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Kaname TsuchiiAkiya Ogawa 《Tetrahedron letters》2003,44(49):8777-8780
Upon irradiation through Pyrex with a xenon lamp (hν>300 nm), terminal acetylenes undergo highly selective selenoperfluoroalkylation with perfluoroalkyl iodide and diphenyl diselenide. In this reaction, perfluoroalkyl and phenylseleno groups are selectively introduced into the terminal and internal positions of acetylenes, respectively. 相似文献
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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·SbF6).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·SbF6的紫外最大吸收波长λmax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·SbF6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. 相似文献
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Polymerization of acrylamide has been initiated by the photochemical reactions of the dianions of croconic acid (1,2-dihydroxycyclopentenetrione) and rhodizonic acid (1,2-dihydroxycyclohexenetetrone) in the presence of various acceptor molecules. Photoinitiation was most efficient with croconic acid where a maximum quantum yield for polymerization of 2 x 103 was observed in neutral solution. Kinetic studies using this initiator showed that the rate of polymerization was a linear function of the concentration of monomer and proportional to the square root of the light absorbed by the croconate dianion. The rate of initiation of radicals calculated from the rate of polymerization was compared with the rate of production of radicals calculated from previous studies of the photochemistry of the croconate dianion and the mechanism of photoinitiation is discussed. © 1992 John Wiley & Sons, Inc. 相似文献
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碘鎓盐/胺复合体系,用作自由基光敏聚合的引发剂具有良好的效果[1],但是关于碘鎓盐和胺相互作用产生有引发活性的自由基的光化学反应机制尚不清楚。 相似文献
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Claude Billaud Mohamed Sarakha Michle Bolte 《Journal of polymer science. Part A, Polymer chemistry》2000,38(21):3997-4005
N‐Vinylpyrrolidone polymerization photoinitiated at 365 and 546 nm by azidopentaammine cobalt(III) {[Co(NH3)5N3]2+} was investigated at room temperature in an argon atmosphere. By excitation into the ligand to metal charge transfer (LMCT), the cobalt complex showed an efficient photoredox process leading to the formation of a cobalt(II) and an azide radical (N, Φphotoredox = 0.24). The same process was found to occur by excitation into the ligand field band with a low but not negligible quantum yield (Φphotoredox = 0.016). Two different domains were clearly present when the plot of the rate of polymerization as a function of the cobalt(III) complex was studied; for [Co(III)] < 2.0 × 10−4 M, the termination step mainly involved a mutual annihilation of growing radicals whereas an oxidative termination was present in the range of 2.0 × 10−4 M < [Co(III)] < 1.0 × 10−3 M. Within the former domain the rate of polymerization (Rp ) varied with the first power of the monomer concentration and with the square root of the absorbed light intensity while for the latter domain the Rp was proportional to the monomer concentration and absorbed light intensity. Further investigations using the viscosity‐average molecular weight data allowed us to corroborate the proposed polymerization mechanism. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3997–4005, 2000 相似文献
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大分子光引发剂可以解决小分子光引发剂残留碎片带来的毒性对其在食品和医用材料领域应用的限制,为此,本文以苯甲酰甲酸(BF)和季戊四醇(PET)为原料,通过酰氯法在季戊四醇主链上引入了4个苯甲酰甲酸酯基团,制备了多官能度的季戊四醇四苯甲酰甲酸酯(PTF)大分子光引发剂。 PTF在225 ℃时失重15%,热稳定性优于2-羟基-2-甲基-1-苯基-1-丙酮(1173)光引发剂,与1173光引发剂相比,用PTF作光引发剂所制备的光固化涂料,在起始分解温度以及失去相同比例质量所需温度均提高了100 ℃以上。 PTF引发三羟甲基丙烷三丙烯酸酯(TMPTA)聚合时最大反应速率为0.037 s-1,最终双键转化率为39.5%,PTF光引发活性大于1173光引发剂。 在同等实验条件下,PTF的相对小分子残留量仅为1173光引发剂的5%。 相似文献
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以季戊四醇四丙烯酸酯(PETA)为聚合单体,安息香乙醚为引发剂,通过紫外光引发生成凝胶,通过真空干燥得到PETA泡沫材料。通过理论计算和实验确定的多元丙烯酸酯交联聚合物的溶解度参数值为19.0左右,含有苯环的脂肪烃和酮类的溶剂会导致引发剂“失活”,而卤代烃、酯、醚和酰胺类溶剂能够保持引发剂的“活性”。 相似文献
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James V. Crivello 《Journal of polymer science. Part A, Polymer chemistry》1999,37(23):4241-4254
The story of the discovery and development of onium salt photoinitiators for cationic polymerization is chronicled. The chemistry of the synthesis of these compounds is outlined, and the mechanisms of their initiation are discussed briefly. Among the most useful of these types of photoinitiators are diaryliodonium and triarylsulfonium salts, which are used widely for photoinduced cationic crosslinking reactions. From the very beginning, onium salt photoinitiated cationic polymerizations have found use in a multitude of practical applications. Specifically discussed in this article are the use of onium salts in coatings, adhesives, printing inks, release coatings, stereolithography, holographic recording, photocurable composites, and microelectronic photoresists. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4241–4254, 1999 相似文献
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Jian Qiu Zi-Chen Li Qing-Yu Gao Guang-Qing Yao Geng-Xu Yang Ju-Xian Zhang Fu-Mian Li 《Journal of polymer science. Part A, Polymer chemistry》1996,34(14):3015-3023
Four acrylic monomers bearing phenothiazine moieties, i.e., N-acrylyl-phenothiazine (APT), N-acrylyl-2-chlorophenothiazine (ACPT), N-acrylyl-2-acetylphenothiazine (AAPT), and 10-acrylyl-1-azaphenothiazine (AAzPT) were synthesized by dehydrohalogenation of the corresponding N-(β-chloropropionyl)-substituted phenothiazine derivatives with 1,8-diazabicyclo[5.4.0]undec-5-ene (DBU). These monomers could easily be polymerized by initiation with AIBN. The emission fluorescence spectra of the monomers and their polymers were recorded, which showed that the polymers displayed much stronger fluorescence than their corresponding monomers at the same chromophore concentrations. This phenomenon, as termed as “structural self-quenching effect,” was commonly observed for acrylic monomers bearing chromophore moieties and ascribed to the coexistence of the electron-donating chromophore and the electron-accepting double bond in the same molecule. Because of the formation of exciplex, the monomer APT, as well as ACPT, AAPT, AAzPT, and their polymers, could initiate the photopolymerization of AN. The charge transfer phenomenon between P(APT), P(ACPT), and C60 was also explored. © 1996 John Wiley & Sons, Inc. 相似文献