CN85105974A

CN85105974A - Preparation method with polymkeric substance of indene structure different sulfur and electrochromism demonstration

Info

Publication number: CN85105974A
Application number: CN85105974.0A
Authority: CN
Inventors: 弗里德·伍德尔; 马萨奥·科巴亚谢; 阿兰·黑格
Original assignee: University of California
Current assignee: University of California
Priority date: 1985-08-07
Filing date: 1985-08-07
Publication date: 1987-02-04
Also published as: CN1045410A; CN1063293A; CN1018874B; CN1023527C; CN1007815B

Abstract

Electrochromic display device is made up of the counter electrode that is attached to the macromolecule conducting film on the conductive, transparent base and be placed under the liquid electrolyte, and this macromolecule conducting film is the polymkeric substance with indene structure different sulfur, can reversibility ground oxidation or reduction.Formula (Ia) and/or (Ib) shown in polyisothianaphthene can be with the preparation of electrochemical polymerization or other polymerization process: And/or In the formula, R ¹, R ²For hydrogen maybe can be connected into the alkyl of condensed ring, X is sulphur, selenium or tellurium.

Description

Preparation method with polymkeric substance of indene structure different sulfur and electrochromism demonstration

In recent years, Electrical and Electronic equipment makes remarkable progress aspect light, thin, microminiaturized, and not only used various electro-conductive materials need develop to light, thin, microminiaturized direction, and material itself also needs new developing.

People have known can use various sulfur heterocyclic ring polymkeric substance, as, the luxuriant polymkeric substance of sulphur, and referring to US Patent No 2,552,796 and U.S. Patent No. 2,658,902; The dibenzothiophene polymkeric substance is referring to U.S. Patent No. 3,585,163; Vinyl thiophthene polymkeric substance is referring to U.S. Patent No. 3,615,384; Various substituted thiophene polymkeric substance are referring to U.S. Patent No. 3,725,362; 2-bromo-8-hydroxyl-5,5-dioxo dibenzothiophene polymkeric substance is referring to United States Patent (USP) NO.3,775,368; Four sulphur pentalene polymkeric substance are referring to U.S. Patent No. 4111,857

In the conducting polymer body field that develops rapidly (" conducting polymer body physics and chemical international conference collected works ", J.physique.Colloque, 1983, c-3), heterocycle polymer is subjected to people and notes, this is because they are easy to film forming, and when exposing in atmosphere, it has better stability than polyacetylene or poly-(phenylene).About in the application aspect the stabilization of semiconductor surface, referring to R.Noufi etc., J.Amer.Chem.Soe.1981, volume 183,184 and reference wherein, the research work for Polythiophene that we carry out in the recent period is exactly the continuity of this respect work.

Carried out the broad research work of novel conductive superpolymer.For example, studying the polyacetylene class, they may be used as secondary battery electrode materials because with the pentafluoride of iodine or arsenic mix the back (referring to, synthetic metal (synthetic metals), volume 1, No.2.101(1979/1980)), their excellent electric conductivity is up to 10 ²To 10 ³S/cm, and have excellent charging one discharge performance.Also make solar cell material with the polyacetylene class in research, this be because their extinction characteristic than near sunlight.But the polyacetylene class also has shortcoming, and itself is easy to oxidation polyacetylene, and (dop, ped) the polyacetylene class of mixing is very responsive to moisture.

Polythiophene class not only can be used as electro-conductive material, or as battery electrode material, this is to have the particular electrical minor structure because of them, it is similar to the conjugated structure of cis-polyacetylene, and sulfur atom-containing, in addition, utilize the dopant states colour-change, people also study with them as electrochromic material.For example, people such as A.M.Druy once reported, made 2,2 '-two thiophene electrochemical polymerizations generate the polymkeric substance with reversibility variable color, be that the blue look reversibilityization of oxidation state becomes and goes back the ortho states redness, utilize this color change, this polymkeric substance can be used as electrochromic material.(referring to Journal de physigue, volume 44, No.6, C3-595(1983))

In view of the above problems, the inventor has carried out broad research, and we find that the polymkeric substance with indene structure different sulfur is a compound also highly stable in air, and can be in redox processes reversibility ground conversion color, variation pattern is stable, is enough to reuse, in addition, this polymkeric substance also belongs to a kind of new polymers, it is oozing assortedly habitual when oozing assorted agent, is easy to demonstrate the electroconductibility higher than 10 s/cm, thereby just finishes the present invention.

We have now synthesized the present invention's poly-(isothianaphthene), a kind of atypical thiophen polymer (M.P.Carn etc., Acc.Chem.Res, 1975, volume 8,139).Be not bound by any theory, we think, the stability (perhaps electroconductibility) of poly-(isothianaphthene) is higher than poly-(thiophene), this is because resonance component 1c shown in Figure 1 and 1d play a major role aspect shell molecular form (1c) stable opening, and, be the high major cause of electric conductivity along skeleton (backbone) delocalization (Id).

Fig. 1

The similar resonance structure (particularly 1d analog) that can not look to gathering (thiophene) electronic structure can become important component, and only under poly-(benzo-thiophene) structure, this is because of 3 of thiophene, 4 keys are incorporated phenyl ring into, produced stability, and this stability improves greatly because of its resonance structure.

Among the preparation method of poly-(thiophene), in two kinds of methods the simplest, the one, the anode electrochemical polymerization of pure thiophene (A.Diaz, chem.Scripta, 1981, volume 17,145; G.Tourillon etc., J.Elechroanal, Chem.1982, volume 135,173, C.Kossmehl etc., Makromol.Chem.Rapid Commun, 1981, volume 2,551; J.Bargon, IBM, J.of Resand Dev., 1983, volume 27,330; K.Kaneto etc., J.Chem.Soc.Chem Com., 1983,382) another kind is 2,5-two fontanels are for chemical coupling (M.Kobayashi etc., Syhthetic Metals, 1984, the volume 9,77 of thiophene; T.yamamoto etc., J.polym SCi., Polym.lett.1980. volume 18,9; J.Lin etc., J.Polym.SCi.Polym, Chem, Edition, volume 18,2869).As with 2,2 '-dithienyl makes parent material, carries out polymerization with first method, improve to some extent (M.A.Druy, J.Physigue, Collogue.1983 of the material property of gained then, volume c-3,595) and electrolysis can the low impressed voltage of electricity (～carry out under 3.5V).From practical viewpoint, cathode electrochemical polymerization more caters to the need, and it is easy, and product is more tough and tensile Lan-Hei filminess.The chemical coupling rule has more theoretical value, because product is an xln, number-average molecular weight is known, but the product of being produced always is Powdered.

We find that the most desirable poly-(isothianaphthene) preparation method makes the isothianaphthene galvanic coupling.(monomer preparation, referring to J.A.Gadvsz etc., Te Trahedron, 1979, volume, 35,2239; M.P.Cara etc., J.Amer.Chem.Soe., 1959, volume 89,4266; M.P.Cara etc., J.Org.Chem., 1971, volume 36,3932.)

In this patent, we will narrate the preparation method (electrochemical and chemical) of poly-(isothianaphthene) from hereinafter seeing, only need can produce needed unsaturated polymer carrying out electrochemical polymerization under the special conditions slightly.

