【作者】 李焱飞；

【导师】 谢川；

【作者基本信息】 四川大学 ， 应用化学， 2007， 硕士

【摘要】 本文以碘苯、二苯醚及二苯硫醚衍生物为主要原料，合成了5种碘鎓盐，它们分别为：[4-（对苯甲酰基苯硫基）苯]苯基碘鎓六氟磷酸盐（Ⅰ），{4-[4-（对硝基苯甲酰基）苯硫基]苯}苯基碘翁六氟磷酸盐（Ⅱ），{4-[4-（对甲基苯甲酰基）苯硫基]苯}苯基碘鎓六氟磷酸盐（Ⅲ），{4-[4-（对甲基苯甲酰基）苯氧基]苯}苯基碘鎓六氟磷酸盐（Ⅳ）和[4-（对苯甲酰基苯氧基）苯]苯基碘鎓六氟磷酸盐（Ⅴ）。其中Ⅰ、Ⅱ、Ⅲ、Ⅳ4种碘鎓盐目前未见报道。对[4-（对苯甲酰基苯硫基）苯]苯基碘鎓六氟磷酸盐（Ⅰ）的合成条件进行了研究。在单因素实验的基础上，运用正交实验设计法确定了最佳实验条件：4-苯硫基二苯甲酮2.033g（0.007mol），羟基对甲苯磺酰氧碘苯3.294g（0.0084mol），催化剂摩尔配比（乙酐／浓硫酸）1.5，浓H₂SO₄用量2ml，反应温度60℃，反应时间24h。以此最佳实验条件重复实验，其平均产率为47.9％。利用红外光谱、质谱、核磁共振氢谱、紫外光谱等测试手段对合成的5种目标产物及部分中间体进行了结构表征；并对5种目标产物进行了光引发性能测试。结果表明5种产物不仅引发聚合速度快，而且具有一定的抗氧阻特性，部分光引发剂具有后固化（也称暗聚合）特征，即本文合成的5种自由基—阳离子杂化型光引发剂同时具有自由基光引发剂和阳离子光引发剂的引发特性。探讨了光引发剂用量对光敏体系固化过程的影响以及光引发剂在预聚物中的贮存稳定性。为了进一步认识该类自由基-阳离子杂化型光引发剂的构效关系，本文对具有不同阳离子结构的该类光引发剂的引发性能进行了研究。实验结果表明，阳离子结构不同的自由基—阳离子光引发剂的引发活性与分子中助色团（供电子基团）的数量多少有关。助色团越多，分子共轭体系增大越多，从而跃迁能量下降，光解速率加快。对存在苯硫基的分子而言，由于C-S键易于断裂而产生自由基，与碘鎓盐产生的超强酸协同作用，引发单体聚合，使相应的自由基—阳离子二芳基碘翁盐的引发性能比结构相似而含苯氧基的引发性能强。更多还原

【Abstract】 In this paper 5 iodonium salts were synthesized from iodobenzene,diphenyl ether or diphenyl sulfide derivatives.The products were: 4-[p-benzoyl （thiophenyl） phenyl] phenyl iodonium hexafluorophosphate（Ⅰ）, {4-[4-p-nitrobenzoyl （thiophenyl） phenyl]}phenyl iodonium hexafluorophosphate（Ⅱ）,{4-[4-p-methylbenzoyl （thiophenyl） phenyl]} phenyl iodonium hexafluorophosphate（Ⅲ）, {4-[4-p-methylbenzoyl （phenoxy） phenyl]}phenyl iodonium hexafluorophosphate （Ⅳ） and 4-[p-benzoyl （phenoxy） phenyl] phenyl iodonium hexafluorophosphate （Ⅴ）. Among them,Ⅰ,Ⅱ,ⅢandⅣare new compounds.The synthesis of 4-[p-benzoyl （thiophenyl） phenyl] phenyl iodonium hexafluorophosphate（Ⅰ）was researched. On the basis of single factor experiments, the optimal reaction conditions were dertermined through orthogonal experiment: 4-thiophenyl benzophenone 2.033g （0.007mol）,hydroxy（tosyloxy）iodobenzene 3.294g （0.0084mol）, mol ratio of catalyst （acetic anhydride/concentrated sulfuric acid） 1.5, and H₂SO₄ 1.5mL,at 60℃for 24h.The average yield was 47.9%.The 5 iodonium salts and some intermediates were characterized by IR, MS, ¹HNMR and UV. With the analysis and discussion of their photoinitiability, it was indicated that the products had not only higher curing rate but also well resistance of oxygen inhibition and parts of them had post curing character, i.e. the 5 free radical-cationic hybrid photoinitiators had the character of radical photoinitiators and cationic photoinitiators. Effect of photoinitiator concentration in UV curing system and storage stability of photoinitiators in prepolymer were researched. In this thesis the structure-activity relationship of the iodonium salts with different cation was investigated. Experiment results showed photoinitiability had relation to quantity of auxochromes （electron-donating group）. The more auxochromes, the larger conjugated system,and transition energy of molecular decreased. So photolysis rate increased.As far as the moleculars with thiophenyl was concerned, for the C-S bond was prone to fracture and produce free radical,which produced synergetic effect with superacid from iodonium salts and initiated polymerization of monomers.As a result of all, photoinitiability of the free radical-cationic iodonium salts were enhanced.更多还原