WO1997008458A1 - Procede a haute sensibilite permettant de deformer un film a base de polymere de pyrrole - Google Patents

Procede a haute sensibilite permettant de deformer un film a base de polymere de pyrrole Download PDF

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Publication number
WO1997008458A1
WO1997008458A1 PCT/JP1996/002410 JP9602410W WO9708458A1 WO 1997008458 A1 WO1997008458 A1 WO 1997008458A1 JP 9602410 W JP9602410 W JP 9602410W WO 9708458 A1 WO9708458 A1 WO 9708458A1
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film
pyrrole
polymer film
deformation
polar solvent
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PCT/JP1996/002410
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English (en)
Japanese (ja)
Inventor
Toshio Kunugi
Hidenori Okuzaki
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Toshio Kunugi
Hidenori Okuzaki
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Application filed by Toshio Kunugi, Hidenori Okuzaki filed Critical Toshio Kunugi
Priority to JP9510121A priority Critical patent/JP3039994B2/ja
Priority to AU68367/96A priority patent/AU6836796A/en
Publication of WO1997008458A1 publication Critical patent/WO1997008458A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • F03G7/06—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for using expansion or contraction of bodies due to heating, cooling, moistening, drying or the like

Definitions

  • the present invention relates to a method for bending and rotating a pyrrole-based polymer film in a gas by the adsorption and desorption of a low-molecular compound on a film surface, particularly the 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 of a pyrrole-based polymer film that causes deformation.
  • Typical stimulus-responsive polymers that have been studied in the past include polymer gels and conductive polymers.
  • 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 a machine or muscle is called a “chemomechanical system” or a “chemomechanical reaction” ( ⁇ ⁇ Osada, “Progress in Polymer Science”). ce, St imuU-Responsive Polymer Gels and Their Appli cat ion to Chemomechanical Systems ", Pergamon Press (1992)) D
  • poly (2-acrylamide-2-methylpropanesulfonate) gel is rapidly brought to the positive electrode side by applying a DC voltage in an aqueous surfactant solution. They have found bending (Y. Osada, H. Okuzaki and H. Hori, Nature, 55, 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.
  • the driving force for gel deformation is the 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 this can be explained by the electrokinetic phenomenon.
  • the material used is soft and brittle.
  • the present invention has been made for the purpose of solving the essential problems of such conventional stimuli-responsive polymers.
  • one object of the present invention is based on a principle different from that of a conventional stimuli-responsive polymer, that is, a film is dried in a gas such as air (dry type) by a small change in relative humidity of several percent or less. It is an object of the present invention to provide a method for deforming and recovering a pyrrole-based polymer film with high sensitivity, which has a large pressing force, and which can be repeatedly deformed and recovered. Another object of the present invention is to provide a method of deforming a polymer film with high sensitivity, which can generate a stress 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 also function as a very sensitive chemical sensor.
  • Another object of the present invention is to provide a pyrrole-based polymer capable of producing a “rotating actuator” that moves while rolling, which was impossible at all with a conventional gel or conductive polymer film.
  • An object of the present invention is to provide a method for deforming a film with high sensitivity.
  • Another object of the present invention is to provide a high-sensitivity deformation method for a polymer film of a pyrrole type, which can be used as a new power source in the future and can produce a "polypyrrole engine” driven only by vaporization of a compound.
  • the present inventors have conducted intensive studies on the above-mentioned problems, and found that the principle based on a principle different from that of a conventional stimuli-responsive polymer, that is, a slight change in relative humidity of several percent or less, caused a change in relative air.
  • a gas dry type
  • a unique and unprecedented phenomenon such as the rapid and large deformation of a pyrrole-based polymer film and its repeated recovery, was discovered.
  • the present inventors have further studied based on this finding, and as a result, have arrived at the present invention.
  • a pyrrole-based polymer film having at least 50 mol% of pyrrole units is used, and the driving force of adsorption and desorption of water and a volatile polar solvent on the film surface is as follows: A high-sensitivity deformation method for a pyrrole-based polymer film, characterized in that the film is deformed.
  • the volatile polar solvent is at least one compound selected from the group consisting of alcohols, ketones, aldehydes, toluene, ethers, dimethylformamides, and alkyl monohalides. 2. The method of claim 1, wherein the method for high-sensitivity deformation of a pyrrole-based film is provided.
  • the surface of a flat, pyrrole-based polymer film having at least 50 mol% of pyrrole units is separated from water and Z or a volatile polar solvent by proximity and / or Z separation.
  • a volatile polar solvent is a pure polar solvent, a mixed solvent of a polar solvent and water, (1) wherein said solvent is supplied from at least one selected from the group consisting of 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. 10. The method for high-sensitivity deformation of a pyrrole-based film according to item 9.
  • 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.
  • the term “in a gas” means that a conventional gel or conductive polymer film operates in a solution or in a swollen state. Then, the polymer film is deformed. In the present invention, particularly preferred is in air.
  • the polymer film that can be used in the present invention has at least a pyrrole unit in a molecular chain.
  • the pyrrole-based polymer of the present invention includes, as monomers, pyrrole, 3-alkylpyrroles such as 3-methylpyrrole, 3-ethylpyrrole, and 3-dodecylvirol; 3,4-Dialkylpyrrole such as methyl-4-dodecylvirol, N-methylpyrrol, N-alkylpyrrol such as N-dodecylvirol, N-methyl-3-methylpyrrol, N-ethyl-3 Pyrrole-based polymers produced by polymerizing N-alkyl-3-alkylpyrrol such as dodecylvirol and 3-carboxypyrrole, or copolymers produced by polymerizing these monomers with other monomers
  • a pyrrole-based polymer which is coalesced and in which at least 50 mol% of these copolymers have a pyrrole unit is used.
  • a chemical oxidation polymerization using a metal ion such as iodine or iron ion as a catalyst or an electrolytic polymerization applying a constant voltage or a constant current can be used. It is. Preferably, it is a method by electrolytic polymerization. Further, the pyrrole-based polymer film of the present invention can be produced simultaneously with the polymerization.
  • chloride ions In the electropolymerization, chloride ions, halide ions such as bromide ions, Phosphoric acid such as perchlorate ion, tetrafluoroborate ion, hexafluoroarsenate ion, sulfate ion, nitrate ion, thiocyanate ion, hexafluorogayate ion, phosphate ion, phenylphosphate ion, hexafluorophosphate ion, etc.
  • Phosphoric acid such as perchlorate ion, tetrafluoroborate ion, hexafluoroarsenate ion, sulfate ion, nitrate ion, thiocyanate ion, hexafluorogayate ion, phosphate ion, phenylphosphate ion, hexafluorophosphate ion,
  • alkylbenzenesulfonic acid ion such as ethylbenzenesulfonic acid ion, dodecylbenzenesulfonic acid ion, alkylsulfonic acid ion such as methylsulfonic acid ion and ethylsulfonic acid ion
  • poly At least one of polymer ions such as acrylate, polyvinylsulfonate, polystyrenesulfonate, and poly (2-acrylamide 2-methylpropanesulfonate) is used as a dopant.
  • the length, width and thickness of the pyrrole-based polymer film used in the present invention are not particularly limited as long as the flexibility and appropriate mechanical strength are not impaired.
  • the thickness of the original film is generally in the range of 1 to 100 m, preferably in the range of 100 to 100 m.
  • the original film is preferably a film that has been uniaxially or biaxially stretched by a known stretching method.
  • 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.
  • the original film can be used in a shape such as a flat shape, a ring shape, a belt shape or a tubular shape. Also, these shapes can be used in combination o
  • the present invention uses a specific solvent (polar liquid), namely water and volatile polar A solvent is used.
  • volatile polar solvents examples include alcohols such as methanol, ethanol and butanol, ketones such as acetone and methyl ethyl ketone, and formaldehyde. And aldehydes such as acetoaldehyde; nitriles such as acetonitrile and succinonitrile; ethers such as getyl ether and tetrahydrofuran; formamides such as N, N-dimethylformamide; And monohalogenated alkyls.
  • the water is pure water and various aqueous solutions, that is, 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 solution of an acid such as dilute sulfuric acid or ammonia water, and an aqueous solution of an alkaline solution. Supplied from various aqueous solutions.
  • the original film When a stimulus is applied to the surface of the original film using these pure water and various aqueous solutions, the original film exhibits a phenomenon of quickly bending to the side opposite to the stimulus. When the stimulus is moved away, the original film quickly returns to its original position.
  • the volatile polar solvent is a pure polar solvent and various solvents and solutions including a polar solvent, that is, a mixed solvent of a polar solvent and water, and a mixed solvent of a polar solvent and another solvent. It is supplied from a solvent and various solvents and solutions including a polar solvent such as a solution in which another substance is dissolved in a polar solvent.
  • the original film 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 the phenomenon. Also, 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 and size, polarity, hydrophilicity, hydrophobicity, volatility, etc. 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 in water and organic polar solvents of formamides such as N, N-dimethylformamide and monohalogenated alkyls such as methane.
  • alkanes such as hexane, heptane, and octane
  • algens such as ethylene and hexene
  • alkynes such as acetylene, carbon tetrachloride, and chromate
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • the method for introducing water and a volatile polar solvent in the present invention is not necessarily limited.
  • the method using absorbent cotton in the air shown in FIG. 1 as long as the principle of the present invention is not deviated, for example, diffusion using capillary action or ultrasonic waves, or a gas such as nitrogen, oxygen, or argon may be used as a carrier. It is also possible to use a spray that has been sprayed.
  • the area and the number of stimuli to be applied are not necessarily limited.
  • the shape, size, thickness, etc., of the pyrrole-based polymer film, the type, number, amount, etc., of water and the volatile polar solvent are stimulated by water and the volatile polar solvent.
  • the size, number, etc. of the region to which is added can be appropriately selected. The deformation of the original film of the present invention will be described in more detail.
  • the original film has a length of 25 mm, a width of 5 mm, a thickness of about 30 and an upper end of 5 mm fixed to a 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.
  • 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 2 mm apart.
  • the deformation at a position 3 mm from the lower end of the original film when the shutter is opened can be measured with a laser displacement meter.
  • temperature and relative humidity at a distance of 1 mm from the original film can be measured simultaneously.
  • the original film When the original film is stimulated with water and Z or a volatile polar solvent using the device shown in Fig. 1, if the area to be stimulated is made larger than the original film, the entire film will bend greatly. Also, when multiple stimuli are applied from the same direction, the original film bends from each point and the bending of the original film increases. Stagger multiple stimuli When added from both sides, the original film bends left and right at each point and transforms into a waveform. On the other hand, if two identical stimuli are applied to the same location on both sides, they will cancel and not deform. When the original film is slightly slacked and both ends are fixed and stimulus is applied, it bows in a bow shape.
  • the ring-shaped film When a part of the ring-shaped film is stimulated, it is transformed into an ellipse.
  • the ring can be rolled in one direction by utilizing such a change in the curvature of the arc.
  • the plies When this ring is hung on two plies and a stimulus is applied to a specific location, the plies begin to rotate.In the device shown in Fig. 1, the lower end of the original film is open, The deformation of the original film can be detected as stress by connecting to a sensitivity strain meter.
  • the apparatus shown in FIG. 1 can be applied to a horizontal type as long as the force of suspending the original film vertically is not changed as long as the principle and concept of the present invention are not changed.
  • the direction of bending of the film is determined by the one-sided expansion and contraction of the film.
