Modular process for purifying conjugated polymers

Abstract

This specification discloses a process for purifying conjugated polymers. The process comprises dissolving the conjugated polymer in a solvent to form a solution, adding an agent to the solution to produce an agent carrying impurities, and removing the agent carrying impurities from the solution to obtain a purified conjugated polymer, wherein the agent is at least one of metal scavenger resins, ion exchange resins, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof. A process for analyzing the purity of the purified conjugated polymer is also disclosed. The purified conjugated polymer is dried to form a thin layer, thermally decomposed, subjected to chemical digestion with a mixture of nitric acid and hydrochloric acid, and then subjected to ICP-MS analysis. The purified conjugated polymer is used in organic electronic applications and / or devices.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 511,001, filed Jun. 29, 2023. The content of the referenced application is hereby incorporated by reference into this application.

[0002] 1. Technical Field This disclosure relates to the field of chemistry. More specifically, but not limited to the following, this disclosure broadly relates to processes (methods) for purifying conjugated polymers. Even more specifically, but not limited to the following, this disclosure broadly relates to processes for removing impurities from conjugated polymers. This disclosure also relates to analytical means for use in combination with processes for analyzing the purity of conjugated polymers.

Background Art

[0003] 2. Related Art Conjugated polymers, more specifically conjugated semiconducting polymers or conductive polymers, are used in numerous commercial applications such as organic solar cells, organic light - emitting diodes (OLEDs), organic field - effect transistors (OFETs), sensors, photovoltaic cells, batteries, capacitors, etc. In many commercial applications, it is important for conjugated semiconducting polymers or conductive polymers to contain no metal impurities or to suppress the presence of any metal impurities as low as possible in order to obtain optimal performance. Typical metal impurities include palladium, nickel, magnesium, ruthenium, tin, and / or zinc. In fact, even trace amounts of these metal impurities can have an adverse effect on the performance of devices containing conjugated conductive polymers. The root cause of the presence of such metal impurities can often be found in the synthesis of the conjugated conductive polymer itself, despite careful work - up (post - treatment) and extensive purification operations. Metal impurities are often ionically bonded, typically, to functional groups present on the conjugated semiconducting polymer or conductive polymer and / or trapped within the polymer matrix.

[0004] Various methods have been used to purify conjugated polymers, including precipitation, Soxhlet extraction, preparative size exclusion chromatography, dialysis, and column chromatography. However, each method has drawbacks such as long processing times, labor-intensive nature, high solvent usage, low scalability, and / or insufficient effectiveness.

[0005] In precipitation purification, conjugated polymers are precipitated from concentrated solutions by adding a second solvent; this method is called "solvent substitution." However, the resulting polymer often contains a significant amount of impurities trapped within the polymer matrix during the precipitation process. Furthermore, precipitation methods often result in product loss because some of the conjugated polymer remains in the solution. Additionally, the use of a second solvent increases the overall environmental impact of the precipitation process.

[0006] Soxhlet extraction is a purification method that removes impurities such as unreacted monomers, undesirable by-products, catalysts or catalyst residues, and low molecular weight oligomers by repeatedly washing the conjugated polymer with one or more high-temperature solvents. However, Soxhlet extraction typically requires considerable processing time and often results in purified products containing metallic impurities, especially if the metallic impurities are trapped within or firmly attached to the polymer matrix.

[0007] Preparative size exclusion chromatography is suitable for removing low molecular weight impurities from conjugated polymers. However, size exclusion chromatography is quite material-intensive and not well-suited for large-scale operations, at least in terms of the costs associated with the gel matrix. Furthermore, metallic impurities often remain trapped in the purified conjugated polymer instead of being retained in the gel matrix. Similarly, silica-based chromatography has similar drawbacks, and strong adhesion between the polymer and silica also leads to product loss. Scaling up preparative size exclusion chromatography is quite expensive, and as a result, this method is limited to purifying sample-scale quantities of product.

[0008] Complexing agents such as N,N-diethyl-2-phenyldiazenecarbothioamide, and chelating agents such as EDTA, 18-crown-6, 8-hydroxyquinoline, tetraethylthiuram disulfide, N,N'-bis(salicylidene)ethylenediamine, dimethylglyoxime, 15-crown-5, and poly(N-isopropylacrylamide) have also been used to address metallic impurities in conjugated polymers. Furthermore, scavengers have also been used to address metallic impurities in conjugated polymers. Scavengers may be in independent forms and include sodium cyanide (NaCN), potassium cyanide (KCN), and ethylenediaminetetraacetic acid (EDTA). Alternatively, metallic scavenger functional groups such as carboxyl groups, amine groups, thiol groups, hydroxyl groups, amide groups, nitrile groups, nitrogen atoms with free lone pairs of electrons, and combinations thereof may be supported on a solid support or on metallic scavenger molecules. However, these complexing agents and / or scavengers are not versatile and are only useful for removing specific metal impurities. Furthermore, excess complexing agents and / or scavengers must then be removed from the purified polymer, which usually requires multiple water extraction steps. This increases the overall environmental burden in the form of contaminated water.

[0009] Phosphorus-based functional groups linked to insoluble matrices such as silica-bonded diphenylphosphine, and triphenylphosphine-modified cross-linked polystyrene have also been used to address metallic impurities in conjugated polymers. Finally, ion exchange resins such as Amberlite, Amberlist, Daiyaion, Duolite, and Sumikilate have also been used to address metallic impurities in conjugated polymers. These matrices and polymer-supported agents and resins are not versatile and are only useful for the removal of specific metallic impurities.

[0010] Novel, inexpensive, and / or scalable processes for purifying conjugated polymers, more specifically conjugated semiconducting polymers or conductive polymers, generally applicable to all types of impurities, are of commercial interest. Such purification processes advantageously reduce impurity levels to acceptable levels for all types of organic photovoltaic (OPV) applications, batteries, capacitors, and the like. Purified conjugated semiconducting polymers or conductive polymers can advantageously provide reproducible performance improvements for devices containing such polymers. [Overview of the project]

[0011] This disclosure broadly relates to processes for purifying conjugated polymers. More specifically, but not limited to, processes for removing metallic and / or inorganic impurities from conjugated polymers. More specifically, this disclosure relates to processes for removing metallic and / or inorganic impurities from conjugated semiconducting polymers or conductive polymers. This disclosure also relates to analytical means to be used in combination with the purification process to analyze the purity of the purified conjugated polymers.

