FR2635907A1 - Conductive polymers derived from aromatic heterocycles substituted by an ether-type group, method for obtaining them, devices containing these polymers, and monomers enabling such polymers to be obtained - Google Patents

Abstract

Electrically conducting polymers containing repeat units derived from 5-membered aromatic heterocyclic monomers substituted, in the position 3 with respect to the heteroatom, by an ether-type substituent linked to the heterocycle via an alkylene radical comprising at least two carbon atoms. The invention also relates to certain monomers enabling the aforementioned conductive polymers to be obtained.

Description

 The present invention relates to electrically conductive polymers derived from aromatic heterocycles substituted by an ether type group.

 It relates more particularly to polymers derived from five-membered aromatic heterocycles containing a hetero atom and substituted in position 3 by a substituent of ether type linked to the heterocycle by an alkylene radical.

 The invention also relates to a process for the manufacture of these polymers.

 It also relates to electroconductive devices containing these polymers.

 Finally, the invention also relates to monomers which can be used for obtaining conductive polymers according to the invention.

 We have already described electrodes obtained by electrochemical polymerization, on a conductive support, of heterocyclic monomers having at least one aromatic heterocycle with 5 catnons, containing a single heteroatom and substituted by at least one group, in particular of the alkyl, alkoxyl or aryl type. , substituted aryl, halogen, cyano, amino or dialkylamino. This monomer can be a derivative substituted in position 3, in position 4 or in position 3 and 4 of pyrrole1 of thiophene or furan, or an indole substituted on the phenyl nucleus by I to 4 groups (patent application FR-A-2527843 ).

 The electrochromic characteristics of polymers derived from these five-membered heterocycles have also been described, in particular those derived from pyrrole, thiophene, 3-methylthiophene, 3,4-dimethylthiophene and 2,2'-dithiophene ( F. Carnier et al, Journal of Electroanalytical Chemistry, 148, 1983, pages 299 to 303).

 Certain electrical applications, such as the production of devices (display screens, switches, memory elements, etc.) based on electrochromism (involving a modification of the light absorption or transmission properties of the material used. , induced by a variation in the applied external voltage), rechargeable battery electrodes, photovoltaic cells, electrochemical cells, etc. require conductive polymers with special properties.

 These particular properties are in particular the most complete electrochemical reversibility and the highest possible stability of the redox cycle between the oxide and reduced forms of the polymer-doping agent system.

 In patent application FR-A-2596566, a family of polymers having, up to a certain degree, the properties mentioned above has been described. These polymers contain recurring units derived from 3-alkylthiophenes, the alkyl substituent of which comprises from six to nine carbon atoms.

 The present invention aims to provide a new family of conductive polymers having the above-mentioned particular properties to an even much higher degree.

 To this end, the invention relates to electrically conductive polymers containing repeating units derived from 5-membered heterocyclic aromatic monomers substituted, in position 3 relative to the heteroatom, by an ether-type substituent linked to the heterocycle by an alkylene radical comprising minus two carbon atoms.

dans laquelle
X représente un atome ou groupement choisi parmi les atomes de
soufre et d'oxygène et le groupe -NR m représente un nombre entier égal ou supérieur à 2 n représente un nombre entier tel que 0 < n # 7 p représente un nombre entier tel que 0 < p C 2 2 la somme de n et de p étant au moins égale à 1.The electrically conductive polymers according to the invention generally derive from heterocyclic aromatic monomers which can be represented by the general formula below

in which
X represents an atom or group chosen from atoms of
sulfur and oxygen and the group -NR m represents an integer equal to or greater than 2 n represents an integer such that 0 <n # 7 p represents an integer such that 0 <p C 2 2 the sum of n and of p being at least equal to 1.

 The polymers according to the invention can therefore be derived from thiophene, furan and pyrrole substituted in position 3.

 The substituent is an ether group; this group, which can comprise, as shown in formula (I), one to eight ether functions, and preferably two or three ether functions, separated by ethylene radicals, is linked to the heterocycle by an alkylene radical comprising at least two carbon atoms, preferably an ethylene or trimethylene radical.

 As examples of polymers derived from monomers corresponding to general formula (I), mention may be made of polymers derived from monomers whose substituent comprises an ether function, such as 2'-methoxy- and 2'-ethoxr ethyl- 3-thiophene, 2'-methoxy- and 2'-ethoxy-ethyl-3-furan and 2'-methoxy- and 2'-ethoxy-ethyl-3-pyrrole, for example; polymers derived from monomers whose substituent comprises two ether functions, such as (dioxa-3 ', 6'-heptyl) - and (dioxa-3', 6'-octyl) -3-thiophene, (dioxa-3 ', 6'-heptyl) - and (dioxa-3', 6'-octyl) -3-furan and the (dioxa-3 ', 61-heptyl) and (dioxa-3', 6'-octyl) -3 -pyrrole, for example; polymers derived from monomers whose substituent comprises more than two ether functions, such as (trioxa-3 ', 6', 9'-decyl) -3-thiophene, -3-furan and -3-pyrrole and the (octaoxa -4 ', 7', 10 ', 13', 16 ', 19', 22 ', 25'-hexadodecyl) -3-thiophene, -3-furan and -3-pyrrole, for example.

