CA1334672C - Conducting substituted polyisothianophthenes - Google Patents
Conducting substituted polyisothianophthenesInfo
- Publication number
- CA1334672C CA1334672C CA000554176A CA554176A CA1334672C CA 1334672 C CA1334672 C CA 1334672C CA 000554176 A CA000554176 A CA 000554176A CA 554176 A CA554176 A CA 554176A CA 1334672 C CA1334672 C CA 1334672C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- group
- hydrogen
- structural formula
- hydrocarbons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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
CONDUCTlNG SUBSTITUTED POLYISOTHIANAPHTHENES
Technical Field This invention relates generally to con~ cting polymers and their use as electrodes in various devices, and in particular relates to certain substituted polyisoll~,anaphthenes (PITN) and their use in electrochromic displays, batteries, solar cells, and the like.
Background With the latest develop,l,e,lls in li~ht~ning I i..nning and mini~hlrization of electric and electronic instruments, the development of new con~ cti~ materials per se has been desired.
Various sulfur-cG..~ g heterocyclic polymers are known in~ 1in~ polymers from thiophene, U.S. patent No. 2,582,796 and U.S. patent No. 2,658,902; polymers from dibenzothiophene, U.S. patent No. 3,585,163; polymers from vinyl bithiophene, U.S. patent No.
~ X
. -2- l 334672 3,615,384; polymers from uarious substituted thiophenes, U.S. Patent No. 3,725,362; polymers from 2-bromo-8-hydroxy-5,5-dioxodibenzothiophene, U.S. Patent No.
3,775,368; and polymers from tetrathiapentalene, U.S.
Patent No. 4,111,857.
~ Within-the rapidly expanding field of polymeric ~ - .
conductors ("Proceedings of the l.nternationaJ. Conference on the Physics and Chemistry of Polymeric Conductors", J. Physique. Colloque., (1983), C-3), the poly(heterocycles) haue received attention because they are easily prepared in film form and are consi.derably more stable to atmospheric exposure than polyacetylene or polyphenylene. For use in stabil-izing a semiconductor surface, see R. Nou~i et al., J-. ~mer.
Chem. Soc., (1981), ~ol. 183, 184 and re~erences therein. ~ further extension of thi.s work is our recent.
entry into the study of polythiophene.
Extensiue i.nuestigati.ons on new conducti.ue polymers haue been conducted. For example, polyacetylenes are under in~esti.gati.on for possib]e auailability as electrode materials in secondary batteries since they show conductiuiti.es as high as to 10 S/cm when doped with iodine or arsenic pentafluoride (cf. Synthetic Metals, Uol. 1, No. 2, 101 (1979/1980)). lhese polymers also display excellent charge-discharge characteristics. Use of polyacetylenes ~in solar batteries is also under inuestigation ~ecause of- the polymers'- ligh-t absorption characteristics which are close to those of sunlight; Howeuer, the .
- polyacetylenes are disadvantageous in that.they are per se susceptible to oxidation and doped polyacetylenes-are extremely sensitive to h~midity.
~ - Poly~hiophenes have been studied not only as conductive materials and as battery electrode materials, ~3 1 334672 but also as electrochromic materials making use of color changes in a doped state. For example, ~.M. Druy, et al ~eported that 2,2'-bithienyl may be electrochemically-polymerized to form a polymer ha~ing a color which re~ersibly ~aries From blue in an oxidized state to red in a reduced state, thus a potentially useful electrochromic material tcf. Journal de Physique, Uol.
44, No. 6, C3-595 (1983)~. Howe~er, polythiophenes, like polyacetylenes,- are generally sensitiue compounds.
In light of the aboue-described problems, the present inventors ha~e conducted extensi~e inuestigations into conductiue polymers and uses thereof, and, as a result, haue found that a polymer ha~ing an isothianaphthene structure is a uery stable compound which is capable of continuously and reuersibly uarying its color in the course of oxidation or reduction. Unsubstituted polyisothianaphthene is described in certain publications by the present inuentors. See, e.g., Wud] et al., J. Orq. Chem., (1984), ~ol. 49, pp. 3382-3384; Wudl et al., Polymer Preprints, Uol. 25(2), pp.257-259; Chemical ~bstracts, (1984), ~ol. 101, part 24, p. 7, 211832q. PITN-type polymers are described in United States Patent number 4,640,748 which was issued on February 3, 1987. See also EPO Pub. No. 164,974 (18 December 1985).
8ecause polyisothianaphthenes are very stable 'and exhibit extremely rapid p-type-electrochemical doping'characteristics' with an associated high contrast color chang'e, many applications of the polymers are clearly feasible. ~ne application--use in electr.ochromic displays--is made possible by ~irtue of the fact that polyisothianaphthene is a transparent, as well as conducti~e, polymer. ~fter doping, a thin film - _4- - 1 3 3 4 6 7 ~ `
of PITN has a uery low optical density in the visible portion of the spectrum. Other applications which make use of the opto-electrochemi.cal properties of PITN
includes use as an electrode in a battery or.
electrochemical cell, a solar energy conuersion deuice, and its general application as (or-in) electroch-romic .
material. ~ limitation, howeuer, is that at uery high dopant leuels PITN can be attacked by the atmosphere with concomitant dedoping. ~ need exists, therefore, for a PlTN-type polymer that retains the ad~antages of PITN, but is resistant to atmospheric attack at hi.gh dopant leuels.
Electrochromic displays represent an improuement ouer liquid crystal de~ices, which have recently been deueloped as "low-energy" disp].ay de~ices with, potentially, a wide range of applications. The display in liqui.d crystal de~ices is dependent on uisual angle and the contrast and resolution are typically poor. No memory function is prouided, nor can the display be prouided ouer a large surface area. ~n order to eliminate these disad~antages, studies haue been extensiuely conducted on low-energy electrochromic display (EC~) de~ices which make use of a material's electrochromic properties, i.e., electrochromic materials haue light absorption characteristics:which uary with application of uoltage or~electric current.
Electrochromic materials which can be used i.n ECD de~ices may be either inorganic or-organic.
Inorganic materials that are con-sidered usable mainly include oxides.of transition me~als,-but these are limited ~ith-res~ect to de.uelopable colors. Transition metal..oxides also cause electrochemical elution of the membrane or deterioration of electrodes when protons are used as color-forming ions, although response speeds may ( be hi.gh. Organic materials used in electrochromic displays typically include uiologen- dyes., phthalocyanine complexes, etc. However, the uiologen dyes are disaduantageous in that repeated use thereof results in precipitation of insoluble-substances, and the phthalocyanine complexes haue an as-yet unsoloed- problem .;
with adhesiueness between a uacuum-euaporated mem~rane and a base plate.
Other electrochromi.c materials which haue recently been proposed include: polyanilines as disc].osed in ~.F. Diaz, et al., Journal of l~lectro-~nalytical Chemistry, Uol. 111, 111 (1980) or Yonemaya et al., ibid, ~)ol. 161, 419 (1984);
polypyrroles as disclosed in ~.F. Diaz et al., _id, ~Jol. 101 (1983) and polythiophenes as disclosed in M.~.
~ruy, et al., ~ournal de Physique, Uol. 44, June, page C3-595 (1983) or Kaneto et al., Japan Journal of ~pplied Physics, Jol. 23, No. 7, page L412 (1983). Howeuer, none of these materials has been put to practica]. use.
Prel~erred characteri.stics for electrochromic materials are rapid response time in e].ectrochromic s~itchi.ng, high contrast and resolution, good color tones and the li.ke. Furthermore, as noted aboue, an e].ectrochromic material such as PITN which is capable of deuelopi.ng a colorless tone will great].y contribute to the ap,olicabil-ity of the de~Jice. This is in contrast to the aforementioned heteroconjugated materials which are colored in the course of conuersion from an oxidized state to a reduced state; Thus, a need also exists for improued PlTN-type pc~lymers for use in ECD deuices.
- -Summary of the Inuention ~ ccordingly, it is a primary-object of the present inuention to prouide a conductiue polymer capable of being reuersibly oxidized or reduced.
It is also an ob]ect oF the present inuention to prouide a polyisothianaphthene-type polymer that is stable to atmospheric attack at high dopant leuels.
It is another object of the in~ention to prouide a high molecular weight, substituted poly-isothianaphthene.
~ t is a further object of the inuention to prouide an electrochromic membrane materi.al that is chemically and physically stable, prouides a hi.gh contrast color change upon oxidation and reduction, and giues a rapid response time in electrochromic switching.
It is another object of the inuention to use substituted polyisothianaphthene as an electrode or electrode coating material, in the production of solar batteries, and, generally, as an electrochromic material .
in reuersible oxi.dation-reduc~ion systems.
l-hese and other objects of the present inuenti.on are achieued by one or more of the following embodiments.
- ~ ~ ~ - ' ;-( -7~ 1 3 3 4 6 7 2 In one embodiment, the present in~ention is directed to a polymer ha~ing a structural formula selected from the group consisting of Ia and Ib wherein:
la = R~2 - b R, I b = R~
O R~
~ ~ ~ n Rl i.s hydrogen or -OR3;
R2 and R3 are selected i.ndependently from the~ group consisting of hydrogen and C1 to C~
hydrocarbons, with the pro~iso that R2 and R3 can link together to form, with both oxygens, a - - - dioxyalkylene substituent on the benzene ring-with -the.
- formula: . ~ ~ -- . -S' '-, - . - . - - /C ~
' ' '' ~ \ /- -' wherein R4 and R5 are selected independently from the group consisting of hydrogen and Cl t~ C4 hydrocarbons; - - ~
X is selected from the group consisting of sulfur, selenium and tellurium;
Y represents an anion of an electro-lyte; - -z repres.ents a number from 0.01 to I showing a ratio of the anion per mol of a monomer; and - n represents a number of from 5 to 500 showing the degree of polymerization.
In another embodiment, the present inuenti.on is directed to a method of preparing a polymer by electrochemical polymerization comprising:
(a) pro~iding a monome.~ ha~ing the formula:
b Rl ~' wherein R1, R2 and X are defi.ned as aboue;
- (b) dissoluing said monomer in an aprotic sol.uent containing electrolyte to prouide a monomer solution, said e].ectrolyte being ionic and a sourc-e o.f nucleophilic anions; and - ~. (c) electrochemically polymerizing said monomer --solution to pro~ide a poly(isothianaphthene).
In other embodiments, the present invent-ion is directed to ECD deuices, electrodes and batteries employing the polymers described above. : -Brief Description of the Fiqures Figure 1 is a schematic cross-sectional ~iew illustrating an example~of the ECD de~ice in accordance with the. present in~ention. --- Figure 2 shows the electronic absorption of a polymer accor.ding to---the present i.n~ention in both a - .
doped and undoped state.
Figure 3 shows the results for a cyclic ~oltammogram experiment with a polymer according to the present in~ention.
Figure 4 is the absorption spectrum of a doped, electroche~ically polymerized film according to the present in~ention in its "as grown" conditi.on.
Figure 5 is the adsorption spectrum of the same polymer film shown in figure 4 after compensation with hydrazine.
-- -lo- 1 3 3 4 6 7 2 ~etailed Description The conducti~e, substituted polyisothia-- naphthene-type polymers of- the present in~ention are gi~en by structure la or Ib:
R2 ` R2 ~ R, ~ - O - R, (la) ' ~ (Ib) ~
n ~ ( X ~ ~ n R1 is hydrogen or -OR3;
R2 and R3 are selected i.ndependent-ly from the group consisting of hydrogen and Cl to C~
hydrocarbons, with the pro~iso that R2 and R3 can link together to form, with both oxygens, a di.oxya].kylene substituent on the benzcne ri.ng witll the formula: R~ Rs \ / '' /c~
O O
\ /
wherein R4 and R5 are selected i.ndependently fron;
the group consisting of hydrogen'and Cl to C4 hy~drocarbons; '-' ' - - X is--selected from the'group consist:ing of '. - -sulfur, selenium and. tellurium; . ' - -- - Y represents an anion of~an electrolyte;
- - - z represents a number from O.OI to 1 showing a ~- ratio.oi the anion .per mole of a monomer;-and n re'presents a number of from 5 to 500, i.e.
represenis the'deqree of polymeri2ation.
1 33467~
Formula Ia represents the po].ymer in its undoped state. Formula Ib represents the polymer in its doped, conducti~e state wherein a positi~e charge is mo~able along the backbone of the ~olymer chain. ~or example, in an electrochromic display de~ice according to the present in~ention, appl.ication of a ~oltage acros-s the polymer mem~rane i.n -the deuice con~erts the neutral, uncharged polymer of ~ormula Ia to the charged polymer of Formula Ib.
In exemplary embodiments, X is sulflJr, Rl i.s -OR3, R2 and R3 are either C1 to C5 hydrocarbons (e.g., methyl, ethyl, etc.), or the dioxyalkylene substituent where R4 and R5 are hydrogen, methyl or ethyl.
Referring to the undoped state of the polymer, exemplary formulas include:
~6 / 7 O O
(Il) ~ ~
~/'~ .
X ~ n where R6 and R7 are selected independently from hydrogen, and C1 to C8 hydrocarbons; and .
- - - . R4 Rs , , - V
/ \
- - O - - O
( I I I ) ~
~~ -12- 1 334672 where X, R4, R5 and n are defined as aboue. The polymers of ~ormulas II and III haue doped structures equiualent to Ib. The ani.on of formula Ib, Y , is preferably selected from the group consisting of:
Cl Br , I , C104, BF4~ PF6, ~sF6, 6 - ~lCl~ r4, FeCl4 and CF3SO3,-but may also be HSO~ or HF2. The ratio i is preferably from about 0.01 to 0.40.
The small bandgap conducting polymers of the present inuention are important because of their high intri.nsic conductiuity and because i.n the course of - doping they are conuerted to transparent conductors--i..e., they change from a deeply colored form (e.g., blue-black) to transparent. When the doping is performed in an electrochemi.ca]. ce].l, this transformation leads to high contrast elect:rochromism.
The substi.tuted PITN polymers of the present inuention were designed to improue the stability of the charged PITN polymer by conjugation with cation-stabilizing oxygen atoms. This stabi.lization is exemplified below with poly(di.oxymethylene-isothianaphthene1(P~OMIT).
- 0~0: +0~0:
- ~)n (~~)n ~ (~)n PJ~N - -P~OMIT
~ -13- 1 3 3 4 6 7 2 ~s can be seen in P~OMI~, the positiue charge is stabilized through resonance by a non-~onded pair of - e].ectrons on an oxygen. In addition,-.there exists the possibility of enhancing i.nterchain i.nteractions through the oxygen atoms, thus increasing the room temperature conducti~ity of the polymer.
~ The substituted PIlN polymers of the present in~ention are prepared, for example, by the electrochemical polymerization of monomers haui.ng the structure IU: - -R\o R, V
(I~J) ~
~/X~ --where R1, R2 and X are the same as described aboue.
Speci.fic examp].es cf the substituted i.sothi.anaphthenes of formula I~ inclllde 5-methoxy-i.sothianaphthene; 5,6-di.hydroxy-isothianaphthene; 5,6-dimethoxy-isothianaphthene; 5,6-di.ethoxy-isothianaphthene;
5,6--di.oxymethylene-isothianaphthene; and 5,6-di.oxy (~,~-dimethylmethylene)-i.sothianaphthene.
Corresponding 1,~-dihydroisothianaphthenes can also sere~e as-monomers, b.eing dehydrated after polymerization as -described in EPO-164,974. --:
The hydroxy and alkoxy-f-orms of mon-omer.I~ can be prepared from the corresponding substituted 1,3-dihydroisothianaphthene, which is treated, for example: with sodium metaperiodate to pro~ide the sulfoxide. The sulfoxide i.s then d~hydrated to gi~e the~-_ -14- l 3 3 4 6 7 2 corresponding hydroxy or alkoxy substitutecl isothianaphthene.
-~lternatively, monomers of formula IU are prepared from~substituted 1,2-bishalomethylbenzene. ~n example of such compounds are 1,2-bischloromethyl-4,5-dioxymethylene benzene, and 1,2-bisc~loromethyl-4,5-dimethoxy benzene. These substituted.halomethylbenzenes are reacted with, for example, sodium sulfide nonahydrate to gi~e.the 1,3-dihydroisothianaphthene deriuatiue. This is then conuerted to the sulfoxide corresponding to formula I~, and then dehydrated to gi~e the isothianaphthene monomer.
Hydroxy substituted polymers can also be prepared directly from PDOMIT by conuerting the dioxymethylene group to hydroxy groups. This is done, for example, by treating PDOMIT with HI, methylmagnesium iodide or aluminum chloride, The monomers of formula I~ are preferably electrochemically polymerized. Electrochemical polymerization of the abo~e-described substituted isothianaphthene compound can be carried out according to the methods generally employed for electrochemical polymerization of thiophene, pyrrole, etc. (e.g., the method described in Solid State Communication, ~ol. 46, No. 5, 389 (1983)). More specifically, either controlled potential electrolysis or controlled current electrolysis can be employed, and it is desirable to form a polymër membrane on a transparent base by using a conducti~e transparent base as a samp1e electrode.
Ele~ ~m;~l olymerization~o-Y~-are taught in United States Patent:~h~r ~64~,7~-and-EPQ Publication Nunber:164,974.
t~
( In a preferred embodiment of the in~ention, an electrochromic disp].ay deuice inc].udes an electrochromic, polymeric membrane comprising the -.
substituted polyisothianaphthenes disclosed herein.
Referring to Figure 1, substituted polyisothianaphthene membrane 3 is formed on display electrode 2, e.g. by electropolymerization, which display electrode is in turn adjacent transparent base 1. Liquid electrolyte 4, which includes a support electrolyte dissolued or di.spersed in a suitable so].~ent, separates the PIrN
membrane from opposi.ng e].ectrode 5. Protecting layer 6 ser~es as a housing for the de~ice. Uoltage is appli.ed across the deuice, i.e. between display electrode 2 and opposing electrode 5, by means of lead-in wi.res 7 which are in electrical contact with the two electrodes.
The thickness of the PITN layer in the electrochromi.c display i.s from about 0.03 to 3011m, preferably from about 0.05 to 22~m, still more preferably from about 0.1 to lo~Lm. When the membranc-thickness is 3.ess than about 0.03~m, clear contrast cannot be attained. ~ thi.ckness exceeding about 3011m pro~ides clear contrast, but is di.saduantageous ~rom the point of-uiew of film strength and response speed.
.The conducti~e transparent base 1 which can be used in the present inuention includes ones which -comprise a transparent insulator such as glass, polyester film,-etc., hauing uacuum e~aporated thereon - -indium-tin oxide, tin oxide, platinum, etc. by sputtering or a like method. These materials are~: :
readily `auailable commercially.
( ~
ECD de~ices can be produced by assembling the thus obtained polymer with an opposing electrode ~ia a li.quid e].ectrolyte. The ].iqui.d electrolyte which can be used is a dispersion or solution of a supporting e].ectrolyte in a sol~ent. The supporting electrolyte which can be used-in-the present in~enti.on includes combinations of (i) anions (i.e., Y in the formula Ib) such as hali.de anions of ~a group e].ements, e.g., PF6, SbF6, ~sF6 and SbCl6; halide anions of IIIa Grbup series element, e.g., BF4; halogen .
ani.ons, e.g., I (I3), Br and Cl ; perchloric acid anions, e.g., Cl04; and (ii) cations such as alkali metal ions, e.g., Li+, Na and K+;
quaternary ammonium ions, e.g., R4N (wherein R
represents a hydrocarbon residue ha~ing 1 to 20 carbon atoms); and phosphoni.um i.ons, e.g., (C6H5)4P .
These examples are merely illustrati~e and not li.mi.ti.ng.
Specific examples of the supporting electrolytes composed of the abo~e-described combinations of anions and cati.ons are LiPF6, LiS~F6, Li~sF6, LiC104, NaI, NaPF6, NaSbF6, Na~sFfi, NaC104, KI, KPF6, KSbF6, K~sF6, KC104, [(n-Bu)4N~ ^
C104, Li.~lC14, LiBF4, (C6H5)4P^BF4, (C6H5)4P^~sF6 and (C6H5)4P~C104. These examples, again, are not limi.ting. Supporting .-electrolytes may be used indi~idually or in combination.
- . The HF2 and HS04 anions can also be used, in addition to-the above-enumerated anions.-Further~ cations which can be used in addition to those enumerated abo~e include pyrylium or pyridinium ions ;.
-: -represented by the following formula (~) and carbonium cations represented by the following formula (UI):
(u): ~ z -(R'!m (R") wherein Z represents an oxygen atom or a nitrogen atom;
R' represents a hydrogen atom, an alkyl group hauing 1-to 15 carbon atoms or an aryl group hauing 6 to 15 carbon atoms; R" represents a halogen atom, an a'l.kyl group hauing 1 to 10 carbon atoms or an aryl group hauing 6 to 15 carbon atoms; m is O when Z is an oxygen atom, or m is 1 when Z is a nitrogen'"atom; and p i.s O or an integer of from 1 to 5; and (UI): R5 \
~3 /
wherein R3, R4 and R5 are independently selected from the group consisting of hydrogen atoms, alk'yl groups hauing 1 to 15 carbon atoms, aryl groups- hauing 6 to 15 carbon atoms 'and -OR wherein R represents an a].~yl group hauing -1 to .10 carbon atoms or an aryl group .
hauing 6 to~15 carbon atoms, with prouiso that R , --R and R5 are not all'hydrogen atoms.
-.~ ' ' , ' - .
( _ -18- 1 334672 The HF2 anion which can be used is usually obtained by dissoluing a hydrofluoride compound represented by the formula (UII), (UIII), or ~IX):
(~II): R'4N HF2 (UIII): ~.HF2 //~l (IX): ~ Z-HF2 ) q wherei.n R' and R" each represents a hydrogen atom, an alkyl group ha~ing 1 to 15 carbon atoms or an aryl group ha~ing 6 to 15 carbon atoms; R" represents an alkyl group ha~ing 1 to 10 carbon atoms or an aryl group ha~i.ng 6 to 15 carbon atoms; Z represents an oxygen atom or a nitrogen atom; q represents O or a positi~e integer of 5 or less; and M represents an alkali metal, as a supporting electrolyte in an appropriate sol~ent Specific examples of the compounds represented by the abo~e formulae (~ , (UIII) and (IX) include ~ -H4N-HF2, Bu4N~HF2, Na.HF2, K-HF2, Li.~HF2 and ~HF2 - - . , .
-the pyrylium or pyridini.um-cations can be - . obtain-ed by dissol~ing a saIt formed between a cation - represented by the formula (~) and an anion, e.g., C104, BF4, ~lC14, FeC14, SnC15, PF6, PC16, PC16, SbF6, ~sF6, CF3S03, HF2, etc., as a supporting electrolyte in an appropriate soluent. Speci.fic examples of such salts include:
~0 'Clo ~ - ~ t C~O~ C~
Cl~
~N _ _ 4 <=~0 - ~SF6 , ~ AsFG
t _ ~0 ' SbF6 ~H3 H3C ~0 SbF6, ~ -HF2 ~ etc.
Specific examples of the carbonium cations represented by the aboue-described formu].a (~I) i.ncl.ude (C6H5)3C , etc. These carboni.um atoms can be obtained by dissoluing or di.spersing a carbonium salt formed between such a cation and an anion as a supporting electrolyte i.n an appropriate soluent.
Suitable anions typically include : -BF4, ~lC14, ~lBr-3cl, Fecl4~- PF6, PC16,-SbC16, SbF6, C10-4, CF3S03, etc., and the-carbonium sal~ s-pecifically includes, for~example, (C6H5) 3C^BF4, (CH3)3C-BF4,- HCQ-~lC14, HCO~BF4, c6H5co~sncl5~ etc.
- The soluents which can.be used in the present inuention may be either aqueous or nonaqueous, although a solution of the aforesaid supporting electrolyte in a nonaqueous organic sol~ent is preferred. The organic soluents used herein are preferab].y aprotic and haue high dielectric constants. For example, ethers, ketones, nitriles, amines, amides, sulfur-compounds, phosphoric ester compounds, phosphorous ester compounds, -.
boric ester compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds and the like can be employed. Of these, ethers, ketones, nitriles, phosphoric'ester compounds, phosphorous ester compounds, boric ester compounds, chlorinated hydrocarbons and carbonates are preferred. Specific examples of suitable solvents include tetrahydrofuran, 2-methyltetra-hydrofuran, 1,4-dioxane, acetonitrile, proprionitrile, 4-methyl-2-pentanone, butyronitrile, ualeronitrile, benzonitrile, 1,2-dichloroethane, ~-butyrolactone, ~alerolactone, di.methoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, di.methyl sulfoxide, ethyl phosphate, methyl phosphate, ethyl phosphite, methyl phosphite, 3-methylsulfolane, etc. ~mong these, nitriles and carbonates are especially preferred in order to increase the response speed. These organic sol~ents may be used alone or in combination.
~ epending upon the model of EC~ deuices-used or the kind of electrodes'used, oxygen or water present in these soluents or protoni.c sol~ents sometimes deteriorate the performance of ECD deuices. Such-'being the case, it is preferable to purify the soluents 'beforehand in the usual manner. - further, in the ECD
deuices -of-the present in'~ention, organic soluents hauing merely dispersed therein a supporting-electrolyte, or an-organic solid electrolyte hauing high ionic conductiuity which is composed of polyethylene oxi.de and NaI, NaSCN, etc, can also be used in addition to the aboue-described electrolytes.
Concentrations of the supporting electrolyte used in the ECD devices of this inuention uary depending on the kind of organic so].~ents used, current and uoltage ualues of applied el.ectricity, operating -.
temperatures, the kind of supporting e].ectrolytes and the like and, therefore cannot generally be fixed. The liquid e].ectrolyte may be either homogeneous or heterogenous, but usual concentrations range from about O.OOl to about lO mol/1. The di.stance between the high molecular weight conductiue membrane and an opposing electrode cannot generally be determined since i.t uaries, depending on the kind of supporting electrolytes, current and uoltage ualues o~ applied electricity, the display surface area as an ~CD deuice and the like, but it is preferably from about 0.05 to about 5 mm. Further, as an opposi.ng electrode, a ~ariety of materials can be emp].oyed according to the end use. For example, when transmitted light is uti.li.zed for displaying, .the conductiue transparent materials are preferably used as opposing electrodes.
If reflected li.ght i.s utilized, howeuer, it is also possible to use opaque conductiue materials as opposing electrodes. Examples of opaque materials include, ~ut are not limited to, metal foil (e.g., nickel or platinum) and gauze. Furthermore, si.nce the ECD deuices prouide-a substantially colorless tone, background plates ha~ing.uarious col-or tones can be selected.
Thus, the ECD deuices of~the present in~ention can be u-sed in a wide uariety of applications owing to the wide s~elec.tion of auailable materials which can be used.
- -Other uses of the polyisothianaphthene family include general use as electrically conductiue or -electrochromic materials, i.e., in applicati.ons where a hi.ghly conductiue polymer--displaying extremely rapid e].ectrochemical dop~ng characteristics--is desired, or where reuersi.ble oxidation and'reduction occurs, with or without simultaneous optical switching.
In one alternatiue embodiment-of the in~ention, -' then, the polyisothianaphthenes of the present in~ention are used as electrodes or as electrode coatings in a battery. For example, a battery may be pro~ided wherein a polyisothianaphthene is the cathode and l.ithium, calci.um or other suitable material is used as an anode.
The electrodes are separated with a porous parti.tioning membrane se].ected such that ions can freely- pass through i.ts structure. The electrode/membrane assembly is then p].aced within a suitable electrolyte so].uti.on, and a ~oltage is app].ied across the electrodes. Such a battery may ~e used repeatedly without substanti.a].
reduction in the charge-discharge efficiency of the de~ice. Furthermore, self-discharging in such a polyisothianaphthene battery is mini.mized.
l~he substituted polyi.sothianaphthene di.sc].osed herei.n are al.so useful i.n a solar energy con~ersion ce].l, as a surface membrane material which i.s rendered conducti~e upon absorption of light. These polymers are particular].y effecti~e in a solar ~attery, as the -polymers' light absorption characteristic are relati~ely c].ose to that'of sunlight. These polyme.rs also represent an improuement o~er the analagous use of polyacetylenes, as those compounds are partic-u].arly susceptible to oxidation and are extremely sensiti~e to humi.dity.
The foliowing examples are prouided for i.llustrati~e purposes only:and are not intended to li.mit -the present in~ention in any way, the scope of which is defined in the claims.
( -' -23- l 3 3 4 6 7 2 Example I
' To solution of 1.5g (6.85 mmol) of 1,2-bisch].oromethyl-4-,5-dioxymethylene benzene Cprepared according to Brit. Pat. 1,159,089; Ger Offen 1,924,747 (C~71:p80934m, C~ 72: p66609y)] i.n 1.5~ of degassed ethanol (100%3 (this high dilution is necessary to a~oid "
formation of a white, i.ntractable polymer), was added 1.81g (1.1 eq., 7.54 mmol) of finely-ground sodium sulfide nonahydrate. The resulting reaction mixture was heated to reflux with stirring for fi~e hours under~-nitrogen. Upon cooling, to the resulting-cloudy solution (separation of sodium chloride) was added an aqueous soluti.on of 1.619 (1.1 eq., 7.54 mmol~ of sodium metaperiodate in 260 mL of water. ~fter 4 hr of reflux the resulting reaction mixture was fi].tered through a glass frit, the filtrate was concentrated, and extracted with chloroform three times followed by drying o~er anhydrous sodium sulfate. E~aporation of the filtered chloroform soluti.on was euaporated and chromatographed on silica gel with chloroform as the eluent to afford a co~orless solid (yi.eld 21%) su].foxide. ~s 196, ir (KBr, cm ) 2880m, 1475s, 1420w, 1370w, 1280s, 1200m, 114-5m, 1020s, 930m, 900w, 840m, 410m, 340w; nmr (CDCl3, rel to TMS) 4.lq 4H, 5.99s 2H, 5.77s 2H. ,-The abo~e sulfoxide was ground with an excess of alumina (acti~ity I), placed in a subli~ner and heated to 110 under 0.25 pressure. The resulting ' dioxymethylene- isothianaphthene (DOM'r)'sublimed onto the -cold finger of the sublimer in the form of white microcrystals. -This heterocycle was apparently more stable than th-e parent ITN. Ms 178, nmr (C~Cl3, ~ -rel to TMS) S;88s 2H,~.77s- 2H, 7.29s 2H.
~ 1 334672 DOMIT, prepared as abo~e, was electropolymerized-in the usual way (EPO 164,974 Sup.) in acetonitrile at room temperature using tetraphenylphosphonium chloride (O.lM) as eletrolyte, ITO glass as an anode and carbon graphite as a cathode.
~he resulti~ng gray film was Soxhlet*extracted ouernight with acetonitrile and tetrahydrofuran to afford a dedoped blue-black film. Figure 2 shows that the electronic absorption of the undoped polymer has absorption extending into the near infrared, indicating that the interband gap is on the order of <leU. The solid line in Figure 2 is the extracted polymer; the broken line is the fllm "as made".
The film could be cycled between transparent gray and blue-black in a typical cycle voltammogram experiment (see Figure 3). In the experiment, the grey, uniform film on ITO glass was used as the electrode, with Pt wire~as the counter electrode in freshly distilled acetonitrile (0.06M-~u4NC104). The reference electrode was ag/~gCl. Uisual obser~ation during electrochemical cycling indicated that PDOMIT is a higher contrast electrochromic than PITN (change from blue-black to transparent gray).
