CN1024067C - Conducting substituted polyisothianaphthenes - Google Patents
Conducting substituted polyisothianaphthenes Download PDFInfo
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- CN1024067C CN1024067C CN91104471A CN91104471A CN1024067C CN 1024067 C CN1024067 C CN 1024067C CN 91104471 A CN91104471 A CN 91104471A CN 91104471 A CN91104471 A CN 91104471A CN 1024067 C CN1024067 C CN 1024067C
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- 239000012780 transparent material Substances 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Polyisothianaphthene substituted in the 5 and/or 6 positions so as to have an oxygen atom adjacent to C5 or C6. Substituents include alkoxys, hydroxys and dioxyalkylenes. The polymers are conducting and useful in electrochromic displays and as electrode materials.
Description
The present invention relates to common conducting polymer and they purposes on various devices as electrode, specifically, relate to polyisothianaphthene (PITN) and their application on electrochromic display device (ECD), storage battery, solar cell and the like of replacement.
In recent years, Electrical and Electronic equipment has been obtained significant progress aspect light, thin, microminiaturized, and not only used various electric conducting materials need develop to light, thin, microminiaturized direction, and material itself also needs new developing.
Known already and can use various sulfur heterocyclic ring polymer, such as, from the luxuriant polymer that makes of sulphur, referring to United States Patent (USP) NO2,582.796 and United States Patent (USP) NO.2,658,902; The polymer that makes from dibenzothiophenes is referring to United States Patent (USP) NO.3,582,163; The polymer that makes from the vinyl bithiophene is referring to United States Patent (USP) NO.3,615,384; The polymer of various substituted thiophenes is referring to United States Patent (USP) NO.3,725,362; 2-bromo-8-hydroxyl-5,5-dioxo dibenzothiophenes polymer is referring to United States Patent (USP) NO.3,775,368; And four sulphur and cycloolefine polymer, referring to United States Patent (USP) NO4,111,857.
The heterocyclic substrate of (" conducting polymer physics and chemical international conference collection of thesis; J.Physique.Collque 1983c-3) polymerization is subjected to people and notes in the conducting polymer body field that develops rapidly; this is because they are easy to film forming; and when exposing to the open air in atmosphere, it has better stability than polyacetylene or poly-(phenylene).About it in the application aspect the stabilization of semiconductor surface, referring to R.Noufi etc., J.Amer.Chem.Sco1981 volume 183,184 and lists of references wherein, the research work for polythiophene that we carry out in the recent period is exactly the further extension of this respect work.
Carried out the extensive studies work of novel conductive high polymer already, for example, studying the polyacetylene class, they may be used as the electrode material of batteries, because after the pentafluoride doping with iodine or arsenic (referring to: synthetic metal (Synthctic metals) volume 1NO.2,101 1979/1980), their conductivity can be up to 10
2To 10
3S/cm, these polymer and charging-discharge performance with excellence.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 the polyacetylene class of mixing is wet very responsive to the lake.
Polythiophene class not only can be used as electric conducting material, and can be used as battery electrode material, and the change color of their dopant states can be used as the usefulness of electrochromic material.For example, people such as A.M.Druy once reported, 2.2-two thiophene can generate the polymer with invertibity variable color through electrochemical polymerization, be that the blue look of oxidation state can be varied to invertibity and goes back the ortho states redness, utilize this color change, this polymer can be used as electrochromic material (referring to Journal de Pysiquo volume 44, NO.6(3-593 1983).Yet polythiophene and polyacetylene are similar, normally sensitive compound.
In view of the above problems, the inventor has carried out extensive studies to conducting polymer and application thereof, we have found that, the polymer with indene structure different sulfur is very stable compound, it can be in oxidation-reduction process invertibity ground conversion color continuously.The poly-benzo-thiophene of non-replacement is delivered some works by the present inventor, referring to, J.Org such as WudI for example, Chem1984, volume 49,3382-3384 page or leaf; Polymer prcprints such as WudI roll up 25(2), the 257-259 page or leaf; The 7th page of 211832q of C.A1984 volume 101,24 fascicles; The polymer of PITN type is in Application No. 736, and 984(1985 applied for May 22) in have illustrated, comprising original relevant list of references; Similarly referring to EPO publication number 164,974(1985 is open December 18).
