CN1513044A - 取代的芴聚合物,其制备方法和在光学设备中的用途 - Google Patents
取代的芴聚合物,其制备方法和在光学设备中的用途 Download PDFInfo
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- CN1513044A CN1513044A CNA028112660A CN02811266A CN1513044A CN 1513044 A CN1513044 A CN 1513044A CN A028112660 A CNA028112660 A CN A028112660A CN 02811266 A CN02811266 A CN 02811266A CN 1513044 A CN1513044 A CN 1513044A
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- C—CHEMISTRY; METALLURGY
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
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Abstract
一种用于在光学设备中使用的聚合物,其中所说的光学设备含有:空穴迁移区,电子迁移区,发射区,所说的聚合物含有式(I)的非必须取代的重复单元:其中每个Ar相同或不同并且含有非必须取代的芳基。
Description
技术领域
本发明涉及用于光学设备、特别是有机电致发光设备的材料,以及它们物理性能的控制。
背景技术
一类光电设备是使用有机材料的设备,其中的有机材料是用于光的发射或检测。这种设备的基本结构是发光有机层,例如聚(对-亚苯基亚乙烯基)(″PPV″)或聚芴,夹在用于向有机层注入负电荷载体(电子)的阴极和用于向有机层注入正电荷载体(空穴)的阳极之间。电子和空穴在有机层中合并,产生光子。在WO 90/13148中,有机发光材料是聚合物。在US 4,539,507中,有机发光材料是一类已知的小分子材料,如(8-羟基喹啉)铝(“Alq3”)。在实际的设备中,电极之一是透明的,以便允许光从设备中发出。
图1举例说明了典型有机发光设备(“OLED”)的横截面结构。OLED一般是在玻璃或塑料基片1上制成的,所说的玻璃或塑料基片1涂敷有透明的第一电极4,如铟-锡-氧化物(“ITO”)。在第一电极上,覆盖有一层至少一种电致发光有机材料3的薄层。最后,阴极2覆盖了电致发光有机材料层。阴极一般是金属或合金的,并且可以含有单层,如铝层,或者诸如钙和铝的多层。可以向设备添加其它层,以便例如改进电荷从电极向电致发光材料的注入。例如,可以在阳极4和电致发光材料3之间设置空穴注入层,如聚(乙烯二氧基噻吩)/聚苯乙烯磺酸酯(PEDOT-PSS)或聚苯胺。当从电源中在电极之间施加电压时,电极之一起作用并且另一个起阳极作用。
对有机半导体而言,重要的特征是结合能,结合能是根据电子能级的真空水平来测定的,特别是“最高占据分子轨道”(HOMO)和“最低未占分子轨道”(LUMO)水平。这些可以从光电子发射的测定、特别是对氧化和还原的电化学潜势的测定来估测。在此领域,公知的是这种能量受许多因素影响,如接近界面的局部环境,并且从中测定曲线上的点(峰)。因此,使用这些值是指示性的而不是定量性的。
聚合物OLEDs领域中的焦点是全色显示器的开发,为此需要红光、绿光和蓝光发射型的材料。对商业应用而言,人们期望OLED具有数千小时的使用期限(“使用期限”是指当在DC驱动下室温操作时,OLED的亮度从100cd/m2降到50cd/m2的时间)。用与开发相关的现有聚合物OLED显示器的一个缺陷是,迄今为止的蓝光发射型材料的使用期限相对较短。发光材料的使用期限可以通过OLED体系结构的最优化来延长;例如,红光、绿光和蓝光材料的使用期限可以依赖于所用的阴极。然而,固有地稳定的聚合物(特别是蓝光发射型电致发光聚合物),即,在各种OLED体系结构中都能具有高度使用期限的聚合物,显然是人们所期望的。
WO 00/55927公开了一种下式(a)的聚合物:
其中w+x+y=1,w<0.5,0≤x+y≤0.5并且n<2。这个应用没有公开含有二苯基芴重复单元的聚合物。
WO 00/22026公开了下式(b)的聚合物:
其中X是97或99并且Y是3或1。这种聚合物据公开用于在电致发光设备中使用。
其它含有二苯基芴重复单元的电致发光聚合物的公开文献包括:
EP1088875,其公开了以9-4-金刚烷基苯基-10-苯基蒽和2-金刚烷基芴重复单元为基础的共聚物;
WO99/20675,其公开了9,9-二正辛基芴和9,9-二(4-甲氧基苯基)芴的1∶1共聚物。
本发明的一个目的是提供一种手段,来增加在上述现有技术聚合物的光学设备中使用的聚合物的使用期限。本发明的另一个目的是提供一种用于在光学设备中使用的长效聚合物,特别是长效蓝光发射型电致发光材料。本发明的又另一个目的是提供一种手段,来增加现有技术聚合物的热稳定性。
发明概述
本发明者意想不到地发现,用于在光学设备中使用的聚合物、特别是电致发光聚合物的使用期限,可以通过掺加可增加聚合物玻璃化温度(Tg)的重复单元来增加。具体说,向电致发光聚合物、特别是蓝光发射型电致发光聚合物中掺加2,7-连接的9,9-二芳基芴重复单元,可以使聚合物的使用期限得到明显增加。除其对聚合物使用期限的有益效果外,聚合物Tg的增加本来就是合意的,因为可以增加热稳定性。
因此,本发明的第一个方面是提供一种用于在光学设备中使用的聚合物,该光学设备含有:
-空穴迁移区
-电子迁移区,和
-发射区
所说的聚合物含有下式(I)的非必须取代的重复单元:
其中每个Ar相同或不同并且含有非必须取代的芳基。
优选,每个Ar独立地选自下式(II)的非必须取代的残基:
其中n=1、2或3并且R是助溶基团或氢。特别优选的基团R是氢和非必须取代的烷基或烷氧基。首选,R是氢或丁基。“丁基”是指正-、仲-或叔-丁基。前述现有技术中公开的聚合物中所存在的9,9-二芳基芴重复单元已被用于电子迁移和/或用作第二重复单元的连接基。为此,这些现有技术的聚合物由50%或更多9,9-二芳基芴单元组成。然而,本发明者确认,同不含式(I)重复单元的相应聚合物比较,为达到增加玻璃化转变温度的目的,使用较低量的式(I)的重复单元是可以的。因此,本发明的聚合物优选含有小于50mol%、更优选10-40mol%的式(I)的重复单元。
优选,聚合物是电致发光聚合物。更优选,聚合物是蓝光发射型电致发光聚合物。“蓝光发射型电致发光聚合物”是指聚合物,其经过电致发光,发射波长为400-500nm、优选430-500nm的射线。
本发明第二个方面提供一种光学设备,优选电致发光设备,含有用于注入正电荷载体的第一电极、用于注入负电荷载体的第二电极和位于第一和第二电极之间的含有聚合物的层,其中所说的层含有:
-空穴迁移区
-电子迁移区
-发射区
所说的聚合物含有下式(I)的重复单元:
其中每个Ar相同或不同并且含有非必须取代的芳基。
本发明第三个方面提供一种控制聚合物的玻璃化转变温度的方法,包括将下式(III)的单体在聚合混合物中聚合:
其中每个Ar相同或不同并且含有非必须取代的芳基,并且每个P是用于聚合的官能团,该方法包括将达到预选玻璃化转变温度所需量的式(III)单体聚合的步骤。
优选,式(III)的单体占聚合混合物中的单体的小于50mol%,更优选10-40mol%。
特别适合于从芳族单体中制备共轭聚合物的两种聚合技术是,例如,WO 00/53656中公开的Suzuki聚合和,例如,“Macromolecules”,31,1099-1103(1998)中公开的Yamamoto聚合。Suzuki聚合必须将卤素和硼衍生物官能团偶联;Yamamoto聚合必须将卤化物官能团偶联。因此,优选,每个P独立地选自(a)硼衍生物官能团,选自硼酸基团、硼酸酯基团和硼烷基团,及(b)卤素官能团。
优选,该方法包括将式(III)的第一单体与第二单体在金属配位络合物催化剂的存在下和在将单体聚合成聚合物的条件下反应的步骤,其中所说的第二单体与第一单体相同或不同。
优选,该方法包括将(a)具有至少两个硼衍生物官能团的第一芳族单体,其中硼衍生物官能团选自硼酸基团、硼酸酯基团和硼烷基团,和具有至少两个反应活性卤素官能团的第二芳族单体,其中第一或第二芳族单体中的至少一个含有式(III)的单体;或者(b)具有一个反应活性卤素官能团和一个硼衍生物官能团的式(III)的芳族单体,其中所说的硼衍生物官能团选自硼酸基团、硼酸酯基团和硼烷基团,在反应混合物中聚合反应的步骤,其中反应混合物中含有催化量的适于催化芳族单体聚合的催化剂,和足够量的将硼衍生物官能团转化成-BX3 -阴离子基团的碱,其中X独立地选自F和OH。
优选,碱是有机碱,更优选如WO 00/53656中公开的四烷基碳酸铵或氢氧化铵。
本发明的第四个方面提供一种下式(I)的非必须取代的重复单元在聚合物、优选电致发光聚合物中,作为玻璃化转变温度增强剂的用途:
其中每个Ar如上定义。
本发明第五个方面提供一种聚合物、优选电致发光聚合物,该聚合物含有小于50mol%、优选10-40mol%下式(I)的非必须取代的重复单元:
其中每个Ar如上定义。
每个区可以含有单一的重复单元或者多个共轭在一起的重复单元。空穴迁移区,电子迁移区和发射区各自可以在聚合物中仅出现一次。一个区可以在聚合物内仅出现一次,特别是当它含有共轭重复单元的伸直链时。或者,可有在聚合物内遍布分布空穴迁移区、电子迁移区和发射区中一个或多个区的多个。应当注意的是,三个区的每个是彼此化学不同的,即,优选,在使用时,指定的区不起空穴迁移区、电子迁移区或发射区的一个以上功能。
术语“空穴迁移区”、“电子迁移区”和“发射区”如下彼此相对照进行定义。
“空穴迁移区”是指HOMO水平低于发射区或电子迁移区HOMO水平的区域。
“电子迁移区”是指LUMO水平高于发射区或空穴迁移区LUMO水平的区域,位于发射区的LUMO水平和使用本发明聚合物的设备阴级的功函数之间。一般来说,阴级的功函数为大约2.5eV。
“发射区”是指HOMO-LUMO带隙小于空穴迁移区或电子迁移区带隙的区域。
聚合物的各区的HOMO和LUMO水平及带隙可以通过用循环伏安法,测定相应均聚物或1∶1共聚物的HOMO水平来精确估测。各区的LUMO水平也可以按此方式来测定;或者,可以通过测定HOMO水平和HOMO-LUMO带隙来计算。此外,发射区是从相应于各区的均聚物或1∶1共聚物的电致发光光谱中容易识别的。
空穴迁移、电子迁移或发射的基本上全部都由满足上述相应定义的区所产生,然而,相对少量的空穴迁移、电子迁移或发射可能起因于不满足相应定义的区。例如,可以从空穴或电子迁移区中观察到相对少量的发射,如果该区的HOMO-LUMO带隙不大于发射区的HOMO-LUMO带隙。
一种典型的电致发光设备包括功函数为4.8eV的阳级。因此,空穴迁移区的HOMO水平优选为大约4.8-5.5eV。类似地,典型设备的阴级所具有的功函数为大约3eV。因此,电子迁移区的LUMO水平优选为大约3-3.5eV。
优选的作为空穴迁移区的是,例如,WO 99/54385中公开的三芳基胺,其内容引入本文作为参考。
优选的作为电子迁移区的是2,7-连接的芴重复单元及其共轭链。特别优选的聚芴包括,例如,EP 0842208公开的2,7-连接的-9,9-二烷基芴,其内容引入本文作为参考;例如,EP 0707020公开的螺二芴,其内容引入本文作为参考,以及茚并芴。除此之外,式(I)的重复单元及其共轭链,可以起电子迁移区的功能以及起增加本发明聚合物玻璃化转变温度的作用。还优选的作为电子迁移区的是1,4-连接的苯基重复单元及其共轭链。
优选的作为发射区的是WO 00/55927和WO 00/46321中公开的发射重复单元,其内容引入本文作为参考。一种特别优选的蓝光发射型重复单元含有下式(IV)的非必须取代的重复单元:
其中每个R’独立地选自氢或助溶基团。
特别优选的助溶基团是非必须取代的烷基或烷氧基。首选,R’是正-丁基。
空穴迁移区、电子迁移区和发射区各自可以是以聚合物主链的一部分提供,例如,WO 00/55927中所公开的。或者,所说的区的一个或多个可以是聚合物主链的侧基,例如,WO 01/49769和WO 02/26859中公开的,其中空穴迁移区是电子迁移主链的侧基。
实施例
单体实施例
按照以下工艺路线制备本发明的单体:
单体实施例M1:2,7-二溴-9,9-二苯基芴
2,7-二溴芴酮
在一3L凸缘式烧瓶中,将芴酮(100.006g,0.555mol)、五氧化磷(110.148g,0.776mol)和磷酸三甲酯(1200mL)混合。在机械搅拌下,快速添加溴(63mL,1.23mol)存在于磷酸三甲酯(200mL)中的溶液。然后,将此透明溶液在120℃下加热22小时。让混合物冷却至室温,然后倾入3L水中。当添加硫代硫酸钠时(50.045g),混合物变黄。保持搅拌1小时,然后将黄色固体滤出。将此固体在甲醇中加热,除去一溴化化合物并且得到176.183g(98%纯,通过HPLC,94%产率)。
1H NMR(CDCl3)7.73(2H,d,J2.0),7.61(2H,dd,J7.6,2.0),7.36(2H,d,J8.0);13CNMR(CDCl3)142.3,137.5,135.3,127.9,123.3,121.8,109.8。
4,4’-二溴-2-羧酸-1,1’-联苯
在一2L凸缘式烧瓶中,放入2,7-二溴芴酮(120.526g,0.356mol)、氢氧化钾(细粉末,168.327g,3.000mol)和甲苯(600mL)。将此混合物在120℃下加热4小时,然后冷却至室温。在剧烈搅拌条件下加水溶解固体(~2L)。除去绿色含水层并且将黄色甲苯层用水洗涤两次。将合并的含水层用浓盐酸酸化,然后将沉淀的固体滤出,干燥后从甲苯中重结晶,得到100.547g灰白色晶体(79%产率);1HNMR((CD3)2CO)8.00(1H,d,J2.0),7.77(1H,dd,J8.0,2.4),7.57(2H,d,J8.0),7.34(1H,d,J8.4),7.29(2H,d,J8.8);
13C NMR((CD3)2CO)167.1,140.4,139.8,134.2,133.5,132.8,132.7,131.2,130.6,121.4,121.1。
4,4’-二溴-2-羧酸-1,1’-联苯的甲基酯
将4,4-二溴-2-羧酸联苯(171.14g,0.481mol)悬浮于甲醇(700mL)和硫酸(15mL)中,然后在80℃下加热21小时。除去溶剂并且将油溶解于乙酸乙酯中。将此溶液用2N氢氧化钠、水、饱和氯化钠洗涤,经硫酸镁干燥,过滤并且蒸发,得到橙色油。将此油用热的甲醇处理,冷却沉淀出的酯并且过滤。将母液蒸发并且将固体重结晶,得到附加产物。获得的酯通过GCMS分析为100%纯,产量123.27g(69%);
1H NMIR(CDCl3)7.99(1 H,d,J2.0),7.64(1H,dd,J8.0,1.6),7.51(2H,d,J8.4),7.19(1H,d,J8.8),7.13(2H,d,J8.8),3.67(3H,s);13C NMR(CDCl3)167.1,140.3,139.1,134.4,132.9,132.1,132.0,131.3,129.8,121.9,121.5,52.3;GCMS:M+=370
4,4’-二溴-2-二苯基醇-1,1’-联苯
将4,4-二溴-2-甲基酯-联苯(24.114g,65.1mmol)溶解于无水二乙醚中(120mL),并且通过使用异丙醇/干冰浴,将此溶液冷却至-60℃。然后,滴加苯基锂(存在于环己烷-乙醚中的1.8M溶液,91mL)。将混合物搅拌并且让其加温至室温。四小时后反应完成。加水(70mL),然后用二乙醚洗涤含水层一次。将合并的有机相用氯化钠洗涤,经硫酸镁干燥,过滤并且蒸发得到黄色粉末。从异丙醇中重结晶,得到19g白色固体(59%产率);GC-MS(m/z,相对强度%)494(M+,100);1HNMR(CDCl3)7.43(1H,dd,J8.4,2.4),7.28(6H,m),7.23(2H,d,J8.0),7.11(4H,m),6.99(1H,d,J2.4),6.94(1H,d,J8.4),6.61(2H,d,J8.4);13CNMR(CDCl3)147.5,146.7,140.3,139.3,134.0,133.0,131.2,131.1,130.3,128.2,128.1,127.8,121.8,121.3,83.2。
2,7-二溴-9,9-二苯基芴
将上述醇(69.169g,140mmol)和冰醋酸(450ml)搅拌并且加热至回流,然后滴加浓盐酸(0.5ml)。当添加完毕时,将混合物加热1小时然后冷却。将此反应混合物倾入水中(500ml),之后滤出固体。将此白色固体从乙酸正丁酯中重结晶三次,得到20.03g所需产物(99.59%,通过HPLC,30%产率)。
1H NMR(CDCl3),δ/ppm:7.58(2H,d,J7.6),7.49(2H,d,1.2),7.48(2H,dd,1.6),7.25(6H,m),7.14(4H,m)。13CNMR(CDCl3),δ/ppm:153.2,144.6,138.3,131.1,129.6,128.7,128.2,127.4,122.0,121.7,65.8。
单体实施例M2-M4
按照上面概述的方案和普通实验过程,制备下表中详述的具有Ar基团的单体。由相应的芳基溴制备下表中所示的对应于Ar基团的芳基锂化合物。
聚合物实施例P1
按照WO 00/53656的过程,制备本发明的蓝光发射型电致发光聚合物,通过将9,9-二-正辛基芴-2,7-二(乙烯基硼酸酯)(0.5当量)、2,7-二溴-9,9-二苯基芴(0.3当量)、N,N-二(4-溴苯基)-仲丁基苯胺(0.1当量)和N,N’-二(4-溴苯基)-N,N’-二(4-正丁基苯基)-1,4-二氨基苯(0.1当量)反应,得到聚合物P1:
聚合物实施例P2-P4
按照实施例P1的方法,制备聚合物,不同之处是聚合物中存在的9,9-二辛基芴重复单元和9,9-二苯基芴重复单元之比如下改变:
实施例号 | 9,9-二苯基芴(mol%) | 9,9-二辛基芴(mol%) |
P2 | 50 | 30 |
P3 | 60 | 20 |
聚合物实施例P5
按照实施例P1的方法制备聚合物。不同之处是使用2,7二溴-9,9-二(联苯)芴(单体实施例M3;0.3当量)代替2,7-二溴-9,9-二苯基芴。
对比聚合物实施例
按照聚合物实施例1制备蓝光发射型聚合物,如WO 00/55927中所公开的,其中将所有的9,9-二苯基芴重复单元用9,9-二正辛基芴重复单元代替。此可以通过按照聚合物实施例1的制备来完成,不同之处是用0.3当量的2,7-二溴-9,9-二正辛基芴代替2,7-二溴-9,9-二苯基芴。
设备实施例
向承载有一定厚度ITO基片的玻璃基片上,通过旋涂沉积聚(乙烯二氧基噻吩)/聚苯乙烯磺酸酯(可获得自BayerTM,以Baytron PTM),厚度为270微米。在其上,通过旋涂沉积本发明的聚合物,厚度为50nm。通过蒸发,在聚合物上沉积一层氟化锂(厚度4nm),接着同样通过蒸发沉积钙的阴极(厚度50nm)。将设备用金属罩包封。
对比设备实施例
按照设备实施例中概述的方法制备设备,不同之处是使用上述的对比聚合物代替本发明的聚合物。
结果
下表给出了关于上述聚合物的玻璃化转变温度数据。
聚合物实施例 | 玻璃化转变温度(℃) |
对比实施例 | 大约80 |
P1 | 140 |
P2 | 210 |
P3 | 240 |
P4 | 175 |
正如所看到的,本发明的聚合物相比对比的现有技术的聚合物,具有明显较高的Tg,说明它们具有较大的热稳定性。Tg随着掺入聚合物中的式(I)重复单元的数量而增加。此外,不同的式(I)重复单元在影响Tg程度的方面是不同的。由此,聚合物P4(含有30%二(联苯)芴重复单元)就比聚合物P1(含有30%二苯基芴重复单元)具有更高的Tg。
除增加热稳定性外,聚合物P1-P4的使用期限为大约3,000小时或更长,而对比聚合物实施例的使用期限为大约1,000小时。
虽然本发明就示例性的实施方案作了描述,但应当理解的是在不背离本发明实质和范围的前提下作出的对本文所公开的特点的各种改进、改变和/或组合,对本领域技术人员来说是显而易见的,本发明的范围由下面权利要求书所定义。
Claims (22)
2、权利要求1的聚合物,其中每个Ar独立地选自下式(II)的非必须取代的残基:
其中n=1、2或3并且R是助溶基团或氢。
3、权利要求2的聚合物,其中R选自非必须取代的烷基或烷氧基。
4、权利要求2的聚合物,其中R是氢或丁基。
5、前述权利要求任一项的聚合物,含有小于50mol%的式(I)的重复单元。
6、权利要求5的聚合物,含有10-40mol%的式(I)的重复单元。
7、前述权利要求任一项的聚合物,其中电子迁移区中含有至少一种式(I)的重复单元。
8、权利要求1-6任一项的聚合物,其中电子迁移区中不含有式(I)的重复单元。
9、权利要求1-8任一项的聚合物,能够发射波长范围为400-500nm、优选430-500nm的光。
10、一种光学设备,含有用于注入正电荷载体的第一电极、用于注入负电荷载体的第二电极和位于第一和第二电极之间的含有权利要求1-9任一项所定义的聚合物的层。
13、权利要求12的方法,其中R选自非必须取代的烷基或烷氧基。
14、权利要求11-13任一项的方法,其中式(III)的单体占聚合混合物中的单体的小于50mol%。
15、权利要求14的方法,其中式(III)的单体占聚合混合物中的单体的10-40mol%。
16、权利要求11-15任一项的方法,其中每个P独立地选自(a)硼衍生物官能团,选自硼酸基团、硼酸酯基团和硼烷基团,及(b)卤素官能团。
17、权利要求11-16任一项的方法,包括将式(III)的第一单体与第二单体在金属配位络合物催化剂的存在下和在将单体聚合成聚合物的条件下反应的步骤,其中所说的第二单体与第一单体相同或不同。
18、一种控制聚合物的玻璃化转变温度的方法,该方法包括将(a)具有至少两个硼衍生物官能团的第一芳族单体,其中硼衍生物官能团选自硼酸基团、硼酸酯基团和硼烷基团,和具有至少两个反应活性卤素官能团的第二芳族单体,其中第一或第二芳族单体中的至少一个含有权利要求16的单体;或者(b)具有一个反应活性卤素官能团和一个硼衍生物官能团的权利要求16的芳族单体,其中所说的硼衍生物官能团选自硼酸基团、硼酸酯基团和硼烷基团,在反应混合物中聚合的步骤,其中反应混合物中含有催化量的适于催化芳族单体聚合的催化剂,和足够量的将硼衍生物官能团转化成-BX3 -阴离子基团的碱,其中X独立地选自F和OH。
19、权利要求17的方法,其中碱是有机碱。
20、权利要求11-19任一项的方法,其中聚合物是电致发光聚合物。
21、下式(I)的非必须取代的重复单元在聚合物中,作为玻璃化转变温度增强剂的用途:
其中每个Ar如权利要求1-4任一项中的定义。
22、权利要求21的聚合物,其是电致发光聚合物。
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CN103339168B (zh) * | 2011-01-31 | 2016-08-10 | 剑桥显示技术有限公司 | 聚合物 |
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EP1385919A1 (en) | 2004-02-04 |
JP2004532325A (ja) | 2004-10-21 |
EP1385919B1 (en) | 2004-08-11 |
EP1385918A1 (en) | 2004-02-04 |
TWI279429B (en) | 2007-04-21 |
DE60200951T2 (de) | 2005-01-27 |
EP1385918B1 (en) | 2005-04-06 |
CN101215370B (zh) | 2012-06-20 |
JP2004527628A (ja) | 2004-09-09 |
DE60203610T2 (de) | 2005-09-15 |
DE60203610D1 (de) | 2005-05-12 |
CN101215370A (zh) | 2008-07-09 |
EP1586617A1 (en) | 2005-10-19 |
WO2002092724A1 (en) | 2002-11-21 |
ATE273363T1 (de) | 2004-08-15 |
GB0111549D0 (en) | 2001-07-04 |
ATE292662T1 (de) | 2005-04-15 |
DE60200951D1 (de) | 2004-09-16 |
CN100417703C (zh) | 2008-09-10 |
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