JP2010235929A - Polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer excellent in ability of selectively permeating oxygen and ability of suppressing carbon dioxide permeation. <P>SOLUTION: A polymer having recurring units represented by formula (1) is provided. In formula (1), R<SP>1</SP>represents H, a halogen atom, a (substituted) alkyl, a (substituted) aromatic hydrocarbon group, a (substituted) aromatic heterocyclic group, a trialkylsilyl group or a trialkylgermyl group; and R<SP>2</SP>is represented by formula (3), wherein m is an integer of 0-5 and when there are plural R<SP>2</SP>s, R<SP>2</SP>s may be the same or different. In formula (3), p is an integer or 5-15. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polymer.

  With the expansion of the application range of polymers, functional polymers having various functions such as gas separation are being studied. A diphenylacetylene polymer is known as a functional polymer having gas separation ability (see Patent Document 1).

Japanese Patent Laid-Open No. 5-271338

  However, in the above, the polymer which can satisfy both the capability of selectively permeating oxygen and the capability of suppressing the permeation of carbon dioxide has not been studied.

  Then, an object of this invention is to provide the polymer which is excellent in the capability to permeate | transmit oxygen selectively, and the capability to suppress permeation | transmission of a carbon dioxide.

  The polymer of the present invention contains a repeating unit represented by the following formula (1).

In formula (1), R ¹ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, tri Represents an alkylsilyl group or a trialkylgermyl group, R ² is represented by the following formula (3), m is an integer of 0 or more and 5 or less, and when there are a plurality of R ² , they are the same or different from each other. May be.

  In formula (3), p is an integer of 5 or more and 15 or less.

  By containing the above-mentioned repeating unit, the polymer of the present invention is excellent in the ability to selectively permeate oxygen and the ability to suppress permeation of carbon dioxide, that is, oxygen / carbon dioxide selective permeability.

R ¹ is preferably a phenyl group or a substituted phenyl group represented by the following formula (2).

In Formula (2), R ³ represents an arbitrary monovalent group, n is an integer of 0 or more and 5 or less, and when there are a plurality of R ³ , they may be the same or different from each other.

When R ¹ has such a structure, the oxygen / carbon dioxide selective permeability of the polymer is further improved, and the change with time of the polymer can be suppressed.

R ³ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, a trialkylsilyl group, or A trialkylgermyl group is preferred.

When the R ³ is in such a structure, the oxygen / carbon dioxide permselective polymer further improved, and also allows for suppressing the change with time of the polymer.

R ³ is more preferably a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a trialkylsilyl group, more preferably a hydrogen atom, a fluorine atom, or a trimethylsilyl group, and a trimethylsilyl group. It is particularly preferred. By making R ³ in this way, the oxygen / carbon dioxide selective permeability of the polymer is further improved, the change of the polymer with time can be suppressed, and further, it is easily dissolved in various organic solvents. Therefore, it is excellent also in film forming property.

  According to the present invention, a polymer having excellent oxygen / carbon dioxide selective permeability can be provided.

  Hereinafter, the present invention will be described in detail.

[Polymer]
The polymer of the present invention contains a repeating unit represented by the following formula (1).

In formula (1), R ¹ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, tri Represents an alkylsilyl group or a trialkylgermyl group, R ² is represented by the following formula (3), m is an integer of 0 or more and 5 or less, and when there are a plurality of R ² , they are the same or different from each other. May be. Incidentally, the repeating unit represented by the plurality Included formula (1) in the polymer may be the position of R ¹ and the phenyl group are horizontally reversed to each other. In addition, the repeating units represented by the formula (1) contained in the polymer may be each independently a cis type or a trans type. The cis type and trans type can be identified by Raman spectroscopic measurement of a polymer film.

  In formula (3), p is an integer of 5 or more and 15 or less.

  By containing the above-mentioned repeating unit, the polymer of the present invention is excellent in the ability to selectively permeate oxygen and the ability to suppress permeation of carbon dioxide, that is, oxygen / carbon dioxide selective permeability.

  In the present specification, the aromatic hydrocarbon group means the remaining atomic group excluding one hydrogen atom bonded to the carbon atom constituting the aromatic ring of the aromatic hydrocarbon, and the aromatic heterocyclic group The term “means” refers to the atomic group remaining after removing one hydrogen atom bonded to the carbon atom or heteroatom constituting the aromatic heterocycle of the aromatic heterocyclic compound. In addition, an aromatic heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, boron as an element constituting a ring among organic compounds having an aromatic cyclic structure. A substance containing a heteroatom such as an atom, silicon atom, selenium atom, tellurium atom or arsenic atom.

