JP5553305B2 - POLYMER AND METHOD FOR PRODUCING POLYMER - Google Patents

Description

  The present invention relates to a polymer and a method for producing the polymer.

  With the expansion of the application range of polymers, functional polymers having various functions such as oxygen permeability are being studied. Patent Document 1 discloses poly [1- (trimethylsilyl) -1-propyne] as a polymer used for the oxygen permeable membrane.

JP-A-1-195678

  By the way, the application range of the oxygen permeable membrane has been expanded, and a new polymer for an oxygen permeable membrane which is not heretofore required is demanded.

  Therefore, an object of the present invention is to provide a novel polymer useful for an oxygen permeable membrane.

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

In formula (1), R ¹ is hydrogen, a branched alkyl group, or a trialkylsilyl group, R ² is represented by the following formula (2), and in formula (2), R ³ is a hydrogen atom, substituted A linear or branched alkyl group having 1 to 12 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is shown.

  The polymer which concerns on this invention can permeate | transmit oxygen by containing the above-mentioned repeating unit. Further, this polymer has higher oxygen permeability than nitrogen permeability, and has oxygen / nitrogen selective permeability.

Here, R ³ is a linear or branched substituted alkyl group having 1 to 12 carbon atoms or a substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, and is a substituted alkyl group or substituted The aromatic hydrocarbon group has one or more substituents, and the substituents are —COOH, —OH, —SH, —NH ₂ , —COH, —F, —Cl, —Br, —I, —COOR ⁴ , It is selected from the group consisting of —OR ⁴ , —SR ⁴ , —N (R ⁴ ) ₂ and —NHR ⁴ (wherein R ⁴ is a linear or branched alkyl group having 1 to 20 carbon atoms). preferable. When two or more substituents are present, these substituents may be the same as or different from each other.

  The substituent is preferably selected from the group consisting of -F, -Cl, -Br or -I.

  More preferably, at least one of the substituents is -F.

The method for producing a polymer of the present invention includes a polymer containing a repeating unit represented by the formula (3), N ₃ -R ³ (wherein R ³ is a hydrogen atom, an optionally substituted straight chain or A branched alkyl group having 1 to 12 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms).

In Formula (3), R ¹ is hydrogen, a branched alkyl group, or a trialkylsilyl group.

  According to the method for producing a polymer according to the present invention, the above novel polymer having oxygen permeability can be obtained.

Here, the polymer containing the repeating unit represented by the formula (3) is in the form of a film, and it is preferable to contact the polymer and N ₃ —R ^{3 in} a solvent in which the polymer is insoluble.

The polymer containing the repeating unit represented by the formula (3) is in the form of a film and has oxygen permeability by contacting the polymer with N ₃ -R ^{3 in} a solvent in which the polymer is insoluble. The polymer film can be easily obtained. Further, the obtained polymer membrane also has oxygen / nitrogen selective permeability.

  According to the present invention, a novel polymer useful as an oxygen permeable membrane can be provided.

It is IR spectrum of the raw material polymer used for the click reaction in Examples 1-4. 2 is an IR spectrum of the polymer obtained in Example 1. 3 is an IR spectrum of the polymer obtained in Example 2. 3 is an IR spectrum of the polymer obtained in Example 3. 4 is an IR spectrum of the polymer obtained in Example 4.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

[Polymer]
The polymer which concerns on this embodiment contains the repeating unit represented by following formula (1).

In formula (1), R ¹ is hydrogen, a branched alkyl group, or a trialkylsilyl group, R ² is represented by the following formula (2), and in formula (2), R ³ is a hydrogen atom, substituted A linear or branched alkyl group having 1 to 12 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms is shown.

In the above polymer, a plurality of repeating units represented by the formula (1) may be reversed in the positions of the phenyl group having R ¹ and the phenyl group having R ² . In addition, the repeating unit represented by the formula (1) contained in the polymer may be 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 the formula (1), examples of the branched alkyl group represented by R ¹ include an isopropyl group, an isobutyl group, and a tert-butyl group. Carbon number becomes like this. Preferably it is 3-12, More preferably, it is 3-6.
Specific examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethyl. Silyl group, octyldimethylsilyl group, octyldiethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, etc. Preferred examples include trimethylsilyl group, triethylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, and diethyl-isopropylsilyl group, and more preferred are trimethylsilyl group, Ethylsilyl group, and the like.

In the formula (2), the linear or branched alkyl group having 1 to 12 carbon atoms that may be substituted for R ³ is a linear or branched unsubstituted alkyl group having 1 to 12 carbon atoms, Alternatively, it means that at least one hydrogen atom bonded to a carbon atom of a linear or branched unsubstituted alkyl group having 1 to 12 carbon atoms is substituted with an atom other than a hydrogen atom or a substituent. Examples of the linear or branched unsubstituted alkyl group having 1 to 12 carbon atoms include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonanyl group, decacil. Group, undecacil group, dodecyl group and the like.

