JP5798979B2 - Functional network polymer composition - Google Patents

Description

The present invention relates to a network polymer having an electron donor acceptor structure that is generated by a covalent bond at the same time as the reaction, using a technique obtained by further developing the click chemistry reaction that has been studied in the field of chemical synthesis in the field of polymer synthesis in recent years. It relates to synthesis.
Specifically, a method for synthesizing a network polymer by reaction between polymers, a network polymer obtained by the method, a thin film using the network polymer and a method for producing the thin film, and a donor acceptor structure such as an organic semiconductor or an organic conductor The present invention relates to a technology for imparting optoelectronic functionality based on the above.

  Further, the present invention relates to the application of the network polymer to a chemical sensor based on the optoelectronic function of the network polymer and its thin film in the sensor material field, and further to the application to an antibacterial composition in the antibacterial / sterilizing material field.

In the field of organic conductors and organic semiconductors, attention has been paid to alternating laminated films that are separated from conventional electrostatic interactions and supramolecular weak intermolecular forces and use strong coupling by covalent bonds. The click chemistry reaction represented by the cycloaddition reaction of alkyne and azide in the presence of a copper catalyst is highly efficient, easy to purify, highly selective, and produces no by-products. Used in a wide range of fields, including chemistry, synthesis of bioactive compounds, functionalization of proteins and polynucleotides, synthesis of dyes, enhanced functionality of polymers, synthesis of new polymers, creation of stimulus response materials, covalent bonding However, there is a problem that the 1,4-triazole ring itself, which is a cycloaddition reaction product of alkyne and azide, does not have the required functionality.
Furthermore, the polymer thin film using electrostatic interaction has a problem that it easily decomposes in a strong acid or a strong base.
In recent years, however, click chemistry reactions defined as quantitative addition reactions that proceed under mild conditions can be used to form network polymers and their thin films by covalent bonds, especially in the case of non-hydrolyzed bonds. It has been found that chemical stability can be maintained.

For example, Caruso (Melbourne University, Australia) et al. Have an alternating laminated film characterized by the formation of 1,4-triazole ring by cycloaddition reaction of alkyne and azide, which are representative of click chemistry, in the side chain of each polymer. For the first time (Non-Patent Document 1). Unfortunately, the 1,4-triazole ring itself does not have the desired function. Recently, many functional thin films using click chemistry reaction such as addition of thiol and alkene and Diels-Alder reaction have been reported, which has become a major trend (Non-Patent Documents 2 to 10, Patent Documents). 13, 14).
The thin film produced by such a method has a chemically stable and higher mechanical strength than the conventional alternating laminated film integrated by electrostatic interaction or supramolecular interaction. However, in order to impart functionality to these laminated films, it is necessary to incorporate in advance a reactive functional group of a click chemistry reaction and a functional functional group or site in the polymer. For this reason, molecular design of multi-stage reaction is required, and it is difficult to synthesize, and the yield is reduced due to multi-stage reaction, resulting in high efficiency, easy purification, high selectivity, and by-products. The current situation is that the advantage of the click chemistry reaction is not fully utilized.

On the other hand, in other fields, in order to prevent the decay of raw materials and products in the lifestyle field of clothing, food and housing, including transportation, or to prevent the growth of fungi in the living environment, and in the medical and nursing field, there are various ways to prevent various disease infections. Antibacterial and bactericidal agents are used.
It is desired that these have excellent antibacterial activity against various harmful microorganisms and exhibit an effect in a minute amount. In recent years, bactericides, antibacterial agents, preservatives and the like using silver ions have been developed and are widely used in daily necessities. It has been well known that silver ions, copper ions, zinc ions and the like have antibacterial properties, and they are widely used in various fields as disinfectants or disinfectants in various forms including aqueous solutions.

  For example, studies have been made to support silver ions on a support. Specifically, zeolite (Patent Documents 1 to 5), amorphous aluminosilicate (Patent Documents 6 to 7), titanium, magnesium, aluminum, etc. A material in which an antibacterial metal ion such as silver is supported on an inorganic powder such as a metal oxide (Patent Document 8) has been developed.

  However, since the antibacterial activity is derived from a metal ion such as silver, even if the ion disappears during use, there is no means for clearly indicating that the antibacterial activity has been deactivated. Since it cannot be judged from the outside, it was necessary to replace everything regularly regardless of the remaining antibacterial performance. However, in some information recording fields, there is an example (Patent Document 9) that proposes a method for making it possible to confirm that the antibacterial layer is worn out and the antibacterial action is being lost, and to attract the user's attention. In the case of reuse, it is necessary to collect and recoat, which is not realistic considering the labor and collection cost. Furthermore, a new method for producing light-stabilized silver-containing hydrophilic, amphoteric and anionic polymers has been disclosed (Patent Document 10). In addition, an aqueous (particularly neutral to alkaline) antibacterial composition comprising a combination of a silver-containing copolymer, an organic antibacterial agent, hydrogen peroxide, and sodium hypochlorite has been proposed (Patent Document 11). However, since these are mainly targeted for water-soluble or water-swellable gels, they are not resistant to water, other organic solvents, acids and alkalis. It is not suitable for the purposes of the present invention.

  Moreover, a quaternary ammonium salt is mentioned as an antimicrobial compound which does not depend on a metal ion. Among quaternary ammonium compounds, those containing long-chain alkyl groups are also called reverse soaps and are used for antibacterial agents and disinfectants. Examples include benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, cetrimonium, dophanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, domifene bromide and the like. They also act against fungi, amoeba and enveloped viruses by disrupting the cell membrane. Bactericidal and antibacterial effects can be exhibited by having quaternary ammonium as a functional group, and it has also been proposed to impart antibacterial properties by introducing a quaternary ammonium group into the side chain of a polymer (patent) Reference 12). However, in this case, since the amount of quaternary ammonium groups is determined in advance by the amount of monomers to be charged, it is difficult to adjust the amount of quaternary ammonium groups to the required amount suitable for the use conditions and environment after coating or at the time of use. It is necessary to adjust the polymer according to the use conditions and the environment.

