Method for producing shaped adsorbent

Abstract

To provide: when producing an adsorbent layer (molded adsorbent) comprising an adsorbent that includes a clay mineral, a method for producing an adsorbent layer (molded adsorbent) by using a simpler dry filling method, the adsorbent layer (molded adsorbent) not generating cracks and collapses; a container having the adsorbent layer (molded adsorbent); and a method for purifying a polymeric compound using the molded adsorbent.SOLUTION: Provided are: a method for producing, in a container having an upper part and a lower part separated by a porous layer, a molded adsorbent on the porous layer, comprising the steps of (1) filling an adsorbent that includes a clay mineral on the porous layer from an upper part of the container by a dry method and by increasing the density of the adsorbent to form an adsorbent layer and (2) evacuating a lower space of the container and passing a solvent through the adsorbent layer to form a molded adsorbent layer; a method for producing a container having the molded adsorbent; and a method for purifying a polymeric compound using the molded adsorbent.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for producing a shaped adsorbent.

Background Art

[0002] For example, a polymer compound is used as a material for an organic electroluminescence (organic EL) element or the like. In order to improve the electrical characteristics, lifespan, etc. of the element, it is desirable that the polymer compound has a low content of impurities such as low molecular weight components.

[0003] The polymer compound can be synthesized, for example, by subjecting an aromatic diboronic acid and an aromatic dihalide to a Suzuki coupling reaction in the presence of a transition metal complex. However, in this synthesis method, impurities such as low molecular weight components and polymer compounds having hydroxyl group terminals are generated as by-products, and thus it is necessary to reduce them.

[0004] For example, Patent Document 1 reports a method of subjecting a mixture containing a polymer compound and a solvent to column chromatography using a stationary phase containing an adsorbent such as activated clay in order to produce a polymer compound having a low content of low molecular weight components.

[0005] As a method of packing an adsorbent into a column, for example, there are a dry packing method in which the adsorbent is packed as a solid and a wet packing method in which the adsorbent is mixed with a solvent to form a slurry and then packed. In the wet packing method, since it is necessary to dilute the adsorbent with a large amount of dispersion solvent (dispersion medium) and then pack it into the column using a high-pressure pump or the like, large-scale equipment is required and the operation becomes complicated. In addition, stirring of the slurry system increases the risk of foreign matter mixing due to equipment wear.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] When the present inventor studied a method for preparing an adsorbent layer (fixed layer) used in the above column chromatography treatment, it was found that when a column was filled with clay minerals such as activated clay and zeolite as an adsorbent by using a dry packing method in which the adsorbent was packed as a solid and then a liquid was passed through, cracks and depressions occurred in the adsorbent layer. When a solution containing a polymer compound is treated using an adsorbent layer having cracks and depressions, the solution passes through concentratedly at the crack and depression sites (generation of uneven flow), and the removal of impurities such as low molecular weight components and polymer compounds having hydroxyl group terminals becomes insufficient, and as a result, a high-purity polymer compound cannot be obtained. In addition, after the column chromatography treatment, when the adsorbent layer is washed with a solvent and the polymer compound remaining in the adsorbent layer is recovered, the recovery rate decreases.

[0008] An object of the present invention is to provide a method for producing an adsorbent layer (formed adsorbent) made of an adsorbent containing a clay mineral that does not generate cracks and depressions when producing the adsorbent layer (formed adsorbent) using a simpler and more workable dry packing method. Another object is to provide a container having the adsorbent layer (formed adsorbent). Furthermore, it is also an object to provide a method for producing a polymer compound with reduced impurities using the adsorbent layer (formed adsorbent).

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventor found that after forming an adsorbent layer by densifying the adsorbent inside the column filled from the upper part of the column by the dry packing method, the lower part of the column was depressurized and a solvent was passed through the adsorbent layer, an adsorbent layer (formed adsorbent) that does not generate cracks and depressions can be produced. Further studies were added to complete the present invention.

[0010] That is, the present invention provides the following [1] to

[12] . [1] A method for producing a molded adsorbent on the porous layer of a container in which the upper and lower portions are separated by a porous layer, comprising: (1) A step of filling an adsorbent containing a clay mineral from the upper part of the container onto the porous layer in a dry state and increasing the density to form an adsorbent layer; and (2) A step of reducing the pressure in the lower space of the container and passing a solvent through the adsorbent layer to form a molded adsorbent. A method for producing a molded adsorbent, comprising the above steps. [2] The production method according to [1], wherein the step (1) includes a step of reducing the pressure in the lower space of the container and increasing the density of the adsorbent. [3] The production method according to [1] or [2], wherein the step (1) includes a step of introducing the adsorbent from the upper part of the container onto the porous layer while reducing the pressure in the lower space of the container to increase the density of the adsorbent. [4] The production method according to any one of [1] to [3], wherein the clay mineral contains at least one selected from the group consisting of smectite and zeolite. [5] The production method according to [4], wherein the smectite is activated clay. [6] The production method according to any one of [1] to [5], wherein the average particle diameter of the clay mineral is 2 μm to 5000 μm. [7] The production method according to any one of [1] to [6], wherein the adsorbent is a mixed adsorbent containing a clay mineral and a non-clay mineral, and the angle of repose of the mixed adsorbent is 56° or less. [8] A method for producing a polymer compound with reduced impurities, characterized in that a molded adsorbent is produced by the production method according to any one of [1] to [7], and a solution of a polymer compound containing impurities is passed through the molded adsorbent to remove the impurities. [9] A method for purifying a polymer compound, characterized in that a molded adsorbent is produced by the production method according to any one of [1] to [7], and a solution of a polymer compound containing impurities is passed through the molded adsorbent to remove the impurities.

[10] A method for producing a container having a molded adsorbent on the porous layer of a container in which the upper and lower portions are separated by a porous layer, comprising: (1) A step of filling an adsorbent containing a clay mineral from the upper part of the container in a dry manner onto the porous layer and increasing the density to form an adsorbent layer, and (2) A step of reducing the pressure in the lower space of the container and passing a solvent through the adsorbent layer to form a molded adsorbent A method for manufacturing a container, comprising the above steps.

[11] A method for manufacturing a light-emitting device having an anode, a cathode, and one or more organic layers provided between the anode and the cathode, wherein at least one of the organic layers is formed using a polymer compound obtained by the manufacturing method described in [8]. A method for manufacturing a light-emitting device.

[12] The manufacturing method according to

[11] , wherein the organic layer formed using the polymer compound is a hole transport layer.

Advantages of the Invention

[0011] According to the manufacturing method of the present invention, even when an adsorbent containing a clay mineral is used, an adsorbent layer (molded adsorbent) can be manufactured without generating cracks and depressions by using a simple dry filling method. Further, when a mixed adsorbent containing a clay mineral and a non-clay mineral is used, an adsorbent layer (molded adsorbent) that more stably does not generate cracks and depressions can be manufactured. Furthermore, according to the manufacturing method of the present invention, a container (such as a column) provided with an adsorbent layer (molded adsorbent) having these excellent performances can be manufactured. By filtering a polymer compound using the molded adsorbent obtained by the manufacturing method of the present invention, impurities such as low molecular weight components and polymer compounds having a hydroxyl group terminal can be effectively removed, and a polymer compound of a desired high purity can be obtained.