In formula (2), the optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{3 is} an unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms or unsubstituted carbon. The aromatic hydrocarbon group of several 6-10 means that at least one hydrogen atom bonded to the carbon atom constituting the aromatic ring is substituted with an atom other than a hydrogen atom or a substituent.
The aromatic hydrocarbon group means the remaining atomic group excluding one hydrogen atom bonded to the carbon atom constituting the aromatic ring. 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. Examples of the unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl group, alkylphenyl group, alkoxyphenyl group, trialkylsilylphenyl group, trialkylgermylphenyl group, 1-naphthyl group, 2- A naphthyl group, a pentafluorophenyl group, etc. are mentioned. Of these, a phenyl group, an alkylphenyl group, and an alkoxyphenyl group are preferable.

Here, R ³ is a linear or branched alkyl group having 1 to 12 carbon atoms or a substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, and is a substituted alkyl group or a substituted alkyl group. The aromatic hydrocarbon group has one or more substituents, and the substituents are —COOH, —OH, —SH, —NH ₂ , —COH, —F, —Cl, —Br, —I, —COOR ^4. , -OR ⁴ , -SR ⁴ , -N (R ⁴ ) ₂ and -NHR ⁴ (wherein R ⁴ is a linear or branched alkyl group having 1 to 20 carbon atoms). Is preferred. When two or more substituents are present, these substituents may be the same as or different from each other.

  The substituent is preferably selected from the group consisting of -F, -Cl, -Br or -I.

  More preferably, at least one of the substituents is -F. Examples of such a linear or branched substituted alkyl group having 1 to 12 carbon atoms include 2- (perfluorobutyl) ethyl, 2- (perfluoropentyl) ethyl, 2- (perfluorohexyl) ethyl, 2- (perfluoroheptyl) ethyl, 2- (perfluorooctyl) ethyl, 2- (perfluorononanyl) ethyl, 2- (perfluorodecyl) ethyl and the like.

  The polymer according to the present embodiment may contain a repeating unit other than the repeating units represented by the formulas (1) and (2), but from the viewpoint of oxygen permeability, the formula (1) and the formula The content of the repeating unit represented by (2) 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 with respect to all the repeating units. More preferably, it is 100 weight% or less.

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 1 × 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, 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 (a differential heat / thermogravimetry apparatus, 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.

  When the polymer according to this embodiment is used as an oxygen permeable membrane, there is no particular limitation on the shape of the membrane, and an appropriate shape can be obtained depending on the purpose of use and application. Examples of the shape of the oxygen permeable membrane include a plate shape and a hollow fiber fiber shape (tubular shape). The oxygen permeable membrane may be a porous membrane or an asymmetric membrane, but is preferably a homogeneous membrane from the viewpoint of suppressing moisture permeation.

  Although there is no restriction | limiting in particular in the film thickness of an oxygen permeable film, From a viewpoint of ensuring oxygen permeability, it is preferable that they are 0.1 micrometer or more and 100 micrometers or less, and it is more preferable that they are 0.1 micrometer or more and 50 micrometers or less. The film thickness can be measured with a micrometer or the like.

  The polymer which concerns on this embodiment can permeate | transmit oxygen by containing the above-mentioned repeating unit. The polymer has oxygen / nitrogen selective permeability. Therefore, for example, it can be used as various oxygen permeable membranes for oxygen supply. However, the use of the polymer according to the present embodiment is not limited to this. The polymer according to the present embodiment is excellent in ability to selectively permeate carbon dioxide and suppress permeation of nitrogen, and therefore can be used as a film that selectively permeates carbon dioxide.

  Then, the manufacturing method of the polymer which concerns on this embodiment is demonstrated.

[Method for producing polymer]
The method for producing a polymer according to this embodiment includes a polymer containing a repeating unit represented by the following formula (3), and N ₃ -R ³ (where R ³ is the same as R ³ described above). And). In formula (3), R ¹ is the same as R ¹ described above.

<Polymer represented by Formula (3)>
In the polymer, a plurality of repeating units represented by the formula (3) may be reversed in the positions of the phenyl group having R ¹ and the phenyl group having a substituent containing an alkyne at the terminal. . In addition, the repeating unit represented by the formula (3) 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.

  The polymer having an alkyne represented by the formula (3) can be obtained, for example, by the following method.

