WO1998046652A1 - Poly(phenylene-vinylene)s et poly(naphthalene-vinylene)s substitues - Google Patents

Poly(phenylene-vinylene)s et poly(naphthalene-vinylene)s substitues Download PDF

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WO1998046652A1
WO1998046652A1 PCT/US1998/007957 US9807957W WO9846652A1 WO 1998046652 A1 WO1998046652 A1 WO 1998046652A1 US 9807957 W US9807957 W US 9807957W WO 9846652 A1 WO9846652 A1 WO 9846652A1
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polymer
substituted
group
yield
reaction
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PCT/US1998/007957
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Robert H. Grubbs
Michael W. Wagaman
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California Institute Of Technology
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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
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes

Definitions

  • the present invention generally relates to electroluminescent polymers and methods for making the same. More particularly, the present invention relates to a novel class of electroluminescent ("EL") polymers that includes repeating units of substituted (p ⁇ ra-phenylenevinylene) (“PV”) and/or substituted (1,4-naphthalenevinylene) (“NV").
  • PV substituted
  • NV substituted (1,4-naphthalenevinylene
  • EL polymers with blue emission for making full colored LED displays. Because full colored LED displays require materials that emit the three primary colors of light (blue, green and red), this technology has been stalled because of the lack of suitable blue emitters.
  • the present invention relates to a novel class of electroluminescent ("EL") polymers that includes repeating units of substituted (p ⁇ ra-phenylenevinylene) (“PV”) and/or substituted (1,4-naphthalenevinylene) (“NV”) and methods for making the same.
  • PV substituted
  • NV substituted (1,4-naphthalenevinylene
  • novel homopolymers, random copolymers, and block copolymers which include at least one repeating unit of either substituted PV or substituted NV having the formula:
  • n is a positive integer
  • X 1 , X 2 , X 3 are each either hydrogen or any electron withdrawing group
  • R, R and R are each hydrogen, halide, or a substituted or unsubstituted moiety selected from a group consisting of C j - C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, and aryl, the moiety optionally functionalized with one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxo, anhydride, carbamate, and halogen.
  • the moiety substitution is selected from a group consisting of C ] -C j0 alkyl, C 2 -
  • C 10 alkenyl, C 2 -C 10 alkynyl, and aryl each of which also may be optionally functionalized with one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxo, anhydride, carbamate, and halogen.
  • the inventive homopolymers, random copolymers, and block copolymers may additionally include one or both repeating units of the formula:
  • m is an integer and X 1 , X 2 , X 3 , R, R 1 , and R 2 are as previously defined.
  • Figure 1 displays the photo luminescence of 100% aromatized di-t-butyl ester PPV and an 80% aromatized di-t-butyl ester PPV.
  • Figure 2A shows the emission intensities of bistrifluoromethyl PPV homopolymer, octyltrichloro PNV homopolymer, bistrifluoromethyl PPV/ octyltrichloro PNV block copolymer and bistrifluoromethyl PPV/ octyltrichloro PNV random copolymer when irradiated at the excitation maximum of bistrifluoromethyl PPV (345 nm).
  • Figure 2B shows the emission intensities of octyltrichloro PNV homopolymer, bistrifluoromethyl PPV/octyltrichloro PNV block copolymer and bistrifluoromethyl PPV/octyltrichloro PNV random copolymer when irradiated at the excitation maximum of octyltrichloro PNV (430 nm).
  • the present invention relates to a novel class of electroluminescent ("EL") polymers that includes repeating units of substituted (p ⁇ r ⁇ -phenylenevinylene) (“PV”) and or substituted (1,4-naphthalenevinylene) (“NV”) and methods for making the same.
  • EL electroluminescent
  • PV substituted (p ⁇ r ⁇ -phenylenevinylene)
  • NV substituted (1,4-naphthalenevinylene)
  • Practice of the present invention allows the synthesis of a diverse set of novel EL polymers with improved luminescent characteristics and added functionalities.
  • the first step in making novel EL polymers is the synthesis of the requisite substituted monomers.
  • the two preferred monomers in the practice of the present invention are substituted benzobarrelenes having the formula:
  • X , X , X are each hydrogen or any electron withdrawing group; R, R and R are each hydrogen, halide, or a substituted or unsubstituted moiety selected from a group consisting of C j -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, and aryl, the moiety optionally functionalized with one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxo, anhydride, carbamate, and halogen.
  • the moiety substitution is selected from a group consisting of CJ-CJ alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, and aryl, each of which may also be optionally functionalized with one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxo, anhydride, carbamate, and halogen.
  • R and R may together form a cyclic moiety.
  • X 1 , X 2 , and X 3 are all selected from the group consisting of hydrogen, fluoride, and chloride and R is C r C 10 alkyl.
  • Illustrative examples of the most preferred embodiments of substituted benzobarrelenes are:
  • R is a C j -C 10 alkyl.
  • substituted barrelenes in which R 1 and R 2 are each an electron withdrawing group is particularly preferred.
  • suitable electron withdrawing group includes but are not limited to C j -C 20 perfluoroalkyl, C j -C 20 carboxylic acid, C j -C 20 carboxy late, C j -C 20 ester, C j - C 20 acid halide, C 2 -C 20 acid anhydride, and C j -C 20 amide.
  • R and R are each selected from the group consisting of hydrogen, C j -C 10 perfluoroalkyls, and CJ-CJ 0 esters.
  • the substituted benzobarrelenes and barrelenes may be made by any conventional methods known in the art. However, because some of the preferred substituted benzobarrelenes and barrelenes could not be synthesized using previously described methods, novel synthetic protocols were developed.
  • one aspect of the invention involves novel protocols for making particular substituted benzobarrelenes and barrelenes.
  • one embodiment of the inventive protocols is for the synthesis of a particularly useful class of alkyltrihalobenzobarrenenes.
  • Compound 2 is further reacted with n-BuLi and alkyliodide (“Rl”) to yield alkyltrifluorobenzobarrelene 3.
  • Compound 2 is further reacted with n-BuLi and alkyliodide (“Rl”) to yield alkyltrichlorobenzobarrelene 3.
  • Scheme 2 illustrates another embodiment of the inventive protocols.
  • the inventive protocol may be used to make both unsubstituted barrelene and substituted barrelenes.
  • either c/_-3,5-cyclohexadiene-l,2-diol 4 or the acetonide protected form of this molecule 5 is reacted with R ! C ⁇ CR 2 6 in a Diels- Alder reaction to yield the barrelene diol 7.
  • reaction with 6 yields an acetal form of compound 7.
  • the acetal is deprotected under acidic conditions to yield compound 7.
  • Compound 7 is converted to thiocarbonate 8 using thiocarbonyldiimidazole ("TCDI").
  • Substituted barrelene 9 is obtained by reacting thiocarbonate 8 with 1,3- dimethyl-2-phenyl-l,3,2-diazaphospholidine ("DPD").
  • TsC ⁇ CR substituted alkynl p - toluenesulfate
  • Another aspect of the present invention relates to novel EL polymers which include at least one repeating unit of either substituted PV or substituted NV having the formula
  • n is a positive integer
  • X , X , X , R, R , and R are as previously defined.
  • X 1 , X 2 , and X 3 are all selected from the group consisting of hydrogen, fluoride, and chloride and R is C,- C 10 alkyl.
  • polymers which include substituted PVs in which R and R are each an electron withdrawing group is particularly preferred.
  • Suitable electron withdrawing group includes but are not limited to C j -C 20 perfluoroalkyl, C j -C 20 carboxylic acid, C j -C ⁇ carboxylate, C j -C 20 ester, C j -C 20 acid halide, C 2 -C 0 acid anhydride, and C j -
  • the EL polymers include at least one repeating unit of an unaromatized precursor of substituted NV having the formula
  • m is a positive integer
  • X 1 , X 2 , X 3 , R, R 1 , and R 2 are as previously defined.
  • the substituted NVs and PVs and their respective unaromatized precursors may be incorporated into polymers as homopolymers, block copolymers, or random copolymers via ring opening polymerization reactions ("ROMP") of the corresponding substituted benzobarrelene or barrelene with a metathesis catalyst or initiator.
  • ring opening polymerization reactions include but are not limited to the following:
  • R C(CH 3 ) 2 CF 3 19
  • metathesis initiators that also form c/_-bonds are generally preferred.
  • activators may also be added to the catalyst composition to enhance the rate of catalyst initiation.
  • An illustrative example of such an initiator is hexafluoro-t-butanol.
  • a modulator that slows the rate of propagation may also be included.
  • Suitable examples of catalyst modulators are Lewis bases which reduce metathesis activity by reversibly coordinating to the metal center.
  • Illustrative examples of catalyst modulators are phosphines, phosphites and tetrahydrofuran (“THF").
  • the most preferred catalyst for the practice of the present invention is compound 18 (henceforth also referred to as the "Mo metathesis initiator”):
  • R 2 is -C(CH 3 )(CF 3 ) 2 .
  • inventive polymers are generally synthesized via ROMP reactions of the corresponding monomers with the Mo metathesis initiator in the presence of HFB and THF.
  • the general protocol is illustrated by Scheme 3:
  • n is a positive integer
  • X 1 , X 2 , X 3 , R, R 1 , and R 2 are as previously defined.
  • the unaromatized precursor polymer, 20 or 21 is then aromatized.
  • a suitable method for this purpose is reacting the precursor polymer with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone ("DDQ").
  • DDQ 2,3-dichloro-5,6-dicyano-l,4-benzoquinone
  • the inventive homopolymers are formed when only one monomer is used during the polymerization reaction.
  • random copolymers are made by mixing at least two monomers together prior to the polymerization reaction.
  • sequential polymerization of the individual monomers is required.
  • the next monomer typically is not added until all the previous monomer is fully consumed (as measured by 1H NMR). Any number of monomers may be polymerized in succession to form block polymers.
  • copolymers made from two monomers wherein one material has a smaller bandgap than the other is generally preferred.
  • block copolymers include:
  • Alkylated trifluorobenzobarrelenes were desired so that the effect of the electron withdrawing fluorines on the band gap of PNV could be studied and compared to the unfluorinated counterparts.
  • attempts to do so using a variation of Method A to prepare 6-undecyl-l,4-dihydro-l,4- ethenonapthalene produced only very low yields of alkylated trifluorobenzobarrelenes. Method A is described in detail below in the Experimental Methods Section.
  • X, X 1 , X 2 , X 3 , X 4 , and X 5 are each a halogen and R is alkyl.
  • compound 1 is either l-bromo-4-chloro-2,3,5,6-tetrafluorobenzene which would result in an alkylated trifluorobenzobarrelene or hexachlorobenzene which would result in an alkylated trichlorobenzobarrelene.
  • Table 1 displays the yields for an illustrative set of alkyltrichlorobenzobarrelenes and alkyltrifluorobenzobarrelenes.
  • alkylated benzobarrelenes were obtained in high yields ( « 97%) by reacting the corresponding alkyltrihalobenzobarrene with Na and t-BuOH to remove the halogens.
  • conversion to the unhalogenated benzobarrelene also offered confirmation of the substitution pattern of the synthetic route described by the above protocol.
  • the product obtained by dechlorination of undecyltrichlorobenzobarrelene (“5-undecyl- 1 ,8-dihydro- 1 ,8-etheno-3,4,6- trichloronaphthalene”) were found to have a 1H NMR spectrum identical to that observed for the undecylbenzobarrelene (“6-undecyl-l,4-dihydro-l,4- ethenonaphthalene”) made as described by Method A in the Experimental Methods Section.
  • TsC ⁇ CR substituted alkynl p -toluenesulfate
  • Living polymerization was achieved using Mo metathesis initiator by activating the catalyst with hexafluoro-t-butanol ("HFB").
  • HFB hexafluoro-t-butanol
  • the percentage of the catalyst that became initiated increased with increasing amounts of HFB.
  • an upper limit is reached at about 50 equivalents of HFB at which point the catalysts begins to decompose.
  • the best activity was observed when between about 14 and about 20 equivalents of HFB was used.
  • the polymerization was much more rapid in the presence of HFB. For example, polymerization of undecylbenzobarrelene (or compound 11) in the presence of 14 equivalents of HFB takes about 35 minutes versus between about 10-18 hours when HFB is not added. To maximize initiation relative to propagation, the activity of the
  • Mo metathesis initiator was further tuned with Lewis bases.
  • any suitable Lewis base may be used to slow the rate of propagation, the use of tetrahydrofuran (“THF”) is especially preferred. The best results were achieved when about 10 equivalents of THF was used during the polymerization reaction.
  • the desired amount of monomer ( « 50 - 150 mg depending on the monomer and the monomer to catalyst ratio desired) was dissolved in 0.5 - 0.6 g of dry degassed benzene and the required amount of dry hexafluoro-t-butanol (usually « 7.8 ⁇ L) was added.
  • Mo metathesis initiator (3.5 - 3.9 mg) dissolved in 10 drops of dry C 6 D 6 was then added to this solution.
  • the reaction mixture changed color from yellow to light orange or orange-brown during the first few minutes after mixing.
  • the solution was transferred into an NMR tube equipped with a J- Young valve.
  • each polymer was dissolved in 50 mL of chloroform to yield solutions of each polymer so that each solution A contained the same concentration of total monomer units. 1 mL of each of these solutions was then diluted to 25 mL using chloroform to yield solutions B. 1 mL of each of these solutions was then diluted to 25 mL using chloroform to yield solutions C. Solutions B and C were used for most luminescence measurements. However, solution A was sometimes used for those polymers that displayed weak luminescence.
  • EXAMPLE 8 The aromatized polymers were usually brightly colored and luminesced strongly under a hand held UV lamp. As shown in Table 2, the different homopolymers exhibited luminescence at a range of wavelengths that cover the visible spectrum from blue ( « 450) to nearly red (579 nm).
  • Polymer 8 Solvent soln. ⁇ em soln. (%) g film undecyl PNV CHC1 3 444 551 c , 561 d 0.5 593 octyltrifluoro PNV CHCI3 416 568 c , 579 d 0.05 e octyltrichloro PNV CHCI3 437 569 14 570
  • the emission of PNVs substituted with electron withdrawing groups exhibited a red shift relative to the unhalogenated PNV.
  • Both the absorbance and emission maxima of the substituted PPVs were also strongly blue shifted relative to films of unsubstituted PPV.
  • the partially aromatized polymer showed a higher quantum yield than the fully conjugated version (see Figure 1).
  • the partially aromatized polymers are also more soluble and thus generally preferred.
  • EL polymers with electron withdrawing groups Another advantage of EL polymers with electron withdrawing groups is their improved oxidative stabilities. Although undecyl PNV and unsubstituted PNV decomposed significantly after exposure to air and room lighting for one day, polymers with electron withdrawing groups showed no appreciable change. In fact, octyltrichloro PNV, di-t-butyl ester PPV, bistrifluoromethyl PPV and trifluoromethylperfluorooctyl PPV were observed to still luminescence strongly after exposure to these conditions for one year. Quantitative measurements of di-t-butyl ester PPV showed that this material retained 70 percent of its original luminescence output after being exposed to intense ultraviolet radiation in air for one hour. In contrast, MEH-PPV and aluminum trisquinolate, two commonly used emissive materials, decomposed almost entirely (with less than 5 percent of its original luminescence) under the same conditions.
  • the block polymers showed transfer of excitons from the larger bandgap material to the smaller bandgap material.
  • Figure 2A shows the emission spectra of bistrifluoromethyl PPV homopolymer, octyltrichloro PNV homopolymer, bistrifluoromethyl PPV/octyltrichloro PNV block copolymer and bistrifluoromethyl PPV/octyltrichloro PNV random copolymer when excited at 345 nm.
  • Figure 2B shows the emission spectra of octyltrichloro PNV homopolymer, bistrifluoromethyl PPV/octyltrichloro PNV block copolymer and bistrifluoromethyl PPV/octyltrichloro PNV random copolymer when excited at 430 nm.
  • the spectrum of the random copolymer shows that its luminescence intensity is increased and that its luminescence maximum is slightly blue shifted relative to that of octyltrichloro PNV homopolymer.
  • the luminescence wavelength maximum of the random copolymer more closely matches that of octyltrichloro PNV homopolymer since electrons and holes formed in larger bandgap segments where the concentration of bistrifluoromethyl PPV is higher, migrate to smaller bandgap segments where the concentration of octyltrichloro PNV homopolymer is higher.
  • the luminescence intensity of the smaller bandgap region is increased since excitons formed in large and small bandgap regions all recombine in the smaller bandgap regions.
  • Emission measured at the wavelength of bistrifluoromethyl PPV is much less intense for the random copolymer than for the block copolymer showing that migration of electrons and holes into smaller bandgap segments of the random copolymer is more complete than for the block copolymer. This more complete migration most likely results from the fact that random copolymer contains units of both materials along the entire polymer chain. In other words, because the random copolymer contains short blocks of the large bandgap and small bandgap materials compared with block copolymers, electrons and holes reach the smaller bandgap segment after traveling a much shorter distance.
  • Excitons become trapped in the smaller bandgap segments of the random copolymer and recombine with emission of light in these segments.
  • the larger bandgap segments have been proposed to prevent migration out of the smaller bandgap regions and thereby diminish the number of electrons and holes that migrate to quenching sites.
  • the emission intensity of the block copolymer is essentially the same as that of the homopolymer since only the octyltrichloro PNV block of the block copolymer is excited by 430 nm radiation. Because excitons in the block copolymer are free to move throughout the entire length of the octyltrichloro PNV region, they are about as likely to reach quenching sites as in the homopolymer.
  • the block copolymer shows luminescence characteristic only of the smaller bandgap homopolymer, octyltrichloro PNV. This more complete migration results from the increased interaction among the polymer chains in the solid state, which allows electrons and holes to be transferred between chains as well as along the polymer chain.
  • the spectrum of a 1 :1 mixture of the two homopolymers does not show complete transport to the smaller bandgap polymer. The difference in these results is due to the fact that the mixture of homopolymers can more readily phase separate into macroscopic regions containing only one type of homopolymer. Migration of electrons and holes from the larger bandgap regions to smaller bandgap regions, thus would occur over larger distances than in films of the block copolymer.
  • polymer 24 containing about 50% unaromatized units was used to result in a highly soluble polymer.
  • the polymer was blended with a photo-acid generator, triphenylsulfonium hexafluoroantimonate, by dissolving both materials in dichloromethane and then spin casting this polymer solution onto a silicon wafer.
  • the wafer was heated at 60 °C to drive off any remaining solvent and irradiated through a mask with deep ultraviolet radiation of 248 nm.
  • triphenylsulfonium hexafluoroantimonate decomposed and generated hexafluoroantimonic acid.
  • the wafer was heated at 150 °C to cause the polymer in the exposed acid containing areas to be converted to anhydride 25.
  • polymer 24 in the unexposed, acid free areas were not transformed at this temperature.
  • the areas where polymer 24 was converted to anhydride 25 were then dissolved by immersing the wafer in an aqueous solution of the base tetramethylammonium hydroxide.
  • polymer 24 when used in conjunction with a photo-acid generator served as a positive photoresist.
  • Acetylenes and protected diols were prepared according to literature procedures.
  • Hexamethylphosphoramide (“HMPA”) was purchased from Aldrich and dried over calcium hydride and then distilled under reduced pressure prior to use. 3,3,3-trifluoropropyne was purchased from PCR incorporated.
  • C/_-3,5-cyclohexadiene-l,2-diol was obtained from ICI.
  • PPTS p -toluenesulfonate
  • 2-ethyl hexanol 2-ethyl hexanol
  • acetylenedicarboxylic acid 2-ethylenedicarboxylic acid
  • hexafluoro-2-butyne SMI 2 in THF
  • UV/Nis spectra were recorded on a HP Vectra ES/12 spectrometer.
  • Thermogravimetric analyses were carried out using a TGA 7 Thermogravimetric Analyzer.
  • Dichloromethane (Burdick and Jackson HPLC grade) was used as the eluent for GPC measurements. Emission spectra were recorded on an SLM 8000 C Spectrofluorometer.
  • Xylene was purchased from Aldrich in a Sure Seal container. Methanol, dichloromethane and chloroform were degassed by purging with dry argon for a minimum of 30 minutes.
  • Hexafluoro-t-butanol (HFB) and THF-d8 were distilled from calcium hydride.
  • 6-octyl-5,7,8-trifluoro-l,2,3,4-tetrahydro-2,3-(benzylidenedioxy)-I,4- ethenonaphthalene (“Octyltrifluorobenzobarrelene”).
  • l-chloro-4- octyltetrafluorobenzene (1.1187 g) and c/_-l,2-benzylidenedioxy-3,5- cyclohexadiene (0.5045 g) were each dissolved in 5 mL of ether in separate flasks and then the two solutions were combined. After cooling this combined solution to 3 °C 2.53 mL of 1.57 M n-butyl lithium was added over 25 minutes.
  • the reaction was stirred at 3 - 5 °C for an additional 20 minutes and then at room temperature for 1.5 hours.
  • the flask was then cooled to 5 °C and 1.25 mL of 1.57M n-butyl lithium was added over 15 minutes.
  • the reaction was quenched by adding 2 mL of water.
  • the total mixture was added into 30 mL of water and this was extracted with (4 x 100 mL) of ether. After drying over magnesium sulfate, the ether was evaporated to yield a viscous oil.
  • the product could not be recrystallized, so it was purified by column chromatography.
  • the silica gel column was eluted first with 5% ethyl acetate/hexane then 10%> ethyl acetate/hexane then 20% ethyl acetate/hexane. Product was obtained as
  • Alkyltrifluorobenzobarrelene The method is analogous to that for alkyltrichlorobenzobarrelene described above except that chlorotrifluorobenzobarrelene was used instead of tetrachlorobenzobarrelene.
  • Dimethylbarrelene-2,3-dicarboxylate (“Di-methylester barrelene”). Under air, a 50 mL round bottom flask (“RBF”) was charged with 9 mL dimethylacetylenedicarboxylate (73.2 mmol) and 4.01 g (35.7 mmol) of cis- 3,5-cyclohexadiene-l,2-diol. The solution was heated at 60 °C for 1 day.
  • TCDI tridecane
  • Di-t-butylbarrelene-2,3-dicarboxylate (“Di-/-butyl ester barrelene”). Acid impurities were removed from the di-t-butyl acetylene dicarboxylate by loading it onto a plug of silica gel and eluting with 10%> ethyl acetate/hexane.
  • reaction mixture was dissolved in ethyl acetate and 25 g of silica gel was added. Solvent was evaporated to yield a free flowing solid which was then loaded onto a plug of 100 mL of silica gel and eluted with 50% ethyl acetate/hexane. Following removal of solvent, 2.12 g (6.302 mmol) of the pale yellow solid di-t-butyl-
  • Di-t-butyl-2,3-dihydroxy-5,7-bicyclooctadiene-5,6-dicarboxylate (2.12 g, 6.30 mmol) and TCDI (1.31 g, 90 %> pure, 6.62 mmol) were loaded into a 100 mL flask, and the flask was purged with argon. 20 mL of dry toluene was added to yield a yellow solution containing undissolved TCDI. The solution was heated in an oil bath that was preheated to 120 °C for 15 minutes.
  • a 100 mL RBF was charged with 13.57 g (35.66 mmol) of di-t-butyl-2,3- thiocarbonate-5,7-bicyclooctadiene-5,6-dicarboxylate and 21 mL of DPD to yield a brown mixture.
  • the mixture was heated under argon in an oil bath at 40 °C for 1 week.
  • the brown solution was then loaded onto a silica gel column and eluted with 10% ethyl acetate/hexane. After evaporation of solvent, the product was obtained as 6.7 g of a white crystalline solid containing «10% of the retro Diels- Alder benzene product.
  • the free flowing solid was loaded onto a column containing 750 g of silica gel and eluted with 20%) ethyl acetate/hexane and then 50%> ethyl acetate/hexane.
  • the major isomer, anti (identified by comparison to similar previously characterized compounds), was a white powder and the minor isomer, syn, was a slightly yellow crystalline solid.
  • 5-perfluorooctyl-6-trifluoromethylbicyclo[2.2.2]octa-5,7-diene- 2,3-diol was made by dissolving 5-perfluorooctyl-6-trifluoromethyl-5,7- bicyclo[2.2.2]octa-5,7-diene-2,3-dimethylacetal (1.29g, 1.94 mmol) in 9 mL of methanol and adding 97 mg of pyridinium p -toluenesulfonate to yield a clear colorless solution. The reaction was heated at 60 °C in an open flask.
  • Ethynyl p- toluenesulfonate can contain acidic impurities which cause rapid exothermic decomposition of cis-3 ,5-cyclohexadiene- 1 ,2-dimethylacetal. This decomposition is especially violent if the two reactants are combined neat. Acid impurities were removed from ethynyl p -toluenesulfonate by eluting it through a plug of silica gel (20% ethyl acetate/hexane).
  • Bicyclo[2.2.2]octa-5,7-diene-2,3-dimethylacetal-5-sulfonate (10.68 g, 32.1 mmol) was put in a 2000 mL round bottom flask and the flask was evacuated and then backfilled with argon three times. The flask was then put in a bath at -20 °C and 1.6 L of Sml 2 solution (0. 1 M in THF) was added while maintaining the bath temperature at or below -20 ° C. 90 mL of HMPA, which had been dried over calcium hydride and then distilled, was then added to the solution and the color changed from blue-green to dark purple.
  • the reaction was stirred under argon for 90 minutes at a temperature of -20 ° C and then 150 mL of a saturated solution of aqueous NH 4 C1 was added. After stirring for one hour, over which time the solution was allowed to warm to room temperature, THF was removed under vacuum. The remaining mixture was diluted with 50 mL of water and the aqueous layer was then extracted with (3x500) mL of ether. The combined organic layers were then extracted with (2x200) mL of brine and (2x200) mL 0.1 M NaOH. These aqueous layers were then extracted with (3x200) mL of ether. The combined organic layers were dried over MgSO 4 and solvent was then removed under vacuum to yield a pink liquid.
  • bicyclo[2.2.2]octa-5,7-diene-2,3- dimethylacetal (3.75 g, 21.04 mmol) was dissolved in 80 mL of methanol and 1.09 g of pyridinium ?-toluene sulfonate was added.
  • the reaction which was left open to the air, was heated at 70 °C and the methanol was replenished periodically as it boiled off. After 1 week, remaining methanol was removed under vacuum and the reaction was purified on a silica gel column eluted with 40%) ethyl acetate/hexane. Removal of solvent under vacuum yielded 1.9 g (13.75 mmol, 66%>) of bicyclo[2.2.2]octa-5,7-diene-2,3- diol as a white crystalline solid.
  • a 250 mL Schlenk flask was charged with 1.8 g (9.99 mmol) of bicyclo[2.2.2]octa-5,7-diene-2,3-thiocarbonate and was then evacuated and filled with argon three times. Under argon, 6 mL (97% pure, 6.13 g, 31.6 mmol) of DPD which had been pumped down to remove all volatile components was added to yield a mixture containing a lot of undissolved bicyclo[2.2.2]octa-5,7-diene-2,3-thiocarbonate. The flask was sealed and the reaction mixture was heated at 40 °C for 5 days. The flask was vented periodically to allow CO 2 formed by the reaction to escape.
  • 5-octylbicyclo[2.2.2]octa-5,7-diene-2,3-dimethylacetal (1.57 g, 5.43 mmol) and pyridinium /7-toluene sulfonate (0.3 g, 1.1 mmol) were dissolved in 100 mL of methanol and heated to 60 °C in an open flask for 3 days. Methanol was removed under reduced pressure and the product purified by flash column chromatography on silica gel (50% ethyl acetate/hexane). Removal of solvent under vacuum yielded 1 g of 5-octylbicyclo[2.2.2]octa-5,7-diene- 2,3-diol (4 mmol, 74%) as a colorless liquid.
  • Octyltrifluoro PNV Reacted 70.1 mg of 5-octyl-l,8-dihydro-l,8-etheno- 3,4,6-trifluoronaphthalene, 3.7 mg of Mo metathesis initiator, 7.8 ⁇ L of HFB, in 0.6 g of C 6 D 6 for 1.5 hours at room temperature resulting in a 99% yield of the corresponding precursor polymer.
  • Polyphenylenevinylene sodium dicarboxylate The sodium salt was prepared by dissolving polyphenylenevinylene anhydride in 0.2 N aqueous
  • Trifluoromethylperfluorooctyl PPV Reacted 106.9 mg of 2,3-bis(2- ethylhexyl)bicyclo[2.2.2]octa-2,5,7-triene-2,3-dicarboxylate, 3.5 mg of Mo metathesis initiator, 7.8 ⁇ L of HFB, in 0.9 g C 6 F 6 /10 drops C 6 D 6 overnight resulting in a 90% yield of the corresponding precursor polymer. 18 mg of this unaromatized polymer was reacted with 16 mg of DDQ in 1.2 mL C 6 F 6 for 3 days at 120°C. This produced a polymer that contained ⁇ 5% unaromatized units.
  • the red-orange thin films of polymer undecyl PNV were obtained by spin-coating their saturated chloroform solution on glass slides. In a dry box, when the thin films were immersed into a glass dish containing a solution of nitrosonium tetrafluoroborate ( « 300 - 400 mg) in acetonitrile (30 mL), the red-orange films immediately turned dark green. After 10 seconds the films were removed from the dopant solution and rinsed with acetonitrile. The doped films were dried under vacuum. The thickness of the films was ca. 500 - 2000 nm.
  • Conductivity was measured with a standard four-point probe using a Princeton Applied Research (PAR) model 173 potentiostat, and a PAR model 175 universal programmer. Thickness of thin films was measured with a Sloan Dektak 3030 Profilingmeter. Conductivities were calculated using the equation:
  • a is the conductivity
  • d is the film thickness
  • i is current
  • V is potential
  • Undecyl-PNV/Octyltrifluoro-PNV Block Copolymer Reacted 68.5 mg of undecylbenzobarrelene, 3.9 mg of Mo metathesis initiator, 7.8 ⁇ L of HFB, 4 ⁇ L of THF in 0.6 g of C 6 D 6 for 4.5 hours. Then added 73.1 mg of octyltrifluorobenzobarrelene dissolved in 10 drops of C 6 D 6 and let the reaction proceed for 3 days. The corresponding precursor was made in 91% yield.
  • Undecyl-P ⁇ V/ Octyltrichloro-P ⁇ V Block Copolymer Reacted 66.2 mg of undecylbenzobarrelene, 3.5 mg of Mo metathesis initiator, 6.9 ⁇ L of HFB,
  • Undecyl-P ⁇ V/di-t-butylester-PPV Block Copolymer Reacted 67.7 mg of undecylbenzobarrelene, 3.7 mg of Mo metathesis initiator, 7.8 ⁇ L of HFB, 20 ⁇ L of THF in 0.5 g of C 6 D 6 for 21 hours. Then added 67.2 mg of di-t-butyl ester barrelene dissolved in 10 drops of C 6 D 6 and let the reaction proceed for
  • Undecyl-PNV/di-t-butylester-PPV Random Copolymer Reacted 67.1 mg of undecylbenzobarrelene, 66.2 mg of di-t-butyl ester barrelene, 3.6 mg of Mo metathesis initiator, 7.8 ⁇ L of HFB and 20 ⁇ L of THF in 0.5 g of C 6 D 6 for 18 hours to yield 90% of the corresponding random polymer precursor.
  • Octyltrifluoro-P ⁇ V/Bistrifluoromethyl-PPV Block Copolymer Reacted 83.9 mg of octyltrifluorobenzobarrelene, 6.8 mg of Mo metathesis initiator,

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Abstract

La présente invention se rapporte à une nouvelle classe d'homopolymères électroluminescents ('EL'), de copolymères statistiques et de copolymères séquencés qui comportent des motifs répétitifs de (para-phénylène-vinylène) ('PV') substitués et/ou de (1,4-naphthalène-vinylène)('NV') substitués, ainsi qu'à des procédés de fabrication de ces polymères. On synthétise généralement les homopolymères et copolymères de cette invention en procédant à des réactions de polymérisation par décyclisation ('ROMP' ring opening polymerization) dans lesquelles on met en contact un initiateur de métathèse avec un benzobarrélène substitué ou un barrélène substitué correspondant. L'invention se rapporte également à de nouveaux procédés de synthèse de benzobarrélènes et de barrélènes substitués.
PCT/US1998/007957 1997-04-17 1998-04-16 Poly(phenylene-vinylene)s et poly(naphthalene-vinylene)s substitues WO1998046652A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001007502A2 (fr) * 1999-07-24 2001-02-01 Cambridge Display Technology Limited Procede de polymerisation
EP1267359A2 (fr) * 2001-06-15 2002-12-18 Toyoda Gosei Co., Ltd. Polymère électroconductif composite et procédé pour la préparation d'un composé aromatique
EP1273569A1 (fr) * 2001-06-15 2003-01-08 Toyoda Gosei Co., Ltd. Polymère conducteur auto-dopé, monomère pour sa préparation, et procédé pour sa préparation
EP1398340A1 (fr) * 2001-04-27 2004-03-17 Sumitomo Chemical Company, Limited Copolymere bloc et element luminescent polymere
EP1497393A1 (fr) * 2002-04-19 2005-01-19 3M Innovative Properties Company Matieres electroluminescentes et procedes de production et d'utilisation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5247190A (en) * 1989-04-20 1993-09-21 Cambridge Research And Innovation Limited Electroluminescent devices
US5753757A (en) * 1996-11-13 1998-05-19 Xerox Corporation Electroluminescent polymer compositions and processes thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5247190A (en) * 1989-04-20 1993-09-21 Cambridge Research And Innovation Limited Electroluminescent devices
US5753757A (en) * 1996-11-13 1998-05-19 Xerox Corporation Electroluminescent polymer compositions and processes thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001007502A2 (fr) * 1999-07-24 2001-02-01 Cambridge Display Technology Limited Procede de polymerisation
WO2001007502A3 (fr) * 1999-07-24 2001-03-22 Cambridge Display Tech Ltd Procede de polymerisation
US7005484B1 (en) 1999-07-24 2006-02-28 Cambridge Display Technology Limited Polymerization method
EP1398340A1 (fr) * 2001-04-27 2004-03-17 Sumitomo Chemical Company, Limited Copolymere bloc et element luminescent polymere
EP1398340A4 (fr) * 2001-04-27 2008-07-30 Sumitomo Chemical Co Copolymere bloc et element luminescent polymere
EP2333006A1 (fr) * 2001-04-27 2011-06-15 Sumitomo Chemical Company, Limited Copolymere bloc et élément luminescent polymère
EP1267359A2 (fr) * 2001-06-15 2002-12-18 Toyoda Gosei Co., Ltd. Polymère électroconductif composite et procédé pour la préparation d'un composé aromatique
EP1273569A1 (fr) * 2001-06-15 2003-01-08 Toyoda Gosei Co., Ltd. Polymère conducteur auto-dopé, monomère pour sa préparation, et procédé pour sa préparation
US6660183B2 (en) 2001-06-15 2003-12-09 Toyoda Gosei Co., Ltd. Self-doped conductive polymer, monomer for synthesizing self-doped conductive polymer, and processes of producing the same
EP1267359A3 (fr) * 2001-06-15 2004-08-25 Toyoda Gosei Co., Ltd. Polymère électroconductif composite et procédé pour la préparation d'un composé aromatique
EP1497393A1 (fr) * 2002-04-19 2005-01-19 3M Innovative Properties Company Matieres electroluminescentes et procedes de production et d'utilisation
US7442421B2 (en) 2002-04-19 2008-10-28 3M Innovative Properties Company Electroluminescent materials and methods of manufacture and use

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