可见激光引发聚合反应

综述了近年来可见激光辐照引发聚合反应的新进展，主要介绍了可见光引发体系的组成及引发反应的机理。     

黄酮/叔胺引发三丙二醇二丙烯酸酯的光聚合反应

采用实时红外光谱(RTIR)研究了黄酮(FL)为紫外光光敏剂, 不同氢给体(如叔胺)为助引发剂时三丙二醇二丙烯酸酯(TPGDA)的光聚合反应. 结果表明, FL分子中的大π共轭体系使其UV吸收峰的摩尔消光系数(ε_max)远远高于商业化光敏剂二苯甲酮(BP). 当FL与不同助引发剂配合使用时, TPGDA光聚合动力学有较大差异, 其中叔胺体系助引发剂能够与激发态FL发生有效的电子/质子转移过程, 产生胺烷基自由基活性种引发TPGDA的光聚合反应, 所得固化膜的最终双键转化率(DC_f)为93%~97%, 接近完全固化; 而芝麻素(SM)及胡椒环(BDO)作为助引发剂时TPGDA的聚合速率则很低, 固化膜的DC_f仅为32%~38%. 当光敏剂质量分数为1.0%, 4-N,N'-二甲氨基苯甲酸乙酯(EDAB)质量分数为1.0%时, FL/EDAB引发TPGDA的聚合动力学与商业化BP/EDAB的相同, 所得固化膜的DC_f均为97%.     

新型水溶性硫杂蒽酮类光引发剂的光引发性能研究

利用红外光谱技术对六种新型水溶性硫杂蒽酮类光引发剂在紫外光聚合反应中的引发性能进行了测试,用相对峰面积法计算了聚合反应的转化率,并据此对引发剂结构与光化学性能之间的关系做了一定的探讨。结果表明该类光引发剂具有很高的光化学活性,而引发剂的结构直接影响引发性能。研究发现硫杂蒽酮母体上甲基的引入使引发剂的引发效率增大,而引发剂侧链上羟基的引入,则由于降低了质量转移的有效性并有可能使引发剂分子缔合,致命引     

偏氟乙烯的聚合反应

本文研究了用有机引发剂引发偏氟乙烯的水相聚合,并对制得的聚偏氟乙烯的性质进行了研究。有机引发剂引发聚合的聚偏氟乙烯的热稳定性、强度、结晶度和熔点均比用过硫酸盐引发聚合的聚偏氟乙烯高。     

几种光引发剂在微乳液体系中的紫外吸收

光引发剂在微乳液体系中所处的位置是微乳液光引发聚合反应引发机理研究的关键之一．利用紫外吸收光谱对不同环境中的光引发剂进行考察,但由于其吸收光谱没有明显的变化,因而未能获得较确切的结论［１,２］．本工作研究了光引发剂α－羟基－α,α－二甲基－（对－羟乙...     

表面引发聚合反应研究进展

表面引发聚合反应作为一种新的聚合反应可广泛应用于固体基底的表面修饰与改性。结合分子自组装技术,几乎各种类型的聚合反应都有可能在固体基底表面进行。本文对表面引发聚合反应的研究进展进行了综述,对反应类型、实验方法、研究动向以及在合成聚合物刷、形成图案化聚合物薄膜等方面的应用与发展前景作了介绍与讨论。     

无机物表面引发聚合反应制备端接枝聚合物膜*

无机物表面引发聚合反应是聚合物合成化学的又一新领域。分子自组装技术的发展使得各种类型的聚合反应都有转移到固体表面进行的可能。本文综述了无机物表面引发聚合反应用于制备高键合密度端接枝聚合物膜的研究进展,并对其今后的发展提出了见解。     

光聚合引发剂研究进展

对最近几年光敏聚合引发体系的研究进展进行了评述，并就一些新型光敏引发体系及引发机理进行了介绍。     

用隐函数方法处理不断引发,链增长自由基聚合反应

利用图形分析方法给出了不断引发、链增长自由基聚合反应的分子量分布函数，结合反应转化率曲线，利用隐函数方法和数学随机模拟法，得到了分子量分布曲线，利用计算结果计算结果讨论了不同终止形式及反应速率对聚合物分子量分布的影响，考虑反应体的扩散控制。给出了苯乙烯本体聚合的分子量分布，得到与实验事实相一致的结论。     