For example, first, in disubstituted acetylene in which one of the phenyl groups to be substituted is a group in which one of the hydrogen atoms of the phenyl group is substituted with a hydroxyl group, the hydroxyl group is protected with an alkylsiloxy group with an alkylhalosilane or the like, Subsequently, the polymer A is obtained by cleaving the triple bond. Then, by returning the alkylsiloxy group of the polymer A to a hydroxyl group with an acid such as perfluoroacetic acid, one of the phenyl groups to be substituted is a group in which one of the hydrogen atoms of the phenyl group is substituted with a hydroxyl group. A polymer B of disubstituted diphenylacetylene is obtained. By contacting the obtained polymer B with a halide having a propargyl group, a polymer represented by formula (3) having a substituent whose terminal is an alkyne can be obtained.
In the case where the polymer of formula (3) is formed into a film, for example, before the polymer A is converted to the polymer B, the polymer A is dissolved in a solvent in advance to prepare a film-forming coating solution. A film-like polymer A may be obtained by applying a coating solution on a substrate and evaporating the solvent. As the solvent used for the preparation of the film-forming coating solution, a solvent having the ability to dissolve the polymer A is preferable. Examples of such a solvent include organic solvents such as toluene, anisole, chlorobenzene, dichlorobenzene, chloroform, and tetrahydrofuran.

<N ₃ -R ³ >
The azide compound represented by N ₃ —R ³ can also be obtained, for example, by the following method.

That is, the NaN _3, by reacting a iodide or bromide with the desired R ₃ group, can generate an azide compound with the desired R ₃ groups.

When the polymer represented by the formula (3) is brought into contact with the azide compound represented by N ₃ —R ³ , an alkyne at the terminal of the substituent of the polymer represented by the formula (3), N ₃ A polymer represented by formula (1) and formula (2) by forming a 1,2,3-triazole group as represented by formula (4) with an azide compound represented by —R ³ Can be obtained. That is, the reaction represented by the following formula (4) is a so-called click reaction. Specifically, the polymer of the formula (3) may be immersed in a solvent in which N ₃ —R ³ is dissolved. Note that since the reaction rate of this reaction increases in the presence of copper ions, CuI, CuBr, CuBr ₂ , CuSO ₄ , CuCl ₂ , CuCl, or the like can be used as a catalyst.

In order to obtain a polymer represented by the formula (1) and the formula (2) having a desired combination of R ¹ and R ³ , a polymer represented by the formula (3) as a raw material, N ₃ -R ³ A combination with the azide compound represented by the above may be selected as appropriate.

Here, the polymer containing the repeating unit represented by the formula (3) is preferably in the form of a film, and the polymer and N ₃ —R ³ are contacted in a solvent in which the polymer is insoluble.

The polymer represented by the formula (3) is formed into a film in advance, and the film-shaped polymer and N ₃ -R ³ are brought into contact in a solvent in which the polymer represented by the formula (3) is insoluble. Thus, a polymer film having oxygen permeability represented by the formulas (1) and (2) can be easily obtained. In addition, when the polymer represented by Formula (1) and Formula (2) finally obtained is difficult to dissolve in a solvent, the effect of easily obtaining a polymer film is high.

Examples of the solvent in which the polymer represented by the formula (3) and the polymers represented by the formulas (1) and (2) are insoluble include dimethylformamide (hereinafter sometimes referred to as “DMF”), Examples thereof include a mixed solution of DMF and H ₂ O (volume ratio 1: 1), tetrahydrofuran (hereinafter sometimes referred to as “THF”), tert-butyl alcohol, ethanol, methanol, acetonitrile, and a mixed solution thereof. However, the azide compound is preferably dissolved in this solvent.

  In the reaction of formula (4), from the viewpoint of reactivity with the polymer of formula (3), the content of the azide compound contained in the solvent is preferably 0.1 to 0.5 mol / L.

  The atmosphere to be reacted is preferably an inert atmosphere such as nitrogen. Moreover, it is preferable to hold | maintain at 20-100 degreeC for 4 to 24 hours, and to advance reaction, stirring.

  After the reaction, if necessary, the polymer or polymer film is washed by immersing it in a liquid of the same type as the solvent used in the reaction such as DMF for 1 to 12 hours, and further immersing in ethanol for 1 to 12 hours. Then, the polymer or polymer film of the formula (1) and the formula (2) can be obtained by drying.

  EXAMPLES Hereinafter, an Example is shown and this invention is demonstrated concretely.

