SYNTHESIS OF POLYACETYLENE BY NOVEL CATALYSTS COMPOSED OF TRANSITION METAL 2-ETHYL HEXYL PHOSPHONATES AND ALUMINIUM TRIALKYLS

Polyacetylene is the most hopeful electrical conductive polymer, which is being exploited to fabricate plastic battery, solar energy cell etc. The catalysts used for the synthesis of high cis-polyacetylene films are mainly Ti(OC_4H_9)_4-AlEt_8 and rare-earth coordination catalysts as well as Co(NO_3)_2-NaBH_4. This paper reports features of acetylene polymerization by novel catalysts composed of transition metal 2-ethyl hexyl phosphonates of the fourth periodic transitional series-Ti, V, Cr, Mn, Fe, Co, Ni and aluminium trialkyls. Except Ni catalyst system, all catalytic systems can promote polymerization of acetylene at room temperature to form a silvery-grey polyacetylene film with rich cis-content and high crystallinity. Under the experimental conditions tested, the catalytic activity of various systems shows the following sequence: Fe>Ti～V>Cr>Mn>Co>Ni The polyacetylene films obtained were characterized.     

稀土聚乙炔电池及其电化学

聚乙炔作为合成的有机金属具有极大的应用潜力。MacDiarmid等发现可用电化学方法对聚乙炔进行可逆掺杂,使其电导率达到金属的水平,而且聚乙炔本身具有一个由微纤维组成的网状结构,有很大的表面积(～60m~2/g),因此适合于作二次电池的电极。人们已在实验室制备了各种类型的聚乙炔电池,它们具有重量轻、能量密度高、功率密度大、可充电等特点,因而具有研究价值。沈之荃等曾应用稀土配合催化剂合成了高含量顺式的、热稳定性较高的和抗氧化稳定性的聚乙炔。本文报道稀土聚乙炔电池及其电化学的研究工作。结果表明:稀土聚乙炔电池的开路电压可达3.5V,短路电流达10mA,平均功率密度达160W/kg,具有进一步开发研究的前景。     

稀土聚乙炔电化学

本文研究了稀土聚乙炔在水溶液中进行电化学掺杂和化学掺杂,及稀土聚乙炔的电位;用掺杂后的稀土聚乙炔作为水溶液体系一次电池的阴极,以镁作阳极构成半塑料电池;并研究了以稀土聚乙炔作为有机电解质体系可再充式电池的阴极,以锂作阳极的化学电源的电性能。     

Nd(P204)3/AlEt3/第三组分体系催化乙炔聚合动力学

本文研究了乙炔在Nd(P)_3-AlEt_3-Ⅲ组分体系中的聚合动力学。结果表明聚合速率R_p与乙炔压力和催化剂浓度分别呈一级关系,即R_p=k＇[cat][P];发现聚合速率随时间按二级定律衰减,即dR~(-1)dt=k;提出活性中心以双分子失活的假设解释了实验结果。     

过渡金属膦酸酯新催化剂合成聚乙炔

聚乙炔是最有希望的导电高分子,目前己在开发应用于制造塑料电池、太阳能电池等。合成聚乙炔膜的主要催化剂有Ti(OC_4H_9)_4-Al(C_2H_5)_3催化剂,稀土络合催化剂及Co(NO_3)_2-NaBH_4等。本文报道新开发的周期表中第22号元素钛至第28号元素Ni的笫四周期过渡金属——Ti,V,Cr,Mn,Fe,Co,Ni的膦酸酯盐与三烷基铝组成的新络合催化剂合成聚乙炔膜的特征。除镍外,这些催化剂都可以使乙炔在室温下聚合生成顺式含量50％以上、高结晶性、有金属光泽的银灰色聚乙炔膜。在实验范围内,各催化体系聚合活性次序如下:Fe>Ti,V>Cr>Mn>Co>Ni,并且表征了所制备的聚乙炔膜,这些新催化剂的开发为合成聚乙炔提供了方便和有利条件。     

多功能聚合物合成有机化学之进展

我们探索了利用钯催化反应合成新型多功能聚合物, 实验结果显示这类反应能与甚多官能团相容, 从而为聚合物化学家提供若干实用之合成方法。     

ELECTROCHEMISTRYOF RARE EARTH POLYACETYLENE

The electrochemical doping of rare earth polyacetylene (PA) employing aqueous electrolyte and the electrical potentials of the rare earth polyacetylene were studied. The half-plastic batteries consisting of doped polyacetylene as cathode and magnesium as anode aS well as aqueous solution as electrolyte were fabricated. Also, the electrical characteristics of the rechargeable battery with doped PA cathode and lithium anode in organic electrolyte were investigated.