a biological membrane was formed. It was named.

(Kunitake, 0kahata, J.
Am, Ohem, Soc, 99.3860 (1
977)) In addition, we conducted a systematic study of hundreds of amphiphilic compounds containing one, two, or three long-chain alkyl groups, or polymerized polymers5) of these compounds, dispersed in water. As a result, it was found that bilayer membrane formation was observed for an extremely wide range of alkyl compounds.

In particular, bilayer membranes such as vesicles and lamellae obtained by dispersing amphiphilic compounds in water, in which a fluorocarbon group is introduced instead of a long-chain alkyl group, have a basic association structure of hydrocarbon molecules. Although it corresponds to a molecular membrane,
It was found that the material exhibits outstanding characteristics in terms of fusibility, compatibility, and ion permeability.

In the present invention, the bilayer membrane refers to a molecular double layer membrane made from an amphipathic compound (a compound containing both hydrophilic and hydrophobic groups).

It is known that liquid fluorocarbon dissolves air extremely well, and artificial blood (artificial oxygen carrier) using fluorocarbon emulsion has been developed using this property. However, there have been very few attempts to utilize this property for separating and concentrating oxygen.
(61 Ternary composite polymer membrane containing liquid fluorocarbon (Proceedings of the Society of Polymer Science and Technology, Vol. 32, No. 3, p. 326 (1983))
It is only disclosed in .

As a result of intensive research to take advantage of the characteristics of fluorocarbons, the present inventors created a bilayer film from an amphiphilic compound containing a fluorocarbon group and a long-chain alkyl group, and conducted an oxygen separation test using this film. , has been found to have excellent oxygen separation ability, and based on this knowledge, the present invention was completed.

The gist of the present invention resides in an oxygen separation/concentration film characterized by comprising a bilayer film made of an amphiphilic compound having a long-chain alkyl group containing a fluorocarbon group.

Typical amphiphilic compounds having a fluorocarbon group-containing long-chain alkyl group include the following compounds.

1) General formula RF RAr RX (wherein, RP is 0F3(OF2)H-+ or 0F2H
(OF2)n-, (however, n represents an integer from 1 to 16), R is (OH2) m% or (CH2)m
a group in which -coo- or 10- is bonded to (where m represents an integer of 1 to 10), Ar is a group in which two or more six-membered aromatic rings are connected or condensed, R2 is (OH2), or ( OH2), a group in which -000- or -〇- is bonded to .

).

Examples of the above-mentioned Ar group include the following groups.

Hydrophilic groups X include, for example, ammonium salts, sulfonium salts, sulfonates, sulfates, carboxylates, phosphates, sulfonates, phosphocholines, H-lyethers, and polyamines contained in ordinary surfactants and lipids. , sugar residues, etc.

When the value of n exceeds 10, it is difficult to obtain and the raw material becomes expensive, so it is preferable that n is 1 to 10. Furthermore, if the sum of n and m is less than 8, it will be difficult to form a bilayer membrane, and if it exceeds 20, there will be a drawback that it will be difficult to disperse in a solvent such as water, so it is necessary that it be in the range of 8 to 20.

(9) 2) General formula (wherein R1 is 0F5(OF2)n-1 or 0F2H
(OF2)n-1 (n represents an integer from 1 to 10), RH is 0H5(OH2)n-1 (n is the same as above), R5 and R4 are (O)(2)rs or (CH2) a group in which r is bonded to -aOO- or -〇- (however, r represents an integer of 1 to 10, and the sum of n and r is 10 to 20), z is OH or IJ, R is (O
H2)s or (CH2)s -000-, -0-,
-NHOO- or a group bonded with a benzene ring (however,
S represents an integer from 1 to 10), and x represents a hydrophilic group, respectively. ).

3) General formula (10) (In the formula, Y is O or N, R,, R, R, R.

RH and X are each the same groups as in 2) above, and the sum of n and r is the same as in 2) above.