[Synthesis of Raw Material Monomer A (1-Phenyl-2- (3-hydroxy) phenylacetylene)]
Three-necked flask 300ml wearing a Dimroth and three-way cock, 22.0 g (100 mmol) of 3-iodophenol, Pd and _{(PPh 3) 2 Cl 2 0.70g} (1.0mmol), the PPh ₃ 1. 05 g (4.0 mmol) and 1.14 g (6.0 mmol) of CuI were weighed, and the inside of the three-necked flask was replaced with nitrogen. To this, 21 ml (150 mmol) of dried Et ₃ N, 60 ml of dried THF, and 11.0 ml (100 mmol) of phenylacetylene were added with a syringe from a rubber septum to obtain a mixed solution. The mixture was stirred with a stirrer. After stirring for 3 hours while heating at 80 ° C., the mixture was allowed to cool to room temperature, and the organic layer was extracted with Et ₂ O. After the obtained organic layer was dried under reduced pressure, silica gel column chromatography (developing solvent, hexane: ethyl acetate = 4: 1 (volume ratio), Rf = 0.45) was performed to isolate the raw material monomer A. The yield was 16.4 g, and the yield was 84.4%. The reaction formula obtained for the raw material monomer A is shown in the following formula (5).
The result of 1H-NMR of the obtained raw material monomer A was as follows.
1H-NMR (270 MHz, CDCl ₃ );
(Δ / ppm): 4.74 (—OH, 1H), 7.28 (Ar—H, 5H), 7.53 (Ar—H, 4H)

[Synthesis of Raw Material Monomer B (1-phenyl-2- (3-tertbutyldimethylsiloxy) phenylacetylene)]
To a 300 ml three-necked flask equipped with a Dimroth and a three-way cock, 8.50 g (43.8 mmol) of raw material monomer A (1-phenyl-2- (3-hydroxy) phenylacetylene), chloro-tert-butyldimethylsilyl 8 .57 g (56.9 mmol) was weighed, and the inside of the three-necked flask was replaced with nitrogen. To this, 18.2 ml of dried Et ₃ N and 76 ml of dried THF were added with a syringe from a rubber septum to obtain a mixed solution. The mixture was stirred with a stirrer. After stirring with heating at 80 ° C. overnight, the mixture was allowed to cool to room temperature, and the organic layer was extracted with Et ₂ O. After the obtained organic layer was dried under reduced pressure, silica gel column chromatography (developing solvent, hexane, Rf = 0.20) was performed to isolate the raw material monomer B. The yield was 10.4 g, and the yield was 81.3%. The reaction formula for obtaining the raw material monomer B is shown in the following formula (6).
The results of 1H-NMR and ¹³ C-NMR of the obtained raw material monomer B were as follows.
¹ H-NMR (270 MHz, CDCl ₃ );
(Δ / ppm): 4.74 (—OH, 1H), 7.28 (Ar—H, 5H), 7.53 (Ar—H, 4H)
¹³ C-NMR (270 MHz, CDCl ₃ )
(Δ / ppm): 155.33, 131.50, 129.29, 128.22, 128.14, 124.77, 124.17, 123.14, 122.98, 120.48, 89.20, 89.10, 77.47, 76.53, 25.85, 25.78, 25.69, 25.62, 18.27

[Synthesis of raw material polymer A]
A 200 ml three-necked flask was fitted with a three-way cock, and the inside of the flask was replaced with nitrogen. To this, 9.6 ml of a toluene solution containing 60.9 ml of toluene and 512 mg (1.43 mmol) of TaCl ₅ and 939 μl of n-Bu ₄ Sn (2.86 mmol) were added with a syringe from a rubber septum to obtain a mixed solution A1. It was. The mixture was stirred with a stirrer while heating at 80 ° C. for 15 minutes. Thereafter, 10.0 ml of a toluene solution containing 6.62 g (21.45 mmol) of the raw material monomer B: 1-phenyl-2- (3-tertbutyldimethylsiloxy) phenylacetylene is added to the mixture A1, and the mixture A2 is added. Obtained. When this mixed liquid A2 was stirred while heating at 80 ° C. for 12 hours, a polymer (raw polymer A) was obtained. The mixed solution A2 after heating and stirring is placed in a 2 L three-necked flask containing 1.0 L of chloroform, stirred at room temperature until the polymer is completely dissolved in the solution visually, and this is dropped into a large amount of methanol. The polymer was precipitated with The precipitated polymer was suction filtered using filter paper, and vacuum-dried in a desiccator for 1 day.
The shape of the raw material polymer A after drying was a yellow solid, the yield was 4.72 g, and the yield was 71.3%.
The reaction formula obtained for the raw material polymer A is shown in the following formula (7).
The results of IR spectrum of the obtained raw material polymer A were as follows.
IR (cm ⁻¹ ) [KBr pellet];
2955 (—C—H), 1475 (—C—H), 1420 (—C—H), 1361 (—Si—CH ₃ ), 1254 (—O—Si), 966 (—O—Si), 834 (-C-H)