JP 60-100504 A JP 60-181002 A JP-A 63-79719 JP-A-63-239205 JP 63-265809 A JP 63-23960 A JP 63-2222058 JP 63-88109 A Japanese Patent Laid-Open No. 10-44651 Special table 2004-514505 gazette JP 2008-120812 A JP 2011-511103 A JP 2011-094066 A JP 2009-270011 A

Alternating layers by covalent bond:
GK Such, JF Quinn, A. Quinn, E. Tjipto, F. Caruso, J. Am. Chem. Soc., 128, 9318, 2006. X. Zhang, H. Chen, H. Zhang, Chem. Commun., 1395, 2007 JF Quinn, APR Johnston, GK Such, AN Zelikin, F. Caruso, Chem. Soc. Rev., 36, 707, 2007. Alkyne-TCNQ addition reaction: T. Michinobu, Chem. Soc. Rev. 40, 2306, 2011. S.-i.Kato, F. Diederich, Chem. Commun. 46, 1994, 2010. Y. Washino, K. Murata, M. Ashizawa, S. Kawauchi, T. Michinobu, Polym. J.43, 364, 2011. Metal ion recognition by cyano group: Y. Li, M. Ashizawa, S. Uchida, T. Michinobu, Macromol.RapidCommun. 32, 1804, 2011. GB Gardner, D. Venkataraman, JS Moore, S. Lee, Nature 274, 792, 1995. D. Venkataraman, GB Gardner, S. Lee, JS Moore, J. Am. Chem. Soc. 117, 11600, 1995. KA Hirsch, SR Wilson, JS Moore, J. Am. Chem. Soc. 119, 10401, 1997. T. Michinobu, Chem. Soc. Rev. 40, 2306, 2011 Y. Washino, K. Murata, M. Ashizawa, S. Kawauchi, T. Michinobu, Polym. J. 43, 364, 2011

In obtaining a polymer having photoelectron functionality based on a donor-acceptor structure, it is not decomposed into an acid-base like a polymer based on electrostatic interaction, and further, such as a cycloaddition reaction of alkyne and azide. The use of a click chemistry reaction that does not produce a 1,4-triazole ring, which is a by-product that does not contribute to the function, and to achieve functionalization and durability in one reaction by direct reaction between polymers, There are several difficulties with this. In the case of polymer-polymer reactions, contact between reactive groups often relies by chance, making quantitative reactions difficult, and reactive groups generally exist at the end of one-dimensional chains of polymers. It is difficult to make three-dimensional.
On the other hand, many examples and proposals have been made for polymers having antibacterial properties, but there are no examples for those having optoelectronic functionality. Some antibacterial polymers themselves have antibacterial properties such as polylysine, but these antibacterial polymers lack water resistance and solvent resistance. In addition, antibacterial properties are expressed by kneading organic / inorganic antibacterial agents into polymers, and many of the products that depend on the physical properties of the polymers themselves are commercially available. However, most of them cannot be judged whether the added antibacterial agent is gradually released by use and the antibacterial property is maintained.

  The present inventors paid attention to the high-yield addition reaction of an electron-rich alkyne containing an electron-donating group and a strong acceptor molecule shown in FIG. Here, EDG represents an electron donating group.

Previously, the inventors of the present invention have proposed a low-molecular compound, such as tetracyanoethylene (TCNE) or tetracyanoquinoquinone having a 1,1-dicyanoethylene skeleton, which is a polymer having a repeating unit containing an electron-rich alkyne containing an electron-donating group. It was found that a donor acceptor site can be constructed by adding dimethane (TCNQ) and its derivatives (Non-patent Document 11 and Patent Documents 13 and 14).
Furthermore, recently, it has also been clarified that a donor acceptor site can be constructed by adding a low molecular weight compound of an electron-rich alkyne to a polymer containing a TCNQ site as a repeating unit (Non-Patent Document 12 and Patent Document 13).

The content is that although the reaction of alkyne substituted with an aromatic amine as an electron-donating group and TCNQ does not proceed at low temperature, it can be reacted by gentle heating (20 to 100 ° C.), that is, temperature conditions. It was found that the occurrence of reaction can be controlled by.
From these facts, the present inventors are not able to obtain a soluble polymer by a reaction between a polymer and a low molecule, but use an approach to obtain an insoluble polymer by a reaction between a polymer and a polymer. The present invention has been completed by eagerly working on the development of the cast film and the cast film.
Reactions between polymers depend on accidental contact between reactive groups, making quantitative reactions difficult, and reactive groups generally exist at the ends of one-dimensional chains of polymers, making them three-dimensional. This is not common because it is difficult. On the other hand, the reactive group of the present invention can be modified in the one-dimensional chain of the polymer, the reactive groups can be accurately accumulated by a π-π stack, and then heated to perform a click chemistry reaction. It is groundbreaking in that it can be made three-dimensional by proceeding. In addition, the reaction of alkyne and azide, which is a general click chemistry reaction, has high selectivity and high yield, but the 1,4-triazole ring produced at that time does not necessarily exhibit the required functionality. On the other hand, the reactive group of the present invention has higher functionality such as the desired optoelectronic function and coordination function in advance, so that it is superior and a highly useful polymer can be obtained.
The three-dimensional polymer thus obtained, so-called network polymer, has a charge transfer absorption band associated with the electron donor acceptor structure. In addition, when an aromatic amine is used as the electron donor group in the electron donor part, the network polymer itself is made to exhibit antibacterial properties by quaternizing the amine part by causing Bronsted acid to act on it. Can do. Furthermore, since TCNQ as an acceptor acts as a ligand for metal ions, for example, by treating with silver trifluoromethanesulfonate, silver ions having high bactericidal and antibacterial effects can be coordinated to the network polymer itself. Since the coordination of these protons and metal ions affects the charge transfer absorption band of the network polymer of the present invention, the coordination amount of the protons and metal ions, that is, the antibacterial performance can be known from the change in the absorption spectrum. . The contents are as follows.

