JP3039994B2 - Highly sensitive deformation method of pyrrole polymer film - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a pyrrole-based high-molecular-weight compound that uses, as a driving force, adsorption and desorption of a low-molecular compound on a film surface in a gas, particularly adsorption and desorption of a low-molecular compound such as water or an organic polar solvent. The present invention relates to a high-sensitivity deformation method for a pyrrole-based polymer film that causes a deformation, such as bending or rotation, of a molecular film.

BACKGROUND ART As typical stimulus-responsive polymers that have been conventionally studied, there are polymer gels, conductive polymers, and the like.

Polymer gels are known to shrink and swell in response to stimuli such as temperature, pH, ions, solvents, electric fields, and light. A system that uses this to convert chemical energy into mechanical energy and perform work like machines and muscles is called "chemomechanical system" or "chemomechanical reaction" (Y. Osada, "Progress in Polymer Science, Stimuli- R
esponsive Polymer Gels and Their Application to Ch
emomechanical Systems ", Pergamon Press (1992)).

Katchalsky and colleagues have prototyped a "rotary mechanochemical engine" using crosslinked collagen gel fibers and driven by the crystallization-melting phase transition in saline solutions with different concentrations (IZSteinberg, A. Oplatka and
A. Katchalsky, Nature, 210, 568 (1966)). Then Sus
sman and colleagues have made a mechanochemical turbine with further improvements to achieve higher performance (MVSussman
and A. Katchalsky, Science, 167, 45 (1970)). With this device, collagen fiber (length 270cm, mass 350g) is 60%
It has been found to contract and exhibit a power of about 30 mW.

The present inventors have recently developed poly (2-acrylamide-2).
-Methylpropanesulfonic acid) gel has been found to quickly bend to the positive electrode side in a surfactant aqueous solution by the application of a DC voltage (Y. Osada, H. Okuzaki and H. Hor).
i, Nature, 355, 242 (1992)). Furthermore, using this principle, we have succeeded in producing an "artificial scale insect" that walks at a speed of about 25 cm per minute. Here, the driving force for gel deformation is a change in free energy when the surfactant and the gel form a molecular assembly, and electrical stimulation controls both the migration direction of the surfactant and the equilibrium of the molecular assembly reaction. It is known that the phenomenon can be explained by the electrokinetic phenomenon.

Since conductive polymers swell and shrink due to electrochemical doping and undoping, application to actuators is being studied. For example, Pei et al. Observed the bending behavior of a film by electrochemically doping and undoping pyrrole on a gold-deposited polyethylene film (Q. Pei and O. Inganas, Synthetic Metals, 55).
−57, 3718 (1993)). When dodecylbenzenesulfonate ion was used as a dopant, the deformation rate of the polypyrrole film was up to 0.5 mm / s.

In these conventionally known techniques, all of the polymer gel and the conductive polymer can be used only in a solution or in a swollen state.

However, the above-mentioned conventional techniques have not yet sufficiently solved some essential problems described below.

(1) Displacement or deformation / recovery speed is small.

(2) Since it is a wet type, its application is limited.

(3) Low energy conversion efficiency.

(4) Low sensitivity.

(5) The material used is soft and brittle.

(6) Reproducibility and reliability of operation are low.

The present invention has been made to solve the essential problems of the conventional stimuli-responsive polymers.

That is, one object of the present invention is based on a principle different from that of the conventional stimuli-responsive polymer, that is, a film is formed in a gas (dry type) such as air by a small relative humidity change of several percent or less. An object of the present invention is to provide a method for deforming and recovering a pyrrole-based polymer film with high sensitivity, which is quick and large and can be repeatedly deformed and recovered.

Another object of the present invention is to provide a highly sensitive method for deforming a pyrrole-based polymer film capable of generating a stress of about 1.5 times its own weight.

Another object of the present invention is to provide a method for deforming a pyrrole-based polymer film with high sensitivity, which can function as a very sensitive chemical sensor.

Another object of the present invention is to provide a high-sensitivity deformation of a pyrrole-based polymer film that can produce a "rotary actuator" that moves while rolling, which was impossible at all with a conventional gel or conductive polymer film. It is to provide a method.

Another object of the present invention is to provide a high-sensitivity method for deforming a pyrrole-based polymer film, which can be used as a new power source in the future and can produce a "polypyrrole engine" driven only by compound vapor. It is in.

DISCLOSURE OF THE INVENTION The present inventors have been diligently studying the above-mentioned problem, and based on a principle different from the conventional stimuli-responsive polymer,
In other words, a very unique phenomenon, such as rapid and large, repeated deformation and recovery of a pyrrole-based polymer film in a gas (dry) such as air due to a small change in relative humidity of several percent or less, was found. Was. And
The present inventors have further studied based on this finding, and have reached the present invention.

 That is, the present invention is as described below.

(1) A pyrrole-based polymer film having at least 50 mol% of a pyrrole unit is used, and the film is transformed into the above-mentioned film in a gas by driving adsorption and desorption of water and / or a volatile polar solvent to the surface of the film. High-sensitivity deformation method of a pyrrole-based polymer film, characterized in that

(2) The pyrrole-based polymer film according to (1), wherein the pyrrole-based polymer film is at least one selected from the group consisting of a flat, ring, belt, and tubular film. High sensitivity deformation method.

(3) The pyrrole polymer film has a thickness of 1 to 1000 μ
m or m.
3. The method for high-sensitivity deformation of a pyrrole-based polymer film according to the above item.