 Among all the polymers mentioned above, the polymers derived from the 3-substituted thiophene and whose substituent comprises two ether functions are preferred, that is to say the polymers derived from the monomer of formula (I) in which X is a sulfur atom, m is 2 or 3, n is 1 and p is 1 or 0.

A very particularly preferred compound, in particular because it leads to polymers exhibiting exceptional reversibility properties of the oxidation-reduction cycle is (dioxa-3 ', 6'-heptyl) -3-thiophene (DHT) (including the polymer is hereinafter referred to as "PDHT" for simplicity).

dans laquelle m' représente les nombres 2 ou 3 p' représente les nombres 0 ou 1
Le monomère tout particulièrement préféré de cette catégorie est le composé pour lequel m' vaut 2 et p' vaut 0 c-à-d le (dioxa-3',6'-heptyl)-3-thiophène. Another object of the invention consists of chemical compounds which can be used as monomers, making it possible in particular to obtain such polymers derived from thiophene, substituted in position 3 and the substituent of which comprises two ether functions, chosen from the monomers of formula (I) for which m is 2 or 3, n is 1 and p is 1 or O. Such monomers can be represented by the general formula (II) below

in which m 'represents the numbers 2 or 3 p' represents the numbers 0 or 1
The most particularly preferred monomer in this category is the compound for which m 'is 2 and p' is 0, ie (dioxa-3 ', 6'-heptyl) -3-thiophene.

 The monomers which can be used to manufacture the polymers according to the invention can be synthesized according to known methods, for example by reaction of (3-thienyl) -, (3-furanyl) - and (3-pyrrolo) -2'ethanol or -3 propanol-1 with the appropriate oxyalkyl halide. Thus, for example, DHT is prepared by reacting (3-thienyl) 2'-ethanol with (chloro-2-ethyl) methyl ether in tetrahydrofuran in the presence of sodium hydride.

The polymers according to the invention can be prepared chemically, in the presence of oxidants such as
FeCl3, for example or electrochemically. Preferably, the process is carried out by electrochemical polymerization, generally in an electrolysis cell, by anodic oxidation of the monomer in a polar solvent and in the presence of suitable electrolytes according to conventional techniques (see for example French patent application FR- A-2527843 and F. Garnier et al., Op. Cit.).

 According to these techniques, the concentration of monomers is generally between 10-3 and I mole per liter of solvent.

 As solvents, polar solvents are preferably used which have dissolving properties both with respect to the monomer and the electrolyte chosen and which are stable in the field of applied potentials. Examples of solvents which can be used are acetonitrile, tetrahydrofuran, methylene chloride, nitrobenzene and propylene carbonate.

 The electrolytes are generally chosen from conductive salts of formula C + A- in which d is a cation and in which A is an anion.

 The cation C + is preferably chosen from alkaline ions, the R4N + and R4P + ions (R being an alkyl radical, such as the ethyl and butyl radicals for example).

 The anion A is preferably chosen from the ions C104, AsF6, SbF6, S042-, C6H5C00 #, C6115S03, BF4, PF6 and CFSSO.

 Typical electrolytes are, for example, fluorophosphates, such as tetrabutylammonium hexafluorophosphate, fluoroborates, such as tetraethylammonium tetrafluoroborate and perchlorates, such as lithium perchlorate and tetrabutylammonium perchlorate.

 The electrolyte concentration is generally between 10-3 and 1 mole per liter of solvent.

 The electrochemical cell within which the polymerization of the monomers according to the invention can take place can operate under potentiostatic or galvanostatic conditions.

 In the first case (potentiostatic control), the cell comprises, in addition to the external current source, three electrodes including a reference electrode for controlling the potential.

 During electrolysis, a layer of polymer is deposited on the conductive element used as the anode of the electrolysis cell. This anode can be made of a noble metal, such as gold or platinum, or of another metal, such as copper, gold or platinum, titanium, nickel or of a conductive glass (tin oxide, indium oxides - tin). After the electrolysis, there is therefore in fact an electrode constituted by a conductive body coated with a polymer film adhering thereto and which contains a certain proportion of the anion originating from the electrolyte. The polymer and the anion thus form a charge transfer complex. The chemical composition of the polymer film can be represented by the empirical formula (M + Ay #) n where M + represents the monomer, A anion or counterion , y the proportion of anion in the polymer expressed per mono unit is lacking (that is to say the doping rate) which, in the case of the polymers of the invention can reach the value of 0.5, and n the degree of polymerization generally impossible to easily determine, given the insoluble nature of the polymer.

