JP2014008483A - Sublimation refining method, and sublimation refining apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To know a coagulation quantity of a treatment object substance without having influence on a temperature of an inner wall surface of a sublimation refining pipe, during sublimation refining.SOLUTION: A sublimation refining apparatus 1 comprises a sublimation refining pipe 4 having an inflow port 2 and an outflow port 3, decompression means 5, heating means 6a and 6b, inert gas supply means 7 and an ultraviolet ray absorbance measuring device 8. In the inside of the sublimation refining pipe 4 at a reduced pressure, a treatment object substance 11 is heated to be sublimated; and the sublimated treatment object substance 11 is carried by inert gas 12 that is discharged from the outflow port 3 after being supplied to the sublimation refining pipe 4 from the inflow port 2 by the inert gas supply means 7. On an inner wall surface of the sublimation refining pipe 4, heated to provide temperature gradient along the carrying direction of the inert gas 12, the carried treatment object substance 11 is coagulated. The ultraviolet ray absorbance of the sublimation refining pipe 4 is measured by the ultraviolet ray absorbance measuring device 8, and the degree of coagulation of the treatment object substance 11 can be known from a change in the ultraviolet ray absorbance during the sublimation refining.

Description

  The present invention relates to a sublimation purification method and a sublimation purification apparatus for purifying and separating a substance to be treated using a difference in sublimation temperature from a mixture containing a sublimable organic compound as a substance to be treated.

  As a conventional sublimation purification method and sublimation purification apparatus, a method of performing sublimation purification by sublimating an organic compound powder and then condensing it inside a sublimation purification tube is known (see, for example, Patent Document 1).

  Hereinafter, the sublimation purification apparatus will be described with reference to FIG.

  As shown in FIG. 7, the sublimation purification apparatus 101 includes a sublimation purification pipe 102, a decompression means 103, heating means 104a and 104b, and an inert gas supply means 105. The sublimation purification pipe 102 includes an inlet 106 and an outlet 107. ing. In the sublimation purification tube 102 decompressed by the decompression means 103, the material to be treated 108 is sublimated by heating the material 108 to be treated by the heating means 104a. Further, an inert gas 109 supplied from the inlet 106 to the sublimation purification pipe 102 by the inert gas supply means 105 and discharged from the outlet 107 is used to transfer the sublimated material 108 and transfer the inert gas 109. The material to be treated 108 is condensed on the inner wall surface of the sublimation purification tube 102 heated by the heating means 104b so as to have a temperature gradient along the direction.

  In such a conventional sublimation purification apparatus, in order to purify the material to be treated containing impurities, the property of sublimation from solid to gas is utilized when the material to be treated is heated under reduced pressure. In other words, since the sublimation temperature of the impurity to be treated differs from that of the substance to be treated, if the substance to be treated is sublimated at a constant temperature, impurities having a high sublimation temperature are not sublimated. When the treatment substance is condensed in another place, a substance to be treated with high purity can be obtained. In addition, impurities with a condensation temperature lower than that of the material to be treated do not condense at the place where the material to be treated condenses, so that the material to be treated is recovered only from the place where the material to be treated has condensed, so Can be obtained.

  That is, the sublimation purification method is to condense a high-purity treated substance on the inner wall surface of the sublimation purification tube using the difference between the impurities contained in the treated substance and the sublimation temperature or condensation temperature of the treated substance. It is important that the temperature of the inner wall surface of the sublimation purification tube is stable below the condensation temperature of the material to be treated. Therefore, in order to stabilize the temperature of the inner wall surface of the sublimation purification tube that condenses the substance to be treated during sublimation purification, the heating means is provided over the entire circumference of the sublimation purification tube.

  Substances to be treated to which a sublimation purification method is applied, such as organic semiconductors and organic dyes, often have a characteristic of being easily decomposed in an atmosphere containing oxygen or moisture, and are purified by sublimation in a state filled with an inert gas.

  In addition, in the conventional sublimation purification method, the material to be treated sublimated by the heating means is conveyed by inert gas, but the vacuum degree of the sublimation purification tube decreases when the flow rate of the inert gas is increased for the purpose of increasing the conveyance speed. For this reason, the substance to be treated cannot sublimate below its decomposition temperature, leading to decomposition of the substance to be treated. Therefore, the flow rate of the inert gas is several tens mL / min. It is limited to a certain extent, and the conveyance speed of the substance to be treated cannot be increased, and it may take several hours to complete the sublimation purification. Further, the timing of completion of sublimation purification is determined by the amount of condensation of the substance to be treated on the inner wall surface of the sublimation purification tube.