Brief Description of the Drawings

[0012]

Figure 1

Embodiments for Carrying Out the Invention

[0013] Hereinafter, preferred embodiments of the present invention will be described in detail.

[0014] 1. Molded adsorbent The shaped adsorbent in this embodiment means an adsorbent formed into a certain shape, specifically, an adsorbent containing clay minerals densely filled inside a container. Since the shaped adsorbent is usually densely filled inside a container to form a layer, it may also be described as an adsorbent layer.

[0015] Adsorbent The adsorbent used in the production of the shaped adsorbent contains clay minerals. This clay mineral can effectively adsorb and remove, for example, low molecular weight components, hydroxyl group-containing polymer compounds, etc. contained as impurities from polymer compounds obtained by polymerization reactions (for example, Suzuki coupling reactions).

[0016] Examples of clay minerals include smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, and stevensite; kaolin minerals such as kaolinite, dickite, nacrite, and halloysite; serpentine minerals such as antigorite, chrysotile, amesite, and lizardite; micas such as tetrasilicic mica, biotite, muscovite, phlogopite, tschermigite, paragonite, serandite, and glauconite; chlorites such as clinochlore, chamosite, sudoite, and donbassite; pyrophyllites such as talc; sepiolites such as palygorskite; zeolites such as analcite and phillipsite; vermiculite, and further compounds obtained by treating these clay minerals with acids, bases, heat, etc. As the clay mineral, smectite is preferred, montmorillonite is more preferred, acid clay and bentonite mainly composed of montmorillonite are even more preferred, and activated clay obtained by heat-treating acid clay with sulfuric acid and / or hydrochloric acid is particularly preferred. The clay mineral can be used alone as one selected from the above, or in combination of two or more.

[0017] Regarding the shape of the clay mineral, in addition to the powder shape, it may also be in the form of granules, pellets, blocks, plates, needles, etc. From the perspective of efficiently removing impurities such as transition metals (such as palladium), low-molecular-weight components, and hydroxyl group-containing polymer compounds contained in the polymer compound, a powder shape or a granular shape, which has a large contact area with the compound to be treated, is preferred. The granules in the granular shape may be spherical, or may have a geometric shape such as a rotational ellipsoid or an octahedron, or an irregular shape with irregularities (amorphous particles), as long as they have an adsorption effect on impurities when used as a formed adsorbent. The average particle size of the clay mineral is preferably 2 μm to 5000 μm, more preferably 5 μm to 3000 μm, and even more preferably 10 μm to 2000 μm. Here, the average particle size means the cumulative 50% particle size based on volume, and can be measured using a laser diffraction scattering type particle size distribution measuring device or a test sieve defined in JIS Z 8801-2:2000. The clay mineral may be a single particle or an aggregate. Also, when the clay mineral is an aggregate, it may be used as it is, or may be used after being ground in a mortar or the like.

[0018] The mesopore volume of the clay mineral is 0.3 cm 3 / g to 0.7 cm 3 / g is preferred, 0.3 cm 3 / g to 0.6 cm 3 / g is more preferred, 0.3 cm 3 / g to 0.5 cm 3 / g is even more preferred. Here, the mesopore usually means a pore with a pore diameter of 2 nm to 50 nm. The mesopore volume can be measured by the BET adsorption method using nitrogen gas.

[0019] The clay mineral preferably has an absolute value of the zeta potential in pure water at pH 7 of 1 mV to 70 mV, more preferably 15 mV to 50 mV, and even more preferably 20 mV to 40 mV. Here, the zeta potential can be measured by the electrophoresis method.

[0020] From the perspective of removing impurities, the amount of the clay mineral used is preferably, for example, 1 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 100 parts by mass or more with respect to 100 parts by mass of the polymer compound containing impurities (hereinafter also referred to as "the polymer compound before chromatographic treatment"). Also, from the perspective of increasing the yield of the polymer compound with reduced impurities, the amount of the clay mineral used is preferably, for example, 10,000 parts by mass or less, more preferably 8,000 parts by mass or less, still more preferably 6,000 parts by mass or less, and particularly preferably 3,000 parts by mass or less with respect to 100 parts by mass of the polymer compound before chromatographic treatment.

[0021] The adsorbent may further contain a non-clay mineral in addition to the clay mineral. When a mixed adsorbent containing a clay mineral and a non-clay mineral is used, the occurrence of cracks and depressions in the adsorbent layer (formed adsorbent) can be further suppressed or reduced when a solvent is passed through the adsorbent layer. This is because the clay mineral is cohesive while the non-clay mineral is non-cohesive. Therefore, in this mixed adsorbent, the aggregation is suppressed by reducing the attraction between the adsorbent particles, and as a result, cracks and depressions are less likely to occur.

[0022] Examples of the non-clay mineral include metal oxides such as silica gel, mesoporous silica, alumina, and magnesium oxide; natural adsorbents mainly composed of metal oxides such as celite and diatomaceous earth; activated carbons such as plant-based activated carbon, coal-based activated carbon, and petroleum-based activated carbon; ion exchange resins such as cation exchange resins and anion exchange resins; and molecular adsorption resins such as styrene-divinylbenzene copolymers. As the non-clay mineral, a metal oxide is preferred, silica gel, mesoporous silica, and alumina are more preferred, and alumina is still more preferred. The non-clay mineral can be used alone or in combination of two or more selected from the above.

[0023] Regarding the shape of the non-clay mineral, in addition to the powder shape, it may also be in the form of granules, pellets, blocks, plates, needles, etc. Since it is easy to mix uniformly with the clay mineral, the powder shape or the granular shape is preferred. The granules in the granular shape may be spherical, or may have a geometric shape such as a rotating ellipsoid or an octahedron, or an irregular shape with unevenness (amorphous particles), as long as there is an adsorption effect on impurities when used as the mixed adsorbent. The average particle diameter of the non-clay mineral is preferably from 2 μm to 5000 μm, more preferably from 5 μm to 3000 μm, and still more preferably from 10 μm to 2000 μm. Here, the average particle diameter means the cumulative 50% particle diameter based on volume, and can be measured using a laser diffraction scattering type particle size distribution measuring device or a test sieve defined in JIS Z 8801-2:2000. The non-clay mineral may be a single particle or an aggregate. Further, when the non-clay mineral is an aggregate, it may be used as it is, or may be used after being ground in a mortar or the like.

[0024] As the mixed adsorbent, specifically, a combination of activated clay and a metal oxide (especially alumina) is preferred.

[0025] The amount of the non-clay mineral used is not particularly limited. From the viewpoint of uniformly mixing with the clay mineral, for example, 10 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 100 parts by mass or more, are preferred with respect to 100 parts by mass of the clay mineral. Also, from the viewpoint of increasing the recovery amount of the polymer compound after treatment, for example, 10000 parts by mass or less, more preferably 8000 parts by mass or less, still more preferably 6000 parts by mass or less, and particularly preferably 3000 parts by mass or less, are preferred with respect to 100 parts by mass of the clay mineral.

[0026] Mixing can be carried out, for example, by applying physical forces such as dropping and vibration in a mixing container, by mixing with an air current or a water current, or by mixing while crushing using a medium stirring type mill or the like. As the shape of the container used for mixing, for example, containers having a horizontal cylindrical shape, an inclined cylindrical shape, a V shape, a conical shape, a cubic shape, an S shape, a W shape, or a flask shape can be used. Mixing can be performed manually using a container without a stirring function or using a mixing container with a stirring function. As a mixing container with a stirring function, for example, a container in which the container itself rotates, a container in which a stirrer such as a paddle, a ribbon, or a screw is attached to the mixing container, and a composite container formed by a combination of both of these can be used.

[0027] When mixing, since condensation occurs and the adsorption performance of the clay mineral deteriorates if the temperature is too low, it is preferably 0 °C or higher, and more preferably 10 °C or higher. When mixing, since the adsorption performance of the clay mineral deteriorates if the humidity is too high, it is preferably 80% or less, more preferably 65% or less, and still more preferably 50% or less.

[0028] The angle of repose of the mixed adsorbent containing the clay mineral and the non-clay mineral is usually 56° or less, preferably 53° or less, and more preferably 51° or less. Also, from the viewpoint of suppressing scattering when filling the mixed adsorbent into a container, the angle of repose is preferably 5° or more. When the angle of repose of the mixed adsorbent is small as in the above range, the occurrence of cracks and sinkholes in the adsorbent layer can be suppressed. The reason for this is not necessarily clear, but the following hypothesis can be considered. When only a clay mineral is used as the adsorbent, when a solvent is passed through, the adsorbent particles attract and aggregate, so cracks and sinkholes are likely to occur in the adsorbent layer. However, when a non-clay mineral is included, since the non-clay mineral is non-aggregating, it is considered that the aggregation of the clay mineral can be reduced. Furthermore, when a mixed adsorbent with a large fluidity having an angle of repose of 56° or less is used, the mixed adsorbent easily flows into the cracks and sinkholes that are occurring, and the occurrence of cracks and sinkholes is effectively suppressed.

[0029] The angle of repose of the mixed adsorbent can be measured by the method described in the examples.

[0030] The formed adsorbent (adsorbent layer) may further contain water or an organic solvent in addition to the adsorbent containing a clay mineral. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, and propanol; ketone solvents such as acetone; aliphatic hydrocarbon solvents such as hexane and pentane; aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as tetrahydrofuran (THF) and 1,4-dioxane; amide solvents such as N,N-dimethylformamide (DMF) and dimethylacetamide (DMA); dimethyl sulfoxide (DMSO); and the like. The solvent may contain only one kind or two or more kinds.

[0031] 2. Container having a molded adsorbent The formed adsorbent of this embodiment is usually filled densely inside the container. A porous layer is provided inside the container to separate the upper part and the lower part, and a formed adsorbent (adsorbent layer) is formed on the upper side of the container of the porous layer.

[0032] The porous layer serves as a filter and is not particularly limited as long as it can pass liquids such as solvents and solutions containing polymer compounds without passing the adsorbent. The material of the porous layer may be determined according to the resistance to the liquid to be permeated and is not particularly limited. For example, paper (such as cellulose); resins (such as polyamide, polyester, and polyolefin); glass; ceramics; or metals (such as stainless steel, iron, aluminum, copper, and nickel) and the like can be mentioned. The pore diameter of the porous layer is, for example, 0.1 μm to 300 μm, preferably 0.5 μm to 200 μm, and more preferably 1 μm to 100 μm.

[0033] Vessels for forming the adsorbent layer can use kettles, filters, packed towers (hereinafter sometimes referred to as columns), etc. The shape of the vessel is not particularly limited, and examples include cylindrical, conical, cubic, inverted conical, etc. Also, the material of the vessel may be determined according to the resistance to the liquid to be permeated and is not particularly limited. For example, stainless steel, glass lining, glass, at least a combination of two or more of them, etc. can be mentioned. Further, the vessel may be provided with a sight glass or the like so that the flow of the fluid inside the vessel can be visually observed.

[0034] The size of the vessel can be freely selected in consideration of the amount of adsorbent, the size of the manufacturing equipment, ease of handling, working space, etc. For example, when a packed tower (column) is selected as the vessel, the length (height) of the column is usually 1 cm to 500 cm, preferably 5 cm to 350 cm, more preferably 10 cm to 200 cm, and its inner diameter is 1 cm to 100 cm, preferably 10 cm to 80 cm, more preferably 15 cm to 60 cm.

[0035] The schematic of an example of the apparatus for manufacturing the shaped adsorbent is shown in FIG. 1. Usually, in order to be able to purify a solution containing a polymer compound by passing it through the shaped adsorbent, there are two openings, a liquid inlet at the upper part of the vessel 1 (column) and a liquid outlet at the lower part of the vessel 1. At the upper part of the vessel, there is a charging valve 4 for introducing liquid, and a pressure regulator 2 and a pressure gauge 3 are provided so that liquid can be passed under pressurized conditions. At the lower part of the vessel, there is a withdrawal valve 5 for discharging liquid, a receiver 6 for accommodating the withdrawn liquid, and a pressure regulator 8 and a pressure gauge 7 are provided so that the lower part of the vessel can be under reduced pressure conditions for passing liquid.

[0036] 3. Method for producing a molded adsorbent The manufacturing method of the shaped adsorbent (adsorbent layer) in this embodiment has the following (1) adsorbent layer forming step and (2) solvent passing step. (1) Adsorbent layer forming step This step is a step of filling an adsorbent containing a clay mineral from the upper part of the vessel in a dry manner onto the porous layer and increasing the density to form an adsorbent layer.

[0037] As a method of filling an adsorbent into a container, a dry filling method of filling the adsorbent powder as a solid is used from the viewpoints of economy and workability. As a method of increasing the density of the filled adsorbent, for example, a method of applying vibration to the container (such as tapping, ultrasonic waves, etc.) to reduce the gaps between the adsorbent particles, a method of physically pressurizing (applying a load to compress) the upper surface and / or the lower surface of the adsorbent layer, a method of compressing the adsorbent using the pressure difference between the upper and lower spaces of the container (for example, pressurizing the upper space, depressurizing the lower space, or using both to densify the adsorbent), and a method combining these can be mentioned.

[0038] Among these, from the viewpoints of workability, efficiency, safety, etc., a method of compressing the adsorbent using the pressure difference between the upper and lower spaces of the container is preferable. In particular, a method of densifying the adsorbent by setting the upper space of the container to atmospheric pressure and depressurizing the lower space of the container is preferable. The pressure when pressurizing the upper space of the container is, for example, 0 kPaG to 300 kPaG, preferably 50 kPaG to 300 kPaG, more preferably 140 kPaG to 300 kPaG, and the pressure when depressurizing the lower space of the container is, for example, -10 kPaG to -100 kPaG, preferably -50 kPaG to -100 kPaG, more preferably -80 kPaG to -100 kPaG.

[0039] The operations of filling and densifying the adsorbent in step (1) may be carried out in this order, or both operations may be carried out simultaneously. For example, while keeping the lower space of the container in a depressurized state, the adsorbent can be introduced from the upper part of the column to perform the filling and densification of the adsorbent simultaneously. Also, when the filling amount of the adsorbent is large, the operations of filling and densifying the adsorbent may be repeated in multiple times. In that case, it is preferable to smooth the surface and make the thickness uniform for each formed adsorbent layer. The compression time for compressing the adsorbent is usually 1 minute to 60 minutes, preferably 30 minutes to 60 minutes.

[0040] The degree of densification of the adsorbent layer after process (1) can be appropriately adjusted according to the type and particle size of the adsorbent, etc., and is usually evaluated by the value (density ratio: ρ2 / ρ1) obtained by dividing the density (ρ2) after packing the adsorbent by the density (ρ1) before packing. Here, the density (ρ1) of the mixed adsorbent before packing is the value (M1 / V1) obtained by putting a predetermined mass of the mixed adsorbent into a graduated cylinder, measuring the volume (V1) of the mixed adsorbent, and dividing the mass (M1) of this mixed adsorbent by the volume (V1). The density (ρ2) of the mixed adsorbent after packing is the value (M2 / V2) obtained by calculating the volume (V2 = H2R2 2 π / 4) of the adsorbent layer from the inner diameter (R2) of the column and the height (H2) of the adsorbent layer after packing, and dividing the charged mass (M2) of this mixed adsorbent by the volume (V2). The density ratio ρ2 / ρ1 usually exceeds 1, preferably is 1.05 - 1.6, and more preferably is 1.1 - 1.5. The density (ρ2) after packing and the density (ρ1) before packing can be determined according to the description of the examples.

[0041] (2) Solvent Passing Process (Forming Process) This is a process of reducing the pressure in the lower space of the container and passing a solvent through the adsorbent layer formed in process (1) to form a formed adsorbent (adsorbent layer). The pressure when reducing the pressure in the lower space of the container can be appropriately adjusted according to the type and particle size of the adsorbent, etc., and for example, it is -10 kPaG to -100 kPaG, preferably -50 kPaG to -100 kPaG, and more preferably -80 kPaG to -100 kPaG.

[0042] As the solvent to be passed through the adsorbent layer, an organic solvent, water, etc. can be used. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, and propanol; ketone solvents such as acetone; aliphatic hydrocarbon solvents such as hexane and pentane; aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as THF and 1,4 - dioxane; amide solvents such as DMF and DMA; DMSO, etc. The solvent may be used alone or in a mixture of two or more. Among these, aromatic hydrocarbon solvents (especially toluene) and alcohol solvents (especially methanol) are preferred.

[0043] The amount of the solvent passed through the adsorbent layer is not particularly limited. From the viewpoints of operability and economy, the mass of the solvent passed is usually 0.5 times or more, preferably 1 to 10 times, more preferably 1 to 5 times, and still more preferably 1 to 3 times the mass of the adsorbent contained in the adsorbent layer. After passing a predetermined amount of the solvent through the adsorbent layer, it is preferable that the adsorbent layer does not contain air and is filled with the solvent. In this state, it can be continuously subjected to the purification treatment of the polymer compound.

[0044] In this step, it is preferable to pass the solvent while reducing the pressure in the lower space of the container and sucking the gas (air) contained in the adsorbent layer. Thereby, the rise of air bubbles from the porous layer in the adsorbent layer can be suppressed, and a molded adsorbent (adsorbent layer) without cracks and depressions can be formed. For example, in Examples 1 to 8, it has been confirmed that no air bubbles are generated on the liquid surface when the solvent passes through the adsorbent layer.

[0045] The temperature when carrying out the above series of steps (1) and (2) is preferably a certain temperature or higher in order to maintain the adsorption performance of the clay mineral without causing dew condensation under reduced pressure conditions. For example, 0°C or higher is preferable, and 10°C or higher is more preferable. Also, the humidity is preferably a certain level or lower in order to prevent moisture adsorption and maintain the adsorption performance of the clay mineral. For example, 80% or lower is preferable, 65% or lower is more preferable, and 50% or lower is still more preferable.

[0046] The bulk density of the obtained molded adsorbent can vary depending on the type of the adsorbent, but is usually preferably 0.3 g / cm 3 or more, and more preferably 0.4 g / cm 3 or more. The bulk density can be obtained as a value (M / V) obtained by calculating the volume (V = HR 2 π / 4) of the molded adsorbent from the inner diameter (R) of the column and the height (H) of the molded adsorbent, and dividing the mass (M) of the charged adsorbent by the volume (V). The filling amount of the adsorbent can be adjusted so that when the length (height) of the container is taken as 100, the thickness of the formed adsorbent (adsorbent layer) is 20 to 90, preferably 40 to 75.

[0047] Thus, a formed adsorbent can be formed on the porous layer in the container. The present embodiment also discloses a method for manufacturing a container having a formed adsorbent, including the above steps (1) and (2).

[0048] 4. Purification of polymer compounds (1) Polymer compound The polymer compound to be purified is obtained by polymerizing a predetermined monomer and is a compound having two or more repeating units (hereinafter also referred to as constituent units) derived from the monomer. The polymer compound has a molecular weight distribution, and the weight average molecular weight (Mw) in terms of polystyrene is 1×10 3 ~1×10 8 , further 3×10 3 ~1×10 7 , particularly in the range of 1×10 4 ~1×10 6 .

[0049] Examples of the polymerization method of the polymer compound include a method of polymerizing a monomer compound by Suzuki coupling reaction, a method of polymerizing by Buchwald coupling reaction, a method of polymerizing by Stille coupling reaction, a method of polymerizing by Kumada coupling reaction, a method of polymerizing by Yamamoto coupling reaction, and the like. Among them, from the viewpoint of adsorbing and removing impurities such as low molecular weight components and hydroxyl group-containing polymer compounds with the above-mentioned formed adsorbent, typically, a polymer compound produced by a method of polymerizing by Suzuki coupling reaction can be mentioned.

[0050] The polymer compound to be purified is typically obtained by the above production method, and due to this production method, impurities such as transition metals (palladium, copper, iron, etc.), low molecular weight components, and hydroxyl group-containing polymer compounds are contained as impurities. The transition metal is due to the transition metal catalyst used in the polymerization reaction. The low molecular weight component is a compound with a low molecular weight due to an insufficient polymerization reaction (for example, the weight average molecular weight (Mw) is 2×10 4 or less). The hydroxyl group-containing polymer compound is, for example, a polymer compound formed by the reaction of a monomer in which a part of the boronic acid (or its ester) group: -B(OR)2 (R is a hydrogen atom, an alkyl group, etc.) is replaced by a hydroxyl group (-OH) in the Suzuki coupling reaction. When these impurities are contained in the polymer compound and used as a material for an organic EL element or the like, it has an adverse effect on the electrical characteristics, lifespan, etc. of the element. Therefore, it is necessary to remove or reduce them to purify the polymer compound.

[0051] (2) Method for purifying polymer compound This purification can be carried out by passing a mixture containing a polymer compound and a solvent (usually a solution containing the polymer compound) containing impurities such as low molecular weight components and hydroxyl group-containing polymer compounds through a container in which the above-mentioned molded adsorbent (adsorbent layer) is formed. The solution that has passed through the molded adsorbent (adsorbent layer) is recovered, and a polymer compound with the above-mentioned impurities removed or reduced can be produced. That is, the polymer compound can be purified. Also, after passing the mixture through the molded adsorbent (adsorbent layer), a solvent (developing solvent) can be further passed through to recover the polymer compound. Furthermore, the solution that has passed through the molded adsorbent (adsorbent layer) can be divided into two or more fractions, and the fractions with the above-mentioned impurities effectively removed can be collected to obtain the polymer compound. The purification by passing a solution containing a polymer compound through a container in which a molded adsorbent (adsorbent layer) is formed may be carried out once or may be repeatedly carried out a plurality of times.

[0052] This purification can usually be carried out by introducing a solution containing a polymer compound containing impurities into the upper part of a container forming a molded adsorbent (adsorbent layer) and pressurizing the upper space of the container. The solvent for dissolving the polymer compound can be selected from various solvents according to the properties of the polymer compound. Usually, it is a good solvent for the polymer compound, and specifically, it can be defined as a solvent in which the solubility (20 °C) of the polymer compound is 1 g / 100 g or more.

[0053] Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, cyclohexylbenzene, and tetralin; ether solvents such as THF, 1,4-dioxane, dimethoxyethane, and anisole; amide solvents such as DMA, DMF, and N-methyl-2-pyrrolidone; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; nitrile solvents such as acetonitrile; halogenated hydrocarbon solvents such as chloroform; ester solvents such as methyl acetate and ethyl acetate; and DMSO. The solvent may be used alone or in combination of two or more.

[0054] The content (concentration) of the polymer compound in the solution containing the polymer compound is usually 0.01% by mass to 80% by mass, preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and still more preferably 1% by mass to 10% by mass.

[0055] The pressure of the upper space of the container when pressurizing the upper space of the container can be appropriately selected according to the size of the container, the thickness of the adsorbent layer, etc. For example, it is 0 kPaG to 300 kPaG, preferably 50 kPaG to 300 kPaG, and more preferably 140 kPaG to 300 kPaG. This pressure may be constant or the pressure may be varied (pressurized or depressurized) over time.

[0056] As the treatment time for passing a liquid through the shaped adsorbent (adsorbent layer), from the viewpoint of effectively removing impurities, 5 minutes or more is preferable, 30 minutes or more is more preferable, and 1 hour or more is even more preferable. Since the shaped adsorbent (adsorbent layer) of the present embodiment has no cracks or depressions, when the liquid is passed through with a constant pressure, it has the characteristic that the flux ratio at the initial stage of liquid passage and at the end of liquid passage hardly changes. By this purification, a polymer compound from which impurities such as low molecular weight components and hydroxyl group-containing polymer compounds have been removed can be obtained.

[0057] As the apparatus for purifying a polymer compound, for example, the apparatus of FIG. 1 described above can be used. Usually, a solution containing a polymer compound and a solvent is introduced from the charging valve 4 at the upper part of the container 1, the pressure regulator 2 and the pressure gauge 3 are adjusted to pressurize the upper space of the apparatus, and the liquid is passed through the adsorbent layer. The liquid discharged from the lower part of the container 1 is introduced into the receiver 6 through the extraction valve 5. The solution accommodated in the receiver 6 contains the purified polymer compound.

[0058] 5. Charge transport material Since the impurities in the polymer compound purified by the method of the present invention are effectively removed or reduced, it can be used as a material for an organic EL element or the like, particularly as a charge transporting material. The charge transporting material may be either a hole transporting material or an electron transporting material.

[0059] The present invention also provides a charge transporting material containing the above-described purified polymer compound. The charge transporting material contains the polymer compound, and may further contain a charge transporting material composed of a low molecular organic compound or the like. Known materials can be used for these charge transporting materials.

[0060] Examples of the hole transporting material include aromatic amines and their derivatives, carbazole and its derivatives, polyparaphenylene and its derivatives.

[0061] Examples of the electron transporting material include oxadiazole and its derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, diphenoquinone and its derivatives, triazine and its derivatives, and metal complexes of 8-hydroxyquinoline and its derivatives.

[0062] The low molecular weight organic compound as the charge transporting material means a charge transporting material having a molecular weight of less than 1000, and includes a host compound and a charge injection / transport compound used in a low molecular weight organic EL element. Specifically, examples thereof include the compounds described in "Organic EL Display" (co-authored by Shizushi Tokito, Chiharu Adachi, and Hideyuki Murata, Ohmsha), page 107, Monthly Display, VOL9, No9, 2003, pages 26 - 30, JP-A-2004-24400, and JP-A-2004-277377.

[0063] Examples of the high molecular weight compound as the charge transporting material include a conjugated high molecular weight compound and a non-conjugated high molecular weight compound, and the conjugated high molecular weight compound is preferred.

[0064] The above-mentioned conjugated high molecular weight compound means a high molecular weight compound containing an aromatic ring in the main chain, and in which 80% or more of the bonds between the aromatic rings contained in the main chain are directly bonded, or are bonded by a conjugated bond group such as a vinylene group, or an atom such as an oxygen atom, a sulfur atom, or a nitrogen atom having an unpaired electron. In the above-mentioned conjugated high molecular weight compound, the above-mentioned bonding form is preferably a direct bond or a nitrogen atom having an unpaired electron, and more preferably a direct bond. The above-mentioned non-conjugated high molecular weight compound means a high molecular weight compound containing an aromatic ring in the main chain, and in which less than 80% of the bonds between the aromatic rings contained in the main chain are directly bonded, or are bonded by a conjugated bond group such as a vinylene group, or an atom such as an oxygen atom, a sulfur atom, or a nitrogen atom having an unpaired electron, or a high molecular weight compound not containing an aromatic ring in the main chain but having an aromatic ring in the side chain.

[0065] Examples of the conjugated polymer compound include polymer compounds in which benzene, naphthalene, phenanthrene, fluorene, etc. are aromatic rings in the main chain. The aromatic ring may be one type or two or more types. The aromatic ring may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an amino group, an aryl group, and a group that may have a crosslinking group. The crosslinking group is a group capable of generating a new bond by being subjected to heating, ultraviolet irradiation, near-ultraviolet irradiation, visible light irradiation, infrared irradiation, or a radical reaction, etc. Examples of the crosslinking group include a vinyl group, a styryl group, a benzocyclobutanyl group, an acetyl group, a norbornyl group, an oxetanyl group, etc.

[0066] In the synthesis of the charge transporting material according to this embodiment, a palladium compound can be used. The palladium compound is usually a palladium catalyst. The palladium catalyst may be a homogeneous transition metal complex catalyst or a heterogeneous transition metal complex catalyst, and preferably, it is a homogeneous transition metal complex catalyst.

[0067] The polymer compound (for example, a charge transporting material) obtained by the production method of the present invention is useful for the production of a light-emitting device. A light-emitting device using the polymer compound obtained by the production method of the present invention has, for example, an anode, a cathode, and one or two or more organic layers provided between the anode and the cathode. In the production of the light-emitting device, at least one of the organic layers is formed using the polymer compound obtained by the production method. Examples of the organic layer formed in this way include a hole transporting layer. Note that the anode, the cathode, and the other organic layers can be produced by known methods using known materials.

Examples

[0068] Hereinafter, examples are shown to explain the present invention in more detail, but the present invention is not limited thereto.

[0069] The adsorbent layers produced in the examples and comparative examples were evaluated as follows. <Evaluation Index for High-Density Formation in the Adsorbent Layer> The degree of high-density formation was evaluated by the value obtained by dividing the density after filling (ρ2) of the adsorbent in the high-density formation process by the density before filling (ρ1) (density ratio: ρ2 / ρ1). The density before filling (ρ1) of the adsorbent was determined by putting a predetermined mass of the adsorbent material into a graduated cylinder, measuring the volume (V1) of the adsorbent material, and taking the value (M1 / V1) obtained by dividing this volume (V1) by the mass (M1). The density after filling (ρ2) of the adsorbent was calculated from the inner diameter (R2) of the column and the height (H2) of the adsorbent layer after filling to obtain the volume of the adsorbent layer (V2 = H2R2 2 π / 4), and taking the value (M2 / V2) obtained by dividing this volume (V2) by the charged mass (M2).

[0070] <Confirmation of the Presence or Absence of Cracks or Depressions in the Adsorbent Layer> The presence or absence of cracks and depressions in the adsorbent layer at the end of liquid passage was visually confirmed. The case without cracks and depressions was evaluated as "A", and the case with at least cracks or depressions was evaluated as "B".

[0071] <Evaluation Index for the Occurrence of Cracks or Depressions in the Adsorbent Layer> When passing a solvent through an adsorbent layer without cracks, the flux stabilizes at a constant value from the initial stage to the end of liquid passage. However, when cracks or depressions occur in the adsorbent layer, the flux during solvent passage tends to gradually increase. Therefore, the flux ratio between the initial stage and the end of liquid passage was used as the evaluation index for the occurrence of cracks or depressions in the adsorbent layer. The initial stage of liquid passage refers to the time when 0.5 mass times the mass of the adsorbent of solvent has been passed, and the end of liquid passage refers to the time when 2.0 mass times the mass of the adsorbent of solvent has been passed.

[0072] <Measurement Method of Angle of Repose> The angle of repose was determined as follows. The adsorbent was dropped from a glass funnel of a certain height onto a cylindrical base with a diameter D (mm) having a retaining edge for holding the powder, which was fixed to a jack with adjustable height. At this time, in order to minimize the impact of the powder falling on the tip of the conical deposit, the jack was adjusted so that the dropping height was in the range of 5 mm to 10 mm from the apex of the deposit. When a stable and symmetric deposit with an inclined angle was obtained, the height H (cm), which is the difference between the highest part of the retaining edge and the highest part of the deposit, was measured. Such formation and measurement of the deposit were carried out 3 times, and by taking the average value as the height H, the angle of repose "θ (°)" = "arctan(H / 2D) × 180 / π" was used to calculate the angle of repose. Specifically, the measured value under the condition that the inner diameter of the glass funnel, which is the supply port of the mixed adsorbent, was 4 mm and D = 24 mm was adopted. The angle of repose was measured indoors at an air temperature of 25°C and a humidity of 50%. The adsorbent was taken out from the reagent bottle and immediately the angle of repose was measured. Also, when mixing the adsorbents, the adsorbents were mixed immediately after being taken out from the reagent bottle, and the angle of repose was measured.

[0073] <Example 1> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (diameter 40 mm, made of glass) was opened (atmospheric pressure), the lower pressure regulator of the column was set to -95 kPaG, 81 g of the adsorbent was charged into the upper part of the column with the lower part of the column under reduced pressure, and after standing under reduced pressure for 1 minute, the height of the adsorbent layer was measured. Thereafter, while maintaining the lower pressure of the column at a reduced pressure state of -95 kPaG, 400 g of toluene was charged into the upper part of the column and passed through the adsorbent layer. When toluene passed through the adsorbent layer, it was confirmed that no bubbles rose on the liquid surface. Furthermore, while maintaining the lower pressure of the column at a reduced pressure state of -95 kPaG, the flow of toluene was continued, and the extraction flow rate over time was measured. The extraction flow rate during the toluene flow was stable at a constant value, and no cracks or depressions were confirmed on the surface of the adsorbent layer after the toluene flow. The diameter of the column used here was 40 mm, the column height was 250 mm, and the effective area was 0.001 m 2That is, as the adsorbent, activated clay (V2, manufactured by Mizusawa Chemical Industry Co., Ltd.) with a volume particle size distribution D50 of 31 μm was used. The volume particle size distribution D50 is a value measured using a particle size analyzer (Master Sizer 3000, manufactured by Malvern). The angle of repose of the adsorbent used was 56.3°.

[0074] <Example 2> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (36 mm in diameter, made of stainless steel) was opened (to atmospheric pressure), the lower pressure regulator of the column was set to -80 kPaG, and 160 g of the adsorbent was charged into the upper part of the column while the lower part of the column was under reduced pressure. After standing for 30 minutes under reduced pressure, the height of the adsorbent layer was measured. Then, while maintaining the lower pressure of the column at a reduced pressure of -80 kPaG, 160 g of toluene was charged into the upper part of the column and passed through the adsorbent layer. When toluene reached the receiver, the extraction valve of the column was closed. When toluene passed through the adsorbent layer, it was confirmed that no bubbles rose on the liquid surface. Furthermore, 320 g of toluene was charged into the upper part of the column, and while the upper pressure regulator of the column was set to 100 kPaG, it was passed through the adsorbent layer. At this time, the extraction valve was opened, and the extraction flow rate over time was measured. The extraction flow rate during toluene passing was stable at a constant value, and no cracks or depressions were confirmed on the surface of the adsorbent layer after toluene passing. The diameter of the column used here was 36 mm, the column height was 500 mm, and the effective area was 0.001 m 2 That is, as the adsorbent, activated clay (V2, manufactured by Mizusawa Chemical Industry Co., Ltd.) with a volume particle size distribution D50 of 31 μm was used. The volume particle size distribution D50 is a value measured using a particle size analyzer (Master Sizer 3000, manufactured by Malvern). The angle of repose of the adsorbent used was 56.3°.

[0075] <Example 3> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (40 mm in diameter, made of glass) was opened (to atmospheric pressure), the lower pressure regulator of the column was set to -95 kPaG, and 81 g of the adsorbent was charged into the upper part of the column while the lower part of the column was under reduced pressure. After standing for 1 minute under reduced pressure, the height of the adsorbent layer was measured. Subsequently, the lower pressure regulator of the column was set to -50 kPaG, 400 g of toluene was charged into the upper part of the column, and it was passed through the adsorbent layer. When the toluene passed through the adsorbent layer, it was confirmed that no bubbles rose on the liquid surface. Furthermore, while maintaining the lower pressure of the column in a reduced pressure state of -50 kPaG, the flow of toluene was continued, and the extraction flow rate over time was measured. The extraction flow rate during the toluene flow was stable at a constant value, and no cracks or depressions were confirmed on the surface of the adsorbent layer after the toluene flow. The diameter of the column used here was 40 mm, the column height was 250 mm, and the effective area was 0.001 m 2 The adsorbent used was activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm. The volume particle size distribution D50 is a value measured using a particle size analyzer (MasterSizer 3000 manufactured by Malvern). The angle of repose of the adsorbent used was 56.3°.

[0076] <Example 4> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (40 mm in diameter, made of glass) was opened (atmospheric pressure), the lower pressure regulator of the column was set to -95 kPaG, 81 g of the adsorbent was charged into the upper part of the column while the lower part of the column was under reduced pressure, and after standing under reduced pressure for 1 minute, the height of the adsorbent layer was measured. Subsequently, the lower pressure regulator of the column was set to -10 kPaG, 400 g of toluene was charged into the upper part of the column, and it was passed through the adsorbent layer. When the toluene passed through the adsorbent layer, it was confirmed that no bubbles rose on the liquid surface. Furthermore, while maintaining the lower pressure of the column in a reduced pressure state of -10 kPaG, the flow of toluene was continued, and the extraction flow rate over time was measured. The extraction flow rate during the toluene flow was stable at a constant value, and no cracks or depressions were confirmed on the surface of the adsorbent layer after the toluene flow. The diameter of the column used here was 40 mm, the column height was 250 mm, and the effective area was 0.001 m 2Specifically, the adsorbent used was activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm. The volume particle size distribution D50 was measured using a particle size analyzer (Master Sizer 3000 manufactured by Malvern). The angle of repose of the adsorbent used was 56.3°.

[0077] <Example 5> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (made of glass lining with a diameter of 500 mm) was opened (to atmospheric pressure), the lower pressure regulator of the column was set to -95 kPaG, and with the lower part of the column under reduced pressure, 49.5 kg of the adsorbent was charged into the upper part of the column in 4 portions. After each charging, the upper surface of the adsorbent was leveled with a spatula for smoothing. After standing for 30 minutes under reduced pressure, the height of the adsorbent layer was measured. Subsequently, while maintaining the lower pressure of the column at a reduced pressure of -95 kPaG, 54 kg of toluene was charged into the upper part of the column and passed through the adsorbent layer. When the toluene reached the receiver, the extraction valve of the column was closed. It was confirmed that no bubbles rose on the liquid surface when the toluene passed through the adsorbent layer. Furthermore, 100 kg of toluene was charged into the upper part of the column, and with the upper pressure regulator of the column set to 100 kPaG, it was passed through the adsorbent layer. At this time, the extraction valve was opened to measure the extraction flow rate over time. The extraction flow rate during the toluene passing was stable at a constant value, and no cracks or depressions were confirmed on the surface of the adsorbent layer after the toluene passing. The diameter of the column used here was 500 mm, the column height was 400 mm, and the effective area was 0.2 m 2 Specifically, the adsorbent used was a mixture of 21.0 kg of activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm and 28.5 kg of alumina with a volume particle size distribution D50 of 50 μm (manufactured by Sumitomo Chemical Co., Ltd., activated alumina KCG - 30) mixed with a mixer. The angle of repose of the adsorbent used was 53.1°.

[0078] <Example 6> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (40 mm in diameter, made of glass) was opened (to atmospheric pressure), the lower pressure regulator of the column was set to -95 kPaG, 103 g of the adsorbent was charged into the upper part of the column while the lower part of the column was under reduced pressure, and after standing for 1 minute under reduced pressure, the height of the adsorbent layer was measured. Thereafter, while maintaining the lower pressure of the column at a reduced pressure of -95 kPaG, 400 g of toluene was charged into the upper part of the column and passed through the adsorbent layer. When toluene passed through the adsorbent layer, it was confirmed that no bubbles rose on the liquid surface. Furthermore, while maintaining the lower pressure of the column at a reduced pressure of -95 kPaG, the flow of toluene was continued, and the extraction flow rate over time was measured. The extraction flow rate during the toluene flow was stable at a constant value, and no cracks or depressions were confirmed on the surface of the adsorbent layer after the toluene flow. The diameter of the column used here was 40 mm, the column height was 250 mm, and the effective area was 0.001 m 2 The adsorbent used was a mixture of 22 g of activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm and 81 g of alumina (manufactured by Sumitomo Chemical Co., Ltd., activated alumina KCG-30) with a volume particle size distribution D50 of 50 μm, which was mixed in a mixer. The volume particle size distribution D50 is a value measured using a particle size analyzer (MasterSizer 3000 manufactured by Malvern). The angle of repose of the adsorbent used was 48.4°.

[0079] <Example 7> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (108 mm in diameter, made of stainless steel) was opened (to atmospheric pressure), the lower pressure regulator of the column was set to -80 kPaG, 750 g of the adsorbent was charged into the column while the lower part of the column was under reduced pressure, and after standing for 30 minutes under reduced pressure, the height of the adsorbent layer was measured. Thereafter, while maintaining the lower pressure of the column at a reduced pressure of -80 kPaG, 750 g of toluene was charged into the upper part of the column and passed through the adsorbent layer. When toluene passed through the adsorbent layer, it was confirmed that no bubbles rose on the liquid surface. Furthermore, 1500 g of toluene was charged into the upper part of the column, and it was passed through the adsorbent layer with the upper pressure regulator of the column set at 100 kPaG. At this time, the extraction valve was opened, and the extraction flow rate over time was measured. The extraction flow rate during toluene passing was stable at a constant value, and no cracks or depressions were observed on the surface of the adsorbent layer after toluene passing. The diameter of the column used here was 108 mm, the column height was 500 mm, and the effective area was 0.009 m 2 and the adsorbent used was zeolite (manufactured by Tosoh Corporation, Zeolam F-9 100#) with a volume particle size distribution D50 of 12 μm. The angle of repose of the adsorbent used was 64.8°.

[0080] <Example 8> Using the apparatus shown in Fig. 1, the upper pressure regulator of the column (40 mm in diameter, made of glass) was opened (atmospheric pressure), the lower pressure regulator of the column was set at -95 kPaG, and 81 g of the adsorbent was charged into the upper part of the column with the lower part of the column under reduced pressure. After standing under reduced pressure for 1 minute, the height of the adsorbent layer was measured. Thereafter, while maintaining the lower pressure of the column at a reduced pressure of -95 kPaG, 400 g of methanol was charged into the upper part of the column and passed through the adsorbent layer. It was confirmed that no bubbles rose on the liquid surface when methanol passed through the adsorbent layer. Furthermore, while maintaining the lower pressure of the column at a reduced pressure of -95 kPaG, the flow of methanol was continued, and the extraction flow rate over time was measured. The extraction flow rate during methanol passing was stable at a constant value, and no cracks or depressions were observed on the surface of the adsorbent layer after methanol passing. The diameter of the column used here was 40 mm, the column height was 250 mm, and the effective area was 0.001 m 2 and the adsorbent used was activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm. The volume particle size distribution D50 is a value measured using a particle size analyzer (manufactured by Malvern, Mastersizer 3000). The angle of repose of the adsorbent used was 56.3°.

[0081] <Comparative Example 1> Using the apparatus shown in Fig. 1 in the same manner as in Example 1, the upper pressure regulator of the column (36 mm in diameter, made of stainless steel) was opened (to atmospheric pressure), the lower pressure regulator of the column was set to -80 kPaG, 160 g of the adsorbent was charged into the column while the lower part of the column was under reduced pressure, and after standing for 30 minutes under reduced pressure, the height of the adsorbent layer was measured. After that, after confirming that the lower pressure regulator of the column was opened (to atmospheric pressure), 480 g of toluene was charged into the upper part of the column, and then the upper pressure regulator of the column was set to 100 kPaG and passed through the adsorbent layer. When observing the liquid level when toluene was charged into the column, a large amount of bubbles were confirmed. Also, the extraction flow rate during toluene passing decreased gradually. When the adsorbent layer was checked after passing toluene, depressions were found on the surface layer. The diameter of the column used here was 36 mm, the column height was 500 mm, and the effective area was 0.001 m 2 and the adsorbent used was activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm. The angle of repose of the adsorbent used was 56.3°.