[0012] In one embodiment, the disclosure relates to a process for purifying a conjugated polymer, the process comprising: dissolving the conjugated polymer in a solvent to form a solution; adding an agent to the solution to produce an agent carrying impurities; and removing the agent carrying impurities from the solution to produce a pregnant solution containing the purified conjugated polymer, the agent being at least one of metal scavenger resins, ion exchange resins, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof. In one embodiment of the disclosure, the process further comprises the step of analyzing the purified conjugated polymer for residual impurities. In one embodiment of the disclosure, the analysis comprises drying the purified conjugated polymer; thermally decomposing the dried purified conjugated polymer; and chemically digesting the thermally decomposed conjugated polymer. In a further embodiment of the disclosure, thermal decomposition comprises heating the purified conjugated polymer to at least 400°C. In further embodiments of the present disclosure, chemical digestion is carried out using at least one of nitric acid and hydrochloric acid. In yet another embodiment of the present disclosure, chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid. In yet another embodiment of the present disclosure, the mixture contains nitric acid and hydrochloric acid in a molar ratio of about 1:3. In yet another embodiment of the present disclosure, the conjugated polymer after digestion is analyzed by inductively coupled plasma mass spectrometry (ICP-MS). In yet another embodiment of the present disclosure, the impurity is a metallic impurity. In yet another embodiment of the present disclosure, the impurity is a transition metal impurity. In yet another embodiment of the present disclosure, the metallic impurity includes 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.

[0013] In one embodiment of the present disclosure, the conjugated polymer is in contact with the agent for at least 30 seconds, the agent being at least one of metal scavenger resins, ion exchange resins, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof. In one embodiment of the present disclosure, the conjugated polymer is in contact with the agent for a period ranging from about 5 minutes to about 72 hours.

[0014] In one embodiment, the present disclosure relates to a process for purifying a conjugated polymer, the process comprising circulating a solution containing the conjugated polymer through a column packed with an agent suitable for removing impurities from the conjugated polymer, and eluting the purified conjugated polymer from the column, the agent being at least one of metal scavenger resins, ion exchange resins, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof. In one embodiment of the present disclosure, the process further comprises the step of analyzing the purified conjugated polymer for residual impurities. In one embodiment of the present disclosure, the analysis comprises drying the purified conjugated polymer, thermally decomposing the dried purified conjugated polymer, and chemically digesting the thermally decomposed conjugated polymer. In a further embodiment of the present disclosure, the thermal decomposition comprises heating the purified conjugated polymer to at least 400°C. In a further embodiment of the present disclosure, the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid. In yet another embodiment of the present disclosure, the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid. In yet another embodiment of the present disclosure, the mixture comprises nitric acid and hydrochloric acid in a molar ratio of about 1:3. In yet another embodiment of the present disclosure, the conjugated polymer after digestion is analyzed by inductively coupled plasma mass spectrometry (ICP-MS). In yet another embodiment of the present disclosure, the impurity is a metallic impurity. In yet another embodiment of the present disclosure, the impurity is a transition metal impurity. In yet another embodiment of the present disclosure, the metallic impurity comprises 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.

[0015] In one embodiment, the disclosure relates to purified conjugated polymers for use in organic electronic applications and / or devices. In one embodiment of the disclosure, organic electronic applications and / or devices include organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, photovoltaic cells, batteries, and / or capacitors.

[0016] Furthermore, embodiments 1 to 105 are disclosed in the context of this disclosure. Embodiment 1 is a process (method) for purifying a conjugated polymer, the process comprising: dissolving the conjugated polymer in a solvent to form a solution; adding an agent to the solution to produce an agent carrying impurities; and removing the agent carrying impurities from the solution to produce a pregnant solution containing the purified conjugated polymer, the agent being at least one of metal scavenger resins, ion exchange resins, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof. Embodiment 2 is the process of Embodiment 1, further comprising stirring the solution after adding the agent. Embodiment 3 is the process of Embodiment 1 or 2, wherein the solution has a temperature in the range of about -20°C to about 200°C. Embodiment 4 is the process of Embodiment 3, wherein the solution has a temperature in the range of about 20°C to about 180°C. Embodiment 5 is the process of Embodiment 1 or 2, wherein the solution is placed under a temperature gradient, and the temperature is in the range of about 0°C to about 200°C. Embodiment 6 is the process of Embodiment 5, wherein the temperature is in the range of 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 in contact with the agent for at least 30 seconds. Embodiment 8 is the process of Embodiment 7, wherein the conjugated polymer is in contact with the agent for a period of 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 any combination thereof. Embodiment 10 is the process of any one of Embodiments 1 to 9, wherein the metal scavenger resin is at least one of trimercaptotriazine and triaminetetraacetate sodium functionalized resin. Embodiment 11 is a process from 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® TP207, 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 agent-to-conjugated polymer mass ratio (w / w) is at least 0.01:1.0. Embodiment 15 is a process of any one of Embodiments 1 to 13, in which the mass ratio (w / w) of agent to conjugated polymer is in the range of about 0.01:1.0 to about 100.0:1.0. Embodiment 16 is a process of any one of Embodiments 1 to 15, in which the impurity-supported agent is removed from the solution by filtration, decantation, or centrifugation to produce an isolated impurity-supported agent. Embodiment 17 is the process of Embodiment 16, in which filtration is assisted by a filter aid. Embodiment 18 is the process of Embodiment 17, in which the filter aid is at least one of silica, alumina, diatomaceous earth, charcoal, sand, and any combination thereof. Embodiment 19 is the process of Embodiment 18, in which the filter aid is Celite®. Embodiment 20 is a process of any one of Embodiments 16 to 19, in which the isolated impurity-supported 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 any combination thereof.Embodiment 23 is the process of Embodiment 21, wherein the same or different solvents are used for multiple extractions. Embodiment 24 is the process of Embodiment 23, wherein the solvent (one or more) is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof. Embodiment 25 is the process of any one of Embodiments 20-24, wherein the extraction is carried out at a temperature from about -20°C to about 200°C. Embodiment 26 is the process of Embodiment 25, wherein the extraction is carried out at a temperature from about 20°C to about 180°C. Embodiment 27 is the process of any one of Embodiments 1-26, wherein the purified conjugated polymer is isolated by precipitation by solvent substitution. Embodiment 28 is the process of Embodiment 27, wherein the solvent substitution is carried out using at least one of methanol, ethanol isopropanol, acetone, pentane, and hexanes. Embodiment 29 is a process from any one of Embodiments 1 to 26, wherein the purified conjugated polymer is isolated by concentrating the noble liquid. Embodiment 30 is a process from any one of Embodiments 1 to 29, further comprising the step of analyzing the purified conjugated polymer for residual impurities. Embodiment 31 is a process from Embodiment 30, wherein the analysis comprises drying the purified conjugated polymer, thermally decomposing the dried purified conjugated polymer, and chemically digesting the thermally decomposed conjugated polymer. Embodiment 32 is a process from Embodiment 31, wherein the thermal decomposition comprises heating the purified conjugated polymer to a temperature of at least 400°C. Embodiment 33 is a process from Embodiment 31, wherein the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid. Embodiment 34 is a process from Embodiment 31, wherein the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid. Embodiment 35 is a process from Embodiment 34, wherein the mixture comprises nitric acid and hydrochloric acid in a molar ratio of about 1:3.Embodiment 36 is a process from any one of Embodiments 31 to 35, in which the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Embodiment 37 is a process from any one of Embodiments 1 to 36, in which the impurity is a metallic impurity.