  From the viewpoint of improving oxygen / carbon dioxide selective permeability and suppressing moisture permeation, m in Formula (1) is preferably 1 or more. From the same viewpoint, p in Formula (3) is preferably 6 or more and 15 or less, and more preferably 8 or more and 15 or less.

Examples of the halogen atom of R ^{1 in} the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable.

Examples of the optionally substituted alkyl group represented by R ^{1 in} the formula (1) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tertiary butyl group, 1- Methylpropyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1-methylpentyl group, 1,1-dimethylpentyl group, 2-methylpentyl group, or hydrogen thereof Those in which a part or all of them are substituted with a halogen atom. Examples of substituted alkyl groups include chloromethyl, chloroethyl, chloropropyl, dichloromethyl, dichloroethyl, trichloromethyl, bromomethyl, bromoethyl, bromopropyl, dibromomethyl, dibromoethyl, mono Fluoromethyl group, monofluoroethyl group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroisobutyl group, perfluoro-1-methylpropyl group, perfluoropentyl group, perfluoro Butyl group, perfluoroisopentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononanyl group, perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group, etc. There are shown as a specific example. Of these, a perfluoro-substituted product is preferable.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ^{1 in} the formula (1) include an unsubstituted aromatic hydrocarbon group, a halogen atom, an alkoxy group, an alkyl group, a trialkylsilyl group, and a trialkylgermyl group. And an aromatic hydrocarbon group substituted with.

The aromatic hydrocarbon group includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded by a single bond or a divalent organic group. The number of carbon atoms of the aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 20. Examples of the aromatic hydrocarbon group include a phenyl _group, C 1 _{-C 12} alkoxyphenyl _group, an alkylphenyl group having C 1 _{-C 12} trialkyl silyl phenyl group, trialkyl germyl phenyl, 1-naphthyl group , 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, pyrenyl group, perylenyl group, pentafluorophenyl group, and among them phenyl _group, alkylphenyl group having C 1 _{-C 12,} A trialkylsilylphenyl group is preferred.

Examples of the optionally substituted aromatic heterocyclic group represented by R ^{1 in} the formula (1) include a monovalent aromatic substituted with a substituent such as an unsubstituted monovalent aromatic heterocyclic group and an alkyl group. Heterocyclic group is mentioned.

The number of carbon atoms of the monovalent aromatic heterocyclic group is usually 4 to 60, preferably 4 to 30, more preferably about 4 to 20, not including the number of carbon atoms of the substituent. . Examples of the monovalent aromatic heterocyclic group, a thienyl _group, alkylthienyl group C 1 _{-C 12,} pyrroyl group, a furyl group, a pyridyl _group, alkylpyridyl group C 1 _{-C 12,} pyridazyl group, pyrimidyl group, A pyrazinyl group etc. are mentioned.

As the trialkylsilyl group of R ^{1 in} the formula (1), a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a dimethyl-isopropylsilyl group, a diethyl-isopropylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, Heptyldimethylsilyl group, octyldimethylsilyl group, octyldiethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, etc. It is done.

Examples of the trialkylgermyl group of R ^{1 in} the formula (1) include trimethylgermyl group, triethylgermyl group, tri-isopropylgermyl group, dimethyl-isopropylgermyl group, diethyl-isopropylgermyl group, pentyldimethylgel. Mill group, hexyl dimethyl gel mill group, heptyl dimethyl gel mill group, octyl dimethyl gel mill group, octyl diethyl gel mill group, 2-ethylhexyl dimethyl gel mill group, nonyl dimethyl gel mill group, decyl dimethyl gel mill group, 3, 7 -Dimethyloctyl-dimethylgermyl group, dodecyldimethylgermyl group and the like.

R ¹ is preferably a phenyl group or a substituted phenyl group represented by the following formula (2).

In Formula (2), R ³ represents an arbitrary monovalent group, n is an integer of 0 or more and 5 or less, and when there are a plurality of R ³ , they may be the same or different from each other.