Because the contrastive colours that polyisothianaphthene is very stable its to be shown the electrochemical doping characteristic of P-type very rapidly and be accompanied by height change, this polymer is to be applicable to very much in many application, first uses-can be used as the purposes of electrochromic display device (ECD)-be transparent and be the advantage of the polymer of conduction according to polyisothianaphthene, after doping, the PITN film partly has very low optical density (OD) at visible spectrum.Another application is utilized PITN light-electrochemical properties, as the electrode of storage battery or electrochemical cell, device for converting solar energy and as the total application on the electrochromic material.Yet, a restriction is arranged, promptly the PITN of very highly doped amount may be because the erosion of atmosphere be accompanied by the process that loses doping.So, must guarantee to keep the advantage of its PITN, and can when highly doped amount, resist the erosion that stops atmosphere as the PITN type polymer.
Electrochromism shows an improvement representing liquid crystal indicator, liquid crystal indicator has obtained development as a kind of need recently with energy display unit seldom, and be widely used in various aspects, but, liquid-crystal apparatus also exists the problem that relies on visual angle and contrast colours and definition, memoryless function does not reach shortcomings such as large tracts of land demonstration.In order to overcome these shortcomings, low energy consumption electrochromic display device (ECD) (ECD) device has been carried out deep research, and the ECD device also belongs to the low power consuming type, and it utilizes the electrochromism property of material, promptly in electrochromic material, optical absorption characteristics is different and different with voltage that applies or electric current.
Electrochromic material used in the ECD device can be divided into inorganic material or organic material.Be considered to the oxide that useful inorganic material mainly comprises transition metal, but their taken place color is limited.Although transition metal oxide since the electrochemistry wash-out that can cause film maybe when the usefulness proton during as the quality ion reaction speed very high, can cause the damage of electrode.The organic material look that is used for the electrochromism demonstration is drawn together purple Luo Qin (Viologen dyes) dyestuff, phthalocyanine complex compound etc.But the shortcoming of purple Luo Qin dyestuff is the precipitation that can cause insoluble matter in repeated use, and the phthalocyanine complex compound 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 compound, referring to, Journal of Eleetro-Analytical Chemistry such as A.F.Diaz volume 111,111(1980) or Yoneyama etc. the same, volume 161,419(1984); Polypyrrole, referring to M.A, Druy etc., 446 months 3-593 pages or leaves (1983) of Journal de physique volume or Kaneto etc., Japan Journal of Appiled physics volume 23, NO.7.L412 page or leaf (1983).But, go back neither one in these materials and dropped into actual use.Preferable electrochromic material should be that fast response time is arranged after electro-chromic switch is opened, and contrast and definition height present excellent tone, or the like.In addition, as mentioned above, electrochromic material such as PITN also should be able to manifest colourless tone.This can greatly open device the application performance scope.Yet these above-mentioned complex conjugate section bar material are to be transformed into variable color the process of going back ortho states from oxidation state entirely.So, need improvement to be used for the polymer of the PITN-type of ECD device.
Therefore, the primary purpose of the present invention provides the conducting polymer of ground oxidation of a kind of energy invertibity or reduction.
The purpose of this invention is to provide the erosion maintenance stable polyisothianaphthene base polymer of a kind of atmosphere simultaneously to highly doped amount.
Another object of the present invention provides the polyisothianaphthene of a kind of HMW, replacement.
That another purpose of the present invention provides is chemically a kind of and physically stable, have the variation of the contrastive colours that height is provided and the electrochromism membrane material of response time fast after electro-chromic switch is opened under oxidation and reduction.
Another object of the present invention provides with the polyisothianaphthene that replaces and is used for the production of solar cell as electrode or electrode coating material, and the electrochromic material that is generally used for energy invertibity ground OR system.
These and other purpose of the present invention will be finished by following embodiment.
