JPS6368687A - Functional ionen polymer - Google Patents

Abstract

PURPOSE:To provide a functional ionen polymer capable of functioning as photochromic, electrochromic, thermochromic material etc. and having excellent mechanical properties, which is represented by a particular structural formula. CONSTITUTION:A functional ionen polymer represented by the formula 1 (wherein X is a polyether residue; R is a satd. or unsatd. aliphatic hydrocarbon group; and n is an integer of 2 or more). A preferable example of the polyether residue includes one having a 2-4C ether unit, particularly poly oxytetramethylene. With respect to R, the aliphatic satd. hydrocarbon group is preferably a 1-3 alkylene group which may have a methyl group, while the aliphatic hydrocarbon group having an unsatd. bond is pref. alkenylene, alkadienylene, alkatrienylene, and alkynylene capable of forming a conjugated structure with a pyridine ring. The anion represented by the A is a monovalent or divalent anion.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is suitable as a functional ionene polymer, more specifically, as a material for photochromism, electrochromism, thermochromism, etc., and is suitable for use in display materials, optical storage elements, etc. This invention relates to a functional ionene polymer that can be used for various purposes.

<Prior art> Conventionally, N,N'-dialkyl-4,4°-diviridinium (viologen) is reduced by -electrons to generate viologen cation radicals and changes from colorless to blue to purple, and is oxidized. It is known to exhibit so-called reversible redox properties, returning to a colorless scation.

Further, the polymer having viologen units is a redox polymer, and can be used as an electron conductor for redox reaction and a light energy conversion film. In addition, the polymers having the viologen units described above also exhibit photochromism and electrochromism, and are expected to be used as light amount control materials, image recording materials, and display materials (J, EIelectrochem, Soc, ,E
Electrochemical Science and
Technology, 130(5), 1080(1
983): J, Phys, Che++,, 87.53
45 (1983)).

Furthermore, as such a viologen polymer, a polymer obtained by a condensation reaction between a diamine having a viologen skeleton and an acid chloride of a dicarboxylic acid is known (Journal of' Polymer Sci.
nce, Polymer Chegistry E
dltion, 13.1 (1975)). However, the above polymer films are glassy, brittle, and have poor mechanical properties, so they are not practical.

Also known is a polymer having viologen units produced by cationically polymerizing tetrahydrofuran and reacting with 4,4゛-dipyridyl using a monofunctional Lewis acid as an initiator (Proceedings of the Society of Polymer Science and Technology, Vol. 31). , 33rd
p. 0, 1982). However, the above-mentioned polymer has only one viologen unit contained in the polymer chain, and not only does it not have sufficient mechanical strength, but also the above-mentioned functions peculiar to viologen are not fully expressed, so that it is poor in practical use.

Furthermore, the above report also reports, as a polymer having other viologen units, a polymer obtained by tosylating both ends of a hydroxyl-terminated polyether and reacting it with 4,4'-dipyridyl.

However, the above-mentioned polymers are dimers or trimers and have insufficient film-forming properties, making them impractical.

Furthermore, electrochromic materials that can withstand repeated use approximately 3,000 times are also known (Japanese Unexamined Patent Publication No. 56-26
Publication No. 974). However, the electrochromic material is a crystalline compound that does not have film-forming properties, and
Since it is used in the form of a solution, there is a problem in that it can only be applied to limited applications.

Summary: This invention was made in view of the above problems, and provides a functional ionene polymer that has functionality as photochromism, electrochromism, thermochromism, etc., and has excellent mechanical properties. The purpose is to

Means and operation for solving the above problems> The present invention solves the above-mentioned conventional problems using a functional ionene polymer represented by the following general formula (1).

(wherein, X represents a polyether residue, R represents a 5] optionally branched saturated or unsaturated aliphatic hydrocarbon group,
(A represents an anion, and n represents an integer of 2 or more) The present invention will be described in detail below.

More specifically, each group shown in the above general formula [1] is as follows.

Examples of polyether residues include polyethers having ether units having 2 to 10 carbon atoms, such as polyoxyethylene, polyoxypropylene, polyoxy(chloromethylethylene), polyoxy(1゜1-di(chloromethyl)).
Examples include polyoxytetramethylene, polyoxypentamethylene, polyoxyhexamethylene, polyoxyheptamethylene, polyoxyoctamethylene, polyoxynonamethylene, and polyoxydecamethylene. Among these polyether residues, carbon number 2
Polyether residues having ~4 ether units are preferred, especially polyoxytetramethylene. The above polyether may have various degrees of polymerization, but from 5 to 100.
Those having a certain degree of polymerization are preferred.

