双光子吸收聚合引发剂EPVPVC的合成和非线性光学性质的研究  

Synthesis and Nonlinear Optical Properties of a New Two-photon Photopolymerization Initiator EPVPVC

作　　者：延云兴[1] 陶绪堂[1] 孙元红[2] 许贵宝[1] 王传奎[2] 杨家祥[1] 于晓强[1] 吴拥中[1] 赵显[1] 蒋民华[1] 

机构地区：[1]山东大学晶体材料国家重点实验室,济南250100 [2]山东师范大学物理系,济南250014

出　　处：《化学学报》2004年第23期2343-2347,共5页Acta Chimica Sinica

基　　金：国家自然科学基金 (Nos.50 32 30 0 6;50 32 531 1;1 0 2 740 4 4 )资助项目

摘　　要：合成了一个新的双光子吸收聚合引发剂 ,9 乙基 3 {2 [4 ( 2 吡啶基 4 乙烯基 ) 苯基 ] 乙烯基 } 9氢咔唑 (EPVPVC) ,用1HNMR谱、13 CNMR谱和元素分析进行了表征 .测试了紫外吸收光谱、单光子荧光光谱、单光子荧光寿命、单光子荧光量子产率和双光子荧光光谱 .量化计算结果表明 ,EPVPVC的双光子吸收截面为 5 6 6× 10 -50 cm4·s·photon-1.在 780nm的飞秒脉冲激光激发下 ,EPVPVC发出较强的上转换荧光 ,荧光峰位于 5 3 6nm .用EPVPVC做引发剂 ,加入丙烯酸酯型齐聚物(CN12 0C80 ) ,在脉冲宽度为 2 0 0fs ,重复频率为 76MHz ,中心波长为 780nm飞秒脉冲激光下 ,制作了一个三维周期性微结构 .在理论计算的基础上 。A new two-photon free-radical photopolymerization initiator 9-ethyl-3-{2-[4-(2-pyrid-4-yl)-vinylphenyl]-vinyl}-carbazole (abbrev. EPVPVC) has been synthesized and structurally characterized by H-1 NMR spectra, C-13 NMR spectra and elemental analyses. Linear absorption, one-photon induced fluorescence. one-photon fluorescence lifetime, one-photon fluorescence quantum yield and two-photon induced fluorescence were experimentally studied. The calculated two-photon absorption cross-section is as high as 56.6 x 10(-50) cm(4).s.photon(-1). When pumped with 780 nm laser irradiation, EPVPVC exhibits strong two-photon induced fluorescence of 536 nm. A microstructure using EPVPVC as initiator has been fabricated under irradiation of 200 fs, 76 MHz Ti: sapphire femtosecond laser at 780 nm. The possible mechanism of photopolymerization was discussed based on quantum chemistry calculations.

关 键 词：双光子吸收截面 非线性光学性质 量化计算 NMR谱 吡啶基 咔唑 上转换荧光 聚合引发剂 合成 齐聚物 

分 类 号：O631[理学—高分子化学]