The present invention has to be selected from the polymer that is included in the group among following structural formula I a and the I b in one embodiment:
In the formula: R
1For hydrogen or-OR
3;
R
2And R
3Be selected from hydrogen and C separately
1-C
8Alkyl, condition are R
2And R
3With two oxygen, two oxyalkylene substituting groups on phenyl ring can form binding with following structure:
R in the formula
4And R
5Be selected from hydrogen and C separately
1-C
4Alkyl;
X is for being selected from sulphur, selenium or tellurium;
Y
-Represent electrolytic anion;
Z is 0.01 to 1, the anion ratio of the every mole of monomer of this numeral; And n is 5 to 500, this numeral degree of polymerization.
In another embodiment, the invention provides a kind of method for preparing polymer by electrochemical polymerization, this method comprises:
(a) provide a kind of monomer with following structural formula:
In the formula, R
1, R
2With X be above-mentioned defined;
(b) the described monomer of dissolving becomes monomer solution in the solvent that contains dielectric non-transmission proton, and described dielectric is Ionized and is the nucleophilic negative ion source; And
(c) described monomer solution is gathered (isothianaphthene) through electrochemical polymer.
In other embodiments, the present invention illustrates ECD device, electrode and the storage battery that adopts above-mentioned polymer.
Fig. 1 is the Cross-section Design figure that the present invention illustrates the ECD dress of embodiment.
Fig. 2 is the Electron absorption of the polymer of doping of the present invention and two states of non-doping.
Fig. 3 is the cyclic voltammetry spectrum result of experiment with polymer of the present invention.
Fig. 4 is the absorption spectra of electrochemical polymerization film under its " growing up to " state of doping of the present invention.
Fig. 5 is polymer film the absorption spectrum with hydrazine compensate after identical with Fig. 4.
Polyisothianaphthene base polymer conduction of the present invention, that replace provides with structural formula I a or I b:
In the formula: R1For hydrogen or-OR3
R
2And R3Be selected from separately hydrogen or C1-C
8Hydrocarbon, condition are R2And R3Be coupled to mutually the following structural formula of stating with two oxygen, one dioxy alkylidene substituting group on phenyl ring:
R in the formula4And R5Be selected from separately hydrogen and C1-C
4Alkyl;
X is for being selected from sulphur, selenium or tellurium;
Y
-Represent electrolytic anion;
Z is 0.01 to 1, the anion ratio of every mole of monomer of this numeral, and
N is 5 to 500, this numeral degree of polymerization.
The polymer that structural formula I a represents oozes assorted state for it non-. Structural formula I b represent for dopant states, the skeleton that positive charge can move polymer chain during conduction state moves. For example: according in an electrochromic display device of the present invention, change its electroneutral with voltage by the film in the device, uncharged structural formula I a becomes the charged polymer of structural formula I b.
In the object lesson of implementing, X is sulphur, R1Be OR3、R
2And R3Be C1-C
5R in alkyl (as: methyl, ethyl etc.) or the dioxy alkylidene substituting group formula4And R5Be hydrogen, methyl or ethyl.
The structural formula of the polymer reference of non-dopant states comprises:
R in the formula6And R7Be selected from separately hydrogen, C1-C
8Alkyl, and
X, R in the formula4、R
5With n such as above-mentioned regulation. The doped structure that the polymer of structural formula II and III has is equivalent to I b. The anion Y of structural formula I b-The better Cl that is selected from-、Br
-、I
-、ClO
- 4、BP
- 4、PI
- 6、AsF
- 6、SbF
- 6、AlCl
-4、AlBr
- 4、FeCl
- 4And CF3SO
- 3, but also can be HSO- 4Or HF- 2 Ratio Z is preferably from about 0.01 to 0.40.
The conducting polymer of little band gap of the present invention is important, because their high inherent electric conductivity and their change in the doping process transparent conductor, namely they become transparent from dark (as: indigo plant-black). When finishing in electrochemically when mixing one, cause the electrochromic conversion of high-contrast.
The design of the PITN polymer of replacement of the present invention is to combine by PITN polymer and anion-stable oxygen atom, to improve its stability. With following poly-(dioxy methylene isothianaphthene) (PDOMIT) as the illustration of stabilisation:
Can see in PDOMIT, positive charge is stablized by the resonance of the duplet of the nonbonding on oxygen atom. In addition, really strengthen the possibility of interchain interaction by oxygen atom, so improved the conductivity at room temperature of polymer.