(4) The pyrrole polymer film has a thickness of 10 to 100 μm
4. The method for high-sensitivity deformation of a pyrrole-based polymer film according to claim 3, wherein the range is m.

(5) The method according to (1) or (2) above, wherein the pyrrole-based polymer film contains at least one kind of ion.

(6) The method according to (1) or (2), wherein the pyrrole-based polymer film is a uniaxially stretched or biaxially stretched film.

(7) The volatile polar solvent is at least one compound selected from the group consisting of alcohols, ketones, aldehydes, nitriles, ethers, dimethylformamides, and alkyl monohalides. 2. The method for deforming a pyrrole film according to claim 1, wherein the method comprises:

(8) In a gas, the surface of a flat pyrrole-based polymer film having at least 50 mol% of pyrrole units and water and / or a volatile polar solvent are brought close to and / or separated from each other to form the film. 2. The high sensitivity of the pyrrole-based polymer film according to claim 1, wherein deformation and recovery of the film are repeatedly caused by adsorption and desorption of the water and / or volatile polar solvent to the surface as a driving force. Deformation method.

(9) In a gas, the surface of a ring-shaped, belt-shaped or tubular-shaped pyrrole-based polymer film having at least 50 mol% of pyrrole units is brought close to water and / or a volatile polar solvent. 2. The pyrrole-based polymer film according to claim 1, wherein the film is deformed and / or rotated by driving the absorption and desorption of the water and / or volatile polar solvent to the film surface as a driving force. High sensitivity deformation method.

(10) The method according to the above (1), (8) or (9), wherein the water is supplied from at least one selected from the group consisting of pure water, an aqueous solution of an inorganic salt, an aqueous solution in which an organic substance is dissolved, an aqueous acid solution, and an aqueous alkaline solution. 10. The method for highly sensitive deformation of a pyrrole film according to claim 9.

(11) A group of volatile polar solvents consisting of pure polar solvents, mixed solvents of polar solvents and water, mixed solvents of polar solvents and other non-polar solvents, and solutions of other substances dissolved in polar solvents. 10. The method according to claim 1, 8 or 9, wherein the method is supplied from at least one selected from the group consisting of:

 Hereinafter, each requirement constituting the present invention will be described.

In the present invention, the term “deformation” means that the polymer film bends or changes its shape from its original state. This deformation causes the ring-shaped and belt-shaped polymer films to rotate.

In the present invention, the term "in a gas" refers to a state in which a conventional gel or conductive polymer film operates in a solution or in a swollen state. The deformation of the polymer film takes place. In the present invention, particularly preferred is air.

The polymer film that can be used in the present invention is a pyrrole-based polymer film having at least 50 mol% of a pyrrole unit in a molecular chain.

That is, the pyrrole-based polymer of the present invention includes, as monomers, pyrrole, 3-alkylpyrroles such as 3-methylpyrrole, 3-ethylpyrrole, and 3-dodecylpyrrole, 3,4-dimethylpyrrole, and 3-methyl- N-alkylpyrroles such as 3,4-dialkylpyrroles such as 4-dodecylpyrrole, N-methylpyrrole, N-dodecylpyrrole, N-alkylpyrroles such as N-methyl-3-methylpyrrole and N-ethyl-3-dodecylpyrrole A pyrrole polymer produced by polymerizing alkyl-3-alkylpyrrole or 3-carboxypyrrole, or a copolymer produced by polymerizing these monomers and other monomers, and A pyrrole polymer having at least 50 mol% of pyrrole units in the copolymer is used.

As a method for polymerizing these pyrrole-based polymers, it is possible to use either chemical oxidation polymerization using a metal ion such as iodine or iron ion as a catalyst, or electrolytic polymerization applying a constant voltage or a constant current. is there. Preferably, a method by electrolytic polymerization is used. Further, the pyrrole-based polymer film of the present invention can be produced simultaneously with the polymerization.

In the electropolymerization, halide ions such as chloride ion and bromide ion, perchlorate ion, tetrafluoroborate ion, hexafluoroarsenate ion, sulfate ion, nitrate ion, thiocyanate ion, hexafluorosilicate ion ,
Phosphate ions such as phosphate ion, phenyl phosphate ion, hexafluorophosphate ion, trifluoroacetate ion, tosylate ion, ethylbenzene sulfonate ion, alkylbenzene sulfonate ion such as dodecylbenzene sulfonate ion, methyl sulfonate ion, ethyl At least one of polymer ions such as alkylsulfonic acid ions such as sulfonic acid ions, polyacrylic acid ions, polyvinylsulfonic acid ions, polystyrenesulfonic acid ions, and poly (2-acrylamido-2-methylpropanesulfonic acid) ions. Ions are used as dopants.

Pyrrole polymer film used in the present invention (hereinafter, referred to as
Sometimes called original film. ) Is not particularly limited with respect to the length, width and thickness of the original film as long as the flexibility and appropriate mechanical strength are not impaired, and it is possible to use an original film having a large area. In order to effectively exhibit the above, it is preferable that the original film be repeatedly bendable, that is, be flexible. For this reason,
The thickness of the original film is generally in the range of 1 to 1000 μm, preferably in the range of 10 to 100 μm.

