JPH0737523B2 - Ionene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention is suitable as a functional ionene polymer, more specifically, as a material for photochromism, electrochromism, thermochromism, and the like, and is used as a display material, an optical storage element, or the like. The present invention relates to a functional ionene polymer that can be used for.

<Prior Art> Conventionally, N, N′-dialkyl-4,4′dipyridinium (viologen) is one-electron reduced to generate a viologen cation radical, which changes from colorless to blue to purple and is oxidized. It is known to exhibit a so-called reversible redox property, returning to a colorless dication.

Further, the polymer having the viologen unit is a redox polymer and can be used as an electron conductor for a redox reaction and a light energy conversion film. Further, the polymer having the viologen unit also exhibits photochromism and electrochromism, and is expected as a light amount control material, an image recording material and a display material for a display (J. Electrochem. Soc., Hlectrochemical Science).
and Technology, 130 (5), 1080 (1983); J.Phys.Che
m., 87, 5345 (1983)).

As such a viologen polymer, a polymer obtained by a condensation reaction of a diamine having a viologen skeleton and an acid chloride of a dicarboxylic acid is known (Journal of Polymer Science, Polymer Chemistry E
dition, 13, 1 (1975)). However, the film of the polymer is glassy and fragile and has poor mechanical properties.
Not practical.

Further, a polymer having a viologen unit obtained by cationically polymerizing tetrahydrofuran with a monofunctional Lewis acid as an initiator and reacting with 4,4'-dipyridyl is also known (Proceedings of the Polymer Society of Japan, Volume 31). , P. 330, 19
(82 years). However, the above-mentioned polymer has only one viologen unit in the polymer chain, is not sufficient in terms of mechanical strength, and does not sufficiently exhibit the above-mentioned function peculiar to viologen, and is not practical.

Further, in the above report, as another polymer having a viologen unit, a polymer obtained by tosylating both ends of a hydroxyl group-terminated polyether and reacting 4,4'-dipyridyl is reported. However, the above-mentioned polymer is a 2-3-mer polymer, which does not have sufficient film-forming properties and is not practical.

Further, an electrochromic material that can be used repeatedly about 3000 times is also known (Japanese Patent Laid-Open No. 56-26974). However, since the electrochromic material is a crystalline compound having no film-forming property and is used in the form of a solution, there is a problem that it can be applied only to limited applications.

<Objective> The present invention has been made in view of the above problems, and provides a functional ionene polymer having not only functionality as photochromism, electrochromism, thermochromism, etc., but also excellent mechanical properties. With the goal.

<Means and Actions for Solving Problems> The present invention solves the above conventional problems by using a functional ionene polymer represented by the following general formula (1).

(In the formula, X is an ether unit having 2 to 10 carbon atoms which may have a halogen atom as a substituent, and has a polymerization degree of 5
Represents a polyether residue of 100, R represents a saturated or unsaturated aliphatic hydrocarbon group whose main chain has 1 to 6 carbon atoms and may be branched, A is an anion, and n is 2 or more. The following is a detailed description of the present invention.

More specifically, each group represented by the general formula (1) is as follows.

As the polyether residue, a polyether having an ether unit having 2 to 10 carbon atoms, for example, polyoxyethylene, polyoxypropylene, polyoxy (chloromethylethylene), polyoxy (1,1-di (chloromethyl) trimethylene) , Polyoxytetramethylene, polyoxypentamethylene, polyoxyhexamethylene, polyoxyheptamethylene, polyoxyoctamethylene, polyoxynonamethylene, polyoxydecamethylene and the like. Of these polyether residues, carbon number 2 to
Polyether residues having 4 ether units, especially polyoxytetramethylene, are preferred. The degree of polymerization of the above polyether is 5 to 100.

