2,4-二甲基苯甲酸的制备反应机理探讨及合成工艺改进

合成了新型光引发剂酰基膦氧化物的中间体2,4-二甲基苯甲酸,并对其合成反应机理进行了探讨,提出了工艺革新,用次氯酸钠代替传统的氯气进行反应,并通过正交实验分别对两步反应的合成条件进行了优化,得到了最优反应条件,即:物料配比n(α-氯代-2,4-二甲基苯乙酮):n(次氯酸钠)为1:1.3,催化剂的苯扎溴铵的用量为15 mL,反应时间为7 h,反应温度为80℃.经重复实验验证,在该最优条件下2,4-二甲基苯甲酸的合成可达到平均收率80%.     

The effect of co-initiator structure on photoinitiating efficiency of photoredox couples composed of quinoline[2,3-b]-1H-imidazo[1,2-a]pyridinium bromide and phenoxyacetic acid or N,N-dimethylaniline derivatives.

Summary  Two groups of electron donors (phenoxyacetic acid derivatives, PAADs, and the family of N,N-dimethylaniline derivatives DMADs) in combination with quinoline[2,3-b]-1H-imidazo[1,2-a]pyridinium bromide (QIPB) were applied as photoinitiator for free radical polymerization induced with UV emission of an argon-ion laser (351 and 361 nm). Analysis of the data obtained for the initial time of photoinitiated polymerization indicates that both, the rate of electron transfer process between QIPB and tested co-initiators as well as the structure of obtained free radical can affect the overall photoinitiation ability of tested photoredox pairs.     

双官能度羟基酮光引发剂的合成及其性能

以1,1,3-三甲基-3-苯基茚满为母体,通过傅克及羟基化反应合成了一种性能优异于传统单官能度小分子光引发剂的双官能度光引发剂。产物通过核磁共振波谱仪、傅里叶变换红外光谱仪进行结构鉴定,并将其性能与单官能度小分子裂解型光引发剂比较。结果表明,该种光引发剂紫外最大吸收较小分子光引发剂红移了约14 nm,固化成膜后其相对迁移率下降了约80%～90%,热稳定性提高,同时保持了小分子光引发剂的高引发效率,是一种性能优良的光引发剂。     

Cyclopentadiene—iron—naphthalene tetrafluoroborate salt as a cationic photoinitiator for preparing photosensitive materials

Abstract

A novel cationic photoinitiator, cyclopentadiene-iron-naphthalene tetrafluoroborate ([Cp-Fe-Naph]BF₄) salt, was synthesized, characterized and used for preparing photosensitive materials. The purification process and the reaction conditions were optimized. The highest yield can reach 82 per cent. Compared with the mono-arene iron complexes, [Cp-Fe-Naph]BF₄ possesses a higher molar extinction coefficient (ε = 893 M^?1 cm^?1) at 373 nm in CH₂C1₂ and is more efficient for the polymerization of epoxide when a high-pressure mercury lamp is used as an ultraviolet light source. The photosensitivity S can reach 78.1 mJ/cm2 when [Cp-Fe-Naph]BF₄ is used to initiate the epoxide E44. When the photosensitizer benzoyl peroxide (BPO) is employed, [Cp-Fe-Naph]BF₄ is rendered much more efficient as a photoinitiator. The best molar ratio of BPO to [Cp-Fe-Naph]BF₄ is 1:1 to 1:2. In the photopolymerization of epoxide initiated by [Cp-Fe-Naph]BF₄, the temperature is very important with respect to the polymerization rate. At 60°C, the polymerization can be completed in a short time.     

一种新型活性稀释剂在自由基/阳离子混杂型光固化体系中的性能

以双酚A型环氧树脂(E-51)、环氧丙烯酸酯(EA-612)、3-乙基-3-烯丙基甲氧基氧杂环丁烷、2-羟基-2-甲基-1-苯基丙酮(UV-1173)和三芳基锍鎓六氟锑酸盐(UV-6976)作为组分制备了一种混杂型紫外光固化材料。较佳配方为:m(E-51)∶m(EA-612)=1∶1,m(预聚物总量)∶m(3-乙基-3-烯丙基甲氧基氧杂环丁烷)=4∶1,m(UV-1173)∶m(UV-6976)=1∶1,并且复配光引发剂总量为7%。实验结果表明其紫外光固化膜的冲击强度为30kg·cm,附着力为2级,柔韧性可通过轴棒6的弯曲测试。     

引发剂对UV油墨固化速度影响的研究

为提高UV油墨的固化速度,研究了羟烷基苯酮类1173、胺烷基苯酮类907、酰基磷氧化物类819、二苯甲酮类BP、硫杂蒽酮类ITX 5种引发剂及复配对UV油墨固化速度的影响。结果表明,引发剂浓度为2%,颜料浓度为4%,单体浓度为30%时,引发剂1173、BP的固化时间分别为20.88 s和70.56 s,引发剂907的光固化时间为7.14 s,引发剂819和ITX的光固化时间均可达到1.5 s。引发剂1173与BP进行1∶3复配时,固化速度是BP的4.9倍;引发剂907与BP进行1∶3复配时,固化速度是BP的4.3倍;引发剂ITX与907进行1∶1复配时,固化速度是907的2.3倍。     

快速光固化用阳离子光引发剂研究进展

介绍了阳离子型光引发剂的引发原理,综述了芳香重氮盐,有机铝络合物/硅烷体系,茂铁盐化合物,二芳基碘鎓盐和三芳基硫鎓盐及其他新型阳离子光引发剂的开发及其改性研究进展。     

Synthesis and photopolymerization kinetics of oxime ester photoinitiators

Oxime Ester (OXE) Photoinitiators were synthesized and characterized by HPLC, FTIR, UV–Vis spectra, and ¹H‐NMR. The UV–Vis spectra of these photoinitiators were similar to Benzophenone (BP) but showed large red‐shifted maximum absorption. OXE were not only soluble in many solvents and (meth) acrylate monomers but also could be dispersed easily in propylene glycol monomethyl ether acetate (PGMEA). The kinetics of polymerization of monomer using OXE as photoinitiator was studied by Real‐time infrared (RTIR) spectra. It showed that OXE were an efficient photoinitiator. The concentration of OXE, functionality of monomer, and light intensity had effect on the photopolymerization kinetics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮的合成

2-甲基-1-(4-甲硫基苯基)2-吗啉基-1-丙酮是一种重要的光引发剂,以1-(4-氯苯基)-2-甲基-1,2-环氧丙烷和吗啉为起始原料,经盐酸酸化,在催化剂作用下用氧气氧化,最后和甲硫醇钠反应得到,总收率为80.9%。     

新型氧酰基肟酯类光引发剂的制备与性能

制备了3种新型氧酰基肟酯类光引发剂。并用TLC、DSC和UV等手段对其溶解稳定性、热稳定性及紫外吸收特性进行了表征,发现其溶解稳定性良好,可溶于常见的有机溶剂,有着非常好的热稳定性,并且在g线(436nm)、i线(365nm)和深紫外处(DUV,248nm)都有很好的紫外吸收;还利用实时红外(RT-IR)红外实验及感光性能测试实验对此类光引发剂的光固化性能进行了测试。结果表明,与常见的自由基引发剂ITX、TPO、261等相比,其更适合用于405nm紫激光自由基光聚合成像体系及其他化学增幅光致抗蚀试剂体系中。