影像科学与光化学 ›› 2018, Vol. 36 ›› Issue (5): 389-397.DOI: 10.7517/issn.1674-0475.180302

• 论文 • 上一篇    下一篇

氟碳链修饰酰基氧化膦长波吸收光引发剂的研究

谢刚1, 杨建文2, 钟荣1   

  1. 1. 南昌航空大学 环境科学与化学工程学院, 江西 南昌 330200;
    2. 中山大学 材料科学与工程学院, 广东 广州 510275
  • 收稿日期:2018-03-05 修回日期:2018-04-12 出版日期:2018-09-15 发布日期:2018-09-15
  • 通讯作者: 钟荣
  • 基金资助:
    国家自然科学基金项目(23174135)资助

Study on Fluorocarbon Chain Modified Acyl Phosphine Oxide as Long Wavelength Absorbing Photoinitiator

XIE Gang1, YANG Jianwen2, ZHONG Rong1   

  1. 1. School of Environmental Science and Chemical Engineering, Nanchang Hangkong University, Nanchang 330200, Jiangxi, P. R. China;
    2. School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, P. R. China
  • Received:2018-03-05 Revised:2018-04-12 Online:2018-09-15 Published:2018-09-15

摘要: 以2,4,6-三甲基苯甲酰基膦酸乙酯(TPO-L)、全氟辛基乙基醇、草酰氯为原料合成了2,4,6-三甲基苯甲酰基膦酸全氟辛基乙酯(TPO-F)光引发剂。利用核磁共振(1HNMR、19FNMR)和红外光谱(FT-IR)对TPO-F进行结构表征;通过紫外吸收光谱测定了TPO-F的最大吸收波长,与TPO-L的吸收曲线类似,但长波范围的摩尔吸光度略高;光引发剂溶液分层吸光度测试表明,TPO-F具备显著迁移富集特征,有助于表面氧阻聚的解决。在氮气氛围下,通过光-差示扫描量热仪(Photo-DSC)对TPO-F进行了光聚合反应动力学研究,探究了光强、引发剂浓度对单体双键的转化率和最大聚合速率的影响。在空气氛围下,通过差示扫描量热仪(DSC)考察了光引发剂的抗氧阻聚性能。研究表明,TPO-F光引发效率显著高于TPO-L,二者组合可进一步提升光引发效率。本研究为后续UV LED光固化技术中存在的氧阻聚瓶颈问题提供了解决途径。

关键词: 光聚合, 光引发剂, 迁移性, 氧阻聚, UV-LED

Abstract: 2,4,6-Trimethylbenzoyl phosphonic acid perfluorooctyl ethyl ester (TPO-F), synthesized with ethyl 2,4,6-trimethylbenzoylphosphonate (TPO-L) and perfluorooctylethyl alcohol and oxalyl chloride.It was characterized by 1HNMR, 19FNMR and FT-IR. The UV absorption spectra of TPO-F were similar to those of TPO-L, the molar absorbance of maximum wavelength is slightly higher. It was confirmed that TPO-F could rapidly immigrate to formulation surface with the UV absorption depth-resolution following of TPO-F solution. The photopolymerization kinetics of acrylate monomer with TPO-L, TPO-F as photoinitiator was investigated by (Photo-DSC). TPO-F exhibits moderate photoinitiation efficiency approximating to TPO-L under nitrogen atmosphere, but improved photoinitiation efficiency for TPOL-F and its combination with TPO-L was resulted under air due to the surface self-concentration effect of TPO-F. Oxygen inhibition effect popularly existing in radical photopolymerization may thus be limited.

Key words: photopolymerization, photoinitiator, migration, oxygen inhibition, UV-LED