When the R ¹ is in such a structure, the oxygen / carbon dioxide selective permeability is further improved, and also allows for suppressing the change with time of the polymer.

As an arbitrary monovalent group of R ^{3 in} the formula (2), a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, or an optionally substituted group. An aromatic heterocyclic group, a trialkylsilyl group, or a trialkylgermyl group is preferred.

When R ³ has such a structure, the oxygen / carbon dioxide selective permeability is further improved, and the change with time of the polymer can be suppressed.

Examples of the halogen atom of R ^{3 in} the formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom and a chlorine atom.

Examples of the optionally substituted alkyl group represented by R ^{3 in} the formula (2) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tertiary butyl group, 1- Methylpropyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1-methylpentyl group, 1,1-dimethylpentyl group, 2-methylpentyl group, or hydrogen thereof Those in which a part or all of them are substituted with a halogen atom. Examples of substituted alkyl groups include chloromethyl, chloroethyl, chloropropyl, dichloromethyl, dichloroethyl, trichloromethyl, bromomethyl, bromoethyl, bromopropyl, dibromomethyl, dibromoethyl, mono Fluoromethyl group, monofluoroethyl group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroisobutyl group, perfluoro-1-methylpropyl group, perfluoropentyl group, perfluoro Butyl group, perfluoroisopentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononanyl group, perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group, etc. There are shown as a specific example. Of these, a perfluoro-substituted product is preferable.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ^{3 in} the formula (2) include an unsubstituted aromatic hydrocarbon group, a halogen atom, an alkoxy group, an alkyl group, a trialkylsilyl group, and a trialkylgermyl group. And an aromatic hydrocarbon group substituted with. The aromatic hydrocarbon group includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded by a single bond or a divalent organic group. The number of carbon atoms of the aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 20. Examples of the aromatic hydrocarbon group include a phenyl _group, C 1 _{-C 12} alkoxyphenyl _group, an alkylphenyl group having C 1 _{-C 12} trialkyl silyl phenyl group, trialkyl germyl phenyl, 1-naphthyl group , 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, pyrenyl group, perylenyl group, pentafluorophenyl group, and among them phenyl _group, alkylphenyl group having C 1 _{-C 12,} A trialkylsilylphenyl group is preferred.

Examples of the optionally substituted aromatic heterocyclic group represented by R ^{3 in} the formula (2) include a monovalent aromatic substituted with a substituent such as an unsubstituted monovalent aromatic heterocyclic group and an alkyl group. Heterocyclic group is mentioned. The number of carbon atoms of the monovalent aromatic heterocyclic group is usually 4 to 60, preferably 4 to 30, more preferably about 4 to 20, not including the number of carbon atoms of the substituent. . Examples of the monovalent aromatic heterocyclic group, a thienyl _group, alkylthienyl group C 1 _{-C 12,} pyrroyl group, a furyl group, a pyridyl _group, alkylpyridyl group C 1 _{-C 12,} pyridazyl group, pyrimidyl group, A pyrazinyl group etc. are mentioned.

Specific examples of the trialkylsilyl group of R ^{3 in} the formula (2) include trimethylsilyl group, triethylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, pentyldimethylsilyl group, hexyl. Dimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, octyldiethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl Groups, preferably trimethylsilyl group, triethylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, more preferably trimethylsilyl group. Examples include a ryl group and a triethylsilyl group.

Specific examples of the trialkylgermyl group represented by R ^{3 in} the formula (2) include trimethylgermyl group, triethylgermyl group, tri-isopropylgermyl group, dimethyl-isopropylgermyl group, and diethyl-isopropylgermyl group. Pentyldimethylgermyl group, hexyldimethylgermyl group, heptyldimethylgermyl group, octyldimethylgermyl group, octyldiethylgermyl group, 2-ethylhexyldimethylgermyl group, nonyldimethylgermyl group, decyldimethylgermyl group 3,7-dimethyloctyl-dimethylgermyl group, dodecyldimethylgermyl group and the like, preferably trimethylgermyl group, triethylgermyl group, tri-isopropylgermyl group, dimethyl-isopropylgermyl group, Diethyl-isopropylgerm Group, more preferably a trimethylgermyl group and a triethylgermyl group.