Specific examples of these compounds include the following compounds.

1 0 Rumor Post + Mi U To form a bilayer film from these amphiphilic compounds, these compounds are added to water and dispersed by ultrasonic irradiation, or dissolved in a solvent, and then dissolved in water or a solvent. This can be done by evaporating.

A bilayer film made from a mixture of these amphiphilic compounds having a long-chain alkyl group containing a fluorocarbon group and an amphiphilic compound containing an alkyl group with a corresponding structure can similarly separate and concentrate oxygen. used for. The mixing ratio is preferably 1:0.1 to 10 in terms of molar ratio.

In addition, if an amphiphilic compound having a long-chain alkyl group containing a fluorocarbon group, or a mixture of this compound and an amphiphilic compound containing an alkyl group with a corresponding structure, and a polar polymer are used, the film It has the advantage of being easy to mold.

Examples of the polar polymer include the following polymers.

Examples include polyvinyl alcohol, poly(IJ-N-vinylpyrrolidone), polyacrylamide, poly-2- and droxyethyl methacrylate, polymethyl methacrylate, and cellulose acetate.

Further, when a film containing a polymer such as polyvinyl alcohol is subjected to radiation treatment or chemical treatment such as formalin treatment, it can be made insolubilized without affecting the separation and concentration of oxygen.

(2) An example of the method for producing the bilayer film of the present invention is given below.

Example 1゜a, polyvinyl alcohol (molecular weight 154,000
.

Saponification value 98.1%) 1 PVA (a) 5oη was heated and dissolved in about 2 liters of distilled water, and 1 liter of water was added to 50 ml of the above compound and dispersed by ultrasonic irradiation. Both were mixed and stirred at room temperature for 1 hour, and after the air bubbles disappeared, the mixture was gently poured into a flat glass petri dish. The container was covered with paper and left at room temperature for 4 days to evaporate the water. The formed film was taken out from the petri dish and dried under vacuum for 48 hours to obtain an almost colorless and transparent film.

Example 2 A slightly devitrified film was obtained in the same manner as in Example 1 using the raw materials a and b, polyvinyl alcohol, (Examples 1 and [) (17)].

Example 3゜1 1 gLt of water was added to this compound 200~ and dispersed by ultrasonic irradiation. Apply this dispersion liquid to MiIJ Bore Filter VS.
(Pore diameter 0.025 μm, filter diameter 4.7
m) and poured it into a container with silicone grease applied around it. A film was prepared by leaving it at room temperature for 2 days to evaporate the water. Although the film strength is inferior to Examples 1 and 2,
Film forming ability was sufficient.

(18) The film was transparent.

Comparative Example 1゜a, polyvinyl alcohol, (same as Example 1) above a
A film was produced in the same manner as in Example 1 using raw materials . Although the film was somewhat devitrified compared to the film of Example 1, the film strength was comparable.

Example 4a, Poly-N-vinylpyrrolidone, (MW, 360,000)
b. The same compound as in Example 1, poly17 N-vinylpyrrolidone 50#v, was dissolved in water 1- at room temperature, water 2- was added to compound b50IIv, and the mixture was dispersed by ultrasonic irradiation. Both were mixed and a film was produced in the same manner as in Example 1.

The film became somewhat devitrified, but its strength increased.

Example 5a Polyacrylamide (MW, 200,000) b, the same compound as in Example 1 A film was produced in the same manner as in Example 1 using the raw materials a and b. The film was colorless and transparent.

Example 6゜a, poly-2-hydroxyethyl methacrylate (
(manufactured by Aldrich Chemical Co.) b, the same compound as in Example 1 Compounds 50 to 50 were mixed with dioxane/water (1:1 by volume) 2-
Compound 50 was dissolved in 1- by heating, and Compound 50 was dispersed in 1- by ultrasonic irradiation. Using this mixed solution, a film was produced in the same manner as in Example 1. The film was colorless and transparent.

