适用于UV-LED光源的新型光引发剂的合成及其性能研究

本文从光活性高的3,4-乙烯二氧噻吩（EDOT）出发,在其两个活性位点上分别引入了一个乙酰基噻吩基团和一个乙酰基基团,合成了一种结构新颖的、适用于UV-LED光固化体系的光引发剂2-（2-乙酰基噻吩）-5-乙酰基-3,4-乙烯二氧噻吩（S-2）。利用核磁共振氢谱对其结构进行了表征,并测试了其紫外吸收特性和热稳定性,还利用实时红外技术对其光引发活性进行了测试。结果表明,此光引发剂在365~405 nm范围内有较好的吸收,其紫外吸收性能和热稳定性优于异丙基硫杂蒽酮（ITX）,光引发活性与ITX相当。     

Characterization of the physical–mechanical properties of dental resin composites reinforced with novel micro-nano hybrid silica particles: An optimization study

Abstract

In the study, dental composites of color A2 using Bis-GMA/UDMA/TEGDMA resins (ratios 70/10/20), and silica filler (70%wt, 75%wt, and 80%wt) which is a hybrid of two silica types in nano and micro dimensions were made using two different photoinitiators namely BAPO and camphorquinone. The optimum photoinitiator was selected based on the mechanical tests results after which the composites were subjected to the following tests: FTIR to evaluate polymerization degree, microhardness test, UTM, and SEM micrographs were taken to analyze the surface fracture of samples. The results of photoinitiator selection (flexural strength test) is 36.54?MPa, 37.62?MPa, and 75.08?MPa for BAPO?+?camphorquinone, camphorquinone, and BAPO respectively. The results show that the BAPO photoinitiator exhibits better results over camphorquinone and also BAPO/camphorquinone initiator systems. Then after choosing the photoinitiator system composites with different filler contents show higher mechanical strength than existing dental composites. The results of the mechanical tests for the composites with different filler contents synthesized after initiator system selection were significantly higher than the values specified in ISO 4049:2009 (102?MPa over 80?MPa). FTIR results indicate that the degree of conversion in these composite is 25.41%, 37.68, and 40.94% for composites with different filler amounts.     

含氟光引发剂的合成及其性能研究

以2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure 2959)和全氟辛酰氯(PFOC)为原料合成了光引发剂全氟辛酸-2-[4-(2-羟基-2-甲基丙酰)苯氧基]乙酯(2959-F),利用红外光谱(FT-IR)和核磁共振(¹⁹F NMR)对2959-F进行了结构表征;通过紫外吸收光谱测定了2959-F的紫外吸收谱;通过实时红外光谱(RT-IR)对合成的含氟光引发剂进行了光聚合反应动力学研究,考察了光强和引发剂浓度对单体的双键转化率和聚合速率影响,并研究了光引发剂2959-F的抗氧阻聚性能.结果表明:随着光强的增大,单体的双键转化率和聚合速率增加;在一定范围内,引发剂的浓度越高,双键转化率越高,聚合速率越快.2959-F具有较高的双键转化率和较快的聚合速率,并且具有较好的抗氧阻聚性.     

A Multicolor Photoinitiator for Cationic Polymerization and Interpenetrated Polymer Network Synthesis: 2,7‐Di‐tert‐butyldimethyldihydropyrene

For polymer synthesis upon visible light, actual photoinitiator operates in a restricted part of the spectrum. As a consequence, several photoinitiators are necessary to harvest all of the emitted visible photons. Herein, 2,7‐di‐tert‐butyldimethyldihydropyrene is used for the first time as a multicolor photoinitiator for the cationic polymerization of epoxides. Upon addition of diphenyliodonium hexafluorophosphate and optionally N‐vinylcarbazole, the originality of this approach is to allow efficient monomer conversions under various excitation light sources in the 360–650 nm wavelength range: halogen lamps, and light‐emitting and laser diodes. The synthesis of an interpenetrated polymer network from an epoxide/acrylate blend using a red light at 635 nm is also feasible. The formed polymer material exhibits a photochromic character.

     

Critical Exponents of Photoinitiated Gelation at Different Light Intensities

A photo-differential scanning calorimetric (Photo-DSC) technique was used to study the photoinitiated radical polymerization of a 75% epoxy diacrylate (EA) and 25% tripropyleneglycoldiacrylate (TPGDA) mixture with 2-mercaptothioxanthone (TX-SH) as photoinitiator by using different light intensities. Photopolymerization reactions were carried out under identical conditions of temperature and initiator concentration. It was observed that all conversion curves during gelation at various UV light intensities present good sigmoidal behavior as predicted by the percolation model. Observations around the critical time, called the glass transition point (t_g), taken for polymerization to reach the maximum rate (Rp _max) show that the gel fraction exponents β obeyed the universal percolation picture. On the other hand, Rp _max, t _g, and final conversion values were found to be dependent on the UV light intensity.     

Universality in gelation of epoxy acrylate with various photoinitiators: a photo differential scanning calorimetric study

Photo-differential scanning calorimetric (Photo-DSC) technique was used to study the gelation of P-3038 (epoxy acrylate (EA) 75% and tripropyleneglycoldiacrylate (TPGDA) 25%) in the presence of various thioxanthone-based initiators, namely, thioxanthone (TX), 5-thia-naphtacene-12-one (TX-NP), 2-(carboxymethoxy) thioxanthone (TX-OCH₂COOH), 2-thioxanthone-thioacetic acid (TX-SCH₂COOH), and 2-mercaptothioxanthone (TX-SH). Photopolymerization reactions were performed under identical conditions of temperature, initiator concentration, and UV light intensity. Photo-DSC technique allowed us to monitor the gelation, without disturbing the system mechanically, and to test the universality of the gelation as a function of some kinetic parameters like initiator concentration. During gelation, it was observed that all conversion curves present a good sigmoidal behavior by predicting to employ percolation model. Observations around the glass transition point, t _g shows that the gel fraction exponents β obeyed the percolation picture. On the other hand, t _g was found to be much higher for the crosslinked networks obtained with TX-OCH₂COOH and TX-SCH₂COOH initiators than those with the other initiators.     

气相色谱-质谱法测定乳制品中光引发剂异丙基硫杂蒽酮的残留量

建立了采用气相色谱（GC）-质谱(MS)检测由包装材料迁移到乳制品中的光引发剂异丙基硫杂蒽酮残留量的方法。使用氘代蒽为内标,样品经Carrez试剂除蛋白质后用丙酮-正己烷(体积比为1∶1)提取,上层提取液用氟罗里硅土固相萃取小柱净化。采用单四极杆质谱进行样品筛选和定量,选取的监测离子为m/z 184,m/z 224,m/z 239,m/z 254(异丙基硫杂蒽酮)和m/z 80,m/z 94,m/z 188,m/z 160(氘代蒽)。疑似样品采用离子阱串联质谱法进行确证,选取的母离子和子离子分别为m/z 254,m/z 239(异丙基硫杂蒽酮)和m/z 188,m/z 160(氘代蒽)。本方法的测定低限(LOQ)分别为7.0 μg/L(GC-MS)和5.0 μg/L(GC-MS/MS),回收率为74.9%~89.6%。采用该方法对11种不同类型的乳制品进行了检测,发现了两例阳性样品。     

新型的含葡萄糖胺的水溶性高分子型硫杂蒽酮光引发剂

将硫杂蒽酮光引发剂(TX)和共引发剂葡萄糖胺(GA)引入同一个高分子链上,合成新型水溶性高分子型硫杂蒽酮光引发剂(PTX-GA).通过改变PTX-GA中TX与GA的比例,合成了PTX-GA1、PTX-GA2、PTX-GA3,并通过光膨胀计实验研究了3种引发剂引发丙烯酰胺聚合的能力.研究表明这种水溶性高分子型硫杂蒽酮光引发剂即使在没有共引发剂胺的情况下,引发丙烯酰胺(AAM)的聚合效率也非常显著.同时由于它具有水溶性,而且含有生物分子,有利于改善光引发剂的生物相容性.     

Sensitized photolysis of diphenyliodonium cation through intra-ion-pair electron transfer—A novel near-UV photoinitiator: Diphenyliodonium 9-acridinecarboxylate

A novel near-UV photoinitiator, diphenyliodonium 9-acridinecarboxylate (DPIOAC), was synthesized by metathesis, characterized, and studied. In media of different polarity, this compound showed different absorption and fluorescence profiles and photochemical properties. When irradiated with near-UV light, the anion absorbed the radiation and sensitized the photolysis of the iodonium cation. The active free radicals thus formed initiated polymerization of vinyl monomers. The facts influencing the form of the existence of the ion pairs influenced the rate and efficiency of the intra-ion-pair electron transfer and, thus, of the polymerization. This new photoinitiator had a much greater photoinitiation ability for polymerization than the previously reported diphenyliodonium anthroate, which has a carbon atom at the nitrogen position of DPIOAC. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4521–4527, 1999