JPH0245534A - Linear phosphazene polymer containing viologen structure in side chain and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, usable even at low temperatures and useful as an electrochromic material without deteriorating even in polar solvents by reacting a linear phosphonitrile dichloride polymer with plural alcohols in the presence of an amine. CONSTITUTION:The objective polymer, consisting of units expressed by formulas I to III [alpha is group having a viologen structure expressed by formula IV (p is 2-10; R1 is 2-10C alkyl; X1 and X2 are halogen); beta is 2-5C fluoroalkyl expressed by -CH2-R2 (R2 is 1-4C fluoroalkyl) as main constituent units], the substituent groups (alpha) being present in an amount of 0.04-12mol%, the substituent groups (beta) being present in an amount of 88-99.96mol%, having a constitution of the above-mentioned constituent units randomly polymerized through head-to-tail bonds and at least one of formulas I and II as the average composition in one molecule with 5-1500 molecular weight and obtained by reacting a linear phosphonitrile dichloride polymer with a fluoroalcohol expressed by formula V and an alcohol expressed by formula VI in the presence of a tertiary amine.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a linear phosphazene polymer containing a viologen structure in its side chain and a method for producing the same.

(Prior Art) Viologen derivatives are attracting attention as electrochromic display elements because they undergo Lee electron reduction through electrolytic redox reaction and reversibly produce radical tsunotion, which is colored. Furthermore, in many cases, similar radical cations are generated by light irradiation, so they are considered promising as photochromic materials.7 Inorganic materials such as tungsten compounds have been considered as electrochromic materials, but Now, research has shifted to the search for organic materials due to the need to produce a wide variety of hues.

Viologen compounds, which are 1, 1'-dialkyl-4,4'-dipyridines, have attracted attention as one compound that satisfies this requirement, and have been shown to reversibly exhibit clear hues in a short response time through cathodic reduction reactions. Understood.

However, with such low-molecular-weight viologen compounds, there is a problem in that the colored substances generated in the reduction reaction spread around the electrode surface, which causes repeated display and shortens memory life, hindering practical application.

In order to overcome these drawbacks, methods of polymerizing viologen compounds have been studied.

Examples of polymers containing a viologen structure in the main chain include a mixture of a monomeric viologen compound and a viologen polymer (Japanese Patent Application Laid-open No. 51-27884), and a urethane-bonded polymer (% Kaisho 57-113
23), viologen polymers linked by alkylene chains (JP-A-59217791), and viologen polymers linked by p-gysilylene chains (JP-A-60-22').
1025) etc. In addition, as a viologen polymer having a pendant viologen structure, styrene derivatives with a viologen structure bonded to a benzene nucleus and styrene (!%
1982-26977), p-aminostyrene (Japanese Patent Publication No. 57-11328) or N-vinylpyrrolidone (
A copolymer of 4-vinylpyridine and styrene, which is quaternized by bonding a viologen structure to a nitrogen atom (Japanese Patent Application Laid-open No. 58-13)
6685) etc.

However, since the glass transition temperature of the formed film in both C] is high, it is inflexible and brittle under normal use conditions, making it difficult to handle when processing surfaces such as bonding it closely to the electrical surface. .

In addition, in such a material, the polymer chains have poor thermal mobility, so that a reversible coloring function cannot be expected at low temperatures.

In order to overcome these drawbacks, rubber-like polymer IJ containing a viologen structure in a part of the main chain of a linear tetrahydrofuran polymer has recently been developed. - has been developed and has attracted attention as it has been found to be a material exhibiting photochromism and electrochromism (Japanese Patent Laid-Open No. 61204224).

However, when a highly hydrophilic polymer like this tetrahydrofuran polymer is used as an electrochromic material, it may dissolve in highly polar solvents such as water or alcohol, which are convenient for dissolving electrolytes, or it may dissolve in electrodes. It is said that there are many defects such as significant deterioration of the polymer during the reaction, and that it cannot be expected to be used as a display element (Pol.
ymer25.1302-6 (1984)].