Example 7゜a, polymethyl methacrylate (MW, 700,000-75
10,000) Polymethyl methacrylate 50~ was dissolved in acetone 2-, and compound b5019 was dissolved in acetone 1-. After pouring the mixture of both liquids into a Petri dish, the acetone was evaporated to produce a film, and the film was dried under vacuum for 24 hours. The film was colorless and transparent.

Example 8a, cellulose acetate b, the same compound as in Example 1 50 ml of cellulose acetate was dissolved in acetone/THF (1:1 by volume) 2-, and compound b 5Qq was dissolved in 1 g Lt of acetone. Both were mixed and stirred at room temperature for 1 hour. This solution was poured into a petri dish, and the solvent was evaporated for about 1 day to produce a film. The film was dried under vacuum for 24 hours. The obtained film has some macroscopic images (
21) Although phase separated, the film was strong.

Example 9 A film produced using the same raw materials and the same method as in Example 1 (bilayer membrane content: 18% by weight) was immersed in water containing formalin and sulfuric acid, and reacted at 70°C for 15 minutes. The obtained film was thoroughly washed with water and dried. Although this film was soaked in water for several hours, no leakage of the bilayer membrane was detected.

Example 10: A film manufactured using the same raw materials and the same method as in Example 1 (bilayer membrane content: 83.3% by weight) was sealed in an ampoule purged with nitrogen, and irradiated with 60 o gamma rays at 10 Mrad. . Even when this film was immersed in water at 100° C. for 30 minutes, there was little leakage of the bilayer film, and the infrared spectra before and after irradiation were almost the same.

Example 11゜ (1) to (14) exemplified as amphipathic compounds in the specification
) was used to form a film in the same manner as in Example 1.

(2) The oxygen and nitrogen permeation rates and permeation rates (ΔP/Δt) of the film of the present invention were measured by a high vacuum method using the apparatus shown in FIG.

In FIG. 1, 1 is a permeation cell, 2 is a constant temperature bath, 3 is a pressure gauge, 4 is a gas storage tank, 5 is a MacLeod vacuum gauge, 6 is a cooling trap, and 7 is an oil rotary vacuum pump.

A film was set in the permeation cell 1, placed in a constant temperature bath 2, and left at 30° C. for 12 hours under high vacuum (0.01 mm 1 g). Thereafter, the gas to be measured was supplied from the gas storage tank 4 to the high pressure side to fill it to about 40 CILHg. The low-pressure side was brought to a high vacuum using the oil rotary vacuum pump 7, and it was confirmed that there were no pinholes, and the pulp on the high-vacuum side was stopped and measurement was started. The pressure increase on the low pressure side was read at predetermined time intervals using the pressure gauge 3, and the pressure increase versus time was plotted. The transmission rate was calculated from the slope of the straight line. Next, the gas was exchanged, and the solution was left under vacuum again for 12 hours, and the permeation rate was determined in the same manner.

The permeability coefficient P was calculated by the following formula using the permeation rate ΔP/Δt.

However, To: 273.2, ■=volume of the system, A=transmission area,! . = film thickness, Po = pressure on high pressure side (1) Next,
Permeation experiments were conducted on films made of polyvinyl alcohol and the following bilayer membrane compounds.

(2) Blend film composition and film thickness (η) Number η (weight%) (μm) F-150125083,
349 F-250210066,735 F-35035050,022 F-46046050,035 F-55055050,080 (3) 02, N2 permeability coefficient number C℃) Po2x 10', PN2X109PN2
F-1300,670,262,6 10021,99,62,3 F-110010,35,81,8 F-31000,0830,0451,8F-4100
2,771,451,9 (4) 0□N by changing the bilayer membrane content in the film
Two permeation experiments were conducted. The results were as follows.

