JP2507823B2 - Oxidation polymerization catalyst and oxidation polymerization composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Industrial Range of Application) The present invention is directed to an oxidative polymerization catalyst which is a peroxidized condensed acid obtained from the reaction of a transition element and / or a compound thereof with hydrogen peroxide, and The present invention relates to an oxidative polymerization composition using the oxidative polymerization catalyst. More specifically, it is oxidatively polymerized using a peroxidized condensed acid obtained by reacting a transition metal and / or a compound thereof with hydrogen peroxide with at least one selected from tungsten, molybdenum, vanadium and zirconium as an oxidative polymerization catalyst. Monomers such as pyrrole, thiophene, furan, phenol, thiophenol, aniline,
Further, the present invention relates to an oxidative polymerization composition obtained by polymerizing at least one of these derivatives.

This is especially easy to obtain an oxidized polymer at room temperature,
Various functional materials such as a conductive polymer or a film thereof, a coating agent, a corrosion resistant coating, a heat resistant coating are provided.

(Prior Art) Pyrrole, thiophene, furan, phenol, thiophenol, aniline, and their derivatives as monomers to be oxidatively polymerized have been conventionally known to be easily obtained as a conductive polymer by electrolytic oxidative polymerization or chemical oxidative polymerization. Is known. However, electrolytic oxidation polymerization has a drawback that a large-area sample cannot be obtained. Further, as oxidizers used for chemical oxidative polymerization, Fe ³⁺ , S ₂ O ₈ ²⁻ , Cl ₂ and Br ₂ as well as RuO ₄ ⁻ , OsO ₄ ⁻ , MnO ₄ ⁻ , IrCl ₆ ²⁻ , PtCl ₆ ²⁻ , PdC
Compounds such as l ₄ ²⁻ and AuCl ₄ ⁻ were used. None of these had film-forming properties, and only acted as an oxidative polymerization catalyst. Further, a copper compound and an amine catalyst were used as catalysts for oxidative polymerization of 2,6 dimethylphenol, which is a phenol derivative, but there were drawbacks depending on the application such as an amine odor remaining in the produced polymer.

(Problems to be solved by the invention) As a result of intensive studies in view of the above-mentioned drawbacks, a peroxidative condensed acid obtained from a reaction between a transition element and / or a compound thereof and hydrogen peroxide is extremely used as an oxidative polymerization catalyst for an oxidative polymerization monomer The present invention has been found to be useful, and has reached the present invention. It is a novel polymerization catalyst that has never been seen before because it has a film-forming property even with a peroxy-condensed acid alone.

Specifically, oxidative polymerization using a peroxidized condensed acid obtained from the reaction of a transition metal and / or a compound thereof with hydrogen peroxide with at least one selected from tungsten, molybdenum, vanadium and zirconium as an oxidative polymerization catalyst. The present invention relates to an oxidative polymerization composition obtained by polymerizing at least one of pyrrole, thiophene, furan, phenol, thiophenol, aniline, which is a monomer to be produced, and derivatives thereof. The peroxidized condensed acid in the present invention itself is a completely novel oxidative polymerization catalyst characterized by having film-forming properties. This is especially easy to obtain an oxidation polymer at room temperature, a conductive polymer, or a film thereof, a coating agent, a corrosion resistant coating,
It provides various functional materials such as heat resistant paints.

[Structure of Invention]

(Means for Solving the Problems) The present invention relates to an oxidative polymerization catalyst using a peroxidative condensed acid obtained by the reaction of a transition element and / or a compound thereof with hydrogen peroxide, and a monomer by which the catalyst is oxidatively polymerized. The present invention relates to an oxidative polymerization composition used as an oxidative polymerization catalyst. Further, it is a catalyst that uses at least one selected from tungsten, molybdenum, vanadium, and zirconium as a transition element, and pyrrole, thiophene, furan, phenol, thiophenol, aniline, and the like as a monomer to be oxidatively polymerized. The present invention provides an oxidative polymerization composition using at least one of the above derivatives.

As transition elements, atomic numbers 21 to 29 of the periodic table,
Basically, elements from 39 to 47 can be used,
Tungsten, molybdenum, vanadium, zirconium and the like are preferable, and furthermore, compounds thereof can be used.
Specific examples shown below can be used, but are not necessarily limited to these, and may be any as long as they react with hydrogen peroxide to give a peroxide condensed acid.

