JPS59102912A - Electrically-conductive material - Google Patents

Abstract

PURPOSE:A good electrically-conductive material having improved stability to oxidation resistance, and stability to heat resistance, comprising an allyl carbide doped with a sulfonating agent. CONSTITUTION:An allyl carbide polymer having a trible bond rigid in terms of molecular structure in a main chain, and a structural unit(e.g., 1,4-phenylene- 1,4-phenylene carbide, etc.) shown by the formula I [R<1> and R<2> are groups shown by the formulas II-VI(A is alkyl, aryl, halogen, nitro, cyano, etc.; n is 0-3), etc.; X<1> and X<2> are halogen; m is 2-20] is doped with a sulfonating agent (e.g., sulfur trioxide, etc.) in a gaseous phase or liquid phase at -50-150 deg.C, preferably at 0-80 deg.C for 1min-50hr, preferably 5min-10hr, to give the desired electrically-conductive material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a conductor made of an aryl carbide polymer.

Conventionally, conductors have been produced by doping conjugated polymers such as polyacetylene, polyparaphenylene, polythenylene, and polypyrrole with various doping agents, such as arsenic pentafluoride, iodine, bromine, transition gold Ffiz/logonides, and sulfonating agents. It is known that wo can be obtained.

However, these conventional polymers are complicated to manufacture, have poor film-forming ability, and poor oxidation stability.
Furthermore, there were problems such as the polymer being easily oxidized by oxygen in the air, deteriorating the polymer, and reducing the amount of conductive dust.

As a polymer improved in this respect, for example, an arylacetylene polymer having a double bond in the main chain has been proposed (Japanese Unexamined Patent Publication No. 703, 1983), but the present inventors have As a result of extensive research into polymers that have improved oxidation and heat resistance stability and are also good electrical conductors, we found that they have a molecularly rigid triple bond in the main chain,
It was discovered that the desired object could be achieved by an aryl carbide polymer having a structural unit conjugated with a divalent aromatic group or a heteroaromatic group, and the present invention was completed. Ta.

That is, the gist of the present invention resides in a conductor made of an aryl carbide polymer doped with a sulfonating agent.

The present invention f: To explain, the aryl carbide polymer of the present invention has a triple bond in the main chain and has a constituent unit conjugated with a euvalent aromatic group or a heteroaromatic group. .

For example, general formula (1) % formula % () a, flukoxy group, aryloxy l;, no 10
l, iU, -tro group, cyano group or amino group, and n represents θ~3. ) represents an atom chosen from force 1, and m represents λ~koO1, preferably 3~lS. ] Examples include polymer crabs shown in

Specific examples of the repeating unit of the main chain include nylene carbide, /, 2-phenylene-/, 1-phenylene carbide, /, +=niphenylene-he-phenylene carbide, /, ll-phenylene- Hayoufuenylenkanokuito, /, 3-phenylene-hayoufuenylenkanokuito, /, 4'-phenylene-havnaphthalinka-/(()(-Chadanaphthalinkano; it,
/,,2-phenylene-/,q,-naphthalene linker/(
It, hadarfueninre 4-ta, IO-anthrasenka noguit (-a=a
Cencarbite, /, 2-phenylene-q, io-anthracenecarbite, /, 4'-naphthalene-/
, darnaphthalin power-] Kuito, l, darnaphthalin-
qllo-anthracencanokite, q, i.

-Anthracene-9,10-anthracene carbide, trimethyl-l, H-phenylene/, Z-phenylene carbide, methyl-/, kunaphthalene-/, 4'-naphthalene carbide, dimethyl- /, lI-naphthalene-7, Hiro-naphthalene carbide, methyl-9,10-anthracene-9,IO-anthracene carbide, dimethyl-9,10-andhracene-dimethyllater, /θ-anthracene carbide, 4/, 'I'-biphenylene-114'-biphenylene carboxylate (-C=C() short)-=C(and (
■), Methylug, Hiro'-biphenyleneta, v'-biphenylenekatskuit, Hadaphenylenuk, Ri'
-Biphenylene force-no(ite, methoxy-/, lI-phenylene-/, 4(-phenylene carbide, dimethoxy-/, Kuphenylene-Haguphenylene carbide, Ethoxy-l, F-phenylene-/ , 4'-phenylene carbide, methoxyethoxyhake-phenylene-/, 4'-phenylene carbide, phenoxy-/,
4/-phenylene-/, 4'-phenylene carbide, diphenoxy-/, gouphenylene-bald-phenylene carbide, methoxyphenoxy/, lI-phenylene-/, 44-phenylene carbide, chloro-phenylene-phenylene -/, 4'-phenylene carbide, dichloro-/, 4'-phenylene-/, 4'-phenylene carbide, methylchlor-/, gouphenylene-/, 4
'-phenylene carbide, nido O-/, '%-phenylene-/, cuphenylene carbide, methyl nitro-
/, lI-phenylene-/, q-phenylene carbide, cyano-barryphenylene-/, lI-phenylene carbide, dicyano-/, lI-phenylene-/I cuphenylene carbide, methylcyano-/, cuphenylene-/ , terphenylene carbide, methoxycyano-/, 4t-phenylene-74-7eth-lene carbide, methylamino-/4-phenylene-/4-phenylene carbide, methoxyamino-/4-phenylene-bald-phenylene Carbide, diamino-7, Hiro-phenylene-l, l-phenylene carbide, , 2,5-thiophene-2,5-thiophene carbide, 3-thiophene carbide, 3-thiophene carbide, 2. 'I-thiophene-2. Cuccio-encarbide, methyl,
2 is monothiophene, S-thiophene carbide, dimethyl-2, left-thiophene-core terthiophene carbide, ethyl-11, terthiophene-, 2,5-thiophene carbide, methyl ethylrouyl, terthiophene-, 2,5 -thiophene carbide, methoxy-2,3
- Thiophene, 3-thiophene carbide, dimethoxy, 2, tertiophene, 5-thiophene carbide, ethoxy - left - Thiophene 12, S-thiophene carbide, methoxyethoxy, 2,5 -thiophene-2,3-thiophene carbide, /, 1. t
-Fueni Vunno, 5-thiophene force-no (It, /,
4'-naphthalene, 1-thiophenecarbide, 6-pyridine, 6-pyridinecarbide, methyl-2,A-pyridine-2,6-pyridinecarbide, dimethylco, 6-pyridine-,2,6- Pyridine carbide, ethyl, 2,6-pyridine, 6-pyridine carbide, 7 ethyl, 6-pyridine, 6-pyridine carbide, S-thiophene, A-pyridine carbide, (it, da, ri), '-diphenylene ether-1I4'-diphenylene ether carbide (-a=
cJ, φ
'-dianthracene ether carbide, +4'-diphenylene ether-1I, 4t'-sinaphthalene ether carbide, da, lI'-diphenylene ether-/
θ, 10'-dianthracene ether carbide, methyl roof, /I/-diguenylene ether carbide, tx'-diphenylene ether carbide, dimethyl-+, +'-diphenylene ether carbide 1I, y'-di Phenylene ether carbide, ethyl-tt, II'-diphenylene ether-ti4'-diphenylene ether carbide,
Methyl ethyl-ti, 41. '-diphenylene ether router, ri'-diphenylene ether, methoxytheta, t'-diphenylene ether-+, lI'-
Diphenylene ether carbide, dimethoxy-4t,
Hiro'-diphenylene ether-tx, y'-diphenylene ether carbide, ethoxy-q review-siphenylene ether-'z, +'-diphenylene needle carbide, methoxyethoxy-4', l! '-Diphenylene ether carbide, ll'-diphenylene ether carbide, +, +'-diphenylene ether, S-thiophene carbide, y, lI'-diphenylene ether carbide, ll'-diphenylene ether carbide, ll'-diphenylene ether carbide, Pie) 1. t,y'-dithionene etherreuil, ot-pyridine carbide.

/4-phenylene diketone-/, Q-7e=L/ton-
/, 4'-phenylene diketone carbide, 1-
/L/ -i, xi-phenylene diketone-/, phenylene diketone carbide, methoxy-/, +-phenylene diketone-/, 4'-phenylene diketone carbide, co, tertiophene diketone, terthiophene diketone Carbide, U, 6-bilysine diketone carbide, 6-pyridine diketone carbide, T, S-thiophene/, 4'-phenylene diketone carbide, 2
．． Examples include A-pyridine/, 4'-phenylene diketone carbide, and the like.

The aryl carbide polymer of the present invention can be synthesized by a known method or in accordance therewith. For example, the following methods may be mentioned.

■ A method of refluxing a digrinard reagent and an organic di-loginide in a solvent such as tetrahydrofuran in the presence of a catalyst such as palladium acetate.

BrMg c=c-R'-CE:0-MgBr+X-R
2X→X -R2f (3=O-R'-0=O-R2-
) – A method in which triethylamine or the like is further added to the catalyst, and the mixture is refluxed in a solvent such as toluene.

CHHO2Rl-C=CH+X-R2-X-SaX-LR
2 ÷ C-EEC-R1-(, = (1!-R2 likelihood X above ■
In methods (2) and (2), the amount of catalyst used can be as small as a molar ratio of /10/10,000 to the raw material monomer, so purified polymers can be easily purified by simple filtration and washing. Obtainable.

The aryl carbide polymer of the present invention is not oxidized by oxygen in the air, and does not undergo thermal decomposition even at temperatures of 20θ°C or higher.

In the present invention, the above-mentioned aryl carbide polymer is doped with a sulfonating agent.

Examples of the sulfonating agent in the present invention include sulfur trioxide, oleum, and adducts of halosulfonic acids (fluorosulfonic acid, chlorosulfonic acid, bromosulfonic acid, etc.) and sulfur trioxide. Sulfur trioxide adducts include sulfur trioxide and complexing agents such as pyridine,
Examples include complexes with trialkylamines, dimethylformamide, dioxane, etc. Among these, sulfur trioxide and fuming silicate acid are suitable.

Doping with dopants other than the sulfonating agent, such as iodine, bromine, ferric chloride, improves the conductivity slightly, but the sulfonating agent does not significantly increase the conductivity.

Doping is carried out by bringing the aryl carbide polymer into contact with the sulfonating agent in a gas phase or a liquid phase. That is, when the aryl carbide polymer is used in powder form or in the form of a film or compression molded product, and in the case of gas phase contact, a mixed gas with a sulfonating agent gas or a diluting gas such as nitrogen or air is used. In the case of liquid phase contact, it is immersed in a solution containing a sulfonating agent.

The temperature of doping with the sulfonating agent is usually −,
5-0-/0°C, preferably θ~go'c.

Doping time varies depending on temperature, concentration of sulfonating agent, and type of sulfonating agent, but is usually 1 minute to 3 minutes.
0 hours, preferably S minutes to io hours. As the doping time increases, the amount of doping into the polymer increases, and by adjusting the doping time, the amount of doping per seven-mer constituent unit of the polymer can be freely changed.

The doping amount is usually θ,oo per monomer constituent unit of the polymer.
i to 2θ molar times, preferably o, oo to 70 molar times.

As mentioned above, conductors obtained by doping aryl carbide polymers with sulfonating agents have excellent electrical properties, oxidation stability, and heat resistance, making them practical. Great value. The conductor of the present invention is useful in applications such as antistatic agents, photoelectric conversion elements, storage batteries, optical memories, terminal devices, solid-state displays, and surface heating elements.

EXAMPLES The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to these examples.

Reference example/l, goujetinylbenzene/, 10A'gr(/, 2
．． θ mmol) and/I-dibromobenzene, 2. g
, 2 gr (/2.0 mmol) was weighed out into a θO ml round bottom flask, and 0.03 g of palladium bistriphenylphosphine chloride, ? J gr,
) Luphenylphosphine 0. / 5/ A gr, cuprous iodide 0, 0.30/gr and triethylamineta O
When the mixture was heated and stirred for 3 hours under reflux under a nitrogen atmosphere, a large amount of yellow powdery precipitate was produced.

The yellow powder was removed from the F side, and the tear residue was washed with water to remove the by-produced HBr.(02H5)3.N salt. The residue after washing with water was dried at 60° C. under reduced pressure for 2 hours to obtain yellow powders. This yellow powder does not melt even when heated to 330°C, and also contains toluene, dichloroethane, acetone, tetrahydrofuran, dimethylformamide, N-
It was insoluble in organic solvents such as methylpyrrolidone, dimethylsulfoxide, and chloroform. The results of elemental analysis of this yellow powder are shown below.

Calculated value as 'AriBr + c-c snow bow I3r Also, as a result of infrared absorption spectrum analysis, absorption at 32 o'clock Otm' indicating CH=C- bond disappeared,
The absorption associated with the alkyne bond of m' also disappeared.

Reference example ii, q'-jethynyldiphenyl ether 2. /g
The procedure was carried out in the same manner as in Reference Example except that 3.27 gr (10.0 mmol) of ri'-dibromidiphenyl ether was used. As a result, a yellow powder 1. Google got i'N, ta. As a result of infrared absorption spectrum analysis of this substance, it is 1m! H: 32k indicating O-binding.
The absorption of Oon' disappeared, and the absorption corresponding to the alkyne bond of 600 to 7θθc1n-' also disappeared.

This yellow powder did not melt even when heated to 30°C, nor was it dissolved in toluene, dichloroethane, tetrahydrofuran, or dimethylformamide.

Reference example 3 /, 3-jethynylbenzene 8, 2A (3r(/θ, θ
mmol) and isophthalic acid chlorite co, 03gr.
(/θ, θ mmol) was used and the reaction temperature was 90°C, but the same procedure as in Reference Example 1 was carried out, and as a result, 3 g of light brown powder was obtained. This powder did not melt even when heated to 3.10°C, and was not dissolved in organic solvents such as toluene, dichloroethane, tetrahydrofuran, dimethylformamide, and chloroform. In addition, as a result of infrared absorption spectrum analysis, 32!
The absorption of Ocm' disappeared, but /A'lθ, /
A new absorption corresponding to a carbonyl bond at 7.30 cm-' was observed.