1) Film composition and thickness PVA180-- 31 F-11802010,040 F-21809033,333 F-318018050,057 F-45011169,022 F-55025083,349 Masu F-60200100,038 Comparison H-1180 4520,049# H-218018050,067 In addition, in F-1 to F-6, the first compound shown in the example ratio was used.

Comparing to 1 1 (-1, H-2, the compound shown in Example 4 was used.
0,025 μm) was used by coating it on a filter.

2) 02, N2 gas permeability coefficient Film bilayer content Permeability coefficient P P.

Number (weight%) PO x 1010, PN2 x 101
0PN2PVA OO,0320,0241,33F-
110,00,0970,0343,13F-233,
30,2380,1012,36F-350,00,4
190,1662,52F-469,02,0410,
8932, 29F-583, 36, 7182, 6002
,58F-6100,0174"76.6" 2.2
7” Comparison H-120, 00, 0600, 0481, 24
H-250,00,1610,1281,26P 1 unit is txt' (STP) ・an/cm2・sec・
caHg: Shows the case where the temperature is 30°C and the temperature is 26°C.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a high vacuum gas permeability measuring device. 1: Permeation cell, 2: Constant temperature chamber, 3: Pressure gauge, 4: Gas storage tank, 5: McLeod vacuum gauge, 6: Cooling trap, 7: Oil rotary vacuum pump. Patent Applicant: New Technology Development Corporation (29) Brown 1. Amendment of Drawing Procedures April 2, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1. Indication of the Case 1947 Patent Application No. 221970' Issued 100
．． Basic. 1. Reduction, A2゜3, Relationship with the case of the person making the amendment Patent applicant No. 51, 2-5-2 Nagatacho, Chiyoda-ku, Tokyo Name: New Technology Development Corporation 6. Number of inventions increased by amendment None 7. Scope of Claims and Detailed Explanation of the Invention in the Specification Subject to Amendment Column 8/Supplement "E" , An oxygen separation and concentration film comprising a bilayer film made of an amphiphilic compound having a long-chain alkyl group containing a fluorocarbon group. 2. An amphiphile having a long-chain alkyl group containing a fluorocarbon group. The film for separating and concentrating oxygen according to claim 1, wherein the chemical compound is a compound represented by the following general formula. , is OF, (OF2)n, or 0F2H(OF
2) n, (where n represents an integer from 1 to 16),
R1 is -coo to (OH2)m% or (CH2)m
- or 10- (where m represents an integer of 1 to 10), Ar is a group consisting of two or more aromatic six-membered rings connected or condensed, R2 is (aI(2), or (OH2) ) A group in which -coo- or 10- is bonded to p (where p represents an integer of (1) from θ to 10), x represents a parent tree group, and n and m
0) whose sum is 8 to 20, 2), a compound represented by the general formula (wherein R, is OF, (OF2)n-1 or 0F2
H(OF2)n-1 (however, n represents an integer from 1 to 16), RH is 0H3(OH2)n-1 (however, n is the same as above), R and R4 are (OH2) r s or (OH2) A group in which r is bonded to -C0〇- or -O- (where r represents an integer from 1 to 10, and the sum of n and r is 10 to 20), z is a group with two structural orientations. R5 is (
-000-, -0- to OH2)6 or (OH2)8
, -NHOO- or a group bonded with a benzene ring (S represents an integer of 1 to 10, x represents a parent tree group), 5), general formula R'', RH and X are the same groups as in 2) above, respectively,
The sum of n and r is the same as in 2) above. 3. Claim 1, which comprises a bilayer film of a mixture of an amphiphilic compound having a fluorocarbon group-containing long-chain alkyl group and an amphiphilic compound having a long-chain alkyl group having a corresponding structure. Separation of oxygen, concentrated film 0 4, a polar polymer is mixed with an amphiphilic compound having a fluorocarbon group-containing long-chain alkyl group, or a mixture of this compound and an amphiphilic compound having a long-chain alkyl group with a structure corresponding to this compound. 2. The oxygen separation and concentration film according to claim 1, which is a film obtained by forming a bilayer membrane using a bilayer film. ” (Please note that 2 who joined this time is Motoki Oyagi (
For example, if >N"<", the example compound (15th
Pages (13) (14)
2) Specification, page 4, line 8 [PO2/PN2 j
Corrected as 2/PN2J. (5) Same page 4 line 16r/PN2J r/PNzJ
I am corrected. (4) Page 5, lines 1 and 4 [PO2/PN2 J
Correct it as [PO2/PN2 J. [Corrected as 0 coo eJ. (6) On page 10, line 9, "zit, CH or N" is corrected as follows. [2 is a connecting part between two structural elements, such as OH, N or a hydrophilic group) N"<r>"<0- (In the case of a hydrophilic group, the R-X part is not required)" (7) On page 11, line 2, "Y is C or N" is corrected as follows. [Y is a connecting part between two constituent elements and does not require O, N or a parent R-X part. (8) On page 11, line 9, "ol" is corrected to l-07j. (9) The formula in page 13 (6) of the same is amended as follows. (10) Page 22, line 12 l-"Or J [60Co
r Correct as J. (1) Correct p. 26, line 3 r PN2 J to “PN2”. (12) Correct p. 26, line 6, 1-F-1j to “F-2J.” (15) P. 26, p. 26, line 6, 1-F-1j. 10 rows 102N2” to “02 +
Correct N2 J. (14) On page 28, line 3, "PN2" is corrected to rh+2J. (15) On page 28, line 13, "P'" is corrected to "P's". (6)