The absorption spectrum of PDOMIT was obtained for the as-grown film (Fig. 4) and for the same.film after compensation with hydrazine (Fig. 5). The results (Fig. 4) indicate that the as-grown film is relatiue]y hea~ily dop~d (consistent with the lower oxidation potential). after compensation, the existence of an energy gap (Eg) bécomes clearly e~ident; extrap~lating-the absorption edge implies ~ ~0.6 e~. The as-grown PDOMIT,.film is stable in air.
(*) Trademark Example II
- 1,3-dihydro-5,6-dimethoxyisothianaphthene is prepared as described in J. Chem. Soc., Parkin Trans. 1 (1980) 8, p. 184126. lhis compound is then treated with sodium metaperiodate, as described in EPO Pub. No.
164,974,~to giue 1,3-dihydro-5,6-dimethoxyisothianaph-thene-2-oxide.- The sulfoxide is then dehydrated and polymeri.zed as described i.n Example I to giue poly(5,6-dimethoxyisothianaphthene).
Example III
Technical Field This invention relates generally to con~ cting polymers and their use as electrodes in various devices, and in particular relates to certain substituted polyisoll~,anaphthenes (PITN) and their use in electrochromic displays, batteries, solar cells, and the like.
Background With the latest develop,l,e,lls in li~ht~ning I i..nning and mini~hlrization of electric and electronic instruments, the development of new con~ cti~ materials per se has been desired.
Various sulfur-cG..~ g heterocyclic polymers are known in~ 1in~ polymers from thiophene, U.S. patent No. 2,582,796 and U.S. patent No. 2,658,902; polymers from dibenzothiophene, U.S. patent No. 3,585,163; polymers from vinyl bithiophene, U.S. patent No.
~ X
. -2- l 334672 3,615,384; polymers from uarious substituted thiophenes, U.S. Patent No. 3,725,362; polymers from 2-bromo-8-hydroxy-5,5-dioxodibenzothiophene, U.S. Patent No.
3,775,368; and polymers from tetrathiapentalene, U.S.
Patent No. 4,111,857.
~ Within-the rapidly expanding field of polymeric ~ - .
conductors ("Proceedings of the l.nternationaJ. Conference on the Physics and Chemistry of Polymeric Conductors", J. Physique. Colloque., (1983), C-3), the poly(heterocycles) haue received attention because they are easily prepared in film form and are consi.derably more stable to atmospheric exposure than polyacetylene or polyphenylene. For use in stabil-izing a semiconductor surface, see R. Nou~i et al., J-. ~mer.
Chem. Soc., (1981), ~ol. 183, 184 and re~erences therein. ~ further extension of thi.s work is our recent.
entry into the study of polythiophene.
Extensiue i.nuestigati.ons on new conducti.ue polymers haue been conducted. For example, polyacetylenes are under in~esti.gati.on for possib]e auailability as electrode materials in secondary batteries since they show conductiuiti.es as high as to 10 S/cm when doped with iodine or arsenic pentafluoride (cf. Synthetic Metals, Uol. 1, No. 2, 101 (1979/1980)). lhese polymers also display excellent charge-discharge characteristics. Use of polyacetylenes ~in solar batteries is also under inuestigation ~ecause of- the polymers'- ligh-t absorption characteristics which are close to those of sunlight; Howeuer, the .
- polyacetylenes are disadvantageous in that.they are per se susceptible to oxidation and doped polyacetylenes-are extremely sensitive to h~midity.
~ - Poly~hiophenes have been studied not only as conductive materials and as battery electrode materials, ~3 1 334672 but also as electrochromic materials making use of color changes in a doped state. For example, ~.M. Druy, et al ~eported that 2,2'-bithienyl may be electrochemically-polymerized to form a polymer ha~ing a color which re~ersibly ~aries From blue in an oxidized state to red in a reduced state, thus a potentially useful electrochromic material tcf. Journal de Physique, Uol.
44, No. 6, C3-595 (1983)~. Howe~er, polythiophenes, like polyacetylenes,- are generally sensitiue compounds.
In light of the aboue-described problems, the present inventors ha~e conducted extensi~e inuestigations into conductiue polymers and uses thereof, and, as a result, haue found that a polymer ha~ing an isothianaphthene structure is a uery stable compound which is capable of continuously and reuersibly uarying its color in the course of oxidation or reduction. Unsubstituted polyisothianaphthene is described in certain publications by the present inuentors. See, e.g., Wud] et al., J. Orq. Chem., (1984), ~ol. 49, pp. 3382-3384; Wudl et al., Polymer Preprints, Uol. 25(2), pp.257-259; Chemical ~bstracts, (1984), ~ol. 101, part 24, p. 7, 211832q. PITN-type polymers are described in United States Patent number 4,640,748 which was issued on February 3, 1987. See also EPO Pub. No. 164,974 (18 December 1985).
8ecause polyisothianaphthenes are very stable 'and exhibit extremely rapid p-type-electrochemical doping'characteristics' with an associated high contrast color chang'e, many applications of the polymers are clearly feasible. ~ne application--use in electr.ochromic displays--is made possible by ~irtue of the fact that polyisothianaphthene is a transparent, as well as conducti~e, polymer. ~fter doping, a thin film - _4- - 1 3 3 4 6 7 ~ `
of PITN has a uery low optical density in the visible portion of the spectrum. Other applications which make use of the opto-electrochemi.cal properties of PITN
includes use as an electrode in a battery or.
electrochemical cell, a solar energy conuersion deuice, and its general application as (or-in) electroch-romic .
material. ~ limitation, howeuer, is that at uery high dopant leuels PITN can be attacked by the atmosphere with concomitant dedoping. ~ need exists, therefore, for a PlTN-type polymer that retains the ad~antages of PITN, but is resistant to atmospheric attack at hi.gh dopant leuels.
Electrochromic displays represent an improuement ouer liquid crystal de~ices, which have recently been deueloped as "low-energy" disp].ay de~ices with, potentially, a wide range of applications. The display in liqui.d crystal de~ices is dependent on uisual angle and the contrast and resolution are typically poor. No memory function is prouided, nor can the display be prouided ouer a large surface area. ~n order to eliminate these disad~antages, studies haue been extensiuely conducted on low-energy electrochromic display (EC~) de~ices which make use of a material's electrochromic properties, i.e., electrochromic materials haue light absorption characteristics:which uary with application of uoltage or~electric current.
Electrochromic materials which can be used i.n ECD de~ices may be either inorganic or-organic.
Inorganic materials that are con-sidered usable mainly include oxides.of transition me~als,-but these are limited ~ith-res~ect to de.uelopable colors. Transition metal..oxides also cause electrochemical elution of the membrane or deterioration of electrodes when protons are used as color-forming ions, although response speeds may ( be hi.gh. Organic materials used in electrochromic displays typically include uiologen- dyes., phthalocyanine complexes, etc. However, the uiologen dyes are disaduantageous in that repeated use thereof results in precipitation of insoluble-substances, and the phthalocyanine complexes haue an as-yet unsoloed- problem .;
with adhesiueness between a uacuum-euaporated mem~rane and a base plate.
Other electrochromi.c materials which haue recently been proposed include: polyanilines as disc].osed in ~.F. Diaz, et al., Journal of l~lectro-~nalytical Chemistry, Uol. 111, 111 (1980) or Yonemaya et al., ibid, ~)ol. 161, 419 (1984);
polypyrroles as disclosed in ~.F. Diaz et al., _id, ~Jol. 101 (1983) and polythiophenes as disclosed in M.~.
~ruy, et al., ~ournal de Physique, Uol. 44, June, page C3-595 (1983) or Kaneto et al., Japan Journal of ~pplied Physics, Jol. 23, No. 7, page L412 (1983). Howeuer, none of these materials has been put to practica]. use.
Prel~erred characteri.stics for electrochromic materials are rapid response time in e].ectrochromic s~itchi.ng, high contrast and resolution, good color tones and the li.ke. Furthermore, as noted aboue, an e].ectrochromic material such as PITN which is capable of deuelopi.ng a colorless tone will great].y contribute to the ap,olicabil-ity of the de~Jice. This is in contrast to the aforementioned heteroconjugated materials which are colored in the course of conuersion from an oxidized state to a reduced state; Thus, a need also exists for improued PlTN-type pc~lymers for use in ECD deuices.
- -Summary of the Inuention ~ ccordingly, it is a primary-object of the present inuention to prouide a conductiue polymer capable of being reuersibly oxidized or reduced.
It is also an ob]ect oF the present inuention to prouide a polyisothianaphthene-type polymer that is stable to atmospheric attack at high dopant leuels.
It is another object of the in~ention to prouide a high molecular weight, substituted poly-isothianaphthene.
~ t is a further object of the inuention to prouide an electrochromic membrane materi.al that is chemically and physically stable, prouides a hi.gh contrast color change upon oxidation and reduction, and giues a rapid response time in electrochromic switching.
It is another object of the inuention to use substituted polyisothianaphthene as an electrode or electrode coating material, in the production of solar batteries, and, generally, as an electrochromic material .
in reuersible oxi.dation-reduc~ion systems.
l-hese and other objects of the present inuenti.on are achieued by one or more of the following embodiments.
- ~ ~ ~ - ' ;-( -7~ 1 3 3 4 6 7 2 In one embodiment, the present in~ention is directed to a polymer ha~ing a structural formula selected from the group consisting of Ia and Ib wherein:
la = R~2 - b R, I b = R~
O R~
~ ~ ~ n Rl i.s hydrogen or -OR3;
R2 and R3 are selected i.ndependently from the~ group consisting of hydrogen and C1 to C~
hydrocarbons, with the pro~iso that R2 and R3 can link together to form, with both oxygens, a - - - dioxyalkylene substituent on the benzene ring-with -the.
- formula: . ~ ~ -- . -S' '-, - . - . - - /C ~
' ' '' ~ \ /- -' wherein R4 and R5 are selected independently from the group consisting of hydrogen and Cl t~ C4 hydrocarbons; - - ~
X is selected from the group consisting of sulfur, selenium and tellurium;
Y represents an anion of an electro-lyte; - -z repres.ents a number from 0.01 to I showing a ratio of the anion per mol of a monomer; and - n represents a number of from 5 to 500 showing the degree of polymerization.
