JPS5998165A - Electroconductive polymer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to conductive polymer compositions.

Known conductive polymers include polysulfur nitride, polyaniline, polyj'ketylenes, polypyrrole, and the like. Although some polymers, such as (SN)x, are inherently conductive, many polymers require oxidation (or) 9 elements to make them sufficiently conductive.

For example, polyethylene requires oxidation or reduction;
Polypyrrole requires oxidation. oxidation (or reduction)
These methods often involve doping and require the incorporation of counterions into the oxidized (or reduced) polymer to balance the ion beam. This counterion A is often called a dopant. Examples of tope agents include BFa-1
Included are 11-1-2 sulfonate, 3r-.

For clarification, the term "conductive 11 polymer" in Mu Ming 1 does not refer to whether the oxidation/iU element of the polymer is carried out to make it conductive and/or the "dopant". is required or actually exists.
C refers to any polymer or olicomer that can be inherently or essentially electrically conductive or semiconductive. The above terms therefore include inorganic polymers, such as polysulfur nitride, and also include organic polymers, such as polypyrrole, in particular in a highly conductive state "doped" or undoped. Also included are organic polymers that are IB2 doped and have poor conductivity.

The terms "doping" and "dedoping" refer to the use of oxidation/reduction methods to change a polymer between a less conductive state and a more conductive state. The term "dopant" refers to a substance used to provide the counterions mentioned above and the counterions that stabilize the more conductive state of the polymer. “Undoped J
, "doping" and "dedoping" have the meanings given above.

The present invention provides a polymer composition comprising a conductive polymer loaded with a polymer dopant that stabilizes the polymer in a conductive state.

The "polymer dopant" used in the present invention is a substance to which the necessary counterions are supplied by the polymer and A ribomer molecules that support the charged groups in the main chain and/or side chains or pendant mill groups of the polymer. That is understood. Examples of such polymeric dopants include ionized sulbone]-, carboxylate 1-
or polymers and oligomers with bosphates,
Includes polyelec 1 to lorite, and ionene (a general term for ionic amines).

By using a polymer dopant according to the invention,
This provides significant advantages over previously used dopants. For example, the physical and/or chemical properties of a polymer dopant can be used to modify such properties of the conductive polymer itself. Additionally, the modifying polymer can also be a dopant. As such, such polymers can be introduced into the η conductive polymer during formation of the conductive polymer in a solution of the toping agent to form a modified polymer film. Modification The resulting polymer films will exhibit different properties than those obtained by forming conventional doped conductive polymers into solvent swollen preformed films of other polymers.

Also, since polymer dopants tend to soak into the conductive polymer, undesirable dopant losses J′3 and 1
A close combination of materials can be provided that exhibits excellent resistance to 112 doping.

Accordingly, another aspect of the invention provides (1) to bring a polymer from a poor conductive state to a superior conductive state in the presence of a polymer dopant that stabilizes the polymer in a more conductive state. A method for producing a conductive polymer comprising (
2) a method for producing a conductive polymer comprising polymerizing a suitable hexamer in the presence of a polymer dopant capable of stabilizing the conductive polymer in a conductive state; (3) a method of producing a suitable hexamer; A method for producing an electrically conductive polymer comprising: avoiding polymerization and bringing the obtained polymer into a conductive state in a solution of a polymer dopant capable of stabilizing the obtained polymer in a conductive state, i15 J: bi(4)
Preferably, the method comprises providing a conductive polymer loaded with a polymerizable heptamer capable of producing in situ a polymer dopant capable of stabilizing the conductive polymer in a conductive state. Provided is a method for producing a conductive polymer comprising a process for producing a dopant by polymerizing -.

The choice of polymer dopant depends on the nature of the conductive polymer being formed. Positively charged dopants are suitable if negatively charged conductive polymers, such as polyacetylene, are used.

Examples of positively charged polymer dopanes 1 to 1 include
Ionene of the formula (I), (I) or (I [l) of the drawing; an acrylamide copolymer, e.g. copoly(acrylamide) of the formula (IV) of the drawing
(3-acrylamido-3-methylbutyl]~limethylammonium chloride); and formula (V) in the attached drawings
Polymers of 2-methylene ammonium or 2-methylene sulfonium salts of 1,3-butadi]-one shown in the formula are included.