  • the molecules to be absorbed and desorbed are vapors of solvent molecules such as water and alcohol.
  • solvent molecules such as water and alcohol.
  • the former expands and the latter contracts.
  • a strong force is generated.
  • water alone works.
  • polypyrrole film is chemically stable and does not deteriorate.
  • the generated stress is high despite its high strength and low expansion coefficient. Also, conductive There is.
  • FIG. 1 is an explanatory diagram 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 filled with hot water at 70 in FIG.
  • FIG. 6 is a graph showing the displacement of the original film and the change in temperature and relative humidity when the finger is moved closer to the target for 5 seconds and separated for 25 seconds in FIG.
  • FIG. 7 is an explanatory view 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 shows the stress generated in the direction perpendicular to the film surface when the finger is approached in Fig. 2.
  • 5 is a graph obtained by measuring.
  • 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 deformed polymer film 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 an 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 is a graph showing the change in adsorption weight when the shutter shown in FIG. 11 is opened for 5 seconds, closed for 25 seconds, and repeated four times using the apparatus shown in FIG.
  • FIG. 15 is a schematic diagram illustrating the principle of a “rotating factor 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.
  • each measurement result such as the measurement result of the displacement was obtained by the method shown in the following (2) and (3) to (9).
  • a platinum plate (length 50 mm, width 20 mm, thickness 0.1 mm) was used for the positive electrode, and aluminum foil (length 200 mm, width 50 mm, thickness 01 mm) was used for the negative electrode.
  • the solution was placed in an electrolytic polymerization cell as shown in FIG. In Fig. 2, 7 is a low-temperature constant temperature bath, 8 is a potentiostat, 9 is a temperature controller, 10 is an electropolymerization cell, 11 is an aluminum foil, 12 is a platinum plate, 13 is a throw cooler, and Reference numeral 14 denotes a refrigerant (ethanol).
  • the resulting dark green polypropylene film was peeled off from the platinum plate and washed in propylene carbonate for about 1 hour. Furthermore, the film was vacuum-dried for one day and used as a sample (original film).
  • the dimensions of the dried polypyrrole film are 50 mm in length, 20 mm in width, and about 30 mm in thickness.
  • This film has an electrical conductivity of 102 SZcm, a Young's modulus of 0.61 GPa, and is cut. It had properties of a strength of 33.7 MPa and a breaking elongation of 25.9%.
  • the polypyrrole film was stretched by 25% at room temperature at a strain rate of 10% Zmin using a normal tensile tester (Tensilon II, Orientec Co., Ltd.).
  • a polypyrrole film about 30 / m thick into a 25 mm long, 5 mm wide tank.
  • the upper end of the film was fixed at 5 mm on 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) with a resolution of 50 zm.
  • Measurement data Amplify with a nit (LB—1200, Keyence Corporation) and read it in the evening at a personal convenience store.
  • 1 is a chuck
  • 2 is a film
  • 3 is absorbent cotton containing a solvent
  • 4 is a shutter
  • 5 is a laser displacement meter.
  • thermo-hygrometer M-P, Panametrics Japan
  • FIG. 1 reference numeral 6 denotes a thermo-hygrometer.
  • a high-sensitivity strain gauge (T7—8—120 (maximum load: 8 g), Orientec Co., Ltd.) to the bottom of the film, and measure the stress generated in the direction perpendicular to the film surface.
  • the output voltage from the high-sensitivity strain gauge is amplified by an amplifier unit (AR-600, Orientec Co., Ltd.) and read into a personal computer.
  • the weight of the adsorption was directly measured by a microphone mouth balance method using a quartz oscillator.
  • the raw film is electropolymerized for 30 minutes on the electrodes of a crystal oscillator (9 MHz, Wakabayashi Seisakusho).
  • the equilibrium adsorption weight on the original film was measured using an apparatus as shown in FIG.