As described above, conventional viologen polymers have various drawbacks1 and lack practicality1-. won.

(Problems to be Solved by the Invention) The present invention exhibits rubber-like elasticity5, can be used at low temperatures, has low solubility in polar solvents, and has minimal deterioration even after repeated use. , conventional viologenpo 11-7. It is an object of the present invention to provide a novel linear phosphazene polymer containing a viologen structure in its side chain, which overcomes the drawbacks of - and a method for producing the same.

(Means for Solving the Problems) For this purpose, the inventors of the present invention have made extensive studies and found that the general formula (A) α f) 2 General formula (B) P2N β and A group having a viologen structure represented by the general formula (C) β -P=N β (p is an integer of 2 to 10, R1 is an alkyl group having 2 to 10 carbon atoms, Xl and X2 are ), and β has the general formula -CH
2-R2 (a fluoroalkyl group having 2 to 5 carbon atoms represented by R2 is a fluoroalkyl group having 1 to S carbon atoms) as the main structural unit, and the substituent α is 0.
04-12 moles 1. and the substituent β is 88 to 99.96
The substitution group α and the substituent β are present in a molar ratio, and the above-mentioned constituent units are randomly polymerized with head-to-tail bonds, and the constituent units (A) and (B) are on average in one molecule. A linear phosphazene polymer containing at least one viologen structure in its side chain with a degree of polymerization of 5 to 150 (L) and general formula (A) -P=N 〇 General formula (B) P=N! General Formula (C) β P=N- β General formula (D) General formula (E) β -P=N- and General formula (F) γ -P=N- 0X0 (p is an integer from 2 to 10, R2 is A group having a viologen structure represented by an argyl group having 2 to 10 carbon atoms, Xl and X2 are halogens, β is a group having a general formula CH2-R2 (
R2 is a fluoroalkyl group having 1 to 4 carbon atoms;
Xl is a halogen, p is an integer of 2 to 10)] as the main structural unit, the substituent α is 004 to 12 mol%, and the substituent β is 83 to 12 mol% 9996 molar ratio and substituent r is less than 5 mol% of O, and substituent α, substituent β, and substituent γ are present, and each of the above structural units has a structure in which the above-mentioned structural units are randomly polymerized with a head-to-tail bond. A linear phosphazene polymer containing a viologen structure in its side chain with a degree of polymerization of 5 to 1,500 and containing at least one structural unit hole (D or hole) in one molecule as an average composition satisfies this purpose. They discovered this and completed the present invention.

The above two groups of polymers are new substances and have the same intended use as I-7, and their structures differ only in whether or not they have quaternary ammonium salt residues in their side chains. Only. According to probabilistic considerations, the abundance ratios of the structural units constituting the above two groups of polymers are as follows.

That is, the structural unit represented by general formula (A) is 1.44
4 mol% or less of the structural unit represented by the general formula (B) is 0.
08 to 21.12 mol%, the structural unit represented by the general formula (C) is 68.89 to 9992 mol%, the structural unit represented by the general formula (D) is 1.2 mol% or less, - the general formula (E )
The structural unit represented by formula (F) is 950 mol % or less, and the structural unit represented by general formula (F) is 0.255 mol % or less. In the first group of polymers, the structural unit (D),
(E) and CF) are not present.

The linear phosphazene polymer containing the viologen structure of the first group in its side chain is synthesized, for example, by the following route.

1) A linear phosphonitrile dichloride polymer having a number average molecular weight of 300.000 or less obtained by ring-opening polymerization of cyclic phosphonitrile chloride in the presence of a hydrochloric acid scavenger of a tertiary amine (eg triethylamine, pyridine, etc.) 2.2.
2-) IJ fluoroethanol, 2.2.3.3.
4.4.4-Heptafluoro-1-butanol 2.2
．． 3.3.4.4.5.5-octafluoro-1-pentanol, 2.2.3.3.3-pentafluoro-1-
Proper tool, 2.2.3゜3-tetrafluoro-1-
General formula (I) HO-CI-■2-R2 of propa tools, etc.
(R2 is a fluoroalkyl group having 1 to 4 carbon atoms) and a fluoroalcohol having 2 to 5 carbon atoms and the general formula (TI) (wherein p is an integer of 2 to IO, Xl and X2 are), rogene, R1 is an alkyl group having 2 to 10 carbon atoms).