[0082] <Comparative Example 2> Using the apparatus shown in Fig. 1, the upper and lower pressure regulators of the column (36 mm in diameter, made of stainless steel) were set to atmospheric pressure (0 kPaG), 160 g of the adsorbent was charged into the upper part of the column, and the height of the adsorbent layer was measured. After charging 320 g of toluene into the upper part of the column, the upper pressure regulator of the column was set to 100 kPaG and passed through the adsorbent layer. At this time, the extraction valve was opened and the extraction flow rate over time was measured. When observing the liquid level when toluene was charged into the column, a large amount of bubbles were confirmed. Also, the extraction flow rate during toluene passing decreased gradually. When the adsorbent layer was checked after passing toluene, depressions were found on the surface layer. The diameter of the column used here was 36 mm, the column height was 500 mm, and the effective area was 0.001 m 2 and the adsorbent used was activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm. The angle of repose of the adsorbent used was 56.3°.

[0083] <Comparative Example 3> Using the apparatus shown in Fig. 1, the upper pressure regulator and the lower pressure regulator of the column (40 mm in diameter, made of glass) were set to atmospheric pressure (0 kPaG), 81 g of the adsorbent was charged into the upper part of the column, and the height of the adsorbent layer was measured. Subsequently, the lower pressure of the column was set to -95 kPaG, 400 g of toluene was charged into the upper part of the column, and passed through the adsorbent layer. When observing the passage of toluene through the adsorbent layer, no bubbles rose on the liquid surface, but cracks occurred on the side surface of the adsorbent layer. Furthermore, while maintaining the lower pressure of the column at a reduced pressure of -95 kPaG, the flow of toluene was continued, and the extraction flow rate over time was measured. The extraction flow rate during the toluene flow gradually decreased. When the adsorbent layer was checked after the toluene flow, cracks were found on the surface layer. The diameter of the column used here was 40 mm, the column height was 250 mm, and the effective area was 0.001 m 2 The adsorbent used was activated clay (manufactured by Mizusawa Chemical Industry Co., Ltd., V2) with a volume particle size distribution D50 of 31 μm. The volume particle size distribution D50 is a value measured using a particle size analyzer (MasterSizer 3000 manufactured by Malvern). The angle of repose of the adsorbent used was 56.3°.

[0084] The above results are shown in Table 1.

Table 1

[0085] From Table 1, since the adsorbent layers (formed adsorbents) of Examples 1 to 8 were manufactured through the adsorbent formation step and the solvent flow-through step of the present invention, cracks and depressions did not occur in the adsorbent layer, and the flux was stable at a constant value from the initial stage to the end of the flow-through. As a result, by subjecting the polymer compound containing impurities to column chromatography treatment with this adsorbent layer, the impurities can be effectively reduced.

[0086] On the other hand, since the adsorbent layer of Comparative Example 1 was manufactured by flowing the liquid through the upper part of the column under pressure in the solvent flow-through step, cracks occurred in the adsorbent layer, and the flux increased from the initial stage to the end of the flow-through. In the adsorbent layer of Comparative Example 2, since the upper part of the column was pressurized to fill the adsorbent in the adsorbent layer forming step and the liquid was passed through while pressurizing the upper part of the column in the solvent passing step, cracks occurred in the adsorbent layer and the flux increased from the initial stage of liquid passing to the end of liquid passing. In the adsorbent layer of Comparative Example 3, since the adsorbent was filled at atmospheric pressure in the adsorbent layer forming step, cracks occurred in the adsorbent layer and the flux increased from the initial stage of liquid passing to the end of liquid passing.

Industrial Applicability

[0087] According to the production method of the present invention, an adsorbent layer (formed adsorbent) that does not generate cracks and depressions can be produced. By filtering using this adsorbent layer (formed adsorbent), impurities such as low molecular weight components and high molecular compounds having hydroxyl group terminals can be effectively removed, so that a high-purity high molecular compound can be produced.

Explanation of Symbols

[0088] 1: Container (column) 2: Upper pressure regulator 3: Upper pressure gauge 4: Charge valve 5: Discharge valve 6: Receiver 7: Lower pressure gauge 8: Lower pressure regulator

Claims

1. A method for manufacturing a molded adsorbent on the porous layer of a container in which the upper and lower parts are separated by a porous layer, comprising: (1) a step of filling an adsorbent containing a clay mineral from the upper part of the container onto the porous layer in a dry state and increasing the density to form an adsorbent layer; and (2) a step of reducing the pressure in the lower space of the container and passing a solvent through the adsorbent layer to form a molded adsorbent. A method for manufacturing a molded adsorbent, comprising the above steps.

2. The manufacturing method according to claim 1, wherein the step (1) includes a step of reducing the pressure in the lower space of the container to increase the density of the adsorbent.

3. The manufacturing method according to claim 1 or 2, wherein the step (1) includes a step of introducing the adsorbent from the upper part of the container onto the porous layer while reducing the pressure in the lower space of the container to increase the density of the adsorbent.

4. The manufacturing method according to any one of claims 1 to 3, wherein the clay mineral contains at least one selected from the group consisting of smectite and zeolite.

5. The manufacturing method according to claim 4, wherein the smectite is activated clay.

6. The manufacturing method according to any one of claims 1 to 5, wherein the average particle diameter of the clay mineral is 2 μm to 5000 μm.

7. The manufacturing method according to any one of claims 1 to 6, wherein the adsorbent is a mixed adsorbent containing a clay mineral and a non-clay mineral, and the angle of repose of the mixed adsorbent is 56° or less.

8. A method for manufacturing a polymer compound with reduced impurities, characterized in that a molded adsorbent is manufactured by the manufacturing method according to any one of claims 1 to 7, and a solution of a polymer compound containing impurities is passed through the molded adsorbent to remove the impurities.

9. A method for purifying a polymer compound, characterized in that a molded adsorbent is manufactured by the manufacturing method according to any one of claims 1 to 7, and a solution of a polymer compound containing impurities is passed through the molded adsorbent to remove the impurities.

10. A method for manufacturing a container having a molded adsorbent on the porous layer of a container in which the upper and lower parts are separated by a porous layer, comprising: (1) a step of filling an adsorbent containing a clay mineral from the upper part of the container onto the porous layer in a dry state and increasing the density to form an adsorbent layer; and (2) a step of reducing the pressure in the lower space of the container and passing a solvent through the adsorbent layer to form a molded adsorbent. A method for manufacturing a container, comprising the above steps.

11. A method for manufacturing a light-emitting device having an anode, a cathode, and one or more organic layers provided between the anode and the cathode, wherein at least one of the organic layers is formed using a polymer compound obtained by the manufacturing method according to claim 8.

12. The manufacturing method according to claim 11, wherein the organic layer formed using the polymer compound is a hole transport layer.

Images