光聚合反应相较于传统的热引发聚合具有显著优势,例如更好的时间可控性以及更快的反应动力学。然而,传统自由基光固化体系仍面临氧阻聚与光引发剂端基残留的问题。为此,本研究开发了一类基于苯并噻二唑衍生物(PBTH、BBTH)的新型光催化剂。通过引入给体-受体 (D-A) 结构,光吸收能力和分子内电荷转移 (ICT) 能力得到提升,从而增强了光催化性能。机理研究表明：激发态光催化剂从叔胺添加剂 (TMEDA) 攫取电子生成自由基阴离子和胺烷基自由基,进而引发丙烯酸酯单体的聚合。催化剂在聚合前后结构保持不变,且不通过共价键连接于聚合物链末端。PBTH在0.37 wt%的极低负载量下,于常氧条件下数分钟内即可实现近乎完全转化,并成功用于“AIE”图案的光刻加工。
Photopolymerization offers significant advantages over traditional thermally initiated polymerization, such as better temporal control and faster reaction kinetics. However, conventional systems suffer from oxygen inhibition and initiator end-group residue. Herein, we developed a series of benzothiadiazole-based photocatalysts (PBTH, BBTH). By introducing donor-acceptor (D-A) structures, light absorption and intramolecular charge transfer (ICT) capability are promoted, thereby enhancing the photocatalytic performance. Mechanistic studies reveal that the photoexcited PC abstracts an electron from the tertiary amine additive (TMEDA), generating a radical anion and an aminoalkyl radical, which subsequently initiates the polymerization of acrylate monomers. The photocatalyst remains intact and is not covalently incorporated into the polymer chain ends. With an extremely low loading of 0.37 wt%, PBTH achieved near-complete conversion within minutes under ambient conditions and was successfully employed in the photolithographic fabrication of an “AIE” pattern.
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