From the viewpoint of oxygen / carbon dioxide permselectivity, the effect of suppressing aging change of the polymer, and film forming property of the polymer, R ³ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a trialkylsilyl. It is preferably a group, more preferably a hydrogen atom, a fluorine atom or a trimethylsilyl group, and even more preferably a trimethylsilyl group.

The polymer of the present invention may contain a repeating unit other than the repeating unit represented by the formula (1). However, from the viewpoint of further enhancing the effect of oxygen / carbon dioxide selective permeability, the polymer of the formula (1) The content of the represented repeating unit is preferably 1% by weight or more, more preferably 10% by weight or more and 100% by weight or less, and more preferably 50% by weight or more and 100% by weight or less with respect to all repeating units. More preferably.
From the viewpoint of oxygen / nitrogen selective permeability, the content of the repeating unit represented by the formula (1) is preferably 20% by weight or more and 60% by weight or less with respect to all the repeating units.

From the viewpoint of film forming property, the weight average molecular weight (M _w ) of the polymer is preferably 1 × 10 ³ or more and 5 × 10 ⁷ or less, and preferably 1 × 10 ⁴ or more and 2 × 10 ⁷ or less. More preferably, it is 1 × 10 ⁵ or more and 1 × 10 ⁷ or less. From the same viewpoint, the number average molecular weight (M _n ) of the polymer is preferably 1 × 10 ³ or more and 2 × 10 ⁷ or less, and preferably 1 × 10 ⁴ or more and 1 × 10 ⁷ or less. More preferably, it is 1 × 10 ⁵ or more and 5 × 10 ⁶ or less. The dispersion ratio (M _w / M _n ) representing the degree of molecular weight distribution of the polymer is preferably 1.0 or more and 10.0 or less, and more preferably 1.1 or more and 8.0 or less. Preferably, it is 1.1 or more and 5.0 or less. In the present invention, the weight average molecular weight (M _w ), number average molecular weight (M _n ) and dispersion ratio (M _w / M _n ) of the polymer are determined in terms of polystyrene by chromatography using tetrahydrofuran as a solvent. As the column, “GPC KF-807L” of KF-800 series manufactured by Shodex may be used.

Furthermore, from the viewpoint of thermal stability, the 5% weight loss temperature (T _d5 ) of the polymer is preferably 380 ° C. or more and 550 ° C. or less, more preferably 390 ° C. or more and 500 ° C. or less, and 400 More preferably, it is at least 490 ° C. Here, the 5% weight reduction temperature of the polymer refers to a value measured by thermogravimetry (as a device, a differential heat / thermogravimetry device, manufactured by Shimadzu Corporation, model: DTG-60 / 60H). The temperature elevation rate during measurement is 10 ° C./min, and the temperature is elevated in a nitrogen atmosphere.

As mentioned above, although the polymer of this invention was demonstrated, since the said polymer has high oxygen / carbon dioxide selective permeability, it can expand | deploy to various uses. For example, it can be used as an oxygen permeable membrane for the following uses. The polymer of the present invention has high oxygen permeability and is suitable for the following uses.
(1) A refining device for producing air or oxygen obtained by removing carbon dioxide from air.
(2) An air intake mechanism for an air cell or a fuel cell that takes in oxygen in the air to generate electric power.

  In addition, these uses are only illustrations and the applicable range of this invention is not limited to these. Further, when used as a film, the film thickness is not particularly limited, but from the viewpoint of suppressing the transmission of carbon dioxide and water vapor and ensuring oxygen permeability, it is preferably 0.1 μm or more and 100 μm or less. Preferably they are 0.1 micrometer or more and 50 micrometers or less.

[Method for producing polymer]
The above-mentioned polymer is, for example, a method of polymerizing a monomer represented by the following formula (A) or a polymer obtained by polymerizing a monomer represented by the following formula (B), if necessary. It can be manufactured by a method of adding ² or the like.

  Polymerization of the monomers represented by the formulas (A) and (B) is performed, for example, by a method of reacting at 40 to 100 ° C. for 2 to 24 hours in the presence of a transition metal catalyst.

