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WO2013066317A1 - Polymères cationiques comprenant des groupes de sel de phosphonium - Google Patents

Polymères cationiques comprenant des groupes de sel de phosphonium Download PDF

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Publication number
WO2013066317A1
WO2013066317A1 PCT/US2011/058751 US2011058751W WO2013066317A1 WO 2013066317 A1 WO2013066317 A1 WO 2013066317A1 US 2011058751 W US2011058751 W US 2011058751W WO 2013066317 A1 WO2013066317 A1 WO 2013066317A1
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Prior art keywords
polymer
substituted
group
phosphonium salt
layer
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Zhang-Lin Zhou
Lihua Zhao
Sity Lam
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Hewlett Packard Development Co LP
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Hewlett Packard Development Co LP
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Priority to PCT/US2011/058751 priority Critical patent/WO2013066317A1/fr
Priority to TW101139061A priority patent/TWI437020B/zh
Publication of WO2013066317A1 publication Critical patent/WO2013066317A1/fr
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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
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/147—Side-chains with other heteroatoms in the side-chain
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/96—Applications coating of particles

Definitions

  • Advanced organic and polymeric electronic devices such as thin film transistors, polymer light emitting devices, and organic photovoltaic devices, frequently consist of a stack of organic and polymeric thin layers, each one performing a specific function that may improve the performance of the overall device or may help to achieve specific desired functionalities in devices.
  • creation of these devices may require placing nanoscale features at desired sites within a thin film stack.
  • layered polymer devices such structures may be formed from a polymer solution by first spin-casting, printing, or otherwise forming thin layers of polymer on top of each other and then, removing the solvent.
  • solvent from freshly deposited films may dissolve or partially dissolve the underlying layer, resulting in loss of the desired device structure and corresponding functionality. Additionally, solvent removal may cause the diffusion of active molecules from one layer into the underlying layer, resulting in an undesirable redistribution of nanoscale features within the polymer. Therefore, researchers continue to develop different materials with different solubilities in different polarities of solvents for forming improved, layered polymer devices.
  • FIG. 1 is a schematic diagram of an example reaction scheme for synthesizing a cationic homo-polymer including phosphonium salt groups.
  • FIG. 2 is a schematic diagram of an example reaction scheme for synthesizing a cationic alternate co-polymer including phosphonium salt groups and a benzene moiety with semiconducting properties.
  • FIG. 3 is a schematic diagram of an example reaction scheme for synthesizing a boron substituted benzene moiety with semiconducting properties and preparing such moiety to be used in the synthesis of a cationic alternate co-polymer including phosphonium salt groups or a cationic random co-polymer including phosphonium salt groups.
  • FIG. 4 is a schematic diagram of an example reaction scheme for synthesizing a cationic random co-polymer including one or more phosphonium salt groups and a benzene moiety with semiconducting properties.
  • Conductive polymers may be used as light emitting, hole and electron transporting materials in light emitting diodes.
  • such materials may be used to form different types of multilayered polymer devices, including electrical devices such as photovoltaic solar cells and organic photoconductors, among other devices.
  • the hole and electron transporting properties of the conductive polymer used facilitates the transfer of electricity from one end of the device to the other end of the device.
  • a deposited layer of polymer may be dissolved during the spin-casting of subsequent layers above such deposited layer.
  • dip coating, inkjet printing, and roll-to-roll processes are other possible deposition methods that can be used to form layered structures; however, in such examples, dissolving of the underlying polymer layer when forming additional layers may also occur.
  • conjugated polymers that are soluble in water or other polar solvents have been studied.
  • the properties of these conjugated polymers may be modified through a number of different mechanisms.
  • the solubility of conjugated polymers may be affected by flexible side 82828091
  • ionic conjugated polymers a class of polyelectrolytes that includes both polyions and electronically active, conjugated backbones.
  • Such ionic conjugated polymers may have applications in the fabrication of photonic devices as well as in the development of highly efficient biosensors.
  • the ionic conjugated polymers used may have high molecular weights, may have high photoluminescence (PL) efficiencies, and may include different types of ionic side groups.
  • ionic polymers soluble in polar solvents may be synthesized using homo-polymerization, co-polymerization, or polymer analogous reactions such as transition metal catalyzed coupling reactions.
  • the water-solubility of semiconducting conjugated polymers has been demonstrated in 3-substituted polythiophenes, poly(para-phenylene vinylene) (PPV) based polymers, and poly(para-phenylene) (PPP) based polymers.
  • these ionic conjugated polymers and other existing ionic conjugated polymers are polyanions that contain either sulfonate or carboxylate functionalities.
  • Such devices are limited in their capabilities as they are water soluble but not alcohol soluble.
  • polymers that are water soluble may be hydroscopic and may be difficult to incorporate into polymer devices, as exposure to water may cause the physical characteristics of the polymer to change.
  • alcohol solubility may be desired as it may improve wettability characteristics in the underlying polymer layer, improving the structure of the multilayer polymer device formed.
  • the synthesis of certain ammonium-functionalized polymers has been studied.
  • the polymers studied were limited to moieties of poly(p-phenylene) (PPPs), which may have undesirable qualities such as low molecular weight resulting in low conductivity in the polymer and which may require complex and expensive processes during synthesis in order to achieve purification.
  • PPPs poly(p-phenylene)
  • Synthesis of certain ammonium-functionalized, fluorene based co- polymers for water and alcohol soluble electron transport materials has also been studied.
  • solubility of such polymers may be limited in water and alcohol, and as such, there may be a limited ability to conduct device fabrication in such solvents.
  • solvents that are highly polar and have high boiling points such as dimethyl sulfoxide (DMSO) or dimethylformamide (DMF) may be required.
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • these ammonium functionalized polymers may be hydroscopic and difficult to handle in the air, resulting in the need for expensive processes in order to use these polymers.
  • a new alcohol-soluble cationic polymer including phosphonium salt terminal groups is disclosed.
  • a method for producing the same is also disclosed.
  • the cationic polymers disclosed herein have sterically hindered, phosphonium salt functional groups.
  • the presence of such phosphonium salt functional groups may allow the overall cationic polymer to be soluble in polar solvents such as methanol, ethanol, iso-propanol or any other polar solvent due to the further inclusion of alkyl substituents and polar cationic groups on the phosphonium salt groups.
  • Solubility in polar solvents may facilitate the use of these cationic polymers in building multilayer devices, such as organic light emitting diodes (OLEDs) or photovoltaic and organic photoconductors, because the device may be built by alternating between layers deposited in polar solvent and layers deposited in non-polar solvent.
  • polar solvents such as alcohols
  • Such an alternating process may minimize damage to underlying polymer 82828091
  • the alkyl substituents may be assembled in a three-dimensional space such that more free volume may be created, resulting in better film morphology.
  • the polymers disclosed herein may be used to construct active layers in organic light-emitting diodes, wherein such active layers may be constructed using any suitable method, including layer-by-layer self-assembly, spin coating, dip coating or roll-to-roll processes, among other processes.
  • active layers may act as a buffer layer or emissive layer for emitting light in fabricated organic light emitting diodes (LEDs).
  • LEDs organic light emitting diodes
  • such active layers may be capable of hole transport or electron transport.
  • such active layers may be highly sensitive, fluorescent sensory materials used in living bodies to detect various biological species.
  • An example general structure for a cationic polymer including phosphonium salt groups may be:
  • R 1 t R2, and R3 are each independently selected from the group consisting of alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, C(0)OR4, N(R 4 )(R 5 ), C(0)N( 4)(R 5 ), F, CI, Br, N0 2 , CN, acyls, carboxylate, and hydroxyl, wherein "C” is carbon, ⁇ " is oxygen, “N” is nitrogen, “F” is fluorine, "CI” is chlorine, "Br” is bromine; wherein R 4 and R 5 are each independently selected from the group consisting of hydrogen, alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, C(0)OR , 82828091
  • X represents any leaving group, such as a halogen (e.g. chlorine, bromine or iodine), tetraphenylborate, trifluoroborate, methanesulfonate, p- toluenesulfonate or other like groups; wherein ⁇ " is any benzene moiety with semiconducting properties; and wherein n, mi , rri2, and 1TI3 are any integer.
  • halogen e.g. chlorine, bromine or iodine
  • n may be any integer between 1 and 30, and mi , and 1 ⁇ 3 may independently be any integer between 0 and 10,000, wherein at least one of mi , rri2, and m 3 is not 0.
  • one R group in Ri, R2, R3. R4, and R5 may be the same or may be different as another R group in Ri, R2, R3, R4, and R 5 .
  • one m group in m ⁇ m 2 , and m 3 may be the same or may be different as another m group in mi, rri2, and m3, provided that at least one of mi , m2, and m3 is not 0.
  • Y or the semiconducting benzene moiety may be substituted fluorene moieties such as:
  • substituted carbazole moieties such as:
  • substituted benzothiadiazole moieties such as:
  • substituted phenothiazine moieties such as: 82828091
  • substituted 2,5-bis(p-phenylene)-1 ,3,4-oxadiazole moieties such as:
  • Y may be any benzene moiety with semiconducting properties.
  • the cationic polymer including phosphonium salt groups disclosed herein may be a homo-polyme ("cationic homo-polymer"). In other examples, the cationic polymer including phosphonium salt groups disclosed herein may be an alternate co-polymer further including a benzene moiety with semiconducting properties ("cationic alternate co-polymer”). Finally, in yet other examples, the cationic polymer including phosphonium salt groups disclosed herein may be a random co-polymer further including a benzene moiety with semiconducting properties ("cationic random copolymer").
  • An example general structure for a cationic homo-polymer, wherein mi and rri 2 are 0 in the example cationic polymer including phosphium salt groups disclosed above, may be: 82828091
  • Ri, R 2 , and R3 are each independently selected from the group consisting of alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, 0( ⁇ ) ⁇ 3 ⁇ 4, N(R 4 )(R 5 ), C(0)N(R4)(R 5 ), F, CI, Br, N0 2 , CN, acyls, carboxylate, and hydroxyl, wherein "C” is carbon, “O” is oxygen, “N” is nitrogen, “F” is fluorine, "CI” is chlorine, "Br” is bromine; wherein R4 and R5 are each independently selected from the group consisting of hydrogen, alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, C(0)OR4, N(R 4 )(R 5
  • n may be any integer between 1 and 30, and 1TI3 may be any integer between 1 and 10,000.
  • one R group in Rn R 2) R3, R 4 , and R5 may be the same or may be different as another R group in i, R 2 , R3, R 4 , and R5.
  • FIG. 1 is a schematic diagram of an example reaction scheme for synthesizing a cationic homo-polymer including phosphonium salt groups 114.
  • the starting material for the reaction may be commercially available 2,7-dibromofluorene 102.
  • 2,7- dibromofluorene 102 may be formed from commercially available fluorene.
  • other less reactive halogens such as chlorine, fluorine or iodine, may be used in place of bromine, and the bromine or other halogens may be in alternative positions on the fluorene. 82828091
  • a halogen substituted fluorene may be formed.
  • such substituted fluorene may be formed by adding liquid bromine or any other liquid halogen drop by drop, under ice-bar or other apparatuses capable of cooling the temperature down to approximately 0°C, to a solution of fluorene and chloroform (CHCI3) or any other non-reactive solvent.
  • the reaction mixture may be stirred using any suitable apparatus for 24 hours or until the product (2,7-dibromofluorene) is formed.
  • a base solution with a pH greater than 9, such as a 50% sodium hydroxide (NaOH) aqueous solution, may be added to the solution in order to remove the excess bromine or excess halogen.
  • the product may be separated and dried.
  • the organic layer (or product) may be separated using any suitable apparatus and washed with brine and dried over anhydrous sodium sulfate (Na2S0 4 ) or other drying agents.
  • Na2S0 4 anhydrous sodium sulfate
  • the chloroform or other solvent may be evaporated or removed under vacuum.
  • the product may be purified using recrystallization from chloroform or flash chromatography in order to yield purified 2,7-dibromofluorene 102, which in some examples, may be a white solid.
  • 2,7-dibromofluorene 102 or any other halogenated fluorene may undergo nucleophilic substitution in order to form a fluorene intermediate including alkyl groups 106.
  • a mixture of 2,7-dibromofluorene 102 or other halogen substituted fluorene, a halogen substituted alkyl 104, and a non-reactive solvent able to dissolve the halogen substituted alkyl 104 may be stirred at a temperature between 70°C to 150°C (depending on the solvent) under nitrogen gas or any other inert gas until the fluorene intermediate with alkyl groups 106 is formed.
  • suitable solvents may include, but are not limited to, acetonitrile and tetrabutylammonium bromide in an aqueous sodium hydroxide solution.
  • the alkyl substituted fluorene intermediate 106 may be separated and dried.
  • the reaction mixture may be 82828091
  • the organic layer may be extracted and washed with brine and water or with any other like compounds.
  • the product (the alkyl substituted fluorene intermediate 106) may be dried over anhydrous sodium sulfate or other suitable drying agents.
  • the solvent and reactant may be evaporated or removed under vacuum.
  • the desired alkyl substituted fluorene intermediate 106 may be purified. In one example, such purification is conducted by chromatography with petroleum ether or other hexanes as the eluent.
  • a salt formation reaction may be used in order to introduce phosphonium salt groups, P(n-C4Hg)3, to the alkyl substituted fluorene intermediate 106.
  • the intermediate product 106 may be mixed with P(n-C 4 Hg)3 or any other phosphonium salt 108 in dimethylformamide (DMF) or other non-reactive solvent capable of dissolving the phosphonium salt 108.
  • DMF dimethylformamide
  • such a mixture may be heated to reflux in order to achieve salt formation.
  • the desired fluorene intermediate including phosphonium salt groups 110 may be separated and purified. In some examples, excess solvent may be removed under reduced pressure, and the residue may be purified by crystallization with acetone and ethyl acetate or any other like suitable solvents. In other examples, other purification processes may be used.
  • the cationic homo-polymer 114 may be prepared by a transition metal catalyzed coupling reaction.
  • a solution capable of catalyzing the polymerization of the fluorene intermediate including one or more phosphonium salt groups 110 may first be formed.
  • a suitable catalyst, one or more non-reactive solvents, and a ligand for facilitating the dissolving of the catalyst in the solvent may be mixed 112.
  • suitable catalysts include nickel-based catalysts such as bis(cyclooctadiene)nickel(0) (Ni(COD)2).
  • Ni(COD)2 bis(cyclooctadiene)nickel(0)
  • suitable ligands include 2,2'-dipyridine or cyclooctadiene
  • suitable solvents include dimethylformamide (DMF) or toluene.
  • the mixture 112 may be prepared by adding all of the components and then, heating the mixture 112 to 80°C for half an hour or at a temperature and for a length of time such that the polymerization reaction may take place.
  • the intermediate product including phosphonium salt 110 may be polymerized.
  • such intermediate product 110 in a non-reactive solvent capable of dissolving the intermediate product 110 may be combined with the prepared mixture 112.
  • the combined mixture may be stirred at 80°C for 4 days or at a temperature and for a length of time such that the polymerization reaction may take place.
  • the desired homo-polymer product 114 may be separated and dried.
  • the homo-polymer product 114 may first be poured into chloroform or other like solvents, such as dichloroform, and then, may be washed with dilute hydrochloric acid or other acids followed by a mixture of brine and water in order to remove impurities.
  • the separated organic layer (the desired homo-polymer product 114) may be dried over magnesium sulfate or any other like suitable drying agent and the excess solvent may be evaporated using any suitable process.
  • the polymer product 114 may be purified. In one example, precipitation from methanol, any methanol and hexane mixtures, or methanol and ethyl acetate mixtures may be used.
  • An example general structure for a cationic alternate co-polymer, or wherein m 2 and rri3 are 1 in the general structure for a cationic polymer disclosed above, may be:
  • Ri , R2, and 3 are each independently selected from the group consisting of alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, C(0)OR4, N(R 4 )(R 5 ), C(0)N(R4)(R 5 ), F, CI, Br, N0 2 , CN, acyls, carboxylate, and hydroxyl; wherein R4 and R 5 are each independently selected from the group consisting of hydrogen, alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, 0( ⁇ ) ⁇ 3 ⁇ 4, N(R 4 )(Rs), C(0)N(R 4 )(R 5 ), F, CI, Br, NO2, CN, acyls, carboxylate, and hydroxyl; wherein "X
  • n may be any integer between 1 and 30, and mi may be any integer between 1 and 5000.
  • one R group in Ri, R2, R3, R 4 , and R 5 may be the same or may be different as another R group in R 1 ( R2, R3, R 4 , and R 5 .
  • FIG. 2 is a schematic diagram of an example reaction scheme for synthesizing a cationic alternate co-polymer including phosphonium salt groups and a benzene moiety with semiconducting properties 206, as discussed above.
  • a halogenated fluorene intermediate including one or more phosphonium salt groups 110 may first be formed using the method described above. Then, the fluorene intermediate 110 may be reacted with a boron substituted benzene moiety with semiconducting properties (seen in FIG. 2 as the Y group) 202 by boron chemistry in order to form an alternate copolymer 206. It should be noted that while a bis(pinacolato)borane moiety of the benzene moiety with semiconducting properties 202 is specifically illustrated in FIG. 2, any boron substituted benzene moiety with semiconducting properties may be used.
  • the halogenated fluorene intermediate including phosphonium salts 110 and the boron substituted benzene moiety with semiconductive properties 202 may be mixed with tetrakis (triphenylphosphine) 82828091
  • the mixture may be degassed using nitrogen gas or other inert gas in order to remove oxygen.
  • tetrahydrofuran (THF) and deionized water or any other non-protonated, non-reactive solvents capable of dissolving the compounds 110 and 202 may be added to the mixture, such as by using a syringe.
  • such syringe may be used to transfer solvent without absorbing oxygen. Then, in such an example, the resulting reaction mixture may be stirred under nitrogen purge at 85°C for 48 hours or at a temperature and for a length of time until the co-polymerization reaction takes place. Afterwards, in some examples, the co-polymer product 206 may be separated and purified. In one example, separation is achieved by first adding water and chloroform, dichloromethane, or other like solvents to the reaction mixture.
  • the separated organic layer (the co-polymer product 206) may be washed with brine and water, dried over anhydrous sodium sulfate or other suitable drying agents, and the excess solvent may be removed or evaporated under reduced pressure.
  • the co-polymer product 206 may be purified. In one example, purification may be achieved by mixing the product 206 with petroleum ether or other solvents such as hexanes or ethyl acetate to yield a precipitate, dissolving the precipitate in a non-reactive solvent, and then, re- precipitating the dissolved precipitate in petroleum ether or other suitable solvents such as hexanes or ethyl acetate.
  • impurities may be removed by placing the co-polymer product 206 in a Soxhlet apparatus and extracting it with refluxed ethyl acetate or with any other non-reactive solvent for 48 hours or for a length of time until substantially all of the small molecules and catalyst residue are removed. In other examples, other suitable procedures may be used. Finally, in some examples, the purified co-polymer product 206 may be dried using any suitable process to yield a solid, wherein 82828091
  • the precipitate may be dried by placing it in a vacuum oven set at a temperature between 25°C to 80°C.
  • the boron substituted benzene moiety with semiconducting properties 202 may be commercially available. In other examples, it may be synthesized.
  • FIG. 3 is a schematic diagram of an example reaction scheme for synthesizing a boron substituted benzene moiety with semiconducting properties and preparing such moiety to be used in the synthesis of a cationic alternate or cationic random co-polymer including phosphonium salt groups. It should be understood that FIG. 3 is one example of how a specific boron substituted fluorene moiety with semiconducting properties may be prepared. In other examples, any other boron substituted benzene moieties may be used and prepared using substantially similar methods.
  • an alkyl substituted fluorene 106 (which may be prepared in the same way described above) may undergo nucleophilic substitution with sodium azide (NaN3) 302 or any other suitable azide, such as potassium azide (KN3) or cesium azide (CSN3), in dimethyl sulfoxide (DMSO) or other non-reactive solvent capable of dissolving the sodium azide 302 or other azide.
  • NaN3 sodium azide
  • KN3 potassium azide
  • CSN3 cesium azide
  • DMSO dimethyl sulfoxide
  • the azide substituted intermediate 304 may be separated and purified.
  • the reaction mixture may be extracted with diethyl ether, hexanes, or ethyl acetate and water.
  • reaction mixture may be separated, washed with water and brine, and dried over anhydrous sodium sulfate or other drying agents. Then, in one example, excess solvent may be removed under reduced pressure using any suitable processes such as a rotatory evaporator. Finally, purification may be achieved using chromatography with petroleum ether or any other suitable eluents or by any other suitable processes such as recrystallization.
  • the azide functional groups of the substituted intermediate 304 may be converted into protected amine moieties.
  • triphenylphosphine (PPh 3 ) or any trialkyl phosphines 306 such as tributyl phosphine or trimethylphosphine may be added to a solution of the intermediate product 304 in tetrahydrofuran (THF) and water or in any other suitable non-reactive solvent. Then, in some examples, the reaction mixture may be stirred at ambient temperatures for 12 hours or at a temperature and for a length of time until the protected amine moieties 308 are formed.
  • THF tetrahydrofuran
  • the solvent may be removed under vacuum or by any other suitable processes, and di-t-butyl dicarbonate in THF or other non-reactive solvents such as acetonitrile or dimethyl formamide may be added to the azide substituted intermediate 304 in order to protect the ends of the alkyl side chains. In one example, such ends are protected in order to prevent them fromreacting.
  • the reactants may be stirred at ambient temperatures for 4 hours or at a temperature and for a length of time until the ends of the alkyl side groups are protected.
  • the protected intermediate product 308 may then be separated and purified.
  • the solvent may be removed using any suitable methods and the intermediate product 308 may be purified using any suitable process such as silica gel column chromatography with petroleum ether, ethyl acetate, or any other suitable solvents such as hexanes, chloroform or dichloromethane as the eluent.
  • any suitable process such as silica gel column chromatography with petroleum ether, ethyl acetate, or any other suitable solvents such as hexanes, chloroform or dichloromethane as the eluent.
  • the protected intermediate product 308 may undergo aromatic substitution to form a boron substituted intermediate 314. It should be noted that while bis(pinacolato)diborane 312 is depicted in FIG. 3, any boron compound may be substituted onto the protected intermediate product 308.
  • the boron substituted product 314 may be separated and purified.
  • the solvent may be removed using any suitable methods and dried over anhydrous sodium sulfate or any other suitable drying chemical.
  • the boron substituted product 314 may be purified using any suitable process such as column chromatography using petroleum ether, ethyl acetate or any other suitable eluent.
  • An example general structure for a cationic random co-polymer, or wherein mi is 0 in the example cationic polymer including phosphonium salt groups disclosed above, may be:
  • Ri , R 2 , and R3 are each independently selected from the group consisting of alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, C(0)OR4, N(R 4 )(R 5 ), C(0)N(R 4 )(R 5 ), F, CI, Br, N0 2 , CN, acyls, carboxylate, and hydroxyl; wherein R 4 and R5 are each independently selected from the group consisting of hydrogen, alkyls, alkenyls, alkynyls, aryls, alkoxies, phenoxies, thioalkyls, thioaryls, C(0)0R4, N(R )(R 5 ), C(0)N(R 4 )(R 5 ), F, CI, Br, N0 2 , CN, acyls, carboxylate, and hydroxyl;
  • n, m 2 , and ⁇ 3 are each independently any integer.
  • n may be any integer between 1 and 30, and m 2 and rri3 may independently be any integer between 1 and 5000.
  • one R group in R ( R 2 , R 3 , R4, and R 5 may be the same or may be different as another R group in R ⁇ R 2 , R3, R 4 . and R 5 . 82828091
  • FIG. 4 is a schematic diagram of an example reaction scheme for synthesizing a cationic random co-polymer including phosphonium salt groups and a benzene substituted moiety 406, as discussed above.
  • the synthesis of the random co-polymer 406, as depicted in FIG. 4 may be achieved using substantially the same method as was used to achieve synthesis of the alternate co-polymer 206 described above in FIG. 2.
  • the only difference may be that the initial mixture including the halogenated fluorene compound including phosphonium salts 110 and the boron substituted benzene moiety with semiconducting properties 202 may further include a halogenated benzene moiety with semiconducting properties 402.
  • such halogenated benzene moiety with semiconducting properties 402 may include alkyl side chains that have been protected according to the method described in FIG. 3, an example of which is the protected intermediate product 314.
  • the halogen substituted benzene moiety 402 may be added in order to control the percentage of phosphonium salt desired in the final co-polymer. For example, if the desired percentage of phosphonium salt is less than 50% by weight, both the halogen substituted benzene moieties and the boron substituted benzene moieties may be added; if the desired percentage of phosphonium salt is more than 50% by weight, only the boron substituted benzene moieties may be added.
  • Example method for the synthesis of the fluorene intermediate 110 including phosphonium salt groups used in the synthesis of the cationic homo-polymer, alternate cationic co-polvmer, and random cationic co-polvmer. as described herein.
  • a halogen substituted fluorene moiety was first formed.
  • a solution of fluorene (30 g, 0.18 mol) and chloroform, CHCI 3 , (250 mL) liquid bromine (72 g, 0.45 mol) 5 was added drop by drop under ice-bar. Afterwards, the reaction mixture was stirred for 24 hours. Next, a 50% NaOH aqueous solution was added to remove excess bromine. The separated organic layer (the desired 2,7- dibromofluorene) was washed with brine and dried over anhydrous a 2 S0 4 , while the chloroform was evaporated under vacuum. Finally, the crude product i o (the halogen substituted fluorene moiety) was purified by recrystallization from chloroform to yield a white solid.
  • a halogenated alkyl substituted 15 fluorene moiety (2,7-dibromo-9,9-bis(6'-bromopropyl)fluorene) was formed.
  • a mixture of 2,7-dibromofluorene (4.86 g, 15 mmol), 1 ,4-dibromopropane (30 mL), tetrabutylammonium bromine (0.1 g), and 50% NaOH aqueous sodium solution (30 mL) was stirred for 12 hours at 70°C under nitrogen gas. After diluting the reaction mixture with chloroform, the organic layer was washed 0 with brine and water.
  • the halogen substituted fluorene moiety including phosphonium salt groups is polymerized to form a homo-polymer.
  • a solution of Ni(COD) 2 (0.85 g, 3 mmol), 2,2'-dipyridine (0.35 g, 2.4 mmol), cyclooctadiene (0.25 g, 2.4 mmol), and DMF (5 mL) is heated to 80°C for half an hour.
  • the product obtained (the homo-polymer including phosphonium salt groups) is purified by precipitation from methanol.
  • a halogenated fluorene moiety including phosphonium salt groups was reacted with a boron substituted benzene moiety to yield an alternate co-polymer including a fluorene moiety (P1 ).
  • the halogenated fluorene moiety including phosphonium salt groups 500 mg, 0.52 mmol
  • the boron substituted fluorene moiety (302 mg, 0.52 mmol)
  • Pd(PPh 3 ) 4 (12 mg, 0.02 mmol)
  • 0.83 g of K 2 C0 3 were added into a two- neck flask. The mixture was degassed by nitrogen gas and then, degassed by THF (8 mL).
  • Reaction Scheme 6 a halogenated fluorene moiety including phosphonium salt groups was reacted with a boron substituted fluorene moiety to yield an alternate co-polymer including a fluorene moiety (P2), a yellow solid.
  • Reaction Scheme 6 progressed in substantially the same manner as Reaction Scheme 5, except that, initially, the following were added into the two-neck flask: a halogenated fluorene moiety including phosphonium salt groups (500 mg, 0.52 mmol), a boron substituted fluorene moiety (334 mg, 0.52 mmol), Pd(PPh 3 ) 4 (12 mg, 0.02 mmol), and K 2 C0 3 (0.83 g). 82828091
  • Reaction Scheme 7 a halogenated fluorene moiety including phosphonium salt groups was reacted with a boron substituted benzene moiety to yield an alternate co-polymer including a benzene moiety (P3), a yellow solid.
  • Reaction Scheme 7 progressed in substantially the same manner as Reaction Scheme 5, except that initially the following were added into the two-neck flask: a halogenated fluorene moiety including phosphonium salt groups (500 mg, 0.52 mmol), a boron substituted benzene moiety (172 mg, 0.52 mmol), Pd(PPh 3 ) 4 (12 mg, 0.02 mmol), and K 2 CO 3 (0.83 g).
  • Reaction Scheme 8 a halogenated fluorene moiety including phosphonium salt groups was reacted with a boron substituted fluorene moiety to yield an alternate co-polymer including a fluorene moiety (P4), a yellow solid.
  • Reaction Scheme 8 progressed in substantially the same manner as 82828091
  • Reaction Scheme 5 except that initially the following were added into the two- neck flask: a halogenated fluorene moiety including phosphonium salt groups (500 mg, 0.52 mmol), a boron substituted fluorene moiety (424 mg, 0.52 mmol), Pd(PPh 3 ) 4 (12 mg, 0.02 mmol), and 0.83 g of K 2 C0 3 .
  • Reaction Scheme 10 a halogenated fluorene moiety including phosphonium salt groups was reacted with a boron substituted fluorene moiety to yield an alternate co-polymer including a fluorene moiety (P6).
  • Reaction Scheme 10 progressed in substantially the same manner as Reaction Scheme 5, except that initially the following were added into the two-neck flask: a i o halogenated fluorene moiety including phosphonium salt groups (500 mg, 0.52 mmol), a boron substituted fluorene moiety (350 mg, 0.52 mmol), Pd(PP i3) 4 (12 mg, 0.02 mmol), and K 2 C0 3 (0.83 g).
  • Table 1 illustrates the cyclic voltammagrams of films of various alternate co-polymers coated on carbon electrodes in a 0.1 mol/L (M) hexafluorophosphate (Bu 4 NPF6) and acetonitrile (CH 3 CN) solution, wherein E ox is the oxidation potential for the polymerization reaction, E re d is the reduction potential for the polymerization reaction, HOMO is the highest occupied molecular orbital, LUMO is the lowest unoccupied molecular orbital, and E gap is the gap potential.
  • M hexafluorophosphate
  • CH 3 CN acetonitrile
  • the number average molecular weight (M n ), the average molecular weights (M w ), and polydispersity (PDI) of the alternate co-polymers P1 , P2, P3, P4, and P5 are listed.
  • M n number average molecular weight
  • M w average molecular weights
  • PDI polydispersity
  • a random co-polymer including phosphonium salt groups and a fluorene moiety is formed.
  • a halogenated fluorene moiety including phosphonium salt groups, a boron substituted fluorene moiety, a halogenated fluorene moiety, Pd(PPh 3 ) 4 (12 mg, 0.02 mmol), and 0.83 g of K2CO3 are added into a two-neck flask.
  • the mixture is degassed by N 2 , degassed by THF (8 ml_), and then, deionized water (4 mL) is injected into the mixture by syringe. Then, the reaction mixture is stirred under nitrogen purge at 85°C for 48 hours. After the mixture is cooled to room temperature, 82828091
  • Reaction Scheme 13 a random co-polymer including phosphonium salt groups and a fluorene moiety (P9) is formed. Reaction Scheme 13 progresses in substantially the same manner as Reaction Scheme 2. 82828091
  • Reaction Scheme 14 a random co-polymer including phosphonium salt groups and a benzene moiety (P10) is formed. Reaction Scheme 14 progresses in substantially the same manner as Reaction Scheme 12.
  • a protected random co-polymer including phosphonium salt groups and a fluorene moiety with tert-Boc-amino capped alkyl groups is made into a random co-polymer including phosphonium salt groups and a fluorene moiety with unprotected alkyl groups (P12).
  • P12 a protected random co-polymer including phosphonium salt groups and a fluorene moiety with tert-Boc-amino capped alkyl groups
  • a 37% HCI solution is added (5 mL). The resulting mixture is stirred for 48 hours at room temperature.
  • Reaction Scheme 17 a random co-polymer including phosphonium salt groups and a fluorene moiety with tert-butyl ester capped alkyl groups (P13) is formed. Reaction Scheme 17 progresses in substantially the same manner as Reaction Scheme 12.
  • a protected random co-polymer including phosphonium salt groups and a fluorene moiety with tert-butyl ester capped alkyl groups is made into a random co-polymer including phosphonium salt groups and a fluorene moiety with free acid capped alkyl groups (P14).
  • P14 a solution of the protected random co-polymer including phosphonium salt 82828091

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  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention concerne un polymère, le polymère ayant la structure générale : R1, R2, et R3 étant chacun indépendamment choisis dans le groupe constitué d'alkyles, alcényles, alcynyles, aryles, alcoxys, phénoxys, thioalkyles, thioaryles, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyles, carboxylate, et hydroxyle ; R4 et R5 étant chacun indépendamment choisis dans le groupe constitué d'hydrogène, alcényles, alcynyles, aryles, alcoxys, phénoxys, thioalkyles, thioaryles, C(O)OR4, N(R4)(R5), C(O)N(R4)(R5), F, Cl, Br, NO2, CN, acyles, carboxylate, et hydroxyle ; X étant un groupe partant quelconque ; Y étant un fragment benzénique ayant des propriétés semi-conductrices ; et n, m1, m2, et m3 étant indépendamment un entier quelconque.
PCT/US2011/058751 2011-11-01 2011-11-01 Polymères cationiques comprenant des groupes de sel de phosphonium Ceased WO2013066317A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5380619A (en) * 1987-06-16 1995-01-10 Agfa-Gevaert, N.V. Polymeric phosphonium mordant and photographic element containing the same
KR20010079343A (ko) * 2001-07-07 2001-08-22 엄제식 플루오렌 중합체 및 이를 포함하는 유기전기발광소자
US20020099157A1 (en) * 1999-09-15 2002-07-25 University Joseph Fourier Monomers, polymers incorporating said monomers and their use in organic electroluminescent devices
WO2010046114A2 (fr) * 2008-10-22 2010-04-29 Eni S.P.A. Copolymères π-conjugués à faible bande interdite contenant des motifs benzotriazole

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5380619A (en) * 1987-06-16 1995-01-10 Agfa-Gevaert, N.V. Polymeric phosphonium mordant and photographic element containing the same
US20020099157A1 (en) * 1999-09-15 2002-07-25 University Joseph Fourier Monomers, polymers incorporating said monomers and their use in organic electroluminescent devices
KR20010079343A (ko) * 2001-07-07 2001-08-22 엄제식 플루오렌 중합체 및 이를 포함하는 유기전기발광소자
WO2010046114A2 (fr) * 2008-10-22 2010-04-29 Eni S.P.A. Copolymères π-conjugués à faible bande interdite contenant des motifs benzotriazole

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