JPH075672B2 - Method for producing highly oriented ultra-long conjugated polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to an electric material, and more particularly, to a method for producing a highly oriented ultralong conjugated polymer having a conjugated bond such as polyacetylene bond exhibiting electrical conductivity or nonlinear optical effect. It is a thing.

Conventional technology Since polymers such as acetylene and its derivatives have a one-dimensional main chain with a π-electron conjugated system in the molecule,
Because of its conductivity and nonlinear optical effect, it has been widely studied as an optical and electronic functional material.

As a conventional method for producing a polymer such as acetylene or a derivative thereof, a polymerization method of Shirakawa et al. Using a Ziegler-Natta catalyst is well known.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, currently known polymers of acetylene and its derivatives are unstable with respect to heat, pressure, ultraviolet rays, etc. in an atmosphere containing oxygen. Has been.

However, a method for stabilizing a polymer of acetylene or its derivative has not been found yet.

Moreover, in the polymer of acetylene or its derivative, the technique of controlling the orientation has not been developed.

In view of the above problems, the present invention provides a method for producing a highly stable and highly oriented ultralong conjugated polymer.

Means for Solving the Problems In the present invention, in order to solve the above-mentioned problems, a chlorosilane-based substance containing a conjugated unsaturated bond-bonded unsaturated group and a (mono-, di-, or tri) chlorosilane group In a water-based organic solvent, at least a hydrophilic substrate is immersed in a monomolecular film forming step of forming a monomolecular film of the substance on the substrate, and the unsaturated group in the monomolecular film is selected. Deactivation step of chemically deactivating, and a polymerization step of polymerizing the unsaturated group remaining in the monomolecular film in the monomolecular film that has not been deactivated in an inert gas, the substrate having a high orientation property. A method for producing an ultralong conjugated polymer is adopted.

By using a linear hydrocarbon derivative having a chlorosilane group (-SiCl _x ) at one end, a monomolecular film of the derivative can be formed on the surface of the hydrophilic substrate by the chemisorption method in an organic solvent. It is known that a cumulative film of the monomolecular film can be formed by irradiating the film with high-energy radiation in a gas containing oxygen to make the surface hydrophilic.

Therefore, use a substance that contains a conjugated unsaturated bond-unsaturated group (eg, acetylene group, diacetylene group, thiophene group, pyrrole group, etc.) as part of the linear hydrocarbon derivative having a chlorosilane group at one end. If the chemisorption method is performed,
A monomolecular film of the unsaturated group derivative of the order of tens of A can be formed, and a multilayer cumulative film can be easily obtained.

In this way, the unsaturated groups in the monomolecular film chemisorbed on the substrate are selectively linearly deactivated in a specific direction, and the remaining conjugated groups in the monomolecular film in the inert gas atmosphere are deactivated. By polymerizing the part of the saturated bond-unsaturated group, a polymer having extremely high orientation, an ultrahigh molecular weight and a very long conjugated system can be produced.

Examples The conjugated unsaturated bond-forming unsaturated group of the present invention includes an acetylene group (-C≡C-) and a diacetylene group (-C≡C-C≡).
Examples include linear carbon compounds having a triple bond such as C-), thiophene rings, pyrrole rings, furan rings, and cyclic compounds such as cyclopentadiene.

Moreover, according to the production method of the present invention, even if it is a polyacetylene-based or polydiacetylene-based, because a stable polymer is formed even in an atmosphere containing oxygen, it may have a linear hydrocarbon compound having a triple bond. Especially effective.

The chlorosilane-based substance of the present invention contains the above-mentioned conjugated unsaturated bond-unsaturated group and chlorosilane group.

The chlorosilane group may be any of monochlorosilane in which one chlorine atom is bonded to silicon, dichlorosilane in which two chlorine are bonded, or trichlorosilane in which three chlorine are bonded.

Since this chlorosilane easily reacts with water or the like to form a siloxy group and deactivates, it is necessary to use a non-aqueous organic solvent when chemically adsorbing the chlorosilane-based substance.

When a trimethylsilane group is bound to one end of the chlorosilane-based substance, the terminal trimethylsilane group can be easily hydrophilized by irradiating it with high-energy radiation after the polymerization step,
It is preferable because a monomolecular film can be further accumulated and an ultralong conjugated polymer having a three-dimensional structure can be formed.