The original film is preferably a film that has been uniaxially or biaxially stretched by a known stretching method. As such a known stretching method, any of stretching methods such as a hot stretching method, a zone stretching method, and a swelling stretching method can be adopted. The original film can improve the mechanical properties such as Young's modulus and cutting strength, and the performance such as thermal stability and electric conductivity by the orientation and tensioning of the polymer chains by such stretching.

Further, the original film can be used in a shape such as a flat shape, a ring shape, a belt shape, or a tubular shape. Further, these shapes can be used in combination.

In the present invention, a specific solvent (polar liquid), that is, water and a volatile polar solvent, is used as a low molecular compound capable of rapidly deforming the original film by stimulating the surface of the original film and absorbing and desorbing the low molecule. Is used.

Examples of the volatile polar solvent include alcohols such as methanol, ethanol and butanol, ketones such as acetone and methyl ethyl ketone, aldehydes such as formaldehyde and acetaldehyde, nitriles such as acetonitrile and succinonitrile, diethyl ether, and tetrahydrofuran. And the like, formamides such as N, N-dimethylformamide, and monohalogenated alkyls such as iodomethane.

In the present invention, the water is pure water and various aqueous solutions, that is, various aqueous solutions such as an aqueous solution of an inorganic salt such as a saline solution, an aqueous solution in which an organic substance such as sugar is dissolved, an aqueous acid solution such as dilute sulfuric acid or ammonia water, and an aqueous alkaline solution. Supplied from

When a stimulus is applied to the surface of the original film using these pure water and various aqueous solutions, the original film shows a phenomenon of quickly bending to the side opposite to the stimulus. Also, if you keep the stimulus away,
The original film quickly returns to its original position.

In the present invention, the volatile polar solvent is a pure polar solvent and various solvents and solutions including a polar solvent,
That is, it is supplied from various solvents and solutions including a polar solvent such as a mixed solvent of a polar solvent and water, a mixed solvent of a polar solvent and another solvent, and a solution in which another substance is dissolved in the polar solvent.

When a stimulus is applied to the surface of the original film using these pure polar solvents and various solvents and solutions including the polar solvent, the original film bends to the same side as the stimulus, contrary to the case of water. Show. When the stimulus is moved away, the original film quickly returns to its original position.

The deformation behavior of the original film caused by water and volatile polar solvents depends on the chemical structure, size, polarity, hydrophilicity / hydrophobicity, volatility, and other properties of the low molecular weight compound that stimulates the surface of the original film. Is different. In the present invention, particularly rapid film deformation was observed with water and organic polar solvents such as formamides such as N, N-dimethylformamide and alkyl monohalides such as iodomethane.

On the other hand, alkanes such as hexane, heptane and octane, alkenes such as ethylene and hexene, alkynes such as acetylene, carbon tetrachloride, chloroform and the like, aromatic hydrocarbons such as benzene, toluene and xylene, and carbonic acid When a low molecular compound such as propylene is used, no matter how much stimulation is applied to the surface of the original film, the original film shows almost no response.

It has been experimentally shown that the mechanism of such deformation behavior of the original film in the present invention is based on weak physical adsorption such as van der Waals force. For example, when moisture approaches the original film, the original film bends,
It is considered that this is because moisture is adsorbed on the film surface due to a minute change in relative humidity due to the approach of moisture, and the film surface slightly expands.

The method for introducing water and a volatile polar solvent in the present invention is not necessarily limited.
In addition to the method of using absorbent cotton in the air shown in FIG. 1, unless it deviates from the principle idea of the present invention, for example, diffusion using capillary action or ultrasonic waves, or a gas such as nitrogen, oxygen, argon or the like as a carrier. It can be sprayed.

In the present invention, the region and the number of stimuli are not necessarily limited.

Thus, in the present invention, the shape, size, thickness, etc. of the pyrrole-based polymer film, the type, number, amount, etc. of the water and the volatile polar solvent, the region to be stimulated by the water and the volatile polar solvent The size, number, and the like of can be selected as appropriate.

The deformation of the original film of the present invention will be described in more detail.

The deformation of the original film due to the adsorption and desorption of low molecules in the present invention can be carried out with a very simple experimental apparatus shown in FIG.

In FIG. 1, the original film is 25 mm long, 5 mm wide,
The thickness is about 30 μm, and the upper end 5 mm is fixed to the chuck. Therefore, the driving portion of the film is a portion obtained by subtracting the inside of the chuck. Its mass is 2.9 mg.
Meanwhile, absorbent cotton soaked with water or a solvent is placed in a box that can be opened and closed by a shutter or the like. The shutter and the original film are 2mm apart. In FIG. 1, the deformation at a position 3 mm from the lower end of the original film when the shutter is opened can be measured by a laser displacement meter. In FIG. 1, the temperature and relative humidity at a distance of 1 mm from the original film can be measured simultaneously.

In the apparatus shown in FIG. 1, when the original film is stimulated with water and / or a volatile polar solvent, if the area to be stimulated is larger than that of the original film, the entire film is greatly curved. Also, when a plurality of stimuli are applied in the same direction, the original film bends from each location and the bending of the original film increases. When a plurality of stimuli are applied from both sides while shifting the position, the original film bends right and left at each location and deforms into a waveform. On the other hand, if two identical stimuli are applied to the same position on both sides, they are canceled and do not deform. When the original film is slightly slackened and fixed at both ends and stimulated, it bows in an arc. Also, when stimulating a part of the ring-shaped film,
Transform into an ellipse. The ring can be rolled in one direction by utilizing such a change in the curvature of the arc. Also, when this ring is hung on two pulleys and stimulated at a specific location,
The pulley starts rotating.

