KR20240012506A - Method for continuous purification of at least one functional substance and device for continuous purification of at least one functional substance - Google Patents

Abstract

The present invention describes a method for continuously purifying at least one functional material usable for the production of functional layers of electronic devices involved in charge injection or charge transport and/or light emission or light outcoupling. The invention also relates to a device for continuously purifying at least one functional substance.

Description

Method for continuous purification of at least one functional substance and device for continuous purification of at least one functional substance

The present invention describes a method for continuously purifying at least one functional material usable for the production of functional layers of electronic devices involved in charge injection or charge transport and/or light emission or light outcoupling. The invention also relates to a device for continuous purification of at least one functional substance.

Electronic devices containing organic, organometallic and/or polymeric semiconductors are becoming increasingly important and are used in many commercial products due to their cost and performance. Examples herein include organic-based charge transport materials (e.g. triarylamine-based hole transporters) in copiers, organic or polymeric light-emitting diodes (OLEDs or PLEDs) in readout and display devices, or organic photoreceptors in copiers. do. Organic solar cells (O-SC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic integrated circuits (O-IC), organic optical amplifiers and organic laser diodes (O-lasers) are It is at an advanced stage of development and could be of great importance in the future.

In many cases, the production of these devices involves the use of sublimable organic or organometallic-based functional materials. These materials must be used in very pure form to obtain good and durable electronic devices.

For this purpose, these materials are typically sublimated and then condensed to reliably remove by-products and solvent residues.

Methods and devices for this performance are described in particular in publications WO2015/022043, KR2020/0123895, KR2017/0122563, CN109646987, KR101835418 B1 and KR2019/0125700.

For example, the teaching according to publication WO2015/022043 does not allow continuous purification of functional substances since the vessel must be removed for recovery of the purified substance. Since it is necessary to take out the collection vessel or condensation plate out of the device by opening the module, this also applies to the teachings of publications KR2017/0122563, CN109646987, KR101835418 B1 and KR2019/0125700.

Additionally, publication KR2020/0123895 proposes the use of ionic liquid obtained by condensing functional materials. As the ionic liquid loaded with the functional material is guided out of the vacuum area and processed, the functional material is removed.

KR101918233 B1 describes an apparatus for continuous purification of functional substances, wherein the apparatus has a common chamber, between 200 and 300 according to the drawing, which can be operated at reduced pressure.

DE1130793 B describes an apparatus for continuous vacuum sublimation of substances that are difficult to sublimate.

Known methods and devices have characteristic profiles available. However, there is a continuing need to improve the properties of these methods and devices.

These characteristics include, inter alia, the economic viability, reliability and complexity of the apparatus for continuous purification of at least one functional substance. In particular, the device must be constructed in a very simple way, without lowering or altering the vacuum for release of the purified functional material. Additionally, the use of circulating purification aids, such as ionic liquids, should be minimized. The use of these auxiliaries should preferably be completely omitted.

A further task could be considered to be to provide a device for the continuous purification of at least one functional substance that can be operated inexpensively and continuously for long periods of time. Additionally, the device must be able to be controlled efficiently and easily. Moreover, the device must be easily scalable and environmentally friendly.

Moreover, the method will result in functional materials of high purity and therefore will not adversely affect the lifetime and other properties of electronic devices obtainable by these materials.

Surprisingly, it has been found that a specific device, described in detail below, accomplishes these tasks and eliminates the shortcomings of the prior art. An apparatus for the purification of at least one functional substance can be operated in an inexpensive and sustainable manner, especially if the discharge device it comprises comprises an exhaust extruder unit or the discharge device is an exhaust extruder unit. Additionally, the device can be configured in a particularly simple way. Moreover, thanks to the purification method, in particular with regard to the purity of materials for the production of electronic devices, improvements can be achieved with very low thermal stresses in the purification of materials for the production of electronic devices. In this context, the use of these materials purified in this way leads to very good properties of organic electronic devices, especially organic electroluminescent devices, especially with regard to lifetime, efficiency and operating voltage.

The invention therefore relates to a method for the purification of at least one functional material usable for the production of functional layers of electronic devices involved in charge injection or charge transport and/or light emission or light outcoupling, characterized in that the apparatus is used. A method is provided, wherein the method includes evaporation or sublimation and/or condensation of at least one functional material, and the device has:

A) at least one feed for at least one functional material, wherein the at least one functional material can be fed continuously through an inlet opening provided in the feed;

B) at least one evaporation device disposed downstream of the feed, wherein the functional material can be introduced into the evaporation device by the feed and the functional material can be continuously evaporated by the evaporation device;

C) at least one condensation device, wherein the functional material is continuously condensable by the condensation device after evaporation in the evaporation device;

D) at least one discharge device disposed downstream of the condensation device, wherein the functional material can be continuously introduced from the condensation device into the discharge device and discharged through an discharge opening present in the discharge device;

and here

The device has an evaporation chamber, in which at least a part of the evaporation device and at least a part of the condensation device are provided, the evaporation chamber being connected or connectable to at least one exhaust device, preferably at least one vacuum pump, and continuous. During operation of the device for purification, a reduced pressure, preferably a high vacuum, can be created in the evaporation chamber, and the discharge device comprises or constitutes an exhaust extruder unit.

The invention therefore likewise provides an apparatus for the continuous purification of at least one functional substance comprising:

A) at least one feed for at least one functional material, wherein the at least one functional material can be fed continuously through an inlet opening provided in the feed;

B) at least one evaporation device disposed downstream of the feed, wherein the functional material can be introduced into the evaporation device by the feed and the functional material can be continuously evaporated by the evaporation device;

C) at least one condensation device, wherein the functional material is continuously condensable by the condensation device after evaporation in the evaporation device;

D) at least one discharge device disposed downstream of the condensation device, wherein the functional material can be continuously introduced from the condensation device into the discharge device and discharged through an discharge opening present in the discharge device;

and here

The device has an evaporation chamber, wherein at least a part of the evaporation device and at least a part of the condensation device are provided in the evaporation chamber, the evaporation chamber being connected or connectable to at least one exhaust device, the evaporation chamber being connected during operation of the device for continuous purification. It is characterized in that a reduced pressure, preferably a high vacuum, can be created therein, the exhaust device comprises or constitutes an exhaust extruder unit, and the evaporation device at least partially encloses the condensation device.

A particularly surprising advantage can be achieved here in that a reduced pressure, preferably a high vacuum, can be created in the evaporation chamber by liquefaction/softening/solidification of the at least one functional material in the discharge device. Therefore, sealing of the device is preferably achieved upon discharge of the functional substance via a discharge unit comprising or constituting a discharge extruder unit. The possibility of creating a reduced pressure, preferably a high vacuum, in the evaporation chamber is achieved in particular by the purified functional material, which may have a viscosity suitable for the purpose, i.e. extruded through an extrudable output extruder unit. In this way, a vacuum can be maintained permanently within the device even when purified material is being withdrawn.

A surprising advantage in that a reduced pressure, preferably a high vacuum, can be created in the evaporation chamber by liquefaction/softening of the at least one functional material in the feed and by increasing the viscosity, preferably solidification, of the at least one functional material in the discharge device. This can be achieved. By this practice, it is surprisingly possible to set up and maintain a vacuum without complex and expensive technical measures.

In a preferred embodiment, the feed may comprise grooved rolls and/or extruder screws, wherein the feed preferably comprises or constitutes a feed extruder unit. This arrangement allows functional materials to be supplied to the device in a particularly simple and reliable way, where the structure of the device can be of uncomplicated configuration. In this case, simple control of the amount added is possible, allowing control of the purification process. Feeds comprising grooved rolls are described in detail in publication WO10/056325 (PCT/US2009/006082); The description of the feed presented in publication WO10/056325 is incorporated into this application by reference thereto. Feeds with extruders or extruder screws are also described in detail in the prior art description in publication WO10/056325; These detailed descriptions in publication WO10/056325 are likewise incorporated into the present application by reference thereto. These include publications US2006/0062918 and US2006/0177576.

Also in WO2006/118837 a feed with an extruder or extruder screw is described; The description of the feed presented in publication WO2006/118837 is incorporated into this application by reference thereto.

The evaporation device may also have an evaporation mass distributor system. The evaporating material distributor system may also comprise at least one wiper system, wherein the functional material can be distributed by a wiper system on the evaporating unit of the evaporating device, wherein the wiper system is preferably a ROTAFILM, a roll wiper or It is configured as a wing wiper system. The evaporation unit preferably consists of an evaporation surface on which an evaporation material distributor system distributes the functional substance to be purified.

The feed may also include at least one vent opening through which solvent may be removed.

The evaporation device can also be heated electrically or by a fluid, preferably hot air or heat transfer oil, more preferably electrically or by heat transfer oil.

Furthermore, preferably the temperature of the feed extruder unit can be controlled.

An apparatus for continuous purification of at least one functional substance comprises an evaporation chamber, in which at least part of the evaporation device and at least part of the condensation device are provided. In the evaporation chamber, at least one functional material is evaporated or sublimated and/or condensed, and these steps purify the functional material. Here, the evaporation device may have an evaporation unit, preferably an evaporation surface, whereby at least one functional material is evaporable and/or sublimable, and the condensation device may comprise a condensation unit, preferably a condensation surface. whereby the at least one functional material is condensable, wherein the evaporation unit and the condensation unit are enclosed by an evaporation chamber. The evaporation chamber preferably encloses the evaporation surface of the evaporation device and the condensation surface of the condensation device.

In a further configuration, the evaporation device can have an evaporation surface by which the functional material can be vaporized, and the condensation device can have a condensation surface by which the functional material can be condensed, wherein The evaporation surface is arranged parallel to the condensation surface. This design makes it possible to achieve particularly low thermal stresses on the functional material during purification, since the time interval between evaporation or sublimation and condensation can be kept very short.

In a preferred configuration, the evaporation device may have an evaporation unit, preferably an evaporation surface, wherein the evaporation unit has an evaporation cylinder, preferably configured as an evaporation cylinder, wherein at least a part of the surface of the evaporation cylinder is evaporated. It can be considered a surface.

The condensation device may also comprise a condensation unit, preferably a condensation surface, wherein the condensation unit has a condensation cylinder, preferably configured as a condensation cylinder, wherein at least a portion of the surface of the condensation cylinder is the condensation surface. can be considered

The condensation device may also be rotatable relative to the evaporation device. This configuration can achieve uniform condensation of the functional material across the condensation zone, increasing the efficiency of the method and lowering the thermal stress on the functional material during the purification process.

A surprising advantage with regard to the construction of the device can be obtained in that the condensing device is rotatable by means of a drive unit.

The feed may also comprise or consist of a feed extruder unit, and the discharge device may comprise or consist of an outlet extruder unit, wherein the extruder screw of the feed extruder unit is connected to the extruder screw of the outlet extruder unit to drive the extruder screw of the feed extruder unit. and the extruder screw of the outlet extruder unit is rotatable by the drive unit.

The condensation device also has a condensing cylinder connected to the extruder screw of the feed extruder unit and to the extruder screw of the discharge extruder unit, such that the extruder screw of the feed extruder unit, the condensation cylinder and the extruder screw of the discharge extruder unit are at least one, preferably exactly one. , may be rotatable by a drive unit.

In a further embodiment, the feed may comprise or constitute a feed extruder unit and the discharge device may comprise or constitute an discharge extruder unit, wherein the extruder screw of the feed extruder unit is rotatable by the drive unit and the discharge extruder unit The extruder screw of is rotatable by the second drive unit, such that the extruder screw of the feed extruder unit is rotatable independently of the extruder screw of the discharge extruder unit.

The second embodiment is somewhat more complex in construction, but has the advantage that the feed can be controlled independently of the discharge. This advantage is particularly advantageous for plant start-up.

The condensation device can also have a condensing cylinder connected to the extruder screw of the feed extruder unit or to the extruder screw of the discharge extruder unit so that the condensation cylinder is rotatable with the extruder screw of the feed extruder unit or the extruder screw of the discharge extruder unit. The device may here comprise at least two drive units, where one drive unit is connected to the extruder screw of the feed extruder unit and the second drive unit is connected to the extruder screw of the discharge extruder unit. It is also possible for the condensing cylinder to be actuable by a separate drive unit, such that the condensing cylinder is rotatable independently of the extruder screw of the feed extruder unit or of the extruder screw of the discharge extruder unit.

In a particularly preferred configuration, the evaporation device may enclose the condensation device.

If the condensation device has a condensate collector, a surprising advantage regarding the construction of the device can be achieved in that the condensed functional material is collectible in the discharge device by means of the condensate collector.

It is also possible for the condensate collector to have a funnel-shaped configuration, in which case the funnel inlet is directed towards the discharge device.

The condensation device can also have a moving unit, in which case the condensed functional material can be peeled off from a part of the condensation device by means of the moving unit. The moving unit therefore facilitates the transfer of the condensed functional material into the discharge device. These mobile units are not strictly necessary. It is not absolutely necessary, the moving unit can be omitted, especially if the viscosity of the condensed functional material is low and flows easily from the condensing device into the discharge device.

In a particularly preferred configuration, the mobile unit may consist of a stripper or wiper system.

Additionally the temperature of the discharge device, preferably the discharge extruder unit, may be controllable.

In a preferred configuration, it may be possible to create a temperature gradient between the evaporation device and the condensation device, where the temperature of the evaporation device is selectable at a higher level than the temperature of the condensation device.

Preferably, the evaporation device and/or the evaporation chamber comprises at least one opening through which a residue collection vessel is connectable or connected. This embodiment allows the device to be operated over particularly long periods of time without the need to interrupt the process. In another configuration, the residue may be collected within the device, in which case the process must be stopped here after a long period of time. The point to be emphasized here is that these residues are generally present only in small quantities in the starting material to be purified, so that in any case an improvement is achieved over the prior art.

In a further development, the evaporation device and/or the evaporation chamber may comprise at least two openings, through each of which a residue collection vessel is connectable or connected. This further development can achieve a further improvement in the method, as it allows exchange and cleaning of the residue collection vessel even during operation. The residue collection vessel is preferably configured to be inertizable and/or evacuable.

The device may also be operable in vertical alignment, in which case the feed is disposed above the evaporation device and the evaporation device is disposed above the discharge device. Preferably the device can be operated in vertical alignment, in which case the functional material can be transferred under gravity from the feed into the evaporation device.

In a preferred configuration, the device can be operated in vertical alignment, where the functional material can be introduced under gravity from the condensation device into the discharge device.

The discharge device is configured to have an discharge opening through which the purified functional material can be removed. Here the discharge opening can be connected to a granulation unit, in which case the granular material obtained can preferably be introduced into the discharge vessel.

A surprising advantage can be achieved in that the device has at least one rotational coupling arranged between the rotatably configured components of the device, wherein the rotational coupling is a rotating bushing sealed with ferrofluid or a double- or triple-action slip ring sealing. In particular, as already described above, the condensation device can be configured to be rotatable relative to the evaporation device. The discharge device further comprises an discharge extruder unit. Additionally, the feed may include a feed extruder unit. These components comprise rotatably configured components, wherein the rotational coupling is preferably of the form detailed above.

The device may also include a camera through which the evaporation and/or condensation of the functional material can be observed.

The device for continuous purification of at least one functional substance is connected or connectable to an exhaust device. The connection to an exhaust device allows a suitable, reduced pressure to be created within the evaporation chamber to achieve evaporation or sublimation. Systems suitable for this purpose are known in the field of expertise and these systems typically comprise or consist of at least one vacuum pump, preferably a vacuum pump system.

In a preferred configuration, the device may comprise at least one vacuum pump system, preferably a multi-stage system comprising a feed pump, in particular an oil pump or a dry operating scroll pump, a rotary piston pump.

As long as the conditions specified in claim 1 are met, the preferred embodiments mentioned above can be combined with each other as desired. In a particularly preferred embodiment of the invention, the above-mentioned preferred embodiments apply simultaneously.

The present invention also provides a method for purifying at least one functional material as described above.

Functional materials for the production of functional layers of electronic devices involved in charge injection or charge transport and/or light emission or light outcoupling are well known in the specialist field. Preferably, the functional materials usable for the production of the functional layer of the electronic device are fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), emitters exhibiting hyperfluorescence or hyperphosphorescence, host materials, excitons. Blocker material, electron injection material, electron transport material, electron blocker material, hole injection material, hole conductor material, hole blocker material, n-dopant, p-dopant, wide bandgap material, charge generating material, or a combination thereof. Can be selected from the group. These materials, which can be used for the production of functional layers of electronic devices as described above, can be used individually or as mixtures of 2, 3, 4, 4, 5 or more materials in the method of the invention. wherein the mixture is usable for the production of functional layers of electronic devices and is involved in charge injection or charge transport and/or light emission or light outcoupling, and is purified according to the invention with exactly 2, exactly 3, exactly 4 or exactly 4 It can be made of five functional substances.

At least one, preferably at least two, more preferably all, of the functional materials usable for the production of the functional layer of such an electronic device are preferably organic materials or comprise organic compounds. Organic compounds contain carbon atoms and preferably hydrogen atoms.

At least one, preferably at least two, more preferably all, of the functional materials to be purified that can be used for the production of functional layers of such electronic devices can be provided, for example as powder/granular material or as organic glass. there is. Additionally, however, the method of the invention can be carried out as a step, especially in the production of functional substances. It is desirable to provide a free-flowing composition of such functional material and introduce it into the feed of the device of the invention.

Preferably, the at least one functional material as described above can be melted without decomposition at a temperature of 50°C or higher, preferably at a temperature of 100°C or higher.

In addition, preferably, the at least one functional material as described above is 1 to 10 ⁴ [1/s], preferably at a temperature of 30°C or higher, preferably at a temperature of 50°C or higher, more preferably at a temperature of 100°C or higher. is 10 to 10 ³ [1/s], more preferably 1 to 10 ²⁰ [mPa s], preferably 10 ³ to 10 ¹⁸ [mPa s], more preferably at a shear rate of 100 [1/s]. May have a viscosity in the range of 10 ⁶ to 10 ¹⁴ [mPa s]. The preferred viscosity measurement procedure is described later.

Additionally, the at least one functional material as described above, in a molten state at the processing temperature, may exhibit a deterioration of 0.1% by weight or less over a storage period of 10 hours. The treatment temperature here may range from 50°C to 500°C. The processing temperature is the temperature at which extrusion is carried out in the output extruder unit. Preferably, at least one, preferably at least two and more preferably all of the functional materials used as described above exhibit a degradation of not more than 0.1% by weight over a storage period of 10 hours at the melt temperature.

In a preferred configuration of the process according to the invention, it is desirable to purify the sublimable material. Preferably, therefore, at least one, more preferably at least two and particularly preferably all of the functional substances to be purified are sublimable. The sublimable material preferably has a low molecular weight, as explained later.

In the output extruder unit, the purified functional material is extruded. Moreover, the feed may include a feed extruder unit. The term “extrusion” is well known in the field of expertise and refers to the extrusion of a solidifiable mass through an opening. For this purpose, an extruder is used. Extruders are likewise known in the specialist field and are commercially available. The term “extruder” means a conveying device for carrying out extrusion. Publication EP 2 381 503 B1, and in particular the description of the extruder contained therein, is hereby incorporated by reference into the present application for disclosure purposes.

For example, single or twin screw extruders can be used. The selection and adjustment of a suitable extruder screw, especially its geometry, based on the corresponding processing functions, such as taking in, conveying, homogenization, softening and compression, forms part of the general knowledge of the person skilled in the art.

In the inlet area of the extruder, preferably a screw extruder, it is desirable to establish a barrel temperature in the range from 50° C. to 450° C., preferably from 80° C. to 350° C., depending on the nature of the functional material. In the input area, it is possible to feed, for example, the functional substances described above or below in the form of powders, free-flowing masses and/or granular substances. This is particularly true if the feed comprises a feed extruder unit. The device of the invention comprises a discharge extruder unit into which the condensed material is introduced. The material can be introduced into the inlet area of the outlet extruder unit in the form of a free-flowing mass, optionally also as a liquid with low viscosity, which is cooled in the outlet extruder unit and thus under reduced pressure, preferably under high vacuum, in the evaporation chamber. This can be created. Alternatively, the condensed material may be introduced into the inlet region of the discharge extruder unit in the form of a condensed solid, in which case this solid may first be gently heated to obtain a viscous mass, thereby reducing the pressure within the evaporation chamber. Preferably, a high vacuum can be created.

The temperature profile used here depends on the functional material used. The temperature profile established in the softening range is preferably 80° C. to 450° C., preferably 90° C. to 350° C., more preferably 100° C. to 300° C., particularly preferably 120° C. to 250° C. and particularly preferably It ranges from 130°C to 230°C. This is particularly true if the feed comprises a feed extruder unit. The temperature in the emission zone is preferably 80° C. to 450° C., preferably 90° C. to 350° C., more preferably 100° C. to 300° C., particularly preferably 120° C. to 250° C. and particularly preferably 130° C. to 230°C. Here, each extruder may have a temperature profile in which the temperature increases or decreases. If a feed extruder unit is used, the temperature may rise in the direction of the evaporation device, so that the powder or granular material is liquefied, but the liquid or mass of relatively low viscosity is solidified by cooling in the discharge extruder unit, thereby leaving the evaporation chamber. It is possible to create reduced pressure, preferably high vacuum. If condensation in the condensation device results in a solid, this may first melt slightly and then solidify, thereby creating a reduced pressure, preferably a high vacuum, in the evaporation chamber. The temperature specified here refers to the barrel temperature and may be measured using a thermocouple, for example a FeCuNi type L or type J, Pt 100 thermometer or an IR thermometer.

Additionally, the at least one functional material can be delivered from the feed into the evaporation device at a temperature that is at least 5° C. higher than the glass transition temperature of the respective functional material, preferably at least 10° C. higher.

In a preferred configuration, the feed to the device may comprise a feed extruder unit by means of which at least one functional material is extruded, wherein the extrusion is performed at a shear rate of 100 [1/s] and a temperature between 150° C. and 150° C. in the range of 1 to 50 000 [mPa s], preferably 10 to 10 000 [mPa s] and more preferably 20 to 1000 [mPa s], measured by the rotating plate-plate method at a temperature in the range of 450° C. It is carried out with substances having viscosity.

The viscosity values described above and below are measured by the rotating plate-plate method. Here rheology measurements can be performed using a Discovery Hybrid Rheometer HR-3 equipped with an ETC heating unit from GmbH - UM TA Instruments, D-65760 Eschborn, Germany. Calibration can be performed with a reference. For example, the following oils can be used for this purpose:

In many cases, viscosity is measured at three different shear rates (10/s, 100/s and 500/s) as a function of temperature; Each condition is described in more detail above and below. The shear rate is preferably 100 s ^-1 . Viscosity values are preferably according to DIN 53019; In particular, it is measured according to DIN 53019-1:2008-09, DIN 53019-2:2001-02, and DIN 53019-3:2008-09.

Preferably, the at least one functional material to be purified according to the invention, usable for the production of functional layers of electronic devices, such as above, has a melting temperature determined according to DIN EN ISO 11357-1 and DIN EN ISO 11357-2. The range is 150°C to 500°C, preferably 180°C to 400°C, more preferably 220°C to 380°C, and particularly preferably 250°C to 350°C. Here the melting temperature is obtained from glass transition temperature measurements in the form of DSC signals; Additional details on melt temperature measurements are described in relation to the measurement of glass transition temperature.

With regard to this process, it is not essential that the material have a melting point. In general, it is sufficient that the material used softens at a sufficiently high viscosity.

Accordingly, at least one functional material to be purified may not have a melting point.

Preferably the at least one functional substance to be purified may be sublimable.

Accordingly, the at least one functional substance to be purified has a sublimation temperature measured according to DIN 51006 of 150°C to 500°C, preferably 180°C to 400°C, more preferably 220°C to 380°C and particularly preferably 250°C to 250°C. It may be in the range of 350°C. Here, the sublimation temperature is obtained from vacuum TGA measurements in which the material sublimates or evaporates in a controlled manner. Measurements can be performed with the TG 209 F1 Libra instrument from Netzsch under the following measurement conditions:

Sample weight: 1 mg

Crucible: open aluminum crucible

Heating rate: 5 K/min

Temperature range: 105-550℃

Atmosphere: Vacuum 10-2 mbar (regulated)

Exhaust time before starting measurement: Approximately 30 minutes. The sublimation temperature used is that at which 5% weight loss occurs.

Additionally, the at least one functional material to be purified may have a decomposition temperature of greater than 340°C, preferably greater than 400°C, and more preferably greater than 500°C. Here, the decomposition temperature is obtained from DSC or TGA measurement, and the decomposition temperature is the temperature at which destruction of the material is detected. The decomposition temperature is considered to be the temperature at which 50% of the substance is detected in a heating operation performed at 5 K per minute (sample size approximately 1 mg). The process of the invention must always be carried out below the decomposition temperature of at least one functional substance.

In a preferred embodiment, the at least one functional substance to be purified has a glass transition temperature measured according to DIN EN ISO 11357-1 and DIN EN ISO 11357-2 of 80° C. to 400° C., preferably 90° C. to 300° C., more preferably 90° C. to 300° C. Preferably it may range from 100°C to 250°C, particularly preferably from 120°C to 220°C and particularly preferably from 130°C to 200°C. Details of the determination of the glass transition temperature are known to those skilled in the art from standards; The glass transition temperature is preferably determined after the first heating and cooling operation. For many materials, a suitable glass transition temperature can be obtained at a heating rate of 20 K/min during the first and second heating runs and a cooling rate of 20 K/min during the first and second cooling runs, and the second or is confirmed as a signal in the third heating operation, preferably in the second heating operation. In a particularly preferred embodiment, the glass transition temperature is determined using a sample prepared by a first heating operation at a heating rate of 20 K/min and a quenching operation by direct cooling of the heated sample in liquid nitrogen, and the glass transition temperature The temperature is then confirmed by a second heating run on the pretreated sample at a heating rate of 50 K/min. Thanks to these means, the glass transition temperature can be reliably determined even for materials whose glass transition is masked by the recrystallization temperature in other processes. This test method, in which the first cooling run is achieved by a quenching operation and the second heating run is performed at a heating rate of 50 K/min, is particularly preferred over others that operate at lower cooling rates or lower heating rates, for example. do. When the melt temperature is below 300°C, the heating range is preferably in the range from 0°C to 350°C. For materials with higher melting temperatures, the heating range is expanded correspondingly at the upper limit, but must remain below the decomposition temperature. Preferably, the upper temperature in the heating range is at least 5°C lower than the decomposition temperature.

The amount of sample preferably ranges from 10 to 15 mg. Additional information regarding the determination of the glass transition temperature can be found in the examples. The examples provide details on particularly preferred measuring equipment.

Additionally, the at least one functional substance to be purified can be used in the form of a mixture, where the mixture preferably comprises at least two such functional substances. In this case, the substances used in the mixture have similar sublimation and/or softening properties. The more similar these properties are, the better the quality of the resulting mixture of purified materials. Therefore preferably at least two functional materials used in a mixture that can be used in particular for the production of functional layers of electronic devices can have essentially similar softening, evaporation and/or sublimation properties.

In a preferred configuration, the evaporation or sublimation and/or condensation of the at least one functional substance can be carried out at a pressure ranging from 10 ^-3 mbar to 10 ^-7 mbar, preferably from 10 ^-4 mbar to 10 ^-6 mbar.

In a further configuration, the at least one functional material to be purified, usable for the production of functional layers of electronic devices, in particular those involved in charge injection or charge transport and/or light emission or light outcoupling, is selected from the group consisting of benzene, fluorene, indenofluorine. Orene, spirobifluorene, carbazole, indenocarbazole, indolocarbazole, spirocarbazole, pyrimidine, triazine, quinazoline, quinoxaline, pyridine, quinoline, isoquinoline, lactam, triarylamine, diamine. Benzofuran, diazadibenzofuran, dibenzothiophene, diazadibenzothiophene, imidazole, benzimidazole, benzoxazole, benzothiazole, 5-arylphenanthridin-6-one, 9,10-di Hydrophenanthrene, fluoranthene, naphthalene, phenanthrene, anthracene, benzanthracene, fluoradene, pyrene, perylene, chrysene, borazine, boroxine, borrole, borazole, azaborole, ketone, phosphine oxide, selected from the group consisting of arylsilanes, siloxanes, biphenyls, triphenyls, terphenyls, triphenylenes, arylgermanes, arylbismuth iodides, metal complexes, chelate complexes, transition metal complexes, metal clusters, and combinations thereof; Here, the metal complex, chelate complex, transition metal complex, metal cluster preferably consists of the elements Li, Na, K, Cs, Be, Mg, B, Al, Ga, In, Ge, Sn, Bi, Se, Te, Sc. , Ti, Zr, Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn.

Functional materials usable for the production of functional layers of electronic devices are in many cases organic compounds that provide the functions mentioned above and below. The terms “functional compound” and “functional substance” should therefore be understood as synonyms in many cases.

A description of examples of suitable functional materials that can be purified according to the invention follows.

Compounds with hole injection properties, also referred to herein as hole injection materials, facilitate or enable the transfer of holes, i.e. positive charges, from the anode into the organic layer.

Compounds with hole transport properties, also referred to herein as hole transport materials, are generally capable of transporting holes, i.e. positive charges, injected from an anode or an adjacent layer, for example a hole injection layer.

Preferred compounds having hole injection and/or hole transport properties include, for example, triarylamine derivatives, benzidine derivatives, tetraaryl-para-phenylenediamine derivatives, triarylphosphine derivatives, phenothiazine derivatives, phenoxazine derivatives. , dihydrophenazine derivatives, thiantrene derivatives, dibenzo-para-dioxine derivatives, fenoxathiin derivatives, carbazole derivatives, azulene derivatives, thiophene derivatives, pyrrole derivatives and furan derivatives.

Particular mention should be made of the following compounds with hole injection and/or hole transport properties: phenylenediamine derivatives (US3615404), arylamine derivatives (US3567450), amino-substituted chalcone derivatives (US 3526501), styrylanthracene derivatives (JP) -A-56-46234), polycyclic aromatic compound (EP 1009041), polyarylalkane derivative (US3615402), fluorenone derivative (JP-A-54-110837), hydrazone derivative (US3717462), acylhydrazone, steel Bene derivative (JP-A-61-210363), silazane derivative (US4950950), polysilane (JP-A-2-204996), aniline copolymer (JP-A-2-282263), thiophene oligomer (JP Heisei 1 (1989) 211399), polythiophene, poly(N-vinylcarbazole) (PVK), polypyrrole, polyaniline and other electrically conductive macromolecules, porphyrin compounds (JP-A-63-2956965, US4720432), aromatic dimethylidene -type compounds, carbazole compounds such as CDBP, CBP, mCP, aromatic tertiary amines and styrylamine compounds (US4127412), such as triphenylamines of the benzidine type, triphenylamines of the styrylamine type and diamine types. of triphenylamine. Arylamine dendrimer (JP Heisei 8 (1996) 193191), monomeric triarylamine (US3180730), triarylamine with at least one functional group with one or more vinyl radicals and/or active hydrogen (US3567450 and US3658520) or tetraaryldiamine It is also possible to use (two tertiary amine units connected via an aryl group). It is possible for even more triarylamino groups to be present in the molecule. Also suitable are phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives and quinoline derivatives, such as dipyrazino[2,3-f:2',3'-h]quinoxalinehexacarbonitrile.

Aromatic tertiary amines with at least two tertiary amine units (US2008/0102311, US4720432 and US5061569), such as NPD (α-NPD = 4,4'-bis[N-(1-naphthyl)-N-phenylamino ]Biphenyl) (US5061569), TPD 232 (= N,N'-bis(N,N'-diphenyl-4-aminophenyl)-N,N-diphenyl-4,4'-diamino-1, 1'-biphenyl) or MTDATA (MTDATA or m-MTDATA = 4,4',4"-tris[3-(methylphenyl)phenylamino]triphenylamine) (JP-A-4-308688), TBDB (= N,N,N',N'-tetra(4-biphenyl)diaminobiphenylene), TAPC (= 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane), TAPPP (= 1,1-bis(4-di- p -tolylaminophenyl)-3-phenylpropane), BDTAPVB (= 1,4-bis[2-[4-[N,N-di(p-tolyl)amino] phenyl] vinyl] benzene), TTB (= N,N,N',N'-tetra- p -tolyl-4,4'-diaminobiphenyl), TPD (= 4,4'-bis[N-3 -methylphenyl]-N-phenylamino)biphenyl), N,N,N',N'-tetraphenyl-4,4"'-diamino-1,1',4',1",4",1 "'-quaterphenyl, and likewise tertiary amines with carbazole units, for example TCTA (= 4-(9H-carbazol-9-yl)-N,N-bis[4-(9H-carbazole- 9-yl)phenyl]benzenamine). Equally preferred are the hexaazatriphenylene compounds according to US2007/0092755 and phthalocyanine derivatives (e.g. H ₂ Pc, CuPc (=copper phthalocyanine), CoPc, NiPc, ZnPc , PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc).

Particularly preferred are documents EP 1162193 B1, EP 650 955 B1, Synth. Metals 1997 , 91(1-3), 209, DE19646119, WO2006/122630, EP1860097, EP1834945, JP08053397, US6251531, US2005/0221124, JP08292586, US7399537, US2006 /0061265, EP1661888 and WO2009/041635 (TA- 1) to (TA-14) are triarylamine compounds. Compounds of the above formulas (TA-1) to (TA-14) may also be substituted:

Additional hole injection, hole transport or electron blocker materials that can be purified according to the present invention include EP0891121, EP1029909, US2004/0174116, WO2013/120577, WO2013/087142, WO2014/067614, WO2014/072017, WO2014/015 937, It is described in WO2014/015935, WO2015/022051, WO2016/078747, WO2016/087017, WO2017/041874, WO2017/016632, WO2017/148564, WO2018/083053.

In principle, any known electron blocker material can be used. In addition to the additional electron blocker materials described elsewhere in this application, suitable electron blocker materials are transition metal complexes, such as Ir(ppz)3 (US2003/0175553).

Compounds with electron injection and/or electron transport properties include, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazines, ketones, phosphine oxides and phenazine derivatives, as well as triarylborane.

Particularly suitable compounds for the electron-transport and electron-injection layers are metal chelates of 8-hydroxyquinoline (e.g. LiQ, AlQ ₃ , GaQ _{3 , MgQ 2} , ZnQ ₂ , InQ _{3 ,} ZrQ ₄ ), BAlQ, Ga oxy Noid complex, 4-azaphenanthrene-5-ol Be complex (US5529853, cf. formula ET-1), butadiene derivative (US4356429), heterocyclic optical brightener (US4539507), benzimidazole derivative (US2007/0273272), For example TPBI (US5766779, cf. formula ET-2), 1,3,5-triazine, for example spirobifluorene-triazine derivatives (for example according to DE102008064200), pyrene, anthracene, tetracene , fluorene, spirofluorene, dendrimer, tetracene (e.g. rubrene derivatives), 1,10-phenanthroline derivatives (JP2003-115387, JP2004-311184, JP2001-267080, WO2002/043449), silacyclopenta Diene derivatives (EP1480280, EP1478032, EP1469533), borane derivatives, for example trialrylborane derivatives with Si (US2007/0087219 A1, cf. formula ET-3), pyridine derivatives (JP2004-200162), phenanthrolines, especially 1,10-phenanthroline derivatives, such as BCP and Bphen, including multiple phenanthrolines linked via biphenyl or other aromatic groups (US2007-0252517) or phenanthrolines linked by anthracene (US2007) -0122656, cf. formulas ET-4 to ET-6), and pyrimidines or triazines, for example those described in formulas ET-7 and ET-8. Compounds of the above formulas (ET-1) to (ET-8) may also be substituted:

Likewise suitable are heterocyclic organic compounds, for example thiopyran dioxide, oxazole, triazole, imidazole or oxadiazole. Examples of the use of 5-membered rings containing N are, for example, oxazoles, preferably 1,3,4-oxadiazoles, for example formulas ET-6, ET-7, ET-8 and ET Compounds of -9 (described in detail in particular in US 2007/0273272 A1); Thiazoles, oxadiazoles, thiadiazoles, triazoles (see in particular US 2008/0102311 A1 and Y.A. Levin, M.S. Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967 (2), 339-341), preferably of the formula ET-10 The compound is a silacyclopentadiene derivative. Preferred compounds are those of the formulas (ET-9) to (ET-10):

It is also possible to use derivatives of organic compounds such as fluorenone, fluorenylidenemethane, perylenetetracarboxylic acid, anthraquinonedimethane, diphenoquinone, anthrone and anthraquinonediethylenediamine.

Preference is given to 2,9,10-substituted anthracenes (by 1- or 2-naphthyl and 4- or 3-biphenyl) or molecules containing two anthracene units (US2008/0193796 A1, cf. formula ET- 11) is. Also very advantageous are compounds of 9,10-substituted anthracene units and benzimidazole derivatives (US 2006 147747 A and EP 1551206 A1, cf. formulas ET-12 and ET-13).

Additional electron injecting or electron transporting materials that can be purified according to the invention include WO2005/053055, WO2010/072300, WO2014/023388, WO2015/049030, WO2016/012075, WO2017/178311, WO2017/016630, WO2018/0 60307, It is described in WO2018/060218.

The functional material used in the process of the present invention may include an emitter. The term “emitter” refers to a material that allows a radiative transition to the ground state with the emission of light, after excitation, which may occur by transfer of any type of energy. Generally, there are two known classes of emitters: fluorescent and phosphorescent emitters. The term “fluorescent emitter” refers to a substance or compound that has a radiative transition from an excited singlet state to the ground state. The term “phosphorescent emitter” preferably refers to a luminescent substance or compound comprising a transition metal.

In cases where a dopant causes the above-described properties in the system, the emitter is often also called a dopant. In systems comprising a matrix material and a dopant, the dopant is understood to mean a smaller proportion of the component in the mixture. Correspondingly, in systems comprising a matrix material and a dopant, the matrix material is understood to mean the component with a greater proportion in the mixture. The term “phosphorescent emitter” can therefore, for example, also be understood to mean a phosphorescent dopant.

Compounds capable of emitting light include fluorescent emitters and phosphorescent emitters. These include stilbene, stilbenamine, styrylamine, coumarin, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, paraphenylene, perylene, phthalocyanine, porphyrin, ketone, quinoline, imine, and anthracene. and/or compounds having a pyrene structure. Compounds that can emit light with high efficiency from the triplet state even at room temperature, that is, compounds that exhibit electrophosphorescence rather than electrofluorescence, often resulting in increased energy efficiency, are particularly desirable. Suitable for this purpose are, first of all, compounds containing heavy atoms with an atomic number greater than 36. Preferred compounds are those containing d or f transition metals that satisfy the above conditions. Particularly preferred here are elements from groups 6 to 10, preferably from groups 8 to 10 (Mo, W, Re, Cu, Ag, Au, Zn, Ru, Os, Rh, Ir, Pd, Pt, preferably Ru, Corresponding compounds containing Os, Rh, Ir, Pd, Pt). Functional compounds useful herein include various complexes described, for example, in WO02/068435 A1, WO02/081488 A1, EP1239526 A2 and WO04/026886 A2.

Preferred compounds that can act as fluorescent emitters are described in detail below by way of example. Preferred fluorescent emitters are selected from the class of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphine, styryl ethers and arylamines.

Monostyrylamine is understood to mean a compound containing one substituted or unsubstituted styryl group and at least one preferably aromatic amine. Distyrylamine is understood to mean a compound containing two substituted or unsubstituted styryl groups and at least one preferably aromatic amine. Tristyrylamine is understood to mean a compound containing three substituted or unsubstituted styryl groups and at least one preferably aromatic amine. Tetrastyrylamine is understood to mean a compound containing four substituted or unsubstituted styryl groups and at least one preferably aromatic amine. The styryl group is more preferably stilbene, which may have additional substituents. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine is understood in the context of the present invention to mean a compound containing a system of three substituted or unsubstituted aromatic or heteroaromatic rings directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyrenamine, aromatic pyrenediamine, aromatic chrysenamine or aromatic chrysendiamine. Aromatic anthraceneamines are understood to mean compounds in which the diarylamino group is bonded directly to the anthracene group, preferably in the 9 position. Aromatic anthracenediamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 2,6 or 9,10 position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined similarly, wherein the diarylamino group is bonded to the pyrene, preferably at the 1 position or the 1,6 position.

Further preferred fluorescent emitters are indenofluorenamines or -diamines, which are described in particular in detail in document WO06/122630; benzoindenofluorenamine or -diamine, especially those described in detail in document WO2008/006449; and in particular dibenzoindenofluorenamines or -diamines described in detail in document WO2007/140847.

Examples of compounds of the class of styrylamines that can be used as fluorescent emitters include substituted or unsubstituted tristilbenamines or dopants described in WO06/000388, WO06/058737, WO06/000389, WO07/065549 and WO07/115610. am. Distyrylbenzene and distyrylbiphenyl derivatives are described in US 5121029. Additional styrylamines can be found in US 2007/0122656 A1.

Particularly preferred styrylamine compounds are the compounds of formula EM-1 described in US 7250532 B2 and the compounds of formula EM-2 described in detail in DE 10 2005 058557 A1:

Particularly preferred triarylamine compounds, or groups or structural elements, are those of formulas EM-3 to EM-18, described in detail in documents CN1583691, JP08/053397 and US6251531, EP1957606, US2008/0113101, US2006/210830, WO08/006449 and DE102008035413. compounds of and its derivatives:

Further preferred compounds that can be used as fluorescent emitters are naphthalene, anthracene, tetracene, benzanthracene, benzophenanthrene (DE 10 2009 005746), fluorene, fluoranthene, periplanthene, indenoperylene, phenanthrene, Perylene (US 2007/0252517 A1), pyrene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US 4769292, US 6020078, US 2007/0252517 A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine, cinnamic acid ester, diketopyrrolopyrrole, acridone and quinacridone (US 2007/0252517 A1) ) is selected from derivatives of.

Particularly preferred among the anthracene compounds are anthracenes substituted at the 9,10 position, for example 9,10-diphenylanthracene and 9,10-bis(phenylethynyl)anthracene. 1,4-bis(9'-ethynylanthracenyl)benzene is also a preferred dopant.

Equally preferred are rubrene, coumarin, rhodamine, quinacridone, for example DMQA (= N,N'-dimethylquinacridone), dicyanomethylenepyran, for example DCM (=4-(dicyanoethylene) -6-(4-dimethylaminostyryl-2-methyl)-4H-pyran), a derivative of thiopyran, polymethine, pyrylium and thiapyrylium salts, periplantene and indenoperylene.

The blue fluorescent emitter is preferably polyaromatic, such as 9,10-di(2-naphthylanthracene) and other anthracene derivatives, tetracene, xanthene, derivatives of perylene, such as 2,5,8, 11-tetra- t -butylperylene, phenylene, such as 4,4'-(bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl, fluorene, fluoranthene , arylpyrene (US 2006/0222886 A1), arylenevinylene (US 5121029, US 5130603), bis(azinyl)imineboron compound (US 2007/0092753 A1), bis(azinyl)methene compound and carbostyryl. It is a compound.

Additional preferred blue fluorescent emitters are described in C. H. Chen et al.: “Recent developments in organic electroluminescent materials” Macromol. Symp. 125, (1997), 1-48 and “Recent progress of molecular organic electroluminescent materials and devices” Mat. Sci. and Eng. R, 39 (2002), 143-222.

Further preferred blue-fluorescent emitters are the hydrocarbons disclosed in DE102008035413. Particularly preferred are the compounds further described in detail in WO2014/111269, especially those having a bis(indenofluorene) base skeleton. The documents DE 102008035413 and WO2014/111269 cited above are incorporated by reference into this application for purposes of disclosure.

Further preferred compounds that can be used as fluorescent emitters are described in WO2010/012328, WO2010/012330, WO2014/037077 and WO2008/145239.

Phosphorescence is understood in the context of the present invention to mean luminescence from excited states with a higher spin multiplicity, i.e. spin states > 1, especially excited triplet states. In the context of the present application, all luminescent complexes with transition metals or lanthanides, in particular all iridium, platinum and copper complexes, should be considered as phosphorescent compounds.

Suitable phosphorescent compounds (=triplet emitters), in particular, when suitably excited, preferably emit light in the visible region and also have an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and 80. It is a compound containing at least one atom, especially a metal with this atomic number, of less than . Preferred phosphorescent emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum.

Examples of the above-described emitters are in applications WO00/70655, WO2001/41512, WO2002/02714, WO2002/15645, EP1191613, EP1191612, EP1191614, WO05/033244, WO05/019373, US2005/0258744. , WO2009/146770, WO2010/015307, WO2010/031485, WO2010/054731, WO2010/054728, WO2010/086089, WO2010/099852, WO2010/102709, WO2011/032626, WO2011/066898, WO2011/15733 9, WO2012/007086, WO2014/008982, WO2014/023377, WO2014/ 094961, WO2014/094960, WO2015/036074, WO2015/104045, WO2015/117718, WO2016/015815, WO2016/124304, WO2017/032439, WO2018/011186, WO20 18/001990, WO2018/019687, WO2018/019688, WO2018/041769, WO2018/054798, WO2018/069196, WO2018/069197, WO2018/069273, WO2018/178001, WO2018/177981, WO2019/020538, WO2019/115423, WO2019/15845 3 and WO2019/179909. In general, all phosphorescent complexes known to the person skilled in the art of organic electroluminescence and used in phosphorescent electroluminescence devices according to the prior art are suitable, and the person skilled in the art will be able to use further phosphorescent complexes without inventive steps.

Preferred ligands are 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2-(2-thienyl)pyridine derivatives, 2-(1-naphthyl)pyridine derivatives, 1-phenylisoquinoline derivatives, 3-phenyliso It is a quinoline derivative or 2-phenylquinoline derivative. All these compounds may be substituted with fluorine, cyano and/or trifluoromethyl substituents, for example for blue. The auxiliary ligand is preferably acetylacetonate or picolinic acid.

Particularly suitable as emitters are complexes of Pt or Pd with tetradentate ligands of the formula EM-19.

Compounds of formula EM-19 are described in more detail in US 2007/0087219 A1, to which reference is made for disclosure purposes for explanation of substituents and indices in the formula.

Additionally suitable are Pt-porphyrin complexes with expanded ring systems (US 2009/0061681 A1) and Ir complexes, for example 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin-Pt(II), tetraphenyl-Pt(II)-tetrabenzoporphyrin (US 2009/0061681 A1), cis -bis(2-phenylpyridinato-N,C ² ')Pt(II), cis -bis(2-(2'-thienyl)pyridinato-N,C ³ ')Pt(II), cis -bis(2-(2'-thienyl)pyridinato-N,C ⁵ ' )Pt(II), (2-(4,6-difluorophenyl)pyridinato-N,C ² ')Pt(II)(acetylacetonate), or tris(2-phenylpyridinato-N ,C ² ')Ir(III) (= Ir(ppy) ₃ , green), bis(2-phenylpyridinato-N,C ² )Ir(III)(acetylacetonate) (= Ir(ppy) ₂ Acetylacetonate, green, US 2001/0053462 A1, Baldo, Thompson et al. Nature 403, (2000), 750-753), bis(1-phenylisoquirolinato-N,C ² ')(2-phenyl Pyridinato-N,C ² ')iridium(III), bis(2-phenylpyridinato-N,C ² ')(1-phenylisoquirolinato-N,C ² ')iridium(III), Bis(2-(2'-benzothienyl)pyridinato-N,C ³ ')iridium(III)(acetylacetonate), bis(2-(4',6'-difluorophenyl)pyridina to-N,C ² ')iridium(III)(picolinate) (FIrpic, blue), bis(2-(4',6'-difluorophenyl)pyridinato-N,C ² ')Ir (III) (tetrakis(1-pyrazolyl)borate), tris(2-(biphenyl-3-yl)-4-tert-butylpyridine)iridium(III), (ppz) ₂ Ir(5phdpym) (US 2009/0061681 A1), (45ooppz) ₂ Ir(5phdpym) (US 2009/0061681 A1), derivatives of the 2-phenylpyridine-Ir complex, for example PQIr (= iridium(III) bis(2-phenylquinolyl- N,C ² ')acetylacetonate), tris(2-phenylisoquirolinato-N,C)Ir(III) (red), bis(2-(2'-benzo[4,5-a]thi) Nyl)pyridinato-N,C ³ )Ir(acetylacetonate) ([Btp ₂ Ir(acac)], red, Adachi et al. Appl. Phys. Lett . 78 (2001), 1622-1624). Also particularly suitable are the complexes described in detail in WO2016/124304. The above-cited documents, especially WO2016/124304, are hereby incorporated by reference into this application for disclosure purposes.

Likewise suitable are complexes of trivalent lanthanides, for example Tb ³⁺ and Eu ³⁺ (J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1) or phosphorescent complexes of Pt(II), Ir(I), Rh(I) with maleonitrile dithiolate (Johnson et al., JACS 105, 1983, 1795), Re(I )-tricarbonyldiimine complexes (Wrighton, JACS 96, 1974, 998 especially), Os(II) complexes with cyano ligands and bipyridyl or phenanthroline ligands (Ma et al., Synth. Metals 94, 1998, 245).

Additional phosphorescent emitters with tridentate ligands are described in US 6824895 and US 10/729238. Red emitting phosphorescent complexes can be found in US 6835469 and US 6830828.

Particularly preferred compounds used as phosphorescent dopants are those described in US 2001/0053462 A1 and Inorg. Chem. 2001, 40(7), 1704-1711, JACS 2001, 123(18), 4304-4312 and derivatives thereof.

Derivatives are described in US7378162, US6835469 and JP2003/253145.

Additionally, compounds of formulas EM-21 to EM-28 and derivatives thereof described in US7238437, US2009/008607 and EP1348711 can be used as emitters.

Additional emitters that can be purified according to the invention include WO00/70655, WO2001/41512, WO2002/02714, WO2002/15645, EP1191613, EP1191612, EP1191614, WO05/033244, WO05/019373, US2005/0258 742, WO2009/146770, WO2010/015307, WO2010/031485, WO2010/054731, WO2010/054728, WO2010/086089, WO2010/099852, WO2010/102709, WO2011/032626, WO2011/06689 8, WO2011/157339, WO2012/007086, WO2014/008982, WO2014/ 023377, WO2014/094961, WO2014/094960, WO2015/036074, WO2015/104045, WO2015/117718, WO2016/015815, WO2016/124304, WO2017/032439, WO20 18/011186, WO2018/001990, WO2018/019687, WO2018/019688, WO2018/041769, WO2018/054798, WO2018/069196, WO2018/069197, WO2018/069273, WO2018/178001, WO2018/177981, WO2019/020538, WO2019/11542 3, described in WO2019/158453 and WO2019/179909.

In a preferred configuration, suitable combinations of compounds preferably form a hyperfluorescent and/or hyperphosphorescent system. These hyperfluorescent and/or hyperphosphorescent systems form preferred embodiments of the functional materials to be purified according to the invention.

Preferably, for this purpose, fluorescent emitters are used in combination with one or more compounds that are phosphorescent (triplet emitters) and/or TADF (thermally activated delayed fluorescence) host substances.

WO2015/091716 and WO2016/193243 disclose OLEDs containing both a phosphorescent compound and a fluorescent emitter in the emitting layer, where energy is transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence). In this context, the phosphorescent compound therefore behaves as a host material. As those skilled in the art know, the host material has higher singlet and triplet energy compared to the emitter such that the energy from the host material can also be transferred to the emitter with maximum efficiency. Systems disclosed in the prior art have exactly this energy relationship.

The fluorescent emitter may preferably be used in combination with a TADF host material and/or a TADF emitter as described above.

A process referred to as thermally activated delayed fluorescence (TADF) is described, for example, in BH Uoyama et al., Nature 2012, Vol. It is described by 492, 234. To enable this process, a relatively small singlet-triplet separation ΔE(S ₁ -T ₁ ) is required at the emitter, for example less than about 2000 cm ^-1 . In order to open the T ₁ → S ₁ transition, which is in principle spin-forbidden as well as the emitter, it is possible to provide additional compounds in the matrix with strong spin-orbit couplings, thus enabling the system through possible interactions and spatial proximity between molecules. Crossover is possible, or spin-orbit coupling is created by metal atoms present in the emitter.

Compounds used as host materials, especially with emitting compounds, include various classes of materials.

The host material has a larger band gap between HOMO and LUMO than the commonly used emitter material. Additionally, a preferred host material exhibits the characteristics of either a hole or an electron transport material. Moreover, the host material may have electron or hole transport properties.

The host material is also called a matrix material in some cases, especially when the host material is used in combination with a phosphorescent emitter in an OLED.

Preferred host or co-host materials, especially for use with fluorescent dopants, are oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), In particular the class of oligoarylenes containing fused aromatic groups, for example anthracene, benzanthracene, benzophenanthrene (DE 10 2009 005746, WO09/069566), phenanthrene, tetracene, coronene, chrysene, fluorene, Spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, oligoarylenevinylene (e.g. DPVBi according to EP 676461 = 4,4'-bis(2,2- diphenylethenyl)-1,1'-biphenyl or spiro-DPVBi), polypodal metal complexes (e.g. according to WO04/081017), especially metal complexes of 8-hydroxyquinoline, for example AlQ ₃ ( = Aluminum(III) tris(8-hydroxyquinoline)) or bis(2-methyl-8-quinolinolato)-4-(phenylphenolinolato)aluminum (including imidazole chelates) (US 2007/ 0092753 A1), and quinoline-metal complexes, aminoquinoline metal complexes, benzoquinoline metal complexes, hole-conducting compounds (e.g. according to WO04/058911), electron-conducting compounds, especially ketones, phosphine oxides, sulfoxides , carbazole, spiro-carbazole, indenocarbazole, etc. (e.g. according to WO05/084081 and WO05/084082), atropisomers (e.g. according to WO06/048268), boronic acid derivatives (e.g. according to WO06/117052) or benzanthracene (for example according to WO08/145239).

Particularly preferred compounds that can serve as host or co-host materials are selected from the class of oligoarylenes containing anthracene, benzanthracene and/or pyrene or atropisomers of these compounds. Oligoarylene in the context of the present invention will be understood to mean a compound in which at least three aryl or arylene groups are bonded to each other.

Preferred host materials are particularly selected from compounds of formula (H-100)

In the formula, Ar ⁵ , Ar ⁶ and Ar ⁷ are the same or different in each case and are an aryl or heteroaryl group having 5 to 30 aromatic ring atoms and which may be optionally substituted, and p is an integer ranging from 1 to 5. ; At the same time, the sum of π electrons in Ar ⁵ , Ar ⁶ and Ar ⁷ is at least 30 when p = 1, at least 36 when p = 2, and at least 42 when p = 3.

More preferably, in the compounds of formula (H-100), the Ar ⁶ group is anthracene and the Ar ⁵ and Ar ⁷ groups are bonded at the 9 and 10 positions, where these groups may be optionally substituted. Most preferably, at least one of the Ar ⁵ and/or Ar ⁷ groups is 1- or 2-naphthyl, 2-, 3- or 9-phenanthrenyl or 2-, 3-, 4-, 5-, 6 - or a fused aryl group selected from 7-benzanthracenyl. Anthracene-based compounds are described in US 2007/0092753 A1 and US 2007/0252517 A1, for example 2-(4-methylphenyl)-9,10-di(2-naphthyl)anthracene, 9-(2-naph) Tyl)-10-(1,1'-biphenyl)anthracene and 9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene, 9,10-diphenylanthracene, 9,10- Bis(phenylethynyl)anthracene and 1,4-bis(9'-ethynylanthracenyl)benzene. Compounds with two anthracene units (US 2008/0193796 A1), such as 10,10'-bis[1,1',4', 1"]terphenyl-2-yl-9,9'-bisanthra Cenyl is also preferred.

Further preferred compounds are arylamine, styrylamine, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, oxadiazole, bisbenzoxazoline. , derivatives of oxazole, pyridine, pyrazine, imine, benzothiazole, benzoxazole, benzimidazole (US 2007/0092753 A1), for example 2,2',2"-(1,3,5-phenyl len)tris[1-phenyl-1H-benzimidazole], aldazine, stilbene, styrylarylene derivatives, such as 9,10-bis[4-(2,2-diphenylethenyl)phenyl] Anthracene and distyrylarylene derivatives (US 5121029), diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, diketopyrrolopyrrole, polymethine, cinnamic acid ester and fluorescent dye.

Particularly preferred are derivatives of arylamines and styrylamines, for example TNB (=4,4'-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl). Metal oxinoid complexes such as LiQ or AlQ ₃ can be used as co-hosts.

Preferred compounds with oligoarylene as matrix include US2003/0027016, US7326371, US2006/043858, WO2007/114358, WO08/145239, JP3148176, EP1009044, US2004/018383, WO2005/061656, EP068 1019, WO2004/013073, US5077142, WO2007/ 065678 and DE 102009005746, particularly preferred compounds are described by formulas H-101 to H-108. Compounds of formula H-101 to H-108 may also be substituted:

Additionally, compounds that can be used as hosts or matrices include materials used with phosphorescent emitters. These compounds, which can also be used as structural elements in polymers, include CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (e.g. WO05/039246, US2005/0069729, JP2004/288381, EP1205527 or WO08/086855 according to), azacarbazole (e.g. according to EP1617710, EP1617711, EP1731584, JP2005/347160), ketone (e.g. according to WO04/093207 or DE102008033943), phosphine oxide, sulfoxide and sulfone ( e.g. according to WO05/003253), oligophenylene, aromatic amines (e.g. according to US2005/0069729), anodic matrix materials (e.g. according to WO07/137725), silanes (e.g. according to WO05/111172) according to), 9,9-diarylfluorene derivatives (e.g. according to DE102008017591), azabolol or boronic acid esters (e.g. according to WO06/117052), triazine derivatives (e.g. according to DE102008036982), Indolocarbazole derivatives (e.g. according to WO07/063754 or WO08/056746), indenocarbazole derivatives (e.g. according to DE102009023155 and DE102009031021), diazaphosphole derivatives (e.g. according to DE102009022858), tria Sol derivatives, oxazole and oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, distyrylpyrazine derivatives, thiopyran dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines. , amino-substituted chalcone derivatives, indoles, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic dimethylidene compounds, carbodiimide derivatives, metal complexes of 8-hydroxyquinoline derivatives, such as AlQ ₃ , 8-hydroxyquinoline complexes may also contain triarylaminophenol ligands (US 2007/0134514 A1), metal complex polysilane compounds and thiophene, benzothiophene and dibenzothiophene derivatives.

Examples of preferred carbazole derivatives are mCP (=1,3-N,N-dicarbazolebenzene (=9,9'-(1,3-phenylene)bis-9H-carbazole)) (formula H-9 ), CDBP (= 9,9'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-9H-carbazole), 1,3-bis(N, N'-dicarbazole)benzene (= 1,3-bis(carbazol-9-yl)benzene), PVK (polyvinylcarbazole), 3,5-di(9H-carbazol-9-yl)bi phenyl and CMTTP (formula H10). Particularly preferred compounds are described in detail in US 2007/0128467 A1 and US 2005/0249976 A1 (formulas H-111 to H-113).

Preferred Si-tetraaryls are described for example in documents US 2004/0209115, US 2004/0209116, US 2007/0087219 A1 and H. Gilman, E.A. Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120. Particularly preferred Si-tetraaryls are described by formulas H-114 to H-121.

Particularly preferred compounds for the production of matrices for phosphorescent dopants are described in particular in detail in DE102009022858, DE102009023155, EP652273, WO07/063754 and WO08/056746, and particularly preferred compounds are described by formulas H-122 to H-125.

With regard to the functional compounds that can be used according to the invention and that can act as host materials, preference is given in particular to substances having at least one nitrogen atom. These preferably include aromatic amines, triazine derivatives and carbazole derivatives. For example, carbazole derivatives show particularly surprisingly high efficiencies. Triazine derivatives lead to unexpectedly long lifetimes of electronic devices containing the mentioned compounds.

Additional host materials that can be purified according to the invention include WO2010/136109, WO2011/057706, WO2011/160757, WO2013/041176, WO2014/015931, WO2014/094963, WO2015/165563, WO2015/169412 , WO2015/192939, WO2016 /015810, WO2016/184540, WO2017/025164, WO2017/071791 and WO2018/050583.

In addition, it is possible to purify compounds that improve the transition from a singlet to a triplet state and are used to support functional compounds with emitter properties to improve the phosphorescence properties of such compounds. Units useful for this purpose are in particular carbazole and crosslinked carbazole dimer units, described for example in WO04/070772 and WO04/113468. Also useful for this purpose are, for example, ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds described in WO05/040302.

n-dopant is herein understood to mean a reducing agent, ie an electron donor. Preferred examples of n-dopants are W(hpp) ₄ and further electron-rich metal complexes according to WO2005/086251, P=N compounds (e.g. WO2012/175535, WO2012/175219), naphthylenecarbodiimide (e.g. For example WO2012/168358), fluorene (for example WO2012/031735), radicals and diradicals (for example EP1837926, WO2007/107306), pyridines (for example EP2452946, EP2463927), N-heterocyclic compounds ( for example WO2009/000237) and acridine and phenazine (for example US2007/145355).

Additionally, the functional material may be a wide bandgap material. Wide bandgap materials are understood to mean materials within the meaning of the disclosure of US7294849. These systems exhibit exceptionally favorable performance data for electroluminescent devices.

In principle, any known hole blocker material for purification can be used. In addition to the hole blocker materials described in detail elsewhere in this application, suitable hole blocker materials include bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (BAlQ), fac- tris(1-phenylpyrazolato-N,C2)iridium(III) (Ir(ppz) ₃ ), phenanthroline derivatives such as BCP, or phthalimides such as TMPP, or WO00/70655, It is a hole blocker material described in WO01/41512 and WO01/93642.

Furthermore, preferred functional materials that can be used for the production of functional layers of electronic devices are compounds of low molecular weight, preferably having a molecular weight of ≤ 2000 g/mol, more preferably ≤ 1500 g/mol, particularly preferably ≦1200 g/mol and most preferably ≦1000 g/mol. Low molecular weight compounds may sublimate or evaporate.

The publications cited above for descriptions of functional materials usable for the production of functional layers of electronic devices are hereby incorporated by reference herein for disclosure purposes.

By this process, a granular material can preferably be obtained. Preferred granular materials can contain all the organic functional materials required for the production of specific functional layers of electronic devices. For example, if the hole transport, hole injection, electron transport or electron injection layer is formed in particular from two functional compounds, the granular material thus comprises in particular those two compounds as organic functional material. When the emitting layer comprises an emitter, for example in combination with a matrix or host material, the formulation may contain an emitter as an organic functional material, in particular as described in more detail elsewhere in the present application. and mixtures of matrix or host materials.

Functional materials are generally organic or inorganic materials introduced between the anode and cathode. Preferably, the organic functional material is a fluorescent emitter, a phosphorescent emitter, an emitter exhibiting TADF (thermally activated delayed fluorescence), an emitter exhibiting hyperfluorescence or hyperphosphorescence, a host material, an exciton blocker material, an electron injection material, an electron It is selected from the group consisting of transport materials, electron blocker materials, hole injection materials, hole conductor materials, hole blocker materials, n-dopants, p-dopants, wide band gap materials, and charge generating materials.

The purified functional material, preferably granular material, preferably serves to produce electronic devices.

Electronic device is understood to mean a device comprising an anode, a cathode and at least one intervening functional layer, said functional layer comprising at least one organic or organometallic compound.

It is noted that variations of the embodiments described herein are encompassed within the scope of the present invention. Any feature disclosed herein, unless explicitly excluded, may be exchanged for an alternative feature that serves the same purpose or an equivalent or similar purpose. Accordingly, any feature disclosed herein, unless otherwise noted, should be considered as an example of a general series or as an equivalent or similar feature.

All features of the invention may be combined with one another in any way, unless certain features and/or steps are mutually exclusive. This corresponds to a particularly desirable feature of the invention. Equally, features in non-mandatory combinations may be used separately (without combination).

It is also noted that many of the features of the invention, and particularly those of the preferred embodiments, should be considered the invention in its own right and not simply as part of the embodiments of the invention. For these features, independent protection may be sought in addition to or as an alternative to any currently claimed invention.

The technical teachings disclosed by the present invention can be extracted and combined with other examples.

A person skilled in the art will be able to produce additional electronic devices of the invention using the details given and thereby practice the invention within its entire claimed scope without resorting to inventive skill.

The invention is hereinafter illustrated by schematic drawings. These drawings show:
Figure 1 A preferred embodiment of the device for continuous purification according to the invention;
Figure 2 A further embodiment of the device for continuous purification according to the invention.

Figure 1 shows a schematic diagram of an apparatus 10 for continuous purification of at least one functional substance according to the invention. The presented device 10 comprises a feed 12 for at least one functional substance, an evaporation device 14, a condensation device 16 and a discharge device 18.

The feed 12 for at least one functional substance in this context is configured as a feed extruder unit and preferably comprises an inertizable storage vessel 20 . The temperature of the feed 12, which is configured as a feed extruder unit, is controllable by a temperature control unit 22, where the latter is able to adjust the temperature of different regions of the feed 12 to different temperatures, so that a temperature gradient is created. possible. Additionally, the feed 12 is provided with a vent opening 24, through which residues of the solvent can be removed.

The evaporation device 14 in this context comprises an evaporation material distributor system 26 which distributes the functional material to be purified onto the surface of the evaporation unit 28 . In this context the evaporation device 14 is heatable with a fluid, wherein the fluid is heatable by means of a heating system 30 for the evaporation device 14 and provides a heating fluid feed 32 to the evaporation unit 28 . is supplied through, and is removed from there through the heating fluid outlet (34).

The evaporation device in this context comprises an opening connected via a residue outlet (36) to a residue collection vessel (38).

The evaporation device 14 in this context, in combination with the feed 12 and the discharge device 18 , forms an evaporation chamber 40 evacuable via a vacuum pump system 42 .

The functional material to be purified is evaporated or sublimated in the evaporation device 14 and condensed in the condensation device 16.

The condensation device 16 is equipped with a condensate collector 44 , where the condensed functional material is collectible in the discharge device 18 by means of the condensate collector 44 .

The condensed functional material is directed through the condensate collector 44 into the discharge device 18 . The discharge device 18 is configured as a discharge extruder unit, the temperature of which is controllable by the temperature control unit 46. In the output extruder unit, the condensed functional material is solidified and a reduced pressure, preferably a high vacuum, can be created in the evaporation chamber 40.

The discharge device 18 comprises a discharge opening, which in this context is connected to a discharge vessel 48 through which the purified functional material can be removed. In a preferred configuration, the discharge opening is connected to the granulation unit and the resulting granular material is introduced into the discharge vessel 48.

Figure 2 shows a further embodiment of the device for continuous purification according to the invention. This embodiment shows similarities with the device for purification of at least one functional substance described in detail in KR 2019/0125700. However, the device described in detail in KR 2019/0125700 does not have an exhaust device with an exhaust extruder unit, but rather has a conventional collection vessel, which must be removed for recovery of the purified material.

Figure 2 is a schematic diagram of an apparatus 110 for continuous purification of at least one functional substance according to the invention. The presented device 110 comprises a feed 112 for at least one functional material, an evaporation device 114, a condensation device 116, an evaporation chamber 120 and an exhaust device 118.

The embodiment described in detail in Figure 2 is not preferred compared to the embodiment described in Figure 1 because the functional material to be purified is subjected to higher thermal stresses and therefore lasts longer.

Essential compared to the prior art is the special configuration of the discharge device 118 comprising an discharge extruder unit. The further details of the outlet extruder unit essentially correspond to the embodiment presented in Figure 1, such that it has an outlet opening through which the purified functional material can be removed. In a preferred configuration, the discharge opening is connected to the granulation unit and the resulting granular material can be introduced into the discharge vessel.

Details of the further components of the embodiment described in detail in FIG. 2 , in particular the feed 112 , the evaporation device 114 , the condensation device 116 and the evaporation chamber 120 for at least one functional material can be found in KR 2019/ It can be found in the description of 0125700 (cf. KR 2019/0125700, Figure 5). These arrangements are presented in particular on pages 10 and 11, paragraphs 75 to 87, where FIG. 5 is described in detail, and in the publication KR 2019/0125700 in relation to the feed, the evaporation device and the condensation device. The description of the construction is incorporated into this application by reference thereto for disclosure purposes.

List of Reference Numbers

10 Device for continuous purification

12 Feed for at least one functional substance

14 evaporation device

16 condensation device

18 discharge device

20 storage vessel

22 temperature control unit

24 vent opening

26 Evaporative mass distributor system

28 evaporation unit

30 heating system

32 heated fluid feed

34 Heated fluid outlet

36 residue outlet

38 Residue collection vessel

40 evaporation chamber

42 vacuum pump system

44 condensate collector

46 temperature control unit

48 discharge vessel

110 Device for continuous purification

112 Feed for at least one functional substance

114 evaporation device

116 condensation device

118 discharge device

120 evaporation chamber

A more detailed description of preferred extruders can be found in the prior art, for example in particular in document EP 2 381 503 B1. They can be used in particular in feed and/or discharge devices for at least one functional substance, as shown above in FIG. 1 or FIG. 2 .

A detailed description of the measurement of glass transition temperature using compounds with transition temperatures that are difficult to measure follows.

Determination of the glass transition temperature (Tg) of bis-4,4'-(N,N'-carbazolyl)biphenyl (CBP; CAS No. 58328-31-7):

CBP has been used as a host material in phosphorescent OLEDs for a long time (see, e.g., MA Baldo et al. , Applied Physics Letters 1999 , 75(1) , 4-6).

Since the glass transition temperature of a material is difficult to measure, this example serves in particular to provide evidence for the feasibility of measuring the glass transition temperature. A particularly preferred configuration of measurements shows that the glass transition temperature of CBP is about 115°C.

The exact procedure for this measurement is described below:

One. repetitive production and purification of the above-mentioned substances; The preparation is carried out by a modified method according to BUCHWALD (cf., e.g., Buchwald et al., J. Am. Chem. Soc. 1998, 120(37), 9722-9723). The modified method is based on patent application WO03/037844.

2. The material is purified by repeated recrystallization from dioxane and finally by double “sublimation” (325° C.; 10-4 mbar; evaporation from the liquid phase; condensation in solid form).

3. The materials are individually analyzed for purity by HPLC (instrument: Agilent 1100; column: Agilent, Sorbax SB-C18, 75 x 4.6 mm, particle size 3.5 μm; eluent mixture: 90% MeOH:THF (90:10, vv) + 10% water, retention time: 6.95 min); This was in the region of 99.9% covering all regioisomers obtained in the reaction in each case.

4. The materials are tested for identity and freedom from solvent by 1H and 13C NMR spectroscopy.

5. Determine the glass transition temperature Tg using two batches, batch A and batch B. Glass transition temperature Tg was determined using a DSC instrument from Netsch, DSC 204/1/G Ph. Confirmed with nix. Samples of 10-15 mg in size were measured.

The glass transition temperature Tg is measured as described in Table 1 (Batch A). For confirmation, another reference measurement is performed using the second batch (Batch B).

Table 1: Measurement of Tg of CBP

Table 1: Measurement of Tg of CBP (continued)

The data presented in Table 1 show that glass transition temperatures can be obtained reliably even for compounds that are difficult to measure. Therefore, it can preferably be quenched after the first heating to obtain a clear glass transition temperature. Additionally, one factor that can present difficulties is recrystallization, which can occur in the temperature range between the glass transition temperature and the melting temperature. This can be reliably reduced by quenching and rapid secondary heating so that the glass transition temperature can be clearly and reliably measured.

Examples:

Device

The device consists of the following series-connected, continuously operating vacuum-sealed components:

Feed extruder unit:

A) Inerted melt vessel with heated feed valve or alternatively

B) Thermo Scientific™ HAAKE™ MiniLab II micro-compounder and its specific devices for feeding, degassing, calcination and extrusion

Evaporator unit:

UIC GmbH, laboratory system modified from model series KDl 5

High vacuum pump combination:

Edwards, TSB4E1001, turbopump station consisting of NEXT240D turbopump with ISO100 flange and nXDS10i as booster pump, TAV5 ventilation valve and WRGSDN25KF pressure sensor, active wide-area measuring tube

Outlet extruder unit:

Thermo Scientific™ HAAKE™ MiniLab II Micro-Compounder and its specific devices for release and extrusion

Table 2 lists functional materials FM and process conditions.

Measuring conditions:

Tg: Glass transition point from DSC, first heating, heating rate 20 K/min, cooling rate 20 K/min, measurement range 0-350°C. Tm: Melting point from DSC, see description of Tg for conditions.

Tsubl. vac. TGA: Evaporation/sublimation temperature is determined by vacuum TGA measurement as above.

Tsubl. Process: Process temperature during evaporation/sublimation

Tdecomp.: Decomposition temperature, from heat exposure tests under high vacuum in melt-sealed Duran glass ampoules in the dark at the specified temperature for 100 hours.

p-process: process pressure during evaporation/sublimation

analyze:

The functional material FM obtained by the above-described process by ¹ H NMR, HPLC and ICP-MS has the same purity profile as the material produced in a batch sublimation plant according to the prior art.

Use of functional materials FM1 to FM4 in OLED components

The functional materials FM1 to FM4 obtained by the above-described process are incorporated, for example, as mixed host materials in the emitting layer of phosphorescent OLED components.

OLEDs are produced by the general method according to WO 2004/058911, adapted to the circumstances described herein (layer thickness, changes in materials used). The materials used are listed in Table 3.

OLED has the following layer structure:

Board

Hole injection layer 1 (HIL1), consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

Hole transport layer 1 (HTL1), composed of HTM1, 40 nm

Hole transport layer 2 (HTL2), HTM2 20 nm

Emitting layer (EML), mixed host FM1:FM3 (40:60) (numbers in parentheses are volume % of functional material in mixture), doped with 15% dopant D

Electron transport layer (ETL2), composed of ETL1, 5 nm

Electron transport layer (ETL1), composed of ETL1 (50%):ETL2 (50%), 30 nm

Electron injection layer (EIL), composed of ETM2, 1 nm

Cathode, made of aluminum, 100 nm

Table 3 summarizes the test results:

Table 4 shows the structural formulas of the materials used.

Claims (15)

A method for purifying at least one functional material usable for the production of a functional layer of an electronic device involved in charge injection or charge transport and/or light emission or light outcoupling, wherein the device (10, 110) is used, the method comprising: evaporating or sublimating and/or condensing at least one functional material, wherein the device (10, 110) comprises:
A) at least one feed (12, 112) for at least one functional material, wherein the at least one functional material can be fed continuously through an inlet opening provided in the feed;
B) at least one evaporation device (14, 114) arranged downstream of the feed (12, 112), wherein the functional material can be introduced into the evaporation device (14, 114) by means of the feed (12, 112), The functional material can be continuously evaporated by the evaporation device 14, 114;
C) at least one condensation device (16, 116), wherein the functional material is continuously condensable by the condensation device (16, 116) after evaporation in the evaporation device (14, 114);
D) at least one exhaust device (18, 118) arranged downstream of the condensation device (16, 116), wherein the functional material is continuously introduced from the condensation device (16, 116) into the exhaust device (18, 118). possible and can be discharged through the discharge openings present in the discharge devices 18, 118;
and here
The apparatus (10, 110) has an evaporation chamber (40, 120), in which at least a part of the evaporation device (14, 114) and at least a part of the condensation device (16, 116) are provided, The evaporation chamber (40, 120) is connected or connectable to at least one exhaust device, and when operating the device (10, 110) for continuous purification, a reduced pressure, preferably a high vacuum, is created in the evaporation chamber (40, 120). Possibly, the method characterized in that the discharge device (18, 118) comprises or constitutes an discharge extruder unit. The method of claim 1, wherein the at least one functional material is a fluorescent emitter, a phosphorescent emitter, an emitter exhibiting TADF (thermal activated delayed fluorescence), an emitter exhibiting hyperfluorescence or hyperphosphorescence, a host material, an exciton blocker material, an electron selected from the group consisting of an injection material, an electron transport material, an electron blocker material, a hole injection material, a hole conductor material, a hole blocker material, an n-dopant, a p-dopant, a wide bandgap material, a charge generating material, or a combination thereof. A method characterized by: An apparatus (10, 110) for the continuous purification of at least one functional substance, comprising:
E) at least one feed (12, 112) for at least one functional material, wherein the at least one functional material can be fed continuously through an inlet opening provided in the feed;
F) at least one evaporation device (14, 114) arranged downstream of the feed (12, 112), wherein the functional material can be introduced into the evaporation device (14, 114) by means of the feed (12, 112), The functional material can be continuously evaporated by the evaporation device 14, 114;
G) at least one condensation device (16, 116), wherein the functional material is continuously condensable by the condensation device (16, 116) after evaporation in the evaporation device (14, 114);
H) At least one discharge device (18, 118) arranged downstream of the condensation device (16, 116), wherein the functional material is continuously introduced from the condensation device (16, 116) into the discharge device (18, 118). possible and can be discharged through the discharge openings present in the discharge devices 18, 118;
From here
The apparatus (10, 110) has an evaporation chamber (40, 120), in which at least a part of the evaporation device (14, 114) and at least a part of the condensation device (16, 116) are provided, The evaporation chamber (40, 120) is connected or connectable to at least one exhaust device, and when operating the device (10, 110) for continuous purification, a reduced pressure, preferably a high vacuum, is created in the evaporation chamber (40, 120). Possibly, the exhaust device (18, 118) comprises or constitutes an exhaust extruder unit, and the evaporation device (14, 114) at least partially encloses the condensation device (16, 116). 4. Apparatus according to claim 3, characterized in that the feed (12, 112) comprises grooved rolls and/or extruder screws. 5. The method according to claim 3 or 4, wherein the feed (12, 112) comprises or constitutes a feed extruder unit and the discharge device (18, 118) comprises or constitutes an discharge extruder unit, wherein the extruder of the feed extruder unit A device characterized in that the screw is connected to the extruder screw of the discharge extruder unit such that the extruder screw of the feed extruder unit and the extruder screw of the discharge extruder unit are rotatable by the drive unit. 5. The method according to claim 3 or 4, wherein the feed comprises or constitutes a feed extruder unit and the discharge device (18, 118) comprises or constitutes an discharge extruder unit, wherein the extruder screw of the feed extruder unit drives the drive unit. A device rotatable through the second drive unit, wherein the extruder screw of the output extruder unit is rotatable through the second drive unit. 7. The method according to any one of claims 1 to 6, wherein the evaporation device (14, 114) has an evaporation surface, by means of which functional material can be evaporated, and the condensation device (16, 116) has a condensation surface. A device wherein the functional material can be condensed by the condensation surface, wherein the evaporation surface is arranged parallel to the condensation surface. 8. Apparatus according to any one of claims 1 to 7, characterized in that the condensation device (16, 116) is rotatable relative to the evaporation device (14, 114). 9. The method according to any one of claims 1 to 8, wherein the condensation device (16, 116) has a condensing cylinder connected to the extruder screw of the feed extruder unit and the extruder screw of the discharge extruder unit, so that the extruder screw of the feed extruder unit, the condensing cylinder and wherein the extruder screw of the discharge extruder unit is rotatable by the drive unit. 10 . The method according to claim 1 , wherein the evaporation device (14, 114) and/or the evaporation chamber (40, 120) comprises at least one opening through which a residue collection vessel (38) is formed. ) A device characterized in that it is connectable or connected. 11. The method according to any one of claims 1 to 10, wherein a temperature gradient can be created between the evaporation device and the condensation device (16, 116), wherein the temperature of the evaporation device (14, 114) is reduced to that of the condensation device (16, 116). A device characterized in that it is selectable at a level higher than the temperature of. 12. Apparatus according to any one of claims 1 to 11, characterized in that the evaporation device (14, 114) has an evaporation mass distributor system (28). 13. The method according to any one of claims 1 to 12, wherein the condensation device (16, 116) has a condensate collector (44), by which the condensed functional material is discharged from the discharge device (18, 118). ) A device characterized in that it is collectable in . 14. The device according to any one of claims 1 to 13, wherein the device is operable in vertical alignment, wherein the feed (12, 112) is arranged above the evaporation device (14, 114) and the evaporation device (14, 114) discharges A device characterized in that it is disposed on the device (18, 118). 15. The method according to any one of claims 1 to 14, wherein the device (10, 110) is operable in vertical alignment and the functional material is introduced from the condensation device (16, 116) into the discharge device (18, 118) under gravity. A device characterized in that it is possible.