CN1063293A

CN1063293A - The preparation method with the polymkeric substance of indene structure different sulfur and electrochromic display

Info

Publication number: CN1063293A
Application number: CN92100766A
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: 1992-02-09
Publication date: 1992-08-05
Anticipated expiration: 2000-08-07
Also published as: CN1045410A; CN1007815B; CN1018874B; CN1023527C; CN85105974A

Abstract

Electrochromic display device is comprised of the counter electrode that is attached to the macromolecule conducting film on conductive, transparent base and be placed under liquid electrolyte, and this macromolecule conducting film is the polymkeric substance with indene structure different sulfur, can reversibly be oxidized or reduce.Formula (Ia) and/or (Ib) shown in polyisothianaphthene can be with the preparation of electrochemical polymerization or other polymerization process:

in formula, R ¹, R ²for hydrogen maybe can be connected into the alkyl of condensed ring, X is sulphur, selenium or tellurium.

Description

The preparation method with the polymkeric substance of indene structure different sulfur and electrochromic display

The application is dividing an application of CN90100116.

In recent years, Electrical and Electronic equipment aspect light, thin, microminiaturized, makes remarkable progress, and not only various electro-conductive materials used need to be to light, thin, microminiaturized future development, and material itself also needs there is 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; Dibenzothiophene polymkeric substance, referring to U.S. Patent No. 3,585,163; Vinyl thiophthene polymkeric substance, referring to U.S. Patent No. 3,615,384; Various substituted thiophene polymkeric substance, referring to U.S. Patent No. 3,725,362; The bromo-8-of 2-hydroxyl-5,5-dioxo dibenzothiophene polymkeric substance, referring to United States Patent (USP) NO.3,775,368; Four sulphur pentalene polymkeric substance, referring to U.S. Patent No. 4111,857 in the conducting polymer body field developing rapidly (" conducting polymer body physics and chemistry international conference collected works ", J.physique.Colloque, 1983, c-3), heterocycle polymer is subject to people and notes, this is because they are easy to film forming, and while exposing in atmosphere, it has better stability than polyacetylene or poly-(phenylene).About the application aspect stabilization of semiconductor surface, referring to R.Noufi etc., J.Amer.Chem.Soc.1981, rolls up 183,184 and reference wherein, and the research work for Polythiophene that we carry out is in the recent period exactly the continuity of this respect work.

Carried out the broad research work of novel conductive superpolymer.For example, studying polyacetylene class, the electrode materials that they may be used as secondary battery because after the pentafluoride doping with iodine or arsenic (referring to, synthetic metal (synthetic metals), rolls up 1, No.2.101(1979/1980)), their excellent electric conductivity, up to 10 ²to 10 ³s/cm, and there is excellent charging-discharge performance.Also in research, by polyacetylene class, make solar cell material, this is because their extinction characteristic approaches sunlight.But polyacetylene class also has shortcoming, polyacetylene itself is easy to oxidation, and doping (dopped) polyacetylene class 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 particular electrical minor structure because of them, it is similar to the conjugated structure of cis-polyacetylene, and sulfur atom-containing, in addition, utilize dopant states colour-change, people also study with them as electrochromic material.For example, the people such as A.M.Druy once reported, made 2,2 '-bis-thiophene electrochemical polymerizations generate the polymkeric substance with reversible shock color change, be that the blue look reversibility of oxidation state becomes reduction-state redness, utilize this color change, this polymkeric substance can be used as electrochromic material.(referring to Journal de phys iguc, rolling up 44, No.6, C3-595(1983))

In view of the above problems, the inventor has carried out broad research, and we find, the polymkeric substance with indene structure different sulfur is also highly stable compound in air, and can among redox processes, reversibly convert 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 while oozing assorted agent, is easy to demonstrate the electroconductibility higher than 10s/cm, thereby just completes the present invention.

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

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 to phenyl ring, produced stability, and this stability greatly improves because of its resonance structure.