In another embodiment, the present inuenti.on is directed to a method of preparing a polymer by electrochemical polymerization comprising:
(a) pro~iding a monome.~ ha~ing the formula:
b Rl ~' wherein R1, R2 and X are defi.ned as aboue;
- (b) dissoluing said monomer in an aprotic sol.uent containing electrolyte to prouide a monomer solution, said e].ectrolyte being ionic and a sourc-e o.f nucleophilic anions; and - ~. (c) electrochemically polymerizing said monomer --solution to pro~ide a poly(isothianaphthene).
In other embodiments, the present invent-ion is directed to ECD deuices, electrodes and batteries employing the polymers described above. : -Brief Description of the Fiqures Figure 1 is a schematic cross-sectional ~iew illustrating an example~of the ECD de~ice in accordance with the. present in~ention. --- Figure 2 shows the electronic absorption of a polymer accor.ding to---the present i.n~ention in both a - .
doped and undoped state.
Figure 3 shows the results for a cyclic ~oltammogram experiment with a polymer according to the present in~ention.
Figure 4 is the absorption spectrum of a doped, electroche~ically polymerized film according to the present in~ention in its "as grown" conditi.on.
Figure 5 is the adsorption spectrum of the same polymer film shown in figure 4 after compensation with hydrazine.
-- -lo- 1 3 3 4 6 7 2 ~etailed Description The conducti~e, substituted polyisothia-- naphthene-type polymers of- the present in~ention are gi~en by structure la or Ib:
R2 ` R2 ~ R, ~ - O - R, (la) ' ~ (Ib) ~
n ~ ( X ~ ~ n R1 is hydrogen or -OR3;
R2 and R3 are selected i.ndependent-ly from the group consisting of hydrogen and Cl to C~
hydrocarbons, with the pro~iso that R2 and R3 can link together to form, with both oxygens, a di.oxya].kylene substituent on the benzcne ri.ng witll the formula: R~ Rs \ / '' /c~
O O
\ /
wherein R4 and R5 are selected i.ndependently fron;
the group consisting of hydrogen'and Cl to C4 hy~drocarbons; '-' ' - - X is--selected from the'group consist:ing of '. - -sulfur, selenium and. tellurium; . ' - -- - Y represents an anion of~an electrolyte;
- - - z represents a number from O.OI to 1 showing a ~- ratio.oi the anion .per mole of a monomer;-and n re'presents a number of from 5 to 500, i.e.
represenis the'deqree of polymeri2ation.
1 33467~
Formula Ia represents the po].ymer in its undoped state. Formula Ib represents the polymer in its doped, conducti~e state wherein a positi~e charge is mo~able along the backbone of the ~olymer chain. ~or example, in an electrochromic display de~ice according to the present in~ention, appl.ication of a ~oltage acros-s the polymer mem~rane i.n -the deuice con~erts the neutral, uncharged polymer of ~ormula Ia to the charged polymer of Formula Ib.
In exemplary embodiments, X is sulflJr, Rl i.s -OR3, R2 and R3 are either C1 to C5 hydrocarbons (e.g., methyl, ethyl, etc.), or the dioxyalkylene substituent where R4 and R5 are hydrogen, methyl or ethyl.
Referring to the undoped state of the polymer, exemplary formulas include:
~6 / 7 O O
(Il) ~ ~
~/'~ .
X ~ n where R6 and R7 are selected independently from hydrogen, and C1 to C8 hydrocarbons; and .
- - - . R4 Rs , , - V
/ \
- - O - - O
( I I I ) ~
~~ -12- 1 334672 where X, R4, R5 and n are defined as aboue. The polymers of ~ormulas II and III haue doped structures equiualent to Ib. The ani.on of formula Ib, Y , is preferably selected from the group consisting of:
Cl Br , I , C104, BF4~ PF6, ~sF6, 6 - ~lCl~ r4, FeCl4 and CF3SO3,-but may also be HSO~ or HF2. The ratio i is preferably from about 0.01 to 0.40.
The small bandgap conducting polymers of the present inuention are important because of their high intri.nsic conductiuity and because i.n the course of - doping they are conuerted to transparent conductors--i..e., they change from a deeply colored form (e.g., blue-black) to transparent. When the doping is performed in an electrochemi.ca]. ce].l, this transformation leads to high contrast elect:rochromism.
The substi.tuted PITN polymers of the present inuention were designed to improue the stability of the charged PITN polymer by conjugation with cation-stabilizing oxygen atoms. This stabi.lization is exemplified below with poly(di.oxymethylene-isothianaphthene1(P~OMIT).
- 0~0: +0~0:
- ~)n (~~)n ~ (~)n PJ~N - -P~OMIT
~ -13- 1 3 3 4 6 7 2 ~s can be seen in P~OMI~, the positiue charge is stabilized through resonance by a non-~onded pair of - e].ectrons on an oxygen. In addition,-.there exists the possibility of enhancing i.nterchain i.nteractions through the oxygen atoms, thus increasing the room temperature conducti~ity of the polymer.
~ The substituted PIlN polymers of the present in~ention are prepared, for example, by the electrochemical polymerization of monomers haui.ng the structure IU: - -R\o R, V
(I~J) ~
~/X~ --where R1, R2 and X are the same as described aboue.
Speci.fic examp].es cf the substituted i.sothi.anaphthenes of formula I~ inclllde 5-methoxy-i.sothianaphthene; 5,6-di.hydroxy-isothianaphthene; 5,6-dimethoxy-isothianaphthene; 5,6-di.ethoxy-isothianaphthene;
5,6--di.oxymethylene-isothianaphthene; and 5,6-di.oxy (~,~-dimethylmethylene)-i.sothianaphthene.
Corresponding 1,~-dihydroisothianaphthenes can also sere~e as-monomers, b.eing dehydrated after polymerization as -described in EPO-164,974. --:
The hydroxy and alkoxy-f-orms of mon-omer.I~ can be prepared from the corresponding substituted 1,3-dihydroisothianaphthene, which is treated, for example: with sodium metaperiodate to pro~ide the sulfoxide. The sulfoxide i.s then d~hydrated to gi~e the~-_ -14- l 3 3 4 6 7 2 corresponding hydroxy or alkoxy substitutecl isothianaphthene.
-~lternatively, monomers of formula IU are prepared from~substituted 1,2-bishalomethylbenzene. ~n example of such compounds are 1,2-bischloromethyl-4,5-dioxymethylene benzene, and 1,2-bisc~loromethyl-4,5-dimethoxy benzene. These substituted.halomethylbenzenes are reacted with, for example, sodium sulfide nonahydrate to gi~e.the 1,3-dihydroisothianaphthene deriuatiue. This is then conuerted to the sulfoxide corresponding to formula I~, and then dehydrated to gi~e the isothianaphthene monomer.
Hydroxy substituted polymers can also be prepared directly from PDOMIT by conuerting the dioxymethylene group to hydroxy groups. This is done, for example, by treating PDOMIT with HI, methylmagnesium iodide or aluminum chloride, The monomers of formula I~ are preferably electrochemically polymerized. Electrochemical polymerization of the abo~e-described substituted isothianaphthene compound can be carried out according to the methods generally employed for electrochemical polymerization of thiophene, pyrrole, etc. (e.g., the method described in Solid State Communication, ~ol. 46, No. 5, 389 (1983)). More specifically, either controlled potential electrolysis or controlled current electrolysis can be employed, and it is desirable to form a polymër membrane on a transparent base by using a conducti~e transparent base as a samp1e electrode.
Ele~ ~m;~l olymerization~o-Y~-are taught in United States Patent:~h~r ~64~,7~-and-EPQ Publication Nunber:164,974.
t~
( In a preferred embodiment of the in~ention, an electrochromic disp].ay deuice inc].udes an electrochromic, polymeric membrane comprising the -.
substituted polyisothianaphthenes disclosed herein.
Referring to Figure 1, substituted polyisothianaphthene membrane 3 is formed on display electrode 2, e.g. by electropolymerization, which display electrode is in turn adjacent transparent base 1. Liquid electrolyte 4, which includes a support electrolyte dissolued or di.spersed in a suitable so].~ent, separates the PIrN
membrane from opposi.ng e].ectrode 5. Protecting layer 6 ser~es as a housing for the de~ice. Uoltage is appli.ed across the deuice, i.e. between display electrode 2 and opposing electrode 5, by means of lead-in wi.res 7 which are in electrical contact with the two electrodes.
The thickness of the PITN layer in the electrochromi.c display i.s from about 0.03 to 3011m, preferably from about 0.05 to 22~m, still more preferably from about 0.1 to lo~Lm. When the membranc-thickness is 3.ess than about 0.03~m, clear contrast cannot be attained. ~ thi.ckness exceeding about 3011m pro~ides clear contrast, but is di.saduantageous ~rom the point of-uiew of film strength and response speed.
.The conducti~e transparent base 1 which can be used in the present inuention includes ones which -comprise a transparent insulator such as glass, polyester film,-etc., hauing uacuum e~aporated thereon - -indium-tin oxide, tin oxide, platinum, etc. by sputtering or a like method. These materials are~: :
readily `auailable commercially.
( ~
ECD de~ices can be produced by assembling the thus obtained polymer with an opposing electrode ~ia a li.quid e].ectrolyte. The ].iqui.d electrolyte which can be used is a dispersion or solution of a supporting e].ectrolyte in a sol~ent. The supporting electrolyte which can be used-in-the present in~enti.on includes combinations of (i) anions (i.e., Y in the formula Ib) such as hali.de anions of ~a group e].ements, e.g., PF6, SbF6, ~sF6 and SbCl6; halide anions of IIIa Grbup series element, e.g., BF4; halogen .
ani.ons, e.g., I (I3), Br and Cl ; perchloric acid anions, e.g., Cl04; and (ii) cations such as alkali metal ions, e.g., Li+, Na and K+;
quaternary ammonium ions, e.g., R4N (wherein R
represents a hydrocarbon residue ha~ing 1 to 20 carbon atoms); and phosphoni.um i.ons, e.g., (C6H5)4P .
These examples are merely illustrati~e and not li.mi.ti.ng.
Specific examples of the supporting electrolytes composed of the abo~e-described combinations of anions and cati.ons are LiPF6, LiS~F6, Li~sF6, LiC104, NaI, NaPF6, NaSbF6, Na~sFfi, NaC104, KI, KPF6, KSbF6, K~sF6, KC104, [(n-Bu)4N~ ^
C104, Li.~lC14, LiBF4, (C6H5)4P^BF4, (C6H5)4P^~sF6 and (C6H5)4P~C104. These examples, again, are not limi.ting. Supporting .-electrolytes may be used indi~idually or in combination.
- . The HF2 and HS04 anions can also be used, in addition to-the above-enumerated anions.-Further~ cations which can be used in addition to those enumerated abo~e include pyrylium or pyridinium ions ;.
