WO1981001287A1 - Viologen derivatives and polymers thereof - Google Patents

Abstract

Vinylbenzylviologen derivatives represented by the following general formula; (FORMULA) (wherein R represents an alkyl group or an aromatic group-substituted alkyl group, A1 and A2 are the same as, or different from, each other and each represent halide ion, perhalogenate ion or tetra-substituted boride ion), homopolymers or copolymers thereof, process of reversible coloration or decoloration, method for providing a difference in electric potential, and process of oxidation and reduction using these compounds.

Description

 Akira 4tn

 TECHNICAL FIELD The present invention relates to a biogen derivative and a polymer thereof.

 More specifically, the present invention relates to a 1-substituted-1'-vinyl pentinole 4,4'-dipyridinium derivative, a method for producing the same, and a method for producing the compound. The present invention relates to a polymer comprising a unit as a constituent and a method for producing the polymer. Further, the present invention relates to a novel use of a pio-pi-gen derivative as a photosensitive / electric shock display material, a photovoltaic cell material, or a redox carrier material.

 The bi-benzyl virogen derived conductor provided by the present invention is represented by the following general formula (I).

(In the formula, 'is an alkyl group or an aromatic-substituted lower alkyl group, and A and A are the same or different and are a halogen ion, an excess halogen, It means gen. Acid ion or 4-substituted boron ion, provided that, when both of A and A are halogen ion,-is the same nitrogen ion. It is.)

Next, the definition of various kinds in the general formula (I) representing the above target compound will be described. , As used herein, the term "an phenol group" means a linear or branched saturated group having 1 to 12 carbon atoms, and is preferably methyl, phenol or phenol. And a lower phenol group having 1 to 6 carbon atoms, such as pinole, butyryl, and hexyl. Further, the aromatic-substituted lower alkyl group means a group having at least one aromatic group as a substituent in the chain of the lower alkyl group as described above. , Preferably benzene, fenenole, feninole alpha pinole, trinole methinole, kissinore methinole, mesi chinoremenoire, kumemenore Alkyl (lower) alkyl groups such as quinolemethyl, naphthynolemethyl, naphthynoletinol, and benzylhydryl are mentioned.

 The aryl moiety of the (lower) phenol group may be a suitable substituent such as a cyano group, a nitro group, an amino group, or a phenol group.

 (E.g., methoxy group, methoxy group, etc.), halogen (cloline, bromine, etc.), etc.

 Examples of the halogen ion of A? And A include chlorine ion, bromine ion and iodine ion. Examples of the perhalogenate ion include perchlorate ion, perbromate ion, and periodate ion, and tetrasubstituted boron ion. Examples of such a material include tetraphenyl borane boron ion and the like.

 The novel vinyl pentylene phenol virogen derivative of the present invention can be produced by any of the methods represented by the following formulas.

Ο ΡΙ

,, IPO « Method A Vinyl benzylation reaction

(In the formula, A _IA Ha α gain emissions of hydrogen acid residue, A¾ your good beauty

A¾ means the same halogen ion,

Is the same as above. )

Method B Anion exchange reaction

 X〇 Y㊀

 One cr-! Pi

/>, v / IO, (In the ^formula, Χ θ your good beauty Y ⁰ means the Ha Russia gain down I on-that is different from was the same or,, your good beauty A§ is Ru said the same Jidea.) Each way of the above ' The law is described in detail below.

Method A: Vinyl benzylation reaction

The target compound (f) can be produced by reacting the starting compound (H) with a methyl styrene residue. - In here, Russia main switch Norre scan switch-les-down image to your only that A c b gain emissions of hydrogen acid residues and to the hydrogen chloride acid of _la, hydrobromic acid, acid such as hydriodic acid Residues.

 This reaction is usually carried out in a solvent. Suitable solvents include methanol, ethanol, isopropyl alcohol and other alcohols, and acetates. Ketones such as benzophenone, methylenethylenolketone, methylisobutylinoleketone, etc., acetonitrile, benzonitritol Nore-te-no-no-ge-disop mouth Pinole-teno-no-te, Tetra-hydra-furan, dioxan, etc., kuro-no-no-no-re-m Aromatic hydrocarbons such as poronodrogenide lanolecans, such as chloronoethane and shiroiden methylene, and aromatic hydrocarbons such as benzene, benzene, xylene, etc. , Dimethylformamide, dimethylphenol oxide, and other organic solvents that do not adversely affect the reaction. Der lever, Ru can be for any use.

 Although the reaction temperature is not particularly limited, it is often the case that the reaction is usually carried out at room temperature or under heating. In addition, the halomethynorylene styrene used in this reaction (1) itself and the reaction product have the property of being polymerized together. Uses a conventional polymerization inhibitor such as hide π-quinone, catheter, etc.

OMPI If added appropriately, undesirable side reactions can be avoided and good results can be obtained. The reaction product is isolated and purified according to a conventional method. The reaction product (1 ') obtained by this reaction was subjected to the anion exchange reaction described in Method B below, and the respective perhalogenate ions were obtained. Can be led to the target compound (I), which is a tetrasubstituted boron ion.

Method B Anion exchange reaction

The target compound (I) can be produced by subjecting the raw material compound (IV) to anion exchange reaction. In the raw material compound (0V), the halogens of X ⁰ and Y ⁰ may be the same or different, such as chlorine ion and bromine. Ion and iodine ion.

 The anion-exchange reaction is carried out by exchanging the cation of the raw material compound 0V) with an anion represented by Α * |. Here, the exchange of the anion is carried out in a conventional manner, but the preferred method is to prepare the desired ion (Α ^ and A) type of anion. A convenient method is to treat the raw material compound (IV) with an ion exchange resin.

Kagei O as a-exchange resin is usually to be of that we have use, for example A down bar la wells IRA- 4 0 0 _c (trade name) is found like

 In addition, this anion exchange reaction can be carried out by a conventional method of metathesis with a desired salt of anion (A ^ and A) in a solution. You can also do it. In this case, the reaction is carried out, for example, by reacting the raw material compound IV) with a perhalogenate or a tetrasubstituted boron salt. Over here

Ο ΡΙ

"V IPO Examples of the salts of halogenates and 4T boron salts include metal salts of aluminum and ammonium, such as sodium perchlorate and perchlorate. Acid permeate, ammonium perchlorate, etc., sodium perbromate, peroxy acid permeate, ammonium perbromide, etc. Examples include lime, potassium periodate, ammonium periodate, and the like, or sodium tetraethyl benzoate, and the like.

 This anion exchange reaction is usually performed in water or a mixed solution of water and a hydrophilic solvent (for example, methanol, ethanol, acetate, etc.).

 Novel vinyl benzyl viologen derivative of the present invention

(I) itself is useful as a photosensitive / electric shock display material or photovoltaic material as described above, and is also useful as a raw material for producing the polymer. is there .

 In particular, in the case of the compound (I) of the object of the present invention, particularly when the halogen is both chlorine and Af. Together with other halogen ions

 (For example, bromine ion), it is more stable, and its polymer is more colorless and transparent. Also A? And? Is a perhalogenate ion or a 4-substituted boron ion. Compound (I) is soluble in an organic solvent, and therefore, is poorly soluble in water and It is noted that the solvent can be advantageously used when producing a copolymer with a soluble polymerizable monomer.

The starting compounds (Π) and (EV) for producing the above-mentioned novel benzylgen π-gen derivative are those represented by the following formulas.

OMPI It can be manufactured by law.

