JP2005313069A - Sublimation/purification apparatus and subliming/purifying method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sublimation/purification apparatus the yield of which when a chemical substance is purified is improved and the operability of which is also improved and to provide a subliming/purifying method. <P>SOLUTION: This sublimation/purification apparatus is provided with: a purification part having a vaporization part for vaporizing the chemical substance and a collection part for collecting the vaporized chemical substance; and an exhausting unit and constituted so that the height Ha of the vaporization part and the height Hb of the collection part satisfy the inequality: Ha>Hb. Alternatively, this sublimation/purification apparatus is provided with: the purification part having the vaporization part for vaporizing the chemical substance and the collection part for collecting the vaporized chemical substance; and the exhausting unit and constituted so that the purification part has a collection inner pipe for collecting the chemical substance and the internal area S1 of the collection inner pipe and the internal area S2 of a collection outer pipe satisfy the inequality: S1≥S2. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a sublimation purification apparatus and a sublimation method for purifying a chemical substance with high yield.

  Chemical substances used in applications where trace amounts of impurities adversely affect performance need to be highly purified. Examples of such chemical substances include organic electroluminescent materials (hereinafter referred to as organic EL materials) that have been actively developed for practical use in recent years.

  The organic EL element using the organic EL material is an organic laminated thin film light emitting element that emits light when an electron injected from a cathode and a hole injected from an anode are recombined in an organic phosphor sandwiched between both electrodes. . This element is attracting attention because it is thin, has high luminance emission under a low driving voltage, and multicolor emission by selecting a fluorescent material.

  The factor that affects the light emission characteristics and durability of the organic EL element is the purity of the organic EL material. If impurities are mixed in the organic EL material, the impurities may trap carriers or cause quenching, resulting in a decrease in emission intensity, emission efficiency, and durability. Therefore, in order to reduce impurities, it is necessary to highly refine the organic EL material.

  Conventionally, column chromatography, recrystallization, distillation, sublimation and the like are known as general purification methods for chemical substances. Among these, column chromatography and recrystallization include a process in which a chemical substance to be purified is dissolved in an organic solvent, and therefore cannot be used for purification of a chemical substance having poor solubility, and in the organic solvent to be used. There is a disadvantage that it can be contaminated with impurities. For this reason, column chromatography and recrystallization are often carried out as a process before the final purification for obtaining a high-purity material.

  Distillation and sublimation are commonly used as purification methods for chemicals that need to be highly purified as described above because there is no process using such organic solvents. However, since distillation is limited to purification of liquid substances at room temperature, sublimation is effective for purification of solid substances such as organic EL materials.

  Sublimation is a purification method in which a solid material is heated and vaporized and collected at a collection unit set to a temperature at which the high-purity material is solidified to obtain a target high-purity material. Sublimation means that gas is converted directly from a solid, but organic EL materials are solid at room temperature but are often melted when heated, and the purification of such materials is expressed as sublimation rather than distillation. Often to do.

  Laboratory equipment for sublimation purification is described in general literature such as “Experimental Chemistry Course”, but some industrial equipment or sublimation methods are also disclosed.

  For example, from the viewpoint of low cost, simple operability, and high yield, a sublimation purification method in which a collection tube for collecting the purified substance is provided has been proposed (for example, see Patent Document 1). However, it has been found that it is difficult to say that this method can obtain a purification yield sufficient for industrial mass purification.

  In the sublimation purification process, when the substance condenses as a liquid, or when it becomes a solid state in the process of condensing as a liquid and cooling to room temperature, a distillation purification apparatus provided with a weir so that the condensate does not mix other than the collection part It has been proposed (see, for example, Patent Document 2). However, it has been found that it is difficult to say that this apparatus has high operability when taking out the collected substance.

In addition, a method of using quartz wool as a nucleation field for purified substances has been proposed (see, for example, Patent Document 3). However, it has been found that this method has little effect on the above-mentioned low crystallinity substances, and it is difficult to say that the purification yield is sufficient.
JP 2003-95992 A JP 2002-200401 A JP 2000-203988 A

  An object of the present invention is to provide a sublimation purification apparatus and a sublimation purification method that solve the problems of the conventional technique and improve the purification yield and operability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found an apparatus structure capable of improving the purification yield, and have completed the present invention.

That is, in order to achieve the above object, the present invention mainly adopts the following structure.
(1) A sublimation purification apparatus having a purification section having a vaporization section for vaporizing a chemical substance and a collection section for collecting the vaporized chemical substance, and an exhaust device, the height Ha of the vaporization section and A sublimation purification apparatus characterized in that the height Hb of the collecting part is Ha> Hb.
(2) A sublimation purification apparatus having a purification section having a vaporization section for vaporizing a chemical substance and a collection section for collecting the vaporized chemical substance, and an exhaust device, and collecting the chemical substance in the purification section A sublimation purification apparatus having a collecting inner pipe, wherein an inner area S1 of the collecting inner pipe and an inner area S2 of the collecting section outer pipe are S1 ≧ S2.
(3) The chemical substance refining apparatus according to claim 1 or 2, wherein the chemical substances are arranged in a multilayer form in the vaporizing section.
(4) A chemical substance purification method using the chemical substance purification apparatus according to any one of (1) to (3).

  By using the sublimation purification apparatus and the sublimation purification method of the present invention, the purification yield and operability of chemical substances during sublimation purification can be improved.

  Hereinafter, the present invention will be described in detail.

  FIG. 1 shows an example of a schematic cross-sectional view of the sublimation purification apparatus of the present invention. The sublimation purification apparatus of the present invention includes a purification unit A having a vaporization unit A-1 for vaporizing a chemical substance and a collection unit A-2 for collecting the vaporized chemical substance, and an exhaust device B.

  The outline of the purification method using the sublimation purification apparatus of the present invention is as follows. First, a chemical substance to be purified is charged into the vaporization section A-1 of the vacuum chamber 1 and the inside of the apparatus is evacuated by the vacuum pump 11. Next, the collection part A-2 is heated to a desired temperature with the heat source 4 and the vaporization part A-1 with the heat source 5, and the chemical substance is vaporized from the vaporization part A-1, and solidified in the collection part A-2. Let them collect. Here, impurities having a solidification temperature lower than the temperature of the collection part A-2 are not collected by the collection part A-2 but collected by the cooling part A-3 or the trap 9. Nonvolatile impurities and impurities with a high vaporization temperature remain as residue in the vaporization part A-1. When sublimation purification is completed, the inside of the apparatus is returned to atmospheric pressure, and the purified chemical substance is collected from the collection unit A-2.

  Normally, in sublimation purification, the chemical substance is vaporized in the solid state, and the vaporized substance is solidified as a solid state. However, in this specification, the chemical substance is once vaporized after being melted, or the chemical substance is in a liquid state. The case of solidification in the process of condensation and cooling to room temperature is also defined as a category of sublimation purification.

  In particular, organic EL materials that require extremely high levels of purification are often used as thin films in organic EL elements, and thus have many amorphous materials due to their physical properties. When such a chemical substance is sublimated and purified, the purified chemical substance may condense as a liquid and become a solid state in the process of cooling to room temperature.

  When the chemical substance is purified by sublimation, it condenses as a liquid in the collection part and flows into the vaporization part, and there is a problem that the purification yield decreases and the chemical substance that flows into the vaporization part is thermally denatured. In order to solve such a problem, the apparatus of the present invention is characterized in that the relationship between the height Ha of the vaporizing section and the height Hb of the collecting section is Ha> Hb with respect to the horizontal plane. . This is to prevent the chemical substance condensed as a liquid in the collection part from flowing again into the vaporization part and the chemical substance flowing in from being thermally denatured, thereby improving the purification yield of the chemical substance.

  Here, the height Ha of the vaporization section and the height Hb of the collection section are distances from the horizontal plane to the lowermost surfaces of the inner surfaces of the vaporization section and the collection section. The arrangement form is not particularly limited, and examples thereof include a step type as shown in FIG. 8 and an inclined type as shown in FIG.

  The purification section A in the present invention is preferably composed of a vaporization section A-1, a collection section A-2, and a cooling section A-3 as shown in FIG. 1, but has a lower solidification temperature than the chemical substance to be purified. When many impurities are not included, the cooling part A-3 may be omitted. Moreover, even if the vaporization part A-1, the collection part A-2, and the cooling part A-3 are an integral type, they may be connected so that each can be removed.

The vaporization part A-1 in the present invention is a part in which a chemical substance to be purified is charged. The shape of the vaporization part A-1 is generally a cylindrical shape, but may be a box shape or a kamaboko shape, and is not particularly limited. The material of the vaporization part A-1 is not particularly limited, but is preferably composed of a chemically inert material. This is to prevent the chemical substance from partially decomposing or causing modification such as polymerization in order to heat the chemical substance to a high temperature during purification. For example, stainless steel, tantalum, tungsten, molybdenum, titanium, Zirconia, SiO ₂ glass, quartz glass, carbon, alumina, boron nitride, silicon nitride, and Teflon (registered trademark) are preferable, and tantalum, molybdenum, titanium, zirconia, and alumina are more preferable.

The chemical substance to be purified is charged into the vaporizing section A-1. As a charging method, there are a method of directly contacting the vacuum chamber 1 or a method of charging a chemical substance to be purified into a sample container 2 such as a sublimation boat as shown in FIG. In order to prevent contamination, it is preferable to put in the sample holder 2. The shape of the sample container is not particularly limited, and examples thereof include a box shape and a cylindrical shape. The material for the sample container is not particularly limited, but is preferably composed of a chemically inert material. This is to prevent the chemical substance from partially decomposing or causing modification such as polymerization in order to heat the chemical substance to a high temperature during purification, for example, stainless steel, tantalum, tungsten, molybdenum, titanium, Zirconia, SiO ₂ glass, quartz glass, carbon, alumina, boron nitride, silicon nitride, and Teflon (registered trademark) are preferable, and tantalum, molybdenum, titanium, zirconia, and alumina are more preferable.

  When purifying a large amount of chemical substances at once, it is necessary to increase the amount of the chemical substance charged. However, if a large amount of chemical substances are put in one sample container, temperature unevenness is likely to occur, causing thermal decomposition. become. In order to solve such a problem, it is preferable to disperse chemical substances in a plurality of sample containers and to charge them in multiple layers. Examples of the multi-layered arrangement include a horizontal type as shown in FIG. 2 and a laminated type as shown in FIGS. 3 and 4, but efficiently in the limited internal space of the vaporizing section A-1 of the sublimation purification apparatus. In order to load a plurality of sample holders, the stacked type as shown in FIGS. 3 and 4 is more preferable.

  As a mechanism for arranging the sample holders in multiple layers, it is preferable to provide a support base for the sample holders in the vaporization part of the vacuum chamber of the sublimation purification apparatus. Examples of the support base are not particularly limited, and examples thereof include a rod-like protrusion as shown in FIG. 3 and a plate-like protrusion as shown in FIG.

The collection part A-2 in this invention is a part which collects the chemical substance refine | purified by the sublimation. The shape of the collection part A-2 is generally a cylindrical shape, but may be a box shape or a kamaboko shape, and is not particularly limited. Although the material of collection part A-2 is not specifically limited, It is preferable to comprise with a chemically inactive material. This is to prevent the chemical substance from partially decomposing or causing modification such as polymerization in order to heat the chemical substance to a high temperature during purification, for example, stainless steel, tantalum, tungsten, molybdenum, titanium, Zirconia, SiO ₂ glass, quartz glass, carbon, alumina, boron nitride, silicon nitride, and Teflon (registered trademark) are preferable, and tantalum, molybdenum, titanium, zirconia, and alumina are more preferable.

  In order to easily take out the collected chemical substance, the collection part A-2 preferably has a detachable collection inner pipe 3 as shown in FIG.

  The sublimation device in the present invention is characterized in that the relationship between the inner area S1 of the collection inner tube 3 and the outer tube inner area S2 of the collection part A-2 is S1 ≧ S2. This is to efficiently collect the purified chemical substance and improve the purification yield.

  As shown in FIG. 5, the inner area S1 of the collecting inner pipe 3 is the total inner area of the collecting inner pipe 3, and the outer pipe inner area S2 of the collecting portion A-2 is a vacuum. It is the total internal area of the collection part A-2 portion of the chamber 1.

  Usually, even if the collection inner pipe of the same shape is provided in the collection part A-2, the total inner area is S1 <S2. The chemical substance vaporized in the vaporization part A-1 is cooled and solidified by the collection part A-2. At this time, the larger the surface area (S1) to be collected, the more efficiently the chemical substance can be collected. The yield is improved.

  The shape of the collecting inner pipe that increases the inner area S1 is not particularly limited, but examples include a bowl shape as shown in FIG. 6, a dam shape, and a shape having a partition plate as shown in FIG. .

The cooling part A-3 in the present invention is a part that collects impurities having a solidification temperature lower than that of the chemical substance to be sublimated and purified or prevents the inflow to the exhaust device B. The shape of the cooling part A-3 is generally a cylindrical shape, but may be a box shape or a kamaboko shape, and is not particularly limited. The material of the cooling part A-3 is not particularly limited, but is preferably composed of a chemically inert material. Examples thereof include stainless steel, tantalum, tungsten, molybdenum, titanium, zirconia, SiO ₂ glass, quartz glass, carbon, alumina, boron nitride, silicon nitride, and Teflon (registered trademark).

The vacuum chamber 1 in the present invention is for separating the outside of the normal pressure from the inside of the vacuum state. The material is not particularly limited, but usually, metal, glass, ceramic and fluororesin can be used. Stainless steel, tantalum, tungsten, molybdenum, titanium, zirconia, SiO ₂ glass, quartz glass, carbon, alumina, boron nitride, silicon nitride, and Teflon (registered trademark) are preferable because they are inert to the chemical substance to be purified. Tantalum, molybdenum, titanium, zirconia, and alumina are more preferable.

  Although the shape of the vacuum chamber 1 is not particularly limited, for example, any shape such as a box shape, a cylindrical shape, a columnar shape, a tank shape, a cubic shape, and the like can be given. It may be constant in the vacuum chamber 1 or may have a partially different cross-sectional shape.

  The heat sources 4 and 5 used in the present invention are for heating or collecting chemical substances in the vacuum chamber 1. The heat source only needs to be able to independently control the temperature of the vaporization section A-1 and the collection section A-2, and may be either an integral type or a connected type. The heating method of the heat source is not particularly limited as long as the vaporization part A-1 and the collection part A-2 can be heated substantially uniformly. For example, a resistance heating type (metal type, nonmetal type, etc.) Examples include a light heating type (infrared heating type, arc radiation heating type, laser heating type, etc.), induction heating type, and the like. The shape of the heat source is not particularly limited, and examples thereof include a planar shape such as a hot plate shape, a block heater in which a heater is embedded in a metal material, and the like. This heat source is generally disposed outside the vacuum chamber 1, but may be disposed inside.

  Although the presence or absence of the heat source 4 for heating the collection part is not limited by the chemical substance to be purified, it has the heat source 4 in order to efficiently remove the contained organic solvent and impurities. It is preferable. 50-200 degreeC is preferable and the heating temperature range of the heat source 4 has more preferable 100 to 200 degreeC.

  The heat source is controlled by a temperature controller 6. Although it does not specifically limit as a control method, A relay switch, ON / OFF of an alternating current, inverter control, PID control, etc. can be mentioned.

  The exhaust device B in the present invention includes a vacuum pump 11 and a piping unit that connects the vacuum pump and the purification unit A.

Although it does not specifically limit as the vacuum pump 11, Usually, the combination of a roughing pump and a super vacuum pump is used. The roughing pump here is, for example, an oil rotary pump (for example, a rotary blade type (Göthe type) oil rotary pump, a cam type (Senko type) oil rotary pump, an induction piston type (Kinney type) oil rotary pump), Mechanical booster pumps (roots pumps), dry pumps (eg, screw-type dry pumps, claw-type dry pumps, scroll-type dry pumps, multistage root-type dry pumps, etc., volume transfer type dry pumps, turbo-type dry pumps, etc.) And a pump having an operating pressure of about 1 × 10 ³ to 1 × 10 ⁻² Pa, such as a dry pump) and a sorption pump. The ultra-vacuum pump here is, for example, a diffusion pump (for example, an oil diffusion pump or a mercury diffusion pump), a turbo molecular pump (for example, a magnetic bearing turbo molecular pump, a wide area (composite) turbo molecular pump), a sputter, or the like. Examples thereof include an ultrahigh vacuum pump having an operating pressure of 1 to 1 × 10 ⁻⁸ Pa or more, such as an ion pump, a cryopump, and a getter pump (for example, Ti room temperature type getter pump, Ti liquid nitrogen type getter pump). Preferred examples of the ultra vacuum pump include a diffusion pump, a turbo molecular pump, and a cryopump.

The inside of the vacuum chamber 1 is kept in a vacuum state using the vacuum pump. In the vacuum chamber 1 of the present invention, the degree of vacuum is usually 1 to 1 × 10 ⁻⁸ Pa, preferably 1 × 10 ^−2. ˜1 × 10 ⁻⁵ Pa, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁴ Pa.

  The structure of the piping section is not particularly limited as long as the degree of vacuum inside the apparatus during the sublimation purification is kept constant, as long as the leakage from the outside is as small as possible. However, as shown in FIG. The vacuum gauge 10 is preferably provided. The valves 7 and 8 are arranged to return the inside of the apparatus to atmospheric pressure after the sublimation purification. The trap 9 is arranged to capture impurities such as moisture and solvent that volatilize during sublimation purification. The vacuum gauge 10 is arranged for monitoring the degree of vacuum in the apparatus.

  Examples of the valves 7 and 8 include, but are not limited to, a manual valve, a solenoid valve, a cylinder valve, and a remote control valve. These may be one type, but may be used in combination of a plurality of types according to the purpose. Examples of the trap 9 include, but are not limited to, a cryogen storage type cooling trap, a condenser, a baffle, and a cooling trap. After completion of sublimation purification, the inside of the apparatus is returned to atmospheric pressure by the above valve, and in this case, it is preferable to introduce an inert gas. This is to prevent contamination of sublimated and purified chemicals with atmospheric impurities (for example, moisture, dust, etc.).

  The method of introducing the inert gas is not particularly limited. However, when a trap is provided in the pipe section, the trap and the purification section are arranged so that the sublimated and purified chemical substances are not contaminated by impurities attached to the trap. It is preferable to introduce an inert gas in between. For example, in the case of using the apparatus of FIG. 1, the valve 8 is closed after the sublimation purification is completed, and the inert gas is introduced from the valve 7. At this time, in order to prevent the entry of fine dust, it is more preferable that the valve 7 includes a filter. As the inert gas, helium, nitrogen, neon, argon, krypton, and xenon are preferable, and nitrogen and argon are particularly preferable.

  The trap 9 is not particularly limited, but a trap having a large surface area is usually used at a low temperature of room temperature or lower in order not to move impurities and gas components generated in the purification process to the vacuum pump 9. The material is not particularly limited, and examples thereof include metal materials and glass exemplified as the material of the vacuum chamber 1.

  Although the said vacuum gauge 10 may be one kind, it is normally used combining the vacuum gauge which measures a vacuum degree at the time of roughing, and the vacuum gauge which measures a vacuum degree at the time of a high vacuum. Examples of vacuum gauges that measure the degree of vacuum during roughing include, but are not limited to, Gaisler tubes and heat conduction vacuum gauges (for example, Pirani gauges), and vacuum that measures the degree of vacuum at high vacuum. Examples of the meter include, but are not limited to, a hot cathode ionization vacuum gauge and a cold cathode ionization vacuum gauge.

  The chemical substance purified by the sublimation purification apparatus of the present invention is not particularly limited as long as it is a substance that is in a solid state at room temperature and is vaporized by heating under vacuum. It is particularly useful for the purification of organic compounds that are prone to degradation and modification. A typical example is an organic EL material.

  Although it does not specifically limit as an example of the said organic EL material, The following materials are mentioned. N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine or N, N′-dinaphthyl- used as a hole transport material Triphenylamines such as N, N′-diphenyl-4,4′-diphenyl-1,1′-diamine, carbazoles such as bis (N-allylcarbazole) and bis (N-alkylcarbazole), indole Derivatives, pyrazoline derivatives, stilbene compounds, hydrazone compounds, oxadiazole derivatives, phthalocyanine derivatives, heterocyclic compounds represented by porphyrin derivatives, and the like. In addition, fused ring derivatives such as anthracene, phenanthrene, pyrene, perylene, chrysene, tetracene, pentacene, naphthopylene, dibenzopyrene, and rubrene, and metal complexes of quinolinol derivatives such as tris (8-quinolinolato) aluminum, which are used as light emitting materials , Benzoxazole derivatives, stilbene derivatives, benzthiazole derivatives, thiadiazole derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, oxadiazole derivatives, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, and quinolinol derivatives Metal complexes combining ligands, oxadiazole derivative metal complexes, benzazole derivative metal complexes, coumarin derivatives, pyrrolopi Gin derivative, pyrrolopyrrole derivative, silole derivative, perinone derivative, thiadiazolopyridine derivative, pyromethene derivative, porphyrin platinum complex, tris (2-phenylpyridyl) iridium complex, tris {2- (2-thiophenyl) pyridyl} iridium complex, Tris {2- (2-benzothiophenyl) pyridyl} iridium complex, tris (2-phenylbenzothiazole) iridium complex, tris (2-phenylbenzoxazole) iridium complex, trisbenzoquinoline iridium complex, bis (2-phenylpyridyl) ) (Acetylacetonato) iridium complex, bis {2- (2-thiophenyl) pyridyl} iridium complex, bis {2- (2-benzothiophenyl) pyridyl} (acetylacetonato) iridium complex, bis ( - phenylbenzothiazole) (acetylacetonato) iridium complex, bis (2-phenyl-benzoxazole) (acetylacetonato) iridium complex, such as bis benzoquinoline (acetylacetonato) iridium complex. Further, quinolinol derivative metal complexes represented by 8-hydroxyquinoline aluminum, tropolone metal complexes, flavonol metal complexes, perylene derivatives, perinone derivatives, naphthalene conductors, coumarin derivatives, pyridine derivatives, quinoline derivatives, which are used as electron transporting materials, Quinoxaline derivatives, benzoquinoline derivatives, phenanthroline derivatives, thiophene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, triazole derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, diphenyl phosphorus oxide derivatives, silole derivatives, triphenylsilane Derivatives, bisstyryl derivatives, pyrazine derivatives and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these examples.

  In this example, purity analysis by a high performance liquid chromatograph (hereinafter referred to as HPLC) was carried out by using a chloroform solution of an organic material as an eluent and HPLC (LC-VP manufactured by Shimadzu Corporation), column (manufactured by Kanto Chemical Co., Ltd.). Migthysil RP-8GP) and a UV detector, and quantified from the area% of the component peak output from the UV detector.

<Example 1>
Sublimation purification of the organic material represented by the following formula (1) was performed using the sublimation purification apparatus shown in FIG.

  In the sublimation purification apparatus of FIG. 1, a Pyrex (registered trademark) tube having a length of 1960 mm, an outer diameter of 286 mm, and a wall thickness of 6 mm was used as the vacuum chamber 1 with the vaporization part side sealed. The length of the vaporization part A-1 was 1000 mm, the length of the collection part A-2 was 600 mm, and the length of the cooling part A-3 was 360 mm. Further, the ground height Ha on the lowermost surface of the vaporization section A-1 is 1200 mm, the ground height Hb on the lowermost surfaces of the collection section A-2 and the cooling section A-3 is 1150 mm, and the vaporization section A-1 and the collection section A. A step of 50 mm was provided between -2. In this implementation, the collection inner tube 3 was not used. A ceramic fiber heater was used for the heat source 4 and the heat source 5, and an SSR drive PID control system was used for the temperature controller 6. For the sample holder 2, a box-shaped tantalum boat having a length of 672 mm, a width of 250 mm, a height of 60 mm, and a plate thickness of 0.5 mm was used. Solenoid valves were used for the valves 7 and 8. A liquid nitrogen trap was used as the trap 9. The vacuum gauge 10 was a hot cathode ionization vacuum gauge. The vacuum pump 11 was a combination of an oil rotary pump for roughing and an oil diffusion pump for high vacuum. The refinement | purification part A and the exhaust apparatus B were connected via the flange with a large gauge port.

Sublimation purification of 300 g of the organic material of the following formula (1) having an HPLC purity (area% at a measurement wavelength of 254 nm) of 98.5% was performed. Sublimation conditions are that after the degree of vacuum reaches 5 × 10 ⁻³ Pa, the temperature of the collection part A-2 is raised to 150 ° C. and held at this temperature, and then the temperature of the vaporization part A-1 is raised to 340 ° C. Raised. The temperature of the cooling part was kept near room temperature, and the collection part A-2 and the vaporization part A-1 were heated for 5 hours while maintaining the above temperature. Subsequently, the collection part A-2 and the vaporization part A-1 were cooled to near room temperature, the valve 8 was closed, high-purity nitrogen was leaked from the valve 7, and the inside of the apparatus was replaced with atmospheric pressure.

  As a result, 240 g (purification yield: 80%) of material was recovered from the collection part A-2, and the HPLC purity (area% at a measurement wavelength of 254 nm) was as extremely high as 99.6%, and the HPLC chart No peak derived from the decomposition product was observed.

<Comparative Example 1>
Sublimation purification was performed in exactly the same manner as in Example 1 except that the ground clearance on the lowermost surfaces of the vaporization section A-1, the collection section A-2, and the cooling section A-3 was all 1200 mm.

  As a result, 180 g (purification yield: 60%) of material was recovered from the collection part A-2, but the liquid formula (1) flowed into the vaporization part A-1 during the collection. The HPLC purity (area% at a measurement wavelength of 254 nm) of the material collected in the collection part A-2 was 99.6%, and an improvement in purity was seen, but the material that flowed into the vaporization part A-1 was A black discoloration was observed, the HPLC purity (area% at a measurement wavelength of 254 nm) was 95.8%, and a peak derived from a thermal decomposition product was observed in the HPLC chart. Eventually, the purification yield of the formula (1) that could be purified was 60%, and the purification yield decreased compared to Example 1. The obtained results are shown in Table 1.

