CN101624441A - Preparation method and application method of 4-9, 9-diaryl fluorene polymer material containing substituted radical - Google Patents

Abstract

Translated fromChinese

4位含有取代基团的9，9－二芳基芴类聚合物材料的制备和应用方法，属于光电材料与有机信息显示科技领域，具体为一种4位含有取代基团的9，9－二芳基芴的均聚或共聚共轭聚合物及其制备方法，并将该类材料应用于有机发光显示等有机电子领域，该材料具有如上结构。聚合物材料I该材料保持了高热稳定性和玻璃化温度等优点。可以预期，该类材料将成为具有商业化潜力的聚合物蓝光材料。

The preparation and application method of a 9,9-diaryl fluorene polymer material containing a substituent group in the 4-position belongs to the field of photoelectric materials and organic information display technology, specifically a 9,9-diaryl fluorene polymer material containing a substituting group in the 4-position A homo- or co-polymerized conjugated polymer of diaryl fluorene and a preparation method thereof, and the application of this type of material in the field of organic electronics such as organic light-emitting display, the material has the above structure. Polymer material I This material maintains the advantages of high thermal stability and glass transition temperature. It can be expected that this type of material will become a polymer blue light material with commercial potential.

Description

Translated fromChinese

4位含有取代基团的9，9-二芳基芴类聚合物材料的制备和应用方法Preparation and application method of 9,9-diarylfluorene polymer material containing substituent group in 4-position

技术领域technical field

本发明属于有机光电材料技术领域。具体涉及一种4位含有取代基团的9，9-二芳基芴聚合物材料及其制备方法，并涉及这些材料在有机电致发光、有机光存储、有机场效应管、有机太阳能电池、有机非线性光学、化学与生物传感和有机激光等领域的应用。The invention belongs to the technical field of organic photoelectric materials. It specifically relates to a 9,9-diaryl fluorene polymer material containing substituent groups at the 4-position and its preparation method, and relates to the application of these materials in organic electroluminescence, organic light storage, organic field effect tubes, organic solar cells, Applications in organic nonlinear optics, chemical and biological sensing, and organic lasers.

技术背景technical background

自1987年美国柯达公司Tang研究小组[Tang，C.W.；Van Slyke，S.A.Appl.Phys.Lett.1987，51，913.]和1990年英国剑桥大学[Burroughes，J.H.；Bradley，D.D.C.；Brown，A.B.；Marks，R.N.；Mackay，K.；Friend，R.H.；Bum，P.L.；Holmes，A.B.Nature 1990，347，539.]分别发表了以有机和聚合物荧光材料制成薄膜型有机电致发光器件(Organic Light-emitting Diodes)和聚合物发光二极管(PolymericLight-emitting Diodes)以来，有机平板显示成为继液晶显示之后的又一代市场化的显示产品。有机和塑料电子产品的优点在于材料制备成本低、工艺简单、具有通用高分子的柔韧性和可塑性。因此，开发具有实用性的市场潜力新型有机光电信息材料吸引了许多国内外大学不同学科的科学家以及研究机构和公司的关注和投入。Since 1987, the Tang Research Group of Kodak Company in the United States [Tang, C.W.; Van Slyke, S.A.Appl.Phys.Lett. 1987, 51, 913.] and the University of Cambridge in 1990 [Burruges, J.H.; Bradley, D.D.C.; Brown, A.B.; Marks, R.N.; Mackay, K.; Friend, R.H.; Bum, P.L.; Holmes, A.B.Nature 1990, 347, 539.] published thin-film organic electroluminescent devices (Organic Light -emitting Diodes) and polymer light-emitting diodes (PolymericLight-emitting Diodes), organic flat panel display has become another generation of market-oriented display products after liquid crystal display. The advantages of organic and plastic electronics lie in the low cost of material preparation, simple process, and the flexibility and plasticity of general-purpose polymers. Therefore, the development of new organic optoelectronic information materials with practical market potential has attracted the attention and investment of many scientists from different disciplines in universities at home and abroad, as well as research institutions and companies.

到目前为止，9位经过二芳基修饰的芴结构单元构建光电材料表现出高的热稳定性和高的玻璃化温度，在芴的9位上引入芳基能够提高材料的溶解度、增大载流子迁移率、调节电子结构。更重要的是还可以通过位阻效应调节材料的聚集态结构，在一定温度范围里保持聚芴的晶型稳定，防止激子在高分子主链之间淬灭，提高材料的发光效率。因此成为一类有希望的实用有机光电子材料。因此，在这方面已经发表了相当的文章和专利。如：Kohki Ebitani，Tomonori Kawabata，Kohji Nagashima，Tomoo Mizugaki and Kiyotomi Kaneda，Green Chemistry，2000，2，157-160；JP10245352A；JP10265423A；JP11158106A；JP2000026349A；JP2000053628A；JP2000169573A；JP2000336082A；JP2002047227A；JP2008120705A。但是在芴的4位含有取代基的9，9-二芳基芴结构单元却很少有报道。Magnus Rueping，Boris J.Nachtsheim，and Winai Ieawsuwana，Adv.Synth.Catal.2006，348，1033-1037；JP2001055368A；JP2002020487A；JP2007137795A。4位含有取代基团的9，9-二芳基芴结构单元的半导体材料表现出如下优点：(1)合成步骤简单、条件温和；(2)保持了高热稳定性和玻璃化温度等优点。另外，通过引入了具有增加溶解度、阻隔发色团聚集或增加稳定性的结构链能扩大该类材料在有机电子、光电子、或光电材料使用范围。因此，本发明通过简单的合成路线开发了一系列4位含取代基团的9，9-二芳基芴聚合物材料，为发展新一类有机电致发光材料提供新的方法。So far, optoelectronic materials constructed by diaryl-modified fluorene structural units at the 9-position have shown high thermal stability and high glass transition temperature. Flow carrier mobility, regulation of electronic structure. More importantly, the aggregate structure of the material can be adjusted through the steric hindrance effect, the crystal form of polyfluorene can be kept stable in a certain temperature range, the excitons can be prevented from being quenched between the polymer main chains, and the luminous efficiency of the material can be improved. Therefore, it becomes a promising class of practical organic optoelectronic materials. Accordingly, considerable articles and patents have been published in this regard.如：Kohki Ebitani，Tomonori Kawabata，Kohji Nagashima，Tomoo Mizugaki and Kiyotomi Kaneda，Green Chemistry，2000，2，157-160；JP10245352A；JP10265423A；JP11158106A；JP2000026349A；JP2000053628A；JP2000169573A；JP2000336082A；JP2002047227A；JP2008120705A。 However, 9,9-diarylfluorene structural units containing substituents at the 4-position of fluorene are rarely reported. Magnus Rueping, Boris J. Nachtsheim, and Winai Ieawsuwana, Adv. Synth. Catal. 2006, 348, 1033-1037; JP2001055368A; JP2002020487A; JP2007137795A. The semiconductor material of the 9,9-diarylfluorene structural unit containing a substituent at the 4-position has the following advantages: (1) the synthesis steps are simple and the conditions are mild; (2) the advantages of high thermal stability and glass transition temperature are maintained. In addition, the use of such materials in organic electronics, optoelectronics, or optoelectronic materials can be expanded by introducing structural chains that increase solubility, block chromophore aggregation, or increase stability. Therefore, the present invention develops a series of 9,9-diarylfluorene polymer materials containing substituent groups at the 4-position through a simple synthesis route, and provides a new method for developing a new class of organic electroluminescent materials.