In 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, roll up 17,145; G.Tourillon etc., J.Elcchroanal, Chem.1982, roll up 135,173, C.Kossmehl etc., Makromol.Chem.Rapid Commun, 1981, roll up 2,551; J.Bargon, IBM, J.of Resand Dev., 1983, roll up 27,330; K.Kancto etc., J.Chem.Soc.Chem Com., 1983,382) another kind be 2,5-, bis-fontanels for the chemical coupling of thiophene (M.Kobayashi etc., Syhthetic.Metals, 1984, roll up 9,77; T.yamamoto etc., J.polym SCi., Polym, lett.1980. volume 18,9; J.Lin etc., J.Polym.Sci.Polym, Chem, Edition, roll up 18,2869).As made parent material with 2,2 '-dithienyl, by first method, carry out polymerization, improve to some extent (M.A.Druy, J.Physigue, Collogue of the material property of gained, 1983, volume c-3,595) and electrolysis can under more electric low impressed voltage (～3.5V), carry out.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.Chemical coupling rule has more theory value, because product is xln, number-average molecular weight is known, but the product of producing is always Powdered.

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

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

As everyone knows, liquid crystal indicator need obtain development by energy display unit seldom as a kind of, and be widely used in all respects, still, liquid-crystal apparatus also exists the problem that relies on visual angle, in addition, also have some other shortcoming, as poor in display resolution, memoryless function, do not reach large-area displays, etc.In order to overcome these shortcomings, ECD device has been carried out to research thoroughly, and ECD device also belongs to low power consuming type, and it utilizes so-called electrochromism (clcctrochromism), in electrochromism body, optical absorption characteristics is different and different with the voltage applying or electric current.In ECD device, electrochromic material used is divided into inorganic materials and organic materials.Be considered to the oxide compound that useful inorganic materials mainly comprises transition metal, special case is 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 viologen dyestuff, phthalocyaninato complex, etc.But the shortcoming of viologen dyestuff is the precipitation that can cause insolubles reusing, phthalocyaninato complex also has the adhesion problem between a vacuum-evaporated film and substrate not yet to solve,

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, rolls up 161,419(1984); Polypyrrole, referring to A.F.Diaz, etc., ibid, rolls up 101, (1983) and Polythiophene, referring to M.A.Druy. etc., Journl de physigue, rolls up 44, page June, page C-595(1983). or Kaneto etc., Japan Journal of Applicd physics, volume, 23, No, 7, page L412(1983), but go back neither one in these materials, be put into use.Especially, electrochromic material should be swift in response, and contrast gradient is high, consumes energy low, manifests excellent tone, etc., in addition, electrochromic material also should be able to manifest colourless tone, and this can greatly open application of installation scope.Yet, the variable color during being transformed into reduction-state process from oxidation state entirely of these hetero conjugation type high molecular weight materials.Improve the method for contrast gradient, for example, use white background plate, setting about studying, but also do not completing.

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

In formula, R ¹and R ²represent separately hydrogen atom or containing the alkyl of 1 to 5 carbon atom, as methyl, methoxyl group and sulphomethyl, condition is R ¹and R ²can be connected, along phenyl ring, form condensed ring, i.e. a naphthalene; X is sulphur, selenium or tellurium; Y ^-for 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 electrochromic display body, on conductive, transparent base, form macromolecule conductive film, this conducting film is used as showing that counter electrode is placed under liquid dielectric, feature of the present invention is that this high molecular conducting film is the polymkeric substance with indene structure different sulfur, and this polymkeric substance can be reversibly oxidized and reduce.

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

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

Poly-(isothianaphthene) and some relevant polymkeric substance can be prepared with several different methods.During with electrochemical method polymerization isothianaphthene, very strong to ionogen dependency.At nucleophilic negatively charged ion (Rr ^-, Cl ^-) under existence, form poly-(benzo-thiophene).No matter at protonic acid (HSO ₄nH ₂o) doped forms is still under muriate doped forms, and the conductivity of poly-(benzo-thiophene) is than high approximately 1 order of magnitude of Polythiophene.

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

In thering is the solvent of dehydration and oxidation effectiveness, as reacted in the vitriol oil, generate the polymkeric substance of required needs.

In addition, needed polymkeric substance also can be from 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 and distils under aluminum oxide exists, and prepares (II b) isothianaphthene to make general formula.Make formula (II b) isothianaphthene carry out following reaction, (I) is under dielectric medium exists, in to aprotic solvent; carry out electrochemical polymerization; (II), using solvent or not using under solvent condition, carries out cationoid polymerisation, then makes two Hydrogen polymkeric substance of gained and oxidant reaction with dehydrogenation; (III) oxypolymerization; Or carry out polymerization by other similar approach.