Here, the reaction temperature is preferably 50 to 200 C1
More preferably, the temperature is 80 to 150C, and the reaction time is preferably 5 to 100 hours, even more preferably 10 to 50 hours.
It's time. Preferred solvents include toluene dioxane, tetrahydrofuran, acetone, and chlorobenzene. After the reaction, the solvent is removed and redissolved in a small amount of the above solvent, and the solution is treated several times with an alkaline aqueous solution such as sodium hydroxide.
refine.

2) The molar ratio of the linear phosphonitrile dichloride polymer to chlorine in the polymer is 088 to 0.999.
A method of first reacting an alkali metal salt of the above-mentioned fluoroalcohol having 2 to 5 carbon atoms, and then reacting an alcohol having a viologen structure represented by the general formula (If) in the presence of a tertiary amine.

In this case, the reaction temperature, reaction time, solvent, hydrochloric acid scavenger, purification method, etc. in each step are the same as in 1) above.

The M-type phosphazene polymer containing the second group of viologen structures in its side chain can be synthesized, for example, by the following route.

3) The above-mentioned fluoroalcoholde having 2 to 5 carbon atoms is added to the linear phosphonitrile dichloride polymer according to the general formula (wherein, X2 is a halogen and R1 is an alkyl group having 2 to 10 carbon atoms).
Compounds represented by and general formula (IV)
For example, ethylene bromohydrin, 3-7
``A method using a halogenated alcohol such as como-1-propatool, 8-promo-1-octatool, etc., and using a trialkylamine or pyridine having an argyl group having 1 to 5 carbon atoms as a tertiary amine as a hydrochloric acid scavenger. .

In this case, the reaction temperature, reaction time, solvent, purification method, etc. are the same as in the case of 1) above.

The polymer of the present invention contains at least one group having a viologen structure in one molecule when considered as an average composition. However, if the content of the group having a viologen structure is too small, electrochromic or photochromic properties will not be exhibited, and if the content is too large, the durability of the above properties will decrease and the glass transition temperature of the polymer will increase. In addition, since it exhibits no rubber elasticity at the temperature of use and its usefulness is reduced, the proportion of groups having a viologen structure is in the range of 0.04 to 12 moles, preferably in the range of I to 0.1 to 5 moles. be.

In addition, in the case of linear phosphazene polymers containing the second group of viologen structures in their side chains, that is, polymers obtained by method 3), the glass transition temperature of the polymer increases as the proportion of quaternary ammonium salt residues increases. Since this is not preferable, the proportion of quaternary ammonium salt residues is 5 mol% or less,
Preferably it is 2 mol% or less. In this way, the polymer obtained by method 3) has no effect on electrochromism or photochromism, and contains quaternary ammonium salt residues that have the effect of raising the glass transition temperature of the polymer compared to fluoroalkyl groups. Although it is disadvantageous in
On the other hand, it is possible to omit the synthesis and purification steps of the alcohol having a viologen structure represented by general formula (II), which is a raw material when carrying out methods 1) and 2), and the general formula (1)
Since the desired polymer can be directly obtained from the compound of formula (1'V) and the logenated alcohol of general formula (1'V), there is a great advantage in that the manufacturing process is simplified and the manufacturing cost is reduced.

The degree of polymerization Vi of the polymer of the present invention is from 5 to 1500,
Preferably, < is 10-1500.