发明内容Contents of the invention

技术问题：本发明的目的在于提出4位含有取代基团的9，9-二芳基芴类聚合物材料的制备和应用方法，设计有效的合成路线来实现该类聚合物材料的制备。指出该类材料在有机电致发光、有机场效应管、有机光存储和有机激光等有机电子领域的应用。Technical problem: The purpose of the present invention is to propose a method for the preparation and application of 9,9-diarylfluorene polymer materials containing substituent groups at the 4-position, and to design an effective synthetic route to realize the preparation of such polymer materials. Point out the application of this kind of material in the field of organic electronics such as organic electroluminescence, organic field effect transistor, organic optical storage and organic laser.

技术方案：本发明的4位含取代基团的9，9-二芳基芴聚合物材料是一种全新的聚合物材料，具有如下通式结构：Technical solution: The 9,9-diarylfluorene polymer material containing substituent groups at the 4-position of the present invention is a brand new polymer material with the following general structure:

聚合物材料I

Polymer I

式中：R出现时相同或者不同，并为氢或具有1至22个碳原子的直链、支链或者环状烷基链以及烷氧基链；Ar、Ar₁、Ar₂为含芳烃共轭结构单元，x为1～10中的数字，y为0～30中的数字，n为1～300中的数字。  其中，R-Ar₂优选如下列结构中的一种：In the formula: R appear the same or different, and are hydrogen or linear, branched or cyclic alkyl chains and alkoxy chains with 1 to 22 carbon atoms; Ar, Ar₁ and Ar₂ are aromatic hydrocarbon-containing co- Yoke structural unit, x is a number from 1 to 10, y is a number from 0 to 30, and n is a number from 1 to 300. Among them, R-Ar₂ is preferably one of the following structures:

Ar₁优选如下列结构中的一种：Ar₁ is preferably one of the following structures:

Ar优选如下列结构中的一种：Ar is preferably one of the following structures:

在4位含取代基团的9，9-二芳基芴聚合物材料中，R-Ar₂、Ar₁、Ar基团改变时化合物的性质相同或者不同；In the 9,9-diarylfluorene polymer material containing substituent groups at the 4-position, the properties of the compounds are the same or different when the R-Ar₂ , Ar₁ , and Ar groups are changed;

当聚合物材料I中Ar₂为氢且y为0时，具有如下结构：When Ar in polymer material I is_hydrogen and y is 0, it has the following structure:

聚合物材料II

Polymer Materials II

当聚合物材料I中R为辛基，Ar₂为氢，Ar₁为苯基，Ar为螺二芴、9，9-二苯基芴、螺二芴氧杂蒽、苯基或芘，x为1且y为0或1时，具有为如下结构：When R in the polymer material I is octyl, Ar₂ is hydrogen, Ar₁ is phenyl, Ar is spirobifluorene, 9,9-diphenylfluorene, spirobifluorene xanthene, phenyl or pyrene, x When it is 1 and y is 0 or 1, it has the following structure:

聚合物材料III               聚合物材料IV               聚合物材料VPolymer Material III Polymer Material IV Polymer Material V

聚合物材料VI                聚合物材料VII              聚合物材料VIIIPolymer Material VI Polymer Material VII Polymer Material VIII

在4位含有取代基团的9，9-二芳基芴聚合物材料的制备方法中，关键通过以格式反应进行后修饰步骤，以聚合物材料III为例，反应具体如下：In the preparation method of the 9,9-diarylfluorene polymer material containing substituent groups at the 4-position, the post-modification step is carried out mainly through the Grignard reaction. Taking the polymer material III as an example, the reaction is as follows:

                                                        聚合物材料IIIPolymer Material III

其反应条件具体是通过：Its reaction condition is specifically through:

步骤(1)拜耳-维立格氧化重排反应制得芴酮的内酯，  具体为2，7-二溴芴酮在三氟乙酸和过碳酸钠的条件下室温反应48小时；Step (1) Bayer-Villiger oxidative rearrangement reaction to prepare lactone of fluorenone, specifically 2,7-dibromofluorenone reacted at room temperature under the conditions of trifluoroacetic acid and sodium percarbonate for 48 hours;

步骤(2)格式反应制得二醇，具体为芴酮的内酯与三倍量的溴苯的格氏试剂反应，溶剂为甲苯，反应时间3小时；Step (2) Grignard reaction to obtain diol, specifically the reaction of the lactone of fluorenone with the Grignard reagent of three times the amount of bromobenzene, the solvent is toluene, and the reaction time is 3 hours;

步骤(3)烷基取代反应，具体为制得的二醇与一倍当量的1-溴辛烷在70℃，K₂CO₃条件下反应24小时；Step (3) alkyl substitution reaction, specifically reacting the prepared diol with one equivalent of 1-bromooctane at 70°C and K₂ CO₃ for 24 hours;

步骤(4)付-克反应制得聚合单体，具体为上步产物在室温下，在三氟化硼-乙醚催化条件下反应24小时制得。Step (4) The Friedel-Crafts reaction to obtain polymerized monomers, specifically, the product of the previous step was prepared by reacting for 24 hours under the catalytic conditions of boron trifluoride-ether at room temperature.

步骤(5)Suzuki偶联反应将单体与其硼酸酯聚合，具体为单体与其硼酸酯比例为1∶1，钯催化剂1-5mol％，溶剂四氢呋喃/甲苯，温度90℃，避光反应48小时。Step (5) Suzuki coupling reaction to polymerize the monomer and its borate, specifically the ratio of the monomer to its borate is 1:1, the palladium catalyst is 1-5mol%, the solvent tetrahydrofuran/toluene, the temperature is 90°C, and the reaction is protected from light 48 hours.

有益效果：通过元素分析、红外光谱(FTIR)、核磁共振(NMR)、色质联机(GCMS)、基质辅助激光解析时间飞行质谱(MALDI-TOF-MS)、凝胶色谱(GPC)表征了高聚物材料结构，通过热重分析和差热分析测试了材料的热稳定性，通过循环伏安法表征了它们的电化学性质。Beneficial effects: characterized by elemental analysis, infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), chromatography-mass on-line (GCMS), matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS), and gel chromatography (GPC) The structure of the polymer materials, the thermal stability of the materials were tested by thermogravimetric analysis and differential thermal analysis, and their electrochemical properties were characterized by cyclic voltammetry.

其中该类材料的热重分析和差热分析测试，表现出了良好的热稳定性；循环伏安法表征的电化学性质表明氧化电势没有明显改变，保持了9，9-二芳基芴良好的电致发光能力。因此，该类材料可以作为高效的稳定蓝光主体材料。Among them, the thermogravimetric analysis and differential thermal analysis tests of this type of material showed good thermal stability; the electrochemical properties characterized by cyclic voltammetry showed that the oxidation potential did not change significantly, and the good stability of 9,9-diaryl fluorene was maintained. electroluminescence capability. Therefore, this type of material can be used as an efficient and stable blue light host material.

在此基础上，设计了初步的电致发光器件评价4位含有取代基团的9，9-二芳基芴聚合物材料的发光性能。其中器件的结构为透明阳极/发光层/电子注入层/阴极，其中4位含有取代基团的9，9-二芳基芴聚合物层通过溶液旋涂或喷墨打印方式制备、阴极通过真空镀膜技术制备。实验结果表明：这些4位含有取代基团的9，9-二芳基芴聚合物显示了高效的蓝光发射性能。On this basis, a preliminary electroluminescent device was designed to evaluate the luminescent properties of 9,9-diarylfluorene polymer materials containing substituent groups at the 4-position. The structure of the device is transparent anode/luminescent layer/electron injection layer/cathode, wherein the 9,9-diarylfluorene polymer layer containing substituent groups at the 4-position is prepared by solution spin coating or inkjet printing, and the cathode is prepared by vacuum Coating technology preparation. The experimental results show that these 9,9-diarylfluorene polymers containing substituent groups at the 4-position exhibit high-efficiency blue light emission properties.

本发明的主要优点在于：The main advantages of the present invention are:

1.合成步骤简单、条件温和；1. The synthesis steps are simple and the conditions are mild;

2.保持了高热稳定性和玻璃化温度。2. Maintain high thermal stability and glass transition temperature.

附图说明Description of drawings

图1.2，7-二溴-4-辛氧基-9，9-二苯基芴MS谱图。Figure 1. MS spectrum of 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene.

图2.1，1’-(4-(辛氧基)-9，9-二苯基-2，7-二基)二芘的荧光吸收-发射图。Figure 2. Fluorescence absorption-emission diagram of 1,1'-(4-(octyloxy)-9,9-diphenyl-2,7-diyl)bipyrene.

具体实施方式Detailed ways

为了更好地理解本发明专利的内容，下面通过具体的实例来进一步说明本发明的技术方案。但这些实施实例并不限制本发明。In order to better understand the content of the patent of the present invention, the technical solution of the present invention will be further illustrated through specific examples below. However, these implementation examples do not limit the present invention.

该材料的重复单元之一是4位含有取代基团的二芳基芴材料，该材料具有如下通式结构：One of the repeating units of this material is a diaryl fluorene material containing substituent groups at the 4-position, which has the following general structure:

聚合物材料I

Polymer I

式中：R出现时相同或者不同，并为氢或具有1至22个碳原子的直链、支链、环状烷基链或者烷氧基链；Ar、Ar₁、Ar₂为含芳烃共轭结构单元，x为1～10中的数字，y为0～30中的数字，n为1～300中的数字。In the formula: R appears the same or different, and is hydrogen or a straight chain, branched chain, cyclic alkyl chain or alkoxy chain with 1 to 22 carbon atoms; Ar, Ar₁ , Ar₂ are aromatic hydrocarbon-containing co- Yoke structural unit, x is a number from 1 to 10, y is a number from 0 to 30, and n is a number from 1 to 300.

实施例1、聚(4-辛氧基-9，9-二苯基芴)Embodiment 1, poly(4-octyloxy-9,9-diphenylfluorene)

Poly(4-(octyloxy)-9，9-diphenyl-9H-fluorene)Poly(4-(octyloxy)-9, 9-diphenyl-9H-fluorene)

6氢-3，8-二溴苯并吡喃-6-酮6H-3,8-Dibromochromen-6-one

3，8-dibromo-6H-benzo[c]chromen-6-one3,8-dibromo-6H-benzo[c]chromen-6-one

实验步骤：取2，7-二溴芴酮2g(5.92mmol)，三氟乙酸11.83ml混合在二颈烧瓶中。在冰水浴的条件下，每隔10分钟加入Na₂CO₄ 0.25g，共五次。恢复到室温，搅拌48小时。取40ml冰水淬灭反应，用二氯甲烷(3×30ml)萃取。10％的NaHCO3洗涤，干燥旋蒸，石油醚∶二氯甲烷混合溶剂(3∶1)硅胶柱纯化，得到白色的固体(产率为70％)。Experimental procedure: 2 g (5.92 mmol) of 2,7-dibromofluorenone and 11.83 ml of trifluoroacetic acid were mixed in a two-necked flask. Under the condition of an ice-water bath, 0.25 g of Na₂ CO₄ was added every 10 minutes, five times in total. Return to room temperature and stir for 48 hours. The reaction was quenched with 40ml of ice water and extracted with dichloromethane (3×30ml). Washed with 10% NaHCO3, dried and rotary evaporated, and purified on a silica gel column with a mixed solvent of petroleum ether:dichloromethane (3:1) to obtain a white solid (yield 70%).

2′-(羟基二苯基甲基)-4，4′-二溴联苯-2-醇2'-(Hydroxydiphenylmethyl)-4,4'-dibromobiphenyl-2-ol

4，4′-dibromo-2′-(hydroxydiphenylmethyl)biphenyl-2-ol4,4'-dibromo-2'-(hydroxydiphenylmethyl)biphenyl-2-ol

实验步骤：取溴-苯(15mmol)与镁(0.36g，15mmol)反应生成格氏试剂，与溶于100ml的甲苯的3，8-二溴-6氢苯并吡喃-6-酮(3mmol)在125℃反应3小时，最后加入饱和色NH₄Cl将格氏盐转化为叔醇。反应完毕后，二氯甲烷萃取，干燥旋蒸，石油醚∶二氯甲烷混合溶剂(1∶1)硅胶柱纯化，得到白色的固体(产率为97.5％)。Experimental procedure: get bromo-benzene (15mmol) and magnesium (0.36g, 15mmol) to react and generate Grignard reagent, and dissolve 3,8-dibromo-6 hydrogen chromen-6-ketone (3mmol) in the toluene of 100ml ) was reacted at 125°C for 3 hours, and finally saturated color NH₄ Cl was added to convert the Grignard salt into a tertiary alcohol. After the reaction was completed, the mixture was extracted with dichloromethane, dried and rotary evaporated, and purified on a silica gel column with a mixed solvent of petroleum ether:dichloromethane (1:1) to obtain a white solid (97.5% yield).

(4，4’-二溴-2(2’-辛氧基联苯)基)二苯基甲醇(4,4'-Dibromo-2(2'-octyloxybiphenyl)yl)diphenylmethanol

(4，4′-dibromo-2′-(octyloxy)biphenyl-2-yl)diphenylmethanol(4,4′-dibromo-2′-(octyloxy)biphenyl-2-yl)diphenylmethanol

实验步骤：取干燥的两口烧瓶，用铝箔纸封闭避光，将溶于DMF中的2′-(羟基二苯基甲基)-4，4′-二溴联苯-2-醇加入其中。将固体K₂CO₃加入到二口烧瓶中，抽真空。70℃温度下，将1-溴辛烷加入到其中。反应24h。加入1M盐酸淬灭反应，乙酸乙酯萃取，干燥旋蒸，石油醚∶二氯甲烷混合溶剂(3∶1)硅胶柱纯化，得到白色的固体(产率为75％)。Experimental procedure: take a dry two-necked flask, seal it with aluminum foil to avoid light, and add 2'-(hydroxydiphenylmethyl)-4,4'-dibromobiphenyl-2-ol dissolved in DMF into it. Add solid K₂ CO₃ into the two-necked flask, and vacuum it. At a temperature of 70°C, 1-bromooctane was added thereto. Reaction 24h. The reaction was quenched by adding 1M hydrochloric acid, extracted with ethyl acetate, dried and rotary evaporated, and purified on a silica gel column with a mixed solvent of petroleum ether:dichloromethane (3:1) to obtain a white solid (yield 75%).

2，7-二溴-4-辛氧基-9，9-二苯基芴2,7-Dibromo-4-octyloxy-9,9-diphenylfluorene

2，7-dibromo-4-(octyloxy)-9，9-diphenyl-9H-fluorene2,7-dibromo-4-(octyloxy)-9,9-diphenyl-9H-fluorene

实验步骤：取干燥的两口烧瓶，将溶于二氯甲烷(10ml)中的(4，4’-二溴-2(2’-辛氧基联苯)基)二苯基甲醇加入其中。将三氟化硼-乙醚加入到恒压滴液漏斗中，缓慢滴加到两口烧瓶中，室温下反应12h。加入过量的乙醇水的混合溶剂(1∶1)淬灭反应，二氯甲烷萃取，干燥旋蒸，石油醚∶二氯甲烷混合溶剂(3∶1)硅胶柱纯化，得到白色的固体(产率为97％)。Experimental procedure: Take a dry two-necked flask, and add (4,4'-dibromo-2(2'-octyloxybiphenyl)yl)diphenylmethanol dissolved in dichloromethane (10ml) into it. Boron trifluoride-ether was added to the constant pressure dropping funnel, slowly added dropwise to the two-necked flask, and reacted at room temperature for 12 hours. Add excess ethanol water mixed solvent (1: 1) to quench the reaction, dichloromethane extraction, drying rotary evaporation, sherwood oil: dichloromethane mixed solvent (3: 1) silica gel column purification, to obtain a white solid (yield was 97%).