JP 2007-246424 A

  That is, in the sublimation purification method over a long period of time, it is necessary to remove the heating means from the sublimation purification tube so that the sublimation purification tube can be visually observed in order to grasp the amount of the substance to be treated on the inner wall surface of the sublimation purification tube. By removing the heating means, the temperature of the inner wall surface of the sublimation purification tube is lowered from a desired temperature, and impurities other than the material to be treated may condense. Therefore, in practice, it is better to avoid removing the heating means during sublimation purification, and the completion time of sublimation purification will be estimated by analogy from past experience. In some cases, sublimation purification was completed while sublimation purification was insufficient.

  In other words, the conventional sublimation purification method cannot visually observe the inner wall of the sublimation purification tube during sublimation purification, and does not affect the temperature of the inner wall surface of the sublimation purification tube during sublimation purification. Had the problem of not being able to grasp.

  Therefore, the present invention solves the above-described conventional problems, and provides a sublimation purification apparatus that can grasp the amount of condensation of the substance to be treated without affecting the temperature of the inner wall surface of the sublimation purification tube during sublimation purification. The purpose is to provide.

  And in order to achieve this object, the present invention measures the ultraviolet absorbance of the sublimation purification tube, and does not affect the temperature of the inner wall surface of the sublimation purification tube during sublimation purification. This is a sublimation purification method for grasping the above, thereby achieving the intended purpose.

  According to the present invention, the ultraviolet absorbance of the sublimation purification tube is measured during the sublimation purification, so that the ultraviolet rays are absorbed by the substance to be treated condensed on the inner wall surface of the sublimation purification tube. By doing so, it is possible to obtain an effect that it is possible to grasp the condensation amount of the substance to be treated on the inner wall of the sublimation purification tube without affecting the temperature of the inner wall surface of the sublimation purification tube during the sublimation purification.

Schematic sectional view of the sublimation purification apparatus of Embodiment 1 of the present invention Schematic sectional view of the sublimation purification apparatus of Embodiment 2 of the present invention Schematic sectional view of a sublimation purification apparatus according to Embodiment 3 of the present invention. Schematic sectional view of a sublimation purification apparatus according to Embodiment 4 of the present invention. The graph which shows the ultraviolet absorption spectrum in the sublimation purification apparatus of Embodiment 4 of this invention. The graph which shows the ultraviolet absorption spectrum in the sublimation purification apparatus of Embodiment 4 of this invention. Schematic sectional view of a conventional sublimation purification device

  In the sublimation purification method according to claim 1 of the present invention, the inner wall surface of the sublimation purification tube heated to have a temperature gradient is conveyed by an inert gas through a sublimation purification tube having a reduced pressure inside. A sublimation purification method for condensing the material to be treated which has been sublimated to the surface, wherein the amount of condensation of the material to be treated is determined by measuring the ultraviolet absorbance of the sublimation purification tube. As a result, it becomes possible to grasp the amount of condensation of the substance to be treated from the degree of attenuation of ultraviolet light absorption by the substance to be treated condensed on the inner wall surface of the sublimation purification tube, so that the sublimation purification can be performed during sublimation purification. There is an effect that the amount of condensation of the substance to be treated can be grasped without affecting the temperature of the inner wall surface of the pipe.

  Further, a sublimation purification pipe having an inlet and an outlet, a decompression means, a heating means, and an inert gas supply means are provided, and the substance to be treated is heated by the heating means inside the sublimation purification pipe decompressed by the decompression means. The substance to be treated is sublimated, and further, the substance to be treated sublimated by the inert gas supplied from the inlet to the sublimation purification pipe and discharged from the outlet by the inert gas supply means. A sublimation purification apparatus for condensing the substance to be treated, which is conveyed, on the inner wall surface of the sublimation purification pipe heated by the heating means so as to have a temperature gradient along the conveyance direction of the inert gas; A sublimation purification device that measures the ultraviolet absorbance of the sublimation purification tube with an ultraviolet absorbance measurement device and grasps the amount of condensation of the substance to be treated from the change in ultraviolet absorbance during sublimation purification. It may be formed. As a result, it becomes possible to grasp the amount of condensation of the substance to be treated from the degree of attenuation of ultraviolet light absorption by the substance to be treated condensed on the inner wall surface of the sublimation purification tube, so that the sublimation purification can be performed during sublimation purification. There is an effect that the amount of condensation of the substance to be treated can be grasped without affecting the temperature of the inner wall surface of the pipe.

  Further, a configuration of a sublimation purification apparatus that grasps the amount of coagulation of the substance to be treated by measuring the ultraviolet absorbance of the sublimation purification tube with an ultraviolet absorbance measurement apparatus having an optical probe may be adopted. As a result, the substance to be treated that condenses on the inner wall surface of the sublimation purification tube absorbs ultraviolet rays, so that the absorbance of the ultraviolet rays received and emitted via the optical probe changes. Since the amount can be ascertained, there is an effect that the amount of condensation of the substance to be treated can be grasped without affecting the temperature of the inner wall surface of the sublimation purification tube during sublimation purification.