[0017] Embodiment 38 is a process for purifying a conjugated polymer, the process comprising circulating a solution containing the conjugated polymer through a column packed with an agent suitable for removing impurities from the conjugated polymer, and eluting the purified solution containing the conjugated polymer from the column, the agent being at least one of metal scavenger resins, ion exchange resins, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof. Embodiment 39 is the process of Embodiment 38, wherein the solution containing the conjugated polymer is circulated in a closed loop through an agent-packed column. Embodiment 40 is the process of Embodiment 38 or 39, wherein the solution containing the conjugated polymer has a temperature in the range of about -20°C to about 200°C. Embodiment 41 is the process of Embodiment 40, wherein the solution containing the conjugated polymer has a temperature in the range of about 20°C to about 180°C. Embodiment 42 is the process of Embodiment 40 or 41, wherein the solution containing the conjugated polymer is placed under a temperature gradient, and the temperature is in the range of about 0°C to about 200°C. Embodiment 43 is the process of Embodiment 42, wherein the temperature is in the range of about 20°C to about 180°C. Embodiment 44 is the process of any one of Embodiments 38 to 43, wherein the solution containing the conjugated polymer is circulated through a packed column for a period of about 5 minutes to about 72 hours. Embodiment 45 is the process of any one of Embodiments 38 to 44, wherein the solution containing the conjugated polymer contains at least one solvent from chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof. Embodiment 46 is the process of any one of Embodiments 38 to 45, wherein the metal scavenger resin is at least one of trimercaptotriazine and sodium triaminetetraacetate functionalized resins. Embodiment 47 is a process from 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® TP207, 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 by solvent substitution. Embodiment 51 is the process of Embodiment 50, wherein the solvent substitution 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 a solution containing the purified conjugated polymer. Embodiment 53 is the process of any one of Embodiments 38 to 52, further comprising the step of analyzing the purified conjugated polymer for residual impurities. Embodiment 54 is the process of Embodiment 53, wherein the analysis includes drying the purified conjugated polymer, thermally decomposing the dried purified conjugated polymer, and chemically digesting the thermally decomposed conjugated polymer. Embodiment 55 is the process of Embodiment 54, wherein the thermal decomposition includes heating the purified conjugated polymer to a temperature of at least 400°C. Embodiment 56 is the process of Embodiment 54, wherein the chemical digestion is performed using at least one of nitric acid and hydrochloric acid. Embodiment 57 is the process of Embodiment 54, in which the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid. Embodiment 58 is the process of Embodiment 57, in which the mixture contains nitric acid and hydrochloric acid in a molar ratio of about 1:3.Embodiment 59 is a process from any one of Embodiments 54 to 58, in which the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Embodiment 60 is a process from any one of Embodiments 38 to 59, in which the impurity is a metallic impurity.

[0018] Embodiment 61 is a process for purifying a conjugated polymer, the process comprising: dissolving the conjugated polymer in a solvent to form a solution; adding an agent to the solution to produce an agent carrying impurities; removing the agent carrying impurities from the solution to produce a noble liquid containing the purified conjugated polymer; and analyzing the purified conjugated polymer for residual impurities, the agent being at least one of metal scavenger resins, ion exchange resins, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof. Embodiment 62 is the process of Embodiment 61, further comprising stirring the solution after the addition of the agent. Embodiment 63 is the process of Embodiment 61 or 62, wherein the solution has a temperature in the range of about -20°C to about 200°C. Embodiment 64 is the process of Embodiment 63, wherein the solution has a temperature in the range of about 20°C to about 180°C. Embodiment 65 is the process of Embodiment 61 or 62, wherein the solution is placed under a temperature gradient, and the temperature is in the range of about 0°C to about 200°C. Embodiment 66 is the process of Embodiment 65, wherein the temperature is in the range of 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 in contact with the agent for at least 30 seconds. Embodiment 68 is the process of Embodiment 67, wherein the conjugated polymer is in contact with the agent for a period of 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 any combination thereof. Embodiment 70 is the process of any one of Embodiments 61 to 69, wherein the metal scavenger resin is at least one of trimercaptotriazine and triaminetetraacetate sodium functionalized resin. Embodiment 71 is a process from 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® TP207, 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 any one of the processes of Embodiments 61 to 73, wherein the agent-to-conjugated polymer mass ratio (w / w) is at least 0.01:1.0. Embodiment 75 is a process of any one of Embodiments 61 to 73, wherein the mass ratio (w / w) of agent to conjugated polymer is in the range of about 0.01:1.0 to about 100.0:1.0. Embodiment 76 is a process of any one of Embodiments 61 to 75, wherein the impurity-supported agent is removed from the solution by filtration, decantation, or centrifugation to produce an isolated impurity-supported agent. Embodiment 77 is the process of Embodiment 76, wherein filtration is assisted by a filter aid. Embodiment 78 is the process of Embodiment 77, wherein the filter aid is at least one of silica, alumina, diatomaceous earth, charcoal, sand, and any combination thereof. Embodiment 79 is the process of Embodiment 78, wherein the filter aid is Celite®. Embodiment 80 is a process of any one of Embodiments 76 to 79, wherein the isolated impurity-supported 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 any combination thereof.Embodiment 83 is the process of Embodiment 81, wherein the same or different solvents are used for multiple extractions. Embodiment 84 is the process of Embodiment 83, wherein the solvent (one or more) is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof. Embodiment 85 is the process of any one of Embodiments 80-84, wherein the extraction is carried out at a temperature from about -20°C to about 200°C. Embodiment 86 is the process of Embodiment 85, wherein the extraction is carried out at a temperature from about 20°C to about 180°C. Embodiment 87 is the process of any one of Embodiments 61-86, wherein the purified conjugated polymer is isolated by precipitation by solvent substitution. Embodiment 88 is the process of Embodiment 87, wherein the solvent substitution is carried out using at least one of methanol, ethanol isopropanol, acetone, pentane, and hexanes. Embodiment 89 is a process of any one of Embodiments 61 to 86, wherein the purified conjugated polymer is isolated by concentrating the noble liquid. Embodiment 90 is a process of Embodiment 61, wherein the analysis includes drying the purified conjugated polymer, thermally decomposing the dried purified conjugated polymer, and chemically digesting the thermally decomposed conjugated polymer. Embodiment 91 is a process of Embodiment 90, wherein the thermal decomposition includes heating the purified conjugated polymer to a temperature of at least 400°C. Embodiment 92 is a process of Embodiment 90, wherein the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid. Embodiment 93 is a process of Embodiment 90, wherein the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid. Embodiment 94 is a process of Embodiment 93, wherein the mixture contains nitric acid and hydrochloric acid in a molar ratio of about 1:3. Embodiment 95 is a process from any one of Embodiments 90 to 94, in which the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Embodiment 96 is a process from any one of Embodiments 61 to 95, in which the impurity is a metallic impurity.Embodiment 97 is a process from 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 a process from Embodiment 97, wherein the organic electronic applications and / or devices include organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, photovoltaic cells, batteries, and / or capacitors.

[0019] 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 decomposing the purified conjugated polymer thin film after drying; and chemically digesting the thermally decomposed conjugated polymer. Embodiment 100 is the method of Embodiment 99, wherein the thermal decomposition includes heating the conjugated polymer to a temperature of at least 400°C. Embodiment 101 is the method of Embodiment 99, wherein the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid. Embodiment 102 is the method of Embodiment 99, wherein the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid. Embodiment 103 is the method of Embodiment 102, wherein the mixture contains nitric acid and hydrochloric acid in a molar ratio of about 1:3. Embodiment 104 is any one of the methods of Embodiments 99 to 103, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Embodiment 105 is one of the methods from Embodiments 99 to 104, wherein the thickness of the thin film is 1 mm or less.

[0020] The words "a" or "an," when used in conjunction with the term "include" in the claims and / or specification, may mean "one," but unless otherwise explicitly stated, they also mean "one or more," "at least one," and "one or more." Similarly, the word "another," unless otherwise explicitly stated, may mean at least a second or more.

[0021] As used herein and in the claims, the words “comprising” (and any form of “comprise” and “comprises”), “having” (and any form of “have” and “has”), “including” (and any form of “include” and “includes”), or “containing” (and any form of “contain” and “contains”) are comprehensive or open-ended and do not exclude additional, unlisted elements or process steps.

[0022] As used herein and in the claims, the word “consisting” and its derivatives are closed-ended terms that specify the presence of the described features, elements, components, groups, and / or steps, and are also intended to exclude the presence of other undescribed features, elements, components, groups, and / or steps.

[0023] As used herein, the term “consisting essentially of” is intended to specify, in addition to the presence of the described features, elements, components, groups, and / or steps, the presence of anything that does not substantially affect the basic and novel features(s) of those features, elements, components, groups, and / or steps.

[0024] As used herein, the terms “about,” “substantially,” and “approximately” mean a reasonable deviation from the modified term such that the final result is not significantly altered. Terms of these degrees should be interpreted as including a deviation of at least ±5% of the modified term, provided that this deviation does not negate the meaning of the modifying word.

[0025] As used herein, the term "agent" refers to any compound, material, or other thing that can remove impurities from a conjugated polymer. The compound, material, or other thing can remove impurities by adsorption, complex formation, or other chemical interactions with them. In embodiments of the present disclosure, the compound, material, or other thing can selectively remove certain impurities, such as metal impurities. In one embodiment of the present disclosure, 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 any combination thereof. After removal of the impurities, the agent is called an agent carrying the impurities.

[0026] As used herein, the term "conjugated polymer" refers to a material that includes a backbone in which single bonds and multiple bonds are alternately arranged, resulting in π-conjugation due to the overlap of π-orbitals and creating a continuum of energy states called a band structure. The alternating single and multiple bonds that make up the conjugated bond system or backbone can include double bonds, aromatic or heteroaromatic rings, or triple bonds. Conjugated polymers exhibit semiconductor or conductive properties useful in the manufacture of electronic devices such as organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, photovoltaic cells, batteries, and / or capacitors.

[0027] As used herein, the term "modified cellulose" refers to chemical changes mainly made to the hydroxyl groups in the cellulose backbone. Each cellulose unit contains both primary and secondary hydroxyl groups, and the primary C6-hydroxyl group exhibits higher reactivity. Non-limiting examples of modified cellulose include methylcellulose (MC), carboxymethylcellulose (CMC), and microcrystalline cellulose (MCC).

[0028] The foregoing and other advantages and features of the present disclosure will become more apparent by reading the following non-limiting detailed description of exemplary embodiments with reference to the accompanying drawings. However, it should be understood that the detailed description and exemplary embodiments of the present disclosure, while indicating certain specific embodiments of the present disclosure, are provided by way of illustration only. This is because various changes and modifications within the spirit and scope of the present disclosure will be apparent to those skilled in the art from this description.

[0029] The following drawings form a part of this specification and are included to further illustrate certain specific aspects of this specification. This specification can be better understood by referring to one or more of these drawings in conjunction with the detailed description.

Brief Description of the Drawings

[0030] [Figure 1] It is a diagram of selected conjugated polymers P1 to P5 according to an embodiment of the present disclosure.

Mode for Carrying Out the Invention

[0031] The present disclosure broadly relates to a process for purifying conjugated polymers. More specifically, but not limited thereto, it broadly relates to a process for removing metals and / or inorganic impurities from conjugated polymers. Even more specifically, the present disclosure relates to a process for removing metals and / or inorganic impurities from conjugated semiconducting polymers or conducting polymers. The present disclosure also relates to analytical means used in combination with the purification process to analyze the purity of the purified conjugated polymers.

[0032] Conjugated polymers often contain residual impurities that are difficult to remove by standard purification procedures. These residual impurities may include unreacted starting materials such as unreacted monomer materials, residual catalysts, and / or residual ligands. Furthermore, some impurities may originate from impurities already present in the raw materials and / or solvents. The presence of these impurities can adversely affect the performance of the conjugated polymer, particularly 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 one embodiment of this disclosure, the impurities are metallic impurities. In yet another embodiment of this disclosure, the impurities are transition metal impurities. In yet another embodiment of this disclosure, the metallic impurities include 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.

[0033] Typical synthetic processes for preparing conjugated polymers involve palladium-catalyzed or nickel-catalyzed cross-coupling reactions that form CC bonds between aromatic, alkenyl, or alkynyl carbons. In at least this respect, such processes differ from those used for preparing unconjugated polymers. Therefore, purification methods aimed at purifying conjugated polymers must consider the removal of different types of impurities, including those resulting from the use of palladium or nickel catalysts.

[0034] Due in part to their conjugated structure, the presence of heteroatoms, and the diverse functional groups introduced in many conjugated polymers to control their photovoltaic properties, significant interactions generally occur within specific chains and / or between adjacent chains, leading to the formation of aggregates. As a result, conjugated polymers tend to retain impurities within these aggregates, making any purification process significantly more difficult. In fact, the presence of any residual palladium or nickel can further promote the formation of such aggregates by interacting with the conjugated structure, heteroatoms, and / or functional groups. The formation of such aggregates can result in the trapping of additional impurities such as unreacted monomer material, residual catalysts, and / or residual ligands. Given their unique applications as semiconductor materials in organic solar cells (OPVs), organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), sensors, batteries, and capacitors, conjugated polymers require high purity to achieve optimal and reproducible performance in these commercial applications. [Examples]

[0035] The following embodiments are provided to illustrate preferred embodiments of the present disclosure. Those skilled in the art will understand that the techniques disclosed in the following embodiments represent techniques that the inventors have found effective in carrying out the present invention and can therefore be considered to constitute preferred forms of the carrying out. However, those skilled in the art will understand that, in view of the present disclosure, many modifications can be made to the specific embodiments disclosed without departing from the spirit and scope of the present disclosure to obtain similar or comparable results.

[0036] Example 1 - General purification procedure A The conjugated polymer was weighed and added to a round-bottom flask, and a suitable solvent was added to prepare the solution. Next, at least one of the following was added to the solution: metal scavenger resin, ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, and modified cellulose. The mass ratio (w / w) of agent to conjugated polymer was in the range of about 0.01:1.0 to about 100.0:1.0. The resulting mixture was stirred for about 5 minutes to about 72 hours. The temperature of the solution was maintained between about 20°C and about 200°C. Finally, the mixture was filtered, optionally with a filter aid if necessary. The conjugated polymer can be advantageously obtained from the filtrate by concentrating the filtrate or by solvent replacement. Next, the purity of the purified conjugated polymer was analyzed by drying the purified conjugated polymer, thermally decomposing the dried purified conjugated polymer, chemically digesting the conjugated polymer after thermal decomposition, and analyzing the digested conjugated polymer by inductively coupled plasma mass spectrometry (ICP-MS).

[0037] Example 2 - Purification of P1 P1 (1 g) was placed in a round-bottom flask, and toluene (50 mL) was added to prepare a solution. Ion exchange resin (Amberlyst® 15, 3 g) was added to the solution, and the resulting mixture was stirred at 90°C for 24 hours. The mixture was then filtered using a pad lined with Celite® 545 or Celite® 512 to a thickness of approximately 1 cm. Before adding the mixture, the Celite was pre-moistened with a small amount of toluene. The filtrate containing the purified conjugated polymer P1 was collected in a clean Erlenmeyer flask, and P1 was precipitated by slowly pouring this into a round-bottom flask containing methanol (250 mL). The toluene / methanol mixture was stirred for 30 minutes to complete the 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 reduced pressure for 15 hours. Table 1 shows the results of metal impurity analysis of crude P1 (unpurified P1) and purified P1 according to embodiments of this disclosure. Table 2 shows the results of metal impurity analysis of crude P1 (unrefined P1) and purified P1 using different agents according to embodiments of this disclosure.

[0038] [Table 1]

[0039] [Table 2]

[0040] Example 3 - General Purification Procedure B The column was packed with at least one of the following: metal scavenger resin, ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, and modified cellulose. Next, the solution containing the conjugated polymer to be purified was passed through the column multiple times using a closed circuit for approximately 5 minutes to approximately 72 hours. This time can be adjusted based on factors such as column size (i.e., amount of packing material), amount of impurities, and amount of polymer to be purified. The solution temperature was maintained between approximately 20°C and approximately 200°C. The purified conjugated polymer could be favorably obtained from the solution by concentrating the solution or by solvent replacement. The purity of the purified conjugated polymer was then analyzed by drying the purified polymer, thermally decomposing the dried polymer, chemically digesting the decomposed polymer, and analyzing the digested polymer by inductively coupled plasma mass spectrometry (ICP-MS).

[0041] Example 4 - Purification of P1 P1 (1 g) was placed in a round-bottom flask, and toluene (50 mL) was added to prepare a solution. A metal scavenger (SiliaMetS® thiol, 3 g) was packed into a column, and the solution was circulated through the column multiple times for 5 hours using a closed circuit. The solution temperature was maintained between approximately 80°C and 110°C. Next, the solution containing the purified P1 was slowly added to a round-bottom flask containing methanol (250 mL) to precipitate P1. 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 reduced pressure for 15 hours.

[0042] Example 5 - Purification of P1 P1 (10g) was placed in a round-bottom flask, and toluene (500mL) was added. The mixture was heated and stirred within a temperature range of approximately 50°C to 110°C. A metal scavenger (SiliaMetS® thiol, 30g) was packed into a column, and the solution was circulated through the column multiple times for 5 hours using a closed circuit. The temperature of the solution was maintained between approximately 80°C and 110°C. The solution was then passed through a second column packed with silica gel particles (250g) and circulated for 1.5 hours. In one embodiment, the solution may be passed through the second column multiple times using a closed circuit. The hot solution was collected at the column outlet and collected in a flask containing a methanol-water mixture to precipitate P1. The solution containing the P1 precipitate was then pumped through another column containing a stainless steel mesh filter. Subsequently, hot acetone and then 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 reduced pressure for 15 hours.

[0043] Example 6 - General purification procedure A (scale-up) The conjugated polymer was weighed and placed in a reaction vessel, and a suitable solvent was added to prepare the solution. Next, at least one of the following was added to the solution: metal scavenger resin, ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, and modified cellulose. The mass ratio (w / w) of agent to conjugated polymer was in the range of approximately 0.01:1.0 to approximately 100.0:1.0. The resulting mixture was stirred for approximately 5 minutes to approximately 72 hours. The temperature of the reaction vessel was maintained between approximately 20°C and approximately 200°C. Finally, the mixture was removed from the reaction vessel and filtered using an optional filter aid. The filtrate was then returned to the reaction vessel, and the purified polymer was precipitated by adding a non-solvent.

[0044] Example 7 - Purification of P5 P5 (54 g) was placed in a reaction vessel (10 L), and chlorobenzene (2.5 L) was added. Then, metal scavenger resin (MP-piperazinomethyl resin, 54 g) and silica gel (60-200 μm, 162 g) were added to the solution in the reaction vessel. The resulting mixture was then stirred for 16 hours. The temperature of the solution was maintained between approximately 80°C and 110°C. The mixture was then removed from the reaction vessel, transferred to one or more centrifuges, centrifuged for 30 minutes, and filtered. The filtrate was then returned to the reaction vessel, and purified P5 was precipitated by gradually adding methanol under stirring. To ensure complete precipitation of P5, an additional methanol (1 L) was added, and the mixture was stirred for 30 minutes. P5 was isolated using a solvent-resistant vacuum filtration membrane and washed with a small amount of methanol. Finally, P5 was dried under reduced pressure for 15 hours.

[0045] Conjugated polymers tend to graphitize during the thermal decomposition process, making subsequent chemical digestion difficult and incomplete. This problem can be advantageously addressed by forming a thin film before thermal decomposition. The thin film can increase contact with oxygen (O2) during the thermal decomposition process, which works to one's advantage. As a result of reduced graphitization, the resulting ash can be completely digested with a mixture of nitric acid and hydrochloric acid (1:3 aqua regia, HNO3:HCl).

[0046] Example 8 - Preparation of samples for ICP-MS analysis A sample of the purified conjugated polymer was dissolved in a suitable solvent (e.g., chlorobenzene). The solution was then slowly evaporated until a thin film of the conjugated polymer was formed. In one embodiment of this disclosure, the thickness of the thin film was not greater than 1 mm. Evaporation may be carried out under heating. The thin layer of the conjugated polymer was then subjected to a thermal decomposition treatment by heating in a furnace at a temperature of at least 400°C. In one embodiment of this disclosure, the conjugated polymer was subjected to a thermal decomposition temperature of 600°C for about 1 to 3 hours. After the decomposed polymer had cooled to room temperature, a mixture of nitric acid and hydrochloric acid (1:3 aqua regia, HNO3:HCl) was added to induce chemical digestion. In one embodiment of this disclosure, chemical digestion may be advantageously carried out within a range of 1 to 12 hours. In yet another embodiment of this disclosure, chemical digestion is carried out at 50°C. The decomposed and digested products were dissolved in Milli-Q water, and the impurity content was analyzed using ICP-MS. The purity analysis results for various conjugated polymers purified according to one embodiment of this disclosure are shown in Table 3.

[0047] All processes and / or methods disclosed and claimed herein can be prepared and carried out in light of this disclosure without requiring excessive experimentation. While the processes and / or methods of this disclosure have been described in relation to preferred embodiments, it will be apparent to those skilled in the art that modifications can be made, for example, to the steps or order of steps of the processes described herein, without departing from the concepts, spirit and scope of this disclosure. More specifically, it will be apparent that certain chemically related agents may substitute for the agents described herein, and that the same or similar results can be obtained in doing so. All such similar substitutions and modifications that are apparent to those skilled in the art are deemed to be within the spirit, scope and concepts of this disclosure as defined by the appended claims.

[0048] [Table 3]

[0049] References 1. U.S. Patent No. 9,045,596 (US9,045,596 B2) Specification 2. Shcherbyna, S., Diethard, KB & Vladimir, IBApplication of Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) for Analysis of Novel Organic Semiconductor Materials.MRS Online Proceedings Library 937,0937-M03-02(2006).https: / / doi.org / 10.1557 / PROC-0937-M03-02

Claims

1. A process for purifying conjugated polymers, Dissolving the conjugated polymer in a solvent to form a solution, Adding an agent to the aforementioned solution to produce an agent carrying impurities, The process includes removing the agent carrying the impurities from the solution to produce a noble liquid containing the purified conjugated polymer, A process in which the agent is at least one of metal scavenger resin, ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof.

2. The process according to claim 1, further comprising stirring the solution after adding the agent.

3. The process according to claim 1 or 2, wherein the solution has a temperature in the range of about -20°C to about 200°C.

4. The process according to claim 3, wherein the solution has a temperature in the range of about 20°C to about 180°C.

5. The process according to claim 1 or 2, wherein the solution is placed under a temperature gradient, and the temperature is in the range of about 0°C to about 200°C.

6. The process according to claim 5, wherein the temperature is in the range of about 20°C to about 180°C.

7. The process according to any one of claims 1 to 6, wherein the conjugated polymer is in contact with the agent for at least 30 seconds.

8. The process according to claim 7, wherein the conjugated polymer is in contact with the agent for a period of about 5 minutes to about 72 hours.

9. The process according to any one of claims 1 to 8, wherein the solvent comprises at least one of chlorobenzenes, xylenes, chloroform, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof.

10. The process according to any one of claims 1 to 9, wherein the metal scavenger resin is at least one of trimercaptotriazine and sodium triaminetetraacetate functionalized resin.

11. The process according to any one of claims 1 to 10, wherein the ion exchange resin is an acidic and / or basic ion exchange resin.

12. The process according to claim 11, wherein the acidic ion exchange resin comprises Amberlyst® 15, Amberlyst® 36, AmberChrome® 50WX2, Dowex® 50WX4, Lewatit® TP207, and Sephadex® C-50.

13. The process according to claim 11, wherein the basic ion exchange resin comprises Amberlite® HPR4811 Cl, Amberlite® FPA66, AmberTec® UP550 OH, Diaion® WA30, Amberlyst® A26, and AmberChrome® 1X8.

14. The process according to any one of claims 1 to 13, wherein the mass ratio (w / w) of the agent to the conjugated polymer is at least 0.01:1.

0.

15. The process according to any one of claims 1 to 13, wherein the mass ratio (w / w) of agent to conjugated polymer is in the range of about 0.01:1.0 to about 100.0:1.

0.

16. The process according to any one of claims 1 to 15, wherein the agent supporting the impurities is removed from the solution by filtration, decantation, or centrifugation to produce an isolated agent supporting the impurities.

17. The process according to claim 16, wherein the filtration is supplemented by a filter aid.

18. The process according to claim 17, wherein the filtration aid is at least one of silica, alumina, diatomaceous earth, charcoal, sand, and any combination thereof.

19. The process according to claim 18, wherein the filtration aid is Celite®.

20. The process according to any one of claims 16 to 19, wherein the isolated impurity-supported agent is extracted with a solvent to remove the unreacted agent.

21. The process according to claim 20, wherein the extraction is performed once or more times.

22. The process according to claim 20 or 21, wherein the solvent is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof.

23. The process according to claim 21, wherein the multiple extractions are performed using the same solvent or different solvents.

24. The process according to claim 23, wherein the solvent (one or more) is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof.

25. The process according to any one of claims 20 to 24, wherein the extraction is carried out at a temperature in the range of about -20°C to about 200°C.

26. The process according to claim 25, wherein the extraction is performed at a temperature in the range of about 20°C to about 180°C.

27. The process according to any one of claims 1 to 26, wherein the purified conjugated polymer is isolated by precipitation using solvent substitution.

28. The process according to claim 27, wherein the solvent substitution is carried out using at least one of methanol, ethanol, isopropanol, acetone, pentane, and hexanes.

29. The process according to any one of claims 1 to 26, wherein the purified conjugated polymer is isolated by concentrating the noble liquid.

30. The process according to any one of claims 1 to 29, further comprising the step of analyzing the purified conjugated polymer for residual impurities.

31. The process according to claim 30, wherein the analysis comprises drying the purified conjugated polymer, thermally decomposing the purified conjugated polymer after drying, and chemically digesting the thermally decomposed conjugated polymer.

32. The process according to claim 31, wherein thermal decomposition includes heating the purified conjugated polymer to at least 400°C.

33. The process according to claim 31, wherein the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid.

34. The process according to claim 31, wherein the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid.

35. The process according to claim 34, wherein the mixture comprises nitric acid and hydrochloric acid in a molar ratio of about 1:

3.

36. The process according to any one of claims 31 to 35, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS).

37. The process according to any one of claims 1 to 36, wherein the impurity is a metallic impurity.

38. A process for purifying conjugated polymers, A solution containing a conjugated polymer is circulated through a column packed with an agent suitable for removing impurities from the conjugated polymer, The process includes eluting a solution containing a purified conjugated polymer from the column, A process in which the agent is at least one of metal scavenger resin, ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof.

39. The process according to claim 38, wherein the solution containing the conjugated polymer is circulated in a closed loop through the agent-packed column.

40. The process according to claim 38 or 39, wherein the solution containing the conjugated polymer has a temperature in the range of about -20°C to about 200°C.

41. The process according to claim 40, wherein the solution containing the conjugated polymer has a temperature in the range of about 20°C to about 180°C.

42. The process according to claim 40 or 41, wherein the solution containing the conjugated polymer is placed under a temperature gradient, and the temperature is in the range of about 0°C to about 200°C.

43. The process according to claim 42, wherein the temperature is in the range of about 20°C to about 180°C.

44. The process according to any one of claims 38 to 43, wherein the solution containing the conjugated polymer is circulated through the agent-packed column for a period of about 5 minutes to about 72 hours.

45. The process according to any one of claims 38 to 44, wherein the solution containing the conjugated polymer comprises at least one solvent from among chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof.

46. The process according to any one of claims 38 to 45, wherein the metal scavenger resin is at least one of trimercaptotriazine and sodium triaminetetraacetate functionalized resin.

47. The process according to any one of claims 38 to 46, wherein the ion exchange resin is an acidic and / or basic ion exchange resin.

48. The process according to claim 47, wherein the acidic ion exchange resin comprises Amberlyst® 15, Amberlyst® 36, AmberChrom® 50WX2, Dowex® 50WX4, Lewatit® TP207, and Sephadex® C-50.

49. The process according to claim 47, wherein the basic ion exchange resin comprises Amberlite® HPR4811 Cl, Amberlite® FPA66, AmberTec® UP550 OH, Diaion® WA30, Amberlyst® A26, and AmberChrome® 1X8.

50. The process according to any one of claims 38 to 49, wherein the purified conjugated polymer is isolated by precipitation using solvent substitution.

51. The process according to claim 50, wherein the solvent substitution is carried out using at least one of methanol, ethanol, isopropanol, acetone, pentane, and hexanes.

52. The process according to any one of claims 38 to 49, wherein the purified conjugated polymer is isolated by concentrating the solution containing the purified conjugated polymer.

53. The process according to any one of claims 38 to 52, further comprising the step of analyzing the purified conjugated polymer for residual impurities.

54. The process according to claim 53, wherein the analysis comprises drying the purified conjugated polymer, thermally decomposing the purified conjugated polymer after drying, and chemically digesting the thermally decomposed conjugated polymer.

55. The process according to claim 54, wherein thermal decomposition includes heating the purified conjugated polymer to at least 400°C.

56. The process according to claim 54, wherein the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid.

57. The process according to claim 54, wherein the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid.

58. The process according to claim 57, wherein the mixture comprises nitric acid and hydrochloric acid in a molar ratio of about 1:

3.

59. The process according to any one of claims 54 to 58, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS).

60. The process according to any one of claims 38 to 59, wherein the impurity is a metallic impurity.

61. A process for purifying conjugated polymers, Dissolving the conjugated polymer in a solvent to form a solution, Adding an agent to the aforementioned solution to produce an agent carrying impurities, The process involves removing the agent carrying the impurities from the aforementioned solution to produce a noble liquid containing the purified conjugated polymer, This includes analyzing the purified conjugated polymer for residual impurities, A process in which the agent is at least one of metal scavenger resin, ion exchange resin, activated clay, charcoal, silica, alumina, diatomaceous earth, cellulose, modified cellulose, and any combination thereof.

62. The process according to claim 61, further comprising stirring the solution after adding the agent.

63. The process according to claim 61 or 62, wherein the solution has a temperature in the range of about -20°C to about 200°C.

64. The process according to claim 63, wherein the solution has a temperature in the range of about 20°C to about 180°C.

65. The process according to claim 61 or 62, wherein the solution is placed under a temperature gradient, and the temperature is in the range of about 0°C to about 200°C.

66. The process according to claim 65, wherein the temperature is in the range of about 20°C to about 180°C.

67. The process according to any one of claims 61 to 66, wherein the conjugated polymer is in contact with the agent for at least 30 seconds.

68. The process according to claim 67, wherein the conjugated polymer is in contact with the agent for a period of about 5 minutes to about 72 hours.

69. The process according to any one of claims 61 to 68, wherein the solvent comprises at least one of chlorobenzenes, xylenes, chloroform, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof.

70. The process according to any one of claims 61 to 69, wherein the metal scavenger resin is at least one of trimercaptotriazine and sodium triaminetetraacetate functionalized resin.

71. The process according to any one of claims 61 to 70, wherein the ion exchange resin is an acidic and / or basic ion exchange resin.

72. The process according to claim 71, wherein the acidic ion exchange resin comprises Amberlyst® 15, Amberlyst® 36, AmberChrom® 50WX2, Dowex® 50WX4, Lewatit® TP207, and Sephadex® C-50.

73. The process according to claim 71, wherein the basic ion exchange resin comprises Amberlite® HPR4811 Cl, Amberlite® FPA66, AmberTec® UP550 OH, Diaion® WA30, Amberlyst® A26, and AmberChrome® 1X8.

74. The process according to any one of claims 61 to 73, wherein the mass ratio (w / w) of agent to conjugated polymer is at least 0.01:1.

0.

75. The process according to any one of claims 61 to 73, wherein the mass ratio (w / w) of agent to conjugated polymer is in the range of about 0.01:1.0 to about 100.0:1.

0.

76. The process according to any one of claims 61 to 75, wherein the impurity-supported agent is removed from the solution by filtration, decantation, or centrifugation to produce an isolated impurity-supported agent.

77. The process according to claim 76, wherein the filtration is supplemented by a filter aid.

78. The process according to claim 77, wherein the filtration aid is at least one of silica, alumina, diatomaceous earth, charcoal, sand, and any combination thereof.

79. The process according to claim 78, wherein the filtration aid is Celite®.

80. The process according to any one of claims 76 to 79, wherein the isolated, impurity-supported agent is extracted with a solvent to remove the unreacted agent.

81. The process according to claim 80, wherein the extraction is performed once or more times.

82. The process according to claim 80 or 81, wherein the solvent is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof.

83. The process according to claim 81, wherein the multiple extractions are performed using the same solvent or different solvents.

84. The process according to claim 83, wherein the solvent (one or more) is at least one of chlorobenzenes, xylenes, chloroform, acetone, hexanes, pentane, toluene, tetrahydrofuran, dioxane, and any combination thereof.

85. The process according to any one of claims 80 to 84, wherein the extraction is carried out at a temperature in the range of about -20°C to about 200°C.

86. The process according to claim 85, wherein the extraction is performed at a temperature in the range of about 20°C to about 180°C.

87. The process according to any one of claims 61 to 86, wherein the purified conjugated polymer is isolated by precipitation using solvent substitution.

88. The process according to claim 87, wherein the solvent substitution is carried out using at least one of methanol, ethanol, isopropanol, acetone, pentane, and hexanes.

89. The process according to any one of claims 61 to 86, wherein the purified conjugated polymer is isolated by concentrating the noble liquid.

90. The process according to claim 61, wherein the analysis comprises drying the purified conjugated polymer, thermally decomposing the purified conjugated polymer after drying, and chemically digesting the thermally decomposed conjugated polymer.

91. The process according to claim 90, wherein thermal decomposition includes heating the purified conjugated polymer to at least 400°C.

92. The process according to claim 90, wherein the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid.

93. The process according to claim 90, wherein the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid.

94. The process according to claim 93, wherein the mixture comprises nitric acid and hydrochloric acid in a molar ratio of about 1:

3.

95. The process according to any one of claims 90 to 94, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS).

96. The process according to any one of claims 61 to 95, wherein the impurity is a metallic impurity.

97. The process according to any one of claims 1 to 96, wherein the purified conjugated polymer is for use in organic electronic applications and / or devices.

98. The process according to claim 97, wherein the organic electronic application and / or device includes an organic solar cell (OPV), an organic light-emitting diode (OLED), an organic field-effect transistor (OFET), a sensor, a photovoltaic cell, a battery, and / or a capacitor.

99. A method for analyzing conjugated polymers for impurities, The conjugated polymer is dried to form a thin film, The purified conjugated polymer thin film after drying is thermally decomposed, Chemical digestion of the thermally decomposed conjugated polymer, Methods that include...

100. The method according to claim 99, wherein thermal decomposition includes heating the conjugated polymer to at least 400°C.

101. The method according to claim 99, wherein the chemical digestion is carried out using at least one of nitric acid and hydrochloric acid.

102. The method according to claim 99, wherein the chemical digestion is carried out using a mixture of nitric acid and hydrochloric acid.

103. The method according to claim 102, wherein the mixture comprises nitric acid and hydrochloric acid in a molar ratio of about 1:

3.

104. The method according to any one of claims 99 to 103, wherein the digested conjugated polymer is analyzed by inductively coupled plasma mass spectrometry (ICP-MS).

105. The method according to any one of claims 99 to 104, wherein the thickness of the thin film is 1 mm or less.

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