The preparation of the PITN polymer of replacement of the present invention, as an example, the electrochemical polymerization of the monomer by having the structural formula IV:
R in the formula1、R
2With X such as above-mentioned defined, the special example of the isothianaphthene of the replacement of structural formula IV comprises: 5-methoxyl group-isothianaphthene; 5,6-dihydroxy-isothianaphthene; 5,6-dimethoxy-isothianaphthene; 5,6-diethoxy isothianaphthene, 5,6-dioxy methylene-isothianaphthene and 5,6-dioxy (α, alpha-alpha-dimethyl methylene)-isothianaphthene. Corresponding 1,3-dihydroxy isothianaphthene class also can be used as monomer, as at EPO164,974 explanations, dewater after the polymerisation.
The monomer IV of hydroxyl and alcoxyl form can be by 1 of corresponding replacement, and the preparation of 3-dihydro isothianaphthene for example, obtains sulfoxide with the sodium metaperiodate processing.This sulfoxide dewaters then, obtains the isothianaphthene that corresponding hydroxyl and alkoxyl replace.
In addition, the single mass system of structural formula IV is by 1 of replacement, and the two benzyl halides of 2-are produced.An example of this compound is 1,2-dichloride methyl-4, and 5-dioxy methylene-benzene, and 1,2-dichloride methyl-4,5-dimethoxy benzene.For example the benzyl halide class of these replacements with the reaction of the vulcanized sodium of nine crystallizations water, obtain 1,3-dihydro isothianaphthene derivative converts to then corresponding to the sulfoxide of structural formula IV and through dehydration and obtains the isothianaphthene monomer.
By becoming hydroxyl can directly prepare the polymer that hydroxyl replaces from its dioxy methylene of PDOMIT conversion.For example, finish dealing with HI, methyl magnesium iodide or alchlor by PDOMIT.
The monomer of structural formula IV is preferably electrochemical polymerization.The electrochemical polymerization of the isothianaphthene compound of the replacement of setting forth above, can be according to the thiophene of common employing, pyrroles's etc. electrochemical polymerization (as: Solid State Communication volume 46, NO.5,389(1983) method of Miao Shuing) carry out.More specifically, can adopt the CONTROLLED POTENTIAL electrolysis maybe can adopt the Control current electrolysis, with the conductive transparent substrates of hope as sample electrode, on transparent base, form polymer film, the detailed process of the method for preferable electrochemical polymerization has been put down in writing corresponding alternative synthetic method in Application No. 736,934.Also can be referring to EPO publication number 164,974; And the name of the Application No. application on December 2nd, 1986 owned together of WudI, Heeger and Koba Ya Sh is called " having the polymer that indene structure different sulfur and electrochromism show " as a reference; Electrochemical polymerization process and at U.S. Patent number 4,640,784 and EPO publication number 164,874, that is disclosed among Japanese patent application No. 109329/1984 and the Chinese patent application NO.85105974 also can be used as reference.
In the preferred embodiment of the present invention, disclose a kind of electrochromic display device, comprise an electrochromic polymer film that contains the polyisothianaphthene of replacement.On show electrode 2, form the polyisothianaphthene film 3 that replaces referring to Fig. 1, for example by electropolymerization, this show electrode switching is transparent basic 1, aqueous electrolyte 4, it comprises a kind of support electrolyte that dissolves or be dispersed in the suitable solvent, can make opposite electrode 5 and PITN film separately.Protective layer 6 is as the shell of device.Voltage promptly between show electrode 2 and opposite electrode 5, is connected two electrodes by lead-in wire 7 by device.
The thickness of PITN layer is preferably from about 0.05 to 22 μ m from about 0.03 to 30 μ m in electrochromism shows, and is best from about 0.1 to 10 μ m.When film thickness during, can not get clearly contrast differences, otherwise thickness though obtain clearly contrast differences, is unfavorable from film strength and response speed during greater than 30 μ m less than 0.03 μ m.