  • reference numeral 21 denotes a crystal unit covered with an original film
  • 22 denotes a vacuum dryer
  • 23 denotes a leak valve
  • 24 denotes a vacuum port.
  • AF indicates a frequency change (Hz) of the crystal oscillator
  • F indicates a natural frequency (9 MHz) of the crystal oscillator.
  • FIG. 11 absorbent cotton soaked in distilled water, chloride, and benzene was placed in a box, and fixed at a distance of 2 mm from the crystal unit 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
  • 3 denotes absorbent cotton containing a solvent.
  • the expansion coefficient (a) of the film surface can be estimated from the following equation (Kinto, "Artificial Muscle”, Journal of the Textile Society of Japan, 50 (12), 628 (1994), Z. Hu, X. Zhang, and Y. Li, Synthesis and Application of Modulated Polymer Gels", Science. 269, 525 (1995)).
  • d indicates the thickness of the film (m)
  • 0 indicates the angle (radian) formed by the tangent lines at both ends of the arc
  • L indicates the initial length (m) of the arc portion.
  • Opening the shutter raised the temperature by about 0.8 ° C, but no deformation of the original film was observed.
  • Example 2 In order to further study the bending phenomenon of the present invention, using the apparatus shown in Fig.
  • Figure 7 shows the deformation (side view) of the original film.
  • t 0 s is the state of the original film before the finger is approached from the right side of the original film
  • 1 s is the state where the finger is approaching
  • 2 s is the state where the finger is approaching and stopped
  • 3 s is the state where the finger is released
  • t 0 s is the state of the original film before the finger is approached from the right side of the original film
  • 1 s is the state where the finger is approaching
  • 2 s is the state where the finger is approaching and stopped
  • 3 s the state where the finger is released
  • Each state is shown.
  • the original film instantly bends to the left side, and when the finger was released one second later, the original state was quickly restored.
  • such quick deformation behavior remained almost unchanged even a few months after the production of the original film.
  • the film according to the present invention has a lifetime 100,000 times or more longer than that of the conventional gel. It can be seen that it is.
  • Example 4 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 approached by the same method as in Example 2 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, causing stress. At this time, the original film was able to generate a stress of 4.6 mg weight. This is more than 1.5 times the original film weight of 2.91118.
  • Example 4 Example 4
  • Fig. 9 shows the change in 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.
  • Table 1 shows the changes in electrical conductivity and mechanical properties when the original film was stretched by 25%.
  • Table 1 Conductivity and mechanical properties of stretched film Stretching conductivity Young's modulus Cutting strength Cutting elongation Magnification (S / cm) (GPa) (MPa) (3 ⁇ 4)
  • Raw film 102 0.61 33.7 25.9 Stretched film 1.25 110 1.12 35.9 9.5
  • the 25% stretching increased the conductivity in the stretching direction by about 8% and improved the mechanical properties of the film.
  • the Young's modulus increased 1.8 times or more compared to the unstretched film. This is because the polypyrrole chains were oriented and tensioned by stretching.
  • organic polar solvents such as alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, aldehydes such as formaldehyde and acetoaldehyde, N, N-dimethylformamide and the like Formamides, nitriles such as acetonitrile and succinonitrile, ethers such as getyl ether and tetrahydrofuran, and monohalogenated alkyls such as eodomethane.
  • alcohols such as methanol and ethanol
  • ketones such as acetone and methyl ethyl ketone
  • aldehydes such as formaldehyde and acetoaldehyde
  • Formamides nitriles such as acetonitrile and succinonitrile
  • ethers such as getyl ether and tetrahydrofuran
  • Fig. 14 shows the change in adsorption weight.
  • the weight increased as soon as the shutter was opened, and the weight change reached about 1.7 ug / cm 2 g in 5 seconds. This indicates experimentally that water molecules are adsorbed on the surface of the polypropylene.
  • benzene adsorbs only about 1/8 the weight of water molecules, and its speed is slow.