As everyone knows, liquid crystal indicator has obtained development as a kind of need with energy display unit seldom, and be widely used in all respects, still, liquid-crystal apparatus also exists the problem that relies on the visual angle, in addition, also have some other shortcoming, poor as display resolution, memoryless function, do not reach big area and show, or the like.In order to overcome these shortcomings, the ECD device has been carried out research completely, and the ECD device also belongs to the low power consuming type, and it utilizes so-called electrochromism (electrochromism), in the electrochromism body, optical absorption characteristics is different and different with voltage that applies or electric current.Used electrochromic material is divided into inorganic materials and organic materials in the ECD device.Be considered to the oxide compound that useful inorganic materials mainly comprises transition metal, special case is a Tungsten oxide 99.999, but their available color is limited, and when with proton as quality (colorforming) although speed of response is very high during ion, can cause that the electrochemistry wash-out (elution) of film or electrode are rotten.On the other hand, organic materials comprises the viologen dyestuff, phthalocyaninato complex, or the like.But the shortcoming of viologen dyestuff is the precipitation that can cause insolubles in repeated use, and phthalocyaninato complex also has the adhesion problem between a vacuum-evaporated film and the substrate still unresolved,

In addition, in the recent period the electrochromic material of suggestion also comprises polyaniline, referring to A.F.Dia2 etc., and Journal of Elechro-Analytical Chemistry, volume .111,111(1980) or Yoneyama, etc., ibid, volume 161,419(1984); Polypyrrole, referring to A.F.Diaz, etc., ibid, volume 101, (1983) and Polythiophene are referring to M.A.Druy, Deng, Journl de physigue, volume 44, page or leaf June, page or leaf C-595(1983). or Kaneto etc., Japan Journal of Applied physics, volume, 23, No, 7, page or leaf L412(1983), come into operation but go back none in these materials.Especially, electrochromic material should be swift in response, the contrast gradient height, and it is low to consume energy, and manifests excellent tone, or the like, in addition, electrochromic material also should be able to manifest colourless tone, and this can greatly open device range of application.Yet these hetero conjugation type high molecular weight materials are gone back variable color the ortho states process being transformed into from oxidation state entirely.Improve the method for contrast gradient, for example, use the white background plate, setting about studying, but also do not finishing.

Briefly, the present invention is the polymkeric substance with indene structure different sulfur, general formula as (I is a) and/or shown in (I b):

In the formula, R ¹And R ²Represent hydrogen atom separately or contain the alkyl of 1 to 5 carbon atom, as methyl, methoxyl group and sulphomethyl, condition is R ¹And R ²Can link to each other, form condensed ring, i.e. a naphthalene along phenyl ring; X is a sulphur, selenium or tellurium; Y ^-Be electrolytic anion; Z is 0.01 to 1, the anion ratio of the every mole of monomer of this numeral; N is 5 to 100, this numeral polymerization degree.

In the electrochromism display body, on the conductive, transparent base, form macromolecule conductive film, this conducting film is used as and shows that counter electrode is placed under the liquid dielectric, characteristics of the present invention are that this high molecular conducting film is the polymkeric substance with indene structure different sulfur, and this polymkeric substance can be by reversibly oxidation and reduction.

In electric, electronic application field, can use above-mentioned polymkeric substance as electrode or electrochromic display device, or be used to produce solar cell, the electric interlock of insulated wire, fixing and transfer equipment, or as the reversible redox system.

Use various polymerization processs, can easily synthesize the present invention's polymkeric substance.

Poly-(isothianaphthene) can prepare with several different methods with some relevant polymkeric substance.During with electrochemical method polymerization isothianaphthene, very strong to the ionogen dependency.At nucleophilic negatively charged ion (Rr ^-, Cl ^-) exist down, form poly-(benzo-thiophene).No matter at protonic acid (HSO ₄NH ₂O) still under the muriate doped forms, the electroconductibility of poly-(benzo-thiophene) can both be than high about 1 order of magnitude of Polythiophene for doped forms.

For example, make general formula as (II a) 1,3-dihydro isothianaphthene-2-oxide compound or derivatives thereof,

In solvent,, then generate the polymkeric substance of required needs as reacting in the vitriol oil with dehydration and oxidation effectiveness.

In addition, needed polymkeric substance also can be from can producing as the isothianaphthene or derivatives thereof of (II b) from general formula,

(II b) isothianaphthene can be produced, and for example, (II compound a) dewaters in the presence of aluminum oxide and distils, and prepares (II b) isothianaphthene to make general formula.Make formula (II b) isothianaphthene carry out following reaction, (ⅰ) in the presence of dielectric medium, in to aprotic solvent, carry out electrochemical polymerization, (ⅱ), carry out cationoid polymerisation, make two Hydrogen polymkeric substance of gained and oxidant reaction then with dehydrogenation using solvent or not using under the solvent condition; (ⅲ) oxypolymerization; Or carry out polymerization with other similar approach.

The used solvent of above-mentioned monomer polymerization is not very strict, can select suitable solvent for use according to polymerization process.Usually, when the isothianaphthene or derivatives thereof of formula (II b) carries out electrochemical polymerization in the presence of dielectric medium, can select the sub-inert solvent of confrontation for use, as, acetonitrile, benzonitrile, propionitrile, diox, tetrahydrofuran (THF), sulforan, Texacar PC, or the like.When the isothianaphthene or derivatives thereof of formula (II b) carried out cationoid polymerisation, the available solvent comprised: methylene dichloride, and chloroform, tetracol phenixin, ethylene dichloride, Tetrafluoroethane, Nitromethane 99Min., nitroethane, oil of mirbane, dithiocarbonic anhydride, or the like.When formula (II dihydro isothianaphthene-2-oxide compound or derivatives thereof a) dewaters-during polymerization, useable solvents has, for example, the vitriol oil and polyphosphoric acid.In addition, when the isothianaphthene or derivatives thereof of formula (II b) carries out the oxidation addition polymerization, the solvent mixture and the Friedel-Crafts catalyzer that can adopt cationoid polymerisation to use.

Polymerization temperature in the above-mentioned process for polymerizing monomers can determine that not strict especially, usually, polyreaction will be carried out according to concrete polymerization process under-80 ℃ to 200 ℃.The method that polymerization time also can adopt, polymerization temperature, monomer structure or the like come to determine, and be general, polymerization time with 0.25 hour to 200 hours for well.

Above-mentioned formula (II a) and the monomeric compound of formula (II b) can be synthetic with currently known methods, for example, referring to the described method of following file, M.P.Cara, etc., Journal of American Chemcal Soeiety, volume 81,4266(1959), and M.P.Cara. etc., Journal of Organic Chemistry, volume 36, No, 25,3932(1971).In addition, in order to provide 1, the yield of 3-dihydro isothianaphthene can adopt the dissolubility lithium sulfide, the dissolubility lithium sulfide can prepare by making lithium triethylborohydride and reaction of Salmon-Saxl, referring to J.A.Gradysz, etc., Tetrahedron letters, volume, 35,2329(1979).

The present invention also comprises the preparation of this new polymers.

The purpose of this invention is to provide a kind of new polymers.

More particularly, the purpose of this invention is to provide a kind of novel conductive polymkeric substance.

Another object of the present invention also is to provide the novel method of producing novel polyisothianaphthene base polymer.

Another object of the present invention and advantage, by the detailed description of bottom, more clear.

Please see accompanying drawing:

Fig. 1 is the infrared absorpting light spectra of the polymkeric substance of routine I preparation.

Fig. 2 is the infrared absorpting light spectra of the polymkeric substance of routine II preparation.

Fig. 3 is the nmr spectrum of the polymkeric substance of routine II preparation.

Fig. 4 is an infrared absorpting light spectra of handling the polymkeric substance that polymkeric substance obtained of routine II preparation with chloranil.

Fig. 5 is the polarographic analysis result diagram of the polymkeric substance that obtained of example 5 electrochromic material use-testings.

Fig. 6 is the relation curve of photoabsorption and voltage, and the high molecular conducting film of routine X IV is immersed in the tetrahydrofuran solution, and every liter of tetrahydrofuran solution contains 0.53 mole of Liclo ₄, make counter electrode with lithium.

Fig. 7 is the cyclic voltammetry spectrum of the high molecular conducting film of routine X IV, with (C ₄H ₉) ₄NCLO ₄Measure, it is dissolved in the acetonitrile, is ionogen, voltage be+1.0V to-0.7V.(and standard calomel electrode comparison)

Fig. 8 is the cross section sketch of the present invention's ECD device.Among the figure, numeral 1 is represented the transparent glass base, and 2 is show electrode, and 3 is electrochromic material, and 4 is liquid electrode, and 5 is electrode, and 6 is protective layer, and 7 are lead-in wire.

Fig. 9 represents to gather the reversibility electrochemical doping of (isothianaphthene).Make an electrode (band standard calomel reference electrode) with aluminium, make another electrode with poly-(isothianaphthene), the polypropylene carbonate ester solution of using the fluoro lithium tetraborate can see that as electrolytic solution the present invention's polymkeric substance can be used as battery electrode.

Fig. 9 test also shows the electrochromic property of the present invention's new polymers.

Have fully novel structure according to the prepared polymer of the present invention, can not only demonstrate significant high conductivity by top layer, and can repeat electrochemical oxidation-reduction reaction, meanwhile, present the inherent colour of each state. In addition, the present invention's polyisothianaphthene is a kind of especially interesting polymer, even because its transparency can not weaken in the further state of oxidation yet. Therefore, the present invention's the polymer with indene structure different sulfur is of great use in Electrical and Electronic industry, for example, make electrode, electrochromic display device, solar cell, the electricity of electromagnetic wire engages, fixing and conversion equipment, and is used for the invertibity oxidation-reduction system.

The son of will giving an example illustrates details, but the present invention's scope is not limited by example.In following, make internal standard with TMS, the spectrophotometer EM-360A mensuration NMR (Nuclear Magnetic Resonance) spectrum that usefulness Varian/Analytical Div. makes (' H-NMR); The light photometer Mode1281 that makes with Perkin-Elmer company measures infrared absorption spectrum (IR),

Example 1

Handle 1 in the vitriol oil, 3-dihydro isothianaphthene-2-oxide compound prepares polyisothianaphthene

(a) .1,3-dihydro isothianaphthene-2-oxygen synthetic

The lithium triethylborohydride that under room temperature and nitrogen atmosphere, 200ml is contained 1mol/l add to fill 3.219(0.1mol) in the SChlenR flask of sulphur powder, reaction takes place at once, the dissolving of sulphur powder forms a yellow suspension.Owing to contact with micro-air.This suspension has become light yellow transparent solution.

Be furnished with dropping funnel for one, agitator, four neck flasks of 2 liter capacities of thermometer and nitrogen intake add 26.4g(0.1mol respectively under nitrogen atmosphere) anhydrous tetrahydro furan of xylylene bromide and 1 liter forms solution.During stirring, the tetrahydrofuran solution of the lithium sulfide for preparing above at room temperature dropwise added with 1.5 hours.After this, tetrahydrofuran (THF) is removed in underpressure distillation, and further distillation leftover is so that obtaining boiling point is the colourless 1 of 74～76 ℃/3mmHg, 3-dihydro isothianaphthene 10.9g(productive rate: 80%).The infrared spectra of product is 3060,3026, and 1582 and 1485cm ^-1Shown sorption based on phenyl; 2910,2840 and 1450cm ^-1Shown sorption based on Ben Yajiaji; At 1195cm ^-1Based on 1,2-substituted-phenyl plane inner deformation has shown sorption; Sorption at 760cm 0-substituted-phenyl; At 740cm ^-1The sorption of thioether.At CHCL ₃In with tetramethylsilane (TMS) as the nucleus magnetic resonance of internal standard (' H-NMR), measuring result is as follows:

4.22（S，4H）;7.20（S，4H）

This compound is very unstable, even be kept at still can be black from xanthochromia under light shield and the air-proof condition.

Then, thus obtained 1,3-dihydro isothianaphthene add 450ml above-mentioned be dissolved with 18.6%(0.086mol) sodium iodate 50%.Methanol aqueous solution, mixture at room temperature stirred 12 hours, isolated the precipitation of generation with filtration method.Filter cake 50ml washed with methanol.Washing lotion and filtrate are mixed and concentrating under reduced pressure.Yellowish white solid recrystallization from ethyl acetate-hexanaphthene of Xing Chenging thus obtains fusing point little yellow crystals of 87～89 ℃.

Resulting crystal further from ethyl acetate-hexanaphthene recrystallization so that obtain fusing point at 90～91 ℃ crystal.The crystal infrared spectra shows, except isothianaphthene absorbs, and the absorption thioether that also splits by force at 1035cm, and at 740cm ^-1Thioether absorb to disappear.At CHCl ₃Middle as follows as the nuclear magnetic resonance spectrum of internal standard measurement with methyl-monosilane:

4.65（S，4H），7.20（S，4H）

C ₈H ₈The SO ultimate analysis:

Calculated value: (%): C63.16; H5.26; S21.05

Measured value: (%): C63.08; H5.15; S20.87

(b). from 1.3-dihydro isothianaphthene-2-oxide compound (II a, R ¹=R ²=H) synthetic polyisothianaphthene

Add the vitriol oil of 1ml in the 1.3-dihydro isothianaphthene of 500 milligrams (3.29mmol), become garnet in the reactive system at once.Mixture was put 70 hours under the greenhouse, injected the methyl alcohol of 400ml after solidifying basically etc. system.The brown precipitate that generates is separated water cleaning down and with centrifuging 60 ℃ of one nights of vacuum-drying.The polymkeric substance that obtains is placed in the Soxhlet's extractor, extracted successively 12 hours with methylene dichloride and chlorobenzene respectively, obtain the chlorobenzene insoluble substance of 203mg.The infrared spectra of resulting polymers as shown in Figure 1.The result of ultimate analysis is C:67.26%; H:3.12%; S:23.59%, if with according to repeating unit with following structure

Calculated value (C:67.19%; H:3.32%; S:23.54%) quite consistent.

The specific conductivity of polymkeric substance (6RT) is to measure with four-terminal-network conductivity measurement device under the room temperature, is 2 * 10 ^-2S/cm.

The example II

Prepare polyisothianaphthene with the oxygenant oxidation from the poly-dihydro isothianaphthene that the cationoid polymerisation of isothianaphthene obtains

(a). synthetic (II 6, the R '=R=H) of isothianaphthene

With 300 milligrams (1.97mmol) according to routine 1(a) synthetic 1.3-dihydro isothianaphthene-2-oxide compound and 450mg(4.41mmol) neutral alumina abundant pulverize in mortar, and thorough mixing, be placed on then in the sublimation apparatus, decompression is heated in an oil bath down.Cooling segment at sublimation apparatus has thoroughly obtained 250mg(1.87mmol) the isothianaphthene white, needle-shaped crystals, be right after thereafter, resulting monomer is dissolved in the methylene dichloride alkane of the 5ml purifying degassing, adds the 10mg trifluoroacetic acid then, then mixture is placed a night.When 50ml methyl alcohol injects reaction mixture, get a white depositions.Resulting polymers dissolves in the N-methylacetamide at chloroform, chlorobenzene, tetrahydrofuran (THF) and N.The infrared spectra of this polymkeric substance and ' the H-nuclear magnetic resonance spectrum respectively as shown in Figures 2 and 3.

In addition, the tetrahydrofuran solution of this polymkeric substance is transformed into polystyrene with gel permeation chromatography (Varian5000), confirms that the molecular weight of polymkeric substance is 2000.

At room temperature, the polymer conductivity of measuring in example 1 same mode (σ RT) is 10 ^-8S/cm or low.

(C ₈H ₆S) ultimate analysis:

Calculated value: (%): C71.64; H4.48; S23.88

Measured value: (%): C71.27; H4.54; S23.96

Except make polymerization starter replacement trifluoroacetic acid with methylsulfonic acid, repeat above-mentioned identical operation and obtain-polymkeric substance.The resulting polymers infrared spectra is consistent with Fig. 2 fully.

These polymer dissolution are handled with the chloranil of twice mole in the 5ml chlorobenzene, form black precipitate.Under the room temperature, the specific conductivity of resulting polymers (δ RT) is 9 * 10 S/cm, and a kind of polymer conductivity of the iodine that mixes is 9 * 10 S/cm.The infrared spectra of this polymkeric substance is shown in Figure 4.Even the polymer compound room temperature of doping iodine is placed down in a week in the air, specific conductivity can not cause change yet.

Except using the 5ml chloroform to replace chlorobenzene; 1.1 doubly the N-chlorosuccinimide of mole replaces outside the chloranil, with above-mentioned same method make a black, fully with Fig. 4 in the identical polymkeric substance of illustrated infrared spectra.Recording the specific conductivity (σ RT) of knowing this polymkeric substance is 2.6 * 10 ^-1S/cm.

Example 3

Oxidation step polymerization isothianaphthene prepares polyisothianaphthene

Example 2(a) same method is synthesized isothianaphthene.Under 35～37 ℃ of temperature, make the isothianaphthene of 250mg, the anhydrous methylene chloride of 5ml, the mixture reaction of the Aluminum chloride anhydrous of 134mg and the anhydrous cupric chloride of 134mg 1 hour produces black precipitate.Such reaction mixture is preserved the methanol solution that will precipitate after 12 hours with hcl acidifying and is handled under said temperature, the water cleaning down is also dry.Use hot methanol successively, hot methylene dichloride and hot chlorobenzene extract exsiccant polymkeric substance, obtain the black polymer of 205mg.The infrared spectra of this product is fully consistent with Fig. 4, and specific conductivity (σ RT) is 2.8 * 10 S/cm.

Example 4

The electrochemical polymerization isothianaphthene prepares polyisothianaphthene

The isothianaphthene electrochemical polymerization method is as follows:

Under room temperature and constant voltage, the platinum plate is made sample panel; Aluminium sheet is made counter electrode; In specific time, make isothianaphthene make ionogen shown in the table 1 and isothianaphthene be dissolved in and carry out electrochemical polymerization in the electrolytic solution made in the polar solvent to be dissolved in normality.On platinum plate anode, generated the polyisothianaphthene film.Helium bubbling in above-mentioned electrolytic solution was blown over 30 minutes at least, so that deoxidation in advance.Constant voltage is 1.5V in the polymerization.

The film of Sheng Chenging is used acetonitrile and methylene dichloride cleaning down and vacuum-drying successively thus.The result that the electrical property of mensuration film obtains is shown in the appended table 1.

Table 1 note:

P ₄ASCl: tetraphenylarsonium chloride

P ₄PCl: chlorinated tetraphenenyl phosphorus

Bu ₄NBr: bromination four (normal-butyl) ammonium

Li Br: lithiumbromide

Bu ₄NPF ₆: hexafluoro phosphorus four (normal-butyl) ammonium

Bu ₄NCl O ₄: perchloric acid four (normal-butyl) ammonium

CH ₃CN: acetonitrile

PCN: benzonitrile

Implement 5

Polyisothianaphthene is as the electrochemistry display element, the use of battery material etc.

Repeat the same operation of routine 4-2, but, polymer chemistry is deposited on the conductive glass thereon with the platinum plate among conductive glass (the vacuum-evaporation Indium sesquioxide is made anode) the replacement example 4-2.The polymer-coated conductive glass of gained is made the work electrode, the platinum line is made counter electrode, standard calomel electrode is made reference electrode, carries out the cyclic voltammetry measurement method by use polarographic analyze (the 174A type that EG and G company make) under the room temperature in the acetonitrile solution of the TBAP that contains 292mmol.The voltage scan rate of using is 20mv/sec, sweep limit from+1.0V to-0.7V(with respect to standard calomel electrode).Fig. 5 has shown resulting result.

As shown in Figure 5 ,+0.58V and-the 0.15V polymkeric substance has shown oxidation peak and reduction peak respectively, and coloured variation: from-0.7V～+ avy blue in the 0.6V voltage range become+0.6V～+ super transparent light green in the 1.0V voltage range.These results show: the avy blue state is a condition in the polymkeric substance, and polymkeric substance is the green color of highly transparent under oxidation state and doping attitude.

Test as battery

The polyisothianaphthene that obtains among the routine 4-1 is cut into the long test piece of the wide and 3cm of 1cm, and one of test piece is with on the electroconductive binder cementation one platinum line.The mode that can permeate fully inwards with electrolytic solution, by means of 1 porous polypropylene separatory membrane that 1cm is thick, test piece is placed on the onesize lithium paper tinsel, then, this system is soaked in the propylene carbonate solution of the lithium perchlorate degree of depth 2cm that contains 0.5mol/l, Zhi Bei battery (wherein polyisothianaphthene is a negative electrode, and the lithium paper tinsel is an anode) is 2.0mA/cm in charging current thus ²And under argon atmospher, charged 30 minutes.After the charging fully at once discharging current be 2.0mA/cm discharge down, when cell voltage drops to 1V, under above-mentioned similarity condition, charge once more simultaneously.When discharging and recharging operation when repeating with aforesaid method, note repetition 590 times, be reduced to 50% up to efficiency for charge-discharge efficient.In addition, 5 times are repeated efficiency for charge-discharge is 99%, and in addition, after battery was in 48 hours charging states, self-discharge rate was 3.2%.

Example 6

Electrochemical polymerization method preparation poly-(dihydro isothianaphthene)

The monomer isothianaphthene is with document (people such as J.A.Gladysz, Tetrahedron, 1979 volumes 35,2239; People such as M.P.Ca Va, J.Amer.chem, Soc., 1959, volume 81,4266; People such as M.P.Ca Va, J.Ora.Chem., 1971, volume 36,3932) the method preparation described, make the back and directly use.Poly-(dihydro isothianaphthene) carries out electrochemical oxidation to this monomer and makes in two electrodes, separating diaphragm battery, platinized platinum is made anode, and graphite oxide is made negative electrode.The isothianaphthene and the 0.30M ionogen Bu that in acetonitrile, add 0.23M ₄NPF ₆, this anhydrous clear solution is used for polyreaction.Directly use acetonitrile (Mallinckrodt) and do not need to be further purified, make power supply with placed in-line 1.5V battery.

All experiments are carried out in dried nitrogen, when these battery two ends connect 4.5V voltage, occur many white powders near the anode immediately, turn off battery after ten minutes.This poly-(dihydro isothianaphthene) white powder separates by suction strainer, with acetonitrile and diethyl ether flushing and vacuum-drying.For carrying out ultimate analysis, resulting solid obtains purifying with tetrahydrofuran (THF)-water redeposition.

When the isothianaphthene sample of new system at hydrogen battery utmost point layer (Bu ₄Nclo ₄Or BU ₄NBF ₄Make supporting electrolyte, the glass (TOG) of stannic oxide coating is made anode) during the electrolysis of lining, a large amount of white precipitate (" WP ") has been full of anode layer.Find that after examining anode at first (instantaneous) has covered extremely thin blue film, after this begins to generate WP immediately.The outward appearance of WP and electrode materials, solvent, or temperature is irrelevant.Separate, CHARACTERISTICS IDENTIFICATION (infrared rays, flexibility analysis) and chemical operation (face as follows) prove: WP is exactly poly-(dihydro isothianaphthene).It should be noted that under these conditions (the chances are adulterated poly-(isothianaphthene), and when being transformed into poly-(dihydro isothianaphthene), thiophene has produced the polymeric film of partial oxidation (" doping ") having precipitated extremely thin blue film when isothianaphthene.For the unique proper explanations of this wonderful observation be: poly-(isothianaphthene) takes on the effect that isothianaphthene is a cationic polymerization initiators.In order to verify this section hypothesis, we are exposed to the isothianaphthene solution of new system in some typical catalyst and cause for positively charged ion, find to make the isothianaphthene polymerization to some extent under all occasions, but the most interesting result is the effect of vitriolic dichloromethane solution, at this moment, isothianaphthene is transformed into the hydration sulfuric acid adulterated poly-(dihydro isothianaphthene) of blue black.Obviously, acid has not only played catalyzer, and has played oxygenant.To " concentrating " inspecting standard of top hypothesis insurance is that the product of tetrachloro-P-benzoquinones dehydrogenation is poly-(a dihydro isothianaphthene) and demonstrate the sulfuric acid polymerized product that is equal to infrared spectra.For the unique proper explanations of this observation be, the infrared spectra of mix poly-(isothianaphthene) is subjected to because the absorption of conduction electron is controlled, and because the absorption of intramolecule vibration is the spectrographic weakness.When shortage is added control test, be difficult to concrete mechanism of supposition and explain this electrolytical effect.

We infer that sulfuric acid can directly change into poly-(isothianaphthene), (H to dihydro isothianaphthene-S-oxide compound ₂SO ₄) x(H ₂O) y.Solid dihydro isothianaphthene-S-oxide compound is added in 98% the sulfuric acid, has in fact generated adulterated poly-(isothianaphthene) (the following Fig. 1) of desired part really.

Fig. 1

In addition, 7,7,8,8 ,-four cyanide quinolines and bismethane can be as the catalyzer of cationoid polymerisation.But product does not demonstrate than the poly-higher specific conductivity of (isothianaphthene) compound of any other doping, points out that acceptor does not probably relate to the solid specific conductivity.For the sort of observation, two kinds of judgements may be advanced, and promptly the receptor molecule probably is not deposited in the small-crystalline zone, and/or exists charge transfer completely.

The above results is explained the essence of the process that poly-(dihydro isothianaphthene) forms, and for the chemosynthesis of poly-(isothianaphthene), has found method cleverly, and The above results still can not provide the way of isothianaphthene electrochemical polymerization.This just needs discover method, prevents that catalyzer is owing to " status nascendi " doping poly-(isothianaphthene) forms poly-(dihydro isothianaphthene).We find that if having in the reaction medium than more nucleophilic molecule formation of isothianaphthene, chainpropagation is cut off step and will be damaged.One related to before electrolytic action and iodide to be added to detection in the anode layer the experiment failed of success, because iodine is oxidized under the electrolytic condition.However, with Li Br, Bu ₄NBr or the most handy Ph ₄ASCl can produce fabulous film during electrolysis on platinum or TOG.The unique proper explanations of this observation is, being subjected to because the control of the absorption of conduction electron of adulterated poly-(isothianaphthene) infrared spectra, and the absorption of intramolecule vibration is the spectrographic weakness.When lacking additional control test, be difficult to infer a this electrolytical effect of concrete mechanism explain.

C ₈H ₆S analytical calculation value: C11.60; H4.51; S 23.89;

Measured value: C71.27; H4.54; S 23.96

Li BF and Bu NCLO can be used as the ionogen of this reaction.

According to the present invention, have been found that at least and can aggregate into the metastable state isothianaphthene high conductive polymers with three kinds of different methods with excellent characteristic; One relates to when having the nucleophilic negatively charged ion, and by the isothianaphthene polymerization, electrochemical preparation is gathered (dihydro isothianaphthene).

Have found that poly-(isothianaphthene) is than the better conductor of Polythiophene.

Embodiment 7

With chemical cationic polymerization preparation poly-(dihydro isothianaphthene).

(396mg 2.96mmol) is dissolved in 10ml and gives earlier through P the monomer isothianaphthene ₂O ₅In the exsiccant methylene dichloride, in this liquid, add a methylsulfonic acid, at once from the colourless redness that becomes, after 90 minutes, become purple in the reaction mixture.After methylene dichloride was removed in evaporation, residue dissolved with tetrahydrofuran (THF).After this solution injected methyl alcohol, poly-(dihydro isothianaphthene) settled out from solution.Separate vacuum-drying with centrifuging.Infrared spectra is identical with poly-(dihydro isothianaphthene) above-mentioned.

Following Example is the present invention's application success example on the spot, but does not plan to limit invention.

Embodiment 8

Electrochemical polymerization method prepares adulterated poly-(isothianaphthene)

Polymerization process is identical with above-mentioned example 6 poly-(dihydro isothianaphthene) basically.The most important is an ionogen.When lithiumbromide is used as ionogen, connect a 1.5V battery, adulterated poly-(isothianaphthene) blue film is gone up at anode (conductive glass) at once and is generated.Bu ₄NBr and Ph ₄As Cl also can be as the ionogen of this reaction.

Embodiment 9

Carry out chemical cationic oxidation polymerization with sulfuric acid and prepare adulterated poly-(isothianaphthene)

Sulfuric acid (5ml) be added to the monomer isothianaphthene (396mg, 2.96mmol) in, monomeric color becomes red-black from leucismus at once.After stirring a night, reaction mixture is injected 400ml methyl alcohol, the doping of brown ceramic powder poly-(isothianaphthene) settles out from this solution.Then, centrifugation with the extraction of soxhlet extractor, is adopted methylene dichloride and chlorobenzene, then vacuum-drying.This reaction also can be carried out with vitriolic methylene dichloride suspension.

Embodiment 10

Use TCNQ(7,7,8,8-four cyanide quinolines and bismethane) carry out chemical cationic oxidation polymerization and prepare adulterated poly-(isothianaphthene).

Monomer isothianaphthene (238mg, 1.77mmol) solution in the 5ml methylene dichloride.Add after a few gram TCNO in solution, its color becomes redness very slowly.After stirring a night, this color becomes blue black.Thereafter, add the TCNQ that doubles monomer isothianaphthene mole to this solution, heating is until 110 ℃ and kept 1 hour.Behind this solution injection methyl alcohol, the blackish green powder is precipitated out from solution.In the Soxhlet extractor, adopt the flushing of methyl alcohol and chlorobenzene, and vacuum-drying.

Embodiment 11

From poly-(dihydro isothianaphthene) preparation poly-(isothianaphthene)

Poly-(the dihydro isothianaphthene) of electrochemical polymerization preparation dissolves in hot chlorobenzene, and this is a light brown solution.When tetrachloro-P-benzoquinones was added in this solution, solution colour became dark green at once.By cooling, powder is precipitated out from this solution, and through suction strainer, with washed with methanol and vacuum-drying, this precipitation obtains separating.Implement the identical infrared spectra that 7～10 all substances of mentioning show.

Therefore, the invention provides the route of three kinds of alternative preparations poly-(isothianaphthene):

1. when having the nucleophilic negatively charged ion to exist, make isothianaphthene carry out electrochemical polymerization.

2. having in the presence of the cationic polymerisation catalyst, making isothianaphthene or dihydro isothianaphthene-s-oxide compound carry out chemical polymerization.

3. poly-(dihydro isothianaphthene) carries out dehydrogenation.

The PRELIMINARY RESULTS of conductivity measurement is collected in the table 2, and poly-(isothianaphthene) band edge is estimated as～1ev(1.1 μ) (under low-doped degree, passing through film transfer), this be lower than Polythiophene (1～2ev, 620nm) ³Nearly 1ev.

Table 2

Poly-(isothianaphthene) compacting conductivity table mixes

Compound (S/cm) ^a

Poly-(isothianaphthene) Cl _x-embodiment 8 4.0 * 10 ^-1

Poly-(isothianaphthene) (HSO ₄) _0.05(H ₂O) _0.033

Implement I b 2.0 * 10 ^-2

Poly-(isothianaphthene) (Al Cl ₄) _x-embodiment 3 2.8 * 10 ^-2

Gather (isothianaphthene) (TCNQ) _x-embodiment 10 1.5 * 10 ^-2

Poly-(isothianaphthene) (tetrachloro-P-benzoquinones) _4x-embodiment 11 1.3 * 10 ^-2

Fig. 9 surface the reversible electrochemical of poly-(isothianaphthene) mix.Therefore, make an electrode (using the standard calomel reference electrode) with aluminium, poly-(isothianaphthene) makes another electrode, and the polypropylene carbonate ester solution of lithium-fluoroborate is an electrolytic solution, and as can be seen, polymkeric substance of the present invention can be used as battery electrode.

The test of Fig. 9 also shows the polymer electrochromic feature that the present invention is new.

In Fig. 6, we prove electrochromic effect; Hotchpotch is clO ^- ₄, reference electrode is a lithium.Energy derive is penetrated in the incident width of cloth, and 0～1st, at infrared region, 1～2nd, visible light is transferred to the spectrum ultraviolet part gradually more than 2.Result displayed has further been pointed out the application of polymkeric substance of the present invention in device for converting solar energy among Fig. 6, because semi-conductor energy gap and solar spectrum coupling are fine.

The contriver has carried out extensive studies to the electrochromic property of polymkeric substance with isothianaphthene mechanism, found that: above-mentioned polymkeric substance is novel electric type off-color material, its response has colourless tone rapidly basically under oxidation state, therefore reached purpose of the present invention.This discovery is beyond thought, and is unknown because this colourless basically electrochromic material still belongs to so far.According to the present invention, electrochromic display device (ECD) by on it by the conductive, transparent base of the conducting film of a molecular weight and be placed on its down the counter electrode under liquid electrolyte form, the conducting film that it is characterized in that described macromolecule is the polymkeric substance with indene structure different sulfur, reversibly oxidation or reduction." liquid electrolyte " used herein speech is meant the dispersion or the solution of supporting electrolyte in the solvent.

The macromolecule conductive film can be used as electrochromic film according to the present invention, its reversibly oxidation or reduction and be the polymkeric substance with indene structure different sulfur (the formula III is represented):

R wherein ¹And R ²Represent hydrogen or have the hydro carbons of 1～5 carbon, X is sulphur, selenium or tellurium, Y ^-Represent negatively charged ion, Z is a value between 0～0.40, represents anionic ratio in each indene structure different sulfur unit, and N represents 5～500 the polymerization degree, be to produce through electrochemical polymerization by the isothianaphthene compound that the following formula IV is represented,

R in the formula ¹, R ²Identical with X and above-mentioned definition.

The isothianaphthene compound object lesson of formula IV representative comprises 1,3-isothianaphthene, 5-methyl isophthalic acid, 3-isothianaphthene, 5,6-dimethyl isothianaphthene, 5-ethyl-1,3-isothianaphthene, 5-methyl-6-ethyl-1,3-isothianaphthene or the like.

The electrochemical polymerization of above-mentioned isothianaphthene compound can be carried out [for example, at Solid state communication, rolling up 46, the 5, the 389(1983) method of Miao Shuing] according to the method that generally is used for electrochemical polymerization thiophene, pyrroles or the like.Particularly can use two control potential electrolysis or control current electrolysis, and wish by using the conductive, transparent base on transparent base, to form polymeric film as sample electrode.

Can be used as transparent base of the present invention comprises: contain transparent insulator (for example: glass, polyester film etc.), have thereon vacuum-evaporation Indium sesquioxide-Xi, stannic oxide, platinum, or the like, use sputter or similar approach.These materials are easy to buy as industrial goods.The polymeric film that electrochemical polymerization generates, thickness be from 0.03～30 μ m, 0.05～22 μ m preferably, and the best is 0.1～10 μ m.Film thickness can be subjected to the control of the magnitude of current in the electrochemical polymerization, when film thickness during less than 0.03 μ m, can not get contrast clearly, therefore as then having considerable damage on the display material economic worth.On the contrary, thickness surpasses 30 μ m provides contrast clearly, but is unfavorable with regard to film strength or response speed.

Counter electrode is inserted in the liquid electrolyte, refills and mix the polymkeric substance that is obtained, promptly produce the ECD display instrument.Employed liquid electrolyte is the dispersion of the supporting electrolyte in solvent or solution.Operable supporting electrolyte comprises that negatively charged ion combines with cationic among the present invention, and (ⅰ) negatively charged ion (is Y in the formula III ^-), resemble the fontanelle compound anionic species of Va elements, for example PF ^- ₆, SbF ^- ₆,

ASF ^- ₆With Sb Cl ^- ₆; The fontanel anionic species of III a family column element is as BF ^- ₄; Halide anion, for example I ^-(I ^- ₃), Br ^-And Cl ^-; Perchloric acid anionic species, for example Cl O ^- ₄; And (ⅱ)

Resemble the alkalimetal ion cationoid, for example Li ⁺, Na ⁺And K ⁺; Quaternary ammonium ion, for example R ₄N ⁺(wherein R represents to have the alkyl of 1～20 carbon atom; Yi is Ji Phosphonium ion, for example (C ₆H ₅) ₄P ⁺But these combinations are not restrictive.

Is LiPF by above-mentioned negatively charged ion (x) and positively charged ion in conjunction with the object lesson of the supporting electrolyte that constitutes ₆, Li Sb F ₆, Li As F ₆, Li Cl O ₄, Na I, Na Sb F ₆, Na A ₅F ₆, Na Cl O ₄, K I, KPF ₆, KSb F ₆, KA ₅F ₆, K Cl O ₄, [(n-Bu) ₄N] ⁺(ASF ₆) ^-, [(n-Bu) ₄N] ⁺(PF ₆) ^-, [(n-Bu) ₄N ⁺] Cl O ₄, Li ALCl ₄, Li BF ₄, (C ₆H ₅) PBF ₄, (C ₆H ₅) ₄PA ₅F ₆(C ₆H ₅) ₄PCl O ₄, but these examples are not restrictive.These supporting electrolytes can use separately, if necessary or two or more combine use.Except that the above-mentioned negatively charged ion of enumerating, also can use HF ^- ₂Negatively charged ion.Spendable positively charged ion also further comprises pyrrole except that the above-mentioned positively charged ion of enumerating Or pyridylium (following formula (V) is represented) and carbocation (following formula VI or (VII) are represented:

Z represention oxygen atom or nitrogen-atoms in the formula; R ' represents hydrogen atom, an alkyl or a 6-15 carbon atom aryl that has 1～15 carbon atom; R " represents halogen atom, an aryl that has the alkyl of 1～10 carbon atom or have 6～15 carbon atoms; When Z is a Sauerstoffatom, m is zero or when Z was nitrogen-atoms, m was 1; P is zero or integer between 1～5.

R in the formula ³, R ⁴, R ⁵Each represents a hydrogen atom, has the alkyl of 1～15 carbon atom, an allyl group, aryl that has 6～15 carbon atoms or-OR ⁷, R wherein ⁷Represent the alkyl of 1～10 carbon atom or have the aryl of 6～15 carbon atoms, condition is R ³, R ⁴And R ⁵Not hydrogen atom simultaneously; R ⁶Represent hydrogen atom, an aryl that has the alkyl of 1～15 carbon or 6～15 carbon are arranged.

Operable HF ^- ₂Negatively charged ion normally by the dissolving following formula (VIII), (IV) or (X) expression compound (hydrofluoride) and obtain,

R ^′ ₄N·HF ₂（Ⅷ）

M·HF ²（Ⅸ）

" each represents a hydrogen atom, an aryl that has the alkyl of 1～15 carbon atom or have 6～15 carbon atoms for R ' and R in the formula;

Representative has the alkyl of 1～15 carbon atom or has the aryl of 6～15 carbon atoms; Z represention oxygen atom or nitrogen-atoms; Q representative zero or one 5 or 5 following integers; M represents basic metal as a kind of supporting electrolyte in appropriate solvent.By following formula (VIII), the compound object lesson of (IV) and (X) representative comprises H ₄NHF ₂; Bu ₄NHF ₂, N _αHF ₂, KHF ₂, Li HF ₂With

The pyrrole of formula 3 representatives

Or pyridine pyridine positively charged ion can dissolution type (V) representative positively charged ion and negatively charged ion (X) Cl O for example ₄, BF ^- ₄, Al Cl ^- ₄, FCl ^- ₄, Sn Cl ^- ₅, PF ^- ₆, PCl ^- ₆, Sb F ^- ₆, As F ^- ₆, CF ₃SO ^- ₃, HF ^- ₂Or the like) between form in appropriate solvent, obtain as the salt of supporting electrolyte.The object lesson of this salt is:

Above-mentioned formula VI or VII) object lesson of carbocation of representative comprises (C ₆H ₅) ₃C ⁺, (CH ₃) ₃C ⁺,

Or the like.

These carbocations can or be dispersed in the salt that forms as supporting electrolyte in the appropriate solvent between positively charged ion and the negatively charged ion (X) (being carbon salt) by dissolving and obtain.Typical case's available negatively charged ion (X) comprises (BF ^- ₄, Al Cl ^- ₄, Al Br ₃Cl ^-, Fe Cl ^- ₄, PF ^- ₆, PCl ^- ₆, SbCl ^- ₆Sb F ^- ₆, Cl O ^- ₄, CF ₃SO ^- ₃Deng, for example carbon salt is particularly including (C ₆H ₅) ₃CBF ₄, (CH ₃) ₃CBF ₄, HCOAl Cl ₄, HCOBF ₄, C ₆H ₅COSn Cl ₄Or the like.

The available solvent both can be that water solvent also can be a non-aqueous solvent among the present invention, but supporting electrolyte solution noted earlier is relatively good in non-aqueous organic solvent, and organic solvent used herein is aprotonic solvent preferably, and high specific inductivity is arranged.For example, can use ether, ketone, nitrile, amine, acid amides, sulphur compound, phosphotidic compound, inferior phosphotidic compound, boric acid ester compound, chlorinated hydrocarbon, ester, carbonic ether, nitro-compound and all classes.Certainly, preferably ether, ketone, nitrile, phosphotidic compound, inferior phosphotidic compound, boric acid ester compound, chlorinated hydrocarbon and carbonic ether.The object lesson of these solvents comprises tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1-4-diox, Monoethylene Glycol (MEG) dme, acetonitrile, propionitrile, 4-methyl-2 pentanone, butyronitrile, valeronitrile, benzonitrile 1-2-ethylene dichloride, r-butyrolactone, valerolactone, glycol dimethyl ether methyl-formiate, Texacar PC, ethylene carbonate, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl thioformamide, ethyl phosphonic acid ester, methyl phosphorodithioate, the inferior phosphide of ethyl phosphorous acid METH, 3-trimethylammonium sulforan or the like.In order to improve response speed, in the middle of them, with nitrile and carbonic ether especially for well.

These organic solvents can use separately also can two kinds, two or more being used in combination.

Oxygen and water in these (proton) solvents make ECD display instrument performance depreciation sometimes, and this depends on the model of employed ECD display instrument or the type of electrodes of use.In this case, preferably give elder generation's purification solvent in normal way, in this external ECD display instrument of the present invention except that can using above-mentioned ionogen, can also use the organic solvent that only spreads to supporting electrolyte, perhaps ionic conduction high, by polyethylene oxide and Na I, the organic solid electrolyte based that Na SCN etc. form.

The supporting electrolyte that uses in the ECD display instrument of the present invention, its concentration depend on use solvent species, apply current/voltage value, working temperature, supporting electrolyte kind and like that, therefore, generally can not fix.Liquid electrolyte can be that homogeneous also can be non-homogeneous, but normally used concentration range is between 0.001～10mol/l.Distance generally be can not determine between macromolecule conducting film and counter electrode.Because the kind of supporting electrolyte, the electric current that applies and magnitude of voltage, ECD display instrument indicator gauge area and all classes are depended in their variation, but preferably from 0.05～5mm.As counter electrode, according to the purpose purposes, can use multiple material in addition, promptly when transmitted light was used to show, aforesaid transparent material was preferably as counter electrode.On the other hand, with regard to the emission light that uses, also can be used as the counter electrode use and resemble the opaque electro-conductive material of tinsel class, for example nickel or platinum and wire cloth.In addition, because the ECD display instrument provides colourless substantially tone, just can select the base plate of different tones for use.Therefore, the ECD display instrument that the present invention obtains can be used for widespread use owing to extensively select the material of use.

Now, explanation the present invention that reference example is more detailed, but should be appreciated that the present invention is not limited to these examples.

Example 12

Containing (the C of 0.08mol/l ₆H ₅) ₄Dissolve 0.0788mol/l1 in the acetonitrile solution of PCl, [compound of formula IV is R wherein for the 3-isothianaphthene ¹=R ²=H] preparation electrolytic solution.Use above-mentioned electrolytic solution, a sheet glass (tin indium oxide is vacuum-evaporation thereon) is made sample electrode, and an aluminium sheet is made counter electrode, is that electrochemical polymerization was carried out in energising in 20 minutes under the 2mA/cm in room temperature and current density.Scribbling on the indium oxide tin glass plate anode, obtaining the slight adulterated avy blue polymkeric substance of electrochemistry.The demonstration base that obtains is also dry with the acetonitrile flushing, and the exsiccant polymeric film is 10 μ m.

It is immersed in consequent demonstration and contains 0.53mol/l Li Cl O ₄Tetrahydrofuran solution in, measure applying the dependence of voltage as counter electrode energising with lithium.The result who obtains is shown in Figure 6.As shown in Figure 6, polymkeric substance at 2.50V(to lithium electrode) under have blue look, but be transformed into transparent light green at 3.50V.Confirm that also this variation is a reversible.

In acetonitrile, use (C then ₄H ₉) ₄NCl O ₄As electrolytic solution, applying voltage-0.7V～1.0V(to standard calomel electrode) under carry out voltammertry.The result who obtains shows in Fig. 7, as can be seen from Figure 7, voltage+0.6～-0.7V between polymeric film have avy blue, and voltage becomes the light green of highly transparent between+0.6～1.0V.

According to these results, produced the ECD display instrument shown in Fig. 8.Contain 0.53mol/l Li BF ₄The polypropylene carbonate ester solution add liquid electrolyte, sealing then.Under the 1HZ frequency to the ECD display instrument apply+0.8V～-square wave of 0.4V so that finish fatigue test.As a result, even 2 * 10 ⁴After inferior variable color and the decolouring work, do not observe the rotten of electrochromic material yet.

Fully describe the present invention, be intended that the restriction that the present invention only is subjected to the scope of law of claim.

Fig. 6 explanation:

The electron spectrum of polyisothianaphthene (elecfronic spectroscopy); As the electric charge function, full line is discharge for 2.5 volts, and full line is charging for 3.5 volts, tests Li in electrochemical cell ⁺ClO ^- ₄, be dissolved among the THF, make ionogen, contain doping agent ClO in this routine oxypolymer ^- ₄,

Fig. 9 explanation:

The electrochemical reversibility of poly-(isothianaphthene) film is a benchmark with the standard calomel electrode, and+0.6=Huang is transparent ,-0.4 volt=Lan-Hei, and opaque, Li ⁺BF ^- ₄, be dissolved in the propylene carbonate, make ionogen.Contain doping agent BF in this routine oxypolymer ₄

Claims

1, preparation has the method for polymkeric substance of indene structure different sulfur, it is characterized in that, this have indene structure different sulfur polymkeric substance structural formula for (I a) and/or (I b):

In the formula, R ¹And R ²Respectively do for oneself hydrogen atom or contain the alkyl of 1 to 5 carbon atom, as methyl, methoxyl group and sulphomethyl, condition is R ¹And R ²Can link to each other and form condensed ring, i.e. naphthalene along phenyl ring; X is sulphur, selenium or tellurium; Y is an electrolytic anion; Z is 0.01 to 1, the anionic ratio of the every mole of monomer of this numeral; N is 5 to 500, this numeral polymerization degree,

The method of preparation poly-(isothianaphthene) comprises three kinds of alternative methods,

1). in the presence of the nucleophilic negatively charged ion, make isothianaphthene carry out electrochemical polymerization,

2). make isothianaphthene or dihydro isothianaphthene-s-oxide compound in the presence of cationic polymerisation catalyst, carry out chemical polymerization,

3). make poly-(dihydro isothianaphthene) carry out dehydrogenation reaction.

2, preparation method according to claim 1, wherein, dielectric medium negatively charged ion Y in the indene structure different sulfur of formula (I b) ^-For: Cl ^-, Br ^-, I ^-, Cl O ^- ₄, BF ^- ₄, PF ^- ₆, A ₅F ^- ₆, Sb F ^- ₆, Al Cl ^- ₄, Al Br ^- ₄, Fe Cl ₄, and CF ₃SO ^- ₃

3, electrochromic display device (elecfrochromic display), wherein, form the high molecular conducting film again on the conductive, transparent base, conducting film is used as and shows base (display base), counter electrode is placed under the liquid electrolyte, it is characterized in that this high molecular conducting film is to have the polymkeric substance of leading the benzo-thiophene structure as preceding arbitrary claim is described, and can carry out to reversibility oxidation or reduction.

4, preparation has the method for new polymers of following repeating unit, it is characterized in that, the structural formula of this new polymers is,

In the formula, R, R ' are respectively hydrogen, methyl, methoxyl group, sulphomethyl; Condition is R, and R ' can be connected, and forms condensed ring, i.e. a naphthalene along phenyl ring; X is sulphur, selenium or tellurium, and n is 5 to 500, the expression polymerization degree,

The method for preparing above-mentioned polymkeric substance comprises alternative method in three:

1) in the presence of the nucleophilic negatively charged ion, make isothianaphthene carry out electrochemical polymerization,

3). make poly-(dihydro isothianaphthene) carry out dehydrogenation reaction.

5, poly-(isothianaphthene) preparation method according to claim 4, wherein, in poly-(isothianaphthene) structural formula, X is a sulphur, R, R ' they are hydrogen.

6, the preparation method of doping according to claim 4 poly-(isothianaphthene) wherein, mixes in poly-(isothianaphthene) structural formula, and X is a sulphur, and R, R ' are hydrogen.

7, reversibility electrochemical doping polymkeric substance as claimed in claim 4.

8, the rechargeable battery electrode is characterized in that, it comprises the described polymkeric substance of claim 4.

9, electrochromic material is characterized in that, it comprises the described polymkeric substance of claim 4.

10, device for converting solar energy, it comprises the described polymkeric substance of claim 4.

11, as the high molecular conducting film of electrochromic layer, it is characterized in that, its with can the reversibility oxidation or the reductive polymer form exist, and have the indene structure different sulfur shown in the logical formula III:

In the formula, R ¹And R ²For hydrogen or contain the alkyl of 1-5 carbon atom, X is sulphur, selenium or tellurium, Y ^-Be negatively charged ion, Z is 0-0.40, represents the unitary anion ratio of each indene structure different sulfur, and n represents the polymerization degree, is 5-500.