 Since the electrochemical polymerization of the monomer takes place on the anode of the electrolysis cell, an electrode covered with a polymer doped with cations cannot be obtained directly.

 To obtain such a cathode, it is possible to use the anode obtained previously and to make it undergo a double reduction. A first electrochemical reduction is possible just after the polymerization by leaving the anode in the electrolysis cell and causing the discharge of the cell. This discharge causes the polymer-doping anions to be extracted.

A second reduction can then be carried out under an inert atmosphere, either chemically or electrochemically.

The chemical route consists in immersing the polymer in a solution containing the desired cations. Thus, to obtain a polymer doped for example with the cations Li +, Na + or (n-type doping to which the polymers according to the invention, especially PDHT, lend themselves particularly well), one can use for example a solution of Naphthalene lithium, Naphthalene sodium or Naphthalene potassium in tetrahydrofuran. your electrochemical path generally consists in placing the electrode as a cathode in an electrolysis cell containing the desired cations in solution. The cations can be, for example, alkaline ions such as those mentioned above, preferably the Li + or K +, or complex ions such as (Bu) 4N + or (Et) 4N + from an electrolyte (preferably Licol04, KPF6, (Bu) 4NC104 and (Et) 4NC104) in solution in a solvent such as acetonitrile, tetrahydrofuran or propylene carbonate. The concentration of electrolyte in the solution is generally between and 1 mole per 1 liter of solvent.

The conductive polymers according to the invention exhibit a set of quite remarkable properties which are mainly - exceptional reversibility and stability of the cycle
redox between their oxidized and reduced forms
thus, in particular, for the preferred of these polymers, the
PDHT, the stability of the redox cycle is such that it
can undergo up to 0.5.107 cycles while still retaining
90% of the initial charge - a significant variation in spectral characteristics
obtained with a very low potential variation, which
makes it interesting and economical to use them as
electrochromic material - good electrical conductivity, generally between
and et102 s.cml; ; - significant absorptions in the field of radiation
near infrared and high frequency.

 These remarkable properties of the conductive polymers according to the invention make them particularly usable for the production of electroconductive devices whose operating principle is based on these properties, and which also constitute an object of the present invention.

By way of nonlimiting examples of electroconductive devices containing conductive polymers derived from heterocyclic aromatic monomers substituted according to the invention, mention may be made of - electrochemical energy storage devices, such as
whether or not rechargeable batteries and rechargeable batteries,
of which the anodes (respectively the cathodes) consist
electrodes coated with films of said polymers doped with
anions (respectively cations); - electrochromic devices based on the modification of the
optical spectrum of said polymers according to their electro state
chemical, which manifests during oxidation and
reduction of polymer films deposited on the anodes
(respectively the cathodes) of these devices during the
charge and discharge; as examples of such availability
electrochemical devices, we can cite display screens
(display), optoelectronic devices, memories and
optical switches.

 The invention is illustrated by the following nonlimiting example.

Example
A. Preparation of the monomer
To a solution of 100 mmol of (3-thienyl) -2'-ethanol (supplied by JANSSEN CHEMICA) in 100 ml of tetrahydrofuran is added 110 mmol of NaH at 60 Z in dispersion in oil and 200 mg of an ether crown marketed by ALDRICH under the name 18 C 6. The suspension is maintained for 2 hours at 200C and then added in 15 minutes, 200 mmol of (chloro-2-ethyl) methyl ether sold by ALDRICH and brought to reflux for 8 hours. The suspension brought back to 200C is treated with HCl. The organic phases are washed with a neutrality strip and then evaporated under vacuum. The crude product is purified by chromatography and then distilled under vacuum.

B. Synthesis of the polymer
The synthesis of the polymer is carried out in a thermostatically controlled cell with a compartment containing - 2.10-1 mole of monomer prepared as in A, - 3.10-2 mole of tetrabutylammonium thxafluorophosphate (supplied
by Fluka) - 25 ml of distilled nitrobenzene.

 The polymer deposits are produced at 50C, under an argon atmosphere, after degassing of the solution by bubbling argon.

For the electrochemical characterizations, the polymer is deposited on solid platinum electrodes with a surface of 0.07 and 0.7 cm2 polished between each experiment. The quantities of charges used vary from 20 to 100 mC / cm2, which corresponds to thicknesses between 600 and 3000 A. The cathode consists of a platinum wire and the reference electrode is a saturated calomel electrode.