Method (1) N-Quaternization of 4, 4'-dipyryl

 ii) Exchange of ion if necessary

(In the formula, A _2a represents a halohydrogen acid residue, and A¾ is the same as described above.)

Method (2) Vinyl benzylation reaction

χΘ _γ Θ (wherein, X represents a halogenated hydrogen residue, and R ^ ⁰ and the same as described above.)

OMPI

Λ '/ ΙΡΟ Each of the above methods will be described below.

 Method (1) N-Quaternization of 4,4'-dipyridyl (V)

 The compound (H) can be produced by reacting 4,4'-dipyridyl (V) with a compound (VD).

 This reaction is usually carried out in a solvent, and the method and conditions (solvent, reaction temperature) similar to the above-mentioned method A for producing vinyl benzyl bio-orogen derivative (I) are used. Etc.).

Compound (Halogenated acid residue of A _{2a in} VD means a residue of a hydrogenated acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, etc. Compounds having a halogenated hydric acid residue such as (e.g., chloride, methyl chloride, butyl chloride, methyl iodide, and the like) Halogenated alkyls, such as chlorobenzene, chlorobenzene, chlorobromide, bromide propyl, bromide isopropyl, bromide isopropyl, etc. Benzyl iodide, benzoyl iodide, trimethyl chloride, xyl chloride methyl chloride, shiridani methyl chloride, bromide ethylene chloride, chloride Al, such as dani-fu-enil-pro-pinole, shii-dani benzohydr, etc.

(Lower) phenolic halogenated compounds.

 The halogen ion represented by A¾ in the compound (Π) obtained by the above reaction may be different from the halogen ion ion, if necessary, due to the anion exchange reaction. Can be converted to. For example, to obtain a compound (H) having a methyl group and A 基 being chlorine, the compound (V) can be obtained by reacting a compound (V) with methyl iodide. Desirable by subjecting the compound (H) in which methyl or A¾ is iodine ion to anion exchange reaction, and exchanging iodine ion in A に for chloride ion. To obtain the compound of

OMPI ring It can be. Incidentally, this anion exchange reaction can be carried out by a method similar to the anion exchange reaction in the above-mentioned method B.

Method (2) A vinyl benzylation reaction compound can be produced by reacting a compound (VD with a compound).

As a by here Shi 'preferred Ha B gain emissions hydrogen acid residues Oite X in compound image unusual the A _2a also the same as the C port gain down hydrocarbon acid residues of the the like et Re Preferred examples of the compound II having such an acid residue include the same as the above-mentioned compound fraction.

 This reaction is usually carried out in a solvent, and is performed under substantially the same method and conditions (solvent, solvent, etc.) as the above-mentioned vinylinolebenzinole virogen derivative (method for producing l). Reaction temperature, etc.) 0

It should be noted that, Ji compound IV) response required also obtained we were in the reaction of this Ri by the Kagei O-exchange reaction to you only that way the same way as described in the above-mentioned X ⁰ your good beauty ^γ θ of It is possible to convert a halogen ion into another π-genion.

 The obtained compound (VD can be used not only as a starting compound for the above method B, but also for a photovoltaic material described later.

The polymer of the present invention can be produced as follows.

(1) Homopolymer of vinyl benzyl virogen derivative (I)

 The homopolymer of vinyl benzoyl pi gen derivative (I) is

CMPI

,, ^{7ΙΡ 〇-} . The compound (I) can be produced by subjecting it to a conventional polymerization reaction, but is preferably polymerized by a liquid polymerization method. In this case, as a solvent to be used, a usual polymerization solvent and a mixed solvent thereof are used.

5 Examples of the solvent include phenolic solvents such as water, methanol, and ethanol, and aromatic hydrocarbons such as benzene, toluene, and the like. Solvents such as ether solvents such as dioxan, tetrahydrofuran, etc., and ditrile solvents such as acetonitrile, benzonitrile, etc. , Polar solvents such as dimethylsulfonamide, dimethylsulfonamide, dimethylsulfoxide, etc. System solvents and the like. Here, when Α and A in compound (I) are halogenogen, water or a mixture of a hydrophilic solvent and water is used as the solvent. I want to do that. Since both the starting compound (I) and the product (polymer) of this reaction are sensitive to oxygen, the polymerization reaction is carried out in an atmosphere of an inert gas such as nitrogen or the like. It is desirable to work under vacuum.

 This polymerization reaction can be carried out simply by heating, but the reaction is usually carried out by adding a polymerization initiator, and a preferable polymerization initiator is not used. Organic peroxides such as benzoic peroxide, benzoyl peroxide, t-butyl chloride, quinolene phenolic oxide, cumene hydride, peroxycide, etc. Butyronitrino, Azovisciano Valeric acid, Azovis-1 5 (2,4—Dimethylinole) Valeronitrino, Azovis-1 (2— Organic cards such as hydrochloride

OMPI

V IPO Inorganic water-soluble radical initiators such as azo compounds, persulfuric acid spheres, ammonium persulfate, sodium persulfate, hydrogen peroxide, and these inorganics A redox system obtained by combining a water-soluble radical initiator with sodium pi-sulfite, sodium bisulfite, divalent iron ion, etc. O 0

 The polymer produced by the reaction is, for example, concentrated to dryness of the reaction solution, freeze-dried, or poured into a solvent in which the produced polymer is hardly soluble. Can be separated and collected by a common method such as precipitation. If further purification is required, the polymer product can be purified by reprecipitation. When the polymer product is water-soluble, it can be purified by dialysis or the like.

 The homopolymer of the vinylene benzene viologen derivative (I) obtained by the above method is a side chain polymer polymerized via a vinyl group. It is shown by the following equation.

 (In the formula, η means the degree of polymerization, and Α and Α§ are the same as above.)

The degree of polymerization of η in the above depends on the temperature in the polymerization reaction, the type of polymerization initiator or the polymerization time, but

OMPI By appropriately selecting these conditions, a polymer having a desired degree of polymerization can be obtained.

 (2) Copolymer of vinyl benzene viologen derivative (I)

 The vinyl phenol divinyl gen derivative (I) is a polymerizable monomer having another ethylenic double bond (hereinafter abbreviated as “copolymerizable monomer (M)”). To form a copolymer. Here, as the polymerizable monomer (M), for example, an alcohol residue

Atari rate or methacrylate rate of Ci ~ ₁₂ (Methino acrylate rate, methine acrylate rate, n-butyl acrylate rate) Release, etc.), polymerizable alcohol (2-hydroxy creatinoleate, hydroxypropyl acrylate, 2) — Hydroxie-meta-relet, Hydroxy-pro'-pinole-meta-relate

 Methacrylic alcohol, etc.), polymerizable oleic acid and its salts (acrynolic acid, methacrylic acid and its salts), Polymerizable amides (such as amide amide amide and methacrylic acid amide), polymerizable nitriles (such as amide acrylonitrile and methacrylic acid amide) Triols, etc.) and polymerizable aromatic compounds (such as styrene, naphthalene styrene, vinylinolenorren ene-butyl styrene, etc.). Refined conjugates (eg, ethylene, propylene), vinyl compounds (eg, vinyl acetate, vinyl propylionate), and vinyl Gene compound

 (Butadiene, isoprene, etc.) and can be used in one kind or in a mixture of two or more kinds.

