紫外光固化涂料耐磨性的研究

讨论了影响紫外光固化涂料耐磨性的几个因素。结果表明涂料的耐磨性与树脂种类、单体官能度、光引发剂用量以及填料的种类、用量有关,并从理论上给出了相关解释。     

UV光固化环氧丙烯酸酯耐磨涂料的研究

以E51和E44环氧树脂和丙烯酸为原料,制备了UV固化环氧丙烯酸酯耐磨涂料。不同光引发剂、稀释剂和助剂等对UV固化环氧丙烯酸酯涂料固化性能均有影响。研究结果表明,用安息香乙醚与二苯甲酮(质量比为2∶1)的混合体系作为光引发剂的引发效率最高,最佳涂料配方:环氧丙烯酸酯∶丙烯酸丁酯∶安息香乙醚∶二苯甲酮∶滑石粉为70∶20∶4∶2∶4(质量比)。     

4,4′-二乙酰胺基二苯基碘六氟磷酸盐的合成

以乙酰苯胺为原料,乙酸为溶剂,在浓硫酸作用下,合成了未见国内外文献报道的阳离子光引发剂4,4′-二乙酰胺基二苯基碘六氟磷酸盐,其结构经IR,1HNMR,MS和UV确认。通过正交实验确定了最佳合成条件:乙酰苯胺30.6 g(0.227 mol)和碘酸钾22 g(0.103 mol),溶剂乙酸用量为100 mL,室温(25℃)反应24 h,产率可达47.6%。     

紫外光固化防腐涂料的研制

在自制的丙烯酸环氧树脂中加入光引发剂和活性稀释剂,得到环保的紫外光固化防腐涂料。     

二茂铁四氟硼酸盐的阳离子光引发性能的研究

制备并研究了[CpFeCp]BF4作为阳离子光引发剂在高压汞灯下引发环氧类预聚物的光引发活性。发现其在紫外及可见光区均有较强吸收（λm=355nm、620nm)；对环氧类预聚物，具有优良的光引发活性，感度值可达41.8mJ/cm^2，优于其它的阳离子光引发剂；[CpFeCp]BF4的最佳使用浓度为3％（质量分数）左右，由于光照后仍有强后聚合活性，发现其在较低浓度（质量分数1％）引发后放置，仍可使聚合完全；同其它的阳离子光引发剂相比，[CpFeCp]BF4制备简单，非常有应用价值。     

两亲性苯甲酰甲酸酯类光引发剂及其引发性能

以苯甲酰甲酸和三乙二醇为原料合成了一种水油两亲性光引发剂苯甲酰甲酸三乙二醇单酯（TGBF），并利用紫外-可见分光光度计、电子自旋共振仪及实时红外光谱仪等手段探究了TGBF的光吸收性能、光降解机理、水中溶解性以及引发光聚合的能力。研究结果表明，TGBF在300 nm以上波长的摩尔消光系数较低，但在405 nm LED光源照射下，能够发生分子内或者分子间的夺氢反应，并产生烷基自由基引发单体聚合。TGBF具有良好的水溶性，可高效地引发油性单体三丙二醇二丙烯酸酯（TPGDA）与水性单体聚乙二醇400二丙烯酸酯（PEG（400）DA）的聚合，最终双键转化率可达到80%以上。更重要的是，TGBF具有优异的引发油性单体TPGDA与水性单体深度聚合的能力，聚合深度分别达到5.6cm和6.5 cm以上,在深层LED光聚合领域表现出极大的应用潜力。     

Photopolymerization kinetics of dimethacrylate‐based light‐cured dental resins

The influence of certain factors [structure and concentration of tertiary amines as coinitiators, monomer composition, presence of inorganic pigments, and incident light intensity (I₀)] on the polymerization rates (R_p), polymerization quantum yields, and conversions of bisphenol A–bis(glycidyl methacrylate) (Bis‐GMA)/triethylene glycol dimethacrylate based resins was studied. The initial rate of bulk polymerization increased and the final conversion decreased with the content of Bis‐GMA in the mixture. In contrast, it was established that, for all monomer compositions, the R_p grew when increasing the I₀, the R_p being directly proportional to the square root of I₀. Such behavior is in agreement with the well‐known kinetic expression for the ideal radical photoinitiated polymerization in solution of monofunctional monomers, in spite of the complexity of the dimethacrylate mixtures that were studied. Both the structure and the concentration of reducing amine affected the efficiency of the initiator system and therefore the kinetic behavior of polymerization of these formulations under irradiation. The rate of polymerization increased with the increase of coinitiator concentration over the interval of 0–1%, but later it diminished when increasing the amine content, suggesting that the excess coinitiator retards the polymerization process. The study of the photoreduction of camphorquinone in the presence of different amines showed that the efficiency of the coinitiator depends not only on its ability to photoreduce camphorquinone, forming amine‐derived radicals, but also on the reactivity of these radicals toward the initiation of acrylic monomer polymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1016–1023, 2005     

Conducting Electroactive Polymers via Photopolymerization: A Review on Synthesis and Applications

Photopolymerization can be considered as an appropriate method in synthesis of conducting electroactive polymers. This paper presents a survey on the major principles of photopolymerization method, then reviews performed researches on photopolymerization leading to conducting electroactive polymer-based materials, and thereby reveals the significant information relevant to their structures and properties. The main focus of this state-of-the-art review is classification of the photoinduced synthesis of conducting electroactive polymers according to predominant mechanism in detail. Furthermore, practical applications of photopolymerization to fabrication of conducting polymeric structures such as films and nanostructures are surveyed from different publications.     

Difunctional monomeric and polymeric photoinitiators: Synthesis and photoinitiating behaviors

The first methacrylate monomers with two type I or type II side-chain photoinitiating groups (PI1, PI2 and PI3) are synthesized from reactions of 2-(chloromethyl)acryloyl chloride and 4-hydroxybenzophenone, 4-hydroxyacetophenone or 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure 2959), and polymerized, giving polymeric photoinitiators (PPI1, PPI2 and PPI3). PI1 is also copolymerized with N,N-dimethylaminoethyl methacrylate (DMAEM) to investigate the photoinitiation efficiency of the resulting polymer featuring built-in amine coinitiator. Activities of these photoinitiators together with acetophenone (AP), benzophenone (BP) and Irgacure 2959 are investigated in photopolymerizations of hexane-1,6-diol diacrylate, using photodifferential scanning calorimeter and the kinetic parameters are correlated with the structures of the photoinitiating systems. The results show different photoinitiating activities compared to small molecule commercial analogs: BP-based photoinitiators, PI1, PPI1 and PPI(PI1-co-DMAEM), are found to be particularly efficient compared to BP. The Irgacure 2959-based ones appear to be promising as type I photoinitiators.     

新型水溶性硫杂蒽酮类光引发剂的光化学性能研究

本文对８种水溶性硫杂蒽酮类光引发剂进行了紫外－可见光谱，荧光光谱以及电子自旋共振光谱（ＥＳＲ）等测试。测定了最大吸收波长，计算了摩尔消光系数，荧光量子产率，测定了ＥＳＲ信号强度等，并对其结构与光化学性能之间的关系进行了讨论。