The present invention relates firstly to the synthesis of a network polymer produced by a covalent bond using a technique obtained by further developing the click chemistry reaction that has been attracting attention in the field of chemical synthesis. Specifically, a polymer-to-polymer reaction between a polymer containing a plurality of electron-rich alkynes having an electron-donating group and a polymer containing a plurality of tetracyanoquinodimethanes (TCNQ) having a 1,1-dicyanoethylene skeleton as an electron acceptor The present invention relates to a method for synthesizing a network polymer according to the present invention, a network polymer produced by the method, and a technique for providing a polymer with photoelectron functionality such as an organic semiconductor and an organic conductor simultaneously with the production of a thin film using the network polymer.
In the synthesis of the network polymer described above, two types of polymers are mixed in advance and heated as they are to form a network polymer, or a thin film of the network polymer is not only produced, but an alternate lamination method is used. Further, the present invention relates to a method for producing a network polymer film having an excellent function and an alternately laminated network polymer film obtained by the method.

Secondly, the present invention relates to a unique application focusing on the fact that the network polymer obtained by covalent bonding at the time of synthesis and the thin film have excellent strength, electrochemical properties, and durability against acids and alkalis. .
That is, the present invention relates to (photoelectronic function) network polymer as a chemical sensor based on a photoelectronic function whose absorption spectrum changes in response to a specific metal ion or pH of the network polymer.
Thirdly, the present invention has a wide range of antibacterial and antifungal activities as an antibacterial composition, and the antibacterial performance is obtained by a change in the functional group of the polymer itself and / or metal ions coordinated thereto. The present invention relates to a functional network polymer composition.
Fourthly, the present invention relates to an antibacterial polymer having a chemical sensor function and capable of easily discriminating a change in antibacterial activity by a change in its absorption spectrum.

(Polymers containing multiple electron-rich alkynes with electron-donating groups)
Polymers containing multiple electron-rich alkynes include polyphenylacetylene derivatives, such as 4-[(4-Ethynylphenyl) ethynyl] -N, N-dihexadecylaniline, which was published by the present inventors in Macromolecules 43,5277 (2010). Or a polymer obtained from the azide-alkyne reaction shown in Patent Document 13, or a conjugated polymer compound shown in Patent Document 14.
Here, as the precursor polymer compound having an azide group (—N ₃ ), polystyrene such as poly (4-azidomethylstyrene), poly (2,2-bis (azidomethyl) -1,3-propanediol glutarate), etc. Polyesters such as Poly (polyazidated caprolactone), Polyurethanes such as glycidyl azide polyurethane, Polycarbonate, Polyacrylic such as poly (6-azidohexyl (meth) acrylate), Polyphenylene vinylene, Poly (vinyl carbazole), Polyfluorene Conjugated polymers such as polyphenanthrene, polyacetylene, etc., and precursor polymer compounds containing terminal alkynes include polystyrene such as poly (4-propargyloxystyrene), polyester, polyamide, polyurethane, polycarbonate , Poly (Puropiiniru (meth) acrylate) such as polyacrylic and polyphenylene vinylene, poly (vinyl carbazole), polyfluorenes, poly phenanthrene, conjugated polymers such as polyacetylene.

The electron-donating group of the electron-rich alkyne polymer (hereinafter referred to as polymer 1) by a combination of these includes naphthalene, anthracene, pyrene, triphenylene, chrysene, tetracene, etc., which are condensed polycyclic aromatic hydrocarbons, or those Derivative-containing groups and amines such as aniline, diethylaniline, indole, tryptophan, serotonin, imidazole, biimidazole, or groups containing their derivatives, azine-based cyanines, carbazoles, acridines, phenothiazines and TTF-based compounds , TTP type, TIF type electron donating group, transition metal coordination complex type electron donating group (metal phthalocyanine, metal porphyrin, metallocene, etc.). Of these, amines, especially aromatic amines, can exhibit higher functions.
As an example of the polymer 1, a polymer having a structural unit of the formula [1] (a) can be mentioned. Among them, a polystyrene derivative (b) in which the substituent R ′ is a C-phenyl group is preferable. As the molecular weight of this polymer, the number average molecular weight is usually 3,000 to 100,000, and the polydispersity index is usually 1.0 to 3.0. Preferably, those having a number average molecular weight of about 30,000 to 70,000 can be used. Moreover, what copolymerized with another monomer arbitrarily by using Formula [1] (a), (b) as a structural unit can also be used.

Formula [1]
R: C atom or skeleton containing carbonyl of ester or amide, or carbazole compound R ′: C atom or N atom, C-phenyl group or N-phenyl group n: any integer EDG: electron donating group

(Polymers containing tetracyanoquinodimethane (TCNQ) as an electron acceptor)
Here, tetracyanoquinodimethane (TCNQ) is a polymer compound containing a 1,1-dicyanoethylene skeleton as an electron acceptor, for example, a hexacyanobutadiene (HCBD) derivative, a cyanoquinodimethane skeleton, 7,8,8-tetracyanoquinodimethane (TCNQ) and substituted derivatives thereof, tetracyanoanthraquinodimethane (TCAQ), benzotetracyanoquinodimethane (benzo-TCNQ), tetracyanonaphthoquinodimethane (TNAP) Thiophene tetracyanoquinodimethane (thiophene-TCNQ), hetero-TCNQ, selenophene tetracyanoquinodimethane (selenophene-TCNQ), and their halogenated, especially fluorinated, alkoxylated and alkylated derivatives Say derivatives, poly Electronic acceptor polymers as the chromatography with those skeleton in the main chain, or an electron acceptor polymer having their derivatives on the side chain not apply if (hereinafter Polymer 2 hereinafter). In particular, a derivative containing a 1,1-dicyanoquinodimethane skeleton is a compound represented by the formula [2], and an electron acceptor polymer bonded through any substituent in ABCD is desirable. In addition to homopolymers of these derivative skeletons, polymers obtained by cocondensation and copolymerization reactions can be used, and the present invention is not limited in any way.