 Vinyl benzyl viologen derivative) and polymerizable monomer

 The copolymer with (M) is vinyl benzoyl □ gen derivative (I)

O PI WIFO. And a polymerizable monomer (M) by subjecting them to a conventional polymerization reaction to produce a polymerizable product. This polymerization reaction is carried out by substantially the same method and under the same conditions as the polymerization reaction for obtaining the homopolymer of the vinyl benzoyl virogen derivative (I) described in (1) above. It is done.

 The copolymer of the vinyl benzodiol derivative (I) and the polymerizable monomer CM) obtained by the above method is a side chain polymerized via a vinyl group. It is a type polymer and can be represented, for example, by the following schematic structure.

(Where, in the formula, the residue obtained by removing the vinyl group from the pulp copolymerizable monomer 、, and m means the composition ratio of each monomer in the polymer. And A are the same as those described above.) In the case of a crosslinked copolymer, for example, it can be represented by the following schematic structure.

_O FI WItO (In the formula, M and M are each a copolymerizable monomer and a residue obtained by removing a vinyl group from M ₂ , and X, y, and z are each a monomer. , And A ?, respectively, are the same as above.)

 A homopolymer of the vinyl benzyl porogen derivative (I) and a copolymer of the vinyl benzyl porogen derivative (I) obtained by the above method. The copolymer with the water-soluble monomer (M) retains the desirable properties of the vinylbenzene'zirviologen derivative, while maintaining transparency and film. It is excellent in formability and is useful as a photosensitive / electric shock display material and the like as described below.

f, _r WHO _¾ Next, compounds having a viologen structure and uses of these polymers will be described.

 (A) Use as photosensitive material

 Homopolymer and vinylene benzene of the vinylinolebenzinolevirogen derivative (I), which are the target substances of the present invention, obtained by the above method. A copolymer of the derivative (I) and the copolymerizable monomer) (hereinafter, these polymers are abbreviated as biopolymer (A)) is a film. Because of its excellent properties, it can be easily converted to a finale. For example, a phenol can be easily converted into a finale by flowing the viologen polymer (A) on a plate-like material. Lum is excellent in transparency and develops a blue or purple color when irradiated with light or passed through an electric current. This phenomenon of color development is reversible, disappears when left alone, and develops again when light is applied or electricity is applied again.

 Therefore, the purpose of the present invention is to irradiate the viologen weight with light or to pass an electric current to the viologen polymer (^ to form a color). For example, the color can be developed by appropriately irradiating light or energizing a phenolic polymer of the porphyrin polymer (A). It can be used as a display panel with blue or purple as an indicator, in which case not only sunlight but also artificial rays can be used as a light source. In addition, when used as an ordinary display material, if necessary, for example, in a pio-porogen polymer (A), for example, if there is a chloride reamer, sodium chloride is used. It's a realm

CMFI WIFO Such an electrolyte may be added.

 The use as a photosensitive / electrical display material will be described below based on test examples.

Test example A — 1

 1-methylol synthesized in Example 8 below: 1,4-divinylbenzene-dichloride and acrylonitrile amide An aqueous solution in which 0.1 ^ of the copolymer was dissolved in water 1 was flown on a teflon (πα plate) so as to have a diameter of about 2 ^, and air-dried while being illuminated. After drying to a certain extent, drying under reduced pressure on a desiccator using thiocyanate pentate as a desiccant yields a slightly yellowish transparent finolem. Was.

 When the transparent film obtained was irradiated with light from a 100 w high-pressure mercury lamp, it turned blue. When this colored film was stored in a dark place or slightly moistened, the color disappeared and it returned to the original transparent film. When the decolored film was irradiated with light again, it recolored blue and was reversible. The coloring phenomenon of the above phenol was the same when sunlight was used in place of the light of the high-pressure mercury lamp.

Test example A — 2

An arbitrary figure was placed on a transparent film obtained in the same manner as in Experimental example A-1 to draw an arbitrary figure, and the light from a high-pressure mercury lamp was applied. The area covered by the luminium foil did not develop color, and the light-irradiated part turned blue, and any figure could be drawn on the finome. Departure When the colored finolem was left in a dark place, it was erased and returned to the original transparent finolem. This phenomenon was the same when using sunlight instead of the high BE mercury lamp.

Test example A-3

 Figures 1 and 2 show the equipment used in this experiment, namely, the nesa glass electrode. .

 In FIG. 1, 3 is a glass plate, 1 is a tin oxide electrode (electrode surface is a square of ίcm × 1 ^), and 2 is a lead portion of the tin oxide electrode.

 1-Methyl-vinyl-vinylbenzene synthesized in Example 8 below on the glass surface (1), 1 ', 4'-dipylidinium jig π Copolymer of LAD and Acrylinoleum,

An aqueous solution prepared by dissolving 0.059 in 0.2 ml of water was poured, and was allowed to dry and solidify naturally while protecting from light. Moisten the obtained finolem with water, place another piece of the same Nesagaras electrode on it, and allow it to air dry. The polymer was used as an adhesive, and the two Nesa glass electrodes were bonded together, as shown in Fig. 2. 'In Fig. 2, 1 is an acid-silicon electrode, 2 is a lead portion of an oxidized steel electrode, 4 is a viologen polymer, and 3 is a glass plate. When energized with one of the negative electrode plates negative and the other positive, the finolem developed a purple color. The purple color gradually disappeared when left to stand, and disappeared immediately when a reverse voltage was applied to the Nesagaras electrode, and returned to its original transparent state. The color develops when the power is turned on again, and it is possible to reversibly repeat the coloring and decoloring.

O PI (B) Use as photovoltaic material

 The inventors of the present invention have found that when an aqueous solution of a compound having a bio-orogen structure is irradiated with light, a reduction reaction occurs, resulting in a marked voltage change (counter electrode). And found that it could be applied to photovoltaic cells.

The compound having a viologen structure used herein is represented by the general formula

 Θ ㊀

 X 'Υ

(Wherein, R 2 is a benzyloxy group, an alkanol group, or an aromatic-substituted (lower) alkyl group R ₃ is an alkynole group, an aromatic-substituted (lower) alkyl group key group, the X ¹⁹ your good beauty ^Υ θ that means the Ha Russia gain down Lee on-that is different from was the same or)

Piologen derivative represented by

And general formula

(Wherein X ^θ and Υθ ^represent the same or different halogen ions, and represents an alkyl group or an aromatic (lower) alkyl group. Homopolymer of vinyl benzyl bio _π- gen derivative represented by the formula (1) and the compound (w) and a polymerizable monomer having an ethylenic double bond (hereinafter referred to as polymerized A copolymer with a functional monomer (体) is used. Here

Ο I Examples of the alkyl group and the aromatic quinoline (lower) alkynole group are the same as those exemplified above. In addition, among the pirogogeni conjugates (K), the compound in which R is a vinylolbenzenolene group is a compound represented by the above-mentioned vinylpenthenolenolynol derivative ( W) is produced by the same method and under the same conditions as in the production method of W), and R ₂ is an alkyl group or an aromatic substituted (lower) phenol group. Compounds in which the compound is an acryloyl group or an aromatic-substituted (lower) alkyl group can be produced according to the method.

In addition, the homopolymer of the vinyl benzobenzene derivative and the copolymer of the vinyl derivative (IV) with the polymerizable monomer (M) are the same as those described above. A method for producing a homopolymer of the oleopiologen derivative (I) and the co-polymerization of the vinylbenzene virogen derivative (I) with the copolymerizable monomer (M) Can be produced by the same method and under the same conditions as for the production of the polymer 0

 A solution of the compound having the pio-gen structure was filled in both of the two opposing tanks cut off by the ion-permeable diaphragm, and electrodes were placed in both tanks, respectively. In a device in which both electrodes are connected with a lead wire, one of the tanks is cut off with light or pits, and power is generated by irradiating the other tank with light. be able to . The tank for irradiating light is made of glass or synthetic resin or other light-passing material.

 In practicing the present invention, the aqueous solution of the compound having the Vio gen structure may be an aqueous solution using pure water, but the oxidation-reduction potential In order to stabilize

OMPI It is preferable to use a buffer. In addition, since compounds having a porogen structure ¾ easily undergo a decomposition reaction in a strongly basic solution, it is desirable to use an aqueous solution consisting of a buffer solution near neutrality. Examples of such a buffer include a phosphate buffer having a pH around neutrality, and a carbonate buffer. ―

 The electrode used in the present invention may be any conductive material as long as it is physically and chemically stable, but is preferably, for example, a platinum, carbon or nesa glass electrode. There are 0.

 Light sources include artificial light sources such as mercury lamps and sunlight, but from the viewpoint of resource saving, the significance of using sunlight is significant. In the photovoltaic cell of the present invention, a benzophenone-based sensitizer, for example, 4-benzoyl-5-monobenzoic acid, 2-benzo-benzoylbenzoic acid, etc. are used in combination. If this is the case, it is sensitized and more favorable results are obtained.

 The use as a photovoltaic material will be described below based on test examples.

'/

O PI Exam B — 1

 Figure 3 shows the equipment used in this test example.

In FIG. 1, 8 is a transparent glass container, 9 is an aqueous solution of a compound having a pi- ologen structure, 1 is a platinum electrode, 3 is a sweet electrode, and 4 is potassium chloride. 1 Agar salt bridge, 7 is a voltmeter, -2 is a lead wire connecting 1 to 7 and 3, 11 is a glass tube that covers the lead wire on the platinum electrode side, and 5 is nitrogen. A glass tube for introducing gas, 6 is a gas outlet, and 10 is rubber. -In the above device, benzyl viologen (1, V-dibenzobenzene) dissolved in PH6.88 phosphate buffer was added. click b La b 10 ml of solution de) (bi O b gain down conversion concentration 4 X 10- ³ molar 1) was injected, it was through its nitrogen gas for about 15 minutes. Subsequently, light was irradiated from a side of the container (8) 5 cm away from the side of the container (8) using a 100 W high-pressure mercury lamp while passing through nitrogen gas. Due to the light irradiation, the solution in the container gradually turned blue. The potential difference between the platinum electrode and the control electrode was measured with a voltmeter, and the electromotive force △ E '(mV) = 4 15 (ΔΕ / sec (mV / sec) = 0.67 〕showed that. The photoreaction was reversible, and the voltage generated gradually decreased when the light irradiation was stopped, and returned to the original voltage when the light irradiation was started again.

 The electromotive force was increased by ΔΕ (mV) = 525 G ^ E / sec (mV / sec) = 3.17] by adding 4-benzoyl benzoic acid (10 mg) to the above solution. I felt it.

Ο PI In addition, when an experiment similar to the above was performed using a citrate buffer as a reaction solution, the electromotive force only showed ΔΕ (mV) = 65.

Test example B — 2

Experimental example B—Synthesized in Example 8 below, dissolved in a phosphate buffer of PH6.88 in the same apparatus as 1—1—Methyl——Vinylbenzene , injected over di pin Li Gini ©厶di click b La I de and § click Li Le a mi de a solution of the copolymer (Pi o π gain down conversion concentration 4 X 10 one ³ molar / 1) 10 ml As a result of the same test, the electromotive force was ΔΕ (mV) = 550 C ^ E / sec (mVZ sec) = 2.0.

Test example B — 3

 A battery consisting of a bright electrode tank and a dark electrode tank was created, and the electromotive force and current were measured.

 Fig. 4 shows the equipment used in this test example. In FIG. 4, 6 is a transparent container made of glass, 11 is an aqueous solution of the compound having the viologen structure, 1 is a platinum electrode, 7 is a voltmeter, 8 is an ammeter, Reference numeral 9 denotes a stitch, 2 denotes a lead wire connecting 1, 9, 7, and 8, and 13 denotes a glass tube that powers the lead wire on the platinum electrode 1 side.

 The vessel is divided into two tanks, and the two tanks are connected by a glass finoletor. 3 is a glass tube for introducing nitrogen gas, 4 is a gas outlet, 12 is a rubber stopper,

Numeral 10 indicates metallic covers for blocking and blocking light, respectively.

0.: FI _ Methylene virogen dissolved in a phosphate buffer of PH 6.88 in the above apparatus (1-dimethyl-4.4-dipyridinium dichloride) Solution (Bio-Equivalent Concentration 6.1)

X 10- ³ mole 1] Each 20 ml All good beauty 4 - injecting base down zone I le repose Kosan a (10 mg) in both the tank and through its nitrogen gas for about 15 minutes. Then, under a stream of nitrogen gas, light was applied from a distance of 5 cm using a 100 W high-pressure mercury lamp to the unremoved tank (a bright electrode tank) with a metal power bath. The other tank (dark pole tank) was cut off so as not to receive light irradiation by the metal cover (10). The solution in the bright electrode bath turned blue by light irradiation.

Akirakyokuso a result the voltage of the measurement of the electromotive force (voltage) between the dark pole tank ΔΕ (mV) =: 480, current and current density (current value platinum electrodes 1 cm ² Ah was Ri) 58.1 ^ It was A / cm ² .

 This photoreaction was also reversible. When the light irradiation was stopped, the electromotive force and current gradually decreased, and when the light irradiation was started again, the values returned to the original values.

In addition, 20 ml each of the citrate buffer solution was injected into both tanks, and the same test was performed.As a result, the electromotive force was ΔΕ (mV) = 75, and the current was 1.7 cm ² as the current density. I did.

Test Example B-4

Benzyl viologen dissolved in phosphate buffer (PH6.88) in each of the bright electrode tank and the electrode tank of the same device as in Test Example B-13 above emissions di Norre one 4.4 '- di Pi Li Gini © beam di click port la protrusive soluble liquid (Pi o α gain down conversion concentration 6.1 X 10 one ³

O! PI

No Mol Z 1) was injected into both tanks with 20 ml each and 4-benzoyl benzoic acid (10 mg), and the same test was carried out. As a result, the electromotive force was (mV) = 425, and the current density was 10.6 / ' A cm ² was shown.

Test example B — 5

In each of the bright electrode tank and the electrode tank of the same apparatus as in Test Example B-3 above, a 1-methylolane synthesized in Example 8 below dissolved in a phosphate buffer of PH 6.88 1 — Vinyl benzonitrile 4.4'-A solution of a copolymer of dipyridinium dichloride and acrylinoleamide (bioequivalent concentration 2.2 X10 ") ³ mol Z 1) were each injected with 20 ml and 4-benzoylbenzoic acid (10 mg) into both tanks, and the same test was carried out. As a result, the electromotive force was △ E (mV) = 495, and the current density was Showed 2.5 ^ A / cm ² .