-: -represented by the following formula (~) and carbonium cations represented by the following formula (UI):
(u): ~ z -(R'!m (R") wherein Z represents an oxygen atom or a nitrogen atom;
R' represents a hydrogen atom, an alkyl group hauing 1-to 15 carbon atoms or an aryl group hauing 6 to 15 carbon atoms; R" represents a halogen atom, an a'l.kyl group hauing 1 to 10 carbon atoms or an aryl group hauing 6 to 15 carbon atoms; m is O when Z is an oxygen atom, or m is 1 when Z is a nitrogen'"atom; and p i.s O or an integer of from 1 to 5; and (UI): R5 \
~3 /
wherein R3, R4 and R5 are independently selected from the group consisting of hydrogen atoms, alk'yl groups hauing 1 to 15 carbon atoms, aryl groups- hauing 6 to 15 carbon atoms 'and -OR wherein R represents an a].~yl group hauing -1 to .10 carbon atoms or an aryl group .
hauing 6 to~15 carbon atoms, with prouiso that R , --R and R5 are not all'hydrogen atoms.
-.~ ' ' , ' - .
( _ -18- 1 334672 The HF2 anion which can be used is usually obtained by dissoluing a hydrofluoride compound represented by the formula (UII), (UIII), or ~IX):
(~II): R'4N HF2 (UIII): ~.HF2 //~l (IX): ~ Z-HF2 ) q wherei.n R' and R" each represents a hydrogen atom, an alkyl group ha~ing 1 to 15 carbon atoms or an aryl group ha~ing 6 to 15 carbon atoms; R" represents an alkyl group ha~ing 1 to 10 carbon atoms or an aryl group ha~i.ng 6 to 15 carbon atoms; Z represents an oxygen atom or a nitrogen atom; q represents O or a positi~e integer of 5 or less; and M represents an alkali metal, as a supporting electrolyte in an appropriate sol~ent Specific examples of the compounds represented by the abo~e formulae (~ , (UIII) and (IX) include ~ -H4N-HF2, Bu4N~HF2, Na.HF2, K-HF2, Li.~HF2 and ~HF2 - - . , .
-the pyrylium or pyridini.um-cations can be - . obtain-ed by dissol~ing a saIt formed between a cation - represented by the formula (~) and an anion, e.g., C104, BF4, ~lC14, FeC14, SnC15, PF6, PC16, PC16, SbF6, ~sF6, CF3S03, HF2, etc., as a supporting electrolyte in an appropriate soluent. Speci.fic examples of such salts include:
~0 'Clo ~ - ~ t C~O~ C~
Cl~
~N _ _ 4 <=~0 - ~SF6 , ~ AsFG
t _ ~0 ' SbF6 ~H3 H3C ~0 SbF6, ~ -HF2 ~ etc.
Specific examples of the carbonium cations represented by the aboue-described formu].a (~I) i.ncl.ude (C6H5)3C , etc. These carboni.um atoms can be obtained by dissoluing or di.spersing a carbonium salt formed between such a cation and an anion as a supporting electrolyte i.n an appropriate soluent.
Suitable anions typically include : -BF4, ~lC14, ~lBr-3cl, Fecl4~- PF6, PC16,-SbC16, SbF6, C10-4, CF3S03, etc., and the-carbonium sal~ s-pecifically includes, for~example, (C6H5) 3C^BF4, (CH3)3C-BF4,- HCQ-~lC14, HCO~BF4, c6H5co~sncl5~ etc.
- The soluents which can.be used in the present inuention may be either aqueous or nonaqueous, although a solution of the aforesaid supporting electrolyte in a nonaqueous organic sol~ent is preferred. The organic soluents used herein are preferab].y aprotic and haue high dielectric constants. For example, ethers, ketones, nitriles, amines, amides, sulfur-compounds, phosphoric ester compounds, phosphorous ester compounds, -.
boric ester compounds, chlorinated hydrocarbons, esters, carbonates, nitro compounds and the like can be employed. Of these, ethers, ketones, nitriles, phosphoric'ester compounds, phosphorous ester compounds, boric ester compounds, chlorinated hydrocarbons and carbonates are preferred. Specific examples of suitable solvents include tetrahydrofuran, 2-methyltetra-hydrofuran, 1,4-dioxane, acetonitrile, proprionitrile, 4-methyl-2-pentanone, butyronitrile, ualeronitrile, benzonitrile, 1,2-dichloroethane, ~-butyrolactone, ~alerolactone, di.methoxyethane, methylformate, propylene carbonate, ethylene carbonate, dimethylformamide, di.methyl sulfoxide, ethyl phosphate, methyl phosphate, ethyl phosphite, methyl phosphite, 3-methylsulfolane, etc. ~mong these, nitriles and carbonates are especially preferred in order to increase the response speed. These organic sol~ents may be used alone or in combination.
~ epending upon the model of EC~ deuices-used or the kind of electrodes'used, oxygen or water present in these soluents or protoni.c sol~ents sometimes deteriorate the performance of ECD deuices. Such-'being the case, it is preferable to purify the soluents 'beforehand in the usual manner. - further, in the ECD
deuices -of-the present in'~ention, organic soluents hauing merely dispersed therein a supporting-electrolyte, or an-organic solid electrolyte hauing high ionic conductiuity which is composed of polyethylene oxi.de and NaI, NaSCN, etc, can also be used in addition to the aboue-described electrolytes.
Concentrations of the supporting electrolyte used in the ECD devices of this inuention uary depending on the kind of organic so].~ents used, current and uoltage ualues of applied el.ectricity, operating -.
temperatures, the kind of supporting e].ectrolytes and the like and, therefore cannot generally be fixed. The liquid e].ectrolyte may be either homogeneous or heterogenous, but usual concentrations range from about O.OOl to about lO mol/1. The di.stance between the high molecular weight conductiue membrane and an opposing electrode cannot generally be determined since i.t uaries, depending on the kind of supporting electrolytes, current and uoltage ualues o~ applied electricity, the display surface area as an ~CD deuice and the like, but it is preferably from about 0.05 to about 5 mm. Further, as an opposi.ng electrode, a ~ariety of materials can be emp].oyed according to the end use. For example, when transmitted light is uti.li.zed for displaying, .the conductiue transparent materials are preferably used as opposing electrodes.
If reflected li.ght i.s utilized, howeuer, it is also possible to use opaque conductiue materials as opposing electrodes. Examples of opaque materials include, ~ut are not limited to, metal foil (e.g., nickel or platinum) and gauze. Furthermore, si.nce the ECD deuices prouide-a substantially colorless tone, background plates ha~ing.uarious col-or tones can be selected.
Thus, the ECD deuices of~the present in~ention can be u-sed in a wide uariety of applications owing to the wide s~elec.tion of auailable materials which can be used.
- -Other uses of the polyisothianaphthene family include general use as electrically conductiue or -electrochromic materials, i.e., in applicati.ons where a hi.ghly conductiue polymer--displaying extremely rapid e].ectrochemical dop~ng characteristics--is desired, or where reuersi.ble oxidation and'reduction occurs, with or without simultaneous optical switching.
In one alternatiue embodiment-of the in~ention, -' then, the polyisothianaphthenes of the present in~ention are used as electrodes or as electrode coatings in a battery. For example, a battery may be pro~ided wherein a polyisothianaphthene is the cathode and l.ithium, calci.um or other suitable material is used as an anode.
The electrodes are separated with a porous parti.tioning membrane se].ected such that ions can freely- pass through i.ts structure. The electrode/membrane assembly is then p].aced within a suitable electrolyte so].uti.on, and a ~oltage is app].ied across the electrodes. Such a battery may ~e used repeatedly without substanti.a].
reduction in the charge-discharge efficiency of the de~ice. Furthermore, self-discharging in such a polyisothianaphthene battery is mini.mized.
l~he substituted polyi.sothianaphthene di.sc].osed herei.n are al.so useful i.n a solar energy con~ersion ce].l, as a surface membrane material which i.s rendered conducti~e upon absorption of light. These polymers are particular].y effecti~e in a solar ~attery, as the -polymers' light absorption characteristic are relati~ely c].ose to that'of sunlight. These polyme.rs also represent an improuement o~er the analagous use of polyacetylenes, as those compounds are partic-u].arly susceptible to oxidation and are extremely sensiti~e to humi.dity.
The foliowing examples are prouided for i.llustrati~e purposes only:and are not intended to li.mit -the present in~ention in any way, the scope of which is defined in the claims.
( -' -23- l 3 3 4 6 7 2 Example I
' To solution of 1.5g (6.85 mmol) of 1,2-bisch].oromethyl-4-,5-dioxymethylene benzene Cprepared according to Brit. Pat. 1,159,089; Ger Offen 1,924,747 (C~71:p80934m, C~ 72: p66609y)] i.n 1.5~ of degassed ethanol (100%3 (this high dilution is necessary to a~oid "
formation of a white, i.ntractable polymer), was added 1.81g (1.1 eq., 7.54 mmol) of finely-ground sodium sulfide nonahydrate. The resulting reaction mixture was heated to reflux with stirring for fi~e hours under~-nitrogen. Upon cooling, to the resulting-cloudy solution (separation of sodium chloride) was added an aqueous soluti.on of 1.619 (1.1 eq., 7.54 mmol~ of sodium metaperiodate in 260 mL of water. ~fter 4 hr of reflux the resulting reaction mixture was fi].tered through a glass frit, the filtrate was concentrated, and extracted with chloroform three times followed by drying o~er anhydrous sodium sulfate. E~aporation of the filtered chloroform soluti.on was euaporated and chromatographed on silica gel with chloroform as the eluent to afford a co~orless solid (yi.eld 21%) su].foxide. ~s 196, ir (KBr, cm ) 2880m, 1475s, 1420w, 1370w, 1280s, 1200m, 114-5m, 1020s, 930m, 900w, 840m, 410m, 340w; nmr (CDCl3, rel to TMS) 4.lq 4H, 5.99s 2H, 5.77s 2H. ,-The abo~e sulfoxide was ground with an excess of alumina (acti~ity I), placed in a subli~ner and heated to 110 under 0.25 pressure. The resulting ' dioxymethylene- isothianaphthene (DOM'r)'sublimed onto the -cold finger of the sublimer in the form of white microcrystals. -This heterocycle was apparently more stable than th-e parent ITN. Ms 178, nmr (C~Cl3, ~ -rel to TMS) S;88s 2H,~.77s- 2H, 7.29s 2H.