  Further, it may be configured as a sublimation purification apparatus that identifies the place where the substance to be treated is condensed on the inner wall surface of the sublimation purification pipe by measuring the ultraviolet absorbance at a plurality of locations of the sublimation purification pipe. As a result, the substance to be treated that condenses on the inner wall of the sublimation purification tube absorbs ultraviolet rays, so it is possible to grasp the amount of condensation of the substance to be treated at multiple locations by measuring the ultraviolet absorbance at multiple locations. In the inner wall surface of the sublimation purification tube, there is an effect that it is possible to grasp a region where the amount of the substance to be treated is large.

  Alternatively, a sublimation purification apparatus may be configured to measure the ultraviolet absorption spectrum of the sublimation purification tube to grasp the composition of the substance to be treated that has condensed on the inner wall surface of the sublimation purification tube. The substance to be treated that condenses on the inner wall surface of the sublimation purification tube is condensed on the inner wall surface of the sublimation purification tube by measuring the absorption spectrum at the wavelength in the ultraviolet region because the wavelength of the absorbed ultraviolet rays differs for each material. This has the effect that the composition of the material to be treated can be grasped.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(Embodiment 1)
FIG. 1 shows a schematic cross-sectional view of the sublimation purification apparatus of the first embodiment. The sublimation purification apparatus 1 includes a sublimation purification pipe 4 having an inlet 2 and an outlet 3, a decompression means 5, a heating means 6 a, a heating means 6 b, an inert gas supply means 7, and an ultraviolet absorbance measurement device 8. The ultraviolet absorbance measuring device 8 includes a light emitting unit 9 and a light receiving unit 10. A substance 11 to be treated is installed on the inlet 2 side in the sublimation purification pipe 4. The sublimation purification pipe 4 is divided at both ends so that the inlet 2 and the outlet 3 can be removed.

  When sublimation purification of the material to be treated 11 is performed by the sublimation purification method, first, the inlet 2 of the sublimation purification pipe is removed, the substance to be treated 11 is installed inside the sublimation purification pipe 4, and the inlet 2 is attached again. The sublimation purification tube 4 is made of quartz glass having high mechanical strength and high heat resistance because the inside of the sublimation purification tube 4 is decompressed and the sublimation purification tube is heated during the sublimation purification.

  In the sublimation purification pipe 4 decompressed by the decompression means 5, the substance 11 to be treated is heated by the heating means 6a installed so as to cover the outer periphery of the cylindrical sublimation purification pipe 4 without a gap. The to-be-processed substance 11 heated above the sublimation temperature under reduced pressure is sublimated. Further, the sublimated substance 11 is transported by the inert gas 12 supplied from the inlet 2 to the sublimation purification pipe 4 by the inert gas supply means 7 and discharged from the outlet 3.

  The inner wall surface of the sublimation purification tube 4 is heated by the heating means 6b so as to have a temperature gradient along the transport direction of the inert gas 12, and is covered in a region that matches the condensation temperature of the transported substance 11 to be treated. The treatment substance 11 is condensed. The heating means 6b is installed so as to cover the outer peripheral portion of the cylindrical sublimation purification pipe 4 without a gap, like the heating means 6a.

  As in the conventional method, the heating temperature by the heating means 6a is lower than the decomposition temperature of the substance 11 to be treated, and the pressure is reduced by the decompression means 5 so that the substance 11 can be sublimated at that temperature.

  The heating temperature by the heating means 6b is close to the condensation temperature of the substance 11 to be treated. It condenses on the inner wall. Among the impurities contained in the substance 11 to be treated, impurities having a sublimation temperature higher than the heating temperature of the heating means 6a do not sublime, so they remain in place and impurities having a condensation temperature lower than the heating temperature of the heating means 6b are inactive. The gas is discharged from the sublimation purification tube 4 together with the gas.

  When the sublimation purification is completed, the heating means 6a, the heating means 6b, the decompression means 5 and the inert gas supply means 7 are stopped, and when the inside of the sublimation purification pipe 4 is lowered to normal temperature and normal pressure, the outlet 3 And the condensed material 11 to be treated is recovered.

  The substance 11 to be treated by sublimation purification in the embodiment of the present invention is an organic dye used for organic EL such as tris (8-quinolinolato) aluminum or an organic semiconductor such as pentacene, and has a characteristic of sublimating under reduced pressure. If it exists, the same effect can be acquired also about another organic compound.

  Further, the inert gas 12 used in the embodiment of the present invention is injected into the sublimation purification tube 4 in order to transport the sublimated material 11 to be processed, and does not react with the material 11 to be processed. A gas is desirable. Specifically, Ar gas or the like is applied.

  In the embodiment of the present invention, unlike a conventional sublimation purification apparatus, an ultraviolet absorbance measurement apparatus 8 having a light emitting unit 9 and a light receiving unit 10 is provided so as to face each other with a sublimation purification tube 4 interposed therebetween. The ultraviolet light emitted from the light emitting unit 9 passes through the sublimation purification tube 4 and is received by the light receiving unit 10. Since the sublimation purification tube 4 is made of quartz glass in order to satisfy the strength and heat resistance, the sublimation purification tube 4 hardly absorbs ultraviolet rays before the sublimation purification is started. When sublimation purification proceeds and the material 11 to be treated condenses on the inner wall of the sublimation purification tube 4, the ultraviolet light emitted from the light emitting portion 9 is absorbed by the material 11 to be treated, and the amount of ultraviolet light at the light receiving portion 10 decreases.

  That is, by measuring the ultraviolet absorbance during the sublimation purification with the ultraviolet absorbance measuring device 8, it is possible to grasp the condensation amount of the substance 11 to be treated on the inner wall of the sublimation purification tube 4. The light-emitting unit 9 and the light-receiving unit 10 of the ultraviolet light absorbance measuring device 8 may be installed so that the sublimation purification tube 4 can transmit ultraviolet rays. As in the conventional sublimation purification device, the sublimation purification tube 4 has an inner wall surface. There is no need to separate the heating means 6a and the heating means 6b from the sublimation purification tube 4 to visually check the condensation state of the substance 11 to be treated, and the temperature of the inner wall surface of the sublimation purification tube 4 is maintained at a desired temperature. It is possible to reduce the possibility that impurities are contained in the material 11 to be condensed.

  Further, by continuously or intermittently measuring the ultraviolet absorbance of the sublimation purification tube 4 with the ultraviolet absorbance measuring device 8, it is possible to grasp that the sublimation purification is completed when the ultraviolet absorbance becomes constant, so that an excessive amount of time is required. To carry out sublimation purification and to complete sublimation purification with insufficient sublimation purification.

  In addition, in this Embodiment, although it does not specifically limit about the structure of the heating means 6a and the heating means 6b, The inner wall surface of the sublimation purification pipe | tube 4 including the heating means etc. which coat | covered the heating wire with heat insulating materials, such as glass fiber, etc. Any structure can be used as long as it can be efficiently heated. In FIG. 1, heating wires of the heating means 6a and the heating means 6b are indicated by broken lines, and surrounding heat insulating materials are indicated by dotted lines. When Joule heat generated by the current flowing in the heating wire is used for heating, a method of stabilizing the heating temperature by controlling the current while measuring the temperature of the heating means with a thermocouple is desirable. Further, the heating means 6a and the heating means 6b are installed so as to cover the outer peripheral portion of the sublimation purification pipe 4 without a gap, but in order to stabilize the temperature of the inner wall surface of the sublimation purification pipe 4, the heating means 6a. The heating means 6b and the sublimation purification pipe 4 are preferably installed close to each other, and the heating means 6a and the heating means 6b are preferably configured in accordance with the outer shape of the sublimation purification pipe 4.

  In the present embodiment, the positional relationship between the heating unit 6b and the light emitting unit 9 and the light receiving unit 10 of the ultraviolet absorbance measuring device 8 is not particularly limited. However, the sublimation purification tube 4 heated by the heating unit 6b has a heat transfer effect. By the action of the inert gas flow, there is a temperature gradient from the heating means 6b to the downstream side of the inert gas, and in consideration of the situation, the ultraviolet absorbance measuring device 8 is provided downstream of the heating means 6b. The light emitting unit 9 and the light receiving unit 10 may be installed.

  That is, the heating temperature of the heating unit 6b is set so that the positions of the light emitting unit 9 and the light receiving unit 10 of the ultraviolet absorbance measuring device 8 installed on the downstream side of the heating unit 6b become the condensation temperature of the substance 11 to be processed. What is necessary is just to maintain temperature higher than the condensing temperature of the substance 11. The positions of the light emitting unit 9 and the light receiving unit 10 of the heating means 6b and the ultraviolet absorbance measuring device 8 may be separated from each other, and the positions of the light emitting unit 9 and the light receiving unit 10 of the ultraviolet absorbance measuring device 8 are set to the condensation temperature of the substance 11 to be treated. The heating temperature of the heating means 6b may be set so that

  In the present embodiment, the wavelength of the ultraviolet light emitted from the light emitting unit 9 of the ultraviolet absorbance measuring device 8 is not particularly limited. However, if light having a wavelength including about 200 nm to 500 nm is irradiated, the substance to be processed 11 can measure the attenuation of ultraviolet absorbance derived from No. 11.

  In the present embodiment, the structures of the light emitting unit 9 and the light receiving unit 10 of the ultraviolet absorbance measuring device 8 are not particularly limited. The light emitting unit 9 is a light emitting device capable of irradiating ultraviolet rays having a desired wavelength, such as a mercury lamp or an ultraviolet LED. The light receiving unit 10 may be an optical semiconductor element that can receive a desired wavelength.

  In the present embodiment, the ultraviolet absorbance of the sublimation purification tube is measured by the ultraviolet absorbance measuring device 8 during the sublimation purification, but it is not limited to this method. The ultraviolet absorbance of the sublimation purification tube 4 may be measured and compared before the start of sublimation purification and at the time when a predetermined time has passed and the sublimation purification is completed. From the degree of change in the ultraviolet absorbance of the sublimation purification tube 4 before and after sublimation purification, the amount of condensation of the substance 11 to be treated can be grasped. Further, the operation of the inert gas supply means 7 may be temporarily stopped during the sublimation purification, and the ultraviolet absorbance of the sublimation purification tube 4 may be measured and compared in a state where the substance 11 to be treated is not transported by the inert gas 12. Since the absorption of ultraviolet rays by the material to be treated 11 not attached to the inner wall of the sublimation purification tube can be eliminated, the amount of condensation of the material to be treated 11 can be accurately grasped.

  In the present embodiment, the structure of the decompression means 5 is not particularly limited, but it is sufficient that the inside of the sublimation purification pipe 4 can be decompressed by a pump such as a rotary pump or a diaphragm pump. May be increased.

  Further, in the present embodiment, the structure of the inert gas supply means 7 is not particularly limited, but a pressure reducing valve and a mass flow controller that can supply a fixed amount of inert gas such as argon gas filled in a gas cylinder may be used. It is only necessary to supply a gas capable of transporting the sublimed material 11 to be processed at a constant flow rate with a gas having low reactivity with the material 11 to be processed.

  In the present embodiment, the method for recovering the material 11 to be processed after sublimation purification is not particularly limited, but after completion of sublimation purification, the outlet 3 is removed from the sublimation purification tube 4 and the material 11 is scraped from the inner wall surface. It may be taken. Alternatively, after the sublimation purification is completed, the sublimation purification tube 4 may be cut before and after the portion where the treatment target material 11 is condensed, and the treatment target material 11 may be scraped off from the inner wall surface of the sublimation purification tube 4. In addition, a sublimation purification recovery tube having an outer diameter that is substantially the same as the inner diameter of the sublimation purification tube 4 is inserted into the sublimation purification tube 4 in advance, and the sublimation purification recovery tube 4 is removed from the sublimation purification tube 4. It is also possible to easily recover the processing substance 11. In the case of using the sublimation purification tube, quartz glass having a high ultraviolet transmittance may be used as in the sublimation purification tube 4.

  In the present embodiment, the decompression means 5 is connected to the outlet 3. However, the present invention is not limited to this method, and impurities having a low condensation temperature contained in the substance to be treated 11 are sucked into the decompression means. Therefore, a cold trap may be provided between the outlet 3 and the decompression means 5.

  In the present embodiment, the substance 11 to be treated is installed inside the sublimation purification tube 4 before sublimation purification and is sublimated by heating by the heating means 6a. However, the present invention is not limited to this method. The material to be treated 11 may be directly heated with a heater or the like in a crucible, and any heating means may be used as long as it can be heated to a temperature at which the material to be treated sublimates under reduced pressure. When 11 is expected to contain a large amount of impurities, it is preferable to heat the substance to be treated 11 in a container so that the residue can be recovered after sublimation purification.

  Moreover, in this Embodiment, although the light emission part 9 and the light-receiving part 10 of the ultraviolet-ray-absorbance measuring apparatus 8 were installed so that it might oppose on both sides of the sublimation purification pipe | tube 4, it is not restricted to this method. The ultraviolet light emitted from the light emitting unit 9 may reach the light receiving unit 10 after passing through the inner wall surface of the sublimation purification tube 4, and the light emitting unit 9 and the light receiving unit 10 are combined into a sublimation purification tube 4 in combination with a quartz reflector. You may arrange | position with respect.

(Embodiment 2)
FIG. 2 shows a schematic sectional view of the sublimation purification apparatus of the second embodiment. The same components as those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.

  In the present embodiment, unlike the first embodiment, the ultraviolet absorbance measurement device 8 has an optical probe 13. The optical probe 13 is a small-diameter quartz fiber having a characteristic of transmitting ultraviolet light emitted from the light emitting unit 9 without attenuation and transmitting ultraviolet light transmitted through the sublimation purification tube 4 to the light receiving unit 10 without attenuation.

  According to this configuration, it is only necessary to install a small-diameter quartz fiber in the vicinity of the heating means 6b, and a clearance enough to pass the small-diameter quartz fiber through the heating means 6b in the outer peripheral portion of the sublimation purification tube 4 is ensured. The possibility of disturbing the temperature gradient of the inner wall surface of the sublimation purification tube 4 formed by heat transfer from the heating means 6b can be reduced.

  Further, since the optical probe 13 is a quartz fiber formed of quartz glass, the thermal conductivity is low, and the possibility of disturbing the temperature gradient of the inner wall surface of the sublimation purification tube 4 can be reduced.

  As in the first embodiment, the amount of condensation of the substance 11 to be treated can be grasped by measuring the change in the UV absorbance of the sublimation purification tube 4. In this embodiment, the temperature gradient of the sublimation purification tube 4 is obtained. Since the ultraviolet absorbance of the sublimation purification tube 4 can be measured without disturbing the temperature, the degree of purification of the substance 11 to be treated can be increased using a uniform temperature gradient.

  In the present embodiment, the light-emitting unit 9 and the light-receiving unit 10 of the ultraviolet absorbance measuring device 8 are installed so as to face each other with the sublimation purification tube 4 interposed therebetween. However, the present invention is not limited to this arrangement. 4 so that the end faces of the two optical probes 13 are opposed to each other so that the sublimation purification tube 4 is sandwiched between them so that the ultraviolet light can be transmitted through the sublimation purification tube 4. Absent. Since the optical probe 13 is a thin quartz fiber, the installation position of the light emitting unit 9 and the light receiving unit 10 can be arbitrarily set by utilizing its flexibility.

  In the present embodiment, the diameter of the optical probe 13 is not particularly limited, but may be any area as long as it can measure the ultraviolet absorbance of the adhesion site of the substance 11 to be treated on the inner wall surface of the sublimation purification tube 4. It is only necessary that the sublimation purification tube 4 is sandwiched by quartz fibers having a cross section of about 0.2 mm so that the optical axes thereof coincide with each other. A quartz fiber of 2 mm or more may be used.

(Embodiment 3)
FIG. 3 shows a schematic cross-sectional view of the sublimation purification apparatus of the third embodiment. The same components as those in FIGS. 1 to 2 are denoted by the same reference numerals, and detailed description thereof is omitted. In the present embodiment, unlike the second embodiment, the ultraviolet absorbance measuring apparatus 8 includes an optical path switching means 14 and a plurality of sets of optical probes 13. Moreover, the heating means 6c and the heating means 6d are provided, and it is installed so that the outer peripheral part of the sublimation purification pipe | tube 4 may be covered without gap similarly to the heating means 6a.

  The optical path switching means 14 can switch the position where the sublimation purification tube 4 transmits ultraviolet rays, and in this embodiment, it can measure ultraviolet absorbances at three different locations.

  By switching the optical path switching unit 14 on the light emitting unit 9 side and the optical path switching unit 14 on the light receiving unit 10 side in conjunction with this configuration, by transmitting ultraviolet light to the optical probe 13 opposed across the sublimation purification tube 4, The ultraviolet absorbance at a plurality of locations of the sublimation purification tube 4 can be measured. That is, it is possible to measure the ultraviolet absorbance at a plurality of locations of the sublimation purification tube 4 by properly using a plurality of sets of optical probes 13 by the optical path switching means 14, and the substance 11 to be treated is condensed at a position where the ultraviolet absorbance is high. Therefore, it is possible to specify the place where the material 11 to be treated is condensed on the inner wall surface of the sublimation purification tube 4.

  Further, this embodiment differs from the first and second embodiments in that it includes four sets of heating means. The heating means 6a is a heating means for sublimating the material 11 to be treated, and exhibits the same action as in the first and second embodiments. The heating means 6b, the heating means 6c, and the heating means 6d are for setting the temperature for condensing the material 11 to be treated. By operating the respective heating means at different heating temperatures, the heating means 6b and the heating means 6d are applied to the inner wall surface of the sublimation purification tube 4. A temperature gradient can be set. Since the sublimed material 11 to be treated is transported by the inert gas 12, the material 11 to be treated is condensed at a site corresponding to the condensation temperature of the material 11 to be treated.

  In the present embodiment, unlike the conventional sublimation purification apparatus, it is possible to identify the site where the material 11 to be treated is condensed during sublimation purification. Therefore, even when the material 11 to be treated whose sublimation temperature is unknown is sublimated and purified. Thus, it becomes possible to change the temperature setting of the heating means while grasping the condensation state during the sublimation purification, and the work efficiency of the sublimation purification can be increased. Further, when the sublimation-purified substance 11 to be treated is collected after the sublimation purification is completed, the place to be collected can be easily specified, and the working efficiency of the sublimation purification can be improved.

  Further, when the degree of vacuum inside the sublimation purification tube 4 or the temperature of the inner wall surface fluctuates for some reason during the sublimation purification, the condensation position of the substance 11 to be treated fluctuates. Since the ultraviolet absorbance at a plurality of locations on the inner wall surface of the purification tube 4 is measured, it is possible to specify the location where the substance 11 to be treated has actually condensed.

  Further, in the conventional sublimation purification method, in order to grasp the sublimation temperature of the substance to be treated 11, the substance to be treated 11 is heated under vacuum using a separate device in advance of the sublimation purification work to reduce the weight. Often, precise thermogravimetric analysis is performed. The relationship between the degree of vacuum and the condensation temperature can be grasped from the results of thermogravimetric analysis, and sublimation purification conditions are set according to the conditions.However, the vacuum degree differs from the results of thermogravimetric analysis in this embodiment. Even when the place where the condensation occurs due to the change in the condensation temperature, it is possible to easily identify the place where the substance 11 to be treated has condensed.

  Similarly to the first and second embodiments, the stable maintenance of the inner wall surface temperature of the sublimation purification pipe 4 is a point that increases the purity of the sublimation purification, so that the heating means 6a, the heating means 6b, and the heating means It is important to install 6c and heating means 6d so as to cover the outer peripheral portion of sublimation purification tube 4 without a gap, and by using optical probe 13 of the present embodiment, there is a gap in the outer peripheral portion of sublimation purification tube 4. It can cope without it.

(Embodiment 4)
FIG. 4 shows a schematic cross-sectional view of the sublimation purification apparatus of the fourth embodiment. The same components as those in FIGS. 1 to 3 are denoted by the same reference numerals, and detailed description thereof is omitted.

  In the present embodiment, the light emitting unit 9 of the ultraviolet absorbance measuring device 8 emits ultraviolet rays in a range including the wavelength absorbed by the substance 11 to be processed. The light receiving unit 10 receives the ultraviolet rays from the light emitting unit 9 and measures the absorbance for each wavelength. When the material 11 to be treated is a mixture of a plurality of substances having different condensation temperatures, the heating temperatures of the heating means 6b, the heating means 6c, and the heating means 6d are set in accordance with the different condensation temperatures. As a result, the high-condensation temperature treated substance 15 and the low-condensation temperature treated substance 16 condense at different sites.

  FIG. 5 shows an ultraviolet absorption spectrum of the substance 15 to be treated with a high condensation temperature. The high-condensation temperature treated substance 15 shows a high absorbance around 255 nm.

  FIG. 6 shows the ultraviolet absorption spectrum of the low-condensation temperature treated substance 16. The low-condensation temperature-treated substance 16 exhibits high absorbance around 240 nm.

  In this configuration, a plurality of sets of optical probes 13 are selectively used by the action of the optical path switching means 14 provided in the ultraviolet absorbance measuring device 8, so that the ultraviolet rays transmitted through the sublimation purification tube 4 can be transmitted to a plurality of positions of the sublimation purification tube 4. The relationship between wavelength and absorbance, that is, the ultraviolet absorption spectrum can be measured. The presence and composition of the high condensation temperature treated substance 15 or the low condensation temperature treated substance 16 condensed on the inner wall surface of the sublimation purification tube 4 can be determined from the ultraviolet absorption spectrum.

  Further, by comparing each ultraviolet absorption spectrum shown in FIG. 5 and FIG. 6 with an ultraviolet absorption spectrum of a known substance, it can be confirmed whether or not the desired substance is purified by sublimation.

  Further, by superimposing the ultraviolet absorption spectra shown in FIGS. 5 and 6, if the mutual absorption peak is not shared, the high condensation temperature treated substance 15 and the low condensation temperature treated substance 16 are separated with high purity. The success or failure can be confirmed.

  That is, if the temperature of the inner wall surface of the sublimation purification tube 4 is arbitrarily set and a plurality of regions having different inner wall surface temperatures can be formed at a plurality of locations as in the present embodiment, the condensing temperatures of the substances to be treated 11 are different. It is possible to easily separate and purify even a mixed substance of a plurality of substances having a concentration, and grasp the composition of the condensed substance 11 to be treated by measuring the ultraviolet absorption spectrum at each condensation site. be able to.