[Synthesis of Raw Material Polymer B: Desilylation Reaction of Raw Material Polymer A]
A toluene solution was prepared for the obtained raw material polymer A (1.0 wt%), cast into a glass petri dish, and slowly evaporated at room temperature. After the solvent was evaporated and dried, a film was formed by peeling off the film.
In a 300 ml beaker, 100 ml of CF ₃ COOH and 25 ml of H ₂ O were put, and the raw material polymer A: poly [1-phenyl-2- (3-tertbutyldimethylsiloxy) phenylacetylene] formed therein was added thereto. 39.1 mg was added and stirred at room temperature for 24 hours. The membrane was collected with tweezers and immersed in a saturated aqueous sodium bicarbonate solution for 24 hours. The membrane was again collected with tweezers, immersed in a methanol solution for 12 hours, and dried at room temperature in a desiccator for 12 hours. The yield of the polymer after desilylation was 24.5 mg, and the yield was 100%.
The desilylation reaction of the raw material polymer A is shown in the following formula (8).
The results of IR spectrum of the obtained film-form raw material polymer B: poly [1-phenyl-2- (3-hydroxy) phenylacetylene] were as follows.
IR (cm ⁻¹ ) [KBr pellet];
3385 (-OH)

[Synthesis of Raw Material Polymer C (Raw Polymer for Click Reaction)]
In a 50 ml three-necked flask equipped with a three-way cock, 1.60 g (12.0 mmol) of 18-crown-6-ether and 1.55 g (12.0 mmol) of K ₂ CO ₃ were weighed, and the flask was filled with nitrogen. Replaced. To this was added 23.0 ml of dried DMF with a syringe from a rubber septum to obtain a mixed solution B1. The mixture was stirred with a stirrer. Further, the stopper of the three-necked flask was removed while circulating nitrogen, and the raw material polymer B: poly [1-phenyl-2- (3-hydroxy) phenylacetylene] film 23.6 mg (0.12 mmol), 3-bromopropyne 924 μl (12.0 mmol) was added to give mixture B2. The mixture B2 was stirred while heating at 250 ° C. for 24 hours, and then allowed to cool to room temperature, and the membrane was collected with tweezers. The film formed from the obtained polymer (raw material polymer C) was immersed in a methanol solution for 12 hours and dried at room temperature in a desiccator for 12 hours.
The yield of the raw material polymer C (polymer used as the raw material for the click reaction) was 27.8 g, and the yield was 90.8%.
The reaction formula for obtaining the raw material polymer C is shown in the following formula (9).
The result of IR spectrum of the obtained polymer C was as follows. The IR spectrum is shown in FIG.
IR (cm ⁻¹ ) [KBr pellet];
32968 (—C≡C—H), 2955 (—C—H), 2120 (—C≡C—H), 1482 (—C—H), 1373 (—C≡C—H), 1245 (Ar— O—CH ₂ ), 638 (—C≡CH)

[Synthesis of azide compounds]
(1) Synthesis of 1-azidooctane In a 100 ml two-necked flask equipped with a three-way cock, 3.3 g (46.6 mmol) of NaN ₃ was weighed, and the inside of the flask was replaced with nitrogen. To this, 30.1 ml of dried DMF and 3.0 g (15.5 mmol) of 1-iodooctane were added with a syringe from a rubber septum, and the mixture was stirred with a stirrer. After stirring at room temperature for 24 hours, the organic layer was extracted with Et ₂ O. After the obtained organic layer was dried under reduced pressure, silica gel column chromatography (developing solvent, hexane, Rf = 0.80) was performed to isolate 1-azidooctane.
The yield of 1-azidooctane was 2.16 g, and the yield was 89.8%. The reaction formula for obtaining 1-azidooctane is shown in the following formula (10).
Further, 1H-NMR and IR results of the obtained compound were as follows.
¹ H-NMR (270 MHz, CDCl ₃ );
(δ / ppm): 4.74 (—OH, 1H), 7.28 (Ar—H, 5H), 7.53 (Ar—H, 4H)
IR (cm ⁻¹ ) [KBr pellet];
2955 (-C-H), 1128 (-N 3)

(2) Synthesis of 2- (perfluorohexyl) ethyl azide 1.43 g (22.0 mmol) of NaN ₃ was weighed into a 100 ml three-necked flask equipped with a three-way cock, and the inside of the flask was replaced with nitrogen. To this were added 14.0 ml of dried DMF and 3.48 g (7.34 mmol) of 2- (perfluorohexyl) ethyl iodide with a syringe from a rubber septum, and the mixture was stirred with a stirrer. After stirring at room temperature for 24 hours, the organic layer was extracted with Et ₂ O. After the obtained organic layer was dried under reduced pressure, silica gel column chromatography (developing solvent, ethyl acetate) was performed to isolate 2- (perfluorohexyl) ethyl azide.
The yield of 2- (perfluorohexyl) ethyl azide was 2.47 g, and the yield was 86.3%. The reaction formula obtained for 2- (perfluorohexyl) ethyl azide is shown in the following formula (10).
Further, 1H-NMR and IR results of the obtained compound were as follows.
¹ H-NMR (270 MHz, CDCl ₃ );
(Δ / ppm): 2.42 (m, —CH ₂ —, 2H), 3.60 (m, —CH ₂ —, 2H) IR (cm ⁻¹ ) [KBr pellet];
_{2955 (-C-H), 1128} (-N 3), 1208 (-Cf 2)

（３）２−（パーフルオロオクチル)エチルアジドの合成
三方コックをつけた１００ｍｌ三口フラスコに、ＮａＮ_３を１．４６ｇ（２０．９ｍｍｏｌ）秤取り、フラスコ内を窒素で置換した。これにラバーセプタムよりシリンジで、２−（パーフルオロオクチル)エチルヨージド４．００ｇ（６．９７ｍｍｏｌ）を含む乾燥させたＤＭＦ１４．０ｍｌを加え、スターラーにより撹拌した。室温で２４時間撹拌後、Ｅｔ_２Ｏを用いて有機層の抽出を行った。得られた有機層を減圧乾燥した後に、シリカゲルカラムクロマトグラフィー(展開溶媒 : 酢酸エチル)を行い単離した。
２−（パーフルオロオクチル)エチルアジドの収量は、２．８９ｇであり、収率は、８４．９％であった。２−（パーフルオロオクチル)エチルアジドの得られる反応式を下記式（１２）に示す。
また、得られた化合物の１Ｈ−ＮＭＲ及びＩＲの結果は以下の通りであった。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ， ＣＤＣｌ₃)；
(δ／ｐｐｍ)：２．４２（ｍ，−ＣＨ_２−，２Ｈ），３．６０（ｍ，−ＣＨ_２−，２Ｈ）ＩＲ（ｃｍ^−１）［ＫＢｒペレット］
２９５５（−Ｃ−Ｈ），１１２８（−Ｎ_３），１２０８（−ＣＦ_２）

(3) Synthesis of 2- (perfluorooctyl) ethyl azide 1.46 g (20.9 mmol) of NaN ₃ was weighed into a 100 ml three-necked flask equipped with a three-way cock, and the inside of the flask was replaced with nitrogen. To this, 14.0 ml of dried DMF containing 4.00 g (6.97 mmol) of 2- (perfluorooctyl) ethyl iodide was added with a syringe from a rubber septum, and the mixture was stirred with a stirrer. After stirring at room temperature for 24 hours, the organic layer was extracted with Et ₂ O. The obtained organic layer was dried under reduced pressure and then isolated by silica gel column chromatography (developing solvent: ethyl acetate).
The yield of 2- (perfluorooctyl) ethyl azide was 2.89 g, and the yield was 84.9%. The reaction formula for obtaining 2- (perfluorooctyl) ethyl azide is shown in the following formula (12).
Further, 1H-NMR and IR results of the obtained compound were as follows.
¹ H-NMR (270 MHz, CDCl ₃ );
(δ / ppm): 2.42 (m, —CH ₂ —, 2H), 3.60 (m, —CH ₂ —, 2H) IR (cm ⁻¹ ) [KBr pellet]
_{2955 (-C-H), 1128} (-N 3), 1208 (-CF 2)

(4) Synthesis of 2- (perfluorodecyl) ethyl azide In a 100 ml three-necked flask equipped with a three-way cock, 2.89 g (44.4 mmol) of NaN ₃ and 10.0 g (14.8 mmol) of 2- (perfluorodecyl) ethyl iodide Were weighed, and the inside of the flask was replaced with nitrogen. To this was added 28.8 ml of dried DMF solution with a syringe from a rubber septum, and the mixture was stirred with a stirrer at 60 ° C. After stirring at 60 ° C. for 24 hours, the organic layer was extracted with Et ₂ O. After the obtained organic layer was dried under reduced pressure, silica gel column chromatography (developing solvent: ethyl acetate) was performed to isolate 2- (perfluorodecyl) ethyl azide.
The yield of 2- (perfluorodecyl) ethyl azide was 7.37 g, and the yield was 84.5%. The reaction formula for obtaining 2- (perfluorodecyl) ethyl azide is shown in the following formula (13).
Further, 1H-NMR and IR results of the obtained compound were as follows.
¹ H-NMR (270 MHz, CDCl ₃ );
(δ / ppm): 2.42 (m, —CH ₂ —, 2H), 3.60 (m, —CH ₂ —, 2H) IR (cm ⁻¹ ) [KBr pellet]
_{2955 (-C-H), 1128} (-N 3), 1208 (-CF 2)

Example 1
In a 50 ml three-necked flask equipped with a three-way cock, 1.26 g (6.6 mmol) of CuI and 3.01 g (155.2 mmol) of sodium L-ascorbate were weighed, and the inside of the flask was replaced with nitrogen. To this, 9.0 ml of dried DMF and 9.0 ml of distilled water were added with a syringe from a rubber septum, and stirred with a stirrer at 60 ° C. Further, while the nitrogen was circulated, the three-necked flask was unsealed, and the raw polymer C (poly [1-phenyl-2- (3-oxypropyne) phenylacetylene]) film 25.6 mg (0.11 mmol) and 1 -512 mg (3.3 mmol) of azidooctane was added. After the above compounds were mixed, the raw material polymer C did not dissolve and remained in a film form. The mixture was stirred at 60 ° C. for 12 hours, and the click reaction represented by the following formula (14) was advanced to obtain the polymer of Example 1. Then, it stood to cool to room temperature, and the film | membrane formed from the polymer of Example 1 was collect | recovered with tweezers. The obtained membrane (thickness 54 μm) was immersed in DMF for 6 hours, and the membrane was collected again with tweezers and immersed in methanol for 6 hours. Then, room temperature drying was performed in a desiccator for 12 hours. The yield of the obtained polymer was 35.8 mg, and the click reaction rate calculated from the nitrogen atom content obtained by elemental analysis was 82%. The results of IR spectrum of the polymer of Example 1 were as follows. The IR spectrum is shown in FIG.
IR (cm ⁻¹ ) [KBr pellet];
2955 (-C-H), 1475 (-C-H), 1420 (-C-H), 834 (-C-H)

(Example 2)
In a 50 ml three-necked flask equipped with a three-way cock, 1.26 mg (6.6 mmol) of CuI and 2.37 g (15.2 mmol) of 2,2′-bipyridine were weighed, and the inside of the flask was replaced with nitrogen. To this was added 18.0 ml of dried DMF with a syringe from a rubber septum, and the mixture was stirred at 60 ° C. with a stirrer. Further, while the nitrogen was circulated, the three-neck flask was unsealed, and the raw material polymer C: poly [1-phenyl-2- (3-oxypropyne) phenylacetylene] film 25.4 mg (0.11 mmol) and 2- 1.28 g (3.3 mmol) of (perfluorohexyl) ethyl azide was added. After the above compounds were mixed, the raw material polymer C did not dissolve and remained in a film form. The mixture was stirred at 60 ° C. for 12 hours, and the click reaction represented by the following formula (15) was advanced to obtain the polymer of Example 2. Thereafter, the film was allowed to cool to room temperature, and the film formed from the polymer of Example 2 was collected with tweezers. The obtained membrane (thickness 84 μm) was immersed in DMF for 6 hours, the membrane was again collected with tweezers, and immersed in methanol for 6 hours. Then, room temperature drying was performed in a desiccator for 12 hours.
The yield of the obtained polymer was 56.6 mg, and the click reaction rate calculated from the fluorine atom content obtained by elemental analysis was 90%. The results of IR spectrum of the polymer of Example 2 were as follows. The IR spectrum is shown in FIG.
IR (cm ⁻¹ ) [KBr pellet];
2955 (-C-H), 1475 (-C-H), 1420 (-C-H), 1208 (-CF 2), 834 (-C-H)

(Example 3)
In a 50 ml three-necked flask equipped with a three-way cock, 1.26 mg (6.6 mmol) of CuI and 2.37 g (15.2 mmol) of 2,2′-bipyridine were weighed, and the inside of the flask was replaced with nitrogen. To this was added 18.0 ml of dried DMF with a syringe from a rubber septum, and the mixture was stirred with a stirrer at 60 ° C. Further, while the nitrogen was circulated, the three-necked flask was unsealed, and the raw material polymer C: poly [1-phenyl-2- (3-oxypropyne) phenylacetylene] film 25.5 mg (0.11 mmol) and 2- 1.61 g (3.3 mmol) of (perfluorooctyl) ethyl azide was added. After the above compounds were mixed, the raw material polymer C did not dissolve and remained in a film form. The mixture was stirred at 60 ° C. for 12 hours, and the click reaction represented by the following formula (16) was advanced to obtain the polymer of Example 3. Then, it stood to cool to room temperature, and the film | membrane formed from the polymer of Example 3 was collect | recovered with tweezers. The obtained film (thickness 99 μm) was immersed in DMF for 6 hours, and the film was collected again with tweezers and immersed in methanol for 6 hours. Then, room temperature drying was performed in a desiccator for 12 hours.
The yield of the obtained polymer was 70.6 mg, and the click reaction rate calculated from the fluorine atom content obtained by elemental analysis was 96%. The results of IR spectrum of the polymer of Example 3 were as follows. The IR spectrum is shown in FIG.
IR (cm ⁻¹ ) [KBr pellet];
2955 (-C-H), 1475 (-C-H), 1420 (-C-H), 1208 (-CF 2), 834 (-C-H)