聚(4-辛氧基-9，9-二苯基芴)Poly(4-octyloxy-9,9-diphenylfluorene)

Poly(4-(octyloxy)-9，9-diphenyl-9H-fluorene)Poly(4-(octyloxy)-9, 9-diphenyl-9H-fluorene)

实验步骤：取2，7-二溴-4-辛氧基-9，9-二苯基芴(0.302g，0.5mmol，1equiv)和9，9-螺二芴-2，7-二硼酸丁基酯(0.307g，0.5mmol，1equiv)混合溶解于20ml甲苯和四氢呋喃的混合溶剂中，加入催化剂Pd(PPh₃)₄(1-5mol％)。避光通氮气，再加入K₂CO₃(1mL，2mol/L，2equiv.)，在90℃的条件下反应48小时，反应后加入水，使用CHCl₃萃取，干燥旋蒸浓缩，投入到100mL的甲醇中。收集得到的固体物在甲醇中萃取提纯3天，重新沉淀在甲醇中，得到粉末状产品0.335g。GPC：M_n＝28 210；PDI＝2.2。Experimental procedure: Take 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene (0.302g, 0.5mmol, 1equiv) and 9,9-spirobifluorene-2,7-diboronic acid butyl The base ester (0.307 g, 0.5 mmol, 1 equiv) was mixed and dissolved in 20 ml of a mixed solvent of toluene and tetrahydrofuran, and the catalyst Pd(PPh₃ )₄ (1-5 mol%) was added. Protect from light and pass nitrogen, then add K₂ CO₃ (1mL, 2mol/L, 2equiv.), react at 90°C for 48 hours, add water after the reaction, extract with CHCl₃ , dry and concentrate by rotary evaporation, and put into 100mL in methanol. The collected solid was extracted and purified in methanol for 3 days, and reprecipitated in methanol to obtain 0.335 g of a powdery product. GPC:_Mn = 28 210; PDI = 2.2.

实施例2、聚-{[2，7-(9，9-螺二芴)]-2，7-[4-(辛氧基)-9，9-二苯基-9H-芴]}Example 2, poly-{[2,7-(9,9-spirobifluorene)]-2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]}

poly-{[2，7-(9，9’-spirobi[fluorene])]-2，7-[4-(octyloxy)-9，9-diphenyl-9H-fluorene]}poly-{[2,7-(9,9'-spirobi[fluorene])]-2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]}

实验步骤：取2，7-二溴-4-辛氧基-9，9-二苯基芴(0.302g，0.5mmol，1equiv)和9，9-螺二芴-2，7-二硼酸丁基酯(0.242g，0.5mmol，1equiv)混合溶解于20ml甲苯和四氢呋喃的混合溶剂中，加入催化剂Pd(PPh₃)₄(1-5mol％)。避光通氮气，再加入K₂CO₃(1mL，2mol/L，2equiv.)，在90℃的条件下反应48小时，反应后加入水，使用CHCl₃萃取，干燥旋蒸浓缩，投入到100mL的甲醇中。收集得到的固体物在甲醇中萃取提纯3天，重新沉淀在甲醇中，得到粉末状产品0.278g。GPC：M_n＝17 250；PDI＝2.5。Experimental procedure: Take 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene (0.302g, 0.5mmol, 1equiv) and 9,9-spirobifluorene-2,7-diboronic acid butyl The base ester (0.242 g, 0.5 mmol, 1 equiv) was mixed and dissolved in 20 ml of a mixed solvent of toluene and tetrahydrofuran, and the catalyst Pd(PPh₃ )₄ (1-5 mol%) was added. Protect from light and pass nitrogen, then add K₂ CO₃ (1mL, 2mol/L, 2equiv.), react at 90°C for 48 hours, add water after the reaction, extract with CHCl₃ , dry and concentrate by rotary evaporation, and put into 100mL in methanol. The collected solid was extracted and purified in methanol for 3 days, and reprecipitated in methanol to obtain 0.278 g of a powdery product. GPC:_Mn = 17 250; PDI = 2.5.

实施例3、聚-{[2，7-(9，9-二苯基-9H-芴)]-2，7-[4-(辛氧基)-9，9-二苯基-9H-芴]}poly-{[2，7-(9，9-diphenyl-9H-fluorene)]-2，7-[4-(octyloxy)-9，9-diphenyl-9H-fluorene]}Example 3, poly-{[2,7-(9,9-diphenyl-9H-fluorene)]-2,7-[4-(octyloxy)-9,9-diphenyl-9H- Fluorene]}poly-{[2,7-(9,9-diphenyl-9H-fluorene)]-2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]}

实验步骤：取2，7-二溴-4-辛氧基-9，9-二苯基芴(0.302g，0.5mmol，1equiv)和9，9-二苯基芴-2，7-二硼酸丁基酯(0.242g，0.5mmol，1equiv)混合溶解于20ml甲苯和四氢呋喃的混合溶剂中，加入催化剂Pd(PPh₃)₄(1-5mol％)。避光通氮气，再加入K₂CO₃(1mL，2mol/L，2equiv.)，在90℃的条件下反应48小时，反应后加入水，使用CHCl₃萃取，干燥旋蒸浓缩，投入到100mL的甲醇中。收集得到的固体物在甲醇中萃取提纯3天，重新沉淀在甲醇中，得到粉末状产品0.271g。GPC：M_n＝19 550；PDI＝1.9。Experimental procedure: take 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene (0.302g, 0.5mmol, 1equiv) and 9,9-diphenylfluorene-2,7-diboronic acid Butyl ester (0.242 g, 0.5 mmol, 1 equiv) was mixed and dissolved in 20 ml of a mixed solvent of toluene and tetrahydrofuran, and the catalyst Pd(PPh₃ )₄ (1-5 mol%) was added. Protect from light and pass nitrogen, then add K₂ CO₃ (1mL, 2mol/L, 2equiv.), react at 90°C for 48 hours, add water after the reaction, extract with CHCl₃ , dry and concentrate by rotary evaporation, and put into 100mL in methanol. The collected solid was extracted and purified in methanol for 3 days, and reprecipitated in methanol to obtain 0.271 g of a powdery product. GPC:_Mn = 19 550; PDI = 1.9.