(Effects of the Invention) Since the linear phosphazene polymer of the present invention contains a viologen structure in the side chain rather than the main chain, it is a rubber-like elastic body with a low glass transition temperature and can be used even at low temperatures. It is a useful rubber-like functional material that hardly dissolves or deteriorates even when used in the environment, and can be used for a long time.

(Example) Examples of synthesis of typical viologen structure-containing intermediates and examples of methods for introducing them into the linear phosphazene borimano side chain are shown below. Polymers are not limited to those obtained by such manufacturing methods.

Reference Example 1 Synthesis of l-n-propyl-4,4'-bipyridinium monopromide 4,4'-bipyridyl 10y-1n was placed in a flask equipped with a stirrer and a reflux cooler under a nitrogen gas atmosphere.
-propyl bromide 71 and acetoni) IJ Le 20
The mixture was added for 30 minutes, and stirring and refluxing was continued for 48 hours.

After the reaction, a small amount of yellow precipitate formed by standing at room temperature was split into portions, and the portion was completely evaporated to obtain a pale colored precipitate, which was washed with a small amount of ether. The remaining solid was recrystallized from an acetonitrile solution to give highly hygroscopic yellow crystals (1-n-propyl-4,4'-bipyridinium monopromide) as 111 (
Yield: 65%) TG.

Reference example 2 1-n~propyl, 1'-(2-hydroxy)ethyl-
Synthesis of 4,4'-biviridinium dipromide 1- was synthesized in the same manner as in Reference Example 1 in a flask equipped with a stirrer and a reflux cooler under a nitrogen gas atmosphere.
14.97 d of n-propyl-4,4'-bipyridinium monopromide, 8.41 d of ethylene bromohydrin and 200 d of acetonitrile were added, and stirring and refluxing were continued for 48 hours.

The yellow crystals formed were split and washed with a small amount of acetonitrile to obtain the desired 1-n-propyl, 1'(2-hydroxy)ethyl-4,4'-bivillinium dibromide, 1335c (yield: 57%). )Obtained.

Example 1 1-n-propyl, 1'-(2-hydroxy)ethyl-4,4'-biviridinium dipropylene synthesized in Reference Example 2 in a flask equipped with a stirrer and a reflux cooler under a nitrogen gas atmosphere. 2.0% trifluoroethanol, 11.07% trifluoroethanol, ) IJ ethylamine 201j and dioxane 20. d was added thereto, and 20 mL of a toluene solution containing linear dichlorophosphazene polymer (number average molecular weight 52.000) 6D was added dropwise thereto over 1 hour at room temperature with stirring. Thereafter, stirring and refluxing were continued for 26 hours. After the reaction, the solvent was evaporated, the remaining solid was dissolved in a small amount of acetone, the solution was poured into an aqueous sodium hydroxide solution for purification, the obtained solid was dissolved again in acetone, and then poured into pure water. After repeating the refining process twice, it turned out to be 4.2? A reddish-purple, rubbery, elastic polymer was recovered.

This polymer is easily soluble in chloroform, acetone, methyl ethyl ketone, ethanol, tetrahydrofuran, dioxane, etc., has a glass transition temperature of -37C, and a number average molecular weight of 2.
It was 6.000. IR and H-N of this polymer
The MR spectra are shown in FIGS. 1 and 2.

In the IR spectrum, in addition to the absorption of the trifluoroethoxy-substituted phosphazene polymer, a characteristic absorption based on the stretching vibration of the pyridinium ion ring is found in 1645Cr11'.
appeared in

The assignment of each peak in the 'H-NMR spectrum shown in FIG. 2 is as follows.

[Yes] ■ OCH□CF3 @-N=P In addition, in the 'H-NMR spectrum, when the composition is determined from the intensity ratio of each peak, ■ / Ki 1. /65 (1 mole)
Met.

The proportions of each structural unit in the polymer obtained from the above results are as follows.

Constituent unit of general formula (A) (hereinafter simply abbreviated as (A) etc.) 002 mol%; (B) 2.98 mol%; (C) 9
7.00 mol% Example 2 Same as Example 1 except that the amount of 1-n-propyl, 1'-(2-hydroxy)ethyl-4,4'-bipyridinium dibromide was changed to 5.01. An experiment was conducted in exactly the same manner as in Example 1.3. A reddish-purple rubbery polymer of g5r- was obtained. Its solubility was similar to that of the polymer obtained in Example 1. However, the glass transition temperature was -22c and the number average molecular weight was 22,000.

The IR and H-NMR spectra of this polymer were
As shown in FIG.

When the composition was determined from the intensity ratio of each peak appearing in the 'H-NMR spectrum, the ratio of and in the structural formula shown in Example 1 was 1/28 (1 mole).

From the above results, the proportions of each structural unit are determined as follows.

(A) 0.12 molar ratio; (B) 6.66 molar ratio;
(C) 93.22 mol% Example 3 Under a nitrogen gas atmosphere, 10 ml of dioxane and a linear dichlorophosphazene polymer (number average, molecular, f1185
,000) 10 rRl of toluene solution containing 354
was added thereto, and 11.6 ml of a tetrahydrofuran solution (4 mol//) of trifluoroethanol sodium salt was added dropwise thereto at room temperature with stirring over 1 hour, followed by continued stirring and reflux for 26 hours. After the contents were brought to room temperature, triethylamine 5rILt and 1n-propyl, 1'
-(2-hydroxy)ethyl, 4. ．． 4'-Biviridinium dipromide l? When added, the system immediately turned dark blue.

After further stirring and refluxing for 24 hours, the contents were subjected to the same post-treatment as in Example 1, and the result was a glass transition temperature of -42C1 with the same solubility as the polymer obtained in Example 1.
A reddish-purple polymer with a number average molecular i of 33,000 is z, 5y
1j% was lost.

When the composition was determined from the intensity ratio of each peak appearing in the 'H-NMIt spectrum, the ratio of and 0 in the structural formula shown in Example 1 was 1/93 (1 mol).

The proportions of each constituent unit are determined from the above results as follows.

(A) 0.01 mol%; (B) 2.11 mol%;
(C) 97.88 mol% Example 4 Under a nitrogen gas atmosphere, 0.777% of ethylene bromohydrin was added to a flask equipped with a stirrer and a reflux cooler.
,) 5.6?1 liters of 1-n-propyl-4,47-bipyridinium monopromide synthesized in Reference Example 1, 10.81 Ll of triethylamine and 1011 Ll of dioxane were added to it (linear dichlorophosphazene). Polymer (number average molecular weight 52,000) 3
) at room temperature with stirring.
It was dripping for about an hour or so.

Thereafter, reflux was continued for 26 hours while stirring. After the reaction is complete,
When the contents were post-treated in the same manner as in Example 1,
A dark reddish-brown comb-shaped polymer with a glass transition temperature of -18C1 number average molecule +J]8.000 exhibiting a solubility similar to that of the polymer obtained in Example (2) has a glass transition temperature of 2.9? Obtained.

The IR and H-NMR spectra of this polymer are shown in FIGS. 5 and 6.

In the IR spectrum, in addition to the absorption of the trifluoroethoxy-substituted phosphazene polymer, a characteristic absorption based on the stretching vibration of the pyridinium ion ring appeared at 1645 crn.
400 crr1-1) could not be confirmed due to the strong absorption of the fluoroethoxyphosphazene polymer.

The assignment of each peak in the 'H-NMR spectrum shown in FIG. 6 is as follows.

0C112CF3 0-N=P Furthermore, from the intensity ratio of each peak appearing in the 'H-NMR spectrum, the ratio of the above structural formula is ■: [F]: Oki 3: 18
It was calculated as 0:1.

The proportions of each constituent unit are determined from the above results as follows.

(A) 0.03 mol%; (B) 3.19 mol%; (C)
0.02 mole ratio: (E) 1
．． o 6 mol %; 1-n-hephthyl-4,4'-bipyridinium monopromide was synthesized in the same manner as in Reference Example 2. Instead of the monopromide synthesized above, and instead of ethylene bromohydrin, 6-bromo-1-
1-n-heptyl, 1'-(6-hydroxy) in the same manner as in Reference Example 2 except that hexanol was used, respectively.
Hexyl-4,4'-bipyridinium dipromide was synthesized.

Next, in Example 1, 1-n-propyl, 1'(2-hydroxy)ethyl-4,4'-biviridinium dibromide 2.01 was replaced with 1 synthesized according to the method of Reference Example 2 above. -n-heptyl, 1'-(6-hydroxy)hexyl-4,4'-bipyricinium dibromide 2.6? An experiment was carried out in exactly the same manner as in Example 1, except that 4.21 reddish-purple rubbery polymers were obtained. Its solubility was similar to that of the polymer obtained in Example 1.

However, the glass transition temperature is -30'c and the number average molecular weight is 3.
It was 0,000.

The IR and 1 H-NMR spectra of this polymer are shown in Figures 7 and 8, respectively.

In the IR spectrum, in addition to the absorption of the trifluoroethoxy-substituted phosphazene polymer, a characteristic absorption based on the stretching vibration of the K and pyridinium ion rings appeared at 1645 crn'.

Each peak in the 11I-NMR spectrum shown in FIG. 8 was assigned as follows.

[Yes] (1) 0CH2CF3 (1) -N=P- In addition, in the 'H-NMR spectrum, the composition was determined from the intensity ratio of each peak, and it was found to be (1) 10 x 1/32 (1 mol).

The proportions of each structural unit were calculated from the above results and were as follows.

(A) 0.09 molar ratio; (B) 5.88 molar ratio; (
C594,03 molar reference example 3 An example of the use of the linear phosphite/polymer containing the viologen structure in the side chain synthesized in Example 5 as an electrochromic display element will be explained with reference to FIG. 9. Cell 1 is formed. At this time, the above polymer is dissolved in acetone, and the solution is applied onto the electrode section 3 of a transparent glass electrode (ITO glass) 4 consisting of a glass substrate 2 and an electrode section 3, and the solvent is evaporated to form a film-like electrochromic. (EC) material layer 5
And nuclear! By covering the pole portion 3, a display electrode 6 is formed. A spacer 8 was inserted between the display electrode 6 and the counter electrode 7, and a space therebetween was filled with a methanol solution of lithium perchlorate to form a solution layer 9. When a voltage of 115 V was applied to the cell 1 thus formed using the display electrode 6 as a cathode, the reddish-purple color before application changed to blue-green. When a reverse voltage was applied in this bluish-green state, it returned to its original reddish-purple color.

This operation was repeated 10,000 times, but the display electrode (
i reversibly changes color, and the electrode part 3 and the film-like EC material layer 5
No change was observed in the color, and no change in hue was observed.

[Brief explanation of the drawing]

Figures 1 and 2 show the I of the polymer obtained in Example 1.
The n spectrum and 'H-NMR spectrum, Figures 3 and 4 are the In spectrum and 'H-NMR spectrum of the polymer obtained in Example 2, Figures 5 and 6.
Figures 7) In spectrum and UIII-NMR spectrum of the polymer soaked in Example 4, Figures 7 and 8 show In spectrum and 'H-NMR spectrum of the polymer soaked in Example 5, Figure 9. 1 shows a cross-sectional view of an example of a cell using the polymer of the present invention as an electrochromic display element.