巯基丙烯酸酯树脂的合成及自引发光聚合反应

以4,4'-二巯基苯硫醚和1,6-己二醇二丙烯酸酯通过"巯基-双键"反应合成了4,4'-二巯基苯硫醚己酯二丙烯酸酯(TBHDA)及苯硫酚改性双三羟甲基丙烷四丙烯酸酯(TP-DiTMP4A)和超支化丙烯酸酯预聚物(TP-P1000As). 采用 ¹H NMR和FTIR谱对产物结构进行了表征. 采用Photo-DSC方法对产物的自引发光聚合反应活性进行了研究, 结果表明, TBHDA本体及与EB605的混合体系均显示出较高的自引发光聚合反应活性, 而TP-DiTMP4A和TP-P1000As的自引发光聚合反应活性较低; 相对TP-P1000As而言, TP-DiTMP4A具有较高的光聚合反应活性是由于其较高的硫醚键和丙烯酸酯双键浓度所致.     

Synthesis and Two-photon Absorption Properties of s-Triazine Derivatives

Two new s-triazine derivatives, which belong to linear dipolar type and triangle octupolar type respectively, have been synthesized. The structure of the dipolar compound has been determined by X-ray diffraction. The two-photon absorption cross-section σ, and the two-photon excited fluorescence (TPEF) intensities are increased significantly from dipolar compound to octupolar compound.     

Two-photon absorption properties of 2,6-bis(styryl)anthracene derivatives: effects of donor-acceptor substituents and the pi center

A series of 2,6- and 2,7-bis(styryl)anthracene derivatives with the donors at the styryl group and acceptors at the 9,10-positions have been synthesized, and their two-photon cross sections (Phidelta(max)) were determined. These compounds exhibit a peak two-photon absorptivity (delta(max)) in the range of 700-2500 GM at 780-1030 nm. Values of lambda(max) and Stokes shifts increase as the acceptor is changed to a stronger one. There is also a parallel increase in lambda(2)max and delta(max) with the same variation of the chromophore structure. Both lambda (2)(max)and Phidelta(max) have been optimized by introducing donor-substituted styryl groups at the 2,6-positions and p-cyanophenyl groups at the 9,10-positions, respectively. The effect of a pi center on the two-photon absorption properties has been assessed by comparing the existing data for a variety of D-pi-D derivatives.     

Two-photon photochromism of diarylethene dimer derivatives.

Photochromic diarylethene dimer derivatives with large two-photon absorption (TPA) cross-sections have been designed and synthesized. The derivatives have a D-pi-D structure in which indole rings are used as donor units (D) and 1,4-bis(ethynyl)benzene or 1,4-bis(ethenyl)benzene as a pi-conjugated chain unit (pi). Compound 5 a, which has oxazole rings as one of the aryl groups, showed a TPA cross-section of 23 GM at 820 nm and exhibited efficient two-photon photochromic reactivity.     

Two-photon dyes containing heterocyclic rings with enhanced photostability

A series of donor-pi-donor derivatives containing phenyl, naphthyl, and anthryl groups as the pi-center and heterocyclic rings as the conjugation bridge have been synthesized and their one- and two-photon spectroscopic properties and photostability were determined. These compounds show bathochromic shifts in the absorption and emission spectra, larger two-photon cross-section, and enhanced photostability in comparison to their open-chain analogues. In addition, a convenient method for the qualitative photostability measurement is proposed.     