When the unsaturated group is an acetylene group, ω-nonadecylinoic trichlorosilane is preferable because both chemisorption and polymerization are easily performed. 1- (trimethylsilyl)
In the case of -ω-nonadecylinoic trichlorosilane, it is preferable from the viewpoint of chemisorption, polymerization and accumulation.

In the deactivation step of the present invention, it depends on the activity of the unsaturated group to be used, but the irradiation with electron beams, X-rays, γ-rays, etc., irradiation with a scanning tunneling microscope, or a chlorosilane-based substance such as a diacetylene derivative In the case of high activity, UV irradiation and the like can be mentioned.

In the polymerization step of the present invention, in addition to the dry process described in the above deactivation step, at least a metal halide catalyst such as MoCl ₅ , WCl ₆ , NbCl ₅ , TaCl ₅ , or Mo (CO) ₅ , W (CO ) ₆ , Nb (C
An immersion polymerization method, which is a wet process of immersing in an organic solvent containing any of metal carbonyl catalysts such as O) ₅ and Ta (CO) ₅ , is also applicable.

Chlorosilane-based substance is an acetylene derivative, and when the dipping method is used in the polymerization step, the orientation is extremely high, and the conjugated system is extremely high in molecular weight, and the conjugated system is very long, and a stable polyacetylene derivative is formed even in an atmosphere containing oxygen, which is preferable. .

Toluene, dioxane, anisole, etc. are mentioned as an organic solvent used for this immersion polymerization method.

Further, in the case of the immersion polymerization method, when a cocatalyst of an organic tin compound or an organic bismuth compound is contained in these catalysts,
Further, the quality of the polymer is improved, which is preferable.

Furthermore, using an acetylene derivative as a chlorosilane-based substance,
When an organic solvent having an oxygen atom such as anisole or dioxane is used as the organic solvent used for the immersion polymerization and molybdenum pentachloride is used as the metal halide catalyst, a cis-type polyacetylene is obtained as the polymer after the polymerization. .

The monomolecular film polymerized in this way can be made into a linear and ultra-high molecular weight polymer (ultra-long conjugated polymer) having a continuous conjugated system by polymerizing in a state of maintaining a certain direction. It has been found that a monomolecular film of the above-mentioned derivative of A order can be formed and a multilayer cumulative film can be easily obtained.

That is, a conjugated unsaturated bond-bonded unsaturated group and a chlorosilane group (-
SiCl _x ) and a non-aqueous organic solvent in which a chlorosilane-based substance is dissolved, the substrate having a hydrophilic surface is immersed, and a monomolecular film of the chlorosilane-based substance is formed on the substrate by a chemical adsorption method. When the unsaturated groups in the monolayer are selectively deactivated linearly and then polymerized, the monolayer of the substance is linearly formed on the substrate in a state in which the polymerization direction of the molecules is neatly aligned. Can be held at.

Furthermore, if a rubbing step of rubbing the chemisorbed monolayer is introduced between the monolayer forming step and the polymerizing step, a more highly oriented polymer is formed because the orientation of the monolayer is more aligned. preferable.

When the chlorosilane-based substance is a diacetylene derivative,
When the monomolecular film that has undergone the polymerization process is further irradiated with high-energy radiation, it is preferable because it remains without being polymerized and the acetylene group is polymerized to form a polyacene bond.

Hereinafter, the details of the present invention will be described using examples.

There are many substances that form a monomolecular film used in this example. One of the acetylene derivatives, ω-nonadecylinoic trichlorosilane HC≡C- (CH ₂ ) _{n-, which} contains one acetylene group at the end, is used. Description will be made using the case of SiCl ₃ (hereinafter abbreviated as NCS. In the examples described below, n is mainly 17, but good results were obtained in the range of 14 to 24).

Example 1 As shown in FIG. 1 (a), a Si film having a diameter of 3 inches was formed on the surface.
On the Si substrate 11 on which the O ₂ film is formed, a silane-based surfactant (hereinafter abbreviated as NCS) HC≡C- (CH ₂ ) ₁₇ -SiCl ₃ as a chlorosilane-based substance is chemically adsorbed, and the surface of the substrate 11 is A monomolecular film 12 is formed on.

At this time, the chlorosilane group (--SiCl ₃ ) of NCS reacts with the --OH group existing on the surface of the SiO ₂ film on the surface of the substrate 11 to form a substrate.
On the surface of 11 The monomolecular film 12 having the structure is formed.

For example, in a solution of 85% n-hexane, 8% carbon tetrachloride and 7% chloroform in which the NCS is dissolved at a concentration of 1.0 × 10 ^{−3 to} 4.0 × 10 ⁻³ mol / l, room temperature is kept for 8 minutes at room temperature for 8 minutes. _When the Si substrate 11 having the _two films formed thereon is immersed, —Si—O— bonds can be formed on the surface of the SiO ₂ film.

Here, on the surface of the substrate 11 The fact that the monomolecular film 12 having the structure
Confirmed by IR.

At this time, the monomolecular film 12 was formed in a nitrogen atmosphere containing no moisture.

Next, as shown in FIG. 1 (b), the unsaturated groups in the monomolecular film 12 were linearly unsaturated in a specific direction by electron beam exposure under an exposure amount of about 5 mJ / cm ^2. Deactivation (However, this deactivation process can be performed by electron beam exposure, drawing by scanning tunneling microscope (ie writing) or X-ray exposure,
After making the exposure dose about 5 mJ / cm ² in either case, irradiating the entire surface with radiation (eg, X-rays, electron beams, gamma rays) at about 5-10 mJ / cm ² in an inert gas atmosphere such as helium gas. As shown in FIG. 1 (c), it was revealed by FT-IR that the acetylene group which was not deactivated and remained remained was linearly polymerized to form a trans-polyacetylene bond 13.

Although the energy levels of X-rays, electron beams and gamma rays were different, similarly polymerized monomolecular films were obtained.

Example 2 As shown in FIG. 2 (a), 1-trimethylsilyl-ω-nonadecylinoic trichlorosilane Me ₃ Si—C≡C— (CH ₂ ) _n —SiCl was formed on the substrate 11 as a chlorosilane-based substance. ₃ (hereinafter abbreviated as TMS-NCS. In this embodiment, n is 17,
Good results were obtained in the range of 14 to 24. ) Monolayer
After forming one layer of 14 and selectively deactivating the acetylene group in the monomolecular film 14 on the substrate 11, the whole surface is irradiated with radiation in an inert gas atmosphere, as shown in FIG. 2 (b). Linear and highly oriented trans containing trimethylsilane group (-SiMe ₃ ).
-A polyacetylene bond 13 was formed.

Example 3 Tricosadiinoic trichlorosilane having one diacetylene group HC≡C—C≡C— (CH ₂ ) ₁₉ —SiCl ₃ was used, and as shown in FIG. After the monomolecular film 15 is formed, the diacetylene group in the monomolecular film 15 is selectively inactivated linearly, and ultraviolet rays (5 to 10 mJ / c) are generated in an inert gas.
Polymerization using m ² ) resulted in a highly oriented ultralong conjugated polymer having linear polydiacetylene bond 16 (poly 1,4-diacetylene) as shown in FIG. 3 (b).

In this case, if X-ray, electron beam or gamma ray irradiation (5 mJ / cm ² ) is used in place of ultraviolet rays, highly oriented material having linear polyacetylene bond 17 (random polydiacetylene) as shown in Fig. 3 (c). An ultralong conjugated polymer was obtained.

Example 4 In the same manner as in Example 1, the monomolecular film 12 was adsorbed on the substrate 11,
After linearly deactivating the unsaturated group in the monomolecular film 12 into a specific direction, the molybdenum pentachloride (M
When the substrate 11 on which one monolayer 12 is formed is immersed in toluene in which oCl ₅ ) is dissolved and the temperature of the solution is raised to about 30 to 70 ° C, it remains without being deactivated as shown in Fig. 4. It was revealed by FT-IR that the acetylene group that had been formed was linearly polymerized to form a trans-polyacetylene bond 13.

When WCl ₆ , NbCl ₅ , TaCl ₅ or the like was used as the catalyst other than the above, a monomolecular film having a similar trans-polyacetylene bond 13 which was polymerized but had a different molecular weight was obtained.

Furthermore, in this immersion polymerization step, even when the substrate was immersed in a solution of Mo (CO) ₆ or W (CO) ₆ dissolved in carbon tetrachloride as a catalyst and irradiated with ultraviolet rays, a reddish brown polymerization reaction occurred although the molecular weight was different. A monolayer having trans-polyacetylene bond 13 was obtained.

Example 5 In the same manner as in Example 2, the monomolecular film 14 was adsorbed on the substrate 11,
After selectively deactivating the acetylene group, tungsten hexachloride (WCl ₆ ) as a catalyst and tetrabutyltin (Bu ₄
(Sn) is immersed in 1: 1 dissolved in toluene and the temperature of the solution is raised to about 30-70 ° C, as shown in Fig. 5, it is oriented in a linear shape containing trimethylsilane group (-SiMe ₃ ). Highly trans-
A polyacetylene bond 13 was formed.

Example 6 A monomolecular film 14 is formed on a substrate 11 in the same manner as in Example 2,
After selectively deactivating the acetylene group, it is immersed in anisole, which is an organic solvent containing oxygen atoms, in a molecule in which molybdenum pentachloride (MoCl ₅ ) is dissolved as a catalyst, and the solution is heated to about 30 to 70 ° C. Upon heating, a highly linear cis-polyacetylene bond 18 was formed as shown in FIG.

Example 7 TMS-NCS was chemically adsorbed on the substrate 11 in the same manner as in Example 2 to selectively deactivate the acetylene group in the monomolecular film 14, and then co-catalyzed with molybdenum pentachloride (MoCl ₅ ) as a catalyst. As a catalyst, triphenylbismuth (Ph ₃ Bi) was mixed at a mixing ratio of 1: 1 in a solution prepared by dissolving anisole, which is an organic solvent containing oxygen atoms in the molecule, and the solution was heated to about 30 to 70 ° C. When the temperature rises,
As shown in FIG. 7, a highly oriented cis-polyacetylene bond 18 containing a trimethylsilane group (-SiMe ₃ ) was formed.

Example 8 As shown in FIG. 8 (a), a monomolecular film 15 was formed on a substrate 11 using tricosadiinoic trichlorosilane having one diacetylene group as in Example 3, and then a monomolecular film 15 was formed. Molecular film
When the diacetylene group in 15 was selectively deactivated linearly and polymerized using the same catalyst as in Example 7, as shown in FIG. 8 (b), trans-polyacetylene bond 19 (poly 1,2 -Diacetylene) was obtained.

Further, as shown in FIG. 8 (c), the monomolecular film having the trans-polyacetylene bond 19 was exposed to an electron beam at an exposure dose of 5 m.
When irradiated with J / cm ² (radiation such as X-rays and gamma rays may be used instead of electron beams), linear polyacetylene bond
A highly oriented ultralong conjugated polymer with 20 was obtained.

Example 9 As in Example 1, as shown in FIG. 1A, the same NCS monolayer 12 as in Example 1 was further adsorbed on the substrate 11.

Next, the loader 21 was placed on the surface of the substrate 11 shown in FIG. 9 where the monomolecular film 12 was not adsorbed, and the rubbing cloth 22 was used for lapping to orient the monomolecular film 12 in a specific direction. After that, by deactivating the unsaturated group in the monomolecular film 12 by the same method as in Example 1 and irradiating with radiation (for example, X-rays of 50 mJ / cm ² ) in an inert gas atmosphere (for example, helium gas), First
FT-IR revealed that a trans-polyacetylene bond 13 having the same structure as that in FIG. 3C but having more aligned alignment direction than in Example 1 was formed.

It should be noted that the same polymerized monomolecular film was obtained even when an electron beam or γ-ray was used as radiation as well as X-ray.

However, polymerization did not occur at all with ultraviolet rays (wavelength 365 nm).

Example 10 Similar to Example 2, as shown in FIG.
One layer of monomolecular film 14 is formed on the substrate 11 of S-NCS, and after rubbing in the same manner as in FIG. 9, radiation (for example, X-rays of 50 mJ / cm is applied in an inert gas atmosphere (for example, helium gas). ² ), the structure is the same as in FIG. 2 (b), but the alignment direction is more aligned than in Example 2, and the trimethylsilane group (--SiMe) is aligned.
_A trans-polyacetylene bond 13 containing ₃ ) was formed.

Example 11 Similar to Example 3, tricosadiinoic trichlorosilane having one diacetylene group was used to form a monomolecular film 15 as shown in FIG. After rubbing, the diacetylene group in the monomolecular film 15 was selectively deactivated linearly and polymerized by using ultraviolet rays, but the structure was the same as in FIG. A highly oriented ultra-long conjugated polymer having a polydiacetylene type bond 16 in which the orientation directions were even was obtained.

Further, when an electron beam or an X-ray was used, the alignment direction was more aligned than in Example 3, although the structure was the same as in FIG. 3 (c). A polydiacetylene-type highly oriented ultralong conjugated polymer having a polydiacene bond 17 was obtained.

Example 12 The same NCS as in Example 1 was chemically adsorbed to obtain a substrate 11 on which a monomolecular film 12 similar to that shown in FIG. 1 (a) was adsorbed.

Then, rubbing is performed using the method shown in FIG.
After orienting the monomolecular film 12 in a specific direction and selectively deactivating the unsaturated group in the monomolecular film 12 by the same method as in Example 1,
The substrate 11 having one layer of the monomolecular film 12 is immersed in toluene containing molybdenum pentachloride (MoCl ₅ ) as a catalyst,
FT-IR reveals that when the temperature of the solution was raised to about 30 to 70 ° C., the structure was the same as that in FIG. 4, but trans-polyacetylene bond 13 with more aligned alignment direction was formed than in Example 4. Became.

When WCl ₆ , NbCl ₅ , TaCl ₅ or the like was used as the catalyst other than the above, a similar monomolecular film having a different polymerization but a similar polymerization reaction was obtained.

Furthermore, even if the substrate is immersed in a solution of Mo (CO) ₆ or W (CO) ₆ in carbon tetrachloride as a catalyst and irradiated with ultraviolet rays, a monomolecular film with a reddish-brown polymerization reaction is obtained, although the molecular weight is different. Was given.

Example 13 Using the same TMS-NCS as in Example 2, one layer of monomolecular film 14 was formed on the substrate 11 in the same manner as in FIG. 2 (a) and rubbed in the same manner as in FIG. After deactivating the unsaturated group in the monomolecular film 14 by a similar method, tungsten hexachloride (WCl) is used as a catalyst.
₆ ) and tetrabutyltin (Bu ₄ Sn) as a co-catalyst were soaked in a 1: 1 solution in toluene, and the temperature of the solution was raised to about 30 to 70 ° C, the structure was the same as in Fig. 5. However, trans containing a trimethylsilane group (-SiMe ₃ ) with a uniform alignment direction
-A polyacetylene bond 13 was formed.

Example 14 A monolayer was adsorbed and rubbed in the same manner as in Example 9 to deactivate an unsaturated group in the monolayer in the same manner as in Example 9, and then molybdenum pentachloride (MoCl ₅ ) was used as a catalyst. Is immersed in a solution dissolved in anisole, which is an organic solvent containing an oxygen atom in the molecule, and the temperature of the solution is raised to about 30 to 70 ° C,
A cis-polyacetylene bond 18 having the same structure as that of FIG. 6 but having a more uniform alignment direction than that of Example 6 was formed.

Example 15 A substrate in which a monolayer of TMS-NCS similar to that in Example 14 was formed and then rubbed and then deactivated in the same manner as in Example 14 was prepared by using molybdenum pentachloride (MoCl ₅ ) as a catalyst and a cocatalyst. Then, with triphenylbismuth (Ph ₃ Bi) at a ratio of 1: 1, soak in a solution dissolved in anisole, which is an organic solvent containing oxygen atoms in the molecule, and raise the temperature of the solution to about 30 to 70 ° C. A cis-polyacetylene bond 18 containing a trimethylsilane group (—SiMe ₃ ), which has the same structure as in FIG. 7 but has a more aligned orientation direction than that in Example 7, was formed.

It was confirmed that the monolayer having the cis-polyacetylene bond 18 accumulated by the above method was insoluble in alcohol.

Example 16 Using tricosadiinoic trichlorosilane having one diacetylene group as in Example 8, a monomolecular film 15 similar to that in FIG. 8 (a) was adsorbed on the substrate 11 and rubbed. After selectively deactivating the unsaturated bond groups in the monomolecular film 15 as in Example 8, polymerization was carried out using the same catalyst as in Example 15, but the structure was the same as in FIG. A monolayer having trans-polyacetylene bonds 19 oriented higher than 8 was obtained.

When the monomolecular film having the trans-polyacetylene bond 19 is further irradiated with an electron beam (which may be radiation such as X-rays or γ-rays), the structure is the same as that in FIG. A highly-oriented ultralong conjugated polymer having polyacene bonds 20 with uniform orientation was obtained.

In Examples 9 to 16, the method of forming only one monomolecular film and performing the polymerization was described, but the rubbing may be performed after the monomolecular films are accumulated in multiple layers, and then the polymerization may be performed. Even if the steps of forming a molecular film, rubbing, and polymerizing are continuously and alternately performed, it is possible to produce a multilayer cumulative film of highly oriented ultralong conjugated polymer.

Further, in Examples 9 to 16, the case where the deactivating step is performed after the rubbing is described, but it goes without saying that the rubbing step may be performed after the deactivating step.

As described in Examples 9 to 16, by introducing a rubbing step of rubbing the adsorbed monomolecular film between the monomolecular film adsorbing step and the polymerizing step of the production method of the present invention, the orientation direction is further improved. There is an effect that uniform ultra long conjugated polymers can be produced.

All the films obtained by polymerizing the monomolecular films obtained in the above-mentioned examples were insoluble in alcohol.

Further, as is clear from the above description, according to the production method of the present invention, a structure-regulated polymer, that is, tran
There is an effect that s-type and cis-type polyacetylene derivatives can be freely selected.

It should be noted that the highly oriented ultra-long conjugated polymers produced in the above-mentioned examples were compared with those produced by the conventional Ziegler-Natta catalyst method, in an atmosphere containing oxygen, against heat, pressure or ultraviolet rays. It was remarkably stable.

Further, in the above-mentioned Examples, the method of forming only one monolayer and performing the polymerization was described. However, after the monolayers are accumulated in multiple layers, the unsaturated groups are selectively deactivated linearly and then the polymerization is performed. Alternatively, a multilayer cumulative film of highly oriented ultralong conjugated polymer can be prepared by alternately performing the steps of monomolecular film formation-linear deactivation-polymerization.

Further, in the above-mentioned examples, the conjugated unsaturated bond-unsaturated groups of the chlorosilane-based substance were all acetylene-based or diacetylene-based, but the present invention is not limited to this acetylene-based, thiophene ring, Pyrrole ring,
Needless to say, the technology can be applied even to a franc ring. However, when the above-mentioned group having a ring structure is used, it is necessary to use high-energy radiation or the like in the polymerization step.

The highly oriented ultra-long conjugated polymer of the present invention described in the above examples is capable of microfabrication and exhibits excellent conductivity, and thus may be applicable to wiring of, for example, molecular elements. Further, since it has a very long conjugate unsaturated bond, it has a large nonlinear optical characteristic, and therefore, it can be applied to, for example, a switch element utilizing the nonlinear optical characteristic which can be microfabricated.

Further, although the present invention is a chlorosilane-based chemical adsorption method as a method for forming a monomolecular film, other methods such as the LB method may be used to form a monomolecular film, and the conjugated unsaturated bond bond Needless to say, the same effect as that of the present invention can be obtained by the method of polymerizing the saturated group.

That is, the present invention produces a monomolecular film containing an unsaturated group capable of forming a conjugated unsaturated bond, and selectively inactivates the unsaturated group in the monomolecular film to a saturated bond having no linear reactivity. By doing so, the reaction direction of the unsaturated bond is defined, and then polymerization is performed to produce a highly oriented ultralong conjugated polymer.

EFFECTS OF THE INVENTION As described above, the present invention provides a process for forming a monomolecular film of a substance containing a conjugated unsaturated bond-containing unsaturated group, and selectively deactivates unsaturated bonds in the monomolecular film in a non-reactive manner. Deactivation process to
Since it is a manufacturing method that includes a polymerization step of polymerizing unsaturated groups that have not been deactivated in the deactivation step, it has excellent conductivity and nonlinear optical effects, and has a highly oriented super stable structure with a molecular weight of several hundreds or more. The long conjugated polymer can be produced with high efficiency.

According to the manufacturing method of the present invention, a continuous conjugated system is several mm.
Alternatively, since it is possible to produce a single linear ultra-high molecular weight highly oriented ultra-long conjugated polymer having a length of several cm or more,
It is extremely effective for manufacturing a device using the nonlinear optical effect.

In addition, by optimizing the type and manufacturing conditions of the conjugated unsaturated bond monomer that will be the raw material in the future, the conjugated system will be stable and linear with a length of several tens of cm or several m or more. It seems that it is possible to produce ultra-high molecular weight highly oriented ultra-long conjugated polymers, and this method may be able to produce organic superconducting materials that do not require cooling.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a method for producing a highly oriented ultra-long conjugated polymer having an NCS monomolecular film and having a trans-polyacetylene bond, and FIG. 1 (a) shows a film after the monomolecular film formation step. Fig. 1 (b) is a conceptual diagram showing how single molecules are adsorbed.
(Irradiation) is used to selectively and linearly deactivate the unsaturated groups in the monolayer, and Fig. 1 (c) shows the unsaturation remaining in the monolayer after the deactivation step. A conceptual diagram of the process of polymerizing bonds by radiation, FIGS. 2 (a) and 2 (b) are TMS-NCS.
FIG. 2A is a conceptual diagram showing a method for producing a highly oriented ultra-long conjugated polymer composed of a monomolecular film and having a trans-polyacetylene bond, FIG. 2A is a conceptual diagram showing a state in which monomolecules are adsorbed after the monomolecular film forming step. 2 (b) is a conceptual diagram of the step of polymerizing by radiation the unsaturated bonds remaining in the monolayer after the deactivation step, and FIGS. 3 (a), (b) and (c) are polydiene FIG. 3 (b) is a process diagram showing a method for producing a highly oriented ultra-long conjugated polymer having an acetylene bond, FIG. 3 (a) is a conceptual diagram showing a state in which a single molecule has been adsorbed after the monomolecular film formation process, and FIG. 3 (b). Is a conceptual diagram of the step of polymerizing the unsaturated bond remaining in the monolayer after the deactivation step by immersing it in a catalyst solution, and FIG. 3 (c) is the monolayer after the deactivation step. Fig. 4 is a conceptual diagram of the process of polymerizing the remaining unsaturated bonds by radiation. Process diagram showing the method of manufacturing the highly-oriented very long conjugated polymer having polymerized trans- polyacetylene bonds by immersion in a catalyst solution, Fig. 5 TM
Fig. 6 is a process chart showing a method for producing a highly oriented ultra-long conjugated polymer having an S-NCS monomolecular film and having a trans-polyacetylene bond polymerized by dipping in a catalyst solution.
Fig. 7 is a process diagram showing a method for producing a highly oriented ultra-long conjugated polymer having a cis-polyacetylene bond, which is composed of an S monolayer and is polymerized by immersing it in a catalyst solution.
FIG. 8 (a) is a process diagram showing a method for producing a highly oriented ultralong conjugated polymer having a cis-polyacetylene bond, which is composed of a monomolecular film and is polymerized by dipping in a catalyst solution.
(B) and (c) are process diagrams showing a method for producing a highly oriented ultra-long conjugated polymer of another example of diacetylene, and FIG. 8 (a) is a monomolecular adsorbed after the monomolecular film forming process. FIG. 8 (b) is a conceptual diagram showing a state, FIG. 8 (b) is a conceptual diagram of a step of polymerizing the unsaturated bond remaining in the monomolecular film after the deactivation step by immersing it in a catalyst solution, FIG. 8 (c). Is a conceptual diagram showing a polymerization process of a highly oriented ultra-long conjugated polymer having a polyacene bond by electron beam irradiation after the polymerization process, and FIG. 9 is a conceptual diagram of a process of lapping a monomolecular film. 11 ... Substrate, 12,14,15 ... Monolayer, 13,19 ... trans-
Polyacetylene bond, 16,17 ... Poly-path acetylene bond, 8 ... cis-polyacetylene bond, 20 ... Polyacene bond

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08J 5/18 CER 9267-4F H01B 1/12 C 7244-5G

Claims (16)

[Claims] 1. A non-aqueous organic solvent in which a chlorosilane-based substance containing a conjugated unsaturated bond-containing unsaturated group and a (mono-, di- or tri) chlorosilane group is dissolved, and a substrate having at least a hydrophilic surface is prepared. A monomolecular film forming step of immersing and forming a monomolecular film of the substance on the substrate; a deactivating step of selectively deactivating the unsaturated group in the monomolecular film; and a deactivating step. And a step of polymerizing the unsaturated substrate remaining in the monomolecular film that has not been deactivated in an inert gas, to produce a highly oriented ultralong conjugated polymer. 2. The method for producing a highly oriented ultra-long conjugated polymer according to claim 1, wherein a rubbing step of rubbing the monomolecular film is performed between the monomolecular film forming step and the polymerizing step. 3. The method for producing a highly oriented ultralong conjugated polymer according to claim 1, wherein the unsaturated group contained in the chlorosilane-based substance is an acetylene group or a diacetylene group. 4. The unsaturated group contained in the chlorosilane-based substance is a diacetylene group.
A method for producing the highly oriented ultra-long conjugated polymer described. 5. The method for producing a highly oriented ultra-long conjugated polymer according to claim 1, 3 or 4, wherein the chlorosilane-based substance is ω-nonadecylinoic trichlorosilane. 6. The trimethylsilane group is bonded to one end of the chlorosilane-based substance, which is characterized in that
Alternatively, the method for producing a highly oriented ultra-long conjugated polymer according to any one of 4 above. 7. The method for producing a highly oriented ultra-long conjugated polymer according to claim 6, wherein the chlorosilane compound is 1- (trimethylsilyl) -ω-nonadecylinoic trichlorosilane. 8. The method for producing a highly oriented ultra-long conjugated polymer according to claim 1, wherein the deactivating step is any one of drawing with a scanning tunneling microscope, electron beam exposure and radiation exposure. 9. The method for producing a highly oriented ultralong conjugated polymer according to claim 1, wherein the polymerization step is either electron beam irradiation or radiation irradiation. 10. The polymerization step is an immersion polymerization step of immersing the monomolecular film on the substrate subjected to the deactivation step in an organic solvent containing at least a metal halide catalyst or a metal carbonyl catalyst. The method for producing a highly-oriented ultralong conjugated polymer according to claim 1 or 2. 11. The method for producing a highly oriented ultra-long conjugated polymer according to claim 10, wherein the metal of the metal halide catalyst or the metal carbonyl catalyst is Mo, W, Nb or Ta. 12. The method according to claim 10 or 11, characterized by containing at least one of an organic tin compound and an organic bismuth compound in addition to at least one of a metal halide catalyst and a metal carbonyl catalyst used for immersion polymerization. A method for producing a highly oriented ultra-long conjugated polymer according to item 1. 13. The high orientation according to claim 10, wherein the organic solvent used in the immersion polymerization contains an oxygen atom in the molecule, and the metal halide catalyst is molybdenum pentachloride. For producing a super long conjugated polymer. 14. The chlorosilane-based material contains at least a diacetylene group, and ultraviolet rays are used in at least one of the deactivation step and the polymerization step.
5. A method for producing a highly oriented ultra-long conjugated polymer as described in 1, 2 or 4. 15. The chlorosilane-based substance contains at least a diacetylene group, and the substrate after the polymerization step is irradiated with high-energy radiation, according to any one of claims 1, 2, 9, 10 and 14. A method for producing the highly oriented ultra-long conjugated polymer described. 16. The method for producing a highly oriented ultra-long conjugated polymer according to claim 15, wherein the radiation is any of X-ray, electron beam and γ-ray.