Further, in the general formula (1), the aliphatic saturated hydrocarbon group represented by R, which has 1 to 6 carbon atoms in the main chain and may be branched, is an alkylene group, for example, methylene, ethylene, Trimethylene, tetramethylene, pentamethylene,
Hexamethylene, methylmethylene, methylethylene, 1
-Methyltrimethylene, 2-methyltrimethylene, 2-
Ethyl trimethylene, 2-propyl trimethylene, 2-
Methyltetramethylene, 3-methylpentamethylene, 4
Examples thereof include ethylhexamethylene. Further, as the aliphatic unsaturated hydrocarbon group which has 1 to 6 carbon atoms in the main chain and may be branched, vinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, 3-pentenylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 4-
Alkenylene such as hexenylene; 1,2-propadienylene, 1,2-butadienylene, 1,3-butadienylene, 1,2
-Pentadienylene, 1,3-Pentadienylene, 1,4-Pentadienylene, 2,4-Pentadienylene, 1,2-Hexadienylene, 1,3-Hexadienylene, 1,4-Hexadienylene, 1,5-Hexadienylene, 2,4-Hexadienylene Alkadieenylene; 1,2,4-pentatrienylene,
Alkatrienylene such as 1,3,4-hexatrienylene;
Ethynylene, 1-propynylene, 2-butynylene, 2-
Pentynylene, 4-pentynylene, 2-hexynylene,
Examples thereof include those having at least one double bond or triple bond such as alkynylene such as 3-hexynylene. 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 Alkenylene, alkadienylene, alkatrienylene and alkynylene are preferred.

Further, in the general formula (1), the anion represented by A is
It is a monovalent or divalent anion. Examples of monovalent anions include halogen anions such as fluoride, chloride, bromide, and iodide; monocarboxylic acid anions such as acetate, trifluoroacetate, and benzoate: sulfate anions such as sulfate and methylsulfate; methanesulfonate, ethanesulfone. Examples thereof include sulfonate anions such as nato, heptane sulfonate, and benzene sulfonate. Examples of the divalent anion include dicarboxylic acid anions such as oxalate, malonate, adipate and suberate; and disulfonic acid anions such as 1,2-ethanedisulfonate.

In the general formula (1), the degree of polymerization represented by n is 2 or more. Since the molecular weight measuring technique of ionene polymer has not been established yet as described later, it is not possible to limit the preferable range than n here, but the intrinsic viscosity number from which the molecular weight of the polymer is estimated is 0.3 to It is preferably 0.9. However, the range of the intrinsic viscosity is just a preferable range, and the intrinsic viscosity of the ionene polymer of the present invention is not necessarily limited to the above range.

The functional ionene polymer of the present invention has various excellent properties as an elastomer, and has photochromism, electrochromism, in any form of solid such as film and solution dissolved in a suitable solvent. It has the property of thermochromism.

As the solvent, various ones can be used, for example, water, an aqueous solution of the alkali metal salt or the like; alcohols such as methanol or ethanol; dimethyl ether,
Ethers such as diethyl ether; pyridine, picoline, dimethylformamide, dimethylsulfoxide, N
-Methyl-2-pyrrolidone and the like can be exemplified.

When the functional ionene polymer of the present invention is used as a photochromism material, a conventionally known photosensitizer,
For example, polyvinylpyrrolidone, proflavin and ethylenediaminetetraacetic acid (EDTA) may be used.

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

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

(In the formula, R ¹ represents a hydrogen atom or a methyl group which may have a halogen atom as a substituent, p and q are positive integers, M represents a cation, and R, n and A are as described above. The same) The functional ionene polymer of the present invention is obtained by cationically polymerizing the cyclic ether represented by the formula (2) by using a cationic polymerization initiator to obtain the polymer of the formula (3). The ionene polymer represented by the formula (5) can be produced by reacting with the compound represented by the formula (4). In addition, since the anion of the above-mentioned polymerization initiator remains in the obtained polymer (5), this residual anion is converted into A by using the salt of the anion represented by the formula (6).
The functional ionene polymer represented by the formula (1a) may be substituted with the anion represented by.