Further, in the general formula (1), the optionally branched aliphatic saturated hydrocarbon group represented by R includes alkyl 1.・N group,
For example, methylene, ethylene, trimethylene, tetra-tramethylene, pentamethylene, hexamethylene, methylmethylene, methylethylene, 1-methyltrimethylene, 2
-Methyltrimethylene, 2-ethyltrimethylene, 2-
Propyltrimethylene, 2-methyltetramethylene, 3
-Methylpentamethylene, 4-ethylhexamethylene, etc. can be exemplified. In addition, examples of the optionally branched aliphatic unsaturated hydrocarbon group include vinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, 3-pentenylene, 1-hexenylene, 2-hexenylene, Alkenylene such as 3-hexenylene, 4-hexenylene; 1,2-propadienylene, 1,2-butadienylene, 1,3-butadienylene, 1,2-pentadienylene, 1,3-pentadienylene, 1.4-pentadienylene, 2,4 - Alkadienylene such as pentadienylene, 1,2-hexadienylene, 1,3-hexadienylene, 1,4-hexadienylene, 1°5-hexadienylene, 2,4-hexadienylene, 1,2,4-pentatrienylene, 1,3.5-
Alkatrienylene such as hexatrienylene; alkynylene such as ethynylene, l-provinylene, 2-butynylene, 2-pentynylene, 4-bentynylene, 2-hexynylene, 3-hexynylene, etc. having at least one double bond or triple bond I can give examples.

Among the above aliphatic saturated hydrocarbon groups, an alkylene group having 1 to 3 carbon atoms which may have a methyl group is preferable, and among the aliphatic hydrocarbon groups having an unsaturated bond, a pyridine ring and a conjugated structure are preferable. alkenylene, alkadienylene,
Alkatrienylene and alkynylene are preferred.

In addition, in the above general formula (1), the anion represented by A is:
- is a valent or divalent anion. Examples of -valent anions include halogen anions such as fluoride, chloride, bromide, and iodite; monocarboxylic acid anions such as acetate, trifluoroacetate, and benzoate; sulfate anions such as sulfate and methyl sulfate; methanesulfonate and ethanesulfonate; Nath,
Examples include sulfonate anions such as heptanesulfonate and benzenesulfonate. Examples of divalent anions include dicarboxylic acid anions such as oxalate, malonate, adipate, and suberate; and disulfonic acid anions such as 1,2-ethanedisulfonate.

The functional ionene polymer of the present invention has various excellent properties as an elastomer, and exhibits photochromic and electrochromic properties in both a solid form such as a film and a solution form dissolved in an appropriate solvent. , has the property of thermochromism.

Various solvents can be used as the solvent, such as water, aqueous solutions of the alkali metal salts, etc.; alcohols such as methanol and ethanol; ethers such as dimethyl ether and diethyl ether; pyridine, picoline,
Examples include dimethylformamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone.

In addition, when the functional ionene polymer of the present invention is used as a photochromic material, conventionally known photosensitizers,
For example, polyvinylpyrrolidone, proflavin and ethylenediaminetetraacetic acid (EDTA), etc. may be used.

The functional ionene polymer of the present invention not only becomes colored by being reduced by light irradiation, but also becomes colored by being reduced electrically in the presence of a suitable reducing agent. That is, when the functional ionene polymer film is immersed in, for example, an aqueous solution of sodium hydrosulfide, it is reduced and colored.

The functional ionene polymer of the present invention can be produced by various methods, for example, by the method shown in the reaction formula below.

2△- or △2′″ (1a) (wherein, R1 represents a hydrogen atom or a methyl group which may have a halogen atom as a substituent, p and q are positive integers, and M represents a cation. and Rln and A are the same as above) The functional ionene polymer of the present invention is obtained by cationically polymerizing a cyclic ether represented by formula (23) using a cationic polymerization initiator to obtain a polymer of formula (3). By reacting this polymer (3) with a compound represented by formula (4), an ionene polymer of formula (S) can be produced. This residual anion is
A functional ionene polymer represented by formula (1a) may be obtained by substituting the anion represented by A using a salt of the anion represented by formula (6).

Examples of the cyclic ether represented by the above formula (2) include cyclic ethers and their derivatives, such as ethylene oxide (oxirane), propylene oxide, epichlorohydrin, oxetane, 3,3-bischloromethyloxetane, tetrahydrofuran (oxolane), and methyltetrahydrofuran. , tetrahydropyran, trioxane, etc. Among the above cyclic ethers, cyclic ethers having 2 to 4 carbon atoms and derivatives thereof are preferred.

Further, as the cationic polymerization initiator, conventionally known cationic polymerization initiators can be used, but it is preferable to use a bifunctional initiator. As the above bifunctional initiator, for example,
Examples include acid anhydrides such as trifluoromethanesulfonic anhydride, fluoromethanesulfonic anhydride, and chloromethanesulfonic anhydride, and dicarbonium salts such as styrene dimer cation salts.

