外电场下光聚合反应动力学的表征方法

外电场下光聚合反应动力学的表征方法李从武，潘昂上海材料研究所，上海２０００８２）关键词光聚合反应、液晶、外电场、动力学、表征近年来，液晶单体在外场（电场、磁场和剪切力）下在位光聚合反应的研究工作受到了很大的关注［’，ＺＩ．众所周知，热致型侧链高分子液...     

马来酸二丁基锡的合成及其共聚合

马来酸二丁基锡的合成及其共聚合刘云桥金根河李福绵（北京大学化学与分子工程学院北京１００８７１）关键词马来酸二丁基锡，醋酸乙烯酯，交替共聚物，光聚合关于马来酸酐［１］，马来酰亚胺 Ｎ 取代物［２，３］与富电子烯类单体如苯乙烯，醋酸乙烯酯，乙烯基烷基醚...     

N-(4-苯甲酰苯基)衣康酰亚胺与甲基丙烯酸-N,N-二甲氨基乙酯组成的可聚合光氧化还原体系引发的丙烯腈光聚合

Ｎ （４ 苯甲酰苯基）衣康酰亚胺与甲基丙烯酸 Ｎ，Ｎ 二甲氨基乙酯组成的可聚合光氧化还原体系引发的丙烯腈光聚合高青雨杨更须崔元臣张福莲张举贤（河南大学化学化工学院开封４７５００１）李福绵（北京大学化学系北京１００８７１）关键词Ｎ （４ 苯甲酰苯基）...     

Photopolymerization induced by a benzophenone derivative photoinitiator

A benzophenone derivative photoinitiator, HBP-TDI-HQ-TDI-HBP （HTCTH）, was synthesized based on 4-hydroxy benzophenone （HBP）, toluene-2,4-diisocyanate （TDI） and hydroquinone （HQ）. HTCTH was a more effective photoinitiator which had longer wavelength absorption in the UV-vis absorption spectra than the low molecular counterpart benzophenone （BP）. It showed that both rate of polymerization （Rp） and final conversion （P） increased with increase of amine and HTCTH concentration in photopolymerization.     

含氧光敏引发体系的研究——Ⅵ.二苯酮/三乙胺体系引发光聚合过程中的再次引发效应

过去,作者曾发表了多种光敏引发体系引发烯类单体光聚合的工作,在研究2,2-二甲氧基苯乙酮在氧存在下引发甲基丙烯酸甲酯光聚合时,结合在聚合物链端的引发剂碎片具有光化学活性,在光聚合反应中产生高分子自由基,发生再次聚合,出现高分子量     

联二炔囊泡的光致聚合、热致变色及应用

物理化学实验为各大高校本科化学教学的主干实验课程之一。虽然各高校的物理化学实验内容已十分丰富,但仍然缺乏将不同章节知识点融会贯通以及与学科前沿密切联系的综合型实验内容。我们根据南开大学郭东升教授课题组发表的一篇有关联二炔程序性响应检测胆碱酯酶的工作设计了“联二炔囊泡的光致聚合、热致变色及应用”的物理化学实验,涉及到联二炔缔合胶体的制备、联二炔的紫外光致聚合反应和聚联二炔的热致变色,进而显示其在防伪领域的潜在应用价值。希望通过此实验,使学生对物理化学中的缔合胶体、光化学、热力学、动力学等章节有更深一步的贯通性掌握,并了解自组装、光聚合、变色材料和防伪等相关研究领域的前沿动态。     

A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS

The photoinduced bulk polymerization of a reactive-hindered amine fight stabilizers(r-HALS), 4-acryloyl-2, 2, 6, 6-tetramethylpiperidinyl (ATMP), was performed at 80℃ by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen.It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d =1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism.     

含氧光敏引发体系的研究——Ⅶ.二苯酮羧酸胺盐的光谱性质和光引发作用

本文合成了一类新的二苯酮羧酸胺盐(BPAA),包括具有不同碳链长度的伯胺盐和叔胺盐二个系列共六种化合物。实验结果表明,BPAA和二苯酮(BP)的光物理性质相似,长碳链BPAA分子具有显著的两亲性质,在非水溶液中可发生分子缔合形成反胶束。由BPAA与叔胺(TEA)组成的体系,引发MMA光聚合反应,聚合速度(R_p)比单用BP快得多,其中BPAA叔胺盐比相应的伯胺盐活性高,长链BPAA比短链BPAA活性高。另外还对比了氧气和氮气条件下的聚合反应速度,氧存在时R_p可增加二倍以上。此外还研究了BPAA/TEA浓度对聚合反应的影响。     

光敏聚合中含二苯酮基高聚物的引发作用

合成了多种不同分子量和不同二苯酮侧基含量的高分子敏化剂PVB,从紫外吸收光谱及发射光谱的测定结果表明,PVB基本保持小分子二苯酮(BP)的光化学特性。采用PVB与叔胺组成光敏引发体系引发MMA光聚合时,聚合速度(R_ο)与小分子相比增加二倍以上。而且R_p随PVB分子中二苯酮基含量的增加而增加,当PVB分子量提高时引发聚合能力加强,这和高分子敏化剂分子链中高效率的能量传递以及色基的密集分布特性有关。     

Photochemical reactions of a dimethacrylate compound containing a chalcone moiety in the main chain

We synthesized the new photosensitive oligomer containing a chalcone moiety in the main chain by end-capping reaction of diepoxide compound with methacrylic acid. The chalcone-epoxy oligomeric compound was synthesized with 4,4^′-dihydroxychalcone and epichlorohydrin. Investigation of the photosensitivity of the newly synthesized chalcone oligomer was carried out by using UV-Vis absorption and infrared spectroscopies under UV exposure. We observed the photodimerization behavior under UV irradiation. At the same time, we could also observe the photopolymerization of the compound with a trace amount of dimethoxyphenyl acetophenone. Thermal properties of UV-cured dimethacrylate compounds were also studied.