Reference example g/, tarjetinylbenzene 8 26 g, r (/ 0
．． 0 mmol) and 2,5-dibromothiophene, Z, V
, 2 gr (10.0 mm IJ mol J) was carried out in the same manner as in Reference Example/, and as a result, a brown powder, g y
'was gotten. As a result of infrared absorption spectrum analysis of this substance, the absorption at 3230 cm-' indicating the OHmiC-bond disappeared, and the absorption at 7730 cm-' indicating the thiophene ring was observed. This powder did not melt even when heated to 3:10° C., nor was it dissolved in organic solvents such as toluene, dichloroethane, chloroform, tetrahydrofuran, and dimethylformamide.

Reference example S /, lI-jethynylbenzene 8, 2&gr (/θ, θ
mmol) and 2.37 g of 2,6-diprompyridine (
The procedure was carried out in the same manner as in Reference Example except that 10, θ mmol) was used, and as a result, 9 grams of brown powder was obtained. As a result of an infrared absorption spectrum analysis of this substance, the absorption at 3.2 cm, indicating a cn=c bond, disappeared, and the absorption at 230 cm, indicating an internal acetylene bond, was observed.

This powder did not dissolve even when heated to 3.30°C, nor was it dissolved in organic solvents such as toluene, dichloroethane, chloroform, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide.

Example 1 Polyphenylene carbide powder θ obtained in Reference Example/
soy was weighed into an ioθd round bottom flask, and the system was purged with nitrogen. Thereafter, at room temperature, dry nitrogen was blown into a reagent bottle containing sulfur trioxide as a white flocculent solid of α type, and the sulfur trioxide gas entrained in the nitrogen was brought into contact with polyphenylene carbide powder while stirring with a stirrer. . Upon contact, the color changed from a yellow powdery solid to a black powdery solid, accompanied by heat generation. After continuing to flow sulfur trioxide gas for 20 minutes, the excess sulfur trioxide gas was removed by keeping it at room temperature under reduced pressure for 30 minutes, and then at θ℃ for 1 hour. As a result, 82/g,
A black powdery solid of r was obtained.

This solid was compression molded to a diameter/cm thickness/cm under pressure at 30θ, and the dielectric conductivity was measured using the four-terminal method in a dry box! ;,, Z x 10''Ω-1m-1.The electrical conductivity of polyphenylene carbide that was not treated with sulfur trioxide gas was 10Ωa.

It was treated in the same way with iodine gas instead of sulfur trioxide, but the conductivity was 0-130-'t1n', and it was immersed in a nitromethane saturated solution of anhydrous ferric chloride at room temperature - day and night, then evaporated and dried. The electric power of the grayish solid obtained is / 0−+
It was 3Ω-'Crn-'. Therefore, the doping effects of iodine and anhydrous ferric chloride were not substantially observed.

Example 3 Polyphenylene ether carbide powder θ obtained in Example 3,! i0gr was used, and the rest was treated with sulfur trioxide gas in the same manner as in Example/. The result was θ, 9.7 g.
A black powdery solid of r was obtained.

The tonic conductivity was measured in the same manner as in Example 1, and the result was x10.
Ω (1). Bo1J phenylene carbide that was not treated with sulfur trioxide gas was light brown in color and had an electrical conductivity of 0-14Ω-'Crn'. It was also found that when polyphenylene ether carbide was treated with sulfur trioxide gas, its electrical conductivity was greatly improved.

Example 3 Reference Example 1″'c The obtained polyphenylene carbide conductivity was 0×/θ−2Ω−′ crn−′.

Example: Polyphenylene ketone carbide powder obtained in Reference Example 3. As a result of treating SOgr with sulfur trioxide gas in the same manner as in Example, a black powdery solid of 0.9Ag and r was obtained. What is the electrical conductivity of this solid, t? X/θ3Ω-
'crn' and the untreated solid is light brown and has a conductivity of io
It was 15Ω-'crn-'. Therefore, it has been found that when polyphenylene ketone carbide is also treated with sulfur trioxide, its electrical conductivity is greatly improved.

Example S The polyphenylene thiophene carbide powder obtained in Reference Example 4Z and the polyphenylene pyridine carbide powder obtained in Reference Example 1 were doped with sulfur trioxide gas in the same manner as in Example 1, resulting in a black color. A powdery solid was obtained. The following results were obtained by determining the conductivity of each.

As is clear from Table/Table/, both polymers exhibited a wide improvement in conductivity.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - Others/names

Claims (2)

[Claims] (1) A conductor made of an aryl carbide polymer doped with a sulfonating agent. (2) The aryl carbide polymer has the general formula,
-R+O::O-R-C:C! -RxX represents a group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyan group or an amine group, and represents nFiO~3. ), xi and X2 represent a halogen atom, and m represents co-20. ] The conductor according to claim 1, which is a polymer represented by: