JP2960859B2 - Self-doping type conductive polymer aqueous solution and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] This invention relates generally to conductive polymers.
Related to the field. More specifically, the present invention
Self-doping by covalently linking acid groups to the polymer backbone
Self-doped conductive polymer aqueous solution and
It relates to the manufacturing method. [0002] BACKGROUND OF THE INVENTION Conductive capacitors used in the electronics and other industries.
The demands on remars are becoming more stringent. Also,
Enables downsizing and weight reduction of electronic components and long-term stability per se
The demand for materials having good properties and excellent performance is also increasing. In order to satisfy such demands, in recent years,
Active development of new conductive polymers or polymer materials
Utilizing such polymer compounds
Many proposals have been made for applications. example
For example, PJ Nigre
y) etc. are chemical communication (Chem. Co.)
mm), 1979, polyacetylene
It discloses that it is used as a secondary battery electrode. Also,
Journal of Electrochemical Society
(J. Electrochem. Soc.), 1981.
Year, page 1651 and thereafter, JP-A-56-136469,
Nos. 57-12168, 59-3870 and 59-
No. 3872, No. 59-3873, No. 59-19656
Nos. 6, 59-196573 and 59-203368
No. 59-203369 are polyacetylene, silica
Polyarylenequino, a quinazone polymer having fu base
, Poly-para-phenylene, poly-2,5-thienyl
Polymer compounds such as len are used as electrode materials for secondary batteries
Teach that it can be done. [0004] In addition, other uses of polymer compounds are proposed.
To do this, polyaniline [Journal of E.
Lecto Analytical Chemistry, Vol. 111,
111 pages (1980), AFM, etc. or
Vol. 161, 419 (1984), Yoneyama et al.]
Lipyrrole [Journal of Electro-Analytical
Cal Chemistry, vol. 149, p. 101 (1983)
Year), A. F. Diaz etc.), polythiophene [di
Journal de Fisique, Vol. 44, June, C3-
595 pages (1983), M.A. Druy, etc., or
Japan Journal of Applied Physics
Su, Vol. 22, No. 7, L412 (1983), Kanto
Et al.) For electrotalomic materials.
You. [0005] These conductive properties known in the art
High polymers typically serve as acceptors or donors.
The doping process makes it conductive. Accept
In doping of acceptor-doped polymers,
Oxidizes the backbone, thereby introducing a positive charge into the polymer chain
I do. Similarly, in donor doping, the polymer is reduced
Thereby introducing a negative charge into the polymer chain. Do
The conductivity of the polymer is induced externally by the polymer.
These mobile positive or negative charges introduced into the chain.
In addition, such “p-type” (oxidized) or “n
-Type (reduction) doping, after doping
Substantially all changes in electronic structure, such as optical or infrared absorption
Induce changes, including changes in the yield spectrum. That is, in the conventional doping method,
Counter ion from an external acceptor or donor function
Inducing. Electrochemical support between neutral and ionic states
Counter ions enter and exit the polymer body during the cycle
Must be done. Counter ion source introduced from outside
Solid state diffusion becomes the rate-limiting step in the circulation process
It is often the case. From this, electrochemical or energy
For electrochromic doping and dedoping operations
Remove this limitation and thereby reduce response time
Is desirable. Response time is required for counter ion migration
It has been found that if the time can be shortened, it can be shortened. Departure
Akira is based on this finding. Conventionally, water-soluble conductive
Conductive polymers or self-doping conductive polymers are known
did not exist. [0007] SUMMARY OF THE INVENTION The present invention provides a fast dopin
Can be doped and de-doped, prior art conductivity
It is possible to maintain a stable doping state for a long time compared to polymers.
To provide a conductive polymer aqueous solution and a method for producing the same.
Offer. Excellent polymer obtained as the aqueous solution of the present invention
Properties make conductive polymers “self-doping”
That is, a counter ion that imparts conductivity to the polymer
-The fact that it can be covalently bonded to itself
I will. Thus, in contrast to prior art polymers,
Eliminates the need to introduce external
Is similarly excluded. [0008] The polymer used in the present invention
At least a conductivity of about 1 S / cm can be exhibited.
Self-doping polymers are used as electrodes in electrochemical cells.
Electrochromic display, field effect
Conductive layers in transistors, Schottky diodes, etc.
As high as showing fast doping kinetics
Use in many applications where conductive polymers are desirable
Can be The invention, in its broadest aspects, comprises:Polymer
ー In the main chainLess about 0.01 to 100 mol% of the unit
And one formed by covalently bonding one Bronsted acid group,
Conductive self-doping type with π-electron conjugate system along main chain
It is directed to an aqueous solution of a polymer and a method for producing the same.
You. The self-doping type polymer used in the present invention
Also includes the zwitterionic form of the polymer. In the present invention
Form the main chain skeleton of the self-doping polymer used
Possible polymer chains include, for example, polypyrrole,
Lithiophene, polyisothianaphthene, polyaniline,
Poly-p-phenylene and copolymers thereof
You. In a preferred embodiment, the self-doping described above is used.
-Type conductive polymer aqueous solution and used in its production method
The resulting polymer has a repeating structure of the following structure (II)
Having, in addition to this, another repeating structure, such as the following structure
The repeating structure of (I) may be combined: Embedded imageEmbedded image Here, in formula I, Ht is a hetero group,₁Is water
Prime or -R₁-X-M₁And M₁Is oxidized
Is an atom or group that gives rise to a monovalent cation;
A Sted acid anion; R₁Is a line having 1 to 10 carbon atoms
State or branched alkylene or ether, ester or
Is an alkylene having an amide bonding group. Formula II
And Y₂, Y₃And Y₄Is independently hydrogen and -R₂-X
-M₂Selected from the group consisting of₂Does not exist
Is a linear or branched alkylene having 1 to 10 carbon atoms or
TeRuAlkylene having a group, M₂Was oxidized
An atom or group that in some cases yields a monovalent cation. In yet another preferred embodiment of the invention,
And the repeating zwitterionic structure according to (IIa)
Depending on the other zwitterionic structure, for example (Ia) below
Conducting Polymers with Repetitive Zwitterionic Structures
Provided is an aqueous solution of Embedded image Embedded image (Where Ht, R₁, R₂And X are as defined above
is there). The present invention further provides a self-doping polymer as described above.
Monomers useful for producing, methods of synthesizing polymers and
It is directed to a device using a polymer. The term "conductive" refers to ionized atoms or electrons.
The ability to transfer charge by passing through a child. "Guide
"Electrically conductive" compounds include or include mobile ions or electrons.
The added compound, as well as oxidized mobile ions or
Including compounds that can contain or add
No. The term “self-doping” refers to conventional doping techniques.
Method to make a substance conductive without introducing ions externally.
Means that it can be done. Self-document disclosed herein
In the case of a polymer, what can be a counter ion
To the main chain of "Bronsted acid"
The term is used as one or more proton sources, ie
A species that can act as a proton-donor
Used for For example, McGraw-Hill's chemical and technical terms
See Dictionary, Third Edition, 1984, page 220.
Thus, examples of Bronsted acids are carboxylic acids, sulfo acids
Including acid and phosphoric acid. [0013] As used herein,
The term `` acid group '' is defined as Blenstag as defined above.
Acid, Bronsted acid anion (ie, proton
Is removed), Brønsted acid anion and monovalent
Acid associated with a cationic counter ion
Means salt. "Monomer" as used herein
“Unit” refers to a repeating structural unit of a polymer. specific
The individual monomer units of a polymer are homopolymer
Or the same as in the case of copolymers
May be different. [0014] The self-doping type port used in the present invention
The rimer may be a copolymer or a homopolymer.
And has a main chain structure giving a π-electron conjugated system. Or
Examples of such polymer backbones are polypyrrole, polythiophene
, Polyisothianaphthene, polyaniline, poly-p-
Including and controlling phenylene and their copolymers
Not limited. One or more of the polymers of the present invention described above may be used.
More than "-R₂-X-M₂"Substituted monomers
-Consists of about 0.01 to about 100 mol% of units
Good. In applications requiring high conductivity, the present invention
The self-doping type polymer used has the substituent.
Usually at least about 10 mol% of monomer units, typically
Is preferably composed of about 50 to 100 mol%. Semiconduct
In body applications, the monomeric units having the group comprise about 10 moles
%, Usually from about 0.1 to about 0.01.
Sometimes as little as mole%. The polyheterosa represented by the formulas I and Ia
The cycle monomer unit is -R₁-X-M₁Depending on the substituent
Monomeric or disubstituted monomer units
including. Similarly, polyaniline represented by the formula II and IIa
The monomer unit is represented by “—R₂-X-M₂"Substituents 1, 2,
Contains 3 or 4 substituted monomer units. The present invention
The self-doping polymers used in these
Copolymers containing substituted monomer units of any type
Also intends. Water-soluble of the present inventionLiquidSelf-doping in
Polymers in both homopolymers and copolymers
About 0.01 to 100 mol% of the
Should be prepared. In a preferred embodiment, the present invention provides
The self-doped polymer to be obtained
Includes an electrically neutral polymer with a repeating structure,
Other repeating structures, such as those given by formula I above
A unit may be included. To make the polymer conductive
To oxidize the polymer, at least one M₁Or
M₂Both the removal of the components and the repetition according to Ia or IIa
Must produce a polymer containing a zwitterionic structure.
No. In a preferred embodiment, for example, Ht is NH, S,
Preferably selected from the group consisting of O, Se and Te; M₁You
And M₂Is independently H, Na, Li or K
X is CO₂, SO₃Or HPO₃What to do
Well; R₁Is a linear alkylene or ether group (i.e.
C,-(CH₂)_x-Or- (CH₂)_yO (C
H₂)_z-(Where x and (y + 2) are from 1 to about 10
A)) and R₂If R is₁Same as
Divalent group. In a particularly preferred embodiment, Ht is N
H or S; M₁And M₂Is H, Li or Na
Yes; X is CO₂Or SO₃And R₁And R₂Is
Linear alkyl having 2 to about 4 carbon atoms;
The replaced monomer unit is -R₁-X-M₁Group or -R₂−
X-M₂The group is mono- or disubstituted. The zwitterionic form of the polymer is "dedoped"
To do so, the opposite direction from using the charge for doping
(Instead, consider a mild reducing agent
May be used as described). M₁Or M₂The polymer in
Move to X⁻Neutralizes anions. In this way,
Process is as fast as the doping process
No. Schemes I and II use the above poly
Oxidation and reduction of mer (showing specific examples of monosubstitution)
That is, the conversion between the electrically neutral form and the conductive zwitterionic form.
Represent the transfer: Embedded image Embedded image X is CO₂Where the electrochemical transition is at pH 1
Strongly dependent on pH in the range of 〜6 (X = CO₂Passing
And M₁PKa when = H is about 5). On the other hand, if X is
SO₃Where the electrochemical reaction is about 1-14
PH independent over a much wider pH range (II
X = SO₃And M₂= Ka when p = about 1
). That is, the sulfonic acid derivative is substantially arbitrary
At pH, the carboxylic acid derivative is charged with low hydrogen
It is charged only at the ON concentration. So the polymer solution
By changing the pH of the solution, the conductivity of the carboxylic acid derivative
Adjusting the conductivity corresponds to the conductivity of the sulfonic acid derivative
Is much easier than adjusting That is,
The choice of the Rönsted acid component depends on the particular application. these
Has a conductivity of at least about
1S / cm (referenceExample 14), and typically
The chain length is on the order of hundreds of monomer units. Typically a chain
Has a length in the range of about 100 to about 500 monomer units.
And a high molecular weight is preferred. In the practice of the present invention, the Bronsted acid
Groups into the polymer to make it self-doping
You. Polymerization after introducing Bronsted acid groups into the polymer
Alternatively, they may be copolymerized. In addition, the unsubstituted mono of the formula II
Make a polymer or copolymer of mer
Ted acid groups may be introduced into the main chain of the polymer. [0020] The Bronsted acid group is added to a polymer or polymer.
It is within the skill of the art to covalently attach
You. For example, Journal of American Chemical
・ Socialie, 70, 1556 (1948)
Teru. As an example, as shown in Scheme III, N-bro
Monomers or polysynthesis using Mostacinimide (NBS)
Linking an alkyl group on the mer backbone to an alkyl halide
Can be: Embedded image The halide is then replaced with sodium cyanide / hydroxide.
Hydrolysis after treatment with thorium or sodium sulfite
To form carboxylic acid or sulfonic acid, respectively. This anti
The reaction is shown in Scheme IV: Embedded image Shows the addition of a Bronsted acid group having an ether linkage group
Another example is shown in Scheme V: Embedded imageVarious monomers useful in the practice of the present invention
The synthesis ofreferenceExamples 1 to 12 are shown. In the present invention
The polymer used is, for example, Sy
nth. Metals 9, 381 (1984)
By the electrochemical method described in
(Wudl) et al. Org. Chem. 49 volumes, 33
82 (1984), Udol et al., Mol. Crys
t. Liq. Cryst. 118, 199 (198
5 years), Synth. Metal
s. 9, 77 (1984)
Can be synthesized by simple chemical coupling methods
You. By electrochemical means (ie, the anode
Above) When synthesizing, directly create a polymeric zwitterion. Conversion
The use of a chemical coupling method results in a neutral polymer.
A preferred synthetic method is an electrochemical method, as described below.
This is exemplified by the production of a heteroheterocyclic species. Monomer
-III: Embedded image (Where Ht, Y₁, R₁, X and M₁Is as described above
A solution containing an electrolyte such as tetrabuty
Luammonium perchlorate or tetrabutylammonium
A suitable solvent, such as
For example, acetonitrile (a sulfonic acid derivative, that is, X =
SO₃Is particularly suitable when is given in). White
Gold, nickel, indium tin oxide (ITO)
Prepare a working electrode of covered glass or other suitable material,
Platinum or aluminum, preferably platinum counter electrode (negative electrode)
Pole). About 0.5-5mA / cm²Current
To the desired degree of polymerization (or the polymer film on the substrate).
Run for several minutes to several hours, depending on the thickness of the
U. The temperature of the polymerization reaction should be between about -30 ° C and about 25 ° C.
But preferably at about 5 ° C to about 25 ° C.
You. The zwitterionic poly thus prepared
Reduction of a mer to a neutral, undoped form
By reduction or any mild reducing agent, such as acetone
Treatment with methanol or sodium iodide in
be able to. This process ensures that the reaction is complete.
Should be allowed to proceed for at least a few hours. Sur
Phonic acid monomer (X = SO₃) Is an alkyl having 1 to 2 carbon atoms
Polymerized as an ester such as a methyl ester (three
ConsiderationSee Examples 14 and 15), while the carboxylic acid derivatives
(X = CO₂) May be prepared in acid form. Sulfonic acid
After polymerizing the derivative, treatment with sodium iodide etc.
The methyl group is removed in the process. The poly represented by the formulas II and IIa
Aniline should be synthesized electrochemically as described above
Or phenylenediamine appropriately substituted
It can be made by reacting with rohexanedione. following
Scheme VI illustrates this latter synthesis: Embedded image(R₂And M₂Is as defined above) I or I
The copolymerization of the different types of monomers of the formula I
This can be done according to the same procedure described above. Preferred
In certain embodiments, most of the monomers are reduced as described above.
At least one -R₁-X-M₁Group or -R₂-X-M₂
With a group. The composite of the polymers of the formulas I and II is treated with water
Soluble polymers such as polyvinyl alcohol (referenceExample 1
7) or with a polysaccharide. The present invention
The self-doping polymer used in
Can be quite brittle,
The use of composite materials to increase flexibility and brittleness
A reduced polymer is obtained. One or more additional
Contains a certain amount of water-soluble polymerIIGiven by formula
Casting films from aqueous polymer solutions
Can be. The key criterion in this process is
By dissolving two or more of these polymers in water
So the only practical limit for additional polymers
Is that the polymer is water-soluble. The self-doping type conductive polymer of the present invention
By removing water from the liquid by drying or other means,
A self-doping conductive polymer is obtained. The poly of the present invention
Self-doping type conductive polymer obtained from polymer solution
A foreign source used as an electrode in an electrochemical cell
Over conventional conductive polymers that require punt ions
Provide unique advantages. Counterion shared by polymer
Due to the coupling, the cell capacity depends on the concentration and solubility of the electrolyte.
Not limited by. This means that in the optimized cell
The total amount of electrolytes and solvents can be significantly reduced,
The energy density of the resulting cell can be increased
Wear. Novel self-doping mechanism provides ion transport
Kinetics that can be easily obtained are equivalent to rapid charging and discharging.
And faster electrochromic switching.
You. Electrodes made using the polymer of the present invention
Or from conventional polymers coated with these polymers
Can be made from a substrate. Conventional substrates include, for example,
Glass, platinum, nickel coated with didium tin oxide
Including palladium, palladium or any other suitable anode material
be able to. When used as an electrode, inside the polymer
Self-doping results in a transition represented by Scheme I
You. The self obtained from the aqueous polymer solution of the present invention
Doped conductive polymers also provide long-term performance.
A variety of punt ions that are not required to be constantly mobile
Migrating dopants for use in device applications
Offers unique advantages over conventional conductive polymers used
I do. Examples of such applications are Schottky diodes,
Including processing of field effect transistors and the like. Self-doping
In typed polymers, dopant ions are shared by the polymer chains
Because of the bonding, ion diffusion problems (eg, contact
Near the junction or interface) is resolved. Change
In the conductive polymer aqueous solution of the present invention, the medium is water.
From the disadvantages associated with the use of organic solvents, such as toxicity and pollution
Etc. can be eliminated and expensive organic solvents can be used.
Because it is not used and there is no need to take toxicity and pollution measures,
It can be manufactured at low cost. In addition, the self-daughter of the present invention
Of conductive polymer and other water-soluble polymer
Reduces the brittleness and increases the flexibility of conductive polymers
Has the advantage of being able to cast film, for example
You. The invention will be described with respect to certain preferred embodiments.
However, the above description and the following examples are set forth in the appended claims.
It is intended to limit the scope of the invention described in the examples.
Not. Other aspects, advantages and variations within the scope of the invention.
Further modifications will be apparent to those skilled in the art to which the invention pertains. [0029] 【Example】Reference Example 1 Synthesis of 2- (3-thienyl) -ethylmethanesulfonate
Success Add 10 ml of freshly distilled dry pyridine with 2- (3-thi
Nyl) ethanol (manufactured by Aldrich Chemical Company) 5.0
g (3.9 × 10^-2Mol) in a solution of
At 〜１０10 ° C., 3.62 ml of methanesulfonyl chloride are added.
A solution dissolved in 20 ml of pyridine was added. Addition is about
Performed gradually over 15-20 minutes. Bring the reaction mixture to room temperature
And then stir overnight, then separate water and ether
It was quenched by pouring into a dough. The layers are separated and the aqueous phase
Extracted three times with tell. Organic extracts are combined and 10% hydrochloric acid
Once, then with water and Na₂SO₄Dry
did. The solvent was evaporated and 5.3 g of light brown oil (65 yield)
%). Tlc (CHCl₃) Is a single spot
showed that. Perform chromatographic purification on silica gel
To give a light yellow oil. NMR (CDCl₃, For TMS
δ): 2.9 s, 3H; 3.1 t, 2H; 4.4 t, 2
H; 7.0-7.4 m, 3H. IR (neat, νcm^-1): 3100w, 2930
w, 2920w, 1415w, 1355s, 1335
s, 1245w, 1173s, 1080w, 1055
w, 970s, 955s, 903m, 850m, 825
w, 795s, 775s, 740w. Mass spectrum (MS) 206.0. [0031]Reference example 2 Synthesis of 2- (3-thienyl) -ethyl iodide The above methanesulfonate (5.3 g, 2.6 × 10
^-2Mol) was converted to a solution of 7.7 g of NaI in 30 ml of acetone.
And reacted at room temperature for 24 hours. Precipitated CH₃S
O₃Na was filtered off. Pour the filtrate into water and add chloroform
And the organic phase is extracted with MgSO₄And dried. Steam solvent
Emission gave a light brown oil which was chromatographed.
Purified to give 5.05 g of light yellow oil (82.5% yield)
Was. NMR and IR spectra were as follows. NMR (CDCl₃, For TMS
δ): 3.2 m, 4H; 7.0-7.4 m, 3H. IR (KBr, νcm^-1): 3100m, 2960
s, 2920s, 2850w, 1760w, 1565
w, 1535w, 1450m, 1428s, 1415
s, 1390w, 1328w, 1305w, 1255
s, 1222m, 1170s, 1152m, 1100
w, 1080m, 1020w, 940m, 900w, 8
57s, 840s, 810w, 770s, 695s, 6
33m. MS 238. [0033]Reference Example 3 Combination of sodium 2- (3-thienyl) ethanesulfonate
Success Na₂SO₃5.347 g (4.2 × 10^-2Mole)
5.05 g of the above iodide was added to 10 ml of the aqueous solution
The reaction mixture was heated to 70 ° C. for 45 hours. Get
The mixture was evaporated to dryness, washed with chloroform and dried.
The reaction iodide (0.45 g) was removed.
Washing with sodium chloride removed the sodium iodide. Remaining solid
The product is contaminated with excess sodium sulfite with the desired sodium salt.
This is a dyed mixture that can be used in the next step without further purification.
Used as appropriate. The NMR and IR spectra are as follows:
Was. NMR (D₂O, TMS propane sulfone
Δ) for sheet: 3.1 s, 4H; 7.0-7.4.
m, 3H; IR (KBr, νcm^-1, Na₂SO₃Peak is the difference
): 1272m, 1242s, 1210s, 1177
s, 1120m, 1056s, 760m, 678w. [0035]Reference example 4 Synthesis of 2- (3-thienyl) ethanesulfonyl chloride reference To a stirred suspension of 2 g of the salt mixture prepared in Example 3,
2 ml of distilled thionyl chloride were added dropwise. Mix for 30 minutes
While stirring. Filter the white solid obtained by quenching with ice water,
Recrystallized from chloroform-hexane to give 800 mg of white
Color crystals were obtained. Melting point was 57-58 ° C. NMR and
And the IR spectrum were as follows. NMR (CDCl₃, For TMS
δ): 3.4 m, 2H; 3.9 m, 2H;
4m, 3H. IR (KBr, νcm^-1): 3100w, 2980
w, 2960w, 2930w, 1455w, 1412
w, 1358s, 1278w, 1260w, 1225
w, 1165s, 1075w, 935w, 865m, 8
30m, 790s, 770w, 750m, 678s, 6
25m. Elemental analysis was as follows. Calculated values: C34.20, H3.35, Cl16.83, S30.43   C₆H₇ClO₂S₂ Obtained: C34.38, H3.32, Cl16.69, S30.24 [0037]Reference Example 5 Methyl 2- (3-thienyl) -ethanesulfonate (separate
Name: Thiophene-3- (2-ethanesulfonic acid methyl ester)
Le)) The above acid chloride (abovereferenceProduced according to Example 4)
105 mg (5 × 10^-4Mol) 1.5 ml of fresh
Add to distilled methanol (from molecular sieve)
1.74 ml of N, N-diisopropane at room temperature
Ropylethylamine was added. Reaction mixture for 12 hours
Stir and then transfer to a separatory funnel containing a dilute aqueous hydrochloric acid solution.
And extracted three times with chloroform. Combine the organic phases and add N
a₂SO₄, And the solvent was distilled off to obtain a light brown oil.
This is chromatographed on silica gel using chloroform as eluent.
Purified by chromatography. The resulting colorless solid (yield 90
%) Had a melting point of 27-28.5C. IR, UV, N
The MR spectrum was as follows. IR (neat film, νcm^-1): 3
100w, 2960w, 2930w, 1450m, 14
15w, 1355s, 1250w, 1165s, 985
s, 840w, 820w, 780m, 630w, 615
w. UV-visible [λ max, MeOH, nm (ε)]: 2
34 (6 × 10³). NMR (CDCl₃, Δ for TMS): 7.42-
7.22q, 1H; 7.18 to 6.80m, 2H;
85s, 3H; 3.6-2.9m, 4H. Elemental analysis was as follows. Calculated values: C 40.76, H 4.89, S 31.08   C₇H₁₀O₃S₂ Obtained values: C 40.90, H 4.84, S 30.92 [0039]Reference example 6 2-carboxyethyl-4- (3-thienyl) butanoic acid
Synthesis of ethyl 11.2 g (69.9) in 60 ml of freshly distilled DMF
(4 mmol) diethyl malonate
2.85 g of a 60% oil dispersion of NaH (69.94
Lmol) was added. After stirring for 30 minutes, 20ml
15.86 g (66.61 mmol) of 2 in DMF
-(3-thienyl) ethyl iodide (as described above)
What was manufactured) was dropped over 10 minutes
Was added. Stir the reaction mixture for 1 hour at room temperature
And then heated to 140 ° C. for 4 hours. After cooling,
The reaction product was poured into ice-cooled diluted hydrochloric acid, and then extracted six times with ether.
Issued. The organic phases are combined, washed with water and Na₂SO₄Dry
And evaporated to give a brown oil. Silica gel (chloropho
(Hexane 50% in rum))
However, a colorless oil was obtained with a yield of 98%. Elemental analysis results
Was as follows. In addition, NMR and IR spectra
Show. [0040] Calculated values: C 57.76, H 6.71, S 11.86   C₁₃H₁₈O₄S Found: C, 57.65; H, 6.76; S, 11.77. NMR (CDCl₃, Δ for TMS): 7.40-
7.20t, 1H; 7.10 to 6.86d, 2H;
18q, 4H; 3.33t, 1H; 2.97 to 1.97
m, 4H; 1.23t, 6H. IR (neat film, νcm^−l): 2980w, 1
730s, 1450w, 1370w, 775w. [0041]Reference Example 7 Synthesis of 2-carboxy-4- (3-thienyl) butanoic acid 1.4 g (24.96 mmol) of potassium hydroxide
Solution dissolved in 7.0 ml of 50% ethanol aqueous solution
ToreferenceThe diester prepared in Example 6 (765 mg, 2.
83 mmol) was added. The resulting reaction is left at room temperature for 2 hours.
Stir and then reflux overnight. The resulting mixture is washed with water
Pour into −10% HCl, then extract with ether for 3 hours.
Performed times. Combine the organic phases and add Na₂SO₄Dry with
A white solid was obtained with a yield of 90%. This is chloroform-
Recrystallization from hexane gave colorless needle crystals. The following characteristics
It had. Melting point: 118-119 ° C. NMR (DMSO / d6, δ for TMS): 12.
60, 2H; 7.53-6.80 m, 3H; 3.20
t, 1H; 2.60t, 2H; 1.99q, 2H. IR (KBr, νcm^-1): 2900w, 1710
s, 1410w, 1260w, 925w, 780s. Elemental analysis values were as follows. Calculated values: C 56.45, H 5.92, S 18.83   C₉H₁₀O₄S Found: C, 56.39; H, 5.92; S, 18.67. [0043]Reference Example 8 Synthesis of 4- (3-thienyl) butyl methanesulfonate 4- (3-thienyl) butanoic acid (CA69: 18565)
x, 72: 112265k)referenceCal prepared in Example 7
Prepared by standard thermal decarboxylation of boric acid.
This compound is also reduced using standard methods to give 4-
(3-thienyl) butanol (CA70: 68035)
r, 72: 112265k). 1.05 g (6.
7 × 10^-3Mol) 4- (3-thienyl) butanol
Was dissolved in 25 ml of freshly distilled dry pyridine.
0.85 g of methanesulfonyl chloride at 25 ° C.
Was added. This addition is made gradually over several minutes.
Was. The reaction mixture was stirred at room temperature for 6 hours, then water-H
Pour into a separatory funnel containing Cl and ether and quench
did. Separate the organic phase and extract the aqueous phase once with 10% hydrochloric acid
And extracted with water, Na₂SO₄And dried. Solvent evaporation
Gave 1.51 g of a light brown oil (95% yield).
tlc (CHCl₃) Indicates a single spot. Analytical
The results were as follows. [0044] Calculated values: C 46.13, H 6.02, S 27.36   C₉H₁₄O₃S₂ Found: C, 45.92; H, 5.94; S, 27.15. NMR (CDCl₃, Δ for TMS): 2.0-
1.5 brs, 4H; 2.67 brt, 2H; 2.97
s, 3H; 4.22t, 2H; 7.07 to 6.80d,
2H: 7.37 to 7.13, 1H. [0045]Reference Example 9 Synthesis of 4- (3-thienyl) butyl iodide reference The above methanesulfonate prepared in Example 8 (1.5
1 g, 6.4 × 10^{− 3}Mol) with 1.93 g of NaI
Add to the solution in 14 ml of acetone and overnight at room temperature
Reacted. The reaction mixture was heated to reflux for 5 hours.
Precipitated CH₃SO₃Na was filtered off. Inject the filtrate into the water
And extracted with chloroform.₄Dry
did. Evaporation of the solvent gave a light brown oil which was chromatographed.
Raffy purification (silica gel, 60% hexane in chloroform)
Then, 1.34 g of a colorless oil (78% yield) was obtained.
The measured values were as follows. NMR (CDCl₃, For TMS
δ): 1.53 to 2.20 m, 4H; 2.64 t, 2
H; 3.17t, 2H; 6.83 to 7.10d, 2H;
7.13-7.37t, 1H. IR (KBr, νcm^−l): 2960s, 2905
s, 2840s, 1760w, 1565w, 1535
w, 1450s, 1428s, 1415s, 1190
s, 750s, 695m, 633m. MS 266.0. Elemental analysis was as follows. Calculated values: C 36.10, H 4.17, I 47.68, S 12.05   C₈H₁₁IS Found: C 37.68, H 4.35, I 45.24, S 12.00. [0047]Reference example 10 Synthesis of sodium 4- (3-thienyl) butanesulfonate
Success 1.271 g (1 × 10^-2Mol) Na₂SO₃2
ml aqueous solution,referenceThe above iodide prepared in Example 9
1.34 g were added. Heat reaction mixture for 18 hours
Shed. The resulting mixture was evaporated to dryness, then chloro
Wash with form to remove unreacted iodide,
Washing with sodium chloride removed the sodium iodide. Remaining solid
The desired sodium salt is contaminated with excess sodium sulfite.
This is a dyed mixture and can be used without further purification.
Used in the process. The measured values were as follows. NMR (D₂O, TMS propane sulfone
.Delta.): 1.53 to 1.97 m, 4H;
47 to 3.13 m, 4H; 6.97 to 7.20 d, 2
H: 7.30 to 7.50q, 1H. IR (KBr, νcm^-1, Na₂SO₃Peak difference
At): 2905w, 1280m, 1210s, 1180
s, 1242m, 1210s, 1180s, 1130
s, 1060s, 970s, 770s, 690w, 63
0s, 605s. [0049]Reference Example 11 4- (3-thienyl) butanesulfonyl chloride The above salt mixture (reference1.00 g to 10 ml from Example 10)
1.43 was added to the stirring liquid suspended in freshly distilled DMS.
g of distilled thionyl chloride was added dropwise. Shake the mixture for 3 hours
mixed. The solution quenched with ice water was extracted twice with ether.
The organic phase is₂SO₄Dry with light yellow oil 56
6 mg was isolated and the oil was chromatographed (silica
Gel and chloroform)
(Mp 26-27 ° C). NMR etc. are as follows
there were. NMR (CDCl₃, For TMS
δ): 1.45 to 2.38 m, 4H; 2.72 t, 2
H; 3.65t, 2H; 6.78 to 7.12d, 2H;
7.18-7.42, 1H. IR (neat film, νcm^-1): 3120 w, 2
920s, 2870m, 1465m, 1370s, 12
78w, 1260w, 1160s, 1075w, 935
w, 850w, 830m, 776s, 680m, 625
w, 585s, 535s, 510s. Elemental analysis was as follows. Calculated values: C 40.25, H 4.64, Cl 14.85, S 26.86   C₈H₁₁ClO₂S₂ Found: C, 40.23; H, 4.69; Cl, 14.94; S, 26.68. [0051]Reference Example 12 Methyl 4- (3-thienyl) butanesulfonate (Also known as:
Thiophene-3- (methyl 4-butanesulfonate))
Synthesis reference 362 mg of the above acid chloride prepared in Example 11 (1.
5 × 10^-3Mole) of 6 ml of freshly distilled (Molecular)
Stirred solution dissolved in methanol
, 392 mg of N, N-diisopropylethylamine
Was added at room temperature. Stir the reaction mixture for 2 hours, then
Transfer to a separatory funnel containing dilute aqueous HCl, and add chloroform
Extraction three times. The organic phases are combined and Na₂SO₄so
After drying, the solvent was evaporated to give a light brown oil. this
Oil using hexane 40% chloroform as eluent
And purified by chromatography on silica gel. Get
The resulting colorless oil (84% yield) had the following properties: Elemental analysis values: Calculated values: C 46.13, H 6.02, S 27.36   C₉H₁₄S₂O₃ Found: C, 45.97; H, 5.98; S, 27.28. IR (neat film, νcm^-1): 3100w, 2
970m, 2860w, 1460m, 1410w, 13
50s, 1250w, 1160s, 982s, 830
m, 800m, 770s, 710w, 690w, 630
w, 613w, 570m. UV-vis [λ max, MeOH, nm (ε)]:
220 (6.6 × 10³). NMR (CDCl₃, Δ for TMS): 7.33-
7.13 (t, 1H), 7.03 to 6.77 (d, 2
H), 3.83 (s, 3H), 3.09 (t, 2H),
2.67 (t, 2H), 2.2-1.5 (m, 4H). [0053]Reference Example 13 Polymerization of thiophene-3-acetic acid Embedded image "Synth. Metals" by S. Hotta and others (existing
Acetonitrile according to the electrochemical polymerization method described in
With LiClO as the solvent₄Chamber as an electrolyte
Polymerizes the thiophene-3-acetic acid of formula IV at elevated temperatures
Was. A blue-black film formed. This is because of the formula Ia (Y₁
= H, R₁= -CH₂−, Ht = S, X = CO₂) Both
5 illustrates the formation of a zwitterionic polymer. This polymer film
When the film is electrochemically cycled,
Was observed to turn yellowish brown. This is because the polymer
Reduction from zwitterionic form to neutral form of formula I
Is shown. The infrared spectrum was consistent with the proposed structure. [0054]Reference Example 14 Poly (thiophene-3- (2-ethanesulfonic acid) nato
Lium salt) Thiophene-3- (methyl 2-ethanesulfonate) (formula
V) was prepared in the manner already described. Embedded image The polymerization of this monomer is carried out at a point where the polymerization temperature is maintained at -27 ° C.
ExceptreferenceThe same procedure as in Example 13 was followed. The resulting polymer
-("P3-ETS methyl", formula VI) in acetone
Treated with sodium iodide to give methyl
The corresponding sodium salt of the polymer
Poly (thiophen-3- (2-ethanesulfonic acid) na
Thorium salt) (“P3-ETSNa”) (Formula VII)
Sufficient yield (about 98%) was obtained. Embedded image Embedded image The above polymer methyl ester and polymer sodium
Salt is infrared and visible ultraviolet absorption spectrometer and elemental analysis
(See FIGS. 1 and 2). sodium
Salts are found to dissolve in water in all proportions,
Can be cast into a film
I understood. The electrochemical cell is constructed in glass, and
In-situ light doping and charge storage
Proven by electrochemical spectrometer. Cell is ITO coated
Of the above polymer on a cover glass (serving as an anode)
Film formed, platinum counter electrode (cathode), silver
/ Silver chloride reference electrode and tetrabutyl ammonium par
It consisted of a chlorate electrolyte. FIG.
P3-ETSN taken for cell charged to open circuit voltage
2 shows a series of visible and near-infrared spectra of FIG. π-π
^*As the transition is exhausted, two characteristics of oscillator strength
In terms of transitioning to the near infrared band, the results obtained are
Typical for conductive polymers. 5 is acceptable
Demonstrating both reverse charge accumulation and electrochromism
I have. The electric conductivity was measured by using a glass having all contacts pre-attached.
A polymer film cast from water on a substrate
Was measured by a standard four-probe technique using bromine
Upon exposure to steam, the electrical conductivity of P3-ETSNa is about
It increased to 1 S / cm. [0057]Reference Example 15 Poly (thiophen-3- (4-butanesulfonic acid) nato
Lium salt) Thiophene-3- (methyl 4-butanesulfonate) (formula
VIII) was prepared in the manner already described. Embedded image Polymerization isreferenceSame conditions and method as described in Examples 13 and 14.
Performed by law. The obtained polymer (“P3-BTS methyl
IX, Formula IX treated with sodium iodide in acetone
However, poly (thiophene-3- (4-butane) has a sufficient yield.
Tansulfonic acid) sodium salt) (“P3-BTSN
a ", formula X). Embedded image Embedded image Polymerized methyl esters (Formula IX) and the corresponding sodium
Salt (Formula X) is spectroscopically measured (IR, UV visible) and elemental analysis
The characteristics were examined by using. Sodium salt in water in all proportions
Film form by dissolving and casting from aqueous solution
It made it possible. The electrochemical cellreferenceConstructed according to Example 14
And through in-situ (In Situ) photoelectrochemical spectroscopy
Electrochemical doping and charge accumulation have been demonstrated. FIG.
7 is the sequence of P3-BTSNa and P3-BTS methyl
A series taken on cells charged to increasing open circuit voltage
1 shows a visible and near-infrared spectrum.referenceAs in Example 14,
π-π^*The transition is exhausted, and the oscillator strength is increased by two
Shifts to the infrared band.
It turned out to be typical.referenceSame as Example 14
6 and 7 show the results of reversible charge storage and electrolysis.
Demonstrate both chromism. [0059]Reference Example 16 Of poly (thiophen-3- (2-ethanesulfonic acid))
Manufacturing and analysis The thiophene-3- (2-ethanesulfo is obtained by the method described above.
Acid) (formula I) (Ht = S, Y₁
= H, R₁= -CH₂CH₂−, X = SO₃, M₁= N
a) is prepared and dissolved in water to form a cation exchange resin in acidic form
Chromatographic separation of poly (thiophene)
Preparation of an aqueous solution of ene-3- (2-ethanesulfonic acid))
did. Atomic absorption analysis of dark reddish brown effluent revealed hydrogen
It was found that it was completely replaced by thorium. FIG. 8
Cyclic voltan performed on polymer film
The results of the metrology are shown (“P3-ETSH” / ITO gas
Glass working electrode, platinum counter electrode, silver in acetonitrile / chloride
Silver reference electrode, fluoboric acid-trifluoroacetic acid electrolysis
quality). The figure shows that P3-ETSH was prepared using silver /
Cycle between + 0.1V and + 1.2V for silver chloride
Indicates that the polymer is electrochemically tough.
ing. The diagram shows two closely spaced oxidation waves
The first one corresponds to the change from orange to green
doing. The polymer can cycle and reach 100 mV / sec.
Corresponding color change without noticeable change in stability
Was observed. The electrochemical cell is constructed in glass,
(In Situ) Electrification by photoelectrochemical spectroscopy
Chemical doping and charge accumulation were established. Cell is ITO
Polymer film on glass (anode), platinum counter electrode
(Cathode), silver / silver chloride reference electrode in acetonitrile,
Consisting of fluorinated boric acid-trifluoroacetic acid electrolyte
there were. FIG. 9 shows a cell charged to a higher open circuit voltage.
2 shows the visible and near-infrared spectrum of P3-ETSH measured by
You. In this case, the polymer is naturally doped in a strong acidic electrolyte.
Was observed. The result in FIG. 9 shows the reversible charge
Demonstrate both accumulation and electrochromism. Short time
Controlling the self-doping level during the balancing circuit
This was achieved by applying a voltage lower than the voltage. [0061]Reference Example 17 Preparation of polymer conjugate Poly (thiophen-3- (2-ethanesulfonic acid))
(Formula I) (Ht = S, Y₁= H, R₁= -CH₂CH₂
−, X = SO₃, M₁= H, "P3-ETSH")three
ConsiderationPrepared according to Example 16, which was prepared as a composite as follows
It was used for. The above compound and polyvinyl alcohol aqueous solution
Mix, cast neutral polymer and dry to form a film
did. Self-sustaining dark orange film (blue-black amphoteric
Excellent charge neutrality unlike ionic polymers)
Has mechanical properties (soft, smooth, flexible)
Chemical doping and undoping.
The method for producing this conductive polymer composite is P3-ETS.
H or any water-soluble polymer associated with P3-BTSH
Can be widely applied to the use of [0062]Reference Example 18 2,5-diethoxycarbonyl-1,4-cyclohexa
Preparation of polymers of Ndion and p-phenylenediamine 8.51 g in 380 ml of freshly distilled butanol
(33.21 mmol) 2,5-diethoxycarboni
-1,4-cyclohexanedione is suspended in the suspension.
3.59 g of p-phenylenediae in 20 ml of butanol
Min was added and then 40 ml of glacial acetic acid
Was added. The resulting mixture was heated to reflux for 36 hours.
And then refluxed by exposure to oxygen for 12 hours, hot filtration
And the solid was washed with ether and placed in a Soxhlet extractor.
And extracted with the following solvent. Chloroform (6 days),
Chlorobenzene (5 days) and ether (4 days).
This treatment gives 8.42 g of dark solids.
Was. Elemental analysis and IR were as follows. [0063] Calculated values: C 65.84, H 6.14, N 8.53   C₁₃H₁₈N₂O₄ Found: C, 65.55; H, 6.21; N, 8.71. IR (KBr, νcm^-1): 3350w, 3240
w, 2980m, 2900w, 1650s, 1600
s, 1510s, 1440m, 1400w, 1220
s, 1090w, 1065s, 820w, 770m, 6
00w, 495w. [0064]Example 1 Polyaniline dicarboxylic acid The above polymer (diester form) is suspended in DMF,
Treated with a 50% (by weight) aqueous solution of sodium oxide. reaction
Heat the mixture to 100 ° C for 48 hours under strict oxygen-free conditions
did. Cool the mixture and pour it into the ice / HCl mixture.
And filtered. Infrared absorption (IR) spec of this product
Torr showed the following intrinsic absorption peaks. 3100 to 290
0br, 1600s, 1500s, 1210s.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an infrared spectrum of poly (methyl thiophen-3- (2-ethanesulfonate)). FIG. 2 is an infrared spectrum of poly (thiophen-3- (2-ethanesulfonic acid) sodium salt). FIG. 3 is an infrared spectrum of poly (methyl thiophen-3- (4-butanesulfonate)). FIG. 4 is an infrared spectrum of poly (thiophene-3- (4-butanesulfonic acid) sodium salt). FIG. 5 shows a series of visible and near infrared spectra of poly (thiophene-3- (2-ethanesulfonic acid) sodium salt). FIG. 6 shows a series of visible and near infrared spectra of poly (thiophene-3- (4-butanesulfonic acid) sodium salt). FIG. 7 shows a series of visible and near-infrared spectra of poly (thiophen-3- (4-butanesulfonate)). FIG. 8 shows the results of cyclic voltammetry performed on films of poly (thiophen-3- (2-ethanesulfonic acid)). FIG. 9 shows a series of visible and near infrared spectra of poly (thiophen-3- (2-ethanesulfonic acid)).

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-39916 (JP, A) JP-A-60-501262 (JP, A) JP-A-1-500835 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) C08G 73/00 C08L 79/00

Claims (1)

(57) [Claims] Po amphoteric ion-shaped structural units under Symbol of structure (IIb)
Self-doping type conductive polymer aqueous solution containing 0.01 to 100 mol% in the limmer main chain : (Wherein Y ₂ , Y ₃ and Y ₄ are independently hydrogen and Selected from the group consisting of, R ₂ is linear or branched in the absent or C1-10 alkylene or ether
Is an alkylene having binding Gomoto, X is ## STR3 ## Or Is). 2. The following structure (II): (Wherein Y ₂ , Y ₃ and Y ₄ are independently hydrogen and —R ₂ —
Selected from the group consisting of X-M _2, R ₂ is alkylene having linear or branched alkylene or <br/> ether formation Gomoto of absent or C1-10, X is [ Formula 6 Or In and, M ₂ is H, Li, method of manufacturing the self-doping type electrically conducting polymer solution of the following, including the step of chemically or electrochemically oxidizing a polymer having a chosen) from the group consisting of Na and K: bottom polymer the serial zwitterionic form the structural units of the structure (IIb) of
-An aqueous solution of a self-doping type conductive polymer containing 0.01 to 100 mol% in the main chain : Wherein Y ₂ , Y ₃ , Y ₄ , R ₂ and X have the same meaning as previously defined.