Although the lower end of the original film is an open end in the apparatus shown in FIG. 1, the deformation of the original film can be detected as stress by connecting it to a high-sensitivity strain gauge. Further, in the apparatus shown in FIG. 1, the original film is suspended vertically, but the invention can be implemented in a horizontal type as long as the principle of the present invention is not changed.

Some features of the present invention described above are listed individually below.

(1) Local absorption and desorption of molecules on one side of the film causes local surface expansion and contraction.

(2) The direction of bending of the film is determined by the one-sided expansion and contraction of the film.

(3) The amount of molecules to be absorbed and desorbed is extremely small. Therefore, desorption occurs instantaneously. Since the adsorption is by a weak force, desorption is extremely easy.

(4) Since absorption and desorption occur on the very surface of the film, no diffusion time is required, and high-speed deformation and complete recovery are achieved. This operation can be repeated any number of times with the same magnitude.

(5) The molecules to be absorbed and desorbed are vapors of solvent molecules such as water and alcohol, and the former expands and the latter contracts. When these opposing behaviors are simultaneously applied, a strong force is generated. Of course, water alone works.

(6) Since it is absorption and desorption by steam, it operates only by approaching it in a non-contact manner.

(7) Conventionally, in most cases, expansion and contraction occur in a gel. In that case, it is performed in a swollen state or in a solution, and the stimulation also depends on the electric field, reagent, pH, temperature, and the like. On the other hand, it is a dry type in air, and its operation and principle are simple.

(8) Compared to gel, polypyrrole film is chemically stable and does not deteriorate. In addition, the generated stress is high despite the high strength and low expansion coefficient. In addition, it has conductivity.

(9) The film reproduces exactly the same behavior several months after the production of the original film. Operation occurs at room temperature and constant pressure and does not require a special atmosphere.

(10) Using a polypyrrole film as a belt, the belt was hung on two pulleys, and rotated with water and an organic solvent. The large pulley rotated 7 times per minute, and the belt ran at 22 cm per minute. There has never been a case where rotational energy is directly extracted by the adsorption and desorption of molecules. The conversion efficiency is high because molecules are not consumed without chemical change. Further, since the solvent supply source and the film are not in contact with each other, there is no friction loss.

(11) Especially when water is used, even if it is released into the air, it does not pollute the environment and can be expected as clean energy. In addition, it keeps rotating by supplying only a little water without cost.

(12) There is also application as a highly sensitive sensor for humidity and organic solvents.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory view of an apparatus used for measuring displacement, measuring temperature and relative humidity, and measuring stress of a polymer film deformation element according to the present invention.

FIG. 2 is a schematic view of an electrolytic polymerization apparatus used for producing a polymer film deformation element according to the present invention.

FIG. 3 is an explanatory view of an apparatus used for measuring the electric conductivity of the polymer film deformation element according to the present invention.

FIG. 4 is a graph showing the displacement of the original film and the changes in temperature and relative humidity when the shutter is opened for 30 seconds in FIG.

FIG. 5 is a graph showing the displacement of the original film and the changes in temperature and relative humidity when the test tube containing the hot water at 70 ° C. in FIG. 2 is approached for 30 seconds.

Fig. 6 shows the finger in Fig. 2 close for 5 seconds and away for 25 seconds,
It is a graph which shows the displacement of an original film when this is repeated, and the change of temperature and relative humidity.

FIG. 7 is an explanatory diagram showing the state of deformation and recovery of the original film when the finger is brought close to the original film in FIG. 2 and then moved away.

FIG. 8 is a graph in which the stress generated in the direction perpendicular to the film surface when the finger is brought close in FIG. 2 is measured.

FIG. 9 is a graph showing a change in conductivity when a finger is brought close to the center of the film in FIG.

FIG. 10 is an explanatory view of an apparatus used for measuring an equilibrium adsorption weight on a polymer film deformation element according to the present invention.

FIG. 11 is an explanatory view of an apparatus used for observing the reversible adsorption / desorption behavior of the polymer film deformation element according to the present invention.

FIG. 12 is an explanatory view of an apparatus used for calculating the expansion coefficient of the polymer film deformation element according to the present invention.

FIG. 13 is a graph showing the weight change of the original film measured using the apparatus of FIG.

FIG. 14 shows an example in which the shutter shown in FIG.
It is a graph which shows the change of adsorption weight at the time of opening for 2 seconds, closing for 25 seconds, and repeating this 4 times.

FIG. 15 is a schematic diagram illustrating the principle of a “rotary actuator” device that moves while rolling, manufactured using the polymer film deformation element according to the present invention.

FIG. 16 is a schematic diagram illustrating the principle of a “polypyrrole engine” device having two pulleys manufactured using the polymer film deformation element according to the present invention.

FIG. 17 is a schematic diagram illustrating the principle of a “polypyrrole engine” device driven by absorbent cotton containing water.

Examples Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

The pyrrole-based polymer film used in each example was obtained by the following methods (1) and (2). In the examples, each measurement result such as the measurement result of the displacement was obtained by the following methods (2) and (3) to (9).

(1) Preparation of pyrrole polymer film 0.4 g of pyrrole and 1.15 g of tetraethylammonium perchlorate were dissolved in propylene carbonate containing 1 vol% of water to make 100 ml.