Claims (1)

[Claims] 1. A film for separating and concentrating oxygen, comprising a bilayer film made of an amphiphilic compound having a long-chain alkyl group containing a fluorocarbon group. 2. The oxygen separation and concentration film according to claim 1, wherein the amphiphilic compound having a long-chain alkyl group containing a fluorocarbon group is a compound represented by the following general formula. 1), general formula R, -R-Ar-R-X (wherein R7 is OF, (OH2)n-1 or 0F2H(OF2)n
-, (where n represents an integer of 1 to 16), R1 is (OH2)m% or (a group of -coo- or 10- bonded to OH21m, and m represents an integer of 1 to 10), Ar is a group consisting of two or more aromatic six-membered rings connected or condensed, R2 is -0 to (OH2)p or (CH2)p
A group bonded with 00- or -〇- (where p is θ~1
(represents an integer of 0), x represents a hydrophilic group, and n
The sum of and m is 8 to 20. ), 2)
, general formula (where RF is 0F3 (OF2), or 0F2H (
OF2)n, (where n represents an integer from 1 to 16), RH is OH, (OH2), 1 (however, n is the same as above), R11 and R4 are (OH2) r% or (OH2) A group in which -ooo- or -〇- is bonded to r (however, r represents an integer of 1 to 10, and the sum of n and r is 10 to 20), z is OH or NSR' is (OH
2) -Coo-, -0- for 6 or (OH2)s. -NHOO-Maku is a group with a benzene ring attached (however,
S represents an integer from 1 to 10) X represents a hydrophilic group) 5) General formula (wherein Y is at or N, RF, R, R. R5, RH and X are the same groups as in 2) above, and the sum of n and r is the same as in 2) above. 3. Oxygen separation characterized by comprising a bilayer film of a mixture of an amphipathic compound having a fluorocarbon group-containing long-chain alkyl group and a long-chain alkyl group-containing amphiphilic compound having a corresponding structure; concentrated film. 4. A polar polymer is mixed with an amphiphilic compound having a long-chain alkyl group containing a fluorocarbon group, or a mixture of the compound and an amphiphilic compound having a long-chain alkyl group with a corresponding structure. An oxygen separation and concentration film characterized by comprising a film formed with a membrane.