  • methane the weight decreased first and then increased. This is because methane in air Indicates that ⁇ is adsorbing water molecules that are equilibrium adsorbed.
  • the coefficient of expansion of the original film surface due to the adsorption of water molecules was calculated to be about 0.3%. Since the value is about 1% in a conductive polymer film operated by electrochemical doping and undoping, and about 49% in a gel, the expansion rate of the polypyrrole film of the present invention is smaller than that of the prior art. It turns out that it is very small, 1 Z 3-1 Z 16. In other words, it means that the film of the present invention is 3 to 160 times more sensitive than the prior art. It is considered that the reason why the film of the present invention does not deteriorate for several months and deforms and recovers at high speed with good reproducibility.
  • FIG. 15 2 indicates a film
  • 2A indicates a ring-shaped film
  • 3A indicates absorbent cotton containing methyl iodide.
  • the length of the film (2) is 25 mm and the width is 5 mm.
  • the stimulated part becomes an elliptical shape that stands out as it stretches.
  • the ring becomes elongated and eventually turns 90 degrees to the opposite side. At this time, it was found that the film rolled at a speed of about 15 cm per minute.
  • the feature of this embodiment is that the movement of the actuator can be controlled without contact in the air, a technology that was not possible with a gel or a conductive polymer film operating in a conventional solution or in a swollen state. It is.
  • Example 1 1
  • Example 10 By further developing Example 10, it is possible to produce a "polypyrrole engine" as shown in FIG. In FIG. 16, 2B is a film, 3A is a cotton wool containing methyl iodide, 3B is a cotton wool containing water or an aqueous solution, 4 is a shutter, and 17 and 17A are pulleys. Shown respectively.
  • the diameter of the pulley (17) is 2 mm
  • the diameter of the pulley (17 A) is 10 mm
  • the distance between the axes of these two pulleys is 20 mm.
  • a belt-like film is hung between two pulleys. Put cotton wool containing methyl iodide as a polar organic solvent on one pulley, and cotton wool containing water or an aqueous solution below.
  • the pulley then starts to rotate clockwise, as the belt tries to straighten above and the belt tries to bend below. At this time, it was found that the belt continued to rotate at a speed of 7 revolutions per minute and the belt continued at a speed of about 22 cm per minute until the solvent evaporated. Since such a “polypyrrole engine” is driven only by compound vapor in air, it can be expected as a new power source in the future.
  • by alternately arranging a plurality of absorbent cottons containing water or a polar organic solvent and accumulating the deformation of the belt it is possible to increase the rotation speed and increase the output.
  • a "polypyrrole engine” was produced.
  • 2 B indicates a film
  • 3 B indicates absorbent cotton containing water
  • 18 indicates a pulley.
  • the diameter of the pulley (18) is 5 mm.
  • the “polypyrrole engine” shown in Fig. 17 is also similar to the “polypyrrole engine” in Example 11, in which the bury wheel rotates for a long time until the water in the absorbent cotton (3B) containing water completely disappears. I continued. Industrial applicability
  • the present invention relates to a field requiring high sensitivity and reproducibility of operation, for example, a sensor utilizing the relationship between molecular adsorption and desorption and film bending, and water vapor and other gas utilizing reversible film bending.
  • An artificial valve that controls the flow rate and direction of the film, an electronic element such as a switch that controls the flow of electric current by incorporating it into an electric circuit by using the fact that the film is conductive, and a job that directly uses deformation of the film Chemodynamic energy
  • the system can be miniaturized, and can be used in a wide range of application fields such as micromachining.