In the formula 43 in the drawings, R represents an appropriate organic substituent, n, x, y IJ represents an appropriate integer, and J-0 appropriate groups and numerical values are known to those skilled in the art. This can be easily determined by a business operator.

However, the negatively charged dopant
- This is particularly important in relation to the rules. Polypyrrole is a preferred type of conductive polymer due to its resistance to aging.

A distinct advantage of the present invention is that flexible, self-supporting films of polypyrrole, which are very brittle and difficult to handle, can be produced. Examples of negatively charged polymer dopants include poly(2
- acrylamide-2-methylpropanesulfonic acid) or copolymers thereof with acrylamide or alkyl methacrylate, sulfonated polystyrene, sulfonated polyevichlorohydrin, sulfonated poly(2,5-dimethyl-phenylene oxide) , sulfonated polyphenylniar sulfone (or
), J3 and sulfonated polyethylene.

Also, polyvinyl sulfonic acid sodium salt (molecular weight, 2.000), polyacrylic acid, which is an elastomer, has a molecular weight of
9'0.000), polymaleic acid, sulfonated EPD
M salts can also be used advantageously. Salts of polycarboxylates, such as polynoacrylic acid, as well as phosphonated polymers, such as the polymers of formula (XI) in the drawings, may also be used. The negatively charged groups may be present on the backbone and/or side chains of the polymer, and the polymer may be aromatic and/or
or aliphatic. copolymer and/or t
Mixtures and blends of the above-mentioned dopants can also be used.

It should be noted that the polymer dopant itself also provides some ionic conductivity, but this is usually distinct from the inherent conductivity of the conductive polymer.

A class of electrically conductive polymers of particular interest is J.
These polymers consist of derivatives of virol or virol or an adjunct that remains unsubstituted in sufficient quantity to permit the desired polymerization. Conducting polymers are generally thought to operate via a conjugated pi-electron system, with certain substituents. Alternatively, combinations of substituents can interfere with the conjugated system and reduce or destroy the conductivity. Suitable substituents can therefore be determined by a simple test of the conductivity of the resulting polymer. can.

Other types of conductive polymers that may benefit from the use of polymeric dopants in accordance with the present invention include polymers of 7-niline J5 cl: Also included are conjugated polymers such as polyacetylene and polyphenylene.

Conductive polymers with polymeric dopants according to the present invention can be made in several different ways.

Electrochemical methods of producing conductive polymers can be employed to produce the polymer doped materials of the present invention, as described below. Generally, two electrodes (e.g., electrodes made from stainless steel, brazier or indium oxide coated glass) are electrochemically immersed in a mixture, suspension; or solution of an electrolyte. cells are used.

The electrolyte includes a polymer with groups that can be ionized to become suitably charged ionic dopant species. The solvent or mixed solvent is selected from protic J3J and aprotic solvents such as acetonyl-1-lyl, tetrahydrofuran, dimethylformamide, water, methanol/J. Added to the electrolyte mixture are monomers that are oxidatively polymerized to form the desired conductive polymer. obtained I (stirring and covering the mixture is necessary to obtain a homogeneous mixture. When the cell is activated, a conductive film is formed on a suitable electrode. A positively charged polymer, e.g. polypyrrole In this case, a film is formed on the anode, partially oxidized, and containing a negatively charged polymer dopant to render the film electrically neutral.
Ru.

Scientific manufacturing methods can also be employed, in which the monomer and polymeric dopant are mixed with the oxidizing agent in a suitable liquid carrier. The oxidizing agent is advantageously supported on the polymeric dopant of the invention by forming a ferric salt of the dopant, such as sulfonated polystyrene. This allows simultaneous oxidative polymerization and doping with a negatively charged polymer dopant. This makes it possible to reduce or avoid the degree of doping of inorganic anions that occurs when ferric chloride is used as an oxidizing agent.

Next, examples will be used to explain the present invention in detail. The conductivity is [7
1- Ganitsuk, Semiconducting, Bolimars J
(edited by J.E. Katon) (Marcel
4- according to the method described in Dekker 1968).
Measured by probe method.

Unless otherwise specified in Examples J5, sulfonated polymer dopants were prepared as follows.

Commercially available chlorosulfonated polyethylene (density 1.28) containing 1.1% by weight of sulfur is hydrolyzed with sulfonated polyethylene (density 1.28) containing about 2% by weight of sulfur. Te5
The O2Cβ group was converted to 18Oa-Na1 (see formula XI) and was used in this form as an electrolyte in electrochemical doping experiments.

Sulfonated borisdyrene 21borisdyrene (average molecular weight 170,000 or less)
Upon treatment with J sulfonic acid, the product was then hydrolyzed to yield an acidic ionizable polymer. This polymer contains 3.233 triples of IA/υtC (degree of sulfonation about 12% by weight).

Sulfonated poly(2,5-dimethylphenylene oxide) - Commercially available poly(2,5-dimethylphenylene A oxide) was treated with chlorosulfonic acid and subsequently hydrolyzed to yield an acidic ionizable polymer. . This polymer is
The degree of sulfonation is 16, which contains 3.54% of A.
1Q%).

Production of sulfonated poly(vinyl alcohol): Chlorosulfonic acid 24.8! II was slowly added to the pyridine 100 cod with vigorous stirring. This solution was added to the molecule ff11
4.000 of poly(vinyl alcohol) 8.8(+) was added to a suspension of 100πβ of pyridine. The mixture was heated at 90°C for 1 hour with continuous stirring, then cooled to room temperature to reduce the solids. The solids were redissolved in 200 in. of distilled water, then 100 πβ of water was removed on a rotary evaporator, and the remaining solution was acidified with 501 β of 1M hydrochloric acid. The polymer was precipitated by the addition of methanol. , redissolved in water, reprecipitated with methanol, washed with methanol, and dried with P205 under reduced pressure.

Degree of sulfonation - 25% by weight (determined by sulfur content).

Preparation of sulfonated styrene/(hydrogenated) butadiene copolymer Two 500-meter addition funnels, high-speed stirrer, reflux condenser,
Dichloromethane at 800° C. was added to a 22 round bottom flask equipped with a nitrogen inlet and a gas outlet attached to an inverted funnel/steam adsorber.

One addition row 1 contained a commercially available styrene/(hydrogenated)butadiene polymer dissolved in 500 πβ dichloromethane, and the other row 1 contained a solution of 3.6 drops of chlorosulfonic acid in 500 ml of dichloromethane. there was.

The reaction flask was cooled to 5° C. and maintained at this humidity during the addition of the reaction mulberry. The solution of chlorosulfonic acid and the solution of the polymer were added slowly at the same time over a period of about 3 hours. Vigorous stirring was continued during the addition.

After the addition is complete, continue stirring () and continue the reaction at 5°C and 161F. ) The quality was raised to room grade, and the reaction was continued for an additional 24 hours () with stirring. The reaction was followed by m of hydrogen chloride evolved. Hydrogen chloride was measured by titrating water in a gas absorber with 1M sodium hydroxide using phenolphthalein as an indicator.

Methane was removed from the precipitated polymer using a combination of decantation, filtration and rotary evaporation.

The polymer was dissolved in T I-IF and added to distilled water with vigorous stirring to precipitate it. T)-IF was removed from the water/polymer suspension by rotary evaporation and the polymer was filtered. The polymer was dried under reduced pressure over sodium hydroxide at 40°C.

CICl5N showed that the addition of sulfonic acid took place on the aromatic part of the polymer.

Atsu 8 right fm = 4.8%. This varies depending on reaction time.

Example 1 Two stainless steel electrodes were used 2 cm apart as the anode and cathode of an electrolyte cell. The electrolyte cell was commercially available poly(2-acrylamide-2-methylpropanesulfone W) (manufactured by A Idric 11) 1 (1,
It contained a mixture of 37% water and 10πβ aretonitrile along with 0.06 moles of virol. The mixture was stirred during cell operation.

The electrolyte cell was powered by a DC power supply.

Electrolyte) Electrolysis of the compound was performed by applying a potential of 5 V to the cell for 1 hour. During that time, the current density is 5 111
It was AcII+2.

A black film (33μ thick) was deposited on the anode and its removal yielded a freestanding film that was tough and flexible while wet. When air-dried, the film becomes brittle.
It could not be folded in half or folded like paper without breaking. The "dry" film had a room temperature conductivity of 253C...-1 (4-probe measurement).

Example 2 The same procedure as in Example 1 was repeated, except that a solution of 2 g of acid form of sulfonated poly(2,5-dimedylnoenylene ogicide) in 7.5 g of water was used as the electrolyte. The cell is 51
It was operated for 45 minutes at a current density of 1+ACII+-2. A black self-supporting film (36μ thick) was obtained. It was very tough and flexible while wet. When dried, the film becomes very brittle and 0.38 cm
-1 room temperature conductivity.

Example 3 A solution of 2 g of acid form of sulfonated poly(2,5-dimethylphenylene oxide) in DMF 50 was used as an electrolyte, and aniline (6.02 mol) was used as a polymerizable compound.
The procedure of Example 2 was repeated, except for a current density of 6 mAcm-2 for 45 minutes.

A black film was deposited on the anode. This is believed to be the first attempt to provide a self-supporting film that is removable and consists essentially of polyaniline and dopant. The film was very fragile and the sample was too small to measure electrical properties.

Example 4 Electrolyte containing 5 g of salt of sulfonated polyethylene, 1.571 Iβ of water, and 5 Q of tetrahydrofuran y
The same procedure as in Example 1 was repeated using a mixture of sl and a current density of 1 + nAcm-2 for 1 hour.

A black film is deposited on the anode, and its removal leaves a film that is flexible when wet (1 bar bendable) and stretchable (
The elongation at break is 30%), and when dry it is approximately 10 33c.
It had a dry conductivity of m-1.

Example 5 Natrilam JM of sulfonated polystyrene as electrolyte
The same procedure as in Example 1 was repeated using the acetonitrile 5Qi6 mixture of 2a and at a current density of lmAcm-2 for 45 minutes.

A shiny black film formed on the anode and was very brittle when dry. (Right conductivity cannot be measured).

Example 6 0.03 mole of sulfonated poly(vinyl alcohol) Bi[J-ru] was dissolved in a solution of 25% sulfonated poly(vinyl alcohol) in 307II2 of DMF 50πβ and 20% water. This solution has a current density of 101
Electrolysis was carried out for 1.5 hours using the same stainless steel electrode as in Example 1 with 11ACI11'-2. A black film of polypyrrole doped with sulfonated polyvinyl alcohol could be removed from the anode.

The film has a thickness of 0.24 cm and a thickness of 2.568 CI1.
It had a conductivity of 1-1. The dried film was strong but limp.

Example 7 0.045 mol of poly(methacrylic acid) virole was mixed with a solution of 10 g of poly(methacrylic acid) sold by BDH in 401 β of water and 50 ml of methanol.
It was dissolved in 0. This solution was electrolyzed for 1.5 hours at a current density of 10 mACl-2 using a stainless steel electrode. A black film of polypyrrole doped with poly(methacrylic acid) could be removed from the anode. The film had a thickness O0Q of 9 mm and a conductivity of 1.708 cm-+.

The dried film was brittle.

Example 8 A sulfonated styrene/(hydrogenated)butadiene copolymer electrolyte solution was prepared by dissolving virol (5 volume ω%) in a tetrahydrofuran/nitrobenzene (75/25 V/V) solution of sulfonated polymer (2 wt%). Manufactured by

This solution was electrolyzed in a cell with a solid stainless steel anode and a stainless steel wire mesh cathode at 5+++ ml/L/. A constant current of lmAcm-2 was applied for 20 minutes. Stirring of the electrolyte solution was continued during electrolysis. The polypyrrole film was peeled off from the anode, washed with detrahydrofuran, and then dried at 50° C. under reduced pressure. The thickness of the film is Q
, 4 mm.

Physical Properties The film was smooth up to t on one side (electrode side) but very rough on the other side (solution side).