  Further, in the present embodiment, monitoring the condensation state of the high condensation temperature treated substance 15 which is the previous stage of the sublimation purification tube 4 mixes the high condensation temperature treated substance 15 and the low condensation temperature treated substance 16. This is important for separation and purification. When the heating temperature of the heating means 6b is lower than the condensing temperature of the low condensing temperature treated substance 16, the high condensing temperature treated substance 15 and the low condensing temperature treated substance 16 are condensed in the same place. Therefore, separation and purification cannot be performed. In that case, by increasing the heating temperature of the heating means 6b, the low-condensation temperature-treated substance 16 sublimes and condenses after the wake of the heating means 6c. And the low-condensation temperature treated substance 16 can be separated and purified without mixing.

  In the present embodiment, the substance to be treated 11 is a mixture of two kinds of substances, that is, the substance to be treated 15 having a high condensation temperature and the substance to be treated 16 having a low condensation temperature. However, the composition is not limited to this. In the case of a mixture of more than one type, the same effect can be obtained with the same configuration if three or more types of temperature regions are set and the ultraviolet absorption spectrum of the region can be measured.

  In addition, even when the substance to be treated 11 is not a mixture of a plurality of substances having different condensation temperatures, the place where the substance to be treated 11 is condensed can be specified as in the third embodiment.

  In the present embodiment, the ultraviolet absorption spectrum is continuously measured in the wavelength range of 200 nm to 500 nm. However, the present invention is not limited to this method. A similar effect can be obtained even if the spectrum is measured at intermittent wavelengths including the ultraviolet absorption peak of the substance 15 and the low condensation temperature treated substance 16.

  In the present embodiment, the structures of the light emitting unit 9 and the light receiving unit 10 of the ultraviolet absorbance measuring device 8 are not particularly limited, but the light emitting unit 9 can irradiate ultraviolet rays having a desired wavelength such as a mercury lamp or a deuterium lamp. The light receiving unit 10 may be a light receiving device such as a light receiving device using a diffraction grating and a photomultiplier tube or a photodiode array so as to receive a desired wavelength range.

  The sublimation purification method and the sublimation purification apparatus according to the present invention make it possible to grasp the condensed amount of a substance to be treated during sublimation purification, and are used for organic EL, organic solar cells, organic semiconductors, and the like. It is useful as a means for purifying and separating organic compounds having sublimation properties.

DESCRIPTION OF SYMBOLS 1 Sublimation purification apparatus 2 Inlet 3 Outlet 4 Sublimation purification pipe 5 Depressurization means 6a Heating means 6b Heating means 6c Heating means 6d Heating means 7 Inert gas supply means 8 Ultraviolet light absorption measuring device 9 Light emitting part 10 Light receiving part 11 Processed substance DESCRIPTION OF SYMBOLS 12 Inert gas 13 Optical probe 14 Optical path switching means 15 High condensing temperature processed substance 16 Low condensing temperature processed substance 101 Sublimation purification apparatus 102 Sublimation purification pipe 103 Decompression means 104a Heating means 104b Heating means 105 Inert gas supply means 106 Flow Inlet 107 Outlet 108 Substance to be treated 109 Inert gas

Claims (5)

A sublimation purification method in which a substance to be treated sublimated in a sublimation purification pipe whose pressure is reduced is conveyed by an inert gas, and the substance to be sublimated is condensed on an inner wall surface of the sublimation purification pipe heated to have a temperature gradient. Because
A sublimation purification method in which the amount of condensation of the substance to be treated is grasped by measuring the ultraviolet absorbance of the sublimation purification tube. A sublimation purification pipe having an inlet and an outlet, a depressurization means, a heating means, and an inert gas supply means, and the substance to be treated is heated by the heating means inside the sublimation purification pipe decompressed by the decompression means. The material to be treated is sublimated with the inert gas supplied from the inflow port to the sublimation purification pipe and discharged from the outflow port by the inert gas supply means. A sublimation purification apparatus for condensing the transferred substance to be treated on the inner wall surface of the sublimation purification tube heated by the heating means so as to have a temperature gradient along the conveying direction of the inert gas,
A sublimation purification apparatus that measures the ultraviolet absorbance of the sublimation purification tube with an ultraviolet absorbance measurement apparatus, and grasps the amount of condensation of the substance to be treated from the change in ultraviolet absorbance during sublimation purification. The sublimation purification apparatus according to claim 2, wherein the amount of condensation of the substance to be treated is determined by measuring the ultraviolet absorbance of the sublimation purification tube with an ultraviolet absorbance measurement apparatus having an optical probe. The sublimation purification apparatus according to claim 2 or 3, wherein a place where the substance to be treated is condensed is identified on an inner wall surface of the sublimation purification pipe by measuring ultraviolet absorbance at a plurality of locations of the sublimation purification pipe. The sublimation purification according to any one of claims 2 to 4, wherein the composition of the substance to be treated condensed on the inner wall surface of the sublimation purification tube is determined by measuring an ultraviolet absorption spectrum of the sublimation purification tube. apparatus.

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