CN100489008C - Poly(2,6)- and poly(2,7)- anthryl ethene derivatives as electroluminescent materials and method for preparing same - Google Patents

Abstract

A poly(2,6)- and poly(2,7)-anthracene vinyl derivative as an electroluminescence material and a preparation method thereof. It is a conjugated polymer composed of 2,6- and 2,7-anthracene vinyl structural units. Ar ¹ , Ar ² and Ar in the structural formula are aryl or substituted aryl groups with 6 to 46 carbon atoms, or are heteroaryl or substituted heteroaryl groups with 4 to 36 carbon atoms; or Ar ¹ and Ar ² are hydrogen atom, cyano group, halogen atom, alkoxy group with 1 to 20 carbon atoms, dialkylamino, Alkylsilyl or alkylmercapto; R' and R" are each a hydrogen atom and a cyano group, or one is a hydrogen atom and the other is a cyano group. The method is Gilch polymerization, Heck coupling or Wittg reaction under base catalysis. It has good The solubility, efficiency and thermal stability, the luminous color can be adjusted by introducing Ar ¹ , Ar ² , especially Ar groups. Other electro-optic properties can also be adjusted by Ar groups, including Ar ¹ , Ar ² changes. It can be widely used in electroluminescent devices.

Description

Poly(2,6)- and poly(2,7)-anthracene vinyl derivatives as electroluminescent materials and their preparation methods

technical field

The invention belongs to the technical field of electroluminescent materials, and more specifically relates to poly(2,6-) and poly2,7-anthracene vinyl derivatives as electroluminescent materials and a preparation method thereof.

Background technique

Since 1990 J.H.Burroughes et al. (J.H.Burroughes, D.D.C.Bradley, A.R.Brown, R.N.Marks, K.Mackay, R.H.Friend, P.L.Burns, A.B.Holmes "Light-emitting diodes based on conjugated polymers", Nature 347, 539) published PPV can be As polymer electroluminescent materials, the research and development of polymer electroluminescent materials and their devices has become a hot spot. A light-emitting diode (LED) is a typical representative of an electroluminescent device, which emits visible light under an applied electric field. Currently, organic polymers and small organic molecules have been used to fabricate light-emitting diodes, and light-emitting diodes made of organic materials have several advantages over other technologies, such as simpler manufacturing processes, low operating voltages, and fabrication of large-area, full-color Display possibility. Organic polymers also offer important processing advantages over small organic molecules, especially for large-area or flexible electroluminescent displays, where high-quality polymer films are readily prepared via solution-casting methods.

Conjugated polymers are a class of polymers that are conjugated with extended π bonds along the polymer backbone. Under the action of light or electric field, their π electrons can be delocalized or excited, and the energy released by the recombination of the generated electrons and holes can be converted into the form of light. To improve polymer solubility, dialkoxy-substituted PPVs such as MEH-PPV, poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylethylene] have been Developed (F.Wudl et al., US Patent No.5 189 136 (1993)). To improve device performance, electroluminescent efficiency has been enhanced through device structure, cathode material selection, and material chemical and physical modification. Other conjugated polymers that have been studied mainly include polydialkylfluorene (Y.Ohmori et al., Jpn.J.Appl.Phys.Part 2, 1991, 20, L1941), polythiophene (Y.Ohmori et al. ., SolidState Commun.1991, 80, 605), polyparaphenylene (PPP) (G.Grem et al., Adv.Mater.1992, 4, 36), etc.

An electroluminescent device is mainly composed of a cathode, an anode and a light-emitting layer. Electroluminescence is caused by electron-hole pair recombination in the light-emitting material layer by cathode-injected electrons and anode-injected holes. Efficient light output depends both on efficient and highly fluorescent materials and on the preparation of high-molecular-weight polymers with good solubility to obtain high-quality polymer films. Anthracene is a fused-ring aromatic hydrocarbon molecule with high fluorescence and high thermal stability. Zheng Shiying et al. used 9,10-diaryl anthracene organic small molecule derivatives as light-emitting materials to prepare electroluminescent devices with high light output and high operational stability (US Patent US -5,935,721 and US-5,972,247), in the Chinese patent CN 1407054A disclosed in 2003, Zheng Shiying etc. carried out Suzuki coupling reaction under palladium catalysis by aromatic diboronic acid ester and aromatic dibromide, prepared anthracene polymer (Polyanthracene) as an electroluminescent device as a light-emitting material. As an analogy, these anthracene-based polymers are equivalent to polyphenylene (PPP) in phenyl polymers, while the anthracene-based polymers in the present invention are equivalent to PPV and MEH-PPV in phenyl polymers, these anthracenyl polymers The polymer (polyanthracene vinyl) is prepared by Gilch polymerization or Heck coupling or Wittg reaction, preferably the Gilch polymerization method is used to prepare high molecular weight anthracene-based polymers.

Contents of the invention

The object of the present invention is to provide a poly(2,6-) and poly(2,7)-anthracene vinyl derivative as an electroluminescent material and a preparation method thereof. It not only provides new anthracene-based light-emitting polymer materials for polymer electroluminescent devices, but also provides light-emitting polymers with different energy band gaps. These poly 2,6- or 2,7-anthracene-based homopolymers or Copolymers containing these anthracene vinyl units can emit a wide range of colors.

The electroluminescent material provided by the invention has many advantages including good solubility, efficiency and thermal stability. The emission color of the polymers can be easily tuned by introducing desired Ar ¹ , Ar ² , especially Ar groups. Moreover, other electro-optic properties can also be adjusted by changing the Ar group, including Ar ¹ and Ar ² groups. The material of the invention can be used to make electroluminescent devices, and can also be used as the host material of other photoelectric materials.