Formula [2]

A, B, C, and D represent hydrogen, a halogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group.

  As an example of the polymer 2 containing the said Formula [2], what has the structure in any one of the structures 1-4 among the polymers of Formula [3] can be mentioned, As molecular weight of these polymers, Usually having a number average molecular weight of 1,000 to 50,000 and a polydispersity index in the range of 1.0 to 3.0, preferably an acid having a number average molecular weight of 3,000 to 7,000. Those having an index of 2.5 or less can be used.

Formula [3]
A, B, C, D: H, C, O, N, or a halogen atom, a hydroxyl group, an alkoxyl group, an alkyl group R, R ′: an alkyl chain containing an ether, ester or amide bond R ″: an ether Represents an ester, an amide bond or an alkyl chain containing a phenyl group or a triazole ring, or a phenyl group n: any integer

In the present invention, the following method is presented as a method for synthesizing a network polymer to provide a novel network polymer.
As a first method, there can be mentioned a method in which the polymer 1 and the polymer 2 are mixed in a solvent to obtain a uniform solution and then heated to obtain a network polymer.
As the second method, a thin film is prepared by applying the above-mentioned uniform solution before heating to the substrate surface, and then heated to cause an alkyne-TCNQ addition reaction to form a network polymer thin film. be able to.
In the thin film method, the film thickness can be adjusted by changing the coating conditions, and the film thickness determined there becomes the final thin film thickness. It can be produced under mild conditions regardless of the type of substrate. Examples of the coating method include spin coating, casting, and spray coating. In some cases, it may be possible to use screen printing, gravure printing, ink jet printing application method, or the like. These are not particularly limited, and can be selected according to required performance and application target. Further, a plurality of coating methods can be combined.

As the third method, an alternate lamination method is exemplified. In this method, a polymer 1 solution is applied to the substrate surface to form a thin film, and then a polymer 2 solution is applied and laminated thereon. Subsequently, the alkyne-TCNQ addition reaction at the interface is advanced by gentle heating, and then the unreacted outermost polymer is washed away. By repeating this operation, the film thickness can be gradually increased, that is, an alternately laminated network polymer can be obtained. Of course, which of the polymer 1 and the polymer 2 is applied first can be changed according to the purpose.
Examples of the spreading method include spin coating, casting, and spray coating. In some cases, it may be possible to use screen printing, gravure printing, ink jet printing application method, or the like. These are not particularly limited, and can be selected according to required performance and application target. Further, a plurality of coating methods can be combined.

  In any method, it is possible to obtain a network polymer having a donor-acceptor structure, or a thin film of a network polymer or an alternately laminated network polymer with a desired thickness. Since the donor acceptor structure to be produced has an absorption spectrum that changes depending on pH and metal ion recognition, it can be used as a chemical sensor by tracking the change in the absorption spectrum. Here, the chemical sensor refers to a sensor whose ultraviolet-visible absorption spectrum changes in response to pH (hydrogen ion concentration) or metal ion concentration.

The network polymer and the alternately laminated network polymer obtained here function as a chemical sensor as described above, but when the donor polymer further has a functional group such as alkylamine, it can be protonated with a Bronsted acid, In this case, as the Bronsted acid, since it is a network polymer having a donor-acceptor structure, those other than those having strong oxidizing properties can be used. For example, carboxylic acids such as hydrochloric acid, acetic acid and citric acid can be used, and more preferable are volatile or sublimable acids such as trifluoroacetic acid and acetic acid because the number of steps can be omitted. As a sublimable organic acid, 2H-Pyran-2-one-4,6-dicarboxylic acid (PDC) which shows a relatively strong acidity can also be used.
Furthermore, an antibacterial function can be imparted by alkylating a functional group such as alkylamine on the donor side with a Lewis acid such as an alkyl halide to form a quaternary alkylammonium.

Moreover, the obtained network polymer and the alternately laminated network polymer can coordinate a metal ion from the donor-acceptor structure produced inside. The present inventors have already found that a cyano acceptor site specifically recognizes a silver ion in the study of soluble polymers (Y. Li, M. Ashizawa, S. Uchida, T. Michinobu, Macromol. Rapid). Commun. 32, 1804, 2011.) confirmed that other metal ions also coordinate, and the type and amount of metal ions can be changed according to the purpose. For example, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, Hg, etc. are coordinate metal ions. Can be mentioned.

In addition to these, lanthanoid and actinide series metals are considered. Examples of the metal compound used for coordination of metal ions include inorganic salts such as metal halides, metal oxides, and metal organic acid salts.
In some cases, a plurality of metal salts can be used to control the oxidation number of the coordinated metal ions. Since the ultraviolet-visible absorption spectrum changes in response to the types and concentrations of various metal ions to be coordinated, it can be used as a metal ion sensor. Furthermore, since copper ions and silver ions have a strong bactericidal action, they can be applied as antibacterial network polymers (membranes).

In the present invention, a covalent bond is formed by an addition reaction of an electron-rich alkyne containing an electron-donating group proposed as a new click chemistry and a tetracyanoquinodimethane (TCNQ) containing a 1,1-dicyanoethylene skeleton as an electron acceptor. It has excellent physicochemical durability formed by the above process, and the product after the reaction has an electron donor acceptor type structure, so it has a charge transfer absorption band and is strongly colored.
Furthermore, using this function, a network polymer and a network polymer thin film produced by using a reaction of an electron-rich alkyne polymer and a polymer containing tetracyanoquinodimethane (TCNQ) containing 1,1-dicyanoethylene skeleton as an electron acceptor. Alternatively, the alternately laminated network polymer thin film recognizes various Lewis acids and causes a spectral change, so that it can be used as a chemical sensor.
Furthermore, antibacterial activity can be expressed in the network polymer obtained by treating the obtained polymer with a specific metal ion or acid.
Furthermore, it is possible to provide an antibacterial network polymer that can easily discriminate a change in antibacterial activity based on a change in absorption spectrum resulting from a chemical sensor function.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention. However, the present invention is not limited to the examples.