Can be used on conductive, transparent base 1 of the present invention comprises: transparent insulators such as glass, polyester film, the indium-tin-oxide, tin oxide, platinum of vacuum evaporation etc. are arranged thereon, and use sputter or similar method.These materials are that industrial goods have been bought easily.
Counterelectrode is inserted in the liquid electrolyte, refill and mix the polymer that is obtained, promptly produce the ECD display instrument.Employed liquid electrolyte is the dispersion or the solution of the supporting electrolyte in solvent.Operable supporting electrolyte comprises that anion and cationic bond comprise that (ⅰ) anion (promptly is the Y in structural formula I b among the present invention
-) such as: the halide of Va elements is cloudy sub from class, for example: PF
6, SbF
6, AsF
6, and SbCl
6; The halide anions of III a family column element, as; BF
4; Halide anion, as: I
-(I
- 3), Br
-And Cl
-; The perchloric acid anion, as: ClO
- 4And (ⅱ) alkalinous metal cation, as: Li
+, Na
+And K
+; Quaternary ammonium ion is as R
4N
+(R represents to have C in the formula
1-C
20The alkyl of carbon atom); And phosphonium ion, as (C
6H
5)
4P
+Composition.These examples only are explanations rather than limit.
By the anion of setting forth above and the cation object lesson in conjunction with the supporting electrolyte that constitutes: LiPF
6, LiSbF
6, LiAsF
6, LiClO
4, NaI, NaPF
6, NaSbF
6, NaAsF
6, NaClO
4, KI, KPF
6, KSbF
6, KAsF
6, KClO
4, [(n-Bu)
4N]
+, ClO
- 4, LiAlCl
4, LiBF
4, (C
6H
5)
4PBF
4, (C
6H
5)
4-PAsF
6And (C
6H
5)
4PClO
4These examples do not limit equally.Supporting electrolyte can use separately or combination is used.
HF
- 2And HSO
- 4Anion can be used equally, can be attached in the above-mentioned anion of enumerating.In addition, applicable cation comprises that pyridinium or pyrans father-in-law are attached in the above-mentioned cation of enumerating, available following structural formula (V) expression, and carbon father-in-law cation is represented by structural formula (VI):
Z represents oxygen atom or nitrogen-atoms in the formula; R ' expression hydrogen atom, has C
1-C
15The alkyl of carbon or C
6-C
15The aryl of carbon atom; " the expression halogen atom has C to R
1-C
10The aryl of carbon atom; M equals 0 during for oxygen atom as Z, or when Z is nitrogen-atoms m-1; And P is the integer of O or 1 to 5; And
R in the formula
3, R
4And R
5Be selected from separately and comprise hydrogen atom, have C
1-C
15The alkyl of carbon atom, has C
6-C
15The aromatic yl group of carbon atom, and-OR
6R in the formula
6Expression has C
1-C
10Carbon atom alkyl group or have C
6-C
15The aromatic yl group of carbon atom, condition are R
3, R
4And R
5Can not all be hydrogen atom.
HF
2Anion can be represented by structural formula (VII, VIII) or (IX) by a kind of hydrofluorocompounds of dissolving usually:
（Ⅶ）：R′
4N·HF
2
（Ⅷ）：M·HF
2
" each represents a hydrogen atom, has C for R ' and R in the formula
1-C
15The alkyl of carbon atom or C
6-C
15The aromatic yl group of carbon atom; R " expression C
1-C
10The alkyl of carbon atom or C
6-C
15The aromatic yl group of carbon atom; Z represents oxygen atom or nitrogen-atoms; Q represents O or is not more than 5 positive integer; And M represents alkali metal, as the supporting electrolyte in appropriate solvent.The special example of the compound of said structure formula (VII), (VIII) and (IX) comprising: H
4NHF
2, Bu
4NHF
2, NaHF
2, KHF
2, LiHF
2With
Pyrans or pyridylium can be by dissolving a kind of cation and anion by structural formula (V) representative, for example: ClO
- 4, BF
- 4, AlCl
- 4, FeCl
- 4, SnCl
- 5, PF
- 6, PCl
- 6, SbF
- 6, AsF
- 6, CF
3SO
- 3, HF
- 2Obtain Deng in suitable solvent, as the salt of supporting electrolyte and obtain.The object lesson of this salt comprises:
The cationic object lesson of carbon father-in-law by said structure formula (VI) representative comprises (C
6H
5)
3C
+Deng.These carbon father-in-law atom can or disperse a kind of carbon father-in-law salt to form between cation and anion by dissolving, the salt that forms as supporting electrolyte in appropriate solvent and obtaining.Typical suitable anion comprises: BF
- 4, AlCl
- 4, AlBr
3Cl
-, FeCl
- 4, PF
- 6, PCl
- 6, SbCl
6, SbF
- 6, ClO
- 4, CF
3SO
- 3Deng, and concrete carbon salt comprises: (C for example
6H
5)
3CBF
4, (CH
3)
3CBF
4, HCOAlCl
4, HCOBF
4, C
6H
5COSnCl
5Deng.