OMPI

V (C) Use as redox carrier material

 The redox carrier material having a piologen structure according to the present invention is obtained by adsorbing a copolymer of a benzyl viologen derivative and a polymerizable amide onto an insoluble carrier, and then adsorbing the same. The copolymer can be produced by cross-linking the amide group of the copolymer via a methylene bond. -More specifically, the invention has the general formula

Θ

(In the formula, ^θ and B ₂ represent the same or different monovalent anions, and: represents an alkylene group or an aromatic-substituted lower alkyl group. )

After adsorbing a copolymer of a vinyl benzene biogen derivative and a polymerizable amide represented by the formula (1) to an insoluble carrier, the amide group is converted to a methylene group. And the copolymerization of a benzyl π-gen derivative (IV) in which the amide group is cross-linked via a methylene group and a polymerizable amide. An object of the present invention is to provide an insoluble carrier coated with a polymer. Here, the monovalent ion means the first dissociation anion of the acid, and examples thereof are shown by A and { ₂ ^} in the above compound (I). Examples include nitrogen, peroxygen acid, and tetrasubstituted boron. Polymerization with benzene virogen derivative (X) used here

fUREA

O PI Copolymers with a soluble amide (hereinafter, these copolymers are abbreviated as viologen copolymers (C)) are referred to as the above-mentioned vinyl benzobenzene derivatives. The copolymer can be produced by the same method and under the same conditions as the method for producing the copolymer of 1). Here, preferable examples of the polymerizable amide include acrylic acid amide and meta-T-acrylic acid amide.

 Examples of the insoluble carrier include glass particles, phenol powder, silicone gel, synthetic resin particles (such as π-porous resin particles), and carbon particles. Any particulate or powdery substance that is inert to the redox reaction itself can be used.

 Here, the methylene group cross-linking reaction of the amide group of the pio π-gen copolymer (C) is treated with an aldehyde compound in the solvent of the pi- ologen copolymer (C). It is done by doing. In this crosslinking reaction, the reaction can be promoted by appropriately adding a small amount of an inorganic or organic acid such as hydrochloric acid, sulfuric acid, and acetic acid. In addition, this reaction is usually performed at room temperature or under heating, but by heating, the reaction is further accelerated.

 Solvents used in the methylene group crosslinking reaction include, for example, alcohols such as methanol, ethanol, propylene, and dioxane. Ethers such as san, tetrahydrofuran and the like can be mentioned, and examples of the aldehyde compound include, for example, aldehyde and acetate. Ledehide, butinole nordehide, and the like. This reaction is specific

OMPI

/, _f V ν / IίPO υ In this case, the viologen copolymer (C) is dissolved in a solvent, the insoluble carrier is immersed in this solution, and the pio-guchigen copolymer (C) is adsorbed and dried. This is done by processing with a head.

 The insoluble particulate carrier coated with the bio-α-gen copolymer (C) in which the amide group obtained by the above method is cross-linked via a methylene group is excellent in oxidation. It has a reducing ability and can be used as a carrier to perform redox reaction, for example, to be used as a carrier filled in a column in the packed column method. Can do

 The oxidation of the present invention is described below based on Examples and Test Examples.

The production method of 3S vault carrier material and its use will be explained.

 Trial C-1

A glass column (1 cm in diameter and 15 cm in length) was filled with 4 g of the glass granule carrier produced in Example 14 below, and then passed through nitrogen gas. Distilled water distilled from it was poured. Next, a solution prepared by dissolving 0.1% sodium dithionite and 0.06 g of carbon dioxide rim in 10 ml of water was passed through the column under a nitrogen gas stream. The carrier packed in the column was reduced and turned purple. Wash the purple-colored carrier with N ₂ gas> 20 ml of the above-mentioned distilled water, and then add 0.35 g of sodium chloride to the salt. When a solution prepared by dissolving 100 ml of ethanol into the ethanol is poured, the red triphenylene triazole is reduced to reduce the salt. Thus, a solution containing the compound was obtained. Colorimetric determination of this solution (λ max = 488 nm ")

O PI As a result, and shows the reducing ability of the carrier g This Ri 2.41 X 1CT ³ millimeter molar.

Test Example C — 2

 The glass granule carrier (abbreviated as G) produced in Example 15 and the cellulose powder carrier (abbreviated as G-2) produced in Example 16 were mixed with a glass column (diameter l). ____________________________________________________________________ Length of each carrier was measured. The results are as shown in the table below.

OMPI r Next, the present invention will be described with reference to examples.

Example 1 1 — Methinole — ί-vinyl benzyl 4, ί

Synthesis of dipyridinium dichloride

1 — Methyl 4 (— pyridinole) pyridinyl iodine

 4, 4'- dipyridinole 25g (0.16 mono) asceton

 Dissolve in 150 ml, add 14.2 g (0.1 m

 (20 ml) was added dropwise at room temperature, followed by stirring at room temperature for 24 hours in a sealed state. The precipitated orange-colored crystals were collected by filtration and washed with acetont. <The crystals were re-used twice with a 99% ethanol-methanol (1: 1) mixed solution. Crystallization yielded 23.3 g of yellow crystalline powder of 1-methyl-4 (4,1-pyridinole) pyridinamide. m. p. 257 ° C (decomposition)

 I. R.

 KB ^ r 30101630. 1595.1540.1520.

 max

 1490.1450.1410.1320.1270.

1210. 1190. 810. 710. 480. cm— ¹

N. MR (D ₂ O) Internal standard: 3 — (trinosilyl) Propion

 Acid sodium salt-D4 8.9 (2H.d)-8.6 (2H.q)-8.2 (2H.d)

 7.8 (2H-q) .4.5 (3H.s)

O PI

V / IFO, Elemental analysis: _Cu H 11 NI

 c H N I

Calculated 44.31 3.72 9.40 42.57

 44.31 3.67 9.36 42.71

(2) 1--Methyl — 4--(4-Pyridine) Pyridinium chloride (monohydrate)

 Dissolve 9 g (0.03 mol) of 1-methyl 4-(4'-pyridyl) pyridinium iodide obtained above in 100 ml of water, Exchange resin (Amberlite IRA-400: trade name) (CI Q type) After passing through a column filled with 500 g, the effluent (blue by hydrogen peroxide-starch test) ) Was concentrated to dryness under reduced pressure to give a pale yellow-brown powder. This powder was dissolved in about 10 ml of 99% ethanol by heating, and then about 70 ml of acetate was added and left to stand. 5.1 g of (4-pyridinole) pyridinum lip (monohydrate) crystals were obtained.

Elemental analysis C _n H „N ₂ C1 H ₂ 0

(3) Methyl 1-vinyl benzene-4 '4 pyridinium dichloride

OMPI

^ν,: ι ο? The above obtained 1-methyl — 4 — (4 '— pyridinole) pyridinyl chloride (monohydrate) 4.13 g (0.018 monol) was added to methanol. Dissolve it in 10 ml of phenol and add 9.16 g (0.06 mol) of dimethylformamide (a mixture of meta- and para-forms) 30 ml), and the mixture was stirred at room temperature for 7 days. The solvent was distilled off under reduced pressure, and the residue was washed several times with a dehydrated ether (inclination method), collected by filtration, and dried under reduced pressure to obtain a powder. This powder was recrystallized (twice) with a mixed solution of 99% ethanol-no-isoprono and ^0- no-no-le (1: 1), and the 1-methyl Nore — 1'-vinyl vinylbenzene 1,4,4 'dipyridinium dichloride 5.4 g was obtained. (These crystals are colorless, but they turn yellow when exposed to air and are highly hygroscopic.)

I. R.

 KBr

 3500-3300. 3050-2990. 1630.max

 1580.1560.1500.1440.1400.

 '' 1340. 1270. 1220 .. 1190. 1160.

 980.920.850.820.800.750.