An electrolytic polymerization cell as shown in Fig. 2 using a platinum plate (length 50mm, width 20mm, thickness 0.1mm) for the positive electrode and aluminum foil (length 200mm, width 50mm, thickness 0.01mm) for the negative electrode, The above solution was added. In FIG. 2, 7 is a low-temperature constant temperature bath, 8 is a potentiostat, 9 is a temperature control device, 10 is an electropolymerization cell, 11 is an aluminum foil, 12 is a platinum plate, 13 is a throw-in cooler, and 14 is a refrigerant ( Ethanol).

After leaving the electrolytic polymerization cell in a low-temperature thermostat for 30 minutes, a constant current of 1.25 mA (current density 0.125 mA / c
m ² ) was applied for 12 hours to carry out electrolytic polymerization. The polymerization temperature is-
20 ° C.

The resulting dark green polypyrrole film was peeled off from the platinum plate and washed in propylene carbonate for about 1 hour. Further, the film was vacuum-dried for one day and used as a sample (original film). The dimensions of the polypyrrole film after drying are 50 mm in length, 20 mm in width, and about 30 μm in thickness. This film has a conductivity of 102 S / cm, a Young's modulus of 0.61 GPa, and a cutting strength of 33.7 MP.
a and physical properties of elongation at break of 25.9%.

(2) Stretching of the pyrrole-based polymer film and tensile test The stretching of the polypyrrole film is performed using a normal tensile tester (Tensilon II, Orientec Co., Ltd.) at room temperature at a strain rate of 10% / min. did.

The tensile tests of the stretched film and the unstretched film were also performed under the same apparatus and conditions. Young's modulus, cutting strength, and cutting elongation were calculated from a stress-strain curve.

(3) Displacement measurement A polypyrrole film with a thickness of about 30 μm is 25 mm long and width
Cut out into 5mm tangs. As shown in FIG. 1, the upper end 5 mm of the film was fixed to a stainless steel chuck, the film was suspended, and the shutter was fixed at a distance of 2 mm from the original film. The displacement at a position 3 mm from the lower end is measured with a laser displacement meter (LB-300, Keyence Corporation) having a resolution of 50 μm. Measured data is transferred to the amplifier unit (LB
-1200, KEYENCE CORPORATION) and read it into a personal computer. In FIG. 1, 1 is a chuck, 2 is a film, 3 is absorbent cotton containing a solvent, 4 is a shutter, and 5 is a laser displacement meter.

(4) Measurement of temperature and relative humidity As in the case of displacement measurement, a film is suspended, and a thermo-hygrometer (MC-P, Nippon Panametrix Co., Ltd.) is placed on its surface.
The probe as close as possible. About 2mm from film
The change in the temperature and relative humidity near the film when a stimulus is applied to the distance is read into a personal computer.
In FIG. 1, reference numeral 6 denotes a thermo-hygrometer.

(5) Measurement of stress A high sensitivity strain gauge (T7-8-120 (maximum load: 8 g), Orientec Co., Ltd.) is attached to the lower end of the film, and the stress generated in the direction perpendicular to the film surface is measured. The output voltage from the high-sensitivity strain gauge is amplified by an amplifier unit (AR-6000, Orientec Co., Ltd.) and read into a personal computer.

(6) Conductivity measurement A polypyrrole film is cut into a length of 20 mm and a width of 5 mm. Using an ion sputtering device (JFC-1100, JEOL Ltd.), as shown in FIG.
Four pieces of gold (thickness: about 0.1 μm) having a width of 1 mm every 4 mm are deposited.
Copper wire (diameter 20μm, length 50mm) with silver paste for each gold deposition
And measured by a DC four-terminal method using a digital multimeter (VOAC-7512, Iwasaki Communication Equipment Co., Ltd.) (measured current value: 10 mA). In FIG. 3, reference numeral 2 denotes a film, 3 denotes absorbent cotton containing a solvent, 4 denotes a shutter, 15 denotes gold deposition, and 16 denotes a digital multimeter.

(7) Measurement of equilibrium adsorption weight In order to further examine the mechanism of the bending phenomenon of the present invention, the adsorption weight was directly measured by a microbalance method using a quartz oscillator. The raw film is electrolytically polymerized on the electrodes of a quartz oscillator (9MHz, Wakabayashi Seisakusho) for 30 minutes. The equilibrium adsorption weight on the original film was measured by an apparatus as shown in FIG. No.
In FIG. 10, reference numeral 21 denotes a quartz crystal resonator covered with the original film, 22.
Is a vacuum dryer, 23 is a leak valve, 24 is a vacuum pump, 25
Indicates an oscillator, 26 indicates a frequency counter, and 27 indicates a personal computer. Change in adsorption weight per unit area (Δm
(Μg / cm ² )) was calculated from the frequency change of the crystal oscillator by the following equation (J. Hlavay and GGGuilbault, “Applica
tions of the Piezoelectric Crystal Detector in Ana
lytical Chemistry ", 49 (13), 1890 (1977)).

Δm = −ΔF / (2.3 × F ² ) Here, ΔF indicates a frequency change (Hz) of the crystal oscillator, and F indicates a natural frequency (9 MHz) of the crystal oscillator.

(8) Observation of reversible adsorption / desorption behavior In FIG. 11, absorbent cotton soaked in distilled water, iodomethane, and benzene was put in a box, and fixed at a distance of 2 mm from the crystal resonator covered with the original film. Reference numeral 21 denotes a crystal oscillator covered with an original film, 25 denotes an oscillator, 26 denotes a frequency counter, 27 denotes a personal computer, 4 denotes a shutter, and 3 denotes absorbent cotton containing a solvent.

(9) Calculation of expansion coefficient As shown in FIG. 12, when the shape of the bent film matches the arc, the expansion coefficient (γ) of the film surface can be estimated from the following equation (Kinto, “Conductivity High”). Artificial Muscle Using Molecules ”, Journal of the Textile Society of Japan, 50 (12), 628 (1994), Z. Hu,
X. Zhang and Y. Li, “Synthesis and Application of Mo
dulated Polymer Gels ", Science, 269, 525 (1995)).

γ (%) = 100dθ / L where d is the thickness (m) of the film, θ is the angle (radian) formed by the tangents at both ends of the arc, and L is the initial length (m) of the arc portion.

Example 1 As an original film, a polypyrrole film using perchlorate ion as a dopant as described in the above section "(1) Preparation of pyrrole-based polymer film" was used. The apparatus shown in FIG. 1 was used as the apparatus.

In FIG. 1, absorbent cotton soaked in distilled water was placed in a box and fixed at a distance of 2 mm from the original film. Temperature 24 ° C, relative humidity 56
The deformation of the film and the changes in temperature and relative humidity when the shutter was opened for 30 seconds under the conditions of% were measured. The results obtained are shown in FIG.

When the shutter was opened, the original film was bent in the opposite direction, and the displacement reached 6 to 7 mm. When the shutter was closed, the original film quickly returned to its original state. The deformation speed and recovery speed at this time are 3.3 mm / s and 3.7 mm / s, respectively.
The recovery process was found to be very fast. This is about seven times the deformation rate compared to conventional polypyrrole films operating in aqueous solutions. At this time, there was almost no temperature change near the original film, and only the relative humidity increased by about 5%.

Comparative Example 1 Deformation of the original film and changes in temperature and humidity were measured in the same manner as in Example 1 except that a test tube filled with hot water at 70 ° C. and plugged was used instead of absorbent cotton soaked with distilled water. The results obtained are shown in FIG.

The temperature rose about 0.8 ° C by opening the shutter,
No deformation of the original film was observed.

From the results obtained in Example 1 and Comparative Example 1, it is understood that the deformation of the original film is caused not by the temperature but by the humidity change.

Comparative Example 2 Instead of the polypyrrole film used in Example 1,
Polythiophene (PPy), polyaniline (PA), nylon (Nylon), polyethylene terephthalate (PET), polystyrene (PS), polyetheretherketone (PEE)
K), a device similar to that of Example 1 using a film of polyethylene (PE), polypropylene (PP), poly-4-fluoroethylene (PTFE) and polycarbonate (PC),
Under the same conditions, deformation of each film was observed. As a result, none of the films showed any deformation.

Example 2 In order to further study the bending phenomenon of the present invention,
Using the device shown in the figure, in place of cotton wool containing distilled water, place your finger close to the distance of 2 mm from the film for 5 seconds and keep it away for 25 seconds. It was measured. The results obtained are shown in FIG.

When the finger was brought close to the fixed end of the original film under the conditions of a room temperature of 24.7 ° C. and a relative humidity of 47%, the original film was bent in the opposite direction, and the displacement reached 9 to 10 mm. When he moved his finger away, he quickly recovered to its original condition. At this time, the deformation speed and recovery speed of the original film were 5.7 mm / s and 4.0 mm, respectively.
/ s reached. This is indeed the traditional polypyrrole film
10 times or more. The relative humidity near the original film is 2
Only 3% has changed, and there is a time delay from when the finger is brought close to when the display on the hygrometer changes,
Since the original film is deformed almost instantaneously, it is understood that the original film has extremely high sensitivity as compared with a commercially available electric resistance type humidity sensor.

FIG. 7 shows how the original film is deformed (side view). t = 0s is the state of the original film before the finger is brought closer from the right side of the original film, 1s is the state where the finger is approaching, 2s is the state where the finger is approached and stopped, and 3s is the state where the finger is released. I have. As shown in FIG. 7, when the finger is approached from the right side, the original film instantly bends to the left side, and
Release your finger after a few seconds and the situation quickly returned to its original state. In addition, such a rapid deformation behavior was kept almost unchanged even several months after the preparation of the original film. In contrast,
When the polymer gel is immersed in a surfactant solution, it shrinks in several hours and becomes unusable, indicating that the film according to the present invention has a service life 1000 times or more longer than that of the gel of the prior art.

Such excellent characteristics of the present invention experimentally show that the film deformation mechanism is based on weak physical adsorption such as van der Waals force.

Example 3 Using the apparatus shown in FIG. 1, a high-sensitivity strain gauge was attached to the lower end of the original film, and the stress (tension) generated in the direction perpendicular to the film surface when a finger was brought close by the same method as in Example 2. It was measured. The results obtained are shown in FIG.

When a finger is brought close to the original film, the film tends to bend to the opposite side, generating stress. At this time, the original film could generate a stress of 4.6 mg weight. This is more than 1.5 times the original film weight of 2.9 mg.

Example 4 FIG. 9 shows a change in electrical conductivity when four copper wires were drawn from gold deposited on the original film shown in FIG. 3 and a finger was brought close to the center of the film.

The conductivity of the original film was 102 S / cm near room temperature, and was almost constant without changing even when the finger was approached.

Example 5 Table 1 shows changes in electrical conductivity and mechanical properties when the original film was stretched by 25%.

By 25% stretching, the conductivity in the stretching direction increases by about 8%,
The mechanical properties of the film were also improved. In particular, the Young's modulus increased 1.8 times or more compared to the unstretched film. This is because the polypyrrole chain was oriented and tensioned by stretching.

Such a stretched film also shows similar deformation behavior, indicating that stretching is very effective for improving the performance of the film.

Example 6 Deformation of an original film was observed in the same manner as in Example 1 except that absorbent cotton soaked with various organic and inorganic compounds and their solutions was used instead of distilled water. Table 2 shows the obtained observation results.

When an aqueous solution in which organic substances such as sugar water was dissolved and an aqueous solution of an inorganic salt such as saline were used, the original film showed the same behavior as that of distilled water, and was bent to the side opposite to the side to which stimulation was applied.

On the other hand, organic polar solvents, for example, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, aldehydes such as formaldehyde and acetaldehyde, formamides such as N, N-dimethylformamide, acetonitrile and succinonitrile When nitriles, ethers such as diethyl ether and tetrahydrofuran, and monohalogenated alkyls such as iodomethane are used, the irritation may be contrary to when water, an aqueous solution in which organic substances are dissolved, and an inorganic salt aqueous solution are used. Flexed to the added side. With organic polar solvents, rapid film deformation was observed, especially in methyl iodide and N, N-dimethylformamide.

On the other hand, when alkanes such as hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, propylene carbonate, dimethyl sulfoxide and carbon tetrachloride were used, the original film was not deformed.

Example 7 In relation to the bending phenomenon of the original film, the weight of water and the like adsorbed on the original film was directly measured.

As the original film, a polypyrrole film using perchlorate ion as a dopant as described in the above section "(1) Preparation of pyrrole-based polymer film" was used. The device shown in FIG. 10 was used as the device.

The crystal unit covered with the original film was left in a vacuum at room temperature for 24 hours until the weight change disappeared. FIG. 13 shows the change in weight of the original film when the leak valve was opened and the inside of the vacuum dryer was returned to normal pressure. With the opening of the valve, the weight of the original film has increased rapidly. This indicates that moisture or the like in the air was adsorbed on the original film. The adsorption reached equilibrium in about 3 minutes, and the adsorption weight was 2.
It reached 89 μg / cm ² . This was about 4% of the weight of the original film polymerized on the quartz oscillator.

Example 8 Using the apparatus shown in FIG. 11, the shutter was opened for 5 seconds,
FIG. 14 shows changes in the weight of the adsorbed cells when the container was closed for 25 seconds and this operation was repeated four times. In the case of using distilled water, the weight increases at the same time as the shutter is opened, and the weight change is about 5 seconds.
1.7 μg / cm ² g was reached. This experimentally indicates that water molecules are adsorbed on the polypyrrole surface. On the other hand, benzene adsorbs only about 1/8 the weight of water molecules, and its speed is slow. In contrast, when iodomethane was used, a phenomenon was observed in which the weight first decreased and then increased. This indicates that iodomethane is adsorbed while stripping water molecules equilibrium adsorbed in the air. In each case, the weight quickly recovered to the original level when the shutter was closed. Since this occurs repeatedly and reversibly, it became clear that the adsorption of the solvent molecules onto the original film was physical adsorption based on a weak interaction such as van der Waals force.

In addition, it can be seen that the manner in which various solvents are adsorbed on the original film and the bending / recovery of the original film match well.
It is considered that the original film bends to the opposite side when distilled water is used because the film surface expands due to the adsorption of water molecules. On the other hand, benzene, which has a low adsorption rate and can only slightly adsorb, cannot cause deformation of the film. In contrast, iodomethane shrinks the film surface to peel off the water molecules already adsorbed. Therefore, the film is considered to bend toward the iodomethane side.

Example 9 Using the apparatus shown in FIG. 12, the coefficient of expansion of the original film surface due to the adsorption of water molecules was calculated to be about 0.3%. The value is about 1% in a conductive polymer film operated by electrochemical doping / de-doping, and about 49% in a gel. Therefore, the expansion coefficient of the polypyrrole film of the present invention is 1/1 compared to the prior art. It turns out that it is very small, 3 to 1/160. In other words, the film of the present invention is three times more than the prior art.
It means that the sensitivity is ~ 160 times higher. It is considered that the reason why the film of the present invention deforms and recovers at high speed with good reproducibility without deterioration for several months or more.

Example 10 By utilizing the responsiveness of an original film to water and / or an organic polar solvent, a "rotary actuator" that moves while rolling can be produced. The principle is shown in FIG. In FIG. 15, 2 is a film,
2A indicates a ring-shaped film, and 3A indicates absorbent cotton containing methyl iodide. The length of the film (2) is 25
mm, width 5 mm.

When the cotton wool soaked in methyl iodide is approached from the side of the ring-shaped film, the stimulated portion becomes an elliptical shape that is prone to stretch. In addition, the ring becomes elongated and eventually turns 90 degrees to the opposite side. At this time, the film is about 15 cm per minute
It turns out that it rolls at the speed of.

The feature of this embodiment resides in that the movement of the actuator can be controlled in a non-contact manner in the air, which is a technique which was not possible with a gel or a conductive polymer film which operates in a conventional solution or in a swollen state.

Example 11 By further developing Example 10, a "polypyrrole engine" can be manufactured as shown in FIG. In FIG. 16, 2B indicates a film, 3A indicates absorbent cotton containing methyl iodide, 3B indicates absorbent cotton containing water or an aqueous solution, 4 indicates a shutter, and 17, 17A indicates a pulley. The diameter of the pulley (17) is 2 mm, the diameter of the pulley (17A) is 10 mm, and the distance between the axes of these two pulleys is 20 mm.

Hang the belt-like film between the two pulleys. Above one pulley, absorbent cotton containing methyl iodide as a polar organic solvent, and absorbent cotton containing water or an aqueous solution beneath. Then, above, the belt is going to be straight,
Below, the pulley begins to rotate clockwise, as the belt tries to bend. At this time, it was found that the pulley continued to rotate at a speed of 7 revolutions per minute and the belt continued to rotate at a speed of about 22 cm per minute until the solvent did not evaporate. Since such a "polypyrrole engine" is driven only by compound vapor in the air, it can be expected as a new power source in the future. Furthermore, by alternately arranging a plurality of absorbent cottons containing water or a polar organic solvent and accumulating the deformation of the belt,
High speed rotation and high output are also possible.

Example 12 As shown in FIG. 17, a “polypyrrole engine” was produced. In FIG. 17, 2B indicates a film, 3B indicates absorbent cotton containing water, and 18 indicates a pulley. The diameter of the pulley (18) is 5 mm.

The “polypyrrole engine” shown in FIG.
Like the "polypyrrole engine", the pulley continued to rotate for a long time until the water in the absorbent cotton (3B) containing water completely disappeared.

Industrial applicability The present invention is a field that requires high sensitivity and reproducibility of operation,
For example, a sensor that uses the relationship between the adsorption and desorption of molecules and the bending of the film, an artificial valve that controls the flow rate and direction of water vapor and other gases using the reversible bending of the film,
Electronic elements, such as switches, that control the flow of current by incorporating them into electrical circuits by utilizing the conductivity of the film, and chemistry that directly uses the deformation of the film to perform work.
It can be used in a wide range of industrial fields, such as mechanical energy conversion materials (chemomechanical materials), actuators (artificial muscles), and polymer engines that rotate continuously by combining films and pulleys.

In addition, since the operation principle is simple, the system can be miniaturized, and can be used in a wide range of application fields such as a micro machine.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) F03G 7/00 C08J 5/18 G01N 27/12

Claims (11)

(57) [Claims] 1. A film comprising a pyrrole-based polymer film having at least 50 mol% of pyrrole units, wherein the film is formed in a gas by driving adsorption and desorption of water and / or a volatile polar solvent to the surface of the film. A highly sensitive method for deforming a pyrrole-based polymer film, characterized by causing deformation of the film. 2. The pyrrole-based polymer film according to claim 1, wherein the pyrrole-based polymer film is at least one selected from the group consisting of flat, ring-shaped, belt-shaped and tubular films. High sensitivity deformation method for polymer film. 3. A pyrrole polymer film having a thickness of 1 to 10
3. The method for deforming a pyrrole-based polymer film with high sensitivity according to claim 1 or 2, wherein the diameter is in the range of 00 μm. 4. A pyrrole polymer film having a thickness of 10 to 10
4. The method according to claim 3, wherein the thickness is within a range of 0 μm. 5. The method of claim 1, wherein the pyrrole-based polymer film contains at least one ion. 6. The pyrrole-based polymer film according to claim 1, wherein the pyrrole-based polymer film is a uniaxially stretched or biaxially stretched film. Sensitivity deformation method. 7. The method according to claim 1, wherein the volatile polar solvent is at least one compound selected from the group consisting of alcohols, ketones, aldehydes, nitriles, ethers, dimethylformamides, and alkyl monohalides. 2. The method of claim 1, wherein the pyrrole film is deformed with high sensitivity. 8. In a gas, the surface of a flat pyrrole-based polymer film having at least 50 mol% of pyrrole units and water and / or a volatile polar solvent are brought close to and / or separated from each other, Adsorption and desorption of the water and / or volatile polar solvent on the film surface as a driving force,
2. The method according to claim 1, wherein the deformation and recovery of the film are repeatedly caused. 9. In a gas, the surface of a ring-shaped, belt-shaped or tubular-shaped pyrrole-based polymer film having at least 50 mol% of pyrrole units is brought into contact with water and / or a volatile polar solvent. 2. The pyrrole system according to claim 1, wherein the film is deformed and / or rotated by driving the adsorption and desorption of the water and / or volatile polar solvent to the film surface as a driving force. High sensitivity deformation method for polymer film. 10. The method according to claim 1, wherein the water is supplied from at least one selected from the group consisting of pure water, an aqueous solution of an inorganic salt, an aqueous solution in which an organic substance is dissolved, an aqueous acid solution, and an aqueous alkaline solution. The method for highly sensitively deforming a pyrrole-based film according to claim 8 or claim 9. 11. The volatile polar solvent is a pure polar solvent,
The solvent is supplied from at least one selected from the group consisting of a mixed solvent of a polar solvent and water, a mixed solvent of a polar solvent and another non-polar solvent, and a solution in which another substance is dissolved in the polar solvent. The method for deforming a pyrrole-based film with high sensitivity according to claim 1, claim 8 or claim 9.