Among the present invention available solvent both can be water also can be nonaqueous solvents, although the solution of foregoing supporting electrolyte is preferable in non-aqueous organic solvent.With herein organic solvent preferably to non-transmission proton and have a high dielectric constant.As an example, ether, ketone, nitrile, amine, amide-type, sulphur compound, phosphate compounds, phosphite ester compound, boric acid ester compound, chlorinated hydrocarbons, ester class, carbonates, nitro compound and the like can be used.Wherein ethers, ketone, nitrile, phosphate compounds, phosphite ester compound, boric acid ester compound, chlorinated hydrocarbons and carbonats compound are preferable.The object lesson of suitable solvent comprises oxolane, 2-methyltetrahydrofuran, 1,4-diox, acetonitrile, propionitrile, 4-methyl-2 pentanone, butyronitrile, valeronitrile, benzonitrile, 1,2-dichloroethanes, gamma-butyrolacton, valerolactone, dimethoxy-ethane, methyl formate propylene carbonate, ethylidene carbonic ester, dimethyl formamide, dimethyl sulfoxide (DMSO), etherophosphoric acid, methyl orthophosphoric acid, phosphorous acid ethyl ester, methyl phosphite, 3-methyl sulfolane etc.In the middle of these, in order to improve response speed, nitrile and carbonic ester are special good in the middle of them.These organic solvents can separately or be used in combination.
According to the used electrode type of pattern of the ECD device that adopts, oxygen or water are present in these solvents or have proton solvent, sometimes will worsen the characteristic of ECD device.For this reason, this solvent adopts common mode to purify in advance to good.In addition, in ECD device of the present invention, except that can using above-mentioned electrolyte, also can use the organic solvent that only spreads to supporting electrolyte, perhaps have high ionic conductance, by the organic solid electrolyte based that polyethylene oxide and NaI, NaSCN etc. form, also can be added in the above-mentioned dielectric and use.
The concentration that is used for the ECD supporting electrolyte among the present invention, according to used solvent types, the kind of the electric current of using and voltage, operating temperature, supporting electrolyte and change such as the different of kind can not be fixed usually.Liquid electrolyte both can be homogeneous also can be heterogeneous body, but common concentration range is between about 0.001 to 10 mole/liter.Distance between this HMW conducting film and the counterelectrode be can not determine usually, change because it is the suchlike variations such as display surface area of the kind according to supporting electrolyte, the electric current of using and voltage, ECD device, but preferably be between from 0.05 to 5 millimeter.In addition, can adopt multiple material according to the purpose purposes as counterelectrode, for example, when being used as demonstration, preferable as counterelectrode with conductive transparent material with emission light.If the application reverberation, so also available opaque material is made counterelectrode, the example of opaque material comprises that (but not being to limit) is as (nickel or platinum) paper tinsel and wire netting.In addition, because the ECD device is substantially colourless tone is provided, just can select to have the base plate of the background of shades of colour tone, therefore ECD device of the present invention can used in the scope widely owing to extensively selecting materials used.
The purposes of other of polyisothianaphthene class comprises general as electric conductor or electrochromic material etc.Be and be applied to need to show very fast electrochemical doping characteristic in the high conducting polymer, or with or reversible oxidation-reduction reaction can take place during optical switch that need not be synchronous.