The addition of R ^{2 to} the polymer obtained by polymerizing the monomer represented by the following formula (B) is, for example, a mixed solvent of (perfluoroalkyl) phenyliodonium trifluoromethanesulfonate with chloroform / acetonitrile. It is carried out by a method of immersing in.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Example 1]
Tetra-n-butyltin (215 μL, 6.55 × 10 ⁻² mmol) was added to a solution of tantalum pentachloride (143 mg, 0.399 mmol) in toluene (17.1 mL) under a nitrogen atmosphere, and the mixture was stirred at 80 ° C. for 10 minutes. did. Separately prepared toluene solution (4.27 mL) of 4-trimethylsilyldiphenylacetylene (1.07 g, 4.27 mmol) was added to the above toluene solution and stirred at 80 ° C. for 3 hours to obtain product A. Further, chloroform (400 mL) was added to dissolve the product A, and the chloroform solution in which the product A was dissolved was added to 2400 mL of an acetone / chloroform mixed solution (acetone: chloroform = 1: 5 (volume ratio)). The desired polymer was precipitated. The precipitate was collected by filtration and dried under reduced pressure overnight to obtain a reddish brown polymer in a yield of 67.8% (0.725 g). The obtained polymer was soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran (hereinafter sometimes referred to as “THF”).

The ¹ H NMR spectrum of the obtained polymer showed a very broad peak. In addition, it was difficult to observe ¹³ C NMR. The IR spectrum is as shown below. : IR (Film) ν = 3053 (ν _C−H ) cm ⁻¹ , 3016 to 2897 (ν _Ph—H ) cm ⁻¹ , 1596 (ν _C═C ) cm ⁻¹ , 1492 to 1387 (ν _{Ph C = ^{C) cm -1, 1247 (δ}} SiC-H) cm -1, 1117 (ν Si-CH3) cm -1, 854 (1,4-Ph) cm -1, 834 (ν Si-CH3) cm -1 , 689 (ν _Si—Ph ) cm ⁻¹ , 552 (ν _{Ph C—H} ) cm ^−1.

In addition, M _w , M _n , M _w / M _n , and 5% weight loss temperature (T _d5 ) of the obtained polymer were as follows.
M _w = 11.3 × 10 ⁶
M _n = 5.89 × 10 ⁶
_Mw / _Mn = 1.92
T _d5 = 399 ° C.

  A toluene solution was prepared for the obtained polymer (1.0 wt%), cast into a glass petri dish, and the solvent was slowly evaporated at room temperature. After the solvent was evaporated and dried, the film was peeled off to obtain a self-supporting polymer film (polymer film of Example 1). The thickness of the polymer film determined by a micrometer was 69 μm. The main reaction formula of Example 1 is shown below.

[Example 2]
Under a nitrogen atmosphere, tetra-n-butyltin (115 μL, 0.349 mmol) was added to a solution of tantalum pentachloride (62.5 mg, 0.175 mmol) in toluene (5 mL), and the mixture was stirred at 80 ° C. for 10 minutes. A separately prepared toluene solution (3.27 mL) of 4-trimethylsilylphenyl-2,5-difluorophenylacetylene (500 mg, 1.75 mmol) was added to the above toluene solution, and the mixture was stirred at 80 ° C. for 3 hours. Got. Further, chloroform (400 mL) was added to dissolve the product B, and the chloroform solution in which the product B was dissolved was added to 2400 mL of an acetone / chloroform mixture (acetone: chloroform = 1: 5 (volume ratio)). The desired polymer was precipitated. The precipitate was collected by filtration and dried under reduced pressure overnight to obtain a reddish brown polymer in a yield of 75.6% (0.378 g). The obtained polymer was soluble in common organic solvents such as toluene, chloroform and THF.

The ¹ H NMR spectrum of the obtained polymer showed a very broad peak. In addition, it was difficult to observe ¹³ C NMR. The IR spectrum is as shown below. : IR (Film) ν = 3073, 3015 (ring C-H), 2956, 2898 (C-H), 1618, 1590, 1491, 1416 (ring C = C), 1247 (δSiC-H), 1115 (νSi) _{-CH 3), 852,816 (δSi-} CH 3) cm -1

In addition, M _w , M _n , M _w / M _n , and 5% weight loss temperature (T _d5 ) of the obtained polymer were as follows.
M _w = 2.6 × 10 ⁶
M _n = 4.64 × 10 ⁵
M _w / M _n = 5.6
T _d5 = 369 ° C.

  A toluene solution was prepared for the obtained polymer (1.0 wt%), cast into a glass petri dish, and the solvent was slowly evaporated at room temperature. After the solvent was evaporated and dried, the film was peeled off to obtain a self-supporting polymer film.

