JPS63264642A - Molding of five-membered cyclic compound polymer - Google Patents

Abstract

PURPOSE:To perform the molding of a specified five-membered heterocyclic compound polymer easily and safely and to obtain an electroconductive molding easily and inexpensively, by molding said polymer by heating to a temperature higher than the softening point of the polymer. CONSTITUTION:A five-membered heterocyclic compound polymer having repeating units derived from a monomer of the formula or this polymer previously doped with a dopant is molded into any desired shape by heating said five- membered heterocyclic compound polymer or said polymer doped with a dopant to a temperature higher than the softening point of the polymer in the presence (absence) of a dopant. This molding is optionally doped with a dopant. In the formula, R is an 8C or higher alkyl, X is O, S, Se, Te, -NR' (wherein R' is H, alkyl or aryl). Said polymer used can be produced usually by the oxidative coupling of a five-membered heterocyclic compound of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for molding a five-membered heterocyclic compound polymer, and further relates to a method for molding a conductive resin.

[Conventional technology]

Polymers such as polypyrrole, polyfuran, polythiophene, and polyselenophene, which have a structure in which five-membered heterocyclic compounds are linked in the main chain, have good heat resistance and excellent chemical stability, and are useful as engineering plastics. It is considered. Also, according to recent research, by doping these polymers with dopants such as iodine and arsenic pentafluoride, they can change from insulators to conductors.
It is known to have excellent properties and is used not only as a conductive material but also as a functional material for sensor materials, optoelectronics, electronic devices, etc.

For example, polythiophene is a polymer obtained by polymerizing thiophene using a chemical oxidative polymerization method, and is known as a powder that is stable up to 500° C. in an inert gas.

Furthermore, it is known that film-like polymers can be obtained by electrochemical oxidative polymerization, and those doped with iodine have high electrical conductivity. Furthermore, similar properties are known for five-membered heterocyclic compound polymers such as polypyrrole, polyfuran, polyselenophene, and polytellurophene.

[Problem that the invention seeks to solve]

However, these polymers are insoluble because they form a crosslinked structure, and they decompose without softening even when heated, and no polymers that melt are known. Since the lid is an infusible and insoluble polymer, it is difficult to mold and process, which has been a major problem from a practical standpoint.

On the other hand, JP-A No. 61-278526 proposes a method for molding a conductive solution and a conductive product comprising a five-membered heterocyclic compound polymer having a specific structure and an organic solvent.

That is, it has been shown that a film can be easily produced from this solution by casting, and that it can also be easily processed into the form of a coated product.

However, the molding methods for solutions are limited, and they can only be used in the form of films, fibers, coatings, etc.
There are problems such as distortion, displacement, and shrinkage after the solvent is removed.

In addition, since it uses a solvent, it is difficult to handle, has problems with transportation and storage, and also poses safety and environmental problems such as poisoning and fire hazards due to the solvent, so there are molding methods that do not use solvents. was desired.

[Purpose of the invention]

The purpose of the present invention is to improve
It is an object of the present invention to provide an excellent molding method that can easily and safely mold a membered cyclic compound polymer, and can also easily and inexpensively produce conductive molded products.

[Means for solving problems]

As a result of intensive studies to achieve the above object, the present inventors found that since the hetero5-membered cyclic compound polymers having a specific structural unit have a softening point, these 5-membered heterocyclic compound polymers The present invention was completed by discovering that molding can be performed at temperatures above the softening point.

That is, the present invention relates to general formula (I) [In formula (I), R is an alkyl group having 8 or more carbon atoms, X is an amino group represented by oxygen, sulfur, selenium, tellurium or -NR', provided that A 5-membered heterocyclic compound polymer whose repeating unit is a monomer unit represented by R/ represents hydrogen, an alkyl group or an aryl group, or a polymer pre-doped with a dopant, used in combination with a dopant. Alternatively, a method in which the five-membered heterocyclic compound polymer or the doped polymer is heated to a temperature equal to or higher than the softening point of the polymer and molded into a desired shape, if necessary. This is a method for molding a five-membered heterocyclic compound polymer, which is characterized by doping a molded product with a dopant.

The 5-membered heterocyclic compound polymer used in the present invention described above has an alkyl group on the 5-membered heterocyclic nucleus of the polymer chain,
In the above formula, the alkyl group having 8 carbon atoms (Ili1 or more) represented by R includes linear alkyl groups such as octyl, nonyl, decyl, undecyl, and dodecyl, as well as cyclic alkyl groups such as cyclooctyl group, Alternatively, examples include alkyl groups having a branched structure.These alkyl groups include halogen, nitro, cyano, alkoxy, aryl,
It may have a group such as alkenyl. Also, nitrogen,
It may also contain heteroatoms such as oxygen and sulfur.