Further, as the compound represented by formula (4), a compound in which a pyridine ring is bonded to both ends of the optionally branched alkylene group, alkenylene group, alkadielene group, alkatrienlene group, alkynylene group, etc. For example, bis(4-pyridyl)methane, 1,2-bis(4
-pyridyl)ethane, 1,2-bis(4-pyridyl)propane, 1,3-bis(4-pyridyl)propane, 1,
2-bis(4-pyridyl)butane, 1,3-bis(4-
pyridyl)butane, 2,3-bis(4-pyridyl)butane, 1,2-bis(4-pyridyl)pentane, 1.3-
Bis(4-pyridyl)alkanes such as bis(4-pyridyl)pentane, 2,4-bis(4-pyridyl)pentane, 1,3-bis(4-pyridyl)hexane; 1,2-bis(4- pyridyl)ethylene, 1,2-bis(4-pyridyl)propylene, 1,3-bis(4-pyridyl)propylene, 1,2-bis(4-pyridyl)-3-butylene,
1.3-bis(4-pyridyl)-2-butylene, 1.4
-bis(4-pyridyl)-2-butylene, 1,3-bis(4-pyridyl)-2-pentene, 2,4-bis(4-
Bis(4-pyridyl) alkenes such as pyridyl)-3-pentene, 1,3-bis(4-pyridyl)-2-hexene; 2,4-bis(4-pyridyl)-1,3-butadiene, 1, Bis(4-pyridyl)alkadienes such as 3-bis(4-pyridyl)-2,4-hexadiene, 2.5-bis(4-pyridyl)-1,3-hexadiene; 2.4-
Bis(4-pyridyl)alkatrienes such as bis(4-pyridyl)-1,3,5-hexatriene; bis(4-pyridyl) such as 1,2-bis(4-pyridyl)ethynylene;
Examples include alkynylene.

Further, as the compound represented by formula (6), any compound can be used as long as it dissociates to produce the anion represented by A above. Examples of these compounds include sodium, potassium, and lithium salts of the anions.

The cationic polymerization of the cyclic ether and its derivatives represented by the above formula ('2J) is carried out using an appropriate amount of a cationic polymerization initiator. The reaction can be carried out under appropriate conditions,
For example, usually -50 to 50°C, preferably -10 to 1
The process is carried out at a temperature of 0° C. for about 5 minutes to 12 hours. In addition,
The molecular weight of the polyether residue X can be adjusted by controlling the polymerization time and the like.

Next, after the above reaction, it is made to react with a compound represented by formula (4). This reaction can be carried out under appropriate conditions, for example, usually -150°C to room temperature, preferably -
It can be carried out at a temperature of 100 to 0°C for about 30 minutes to 24 hours. In addition, in the above reaction, the molecular weight of the polymer can be adjusted by controlling the concentration of the compound shown in (4) above.

Note that all of the above reactions may be performed in the presence of an inert solvent.

<Example> Hereinafter, this invention will be explained in more detail based on Examples.

Example 1 A 300 ml eggplant flask was charged with 100 g of dehydrated and purified tetrahydrofuran, and the flask was purged with nitrogen. While stirring tetrahydrofuran vigorously in a constant temperature water bath at 2°C,
3.85 g of trifluoromethanesulfonic anhydride (
0.12 mol/g) was added and polymerized for 15 minutes. On the other hand, an equimolar amount of 1
, 100 ml of tetrahydrofuran solution in which 2-bis(4-pyridyl)ethane was dissolved was cooled to about -70°C,
The above polymerization reaction solution was added thereto and reacted for 1 hour. Next, at room temperature, the reaction solution was gradually poured into 400 ml of 0.5N aqueous sodium bromide solution with stirring to precipitate the produced polymer. After washing the obtained polymer with pure water, it was reprecipitated with methanol and a 0.5N aqueous sodium bromide solution, and further reprecipitated with methanol and pure water for purification to obtain 1,2-bis(4 -pyridyl)ethane units (hereinafter referred to as PE-PT) was obtained.

Example 2 12.In place of 2-bis(4-pyridyl)ethane, 1.
A polymer having 1,2-bis(4-pyridyl)propane units was prepared in the same manner as in Example 1 above, except that 2-bis(4-pyridyl)propane and 1°2-bis(4-pyridyl)ethylene were used. (hereinafter referred to as PP-PT)
A polymer having 1,2-bis(4-pyridyl)ethylene units (hereinafter referred to as PEY-PT) was obtained.

For PEY-PT, methanol and 0.5
It was purified by reprecipitating twice with an aqueous N-sodium bromide solution and washing with pure water.

