Photoinitiators for UV and visible curing of coatings: Mechanisms and properties

The radiation curing industry is one of the most rapidly developing fields in the entire coatings industry. The low toxicity, cheapness, speed, control and ease of formulation and operation are some of the main advantages of this growing technology. UV and/or visible light radiation is used to induce photochemical polymerization or crosslinking of a monomer, oligomer or prepolymer formulation containing a certain type of unsaturation, such as an acrylic group, and an appropriate initiator. The latter is used to absorb the light energy and transform it into active species, such as radicals or ions, capable of inducing such reactions. Applications extend to general coatings for paper, board, wood, tapes, compact discs and holograms, inks, photoresists for imaging processes and adhesives for welding and sealing in electronic circuit boards. The photoinitiator is the key to the control of these processes and, in recent years, has seen many new developments. These include the need for water-soluble, co-reactive and polymeric structures with low migration rates, as well as cheaper UV/ visible sensitizers with enhanced speed. New and effective cationic systems are also on the scene and, although expensive, are attracting significant academic and commercial interest.     

水溶性光聚合引发剂研究进展

近几年发展起来的水溶性光聚合引发剂（ＷＳＰ）属自由基引发剂，按结构可分为芳酮类，稠环类烃类，聚硅烷类，酰基膦酸盐等，偶氮类及金属有机配合物类，本文综述了这些光引发剂的结构特性，光化学行为，光引发效率及光反应机理等。     

UV/Vis-LED激发的香豆素吡啶鎓盐光引发剂的合成及性能

设计合成了3种基于香豆素骨架的紫外-可见发光二极管(UV/Vis-LED)可激发的新型吡啶鎓盐光引发剂, 并研究了这3种香豆素吡啶鎓盐的构效关系及其作为单组分自由基光引发剂在丙烯酸酯体系中的光引发活性. 紫外-可见吸收光谱分析表明, 这3种香豆素吡啶鎓盐在300~400 nm区域有较强吸收. 在LED@365 nm和LED@405 nm光源辐照下, 研究了3种光引发剂的稳态光解和光聚合动力学. 研究表明, 这3种香豆素吡啶鎓盐光引发剂在相应光辐照下都具有较好的光解速率. 此外, 3种光引发剂对丙烯酸酯都具有较好的引发活性. 构效关系研究表明, 吡啶环4号位引入推电子的甲氧基会使其引发丙烯酸酯单体聚合的活性降低; 而引入吸电子的乙酰基会使其引发丙烯酸酯单体聚合的活性增加. 差示扫描量热(DSC)实验表明, 此类吡啶鎓盐光引发剂具有较好的热稳定性. 当3种光引发剂与丙烯酸单体混合时可提升体系的热稳定性; 通过电子自旋共振(ESR)证明了活性物种的产生, 并对该类引发剂的引发机理进行了探讨.     

光引发体系对有机硅光固化材料感光性能的影响

裂解型光引发剂中以IR1700的引发效果最好,其感度值为10.6 mJ.cm-2,二苯甲酮(BP)和三乙醇胺(TEOA)组成的夺氢光引发体系的最高感度为26.8 mJ.cm-2,BP和TEOA的最佳质量比为1∶2。混合光引发体系的引发效果最好,其最佳组成为IR651∶TEOA∶IR1700=1∶1∶1(质量比),感度最高可达7.9 mJ.cm-2。光引发剂最佳含量为4%(wt)~6%(wt)。     

Non-extractable photoinitiators based on thiol-functionalized benzophenones and thioxanthones

Non-extractable photoinitiators could be advantageous for use in biological, electronic, and food packaging applications. Therefore, thioxanthone and benzophenone derivatives were synthesized from 1,6-hexane dithiol and chlorinated benzophenone or thioxanthone. The efficiency of thiol-functionalized photoinitiators in combination with amine co-initiators was compared to benzophenone and isopropylthioxanthone with amine co-initiators, and the cleavage of photoinitiator 2,2-dimethoxy-1,2-diphenylethan-1-one in acrylic resins. The reaction kinetics were analyzed using photo-differential scanning calorimetry and real-time FTIR. Coating physical properties were evaluated by pendulum and pencil hardness, steel-wool scratch and mandrel bend tests. The non-extractable photoinitiators had higher absorbance than their benzophenone or isopropylthioxanthone counterparts due to the sulfide substitution on the phenyl ring, and the free thiol groups reacted with the acrylate by either an amine catalyzed Michael addition or a free-radical chain process. The combination of thiol-functionalized photoinitiators with secondary amines provides an efficient photoinitiator system that is locked into the photopolymerized network and cannot be extracted with typical solvents.     

自由基型光引发剂的瞬态及稳态荧光特性研究

利用荧光光谱技术研究了不同自由基型光引发剂的瞬态及稳态荧光光谱特性,从分子结构出发分析了共轭结构对光引发剂荧光光谱的影响.实验结果表明随共轭效应的增强,荧光激发与发射峰波长逐渐增大;瞬态荧光谱的衰减受电子基团的影响较为明显,含有吸电子基团的光引发剂荧光衰减快,而含有给电子基团的光引发剂荧光衰减慢.通过对溶剂极性及粘度研...     

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...     

紫外光引发剂907及其反应中间体的气相色谱测定

建立了光引发剂907合成工艺控制中反应原料、中间体及产物的气相色谱分析方法。采用SE-54石英毛细管柱,程序升温进行分离,氢火焰离子化检测器(FID)进行检测。结果表明,原料苯甲硫醚,反应中间体807A、807B、907C和产物907线性范围分别为0.2～14.0μg/mL、0.4～20.0μg/mL、0.5～22.0μg/mL和0.6～19.0μg/mL,线性相关系数R均大于0.999,相对标准偏差小于2.5%,回收率为93.6%～106.8%。产物结构通过红外光谱进行表征。该方法线性关系、准确度和精密度良好,适用于光引发剂907合成工艺的快速监控及产品定量分析。     

Semi-groupes de Riesz d'ordre α sur le demi-espace

Nous donnons une forme équivalente de la densité du semi-groupe de Riesz d'ordre sur le demi-espace. La nouvelle forme nous permet d'établir des critères de comparaison du semi-groupe de Riesz d'ordre et de la résolvante associée avec leurs perturbés par une mesure de Radon positive. Abstract. We give an equivalent form of the density of the Riesz semigroup on the half space. The new form allows us to establish criterions of comparison of the Riesz semigroup and the associated resolvent with their perturbed by a nonnegative Radon measure.     

Electrochemical Studies on the Photolysis of Iron-Arene Complex Photoinitiator

Iron-arene complex was first introduced by researchers in Ciba-Geigy as an effective photoinitiator for the photocuring of epoxy resin. The photolysis of these complexes has been studied by some authors. The electrochemical study reported in this note provides further evidence for the photolysis process which is crucial for the understanding of the photoinitiation mechanism.