含乙撑二氧基噻吩的萘基喹喔啉共轭聚合物的合成及性能
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摘要
喹喔啉类化合物是一类重要的苯并吡嗪杂环类缺电子型化合物,具有广泛的生理活性并在有机发光,光伏电池等领域有一定的应用。含有喹喔啉环的聚合物的制备及其电致变色方面的研究是最近的研究热点。虽然含有喹喔啉环聚合物的研究一直没有间断过,但是侧链是平面结构的喹喔啉单体与其他富电子环组成的聚合物研究尚鲜见报道。噻吩类化合物是一种典型的富电子单元,能够与其他缺电子单元组成电荷转移型结构。与噻吩相比,乙撑二氧噻吩(EDOT)噻吩环的3和4位被取代,防止了聚合时噻吩α-β环的连接,使聚合物分子链更为规整有序。基于以上思路,本文合成了电荷移动性共轭分子(5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉)。论文的主要内容介绍如下:
1.合成了具有较低氧化电位、窄禁带能隙的新型电荷移动性共轭分子—5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉。通过紫外可见光谱,荧光光谱,核磁共振氢谱等测试手段进行了结构表征。通过电化学聚合制备了聚(5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉)膜。此聚合物膜在-2.0 ~ +1.5 V有电致变色性能,膜颜色由深绿色变透明的浅蓝色(氧化态),变红色(还原态)。其电致变色响应时间较快有望利用在电致变色材料中。
2.以FeCl3为氧化剂,通过溶液及固相聚合法制备了聚(5,8-二(3,4-乙撑二氧噻基) -萘基喹喔啉)。通过比较两种方法合成的聚合物的导电率,电极行为来确定了最佳氧化剂用量及聚合方法。结果表明:氧化剂与单体摩尔数为2:1固相聚合合成的聚合物具有高比电容和良好的循环稳定性,在酸性电解质中电流密度为1 mA.cm-2时,首次放电比电容达到114 F. g-1,经过1000次充放电后容量保持率在94%。
3.为了提高聚合物的导电率,在固相聚合最佳合成条件下选几种磺酸作为掺杂剂合成了掺杂的聚合物,结果表明当萘磺酸掺杂时其导电率提高四个数量级,但对其电化学行为的影响不大。
4.通过Sonogashira偶合反应将5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉与带有不同长链烷氧基的对苯乙炔进行交替共聚,得到了两种具有较好热稳定性和电化学活性的可溶性聚合物。
Compounds with quinoxaline aromatic rings which have an electron-deficient nature are used as raw materials for organic light-emitting devices, light-emitting cells and optoelectronic devices. Although preparation and electrochromic properties of quinoxaline containing polymers have drawn a wide interest, planar fused acenaphthene substituted quinoxaline unit has not been paid much attention. On the other hand, thiophenes are belonging to the most typical electron-rich aromatic rings used in CT-type structure. Compared with thiophene, while the polymerization of 3,4-ethylenedioxythiophene theα-βandβ-βmislinkage are forbidden by blocking theβpositions of the thiophene units with the electron donating oxygen atoms, and the ethylene bridges minimize steric distortion effects resulting in a high stereo regularity of the polymer chain so that goodπ-conjugation is guaranteed. Hence in this paper we have successfully synthesized bis-3,4-ethylenedioxythiophene substituted acenaphthe -nequinoxaline. The main content is as follows:
A new EDOT-substituted acenaphthenequinoxaline was synthesized via Stille coupling reaction, which has a low oxidation potential of 0.73 V vs. Ag/Ag+, and was electrochemically polymerized. The electrochemically coated polymer film exhibited electrochromic behavior between -2 V and +1.5 V vs. Ag/Ag+. The film color changed from more green (neutral) to transmissive light blue in the oxidized state and reddish in the reduced state. Considering these properties, this polymer can be utilized in electrochromic device applications.
Poly (8,11-bis(3, 4-ethylenedioxy -thiophen-2-yl) acenaphtho [1, 2-b]quinoxaline) (PBEAQ) was synthesized by oxidative solution or solid-state polymerization using ferric chloride (Ⅲ) as an oxidant. The optimum mole ratios of monomer to oxidant and polymerization method were selected by comparison of the conductivity and electrochemical performances of the obtained polymers. Results show that the solid-state polymerized polymer using monomer/oxidant mole ratio of 1/2 possessed high specific capacitance and good cyclic performance, having the initial capacity of 114 F.g-1 and kept 94% of the initial value at 1000th cycle.
For the purpose of increasing conductivity of the polymer, using the optimum condition of solid-state polymerization we synthesized polymers doped with some of sulfonic acids. Results show that when the naphthalene sulfonic acid was used as a dopant the conductivity of the polymer increased by 10000 times. But other electrochemical properties were remaining almost unchanged.
Two copolymers of 5,8-bis(3,4-ethylenedioxythiophenyl)-acenaphthenequino -xaline with 1,4-Diethynyl-2,5-dialkoxybenze were synthesized by Sonogashira reaction. The obtained copolymers are soluble in common organic solvents and have a certain thermal stability and were electrochemically active.
1.合成了具有较低氧化电位、窄禁带能隙的新型电荷移动性共轭分子—5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉。通过紫外可见光谱,荧光光谱,核磁共振氢谱等测试手段进行了结构表征。通过电化学聚合制备了聚(5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉)膜。此聚合物膜在-2.0 ~ +1.5 V有电致变色性能,膜颜色由深绿色变透明的浅蓝色(氧化态),变红色(还原态)。其电致变色响应时间较快有望利用在电致变色材料中。
2.以FeCl3为氧化剂,通过溶液及固相聚合法制备了聚(5,8-二(3,4-乙撑二氧噻基) -萘基喹喔啉)。通过比较两种方法合成的聚合物的导电率,电极行为来确定了最佳氧化剂用量及聚合方法。结果表明:氧化剂与单体摩尔数为2:1固相聚合合成的聚合物具有高比电容和良好的循环稳定性,在酸性电解质中电流密度为1 mA.cm-2时,首次放电比电容达到114 F. g-1,经过1000次充放电后容量保持率在94%。
3.为了提高聚合物的导电率,在固相聚合最佳合成条件下选几种磺酸作为掺杂剂合成了掺杂的聚合物,结果表明当萘磺酸掺杂时其导电率提高四个数量级,但对其电化学行为的影响不大。
4.通过Sonogashira偶合反应将5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉与带有不同长链烷氧基的对苯乙炔进行交替共聚,得到了两种具有较好热稳定性和电化学活性的可溶性聚合物。
Compounds with quinoxaline aromatic rings which have an electron-deficient nature are used as raw materials for organic light-emitting devices, light-emitting cells and optoelectronic devices. Although preparation and electrochromic properties of quinoxaline containing polymers have drawn a wide interest, planar fused acenaphthene substituted quinoxaline unit has not been paid much attention. On the other hand, thiophenes are belonging to the most typical electron-rich aromatic rings used in CT-type structure. Compared with thiophene, while the polymerization of 3,4-ethylenedioxythiophene theα-βandβ-βmislinkage are forbidden by blocking theβpositions of the thiophene units with the electron donating oxygen atoms, and the ethylene bridges minimize steric distortion effects resulting in a high stereo regularity of the polymer chain so that goodπ-conjugation is guaranteed. Hence in this paper we have successfully synthesized bis-3,4-ethylenedioxythiophene substituted acenaphthe -nequinoxaline. The main content is as follows:
A new EDOT-substituted acenaphthenequinoxaline was synthesized via Stille coupling reaction, which has a low oxidation potential of 0.73 V vs. Ag/Ag+, and was electrochemically polymerized. The electrochemically coated polymer film exhibited electrochromic behavior between -2 V and +1.5 V vs. Ag/Ag+. The film color changed from more green (neutral) to transmissive light blue in the oxidized state and reddish in the reduced state. Considering these properties, this polymer can be utilized in electrochromic device applications.
Poly (8,11-bis(3, 4-ethylenedioxy -thiophen-2-yl) acenaphtho [1, 2-b]quinoxaline) (PBEAQ) was synthesized by oxidative solution or solid-state polymerization using ferric chloride (Ⅲ) as an oxidant. The optimum mole ratios of monomer to oxidant and polymerization method were selected by comparison of the conductivity and electrochemical performances of the obtained polymers. Results show that the solid-state polymerized polymer using monomer/oxidant mole ratio of 1/2 possessed high specific capacitance and good cyclic performance, having the initial capacity of 114 F.g-1 and kept 94% of the initial value at 1000th cycle.
For the purpose of increasing conductivity of the polymer, using the optimum condition of solid-state polymerization we synthesized polymers doped with some of sulfonic acids. Results show that when the naphthalene sulfonic acid was used as a dopant the conductivity of the polymer increased by 10000 times. But other electrochemical properties were remaining almost unchanged.
Two copolymers of 5,8-bis(3,4-ethylenedioxythiophenyl)-acenaphthenequino -xaline with 1,4-Diethynyl-2,5-dialkoxybenze were synthesized by Sonogashira reaction. The obtained copolymers are soluble in common organic solvents and have a certain thermal stability and were electrochemically active.
引文
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