Reference Example 3 The technology for measuring the molecular weight of ionene polymers has not yet been established (K, Kataoka et al, Makro
mol, CheL Vol. 180, p. 65, 1979), so the above PE-PT, PP-PT and PEY-
In order to estimate the molecular weight of PT, instead of the above 1,2-bis(4-pyridyl)-ethane, -
A polymer having pyridine units (hereinafter referred to as PT-PT) was prepared in the same manner as in Synthesis Example 1 above, except that pyridine, which is a functional amine, was used in a molar ratio of pyridine/trifluoromethanesulfonic anhydride-2,0. I got it. In addition,
In this PT-PT, both ends of polytetrahydrofuran are bonded to the nitrogen atoms of the pyridine ring and blocked.

The physical properties of the polymers obtained in the above Examples and Reference Examples are shown below.

Spectral analysis Spectral analysis of the above polymer by NMR (solvent: CD30D) revealed that in PP-PT, protons at the β position of the pyridine ring (δ-8, lppm) and α
A peak of protons at δ-8.9 ppm was observed. In addition, in PEY-PT, β of the pyridine ring
Proton at position (δ-8.4ppm), proton at α position (
δ-9,lppm) and ethylene (δ-8,1ppm)
A peak of I11) was observed. Further, in the above polymer, peaks of β-methylene and α-methylene of polytetrahydrofuran were both observed.

In addition, according to the infrared absorption spectrum, all polymers have a peak (1
6500111-1) was observed.

α-alumina was used as the standard material for thermal analysis, and the heating rate was 10℃/
1n, the above PE-PTSPP-PT and PE
When Y-PT was thermally analyzed, the TG curve showed 2
No significant weight loss was observed up to 50°C. Also, D
In the SC curve, an endothermic peak that is thought to be based on the melting of polytetrahydrofuran is seen at around 40°C, and a peak that is thought to be based on the thermal decomposition of the polymer is seen at around 250°C.
This was seen on the higher temperature side.

Softening Point The softening points of the above PP-PT and PE-PT were measured, and the results shown in Table 1 were obtained.

Table 1 Softening point ("C) Intrinsic viscosity When the intrinsic viscosity number was determined from the viscosity measurement in a 0.1N lithium bromide methanol solution, the results shown in Table 2 were obtained. In addition, the above PP-PT etc. The intrinsic viscosity number of the above-mentioned PT-PT synthesized to estimate the molecular weight of
9,400.

Table 2 Films were easily obtained by casting the methanol solutions of PE-PT, PP-PT, and PEY-PTF.

After drying the obtained film under reduced pressure, it was subjected to the following tests.

Tensile Test A tensile test was conducted using the film obtained as described above, and the results shown in Table 3 were obtained. .

The tensile test was performed using a tensile tester TO manufactured by Shinko Tsushin Kogyo Co., Ltd.
Using M200D, a sample with a thickness of about IM (inner diameter 11.8
M% outer diameter 13.8 mm), tensile speed 10 mm/
I did it in minutes.

Table 3 From the results shown in Table 3, the film was found to be a high strength elastomer with good tensile properties.

■Using a photochromism high-pressure mercury lamp to cut off ultraviolet rays of 290 nm or less, PP-PT was irradiated with light in a vacuum at room temperature.
The film of PEY-PT was colored from colorless to blue, and the film of PEY-PT was colored from reddish brown to deep reddish brown.

(2) Thermochromism When the vacuum-degassed film was heated, the PP-PT film changed color from colorless to blue at around 130°C.

Furthermore, when the film was left in the air to cool, the PP-PT film returned to its original color, indicating that it was reversible.

■Electrochromism PEY-PT with N,N-dimethylformamide (DMF)
), and tetraethylammonium tosylate (TEAT) as an indicator electrolyte was dissolved to a concentration of 0.2N. To this solution, 10 mA under nitrogen atmosphere,
When applied under the condition of 29V, the color changed from yellow to deep purple. In addition, when applied in the opposite direction to the above, the original color returned, and it was found that the color was reversible. Note that a platinum electrode was used as the electrode.

<Effects of the Invention> As described above, according to this invention, photochromism,
It is possible to provide a functional ionene polymer that has properties such as electrochromism and thermochromism, can be easily formed into a film, has excellent processability, and has properties as a high-strength polymer.

Patent applicant Sumitomo Electric Industries, Ltd. Koei Chemical Industry Co., Ltd. Representative Patent attorney Kamei
Hirokatsu (3 idiots)

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 2 A^- or A^
2^- (wherein, X represents a polyether residue, R represents a saturated or unsaturated aliphatic hydrocarbon group which may be branched, and A
is an anion, n is an integer of 2 or more) A functional ionene polymer represented by: