CN114106295B - Crosslinkable polymer, preparation method and application thereof - Google Patents
Crosslinkable polymer, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a crosslinkable polymer, a preparation method thereof and an electron transport material. The crosslinkable polymer has a structure shown in a general formula (I). The polymer formed after crosslinking is not easy to be dissolved by a conventional solvent, so that the crosslinked functional layer is not easy to be mutually dissolved or mixed with the next functional layer, and the influence on the performance of a device is avoided. Furthermore, the crosslinkable polymer has good thermal stability at room temperature, excellent electron transport property and excellent heat resistanceHigher triplet energy levels, in addition, can achieve crosslinking at high temperatures without producing any byproducts, has great potential in dissolvable OLED devices.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a crosslinkable polymer, a preparation method thereof and an electron transport material.
Background
The solution processing method for preparing the OLED device is a low-cost processing method, can be used for preparing the OLED device in a large area, and can be used for obtaining a large-size OLED display panel, so that the method is interesting for a plurality of manufacturers. The OLED device is formed by stacking a carrier injection layer, a carrier transport layer, and a light emitting layer. On the one hand, if the conventional solution processing method is used, the mixing between the functional layers is likely to be caused, so that the performance of the device is reduced, and how to implement solution processing of multiple functional layers without affecting the performance of the device is a problem to be solved. On the other hand, most of the electron transport layer materials on the market at present are based on vacuum vapor deposition type materials, and there are few electron transport layer materials suitable for solution processing. Thus, there remains a great challenge to develop fully solubilized processed OLED devices.
The design of the solubilized electron transport layer material is divided into two ideas: the small molecular electron transport layer material is a small molecular electron transport layer material, and the structure is subjected to modification design again so that the small molecular electron transport layer material can be subjected to dissolution processing, however, the small molecular electron transport layer material is easily dissolved by a solvent of a next functional layer in the solution processing process, and because the common organic small molecular material has good solubility in a common organic solvent, the solvent used in a later layer is difficult to ensure that the solvent does not dissolve a deposited material of a previous layer, so that the solvent can be selected in a narrow range. The other type is a polymer type electron transport layer material, and the design thought is different from that of a small molecular electron transport layer material, so that the synthesis difficulty is high, and few reports based on the polymer type electron transport layer material are provided at present.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a crosslinkable polymer which can be dissolved in a solvent before crosslinking, but the polymer formed after crosslinking is not easily dissolved by a conventional solvent, so that the crosslinked functional layer is not easily mutually dissolved or mixed with the next functional layer, thereby avoiding affecting the performance of a device. Moreover, the crosslinkable polymer has good thermal stability at room temperature, excellent electron transport property and higher triplet state energy level, and can realize crosslinking at high temperature without generating any byproducts, thus having great potential in a dissolvable OLED device.
The crosslinkable polymer has a structure as represented by the general formula (1):
R 1 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
m and n each represent the number of structural units, m: n=1:99-99:1.
The invention also provides a preparation method of the crosslinkable polymer.
The preparation method of the crosslinkable polymer comprises the following steps:
polymerizing a compound having a structure of formula a, a compound having a structure of formula B, and a compound having a structure of formula C;
wherein:
R 1 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 selected from single bonds, takeAn aryl group having 5 to 20 ring atoms substituted or unsubstituted;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
X 0 represents halogen.
The present invention further relates to an electron transport material comprising the crosslinkable polymer as described above, or comprising the crosslinkable polymer prepared by the above-described preparation method.
The invention further relates to a light emitting diode comprising an electron transport layer, the material of which comprises the crosslinkable polymer as described above, or comprises the crosslinkable polymer prepared by the preparation method as described above, or comprises the electron transport material as described above.
The beneficial effects are that:
the crosslinkable polymer provided by the invention consists of a main chain structural unit, an electron transmission structural unit and a crosslinkable structural unit. The main chain structural unit is selected from phenyl structural units with side chains, wherein the phenyl structural units have stability and solubility, the electron transmission structural unit is selected from sulfonyl structural units, and the structural units have good electron transmission performance and good heat resistance stability; the crosslinkable structural unit is a derivative based on a benzocyclobutene structure, the structure has good stability at room temperature, but can be subjected to ring opening crosslinking at high temperature, the crosslinkable polymer can be dissolved in a solvent before crosslinking, and the polymer formed after crosslinking is not easy to be dissolved by a conventional solvent, so that the polymer has good solvent resistance. And the polymer constructed based on the three structural units has good thermal stability at room temperature, simultaneously keeps the excellent electron withdrawing capability of the sulfonyl structural units, has good electron transmission performance, has higher triplet state energy level, and can effectively block quenching of excitons. In addition, the compounds have great potential in soluble OLED devices due to the ability to achieve crosslinking at high temperatures without the generation of any by-products.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting diode device.
Detailed Description
The invention provides a crosslinkable polymer, a preparation method thereof and an electron transport material. The present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the present invention, "substituted" means that a hydrogen atom in a substituted group is substituted by a substituent.
In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. Containing a plurality of R as shown in the general formula 1 R is then 1 May be independently selected from different groups.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with groups acceptable in the art, including but not limited to: c (C) 1-30 Alkyl, heterocyclyl having 3 to 20 ring atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, -NRR', cyano, isocyano, thiocyanate, isothiocyanate, hydroxy, trifluoromethyl, nitro or halogen, and which may be further substituted with substituents acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with a group acceptable in the art, including but not limited to H, C 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms or heteroaryl having 5 to 10 ring atoms; the C is 1-6 Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, aryl having 5 to 20 ring atoms, or heteroaryl having 5 to 10 ring atoms is optionally further substituted with one or more of the following groups:C 1-6 alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, e.g., "C 1-9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-hexyldodecyl, 2-dodecyldodecylA group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 2-ethyleicosyl group, 2-butyleicosyl group, 2-hexyleicosyl group, 2-octyleicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, adamantane and the like.
An aryl group refers to a hydrocarbon group containing at least one aromatic ring. Heteroaryl refers to an aromatic hydrocarbon group containing at least one heteroatom. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. Fused ring aromatic group means that the ring of the aromatic group may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. Fused heterocyclic aromatic groups refer to fused ring aromatic hydrocarbon groups containing at least one heteroatom. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic ring systems but also non-aromatic ring systems. Thus, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, and the like are also considered aromatic or heterocyclic aromatic groups for the purposes of this invention. For the purposes of the present invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heterocyclic aromatic groups may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, and the like are also considered fused ring aromatic ring systems for the purposes of this invention.
In a preferred embodiment, the aromatic group is selected from the group consisting of: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaryl group is selected from the group consisting of triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primary pyridines, quinazolines, quinazolinones, and derivatives thereof.
"amine group" refers to a derivative of ammonia having the formula-N (X) 2 Wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amine groups include-NH 2 -N (alkyl) 2 -NH (alkyl), -N (cycloalkyl) 2 -NH (cycloalkyl), -N (heterocyclyl) 2 -NH (heterocyclyl), -N (aryl) 2 -NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
In the present invention "×" associated with a single bond represents a linking or fusing site;
in the present invention, when no linking site is specified in the group, an optionally-ligatable site in the group is represented as a linking site;
in the present invention, when no condensed site is specified in the group, it means that an optionally condensed site in the group is used as a condensed site, and preferably two or more sites in the group at ortho positions are condensed sites;
a crosslinkable polymer having a structure according to formula (I):
wherein:
R 1 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branchedAlkyl or C3-C25 cycloalkyl;
L 1 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
m and n each represent the number of structural units, m: n=1:99-99:1.
It will be appreciated that the ratio of m/n will be different, the molecular structure will be different and the properties will be different. The number of defined building blocks can be calibrated by measuring their molecular weight.
In a preferred embodiment, the crosslinkable polymer has a structure as shown in formula (II):
preferably L 1 Selected from single bonds, and from substituted or unsubstituted aryl groups having 5 to 10 ring atoms. More preferably L 1 Selected from single bond or phenyl.
Preferably L 2 Selected from single bonds, and from substituted or unsubstituted aryl groups having 5 to 10 ring atoms. More preferably L 2 Selected from single bond or phenyl.
In a preferred embodiment, the crosslinkable polymer has a structure as shown in formula (II-1) or formula (II-2):
in some preferred embodiments, R 1 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl.
Further preferably, R 2 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
The structure of the crosslinkable polymer of the present invention includes, but is not limited to:
wherein, -C 6 H 13 and-C 8 H 17 All represent straight chain alkyl groups.
m is 6, n is 1, and it does not indicate that the number of structural units is 6 and 1, but indicates that the number of structural units is 6 parts and 1 part. Similarly, m is 11 and n is 2, and it does not indicate that the number of structural units is 11 and 2, but indicates that the number of structural units is 11 parts and 2 parts.
The preparation method of the crosslinkable polymer comprises the following steps:
polymerizing a compound having a structure of formula a, a compound having a structure of formula B, and a compound having a structure of formula C;
wherein:
R 1 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
L 2 an aromatic group selected from a single bond, a substituted or unsubstituted ring atom number of 5 to 20;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
X 0 representing halogenAnd (5) plain.
Preferably, the compound having the structure of formula A has a structure as shown in general formula (A-1):
preferably, the compound having the structure of formula B has a structure as shown in the general formula (B-1):
preferably L 1 Selected from single bonds, and from substituted or unsubstituted aryl groups having 5 to 10 ring atoms. More preferably L 1 Selected from single bond or phenyl.
Preferably L 2 Selected from single bonds, and from substituted or unsubstituted aryl groups having 5 to 10 ring atoms. More preferably L 2 Selected from single bond or phenyl.
In a preferred embodiment, the compound having the structure of formula C has a structure as shown in formula (C-1) or (C-2):
in some preferred embodiments, R 1 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
In some preferred embodiments, R 2 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
An electron transport material comprising the crosslinkable polymer described above, or comprising a crosslinkable polymer produced by the production method described above.
In one embodiment, the electron transport layer is prepared by printing or coating. In one embodiment, the light emitting diode of the present invention is selected from solution type light emitting diodes, and the functional layers thereof are all prepared by printing or coating.
In the light emitting device, especially the OLED, the light emitting device comprises a substrate, an anode, at least one light emitting layer and a cathode.
The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or a light emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
The cathode may comprise a conductive metal or metal oxide. The cathode can be easilyElectrons are injected into the EIL or ETL or directly into the light emitting layer (EML). In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the emitter in the light emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF 2 /Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may further include other functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL).
The invention also relates to the use of the light emitting diode according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The invention also relates to an electronic device comprising a light emitting diode according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor, etc.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In the following examples, the substituents are not explicitly indicated and all represent straight-chain structures, i.e. -C 6 H 13 and-C 8 H 17 All represent straight chain alkyl groups.
In the following examples, toluene was used as a solvent; palladium acetate is the catalyst; tris (2-methoxyphenyl) phosphine is a catalyst ligand; tetraethylammonium hydroxide is a base and plays a role in promoting the reaction; phenylboronic acid is the last molecule to be used as a polymer end cap, the end cap concept being the reaction of unreacted bromo groups in the polymer with phenylboronic acid, thereby leaving no bromine in the polymer chain. Because the presence of bromine atoms quenches luminescence to some extent.
1. Synthesis of Compounds
Example 1 Compound P1 and method for preparing the same
Into a 100mL two-necked flask, 4.2mmol of the borate derivative having a side chain phenyl group was sequentially added
3.6mmol of sulphonyl derivatives->
0.6mmol benzocyclobutene derivatives
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P1 polymer was obtained. GPC was used to determine its molecular weight, mn=54000, mw=120000.
The synthetic route for this example is as follows:
example 2 Compound P2 and method for preparing the same
Into a 100mL two-necked flask, 4.2mmol of the borate derivative having a side chain phenyl group was sequentially added
3.56mmol of sulphonyl derivatives->
0.64mmol benzocyclobutene derivatives +.>
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P2 polymer was obtained. GPC was used to determine its molecular weight, mn=62000, mw=130000.
The synthetic route for this example is as follows:
example 3 Compound P3 and method for preparing the same
Into a 100mL two-necked flask, 4.2mmol of the borate derivative having a side chain phenyl group was sequentially added
3.6mmol of sulphonyl derivatives->
0.6mmol benzocyclobutene derivatives
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then the vacuum pumping and nitrogen changing operation are carried out, the operation is repeated for 3 times, then 20wt percent tetraethylammonium hydroxide solution is added by a syringe, then 60mL toluene solvent is added, and the temperature is 110 ℃ under the nitrogen atmosphereRefluxing for 6 hours; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P3 polymer was obtained. GPC was used to determine the molecular weight, mn=60000, mw=133000.
The synthetic route for this example is as follows:
example 4 Compound P4 and method for preparing same
Into a 100mL two-necked flask, 4.2mmol of the borate derivative having a side chain phenyl group was sequentially added
3.56mmol of sulphonyl derivatives->
0.64mmol benzocyclobutene derivatives +.>
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P4 polymer was obtained. GPC was used to determine the molecular weight, mn=65000, mw= 136000.
The synthetic route for this example is as follows:
example 5 Compound P5 and method for preparing same
Into a 100mL two-necked flask, 4.2mmol of the borate derivative having a side chain phenyl group was sequentially added
3.56mmol of sulphonyl derivatives->
0.64mmol benzocyclobutene derivatives +.>
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P5 polymer was obtained. GPC was used to determine the molecular weight, mn=58000, mw= 174000.
The synthetic route for this example is as follows:
example 6 Compound P6 and method for preparing same
Into a 100mL two-necked flask, 4.2mmol of the borate derivative having a side chain phenyl group was sequentially added
3.56mmol of sulphonyl derivatives->
0.64mmol benzocyclobutene derivatives +.>
26.5. Mu. Mol of tris (2-methoxyphenyl) phosphine, 5. Mu. Mol of palladium acetate Pd (OAc) 2 Then carrying out vacuumizing and nitrogen exchange operation, repeating for 3 times, adding 20wt% tetraethylammonium hydroxide solution by a syringe, adding 60mL of toluene solvent, and refluxing at 110 ℃ for 6 hours under nitrogen atmosphere; then, 4mmol of phenylboronic acid was added to the mixture, and the reaction was continued for 12 hours. Adding the sodium diethyl dithiocarbamate solution into the mixed solution after the reaction is completed, and stirring for 2 hours at 85 ℃; then washing the oil phase for multiple times, and separating and purifying by using a chromatographic column; precipitating in methanol after purification, filtering, and oven drying. The P6 polymer was obtained. GPC was used to determine the molecular weight, mn=68000, mw= 153000.
The synthetic route for this example is as follows:
2. organic light-emitting diode component and preparation thereof
The structure of the organic light emitting diode component is as follows: a first electrode, an electron injection layer formed on the first electrode, an electron transport layer formed on the electron injection layer, a light emitting layer formed on the electron transport layer, a hole transport layer formed on the light emitting layer, a hole injection layer formed on the hole transport layer, a second electrode on the hole injection layer, and the electron transport layer comprises the crosslinkable polymer described above, as shown in fig. 1.
Examples: ITO/ZnO (35 nm)/P1 (20 nm)/mCP Ir (ppy) 2 acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Al(120nm)。
Wherein ZnO is used as an electron injection layer and can be crosslinkedPolymer P1 as electron transport layer, mCP as host material, ir (ppy) 2 acac as a guest material, TAPC as a hole transport layer material and an electron blocking layer material, NPB as a hole transport layer material, HAT-CN as a hole injection layer material, and Ag as an anode.
The preparation method comprises the following steps:
firstly, cleaning an ITO substrate according to the following sequence: ultrasonic treatment with 5% KOH solution for 15min, ultrasonic treatment with pure water for 15min, ultrasonic treatment with isopropanol for 15min, and oven drying for 1h; the substrate was then transferred to a UV-OZONE apparatus for surface treatment for 15min, and immediately transferred to a glove box after the treatment. A layer of ZnO nanoparticles was spin coated on a clean ITO substrate and then baked at 120 ℃ for 15min. Dissolving crosslinkable polymer with solvent (such as o-xylene) as electron transport layer material, spin coating the electron transport layer material on ZnO nano layer, baking at 120deg.C for 10min to remove residual solvent, and ring-opening crosslinking at 200deg.C for 30-60 min; spin-coating luminous layer ink; the upper hole transport layer, the hole injection layer, and the cathode are vapor deposited by vacuum vapor deposition. Finally, the device is prepared by UV curing packaging and heating and baking for 20 min. And is denoted as "T1 device".
With reference to the above method, P2-P6 are used to replace P1 respectively, and an organic light emitting diode component is prepared as an electron transport layer material and is respectively denoted as a "T2 component", "T3 component", … … and a "T6 component".
Contrast device and method of making the same
The structure of the contrast device is as follows: ITO/ZnO (35 nm)/TPBi (20 nm)/mCP: ir (ppy) 2 acac,7w％(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm)/Al(120nm)。
Firstly, cleaning an ITO substrate according to the following sequence: ultrasonic treatment with 5% KOH solution for 15min, ultrasonic treatment with pure water for 15min, ultrasonic treatment with isopropanol for 15min, and oven drying for 1h; the substrate was then transferred to a UV-OZONE apparatus for surface treatment for 15min, and immediately transferred to a glove box after the treatment. A layer of ZnO nanoparticles was spin coated on a clean ITO substrate and then baked at 120 ℃ for 15min. Evaporating an upper electron transport layer material TPBi in a vacuum evaporation mode, wherein the thickness is 20nm, and the evaporation rate is 0.1nm/s; after spin-coating the luminescent layer ink, evaporating a hole transport layer, a hole injection layer and a cathode by vacuum evaporation. Finally, the device is obtained by UV curing encapsulation and heating and baking for 20min, and is marked as a 'contrast device'.
The related material structure is as follows:
performance test:
the prepared devices were measured for light emitting performance by an IV-L test system, the model of the machine used was an F-star CS2000A instrument, and the device performance was as shown in table 1:
TABLE 1
It can be seen that the electron transport layer can be prepared by a solution method using the crosslinkable polymer of the present invention as an electron transport layer material, and that the crosslinked polymer is insoluble in a solvent of the light emitting layer when the light emitting layer is continuously prepared on the electron transport layer by a solution method. The performance of the T1 device is equivalent to that of a device with an electron transport layer formed by a traditional vapor deposition method, and the T2 device can even exceed that of the traditional device. Meanwhile, the crosslinkable polymer disclosed by the invention has high electron transmission capability, can effectively promote electron transmission, has good thermal stability, is suitable for constructing a thermal crosslinking electron transmission layer material, and is suitable for obtaining a large-area and low-cost OLED device through solution film formation.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (11)
1. A crosslinkable polymer characterized in that: has a structure shown in a general formula (I):
wherein:
R 1 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group having 6 to 20 ring atoms selected from a single bond, substituted or unsubstituted;
L 2 an aromatic group having 6 to 20 ring atoms selected from a single bond, substituted or unsubstituted;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
m and n each represent the number of structural units, m: n=1:99-99:1.
2. The crosslinkable polymer according to claim 1, characterized in that: the crosslinkable polymer has a structure according to formula (II):
3. the crosslinkable polymer according to claim 2, characterized in that: l (L) 1 Selected from single bonds, and from substituted or unsubstituted aryl groups having 6 to 10 ring atoms.
4. A crosslinkable polymer according to claim 3, characterized in that: l (L) 2 Selected from single bonds, and from substituted or unsubstituted aryl groups having 6 to 10 ring atoms.
5. The crosslinkable polymer according to claim 4, characterized in that: the crosslinkable polymer has a structure represented by the general formula (II-1) or the general formula (II-2):
6. the crosslinkable polymer according to any one of claims 1-5, characterized in that: r is R 1 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, C5-C15 cycloalkyl.
7. The crosslinkable polymer according to any one of claims 1-5, characterized in that: r is R 2 Independently selected from the group consisting of C5-C15 straight chain alkyl, C5-C15 branched alkyl, and C5-C15 cycloalkyl.
8. A method for preparing a crosslinkable polymer, characterized by: the method comprises the following steps:
polymerizing a compound having a structure of formula a, a compound having a structure of formula B, and a compound having a structure of formula C;
R 1 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
R 2 independently selected from the group consisting of C1-C25 straight chain alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl;
L 1 an aromatic group having 6 to 20 ring atoms selected from a single bond, substituted or unsubstituted;
L 2 an aromatic group having 6 to 20 ring atoms selected from a single bond, substituted or unsubstituted;
a represents an integer of 1 to 4;
b represents an integer of 1 to 3;
X 0 represents halogen.
9. The method for producing a crosslinkable polymer according to claim 8, wherein: the compound having the structure of formula C has a structure represented by the general formula (C-1) or (C-2):
10. an electron transport material characterized by: comprising the crosslinkable polymer according to any one of claims 1 to 7, or comprising the crosslinkable polymer produced by the production method according to claim 8 or 9.
11. A light-emitting diode, characterized in that a material comprising an electron transport layer comprises the crosslinkable polymer according to any one of claims 1 to 7, or comprises the crosslinkable polymer produced by the production method according to claim 8 or 9, or comprises the electron transport material according to claim 10.
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