~ 1 334672 DOMIT, prepared as abo~e, was electropolymerized-in the usual way (EPO 164,974 Sup.) in acetonitrile at room temperature using tetraphenylphosphonium chloride (O.lM) as eletrolyte, ITO glass as an anode and carbon graphite as a cathode.
~he resulti~ng gray film was Soxhlet*extracted ouernight with acetonitrile and tetrahydrofuran to afford a dedoped blue-black film. Figure 2 shows that the electronic absorption of the undoped polymer has absorption extending into the near infrared, indicating that the interband gap is on the order of <leU. The solid line in Figure 2 is the extracted polymer; the broken line is the fllm "as made".
The film could be cycled between transparent gray and blue-black in a typical cycle voltammogram experiment (see Figure 3). In the experiment, the grey, uniform film on ITO glass was used as the electrode, with Pt wire~as the counter electrode in freshly distilled acetonitrile (0.06M-~u4NC104). The reference electrode was ag/~gCl. Uisual obser~ation during electrochemical cycling indicated that PDOMIT is a higher contrast electrochromic than PITN (change from blue-black to transparent gray).
The absorption spectrum of PDOMIT was obtained for the as-grown film (Fig. 4) and for the same.film after compensation with hydrazine (Fig. 5). The results (Fig. 4) indicate that the as-grown film is relatiue]y hea~ily dop~d (consistent with the lower oxidation potential). after compensation, the existence of an energy gap (Eg) bécomes clearly e~ident; extrap~lating-the absorption edge implies ~ ~0.6 e~. The as-grown PDOMIT,.film is stable in air.
(*) Trademark Example II
- 1,3-dihydro-5,6-dimethoxyisothianaphthene is prepared as described in J. Chem. Soc., Parkin Trans. 1 (1980) 8, p. 184126. lhis compound is then treated with sodium metaperiodate, as described in EPO Pub. No.
164,974,~to giue 1,3-dihydro-5,6-dimethoxyisothianaph-thene-2-oxide.- The sulfoxide is then dehydrated and polymeri.zed as described i.n Example I to giue poly(5,6-dimethoxyisothianaphthene).
Example III
2,2-dibromopropane is reacted wi.th catecho]. to gi~e 1~2-dioxy(~-dimethylmethylene)benzene (ODMB) accordin~ the method disclosed in G.8~ Patent Spec. No.
1,097,270. DDMB has the following structure:
CH ~ CH3 O O
~. ' DDMB is then reacted as described in Example I to gi~e poly(5,6-dioxy(~,a-dimethylmethylene)i.sothianaphthene) .
~ Example IU
- - .
- - 3,4-bisbromomethylanisol is prepared according - ~
to-G.8; Patent Spec. 1,268,243. It is the con~erted to - - the corresponding iso.thianaphthene and polymerized, as describe~: in Example -I, to gi~e poly(5-methoxy-isothianaphthene).
-~- While the-present in~ention has been described by way of specific embodiments, uariations will be apparent to those i.n the art from the foregoing descri.ption and the practice of the present inuention,.
Thus, the present i.nuention is not ].imited to~the foregoi.ng specific embodiments, but is defined by the following claims.
1,097,270. DDMB has the following structure:
CH ~ CH3 O O
~. ' DDMB is then reacted as described in Example I to gi~e poly(5,6-dioxy(~,a-dimethylmethylene)i.sothianaphthene) .
~ Example IU
- - .
- - 3,4-bisbromomethylanisol is prepared according - ~
to-G.8; Patent Spec. 1,268,243. It is the con~erted to - - the corresponding iso.thianaphthene and polymerized, as describe~: in Example -I, to gi~e poly(5-methoxy-isothianaphthene).
-~- While the-present in~ention has been described by way of specific embodiments, uariations will be apparent to those i.n the art from the foregoing descri.ption and the practice of the present inuention,.
Thus, the present i.nuention is not ].imited to~the foregoi.ng specific embodiments, but is defined by the following claims.
Claims (35)
1. A polymer having a structural formula selected from the group consisting of Ia and Ib wherein:
Ia =
Ib =
R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y- represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
Ia =
Ib =
R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y- represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
2. The polymer of claim 1 wherein R1 is -OR3; R2 and R3 are either (i) selected from the group consisting of methyl and ethyl, or (ii) together with the oxygens form said dioxyalkylene where R4 and R5 are selected from the group consisting of hydrogen, methyl and ethyl; and X is sulfur.
3. The polymer of claim 2 wherein R2 and R3 are methyl or ethyl, and R2=R3.
4. The polymer of claim 2 wherein R2 and R3 are methyl.
5. The polymer of claim 2 wherein R2 and R3 together from said dioxyalkylene, R4 and R5 are hydrogen or methyl, and R4=R5.
6. The polymer of claim 5 wherein R4 and R5 are hydrogen.
7. The polymer of claim 2 wherein said structural formula is Ia.
8. The polymer of claim 3 wherein said structural formula is Ia.
9. The polymer of claim 4 wherein said structural formula is Ia.
10. The polymer of claim 5 wherein said structural formula is Ia.
11. The polymer of claim 6 wherein said structural formula is Ia.
12. The polymer of claim 2 wherein said structural formula is Ib.
13. The polymer of claim 3 wherein said structural formula is Ib.
14. The polymer of claim 4 wherein said structural formula is Ib.
15. The polymer of claim 5 wherein said structural formula is Ib.
16. The polymer of claim 6 wherein said structural formula is Ib.
17. The polymer of claim 12 wherein Y- is selected from the group consisting of Cl-, Br-, I-, ClO?, BF?, PF?, AsF?, SbF?, AlCl?, AlBr?, FeCl?, and CF3SO?.
18. The polymer of claim 13 wherein Y- is selected from the group consisting of Cl?, Br?, I?, ClO?, BF?, PF?, AsF?, SbF?, AlCl?, AlBr?, FeCl?, and CF3SO?.
19. The polymer of claim 14 wherein Y- is selected from the group consisting of Cl?, Br?, I?, ClO?, BF?, PF?, AsF?, SbF?, AlCl?, AlBr?, FeCl?, and CF3SO3.
20. The polymer of claim 15 wherein Y- is selected from the group consisting of Cl?, Br? , I?, C1O?, BF?, PF?, AsF?, SbF?, AlCl?, AlBr?, FeCl?, and CF3SO?.
21. The polymer of claim 16 wherein Y- is selected from the group consisting of Cl?, Br?, I?, ClO?, BF?, PF?, AsF?, SbF?, AlC1?, AlBr?, FeC1?, and CF3SO3.
22. The polymer of claim 12 wherein Y- is HSO?.
23. The polymer of claim 13 wherein Y- is HSO?.
24. The polymer of claim 14 wherein Y- is HSO?.
25. The polymer of claim 15 wherein Y? is HSO?.
26. The polymer of claim 16 wherein Y? is HSO?.
27. A method of preparing a poly(isothianaphthene) polymer by electrochemical polymerization comprising:
(a) providing a monomer having the formula:
R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 can link together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 and C4 hydrocarbons;
(b) dissolving said monomer in an aprotic solvent containing electrolyte to provide a monomer solution, said electrolyte being ionic and a source of nucleophilic anions;
and (c) electrochemically polymerizing said monomer solution to provide a poly(isothianaphthene).
(a) providing a monomer having the formula:
R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 can link together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 and C4 hydrocarbons;
(b) dissolving said monomer in an aprotic solvent containing electrolyte to provide a monomer solution, said electrolyte being ionic and a source of nucleophilic anions;
and (c) electrochemically polymerizing said monomer solution to provide a poly(isothianaphthene).
28. The method of claim 27 wherein said monomer is 5,6-dioxymethylene-isothianaphthene.
29. The method of claim 27 wherein said monomer is 5,6-dimethoxy-isothianaphthene.
30. The method of claim 27 wherein said polymerization forms said poly(isothianaphthene) into a membrane on a transparent conductive base.
31. The method of claim 28 wherein said polymerization forms said poly(isothianaphthene) into a membrane on a transparent conductive base.
32. An electrochromic display wherein a high molecular weight conductive membrane formed on a conductive transparent base is used as a display base and an opposing electrode is arranged thereunder via a liquid electrolyte, said high molecular weight conductive membrane comprising a polymer having an isothianaphthene structure and capable of being reversibly oxidized or reduced, having a structural formula selected from the group consisting of Ia and Ib wherein:
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
33. An electrode wherein the improvement includes a supporting member coated with polyisothianaphtene, having a structural formula selected from the group consisting of Ia and Ib wherein:
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
34. A battery comprising an anode and a polyisothianaphthene-coated cathode separated from the anode by a porous partitioning membrane, having a structural formula selected from the group consisting of Ia and Ib wherein:
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
35. A solar energy conversion device in which the improvement comprises a surface membrane material that is rendered conductive upon absorption of light, the surface membrane material comprising polysiothianaphtene, having a structural formula selected from the group consisting of Ia and Ib wherein:
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
Ia = Ib = R1 is hydrogen or -OR3;
R2 and R3 are selected independently from the group consisting of hydrogen and C1 to C8 hydrocarbons, with the proviso that R2 and R3 may be linked together to form, with both oxygens, a dioxyalkylene substituent on the benzene ring with the formula:
wherein R4 and R5 are selected independently from the group consisting of hydrogen and C1 to C4 hydrocarbons;
X is selected from the group consisting of sulfur, selenium and tellurium;
Y? represents an anion of an electrolyte;
z represents a number from 0.01 to 1 showing a ratio of the anion per mol of a monomer; and n represents a number of from 5 to 500 showing the degree of polymerization.