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

Polymerization temperature in above-mentioned process for polymerizing monomers can be definite according to concrete polymerization process, not strict especially, and conventionally, polyreaction will be carried out at-80 ℃ to 200 ℃.The method that polymerization time also can adopt, polymerization temperature, monomer structure etc. determines, 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 method described in following file, M.P.Cara, Deng, 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 dissolubility lithium sulfide, dissolubility lithium sulfide can be by preparing lithium triethylborohydride and reaction of Salmon-Saxl, referring to J.A.Gradysz, Deng, Tetrahedron letters, volume, 35, 2329(1979).

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

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

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

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

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

Please see accompanying drawing:

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

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

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

Fig. 4 is the infrared absorpting light spectra of the polymkeric substance that obtains with polymkeric substance prepared by chloranil processing example II.

Fig. 5 is the polarographic analysis result diagram of the polymkeric substance that obtains 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 tetrahydrofuran solution, and every liter of tetrahydrofuran solution is containing 0.53 mole of Liclo ₄, with lithium, make counter electrode.

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 acetonitrile, is ionogen, voltage be+1.0V extremely-0.7V.(and standard calomel electrode comparison)

Fig. 8 is the cross section sketch of the present invention's ECD device.In figure, numeral 1 represents 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 is lead-in wire.

Fig. 9 represents to gather the reversibility electrochemical doping of (isothianaphthene).With aluminium, make an electrode (band standard calomel reference electrode), with poly-(isothianaphthene), make another electrode, with the polypropylene carbonate ester solution of fluoro lithium tetraborate, as electrolytic solution, can see, 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.

With a completely new structure according to the prepared polymer, not only through the top shows high conductivity significantly, but also repeated electrochemical oxidation - reduction reaction, at the same time, the natural color of each state. In addition, the invention of the poly isothianaphthene is a particularly interesting polymer, because of its transparency even further oxidation state not to weaken. Therefore, the invention of a polymer having ISOTHIAINDENE structure is very useful in the electrical and electronic industry, for example, as electrode, electrochromic display device, solar battery, electromagnetic wire electric bonding, fixation and conversion device, as well as for the reversible redox system.

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

Example 1

In the vitriol oil, process 1,3-dihydro isothianaphthene-2-Preparation polyisothianaphthene

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

The lithium triethylborohydride that under room temperature and nitrogen atmosphere, 200ml is contained to 1mol/l add to fill 3.219(0.1mol) in the SChlen R flask of sulphur powder, reaction occurs at once, sulphur powder dissolves formation-yellow suspension.Owing to contacting 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 respectively 26.4g(0.1mol under nitrogen atmosphere) anhydrous tetrahydro furan of xylylene bromide and 1 liter forms solution.During stirring, the tetrahydrofuran solution of the lithium sulfide of 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 ^-1based on phenyl, shown sorption; 2910,2840 and 1450cm ^-1based on α-tolylene, shown sorption; At 1195cm ^-1based on 1,2-substituted-phenyl plane inner deformation, shown sorption; Sorption at 760cm 0-substituted-phenyl.At 740cm ^-1the sorption of thioether.At CHCL ₃the middle tetramethylsilane (TMS) of using is as the nucleus magnetic resonance (' H-NMR) of internal standard, and measuring result is as follows:

4.22（S，4H）;7.20（S，4H）

This compound is very unstable, and being even kept at still can be black from xanthochromia under light shield and 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 stirs 12 hours, isolates the precipitation of generation with filtration method.Filter cake 50ml washed with methanol.Washing lotion and filtrate are mixed and concentrating under reduced pressure.The yellowish white solid recrystallization from ethyl acetate-hexanaphthene forming thus, obtains at molten o'clock micro-yellow crystals of 87～89 ℃.

Resulting crystal further from ethyl acetate-hexanaphthene recrystallization to obtain at molten o'clock at the crystal of 90～91 ℃.Crystal infrared spectra shows, except isothianaphthene absorbs, and the absorption thioether also splitting by force at 1035cm, and at 740cm ^-1thioether absorb to disappear.At CHCl ₃the middle nuclear magnetic resonance spectrum of measuring as internal standard with methyl-monosilane is as follows:

4.65（S，4H），7.20（S，4H）

C ₈h ₈sO 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

The vitriol oil that adds 1ml in the 1.3-dihydro isothianaphthene of 500 milligrams (3.29mmol), becomes garnet at once in reactive system.Mixture is put 70 hours under greenhouse, etc. system, substantially solidifies the methyl alcohol that later injects 400ml.With centrifuging, the brown precipitate generating is separated, water cleaning down and 60 ℃ of one nights of vacuum-drying.The polymkeric substance obtaining is placed in Soxhlet's extractor, with methylene dichloride and chlorobenzene, extracts successively 12 hours 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 thering is the repeating unit of following structure

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

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

Example II

With oxygenant, be oxidized the poly-dihydro isothianaphthene obtaining from the cationoid polymerisation of isothianaphthene and prepare polyisothianaphthene

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

By 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 fully mix, then be placed in sublimation apparatus, under decompression, in an oil bath, heat.Cooling segment at sublimation apparatus has thoroughly obtained 250mg(1.87mmol) isothianaphthene white, needle-shaped crystals, immediately thereafter, resulting monomer is dissolved in the degassed methylene dichloride alkane of 5ml purifying, then adds 10mg trifluoroacetic acid, then mixture is placed to a night.When 50ml methyl alcohol injects reaction mixture, obtain a white depositions.Resulting polymers, at chloroform, chlorobenzene, tetrahydrofuran (THF) and N, dissolves in N-methylacetamide.The infrared spectra of this polymkeric substance and ' H-nuclear magnetic resonance spectrum respectively as shown in Figures 2 and 3.

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

At room temperature, take the polymer conductivity (υ RT) that the same mode of example 1 measures is 10 ^-8s/cm or lower.

(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 obtain-polymkeric substance of identical operation.Resulting polymers infrared spectra is consistent with Fig. 2 completely.

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

Except using 5ml chloroform to replace chlorobenzene; The N-chlorosuccinimide of 1.1 times moles replaces outside chloranil, makes a polymkeric substance black, complete and that in Fig. 4, illustrated infrared spectra is identical with above-mentioned same method.Record and know that the specific conductivity (υ RT) of this polymkeric substance is 2.6 * 10 ^-1s/cm.

Example 3

Oxidation step polymerization isothianaphthene is prepared polyisothianaphthene

Example 2(a) the synthetic isothianaphthene of same method.At 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 after 12 hours precipitation is processed with the methanol solution of hcl acidifying under said temperature, and water cleaning down is also dry.Use successively hot methanol, hot methylene dichloride and hot chlorobenzene extract oneself dry polymkeric substance, obtain the black polymer of 205mg.The infrared spectra of this product is completely consistent with Fig. 4, and specific conductivity (υ RT) is 2.8 * 10S/cm.

Example 4

Electrochemical polymerization isothianaphthene is prepared polyisothianaphthene

Isothianaphthene electrochemical polymerization method is as follows:

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

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

Table 1 annotation:

P ₄aSCl: Lvization Si Ben Arsenic

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 electrochemistry display element, the use of battery material etc.

Repeat the same operation of routine 4-2, but replace platinum plate in example 4-2 with conductive glass (vacuum-evaporation Indium sesquioxide is made anode) thereon, make thus polymer chemistry be deposited on conductive glass.The polymer-coated conductive glass of gained is made working electrode, platinum line is made counter electrode, standard calomel electrode is made reference electrode, by using polarographic analyze (the 174A type that EGHe G company manufactures) to carry out cyclic voltammetry under 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-0.15V polymkeric substance has shown respectively oxidation peak and reduction peak, and coloured variation: from the avy blue in-0.7V～+ 0.6V voltage range, become the super transparent light green in+0.6V～+ 1.0V voltage range.These results show: avy blue state is condition in polymkeric substance, and under oxidation state and doping state, polymkeric substance is the green color of highly transparent.

Test as battery

The polyisothianaphthene obtaining in routine 4-1 is cut into the long mode of the wide and 3cm of 1cm, and one of test piece is with on 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 onesize lithium paper tinsel, then, this system is soaked in the acrylate solution of the lithium perchlorate degree of depth 2cm that contains 0.5mol/l, the battery (wherein polyisothianaphthene is negative electrode, and lithium paper tinsel is anode) of preparation, is 2.0mA/cm in charging current thus ²and under argon atmospher, charge 30 minutes.After charging completely, discharging current is to discharge under 2.0mA/cm at once, when cell voltage drops to 1V, under above-mentioned similarity condition, again charges simultaneously.When discharging and recharging operation while repeating with aforesaid method, record repetition 590 times, until efficiency for charge-discharge Efficiency Decreasing to 50%.In addition, 5 times are repeated efficiency for charge-discharge is 99%, and in addition, battery is after 48 hours charging states, and self-discharge rate is 3.2%.

Example 6

Electrochemical polymerization method preparation poly-(dihydro isothianaphthene)

Monomer isothianaphthene is with document (people such as J.A.Gladysz, Tetrahedron, 1979 volumes 35,2239; The people such as M.P.Ca Va, J.Amer.chem, Soc., 1959, roll up 81,4266; The people such as M.P.Ca Va, J.Ora.Chem., 1971, rolls up 36,3932) prepared by the method described, make rear direct use.Poly-(dihydro isothianaphthene) carries out electrochemical oxidation to this monomer and makes in two electrodes, separating diaphragm battery, and 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 for polyreaction.Directly use acetonitrile (Mallinckrodt) and do not need to be further purified, with the 1.5V battery of connecting, making power supply.

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

When the isothianaphthene sample of new system is 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 inner electrolysis, a large amount of white precipitate (" WP ") has been full of anode layer.After examining, find, anode first (instantaneous) has covered very thin blue film, after this starts immediately to generate WP.The outward appearance of WP and electrode materials, solvent, or temperature is irrelevant.Separation, CHARACTERISTICS IDENTIFICATION (infrared rays, flexibility analysis) and chemical operation (below seeing) prove: WP is exactly poly-(dihydro isothianaphthene).It should be noted that under these conditions, when isothianaphthene, having precipitated very thin blue film, (poly-(isothianaphthene) of doping that the chances are, while being transformed into poly-(dihydro isothianaphthene), thiophene has produced the polymeric film of partial oxidation (" doping ").For the unique rational explanation of this wonderful observation, be: the effect that poly-(isothianaphthene) takes on isothianaphthene cationic polymerization initiators.In order to verify this section of hypothesis, we are exposed to the isothianaphthene solution of new system in some typical catalyst and cause for positively charged ion, find to make to some extent isothianaphthene polymerization under all occasions, but the most interesting result is the dichloromethane solution effect for sulfuric acid, now, isothianaphthene is transformed into poly-(the dihydro isothianaphthene) of the hydration sulfuric acid doping of blue black.Obviously, acid has not only played catalyzer, and has played oxygenant.The product that is the dehydrogenation of tetrachloro-P-benzoquinones to " concentrating " inspecting standard of hypothesis insurance above is poly-(dihydro isothianaphthene) and the product that demonstrates the sulfuric acid polymerization being equal to infrared spectra.For the unique rational explanation of this observation, be, the infrared spectra of doping poly-(isothianaphthene) is subject to because the absorption of conduction electron is controlled, and because the absorption of intramolecule vibration is the weakness of spectrum.When lacking additional Control experiment, be difficult to a concrete mechanism of supposition and explain this electrolytical effect.

We infer that sulfuric acid can directly change into poly-(isothianaphthene), (H dihydro isothianaphthene-S-oxide compound ₂sO ₄) _x(H ₂o) _y.Solid dihydro isothianaphthene-S-oxide compound is added in 98% sulfuric acid, has in fact really generated poly-(isothianaphthene) (Fig. 1 below) of desired part doping.

In addition, 7,7,8,8 ,-tetra-cyanide quinolines 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, acceptor does not probably relate to the specific conductivity of solid.For that observation, two kinds of judgements may be advanced, and receptor molecule is not probably deposited in small-crystalline region, 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 because " status nascendi " doping poly-(isothianaphthene) forms poly-(dihydro isothianaphthene).We find, if in reaction medium, have than isothianaphthene more the molecule of nucleophilic form, chainpropagation is cut off step and will be damaged.One related to before electrolytic action and iodide to be added to detection in anode layer the experiment failed of success, because iodine is oxidized under 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 rational explanation of this observation is, poly-(isothianaphthene) infrared spectra of doping be subject to the control due to the absorption of conduction electron, the absorption of intramolecule vibration is the weakness of spectrum.When lacking additional Control experiment, be difficult to infer a this electrolytical effect of concrete mechanism explain.

C ₈h ₆s analytical calculation value: C11.60; H4.51; S23.89;

Measured value: C71.27; H4.54; S23.96

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 metastable state isothianaphthene be aggregated into three kinds of different methods to the high conductive polymers with excellent characteristic; One relates to when there is the negatively charged ion of nucleophilic, by isothianaphthene polymerization, and electrochemistry preparation poly-(dihydro isothianaphthene).

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

Embodiment 7

With chemical cationic polymerization preparation poly-(dihydro isothianaphthene)

Monomer isothianaphthene (396mg, 2.96mmol) is dissolved in 10ml and gives and first pass through P ₂o ₅in dry methylene dichloride, in this liquid, add a methylsulfonic acid, in reaction mixture, at once from the colourless redness that becomes, after 90 minutes, become purple.Evaporation is removed after methylene dichloride, and residue dissolves with tetrahydrofuran (THF).When this solution injects after methyl alcohol, poly-(dihydro isothianaphthene) settles out from solution.With centrifuging, carry out separation, vacuum-drying.Infrared spectra is identical with poly-(dihydro isothianaphthene) above-mentioned.

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

Embodiment 8

Poly-(isothianaphthene) of electrochemical polymerization method preparation doping

Polymerization process is substantially identical with above-mentioned example 6 poly-(dihydro isothianaphthene).The most important is ionogen.When lithiumbromide is used as ionogen, connect a 1.5V battery, poly-(isothianaphthene) blue film of doping is at once in the upper generation of anode (conductive glass).Bu ₄nBr and Ph ₄as Cl also can be as the ionogen of this reaction.

Embodiment 9

With sulfuric acid, carry out poly-(isothianaphthene) of chemical cationic oxidation polymerization preparation doping

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

Embodiment 10

With TCNQ(7,7,8,8-, tetra-cyanide quinolines bismethane) poly-(isothianaphthene) that carry out chemical cationic oxidation polymerization preparation doping.

Monomer isothianaphthene (238mg, 1.77mmol) is solution in 5ml methylene dichloride.Add several grams of TCNO in solution after, its color becomes redness very slowly.Stir after the night, this color becomes blue black.Thereafter, add the TCNQ that doubles monomer isothianaphthene mole to this solution, heating is until 110 ℃ and keep 1 hour.This solution is injected after methyl alcohol, and blackish green powder is precipitated out from solution.In Soxhlcl extractor, adopt methyl alcohol and chlorobenzene to rinse, and vacuum-drying.

Embodiment 11

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

Poly-(dihydro isothianaphthene) prepared by electrochemical polymerization dissolves in hot chlorobenzene, and this is light brown solution.When tetrachloro-P-benzoquinones is added in this solution, solution colour becomes 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 separation.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 nucleophilic negatively charged ion to exist, make isothianaphthene carry out electrochemical polymerization.

2. having under cationic polymerisation catalyst existence, make 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 table 2, poly-be estimated as～1ev(1.1 of (isothianaphthene) band edge μ) (under low-doped degree, passing through film transfer), this is lower than Polythiophene (1～2ev, 620nm) ³nearly 1ev.

Table 2

Poly-(isothianaphthene) compacting specific conductivity table of doping

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 2.8 * 10 ^-2

Poly-(isothianaphthene) (AlCl 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 doping of poly-(isothianaphthene).Therefore, with aluminium, make an electrode (using standard calomel reference electrode), poly-(isothianaphthene) makes another electrode, and the polypropylene carbonate ester solution of lithium-fluoroborate is electrolytic solution, can find out, 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 lithium.Energy derive is in incident radiation, and 0～1st, in infrared region, 1～2nd, visible ray, more than 2 transfers to spectrum ultraviolet part gradually.The result showing in Fig. 6 has further been pointed out the application of polymkeric substance of the present invention in device for converting solar energy, fine because semi-conductor energy gap is mated with solar spectrum.

Contriver conducts extensive research having the electrochromic property of the polymkeric substance of isothianaphthene mechanism, found that: above-mentioned polymkeric substance is novel electric type off-color material, its response rapidly, substantially has colourless tone under oxidation state, has therefore reached object of the present invention.This discovery is beyond thought, unknown because this colourless electrochromic material substantially still belongs to so far.According to the present invention, electrochromic display device (ECD) is by being comprised of the conductive, transparent base of the conducting film of a molecular weight and the counter electrode being placed under its lower liquid electrolyte on it, the conducting film that it is characterized in that described macromolecule is the polymkeric substance with indene structure different sulfur, can plastically be oxidized or reduce." liquid electrolyte " used herein word refers to dispersion or the solution of supporting electrolyte in solvent.

Macromolecule conductive film, can be used as electrochromic film according to the present invention, and it can reversibly be oxidized or reduce and be the polymkeric substance with indene structure different sulfur (formula III is represented):

R wherein ¹and R ²represent hydrogen or with 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 the ratio of negatively charged ion in each indene structure different sulfur unit, and N represents 5～500 the polymerization degree, is that the isothianaphthene compound being represented by following formula IV produces through electrochemical polymerization,

R in formula ¹, R ²with X with defined above identical.

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 etc.

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

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, etc., use sputter or similar approach.These materials are easy to buy as industrial goods.The polymeric film that electrochemical polymerization generates, thickness is from 0.03～30 μ m, 0.05～22 μ m preferably, the best is 0.1～10 μ m.Film thickness can be subject to the control of the magnitude of current in electrochemical polymerization, when film thickness is during less than 0.03 μ m, can not get contrast clearly, therefore as having considerable damage in 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 liquid electrolyte, refills and mix obtained polymkeric substance, produce ECD display instrument.The liquid electrolyte using is, the dispersion of the supporting electrolyte in solvent or solution.In the present invention, operable supporting electrolyte comprises negatively charged ion and cationic combination, and (I) negatively charged ion (is Y in 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, 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 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 for example, Ji Phosphonium ion, (C ₆h ₅) ₄p ⁺.But these combinations are not restrictive.

Object lesson by the above-mentioned negatively charged ion supporting electrolyte that (x) combination forms with positively charged ion is LiPF ₆, Li Sb F ₆, Li As F ₆, Li Cl O ₄, Na I, Na Sb F ₆, Na A _sf ₆, Na Cl O ₄, K I, KPF ₆, K Sb F ₆, KA ₅f ₆, KCl O ₄, [(n-Bu) ₄n] ⁺(ASF ₆) ^-, [(n-Bu) ₄n] ⁺(PF ₆) ^-, [(n-Bu) ₄n ⁺] Cl O ₄, Li AL Cl ₄, Li BF ₄, (C ₆h ₅) PBF ₄, (C ₆h ₅) ₄pA _sf ₆(C ₆h ₅) ₄pCl O ₄, but these examples are not restrictive.These supporting electrolytes can be used separately, if necessary or two or more combine use.Except the above-mentioned negatively charged ion of enumerating, also can use HF ^- ₂negatively charged ion.Except the above-mentioned positively charged ion of enumerating, spendable positively charged ion also further comprises pyrrole

or pyridylium (following formula (V) is represented) and carbocation (lower formula VI or (VII) are represented:

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

R in formula ³, R ⁴, R ⁵each represents a hydrogen atom, with the alkyl of 1～15 carbon atom, an allyl group, aryl with 6～15 carbon atoms or-OR ⁷, R in base ⁷represent the alkyl of 1～10 carbon atom or with the aryl of 6～15 carbon atoms, condition is R ³, R ⁴and R ⁵when different, are hydrogen atoms; R ⁶represent hydrogen atom, an alkyl with 1～15 carbon or have the aryl of 6～15 carbon.

Operable HF ^- ₂negatively charged ion is normally by dissolving following formula (VIII), the compound (hydrofluoride) that (IV) or (X) represents and obtaining,

R ₄′N·HF ₂（Ⅷ）

M·HF ²（Ⅸ）

" each represents a hydrogen atom, alkyl with 1～15 carbon atom or with the aryl of 6～15 carbon atoms for R ' and R in formula; R ' ' ' representative is with the alkyl of 1～15 carbon atom or with the aryl of 6～15 carbon atoms; Z represention oxygen atom or nitrogen-atoms; Q representative zero or the integer below 5 or 5; M represents that basic metal is as a kind of supporting electrolyte in appropriate solvent.By above formula (VIII), the compound object lesson of (IV) and (X) representative comprises H ₄nHF ₂; Bu ₄nHF ₂, N _ahF ₂, KHF ₂, LiHF ₂with

The pyrrole of formula 3 representatives

or pyridylium 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, A _sf ^- ₆, CF ₃sO ^- ₃, HF ^- ₂etc.) between form in suitable solvent, as the salt of supporting electrolyte, obtain.The object lesson of this salt is:

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

etc..

These carbocations can obtain by dissolving or being dispersed in the salt forming as supporting electrolyte in appropriate solvent between positively charged ion and negatively charged ion (X) (being carbon salt).The available negatively charged ion (X) of typical case comprises (BF ^- ₄, Al Cl ^- ₄, Al Br ₃cl ^-, Fe Cl ^- ₄, PF ^- ₆, PCl ^- ₆, Sba ^- 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 ₄etc..

In the present invention, available solvent can be both that water solvent can be also non-aqueous solvent, but supporting electrolyte solution noted earlier is relatively good in non-aqueous organic solvent, and organic solvent used herein is aprotonic solvent preferably, and has high specific inductivity.For example, can use ether, ketone, nitrile, amine, acid amides, sulphur compound, phosphotidic compound, sub-phosphotidic compound, boric acid ester compound, chlorinated hydrocarbon, ester, carbonic ether, nitro-compound and all classes.Certainly, preferably ether, ketone, nitrile, phosphotidic compound, sub-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 sub-phosphide of ethyl phosphorous acid METH, 3-trimethylammonium sulforan etc.In order to improve response speed, in the middle of them, with nitrile and carbonic ether especially for well.

These organic solvents can be used separately also can two kinds, two or more being combined with.

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

The supporting electrolyte using in 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 homogeneous phase can be also heterogeneous, but normally used concentration range is between 0.001～10mol/l.Macromolecule conducting film and counter electrode spacing generally be can not determine, because the kind of supporting electrolyte, the electric current applying and magnitude of voltage, ECD display instrument indicator gauge area and all classes are depended in their variation, but preferably from 0.05～5mm.In addition as counter electrode, according to object purposes, can use multiple material,, when transmitted light is used for showing, transparent material as above is preferably as counter electrode.On the other hand, with regard to the utilizing emitted light using, also can be used as counter electrode use and resemble the opaque electro-conductive material of tinsel class, for example nickel or platinum and wire cloth.In addition,, because ECD display instrument provides colourless tone substantially, just can select the base plate of different tones.Therefore, the ECD display instrument that the present invention obtains, can be in widespread use owing to extensively selecting 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) ₄in the acetonitrile solution of PCl, dissolve 0.0788mol/ll, [compound of formula IV is R wherein for 3-isothianaphthene ¹=R ²=H] prepare 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, in room temperature and current density, is under 2mA/cm, to switch on within 20 minutes, carrying out electrochemical polymerization.Scribbling on indium oxide tin glass plate anode, obtaining the avy blue polymkeric substance of the slight doping of electrochemistry.The demonstration base obtaining rinses and is dried with acetonitrile, and dry polymeric film is 10 μ m.

Consequent demonstration base is immersed in and contains 0.53mol/l Li Cl O ₄tetrahydrofuran solution in, with lithium, as counter electrode energising, measure executing alive dependence.The result obtaining is shown in Figure 6.As shown in Figure 6, polymkeric substance at 2.50V(to lithium electrode) under there is blue look, but be transformed into transparent light green at 3.50V.Also confirm, this variation is reversible.

Then in acetonitrile, use (C ₄h ₉) ₄nCl O ₄as electrolytic solution, applying voltage-0.7V～1.0V(to standard calomel electrode) under carry out voltammertry.The result obtaining shows in Fig. 7, and as can be seen from Figure 7, voltage polymeric film between+0.6～-0.7V has 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 ₄polypropylene carbonate ester solution add liquid electrolyte, then sealing.Under 1HZ frequency to the square wave of apply+0.8V of ECD display instrument～-0.4V, to complete fatigue test.As a result, even 2 * 10 ⁴after inferior variable color and 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 is only subject to the scope of law of claim.

Claims

1, rechargeable battery electrode, is characterized in that, this electrode contains a kind of new polymers, and the structural formula of this new polymers is,

In formula, R, R ¹be respectively hydrogen, methyl, methoxyl group, sulphomethyl; Condition is R, R ¹can be connected, along phenyl ring, form condensed ring, i.e. a naphthalene; X is that sulphur, selenium or tellurium, n are 5 to 500, represents the polymerization degree.

2, electrochromic material, is characterized in that, this material contains a kind of new polymers, and the structural formula of this new polymers is,

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

3, device for converting solar energy, is characterized in that, this device contains a kind of new polymers, and the structural formula of this new polymers is,

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

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