Claims (8)

[Claims] (1) General formula (A) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, General formula (B) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, and General formula (C) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [Here, α is a general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (p is an integer of 2 to 10, R_1 is an alkyl group having 2 to 10 carbon atoms, X_1 and X_2 are halogens) a group having the structure, and β is the general formula −
CH_2-R_2 (R_2 is a fluoroalkyl group having 1 to 4 carbon atoms) is a fluoroalkyl group having 2 to 5 carbon atoms] as the main structural unit, and the substituent α is 0.04 to 12 mol. % and substituent β is 88-9
Substituent α and substituent β are present in a ratio of 9.96 mol%,
The above structural units have a structure in which they are randomly polymerized with head-to-tail bonds, and each molecule contains at least one structural unit (A) or (B) as an average composition.The degree of polymerization is 5 to 1500.
A linear phosphazene polymer containing a viologen structure in its side chain. (2) R_2 is a trifluoromethyl group, p is 2, R_1
The polymer of claim 1, wherein n-C_3H_7. (3) R_2 is trifluoromethyl group, p is 6, R_1
The polymer of claim 1, wherein n-C_7H_1_5. (4) A linear phosphonitrile dichloride polymer containing a fluoroalcohol represented by the general formula (I) HO-CH_2-R_2 (in the formula, R_2 is a fluoroalkyl group having 1 to 4 carbon atoms) and the general formula (II) ▲Math. , chemical formulas, tables, etc.▼(II) (In the formula, p is an integer of 2 to 10, X_1 and X_2 are halogens, and R_1 is an alkyl group having 2 to 10 carbon atoms.)
The method for producing a polymer according to claim 1, characterized in that the alcohol having a viologen structure represented by: is reacted in the presence of a tertiary amine. (5) The molar ratio of the linear phosphonitrile dichloride polymer to chlorine in the polymer is 0.88 to 0.9996
with the general formula (I') MO-CH_2-R_2 (in the formula, R
(_2 is a fluoroalkyl group having 1 to 4 carbon atoms, M is an alkali metal) is reacted with an alkali metal salt of a fluoroalcohol represented by general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( II) (wherein p is an integer of 2 to 10, X_1 and X_2 are halogens, and R_1 is an alkyl group having 2 to 10 carbon atoms)
Claim 1 characterized in that an alcohol having a viologen structure represented by is reacted in the presence of a tertiary amine.
A method for producing the polymer described in . (6) General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, General formula (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, General formula (C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , General formula (D) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, General formula (E) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, and General formula (F) ▲ Contains mathematical formulas, chemical formulas, tables, etc. 〔 Here, α is the viologen structure represented by the general formula ▲ Numerical formula, chemical formula, table, etc. The group β has the general formula -CH_
2-R_2 (R_2 is a fluoroalkyl group having 1 to 4 carbon atoms) and γ is a general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (R_3)_3X＾ ■＿１ or ▲Mathematical formulas, chemical formulas, tables, etc.▼(R_3 is an alkyl group with 1 to 5 carbon atoms,
_1 is a halogen, p is an integer of 2 to 10) is a quaternary ammonium salt residue] as the main structural unit, the substituent α is 0.04 to 12 mol%, and the substituent β is Substituent α, substituent β, and substituent γ are present at a ratio of 83 to 99.96 mol% and substituent γ is greater than 0 and 5 mol% or less, and each of the above structural units is randomly polymerized with a head-to-tail bond. The structural units (A) and (B) are contained in one molecule.
) or (D) as an average composition, a linear phosphazene polymer containing a viologen structure in its side chain and having a degree of polymerization of 5 to 1500. (7) R_2 is trifluoromethyl group, p is 2, R_1
is n-C_3H_7 and γ is -CH_2CH_2N^
7. The polymer according to claim 6, which is ■(C_2H_5)_3X^■_1. (8) Linear phosphonitrile dichloride polymer, general formula (I) fluoroalcohol represented by HO-CH_2-R_2 (in the formula, R_2 is a fluoroalkyl group having 1 to 4 carbon atoms), and general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, X_2 is a halogen, R_1 is an alkyl group having 2 to 10 carbon atoms) and the general formula (
IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, p is an integer of 2 to 10, and X_1 is a halogen. 7. The method for producing a polymer according to claim 6, wherein the reaction is carried out using a trialkylamine or pyridine having an alkyl group.