720.710.690cm- ¹

NM. (METHANOL Norre one ^D 4)

Internal standard: Tetramethyl silane

9.2 (4H.m) .8.7 (4H.m) .7.5 (4H.m) 6.75 (1H.q) 6.0 (2H.s) .5.8 (1H.q)-5.3 (1H.q) ■ 4.5 ( 3H.s) Example 21 1-Methyl-vinyl-vinyl-benzene 1-, 4'-pi-Rigi-Ni-M-Te-Traf-E-L-Polyate Synthesis of 1-methyl-1'-vinyl benzene 1,4,1-dipyridinium dichloride synthesized in Example 1 0.3 g was dissolved in water 10 ml Then, an aqueous solution (10 ml) of sodium tetrafluoroborate [NaB (gap) 4] (0.8 g) was added dropwise. The precipitated CO yellow precipitate was collected by filtration, washed with water and methanol, dried under reduced pressure, and dried under reduced pressure to obtain a yellow powder of 1-methylol-1'-vinylolbenzene. 4, 4 '— pyridinium ditetrafluoroethylene 0.7 lg was obtained. 'I. R.

 KB

 max x: 3050. 1630. 1580. 1560. 1500. 1475.

 1440.1420.1265.1030.910.840.

820.730.705 cm- ¹ Elemental analysis ^C 68 H ₆₀ N ₂ c ₂

C H N

Calculated value

3.02

 87.98 6.35 3.28

Example 3 Synthesis of 1-methyl benzene 1'-vinyl benzene-4 '4 -dipyridine

2.5 g of 1-methyl benzene 1-vinyl benzene synthesized in Example 1 was added to water 15 g. It was dissolved in addition to mi. An aqueous solution (15 ml) of 2.2.5 g (0.02 mol) of sodium perchlorate was added dropwise with stirring, and a viscous oil precipitated. The supernatant is decanted and treated with water, then crystallized from water-ethanol (1: 1) and further recrystallized to give 1-mesh of yellow needles. Chill-1'-vinyl benzene-4,4-dipyridinium dimethyl tetra.- 2.8 g of lip for mouth opening was obtained.

m. p. 142. ~ 1 43 ° C

I. R. v ^KBr : 3000. 1630. 1560. 1500. 1440. 1400. 1350. max.

 1270.1135.1110.1080.1000.920.825.

800cm " ¹

N. M R. (di main switch Honoré scan Honoré scion Size Lee de - D ₆₎

 Internal standard: Tetramethylsilane

 9.5 (2H.d), 9.2 (2H.d) .8.7 (4H.m).

 7.6 (4H.m) .6.8 (1H.q) .6.0 (2H.d):

 5.8 (1H.q) .5.4 (1H.q) 4.5 (2H.s)

Example 4 1 — Benzinolone 1 ′ — Synthesis of Benzinolene Benzinolene 4,4′-dipiridine

 (1) 1 page (4, — pyridyl)

Dissolve 11.7 g (0.075 mol) of 4,4'-dipyridinole and 6.3 g (0.05 mol) of benzene chloride in 99% ethanol (100 ml), and add 50 g The mixture was heated under reflux at ° C for 20 hours. After cooling, After adding 100 ml of acetate and filtering off the insoluble matter, Isoproviranol (70 ml) was stirred into the insoluble matter, and the mixture was stirred. Pi nore a nore ko nore mouth 1

It was collected and concentrated to give a white powder. This powder was dissolved again in Pinole Real Call Co., added with acetone and allowed to stand, the precipitate was filtered off, and the same operation was repeated. 1-benzyl (4-pyridyl) as a white powdery crystal) 8.7 g of pyridinium chloride was obtained.

I. R. K ^Br : 2950. 1630. 1590. 1520. 1490. 1440.

 ma X

 1400.1210.1200.1160.1150.870.

820.800.710.680cm- ¹

N. M R. (¾ 0)

Internal standard: 32 (trimethylsilyl) sodium salt of propionate — D ₄

 s: 9.1 (2H.d). 8.85 (2H.d). 8.5 (2H.d). 8.0 (2H.d).

7.6 (5H. S). 5.95 (2H. S) Elemental Analysis _{C 17 H 15 N 2 a ·} H

 c H N CI

Calculated 67.87 5.70 9.31 11.80

 67.63 5.64 9.44 11.89

OMPI

. IPO (2) 1 Benzinol — 1, 1binolen Benzinolet 1,4,4'1 Benzinolium 1 benzene obtained on dichloride chloride Nole-4-(4,-pyriforme) Pyridinic lip mouth 8. Og (0.027 mol) is replaced with dimethyl quinolone amide (5 Oml) And 9.4 g (0.062 mol) of chloromethinolestyrene (a mixture of a meta-form and a para-form) was added thereto, followed by stirring at room temperature for 7 days. The solvent was distilled off under reduced pressure, and the residue was washed with dehydrated ether. The insoluble matter was collected by filtration and dried under reduced pressure to obtain a white powder. This powder is dissolved in 99% ethanol, and the mixture is left unheated and left undisturbed, and the precipitated crystals are removed with the Isono pinhole. When recrystallized, colorless flaky crystals of 1-benzo-γ-vinyl

 4, 7.7 g

(The day it turns yellow when it touches the air.)

 I. R.

KBr ■

 : 3100. 3050. 1630. 1550. 1500. 1445. 1405.ma

1350. 1270. 1220. 1150. 1000. 920. 840. 800. 760. 750. 730. 710cm— ¹

NMR (metano-nore D ₄ )

 Internal standard: Tetramethylensilylane 9.3 (4H.d). 8.6 (4H.d) .7.5 (9H.m). 6.7 (1H.q) 6.0 (4H.s) .5.8 (1H.q) 5.2 (1H.q)

OMPI

V / IPO Example 5 1 1 benzene 1 benzene 2 benzene 4 and 4 '

-Synthesis of dipyridinium ditetrafluorophenol

 Dissolve 0.2 g of 1-benzylamine 1'-vinylbenzene synthesized in Example 4, 0.2 g of 1,4'-dipyridinium dichloride in 1 Oml of water An aqueous solution (0.8 ml of -10 ml: 'dropped') of sodium terephthalate (20 ml: 'dropped'). The precipitated yellow precipitate was collected by filtration and washed with water. After washing with methanol and drying under reduced pressure, a yellow powder of 1-benzyl benzene-1-vinyl benzene-4,4'-dipyridinium ditetrafluoroethylene 0.4 g of enilepo and latex were obtained.

Elemental analysis As C ₇₄ H ₆₅ N ₂ B ₂

 C H N

 Calculated value 88.53 6.53 2.79

 Experimental value 88.43 6.49 3.07 Example 6 1 1-, 1-, 2-, 4-, 4'-pyridinidine Of

3 g of 1-benzylamine synthesized in Example 4-gamma-vinylenebenzene-4,4'-dipyridinium dimethyl chloride was added to 15 ml of water. Dissolved. An aqueous solution (15 ml) of 2.5 g (0.02 mol) of sodium perchlorate was added dropwise thereto with stirring, and a viscous oil precipitated. The supernatant was decanted, treated with water, then crystallized from water-ethanol (1: 1), recrystallized, and re-crystallized to obtain a pen of yellow needles. di Honoré -1 'single bi two Honoré Baie emissions di Honoré one 4, 4 ⁷ - di Pi Ri Gini ©

O PI · Re

Ή · ΐ Ή

Ο

Example 7 Synthesis of Homopolymer of Methyl 1'-Vinyl Benzene 14-, 4-Dipyridinium Dichloride

 1-methyl benzene 1-vinyl benzene obtained in Example 1-4,4-di-pyridinium chloride 0.72 g (2 mimol) Was dissolved in 4 ml of water, passed through with nitrogen gas for 15 minutes, and then heated at 50 while passing through nitrogen gas.Then, 0.03 ml of 35% hydrogen peroxide solution was added, and 50 ° 8 hours at 60 ° C. This aqueous solution was added to acetone, and the precipitate that precipitated was collected by filtration. Next, this precipitate is dissolved in methanol and reprecipitated (two times) in a 99% ethanolacetone (1: 4) mixed solution to obtain a hygroscopic substance. Thus, 0.35 g of a pale yellow powdery homopolymer of 1-methyl-1'-vinylvinyl-1,4,4-dipyridinium dichloride was obtained.