  The resulting polymer film was subjected to a desilylation reaction. Specifically, the membrane was immersed in a mixed solution of trifluoroacetic acid / hexane (trifluoroacetic acid: hexane = 1: 1 (volume ratio)) for 24 hours, and then triethylamine / hexane (triethylamine: hexane = 1: 1 ( It was immersed in the mixed solution of volume ratio)) for 24 hours. Finally, after immersing in methanol for 24 hours, the membrane was dried at room temperature. A desilylated polymer film (polymer film of Example 2) was obtained as described above. Moreover, the thickness of this film | membrane calculated | required with the micrometer was 43 micrometers. The main reaction formula of Example 2 is shown below.

[Example 3]
The polymer membrane of Example 1 (8.23 mg, 0.0329 mmol) was added to (perfluorodecyl) phenyliodonium trifluoromethanesulfonate (24.3 mg, 0.0329 mmol) and pyridine (2.67 μL, 0) in an air atmosphere. .0329 mmol) was immersed in 0.66 mL of a dichloromethane / acetonitrile mixed solution (dichloromethane: acetonitrile = 3: 2 (volume ratio)) at 80 ° C. for 5 minutes. The membrane was taken out from the above mixed solution, further immersed in methanol for 1 hour, and then dried at room temperature to obtain a polymer membrane of Example 3. Moreover, the thickness of this film | membrane calculated | required with the micrometer was 87 micrometers.

From the IR spectrum, the resulting polymer film was confirmed to have a CF bond-derived peak at 1200 cm ⁻¹ . It was insoluble in common organic solvents. The main reaction formula of Example 3 is shown below.

[Comparative Example 1]
A polydimethylsiloxane film (As One Co., Ltd., trade name: silicon film 6-9085-01) having a thickness of 50 μm was prepared.

[Comparative Example 2]
A polyimide film having a thickness of 45 μm (manufactured by Ube Industries, trade name: Upilex-S (registered trademark)) was prepared.

[Evaluation of polymer membrane (gas permeation test)]
The polymer membranes of Examples 1 to 3 and Comparative Examples 1 and 2 were subjected to gas permeation of oxygen and carbon dioxide at 23 ° C. and a humidity of 60% using a gas permeability measuring device (GTR-30X, manufactured by GTR Tech). Coefficients (P _O2 and P _CO2 , the unit is cm ³ (STP) · cm / cm ² · sec · cmHg) were measured. In addition, α _{O2 / CO2} ( _PO2 / _PC02 ) exhibiting oxygen / carbon dioxide selective permeability was calculated from the measured _PO2 and _PC02 . Table 1 shows the evaluation results of the films of Examples 1 to 3 and Comparative Examples 1 and 2.

  From the above results, it was confirmed that the polymer films of Examples 1 to 3 were excellent in oxygen / carbon dioxide selective permeability as compared with the polymer films of Comparative Examples 1 and 2.

[Example 4]
The polymer membrane of Example 1 (35.5 mg, 0.143 mmol) was added to (perfluorodecyl) phenyliodonium trifluoromethanesulfonate (124 mg, 0.172 mmol) and pyridine (13.6 μL, 0.176 mmol) in an air atmosphere. ) Was added to 16.6 mL of a dichloromethane / acetonitrile mixed solution (dichloromethane: acetonitrile = 3: 2 (volume ratio)) at 80 ° C. for 5 minutes. The membrane was taken out from the above mixed solution, further immersed in methanol for 1 hour, and dried at room temperature to obtain a polymer membrane of Example 4. Moreover, the thickness of this film | membrane calculated | required with the micrometer was 133 micrometers.

From the IR spectrum, the resulting polymer film was confirmed to have a CF bond-derived peak at 1218 cm ⁻¹ . It was insoluble in common organic solvents. Elemental analysis confirmed that perfluorododecyl groups were introduced into 24% of the monomer units in the polymer.

[Example 5]
The polymer membrane of Example 1 (21.1 mg, 0.0843 mmol) was added to (perfluorodecyl) phenyliodonium trifluoromethanesulfonate (73.5 mg, 0.0843 mmol) and pyridine (6.8 μL, 0) under air atmosphere. 0.0843 mmol) was added to 16.6 mL of a dichloromethane / acetonitrile mixed solution (dichloromethane: acetonitrile = 3: 2 (volume ratio)) at 80 ° C. for 5 minutes. The membrane was taken out from the above mixed solution, further immersed in methanol for 1 hour, and dried at room temperature to obtain a polymer membrane of Example 5. Moreover, the thickness of this film | membrane calculated | required with the micrometer was 37 micrometers.

