Enhanced One/Two-Photon Initiating Performance of Nitro-Carbazole-Styrene Based Oxime/Ketoxime Esters  

作　　者：Jie Xie Yonghui Wang Xiaobin Wang Xuefeng Fang Qinyan Zhu Chun Cao Ming Jin 

机构地区：[1]Department of Polymer Materials,School of Materials Science and Engineering,Tongji University,No.4800 Caoan Road,Shanghai 201804,China [2]Research Center for Intelligent Sensing,Zhejiang Lab,No.1818 Wenyi West Road,Hangzhou,Zhejiang 311100,China [3]Zhejiang Yangfan New Materials Co.,Ltd.,No.25 Weisan Road,Shaoxing,Zhejiang 312369,China

出　　处：《Chinese Journal of Chemistry》2024年第23期3013-3022,共10页中国化学(英文版)

基　　金：supported by the National Natural Science Foundation of China(51873154);the"Pioneer"and"Leading Goose"R&D program of Zhejiang Province(2023C01186).

摘　　要：Photoinitiators of the oxime ester(OXE)or ketoxime ester(OXE-CO)type can rapidly undergo N—O bond cleavage and generate free radicals to initiate photopolymerization under LED excitation,occupying an important position in the field of photocuring.However,the commercial OXEs,e.g.,OXE 01 and 02 withλ_(max)'s at 326 and 344 nm,respectively,still do not well match the emission spectra of LEDs.Developing novel OXEs/OXE-COs with high photosensitivity for long-wavelength LEDs has great significance.Here,four new OXEs/OXE-COs with nitro-carbazole-styrene conjugated chromophore were designed,synthesized,and used as photoinitiators.Results demonstrated that all photoinitiators had strong absorption within the UV–vis range(λ_(max):381—392 nm,ε_(max):8200—11500 M^(−1)·cm^(−1)).Molecular design of the oxime ester cleavage to produce a small volume methyl group and a methacryl group with an unsaturated double bond brings high activity and low migration,respectively,in one-photon polymerization under 365—450 nm LEDs excitation.Moreover,OXEs/OXE-COs with PETA exhibited a wide processing window,high resolution(line accuracy~100 nm)and good nano-patterning capability under 780 nm femtosecond laser irradiation in two-photon polymerization,indicating their great potential in 2D/3D microfabrication technologies.

关 键 词：Radical reactions PHOTOCHEMISTRY PHOTOLYSIS Oxime/ketoxime esters CARBAZOLE PHOTOINITIATOR Two-photon polymerization 

分 类 号：O62[理学—有机化学]