CN100586981C - Silicon group-containing 1,4-phenylene vinylidene and its preparation method and application - Google Patents

Silicon group-containing 1,4-phenylene vinylidene and its preparation method and application Download PDF

Info

Publication number
CN100586981C
CN100586981C CN 200410068054 CN200410068054A CN100586981C CN 100586981 C CN100586981 C CN 100586981C CN 200410068054 CN200410068054 CN 200410068054 CN 200410068054 A CN200410068054 A CN 200410068054A CN 100586981 C CN100586981 C CN 100586981C
Authority
CN
Grant status
Grant
Patent type
Prior art keywords
alkyl
hours
benzene
reaction
containing
Prior art date
Application number
CN 200410068054
Other languages
Chinese (zh)
Other versions
CN1631931A (en )
Inventor
姚红兵
徐良衡
想 李
Original Assignee
徐良衡
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Abstract

The invention is the method for preparing 1,4- containing silicon silicon group (Si-PPV) and its application. Compared with the present technology which has complex equipment, low lightening efficiency and unsatisfying heat stability, the invention uses polymer 3 as the raw material, generates 4 which then has coupling reaction with 6, generating 7, and the acquiring the active monomer through mole without water existence, the active monomer is changed into Si-PPV through Gilch reaction. The polymer has outstanding film-making performance, heat stability and lightening efficiency.

Description

含硅基团的l,4-亚苯基亚乙烯基及其制备方法、应用 l silicon-containing group, 4-phenylene vinylene and its preparation method, application

发明领域 Field of the Invention

本发明公开了电场发光的高发光性能的一类含硅基团的1,4-亚苯基亚乙烯基,即Si 一PPV及其制备方法和应用。 Disclosed is an electroluminescence light-emitting characteristics of a class of 1,4-phenylene vinylene silicon-containing groups, i.e., Si-PPV and its preparation method and application. 该聚合物可用于发光器件、光电池、发光二极管等领域。 The polymer can be used in the field of light emitting devices, photovoltaic cells, light-emitting diodes. 发明背景 BACKGROUND OF THE INVENTION

自二十世纪九十年代开始至今,人们对聚合物电致发光有了更加深入的了解。 Since the 1990s and since then, people polymer electroluminescence have a more in-depth understanding. 电致发光是由电能转化为光能的过程,即载流子双注入式发光。 Electroluminescence is converted from electric energy into light energy process, i.e., the carrier dual injection type light emission. 与地极管发光具有基本相同的发光机理,因而它们也可以被看作是一种发光二极管:在外界电压的驱动下,由正极注入的空穴和由负极注入的电子分别传输到发光层并发生复合,从而释放出能量,再将能量传递给发光物质分子,使其受到激发,从基态跃迁到激发态,当受激分子从激发态回到基态时因辐射跃迁而产生发光现象。 And a ground electrode tube lighting have substantially the same light-emitting mechanism, so that they may be seen as a light-emitting diode: driven by the external voltage, the positive holes injected from the anode and electrons injected are transmitted to the light-emitting layer and recombination occurs, thereby releasing the energy, then the energy transmitted to the light-emitting substance molecules to be excited from the ground state to the excited state, when excited molecular state returns to a ground state from the excited due to radiative transitions to produce light emission phenomenon. 聚合物电致发光材料,因其挠曲性,易加工成型,不易结晶, 同时链状共轭聚合物是一维结构,其能带隙数值与可见光能量相当。 Polymer electroluminescent material, because of its flexibility, easy processing, easy crystallization, while the chain conjugated polymer is a one-dimensional structure, energy band gap values ​​comparable to visible light energy. 可溶性聚合物又具有优良的机械性能和良好的成膜性,成为目前电致发光领域研究的热点。 Soluble polymer and having excellent mechanical properties and good film-forming property, has become a hot research field of luminescence current electroluminescence of. 这类聚合物主要有: 聚乙炔(polyaR3etylene ), 聚吡咯(polypyttole ), 聚(3 —垸基噻吩) (Poly(3-alkylthiophene),P3AT),聚苯胺(polyaniline, PANi),聚对苯(poly(para-phenylenel), PPP),聚呋喃(polyfliran),聚苯乙炔(poly(para-phenylene-vinylene, PPV),聚荷(polyfluorene, PFO),聚乙烯咔唑(Poly(N-VinylR3arbazole),PVR3z)等半导电聚合物或者发光聚合物及其他们的衍生物或者共聚物,其中PPV及其衍生物是目前国际上研究和使用最多、效果最好的一类聚合物。含PPV结构的聚合物数不胜数。其中,人们研究较多的是,聚(1, 4一亚苯基亚乙烯基(即PPV)(JHBurroughs,DDR3.Bradley,ARBrown等,自然347,539(1990)); 聚(2—甲氧基一5— (2' —乙基己氧基)一1, 4—亚苯基亚乙烯基)即MEH—PPV (美国专利5189136); DMO-PPV; R3N-PPV; BR3HA-PPV; PDM-PPV; DMOP-PPV; P-PPV; BuEH-PPV; R3HEN-PPV等单一重复单元的聚合物,以及由不同重复单 Such polymers are: polyacetylene (polyaR3etylene), polypyrrole (polypyttole), poly (3 - alkyl with thiophene) (Poly (3-alkylthiophene), P3AT), polyaniline (polyaniline, PANi), polyparaphenylene ( poly (para-phenylenel), PPP), poly furan (polyfliran), polyphenylacetylene (poly (para-phenylene-vinylene, PPV), poly Netherlands (polyfluorene, PFO), polyvinyl carbazole (poly (N-VinylR3arbazole) , PVR3z) other semiconductive polymer or a light emitting polymers and their derivatives or a copolymer, wherein PPV and its derivatives is studied and used internationally most, the best class of polymers. containing PPV structure polymer numerous wherein many people study, poly (1, 4-phenylene vinylene (i.e. PPV) (JHBurroughs, DDR3.Bradley, ARBrown al., Nature 347, 539 (1990)); poly (2 - methoxy-5- (2 '- ethylhexyl oxy) -1, 4-phenylene vinylene) that is MEH-PPV (US Patent 5189136); DMO-PPV; R3N-PPV; BR3HA-PPV; PDM-PPV; DMOP-PPV; P-PPV; BuEH-PPV; polymer single repeating unit R3HEN-PPV and the like, as well as different repeating units 元,例如,恶二唑单元、薪及其改性单元、噻吩及其改性单元等与PPV单元共聚、接枝、縮聚、均聚等共聚物。 Element, e.g., oxadiazole, salary and modifying units, polythiophene and modifying unit or the like and PPV unit copolymerization, graft, polycondensation, homopolymerization of a copolymer.