Example 4
In a 50 ml three-necked flask equipped with a three-way cock, 1.26 mg (6.6 mmol) of CuI and 2.37 g (15.2 mmol) of 2,2′-bipyridine were weighed, and the inside of the flask was replaced with nitrogen. To this was added 18.0 ml of dried DMF with a syringe from a rubber septum, and the mixture was stirred with a stirrer at 60 ° C. Further, while the nitrogen was circulated, the three-necked flask was unsealed, and the raw material polymer C: poly [1-phenyl-2- (3-oxypropyne) phenylacetylene] film 25.4 mg (0.11 mmol) and 2- 1.94 g (3.3 mmol) of (perfluorodecyl) ethyl azide was added. After the above compounds were mixed, the raw material polymer C did not dissolve and remained in a film form. The mixture was stirred at 60 ° C. for 12 hours, and the click reaction represented by the following formula (17) was advanced to obtain the polymer of Example 4. Then, it stood to cool to room temperature, and the film | membrane formed from the polymer of Example 4 was collect | recovered with tweezers. The obtained membrane (thickness 127 μm) was immersed in DMF for 6 hours, and the membrane was collected again with tweezers and immersed in methanol for 6 hours. Then, room temperature drying was performed in a desiccator for 12 hours.
The yield of the obtained polymer was 78.1 mg, and the click reaction rate calculated from the fluorine atom content obtained by elemental analysis was 96%. The results of IR spectrum of the polymer of Example 4 were as follows. The IR spectrum is shown in FIG.
IR (cm ⁻¹ ) [KBr pellet];
2955 (-C-H), 1475 (-C-H), 1420 (-C-H), 1208 (-CF 2), 834 (-C-H)

[Evaluation of polymer membrane (gas permeation test)]
Each of the membranes obtained in Examples 1 to 4 was subjected to a gas permeability coefficient (P) of oxygen, nitrogen, and carbon dioxide at 23 ° C. and a humidity of 60% using a gas permeability measuring device (GTR Tech, TR-30X). _{O 2,} P _{N 2,} and P _{CO 2} , the unit being cm ³ (STP) · cm / cm ² · sec · cmHg) were measured. The results of the oxygen permeation test are shown in Table 1, and the results of the nitrogen and carbon dioxide permeation test are shown in Table 2.
From Table 1, it can be seen that the polymer of the present invention is useful for an oxygen permeable membrane.

Further, from the measured P _O2 , P _N2 , and P _CO2 , α _{O2 / N2} (P _O2 / P _N2 ) showing oxygen / nitrogen selective permeability and α _{CO2 / N2} showing carbon dioxide / nitrogen selective permeability ( _PC02 / _PN2 ) was calculated. Table 3 shows the evaluation results of the films of Examples 1 to 4.

From the above results, the membranes of Examples 1 to 4 were found to have oxygen / nitrogen selective permeability and carbon dioxide / nitrogen selective permeability.

Claims (6)

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

[In Formula (1), R ¹ is hydrogen, a branched alkyl group, or a trialkylsilyl group, R ² is represented by the following Formula (2), and in Formula (2), R ³ is a hydrogen atom, substituted Or a linear or branched alkyl group having 1 to 12 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. ]

R ³ is a linear or branched substituted alkyl group having 1 to 12 carbon atoms or a substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, and the substituted alkyl group or substituted aromatic hydrocarbon group is Having one or more substituents, the substituents being —COOH, —OH, —SH, —NH ₂ , —COH, —F, —Cl, —Br, —I, —COOR ⁴ , —OR ⁴ , — Selected from the group consisting of SR ⁴ , —N (R ⁴ ) ₂ and —NHR ⁴ (wherein R ⁴ is a linear or branched alkyl group having 1 to 20 carbon atoms), and two or more substituents are The polymer according to claim 1, wherein when present, the substituents may be the same or different from each other.   The polymer according to claim 2, wherein the substituent is selected from the group consisting of -F, -Cl, -Br or -I.   The polymer according to claim 3, wherein at least one of the substituents is -F. A polymer containing a repeating unit represented by the following formula (3);
N ₃ —R ³ (where R ³ is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms, or an optionally substituted aromatic group having 6 to 10 carbon atoms) A method for producing a polymer, comprising a step of contacting a hydrocarbon group.

[In the formula ( 3 ), R ¹ represents hydrogen, a branched alkyl group, or a trialkylsilyl group. ]
The polymer containing the repeating unit represented by the formula (3) is in a film form, and the polymer and N ₃ -R ³ are contacted in a solvent in which the polymer is insoluble. A method for producing the polymer.

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