  4-Ethynylstyrene was synthesized according to the literature (J. Am. Chem. Soc. 2005, 127, 14942-14949). 4-Iodo-N, N-dihexylaniline was synthesized according to the literature (Helv. Chim. Acta Vol. 87, No. 5, 1130-1157, 2004). Other reagents used were commercially available chemicals (Tokyo Kasei, Kanto Chemical, Wako Pure Chemical, Aldrich products).

(Synthesis Example 1)
4-Ethynylstyrene (603.5 mg, 4.709 mmol), 4-iodo-N, N-dihexylaniline (2.709 g, 6.998 mmol) and diisopropylamine (70 ml) were charged into a 100 ml three-necked flask equipped with an Ar balloon. Then, ultrasonic deaeration was performed while Ar bubbling was performed. Thereafter, bis (triphenylphosphine) palladium (II) dichloride (49.0 mg, 0.07 mmol) and cuprous iodide (27.0 mg, 0.142 mmol) were added and reacted at 20 ° C. for 18 hours. After completion of the reaction, the salt was removed by filtration through a filter. After evaporating the solvent of the filtrate under reduced pressure, the residue was purified by a silica gel column (hexane → hexane / ethyl acetate = 5: 1) to obtain the desired product N, N-dihexyl-4-[(4-vinylphenyl) ethynyl] aniline. Obtained (1.55 g, yield 84.9%).

1H NMR (400 MHz; C6D6) δ 0.89 (t, J = 6.0 Hz, 6 H), 1.18 (m, 12 H), 1.39 (m, 4 H), 2.99 (t, J = 8.0 Hz, 4 H) , 5.05 (d, J = 12.0 Hz, 1 H), 5.53 (d, J = 16.0 Hz, 1 H), 6.47 (m, 1 H), 6.54 (d, J = 8.0 Hz, 2 H), 7.09 ( d, J = 8.0 Hz, 2 H), 7.53 (d, J = 8.0 Hz, 2 H), 7.65 ppm (d, J = 12.0 Hz, 2 H); 13C NMR (100 MHz; C6D6) d
14.31, 23.08, 27.08, 27.54, 32.06, 51.08, 88.22, 92.73, 109.97, 111.89, 114.03,
124.48, 126.61, 131.86, 133.50, 136.79, 136.90, 148.35 ppm; IR (neat) n 3088, 3040, 3004, 2953, 2926, 2855, 2206, 2164, 1909, 1871, 1820, 1714, 1608, 1598, 1520, 1465, 1421, 1401, 1367, 1316, 1294, 1254, 1227, 1196, 1178, 1135, 1110, 1027, 1014, 1004, 986, 950, 930, 904, 840, 811, 744, 725, 642, 615, 583, 570, 537, 526, 510 cm-1; MALDI-TOF MS calcd for C28H37N + ([M] +): 387.29; found 387.08 ([M] +).

(Synthesis Example 2: Polymer 1)
N, N-dihexyl-4-[(4-vinylphenyl) ethynyl] aniline (496.2 mg, 1.280 mmol), azobisisobutylnitrile (2.10 mg, 0) obtained in Synthesis Example 1 in a 10 ml ampule tube. 0.128 mmol) and dehydrated benzene (1.19 ml) were charged. After connecting to a vacuum line and sufficiently degassing, it was sealed and polymerized at 60 ° C. for 60 hours. After completion of the polymerization, the reaction solution was poured into methanol and the precipitate was recovered. A small amount of dichloromethane was added for dissolution, followed by reprecipitation purification with methanol. The precipitate was filtered and collected to obtain the desired product. (404.0 mg, 81.42% yield)
GPC measurement was performed by JASCO's molecular weight distribution measurement system (intelligent HPLC pump PU-2080, triple degasser DG-2080-53, intelligent autosampler AS-2055, intelligent UV-visible detector UV-2075, intelligent column oven CO- 2065, chromatography data station ChromNAV), the solvent was tetrahydrofuran, and the outflow rate was 1.0 mL · min ⁻¹ . [Chemical Formula 1] shows the chemical formula, molecular weight, and polydispersity index. At this time, the polydispersity index is average weight molecular weight / average number molecular weight.

GPC (THF) Mn 51,000; 1H NMR (400 MHz; C6D6) d 0.92 (br, 6 H), 1.28 (br, 18 H), 2.02 (br, 1 H), 3.05 (br, 4 H), 6.53 ( br, 4H), 7.69 (br, 4H); IR (neat) n 3092, 3080, 3042, 3029, 2952, 2925, 2855, 2208, 2166, 1907, 1873, 1601, 1520, 1465, 1399, 1367, 1294 , 1254, 1227, 1195, 1135, 1107, 1017, 1004, 983, 887, 827, 811, 724,646, 617, 586, 562, 527, 519 cm-1.

(Synthesis Example 3: Polymer 2)
2,2 ′-[2,5-bis (2-hydroxyethoxy) cyclohexa-2,5-diene-1,4-diylidene] dipropanedinitrile (302 mg, 0.932 mmol) and sebacic acid dichloride (0.200 ml, 0.937 mmol) was stirred in dehydrated dimethylacetamide (10 ml) at 20 ° C. for 48 hours. The resulting solution was poured into methanol and the precipitate was collected. Re-purification with methanol gave TCNQ polyester (302 mg, 92% yield). [Chemical Formula 2] shows the chemical formula, molecular weight, and polydispersity index.

1H NMR (300MHz, CDCl3, 293K) d 1.27 (s, 8n H), 1.59 (m, 4n H), 2.36 (t,
J1 / 47.5Hz, 4n H), 4.00-4.80 (m, 8n H), 6.45 ppm (s, 2n H); 13C NMR
(75MHz, CDCl3, 293K) d 24.6, 28.9, 29.0, 33.9, 60.6, 68.8, 82.8, 103.6, 112.7,
113.2, 147.6, 154.9, 173.5 ppm; IR (neat): n 2915, 2849, 2359, 2217, 1727,
1562, 1527, 1457, 1369, 1332, 1239, 1173, 1153, 1042, 993, 843, 801, 719cm1;
elemental analysis calcd. (%) for (C26H26N4O6) n: C 63.66, H 5.34, N 11.42;
found: C 62.82, H 5.22, N 11.42.

(Example 1: Mixed film-forming method)
The two polymers obtained in Synthesis Example 2 and Synthesis Example 3 were uniformly dissolved in tetrahydrofuran and spin-coated on a glass substrate through a 0.2 μm filter. When spin coating was performed at 1,000 rpm for 60 seconds, the film thickness was about 50 nm. Since the alkyne and the TCNQ site do not react at room temperature (or the reaction rate is very slow), the thin film on the glass substrate is yellow. When heated to 100 ° C., the addition reaction between alkyne and TCNQ begins to progress, the peak around 330 nm derived from polymer 1 and the peak around 420 nm derived from polymer 2 decrease, and the charge transfer absorption band has a maximum around 680 nm. Appeared (Fig. 2). The absorbance of the network polymer is the result of film formation (spin coating, casting, spray coating, etc.) on a transparent substrate (glass, ITO, quartz, etc.) and then cross-linking by heating. The absorption spectrum was measured using an ultraviolet-visible near-infrared spectrophotometer V-670 (manufactured by JASCO Corporation). Furthermore, when the surface of the thin film was observed with an atomic force microscope (AFM), the mean square deviation (RMS value: Root Mean Square value) representing the size of the unevenness gradually decreased as the reaction time increased (FIG. 3). ). This suggests that as the reaction proceeds, the voids inside the film are reduced and a dense film is formed.
At this time, AFM was measured with cantilever PRC-DF40P using Nanotechnology Nanocut made by SII.

Fig. 2 Absorption spectrum change by heating (100 ℃) of mixed thin film of electron rich alkyne polymer and TCNQ polyester, and correlation between heating time and reaction rate

Fig. 3 Relationship between time to heat (100 ° C) the mixed thin film of electron rich alkyne polymer and TCNQ polyester and atomic force microscope (AFM) image

  Fig. Fig. 4 shows an image of a scheme of a thin film manufacturing method by a mixed film forming method.

Fig. 4 Image of scheme of thin film fabrication by mixing method

(Example 2: alternating lamination method)
A dimethylacetamide solution of TCNQ polyester obtained in Synthesis Example 3 (10 mM repeat unit ⁻¹ ) was spin-coated on an ITO glass substrate at 1,000 rpm for 60 seconds. Next, the toluene solution of the electron-rich alkyne polymer obtained in Synthesis Example 2 (10 mM repeat unit ⁻¹ ) was spin-coated under the same conditions, and then heated at 100 ° C. for 10 minutes to advance the addition reaction. Thereafter, unreacted electron-rich alkyne polymer was removed by washing with toluene. Furthermore, after spin-coating a dimethylacetamide solution of TCNQ polyester (10 mM repeat unit ⁻¹ ), the addition reaction was allowed to proceed by heating at 100 ° C. for 10 minutes. Unreacted TCNQ polyester was washed away with dimethylacetamide. By repeating this operation, the film thickness was increased to 20 layers.

  The progress of the addition reaction was confirmed from the UV-visible near-infrared absorption spectrum. FIG. 5A shows an actual absorption spectrum. The 330 nm absorption is mainly derived from the electron rich alkyne polymer. The absorption at 420 nm is mainly derived from TCNQ polyester. The absorption at 680 nm is derived from a donor acceptor structure as a product. FIG. 5B shows the correlation between the intensity of each absorption and the number of stacked layers. When the electron-rich alkyne is an even layer, the intensity of 330 nm is stronger than the adjacent odd layer, which means that a sufficient amount of reactive alkyne sites are present on the outermost surface. Similarly, when the TCNQ polyester is an odd layer, the strength of 420 nm is stronger than the adjacent even layer, which means that a sufficient amount of reactive TCNQ sites are present on the outermost surface. On the other hand, the absorption intensity at 680 nm increases as the number of layers increases. This corresponds to a charge transfer absorption band, suggesting that the donor-acceptor addition reaction proceeds and the film thickness gradually increases. When 20 layers were laminated, the film thickness was about 90-100 nm, and the film thickness per layer was 4.5-5.0 nm.

Fig. 5 (a) Change in UV-Vis near-infrared absorption spectrum and (b) Correlation between the number of layers and absorption intensity of an alternating layer film in which TCNQ polyester is odd-numbered and electron-rich alkyne polymer is even-numbered on an ITO substrate.

  The progress of the addition reaction was also confirmed by electrochemical analysis using a cyclic voltammogram. FIG. 6 shows a cyclic voltammogram for each lamination of the alternately laminated films. The reduction wave of the alternating laminated film shifts to a negative potential as the number of laminated layers increases, exhibiting a quasi-reversible behavior, and the response current is also increased. This indicates that the number of layers increases and the addition reaction proceeds.

Fig. 6 Cyclic voltammogram of alternating laminated films (1-10 layers)

(Example 3: stability of membrane)
<Solvent resistance>
All of the network polymers prepared by heating and crosslinking in Example 1 (mixed film forming method) and Example 2 (alternate lamination method) were insoluble in the solvent used for sample preparation. In fact, the film does not peel off when immersed in various organic solvents such as dichloromethane, 1,2-dichloroethane, chloroform, tetrahydrofuran, dimethylformamide, dimethylacetamide, etc., and it is clear that it adheres extremely strongly to the substrate surface. Thus, it can be seen that the solvent resistance of the film produced by each method is remarkably high.