The smooth side was irritating the conductive 1'l of 5x1O-3 SC1, while the rough side was essentially non-conductive. When the film was observed under a microscope, a laminated structure was revealed. The film can be easily formed under heat and pressure, resulting in a completely smooth film. In addition, by folding the film in half and pressing it in half, I was able to make 1q of film with right-hand conductivity on both sides.

Film properties: Thickness 0.4IllI111 Ultimate elongation 4
10%, stress at break 18 MPa.

Press film: thickness 0.27mm, elongation at 4m limit 39
0%, stress at break 32MPa0

[Brief explanation of drawings]

FIG. 1 and FIG. 2 are diagrams showing the repeating units of the polymer used in the present invention, respectively. Patent Applicant Raychem Limited Agent Patent Attorney 3 persons Figure 1 (X■) Procedural Amendment (,3) Commissioner of the Patent Office 1, Indication of Case Patent Application No. 142373 of 1988 2. Name of the invention Conductive polymer composition 3. Relationship with the person making the amendment Patent applicant 11 Places: England, United Kingdom, London Easy 4.1 N.L., 7 E. Nta Ichiban Lane, Rollless
Bildinges No. 7, Rolls House Name Raychem Limited 4, Agent (Attachment) Claims: (1) Containing a conductive polymer blended with a polymer dopant that stabilizes the polymer in a conductive state. Polymer composition. (2) The composition according to item 1, wherein the conductive polymer is positively charged and the dopant is negatively charged. (3) The composition according to item 2, wherein the tetraelectric 1/1 polymer is aniline or substituted aniline polymer C. (4) The composition according to item 21, wherein the conductive polymer is a polymer of pyrrole or substituted pyrrole. (5) Polysulfide that can be anionized as a polymer dopant
The composition according to any one of paragraphs 2 to 4, wherein the dopant is sulfonated polyethylene. (7) The composition according to paragraph 5, wherein the dopant is sulfonated polyethylene. The composition according to paragraph 5, which is a (hydrogenated) butadiene copolymer. (8) A self-supporting film comprising the composition according to any one of paragraphs 1 to 710. (9) A high concentration of conductive polymer on one side. , H1 of the C-doped agent on the surface of the song, ``f is human 8II
′! A film about the history of the gods. (1(')) Conductive 1 (1 Poly 7- in a conductive state-
(Preparation of a conductive polymer comprising a suitable polymer in the presence of a polymer dopant). (11) Coq electricity ('l polymer becomes conductive in 4 forms/
The method according to paragraph 1010, wherein the oxidation is carried out on the Φ mold J3 and/or the Φ mold. (12) The oxidation is coupled to a polymer tope. No. 11] I: No. 5 method of manufacturing the preparation using the agent.

Claims (12)

[Claims] (1) A polymer composition containing a conductive polymer, which is blended with a polymer dopant that stabilizes the polymer in a conductive state. (2) The composition according to item 1, wherein the conductive polymer is positively charged and the dopant is negatively charged. (3) The composition according to item 2, wherein the conductive polymer is a polymer of noaniline or directly converted aniline. (4) The composition according to item 2, wherein the conductive polymer is a polymer of pyrrole or directly converted pyrrole. (5) The composition according to any one of items 2 to 4, wherein the polymer dopant is an ionizable polysulfonate. (6) The composition according to item 5, wherein the dopant is sulfonated polyethylene. (7) The composition according to item 5, wherein the dopant is a sulfonated styrene/(hydrogenated) butadiene copolymer. (8) A self-supporting film comprising the composition according to any one of items 1 to 7, wherein the conductive polymer is an aniline or substituted aniline polymer. (9) A self-supporting film comprising the composition according to any one of items 1 to 7, wherein the concentration of the conductive polymer is high on one side and the ia degree of the dopant is high on the other side. (10) A method for making a conductive polymer comprising polymerizing a suitable mono-7- in the presence of a polymeric dopant that stabilizes the conductive polymer in a conductive state. (11) The method according to item 10, wherein the conductive polymer requires oxidation to make it conductive, and the oxidation is carried out in the undercarriage and/or after the polymerization. (12) The method of claim 11, wherein the oxidation is carried out using an oxidizing agent bound to a polymer dopant.