不同官能度环氧树脂的阳离子光固化研究

对4种不同官能度的环氧树脂在紫外光辐照下用一种二苯基碘钅翁盐或两种二烷基苯甲酰锍盐光引发剂进行阳离子光固化的体系作了系统的研究。研究结果表明,二氨基二苯甲烷环氧树脂AG-80不能阳离子光固化,而E-51,711和TDE-85均可在二苯基碘钅翁六氟磷酸盐或1-甲基-1-十二烷基苯甲酰甲基六氟锑酸锍盐作用下进行紫外光引发阳离子聚合,其中二苯基碘钅翁六氟磷酸盐引发E-51环氧树脂阳离子光固化的效果最好,该树脂体系可用做紫外光固化复合材料的树脂基体。研究还发现,在停止紫外光辐照后,由于阳离子聚合链终止困难而使碘钅翁盐引发的环氧树脂光固化体系存在后固化现象,后固化速度与后固化时的温度有关。     

双－（p－N，N－二甲氨基苄叉）酮／二苯基碘鎓盐复合体系的电子转移光显色

不同的双－（ｐ－Ｎ，Ｎ－二甲氨基苄叉）酮ＤＭＢＫ和二苯基碘盐（ＤＰＩＯＦ）复合，组成一种新型的电子转移光显色体系，ＤＭＢＫ／ＤＰＩＯＦ复合体系在暗处有良好的热稳定性。在光作用下很快发生从激发态ＤＭＢＫ至ＤＰＩＯＦ的电子转移，并伴随ＤＭＢＫ染料的褪色，测得ＤＭＢＫ光褪色速度的次序为：ＤＭＢＡ＞ＤＭＢＰ＞ＤＭＢＨ。与此同时，电子转移又引起新的光显色反应，对ＤＭＢＡ化合物，在７００ｎｍ处出现新吸收峰。其光密度随光照时间而增长，然而，ＤＭＢＰ和ＤＭＢＨ体系这种光显色现象并未观察到，这可能由于它们的中间产物不能共平面的缘故，ＤＭＢＡ的光显色速度和最大密度明显取决于浓度和溶剂性质。本文对这种短波区光褪色和长波区光显色的光化学反应过程作了讨论。     

新型染料敏化体系──荧光素染料碘鎓盐的光谱研究

本文合成了一系列荧光素类染料碘盐，并研究了其光谱及光化学性质。结果表明，通过改变结构，可改变它们的吸收光谱。提出可用Ｉ＿Ⅰ／Ｉ＿Ⅱ值来表征这类化合物在溶剂中的相对解离程度。随溶剂极性，染料母核Ｃ－６位周围（Ｃ－７，Ｃ－８位）空间位阻增大和染料母核上吸电子取代基增多，Ｉ＿Ⅰ／Ｉ＿Ⅱ值增大，它们的相对解离程度升高，光谱性质显著变化，光化学反应速度下降。在极性和非极性溶剂中，浓度对光谱和光化学性质具有不同的影响。显示这类化合物除可用作可见光敏化聚合和交联的光引发体系外，还可能用作探针探测周围环境的变化。     

Oxidative Cycloaddition of Aldoximes with Maleimides using Catalytic Hydroxy(aryl)iodonium Species

A mild catalytic procedure for the efficient oxidative cyclization of aldoximes with maleimides mediated by hypervalent iodine(III) active species has been developed. This catalytic cyclization affords the corresponding pyrrolo‐isoxazole products in generally good yields. The catalytic cycle involves active hydroxy(aryl)iodonium species generated in situ from 2‐iodobenzoic acid as precatalyst and m‐chloroperoxybenzoic acid (m‐CPBA) as terminal oxidant in the presence of trifluoromethanesulfonic acid. The presence of active hydroxy(aryl)iodonium species in this reaction has been confirmed by ESI‐mass spectrometry and ¹H NMR spectroscopy.

     

Sunlight photodepolymerization of transient polymers

The study and development of transient devices is an emerging field where the disposal of a device after use is desired to avoid reverse engineering and minimize the environmental impact. Polyaldehydes with phototriggers have been investigated because the radiation wavelength can be adjusted to meet the transient application. Polynuclear aromatic hydrocarbons (PAHs) were used as the optical sensitizer for photoacid generators (PAGs). Photoinduced electron transfer (PET) with an iodonium-based PAG was used to expand the spectral sensitivity range. Anthracene, tetracene, and pentacene derivatives were synthesized with appended phenylethynyl groups to improve the solubility of the sensitizer and adjust the absorption wavelength. Sensitization of the iodonium-based PAG with the PAH derivatives was found to have thermodynamically favorable PET reactions for depolymerization of poly(propylene carbonate) and poly(phthalaldehyde) (PPHA). The Rehm–Weller equation and Stern–Volmer analysis were used to study the electron transfer and the fluorescence quenching rates of the PAHs with the iodonium salts, respectively. The photosensitivity, efficiency, and byproducts of the PET reactions in the decomposable polymer films are reported. A rapid photoreaction is reported for the depolymerization of PPHA exposed to a sunlight dose of <6 J cm⁻² (i.e., 1 min of direct sunlight) with a pentacene-based sensitizer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47141.     

Photoinitiated cationic oligomerization of terminal and internal epoxides

The iodonium salt‐catalyzed, photoinduced cationic oligomerization of terminal and internal monoepoxides from oleochemical as well as the petrochemical origin was studied. The ring‐opening of terminal epoxides (1,2‐octene oxide, phenyl glycidyl ether, 9,10‐epoxy decanoic acid methyl ester and 10,11‐epoxy undecanoic acid methyl ester) predominantly led to macrocyclic oligoethers (M_n = 650—1,100 g/mol) via backbiting in quantitative yields. Mixtures of cyclic and bishydroxy‐terminated oligoethers (M_n = 1,050—1,500 g/mol) were achieved by the conversion of internal epoxides (7,8‐tetradecene oxide and cis‐9,10‐epoxy octadecanoic acid methyl ester) in yields of 80—95%. Macrocyclization was completely suppressed by addition of 20 mol‐% water or ethylene glycol receiving diol‐oligoethers for potential application as soft segments for polyurethanes with molecular weights of approximately 1,300 g/mol.     

荧烷染料的光诱导显色反应和机制的研究

荧烷染料的光诱导显色反应和机制的研究＊周文慧刘建民李妙贞王尔＊＊（中国科学院感光化学研究所，北京１００１０１）关键词荧烷染料，碘盐，电子转移，光显色反应荧烷染料是一类重要的功能性染料，广泛地应用于热敏和压敏记录材料．通常采用在酸作用下，使荧烷染料...     

过渡金属催化下有机高价碘盐参与的反应研究(一)

根据不同反应类型对过渡金属催化下有机高价碘盐在有机合成中的应用研究进行总结。     

碘鎓盐引发的环氧—丙烯酸酯复合光敏胶的研制

用合成的二苯基碘钅翁六氟磷酸盐作光引发剂 ,对不同比例的双酚A环氧树脂E5 1 和丙烯酸酯预聚物AE组成的复合树脂进行了光固化研究 ,证明了碘钅翁盐具有同时引发环氧和丙烯酸酯复合树脂按阳离子和自由基两种不同机理进行光固化的能力 ;考察了树脂的不同比例对固化速度的影响 ;同时选择一定比例的光敏复合树脂研究了增感剂 (DA)对光固化速度的影响。结果表明 ,这种复合光敏胶具有粘度低 ,光固化速度快 ,粘合力强 ,玻璃化转变温度低 ,耐水煮沸性好的优点 ,可作为新型UV -固化胶粘剂和防水性密封胶加以应用。     

大分子阳离子光引发剂聚苯乙烯-碘鎓六氟锑酸盐的合成及其感光性能的研究

本文用羟基对甲苯磺酰氧基碘苯与聚苯乙烯进行亲电取代反应,得到大分子阳离子碘鎓盐光引发剂聚苯乙烯碘鎓-六氟锑酸盐(PS-I·SbF_6).用核磁共振仪、傅立叶红外光谱仪、凝胶渗透色谱仪、差示扫描量热仪、紫外分光光度仪对其进行了表征.与小分子碘鎓盐系光引发剂相比,PS-I·SbF_6的紫外最大吸收波长λ_(max)红移,在240—270 nm范围内有较强的吸收;固化成膜后其相对迁移率较小分子光引发剂有显著下降.初步研究了PS-I·SbF_6在环氧体系中的光固化性能,结果表明该体系有较好的光固化和后固化特性.