Applications Claiming Priority (2)
| 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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334672C true CA1334672C (en) | 1995-03-07 |
Family
ID=25480864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000554176A Expired - Lifetime CA1334672C (en) | 1986-12-18 | 1987-12-11 | Conducting substituted polyisothianophthenes |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4795242A (en) |
| EP (1) | EP0273643B1 (en) |
| JP (1) | JPH0798858B2 (en) |
| CN (1) | CN1015628B (en) |
| CA (1) | CA1334672C (en) |
| DE (1) | DE3788950T2 (en) |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0248915A1 (en) * | 1985-12-06 | 1987-12-16 | Showa Denko Kabushiki Kaisha | Polymers having isoindole structure and process for their preparation |
| US5151224A (en) * | 1988-05-05 | 1992-09-29 | Osaka Gas Company, Ltd. | Tetrasulfonated metal phthalocyanine doped electrically conducting electrochromic poly(dithiophene) polymers |
| US4893908A (en) * | 1988-06-27 | 1990-01-16 | Allied-Signal Inc. | Adjustable tint window with electrochromic conductive polymer |
| US5151816A (en) * | 1989-12-29 | 1992-09-29 | Donnelly Corporation | Method for reducing current leakage and enhancing uv stability in electrochemichromic solutions and devices |
| JP2892681B2 (en) * | 1989-05-23 | 1999-05-17 | 昭和電工株式会社 | Radical polymerizable composition |
| US5140455A (en) * | 1989-11-29 | 1992-08-18 | Donnelly Corporation | High performance electrochemichromic solutions and devices thereof |
| US5187608A (en) * | 1991-03-04 | 1993-02-16 | General Electric Company | Substituted 3,4-polymethylenedioxythiophenes, and polymers and electro responsive devices made therefrom |
| US5239405A (en) * | 1991-09-06 | 1993-08-24 | Donnelly Corporation | Electrochemichromic solutions, processes for preparing and using the same, and devices manufactured with the same |
| US5233461A (en) * | 1991-09-06 | 1993-08-03 | Donnelly Corporation | Methods for sealing electrochromic devices and devices manufactured thereby |
| US5500760A (en) * | 1991-09-06 | 1996-03-19 | Donnelly Corporation | Electrochemichromic solutions, processes for preparing and using the same, and devices manufactured with the same |
| US5688873A (en) * | 1991-12-04 | 1997-11-18 | Showa Denko K.K. | Electroconductive polymer and process for producing the polymer |
| US5648453A (en) * | 1991-12-04 | 1997-07-15 | Showa Denko K.K. | Electroconductive polymer and process for producing the polymer |
| JP3182239B2 (en) * | 1991-12-04 | 2001-07-03 | 昭和電工株式会社 | Novel water-soluble conductive polymer and method for producing the same |
| BE1006640A3 (en) * | 1993-01-29 | 1994-11-03 | Dsm Nv | Process for the preparation of a polymer. |
| EP1004649A3 (en) * | 1993-02-26 | 2000-07-26 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
| US5910854A (en) | 1993-02-26 | 1999-06-08 | Donnelly Corporation | Electrochromic polymeric solid films, manufacturing electrochromic devices using such solid films, and processes for making such solid films and devices |
| JP3814830B2 (en) * | 1993-05-28 | 2006-08-30 | 昭和電工株式会社 | Antistatic material, antistatic method and observation or inspection method using the same, and antistatic article |
| US5668663A (en) * | 1994-05-05 | 1997-09-16 | Donnelly Corporation | Electrochromic mirrors and devices |
| US5510457A (en) * | 1995-04-24 | 1996-04-23 | National Science Council | Method for preparing processable polyisothianaphthene |
| US5696206A (en) * | 1996-01-11 | 1997-12-09 | National Science Council | Method for preparing processable polyisothianaphthene |
| US5986206A (en) * | 1997-12-10 | 1999-11-16 | Nanogram Corporation | Solar cell |
| DE19824185A1 (en) * | 1998-05-29 | 1999-12-02 | Bayer Ag | Electrochromic arrangement based on poly (3,4-ethylenedioxy-thiophene) derivatives in combination with a lithium niobate counter electrode |
| DE19824215A1 (en) * | 1998-05-29 | 1999-12-02 | Bayer Ag | Electrochromic arrangement based on poly (3,4-ethylenedioxy-thiophene) derivatives in the electrochromic and ion-storing functional layers |
| US7167796B2 (en) * | 2000-03-09 | 2007-01-23 | Donnelly Corporation | Vehicle navigation system for use with a telematics system |
| US7370983B2 (en) | 2000-03-02 | 2008-05-13 | Donnelly Corporation | Interior mirror assembly with display |
| US7446924B2 (en) * | 2003-10-02 | 2008-11-04 | Donnelly Corporation | Mirror reflective element assembly including electronic component |
| JP4877228B2 (en) * | 2005-05-31 | 2012-02-15 | コニカミノルタホールディングス株式会社 | Electrochromic display element and full-color electrochromic display element |
| US8345345B2 (en) | 2007-06-27 | 2013-01-01 | Gentex Corporation | Electrochromic device having an improved fill port plug |
| US7884995B2 (en) * | 2007-06-27 | 2011-02-08 | Gentex Corporation | Electrochromic device having an improved fill port plug |
| US20100283040A1 (en) * | 2007-09-10 | 2010-11-11 | Michael Bendikov | Selenophenes and selenophene-based polymers, their preparation and uses thereof |
| WO2010036765A1 (en) | 2008-09-25 | 2010-04-01 | Universal Display Corporation | Organoselenium materials and their uses in organic light emitting devices |
| WO2011097756A1 (en) * | 2010-02-11 | 2011-08-18 | 上海贝尔股份有限公司 | Method and device for allocating frequency bands by using frequency reuse |
| WO2014151083A1 (en) | 2013-03-15 | 2014-09-25 | Gentex Corporation | Fill port plugs for electrochromic devices |
| US9454054B2 (en) | 2013-11-18 | 2016-09-27 | Magna Mirrors Of America, Inc. | Electro-optic mirror element and process of making same |
| WO2017061995A1 (en) * | 2015-10-07 | 2017-04-13 | Iglass Technology Llc | Electochromic composition and electromic device using same |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2658902A (en) * | 1947-05-03 | 1953-11-10 | Socony Vacuum Oil Co Inc | Thiophene polymers |
| US2552796A (en) * | 1950-03-23 | 1951-05-15 | Socony Vacuum Oil Co Inc | Thiophene-sulfur monochloride synthetic resins |
| US3524835A (en) * | 1963-11-27 | 1970-08-18 | Phillips Petroleum Co | Heat treatment of poly(arylene sulfide) resins |
| GB1178596A (en) * | 1964-02-20 | 1970-01-21 | Monsanto Chemicals | Aromatic Polymers |
| GB1046209A (en) * | 1964-07-24 | 1966-10-19 | Shell Int Research | Insecticidal compositions |
| US3574072A (en) * | 1968-04-03 | 1971-04-06 | Universal Oil Prod Co | Polymerization of heterocyclic compounds |
| GB1159089A (en) * | 1968-05-16 | 1969-07-23 | Shell Int Research | Methylenedioxyphenyl Compounds |
| GB1303252A (en) * | 1969-07-31 | 1973-01-17 | ||
| US3615384A (en) * | 1970-06-29 | 1971-10-26 | Ibm | Electrophotographic process employing vinyl bithiophene polymeric photoconductors |
| US3725362A (en) * | 1971-03-08 | 1973-04-03 | Phillips Petroleum Co | Poly(arylene sulfide) composition and method for decreasing the melt flow of poly(arylene sulfide) |
| US4111857A (en) * | 1977-03-31 | 1978-09-05 | International Business Machines Corporation | Highly conducting organometallic polymers |
| US4461691A (en) * | 1983-02-10 | 1984-07-24 | The United States Of America As Represented By The United States Department Of Energy | Organic conductive films for semiconductor electrodes |
| US4640748A (en) * | 1984-05-31 | 1987-02-03 | The Regents Of The University Of California | Polyisothianaphtene, a new conducting polymer |
| EP0164974B1 (en) * | 1984-05-31 | 1990-05-23 | The Regents Of The University Of California | Polymer having isothianaphthene structure and electrochromic display |
| US4749260A (en) * | 1984-08-31 | 1988-06-07 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Variable color transparent panels |
-
1986
- 1986-12-18 US US06/944,138 patent/US4795242A/en not_active Expired - Lifetime
-
1987
- 1987-12-11 CA CA000554176A patent/CA1334672C/en not_active Expired - Lifetime
- 1987-12-16 DE DE3788950T patent/DE3788950T2/en not_active Expired - Lifetime
- 1987-12-16 EP EP87311095A patent/EP0273643B1/en not_active Expired - Lifetime
- 1987-12-17 CN CN87108150A patent/CN1015628B/en not_active Expired
- 1987-12-18 JP JP62319119A patent/JPH0798858B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798858B2 (en) | 1995-10-25 |
| CN87108150A (en) | 1988-08-31 |
| DE3788950T2 (en) | 1994-07-07 |
| EP0273643B1 (en) | 1994-01-26 |
| US4795242A (en) | 1989-01-03 |
| JPS63248826A (en) | 1988-10-17 |
| CN1015628B (en) | 1992-02-26 |
| EP0273643A3 (en) | 1990-03-07 |
| DE3788950D1 (en) | 1994-03-10 |
| EP0273643A2 (en) | 1988-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1334672C (en) | Conducting substituted polyisothianophthenes | |
| US4640748A (en) | Polyisothianaphtene, a new conducting polymer | |
| CA1318063C (en) | Highly conductive polymer composition and process for producing the same | |
| KR880701254A (en) | Magnetic Doping Polymers | |
| Nawa et al. | Synthesis of a novel type of electrochemically doped vinyl polymer containing pendant terthiophene and its electrical and electrochromic properties | |
| Sotzing et al. | Poly [trans-bis (3, 4-ethylenedioxythiophene) vinylene]: a low band-gap polymer with rapid redox switching capabilities between conducting transmissive and insulating absorptive states | |
| Walton | Electrically conducting polymers | |
| US4772940A (en) | Polymer having isothianaphthene structure and electrochromic display | |
| US4954590A (en) | Preparation of polymer having isoindole structures | |
| US4874481A (en) | N,N'-diphenylbenzidine polymer and method of producing the same | |
| JPS63215722A (en) | Production of electroconductive polyaniline compound | |
| US4892678A (en) | Thiophene derivative polymer and a polymer composition thereof | |
| EP0164974B1 (en) | Polymer having isothianaphthene structure and electrochromic display | |
| Kanbara et al. | Preparation of new redox-active quaternized poly (quinolinium) and poly (isoquinolinium) salts showing viologen-like redox behavior | |
| US4877852A (en) | Thiophene derivative polymer and a polymer composition thereof | |
| JPH0794538B2 (en) | Novel polymer and method for producing the same | |
| Kawai et al. | Novel Photo-Memory Effect in Photoconductivity of Conducting Polymer Containing Photochromic Dye. | |
| Jeon et al. | Electrochemical doping of poly (3-vinylperylene) and electrical properties of doped polymers | |
| US5310829A (en) | Quaternary poly(iso) quinolinediyl and preparation thereof | |
| JP2960859B2 (en) | Self-doping type conductive polymer aqueous solution and method for producing the same | |
| JPH0211614B2 (en) | ||
| Shirota et al. | Synthesis, properties and application of electrically conducting non-conjugated polymers having a pendant perylenyl group | |
| Casalbore-Miceli et al. | Electrochromic properties of poly (N-methyl-10, 10-dimethyl-phenazasiline) | |
| JPS6411207B2 (en) | ||
| Choi et al. | Chemical and physical properties of electrochemically prepared polyaniline p-toluenesulfonates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |