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    两相溶液法制备有机质子酸掺杂Py-MMA共聚物及其导电与溶解性能研究

    Conductivity and Solubility of Py-MMA Copolymers Doped with Organic Protonic Acid in Two-Phase Solution

    • 摘要: 采用4种有机质子酸为掺杂剂,氯化铁为氧化剂,通过化学氧化法制备了有机质子酸掺杂聚吡咯(PPy)。在两相溶液中制备了吡咯-甲基丙烯酸甲酯(Py-MMA)共聚物,研究了掺杂剂含量、氧化剂含量、单体甲基丙烯酸甲酯(MMA)含量、反应温度等因素对Py-MMA共聚物电导率及溶解性能的影响。结果表明,有机质子酸掺杂PPy可有效提高PPy的电导率。当以对甲苯磺酸(TsOH)作掺杂剂,掺杂剂与吡咯(Py)、氧化剂与Py单体物质的量之比均为1∶3、反应温度为5 ℃、反应时间为12 h时,所制得的有机质子酸掺杂PPy的导电性能最好。与PPy相比,Py-MMA共聚物的溶解性能得到明显提高。当MMA、K2S2O8、Py、TsOH物质的量之比为2∶3∶6∶4,反应温度为40 ℃,反应时间为4 h时,所制得的Py-MMA共聚物的溶解性能最佳,70 ℃时其在乙酸乙酯中的溶解度为5.56 g,表面电阻率为0.76 Ω·cm。

       

      Abstract: PPy(polypyrrole) has been a kind of widely used electrical polymer during the last few decades, owing to its excellent conductivity. However, the processing of PPy materials is still very difficult. Enhancing the solubility of PPy may provide a solution to improve such issue. In this paper, PPy was synthesized by chemical oxidation method, four kinds of organic protonic acid were used as dopant and FeCl3 was used as oxidant. Several factors which might cause fluctuation of electrical conductivity, including the type of dopant, reaction temperature, dosage of dopant and oxidant, duration of reaction, and significance testing, were investigated and analyzed under orthogonal experiments, leading to influence order from significant to indistinctive as usage of dopant, usage of oxidant, reaction temperature, reacting duration, and kind of dopant. On this basis, Py and methyl methacrylate (MMA) were copolymerized in a two-phase solution to prepare soluble Py-MMA copolymers dissolving in ethyl acetate. Furthermore, factors including dosage of dopant, oxidant and MMA monomer, reacting temperature were analyzed to reveal the variations of conductivity and solubility. The results indicated that using organic protonic acids to dope PPy enhanced its conductivity, the optimal condition was associated with the using of TsOH, n(Dopant)∶n(Py)=1∶3, n (Oxidant)∶n(Py)=1∶3, 12-hour-reaction. Interestingly, as compared to PPy, the solubility of Py-MMA copolymers was obviously enhanced. The optimal conditions were at a temperature of 40 ℃, n(MMA)∶n(K2S2O8)∶n(Py)∶n(TsOH)=2∶3∶6∶4, 4-hour-reaction. In this way, the solubility of the prepared Py-MMA copolymers was 5.56 g in ethyl acetate (70 ℃), and corresponding surface resistance was 0.76 Ω·cm.

       

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