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,
Examples include tetrahydrofuran (oxolane), methyltetrahydrofuran, tetrahydropyran, trioxane and the like. Among the above cyclic ethers, cyclic ethers having 2 to 4 carbon atoms and derivatives thereof are preferable.

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

Further, examples of the compound represented by the formula (4) include compounds having a pyridine ring bonded to both ends of the optionally branched alkylene group, alkenylene group, alkadienylene group, alkatrienylene group, alkynylene group, and the like. , 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) pentane, 2,4-bis (4-pyridyl) pentane,
Bis (4-pyridyl) alkane such as 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-pyridyl) -3-pentene, 1,3-bis (4
-Pyridyl) -2-hexene and other bis (4-pyridyl)
Alkene; 2,4-bis (4-pyridyl) -1,3-butadiene, 1,3-bis (4-pyridyl) -2,4-hexadiene,
Bis (4-pyridyl) alkadienes such as 2,5-bis (4-pyridyl) -1,3-hexadiene; Bis (4 such as 2,4-bis (4-pyridyl) -1,3,5-hexatriene Examples include -pyridyl) alkatriene; bis (4-pyridyl) alkynylene such as 1,2-bis (4-pyridyl) ethynylene.

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

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

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

The above reactions may be carried out in the presence of an inert solvent.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A 300 ml eggplant-shaped flask was charged with 100 g of dehydrated and purified tetrahydrofuran, and the atmosphere was replaced with nitrogen. While vigorously stirring tetrahydrofuran in a constant temperature water of 2 ° C., 3.85 g (0.12 mol /) of trifluoromethanesulfonic anhydride was added and polymerization was carried out for 15 minutes. On the other hand, 1,2-bis (4-pyridyl) in an equimolar amount to the above trifluoromethanesulfonic anhydride
About 100 ml of a tetrahydrofuran solution in which ethane is dissolved,
After cooling to about -70 ° C, the above-mentioned polymerization reaction liquid was added thereto and reacted for 1 hour. Next, at room temperature, the reaction solution was gradually poured into 0.5N-sodium bromide aqueous solution 400 ml while stirring,
The produced polymer was deposited. The polymer obtained was washed with pure water, reprecipitated with methanol and a 0.5N-sodium bromide aqueous solution, and further reprecipitated with methanol and pure water to purify the product, and 1,2-bis (4- A polymer having a (pyridyl) ethane unit (hereinafter referred to as PE-PT) was obtained.

Example 2 The above Example 1 except that 1,2-bis (4-pyridyl) propane and 1,2-bis (4-pyridyl) ethylene were used instead of 1,2-bis (4-pyridyl) ethane. Similarly, a polymer having a 1,2-bis (4-pyridyl) propane unit (hereinafter, referred to as PP-PT) and a polymer having a 1,2-bis (4-pyridyl) ethylene unit (hereinafter, PEY- (Named PT). The PEY-PT was purified by reprecipitation with methanol and 0.5N-sodium bromide aqueous solution twice and washing with pure water.

Reference Example 3 A molecular weight measuring technique for an ionene polymer has not been established yet (K. Kataoka et al, Makromol. Chem. Vol. 180.65.
Pp. 1979), therefore, in order to estimate the molecular weight of PE-PT, PP-PT and PEY-PT, as a comparative polymer,
Instead of -bis (4-pyridyl) -ethane, a pyridine unit is used in the same manner as in Synthesis Example 1 except that pyridine, which is a monofunctional amine, is used at a molar ratio of pyridine / trifluoromethanesulfonic anhydride = 2.0. Was obtained (hereinafter referred to as PT-PT). In addition, this PT-PT
Indicates that both ends of polytetrahydrofuran are bonded and blocked with the nitrogen atoms of the pyridine ring.

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

Spectral analysis The above polymer was subjected to spectral analysis by NMR (solvent: CD ₃ OD). As a result, in PP-PT, β-position protons (δ = 8.1 ppm) and α-position protons (δ = 8.
9 ppm) peak was observed. In PEY-PT, the β-position proton of the pyridine ring (δ = 8.4 ppm), the α-position proton (δ = 9.1 ppm) and ethylene (δ = 8.1 pp) were used.
m) peak was observed. Further, in the above polymer, both peaks of β-methylene and α-methylene of polytetrahydrofuran were observed.

In addition, according to the infrared absorption spectrum, all of the polymers had a peak based on the -C = N-ring stretching of the pyridine ring (16
50 cm ^-1 ) was recognized.

Thermal analysis Using α-alumina as a standard substance, heating rate of 10 ℃ / mi
When the above PE-PT, PP-PT and PEY-PT were subjected to thermal analysis under the condition of n., a weight reduction was not observed so much up to 250 ° C in the TG curve. In addition, in the DSC curve, an endothermic peak, which is considered to be due to the melting of polytetrahydrofuran, was observed at around 40 ° C, and a peak which was believed to be due to the thermal decomposition of the polymer was observed at a temperature higher than 250 ° C.

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

Intrinsic Viscosity The intrinsic viscosity number was determined from the viscosity measurement in a 0.1N-lithium bromide methanol solution, and the results shown in Table 2 were obtained. In addition, the intrinsic viscosity number of the PT-PT synthesized to estimate the molecular weight of the PP-PT and the like is also shown.
PT-PT had a polystyrene reduced molecular weight of 3400 from the peak value of gel permeation chromatography.

Film Forming A film could be easily obtained by casting the above PE-PT, PP-PT and PEY-PTF methanol solutions.

The obtained film was dried under reduced pressure and then 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.

In addition, the tensile test is a tensile tester TOM2 manufactured by Shinko Communication Industry Co., Ltd.
Using 00D, a sample with a thickness of about 1 mm (inner diameter 11.6 mm, outer diameter 13.6 mm
mm) and a pulling speed of 10 mm / min.

From the results shown in Table 3, it was found that the film was a high-strength elastomer having good tensile properties.

Observation of photochromism, thermochromism and electrochromism Photochromism A high-pressure mercury lamp was used to cut off ultraviolet rays of 290 nm or less, and when light was irradiated at room temperature in vacuum, the PP-PT film changed from colorless to blue, and PEY- The film of PT was colored from reddish brown to deep reddish brown.

Thermochromism When the vacuum degassed film was heated, the PP-PT film was colored from colorless to blue at around 130 ° C. Also,
When the film was left to stand in the air and cooled, PP-
The PT film returned to its original color and was found to be reversible.

Electrochromism PEY-PT was dissolved in N, N-dimethylformamide (DMF), and tetraethylammonium tosylate (TEAT) was dissolved as an indicator electrolyte to a concentration of 0.2N. When this solution was applied under a nitrogen atmosphere at 10 mA and 29 V, the color changed from yellow to deep purple. When applied in the opposite direction to the above, the original color was restored and it was found to have reversibility. A platinum electrode was used as the electrode.

<Effects of the Invention> As described above, according to the present invention, photochromism,
It is possible to provide a functional ionene polymer having properties such as electrochromism and thermochromism, capable of easily forming a film, excellent in processability, and having properties as a high-strength polymer.

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yoshitaka Osawa 1-3 Shimano, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Electric Industries, Ltd. Osaka Works (72) Inventor Toshihiro Kushiro Wakaehonmachi, Higashi Osaka City, Osaka Prefecture 1-12-12-1 (72) Inventor Manharu Yamaji 1-chome, Nakatobigaoka Nara, Nara 1994-3 D46 ・ 404

Claims (2)

[Claims] 1. A general formula (1) (In the formula, X is an ether unit having 2 to 10 carbon atoms which may have a halogen atom as a substituent, and has a polymerization degree of 5
Represents a polyether residue of 100, R represents a saturated or unsaturated aliphatic hydrocarbon group whose main chain has 1 to 6 carbon atoms and may be branched, A is an anion, and n is 2 or more. Indicates an integer. ) An ionene polymer represented by. 2. The ionene polymer according to claim 1, which has an intrinsic viscosity of 0.3 to 0.9.