对于发光聚合物材料的要求主要在于良好的发光效率和较好的热稳定性。 Requirements for the light emitting polymer material mainly good luminous efficiency and good thermal stability. 要提高材料的发光效率,从上面的发光原理看出,为使整个发光过程能够顺利地进行,需要电致发光器件满足一定内在的要求,包括载流子的有效注入,两种载流子的均衡传输以及激子能量的有效利用等方面。 To improve the luminous efficiency material, seen from the light-emitting principle above to ensure that the entire light emission process can be carried out smoothly, it is necessary electroluminescent device meet certain inherent requirements, including the carrier effective injection two carriers aspect of the equalized transmission and the effective use exciton energy and the like. 这样单一的PPV材料就不能满足其要求。 Such single PPV materials can not meet their requirements. 因此有人采用添加载流子传输层的方法,由于层间的缺陷及界面效应,影响了器件的性能,也增加了器件制作的复杂性。 Therefore, it was employed a method of adding a carrier transport layer, due to defects and interfacial effect between the layers, affecting the performance of the device, but also increases the complexity of device fabrication.

发明内容 SUMMARY

本发明的目的是提供一种成膜性好,发光效率高,热稳定性好,载流体注入及传输能力好的发绿光的聚合物及其制备方法、应用领域。 Object of the present invention is to provide a film-forming, high luminous efficiency, good thermal stability, the carrier fluid injection and transport capabilities good green emitting polymers and preparation method, applications.

本发明的一种含硅基团的PPV材料Si—PPV,其结构如下 PPV material Si-PPV one inventive silicon-containing group, the following structure

<formula>formula see original document page 5</formula> <Formula> formula see original document page 5 </ formula>

其中,R卜R2是H埂子,或者是d—Cu)的烷基、垸氧基,R3是CVC2o的垸基,n=3 一10000。 Wherein, R BU R2 is H ridge promoter, or d-Cu) alkyl, embankment group, R3 is CVC2o the embankment group, n = 3 a 10000.

本发明中,聚合物的分子量为10万一150万。 The present invention, the molecular weight of the polymer is 10 in case of 1.5 million. 本发明中,先合成含活性基团的聚合单体。 The present invention, the first synthetic polymeric monomer containing the reactive group.

其中Ri、 R2是氢原子,或者是C广do的烷基、垸氧基,R3是C广C20的直链烷基或 Wherein Ri, R2 is a hydrogen atom or a C wide do alkyl, embankment group, R3 is a C wide-C20 straight chain alkyl or

带侧链的烷基,X是卤素。 Alkyl sidechain, X is a halogen.

(1) 以无水四氢呋喃为溶剂,一70'C〜一80'C下与垸基锂反应1-10小时,得双锂代化合物,对二卤苯与垸基锂的摩尔比为1: (2—6); (1) in anhydrous tetrahydrofuran as a solvent, the reaction with alkyl with lithium 70'C~ a 80'C under 10 hours, double-lithio compound, the molar ratio of dihalogen benzene and alkyl with lithium was 1: (2-6);

(2) 上步双锂代化合物与一氯硅烷偶合反应,得对二硅垸基苯,反应温度一70'C〜一80 °C,时间l一5小时,然后在0.5—3小时内升温至室温下反应3 — 12小时,水洗、干燥、 减压蒸馏,得对二硅烷基苯,以对二卤苯计,对二卤苯与一氯硅烷的摩尔比为l: (2—8);(3) 对二硅垸基苯在无水条件下,以1,4一二氧六环或乙酸为溶剂,与多聚甲醛、卤化氢反应,经双卤甲基化得含活性的聚合单体2,5 — 二硅垸基对二卤甲基苯,反应温度为0 'C〜80'C,时间为3—48小时,对二硅垸基苯与多聚甲醛的摩尔比为1: (2—10),卤化氢在溶剂中的含量为30wtQ/。 (2) Step bis lithio compound is reacted with a chlorosilane coupling to afford p-silicon embankment benzene, the reaction temperature is a 70'C~ a 80 ° C, time l-five hours, then warmed within 0.5 to 3 hours the reaction temperature to room temperature 3--12 hours and washed with water, dried and distilled under reduced pressure to obtain p-Si benzene to p-halophenyl terms, the molar ratio of dihalogen benzene with a chlorosilane of l: (2-8) ; (3) p-silicon embankment benzene under anhydrous conditions, to 1,4-dioxane or acetic acid as the solvent, paraformaldehyde, hydrogen halide is reacted with, by double halomethylated obtained containing polymerization activity monomeric 2,5 - silicon alkyl with p-halo-methylbenzene, the reaction temperature is 0 'C~80'C, time is 3-48 hours, p-silicon embankment benzene molar ratio of paraformaldehyde to 1 : (2-10), the content of hydrogen halide in the solvent is 30wtQ /. 至饱和; To saturation;

含活性的聚合单体通过Gilch反应,得目标产物; Containing an active polymerized monomer by Gilch reaction, to give the desired product;

(4) 无水四氢呋喃为溶剂,在氮气保护下,以醇钠或醇钾为催化剂,在一70'C〜一8(TC 下聚合反应2—48小时,得Si-PPV目标产物,其中单体与催化剂的摩尔比为1: (3-10)。 (4) anhydrous tetrahydrofuran as a solvent under a nitrogen atmosphere to a sodium alkoxide or potassium alkoxide as the catalyst, the polymerization reaction 2-48 hours (the TC is a 70'C~ a 8 to give Si-PPV desired product, wherein the single the molar ratio of the body to catalyst of 1: (3-10).

各步反应流程如下: Each step reaction process is as follows:

R3 R2 R3 R2

R/ R3 R《 r3 R / R3 R "r3

上式中,X为卤素,THF为四氢呋喃,R!、 R2、 R3为垸基,溶剂为1,4一二氧六环或乙酸。 In the above formula, X is halogen, THF is tetrahydrofuran, R !, R2, R3 is alkyl with the solvent is 1,4-dioxane or acetic acid.

本发明聚合速度比较均匀,产物的分散度较小,平均分子量较大,所得材料的发光性能较好。 The polymerization rate of the present invention is relatively uniform, small dispersion product, large average molecular weight, preferably luminescent properties of the resulting material.