Intrinsic viscosity

 0.08 (d 1 / g (in S0—in KC1 solution)

 I · R ·.

 Re: 3050 ~ 2900.1640.1560.1510.1450.1340.1270.

 — 1

 1210.1190.1150 .830.790cm

Elemental analysis:

 C H N C1

 58.34 6.23 6.68 18.57 Example 8 1 — Methinorane 1-vinyl benzene benzene 1, 4 dipyridinium dimethyl chloride and acrylolane (preparation mode) Of a copolymer having a ratio of 1: 5)

OMPI. 1-methyl vinyl chloride obtained in Example 1—4,4′-vinyl pyridinium dichloride 0.72 g (2 milliliters), acrylic Dissolve 0.71 g (10 milliliters) of noreamide in 7 ml of water, pass nitrogen gas through it for 15 minutes, and further heat to 50 ° C under a stream of nitrogen gas. Next, 0.05 ml of 35% hydrogen peroxide solution was added, and the mixture was heated and stirred at 50 ° to 60 ° for 7 hours. This reaction product was added to acetone, and the precipitate that precipitated was collected by filtration. The obtained precipitate was dried under reduced pressure, dissolved in 5 ml of water, added to 500 ml of 99% ethanol and reprecipitated (twice), and the obtained precipitate was dried under reduced pressure. Dry, hygroscopic, slightly yellowish white powder 1-methylene 1'-vinylinyl benzyl-4,4'-dipyridinium dichloride 0.94 g of a copolymer of light and acrylonitrile was obtained.

 I · R.

3500-3100.3050.2950.1700-1640.1610.1560

 1500.1450.1420.1340.1320.1220.1190.1120

830 -790cm — 1 elemental analysis

 C H N C1

 Experimental value I 51.74 6.88 12.39 8.69

From the N / C1 ratio in the elemental analysis, the ratio of the pyridine group to the acrylamide group of this polymer is 16.4: 83.6 (molar ratio). Intrinsic viscosity

 0.65 (dl / g) (30 in C—in KC1 solution)

Example 9 1 — Met 1 1 ′ — 2 N 4 1 4 ′ 4

Ο ΡΙ Synthesis of copolymer of pyridinium dichloride and acrylonitrile amide (prepared molar ratio 1: 1)

 1-methyl benzene obtained in Example 1 1'-vinyl benzene-4,4'-dipyridinium dichloride 0J2g (2 mil) 0.14 g (2 millimol) of phenol amide was dissolved in 5 ml of water and transferred to a glass polymerization tube. While passing through nitrogen gas, add 0.0 l ml of 35% hydrogen peroxide solution, convert the mixture with nitrogen gas, then seal the tube and heat at 50-60 ° C for 48 hours. Was. The reaction solution was added to acetonitrile, and the precipitate which precipitated was collected by filtration, dried under reduced pressure, dissolved in methanol, and dissolved in 99% ethanol. After re-precipitating (2 times) in a mixed solvent of 1: 1 (1: 1), a white powdery, hygroscopic, yellowish yellow powder was obtained. 0.37 g of a copolymer of 4,4′-dipyridyldimethyldichloride and acrylamide was obtained.

Intrinsic viscosity

 0.37 (dl / g) (in 1 KC1 solution at 30 ° C)

I. R.

3600-3100.3050.2950.16601640.1600.1560.

 1500.1440.1330.1270.1220.1180.1150.820

790cm- ¹

Elemental analysis

 C H N C1

 56.93 7.16 9.39 13.90

According to the elemental analysis ratio, the viogen group and a

O PI

Vr ^r IPO 4 丄 The ratio of phenol amide group is 41.3%: 58.7% (mol ratio) 0

Example 10 1——Methyl-N-Vinyl-Venyl-1,4′-Dipyridine-Dimethyl-J-Mouth Lid and Co-Acrylic Acid Manufacturing of coalescence

 0.72 g (2 mimol) of 1-methylene 1 'vinyl benzene 4,4'-dipyridinium dichloride obtained in Example 1 0.72 g (2 mimol) of acrylinoleic acid was dissolved in 5 ml of water. After passing the mixture through nitrogen gas for 15 minutes, the mixture was further heated to 50 under a stream of nitrogen gas, then added with 0.03 ml of 35% hydrogen peroxide and water, and stirred at 50 ° C for 4 hours. did. This aqueous solution is added to acetonitrile, and the precipitate that precipitates is collected by filtration, dried under reduced pressure, dissolved in water, and the aqueous solution is added to ethanol (1: 4). ) Add to the mixed solution and re-precipitate (twice) to obtain a white powder 1-Methylene 1'-Vininolene Benzinole 1,4,4'-dipyridinium 1.26 g of a copolymer of dichloride and acrylic acid was obtained. ·

 I .R.

^{v ax: 3100 ~ 2900 -1720.1640.1560.1500.1450 ·} 1330.

1250.1220.1190.1150.1110.870.820.790cm- ¹ elemental analysis

 C H N C1

 56.56 6.20 4.07 12.70

From the N / 'C ratio of the elemental analysis, the ratio of the pyridine group to the acrylate group in this polymer is 19.4% to 80.6% (monole ratio).

One ΟΜΡΙ Example 11 1 Benzene No. 1 'one No. Benzene No. 1, 4'-Preparation of a copolymer of dichlorinated dimethyl chloride

 1—Pendinole synthesized in Example 4; —Binolenium Benzinole-4,4′—Dipyridinium dichloride 0.43 g (1 mi)

-Limol) and 0.71 g of acrylonitrile (10 milliliters) are dissolved in 5 ml of water. After passing nitrogen gas through the mixture for 15 minutes, the mixture was further heated to 50 ° C under a nitrogen gas stream, and then 0.03 ml of 35% hydrogen peroxide was added thereto, followed by stirring for 2 hours. The reaction product was added to acetone, the precipitate was collected by filtration, dried under reduced pressure, dissolved again in water, and mixed with 99% ethanol / norreaceton (1: 1). It was added to the solution and reprecipitated (twice). The resulting precipitate is dried under reduced pressure to obtain a hygroscopic, white powder of 1-benzene-1,4-vinyl-benzene 1,4,4'-dipyridinium dimethyl 5-chloro. 0.48 g of a copolymer of ride and acrylamide was obtained.

 I.R ...

 ^^: 3500-3100.3050.2950.1700 1630.1600.1550.

 1500.1440.1410.1340.1310.1210.1150 -810.

800-760.700cm ^-1

0 elementary analysis value

 C H N C1

 54.14 6.36 11.40 7.20

N / C ratio or these elemental analysis, the composition ratio of peak o b gain down group and § click Re Le § Mi de groups of this polymer is 14.2: 85.8 (Mo Honoré ratio) ⁵ ing.

