JPH049164B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a polyacetylene film,
In particular, it relates to a method suitable for obtaining a film with a large thickness. Polyethylene is the simplest chain conjugated polymer compound with one carbon _and one hydrogen atom as _a constituent unit, and has semiconductor properties _. -Al( _{C2H5 ) 3}
The polyacetylene film obtained by acetylene polymerization using acetylene polymerization system) has a fibril (fibrous microcrystalline) network structure with a diameter of about 200 mm, and it can be slightly doped with halogen gas or arsenic pentafluoride. The conductivity can be varied widely depending on the conductivity. In addition, such a polyacetylene film is chemically extremely stable, lightweight, and has a fibrillar network structure as mentioned above, so it can occupy a very large surface area, so it can be used as a secondary material. It is already attracting attention as a promising electrode material for batteries and for its application in integrated circuits. As a method for producing the polyacetylene membrane, the Al/
The molar ratio of Ti was adjusted to 3 to 4, and this was cooled to -78°C with a dry ice/methanol refrigerant.
It is already known that by spraying acetylene gas onto this catalyst, the gas is polymerized near the gas phase-liquid phase boundary on the surface of the catalyst solution. However, when using the above-mentioned normal manufacturing method, it is impossible to obtain a film with a thickness of only about 150 μm. When we consider the reason for this, we find that when a highly concentrated Ziegler-Natsuta catalyst is used, the viscosity of the catalyst increases, and as a result, a polyacetylene film is formed on the Ziegler-Natsuta catalyst surface formed on a given surface. This is considered to be because as the fibril network structure grows, the highly viscous catalyst becomes difficult to penetrate into the grown film, and eventually the growth of the film stops at a certain limit. Therefore, when a low concentration Ziegler-Natsuta catalyst is used, a thicker film can be grown than when using a high concentration due to its low viscosity, but the polyacetylene film obtained in this way has a very high density (g/cm ³ ). Therefore, it is impossible to produce a polyacetylene film having the desired thin thickness and optimum density using the conventional method described above, thereby obtaining a large short-circuit current value. It was possible. In view of the above problems, we further supply a Ziegler-Natsuta catalyst on the polyacetylene film obtained by the conventional method to form a polyacetylene film in a layered manner, thereby creating an integral thick polyacetylene film product. It has already been proposed to finish the
−189107). However, in the above proposal, the polyacetylene film that is formed first is a thin layer, and the polyacetylene film that is laminated on top of it is a thicker layer. The laminated product has a defect in that the adhesion between the two laminated layers is not good, and as a result, the specific resistance of the product increases. The present invention has investigated the above-mentioned problems and attempts to solve them.The present invention is characterized by depositing a first thin layer of Ziegler-Natsuta catalyst on a predetermined surface within the closed vessel body. The basic step is to form a polyacetylene base film at the thin layer location by supplying acetylene gas into the container body, and to form a second thin layer using a Ziegler-Natsuta catalyst on the surface of the polyacetylene base film. An additional step of forming a thinner layer than a thin layer, and further adhering a polyacetylene additive film mainly on the polyacetylene base film by supplying acetylene gas, and optionally applying a Ziegler-Natsuta catalyst on the surface of the polyacetylene additive film. A third thin layer is formed to be thinner than the first thin layer, and one or more additional steps are performed in which a polyacetylene additional film is produced and deposited on the polyacetylene additional film by supplying acetylene gas. There is a particular thing. In order to describe the method according to the present invention in detail below, the manufacturing apparatus used for carrying out the method will first be explained with reference to FIG.
and a support opening 1b suspended at a predetermined location by support arms 2, 2', and both 1a, 1b are connected by a mechanical seal 1c.
The main body 1a can be rotated by driving a rotating shaft 3 projecting downward from the bottom of the main body 1a. On the ceiling wall of the support port 1b, there are catalyst piping 4 that can supply the Ziegler-Natsuta catalyst into the closure body 1 through the respective regulating valves 4a, 5a, and 6a, and a pipe 4 that is not connected to the closure body 1. An inert gas pipe 5 capable of supplying active gas and an acetylene supply/discharge pipe 6 capable of supplying and discharging acetylene gas are vertically installed through the main body 1a. A plane 7 is provided, and a catalyst reservoir recess 9 is provided between the circumferential wall 8 and the plane 7. Therefore, in order to carry out the present invention using the above device, first, the regulating valve 5a is opened in the closing device body 1 to fill inert gas, and the closing device body 1 is driven by the rotating shaft 3. While rotating at about 100rpm,
The adjustment valve 4a is opened and the Ziegler-Natsuta catalyst is dripped from the catalyst pipe 4 onto the center of the raised plane 7. Here, the Ziegler-Natsuta catalyst used was a mixture of triethylaluminum and tetrabutoxytitanium in toluene at a molar ratio of aluminum to titanium of 4:1 and a titanium concentration of 300 mmol/l. When the catalyst has spread to the raised plane 7 and the peripheral side 8 and the first thin layer 10 has been deposited, the operation of the rotating shaft 3 is stopped and the inert gas filled in the closure body 1a is adjusted. Exhaust by opening the valve 5a,
By opening the regulating valve 6a, a constant pressure of 1 atm and a polymerization temperature of -
A polyacetylene base is formed on the first thin layer 10 by introducing acetylene gas at 78° C. for 10 minutes. Here, the first thin layer 10 has a desired density and is formed as thick as possible.
The amount of catalyst was adjusted to about 0.007ml/cm ² , but in the next addition step, the closure body 1 was again filled with inert gas in the same manner as before, and the
Rotate at 100 rpm, drop the Ziegler-Natsuta catalyst, stop the rotation, and after exhausting the inert gas, supply acetylene for 10 minutes at a constant pressure of 1 atm and -78°C. That is, the catalyst is dropped in the same step onto the polyethylene base film formed in the previous step, and at this time, the thickness of the second thin layer formed by the catalyst is equal to the first thin layer 10. By doing so, the polyacetylene additional film formed as the second thin layer is integrally formed and adhered to the polyacetylene base film without peeling off. At this time, the thickness of the second thin layer is
It is desirable to set the layer thickness to about 0.0006ml/cm ² to 0.0033ml/cm ² .If the layer is thinner than 0.006ml/cm ² , the resulting polyacetylene addition film will become too thin, making it unsuitable for thick film production. As the thickness increases beyond 0.0033ml/cm ² , the specific resistance gradually increases, which indicates that the polyacetylene base film and the polyacetylene additional film are not sufficiently connected. . Through the above additional steps, a product with a thicker wall than the conventional product can be obtained, but if you want to obtain an even thicker film, the following additional step is performed the desired number of times. In this case as well, Ziegler® is applied to the surface of the polyacetylene-added film as in the previous step.
A third thin layer of Natsuta catalyst is also applied to the first layer.
Formed in a thinner layer than a thin layer, preferably as before
By supplying acetylene gas at 0.0006 to 0.0033 ml/cm ² , the same polyacetylene-added film is further formed and deposited. Here, the film thickness and specific resistance of the polyacetylene thick film obtained by the method according to the present invention were measured, and the results shown in Table 1 are obtained.

[Table] On the other hand, in the additional process, if the second, third,...thin layers were made to have the same thickness as the first thin layer, the measurement results in Table 2 would be obtained. .

[Table] As is clear from a comparison of the two tables above, the film thickness of the product can be increased by increasing the thickness of the second and subsequent thin layers of the catalyst, but the specific resistance increases, making it difficult to create a desirable product. I realized that it would be difficult to obtain
Furthermore, if the amount of catalyst is 0.008ml/ ^cm2 , the specific resistance is
10 ¹¹ Ωm, reaches 10 ¹² Ωm in the case of 0.010ml/ ^cm2 ,
In such a case, it can be seen that the bond between the films has become even more insufficient as described above. As described above, according to the present invention, compared to the conventional method,
Only products with a diameter of about 150 μm could be obtained, and even if thick products were produced by lowering the concentration of Ziegler-Natsuta catalyst, only products with a low density of 0.1 g/cm ³ or less could be obtained, whereas polyacetylene Rather than simply laminating films, the production weight of a polyacetylene film that satisfies the condition that the second and third thin layers are formed thinner than the first thin layer is determined by the Ziegler-Natsuta catalyst. Depending on the product, 400μ
It has become possible to produce a product with a resistivity of 0.4 g/cm 3 or more, a low resistivity, and a density of about 0.4 g/cm ³ .

[Brief explanation of drawings]

The figure is a longitudinal sectional front view showing an example of a polyacetylene thick film manufacturing apparatus that can be used to carry out the present invention. 1... Closer body, 10... First thin layer.

Claims (1)

[Scope of Claims] 1. A first thin layer of Ziegler-Natsuta catalyst is deposited on a predetermined surface inside the closed vessel body, and acetylene gas is supplied into the closed vessel body to form a polyacetylene group in the thin layer portion. The basic step of forming a membrane is to form a second thin layer using a Ziegler-Natsuta catalyst on the surface of the polyacetylene base film, which is thinner than the first thin layer, and further to supply acetylene gas to the polyacetylene base film. an additional step of forming and adhering a polyacetylene-added film on the polyacetylene-added film, and optionally forming a third thin layer using a Ziegler-Natsuta catalyst on the surface of the polyacetylene-added film, which is thinner than the first thin layer; A method for producing a polyacetylene thick film, which comprises performing one or more additional steps of forming and depositing a polyacetylene added film on the polyacetylene added film by supplying acetylene gas. 2 The thickness of the second thin layer formed by the Ziegler-Natsuta catalyst on the surface of the polyacetylene base film and the third thin layer formed by the Ziegler-Natsuta catalyst on the surface of the polyacetylene added film is 0.0006 ml/cm ² to 0.0033.
ml/cm ² . The method for producing a polyacetylene thick film according to claim 1.