Radiation-induced polymerization of 3-hexylthiophene in oxygen-free and oxygen-saturated dichloromethane solvent,Radiation Physics and Chemistry

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Radiation-induced polymerization of 3-hexylthiophene in oxygen-free and oxygen-saturated dichloromethane solvent
Radiation Physics and Chemistry ( IF 2.9 ) Pub Date : 2020-11-25 , DOI: 10.1016/j.radphyschem.2020.109291
Teseer Bahry , Zhenpeng Cui , Alexandre Dazzi , Matthieu Gervais , Cyrille Sollogoub , Fabrice Goubard , Thanh-Tuân Bui , Samy Remita

As alternative radiolytic approach, the synthesis of P3HT was made possible thanks to the oxidation of 3HT monomers by chloromethyl and dichloromethyl radicals or by their corresponding peroxyl radicals in situ produced by dichloromethane solvent radiolysis. Under two different experimental conditions, in oxygen-free solution and in oxygen-saturated solution, two different polymers, “ $P 3 H T_{N_{2}}$ ” and “ $P 3 H T_{O_{2}}$ ” respectively, were successfully synthesized. Both produced materials were discerned by several analytical and spectroscopic techniques. UV–Vis absorption spectroscopy results showed that the radiolytic yield of 3HT oxidation in dichloromethane solvent is higher under O₂ atmosphere. Indeed, a dose of 75 kGy was needed to polymerize 10 mM in 3HT under N₂ atmosphere, meanwhile a dose of 35 kGy was sufficient to polymerize the same amount of 3HT under O₂. The average molecular weight of $P 3 H T_{O_{2}}$ was found higher than that of $P 3 H T_{N_{2}}$ as revealed by SEC chromatography analysis. Also, $P 3 H T_{O_{2}}$ exhibits better thermal stability than $P 3 H T_{N_{2}}$ . ATR-FTIR spectroscopy revealed the specific presence into $P 3 H T_{O_{2}}$ polymers of some functional groups such as carbonyl, hydroxyl and carboxyl moieties, which clearly explains the difference between the morphological structures of $P 3 H T_{N_{2}}$ and $P 3 H T_{O_{2}}$ as highlighted by cryo-TEM, SEM and AFM microscopies. Finally, both radio-synthesized $P 3 H T_{N_{2}}$ and $P 3 H T_{O_{2}}$ polymers were found characterized by remarkably significant conductive, electronic and optical properties.

中文翻译：

在无氧和氧饱和的二氯甲烷溶剂中辐射诱导的3-己基噻吩聚合

作为替代的辐射分解方法，由于3HT单体被氯甲基和二氯甲基自由基或由二氯甲烷溶剂辐射分解原位生成的相应的过氧自由基氧化，使得P3HT的合成成为可能。在两种不同的实验条件下，在无氧溶液和氧饱和溶液中，两种不同的聚合物“ $P 3 H Ť_{ñ_{2}}$ ”和“ $P 3 H Ť_{Ø_{2}}$ 分别成功合成。通过几种分析和光谱技术可以分辨出两种材料。UV-Vis吸收光谱结果表明，在O ₂气氛下，二氯甲烷中3HT的氧化分解产率较高。实际上，需要75 kGy的剂量才能在N ₂气氛下在3HT中聚合10 mM ，同时35 kGy的剂量足以在O ₂下聚合相同量的3HT 。平均分子量 $P 3 H Ť_{Ø_{2}}$ 被发现高于 $P 3 H Ť_{ñ_{2}}$ 如SEC色谱分析所示。也， $P 3 H Ť_{Ø_{2}}$ 表现出比以下更好的热稳定性 $P 3 H Ť_{ñ_{2}}$ 。ATR-FTIR光谱揭示了特定的存在 $P 3 H Ť_{Ø_{2}}$ 某些官能团（如羰基，羟基和羧基部分）的聚合物，这清楚地解释了 $P 3 H Ť_{ñ_{2}}$ 和 $P 3 H Ť_{Ø_{2}}$ 如低温TEM，SEM和AFM显微照片所突出显示的那样。最后，两者都是无线电合成的 $P 3 H Ť_{ñ_{2}}$ 和 $P 3 H Ť_{Ø_{2}}$ 发现聚合物具有明显显着的导电，电子和光学性能。

更新日期：2020-12-04

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