Generally, the longer the alkyl chain of the substituent of a polymer, the lower the softening point of the polymer, and conversely, the shorter the alkyl chain, the higher the softening point of the polymer. For example, when an octyl group with 8 carbon atoms is present, the softening point of the polymer is 156°C, but when the length of the substituent is shorter than that, the polymer does not have a softening point. It was fusible.

The 5-membered heterocyclic compound polymer used in the present invention is usually produced by an oxidative coupling reaction of the 5-membered heterocyclic compound represented by the general formula (I).

Alternatively, it can be synthesized by a method in which a 2,5-dihalogenated five-membered heterocyclic compound is reacted with magnesium to form a Digrinya salt, and then coupled with a nickel catalyst to produce a polymer.

The 5-membered heterocyclic compound polymer used in the present invention is a polymer in which compound units of general formula (I) are repeatedly bonded at the 2.5-position or 2.4-position, or a polymer having a partially crosslinked structure. It may be a polymer having the following. Specific polymerization methods using oxidative coupling reactions of five-membered heterocyclic compounds include polymerization methods using oxidizing agent catalysts, electrochemical polymerization methods, etc. Among them, polymerization methods using oxidizing agent catalysts, etc. A method of polymerization is preferable as it is a means to easily obtain a polymer at low cost.

Examples of these polymerization catalysts include compounds known as Lewis acids such as aluminum chloride, iron chloride, molybdenum chloride, tungsten chloride, tin chloride, antimony chloride, and arsenic pentafluoride. Among these, those having no oxidizing power or having weak oxidizing power, such as aluminum chloride, are preferably used in combination with an oxidizing agent such as cupric chloride, manganese dioxide, or oxygen.

By adding these oxidizing agent catalysts to the alkyl-substituted five-membered heterocyclic compound, the five-membered heterocyclic compound polymer used in the present invention can be easily produced at room temperature. It is also a preferable method to add an inert solvent to the reaction system, if necessary, since this makes it easier to control the reaction.

In the present invention, a molded article can be easily obtained by raising the temperature of a five-membered heterocyclic compound polymer to a temperature higher than its softening point to soften or melt the polymer, and then molding it into a suitable shape.

Specifically, as such a method, a general molding method for so-called thermoplastic resins can be used, and examples thereof include extrusion molding, injection molding, inflation molding, roll molding, and calendar molding.

According to the present invention, conductive products can be manufactured by further doping the thus formed polymer with a suitable dopant, if necessary.

There are no particular restrictions on the dopant used here (,
Known compounds can be used as dopants for doping to form electrically conductive five-membered heterocyclic compound polymers. Such dopants include halogen compounds such as iodine, bromine, chlorine, and iodine trichloride;
Protic acids such as sulfuric acid, nitric acid, perchloric acid, and hydrofluoric acid, aluminum trichloride, iron trichloride, molybdenum chloride,
Lewis acids such as tungsten chloride, antimony chloride, arsenic pentafluoride, sulfur trioxide, nitrosyl hexafluoroantimonate (No S b Fe ), nitrosyl hexafluoroarsenate (NOA s Fs ), nitrosyl trifluoromethanesulfonate (N.

CF3503), nitroyl hexafluoroantimonate (NO2S b Fe ), nitroyl trifluoromethanesulfonate (NO2CF3 SO:] ), oxidizing agents, lithium (Li), sodium (Na)
, potassium (K), rubidium (Rb), cesium (C
alkali metals such as s), tetra- represented by R4NA
Various dopant substances such as alkylammonium salts (where A represents an anionic group) can be used.

There are no particular restrictions on the method of doping these dopants into a molded article, and generally it is sufficient to bring the molded article into contact with the dopant substance, which is often carried out in a gas phase or a liquid phase.

Or lithium perchlorate (LiC1o4), lithium tetrafluoroborate (LiBF4), lithium hexafluoroborate (LiAsFe), tetrabutylammonium tetrafluoroborate (Bu4NBF4), tetrabutylammonium perchlorate (Bu4 NC104), etc. A method of electrochemical doping in an electrolyte solution containing an electrolyte salt of

Other embodiments of the invention include a mixture of a five-membered heterocyclic compound polymer and a dopant, or a pre-doped polymer containing a dopant, or a pre-doped polymer containing a dopant. A conductive molded product can be easily formed by mixing the polymer with a dopant, raising the temperature above its softening point (melting point) to soften or melt the polymer, and then molding it into an appropriate shape. can do.

The specific molding method is the same as the method described above.

Note that, if necessary, these molded products may be further doped with a dopant.

In the present invention, it is within the intention of the present invention to add an appropriate plasticizer or inorganic filler during the molding process for the purpose of improving the physical properties such as fluidity during molding and mechanical strength of the molded product. The inclusion is easily understood.

〔Example〕

The present invention will be explained in more detail with reference to Synthesis Examples and Examples below.