In another instantiation of the present invention, polyisothianaphthene of the present invention is as electrode or be used as electrode coating in a storage battery.For example: can provide one to be anode, lithium, calcium or other suitable material storage battery as negative electrode with the polyisothianaphthene.This electrode and porous barrier film separately, these selected ions can be freely by its structure.Then this electrode/membrane device is placed in the suitable electrolyte solution, the voltage that applies is by this electrode.So storage battery can be reused, and does not reduce the charging-discharging efficiency of device basically.In addition, the self-discharge in this polyisothianaphthene storage battery can reduce to minimum.
The polyisothianaphthene of the replacement of Jie Shiing also is useful in the solar energy converting battery herein, and it conducts electricity after absorbing light as the skin covering of the surface material.These polymer are effective especially in solar storage battery, and so the polymer light absorption quite approaches daylight.These polymer have been expressed the improvement to the analog purposes of polyacetylene class simultaneously, and these polyacetylene compounds are responsive especially and very responsive to moisture to oxidation.
The embodiment that provides below is as an illustration purpose only, is not that in office where face limits the present invention, fixed scope limited by claim.
Embodiment 1:
To 1.5 gram (6.85 mMs) 1,2-dichloride methyl-4,5-dioxy methylene-benzene (according to BP1,159,089; Ger offen1,924,747(CA71:P80934m, CA72:P6609V) preparation] in the solution of 100% ethanol that 1.5 liters outgas, (such high dilution needs, to avoid the formation of unmanageable polymer of white) add fully levigate vulcanized sodium that contains 9 crystallizations water of 1.81 grams (1.1 equivalents, 7.54 mMs).The reactant mixture that should produce under blanket of nitrogen is reflux five hours under agitation.Add the solution of 1.61 gram (1.1 equivalents, 7.54 mMs) sodium metaperiodates in the solution of the muddiness that (after separating sodium chloride) produces under the cooling at 260 ml waters.The reactant mixture that produces after four hours that refluxes filters by glass clinkering funnel, and filtrate concentrates, also then passes through anhydrous sodium sulfate drying three times with chloroform extraction.Boil off chloroform and also obtain colorless solid (yield 21%) sulfoxide with the chloroform elution by the silica gel column chromatography chromatography.Mass spectrum (Ms) 196, infrared (KBr, Cm
-1): 2880m, 1475s, 1420w, 1370w, 1280s, 1200m, 1145m, 1020s, 930m, 900w, 840m, 410m340w; Nulcear magnetic resonance (NMR) (deuterochloroform δ is with respect to tetramethylsilane): 4.1 η AH, 5.99s2H, 5.77s2H.
Above-mentioned sulfoxide is levigate with excessive aluminium oxide (active I number), puts into a sublimator, is heated to 110 ℃ under 0.25 pressure.Dioxy methylene isothianaphthene (DOMT) the distillation cooling that produces forms white micro-crystals on the vial of sublimator.This heterocycle is more stable significantly than original ITN.Mass spectrum (Ms) 178, nulcear magnetic resonance (NMR) (deuterochloroform δ is with respect to tetramethylsilane) 5,88s, 2H, 6.77s, 2H, 7.29s, 2H.
As above-mentioned preparation: DOMIT, carrying out electrolysis polymerization (EPO164,974) through general commonly used method is cathode electrode as electrolyte, ITD glass electrode as positive electrode and graphite with (0.1M) tetraphenylphosphonichloride chloride phosphorus in room temperature in acetonitrile.The grey film that produces obtains an indigo plant-black film that mixes at Soxhlet's extractor with acetonitrile and oxolane extracted overnight.Fig. 2 represents the Electron absorption of the polymer of non-doping, and its absorption expands to near-infrared, and the clearance gap of indication is in≤1cv grade.The solid line of Fig. 2 is the polymer of extraction, and dotted line is " making " film.
In typical cyclic voltammetry spectrum experiment, this film can between transparent grey and indigo plant-black, circulate (referring to, Fig. 3).In experiment, this grey, the uniform film on ito glass is as electrode, and (0.06M Bu NClO) and platinum coil are made opposite electrode in the acetonitrile of new distillation, and reference electrode is Ag/AgCl.Range estimation is in electrochemistry cycle period, and the electrochemistry contrast of PDOMIT changes transparent grey than PITN(into from indigo plant-black) show higher contrast.
The absorption spectra that (Fig. 4) obtains for the absorption spectra of " growing up to " film and (Fig. 5) is the absorption spectra of this identical film after with the hydrazine compensation.Result (Fig. 4) shows that " growing up to " film is for relatively having high doping (consistent with lower oxidizing potential gesture).After the compensation, an energy gap (Eg) of existence is fairly obvious.This absorption edge Eg ≈ 0.6cV that promptly extrapolates anticipates.The PDOMIT film that is somebody's turn to do " growing up to " is stable in air.
The embodiment II:
1,3-dihydro-5,6-dimethoxy isothianaphthene be according to J.Chem, Soc, Parkin Trans I(1980) 8, P, 184126 preparations of setting forth.This compound is handled with sodium metaperiodate then, and (as at EPD publication number No, describing in 164,974) obtains 1,3-dihydro-5,6-dimethoxy isothianaphthene-2-oxide.This sulfoxide dewaters then and as the polymerization that the embodiment I is described, is gathered (5,6-dimethoxy isothianaphthene).
The embodiment III
According to G, P1, the method for 097,270 specification, 2,2-dibromopropane and catechol reaction obtain 1,2-dioxy (α, alpha-alpha-dimethyl methylene) benzene (DDMB).DDMB has following structure:
DDMB is gathered (5,6-dioxy (α, alpha-alpha-dimethyl methylene) isothianaphthene) by the method reaction that the embodiment I is described then.
The embodiment IV
According to G.B1, the method for 268,243 specifications, preparation 3,4-xylylene bromide methyl ether.Change into corresponding isothianaphthene by it, and, gathered (5-methoxyl group isothianaphthene) according to the method polymerization that the embodiment I is described.
With embodiments of the invention the present invention was described already, narration above the present invention and the practice, can does tangible change technically.The particular example that the present invention will not be subjected to narrate above limits, and only is subjected to the restriction of the scope of law of claim of the present invention.
Claims (4)
1, a kind of polymer is selected from the application that comprises following structural formula I a and I b polymer:
R
1For hydrogen or-OR
3, R
2And R
3Be selected from separately and comprise hydrogen and C
5-C
8Alkyl, condition are R
2And R
3Can be with two oxygen, dioxy methylene substituting group on phenyl ring with binding that following structural formula is formed:
In the formula:
R
4And R
5Be selected from separately and comprise hydrogen and C
1-C
4Alkyl;
X comprises sulphur, selenium and tellurium for being selected from;
Y represents an electrolytical anion;
Z is 0.01 to 1, the anion ratio of the every mole of monomer of this numeral; And
N is 5 to 500, this numeral degree of polymerization; It is characterized in that as a kind of electrode that is coated with the support of described polymer.
2, the application of polymer as claimed in claim 1 is characterized in that the electrode as a kind of storage battery.
3, the application of polymer as claimed in claim 1 is characterized in that the electrode as solar cell.
4, the application of polymer as claimed in claim 1 is characterized in that the film as electrochromic display device (ECD).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US944,138 | 1986-12-18 | ||
| US06/944,138 US4795242A (en) | 1985-05-22 | 1986-12-18 | Conducting substituted polyisothianaphthenes |
| CN87108150A CN1015628B (en) | 1986-12-18 | 1987-12-17 | Conducting substituted polyisothianphthenes |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87108150A Division CN1015628B (en) | 1986-12-18 | 1987-12-17 | Conducting substituted polyisothianphthenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062148A CN1062148A (en) | 1992-06-24 |
| CN1024067C true CN1024067C (en) | 1994-03-16 |
Family
ID=25742393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91104471A Expired - Lifetime CN1024067C (en) | 1986-12-18 | 1987-12-17 | Conducting substituted polyisothianaphthenes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024067C (en) |
-
1987
- 1987-12-17 CN CN91104471A patent/CN1024067C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1062148A (en) | 1992-06-24 |
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