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Abstract

L'invention porte sur un procédé à haute sensibilité qui permet de déformer, dans le milieu ambiant, des films à base d'un polymère de pyrrole, comportant au moins 50 unités de pyrrole en pourcentage molaire, en faisant intervenir les phénomènes d'adsorption et de désorption d'eau et/ou d'un solvant polaire volatil à la surface du film. Ce procédé, qui met en oeuvre un principe se démarquant du principe classique faisant intervenir des polymères sensibles à un stimulus, permet de procéder, dans le milieu ambiant, à d'importantes déformations répétées du film et à lui faire recouvrer rapidement sa forme en utilisant des modifications hygrométriques relatives par minute d'une valeur égale ou inférieure à plusieurs unités pour cent. L'invention porte également sur un procédé à haute sensibilité permettant de déformer des films à base d'un polymère de pyrrole agissant également comme capteur chimique à haute sensibilité, ce qui permet de produire, d'une part un 'actionneur rotatif' se déplaçant tout en tournant, ce qui était impossible avec les gels ou les films polymériques conducteurs habituels et, d'autre part un 'moteur à polypyrrole' seulement mû par la vapeur du composé, moteur que l'on s'attend à voir se comporter, dans l'avenir, comme nouvelle source d'énergie.
PCT/JP1996/002410 1995-08-31 1996-08-28 Procede a haute sensibilite permettant de deformer un film a base de polymere de pyrrole WO1997008458A1 (fr)

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JP9510121A JP3039994B2 (ja) 1995-08-31 1996-08-28 ピロール系高分子フィルムの高感度変形方法
AU68367/96A AU6836796A (en) 1995-08-31 1996-08-28 High-sensitivity method of deformation of pyrrole polymer film

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JP24525495 1995-08-31
JP7/245254 1995-08-31
JP8900296 1996-03-19
JP8/89002 1996-03-19

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004075389A1 (fr) * 2003-02-18 2004-09-02 Eamex Corporation Commande
WO2004078830A1 (fr) * 2003-03-04 2004-09-16 Eamex Corporation Film de polypyrrole deformable a haute resistance
JP2005006490A (ja) * 2003-02-18 2005-01-06 Eamex Co アクチュエータ
WO2015172067A1 (fr) * 2014-05-08 2015-11-12 The Trustees Of Columbia University In The City Of New York Moteurs entraînés par évaporation
US11603827B1 (en) 2016-11-11 2023-03-14 The Trustees Of Columbia University In The City Of New York Systems and methods for fabricating water-responsive actuators

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5952644B2 (ja) * 1976-08-25 1984-12-20 ダイキン工業株式会社 メカノケミカル系非水溶性共重合体の製造法
JPH0650950B2 (ja) * 1984-03-02 1994-06-29 株式会社東芝 アクチユエ−タ
JPH0679001B2 (ja) * 1990-07-27 1994-10-05 財団法人韓国科学技術研究院 高分子湿度センサ及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5952644B2 (ja) * 1976-08-25 1984-12-20 ダイキン工業株式会社 メカノケミカル系非水溶性共重合体の製造法
JPH0650950B2 (ja) * 1984-03-02 1994-06-29 株式会社東芝 アクチユエ−タ
JPH0679001B2 (ja) * 1990-07-27 1994-10-05 財団法人韓国科学技術研究院 高分子湿度センサ及びその製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004075389A1 (fr) * 2003-02-18 2004-09-02 Eamex Corporation Commande
JP2005006490A (ja) * 2003-02-18 2005-01-06 Eamex Co アクチュエータ
WO2004078830A1 (fr) * 2003-03-04 2004-09-16 Eamex Corporation Film de polypyrrole deformable a haute resistance
WO2015172067A1 (fr) * 2014-05-08 2015-11-12 The Trustees Of Columbia University In The City Of New York Moteurs entraînés par évaporation
US10415550B2 (en) 2014-05-08 2019-09-17 The Trustees Of Columbia University In The City Of New York Evaporation-driven engines
US11603827B1 (en) 2016-11-11 2023-03-14 The Trustees Of Columbia University In The City Of New York Systems and methods for fabricating water-responsive actuators

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AU6836796A (en) 1997-03-19
JP3039994B2 (ja) 2000-05-08

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