Synthesis Example 13 - Synthesis Example of Octylthiophene 3 - In 300 ml of anhydrous ether containing 81.5 g (0.5 mol) of bromothiophene and 1 g of diphenylphosphinopenknickel dichloride, 108.5 g (0.5 mol) of octylmagnesium bromide was added. ) was added dropwise at 0°C.
After refluxing for an hour, water was added for hydrolysis.

Next, the organic layer was extracted with ether, and the resulting ether solution was distilled under reduced pressure to obtain 75% of 3-octylthiophene.
% yield (theory).

Similarly, 3-dodecylthiophene, 3-hexadecylthiophene and 3-tocosylthiophene were obtained by using various Grignard reagents.

(Note) Monomers can also be obtained by coupling reactions in the presence of nickel catalysts.

Synthesis Example 2 Synthesis Example of Polymer of 5-Membered Heterocyclic Compound After 240 g of anhydrous ferric chloride was added to 3.000 ml of chloroform, 60 g of 3-octylthiophene was further added and stirred at room temperature for 24 hours.

After the reaction mixture was added to 10,000 rails of methanol and stirred well, insoluble matter was collected by filtration, washed with methanol, diluted hydrochloric acid, water, and aqueous ammonia, and then dried under reduced pressure at 80° C. for 10 hours.

51 g of dark green polymer was obtained.

The softening point of this polymer was measured and found to be 156°C.

Furthermore, the molecular weight (MW) of this polymer was determined in terms of polystyrene by gel permeation chromatography using a tetrahydrofuran solvent, and was found to be 146.
It was 000.

Similarly, poly-3-dodecylthiophene (Mw:
109.000), poly-3-hexadecylthiophene, poly-3-tocosylthiophene (MW: 1
Polythiophenes having an alkyl group at the 3-position such as 35.000) were obtained.

Example 1 Poly-3-tocosylthiophene was melted by heating at 165° C. for 5 minutes, and then cast onto a Teflon sheet and cooled to obtain a sheet-like molded product with a thickness of 1 am.

When this sheet was brought into contact with iodine gas at saturated vapor pressure at room temperature for 24 hours, it exhibited an electrical conductivity of 0.2 S/am.

Example 2 Poly-3-hexadecylthiophene was heated at 185° C. for 5 minutes to melt it, then poured into a glass tube with an inner diameter of 511 and cooled. When the glass tube was removed, a rondo-shaped molded product with a diameter of 5u was obtained.

When this Rondo was brought into contact with iodine gas at saturated vapor pressure at room temperature for 24 hours, it exhibited an electrical conductivity of IS/am.

Example 3 Poly-3-octylthiophene powder was sandwiched between two iron plates having a gap of 0.1 mm and hot pressed at 200°C for 5 minutes, resulting in a sheet with a thickness of 0.1 mm. A molded product was obtained.

When this sheet was brought into contact with iodine gas at saturated vapor pressure at room temperature for 24 hours, it exhibited an electrical conductivity of 16 S/cm.

Example 4 Poly-3-dodecylthiophene was heated and melted at 165°C (wheat, extruded through a nozzle with an inner diameter of 0.5 mm 1:
By winding while stretching at a rate of 5%, the thickness is 0.1
(1) A fibrous molded product was obtained.

When this fiber was brought into contact with iodine gas at saturated vapor pressure at room temperature for 24 hours, it exhibited an electrical conductivity of 13 S/am.

Example 5 In Example 3, poly-3-octylthiophene doped with iodine was used instead of poly-3-octylthiophene, and hot pressing was performed in the same manner as in Example 3, resulting in a sheet-like molding with a thickness of Q and 1 mm. I got something. The electrical conductivity of this sheet was measured and found to be 12 S/cm.

Comparative Example In Example 3, poly-3-butylthiophene was used instead of poly-3-octylthiophene and hot pressing was carried out in the same manner as in Example 3, but the powder remained and no molded product was obtained. Although the temperature was further increased to 400"C, the powder did not melt and no molded product was obtained.

〔Effect of the invention〕

By carrying out the method of the present invention, it is possible to easily mold a 5-membered heterocyclic compound polymer, which has been difficult in the past, and to produce molded products of a 5-membered heterocyclic compound polymer and conductive molded products at low cost. It is extremely valuable industrially.

Claims (1)

[Claims] General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In formula (I), R is an alkyl group having 8 or more carbon atoms,
is an amino group represented by oxygen, sulfur, selenium, tellurium, or -NR', where R' is hydrogen, an alkyl group, or an aryl group. A cyclic compound polymer, or a doped polymer pre-doped with a dopant, with or without a dopant, at a temperature equal to or higher than the softening point of the 5-membered heterocyclic compound polymer or a doped polymer. 1. A method for molding a five-membered heterocyclic compound polymer, the method comprising: heating the polymer to form a desired shape, and further comprising doping the molded product with a dopant, if necessary.