实施例4、聚-{[2，7-螺[芴-9，9’-氧杂蒽]-[2，7-[4-(辛氧基)-9，9-二苯基-9H-芴]]}Example 4, poly-{[2,7-spiro[fluorene-9,9'-oxanthene]-[2,7-[4-(octyloxy)-9,9-diphenyl-9H- fluorene]]}

poly-{[2，7-(spiro[fluorene-9，9′-xanthene])]-2，7-[4-(octyloxy)-9，9-diphenyl-9H-fluorene]}poly-{[2,7-(spiro[fluorene-9,9′-xanthene])]-2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]}

实验步骤：取2，7-二溴-4-辛氧基-9，9-二苯基芴(0.302g，0.5mmol，1equiv)和螺芴-9，9’-氧杂蒽-2，7-二硼酸丁基酯(0.250g，0.5mmol，1equiv)混合溶解于20ml甲苯和四氢呋喃的混合溶剂中，加入催化剂Pd(PPh₃)₄(1-5mol％)。避光通氮气，再加入K₂CO₃(1mL，2mol/L，2equiv.)，在90℃的条件下反应48小时，反应后加入水，使用CHCl₃萃取，干燥旋蒸浓缩，投入到100mL的甲醇中。收集得到的固体物在甲醇中萃取提纯3天，重新沉淀在甲醇中，得到粉末状产品0.292g。GPC：M_n＝20 430；PDI＝2.1。Experimental procedure: Take 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene (0.302g, 0.5mmol, 1equiv) and spirofluorene-9,9'-oxanthene-2,7 - Butyl diboronate (0.250 g, 0.5 mmol, 1 equiv) was mixed and dissolved in 20 ml of a mixed solvent of toluene and tetrahydrofuran, and a catalyst Pd(PPh₃ )₄ (1-5 mol%) was added. Protect from light and pass nitrogen, then add K₂ CO₃ (1mL, 2mol/L, 2equiv.), react at 90°C for 48 hours, add water after the reaction, extract with CHCl₃ , dry and concentrate by rotary evaporation, and put into 100mL in methanol. The collected solid was extracted and purified in methanol for 3 days, and reprecipitated in methanol to obtain 0.292 g of a powdery product. GPC:_Mn = 20 430; PDI = 2.1.

实施例5、聚-{[1，4-苯-[2，7-[4-(辛氧基)-9，9-二苯基-9H-芴]]}Example 5, poly-{[1,4-benzene-[2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]]}

poly-{[1，4-benzene]-2，7-[4-(octyloxy)-9，9-diphenyl-9H-fluorene]}poly-{[1,4-benzene]-2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]}

实验步骤：取2，7-二溴-4-辛氧基-9，9-二苯基芴(0.302g，0.5mmol，1equiv)和苯-1，4-二硼酸丁基酯(0.123g，0.5mmol，1equiv)混合溶解于20ml甲苯和四氢呋喃的混合溶剂中，加入催化剂Pd(PPh₃)₄(1-5mol％)。避光通氮气，再加入K₂CO₃(1mL，2mol/L，2equiv.)，在90℃的条件下反应48小时，反应后加入水，使用CHCl₃萃取，干燥旋蒸浓缩，投入到100mL的甲醇中。收集得到的固体物在甲醇中萃取提纯3天，重新沉淀在甲醇中，得到粉末状产品0.201g。GPC：M_n＝25 120；PDI＝2.3。Experimental procedure: Take 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene (0.302g, 0.5mmol, 1equiv) and benzene-1,4-diboronic acid butyl ester (0.123g, 0.5 mmol, 1 equiv) were mixed and dissolved in 20 ml of a mixed solvent of toluene and tetrahydrofuran, and the catalyst Pd(PPh₃ )₄ (1-5 mol%) was added. Protect from light and pass nitrogen, then add K₂ CO₃ (1mL, 2mol/L, 2equiv.), react at 90°C for 48 hours, add water after the reaction, extract with CHCl₃ , dry and concentrate by rotary evaporation, and put into 100mL in methanol. The collected solid was extracted and purified in methanol for 3 days, and reprecipitated in methanol to obtain 0.201 g of a powdery product. GPC:_Mn = 25 120; PDI = 2.3.

实施例6、聚-{[1，6-芘-[ 2，7-[4-(辛氧基)-9，9-二苯基-9H-芴]]}Embodiment 6, poly-{[1,6-pyrene-[2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]]}

poly-{[1，6-pyrene]-2，7-[4-(octyloxy)-9，9-diphenyl-9H-fluorene]}poly-{[1,6-pyrene]-2,7-[4-(octyloxy)-9,9-diphenyl-9H-fluorene]}

实验步骤：取2，7-二溴-4-辛氧基-9，9-二苯基芴(0.302g，0.5mmol，1equiv)和芘-1，6-二硼酸丁基酯(0.185g，0.5mmol，1equiv)混合溶解于20ml甲苯和四氢呋喃的混合溶剂中，加入催化剂Pd(PPh₃)₄(1-5mol％)。避光通氮气，再加入K₂CO₃(1mL，2mol/L，2equiv.)，在90℃的条件下反应48小时，反应后加入水，使用CHCl₃萃取，干燥旋蒸浓缩，投入到100mL的甲醇中。收集得到的固体物在甲醇中萃取提纯3天，重新沉淀在甲醇中，得到粉末状产品0.235g。GPC：M_n＝19 350；PDI＝2.1。Experimental procedure: Take 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene (0.302g, 0.5mmol, 1equiv) and pyrene-1,6-diboronic acid butyl ester (0.185g, 0.5 mmol, 1 equiv) were mixed and dissolved in 20 ml of a mixed solvent of toluene and tetrahydrofuran, and the catalyst Pd(PPh₃ )₄ (1-5 mol%) was added. Protect from light and pass nitrogen, then add K₂ CO₃ (1mL, 2mol/L, 2equiv.), react at 90°C for 48 hours, add water after the reaction, extract with CHCl₃ , dry and concentrate by rotary evaporation, and put into 100mL in methanol. The collected solid was extracted and purified in methanol for 3 days, and reprecipitated in methanol to obtain 0.235 g of a powdery product. GPC:_Mn = 19 350; PDI = 2.1.