<Example 2>
In the collection part A-2 of the same sublimation purification apparatus as in Comparative Example 1, a collection inner pipe (outer dimensions: length 300 mm, outer diameter 270 mm, three ring-shaped rods having a height of 80 mm shown in FIG. 10, Two Pyrex (registered trademark) tubes having a wall thickness of 5 mm are installed in parallel, and instead of the organic material of the formula (1), the following formula (9% HPLC purity (area% at a measurement wavelength of 254 nm)) Sublimation purification was performed in the same manner as in Example 1 except that the organic material shown in 2) was used, the temperature of the collection part A-2 was 200 ° C., and the temperature of the vaporization part A-1 was 350 ° C. In this embodiment, the total inner area S1 of the collection inner pipe was 10078 cm ² , and the total inner area S2 of the vacuum chamber 1 of the collection part A-2 was 5162 cm ² .

  As a result, 255 g (purification yield 85%) of material was recovered from the collection and collection inner tube, and the HPLC purity (area% at a measurement wavelength of 254 nm) was extremely high at 99.9%, and the HPLC chart No peak derived from the decomposition product was observed.

<Comparative example 2>
Example except that two collecting inner pipes (outer dimensions: length 300 mm, outer diameter 270 mm, wall thickness 5 mm) shown in FIG. 11 are installed in parallel. Sublimation purification was performed in the same manner as in No. 2. The total inner area S1 of the collection inner tube in this embodiment was 4898 cm ² , and the total inner area S2 of the vacuum chamber 1 of the collection part A-2 was 5162 cm ² .

  As a result, 200 g (purification yield 67%) of material was recovered from the collection inner tube with HPLC purity (area% at a measurement wavelength of 254 nm) of 99.9%, but the collection inner tube with a large inner area was used. The purification yield was reduced as compared to Example 2. The obtained results are shown in Table 2.

It is the cross-sectional schematic of an example of the sublimation purification apparatus of this invention. It is the schematic of an example of multilayer arrangement of a sample container. It is the schematic of another example of the multilayered arrangement | positioning of a sample container. It is the schematic of another example of the multilayered arrangement | positioning of a sample container. It is a section schematic diagram of an example of a collection part outer pipe and a collection inner pipe. It is the cross-sectional schematic of another example of a collection part outer tube | pipe and a collection inner tube | pipe. It is the cross-sectional schematic of another example of a collection part outer tube | pipe and a collection inner tube | pipe. It is the cross-sectional schematic of the example of arrangement | positioning of a vaporization part and a collection part. It is the cross-sectional schematic of another example of arrangement | positioning of a vaporization part and a collection part. 6 is a schematic cross-sectional view of a collecting inner tube used in Example 2. FIG. 6 is a schematic cross-sectional view of a collecting inner tube used in Comparative Example 2. FIG.

Explanation of symbols

A Purification unit B Exhaust device A-1 Vaporization unit A-2 Collection unit A-3 Cooling unit 1 Vacuum chamber 2 Sample holder 3 Collection inner tube 4 Heat source 5 Heat source 6 Temperature controller 7 Valve 8 Valve 9 Trap 10 Vacuum gauge 11 Vacuum pump 12 Ring-shaped weir S1 Total inner area S2 of the collection inner pipe Ha Total inner area Ha of the vacuum chamber collection part Ha Distance from the horizontal surface to the lowermost surface of the vaporization part inner surface Hb From horizontal surface to the lowermost surface of the collection part inner surface Distance of

Claims (4)

A sublimation purification apparatus having a purification section having a vaporization section for vaporizing a chemical substance and a collection section for collecting the vaporized chemical substance, and an exhaust device, wherein the height Ha of the vaporization section and the collection section A sublimation purification apparatus characterized in that the height Hb is Ha> Hb. A sublimation purification apparatus having a purification section having a vaporization section for vaporizing a chemical substance and a collection section for collecting the vaporized chemical substance, and an exhaust device, wherein the purification section captures the chemical substance. A sublimation purification apparatus having a collecting pipe, wherein an inner area S1 of the collecting inner pipe and an inner area S2 of the collecting section outer pipe are S1 ≧ S2. The sublimation purification apparatus according to claim 1 or 2, further comprising a mechanism for arranging chemical substances in a multilayered manner in the vaporization section. A sublimation purification method using the sublimation purification apparatus according to claim 1.

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