Tungsten and its compounds are tungsten,
Tungsten carbide, tungstic acid, tungsten trioxide, tungstic anhydride, silicotungstic acid, ammonium metatungstate, ammonium paratungstate, phosphotungstic acid, silicotungstic acid, borotungstic acid, lithium tungstate, sodium tungstate, tungstate Examples include potassium, sodium metatungstate, sodium paratungstate, ammonium pentatungstate, ammonium heptatungstate, sodium phosphotungstate, and barium borotungstate.

Molybdenum and its compounds include molybdenum, molybdic acid, molybdic acid trioxide, ammonium phosphomolybdate, ammonium oxychloride, ammonium metamolybdate, ammonium paramolybdate, phosphomolybdate, silicomolybdate, boromolybdate, and molybdenum. Examples thereof include lithium oxide, sodium molybdate, potassium molybdate, ammonium heptamolybdate, sodium phosphomolybdate, phosphomolybdate, zinc molybdate, calcium molybdate, magnesium molybdate, strontium molybdate, and barium molybdate.

Vanadium and its compounds include vanadium, vanadium pentoxide, lithium orthovanadate, sodium orthovanadate, lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, sodium pyrovanadate, and the like. It is not limited. For example, instead of phosphorus, silicon, boron, etc., chromium, manganese, iron, cobalt, copper,
It is also possible to use bismuth, antimony, arsenic, tellurium and the like.

Zirconium and its compounds include zirconium nitrate, zirconium sulfate, basic zirconium acetate, zirconium acetylacetone, zirconium ethylenediaminetetraacetate, zirconium nitrilotriacetate, zirconyl chloride, zirconyl nitrate, zirconyl acetate, zirconyl sulfate, zirconyl carbonate, and other zirconyl salts Can be used, but is not limited thereto. Of these, zirconium oxychloride is most commonly used because it is inexpensive in price and affords a relatively high yield of zirconia.

As described above, one or more of these transition elements and / or compounds thereof can be mixed as necessary, and can be appropriately used under the condition that a peroxide condensed acid can be obtained by reacting with hydrogen peroxide. What is important here is that the peroxidized condensed acid obtained in the present invention has a film-forming property unlike conventional oxidizers. Further, it is different from any of oxyacids or oxyacid salts such as tungstic acid, molybdic acid, sodium tungstate, and sodium molybdate. These oxyacids or oxyacid salts do not have film-forming properties.

The peroxidized condensed acid obtained by the present invention is considered to be one kind of polyacid, but it is not always known in detail. Generally, polyacids are classified into two types. Two of them
An acid produced by more than one metal is called a heteropolyacid, which is formed by coordinating one metal (or its equivalent) with a central atom and a polyacid group of another metal. Often. On the other hand, in contrast to heteropolyacid, the acid produced by only one kind of metal is called isopolyacid. The structure of the peroxide condensed acid obtained according to the present invention is not clear because many of them are obtained as an amorphous substance. However, a peroxo group (OO) or a negative ion such as OH may be directly or other such as water. It is thought that it has a network structure connected via the molecule. Therefore, the peroxidized condensed acid obtained by this method can be freely mixed with a hydrophilic organic solvent, and can also be completely replaced with an organic solvent. Furthermore, this peroxidized condensed acid has a film-forming property. Therefore, it is considered to be fundamentally different from the conventional oxidizer, oxygen acid or oxyacid salt.

The synthesis of the peroxide condensed acid in the present invention can be easily obtained by reacting with hydrogen peroxide in the range of room temperature to 100 ° C., depending on the type of the transition element. The hydrogen peroxide used here may be a commercially available one having a concentration of about 30 to 60%, or may be used as it is or after diluted to an appropriate concentration. The amount of hydrogen peroxide used should be at least about 1 gram mole per gram atom of transition metal. The reaction rate tends to increase as the ratio of hydrogen peroxide / transition metal (gram mole / gram atom) increases. It is not preferable from the economical and safety point of view that a large excess of hydrogen peroxide remains after the reaction. Therefore, the amount of hydrogen peroxide used is appropriately about 1 to 5, preferably 1.2 to 3 gram mol per gram atom of the transition element. Hydrogen peroxide may be added in a required amount at the start of the reaction, or may be added dropwise little by little while observing the progress of the reaction. The same applies to how to add a transition metal.

Examples of the oxidative polymerization monomer include phenol, thiophenol, aniline, and aromatic compound derivatives thereof. Further, derivatives of hetero compounds such as pyrrole, thiophene, and furan can also be mentioned.