From the IR spectrum, the resulting polymer film was confirmed to have a CF bond-derived peak at 1218 cm ⁻¹ . It was insoluble in common organic solvents. Elemental analysis confirmed that perfluorododecyl groups were introduced into 41% of the monomer units in the polymer.

[Example 6]
The polymer membrane of Example 1 (28.2 mg, 0.133 mmol) was added to (perfluorodecyl) phenyliodonium trifluoromethanesulfonate (491 mg, 0.563 mmol) and pyridine (45.3 μL, 0.563 mmol) in an air atmosphere. ) Was added to 16.6 mL of a dichloromethane / acetonitrile mixed solution (dichloromethane: acetonitrile = 3: 2 (volume ratio)) at 80 ° C. for 5 minutes. The membrane was taken out from the above mixed solution, further immersed in methanol for 1 hour, and dried at room temperature to obtain a polymer membrane of Example 6. Moreover, the thickness of this film | membrane calculated | required with the micrometer was 135 micrometers.

From the IR spectrum, the resulting polymer film was confirmed to have a CF bond-derived peak at 1218 cm ⁻¹ . It was insoluble in common organic solvents. Elemental analysis confirmed that perfluorododecyl groups were introduced into 59% of the monomer units in the polymer.

[Example 7]
The polymer membrane of Example 1 (27.8 mg, 0.111 mmol) was added to (perfluorodecyl) phenyliodonium trifluoromethanesulfonate (484 mg, 0.555 mmol) and pyridine (43.9 μL, 0.555 mmol) in an air atmosphere. ) Was added to 16.6 mL of a dichloromethane / acetonitrile mixed solution (dichloromethane: acetonitrile = 3: 2 (volume ratio)) at 80 ° C. for 5 minutes. The membrane was taken out from the above mixed solution, further immersed in methanol for 1 hour, and dried at room temperature to obtain a polymer membrane of Example 7. Moreover, the thickness of this film | membrane calculated | required with the micrometer was 134 micrometers.

From the IR spectrum, the resulting polymer film was confirmed to have a CF bond-derived peak at 1218 cm ⁻¹ . It was insoluble in common organic solvents. Elemental analysis confirmed that perfluorododecyl groups were introduced into 62% of the monomer units in the polymer.

[Evaluation of polymer membrane (gas permeation test)]
The polymer membranes of Examples 4 to 7 were subjected to oxygen permeability and nitrogen gas permeability coefficients (P _O2 and P _{N2 at} 23 ° C., in units of cm) using a gas permeability measuring device (GTR-30X, manufactured by GTR Tech). ³ (STP) · cm / cm ² · sec · cmHg.). In addition, α _{O2 / N2} ( _PO2 / _PN2 ) indicating oxygen / nitrogen selective permeability was calculated from the measured _PO2 and _PN2 . The evaluation results of the films of Examples 4 to 7 are shown in Table 2.

Claims (6)

The polymer containing the repeating unit represented by following formula (1).

[In the formula (1), R ¹ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, Represents a trialkylsilyl group or a trialkylgermyl group, R ² is represented by the following formula (3), m is an integer of 0 or more and 5 or less, and when there are a plurality of R ² , they are the same or different from each other; It may be. ]

[In Formula (3), p is an integer of 5-15. ] The polymer according to claim 1, wherein R ¹ is a phenyl group or a substituted phenyl group represented by the following formula (2).

[In Formula (2), R ³ represents an arbitrary monovalent group, n is an integer of 0 or more and 5 or less, and when there are a plurality of R ³ , they may be the same as or different from each other. ] R ³ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, a trialkylsilyl group, or The polymer according to claim 2, which is a trialkylgermyl group. The polymer according to claim 2 or 3, wherein R ³ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a trialkylsilyl group. The polymer according to any one of claims 2 to 4, wherein R ³ is a hydrogen atom, a fluorine atom, or a trimethylsilyl group. The polymer according to any one of claims 2 to 5, wherein R ³ is a trimethylsilyl group.