本发明中,烷基锂是含1-10个碳原子的垸基锂化合物,如正丁基锂,异辛基锂等。 The present invention, the alkyl lithium containing 1 to 10 carbon atoms, alkyl with a lithium compound such as n-butyllithium, iso-octyl lithium.

本发明中,对二卤苯的质量与溶剂之比为l克:(5-100毫升)。 The present invention, the ratio of mass to solvent-dihalobenzene is l g: (5-100 mL).

本发明中,聚合反应催化剂为含1一10个碳原子的醇钠或醇钾。 The present invention, the polymerization catalyst containing 1 to 10 alcoholic sodium or potassium alkoxide carbon atoms. 本发明中,单体与溶剂之比为l克:(50~-300毫升)。 The present invention, the ratio of monomer to solvent l grams: (50 ~ -300 mL).

本发明中,将聚合物溶解在四氢呋喃或甲苯中,浓度为0.1〜20mg/ml,得透明溶液后, 过滤除去杂质,室温下流延成膜至光刻好的阳极基体得到厚度均勾的薄膜,然后真空蒸镀铝作为阴极。 The present invention, the polymer is dissolved in tetrahydrofuran or toluene, at a concentration of 0.1~20mg / ml, the obtained clear solution was filtered to remove impurities, rt downstream cast film to a photolithography good anode substrate to give a film thickness of each hook, then vacuum evaporated aluminum as the cathode.

本发明中,聚合物溶液的浓度是5〜15mg/ml。 The present invention, the concentration of the polymer solution is 5~15mg / ml.

本发明中,聚合物溶解的溶剂是四氢呋喃。 The present invention, the polymer is dissolved in the solvent is tetrahydrofuran.

上述聚合物溶解时,可适当加热,提高效率。 When the above polymer is dissolved, it can be properly heated, to improve efficiency. 聚合物溶解后,可通过微米过滤器,一般0.1-5微米,以除去可能含有的不必要杂质。 After the dissolution of the polymer, it can be filtered through a micron filter, typically 0.1 to 5 microns, in order to remove unwanted impurities that may be contained. 然后在室温下通过旋转流延、浸涂流延、 下滴流延、喷墨打印或者其它以溶液为主体的成膜方式在基体,如玻璃、塑料、或者其它基体上形成光学可用的无针孔薄膜。 Then print or other film-forming manner in a solution mainly formed of the optical available needleless on a substrate, such as glass, plastic, or other substrate at room temperature by spin casting, dip casting, dripping casting, inkjet apertured films.

本发明中,Si-PPV制备电致发光器件的层次是:阳极基体/Si-PPV层/铝阴极。 The present invention, Si-PPV electrophotographic level electroluminescent devices are: an anode substrate / Si-PPV layer / aluminum cathode.

6最典型的是可选用已光刻好的ITO(玻璃)为阳极,将Si-PPV旋涂到ITO玻璃表面,然 6 is the most typical choice is photolithography good ITO (glass) as the anode, the Si-PPV spin-coated onto ITO glass surface, then

后真空蒸镀铝作为阴极。 After vacuum vapor deposition of aluminum as the cathode.

本发明中,制得的Si-PPV可以在发光器件领域应用。 The present invention, the resulting Si-PPV can be used in the field of the light emitting device.

本发明制得的Si-PPV可用于发光器件领域,如场致发光元件、发光二极管、光电池、 The present invention is made of Si-PPV can be used in the light emitting device field, such as electroluminescent devices, light emitting diodes, photovoltaic cells,

光敏元件、光电开关、各种电极/聚合物/电极等元件。 Member photosensitive member, a photoelectric switch, various electrode / polymer / electrodes.

本发明的含硅基团的PPV材料,具有良好的成膜性能、良好的热稳定性及较高的发光 Containing PPV material silicon group of the present invention has good film forming properties, good thermal stability and high emission

性能,具有较好的载流体注入及传输能力。 Performance, having good charge carrier injection and transport capabilities. 其单体合成应用对二卤苯为原料,制得双锂代 Which monomer synthesis applications dihalo benzene as starting material to give bis lithio

化合物,然后与一氯硅烷偶合反应,生成对二硅垸基苯,其副反应较少;在无水条件下经双卤甲基化后得2,5 — 二硅垸基对二卤甲基苯,避免了常规合成方法中卤代反应时多种卤 Compound, and then reacted with a chlorosilane coupling, generates two silicon embankment benzene, less its side reactions; under anhydrous conditions after bis halomethylated obtained 2,5 - Silicon alkyl with p-halomethyl benzene, avoiding the more halogen when a conventional synthesis method halogenation

代物难以分离而导致收率很低的缺点。 Generation was difficult to separate the resulting yield low drawbacks. 在单体聚合时,采用低温聚合,使聚合物分散度较小,分子量较高,从而克服了常规合成中的分散度大和小分子量产物对发光纯度及发光寿命的影响。 When monomer is polymerized, low temperature polymerization, the polymer dispersion is small, a higher molecular weight, thereby overcoming the effects of conventional synthesis of large dispersion and small molecular weight products of the emitting purity and luminescence lifetime. 本发明的聚合物成膜性好,发光效率高,热稳定性好,载流体注入及传输能力好。 Polymers of the present invention the film is good, high luminous efficiency, good thermal stability, the carrier fluid injection and transport well capacity.

具体实施方式 Detailed ways

下面将结合实例进一步说明本发明,但实施实例并不限制本发明的保护范围。 Below in conjunction with examples further illustrate the present invention, but the embodiment examples do not limit the scope of the present invention. 实施例 Example

实施例一合成2,5 — 二(双甲氧基辛基硅基)一PPV:结构式如下: Example a Synthesis of 2,5 embodiments - bis (bis methoxyoctyl silicon) a the PPV: the following structural formula:

H3CO H3CO

H3CO—Si \ H3CO-Si \

(1)合成1,4一二(双甲氧基辛基硅基)苯:IO.O克(42rnmo1)对二溴苯溶于100ml无水四氢呋喃中,通入N2保护,于一78'C缓慢滴加2M的新制备的正丁基锂四氢呋喃溶液50ml(100mmo1),保持该温度反应3小时后,于一78t)缓慢滴加20克(84mmo1) 二甲氧基辛基氯硅垸,反应2小时后,在3小时内缓慢升温到室温,于室温反应6 小时结束。 (1) Synthesis of 1,4-0112 (bis methoxyoctyl silicon) benzene: IO.O g (42rnmo1) p-dibromobenzene was dissolved in 100ml of anhydrous tetrahydrofuran, into N2 protection, in a 78'C slowly dropped 2M of freshly prepared n-butyl lithium in tetrahydrofuran 50ml (100mmo1), maintained at that temperature for 3 hours, in a 78t) was slowly added dropwise 20 g (84mmo1) dimethoxy-octyl chloride silicon embankment, reaction 2 hours, 3 hours in the slowly warming to room temperature, at room temperature for 6 hours to complete. 反应物经水洗,干燥后减压蒸馏得产物。 The reaction was washed with water, dried and evaporated under reduced pressure to give the product. 沸点:173'C/0.2mmHg。 Boiling point: 173'C / 0.2mmHg. 产物的分析结果如下- Analysis of the product are as follows -

!HNMR(R3DR3l3): S (ppm) 7.08(4H,单峰,Rlr-H), ,1.45 —U5(24H,多重峰),0.97-0.75(10H,多重峰),0.19 (12H,单峰)。 ! HNMR (R3DR3l3): S (ppm) 7.08 (4H, singlet, Rlr-H),, 1.45 -U5 (24H, multiplet), 0.97-0.75 (10H, multiplet), 0.19 (12H, singlet) . 由此可以证实下列结构- It was confirmed the following structure -

<formula>formula see original document page 8</formula> <Formula> formula see original document page 8 </ formula>

(2) 合成2,5—二(双甲氧基辛基硅基)对二氯苄:10克(21mmo1)1,4—二(双甲氧基辛基硅基)苯溶于60ml无水1,4—二氧六环中,加入2.0克(67mmol)多聚甲醛,降温到0—5'C,通入氯化氢气体至饱和,反应1小时后升温到室温反应24小时后,升温到8(TC反应4小时。减压蒸除溶剂后,经过柱得产物,为无色液体。 (2) Synthesis of 2,5-bis (double methoxyoctyl silicon) to dichlorobenzyl: 10 g (21mmo1) 1,4- Bis (double methoxyoctyl silicon) benzene was dissolved in 60ml anhydrous 1,4-dioxane was added 2.0 g (67mmol) of paraformaldehyde, cooled to 0-5'C, hydrogen chloride gas until saturated, after 1 hour warmed to room temperature for 24 hours, allowed to warm to 8 (TC 4 hours. evaporate the solvent later, after column to give the product as a colorless liquid.

产物的分析结果如下: Analysis of the product are as follows:

力NMR(R3DR313): S (ppm) 7.36(2H,单峰,Rlr-H), 4.22 (4H,单峰,Rlr— R3H2R31) ,1.45 — U5(24H,多重峰),0.92-0.72(10H,多重峰),0.20 U2H,单峰)。 Force NMR (R3DR313): S (ppm) 7.36 (2H, singlet, Rlr-H), 4.22 (4H, singlet, Rlr- R3H2R31), 1.45 - U5 (24H, multiplet), 0.92-0.72 (10H, multiplet), 0.20 U2H, singlet).

由此可以证实下列结构: It was confirmed the following structure:

<formula>formula see original document page 8</formula>(3) 合成2,5 —二(双甲氧基辛基硅基)一PPV: 2.0克(3.4mmol)2,5—二(双甲氧基辛基硅基)对二氯苄溶于100ml无水四氢呋喃中,在氮气保护下搅拌,降温至一7(TC于15分钟内滴加1M的甲醇钠10ml,滴加完毕,保持该温度继续反应4小时,然后沉降于500ml甲醇中,抽滤,将所得固体溶于100ml四氢呋喃,再沉降于500ml甲醇中,抽滤,重复三次后所得固体真空干燥后得产物。GPR3分析:重均分子量:180,000, 分散度:2.17。 <Formula> formula see original document page 8 </ formula> (3) Synthesis of 2,5 - (bis-methoxyoctyl silicon) a PPV: 2.0 g of (3.4 mmol) 2,5-bis (bis-methoxy octyl silicon) on dichlorobenzyl dissolved in 100ml of anhydrous tetrahydrofuran was stirred under nitrogen, cooled to a 7 (TC dropwise sodium methoxide 10ml 1M in over 15 minutes, the addition was complete, maintaining the temperature continues for 4 hours, then allowed to settle in 500ml of methanol, filtered off with suction, and the resulting solid was dissolved in 100ml of tetrahydrofuran, and then settle in 500ml of methanol, filtered off with suction, repeated three times to give the product after the resultant solid was dried in vacuo .GPR3 analysis: average molecular weight: 180,000, dispersion: 2.17.

实施例二合成2,5 — 二(甲氧基丁氧基辛基硅基)一PPV:结构式如下:<formula>formula see original document page 9</formula> Example Two Synthesis of 2,5 embodiments - bis (methoxybutyl oxygen octyl silicon) a PPV: the following structural formula: <formula> formula see original document page 9 </ formula>

(2)合成2,5 — 二(甲氧基丁氧基辛基硅基)对二氯节:10克(18mmol) 1,4—二(甲氧基丁氧基辛基硅基)苯溶于200ml无水1,4一二氧六环中,加入3.0克(100mmol)多聚甲醛,降温到0—5'C,通入氯化氢气体至饱和,反应1小时后升温到室温反应24小时后,升温到8(TC反应4小时。减压蒸除溶剂后,经过柱得产物,为无色液体。 (2) Synthesis of 2,5 - bis (methoxybutyl oxygen octyl silicon) of dichloro-section: 10 g (18mmol) 1,4- bis (methoxybutyl oxygen octyl silicon) benzene soluble after in 200ml of anhydrous 1,4-dioxane was added 3.0 g (100 mmol) of paraformaldehyde, cooled to 0-5'C, hydrogen chloride gas until saturated, for 1 hour warmed to room temperature for 24 hours , allowed to warm to 8 (TC 4 hours. after evaporating the solvent under reduced pressure, by column to give the product as a colorless liquid.