实施例7、1，1’-(4-(辛氧基)-9，9-二苯基-9氢-2，7-二基)二芘Example 7, 1,1'-(4-(octyloxy)-9,9-diphenyl-9 hydrogen-2,7-diyl)bipyrene

1，1′-(4-(octyloxy)-9，9-diphenyl-9H-fluorene-2，7-diyl)dipyrene1,1'-(4-(octyloxy)-9,9-diphenyl-9H-fluorene-2,7-diyl)dipyrene

实验步骤：取2，7-二溴4-辛氧基-9，9-二苯基芴(0.302g，0.5mmol，1equiv)和1-芘硼酸丁基酯(0.314g，1.1mmol，2.2equiv)混合溶解于20ml甲苯和四氢呋喃的混合溶剂中，加入催化剂Pd(PPh3)4(1-5mol％)。避光通氮气，再加入K2CO3(1mL，2mol/L，2equiv.)，在90℃的条件下反应48小时，反应后加入水，使用CHCl₃萃取，干燥旋蒸，石油醚硅胶柱纯化，得到固体1，1’-(4-(辛氧基)-9，9-二苯基-9氢-2，7-二基)二芘(0.324g，73％)。Experimental procedure: Take 2,7-dibromo-4-octyloxy-9,9-diphenylfluorene (0.302g, 0.5mmol, 1equiv) and 1-pyrene butyl borate (0.314g, 1.1mmol, 2.2equiv ) were mixed and dissolved in a mixed solvent of 20ml toluene and tetrahydrofuran, and a catalyst Pd(PPh3)4(1-5mol%) was added. Protected from light and vented with nitrogen, then added K2CO3 (1mL, 2mol/L, 2equiv.), reacted at 90°C for 48 hours, added water after the reaction, extracted with_CHCl3 , dried and rotary evaporated, and purified on a petroleum ether silica gel column to obtain Solid 1,1'-(4-(octyloxy)-9,9-diphenyl-9hydro-2,7-diyl)bipyrene (0.324 g, 73%).

实施例8、聚(二芳基芴)半导体材料的光致发光光谱测定：Embodiment 8, the photoluminescence spectrum measurement of poly(diarylfluorene) semiconductor material:

把产物配成准确的1μM的三氯甲烷稀溶液，并通过氩气冲洗去掉氧气。采用岛津UV-3150紫外可见光谱仪和RF-530XPC荧光光谱仪进行吸收光谱和发射光谱测定，光致发光光谱是在紫外吸收的最大吸收波长下测定的。固体膜通过溶液旋涂成膜技术制备，膜厚为300nm。The product was made into a precise 1 μM dilute solution in chloroform and flushed with argon to remove oxygen. Shimadzu UV-3150 ultraviolet-visible spectrometer and RF-530XPC fluorescence spectrometer were used to measure the absorption spectrum and emission spectrum, and the photoluminescence spectrum was measured at the maximum absorption wavelength of ultraviolet absorption. The solid film was prepared by solution spin-coating film forming technology, and the film thickness was 300nm.

实施例9、聚(二芳基芴)半导体材料的热分析测定：Embodiment 9, thermal analysis and determination of poly(diarylfluorene) semiconductor material:

热重分析(TGA))在岛津公司(Shimadzu)DTG-60H热重分析仪上进行，加热扫描速度为10℃/min，并且氮气流速为20cm3/min。示差扫描量热分析(DSC)在岛津公司(Shimadzu)DSC-60A测试仪上进行，样品首先以10℃/min的速度加热到样品分解温度低十度的状态，然后，在液氮条件下降温回到开始温度，同样第二次以10℃/min的速度加热升温扫描。Thermogravimetric analysis (TGA)) was performed on a Shimadzu DTG-60H thermogravimetric analyzer with a heating scan rate of 10°C/min and a nitrogen flow rate of 20 cm3/min. Differential scanning calorimetry (DSC) was carried out on a Shimadzu DSC-60A tester. The sample was first heated at a rate of 10°C/min to a state ten degrees lower than the decomposition temperature of the sample, and then, under liquid nitrogen conditions The temperature was lowered back to the starting temperature, and the temperature was scanned at a rate of 10°C/min for the second time.

实施例10、聚(二芳基芴)半导体材料的电化学测定：Embodiment 10, the electrochemical determination of poly(diarylfluorene) semiconductor material:

电化学循环伏安(CV)实验在一个Eco Chemie B.V.AUTOLAB potentiostat伏安分析仪上完成，采用三电极体系，包括铂碳工作电极、Ag/Ag⁺为参比电极、铂丝为对电极。氧化过程采用二氯甲烷作为溶剂，还原过程采用四氢呋喃作为溶剂，六氟磷四丁基铵(Bu₄N⁺PF₆^-)作为支持电解质，浓度为0.1M。所有的电化学实验都是在常温条件氮气气氛下进行，电压扫描速度0.1V/s。使用二茂铁(FOC)作为基准，通过测量氧化和还原过程的开始电压可以计算材料的HOMO和LUMO能级。Electrochemical cyclic voltammetry (CV) experiments were performed on an Eco Chemie BVAUTOLAB potentiostat voltammetry analyzer using a three-electrode system, including a platinum-carbon working electrode, Ag/Ag⁺ as a reference electrode, and a platinum wire as a counter electrode. Dichloromethane was used as a solvent in the oxidation process, tetrahydrofuran was used as a solvent in the reduction process, tetrabutylammonium hexafluorophosphine (Bu₄ N⁺ PF₆^- ) was used as a supporting electrolyte, and the concentration was 0.1M. All electrochemical experiments were carried out under nitrogen atmosphere at room temperature, and the voltage scanning speed was 0.1V/s. Using ferrocene (FOC) as a benchmark, the HOMO and LUMO energy levels of the material can be calculated by measuring the onset voltages of the oxidation and reduction processes.

Claims (7)

1. one kind 4 contain 9 of substituted radical, and 9-Diarylfluorene polymer materials, one of repeating unit that it is characterized in that this material are 4 diaryl fluorene materials that contain substituted radical, and this material has following formula:

In the formula: identical or different when R occurs, and be hydrogen or straight chain, side chain, cyclic alkyl chain or the oxyalkyl chain with 1 to 22 carbon atom; Ar, Ar₁, Ar₂For containing aromatic hydrocarbons conjugated structure unit, x is the numeral in 1～10, and y is the numeral in 0～30, and n is the numeral in 1～300.

2. 4 according to claim 1 contain 9 of substituted radical, and 9-Diarylfluorene polymer materials is characterized in that described R-Ar₂Be preferably as follows a kind of in the array structure:

Ar₁Be preferably as follows a kind of in the array structure:

Ar is preferably as follows a kind of in the array structure:

3. 4 according to claim 1 and 2 contain 9 of substituted radical, and 9-Diarylfluorene polymer materials is characterized in that among 4 diaryl fluorene conjugated polymer material I that contain substituted radical Ar₂For hydrogen and y are, have following structure at 0 o'clock:

Polymer materials II

4. 4 according to claim 1 and 2 contain 9 of substituted radical, and 9-Diarylfluorene polymer materials is characterized in that among 4 diaryl fluorene conjugated polymer material I that contain substituted radical, when R is an octyl group, and Ar₂Be hydrogen, Ar₁Be phenyl, Ar is spiral shell two fluorenes, 9.9-diphenylfluorene, spiral shell two fluorenes xanthenes, phenyl or pyrene, x be 1 and y be 0 or 1 o'clock, have and be following structure:

Polymer materials III polymer materials IV polymer materials V

Polymer materials VI polymer materials VII polymer materials VIII.

5. one kind 4 as claimed in claim 1 contain 9 of substituted radical, the preparation method of 9-Diarylfluorene polymer materials, it is characterized in that 4 diaryl fluorene conjugated polymer material I that contain substituted radical contain 9 of substituted radical by 4,9-diaryl fluorene monomer and aryl monomer carry out the reaction of Suzuki condensation polymerization and obtain, and concrete reaction expression is as follows:

Wherein, when dibromo 4 replacements 9, the two boric acid esters of 9-diaryl fluorene and 4 substituted diaryl fluorenes carry out the Suzuki polyreaction and obtain alternative polymer materials I:

Wherein the Suzuki polyreaction is meant palladium catalysis biphenyl boric acid and dibromo spiral shell thiophene fluorenes generation carbon-carbon bond linked reaction, and reaction conditions is as follows: the consumption of palladium catalyst is 1 to 5mol%; Suitable solvent is low-pole or aprotic, polar organic solvent or its mixed solvent; Be reflected at 30 to 150 ℃ of temperature; Reaction times is 1 to 7 day.With polymer materials III is example, and concrete reaction conditions is as follows: get 2, and 7-two bromo-4-octyloxies-9,9-diphenylfluorene and 9,9-spiral shell two fluorenes-2,7-hypoboric acid butyl ester mixed dissolution add catalyst P d (PPh in the mixed solvent of 20ml toluene and tetrahydrofuran (THF)₃)₄Lucifuge is led to nitrogen, adds 2mol/L K again₂CO₃Solution, reaction is 48 hours under 90 ℃ condition, adds entry after the reaction, uses CHCl₃Extraction, drying is revolved inspissation and is contracted, and puts in the methyl alcohol of 100ml.The solids that collection obtains purification by liquid extraction 3 days in methyl alcohol is deposited in the methyl alcohol again, obtains powdery product.

6. one kind 4 as claimed in claim 5 contain 9 of substituted radical, the preparation method of 9-Diarylfluorene polymer materials, it is characterized in that 4 contain 9 of substituted radical, 9-diaryl fluorene monomer is reset laggard row format prepared in reaction by Bayer-Wei Lige and made, and is specific as follows:

Step 1: Bayer-Wei Lige oxidation rearrangement reaction makes the lactone of Fluorenone, is specially 2,7-dibromo fluorenone room temperature reaction 48 hours under the condition of trifluoroacetic acid and SPC-D;

Step 2: grignard reaction makes the tertiary alcohol, is specially the Grignard reagent reaction of the bromobenzene of the lactone of Fluorenone and triplication, and solvent is a toluene, 3 hours reaction times;

Step 3: alkyl substitution is specially the tertiary alcohol that makes and one times of normal 1-bromooctane at 70 ℃, K₂CO₃Reaction is 24 hours under the condition;

Step 4: friedel-crafts reaction makes polymerization single polymerization monomer, is specially the step product at room temperature, and reaction made in 24 hours under boron trifluoride-ether catalytic condition.

7. one kind 4 as claimed in claim 1 contain 9 of substituted radical, the application of 9-diaryl fluorene polymer materials, it is characterized in that being applied to LED device, wherein the structure of LED device is transparent anode/luminescent layer/electron injecting layer/negative electrode, wherein, 4 contain substituently 9, and 9-diaryl fluorene polymer materials is as luminescent layer.

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