Poly(1,6-heptadiyne), a free-standing polymer film dopable to high electrical conductivity
Poly(1,6-heptadiyne), a free-standing polymer film dopable to high electrical conductivity
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聚(1,6-庚二炔)，一种可掺杂高导电性的独立聚合物薄膜
DOI：
10.1021/ja00351a048
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发表时间：
1983
影响因子：
15
通讯作者：
J. M. Pochan
中科院分区：
文献类型：
--
作者：
H. Gibson;F. C. Bailey;A. Epstein;H. Rommelmann;S. Kaplan;J. Harbour;X. Yang;D. Tanner;J. M. Pochan
1，6-庚二炔在均相齐格勒-纳塔催化剂的浓溶液表面上的聚合导致具有金属光泽的不溶性独立膜。通过用受体处理对这些膜进行“掺杂”导致电导率高达1 S/cm。该聚合物的特征在于其分子结构，其固态结构和物理性质，掺杂过程的性质，以及其热稳定性和氧化稳定性。聚（1，6-庚二炔）在其分子和固态结构方面与聚乙炔形成了许多对比，这些对比产生了有关导电聚合物要求的一些信息。导电聚合物至少在过去25年中一直是零星兴趣的主题。制备聚乙炔4的自支撑膜的方法的发现引发了对这种以前以粉末形式研究的共轭多烯的兴趣的重生。随后发现，一些掺杂剂可有效地将导电性提高到金属状态。6在本研究开始时，在聚合过程中，没有其他取代的多烯原位形成膜。我们最初的目标是确定其他共轭多烯是否可以首先原位聚合成自支撑膜，然后掺杂成高电导率。如果可以达到这一目标，则可以通过改性多烯链上的取代基来实现诸如柔性、延展性、热转变、氧化稳定性等性能的优化。然而，已知并随后通过使用白川催化剂 * 证实，取代的乙炔，例如，甲基和乙基衍生物，与乙炔本身相比反应缓慢。由于环化聚合在合成取代的烯烃衍生的聚合物中具有这样的实用性，因此我们相信二乙炔的环化聚合可以证明在制备取代的聚乙炔中是有用的。使用不溶性聚合物聚合1，6-庚二炔（1），
Polymerization of 1,6-heptadiyne on the surfaces of concentrated solutions of homogeneous Ziegler-Natta catalysts leads to insoluble, free-standing films with metallic luster. “Doping” of these films by treatment with acceptors results in conductivities up to 1 S/cm. The polymer has been characterized in terms of its molecular structure, its solid-state structure and physical properties, the nature of the doping process, and its thermal and oxidative stability. Poly( 1,6-heptadiyne) provides a number of contrasts to polyacetylene in its molecular and solid-state structure which yield some information about the requirements for conductive polymers. Electrically conductive polymers have been the subject of sporadic interest for at least the last 25 The discovery of a method of preparation of free-standing films of polyacetylene4 sparked a rebirth of interest in this conjugated polyene that had been previously studied in powder form.s The films were more amenable to study of physical properties and for many potential applications. A number of dopants were subsequently found to be effective for raising the conductivity into the metallic regime.6 At the inception of the present study, no other substituted polyenes had been formed as films in situ during polymerization. Our initial goal was to determine whether other conjugated polyenes could first be polymerized in situ to free-standing films and then doped to high electrical conductivity. If this goal could be reached, optimization of properties such as flexibility, ductility, thermal transitions, oxidative stability, etc. might be achieved by modification of substituents on the polyene chain. It was known,’ however, and subsequently confirmed by using the Shirakawa catalyst* that substituted acetylenes, e.g., methyl and ethyl derivatives, polymerize sluggishly in comparison to acetylene itself. Because cyclopolymerization was of such utility in the synthesis of substituted olefin derived polymer^,^ it was our belief that cyclopolymerization of diacetylenes might prove useful in the preparation of substituted polyacetylenes. The polymerization of 1,6-heptadiyne (1) using an insoluble