苯并噻唑衍物的合成及结构-双光子吸收光物理特性关系

报道了三个具有典型A-π-A'型共轭结构的苯并噻唑衍生物的合成及结构-双光 子吸收光物理特性关系。通过对三个化合物的共轭结构增长和拉电子基强度变化对 化合物单光子荧光光谱、双光子诱导荧光光谱和双光子吸收截面等特性的影响研究 ，我们发现，苯并噻唑杂环中的杂原子硫在化合物共轭链链短时对其光物理特性影 响很强，在共轭链较长时影响减弱甚至消失。通常情况下，共轭链长度和拉电子基 强度共同对双光子吸收截面作贡献，我们的研究表明，当共轭链较长时，共轭链的 增长对增强分子双光子吸收截面的贡献远大于拉电子基强度变化的贡献。其中，新 化合物2（2-{4-[2-（4-硝基苯基）-乙烯基]苯基}-乙烯基）苯并噻唑具有双光子 吸收截面大(181*10~(-50)cm~4s/photon)和荧光量子产率高(13.8%)的特点，是双 光子荧光显微与成像应用的一个良好的候选材料。     

多枝[1,3,4]-噁二唑衍生物的双光子吸收和光功率限幅特性

采用非线性透过率法测定了多枝[1,3,4]-噁二唑衍生物的双光子吸收性质. 测定了化合物的单光子荧光光谱和双光子荧光光谱, 在800 nm波长的激光激发下, 9-乙基-3,6-双{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基}-咔唑(3)和三-{5-(4-叔丁基苯基)-[1,3,4] 噁二唑-2-苯乙烯基-4-苯基}-胺(4)能够发出很强的蓝色和黄绿色双光子上转换荧光, 荧光峰分别位于485和547 nm. 这些多枝结构化合物的双光子吸收截面较大(数值超过104 GM), 并具有很强的光限幅效应. 多枝分子中重复单元的推拉电子结构和协同效应有效地增强了分子的双光子吸收性质.     

Synthesis and Ultrafast Broadband Optical Limiting Properties of a Two-Branched Twistacene

A novel two-branched twistacene (PyDN) has been designed and synthesized for application on ultrafast optical limiting. This twistacene exhibits excellent two photon absorption and two photon absorption-induced excited singlet state absorption, which was systematically investigated with a femtosecond Z-scan experiment, transient absorption spectrum, and two-photon excited fluorescence experiments. The admirable two photon absorption is attributed to the high degree of π electron delocalization in twistacene which is caused by introduction of two strong donors. The excited singlet state absorption cooperates with two-photon absorption to provide an excellent ultrafast optical limiting behavior with high linear transmittance, where the thresholds are 2.3–5.3 mJ/cm² in the spectral region of 532–800 nm of femtosecond laser and 133 mJ/cm² for picosecond pulse at 532 nm. These thresholds are lower than that of most of the optical limiters reported previously, which indicates PyDN is a promising candidate for ultrafast optical limiting.     

One‐ and Two‐Photon Absorption: Physical Principle and Applications

We introduce the principle and applications of one‐photon absorption (OPA) and two‐photon absorption (TPA) controlled by external electric fields. The physical mechanism of OPA and TPA are firstly introduced, which can visually promote thoroughly understanding of principle and physical analysis. Secondly, the applications of different molecules in OPA and TPA with and without external electric field are introduced in detail. The effect of the external electric field on the charge transfer during the absorption process is also exemplified. Furthermore, the external electric field on the molecular orbital wave function is visualized through the charge transfer process in the excited state transitions. The purpose of this review is to deepen the understanding of the types of charge transfer under linear and non‐linear absorption in different systems.     

Two‐Photon Absorption Circular Dichroism: A New Twist in Nonlinear Spectroscopy

Herein we report on the full experimental measurement of the two‐photon absorption circular dichroism spectra of (S)‐(?)‐1,1′‐bi(2‐naphthol) and (R)‐(+)‐1,1′‐bi(2‐naphthol), their analysis, and theoretical support. The finding of new nonlinear optical fingerprints in chiral molecules offers new opportunities in the recognition and understanding of optically active systems in regions where CD could present strong limitations.     

Two—photon Excited Fluorescence of Bithiophene Derivatives

Two new bithiophene derivatives named as 5,5‘‘-bis(p-N,N-dimethylaminostyryl)-2,2‘-bithiophene (BMSBT),and 5,5‘-bis(p-N,N-diethylaminostyryl)-2,2‘-bithiophene (BESBT) have been synthesized.Both compounds can emit strong single-photon excited fluorescence (SPEF) and two-photon excited fluorescence (TPEF) with the emission peaks around-560nm and with the lifetime of-1ns.