OMPI_

. V / IPO Example 12 1 Methyl Nore 1-Vinyl Nozzle Benzene No. 1,4 Divinyl Chloride and Acrynorea N.N Methylene Visc Manufacture of terpolymer (crosslinking polymer) with lilamide (charged mole ratio 1: 2: 0.08)

 1-methyl alcohol 1 'obtained from Example 1 1-vinyl vinyl chloride 1,4,4'-diphenyl dimethyl chloride 1.8 g (5 mimol) , Acrylinoleamide 0.71 g (10 milliliters), Ν.Ν'-Methylene bisacrylamide 0.06 g (0.39 milliliters) in 20 ml of water Dissolve in. After passing through a nitrogen gas for 15 minutes, the mixture was heated to 50, 0.05 ml of 35% hydrogen peroxide solution was added, and the mixture was polymerized for 5 hours under a nitrogen gas flow. This reaction product was added to acetate, and the supernatant was discarded by the gradient method. To the precipitate obtained, methanol was added, and the mixture was allowed to stand overnight. This operation was repeated three times, and the obtained acetone precipitate was dried under reduced pressure to obtain 2.2 g of a light brown powder. (When this product is placed in water,

Elemental analysis value

 C H N C1

 Experimental value 58.99 7.40 1 1.03 13.53

Example 13 1 — Methinole — Vinyl No. Benzene No. 1,4,4 — Dipiridine Dummy tetrachloride and styrene

Synthesis of copolymer (charge ratio 10: 8.7)

 1—Methanore 1 ′ obtained in Example 3—Binore Benzene 1,4,4′-dipyridinium dimethyl tetrachloride 4.87 g (10 milliliters, styrene 1 ml (8.7 milliliters),

OMPI WIPO Dissolve 40 mg of Zobisisobutyronitrile in 20 ml of acetonitrile, charge the mixture in a glass polymerization tube, replace with nitrogen gas, and polymerize at 65 ° C for 24 hours. I let you. The upper and lower layers of the reaction product separated into two layers in the polymerization tube were separated. After dissolving the lower layer in dimethylaminophenol, this was added to methanol and precipitated (twice). The resulting precipitate is further dissolved in dimethyl honole amide, which is added to dimethyl honole amide water and reprecipitated to give a slightly brown color. 1'-Methyl 1'-Vinylone Benzinole-4,4-Dipiridine Dietary Cyclolide and Styrene 2.5 g of a copolymer were obtained.

 I .R.

3080.3000 2900.1630.1550.1490.1480.1440.

 '1330.1260.1210.1140.1100.1070.820.790.

700cm— ¹

Example 14 Production of _Pio_Port _Glass Coated _Glass Particles (1)

Into glass particles (100 mesh) 15, 1-methyl benzene 1-vinyl acetate synthesized in Example 8 was added to 4,4-dipyridinium dichloride. An aqueous solution obtained by dissolving 0.1 g of a copolymer of light and acrylamide in 5 ml of water was added and mixed. After mixing, the glass particles were subjected to gravity filtration through a glass filter to remove the aqueous solution, and then dried under reduced pressure on a desiccator using pentafluoride as a desiccant. The dried glass particles are 99% ethanol 45 ml, 37% aqueous solution of holmaline 5 ml, 、, ⁰ホ ホ ホ レ レ

ΟΜΡΙ The solution was added to a mixed solution of 0.5 g and 0.2 ml of concentrated hydrochloric acid, left for 6 hours, and further heated at 50 to 60 ° C for 6 hours. The glass particles are filtered from the reaction mixture, washed with warm water and methanol, dried under reduced pressure, and the yellow, amide group is cross-linked via the methylene bond. Glass particles coated with the above viologen polymer were obtained. -Example 15 — Production of glass particles coated with a pio α-gen polymer (2)

 To 15 g of glass particles (100 mesh), add 1-methyl alcohol 1-vinyl vinyl alcohol synthesized in Example 9 to 1,4-dipyridine An aqueous solution obtained by dissolving 0.2 g of a copolymer of mujichloride and acrylamide in 5 ml of water was added and mixed. Next, glass particles were collected from the mixture by filtration and dried under reduced pressure. 'Add the dried glass particles to a mixed solution of 45 ml of dioxan, 5 ml of 37% honole marin, 0.5 g of para honole manganese dehydrate and 0.2 ml of concentrated hydrochloric acid. Then, the mixture was heated at room temperature for 6 hours and further at 50 ° to 60 ° C. for 6 hours. The glass particles were collected by filtration, washed with warm water and methanol, and then dried under reduced pressure.A yellow, amide group was cross-linked via a methylene bond. Glass particles coated with the above bio-α-gen polymer were obtained.

Example 16—Production of Cellulose Powder Coated with Pio Mouth_Gen Polymer

 To 1 g of phenolic powder synthesized in Example 8 was added to 2 g of phenolic powder in Example 8 and 1,4-vinylidene dihydrogenide was added. 0.3 g of acrylamide copolymer in 5 ml of water

O PI

w ^ipo- The dissolved aqueous solution was added, mixed, and dried under reduced pressure. The dry cell mouth powder was mixed with 99% ethanol 45 ml 37% formalin 5 ml, paraformaldehyde 5 g and concentrated hydrochloric acid 0.2 ml. The mixture was added, and the mixture was heated at room temperature for 5 hours and further at 50 ° 60 ^ for 5 hours. The obtained cellulose powder was collected by filtration, washed with warm water and methanol, and dried under reduced pressure. The yellow, amide group was linked via a methylene bond. Thus, a cell α-source powder coated with the above-mentioned bio π-gene polymer crosslinked was obtained.

Claims

1. General formula

Yo blue

 ㊀ Θ

Αι Α ₂

 of

3> one

(Wherein, is an alkyl group or an aromatic-substituted lower alkyl group, and Αι ^Θ and Α ₂ ^Θ are a halogen ion or a perhalogen acid. or 4 a replacement boron i on- means Re its Resolution, door-out Αι your good beauty Α ^₂ Θ is a leaf Russia gain down i on-the co is Ru Oh the same Ha Russia gain down Lee on- )

 By passing electricity through a vinylinolepene dinorrelogogen derivative, a homopolymer thereof, or a copolymer thereof with a copolymerizable monomer represented by A method for coloring a homopolymer or a copolymer with a copolymerizable monomer of the nolbenzylylogen derivative.

ΟΜΡΙ

crane:

2. General formula colored by energization

(In the formula, R!, Αι ^Θ your good beauty Α ^₂ Θ is bi-two Le Pen di Norre bi-O Russia gain down derivatives that will be shown on 'Symbol and the same meaning, homopolymer or a copolymer Color by applying a voltage to the copolymer with the reactive monomer and applying a current

3. The homopolymer of the vinyl benzyl bio π-gen derivative or the copolymer with the copolymerizable monomer is in the form of a film as defined in claims 1 and 2. And the method of paragraph 2.

 4. General formula

(In the formula, is the A Le key Rumotoma other aromatic-substituted alkyl group, Α] is ^Θ your good beauty Α ₂ Θ was the same or in a different one, was or over-Ha Russia gain phosphate. I on- Is a 4-substituted boron ion).

^5. Αι Θ your good beauty Α ^₂ Θ is Caja Russia gain phosphate I on-der area by the compound of the fourth term of the claim.

^Α! Θ your good beauty Α ^₂ Θ compounds scope of paragraph 4 of claims Ru Oh chlorine acid I O emissions