<Electrochemical stability>
About Example 1, the cyclic voltammogram and the ultraviolet-visible absorption spectrum were measured simultaneously, and electrochemical stability was evaluated. The cyclic cyclic voltammogram of the network polymer is shown in FIG. 7 (a), and the measurement result of the change in absorbance is shown in FIGS. 7 (b) and 7 (c). From the result of the cyclic voltammogram, no change appears in the peak of the reduction wave even if the sweep is repeatedly performed from 0.2 to -0.5V. Further, even when the potential is repeatedly swept, the change of the peak at 730 nm and 822 nm of the charge transfer absorption band is reversible. From these results, it can be seen that the acceptor site is reversibly reduced and then returned to the original neutral state. It turns out that it is a network polymer with extremely high electrochemical stability.

Fig. 7 Cyclic voltammogram (a) of network polymer by the mixed film forming method, changes in absorbance wavelength (b) when the potential is swept, and changes in absorbance at 730 nm and 822 nm

(Application 1)
(Sensor function 1)
The thin film obtained in Example 1 was immersed in chloroform, and the pH response was investigated. As the organic acid trifluoroacetic acid (TFA) was added, the intensity of the charge transfer absorption band near 680 nm gradually decreased and disappeared almost completely in the 31.0 mM TFA solution (FIG. 8 (a )). This suggests that the dialkylaniline moiety has been protonated and has no electron donating property.
From these facts, it was confirmed that it functions as a sensor for acid by performing spectrum measurement. At the same time, the dialkylaniline moiety is protonated to form a quaternary ammonium salt, which is known to exhibit antibacterial properties. From these results, the ratio of the quaternary ammonium salt, that is, the antibacterial property can be determined by the absorption spectrum.

(Application example 2)
(Sensor function 2)
When the thin film obtained in Example 1 shown in Application Example 1 is dipped and triethylamine (TEA) as a base is added to the chloroform solution to which TFA is added, the charge transfer absorption band gradually recovers, and the neutral to Under basic conditions, the strength returned almost completely (Fig. 8 (b)). This indicates that the dialkylaniline portion that was a quaternary ammonium salt was deprotonated and the electron donating property was recovered. That is, it can be used as a pH sensor due to the intensity of absorption at 680 nm. In addition, it had high chemical stability even under the strong acid condition shown in Application Example 1 that would destroy a thin film produced by electrostatic interaction.

Fig. 8 (a) UV-Vis near-infrared absorption spectrum change when trifluoroacetic acid (TFA) is added to a crosslinked thin film immersed in chloroform, and (b) Absorption spectrum change when triethylamine (TEA) is added thereafter.

(Application 3)
(Sensor function 3)
The polymer film obtained in Example 1 was immersed in a 1,2-dichloroethane solution of silver trifluoromethanesulfonate having a concentration of 0.2 mM, and the change in the UV-visible absorption spectrum was observed. The measurement interval was 5 seconds and measured for 600 seconds. The obtained results are shown in FIG. The charge transfer absorption band at 680 nm is shifted to the longer wavelength side depending on the immersion time in the silver trifluoromethanesulfonate solution. This indicates that the band width of the charge transfer is changed by the coordination of the cyano group of TCNQ on the acceptor side to the silver ion.

Fig. 9 Change in UV-visible absorption spectrum

  From this result, it can be used as a functional film as a chemical sensor capable of discriminating the silver ion concentration by the absorption spectrum, and further, since it undergoes a crosslinking reaction, it can be used even in an organic solvent such as 1,2-dichloroethane.

(Application 4)
(Antimicrobial evaluation)
The polymer membrane obtained in Example 1 is a 1,2-dichloroethane solution having a concentration of 0.02 mM (4-1), 0.2 mM (4-2), and 2.0 mM (4-3), respectively, in silver trifluoromethanesulfonate. After 30 minutes of immersion in the solution, remove from the solution and wash with 1,2-dichloroethane.
A variety of silver-supported polymer films were obtained. Table 1 shows the silver ion concentration of each polymer film by inductively coupled plasma emission spectroscopy (ICP-AES analysis). At this time, Prodigy ICP manufactured by Leeman Labs was used as the apparatus.

  It can be seen from these that the amount of silver ions can be arbitrarily supported on the polymer. Using these silver-supported membranes (4-1 to 3) and the polymer membrane (application example 4-4) in which the dialkylaniline site prepared in application example 1 is treated with acid and quaternized, an antibacterial test against E. coli is performed. went. The results are shown in Table 2.

  The glass plate as a control and the untreated crosslinked polymer did not show antibacterial and bactericidal activity, but the application examples 4-1 to 3 and acid treatment (application example 4-4) treated with silver ions had antibacterial and bactericidal activity. Indicated.

  As reference examples, antibacterial tests were also performed on 0.002 mM and 0.0002 mM Ag. However, in these test examples, advantageous antibacterial / bactericidal activity could not be obtained.

<Activity value calculation method>
・ Calculation of the number of viable bacteria Obtain the viable count of each sample.
N = C × D × V
N: Viable count (per test piece)
C: number of colonies D: multiple of dilution V: volume of SCDLP medium used for washing (ml)

・ Calculation of antibacterial activity value The antibacterial activity value is obtained from the viable count obtained above.

-Calculation of bactericidal activity value The bactericidal activity value is determined from the number of viable bacteria determined above.
R: Antibacterial activity value L: Bactericidal activity value A: Unprocessed (blank) number of viable bacteria immediately after inoculation of test piece (pieces)
B: Viable count (pieces) after 24 hours of unprocessed (blank) test piece
C: Number of viable bacteria after 24 hours of antibacterial processed test piece
Table 3 shows the results of ICP-AES analysis of the silver concentration of the polymer film after treatment with each silver trifluoromethanesulfonate concentration solution used in Application Examples and Reference Examples.

As described above, from the results of Application Example 4 and Reference Example, the silver concentration in the polymer per unit area is at least 2.26 × 10 ⁻⁵ mg / mm ² , preferably 4.24 × 10 ⁻⁵ mg / mm ^2. If it is above, practical antibacterial and bactericidal activity can be obtained.

In the present invention, when synthesizing a network polymer having an optoelectronic function having a donor-acceptor structure, a polymer having high physicochemical stability via a covalent bond by a reaction between a polymer and a polymer using a click chemistry reaction. Is obtained. As a result, conventional materials have no resistance to acids and alkalis, and are not practical in terms of physicochemical strength. On the other hand, the present invention is put to practical use as a polymer having an organic photoelectron function. Open the way.
In addition, it can be used as a chemical sensor material from the donor acceptor structure, and further, it can be made into an antibacterial functional network polymer by protonating the amine structure on the donor side and coordinating metal ions on the acceptor side. Is also possible. Furthermore, antibacterial activity can be detected in combination with the chemical sensor function, UV-visible absorption spectrum, or visually in the visible region. It provides a tool that can accurately determine

Claims (9)

This is a method for producing a network polymer obtained by a click chemistry reaction between an electron-rich alkyne polymer containing an electron-donating group and a tetracyanoquinodimethane (TCNQ) -containing polymer containing a 1,1-dicyanoethylene skeleton as an electron acceptor. And
An electron-rich alkyne polymer containing an electron donating group is a polymer having a structure represented by the following formula [1],
The tetracyanoquinodimethane (TCNQ) -containing polymer containing a 1,1-dicyanoethylene skeleton as an electron acceptor is a tetracyanoquinodimethane (TCNQ) containing a 1,1-dicyanoethylene skeleton represented by the following formula [2]. And an electron acceptor polymer that is bonded through one or two substituents of the substituent ABCD, and is any one of structures 1 to 4 of the following formula [3] A method for producing a network polymer , characterized in that :
Formula [1]
R: C atom, or skeleton containing carbonyl of ester or amide, or carbazole compound R ′: C atom or N atom, C-phenyl group or N-phenyl group n: any integer EDG: electron donating group Formula [2 ]
A, B, C, and D represent hydrogen, a halogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group. Formula [3]
A, B, C, D: H, C, O, N, or R, R ′ representing a halogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group, R ″ representing an alkyl chain containing an ether, ester, or amide bond , An ester, an amide bond or an alkyl chain containing a phenyl group or a triazole ring, or a phenyl group, n: any integer An electron-rich alkyne polymer containing an electron-donating group and a tetracyanoquinodimethane (TCNQ) -containing polymer containing a 1,1-dicyanoethylene skeleton as an electron acceptor are mixed and then applied to the substrate. A method for producing a film-like network polymer obtained by subjecting a polymer to a click chemistry reaction,
An electron-rich alkyne polymer containing an electron donating group is a polymer having a structure represented by the following formula [1],
The tetracyanoquinodimethane (TCNQ) -containing polymer containing a 1,1-dicyanoethylene skeleton as an electron acceptor is a tetracyanoquinodimethane (TCNQ) containing a 1,1-dicyanoethylene skeleton represented by the following formula [2]. And an electron acceptor polymer that is bonded through one or two substituents of the substituent ABCD, and is any one of structures 1 to 4 of the following formula [3] A process for producing a film-like network polymer , characterized in that
Formula [1]
R: C atom, or skeleton containing carbonyl of ester or amide, or carbazole compound R ′: C atom or N atom, C-phenyl group or N-phenyl group n: any integer EDG: electron donating group Formula [2 ]
A, B, C, and D represent hydrogen, a halogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group. Formula [3]
A, B, C, D: H, C, O, N, or R, R ′ representing a halogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group, R ″ representing an alkyl chain containing an ether, ester, or amide bond , An ester, an amide bond or an alkyl chain containing a phenyl group or a triazole ring, or a phenyl group, n: any integer After applying an electron-rich alkyne polymer containing an electron-donating group to the substrate, apply a tetracyanoquinodimethane (TCNQ) -containing polymer containing a 1,1-dicyanoethylene skeleton as an electron acceptor, and then click on both polymers A method for producing a multilayer alternately laminated film-like network polymer obtained by repeating a step of making a chemistry reaction to form a film-like network polymer,
An electron-rich alkyne polymer containing an electron donating group is a polymer having a structure represented by the following formula [1],
The tetracyanoquinodimethane (TCNQ) -containing polymer containing a 1,1-dicyanoethylene skeleton as an electron acceptor is a tetracyanoquinodimethane (TCNQ) containing a 1,1-dicyanoethylene skeleton represented by the following formula [2]. And an electron acceptor polymer that is bonded through one or two substituents of the substituent ABCD, and is any one of structures 1 to 4 of the following formula [3] A method for producing a multilayered network-like network polymer , characterized in that
Formula [1]
R: C atom, or skeleton containing carbonyl of ester or amide, or carbazole compound R ′: C atom or N atom, C-phenyl group or N-phenyl group n: any integer EDG: electron donating group Formula [2 ]
A, B, C, and D represent hydrogen, a halogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group. Formula [3]
A, B, C, D: H, C, O, N, or R, R ′ representing a halogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group, R ″ representing an alkyl chain containing an ether, ester, or amide bond , An ester, an amide bond or an alkyl chain containing a phenyl group or a triazole ring, or a phenyl group, n: any integer The method for producing a network polymer according to any one of claims 1 to 3, wherein the electron-donating group of the electron-rich alkyne polymer containing an electron-donating group is an aromatic amine. The network polymer according to any one of claims 1 to 4 is used alone or in combination, and the amount of coordination of protons and metal ions is detected by measuring an ultraviolet-visible absorption spectrum or a color change in the network polymer. A method for manufacturing a chemical sensor. A method for producing an antibacterial material , wherein a metal ion is coordinated to the network polymer according to claim 1. The method for producing an antibacterial material according to claim 6, wherein the metal coordinated to the network polymer according to any one of claims 1 to 4 is silver and / or copper. A method for producing an antibacterial material , wherein the network polymer according to claim 4 is treated with a Bronsted acid or a Lewis acid. The method for producing an antibacterial material according to any one of claims 6 to 8, wherein the time-dependent change of the antibacterial effect can be confirmed by measuring an ultraviolet-visible absorption spectrum in the network polymer or visually observing a change in color. .