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WO2008118704A2 - Variable color dioxyheterocycle copolymers - Google Patents

Variable color dioxyheterocycle copolymers Download PDF

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Publication number
WO2008118704A2
WO2008118704A2 PCT/US2008/057420 US2008057420W WO2008118704A2 WO 2008118704 A2 WO2008118704 A2 WO 2008118704A2 US 2008057420 W US2008057420 W US 2008057420W WO 2008118704 A2 WO2008118704 A2 WO 2008118704A2
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alkyl
aryl
substituted
copolymer
monomer
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WO2008118704A3 (en
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John R. Reynolds
June-Ho Jung
Ryan M. Walczak
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University of Florida
University of Florida Research Foundation Inc
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University of Florida
University of Florida Research Foundation Inc
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    • 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
    • C08G61/124—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 with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • C08G61/125—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 with a five-membered ring containing one oxygen atom in the ring
    • 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
    • C08G61/126—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 with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers

Definitions

  • the invention is directed to dioxyheterocycle copolymers and methods of forming the same which demonstrate tunable band gaps providing variable colored materials.
  • Electroactive polymers have utility in a broad range of applications including: electrochromic smart windows, mirrors, and displays; photovoltaic devices; transparent conductors; charge storage devices; thin-film transistors; polymer LEDs; antistatic coatings; and biological applications.
  • Some of the most widely investigated of these polymers are polyheterocycles, particularly those with pyrrole or thiophene repeating units.
  • the families of 3,4-alkylenedioxythiphene and 3,4-alkylenedioxypyrrole compounds have been electropolymerized to form electron rich electroactive polymers that display stable redox switching capabilities and a wide palette of electrochromic states.
  • Electropolymerization of heterocycles to conjugated polymers typically occurs with low monomer conversion, low molecular weights, and produces insoluble materials, which are essentially unprocessable. For these reasons, the industrial development of devices exploiting the unique properties of these materials has been underwhelming.
  • the electrochemical process developed for one polyheterocycle is of limited value at determining conditions for a process to prepare the new polyheterocycle.
  • devices such as an electrochromic display, where multiple polyheterocycles are needed to form the device, multiple electropolymerization processes would be particularly complicated due to the series of different processes needed and the limited choice of supports upon which electropolymerization is feasible.
  • the invention is directed to dioxyheterocycle copolymers having tunable band gaps to provide variable colored materials and methods of forming the copolymers.
  • the invention is directed to copolymers with electrochromic properties having the structure:
  • R 1 , R 2 , R 3 , and R 4 are independently H, alkyl, aryl, substituted alkyl, or substituted aryl, or (R 1 and R 2 ) and/or (R 3 and R ) in combination are alkylene, arylene, substituted alkylene, or substituted arylene;
  • R is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O) 2 alkyl, HOC(O)alkyl, (HO) 2 P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O) 2 aryl, HOC(O)aryl or (HO) 2 P(O)aryl;
  • X is O, S or NR 6 , where R 6 isH, alkyl, aryl, substituted alky
  • the copolymer is preferably soluble in at least one solvent, such that the copolymer can be formed independently of its incorporation in a device to use the copolymer.
  • the copolymer can contain additional types of repeating units that are conjugated such as aromatic hydrocarbon units including phenylene, fluorene, phenylene vinylene, thiophene, pyrrole, and furan.
  • the invention is also directed to a method of preparing an electrochromic copolymer where a first heterocyclic monomer whose homopolymer in the neutral state has high transmissivity through the visible spectrum and a second heterocyclic monomer whose homopolymer in the neutral state displays a highly colored state, where one or both of the monomers have a corresponding homopolymer that is soluble, are provided and chemically copolymerized with a ratio of comonomers that yields a copolymer with a predetermined band gap and/or color.
  • the first heterocyclic monomer can be a pyrrole of the structure:
  • R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkylene, arylene, substituted alkylene, or substituted arylene; and R' is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O) 2 alkyl, HOC(O)alkyl, (HO) 2 P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O) 2 aryl, HOC(O)aryl or (HO) 2 P(O)aryl.
  • first monomers include:
  • the second heterocyclic monomer can have the structure:
  • R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkylene, arylene substituted alkylene, or substituted alkylene;
  • X is O, S or NR 1 ;
  • Z is S, O, or NR 2 ; and where R 1 and R 2 are independently H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O) 2 alkyl, HOC(O)alkyl, (HO) 2 P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O) 2 aryl, HOC(O)aryl or (HO) 2 P(O)aryl.
  • An example of the second monomer is:
  • a method to produce an electrochromic copolymer involves providing a heterocyclic oligomer having terminal repeating units that differ from interior repeating units, providing at least one heterocyclic monomer of the same heterocycle as the terminal repeating units in the oligomer, wherein at least one of the monomers or the oligomer has a corresponding homopolymer that is soluble, and copolymerizing the oligomers and monomers chemically in a ratio that yield a copolymer with a predetermined band gap.
  • the terminal repeating units of the oligomer can yield a homopolymer that has high transmissivity through the visible range of the light spectrum in the neutral state and one or more interior repeating units whose homopolymer in the neutral state displays a highly colored state.
  • the oligomer can also have the opposite construction where the terminal units are those that give a highly colored homopolymer in the neutral state and one or more interior units are those of a highly transmissive homopolymer in the neutral state. In this manner, additional control of sequence size and size distribution is possible.
  • Another embodiment to a method of forming an electrochromic copolymer where an oligomer is copolymerized with at least one monomer is by providing an asymmetric dimer of two monomers whose corresponding homopolymers in the neutral state are transmissive throughout the visible range of light for one unit and highly colored for the other, and providing one of the monomers that constitutes the dimer or a mixture of both monomers of the dimer, and copolymerizing the mixture of dimers an monomers to yield a copolymer with a predetermined band gap.
  • Figure 1 shows a general copolymerization embodiment of the present invention.
  • Figure 2 shows the preparation of a copolymer according to an embodiment of the invention by the condensation of a (3,4-dialkoxythiophene)-(iV-substituted 3,4- dialkoxypyrrole)-(3,4-dialkoxythiophene) trimer with 3,4-dialkoxythiophene in a ratio of 1 :2.
  • Figure 3 shows the preparation of copolymers according to an embodiment of the invention by the condensation of a (3,4-dialkoxythiophene)-(7V-substituted 3,4- dialkoxypyrrole) dimer with either 3,4-dialkoxythiophene or TV-substituted 3,4- dialkoxypyrrole.
  • Figure 4 shows a specific copolymerization embodiment of the present invention.
  • Figures 5A-5C show UV-vis-NIR absorption spectroelectrochemistry for the copolymers from 0.8 ( Figure 5A), 0.5 ( Figure 5B), and 0.3 ( Figure 5C) mole fraction of TV- dodecyl-3,4-propylenedioxypyrrole monomer used in the copolymerization of Figure 2.
  • a series of heterocyclic copolymers are described that display electrochromic properties that vary depending upon the ratio of two (or more) repeating units in the polymer backbone are prepared by a chemical polymerization of heterocyclic comonomers.
  • the mode by which the electrochromic properties can vary is controlled by the comonomer feed ratio.
  • the comonomer's reactivity is similar, the incremental variation in the repeating unit ratio leads to incremental differences in the band gap, and hence the color, displayed by the electrochromic copolymers.
  • the copolymer contains blocks of the two repeating units; the relative intensities of the optical absorbance from these blocks, whose size and proportions depend on the comonomer feed ratio, yields the color control. Therefore, although the mode of color control can differ, any desired color that ranges from that inherent to the homopolymer of one monomer, through any given proportion of comonomer repeating units, to the color inherent to the homopolymer of the other monomer can be specifically prepared by changing the ratio of the comonomers in the polymerization mixture without any other significant changes to the process. In similar fashion, the copolymer can also incorporate one or more additional heterocyclic repeating units.
  • Comonomers used in the invention form soluble copolymers, hence permitting the decoupling of the copolymer synthesis from the fabrication of the electrochromic device.
  • the relationship of the color at various applied potentials employed for an electrochromic device can be correlated to the copolymer composition. In this manner, when a particular color, at a given potential, is needed for a device, the preparation of the material can readily be determined and implemented in a production process by changing the monomer feed ratios without any other significant changes to the process. Because the process utilizes chemical polymerization rather than electrochemical polymerization, and the resulting copolymer is soluble, the preparation of the copolymer is independent of the deposition of the copolymer on a substrate of the device.
  • Fig. 1 The copolymerization of two (or more) monomers according to one embodiment of the invention is shown in Fig. 1.
  • x' is the monomer mole fraction of a /V-substituted 3,4-dialkoxypyrrole
  • x is the repeating unit mole fraction of TV-substituted 3,4-dialkoxypyrrole
  • n is the degree of polymerization
  • N is the total number of monomers in the feed.
  • the value of x need not equal x' due to differences in reactivity ratios of the comonomer, other polymerization effects, and/or any fractionation during isolation of the copolymer. Nevertheless, the composition of the final copolymer, which determines physical properties important for their use, can be correlated to the value of x or x' for any given consistent protocol for the preparation, purification, and isolation of the copolymer. It is preferable that the degree of polymerization be between 10 and 10,000. In this size range, the polymers reach their conjugation limit (reproducible color contribution from each polymer chain), and films with reasonable mechanical properties can be formed from the soluble copolymers.
  • the copolymer is prepared from a mixture of two monomers.
  • One of the monomers is an TV-substituted dialkoxypyrrole and the other monomer can be another pyrrole, a thiophene or a furan.
  • the resulting copolymer has the following structure:
  • R 1 , R 2 , R 3 , and R 4 are independently H, alkyl, aryl, substituted alkyl, or substituted aryl, or (R 1 and R 2 ) and/or (R 3 and R 4 ) in combination are alkylene, arylene, substituted alkylene, or substituted arylene;
  • R 5 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O) 2 alkyl, HOC(O)alkyl, (HO) 2 P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O) 2 aryl, HOC(O)aryl or (HO) 2 P(O)aryl;
  • X is O, S or NR 6 where R 6 is H, alkyl, aryl, substituted alky
  • the distribution of sequence lengths can vary considerably depending on the reactivity ratios of the two monomers.
  • the sequence distribution can be statistical with a reactivity ratio of unity for the comonomers. Regardless of the average block size distribution, a variation of the color depends ultimately on the composition of the comonomer feed.
  • the copolymers are formed from two heterocyclic monomers where neither monomer is a pyrrole, as long as one monomer's neutral homopolymer displays a relatively high band gap and is essentially highly transmissive through the entire visible spectrum of light, while the other monomer's neutral homopolymer displays a relatively low band gap and is highly colored.
  • inventions of the invention can include at least one additional monomer to incorporate additional types of repeating units in the copolymer to modify the electrochromic or other properties of the resulting copolymer.
  • additional monomers can be, but are not necessarily, heterocyclic monomers.
  • These additional monomers can be included to modify properties that are not dependent upon the conjugation of the copolymer.
  • a monomer can be incorporated that permits the modification of viscosities in solution or in the solvent free state, provide sites for cross-linking of the copolymer after fabrication of a desired shape or device, or enhance the affinity of the copolymer for a specific chemical agent, polymer or surface, such as a graphene, metal, metal oxide or semiconductor surface.
  • alkyl is a straight or branched chain of, for example, 1-24 carbon atoms and is, for example, methyl, ethyl, n-propyl, n-butyl, sec butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or dodecanyl and the like.
  • Alkyl ene is a chain of, for example, 1-12 carbon atoms and is, for example, methylene, ethylene, propylene, butylene, pentalene, hexylene, octylene, 2-ethylhexyl, n-nonyl, n-decylene or dodecylene and the like; for example, methylene, ethylene, propylene or butylene.
  • the alkyl or alkylene may be interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, -SO-, -SO 2 -, carbonyl, -COO-, -CONH-, -NH-,-CON(Ci -8 alkyl)- or -N(C 1 - S alkyl)- and the like.
  • the alkyl group may be interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -NH- or -N(C 1-8 alkyl)-.
  • the uninterrupted or interrupted alkyl or alkylene may also be substituted, one or more times, by one or more C 3-6 cycloalkyl groups, halogen, -OR, -COOR, -COOM, -SO 3 M, -SO 3 H, phosphonic acid, halogen, -CONR' R, -NR' R, phosphonate salt, ammonium salt or group of the formulae -L-Ar or -C(O)-L-Ar wherein M is a nitrogen cation or metal cation, R and R', independently of any other R or R' that may be present is hydrogen; a group -L-Ar, -C(O)-L- Ar, or -C(O)-O-L-Ar; C 1-24 alkyl, C 3-24 alkenyl, C 3-6 cycloalkyl or C 1-24 alkylcarbonyl which is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms,
  • alkylene or interrupted alkylene may also be substituted by a group -L- Ar, -C(O)-L-Ar, or -C(O)-O-L-Ar; C 1-24 alkyl, C 3-6 cycloalkyl or Ci -24 alkylcarbonyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -CONH-, -NH-,-CON(Ci_ 8 alkyl)- or -N(Ci -8 alkyl)- that is uninterrupted or interrupted alkyl, cycloalkyl or alkylcarbonyl and is unsubstituted or substituted, one or more times, by one or more halogen, -OH, C 7-12 aralkyl, C 2-12 alkylcarbonyl, C] -24 alkoxy, C 2-24 alkylcarboxy, -COOM, -CONH 2 , -CON(H)
  • R 1 , R 2 , R 3 , R 4 and R 5 are, independently of each other, Ci -24 alkyl uninterrupted or interrupted by one or more oxygen atoms, carbonyl, -COO-, -NH- or -N(C 1-8 alkyl)- and/or substituted, one or more times, by one or more OH, C 1-8 alkoxy, C 2-6 alkylcarboxy, NH 2 , N(H)(Cj -8 alkyl), N(C 1-8 alkyl) 2 , halogen, phenyl or phenyl substituted, one or more times, by C 1-4 alkyl, OH, C 1-8 alkoxy, C 2-6 alkylcarboxy or halogen.
  • R 1 , R 2 , R 3 , R 4 and R 5 are, independently of each other, C 1-24 alkyl uninterrupted or interrupted by one or more oxygen atoms, -COO-, -NH- or -N(C 1-8 alkyl) - and /or substituted, one or more times, by one or more OH, C 1-8 alkoxy, C 2-6 alkylcarboxy, phenyl or phenyl substituted, one or more times, by Ci -4 alkyl, OH, C 1-8 Alkoxy or C 2-6 alkylcarboxy.
  • R 1 and R , and/or R 3 and R 4 are, independently of each other, alkylene of 1 -6 carbon atoms that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -NH- or -N(Ci -8 alkyl)- and/or substituted, one or more times, by one or more OH, Cj -8 alkoxy, C 2-6 alkylcarboxy, halogen, NH 2 , N(H)(Ci -8 alkyl), N(C] -8 alkyl) 2 , halogen, phenyl, phenyl substituted, one or more times, by Cj -4 alkyl, OH or Ci -8 alkoxy, C 2-6 alkylcarboxy or halogen; or the alkylene is substituted by one or more unsubstituted Ci -24 alkyl or Ci -24 alkyl which is uninterrupted or interrupted, one or more times,
  • R 1 and R , and/or R 3 and R 4 are, independently of each other, alkylene of 1 -6 carbon atoms that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -NH- or -N(Ci -8 alkyl)- and/or substituted, one or more times, by one or more OH, Ci -8 alkoxy, C 2-6 alkylcarboxy, halogen, NH 2 , N(H)(Cj -8 alkyl), N(C] -8 alkyl) 2 , phenyl, phenyl substituted, one or more times, by Ci -4 alkyl, OH or C 1- 8 alkoxy, C 2-6 alkylcarboxy or halogen; or the alkylene is substituted by one or more unsubstituted Ci -24 alkyl or Ci -24 alkyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms
  • R ! and R 2 , and/or R 3 and R 4 are, independently of each other, ethylene or propylene that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, -NH- or -N(Cj -8 alkyl)- and/or substituted, one or more times, by one or more OH, Ci -8 alkoxy, C 2-6 alkylcarboxy, N(H)(Ci -8 alkyl), N(Cj -8 alkyl) 2 , phenyl, phenyl substituted one or more times by Ci -4 alkyl, OH or C 1-8 alkoxy, C 2-6 alkylcarboxy, or ethylene or propylene substituted by one or more unsubstituted Ci -24 alkyl or C 1-24 alkyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, -COO-, -CONH-, -NH-, - CON(Ci-8 alkyl)-
  • R and R , and/or R and R 4 are, independently of each other, ethylene or propylene that is unsubstituted or substituted ,one or more times, by one or more OH, C 1-8 alkoxy, C 2-6 alkylcarboxy, Ci -24 alkyl, C) -24 alkyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, -COO-, -CONH-, that have uninterrupted or interrupted Cj -24 alkyl that is unsubstituted or substituted, one or more times, by one or more - OH, C 2-I2 alkylcarbonyl, Cj -24 alkoxy or C 2-24 alkylcarboxy.
  • R is methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n- octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n- hexadecyl, n-octadecyl, benzyl, hydroxyethyl, hydroxypropyl, Cj -24 alkyl substituted by C 2-24 alkylcarboxy or Cj -24 alkyl substituted, one or more times, by Cj -8 alkoxy.
  • a family of copolymers for color control can also be achieved where the band gap varies by condensing either a 3,4-dialkoxythiophene or an N- substituted 3,4-dialkoxypyrrole with a preformed symmetric oligomer with terminal units of the same repeating unit, or of the same heterocycle, that will form from the chosen monomer, but where the interior unit in a trimer, or multiple interior units in a larger oligomers, is derived from the other possible heterocyclic monomer, or of the same heterocycle.
  • This route is easily pursued with a trimer as illustrated in Figure 2.
  • a trimer with the structure 3,4-dialkoxythiophene-7V-substituted-3,4-dialkoxypyrrole-3,4-dialkoxythiophene is copolymerized with a 3,4-dialkoxythiophene in a ratio of 1 :2.
  • a copolymer with an average of four 3,4-dialkoxythiophene units between isolated N- substituted 3,4- dialkoxypyrrole units is formed.
  • the band gap is tuned by the content of the TV-substituted 3,4-dialkoxypyrrole in the thiophene polymer.
  • the polymerization reactivity of the oligomer and monomelic thiophene units is similar.
  • the distributions of repeating unit sequences are narrower than a random (normal) distribution by this copolymerization of a trimer and monomers when the terminal units of the trimer and the monomer have equal reactivity.
  • a 3,4-dialkoxythiophene block size distribution of approximately 1.67 results when all 3,4-dialkoxythiopheneties have equal reactivity, rather than the normal distribution for a tetramer of a homopolymer of 1.75.
  • the entire range of possible band gaps can be achieved when at least two complementary ended oligomers and the two complementary monomers are available to construct copolymers.
  • the copolymerization of an asymmetric dimer of 3,4-dialkoxythiophene and TV-substituted 3,4-dialkoxypyrrole can be used with a 3,4- dialkoxythiophene, an TV-substituted 3,4-dialkoxypyrrole, or a combination of both, to achieve the entire range of band gaps.
  • a single dimer copolymerized with either the 3,4-dialkoxythiophene monomer or the TV-substituted 3,4-dialkoxypyrrole monomer can yield the entire range of band gaps available from a copolymer and retain the systematic variation based on simply varying the feed ratio of dimer to monomer (or monomers).
  • Figure 3 shows one pyrrole-to-thiophene coupling and one pyrrole-to- pyrrole coupling in the copolymerization of the asymmetric dimer with 3,4- dialkoxythiophene monomer. Even where one mode of coupling, either homocoupling of like units or heterocoupling of unlike units, dominates over the other mode of coupling, the distribution of block lengths is controlled in this copolymerization.
  • the band gap can be selected by the selection of the monomer and ratio of the monomer and asymmetric dimer included in a copolymerization.
  • copolymers were prepared by varying the mole fraction of 7V-dodecyl-3,4- propyl enedioxypyrrole used to yield copolymers with 3-methyl-3-(2-ethylhexyloxymethyl)-
  • the mole fraction of the monomer iV-dodecyl-3,4-propylenedioxypyrrole used in the copolymerization was varied from 0.0, 0.3, 0.5, to 0.8 which gave cast copolymer films which varied in color from purple to red, orange and yellow, respectively. These color differences were also observed in solution.
  • the band gap of the copolymer decreased.
  • the fluorescence X 1113x was red shifted.
  • the copolymers of Example 1 were spray cast from 1 % (w/V) toluene solutions onto ITO/glass working electrodes.
  • the UV-vis-NIR absorption spectroelectrochemistry is shown in Figures 5A-5C for the copolymers from 0.8 ( Figure 5A), 0.5 ( Figure 5B), and 0.3 ( Figure 5C) mole fraction pyrrole monomer in the copolymerization mixture.
  • the spectra change significantly from the neutral to/>-doped state.
  • a shift from a red-purple neutral copolymer to a blue /?-doped copolymer occurs.

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Abstract

Soluble copolymers of heterocyclic monomers that have electrochromic properties are prepared chemically, where the properties are dependent on the proportions and block sizes of the monomer sequences in the copolymer. By the judicious choice of the comonomers and their proportions, the color and/or band gap of the resulting copolymer can be predetermined and achieved, with little, if any, change in a polymerization process other than the monomer feed ratio. Additional control can be achieved of the block size distribution and resulting copolymer properties by the copolymerization of an oligomer, with a core of one monomer and termini of another, with a monomer of the same or similar heterocyclic structure as the termini of the oligomer. In another embodiment an asymmetric dimer of two heterocyclic monomers can be copolymerized with the same or similar heterocyclic structure as either or both heterocyclic monomers of the dimer to achieve electrochromic copolymers of a predetermined band gap and/or color.

Description

DESCRIPTION
VARIABLE COLOR DIOXYHETEROCYCLE COPOLYMERS
CROSS-REFERENCE TO RELATED APPLICATION
The present application claims the benefit of U.S. Provisional Application Serial No. 60/896,626, filed March 23, 2007, which is hereby incorporated by reference herein in its entirety, including any figures, tables, nucleic acid sequences, amino acid sequences, and drawings.
FIELD OF THE INVENTION
The invention is directed to dioxyheterocycle copolymers and methods of forming the same which demonstrate tunable band gaps providing variable colored materials.
BACKGROUND OF THE INVENTION
Electroactive polymers have utility in a broad range of applications including: electrochromic smart windows, mirrors, and displays; photovoltaic devices; transparent conductors; charge storage devices; thin-film transistors; polymer LEDs; antistatic coatings; and biological applications. Some of the most widely investigated of these polymers are polyheterocycles, particularly those with pyrrole or thiophene repeating units. For example, the families of 3,4-alkylenedioxythiphene and 3,4-alkylenedioxypyrrole compounds have been electropolymerized to form electron rich electroactive polymers that display stable redox switching capabilities and a wide palette of electrochromic states. Electropolymerization of heterocycles to conjugated polymers typically occurs with low monomer conversion, low molecular weights, and produces insoluble materials, which are essentially unprocessable. For these reasons, the industrial development of devices exploiting the unique properties of these materials has been underwhelming. When one desires the properties of a new polyheterocycle, the electrochemical process developed for one polyheterocycle is of limited value at determining conditions for a process to prepare the new polyheterocycle. For devices, such as an electrochromic display, where multiple polyheterocycles are needed to form the device, multiple electropolymerization processes would be particularly complicated due to the series of different processes needed and the limited choice of supports upon which electropolymerization is feasible. In such systems, polymerization is carried out on a substrate that becomes part of the device. Such a complicated process is described in Liu et al, U.S. Patent Application Publication 2005/0200935, for the fabrication of a switchable window. Liu discloses that two different polyheterocycles must be electropolymerized on separate transparent supports which are then stacked to permit subtractive color mixing. Each electropolymerized film must be controlled in thickness to achieve a working device.
Liu et al. suggests that the required films be of specifically designed homopolymers, as one could only "hope that the copolymers will exhibit different colors" with "copolymers based on existing and/or new monomers". However, a family of copolymers prepared by electropolymerization is disclosed in Gaupp et al. Macromolecules 2003, 36, (17), 6305-15 that displays a range of color states depending upon the copolymer composition. In this system, one monomer containing a conjugation breaking carbazole unit is copolymerized with a second monomer, which can form a fully conjugated homopolymer, leading to differing average conjugation length segments by a statistical copolymerization of the two monomers. This approach permits a directed change of color from a heterocycle copolymer without a significant change in processing conditions other than the comonomer ratios. Nevertheless, this method still displays a number of the processing complications common to electropolymerization systems.
To overcome the process limitations of electropolymerization, a series of soluble electroactive heterocyclic polymers that can be prepared by chemical methods have been developed. These chemically homopolymerized soluble polyheterocycles have been shown to be useful in photovoltaic cells and electrochromic devices. Such polymers, processes, and devices are disclosed in Cirpan et al. J. Mater. Chem, 2003, 13, (10) 2422-28; Reeves et al. Macromolecules 2004, 37 (20), 7559-69; and Galand et al. Macromolecules 2006, 39, (21), 7286-94.
Although many processing challenges to electrochromic heterocyclic polymers and copolymers have been overcome, no system has been disclosed that allows the specific design of a polymer displaying a specific band gap out of a palette of band gaps or ratio of absorbances from multiple absorbance peaks based on a relatively simple and achievable change in composition. Hence, there remains a need to develop a family of readily processable polymers where required processing changes are essentially the differences in reagent blends and the synthesis of the polymer is decoupled from the final fabrication of the device.
BRIEF SUMMARY OF THE INVENTION
The invention is directed to dioxyheterocycle copolymers having tunable band gaps to provide variable colored materials and methods of forming the copolymers. The invention is directed to copolymers with electrochromic properties having the structure:
Figure imgf000004_0001
where R1, R2, R3, and R4 are independently H, alkyl, aryl, substituted alkyl, or substituted aryl, or (R1 and R2) and/or (R3 and R ) in combination are alkylene, arylene, substituted alkylene, or substituted arylene; R is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; X is O, S or NR6, where R6 isH, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; Z is S, O, or NR7 where R7 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; 0 < x < 1; y = 1-x; and n is 10 to 10,000. The copolymer is preferably soluble in at least one solvent, such that the copolymer can be formed independently of its incorporation in a device to use the copolymer. By the appropriate choice of the comonomers, and knowledge of the reactivity ratios between comonomers, the structure of the copolymer and its band gap and/or color can be predetermined and achieved. The copolymer can contain additional types of repeating units that are conjugated such as aromatic hydrocarbon units including phenylene, fluorene, phenylene vinylene, thiophene, pyrrole, and furan.
The invention is also directed to a method of preparing an electrochromic copolymer where a first heterocyclic monomer whose homopolymer in the neutral state has high transmissivity through the visible spectrum and a second heterocyclic monomer whose homopolymer in the neutral state displays a highly colored state, where one or both of the monomers have a corresponding homopolymer that is soluble, are provided and chemically copolymerized with a ratio of comonomers that yields a copolymer with a predetermined band gap and/or color. The first heterocyclic monomer can be a pyrrole of the structure:
R R
N
I R1 where R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkylene, arylene, substituted alkylene, or substituted arylene; and R' is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl. Examples of such first monomers include:
Figure imgf000005_0001
The second heterocyclic monomer can have the structure:
Figure imgf000005_0002
where R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkylene, arylene substituted alkylene, or substituted alkylene; X is O, S or NR1; Z is S, O, or NR2; and where R1 and R2 are independently H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl. An example of the second monomer is:
Figure imgf000006_0001
In another embodiment a method to produce an electrochromic copolymer involves providing a heterocyclic oligomer having terminal repeating units that differ from interior repeating units, providing at least one heterocyclic monomer of the same heterocycle as the terminal repeating units in the oligomer, wherein at least one of the monomers or the oligomer has a corresponding homopolymer that is soluble, and copolymerizing the oligomers and monomers chemically in a ratio that yield a copolymer with a predetermined band gap. The terminal repeating units of the oligomer can yield a homopolymer that has high transmissivity through the visible range of the light spectrum in the neutral state and one or more interior repeating units whose homopolymer in the neutral state displays a highly colored state. The oligomer can also have the opposite construction where the terminal units are those that give a highly colored homopolymer in the neutral state and one or more interior units are those of a highly transmissive homopolymer in the neutral state. In this manner, additional control of sequence size and size distribution is possible. Another embodiment to a method of forming an electrochromic copolymer where an oligomer is copolymerized with at least one monomer is by providing an asymmetric dimer of two monomers whose corresponding homopolymers in the neutral state are transmissive throughout the visible range of light for one unit and highly colored for the other, and providing one of the monomers that constitutes the dimer or a mixture of both monomers of the dimer, and copolymerizing the mixture of dimers an monomers to yield a copolymer with a predetermined band gap. In this manner, it is possible to have a process that can achieve all possibilities form the extremes of the two homopolymers by solely being able to vary the blend of the dimer and two monomers.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a general copolymerization embodiment of the present invention.
Figure 2 shows the preparation of a copolymer according to an embodiment of the invention by the condensation of a (3,4-dialkoxythiophene)-(iV-substituted 3,4- dialkoxypyrrole)-(3,4-dialkoxythiophene) trimer with 3,4-dialkoxythiophene in a ratio of 1 :2. Figure 3 shows the preparation of copolymers according to an embodiment of the invention by the condensation of a (3,4-dialkoxythiophene)-(7V-substituted 3,4- dialkoxypyrrole) dimer with either 3,4-dialkoxythiophene or TV-substituted 3,4- dialkoxypyrrole.
Figure 4 shows a specific copolymerization embodiment of the present invention. Figures 5A-5C show UV-vis-NIR absorption spectroelectrochemistry for the copolymers from 0.8 (Figure 5A), 0.5 (Figure 5B), and 0.3 (Figure 5C) mole fraction of TV- dodecyl-3,4-propylenedioxypyrrole monomer used in the copolymerization of Figure 2.
DETAILED DESCRIPTION OF THE INVENTION A series of heterocyclic copolymers are described that display electrochromic properties that vary depending upon the ratio of two (or more) repeating units in the polymer backbone are prepared by a chemical polymerization of heterocyclic comonomers. The mode by which the electrochromic properties can vary is controlled by the comonomer feed ratio. When the comonomer's reactivity is similar, the incremental variation in the repeating unit ratio leads to incremental differences in the band gap, and hence the color, displayed by the electrochromic copolymers. When the comonomer's reactivity is very different, the copolymer contains blocks of the two repeating units; the relative intensities of the optical absorbance from these blocks, whose size and proportions depend on the comonomer feed ratio, yields the color control. Therefore, although the mode of color control can differ, any desired color that ranges from that inherent to the homopolymer of one monomer, through any given proportion of comonomer repeating units, to the color inherent to the homopolymer of the other monomer can be specifically prepared by changing the ratio of the comonomers in the polymerization mixture without any other significant changes to the process. In similar fashion, the copolymer can also incorporate one or more additional heterocyclic repeating units.
Comonomers used in the invention form soluble copolymers, hence permitting the decoupling of the copolymer synthesis from the fabrication of the electrochromic device. The relationship of the color at various applied potentials employed for an electrochromic device can be correlated to the copolymer composition. In this manner, when a particular color, at a given potential, is needed for a device, the preparation of the material can readily be determined and implemented in a production process by changing the monomer feed ratios without any other significant changes to the process. Because the process utilizes chemical polymerization rather than electrochemical polymerization, and the resulting copolymer is soluble, the preparation of the copolymer is independent of the deposition of the copolymer on a substrate of the device.
The copolymerization of two (or more) monomers according to one embodiment of the invention is shown in Fig. 1. In this copolymerization: x' is the monomer mole fraction of a /V-substituted 3,4-dialkoxypyrrole; y', where y' = 1-x', is the monomer mole fraction of a 3,4-dialkoxythiophene or other monomer of lower band gap than the TV-substituted 3,4- dialkoxypyrrole; x is the repeating unit mole fraction of TV-substituted 3,4-dialkoxypyrrole; y, where y = 1-x, is the repeating unit mole fraction of 3,4-dialkoxythiophene or other monomer in a copolymer; n is the degree of polymerization; and N is the total number of monomers in the feed. The value of x need not equal x' due to differences in reactivity ratios of the comonomer, other polymerization effects, and/or any fractionation during isolation of the copolymer. Nevertheless, the composition of the final copolymer, which determines physical properties important for their use, can be correlated to the value of x or x' for any given consistent protocol for the preparation, purification, and isolation of the copolymer. It is preferable that the degree of polymerization be between 10 and 10,000. In this size range, the polymers reach their conjugation limit (reproducible color contribution from each polymer chain), and films with reasonable mechanical properties can be formed from the soluble copolymers.
In one embodiment of the invention, the copolymer is prepared from a mixture of two monomers. One of the monomers is an TV-substituted dialkoxypyrrole and the other monomer can be another pyrrole, a thiophene or a furan. The resulting copolymer has the following structure:
Figure imgf000009_0001
where R1, R2, R3, and R4 are independently H, alkyl, aryl, substituted alkyl, or substituted aryl, or (R1 and R2) and/or (R3 and R4) in combination are alkylene, arylene, substituted alkylene, or substituted arylene; R5 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; X is O, S or NR6 where R6 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; Z is S, O, or NR7 wherein R7 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; 0 < x < 1; y = 1-x; and n is 10 to 10,000. The distribution of sequence lengths can vary considerably depending on the reactivity ratios of the two monomers. The sequence distribution can be statistical with a reactivity ratio of unity for the comonomers. Regardless of the average block size distribution, a variation of the color depends ultimately on the composition of the comonomer feed. In another embodiment of the invention the copolymers are formed from two heterocyclic monomers where neither monomer is a pyrrole, as long as one monomer's neutral homopolymer displays a relatively high band gap and is essentially highly transmissive through the entire visible spectrum of light, while the other monomer's neutral homopolymer displays a relatively low band gap and is highly colored. Other embodiments of the invention can include at least one additional monomer to incorporate additional types of repeating units in the copolymer to modify the electrochromic or other properties of the resulting copolymer. These additional monomers can be, but are not necessarily, heterocyclic monomers. These additional monomers can be included to modify properties that are not dependent upon the conjugation of the copolymer. For example, a monomer can be incorporated that permits the modification of viscosities in solution or in the solvent free state, provide sites for cross-linking of the copolymer after fabrication of a desired shape or device, or enhance the affinity of the copolymer for a specific chemical agent, polymer or surface, such as a graphene, metal, metal oxide or semiconductor surface.
With respect to the polymer structure above, alkyl is a straight or branched chain of, for example, 1-24 carbon atoms and is, for example, methyl, ethyl, n-propyl, n-butyl, sec butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or dodecanyl and the like. Alkyl ene is a chain of, for example, 1-12 carbon atoms and is, for example, methylene, ethylene, propylene, butylene, pentalene, hexylene, octylene, 2-ethylhexyl, n-nonyl, n-decylene or dodecylene and the like; for example, methylene, ethylene, propylene or butylene. The alkyl or alkylene may be interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, -SO-, -SO2 -, carbonyl, -COO-, -CONH-, -NH-,-CON(Ci-8 alkyl)- or -N(C1-S alkyl)- and the like. For example, the alkyl group may be interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -NH- or -N(C1-8 alkyl)-. The uninterrupted or interrupted alkyl or alkylene may also be substituted, one or more times, by one or more C3-6 cycloalkyl groups, halogen, -OR, -COOR, -COOM, -SO3M, -SO3H, phosphonic acid, halogen, -CONR' R, -NR' R, phosphonate salt, ammonium salt or group of the formulae -L-Ar or -C(O)-L-Ar wherein M is a nitrogen cation or metal cation, R and R', independently of any other R or R' that may be present is hydrogen; a group -L-Ar, -C(O)-L- Ar, or -C(O)-O-L-Ar; C1-24 alkyl, C3-24 alkenyl, C3-6 cycloalkyl or C1-24 alkylcarbonyl which is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -CONH-, -NH-, -CON(C1-8 alkyl)- or -N(C1-8 alkyl)-, where uninterrupted or interrupted alkyl, alkenyl, cycloalkyl or alkylcarbonyl are unsubstituted or substituted, one or more times, by one or more halogen, -OH, C7-J2 aralkyl, C2-I2 alkylcarbonyl, Ci-24 alkoxy, C2-24 alkylcarboxy, -COOM, -CONH2, -CON(H)(C1 -8 alkyl), - CON(C1-8 alkyl)2, -NH2, -N(H)(Ci-8 alkyl), -N(C1-8 alkyl)2, -SO3M, phenyl, phenyl substituted, one or more times, by one or more C1-8 alkyl, naphthyl, naphthyl substituted, one or more times, by one or more Ci-8 alkyl ammonium salt, phosphonic acid or phosphonate salt or when attached to a nitrogen atom, R and R', together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered ring that is uninterrupted or interrupted by -O-, - NH- or -N(Ci-I2 alkyl)-; L is a direct bond or Ci-J2 alkylene that is uninterrupted or interrupted by one or more oxygen atoms and is unsubstituted or substituted, one or more times, by one or more -OH, halogen, C1-8 alkyl, C1-24 alkoxy, C2-24alkylcarboxy, -NH2, - N(H)(Ci-S alkyl), -N(C1-8 alkyl)2 or ammonium salt; Ar is C6-1O aromatic or C1^ saturated or unsaturated heterocycle that is unsubstituted or substituted, one or more times, by one or more halogen, -OH, Ci-24 alkoxy, C2-24 alkylcarboxy, -COOQ", -CONH2, -CON(H)(C1-8 alkyl), -CON(Ci-8 alkyl)2, -NH2, N(H)(Ci-8 alkyl), -N(C1-8 alkyl)2, -SO3M, SO3H, ammonium salt, phosphonic acid, phosphonate salt, C]-24 alkyl that is unsubstituted or substituted, one or more times, by one or more halogen, wherein Q" is hydrogen, metal cation, glycol ether, phenyl or benzyl, or phenyl or benzyl substituted, one or more times, by one or more halogen, hydroxy, C]-24 alkoxy or C]-J2 alkyl.
Additionally, alkylene or interrupted alkylene may also be substituted by a group -L- Ar, -C(O)-L-Ar, or -C(O)-O-L-Ar; C1-24 alkyl, C3-6 cycloalkyl or Ci-24 alkylcarbonyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -CONH-, -NH-,-CON(Ci_8 alkyl)- or -N(Ci-8 alkyl)- that is uninterrupted or interrupted alkyl, cycloalkyl or alkylcarbonyl and is unsubstituted or substituted, one or more times, by one or more halogen, -OH, C7-12 aralkyl, C2-12 alkylcarbonyl, C]-24 alkoxy, C2-24 alkylcarboxy, -COOM, -CONH2, -CON(H)(C1-8 alkyl), -CON(C]-8 alkyl)2, -NH2, -N(H)(C1-8 alkyl), -N(C1-8 alkyl)2, -SO3M, phenyl, phenyl substituted, one or more times, by one or more C]-8 alkyl, naphthyl, naphthyl substituted, one or more times, by one or more C]-8 alkyl, ammonium salt, phosphonic acid or phosphonate salt or when attached to a nitrogen atom, R and R', together with the nitrogen atom to which they are attached, form a 5-, 6- or 7- membered ring that is uninterrupted or interrupted by -O-, -NH- or -N(Ci-I2 alkyl)-. For example, R1, R2, R3, R4 and R5 are, independently of each other, Ci-24 alkyl uninterrupted or interrupted by one or more oxygen atoms, carbonyl, -COO-, -NH- or -N(C1-8 alkyl)- and/or substituted, one or more times, by one or more OH, C1-8 alkoxy, C2-6 alkylcarboxy, NH2, N(H)(Cj-8 alkyl), N(C1-8 alkyl)2 , halogen, phenyl or phenyl substituted, one or more times, by C1-4 alkyl, OH, C1-8 alkoxy, C2-6 alkylcarboxy or halogen. For example, R1, R2, R3, R4 and R5 are, independently of each other, C1-24 alkyl uninterrupted or interrupted by one or more oxygen atoms, -COO-, -NH- or -N(C1-8 alkyl) - and /or substituted, one or more times, by one or more OH, C1-8 alkoxy, C2-6 alkylcarboxy, phenyl or phenyl substituted, one or more times, by Ci-4 alkyl, OH, C1-8 Alkoxy or C2-6 alkylcarboxy.
For example, R1 and R , and/or R3 and R4 are, independently of each other, alkylene of 1 -6 carbon atoms that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -NH- or -N(Ci-8 alkyl)- and/or substituted, one or more times, by one or more OH, Cj-8 alkoxy, C2-6 alkylcarboxy, halogen, NH2, N(H)(Ci-8 alkyl), N(C]-8 alkyl)2 , halogen, phenyl, phenyl substituted, one or more times, by Cj-4 alkyl, OH or Ci-8 alkoxy, C2-6 alkylcarboxy or halogen; or the alkylene is substituted by one or more unsubstituted Ci-24 alkyl or Ci-24 alkyl which is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, carbonyl, -COO-, -CONH-, -NH-CON(C1-8 alkyl)- or -N(Ci-8 alkyl)-, that is uninterrupted or interrupted alkyl, unsubstituted or substituted, one or more times, by one or more halogen, -OH, C7-I2 aralkyl, C2-I2 alkylcarbonyl, Ci-24 alkoxy, C2-24 alkylcarboxy, -COOM, -CONH2, -CON(H)(Ci-8 alkyl), - CON(Ci-8 alkyl)2, -NH2, -N(H)(C1-8 alkyl), -N(Ci-8 alkyl)2, phenyl, phenyl substituted, one or more times, by one or more -OH, C1-8 alkyl, Ci-24 alkoxy or C2-24 alkylcarboxy.
For example, R1 and R , and/or R3 and R4 are, independently of each other, alkylene of 1 -6 carbon atoms that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, sulfur atoms, carbonyl, -COO-, -NH- or -N(Ci-8 alkyl)- and/or substituted, one or more times, by one or more OH, Ci-8 alkoxy, C2-6 alkylcarboxy, halogen, NH2, N(H)(Cj-8 alkyl), N(C]-8 alkyl)2 , phenyl, phenyl substituted, one or more times, by Ci-4 alkyl, OH or C1- 8 alkoxy, C2-6 alkylcarboxy or halogen; or the alkylene is substituted by one or more unsubstituted Ci-24 alkyl or Ci-24 alkyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, carbonyl, -COO-, -CONH-, -NH-,-CON(C1-8 alkyl)- or -N(Ci-8 alkyl)-, that has uninterrupted or interrupted alkyl, unsubstituted or substituted, one or more times, by one or more halogen, -OH, C7-I2 aralkyl, C2-I2 alkylcarbonyl, Ci-24 alkoxy, C2-24 alkylcarboxy, -COOM, -CONH2, -CON(H)(Ci-8 alkyl), -CON(Ci-8 alkyl)2, -NH2, -N(H)(Ci-8 alkyl), -N(Ci-8 alkyl)2, phenyl, phenyl substituted, one or more times, by one or more -OH, Ci-8 alkyl, Ci-24 alkoxy or C2-24 alkylcarboxy.
For example, R! and R2, and/or R3 and R4 are, independently of each other, ethylene or propylene that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, -NH- or -N(Cj-8 alkyl)- and/or substituted, one or more times, by one or more OH, Ci-8 alkoxy, C2-6 alkylcarboxy, N(H)(Ci-8 alkyl), N(Cj-8 alkyl)2 , phenyl, phenyl substituted one or more times by Ci-4 alkyl, OH or C1-8 alkoxy, C2-6 alkylcarboxy, or ethylene or propylene substituted by one or more unsubstituted Ci-24 alkyl or C1-24 alkyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, -COO-, -CONH-, -NH-, - CON(Ci-8 alkyl)- or -N(Ci-8 alkyl)-, where uninterrupted or interrupted alkyl is unsubstituted or substituted, one or more times, by one or more -OH, C2-J2 alkylcarbonyl, C1-24 alkoxy, C2-24 alkylcarboxy, -COOM, -N(H)(Ci-8 alkyl), -N(Ci-8 alkyl)2, phenyl or phenyl substituted one or more times by one or more -OH, Ci-8 alkyl, C]-24 alkoxy or C2-24 alkylcarboxy.
For example, R and R , and/or R and R4 are, independently of each other, ethylene or propylene that is unsubstituted or substituted ,one or more times, by one or more OH, C1-8 alkoxy, C2-6 alkylcarboxy, Ci-24 alkyl, C)-24 alkyl that is uninterrupted or interrupted, one or more times, by one or more oxygen atoms, -COO-, -CONH-, that have uninterrupted or interrupted Cj-24 alkyl that is unsubstituted or substituted, one or more times, by one or more - OH, C2-I2 alkylcarbonyl, Cj-24 alkoxy or C2-24 alkylcarboxy.
For Example, R is methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n- octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n- hexadecyl, n-octadecyl, benzyl, hydroxyethyl, hydroxypropyl, Cj-24 alkyl substituted by C2-24 alkylcarboxy or Cj-24 alkyl substituted, one or more times, by Cj-8 alkoxy.
In one embodiment of the invention, a family of copolymers for color control can also be achieved where the band gap varies by condensing either a 3,4-dialkoxythiophene or an N- substituted 3,4-dialkoxypyrrole with a preformed symmetric oligomer with terminal units of the same repeating unit, or of the same heterocycle, that will form from the chosen monomer, but where the interior unit in a trimer, or multiple interior units in a larger oligomers, is derived from the other possible heterocyclic monomer, or of the same heterocycle. This route is easily pursued with a trimer as illustrated in Figure 2. As shown in Figure 2, a trimer with the structure 3,4-dialkoxythiophene-7V-substituted-3,4-dialkoxypyrrole-3,4-dialkoxythiophene is copolymerized with a 3,4-dialkoxythiophene in a ratio of 1 :2. In this manner a copolymer with an average of four 3,4-dialkoxythiophene units between isolated N- substituted 3,4- dialkoxypyrrole units is formed. By increasing the content of the 3,4-dialkoxythiophene in the copolymer, the band gap is tuned by the content of the TV-substituted 3,4-dialkoxypyrrole in the thiophene polymer. The polymerization reactivity of the oligomer and monomelic thiophene units is similar. The distributions of repeating unit sequences are narrower than a random (normal) distribution by this copolymerization of a trimer and monomers when the terminal units of the trimer and the monomer have equal reactivity. For the polymerization given in Figure 2, a 3,4-dialkoxythiophene block size distribution of approximately 1.67 results when all 3,4-dialkoxythiophene moieties have equal reactivity, rather than the normal distribution for a tetramer of a homopolymer of 1.75. For this embodiment, where an oligomer is copolymerized with a monomer of the same repeating units as the oligomer termini, the entire range of possible band gaps can be achieved when at least two complementary ended oligomers and the two complementary monomers are available to construct copolymers.
In another embodiment of the invention the copolymerization of an asymmetric dimer of 3,4-dialkoxythiophene and TV-substituted 3,4-dialkoxypyrrole can be used with a 3,4- dialkoxythiophene, an TV-substituted 3,4-dialkoxypyrrole, or a combination of both, to achieve the entire range of band gaps. As shown in Figure 3, a single dimer copolymerized with either the 3,4-dialkoxythiophene monomer or the TV-substituted 3,4-dialkoxypyrrole monomer can yield the entire range of band gaps available from a copolymer and retain the systematic variation based on simply varying the feed ratio of dimer to monomer (or monomers). Figure 3 (bottom) shows one pyrrole-to-thiophene coupling and one pyrrole-to- pyrrole coupling in the copolymerization of the asymmetric dimer with 3,4- dialkoxythiophene monomer. Even where one mode of coupling, either homocoupling of like units or heterocoupling of unlike units, dominates over the other mode of coupling, the distribution of block lengths is controlled in this copolymerization. The band gap can be selected by the selection of the monomer and ratio of the monomer and asymmetric dimer included in a copolymerization.
The invention is illustrated by the following examples. It should be understood that the examples described below are provided for illustrative purposes only and do not in any way limit the scope of the invention.
EXAMPLES Example 1
A series of copolymers were prepared by varying the mole fraction of 7V-dodecyl-3,4- propyl enedioxypyrrole used to yield copolymers with 3-methyl-3-(2-ethylhexyloxymethyl)-
3,4-dihydro-2H-thieno[3,4-b][l,4]dioxypine as shown in Figure 4. These monomers were synthesized as disclosed in Zong et al. J. Org. Chem. 2001, 6873-82 and Walczak et al. Chem. Commun. 2006, 1604-6. Oxidative copolymerization was carried out using FeCl3 in CH3CN to yield stable soluble copolymers. All copolymers displayed number average molecular weights between 3,000 and 8,000 g/mol and polydispersity indexes from 1.4 to 2.0 as measured by GPC of THF solutions versus polystyrene standards. The mole fraction of the monomer iV-dodecyl-3,4-propylenedioxypyrrole used in the copolymerization was varied from 0.0, 0.3, 0.5, to 0.8 which gave cast copolymer films which varied in color from purple to red, orange and yellow, respectively. These color differences were also observed in solution. As the mole fraction of the pyrrole monomer used in the copolymerization decreased, the band gap of the copolymer decreased. As the mole fraction of the pyrrole monomer used in the copolymerization decreased, the fluorescence X1113x was red shifted.
Example 2
The copolymers of Example 1 were spray cast from 1 % (w/V) toluene solutions onto ITO/glass working electrodes. The UV-vis-NIR absorption spectroelectrochemistry is shown in Figures 5A-5C for the copolymers from 0.8 (Figure 5A), 0.5 (Figure 5B), and 0.3 (Figure 5C) mole fraction pyrrole monomer in the copolymerization mixture. The spectra change significantly from the neutral to/>-doped state. As in the case of the 0.5 mole fraction pyrrole monomer derived copolymer, a shift from a red-purple neutral copolymer to a blue /?-doped copolymer occurs. Because of the ease with which the electrical and electrochromic properties of the resulting copolymers can be varied with the monomer feed ratio while using nearly identical polymerization conditions, a host of materials with specific properties can readily be generated. Furthermore, the comonomer structures and chemical polymerization process lead to soluble copolymers, which can be readily processed for a variety of applications, including, but not limited to, the fabrication of electrochromic windows, mirrors and displays, electronic paper, camouflage, photovoltaic devices, anti-stat conductors, and field effect transistors, supercapacitors, batteries, and other electronic components.
This invention can be embodied in other forms without departing from the spirit or essential attributes thereof, and accordingly, reference should be had to the following claims rather than the foregoing specification as indicating the scope of the invention.

Claims

CLAIMS We claim:
1. A copolymer with electrochromic properties comprising the structure:
Figure imgf000016_0001
where R1, R2, R3, and R4 are independently H, alkyl, aryl, substituted alkyl, or substituted aryl, or (R1 and R2) and/or (R3 and R4) in combination are alkylene, arylene, substituted alkylene, or substituted arylene; R5 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; X is O, S or NR6, where R6 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; Z is S, O, or NR7 where R7 is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl; 0 < x < 1; y = 1-x; and n is 10 to 10,000.
2. The copolymer of claim 1, wherein the copolymer is soluble in at least one solvent.
3. The copolymer of claim 1 wherein the copolymer contains additional repeating unit structures comprising aromatic hydrocarbon units or other conjugated units.
4. A method to produce an electrochromic copolymer comprising the steps of: providing a first heterocyclic monomer whose homopolymer in the neutral state has high transmissivity through the visible spectrum; providing a second heterocyclic monomer whose homopolymer in the neutral state displays a highly colored state, wherein one or both of said monomers have a corresponding homopolymer that is soluble; and copolymerizing said first and second monomers chemically, in a ratio that yields a copolymer with a predetermined band gap.
5. The method of claim 4, wherein said first monomer comprises the structure:
R R
N
I
R1 where R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkylene, arylene, substituted alkylene, or substituted arylene; and R' is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)?aryl, HOC(O)aryl or (HO)2P(O)aryl.
6. The method of claim 5, wherein said first monomer comprises:
Figure imgf000017_0001
7. The method of claim 5, wherein said first monomer comprises:
Figure imgf000018_0001
8. The method of claim 4, wherein said first monomer comprises about 0.01 to about 0.99 mole fraction of said comonomer mixture.
9. The method of claim 4, wherein said second monomer comprises the structure:
Figure imgf000018_0002
where R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkyl ene, arylene substituted alkyl ene, or substituted alkylene; X is O, S or NR1 ; Z is S, O, or NR2; and where R1 and R2 are independently H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl.
10. The method of claim 9, wherein said second monomer comprises:
Figure imgf000018_0003
11. A method to produce an electrochromic copolymer comprising the steps of: providing a first heterocyclic monomer whose homopolymer in the neutral state has high transmissivity through the visible spectrum; providing a second heterocyclic monomer whose homopolymer in the neutral state displays a highly colored state, wherein one or both of said monomers have a corresponding homopolymer that is soluble; and copolymerizing said first and second monomers chemically, in a ratio that yields a copolymer with a predetermined color.
12. The method of claim 11, wherein said first monomer comprises the structure:
R R
N
I
R1 . where R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkylene, arylene, substituted alkylene, or substituted arylene; and where R' is H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl.
13. The method of claim 12, wherein said first monomer comprises:
N /7-C12H 25
14. The method of claim 12, wherein said first monomer comprises:
Figure imgf000020_0001
15. The method of claim 11, wherein said first monomer comprises about 0.01 to about 0.99 mole fraction of said comonomer mixture.
16. The method of claim 11 wherein said second monomer comprises monomer of the structure:
/
Figure imgf000020_0002
where R groups are independently H, alkyl, aryl, substituted alkyl, substituted aryl, or where two R groups in combination are alkylene, arylene substituted alkylene, or substituted alkylene; X is O, S or NR1; and Z is S, O, or NR2, where R1 and R2 are independently H, alkyl, aryl, substituted alkyl, substituted aryl, oligoether, aminoalkyl, hydroxyalkyl, alkoxyalkyl, acyloxyalkyl, HOS(O)2alkyl, HOC(O)alkyl, (HO)2P(O)alkyl, aminoaryl, hydroxyaryl, alkoxyaryl, acyloxyaryl, HOS(O)2aryl, HOC(O)aryl or (HO)2P(O)aryl.
17. The method of claim 16, wherein said second monomer comprises:
Figure imgf000020_0003
18. A method to produce an electrochromic copolymer comprising the steps of: providing a heterocyclic oligomer having terminal repeating units whose homopolymer in the neutral state has high transmissivity through the visible range of the light spectrum and at least one interior repeating unit whose homopolymer in the neutral state displays a highly colored state, or having terminal repeating units whose homopolymer in the neutral state displays a highly colored state and at least one interior repeating unit whose homopolymer in the neutral state has high transmissivity through the visible range of the light spectrum; providing at least one heterocyclic monomer of the same heterocycle as the terminal repeating units of said oligomers, wherein at least one of said monomers and said oligomer have a corresponding homopolymer that is soluble; and copolymerizing said oligomer with said monomer chemically in a ratio to yield a copolymer with a predetermined band gap.
19. A method to produce an electrochromic copolymer comprising the steps of: providing a heterocyclic dimer with one subunit whose homopolymer in the neutral state has high transmissivity through the visible range of the light spectrum and one subunit whose homopolymer in the neutral state displays a highly colored state; providing a heterocyclic monomer of the same heterocycle as one of the subunits of said dimer or a mixture of two or more heterocyclic monomers of the same type as either heterocycle of the subunits of said dimer, wherein at least one of said monomers and said dimer have a corresponding homopolymer that is soluble; and copolymerizing said dimer and said monomers chemically in a ratio to yield a copolymer with a predetermined band gap.
PCT/US2008/057420 2007-03-23 2008-03-19 Variable color dioxyheterocycle copolymers Ceased WO2008118704A2 (en)

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