In order to achieve the above object, poly(2,6-) and poly 2,7-anthracene vinyl derivatives of the present invention are conjugated polymers containing 2,6 and 2,7-anthracene vinyl structural units as electroluminescent materials , has the following structural formula I:

Structural formula I

wherein Ar ¹ , Ar ² and Ar are each aryl or substituted aryl of 6 to 46 carbon atoms; or Ar ¹ , Ar ² and Ar are heteroaryl or substituted heteroaryl of 4 to 36 carbon atoms respectively or Ar ¹ and Ar ² are each a hydrogen atom, a cyano group, a halogen atom, an alkoxy group of 1 to 20 carbon atoms, a dialkylamino group, an alkylsilyl group or an alkylmercapto group; each of R' and R" is A hydrogen atom and a cyano group, or one hydrogen atom and the other a cyano group.

The introduction of Ar groups, including Ar ¹ and Ar ² groups, has the following characteristics: further improving the solubility of polymers; obtaining balanced electron-hole injection and recombination of charge carriers; improving electron or hole transport capabilities; Improves the glow color of polymers.

In the structural formula I, Ar ¹ and Ar ² each represent one of the following structural formulas or a combination thereof:

Wherein: substituents R ¹ , R ² , R ³ , R ⁴ can be hydrogen, cyano, halogen; or alkoxy, dialkylamino, alkylmercapto or alkylsilyl with 1 to 20 carbon atoms; or R ^1. R ² and R ³ are aryl or substituted aryl with 6-36 carbon atoms, or heteroaryl or substituted heteroaryl with 4 to 36 carbon atoms.

In structural formula I, Ar represents one of the following structural formulas or their combination:

Wherein: substituents R ¹ , R ² , R ³ , R ⁴ can be hydrogen, cyano, halogen; or alkoxy, dialkylamino, alkylmercapto or alkylsilyl with 1 to 20 carbon atoms; or R ^1. R ² and R ³ are aryl or substituted aryl with 6-36 carbon atoms, or heteroaryl or substituted heteroaryl with 4 to 36 carbon atoms.

Poly(2,6-) and poly-2,7-anthracene vinyl derivatives can be prepared as electroluminescent materials by methods such as Gilch polymerization under base catalysis, Heck coupling or Wittg reaction. The synthetic technical route is:

In the formula, 35 grams of 1,4-p-benzoquinone, 80 milliliters of isoprene and 350 milliliters of ethanol were added to a 1000 milliliter single-necked flask for compound C1, heated and stirred under reflux for 30-40 hours, cooled in ice water, and filtered to obtain a white Solid crystal C1, yield 68%; Compound C2 was obtained from C1 through ethanol recrystallization twice; Compound C3 was dissolved in 4% KOH from C1 and reacted at 40-50 degrees for 8 hours under air blowing, and the product was filtered with ethanol Wash and dry to give, the yield is 91%; compound C4 is added 200 milliliters of ammonia water by adding 15 grams of compound C3, then add 0.05-0.15 grams of copper sulfate and 10 grams of zinc powder, stir the mixture and heat up to 80 degrees for 6 hours , cooled, filtered and washed with water, the solid was leached with acetone, the leached solution was evaporated to dryness and dissolved in propanol, the solution was acidified with hydrochloric acid, filtered and washed with methanol, and dried to obtain the yield of 67%; compound C5 was prepared according to the method of compound C3 Compound C6 is prepared by compound C4 method; Compound C7 is added dropwise in 200 milliliters of methylene chloride containing 1.1 milliliters of 3.3 grams of bromine after 2.1 grams of compound C6 are dissolved in 30 milliliters of dichloromethane, and stirring reaction at normal temperature removes solvent after 2 hours , adding methanol, stirring, filtering, and drying to obtain 3.5 g, yield 94%.

Prepared by Gilch polymerization, Heck coupling or Wittg reaction method under base catalysis, the synthetic technical route can also be:

In the formula, compound C8 is made of 11.1 grams of catechol, 17.5 grams of 2-ethylhexyl bromide, and 20 grams of potassium carbonate in 100 ml of DMF, stirred and reacted at 80 degrees for 16 hours, then extracted with ether, washed three times with water, and the organic phase was washed with sulfuric acid. After the magnesium is dried, the solvent is removed, and 15.2 grams are obtained by drying; Compound C9 is dissolved in 80 milliliters of DMF by 9.6 grams 43.2 mmol of compound C8, and 7.7 grams 43.2 mmol of NBS is dissolved in 30 milliliters of DMF, and the two solutions are stirred and mixed at 0 degrees After 2 hours of reaction, water was added, extracted with ether, washed with water three times, and the solvent was evaporated to obtain 12 grams; compound C10 was added to 70 ml of DMF by adding 8.3 grams of compound C9, 6.5 grams of 2-ethylhexyl bromide, and 7 grams of potassium carbonate. Stir and react at 80°C for 16 hours, extract with ether, wash with water three times, dry over magnesium sulfate, remove the solvent, add methanol, stir and filter, and dry to obtain 9.7 g; compound C11 is under the protection of nitrogen, and 7.5 g of compound C10 (18.2 mmol) is dissolved in Anhydrous 50 ml of THF was placed in a dry ice-acetone bath, 13 ml of n-butyllithium was added dropwise, and 3 ml of trimethyl borate was added after stirring for 1 hour. After 10 minutes, it was raised to room temperature and continued to stir for 10 hours. Then add 2M hydrochloric acid to terminate the reaction, extract with ether, wash with water three times, dry over magnesium sulfate, remove the solvent, and separate by column chromatography with ethyl acetate/n-hexane to obtain 4.8 g;

Compound C12 is under the protection of nitrogen, 50 milliliters of toluene and 60 milliliters of 2M sodium carbonate aqueous solution are added in the two-necked flask that compound C114.6 grams, compound C71.82 grams, tetrakis-triphenylphosphopalladium 0.82 grams are housed, heating After reflux and stirring for 24 hours, the organic layer was separated, the solvent was removed after drying over magnesium sulfate, and 4.0 g was obtained after separation by column chromatography with dichloromethane/n-hexane;

Compound C13 is under the protection of nitrogen, 3.2 grams of compound C12, 1.4 grams of NBS, BP096 milligrams are dissolved in 80 milliliters of carbon tetrachloride, and the solvent is removed after reflux and stirring reaction for 3 hours, and the residue is separated from dichloromethane by short column chromatography. 2.7 grams were obtained after separation of n-hexane; Compound C14 was added 1.5 grams of compound C13 into 7 milliliters of triethoxyphosphorus P(OC ₂ H ₅ ) _and refluxed for 6 hours. After 6 hours, the solvent was removed under reduced pressure, and the crude product was subjected to short column chromatography. 1.1 g were obtained after separation with ethyl acetate/n-hexane;

Polymer 4 was synthesized by placing 0.48 g of compound C13 and 53 mg of p-tert-butylbenzyl bromide in a 250 ml dry single-necked flask, closing it with a reverse rubber stopper and replacing it with nitrogen, introducing 70 ml of anhydrous THF and placing In an ice-water bath, slowly add 4 ml of 1M potassium tert-butoxide tetrahydrofuran solution with a syringe under stirring. After stirring and reacting for 4 hours, the mixture is poured into a large amount of methanol to precipitate the polymer, filtered and washed with 2:1 methanol/water, methanol, vacuum The dried polymer was dissolved in chloroform and reprecipitated twice with methanol to obtain 0.23 g. Gel permeation chromatography analysis showed that the weight-average molecular weight of the polymer was 207,000, and the polydispersity was 4.3. Thermal analysis showed that the thermal decomposition temperature of the polymer was 385° C. , no glass transition temperature was observed before 385 °C.

The synthetic technical route can also be:

In the formula, compound C15 is obtained by separating 2.2 g of m-phenylenediamine and excess tributyl phosphate PO(OC ₄ H ₉ ) ₃ at 180°C for 12 hours under reflux, and separating the mixture with ethyl acetate/n-hexane by column chromatography 5.4 g; Compound C16 was dissolved in 3.5 g of compound 15 in DMF distilled on calcium hydride, slowly added 2.5 ml of phosphorus oxychloride, stirred and reacted at room temperature for 3 hours, added water and extracted with dichloromethane, washed three times with water, evaporated After removing the solvent, 3.5 grams were obtained by column chromatography with ethyl acetate/n-hexane;

Polymer 20 was synthesized by placing 0.5001 g of compound C14 and 0.1700 g of compound C16 in two 50 ml dry single-necked flasks, sealing them with reverse-mouthed rubber stoppers and replacing them with nitrogen, and introducing 10 ml of anhydrous THF into each of them. Place the single-necked flask containing compound C14 in a dry ice acetone bath, slowly add 0.7 ml of 1.5M LDA cyclohexane solution with a syringe under stirring, stir and react for 1 hour, slowly add compound C16 solution with a syringe, and continue to stir the reaction After 30 minutes, put it at room temperature to react for 5 hours, then add a small amount of p-dimethylaminobenzaldehyde and react for 2 hours, stop with a small amount of water, extract with dichloromethane-water, dry the organic phase with anhydrous sodium sulfate, and filter Pour into methanol for precipitation, reprecipitate three times and vacuum dry to obtain 0.46 g of polymer 20. Gel permeation chromatography analysis showed that the weight average molecular weight and polydispersity of the polymer were 42,000 and 1.95, respectively, and thermal analysis showed that the polymer started thermally decomposing. The temperature was 370 degrees, and no glass transition temperature was observed before 370 degrees.

The polymerization method and molecular weight of the resulting polymer used in the present invention are illustrative only. Polymers can be prepared by base-catalyzed Gilch polymerization, Heck coupling and Wittg reaction. Exemplary polymer and monomer synthetic routes and their characterization are in the Examples. These are merely illustrative, and any monomer and polymerization method can be used as long as the prepared polymer satisfies the following general formula.

The present invention provides anthracene-based light-emitting conjugated polymers containing 2,6- or 2,7-anthracene-ethene structural units as shown in structural formula I and having good solubility and thermal stability, the rigidity in the polymer main chain Chromophores add rigidity to the polymer backbone and improve thermal performance. Polymers containing these chromophores are highly fluorescent and efficient light emitting materials. The polymer represented by structural formula I is prepared by Gilch polymerization or Heck coupling or Wittg reaction. The 2,6(2,7)-anthracene vinyl homopolymer or its copolymer is preferably Gilch polymerized. This is only illustrative, as long as the prepared polymer satisfies the structure shown in Formula I, any monomer and polymerization method can be used.

The invention provides a poly(2,6-) and poly 2,7-anthracene vinyl derivative as an electroluminescence material and a preparation method thereof. Not only provide new anthracene-based light-emitting polymer materials for polymer electroluminescent devices, but also provide light-emitting polymers with different energy band gaps, these poly 2,6- or 2,7-anthracene-based homopolymers or containing these A copolymer of anthracene vinyl units, capable of emitting a wide range of colors.

The electroluminescent material provided by the invention has many advantages including good solubility, efficiency and stability. The emission color of the polymers can be easily tuned by introducing desired Ar ¹ , Ar ² , especially Ar groups. Moreover, other electro-optic properties can also be adjusted by changing the Ar group, including Ar ¹ , Ar ² groups. The materials of the present invention can also be used as host materials for other optoelectronic materials.

The anthracene-based polymers provided by the present invention have been used in electroluminescent devices. The device consists of an anode, a cathode, and a polymer light-emitting layer placed between the anode and cathode. They can be multi-layer structure, double-layer structure and single-layer structure, such as: there is an emissive layer between the transparent anode and the metal cathode, and the emissive layer is both an electroluminescent medium and a charge carrier layer. Such an electroluminescent device is a single Layer structure, it is possible to use the polymers of the present invention as emissive layers. The double-layer structure electroluminescent device comprises a hole transport layer close to the anode layer and an electron transport layer close to the hole transport layer, the electron transport layer is also an emission layer for generating electroluminescence, and the cathode is close to the electron transport layer. The hole-transporting layer and the electron-transporting layer together constitute the electroluminescent medium, and the device can use the polymer of the present invention as the emissive layer.

The electroluminescent medium of the multilayer structure electroluminescent device is composed of a hole transport layer, an emission layer and an electron transport layer. The hole transport layer is close to the anode, and the electron transport layer is close to the cathode. Between the hole transport layer and the electron transport layer There is an emission layer in between. The emissive layer produces electroluminescence, and the device can use the polymer of the present invention as the emissive layer. The above structural description is only used to illustrate the present invention, and the thickness of the emitting layer can vary within 10-1000 nm.

Description of drawings

Figure 1 shows the absorption, emission, and photoluminescence spectra of polymer 4. Figure 2 shows the absorption, emission and photoluminescence spectra of polymer 20. FIG. 3 shows the electroluminescence spectra of single-layer electroluminescent devices fabricated from polymer 4 and polymer 20. FIG. Fig. 4 is a general structural formula of the electroluminescent material.

Specific implementation examples

Example 1. A kind of poly(2,6-) and poly-2,7-anthracene vinyl derivatives are used as electroluminescent materials, and its structural formula is shown in Polymer 1 below.

Polymer 1 Polymer 2

Example 2. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives, whose structural formula is shown in the polymer 2 listed above.

Example 3. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives, whose structural formula is shown in Polymer 3 below.

Polymer 3 Polymer 4

Example 4. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives, whose structural formula is shown in the polymer 4 listed above.

Example 5. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives, whose structural formula is shown in Polymer 5 below.

Polymer 5 Polymer 6

Example 6. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives, whose structural formula is shown in the polymer 6 listed above.

Example 7. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives, whose structural formula is shown in Polymer 7 below.

Polymer 7 Polymer 8

Example 8. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives for the light-emitting layer, whose structural formula is shown in the polymer 8 listed above.

Example 9. An electroluminescent material in which poly(2,6-) and poly(2,7-anthracene) derivatives constitute the light-emitting layer. Its structural formula is shown in Polymer 9 below.

Polymer 9

Polymer 12

Example 10. An electroluminescent material in which poly(2,6-) and poly2,7-anthracene vinyl derivatives constitute the light-emitting layer, and its structural formula is shown in the polymer 12 listed above.

Example 11. An electroluminescent material in which poly(2,6-) and poly2,7-anthracene vinyl derivatives constitute the light-emitting layer, and its structural formula is shown in Polymer 13 below.

Polymer 13

Example 12. An electroluminescent material in which poly(2,6-) and poly(2,7-anthracene) derivatives constitute the light-emitting layer. Its structural formula is shown in Polymer 15 below.

Polymer 15 Polymer 16

Example 13. An electroluminescent material composed of poly(2,6-) and poly-2,7-anthracene vinyl derivatives for the light-emitting layer, whose structural formula is shown in the polymer 16 listed above.

Example 14. An electroluminescent material in which poly(2,6-) and poly2,7-anthracene vinyl derivatives constitute the light-emitting layer, and its structural formula is shown in Polymer 17 below.

Polymer 17

Example 15. An electroluminescent material in which poly(2,6-) and poly2,7-anthracene vinyl derivatives constitute the light-emitting layer, and its structural formula is shown in Polymer 18 below.

Polymer 18

Example 16. An electroluminescent material in which poly(2,6-) and poly(2,7-anthracene) derivatives constitute the light-emitting layer. Its structural formula is shown in Polymer 19 below.

Polymer 19

Example 17. An electroluminescent material in which poly(2,6-) and poly(2,7-anthracene) derivatives constitute the light-emitting layer, and its structural formula is shown in Polymer 20 below.

Example 18. An electroluminescent material in which poly(2,6-) and poly(2,7-anthracene) derivatives constitute the light-emitting layer. Its structural formula is shown in Polymer 21 below.

Polymer 20 Polymer 21

The above-mentioned embodiments 1-21 can be widely used in the manufacture of electroluminescent devices. A preferred electroluminescent device structure is a single emitting layer structure comprising an anode, a cathode and a single layer of electroluminescent medium. This electroluminescent layer is both an emissive layer and capable of transporting electrons and holes. This layer may comprise a mixture of one or more of the polymers of Examples 1-21 above; or a polymer of the present invention doped with one or more fluorescent dyes, phosphorescent materials or other luminescent materials.

The electroluminescent materials of Examples 1-21 have many advantages including good solubility, high luminous efficiency and high thermal stability. The emission color of the polymers can be easily tuned by introducing desired Ar ¹ , Ar ² , especially Ar groups. Moreover, other electro-optic properties can also be adjusted by changing the Ar group, including Ar ¹ , Ar ² groups. The materials of the present invention can also be used as host materials for other optoelectronic materials.

The above mentioned polymers can be deposited as high quality transparent films by spin coating or inkjet printing of polymer solutions, preferably spin coating techniques and a single electroluminescent medium layer.

Exemplary monomer and polymer synthesis routes are shown in Schemes 1-3 and their descriptions:

plan 1

In scheme 1, compound C1 was added by adding 35 grams of 1,4-p-benzoquinone, 80 milliliters of isoprene and 350 milliliters of ethanol into a 1000 milliliter single-necked flask, heated vigorously, stirred and refluxed for 30-40 hours, cooled in ice water, and filtered to obtain White solid crystal C1, yield 68%.

Compound C2 was obtained from C1 through ethanol recrystallization twice.

Compound C3 was dissolved in 4% KOH from C1 and then reacted at 40-50°C for 8 hours under air blowing. The product was washed with ethanol and dried to give the yield of 91%. ¹ H-NMR (300MHz, CDCl ₃ ) , δ(ppm): 8.18(d, 2H, J=9.0Hz), 8.08(s, 2H), 7.58(d, 2H, J=9.0Hz), 2.53(s, 6H);

Compound C4 was added 15 g of compound C3 to 200 ml of ammonia water, then 0.05-0.15 g of copper sulfate and 10 g of zinc powder were added, the mixture was stirred and heated to 80° C. for 6 hours. Cool, filter and wash with water, leaching the solid with acetone, evaporate the leaching solution to dryness, add propanol to dissolve, acidify the solution with hydrochloric acid, filter and wash with methanol, and dry to obtain, the yield is 67%, ¹ H-NMR (300MHz, CDCl ₃ ), δ(ppm): 8.33(s, 1H), 8.27(s, 2H), 8.21(s, 1H), 7.89(d, 4H, J=9.0Hz), 7.73(d, 4H, J=9.0 Hz), 7.28(dd, 4H, J ₁ =9.0Hz, J ₂ =3.0Hz), 2.54(s, 12H);

Compound C5 was prepared according to the method of compound C3, ¹ H-NMR (300MHz, CDCl ₃ ), δ (ppm): 818 (d, 2H, J = 9.0Hz), 8.08 (s, 2H), 7.58 (d, 2H, J =9.0Hz), 2.53(s, 6H);

Compound C6 was prepared according to the method of compound C4, ¹ H-NMR (300MHz, CDCl ₃ ), δ (ppm): 8.27 (s, 2H); 7.88 (d, 2H, J=9.0Hz), 7.73 (d, 2H, J =9.0Hz), 7.28(d, 2H, J=9.0Hz), 2.54(s, 6H);

Compound C7 was dissolved in 30 milliliters of dichloromethane by 2.1 grams (10.2 mmol) of compound C6 and added dropwise in 200 milliliters of dichloromethane containing 1.1 milliliters of 3.3 grams (20.6) of bromine, stirred at room temperature for 2 hours, then removed the solvent, added Methanol was stirred and filtered, and dried to obtain 3.5 g (yield 94%), ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 8.42 (d, 2H, J=9.0Hz), 8.28 (s, 2H), 7.42(d, 2H, J=9.0Hz), 2.60(s, 6H).

Scenario 2

Compound C8 in Scheme 2: catechol 11.1 g, 2-ethylhexyl bromide 17.5 g, and potassium carbonate 20 g were added to 100 ml of DMF, stirred and reacted at 80°C for 16 hours, extracted with ether, washed three times with water, and used for the organic phase After drying over magnesium sulfate, the solvent was removed and dried to obtain 15.2 g (containing a small amount of disubstituted products, yield 73%), ¹ H-NMR (300MHz, CDCl ₃ ), δ (ppm): 6.94 (d, 2H, J=9.0Hz ), 6.85(m, 3H), 5.61(s, 1H), 3.93(d, 2H, J=6.0Hz), 1.77(m, 1H), 1.48(m, 4H), 1.33(m, 4H), 0.94 (m, 6H);

Compound C9 was dissolved in 9.6 g (43.2 mmol) of compound C8 in dry 80 ml of DMF, 7.7 g (43.2 mmol) of NBS was dissolved in 30 ml of DMF, and the two solutions were stirred and mixed at 0 ° C, and water was added after 2 hours of reaction , extracted with ether, washed three times with water and distilled off the solvent to obtain (92% yield) 12 g, ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 6.97 (m, 2H), 6.80 (d, 1H, J=9.0Hz), 5.54(s, 1H), 3.90(d, 2H, J=6.0Hz), 1.77(m, 1H), 1.45(m, 4H), 1.33(m, 4H), 0.94(m, 6H);

Compound C10 was added 8.3 g of compound C9, 6.5 g of 2-ethylhexyl bromide, and 7 g of potassium carbonate into 70 ml of DMF, stirred and reacted at 80°C for 16 hours, extracted with ether, washed three times with water, dried over magnesium sulfate, and the solvent was removed. Added methanol, stirred and filtered, dried to obtain (85% yield) 9.7 g, ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 6.80 (d, 1H, J=9.0Hz), 6.72 (s, 1H) , 6.68(d, 1H, J=9.0Hz), 3.85(m, 4H), 2.54(t, 2H, J=7.5Hz), 1.75(m, 2H), 1.50(m, 8H), 1.34(m, 8H), 0.94(m, 12H);

Compound C11: Under nitrogen protection, 7.5 g (18.2 mmol) of compound C10 was dissolved in 50 ml of anhydrous THF and placed in a dry ice-acetone bath, and 13 ml of n-butyl lithium (1.6M n-hexane solution) was added dropwise, After stirring for 1 hour, add 3 ml of trimethyl borate, rise to room temperature after 10 minutes and continue to stir for 10 hours, then add 2M hydrochloric acid to terminate the reaction, extract with ether, wash with water three times, dry over magnesium sulfate, remove the solvent, pass through the column After chromatographic (ethyl acetate/n-hexane) separation (yield 71%) 4.8 g, ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 7.82 (d, 1H, J = 9.0 Hz), 7.68 (s, 1H), 6.90 (d, 1H, J = 9.0Hz), 4.01 (d, 2H, J = 6.0Hz), 3.96 (d, 2H, J = 6.0Hz), 1.81 (m, 4H), 1.52 (m, 8H), 1.36(m, 8H), 0.94(m, 12H).

Compound C12: Under the protection of nitrogen, add 4.6 grams (12 mmol) of compound C11.82 grams (5 mmol) of compound C and 0.82 grams (0.71 mmol) of tetrakis-(triphenylphosphine) palladium to the two-necked flask 50 milliliters of toluene and 60 milliliters of 2M sodium carbonate aqueous solution were heated to reflux and stirred for 24 hours to separate the organic layer, dried over magnesium sulfate and removed the solvent, and obtained after separation by column chromatography (dichloromethane/n-hexane) (yield 92%) 4.0 g, ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 7.66 (d, 2H, J=9.0Hz), 7.50 (s, 2H), 7.17 (d, 2H, J=9.0Hz), 7.11(d, 2H, J=9.0Hz), 6.97(m, 4H), 4.04(d, 4H, J=6.0Hz), 3.85(d, 4H, J=6.0Hz), 2.41(s, 6H), 1.88(m, 2H), 1.78(m, 2H), 1.48(m, 16H), 1.33(m, 16H), 0.97(m, 24H);

Compound C13: Under nitrogen protection, dissolve 3.2 grams (3.6 mmol) of compound C12 (3.6 mmol), 1.4 grams (7.9 mmol) of NBS (7.9 mmol), and 96 mg (0.4 mmol) of BPO in 80 ml of carbon tetrachloride, reflux and stir for 3 hours to remove Solvent, the residue was separated by short column chromatography (dichloromethane/n-hexane) to obtain 2.7 g (yield 73%), ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 7.78 (d, 2H, J=9.0Hz), 7.72(s, 2H), 7.36(d, 2H, J=9.0Hz), 7.10(d, 2H, J=9.0Hz), 6.94(m, 4H), 4.56(s, 4H) , 4.04(d, 4H, J=6.0Hz), 3.85(d, 4H, J=6.0Hz), 1.88(m, 2H), 1.78(m, 2H), 1.51(m, 16H), 1.37(m, 16H), 0.97(m, 24H).

Compound C14 was added 1.5 grams of compound C13 into 7 milliliters of triethoxyphosphorus (P(OC ₂ H ₅ ) ₃ ) and refluxed for 6 hours. After 6 hours, the solvent was removed under reduced pressure, and the crude product was subjected to short column chromatography (ethyl acetate/n-hexane ) after separation (yield 68%) 1.1 g, ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 8.44 (d, 2H, J = 9.0 Hz), 8.30 (s, 2H), 7.78 ( d, 2H, J = 9.0 Hz), 7.37 (d, 2H, J = 9.0 Hz), 6.64 (m, 4H), (s, 4H). 4.14(m, 8H), 4.07(m, 8H), 3.32(d, 4H, J=21.0Hz), 1.88(m, 2H), 1.78(m, 2H), 1.51(m, 16H), 1.37(m , 16H), 1.30(t, 12H, J=6.0Hz), 0.97(m, 24H);

Polymer 4 was synthesized by placing 0.48 g (0.47 mmol) of compound C13 and 53 mg (0.24 mmol) of p-tert-butylbenzyl bromide in a 250 ml dry single-necked flask, sealing it with a reverse rubber stopper and replacing it with nitrogen, and introducing About 70 ml of anhydrous THF was placed in an ice-water bath, and 4 ml of 1M potassium tert-butoxide tetrahydrofuran solution was slowly added with a syringe under stirring. After stirring and reacting for 4 hours, the mixture was poured into a large amount of methanol to precipitate the polymer, filtered and washed with methanol/water (2:1), washed with methanol, and the vacuum-dried polymer was dissolved in chloroform and reprecipitated twice by methanol to obtain 0.23 grams. Gel permeation chromatography (GPC, eluent THF, standard substance is polystyrene) analysis showed that the polymer The weight-average molecular weight is 207000, the polydispersity is 4.3, and the thermal analysis shows that the thermal decomposition temperature of the polymer is 385°C, and no glass transition temperature is observed before 385°C.

Option 3

In scheme 3, compound C15 was reacted by 2.2 grams of m-phenylenediamine and excess tributyl phosphate (PO(OC ₄ H ₉ ) ₃ ) at 180°C for 12 hours under reflux, and the mixture was subjected to column chromatography (ethyl acetate/n-hexane alkane) to obtain (yield 80%) 5.4 g, ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm): 7.01 (t, 1H, J=7.5Hz), 6.05 (d, 2H, J=9.0 Hz), 6.01(s, 1H), 3.16(t, 8H, J=6.0Hz), 1.84(m, 8H), 1.45(m, 8H), 0.92(t, 12H, J=7.5Hz);

Compound C16 was dissolved in 3.5 g of compound 15 in DMF distilled from calcium hydride, slowly added 2.5 ml of phosphorus oxychloride, stirred at room temperature for 3 hours, added water and extracted with dichloromethane, washed three times with water, and evaporated the solvent After separation by column chromatography (ethyl acetate/n-hexane) (85% yield) 3.5 g, ¹ H-NMR (300 MHz, CDCl ₃ ), δ (ppm) 9.80 (s, 2H), 8.11 (s, 1H ), 6.28(s, 1H), 3.21(t, 8H, J=6.0Hz), 1.88(m, 8H), 1.47(m, 8H), 0.92(t, 12H, J=7.5Hz);

Synthesis of Polymer 20: 0.5001 g (0.4372 mmol) of compound C14 and 0.1700 g (0.4372 mmol) of compound C16 were respectively placed in two 50 ml dry single-necked flasks, sealed with reverse-mouthed rubber stoppers and replaced with nitrogen, each After introducing about 10 ml of anhydrous THF, place the one-necked flask containing compound C14 in a dry-ice acetone bath, slowly add 0.7 ml of 1.5 M LDA cyclohexane solution with a syringe under stirring, and stir the reaction for 1 hour. Compound C16 Slowly add the solution with a syringe, continue to stir for 30 minutes, then place it at room temperature for 5 hours, then add a small amount of p-dimethylaminobenzaldehyde and react for 2 hours, stop with a small amount of water and extract with dichloromethane-water, the organic phase Dry with anhydrous sodium sulfate, filter and pour into methanol to precipitate, reprecipitate three times and vacuum dry to obtain 0.46 g of polymer 20, gel permeation chromatography (GPC, eluent THF, standard is polystyrene) analysis shows that the polymer The weight-average molecular weight and polydispersity of the compound were 42000 and 1.95, respectively. Thermal analysis showed that the thermal decomposition temperature of the polymer was 370 degrees, and no glass transition temperature was observed before 370 degrees.

The electroluminescent device of the single polymer film light-emitting layer of the present invention is constructed according to the following procedures:

The glass substrate coated with indium-tin oxide (ITO) was washed sequentially with detergent, distilled water and ethanol, and then exposed to ultraviolet light and ozone for several minutes. PEDOT+PSS (Bayer) aqueous dispersion was spin-coated on ITO to form a film with a thickness of 100 nm, and dried at 105° C. for 10 minutes. Next, a polymer solution (6 mg/ml in chloroform) filtered through a 0.25 μm PTFE filter was spin-coated thereon to form a polymer film with a thickness of about 80 nm. On the polymer film, about 200nm Ba is thermally deposited at 5×10 ^-4 Pa, and then 150nm Al is thermally deposited, and the device structure is such as ITO/PEDOT+PSS/polymer film/Ba/Al. The test work is carried out in normal environment at room temperature.

Figure 1 is the absorption and emission spectra of polymer 4 in toluene solution and the emission spectrum in film state.

Fig. 2 is the absorption and emission spectrum of polymer 20 in toluene solution and the emission spectrum in film state.

Figure 3 is the electroluminescence spectra of single layer devices of polymers 4 and 20.

Claims (3)

1. one kind is gathered 2, and 6-reaches and gathers 2, and 7-anthryl ethene derivatives is characterized in that as the preparation method of electroluminescent material the synthetic technology route is with the Gilch polymerization under the base catalysis, Heck coupling or the preparation of Wittg reaction method:

Compound C 1 is by 1 in the formula, and 4-para benzoquinone 35 grams, 80 milliliters of isoprene and ethanol add in 1000 milliliters of single port flasks for 350 milliliters, and violent heated and stirred back flow reaction was cooled off in frozen water after 30-40 hour, filter white crystalline solid thing C1, yield 68%;

Compound C 2 is obtained through the ethyl alcohol recrystallization secondary by C1; Compound C 3 is dissolved in behind the 4%KOH by C1 and is blasting under the air in 40-50 degree reaction 8 hours, product ethanol diafiltration, and drying provides, yield 91%; Compound C 4 is added in 200 milliliters of ammoniacal liquor by 15 grams of Compound C 3, add 0.05-0.15 gram copper sulfate and 10 gram zinc powders again, stir this mixture and be warming up to 80 degree reactions 6 hours, cold filtration and washing, solids leaches with acetone, adds the propyl alcohol dissolving behind the leaching liquid evaporate to dryness, the solution hcl acidifying, filtration is also used the methyl alcohol diafiltration, and drying obtains, productive rate 67%;

Compound C 5 is by the preparation of Compound C 3 methods; Compound C 6 is by the preparation of Compound C 4 methods;

Compound C 7 is dissolved in by 2.1 grams of Compound C 6 and is added drop-wise to behind 30 milliliters of methylene dichloride in 200 milliliters of methylene dichloride that contain 1.1 milliliter of 3.3 gram bromine, and the stirring at normal temperature reaction removes after 2 hours and desolvates, and adds the methyl alcohol agitation and filtration, and drying obtains 3.5 grams, yield 94%.

2. one kind is gathered 2, and 6-reaches and gathers 2, and 7-anthryl ethene derivatives is characterized in that as the preparation method of electroluminescent material the synthetic technology route is with the Gilch polymerization under the base catalysis, Heck coupling or the preparation of Wittg reaction method:

Compound C 8 is added among 100 milliliters of DMF by pyrocatechol 11.1 grams, 2-ethylhexyl bromine 17.5 grams, salt of wormwood 20 grams in the formula, 80 degree stirring reaction are down used extracted with diethyl ether after 16 hours, wash three times, organic phase is removed after with dried over mgso and is desolvated, and drying obtains 15.2 grams;

Compound C 9 is dissolved among 80 milliliters of DMF of exsiccant by 9.6 gram 43.2mmol of Compound C 8, NBS7.7 gram 43.2mmol is dissolved in 30 milliliters of DMF, and two solution are mixed in 0 degree, reacts to add entry after 2 hours, use extracted with diethyl ether, steam solvent after washing three times and obtain 12 grams;

Compound C 10 is added among 70 milliliters of DMF by 8.3 grams, 2-ethylhexyl bromine 6.5 grams, salt of wormwood 7 grams of Compound C 9,80 degree stirring reaction are down used extracted with diethyl ether after 16 hours, wash three times, remove after the dried over mgso and desolvate, add the methyl alcohol agitation and filtration, drying obtains 9.7 grams;

Compound C 11 is under nitrogen protection, 7.5 gram 18.2mmol of Compound C 10 are dissolved in anhydrous 50 milliliters of THF and place dry ice-propanone to bathe, drip 13 milliliters of n-Butyl Lithiums, stirring reaction adds 3 milliliters of trimethyl-boron acid esters after 1 hour, rise to room temperature after 10 minutes and continued stirring reaction 10 hours, use extracted with diethyl ether after adding 2M hydrochloric acid termination reaction again, wash three times, remove after the dried over mgso and desolvate, after column chromatography is separated with ethyl acetate/normal hexane, obtain 4.8 grams;

Compound C 12 is under nitrogen protection, add 50 milliliters and 60 milliliters 2M aqueous sodium carbonates of toluene with being equipped with in the twoport flask that Compound C 114.6 restrains, Compound C 71.82 restrains, four-triphenyl phosphorus palladium 0.82 restrains, the reflux stirring reaction was told organic layer after 24 hours, remove after the dried over mgso and desolvate, after column chromatography is separated with methylene dichloride/normal hexane, obtain 4.0 grams;

Compound C 13 is under nitrogen protection, 3.2 grams, NBS1.4 gram, the BP096 milligram of Compound C 12 are dissolved in 80 milliliters of tetracol phenixin, the backflow stirring reaction removes after 3 hours and desolvates, and resistates obtains 2.7 grams after short column chromatography separates with methylene dichloride/normal hexane; Compound C 14 adds 7 milliliters of triethoxy phosphorus P (OC by 1.5 grams of Compound C 13 ₂H ₅) ₃Middle back flow reaction removal of solvent under reduced pressure after 6 hours, crude product obtains 1.1 grams after short column chromatography separates with ethyl acetate/normal hexane;

The synthetic of polymkeric substance 4 places 250 milliliters of dry single port flasks by 0.48 gram of Compound C 13 with to 53 milligrams of tertiary butyl bromotoluenes, with anti-chewing-gum plug sealing back nitrogen replacement, importing 70 milliliters of anhydrous THF is placed in the ice-water bath, under agitation slowly add 4 milliliters of 1M potassium tert.-butoxide tetrahydrofuran solutions with syringe, stirring reaction after 4 hours mixture pour precipitation polymers in a large amount of methyl alcohol into, filter and with 2: 1 methanol, methyl alcohol is washed, vacuum drying polymkeric substance is dissolved in chloroform through methyl alcohol reprecipitation secondary, obtain 0.23 gram, gel osmoticing chromatogram analysis shows that the polymkeric substance weight-average molecular weight is 207000, polydispersity 4.3, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 385 ℃, does not observe second-order transition temperature before 385 ℃.

3. one kind is gathered 2, and 6-reaches and gathers 2, and 7-anthryl ethene derivatives is characterized in that as the preparation method of electroluminescent material the synthetic technology route is with the Gilch polymerization under the base catalysis, Heck coupling or the preparation of Wittg reaction method:

Compound C 14 adds 7 milliliters of triethoxy phosphorus P (OC by 1.5 grams of Compound C 13 in the formula ₂H ₅) ₃Middle back flow reaction removal of solvent under reduced pressure after 6 hours, crude product obtains 1.1 grams after short column chromatography separates with ethyl acetate/normal hexane;

Compound C 15 is by meta phenylene diamine 2.2 gram and excessive Tributyl phosphate ester PO (OC ₄H ₉) ₃After 12 hours, this mixture obtains 5.4 grams through column chromatography with ethyl acetate/normal hexane separation 180 ℃ of back flow reaction;

Compound C 16 is dissolved in behind distillatory DMF on the hydrolith by 3.5 grams of compound 15, slowly add 2.5 milliliters of phosphorus oxychloride, the stirring at normal temperature reaction added the entry dichloromethane extraction after 3 hours, wash three times, steam solvent after column chromatography is separated with ethyl acetate/normal hexane and obtain 3.5 grams;

The synthetic of polymkeric substance 20 is that 0.5001 gram of Compound C 14 and 0.1700 gram of Compound C 16 are placed two 50 milliliters of dry single port flasks respectively, with anti-chewing-gum plug sealing back nitrogen replacement, after each imports 10 milliliters of anhydrous THF, the single port flask that fills Compound C 14 is placed dry ice acetone bath, the LDA cyclohexane solution that under agitation slowly adds 0.7 milliliter of 1.5M with syringe, stirring reaction slowly added Compound C 16 solution with syringe after 1 hour, continue stirring reaction and be placed on room temperature reaction in 30 minutes 5 hours, added micro-Paradimethylaminobenzaldehyde afterreaction 2 hours again, stopping the back with less water extracts with methylene dichloride-water, the organic phase anhydrous sodium sulfate drying, pour in the methyl alcohol after the filtration and precipitate, three final vacuum dryings of reprecipitation obtain 0.46 gram polymkeric substance 20, gel osmoticing chromatogram analysis shows that the weight-average molecular weight of polymkeric substance and polydispersity are respectively 42000 and 1.95, the initial heat decomposition temperature of hot analysis revealed polymkeric substance is 370 degree, does not observe second-order transition temperature before 370 degree.

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