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WO2025000098A1 - Processus modulaire de purification de polymères conjugués - Google Patents

Processus modulaire de purification de polymères conjugués Download PDF

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Publication number
WO2025000098A1
WO2025000098A1 PCT/CA2024/050872 CA2024050872W WO2025000098A1 WO 2025000098 A1 WO2025000098 A1 WO 2025000098A1 CA 2024050872 W CA2024050872 W CA 2024050872W WO 2025000098 A1 WO2025000098 A1 WO 2025000098A1
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Prior art keywords
conjugated polymer
agent
solution
purified
solvent
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Inventor
Philippe BERROUARD
Pierre-Olivier Morin
François GRENIER
Carl Roy
Charles-olivier GILBERT
Amélie ROBITAILLE
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Brilliant Matters Organic Electronics Inc
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Brilliant Matters Organic Electronics Inc
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/34—Purifying; Cleaning
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4044—Concentrating samples by chemical techniques; Digestion; Chemical decomposition
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples
    • 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

Definitions

  • This disclosure relates to the field of chemistry. More specifically, but not exclusively, the present disclosure broadly relates to a process for purifying conjugated polymers. Yet more specifically, but not exclusively, the present disclosure broadly relates to a process for removing impurities from conjugated polymers. The present disclosure also relates to analytical means for use in conjunction with the process for analyzing the purity of the conjugated polymers.
  • Conjugated polymers more specifically conjugated semi-conducting or conducting polymers, are found in several commercial applications such as in organic solar cells, organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, photovoltaic cells, batteries, capacitors, and the like.
  • OLEDs organic light-emitting diodes
  • OFETs organic field-effect transistors
  • sensors photovoltaic cells
  • batteries capacitors
  • metal impurities include palladium, nickel, magnesium, ruthenium, tin and/or zinc. Indeed, even trace amounts of these metal impurities can adversely impact the performance of devices comprising conjugated conducting polymers.
  • metal impurities are often bound, typically ionically, by the functional groups present on the conjugated semi-conducting or conducting polymers and/or entrapped in the polymer matrix.
  • the conjugated polymer is precipitated out of a concentrated solution through the addition of a second solvent, a method referred to as “solvent displacement’.
  • solvent displacement a method referred to as “solvent displacement’.
  • the resulting polymer will often contain non- negligible amounts of impurities that become trapped in the polymer matrix while the polymer precipitates out of the solution.
  • precipitation is often accompanied by product loss as a result of some of the conjugated polymer remaining in solution.
  • the use of a second solvent increases the total environmental footprint of the precipitation process.
  • the conjugated polymer is repeatedly washed with one or more hot solvents, resulting in the removal of impurities such as non-reacted monomers, undesired side-products, catalyst or catalytic residues, and low molecular weight oligomers.
  • Soxhlet extraction typically entails significant processing times and frequently yields a purified product comprising metal impurities, especially when these metal impurities are entrapped in the polymer matrix and/or adhere strongly thereto.
  • the scavenger may be in free standing form and includes sodium cyanide (NaCN), potassium cyanide (KCN) and ethylenediaminetetraacetic acid (EDTA), or the metal scavenging functional groups, such as a carboxyl, amine, thiol, hydroxyl, amide, nitrile, nitrogen with a free lone pair of electrons, and combinations thereof, may be carried on a solid support or on metal scavenging molecules.
  • these complexing agents and/or scavengers are not broadly applicable and are useful only for the removal of selected metal impurities.
  • excess complexing agent and/or scavenger subsequently needs to be removed from the purified polymer, typically by multiple water extraction steps, increasing the total environmental footprint in the form of contaminated water.
  • Phosphorus-based functionalities linked to an insoluble matrix such as silica bound diphenyl phosphine, and triphenylphosphine-modified crosslinked polystyrene have also been used to address metal-based impurities in conjugated polymers.
  • ion exchange resins such as Amberlite, Amberlist, Daiyaion, Duolite, and Sumichelate have been used to address metal-based impurities in conjugated polymers.
  • a novel process for purifying conjugated polymers, more specifically conjugated semi-conducting or conducting polymers that is generally applicable to all manner of impurities, inexpensive and/or scalable is of commercial interest.
  • Such purification process advantageously reduces the levels of the impurities to levels acceptable for all manner of organic photovoltaic (OPV) applications, batteries, capacitors, and the like.
  • the purified conjugated semi-conducting or conducting polymers may advantageously provide for enhanced reproducible performance of devices comprising such polymers.
  • the present disclosure broadly relates to a process for purifying conjugated polymers. More specifically, but not exclusively, the present disclosure broadly relates to a process for removing metal and/or inorganic impurities from conjugated polymers. Yet more specifically, the present disclosure relates to a process for removing metal and/or inorganic impurities from conjugated semi-conducting or conducting polymers. The present disclosure also relates to analytical means for use in conjunction with the purification process for analyzing the purity of the purified conjugated polymers.
  • the present disclosure relates to a process for purifying a conjugated polymer, the process comprising: dissolving a conjugated polymer in a solvent to provide a solution; adding an agent to the solution to produce an impurity laden agent; and removing the impurity laden agent from the solution to produce a pregnant solution comprising the purified conjugated polymer; wherein the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof.
  • the process further comprises a step of analyzing the purified conjugated polymers for residual impurities.
  • the analyzing comprises drying the purified conjugated polymer, thermally degrading the dried purified conjugated polymer and chemically digesting the thermally degraded conjugated polymer.
  • the thermally degrading comprises heating the purified conjugated polymer to a temperature of at least 400°C.
  • the chemical digestion is performed using at least one of nitric and hydrochloric acid.
  • the chemical digestion is performed using a mixture of nitric and hydrochloric acid.
  • the mixture comprises a molar ratio of about 1 :3 of nitric and hydrochloric acid.
  • the digested conjugated polymer is analyzed by inductively coupled plasma mass spectroscopy (ICP-MS).
  • the impurities are metal impurities.
  • the impurities are transition metal impurities.
  • the metal impurities comprise at least one of Li, B, Na, Mg, P, Ti, Fe, Ca, V, Cr, Mn, Co, Ni, Cu, Zn, As, Pd, Ag, Cd, In, Sn, Mo, Cs, Ba, Tl, Pb, K, and Al.
  • the conjugated polymer is contacted with the agent for at least 30 seconds, wherein the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof.
  • the conjugated polymer is contacted with the agent for a period ranging from about 5 minutes to about 72 hours.
  • the present disclosure relates to a process for purifying a conjugated polymer, the process comprising: circulating a solution comprising a conjugated polymer through a column packed with an agent suitable for removing impurities from the conjugated polymer; and eluding a purified conjugated polymer from the column; wherein the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof.
  • the process further comprises a step of analyzing the purified conjugated polymers for any residual impurities.
  • the analyzing comprises drying the purified conjugated polymer, thermally degrading the dried purified conjugated polymer and chemically digesting the thermally degraded conjugated polymer.
  • the thermally degrading comprises heating the purified conjugated polymer to a temperature of at least 400°C.
  • the chemical digestion is performed using at least one of nitric and hydrochloric acid.
  • the chemical digestion is performed using a mixture of nitric and hydrochloric acid.
  • the mixture comprises a molar ratio of about 1 :3 of nitric and hydrochloric acid.
  • the digested conjugated polymer is analyzed by inductively coupled plasma mass spectroscopy (ICP-MS).
  • the impurities are metal impurities.
  • the impurities are transition metal impurities.
  • the metal impurities comprise at least one of Li, B, Na, Mg, P, Ti, Fe, Ca, V, Cr, Mn, Co, Ni, Cu, Zn, As, Pd, Ag, Cd, In, Sn, Mo, Cs, Ba, TI, Pb, K, and Al.
  • the present disclosure relates to purified conjugated polymers for use in organic electronic applications and/or devices.
  • the organic electronic applications and/or devices comprise organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, photovoltaic cells, batteries, and/or capacitors.
  • Embodiment 1 is a process for purifying a conjugated polymer, the process comprising: dissolving a conjugated polymer in a solvent to provide a solution; adding an agent to the solution to produce an impurity laden agent; and removing the impurity laden agent from the solution to produce a pregnant solution comprising the purified conjugated polymer; wherein the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof.
  • Embodiment 2 is the process of embodiment 1 , further comprising stirring the solution following the addition of the agent.
  • Embodiment 3 is the process of embodiment 1 or 2, wherein the solution has a temperature ranging from about -20°C to about 200°C.
  • Embodiment 4 is the process of embodiment 3, wherein the solution has a temperature ranging from about 20°C to about 180°C.
  • Embodiment 5 is the process of embodiment 1 or 2, wherein the solution is subjected to a temperature gradient, wherein the temperature ranges from about 0°C to about 200°C.
  • Embodiment 6 is the process of embodiment 5, wherein the temperature ranges from about 20°C to about 180°C.
  • Embodiment 7 is the process of any one of embodiments 1 to 6, wherein the conjugated polymer is contacted with the agent for at least 30 seconds.
  • Embodiment 8 is the process of embodiment 7, wherein the conjugated polymer is contacted with the agent for a period ranging from about 5 minutes to about 72 hours.
  • Embodiment 9 is the process of any one of embodiments 1 to 8, wherein the solvent comprises at least one of chlorobenzenes, xylenes, chloroform, hexanes, pentane, toluene, tetrahydrofuran, dioxane and combinations of any thereof.
  • Embodiment 10 is the process of any one of embodiments 1 to 9, wherein the metal scavenger resin is at least one of a trimercaptotriazine and a sodium triaminetetraacetate functionalized resin.
  • Embodiment 11 is the process of any one of embodiments 1 to 10, wherein the ion exchange resin is an acidic and/or basic ion exchange resin.
  • Embodiment 12 is the process of embodiment 11 , wherein the acidic ion exchange resin comprises Amberlyst® 15, Amberlyst® 36, AmberChrom® 50WX2, Dowex® 50WX4, Lewatit® TP 207 and Sephadex® C-50.
  • Embodiment 13 is the process of embodiment 11 , wherein the basic ion exchange resin comprises Amberlite® HPR4811 Cl, Amberlite® FPA66, AmberTec® UP550 OH, Diaion® WA30, Amberlyst® A26 and AmberChrom® 1X8.
  • Embodiment 14 is the process of any one of embodiments 1 to 13, wherein the mass ratio (w/w) of agent to conjugated polymer is at least 0.01 :1.0.
  • Embodiment 15 is the process of any one of embodiments 1 to 13, wherein the mass ratio (w/w) of agent to conjugated polymer ranges from about 0.01 :1.0 to about 100.0:1.0.
  • Embodiment 16 is the process of any one of embodiments 1 to 15, wherein the impurity laden agent is removed from the solution by filtration, decantation or centrifugation to produce an isolated impurity laden agent.
  • Embodiment 17 is the process of embodiment 16, wherein the filtration is complemented by a filtration aid.
  • Embodiment 18 is the process of embodiment 17, wherein the filtration aid is at least one of silica, alumina, diatomaceous earth, charcoal, sand, and combinations of any thereof.
  • Embodiment 19 is the process of embodiment 18, wherein the filtration aid is Celite®.
  • Embodiment 20 is the process of any one of embodiments 16 to 19, wherein the isolated impurity laden agent is extracted with a solvent to remove any unreacted agent.
  • Embodiment 21 is the process of embodiment 20, wherein the extraction is performed once or multiple times.
  • Embodiment 22 is the process of embodiment 20 or 21 , wherein the solvent is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane and combinations of any thereof.
  • Embodiment 23 is the process of embodiment 21 , wherein the multiple extractions are performed using the same solvent or different solvents.
  • Embodiment 24 is the process of embodiment 23, wherein the solvent or solvents are at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane and combinations of any thereof.
  • Embodiment 25 is the process of any one of embodiments 20 to 24, wherein the extraction is performed at temperatures ranging from about -20°C to about 200°C.
  • Embodiment 26 is the process of embodiment 25, wherein the extraction is performed at temperatures ranging from about 20°C to about 180°C.
  • Embodiment 27 is the process of any one of embodiments 1 to 26, wherein the purified conjugated polymer is isolated by precipitation using solvent displacement.
  • Embodiment 28 is the process of embodiment 27, wherein the solvent displacement is performed using at least one of methanol, ethanol isopropanol, acetone, pentane and hexanes.
  • Embodiment 29 is the process of any one of embodiments 1 to 26, wherein the purified conjugated polymer is isolated by concentrating the pregnant solution.
  • Embodiment 30 is the process of any one of embodiments 1 to 29, further comprising a step of analyzing the purified conjugated polymer for any residual impurities.
  • Embodiment 31 is the process of embodiment 30, wherein the analyzing comprises drying the purified conjugated polymer, thermally degrading the dried purified conjugated polymer and chemically digesting the thermally degraded conjugated polymer.
  • Embodiment 32 is the process of embodiment 31 , wherein thermally degrading comprises heating the purified conjugated polymer to a temperature of at least 400°C.
  • Embodiment 33 is the process of embodiment 31 , wherein the chemical digesting is performed using at least one of nitric and hydrochloric acid.
  • Embodiment 34 is the process of embodiment 31 , wherein the chemical digesting is performed using a mixture of nitric and hydrochloric acid.
  • Embodiment 35 is the process of embodiment 34, wherein the mixture comprises a molar ratio of about 1 :3 of nitric and hydrochloric acid.
  • Embodiment 36 is the process of any one of embodiments 31 to 35, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectroscopy (ICP-MS).
  • Embodiment 37 is the process of any one of embodiments 1 to 36, wherein the impurities are metal impurities.
  • Embodiment 38 is a process for purifying a conjugated polymer, the process comprising: circulating a solution comprising a conjugated polymer through a column packed with an agent suitable for removing impurities from the conjugated polymer; and eluding a solution comprising a purified conjugated polymer from the column; wherein the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof.
  • Embodiment 39 is the process of embodiment 38, wherein the solution comprising the conjugated polymer is circulated through the agent-packed column in a closed-loop.
  • Embodiment 40 is the process of embodiment 38 or 39, wherein the solution comprising the conjugated polymer has a temperature ranging from about - 20°C to about 200°C.
  • Embodiment 41 is the process of embodiment 40, wherein the solution comprising the conjugated polymer has a temperature ranging from about 20°C to about 180°C.
  • Embodiment 42 is the process of embodiment 40 or 41 , wherein the solution comprising the conjugated polymer is subjected to a temperature gradient, wherein the temperature ranges from about 0°C to about 200°C.
  • Embodiment 43 is the process of embodiment 42, wherein the temperature ranges from about 20°C to about 180°C.
  • Embodiment 44 is the process of any one of embodiments 38 to 43, wherein the solution comprising the conjugated polymer is circulated through the agent-packed column over a period ranging from about 5 minutes to about 72 hours.
  • Embodiment 45 is the process of any one of embodiments 38 to 44, wherein the solution comprising the conjugated polymer comprises at least one solvent selected from chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane and combinations of any thereof.
  • Embodiment 46 is the process of any one of embodiments 38 to 45, wherein the metal scavenger resin is at least one of a trimercaptotriazine and a sodium triaminetetraacetate functionalized resin.
  • Embodiment 47 is the process of any one of embodiments 38 to 46, wherein the ion exchange resin is an acidic and/or basic ion exchange resin.
  • Embodiment 48 is the process of embodiment 47, wherein the acidic ion exchange resin comprises Amberlyst® 15, Amberlyst® 36, AmberChrom® 50WX2, Dowex® 50WX4, Lewatit® TP 207 and Sephadex® C-50.
  • Embodiment 49 is the process of embodiment 47, wherein the basic ion exchange resin comprises Amberlite® HPR4811 Cl, Amberlite® FPA66, AmberTec® UP550 OH, Diaion® WA30, Amberlyst® A26 and AmberChrom® 1X8.
  • Embodiment 50 is the process of any one of embodiments 38 to 49, wherein the purified conjugated polymer is isolated by precipitation using solvent displacement.
  • Embodiment 51 is the process of embodiment 50, wherein the solvent displacement is performed using at least one of methanol, ethanol, isopropanol, acetone, pentane and hexanes.
  • Embodiment 52 is the process of any one of embodiments 38 to 49, wherein the purified conjugated polymer is isolated by concentrating the solution comprising the purified conjugated polymer.
  • Embodiment 53 is the process of any one of embodiments 38 to 52, further comprising a step of analyzing the purified conjugated polymer for any residual impurities.
  • Embodiment 54 is the process of embodiment 53, wherein the analyzing comprises drying the purified conjugated polymer, thermally degrading the dried purified conjugated polymer and chemically digesting the thermally degraded conjugated polymer.
  • Embodiment 55 is the process of embodiment 54, wherein thermally degrading comprises heating the purified conjugated polymer to a temperature of at least 400°C.
  • Embodiment 56 is the process of embodiment 54, wherein the chemical digesting is performed using at least one of nitric and hydrochloric acid.
  • Embodiment 57 is the process of embodiment 54, wherein the chemical digesting is performed using a mixture of nitric and hydrochloric acid.
  • Embodiment 58 is the process of embodiment 57, wherein the mixture comprises a molar ratio of about 1 :3 of nitric and hydrochloric acid.
  • Embodiment 59 is the process of any one of embodiments 54 to 58, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectroscopy (ICP- MS).
  • Embodiment 60 is the process of any one of embodiments 38 to 59, wherein the impurities are metal impurities.
  • Embodiment 61 is a process for purifying a conjugated polymer, the process comprising: dissolving a conjugated polymer in a solvent to provide a solution; adding an agent to the solution to produce an impurity laden agent; removing the impurity laden agent from the solution to produce a pregnant solution comprising the purified conjugated polymer; and analyzing the purified conjugated polymer for any residual impurities, wherein the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof.
  • the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof.
  • Embodiment 62 is the process of embodiment 61 , further comprising stirring the solution following the addition of the agent.
  • Embodiment 63 is the process of embodiment 61 or 62, wherein the solution has a temperature ranging from about -20°C to about 200°C.
  • Embodiment 64 is the process of embodiment 63, wherein the solution has a temperature ranging from about 20°C to about 180°C.
  • Embodiment 65 is the process of embodiment 61 or 62, wherein the solution is subjected to a temperature gradient, wherein the temperature ranges from about 0°C to about 200°C.
  • Embodiment 66 is the process of embodiment 65, wherein the temperature ranges from about 20°C to about 180°C.
  • Embodiment 67 is the process of any one of embodiments 61 to 66, wherein the conjugated polymer is contacted with the agent for at least 30 seconds.
  • Embodiment 68 is the process of embodiment 67, wherein the conjugated polymer is contacted with the agent for a period ranging from about 5 minutes to about 72 hours.
  • Embodiment 69 is the process of any one of embodiments 61 to 68, wherein the solvent comprises at least one of chlorobenzenes, xylenes, chloroform, hexanes, pentane, toluene, tetrahydrofuran, dioxane and combinations of any thereof.
  • Embodiment 70 is the process of any one of embodiments 61 to 69, wherein the metal scavenger resin is at least one of a trimercaptotriazine and a sodium triaminetetraacetate functionalized resin.
  • Embodiment 71 is the process of any one of embodiments 61 to 70, wherein the ion exchange resin is an acidic and/or basic ion exchange resin.
  • Embodiment 72 is the process of embodiment 71 , wherein the acidic ion exchange resin comprises Amberlyst® 15, Amberlyst® 36, AmberChrom® 50WX2, Dowex® 50WX4, Lewatit® TP 207 and Sephadex® C-50.
  • Embodiment 73 is the process of embodiment 71 , wherein the basic ion exchange resin comprises Amberlite® HPR4811 Cl, Amberlite® FPA66, AmberTec® UP550 OH, Diaion® WA30, Amberlyst® A26 and AmberChrom® 1X8.
  • Embodiment 74 is the process of any one of embodiments 61 to 73, wherein the mass ratio (w/w) of agent to conjugated polymer is at least 0.01 :1.0.
  • Embodiment 75 is the process of any one of embodiments 61 to 73, wherein the mass ratio (w/w) of agent to conjugated polymer ranges from about 0.01 :1.0 to about 100.0: 1 .0.
  • Embodiment 76 is the process of any one of embodiments 61 to 75, wherein the impurity laden agent is removed from the solution by filtration, decantation or centrifugation to produce an isolated impurity laden agent.
  • Embodiment 77 is the process of embodiment 76, wherein the filtration is complemented by a filtration aid.
  • Embodiment 78 is the process of embodiment 77, wherein the filtration aid is at least one of silica, alumina, diatomaceous earth, charcoal, sand, and combinations of any thereof.
  • Embodiment 79 is the process of embodiment 78, wherein the filtration aid is Celite®.
  • Embodiment 80 is the process of any one of embodiments 76 to 79, wherein the isolated impurity laden agent is extracted with a solvent to remove any unreacted agent.
  • Embodiment 81 is the process of embodiment 80, wherein the extraction is performed once or multiple times.
  • Embodiment 82 is the process of embodiment 80 or 81 , wherein the solvent is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane and combinations of any thereof.
  • Embodiment 83 is the process of embodiment 81 , wherein the multiple extractions are performed using the same solvent or different solvents.
  • Embodiment 84 is the process of embodiment 83, wherein the solvent or solvents are at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane and combinations of any thereof.
  • Embodiment 85 is the process of any one of embodiments 80 to 84, wherein the extraction is performed at temperatures ranging from about -20°C to about 200°C.
  • Embodiment 86 is the process of embodiment 85, wherein the extraction is performed at temperatures ranging from about 20°C to about 180°C.
  • Embodiment 87 is the process of any one of embodiments 61 to 86, wherein the purified conjugated polymer is isolated by precipitation using solvent displacement.
  • Embodiment 88 is the process of embodiment 87, wherein the solvent displacement is performed using at least one of methanol, ethanol isopropanol, acetone, pentane and hexanes.
  • Embodiment 89 is the process of any one of embodiments 61 to 86, wherein the purified conjugated polymer is isolated by concentrating the pregnant solution.
  • Embodiment 90 is the process of embodiment 61 , wherein the analyzing comprises drying the purified conjugated polymer, thermally degrading the dried purified conjugated polymer and chemically digesting the thermally degraded conjugated polymer.
  • Embodiment 91 is the process of embodiment 90, wherein thermally degrading comprises heating the purified conjugated polymer to a temperature of at least 400°C.
  • Embodiment 92 is the process of embodiment 90, wherein the chemical digesting is performed using at least one of nitric and hydrochloric acid.
  • Embodiment 93 is the process of embodiment 90, wherein the chemical digesting is performed using a mixture of nitric and hydrochloric acid.
  • Embodiment 94 is the process of embodiment 93, wherein the mixture comprises a molar ratio of about 1 :3 of nitric and hydrochloric acid.
  • Embodiment 95 is the process of any one of embodiments 90 to 94, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectroscopy (ICP- MS).
  • Embodiment 96 is the process of any one of embodiments 61 to 95, wherein the impurities are metal impurities.
  • Embodiment 97 is the process of any one of embodiments 1 to 96, wherein the purified conjugated polymer is for use in organic electronic applications and/or devices.
  • Embodiment 98 is the process of embodiment 97, wherein the organic electronic applications and/or devices comprise organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, photovoltaic cells, batteries, and/or capacitors.
  • OLEDs organic solar cells
  • OFETs organic field-effect transistors
  • sensors photovoltaic cells, batteries, and/or capacitors.
  • Embodiment 99 is a method for analyzing a conjugated polymer for impurities, the method comprising: drying the conjugated polymer to form a thin film; thermally degrading the dried purified conjugated polymer thin film; and chemically digesting the thermally degraded conjugated polymer.
  • Embodiment 100 is the method of embodiment 99, wherein thermally degrading comprises heating the conjugated polymer to a temperature of at least 400°C.
  • Embodiment 101 is the method of embodiment 99, wherein the chemical digesting is performed using at least one of nitric and hydrochloric acid.
  • Embodiment 102 is the method of embodiment 99, wherein the chemical digesting is performed using a mixture of nitric and hydrochloric acid.
  • Embodiment 103 is the method of embodiment 102, wherein the mixture comprises a molar ratio of about 1 :3 of nitric and hydrochloric acid.
  • Embodiment 104 is the method of any one of embodiments 99 to 103, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectroscopy (ICP-MS).
  • Embodiment 105 is the method of any one of embodiments 99 to 104, wherein the thin film has a thickness not exceeding 1 mm.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as “contain” and “contains”), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.
  • agent refers to any compound, material or other that is capable of removing impurities from conjugated polymers.
  • the compound, material or other may remove the impurities by adsorption, complexation or other chemical interaction therewith.
  • the compound, material or other may selectively remove certain impurities such as metal impurities.
  • the agent is at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and combinations of any thereof. After the removal of the impurities, the agent is referred to as an impurity laden agent.
  • conjugated polymer refers to materials comprising a backbone of alternating single and multiple bonds resulting in 7c-conjugation by overlap of the 7c-orbitals, giving rise to a continuum of energy states called band structure.
  • the alternating single and multiple bonds making-up a conjugated binding system or backbone may comprise double bonds, aromatic or heteroaromatic rings, or triple bonds.
  • the conjugated polymers exhibit semiconducting or conducting properties useful in the manufacture of electronic devices such as organic solar cells (OPVs), organic lightemitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, photovoltaic cells, batteries, and/or capacitors.
  • modified cellulose refers to chemical changes made primarily to the hydroxyl groups in the cellulose backbone. Each cellulose unit contains both primary and secondary hydroxyl groups, with the primary C6-hydroxyl group exhibiting higher reactivity.
  • modified cellulose include methylcellulose (MC), carboxymethyl cellulose (CMC), and microcrystalline cellulose (MCC).
  • FIG. 1 Illustration of selected conjugated polymers P1-P5 in accordance with embodiments of the present disclosure.
  • the present disclosure broadly relates to a process for purifying conjugated polymers. More specifically, but not exclusively, the present disclosure broadly relates to a process for removing metal and/or inorganic impurities from conjugated polymers. Yet more specifically, the present disclosure relates to a process for removing metal and/or inorganic impurities from conjugated semi-conducting or conducting polymers. The present disclosure also relates to analytical means for use in conjunction with the purification process for analyzing the purity of the purified conjugated polymers.
  • Conjugated polymers often comprise residual impurities difficult to remove by standard purification procedures. These residual impurities may comprise unreacted starting materials such as unreacted monomeric materials, residual catalyst, and/or residual ligand. Moreover, some of the impurities may arise from impurities already contained in the raw materials and/or solvents. The presence of these impurities may adversely impact the performance of the conjugated polymers, especially when used in devices such as organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, and/or photovoltaic cells. In an embodiment of the present disclosure, the impurities are metal impurities.
  • the impurities are transition metal impurities.
  • the metal impurities comprise at least one of Li, B, Na, Mg, P, Ti, Fe, Ca, V, Cr, Mn, Co, Ni, Cu, Zn, As, Pd, Ag, Cd, In, Sn, Mo, Cs, Ba, Tl, Pb, K, and Al.
  • Typical synthetic processes for the preparation of conjugated polymers comprise palladium or nickel-catalyzed cross-coupling reactions to create C-C bonds between aromatic, alkenyl or alkynyl carbons. At least in this aspect, such processes are different from those employed to prepare non-conjugated polymers. As a result, the purification procedures aimed at purifying conjugated polymers need to take into account the removal of a different set of impurities, such as those generated by the use of palladium or nickel catalysts.
  • conjugated polymers require a high degree of purity in order to provide optimal and reproducible performance in such commercial applications.
  • a conjugated polymer was weighed and added to a round bottom flask followed by the addition of a suitable solvent to produce a solution. At least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, and modified cellulose was then added to the solution.
  • the mass ratio (w/w) of agent to conjugated polymer ranges from about 0.01 :1.0 to about 100.0:1.0.
  • the resulting mixture was subsequently stirred over a period of time ranging from about 5 minutes to about 72 hours. The temperature of the solution was maintained between about 20°C to about 200°C. Finally, the mixture was filtered, optionally complemented by a filtration aid.
  • the conjugated polymer may be advantageously obtained from the filtrate by concentrating the latter or by solvent displacement.
  • the purity of the conjugated polymer was then analyzed by drying the purified conjugated polymer, thermally degrading the dried purified conjugated polymer, chemically digesting the thermally degraded conjugated polymer, and analyzing the digested conjugated polymer by inductively coupled plasma mass spectroscopy (ICP-MS).
  • ICP-MS inductively coupled plasma mass spectroscopy
  • the toluene/methanol mixture was stirred for 30 minutes to ensure complete precipitation of P1.
  • P1 was isolated using a solvent-resistant vacuum filtration membrane and washed with a small amount of methanol. Finally, P1 was dried under vacuum over a period of 15 hours.
  • Table 1 The metal impurity analysis for crude P1 and purified P1 , in accordance with an embodiment of the present disclosure, is illustrated in Table 1.
  • Table 2 The metal impurity analysis for crude P1 and purified P1 using different agents, in accordance with an embodiment of the present disclosure, is illustrated in Table 2.
  • Table 1 Metal impurity analysis for crude and purified P1 by ICP-MS.
  • Table 2 Metal impurity analysis for crude and purified P1 by ICP-MS.
  • a column was packed with at least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, and modified cellulose.
  • a solution comprising a conjugated polymer to be purified is subsequently passed through the column over a period of time ranging from about 5 minutes to about 72 hours using a closed circuit, providing for multiple passages through the column.
  • the time can be adjusted based on factors such as column size (/.e., quantity of packing agent), amount of impurities, and amount of polymer requiring purification.
  • the temperature of the solution is maintained between about 20°C to about 200°C.
  • the purified conjugated polymer may be advantageously obtained from the solution by concentrating the latter or by solvent displacement.
  • the purity of the conjugated polymer is then analyzed by drying the purified conjugated polymer, thermally degrading the dried purified conjugated polymer, chemically digesting the thermally degraded conjugated polymer, and analyzing the digested conjugated polymer by inductively coupled plasma mass spectroscopy (ICP-MS).
  • ICP-MS inductively coupled plasma mass spectroscopy
  • P1 (10 g) was added to a round-bottom flask, followed by the addition of toluene (500 mL). The mixture was heated and stirred at temperatures ranging from about 50°C to about 110°C.
  • a column was packed with a metal scavenger (SiliaMetS® Thiol, 30 g), and the solution was circulated through the column over a period of 5 hours using a closed circuit, allowing for multiple passages through the column. The temperature of the solution was maintained between about 80°C and about 110°C.
  • the solution was then passed through a subsequent column packed with silica gel particles (250 g), and circulated through the column over a period of 1.5 hours.
  • the solution may be passed through the second column using a closed circuit, allowing for multiple passages therethrough.
  • the hot solution was collected in a flask containing a mixture of methanol and water, resulting in the precipitation of P1.
  • the solution containing the precipitate of P1 was then pumped through a further column containing a stainless steel metal mesh filter. Hot acetone followed by hot hexane were passed through the column in a closed system. Finally, P1 was transferred from the column to a clean container and dried under vacuum for a period of 15 hours.
  • a conjugated polymer was weighed and added to a reactor vessel followed by the addition of a suitable solvent to produce a solution. At least one of a metal scavenger resin, an ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, and modified cellulose was then added to the solution.
  • the mass ratio (w/w) of agent to conjugated polymer ranges from about 0.01 :1.0 to about 100.0:1.0.
  • the resulting mixture was subsequently stirred over a period of time ranging from about 5 minutes to about 72 hours. The temperature of the reactor was maintained between about 20°C to about 200°C. Finally, the mixture was removed from the reactor and filtered, optionally complemented by a filtration aid. The filtrate was then returned to the reactor followed by the addition of a non-solvent to precipitate the purified polymer.
  • P5 54 g was added to a reactor vessel (10 L) followed by the addition of chlorobenzene (2.5 L).
  • a metal scavenger resin MP-Piperazinomethyl Resin, 54 g
  • Silica gel 60 - 200 pm, 162 g
  • the temperature of the solution is maintained between about 80°C to about 110°C.
  • the mixture was then removed from the reactor vessel and transferred to one or more centrifuge containers and separated by centrifugation for 30 minutes and filtered. The filtrate was then returned to the reactor vessel followed by the slow addition of methanol under stirring to precipitate purified P5.
  • Conjugated polymers have a tendency to graphitize during thermal degradation, rendering the subsequent chemical digestion difficult and incomplete. This problem can be advantageously addressed by the formation of a thin film prior to thermal degradation. A thin film advantageously provides for increased contact with O2 during the thermal degradation process. As a result of the reduced graphitization, the resulting ash can be completely digested such as by a mixture of nitric and hydrochloric acid (1 :3 aqua regia HNO 3 :HCI).
  • a sample of purified conjugated polymer was solubilized in a suitable solvent (e.g., chlorobenzene). The solution was then slowly evaporated until a thin film of conjugated polymer was formed. In an embodiment of the present disclosure, the thin film has a thickness not exceeding 1 mm. The evaporation may be performed under heating. The thin layer of conjugated polymer was then subjected to thermal degradation by heating in an oven at a temperature of at least 400°C. In an embodiment of the present disclosure, the conjugated polymer was subjected to a thermal degradation temperature of 600°C over a period of time ranging from about 1 to 3 hours.
  • a suitable solvent e.g., chlorobenzene
  • nitric and hydrochloric acid (1 :3 aqua regia HNO 3 :HCI) was added in order to effect the chemical digestion.
  • the chemical digestion may be advantageously performed over a period of 1-12 hours.
  • the chemical digestion is performed at a temperature of 50°C.
  • the degraded and digested product was taken-up in Milli-Q water and analyzed for its impurity content using ICP-MS.
  • the purity analysis for various conjugated polymers, purified in accordance with an embodiment of the present disclosure is illustrated in Table 3.

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Abstract

L'invention divulgue un processus de purification d'un polymère conjugué. Le processus consiste à dissoudre un polymère conjugué dans un solvant pour fournir une solution ; à ajouter un agent à la solution pour produire un agent chargé d'impuretés ; et à éliminer l'agent chargé d'impuretés de la solution pour produire un polymère conjugué purifié ; l'agent étant au moins l'un parmi une résine de piégeage de métal, une résine échangeuse d'ions, de l'argile activée, du charbon, de la silice, de l'alumine, de la terre de diatomées, de la cellulose, de la cellulose modifiée et des combinaisons de n'importe lequel de ceux-ci. L'invention divulgue également un processus d'analyse de la pureté du polymère conjugué purifié. Le polymère conjugué purifié est séché pour former une couche mince, thermiquement dégradé, et soumis à une digestion chimique à l'aide d'un mélange d'acide nitrique et chlorhydrique, suivie d'une analyse ICP-MS. Le polymère conjugué purifié est destiné à être utilisé dans des applications et/ou des dispositifs électroniques organiques.
PCT/CA2024/050872 2023-06-29 2024-06-28 Processus modulaire de purification de polymères conjugués Pending WO2025000098A1 (fr)

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Citations (4)

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