产物的分析结果如下: Analysis of the product are as follows:

NMR(R3DR313): S (ppm) 7.34(2H,单峰,Rlr-H), 4.20 (4H,单峰,Rlr— NMR (R3DR313): S (ppm) 7.34 (2H, singlet, Rlr-H), 4.20 (4H, singlet, Rlr-

9 9

H3CO H3CO

\ \

Si—OCaH, Si-OCaH,

_^- _ ^ -

H3CO H3CO

\ \

H9C40——: H9C40--:

C8H17 C8H17

(1)合成1,4一二(甲氧基丁氧基辛基硅基)苯:10.0克对二溴苯(42mmol)溶于500ml 无水四氢呋喃中,通入N2保护,于一7(TC缓慢滴加2M的新制备的正丙基锂四氢呋喃溶液100ml(200mmo1),保持该温度反应3小时后。于一70。C缓慢滴加40克(142mmol)甲氧基丁氧基辛基氯硅垸,反应2小时后,在3小时内缓慢升温到室温, (1) Synthesis of 1,4-0112 (methoxybutyl oxygen octyl silicon) benzene: 10.0 g of p-dibromobenzene (42 mmol) was dissolved in 500ml of anhydrous tetrahydrofuran, into N2 protection, in a 7 (TC n-propyl lithium tetrahydrofuran 100ml (200mmo1) freshly prepared 2M slowly dropwise, maintaining the temperature after 3 hours in a 70.C was slowly added dropwise 40 g (142mmol) methoxybutanol oxygen octyl chlorosilane embankment, after reaction for 2 hours, within 3 hours was slowly warmed to room temperature,

于室温反应12小时结束。 For 12 hours to complete at room temperature. 反应物经水洗,干燥后减压蒸馏得产物。 The reaction was washed with water, dried and evaporated under reduced pressure to give the product. 沸点:isrc Boiling point: isrc

/0.2腿Hg。 /0.2 leg Hg.

产物的分析结果如下- Analysis of the product are as follows -

iHNMR(R3DR3l3): S (ppm) 7.06(4H,单峰,Rlr-H), ,1.48—U3(32H,多重峰), 0.95-0.34(20H,多重峰),0.19 (6H,单峰)。 iHNMR (R3DR3l3): S (ppm) 7.06 (4H, singlet, Rlr-H),, 1.48-U3 (32H, multiplet), 0.95-0.34 (20H, multiplet), 0.19 (6H, singlet).

由此可以证实下列结构: It was confirmed the following structure:

H3CO H3CO

\ \

Si—OC4H9 Si-OC4H9

_/\(3)合成2,5 —二(甲氧基丁氧基辛基硅基)一PPV: 2.0克(3.0mmo1)2,5 —二(甲氧基丁氧基辛基硅基)对二氯节溶于100ml无水四氢呋喃中,在氮气保护下搅拌,降温至一80。 _ / \ (3) Synthesis of 2,5 - bis (methoxybutyl oxygen octyl silicon) a PPV: 2.0 g of (3.0mmo1) 2,5 - bis (methoxybutyl oxygen octyl silicon) of dichloro-section was dissolved in 100ml of anhydrous tetrahydrofuran was stirred under nitrogen, cooled to-80. C于15分钟内滴加1M的乙醇钠20ml (20mmo1),滴加完毕,保持该温度继续反应4小时,然后沉降于500ml甲醇中,抽滤,将所得固体溶于100ml四氢呋喃, 再沉降于500ml甲醇中,抽滤,重复三次后所得固体真空干燥后得产物。 C was added dropwise over 15 minutes sodium ethoxide 20ml (20mmo1) 1M, the addition was complete, maintaining the temperature the reaction was continued for 4 hours and then allowed to settle in 500ml of methanol, filtered off with suction, and the resulting solid was dissolved in 100ml of tetrahydrofuran, and then settling to 500ml methanol, filtered off with suction, after repeated three times to give the product the resulting solid was dried under vacuum. GPR3分析:重均分子量:230,000,分散度:2.09。 GPR3 Analysis: average molecular weight: 230,000, degree of dispersion: 2.09.

实施例三合成2,5—二(甲基辛基十八烷基硅基)一PPV:结构式如下: A PPV Example Three Synthesis of 2,5-bis (methyloctyl octadecyl silicon) embodiments: the following structural formula:

\ \

S^~C8H17 C18H37 S ^ ~ C8H17 C18H37

c18H37 c18H37

(1)合成1,4—二(甲基辛基十八烷基硅基)苯:10.0克(42mrno1)对二溴苯溶于200ml 无水四氢呋喃中,通入N2保护,于一8(TC缓慢滴加2M的新鲜异辛基锂四氢呋喃溶液120ml(240mmo1),保持该温度反应8小时后。于一8(TC缓慢滴加130克(292mmo1) (1) Synthesis of 1,4-bis (methyloctyl octadecyl silicon) benzene: 10.0 g (42mrno1) p-dibromobenzene was dissolved in 200ml of anhydrous tetrahydrofuran, into N2 protection, in a 8 (TC was slowly added dropwise fresh iso-octyl lithium tetrahydrofuran 120ml (240mmo1) 2M is maintained after the temperature of the reaction for 8 hours. in an 8 (TC was slowly added dropwise 130 g (292mmo1)

甲基辛基十八垸基氯硅烷,反应5小时后,在3小时内缓慢升温到室温,于室温反 Methyloctyl eighteen alkyl with chlorosilane, after 5 hours, within 3 hours was slowly warmed to room temperature, anti at room temperature

10 10

R3H2R31) ,1.48—1.10(32H,多重峰),0.97-0.30(20H,多重峰),0.19 (6H,单峰X R3H2R31), 1.48-1.10 (32H, multiplet), 0.97-0.30 (20H, multiplet), 0.19 (6H, singlet X

由此可以证实下列结构: It was confirmed the following structure:

H3CO H3CO

\ \

Si—OC4H9 Si-OC4H9

CI CI

8n17应12小时结束。 8n17 should end 12 hours. 反应物经水洗,干燥后减压蒸馏得产物。 The reaction was washed with water, dried and evaporated under reduced pressure to give the product. 沸点:168。 Boiling point: 168. C/0.1mmHg。 C / 0.1mmHg.

产物的分析结果如下: Analysis of the product are as follows:

^NMR(R3DR3l3): S (ppm) 7.23(4H,单峰,Rlr-H), 1.50—1.10(88H,多重峰), 0.99-0.73(20H,多重峰),0.28 (6H,单峰)。 ^ NMR (R3DR3l3): S (ppm) 7.23 (4H, singlet, Rlr-H), 1.50-1.10 (88H, multiplet), 0.99-0.73 (20H, multiplet), 0.28 (6H, singlet). 由此可以证实下列结构: It was confirmed the following structure:

~C8H17 ~ C8H17

(2)合成2,5 — 二(甲基辛基十八垸基硅基)对二溴苄:10克(llmmol)l,4一二(甲基辛基十八烷基硅基)苯溶于含HR2r30。 (2) Synthesis of 2,5 - bis (methyloctyl eighteen alkyl with silicon) on dibromobenzyl: 10 g (llmmol) l, 4 0112 (methyloctyl octadecyl silicon) benzene soluble containing HR2r30. /。 /. 的100ml无水乙酸中,降温到0—5"C,加入3.0克(100mmol)多聚甲醛,反应1小时后升温到室温反应36小时后,升温到80'C 反应4小时。减压蒸除溶剂后,经过柱得产物,为无色液体。 产物的分析结果如下: In 100ml of anhydrous acetic acid, cooled to 0-5 "C, 3.0 g (100 mmol) of paraformaldehyde, after 1 hour warmed to reaction at room temperature 36 hours, heated to 80'C for 4 hours. Distilled off under reduced pressure the solvent, by column to give the product as a colorless liquid. the product analysis results are as follows:

JH NMR(R3DR313): S (ppm) 7.42(2H,单峰,Rlr-H), 4.48 (4H,单峰,Rlr— R3H2R2r) ,1.50—U0(88H,多重峰),0.95-0.70(20H,多重峰),0.30 (6H,单峰)。 JH NMR (R3DR313): S (ppm) 7.42 (2H, singlet, Rlr-H), 4.48 (4H, singlet, Rlr- R3H2R2r), 1.50-U0 (88H, multiplet), 0.95-0.70 (20H, multiplet), 0.30 (6H, singlet).

由此可以证实下列结构: It was confirmed the following structure:

H3C H3C

Hi7。8—S、 Hi7.8-S,

c18H37 c18H37

(3)合成2,5—二(甲基辛基十八垸基硅基)一PPV: 2.0克(2.0mmol)2,5—二(甲基辛基 (3) Synthesis of 2,5-bis (methyloctyl eighteen alkyl with silicon) a PPV: 2.0 g of (2.0 mmol) 2,5-bis (methyloctyl

十八烷基硅基)对二溴苄溶于500ml无水四氢呋喃中,在氮气保护下搅拌,降温至 Octadecyl silicon) on dibromobenzyl was dissolved in 500ml of anhydrous tetrahydrofuran was stirred under nitrogen, cooled to

11一80"C于15分钟内滴加的叔丁醇钾20ml(20mmo1),滴加完毕,保持该温度继 11 a 80 "C dropwise over 15 minutes potassium tert-butoxide 20ml (20mmo1), complete addition, maintaining the temperature following

续反应40小时,然后沉降于500ml甲醇中,抽滤,将所得固体溶于100ml四氢呋喃,再沉降于500ml甲醇中,抽滤,重复三次后所得固体真空干燥后得产物。 The reaction was continued for 40 hours and then settle in 500ml of methanol, filtered off with suction, and the resulting solid was dissolved in 100ml of tetrahydrofuran, and then settle in 500ml of methanol, filtered off with suction, to give the product The resulting solid was dried under vacuum was repeated three times. GPR3 GPR3

分析:重均分子量:950,000,分散度:2.15。 Analysis: average molecular weight: 950,000, degree of dispersion: 2.15. 实施例四合成2,5 — 二(双已基十六垸基硅基)一PPV:结构式如下: Example Four Synthesis of 2,5 embodiments - bis (bis hexyl sixteen alkyl with silicon) on the PPV: the following structural formula:

H13C6 H13C6

C16H33 C16H33

(1)合成1,4一二(双已基十六烷基硅基)苯:10.0克对二溴苯(42mmo1)溶于800ml 无水四氢呋喃中,通入N2保护,于一75'C缓慢滴加2M的新鲜正已基锂四氢呋喃溶液70ml,保持该温度反应2小时后。 (1) Synthesis of 1,4-0112 (bis-hexyl hexadecyl silicon) benzene: 10.0 g of p-dibromobenzene (42mmo1) was dissolved in 800ml of anhydrous tetrahydrofuran, into N2 protection, was slowly in a 75'C was added dropwise 2M fresh n-hexyl lithium in tetrahydrofuran 70ml, after the temperature of the reaction for 2 hours holding. 于一75T:缓慢滴加77克(168mmo1)双己基十六烷基氯硅垸,反应1小时后,在1小时内缓慢升温到室温,于室温反应3小时结束。 To a 75T: was slowly added dropwise 77 g (168mmo1) bis hexyl cetyl chlorosilane embankment, after 1 hour, in 1 hour was slowly warmed to room temperature, at room temperature the reaction ended 3 hours. 反应物经水洗,干燥后减压蒸馏得产物。 The reaction was washed with water, dried and evaporated under reduced pressure to give the product. 沸点:172°C/0.1mmHg。 Boiling point: 172 ° C / 0.1mmHg. 产物的分析结果如下: Analysis of the product are as follows:

^NMR(R3DR3l3): S (ppm) 7.23(4H,单峰,Rlr-H), 1.52—1.08(88H,多重峰), 0.99-0.73(30H,多重峰)。 ^ NMR (R3DR3l3): S (ppm) 7.23 (4H, singlet, Rlr-H), 1.52-1.08 (88H, multiplet), 0.99-0.73 (30H, multiplet).

由此可以证实下列结构: It was confirmed the following structure:

H13C6 H13C6

\ \

/7 ^ C16H33 / 7 ^ C16H33

(2)合成2,5 — 二(双已基十六烷基硅基)对二溴苄:10克(llmmo1)1,4—二(双己基十 (2) Synthesis of 2,5 - (bis-hexyl hexadecyl silicon) on dibromobenzyl: 10 g (llmmo1) 1,4- bis (bis-hexyl ten

12六烷基硅基)苯溶于含HR2r30。 12 six alkyl silyl) benzene was dissolved in containing HR2r30. /。 /. 的150ml无水乙酸中,降温到0—5°C,加入2.0 克(67mmol)多聚甲醛,反应1小时后升温到室温反应30小时后,升温到8(TC反应8小时。减压蒸除溶剂后,经过柱得产物,为无色液体。 产物的分析结果如下- In 150ml of anhydrous acetic acid, cooled to 0-5 ° C, was added 2.0 g (67mmol) of paraformaldehyde, room temperature 30 hours after 1 hour warmed to, raised to 8 (TC 8 hours. Evaporated under reduced pressure after the solvent was subjected to column to give the product as a colorless liquid analysis of the product are as follows. -

& NMR(R3DR313): S (ppm) 7.40(2H,单峰,Rlr-H), 4.48 (4H,单峰,Rlr— R3H2R2r) ,1.50—U0(88H,多重峰),0.92-0.74(30H,多重峰)。 & NMR (R3DR313): S (ppm) 7.40 (2H, singlet, Rlr-H), 4.48 (4H, singlet, Rlr- R3H2R2r), 1.50-U0 (88H, multiplet), 0.92-0.74 (30H, multiplet).

由此可以证实下列结构: It was confirmed the following structure:

<formula>formula see original document page 13</formula> <Formula> formula see original document page 13 </ formula>

(3)合成2,5 —二(双已基十六垸基硅基)一PPV: 2.0克(1.8mmol)2,5 — 二(双已基十六烷基硅基)对二溴苄溶于400ml无水四氢呋喃中,在氮气保护下搅拌,降温至一80 °。 (3) Synthesis of 2,5 - (bis-hexyl sixteen alkyl with silicon) a PPV: 2.0 g of (1.8 mmol) of 2,5 - bis (bis been hexadecyl silicon) on dibromobenzyl solution in 400ml of anhydrous tetrahydrofuran in a nitrogen atmosphere with stirring, cooling to a 80 °. 于15分钟内滴加1M的叔丁醇钾12ml,滴加完毕,保持该温度继续反应40小时, 然后沉降于500ml甲醇中,抽滤,将所得固体溶于100ml四氢呋喃,再沉降于500ml 甲醇中,抽滤,重复三次后所得固体真空干燥后得产物。 Added dropwise over 15 min potassium tert-butoxide 12ml 1M, the addition was complete, maintaining the temperature the reaction was continued for 40 hours and then settle in 500ml of methanol, filtered off with suction, and the resulting solid was dissolved in 100ml of tetrahydrofuran, and then settle in 500ml of methanol , suction filtration was repeated three times to give the product the resulting solid was dried under vacuum. GPR3分析:重均分子量: 1310,000,分散度:2.25。 GPR3 Analysis: The weight average molecular weight: 1310,000, dispersion: 2.25.

实施例五制作电致发光的夹层器件 Five making electrical embodiment electroluminescent sandwich device embodiment

制备夹层结构的薄膜元件,其各层的次序如下:ITO阳极/聚合物发光材料/铝阴极。 Thin film element of preparing a sandwich structure, the order of the layers is as follows: ITO anode / polymeric light emitting material / aluminum cathode.

聚合物发光材料分别为实施例1、 2制备的发光材料,参比材料为纯PPV及常规合成的Si —PPV。 Polymeric light emitting material were luminescent material prepared in Example 1, Example 2, the reference material is a pure PPV and conventional synthesis of Si -PPV. 基材为玻璃。 Substrate is glass. 各层厚度分别如下:100/300/100 ,单位:纳米。 Thickness of each layer are as follows: 100/300/100, unit: nanometer. 发光区域0.25R3m2。 Light emitting region 0.25R3m2. 旋涂所用溶剂都是THF。 Spin-coating the are with THF solvent. 数据列于下表:<table>table see original document page 14</column></row> <table> **——为电压8V时的寿命。 Data are tabulated below: <table> table see original document page 14 </ column> </ row> <table> ** - life time voltage is 8V.

可以看出,多了硅侧链后,材料的亮度及发光效率与寿命都有了很大提高。 As can be seen, the multi-silicon side chain, brightness and luminous efficiency and life of the material has greatly improved. 而以本发明所述合成方法合成的Si—PPV与通常方法合成的相比性能又有了很大提高。 And in the present invention is the synthetic method for the synthesis of Si-PPV and normally synthesized by the method as compared to the performance, there has been greatly improved.

上面的描述和实例公开了本发明的几种方法和材料,但本发明不限于上述的具体实例,它包括本发明权利要求书中所限定的本发明的精神和范围内的所有改进和变化。 The above description and examples disclose several methods and materials of the present invention, but the present invention is not limited to the particular examples described above, it includes all modifications and variations within the spirit and scope of the invention as claimed in the present invention as defined by the claims.

14 14

Claims (4)

1、一种含硅基团的1,4-亚苯基亚乙烯基聚合物的制备方法,其特征是先合成含活性基团的聚合单体: 其中R1、R2是氢原子,或者是C1-C10的烷基、烷氧基,R3是C1-C20的直链烷基或带侧链的烷基,X是卤素, (1)以无水四氢呋喃为溶剂,对二卤苯在-70℃~-80℃下与烷基锂反应1-10小时,得双锂代化合物,对二卤苯与烷基锂的摩尔比为1∶2-6; (2)上述双锂代化合物与一氯硅烷偶合反应,得对二硅烷基苯,反应温度-70℃~-80℃,时间1-5小时,然后在0.5-3小时内升温至室温下反应3-12小时,水洗、干燥、减压蒸馏,得对二硅烷基苯,以对二卤苯计,对二卤苯与一氯硅烷的摩尔比为1∶2-8; (3)对二硅烷基苯在无水条件下,以1,4-二氧六环或乙酸为溶剂,与多聚甲醛、卤化氢反应,经双卤甲基化得含活性基团的聚合单体2,5-二硅烷基对二卤甲基苯,反应温度为0℃~80℃, 1, 1,4 preparing phenylene vinylene polymer is a silicon-containing groups, wherein the first synthetic polymeric monomer containing the reactive group: wherein R1, R2 is a hydrogen atom or a C1 -C10 alkyl group, an alkoxy group, R3 is a linear alkyl C1-C20 or sidechain alkyl, X is halogen, (1) in anhydrous tetrahydrofuran as a solvent, for dihalobenzene at -70 ℃ ~ the reaction at -80 ℃ with an alkyl lithium to 10 hours, double-lithio compound, the molar ratio of dihalogen benzene to lithium alkyl is 1:2-6; (2) the twin lithio compound with a chlorine silane coupling reaction, to obtain p-Si benzene, the reaction temperature is -70 ℃ ~ -80 ℃, time of 1-5 hours, then allowed to warm to room temperature over 0.5-3 hours reaction is 3-12 hours, washed with water, and dried under reduced pressure distillation, dimethyl silicone benzene to p-halophenyl terms, the molar ratio of dihalogen benzene with a chlorosilane of 1:2-8; (3) p-Si benzene under anhydrous conditions to a , 4-dioxane or acetic acid as solvent, is reacted with paraformaldehyde, hydrogen halide, the polymerizable monomer by double halomethylated have reactive group-containing 2,5-silyl p-halomethyl benzene, The reaction temperature is 0 ℃ ~ 80 ℃, 间为3-48小时,对二硅烷基苯与多聚甲醛的摩尔比为1∶2-10,卤化氢在溶剂中的含量为30wt%至饱和; 含活性基团的聚合单体通过Gilch反应,得目标产物: (4)无水四氢呋喃为溶剂,在氮气保护下,以醇钠或醇钾为催化剂,在-70℃~-80℃下聚合反应2-48小时,得目标产物,其中单体与催化剂的摩尔比为1∶3-10; 所述含硅基团的1,4-亚苯基亚乙烯基聚合物的结构如下: 其中R1,R2是H原子,或者是C1-C10的烷基、烷氧基,R3是C1-C20的烷基,n=3-10000。 Is between 3-48 hours, the molar ratio of disilazane of benzene and paraformaldehyde is 1:2-10, the content of hydrogen halide in the solvent is 30wt% to saturation; polymerizable monomers containing reactive groups by reaction Gilch to give the desired product: (4) of anhydrous tetrahydrofuran as a solvent under a nitrogen atmosphere to a sodium alkoxide or potassium alkoxide as the catalyst, the polymerization at -70 ℃ ~ -80 ℃ reaction 2-48 hours to give the desired product, in which a single body and the molar ratio of catalyst 1:3-10; structure 1,4-phenylene vinylene polymer of the silicon-containing groups as follows: wherein R1, R2 is H atom or a C1-C10 of alkyl, alkoxy, R3 is C1-C20 alkyl, n = 3-10000.
2、 如权利要求l所述的方法,其特征是垸基锂是含1-10个碳原子的烷基锂化合物。 2. The method of claim l in claim, wherein alkyl with lithium containing 1 to 10 carbon atoms, an alkyl lithium compound.
3、 如权利要求l所述的方法,其特征是对二卤苯的质量与溶剂之比为1克:5-100毫升。 3. The method of l according to claim, characterized in that the quality of the dihalobenzene and the ratio of the solvent of 1 g: 5-100 ml.
4、 如权利要求1所述的方法,其特征是聚合反应催化剂为含1一10个碳原子的醇钠或醇钾。 4. The method of claim 1, wherein the polymerization catalyst containing 10 1 a potassium alkoxide or sodium alkoxide carbon atoms.
CN 200410068054 2004-11-11 2004-11-11 Silicon group-containing 1,4-phenylene vinylidene and its preparation method and application CN100586981C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200410068054 CN100586981C (en) 2004-11-11 2004-11-11 Silicon group-containing 1,4-phenylene vinylidene and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200410068054 CN100586981C (en) 2004-11-11 2004-11-11 Silicon group-containing 1,4-phenylene vinylidene and its preparation method and application

Publications (2)

Publication Number Publication Date
CN1631931A true CN1631931A (en) 2005-06-29
CN100586981C true CN100586981C (en) 2010-02-03

Family

ID=34846730

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200410068054 CN100586981C (en) 2004-11-11 2004-11-11 Silicon group-containing 1,4-phenylene vinylidene and its preparation method and application

Country Status (1)

Country Link
CN (1) CN100586981C (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5945502A (en) 1997-11-13 1999-08-31 Xerox Corporation Electroluminescent polymer compositions and processes thereof
CN1419575A (en) 2000-04-11 2003-05-21 杜邦显示器股份有限公司 Soluble poly(aryl-oxadiazole) conjugated polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5945502A (en) 1997-11-13 1999-08-31 Xerox Corporation Electroluminescent polymer compositions and processes thereof
CN1419575A (en) 2000-04-11 2003-05-21 杜邦显示器股份有限公司 Soluble poly(aryl-oxadiazole) conjugated polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A Family of ElectroluminescentSilyl-SubstitutedPoly(p-phenylenevinylene)s:synthesis,Characterization,andStructure-Property Relationships. Z.K.Chen, et al.MACROMOLECULES,Vol.33 No.24. 2000

Also Published As

Publication number Publication date Type
CN1631931A (en) 2005-06-29 application

Similar Documents

Publication Publication Date Title
US20040135131A1 (en) Conjugated polymers containing spirobifluorene units and fluorene units, and the use thereof
Beaupre et al. Fluorene‐Based Copolymers for Red‐Light‐Emitting Diodes
Yu et al. Spiro‐Functionalized Polyfluorene Derivatives as Blue Light‐Emitting Materials
US20040097699A1 (en) Twisted polymers, uses thereof and processes for the preparation of statistical copolymers
US20070138483A1 (en) Conducting polymer composition and electronic device including layer obtained using the conducting polymer composition
US6824890B2 (en) Soluble tetrahedral compounds for use in electroluminescent devices
US20060058494A1 (en) Conjugated polymers containing arylamine units, the representation thereof and the use of the same
EP2075274A1 (en) Soluble polythiophene derivatives
US20020013451A1 (en) Blue electroluminescent materials for polymer light-emitting diodes
Zou et al. Unexpected Propeller‐Like Hexakis (fluoren‐2‐yl) benzene Cores for Six‐Arm Star‐Shaped Oligofluorenes: Highly Efficient Deep‐Blue Fluorescent Emitters and Good Hole‐Transporting Materials
US20110006287A1 (en) Polymers with tunable band gaps for photonic and electronic applications
US20060094859A1 (en) Class of bridged biphenylene polymers
WO2007017066A1 (en) Electroluminescent polymers and use thereof
US20070032632A1 (en) Electroluminescence polymer, organic el device, and display
Huang et al. Synthesis, photophysics, and electroluminescence of high-efficiency saturated red light-emitting polyfluorene-based polyelectrolytes and their neutral precursors
WO2012030942A1 (en) Photovoltaic cell containing novel photoactive polymer
US20020093005A1 (en) Electroluminescent polymer having good carrier transport balance and electroluminescent device using the same
WO2001062869A1 (en) Luminescent polymer
JP2004534863A (en) Monomers for use in preparing the polymer to be used in optical devices
WO2005030828A1 (en) Conjugated polymers, their preparation and use thereof
CN101501862A (en) Polymers with low band gaps and high charge mobility
JP2006063334A (en) Polymer compound, polymer film and polymer film element using the same
JP2008109114A (en) Organic photoelectric conversion element
JP2007302886A (en) Organic electronic material and organic electronic device and organic electroluminescent device using the material
US20090299029A1 (en) Soluble polythiophene derivatives

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model
EXPY Termination of patent right or utility model