CN101133104B - 由具有各向异性形态粒子构成的导电聚合物 - Google Patents
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- CN101133104B CN101133104B CN2006800065654A CN200680006565A CN101133104B CN 101133104 B CN101133104 B CN 101133104B CN 2006800065654 A CN2006800065654 A CN 2006800065654A CN 200680006565 A CN200680006565 A CN 200680006565A CN 101133104 B CN101133104 B CN 101133104B
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Abstract
本发明涉及一种导电聚合物或有机金属,其特征在于由所述导电聚合物或有机金属制备纳米粒子,所述纳米粒子的粒度小于100nm,其具有非球形的各向异性形态,并具有大于1.2的长径比(“L/D”)。本发明还涉及制备该聚合物的方法,和其用于制备模制部件、自支撑薄膜或导电涂层的用途,特别是在各向异性基底或在各向异性介质和领域中的用途。
Description
技术领域
本发明涉及由具有各向异性形态的粒子构成的导电聚合物,制备其的方法,以及其用于制备成形部件(模制品)、薄片或涂层的用途。
背景技术
术语导电聚合物,以及“本征导电聚合物”或“有机金属”用于描述得自低分子化合物(单体)的物质,为至少通过聚合得到的低聚物,因此至少包含3个通过化学键连接的单体单元,在中性(非导电)状态下具有共轭π电子体系,并可以通过氧化、还原或质子化(通常描述为“掺杂”)转变成为离子形式,其为导电的。电导率至少为10-7S/cm。
在通过氧化掺杂的情况下,使用例如碘、过氧化物、路易斯酸和质子酸作为掺杂剂,或在通过还原掺杂的情况下使用例如钠、钾、钙作为掺杂剂。
导电聚合物还可以具有特别变化的化学组成。已经证实例如乙炔、苯、萘、吡咯、苯胺、噻吩、苯硫醚、周萘等,和其衍生物,例如磺基苯胺、亚乙基二氧噻吩、噻吩并噻吩(thienothiophene)及其它的,和其烷基或烷氧基衍生物或具有其它侧基例如磺酸酯/盐、苯基和其它侧基的衍生物可以作为单体。也可以使用上述单体的组合作为单体。例如偶联苯胺和苯硫醚,然后将该A-B二聚体用作单体。取决于目标,可以彼此连接例如吡咯、噻吩或烷基噻吩、亚乙基二氧噻吩、噻吩并噻吩、苯胺、苯硫醚及其它的,以形成A-B结构,然后使这些反应形成低聚物或聚合物。替代地,可以共同地聚合两种或更多种,例如三种不同的单体。
当温度增加时,大多数导电聚合物显示出电导率或多或少的增加,这说明它们是非金属导体。这类物质的几种代表至少在室温附近的温度范围表现出金属性能,就电导率而言,随温度升高而下降。检测金属性能的另外的方法为在低温(接近0K)绘制电导率相对于温度的所谓“活化能降低”图。对电导率具有金属作用的导体在低温表现出正斜率曲线。 该物质称为“有机金属”。
该有机金属已经由Weβling等人公开于Eur.Phys.J.E 2,2000,207-210中。在完成本征导电聚合物的合成后,通过单级摩擦或分散过程实现从非金属状态到至少部分金属导体的转化。本发明中分散过程也增加电导率,而所用导电聚合物的化学组成基本上没有变化。
在现有技术中可以找到明显增加电导率的许多成就。特别是使用产生导电聚合物溶液(任选使用特定的掺杂剂),然后在流延或其它处理并随后干燥后,拉伸所得到的产物(薄膜,纤维)的策略。
除了Synthetic Metal(Special Issue,Vol.65,Nos.2-3,1994年8月)之外,由Epstein等人和Heeger等人的论文给出了这些方法的好的综述(Handbook of Conductive Polymers,Skotheim,Eisenbanner,Reynolds(ed.),M.Dekker,N.Y.1998)。
虽然合成后通常得到5S/cm左右或以下的电导率范围,但用不同方法可得到几十,有时也为数百S/cm的数值。例如在15年以前的Synthet.Met.,22,1(1987)中,由Naarmann和Theophilou基于特定聚合方法用聚乙炔并随后拉伸,实现的几千或几万S/cm的电导率数值,到现在为止不能用其它导电聚合物体系实现。然而Naarmann等人的方法具有难以实施并且难于再现的缺点。此外,它产生非空气和氧化稳定的产物,此外不能进一步处理。
Kohlman和Epstein在上述手册中的图3.2给出非常好的目前获得的电导率数值的综述,其中通常仅在拉伸从本征导电聚合物生产的薄片或纤维后,获得较高的102S/cm值。
在聚苯胺的情况下,方法为例如在盐酸水溶液中聚合苯胺,其中形成质子化的聚苯胺的氯化物盐。通过强碱例如氨进行中和,以除去HCl。从而得到所谓的翠绿亚胺碱。将其在二甲苯或三氯甲烷中的毒性间甲酚的存在下用樟脑磺酸溶解。随后从该溶液流延薄膜,然后拉伸。拉伸后,得到大约102S/cm的电导率。
该方法称为第二掺杂,参见MacDiarmid和Epstein,Synth.Met.(Special Issue)Vol.65,Nos.2-3,1994年8月,103-116页,其以许多 变型进行,例如由Holland、Monkman等人在J.Phys.Condens.Matter8(1996),2991-3002或Dufour、Pron等人,Synth.Met.(2003),No.133-136,63-68页的论文中,其中改变酸和第二掺杂剂(“第二掺杂剂”)。Monkman等人的另外的论文公开于:Polymer41,2265(2000);J.Mater.Sci.36(13),3089-3095(2001),Synth.Met.(102),685(1999);PN Adams等人J.Phys.:Condens.Matter108293-8303(1998),标题为“A new acid-processing route to polyaniline films which exhibitmetallic conductivity and electrical transport strongly dependent uponintrachain molecular dynamics”。
在该方法的进一步变型中,Mattes等人,US-A-6123883,在拉伸后生产了也具有大约102S/cm电导率的纤维。在这方面的其它论文由von Mattes等人公开于Synth.Metals84,45-49(1997);US5,981,695和WO2004/042743A1。
全部这些论文的共同之处在于由导电聚合物的分子溶液开始,并在蒸发溶剂后,试图拉伸聚合物的链,从而使其取向(平行),即使它们排列。非常清楚用这种方法可以使电导率增加100倍,并可能产生各向异性效果(即电导率或一些光学性质的优先取向,其对于某些应用有利,对于其它应用没有不利)。
然而,如果与此相反使用不可溶的导电聚合物或有机金属,因此不从溶液加工,而是从分散体加工,拉伸不能导致分散的纳米粒子取向并随后增加电导率,甚至没有链取向。聚合物粒子(初级粒子)通常以球形存在于分散体中,即为各向同性结构(形态)。当这些粒子聚集的时候,尤其是在从分散体除去分散剂来形成层时的时候,形成类似的各向同性的第二形态。
近来,技术文献中已经记载了可能的所谓“纳米纤维”(英语也称为“nanofibrils”),其由原则上取向和拉伸的聚苯胺制成。然而,近来这些纳米纤维的研究表明由于它们部分由球形初级粒子构成,一方面不能拉伸,另一方面不具有特别高的初始电导率(只有几S/cm)。此外,纤维的尺寸(直径100-200nm)决不能证实它们属于“纳米领域″。
基于导电聚合物的真正的纳米纤维(尺寸类似于碳纳米纤维,更不用 说具有足够高电导率的那些)迄今为止不是已知的。
初级粒子无论如何从开始在优选方向上排列、取向,但是由于迄今可用的导电聚合物和有机金属的初级粒子(纳米粒子)基本上为各向同性的,所以到现在为止不能通过拉伸从分散体沉积的薄片、薄膜或纤维,来增加电导率(因此也不能通过拉伸该产物增加电导率)。
发明内容
因此本发明目的是产生可能取向(排列)的导电聚合物或有机金属的初级粒子,即提供具有合适于取向(排列)的形态的导电聚合物或有机金属。
根据本发明,用本征导电聚合物或有机金属实现上述目的,其特征在于,由聚合物形成的粒度小于100nm的纳米粒子具有各向异性形态,其特征在于,偏离球体形态,并具有大于1.2的长径比(“L/D”)。
在进一步加工成为涂层、薄片或片材之前,通常以稳定分散体形式得到本发明的聚合物粒子,其包含至少本征导电聚合物的粒子,其中平均粒度(重量)低于1μm,其中所述分散剂在室温下是液体。除去分散剂后,从该分散体形成的层、薄片或片材通常具有>100S/cm的电导率。
此外本发明的主题还是制备上述聚合物粒子的方法,其中以分散体形式得到聚合物粒子,并且其中依次包括
(a)从单体制备本征导电聚合物,其中控制聚合期间的温度,使得它不升高到超过起始温度1℃的值,
(b)在对于导电聚合物惰性的非导电、非聚合极性物质存在下,任选地还在非导电聚合物的存在下,施加足够剪切力,将步骤(a)的产物研磨和/或分散,其中导电聚合物和极性物质之间的重量比是2:1至1:10,任选在低于250℃的温度将步骤(b)的产物分散在其它分散剂中,优选温度低于180℃,特别优选低于100℃,其中导电聚合物和分散剂之间的重量比小于1:10,其中在非导电聚合物的存在下进行分散的情况下,温度不超过所述限制,同时高于该非导电聚合物的玻璃化转变点5℃到至多80℃。
进行该方法使得粒子获得本发明所需的形态,其可以通过分析方法例如扫描隧道显微镜或扫描力显微镜和透射电子显微镜检查。
此外令人惊讶的是聚合期间可以使用光学活性抗衡离子。该抗衡离子的实例是D或L樟脑磺酸、氨基酸或例如光学活性取代的芳香族磺酸(例如对磺基苯基丙氨酸)。
此外本发明主题是如上所述的分散体或根据上述方法制备的分散体,在制备导电的成形部件(模制品)、自支撑薄片或涂层中的用途。
本发明的其它优选实施方式在从属权利要求中。
附图说明
图1是扫描隧道显微照片,其显示了聚苯胺的球形初级粒子的附聚物。
图2是透射电子显微照片,其显示了聚苯胺次级粒子结构,其中具有球形初级粒子的细微结构。
图3是薄片的扫描电子显微照片,该薄片从聚苯胺分散体流延然后干燥,其由球形初级粒子构成。可知干燥后也存在球形第二或第三形态。
图4是从基于二甲苯的分散体沉积的聚苯胺粒子的透射电子显微照片,其除无定形干残留物之外显示球形初级和次级粒子。
图5是高分辨率透射电子显微镜照片,其展示了从聚苯胺分散体沉积的初级粒子,其位于彼此之上。
图6显示了聚苯胺初级粒子的扫描力显微照片,该初级粒子相互并排排列,具有本发明的形态。
具体实施方式
本申请中使用的术语“导电聚合物”包括本征导电聚合物和上述所谓的有机金属。
本申请中“初级粒子”是指分散体中分离出现的最小形态单元,或在扫描或透射电子显微镜中可识别的最小形态单元,即导电聚合物的超分子结构单元。
“次级粒子”或“二级结构”是指更高级的结构(二级和三级结构),其得自初级粒子的相互积聚(聚集)。“聚集体”是指通过初级粒子聚结并通过初级粒子的材料桥接稳定的集合。因此“附聚物”仅是指基本上包含初级粒子点状接触的聚结物。可以破坏基质中的附聚物,并分散成为初级粒子,但是在聚集体的情况下不破坏化学键无法实现。该限定通常在颜料技术中(参见Herbst/Hunger,“Industrielle OrganischePigmente”,VCH1987)。也用于此处。应该特别注意该技术领域的早期阶段不总是注意上述限定,但是讨论“附聚物”时没有任何区别。
因此本发明的成果是令人惊讶的,特别是因为分散过程本身没有优选的方向,因此没有预期得到的形态偏离球体形态(其在第一分散步骤之前,在聚合后直接以未加工状态存在)。此外,极其令人惊讶的是:聚合期间使用的光学活性抗衡离子有助于形成各向异性初级粒子的事实。尽管已经记载了具有光学活性抗衡离子的导电聚合物,但是无论如何没有观察到偏离的初级形态。
本发明获得的成果也是令人惊讶的,这是因为通常认为分散过程对聚合物的电导率有害。大部分专家认为分散期间导电聚合物链断裂,因此电子传导性(沿着这些链)变差。因此,如背景技术中所述的,试图由此制备导电聚合物的真正溶液。此外通常认为使用分散剂和添加剂也是不利的,这是因为它们可以升高并增强电子传输的势垒。在真正的本发明的方法中,事实上优选两个分散步骤。
最后,本发明方法令人惊讶的是,在第一分散步骤(步骤(b))后,如下更详细说明的,在任选进行第二分散步骤之前,完全除去任选存在的非导电聚合物实际上不是必需的。
本发明得到一系列优点,例如获得导电性的优选方向、或其它(例如光学或机械)性能的可能性,制备具有增加电导率(任选也增加机械载荷承载能力)的拉伸薄片和纤维、或在各向异性环境(例如电场或磁场或各向异性结构基质)中沉积导电聚合物,以及如此实现的性能改进。
不希望限于特定理论,认为由于分散过程得到本发明的粒子形态,其中通过在最可能低的温度进行分散过程,产生最小的流向差异,从而产生作用于粒子的力的优选方向,这可以导致初级粒子各向异性变形。聚合期间根据本发明提出的温度程序在本发明中可以有助于链的有序度,其可能对之后的各向异性成形是有利的。使用光学活性抗衡离子可以引入相同的方向。
包含根据本发明的导电聚合物的分散体也具有稳定的优点。因此制备后即时或制备后至少短时间不需要进一步处理本发明的稳定分散体,而且可以储存较长时间,例如几个小时,例如5-10小时,或几天,例如1-3天或4-6天,或几周,例如一周以上至几个月,例如1个月以上,优选超过三个月。上述储存细节涉及环境条件。“环境条件”具体是指温度大约为室温,即大约5至25℃,压力大约为大气压,即1013kPa。然而本领域技术人员清楚取决于储存位置,上述陈述也稍微偏离通常的环境条件。
本发明的本征导电聚合物或有机金属的实例是在说明书开始时提到的那些。特别是以下实例:聚苯胺(PAni),聚噻吩(PTh),聚(3,4-亚乙基二氧噻吩)(PEDT),聚二乙炔,聚乙炔(PAc),聚吡咯(PPy),聚异硫茚(PITN),聚亚杂芳基亚乙烯基(PArV),其中亚杂芳基可以为例如噻吩、呋喃或吡咯,聚对亚苯基(PpP),聚苯硫醚(PPS),聚周萘(PPN),聚酞菁(PPc)及其它的,以及其衍生物(其例如由侧链或基团取代的单体形成),其共聚物和其物理混合物。特别优选聚苯胺(PAni)、聚噻吩(PTh)、聚(3,4-亚乙基二氧噻吩)(PEDT)、聚噻吩并噻吩(PTT)和其衍生物。优选本征导电聚合物的二元混合物是PAni和PTh、PAni和PEDT、PAni和PPy、PEDT和PPy、以及PEDT和PTh的混合物。最优选聚苯胺。
在根据本发明方法的步骤(a)中,通常按照EP-A-0 329 768制备可分散的本征导电聚合物,优选为聚苯胺。特别参考EP-A-0 329 768中使用的定义。这也应用于本发明,用于实施本发明方法的步骤(a)。
优选在本发明方法的步骤(a)中控制温度,因此不同于EP-A-0 329768的方法,使得聚合期间的温度不升高到超过起始温度1℃的值,并且聚合期间升温速度不超过1K/分钟。优选操作反应,使得升温<0.5℃,其中升温速度从不超过0.2K/分钟。
通常可以获得控制温度所必需的冷却,冷却速度至少0.02K/分钟,优选0.05K/分钟。通过在每种情况下使用的反应器中,在启动冷却期间不开始反应地测量温度的变化,来确定冷却速度。
根据本发明,在步骤(a)后得到的(中间)产物通常具有约5S/cm的电导率。
得自步骤(a)的中间产物通常以粉末形式存在,其中80wt%的初级粒子小于500nm,并且其中不超过20wt%的聚集成为大于1μm的聚集体。这可以从干燥固体的扫描电子显微照片、和聚合物共混物的分散体的光学显微镜观测看出。它们的初级粒子形态继续为基本上的球形。
本发明的固体通过直接分散在测试聚合物中或借助于密闭式混合机作为浓缩物在测试聚合物中分散,来进行光学显微镜观测。PCL或PVC是合适的测试聚合物。待分散的物质浓度通常是0.5wt%。挤出该混合物形成薄膜。使用本发明的原料,识别出均匀的强烈染色的半透明物质;该颜色来自于分散的初级粒子。此外,有时候识别出未分散的0.5-1μm的粒子和单个更粗糙的粒子。
在本发明方法的步骤b中,在聚合和处理后(所得聚合物是否完全干燥不是重要的),在非聚合极性物质的存在下分散所述聚合物,或与其一起研磨。极性物质(也可以称为“分散助剂”)具有下列性能:
它可以是液体或固体,
这种极性物质的实例是
a)固体:硫酸钡;二氧化钛,特别是粒度小于300nm的超细二氧化钛;有机颜料例如颜料黄18;
b)惰性溶剂:水、DMF、DMSO、γ-丁内酯、NMP和其它吡咯烷酮衍生物,例如正甲基-2-吡咯烷酮、二噁烷、THF;
其中该清单是举例,决不是限定。
通常可以在分散装置例如高速混合器(例如所谓的流体混合器)中或在超声波下、在球磨机、珠粒磨机、双辊或三辊磨机或高压分散装置(Microfluidics类型)中,用极性物质进行分散或研磨。
在高速混合器中或在超声波下,处理时间至少是3分钟。在球磨机中,在双辊或三辊磨机上或在其它具有高剪切力单元中,需要较长的处理时间,例如至少30分钟。同时使用电场,特别是校正电场可以是有利的;在这种情况下大都需要24小时以上。
对于本征导电聚合物惰性的极性非导电物质的使用量使得导电聚合物粉末和极性物质之间的重量比为2:1至1:10。
优选,当进行步骤(b)时,至少还存在非导电聚合物,特别是热塑性聚合物。例如可以使用可从Eastman Kodak或Degussa商购的聚对苯二甲酸乙二醇酯共聚物,或来自Degussa的聚甲基丙烯酸甲酯(PMMA)。热塑性聚合物的存在需要在高剪切和低于250℃同时高于所述非导电聚合物玻璃化转变点5到至多80℃的温度下进行分散,优选温度低于180℃,特别优选温度低于100℃。
冷却后,得到固体混合物、聚合物共混物,其相对于在室温下是固体的从步骤(b)得到的产品组合物组分,包含20至60wt%、优选约35wt%导电聚合物,所述组合物组分包含导电聚合物、极性物质和任选的其它非导电聚合物。进行步骤(b)后,导电聚合物通常具有大约60S/cm的电导率。
步骤(b)后,可以通过洗涤或萃取,部分或几乎完全除去加入的极性、惰性和非导电物质或同样存在的非导电聚合物。优选在上述段落中所述的步骤(b)结束后,优选进行第二处理步骤。可替代地,也可以在步骤(b)期间开始进行第二处理。
第二处理的目的是处理(调节)步骤(b)的产物,用于随后的任选分散 步骤,该第二处理也可以称作调节步骤(b)的产物用于其它随后任选的分散步骤。可以使用多种物质洗涤或萃取,例如芳族化合物、醇、酯、醚、酮,例如二甲苯、甲苯、乙醇、异丙醇、氯苯、二异丙基醚等。也可以使用溶剂和助剂,其支持随后的分散步骤。这些可以是例如二甲苯或氯苯和十二烷基苯磺酸(DBSH)。
在步骤(b)产物的第二处理期间,相对于在室温下为固体的产物的组分,优选提高产物中导电聚合物的比例至少5wt%,优选10wt%,特别是20wt%。
替代地,例如如果加入物质的存在不干扰其它的处理和导电聚合物的使用,则可以连续处理而不降低或除去极性物质或热塑性聚合物。极性物质或热塑性聚合物的存在不影响聚合物粉末的电导率。
优选相对于整个组合物,步骤(b)和第二处理后获得的导电聚合物的浓度为45至99wt%,优选55至70wt%。例如步骤(b)的产物可以是湿润的糊剂,具有相对高比例的用于第二处理的溶剂或助剂。此外在进行本发明方法的其它分散步骤之前,非常大量地除去第二处理期间使用的物质对于本发明而言不是必要的,但是在工业实践中这可以是有利的。
本发明方法的其它分散步骤是在有机或含水介质(分散剂)中进行的分散,并且通常在室温下进行,或温度仅稍微不同。作为分散聚集体,特别考虑可以将高分散能量引入系统的机械。这些可以例如为比如Ultraturrax、Disolver、珠粒磨机、球磨机、高压分散装置例如Microfluidics类型的那些、或超声波系统的单元。分散时间可以是几分钟,例如20分钟,直至几小时,例如1至3小时,例如2.5小时。
特别合适作为分散剂的是表面张力至少25mN/m的溶剂。本发明的分散剂在室温下为液体,并且尤其是具有<10,000的相对粘度,例如<5,000,特别是<1,000。
本发明分散剂的实例是二甲苯、氯酚、二氯乙酸、N-甲基吡咯烷酮、二甲基亚砜、辛醇、或苯甲醇或高级醇,例如烷烃或芳香的C9-C20醇或其混合物。
将如此量的分散剂加入本发明方法的步骤(b)的产物,使得相对于本 征导电聚合物,分散剂(重量比)过量。特别是导电聚合物和分散剂之间的重量比小于1:10,优选小于1:15,例如1:18。
该分散步骤通常得到的产物为高粘度糊剂或液体、低粘度分散体,其中相对于全部分散体,导电聚合物的浓度通常不超过约10wt%。取决于调节的程度,该分散步骤后得到的分散体优选包含小比例的用于步骤(b)的极性物质和非导电聚合物。
当生产具有导电性的模制品、自支撑薄片或涂层时,为了准备使用本发明的分散体,在上述分散步骤后或替代地在该分散步骤期间,可以加入助剂和添加剂。这些可以为例如粘度调节剂、湿润助剂、基质聚合物例如清漆粘合剂、成膜物质、稳定剂、湿润助剂、蒸发调节剂例如蒸发促进剂或蒸发延缓剂、或其它助剂和添加剂。然后得到稳定的分散体,其包含对产物的进一步成形和性能有用或重要的全部成分。
在包括第二处理和配制的分散之后得到的分散体,可以在任选地进行另外的分散和第二处理步骤后,用于制备具有导电性(成形)的成形部件(模制品)、多种层厚度的自支撑薄片或涂层。
可以通过一系列方法成形,例如浸渍、液滴润湿、喷雾、旋涂、印刷(例如丝网印刷、胶印、喷墨及其它的)、挤出、流延、刮刀涂敷、静电纺丝及其它的。特别优选通过浸渍、流延、液滴润湿、旋涂或印刷进行成形。
除去分散剂后,得到的层、涂层、薄片、片材或其它成形部件或组件具有>100S/cm的电导率,优选至少200S/cm或更大,例如大于250S/cm,特别是至少500S/cm,例如200至200,000S/cm,200至20,000S/cm或500至10,000S/cm,例如300至3,000或500至1000S/cm。
此外,本发明分散体的粒子的特征在于,X射线衍射图例如聚苯胺(用对甲苯磺酸“计量”)的没有锐利反射,在2θ=大约3°可见反射,并且在与2θ=大约19°相比,得自本发明分散体的聚苯胺情况下具有高强度。与此相比,步骤(a)的“未加工”粉末通常在此处没有峰或仅有非常弱的强度,而任何速度的根据步骤(b)的第一研磨/分散过程后,聚苯胺至少显示了清晰的反射,但是弱于大约19°的峰。
第二分散后,并仅对于本发明进行的分散,因此得到>100S/cm的电导率,该反射清晰地为最强的,并且其它反射随着电导率增加逐渐变弱。
另外,扫描力显微镜研究中,可以清晰地发现初级粒子不再是球形,而是具有约2的L/D比,并且长度大约为8-11nm,宽度为约4nm(参见图6)。
不同于具有各向同性粒子形态的导电聚合物/有机金属,现在可以从各向异性介质例如液晶(低分子或高分子)物质中、或在各向异性电场和/或磁场的影响下、或在取向或预结构化的取向基质(例如HOPG、拉伸取向聚丙烯或其它塑料薄片,优选单轴拉伸薄片)上成形,并可用于或使得产生具有各向异性性能的成形(模制)部件和表面涂层。如此,通过将本发明的聚合物粒子沉积到取向基质(例如取向聚丙烯)上,可以得到大约1000S/cm和以上的电导率。与此相比,在从相同分散体在各向同性基质(例如玻璃)上沉积的情况下,得到大约300S/cm的电导率。
可以通过成形和进一步的加工产生抗静电或导电涂层、透明和非透明电极、清漆,其适用于EMI屏蔽,电子设备中触点或场效应晶体管中的“源极”、“漏极”或“栅极”,以及天线、振荡电路、逻辑电路、电容中的导体或反极、电解质电容器或所谓“超电容”,并且可以起许多功能,例如传统金属、电极的高度掺杂半导体或氧化还原活性涂层在传统电气工程和电子设备中起的作用。
通过干燥或通过进行一种上述成形方法可得到的制品是本发明的实施方案,所述制品包含可从本发明分散体得到的导电聚合物。优选上述制品基本上由导电聚合物构成。
新型初级粒子形态对多种应用产生重要的优点,这通常因为较高的电导率,其中任选仅在一个优选方向上高于惯例的电导率并不是缺点(例如EMI屏蔽中,它是不相干的,无论电导率是各向同性或各向异性地高,该电导率对于屏蔽效率是重要的)。
对于一些应用,该新形态使得可以首次使用导电聚合物,因此在聚合物电子设备中,其中可以使用迄今惯用具有导电性的“源极”、“漏极”和“栅极”,但是用蒸气沉积金属实现有机场效应晶体管的引线(“互连”) 和其导电。此外在这里通过在“互连”方向提高电导率,首次使用导电聚合物/有机金属。
举例来说可以是下列应用:
-用作电导体(例如电触点、电导线、按钮开关、电极等)或半导体,
-用于防静负荷,
-屏蔽电磁波(EMI屏蔽),
-吸收微波(用于屏蔽或加热目的),
-用于产生电容或作为电解质电容器的电解质替代物,
-用作所谓“超电容”中的电极或电极组分(这类电容也称为双电层电容器(DLC),其特征在于,形成双电层,通常基于碳黑和/或石墨。术语“电化学双层电容”经常以英文使用。),
-用于产生半导体元件,例如二极管、晶体管及其它的,
-作为光电导体或用于光电能量转化,
-用于与金属或半金属组合物,或用于与利用热电效应作为温度传感器(IR吸收)的不同导电聚合物的组合物,或用于热电能量转化,
-作为传感器,
-作为指示剂,例如通过电致变色、微波吸收、热电电势等,
-用于电解或电合成方法,作为电催化电极(例如用于燃料电池),
-用于光电催化或合成,以及用于光电效应,
-用于防腐蚀,例如阳极防腐蚀,
-用作蓄电池中的电极,
-用作紫外线和光稳定颜料。
-用作电致发光阵列中的电极或引线(例如,作为不透明的所谓“背 电极”或作为透明的所谓“前电极”)
-用作有机/聚合物发光二极管或太阳能电池中的空穴注入层或阳极缓冲层或作为透明阳极。
Claims (23)
1.一种导电聚合物,其特征在于,其以粒度小于100nm的纳米初级粒子的形式存在,所述纳米初级粒子具有非球形的各向异性的形态,并具有大于1.2的长径比(“L/D”),和在除去分散剂后,由所述聚合物的分散体形成的层、薄片或片材具有>100S/cm的电导率,
所述聚合物选自聚苯胺、聚噻吩、聚(3,4-亚乙基二氧噻吩)、聚二乙炔、聚乙炔、聚吡咯、聚异硫茚、聚亚杂芳基亚乙烯基、聚对亚苯基、聚苯硫醚、聚周萘、聚酞菁、聚噻吩并噻吩及其共聚物和其物理混合物。
2.权利要求1的聚合物,其特征在于,所述聚亚杂芳基亚乙烯基中的亚杂芳基为噻吩、呋喃或吡咯。
3.权利要求1的聚合物,其特征在于,所述电导率大于或等于200S/cm。
4.权利要求3的聚合物,其特征在于,所述电导率是300S/cm至3000S/cm。
5.权利要求1至4之一的聚合物,其特征在于,所述聚合物选自聚苯胺、聚噻吩、聚噻吩并噻吩、聚吡咯、和这些聚合物单体的共聚物。
6.权利要求1至4之一的聚合物,其特征在于,其以分散体存在,并且分散剂具有<10,000的相对粘度。
7.一种制备权利要求1至6任何一项的聚合物的方法,其中,依次包括
(a)由单体制备本征导电聚合物,其中在聚合期间控制温度,使得它不升高到大于起始温度1℃以上的值,
(b)在对于所述导电聚合物是惰性的非导电非聚合极性物质存在下、任选地在非导电聚合物的存在下、施加足够剪切力,来研磨和/或分散得自步骤(a)的所述产物,其中所述导电聚合物和所述极性物质之间的重量比是2∶1至1∶10,和
(c)在低于250℃的温度下在其它分散剂中分散得自步骤(b)的所述产物,其中所述导电聚合物和所述分散剂之间的重量比小于1∶10。
8.权利要求7的方法,其特征在于,在聚合期间,在步骤(a)中使用光学活性抗衡离子。
9.权利要求7或8的方法,其特征在于,在低于180℃下进一步分散得自步骤(b)的所述产物。
10.权利要求9的方法,其特征在于,在低于100℃下进一步分散得自步骤(b)的所述产物。
11.权利要求7或8的方法,其特征在于,在非导电聚合物的存在下进行所述分散,并且所述温度高于所述非导电聚合物玻璃化转变点5到至多80℃。
12.权利要求8的方法,其特征在于,在聚合期间,在步骤(a)中升温速度从不超过0.2K/分钟。
13.权利要求7或8的方法,其特征在于,所述非导电聚合物是热塑性聚合物。
14.权利要求7或8的方法,其特征在于,对得自步骤(b)的所述产物进行二次处理。
15.权利要求14的方法,其特征在于,在二次处理期间,通过洗涤或萃取降低得自步骤(b)的所述产物中极性物质或非导电聚合物的比例。
16.权利要求7或8的方法,其特征在于,加入支持随后的分散步骤的溶剂和/或助剂。
17.权利要求7或8的方法,其特征在于,对第二分散的产物进行二次处理。
18.权利要求7或8的方法,其特征在于,加入粘度调节剂、湿润助剂、基质聚合物、稳定剂、湿润辅剂、蒸发调节剂和/或其它助剂和添加剂,其支持随后任选的成形过程。
19.权利要求18的方法,其特征在于,在所述第二分散步骤之前或期间进行所述加入。
20.权利要求14的方法,其特征在于,在得自步骤(b)的所述产物的二次处理期间和/或在第二分散步骤期间,使用表面张力超过25mN/m的有机溶剂。
21.权利要求1至6之一的导电聚合物,或根据权利要求7至20之一的方法制备的分散体,在制备具有导电性的成形部件、自支撑薄片或涂层中的用途。
22.权利要求21的用途,其特征在于,所述成形部件、自支撑薄片或涂层是电极、天线、聚合物电子元件、电容器和双电层电容器(DLC)。
23.权利要求21或22的用途,其特征在于,在各向异性材料和/或各向异性场中进行所述成形,或沉积到各向异性基质上。
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PCT/EP2006/001872 WO2006092292A1 (de) | 2005-03-02 | 2006-03-01 | Leitfähige polymere aus teilchen mit anisotroper morphologie |
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JP2008531797A (ja) | 2008-08-14 |
KR101135934B1 (ko) | 2012-04-18 |
WO2006092292A1 (de) | 2006-09-08 |
DE102005010162A1 (de) | 2006-09-07 |
US20080265215A1 (en) | 2008-10-30 |
CA2599655A1 (en) | 2006-09-08 |
CN101133104A (zh) | 2008-02-27 |
EP1853647A1 (de) | 2007-11-14 |
DE102005010162B4 (de) | 2007-06-14 |
US7947199B2 (en) | 2011-05-24 |
JP5139088B2 (ja) | 2013-02-06 |
KR20070117587A (ko) | 2007-12-12 |
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