 The polymer films intended for spectroscopic studies and for conductivity measurements were synthesized under the same conditions, the working electrode consisting of a strip of conductive glass and the cathode of an aluminum plate. Deposits are made under galvanostatic conditions with current densities between 2 and 5 mA / cm2. The spectroelectrochemical characterizations were carried out in a spectrometry cell with a 1 cm optical path equipped with a cathode made up of a platinum wire and a reference electrode made up of a silver wire.

 The polymer films intended for long-term stability tests in redox reversibility were synthesized on a solid platinum electrode of 0.7 cm 2. This electrode is then placed in a cell equipped with a circular counter electrode consisting of a platinum wire and a reference electrode consisting of a silver wire. The cell is equipped with an optical window allowing the measurement of the response time by reflection using a helium-neon laser (\ a 632.8 nm) and a GaAsP photodiode. The redox cycling is carried out in an electrolytic medium consisting of propylene carbonate containing 5.10-1 mole of anhydrous lithium perchlorate.

 The doping tests n were carried out in propylene carbonate containing 5.10-2 mole of tetraethylammonium perchlorate.

The electrochemical properties of the polymers were measured from the cyclic voltammogram recorded using a potentiometer PAR model 173 and from the recorded intensity peaks. your anode wave includes two oxidation peaks 0.4 and 0.8 VESCE (calomel reference electrode). For these two systems the ratio Ipa / IpC between the intensities of oxidation current (Ipa) and of reduction (Ipc ) is about 1
For the first system, the stability of the redox reversibility is, expressed as a percentage of charges still exchanged, after 0.65.106 cycles: 100 Z 1.5.106 cycles: 96 Z 3.25.106 cycles: 92 Z 0.5.107 cycles: 90 Z
The "n" doping of the polymer is evaluated by an observation of a reversible cathode system between -1.7 and -2.2 V / Ag
The optical and spectroscopic characteristics are the high absorption in the red (absorption band at X 1600 nm) of the polymer and the very low absorption beyond 600 nm of the dedoped polymer.

 On the other hand, the doped polymer has a large absorption band in the far red and the near infrared.

 This phenomenon is at the origin of a particular electrochromic behavior. Indeed, when we analyze the variation in the intensity of the reflection of a laser beam (helium-neon: k = 632.8 nm) on a polymer film subjected to potential pulses, we observe two stable states for values of applied potential going up to 0.7 V / Ag while beyond, one obtains only one stable state. This threshold effect phenomenon can be used for optoelectronic applications.

Claims (11)

 1 - Electrically conductive polymers containing repeating units derived from 5-membered aromatic heterocyclic monomers substituted, in position 3 with respect to the heteroatom, by an ether-type substituent linked to the heterocycle by an alkylene radical comprising at least two carbon atoms.  2 - Conductive polymers according to claim 1, characterized in that they derive from heterocyclic aromatic monomers represented by the general formula

 in which X represents an atom or group chosen from atoms of  sulfur and oxygen and the group -NH; m represents an integer equal to or greater than 2; n represents an integer such that 0 c n <7 7 p represents an integer such that O <p <2 the sum of n and p being at least equal to 1.  3 - Conductive polymers according to claim 1 or 2, characterized in that the heterocyclic aromatic monomer from which they are derived is the thiophene substituted in position 3.  4 - Conductive polymers according to one of claims 1 to 3, characterized in that the heterocyclic aromatic monomer from which they are derived is (dioxa-3 ', 6'-heptyl) -3-thiophene.  5 - Process for the manufacture of pc1ym # res electrically conductive characterized in that # electrochemically polymerized, by anodic oxidation in a polar solvent and in the presence of an appropriate electrolyte, a monomer chosen from aromatic heterocycles with five kittens substituted, in position 3 with respect to the heteroatom, by an ether-type substituent linked to the heterocycle by an alkylene radical comprising at least two carbon atoms.  6 - Process according to claim 5, characterized in that the monomer is (dioxa-3'-6'-heptyl) -3-thiophene.  7 - Electrically conductive devices containing a polymer according to any one of claims 1 to 4.  8 - Electrochemical energy storage devices whose anodes (respectively cathodes) consist of electrodes coated with polymer films according to any one of claims 1 to 4 doped with anions (respectively cations).  9 - Electrochromic devices in which the anodes (respectively the cathodes) are coated with polymer films according to any one of claims 1 to 4.  10 - Devices for absorbing near and high frequency infrared radiation based on polymers according to any one of claims 1 to 4.  11 - Monomers which can be used to obtain conductive polymers according to claim 3, characterized in that they correspond to the general formula

 in which m 'represents the numbers 2 or 3 and p' represents the numbers 0 or 1.