The method of oxidative polymerization is not particularly limited, but normally, the polymerization is completed in several minutes to several hours at room temperature and atmospheric pressure by adding the above-mentioned monomer to be oxidatively polymerized to an aqueous solution of these peroxidized condensed acids. In these methods, the oxidized polymer can be obtained as a solution or powder, but a method of directly obtaining it in a coated state is also possible. For example, a polymer solution obtained by blending these peroxidized condensed acids may be applied to a substrate and then immersed in a monomer that undergoes oxidative polymerization, applied, or oxidatively polymerized in a saturated vapor atmosphere. Further, among the oxidatively polymerized polymers obtained, the polymers such as aniline, pyrrole and thiophene can be imparted with conductivity by treating with a Lewis acid or a halogen-based compound such as iodine.

In the present invention, the use ratio of the peroxide-condensed acid and the monomer to be oxidatively polymerized is not particularly limited because the peroxide-condensed acid alone has a film-forming property. The amount of the oxidative polymerization monomer used may be adjusted according to the application.

Further, various additives can be added according to the application. Examples thereof include pigments, preservatives, rust preventives, leveling agents, flame retardants and the like.

The coating of the present composition may be carried out by a conventionally known method, for example, a method such as brush coating, spray coating, roll coating, spin coater coating or dip coating can be used.

Hereinafter, Production Examples, Examples and Comparative Examples are shown. These examples illustrate the invention in more detail and do not limit the invention in any way. Parts and% indicate parts by weight and% by weight.

Production Example 1 30 parts of a 15% aqueous hydrogen peroxide solution is put into a beaker. Thereafter, 8 parts of metal molybdenum powder was added over 30 minutes. The molybdenum powder was immediately dissolved through a vigorous reaction accompanied by foaming, and a clear aqueous solution of acidic, pale yellow peroxide-condensed molybdic acid was obtained. Thereafter, 70 parts of isopropyl alcohol was added, and the mixture was left at room temperature for 24 hours.

Production Example 2 8 parts of metal tungsten powder was placed in a beaker, and
70 parts of a 15% aqueous hydrogen peroxide solution were added. Through a vigorous reaction accompanied by foaming, the tungsten powder was dissolved in about 30 minutes to obtain an acidic, pale yellow, transparent aqueous solution of peroxycondensed tungstic acid. Then add 30 parts of butyl cellosolve and add 24
Left at room temperature for hours. Thereafter, a platinum mesh with platinum black was immersed in this to decompose unreacted hydrogen peroxide.

Production Example 3 6 parts metallic tungsten powder and 2 vanadium pentoxide powder
Part into a beaker and add 30% aqueous hydrogen peroxide solution
Add parts. The metal powder reacted slowly and dissolved after 30 minutes. An acidic, pale yellow, transparent aqueous solution of the peroxide condensed acid was obtained. Thereafter, 30 parts of isopropyl alcohol was added.

Production Example 4 10 parts of zirconium oxychloride and 20 parts of ion-exchanged water were placed in a flask, the reaction temperature was adjusted to about 50 ° C., and 20 parts of 15% hydrogen peroxide was added dropwise over 30 minutes. 10 minutes after dropping,
After completion of dropping, the mixture was aged for 1 hour. Thereafter, 100 parts of isopropyl alcohol was added, and the mixture was concentrated with an evaporator. A clear condensed zirconium alcohol solution of about 50% solids was obtained. And it was left at room temperature for 24 hours.

Production Example 5 8 parts of tungsten carbide powder was placed in a beaker,
70 parts of a 15% aqueous hydrogen peroxide solution were added. Through a vigorous reaction accompanied by foaming, the tungsten carbide powder was dissolved in about 30 minutes to obtain an acidic, pale yellow, transparent aqueous solution of peroxycondensed tungstic acid. Then, add isopropyl alcohol for 30
All of them were left at room temperature for 24 hours. Thereafter, a platinum mesh with platinum black was immersed in this to decompose unreacted hydrogen peroxide.

Production Example 6 4 parts of ammonium tungstate, 4 parts of metal molybdenum powder, and 20 parts of ion-exchanged water were put into a beaker, and 15 parts of
50 parts of a 50% aqueous hydrogen peroxide solution were added. Through a vigorous reaction accompanied by foaming, the metal molybdenum powder was dissolved in about 20 minutes, and a clear aqueous solution of an acidic, pale yellow peroxycondensed acid was obtained. Thereafter, 20 parts of butyl cellosolve was added, and the mixture was left at room temperature for 24 hours. Thereafter, a platinum mesh with platinum black was immersed in this to decompose unreacted hydrogen peroxide.

Production Example 7 Eight parts of tellurium dioxide powder was taken and suspended in 50 parts of pure water. To this, 3.9 parts of ammonium paratungstate was added and dissolved. This was heated to 90 ° C., and 30 parts of 35% hydrogen peroxide aqueous solution was added little by little. It dissolved completely after 20 minutes.

Example 1 50 parts of purified water and 50 parts of isopropyl alcohol at room temperature
5 parts of 2,6 dimethylphenol was added, and 5 parts of the solution of Preparation Example 1 was added with stirring. The reaction was carried out at room temperature for 6 hours while blowing air. As a result, a fine slurry of polyphenylene oxide was obtained.

Example 2 At room temperature, 5 parts of aniline was added to 100 parts of purified water, and 5 parts of the solution of Preparation Example 2 was added with stirring. The color changed from dark green to black immediately, and viscous polyaniline was obtained in about 30 minutes. When this product was applied onto a glass plate and dried at 120 ° C. for 20 minutes, a film having a very high gloss was obtained.

Example 2 At room temperature, 5 parts of phenol was added to 100 parts of purified water, and 5 parts of the solution of Production Example 3 was added with stirring. The color changed from dark green to black immediately, and viscous polyphenol was obtained in about 30 minutes. This product is coated on a glass plate and 120 ℃ -20
After minute drying, a very glossy film was obtained.

Example 4 At room temperature, 5 parts of pyrrole was added to 100 parts of purified water, and 5 parts of the solution of Preparation Example 4 was added with stirring. Immediately, the color changed from dark green to black, and fine polypyrrole powder was obtained in about 30 minutes.

Example 5 At room temperature, 100 parts of purified water and 5 parts of thiophene were added to a well-sealed glass container equipped with a stirrer, and 5 parts of the solution of the above Production Example 5 was added while stirring. After reacting for 6 hours, the color changed from dark green to black and a viscous solution of polythiophene was obtained.

Example 6 At room temperature, 100 parts of purified water and 5 parts of thiophenol were added to a well-sealed glass container equipped with a stirrer, and 5 parts of the solution of Production Example 6 was added with stirring. As a result of reacting for 6 hours while blowing air, a viscous solution was obtained.

Example 7 At room temperature, 5 parts of aniline was added to 100 parts of purified water, and 5 parts of the solution of Preparation Example 7 was added with stirring. The color changed from dark green to black immediately, and viscous polyaniline was obtained in about 30 minutes. When this product was applied onto a glass plate and dried at 120 ° C. for 20 minutes, a film having a very high gloss was obtained. Further, when this film was exposed to a saturated vapor of iodine for 8 hours, it was 10 ⁴ ohm cm.

Comparative Example 1 50 parts of purified water and 50 parts of isopropyl alcohol at room temperature
Add 5 parts of 2,6 dimethylphenol and stir 20
5 parts of a% adjusted hydrogen peroxide solution was added. The reaction was carried out at room temperature for 6 hours while blowing air, but no polymer was obtained.

Comparative Example 2 At room temperature, 5 parts of aniline was added to 100 parts of purified water, and 5 parts of a 20% adjusted hydrogen peroxide aqueous solution was added with stirring. However, nothing changed after 6 hours.

Comparative Example 4 At room temperature, 5 parts of phenol was added to 100 parts of purified water, and 2 parts of sodium tungstate was added with stirring. However, no change was observed even after 6 hours.

Comparative Example 5 At room temperature, 5 parts of pyrrole was added to 100 parts of purified water, and 2 parts of sodium molybdate was added with stirring. However, no change was observed even after 6 hours.

〔The invention's effect〕

In the present invention, an oxidative polymerization composition comprising a transition element and / or a compound thereof which is obtained by the reaction of hydrogen peroxide with a peroxidative condensed acid as an oxidative polymerization catalyst is particularly easy to obtain an oxidative polymer at room temperature, The present invention provides various functional materials such as a conductive polymer or a film thereof, a coating agent, a corrosion resistant paint, and a heat resistant paint, and a coating composition which is extremely useful industrially.

Claims (4)

(57) [Claims] 1. An oxidative polymerization catalyst characterized by using a peroxidative condensed acid obtained from the reaction of a transition element and / or a compound thereof with hydrogen peroxide. 2. The oxidation polymerization catalyst according to claim 1, wherein at least one selected from tungsten, molybdenum, vanadium and zirconium is used as the transition element. 3. An oxidative polymerization composition characterized by using a peroxidative condensed acid obtained from the reaction of a transition element and / or a compound thereof with hydrogen peroxide as an oxidative polymerization catalyst for a monomer. 4. A pyrrole as a monomer to be oxidatively polymerized,
The oxidative polymerization composition according to claim 3, wherein at least one kind of thiophene, furan, phenol, thiophenol, aniline and derivatives thereof is used.