新型紫外光固化大分子光引发剂的研究进展

综述了大分子光引发剂中改良型紫外光(UV)固化引发剂(有机硅、超支化聚合物改性)和新型UV固化引发剂(阳离子、可聚合和水性)在合成方法、结构性能等方面的最新研究进展。最后指出了大分子光引发剂仍存在的不足之处,并就其在阳离子-自由基混杂型、高Mr(相对分子质量)型及可见光型等方面的发展前景作了展望。     

高分子光引发剂研究进展

基于大分子光引发剂具有低迁移、耐黄变等优点,本文介绍了自由基、阳离子及其他大分子光引发剂的研究状况,简要叙述了一些大分子光引发剂的制备、引发的效果以及引发机理,并对以后光引发剂的发展趋势进行了展望。     

新型紫外光固化二苯甲酮类光引发剂的研究进展

重点综述了3种新型光引发剂[改良型(超支化型、可聚合型)、自由基-阳离子混杂型和大分子型UV(紫外光)固化BP(二苯甲酮)类光引发剂]的最新研究进展,并对其合成工艺、性能优势等进行了探讨。最后对UV固化BP类光引发剂的发展方向进行了展望。     

UV固化塑料涂料中低迁移性光引发剂的研究进展

为了克服小分子光引发剂的弊端,尤其是迁移性问题,介绍了双官能度光引发剂、可聚合光引发剂、单组分夺氢型光引发剂、大分子光引发剂和可聚合单组分夺氢型光引发剂,在不同条件下光聚合动力学的研究表明,合成的光引发剂引发光聚合的性能不低于传统的小分子光引发剂。     

水性UV固化涂料用超支化大分子光引发剂的合成与表征

通过季戊四醇、2,2-二羟甲基丙酸(DMPA)、甲苯-2,4-二异氰酸酯(TD I)、2-羟基-2-甲基-1-苯基-1-丙酮(HMPP)、马来酸酐等合成了一种可参与紫外光固化的超支化大分子光引发剂,利用傅里叶红外光谱、核磁共振谱、紫外、DSC、TG对其结构和性能进行了表征,发现当引发剂含量在4%时引发效果最佳,反应初始阶段大分子的引发效率高于小分子光引发剂,随着反应的进行大分子光引发剂的引发效率逐渐小于小分子。大分子光引发剂在纯水中的溶解度很小,而在含有碱性中和剂的水性光固化体系中可以很好地溶解。     

大分子光引发剂研究进展（二）

(接上期 )4　苯甲酮类大分子光引发剂早在 80年代末 ,大分子苯甲酮类光引发剂就在我国开始研究。中国科学院感光化学所的李妙贞、王尔监等人在此方面进行了很多合成及产品性能方面的研究。此类光引发剂的小分子化合物在使用过程中经常会出现一些光引发剂与反应物难以分离、和体系的互溶性不好、易于凝集和析出等问题 ;对其进行结构修饰 ,克服其缺点 ,旨在涂料、印刷及电子等行业中具有更广泛的应用前景。GerdRehmer等介绍了式 (2 0 )所示大分子光引发剂的合成及其性能。　　J Mateo等以聚苯乙烯与苯异腈酸酯为原料 ,在无水三氯化铝作用下…     

UV-LED光固化体系光引发剂研究新进展

综述了可用于UV-LED光固化体系光引发剂的研究进展,包括传统光引发剂及其衍生物(硫杂蒽酮类、二苯甲酮类和酰基膦氧化物)、新型基团的光引发剂(咔唑基、萘酰亚胺基、吩嗪基、苯丙二茂基、咪唑基和三嗪基)以及高分子光引发剂。传统光引发剂的改性和大分子光引发剂的合成可以提高引发剂的稳定性。新型光引发剂的吸收波长与UV-LED光固化的发射波长匹配性较好,但该类光引发剂常需要加入助剂。此外,描述了氧阻聚对光固化体系的影响,指出了目前UV-LED光引发剂存在的不足,并展望了其发展应用前景。     

UV-LED光固化体系光引发剂的新进展

本文综述了可用于UV-LED光固化体系光引发剂的研究进展，包括传统光引发剂及其衍生物（硫杂蒽酮类、二苯甲酮类和酰基膦氧化物）、新型基团的光引发剂（咔唑基、萘酰亚胺基、吩嗪基、苯丙二茂基、咪唑基和三嗪基）以及高分子光引发剂。传统光引发剂的改性和大分子光引发剂的合成，可以提高引发剂的稳定性。新型光引发剂的吸收波长与UV-LED光固化的发射波长匹配性较好，但该类光引发剂常需要加入助剂。此外，描述了氧阻聚对光固化体系的影响，指出了目前UV-LED光引发剂存在的不足，并展望了其发展应用前景。。     

大分子光引发剂研究进展（一）

大分子光引发剂具有挥发度低、抗迁移能力强、环境兼容性好、树脂相容性好、功能多样性等优点 ,目前市场上已经有部分工业化的产品 ,如 :α 羟基酮类、双官能度的苯甲酮类、α 氨基酮类和双官能度的阳离子类。本文详细介绍了阳离子类、α 羟基酮、α 氨基酮、苯甲酮及其他大分子光引发剂的研究进展 ,以及光引发剂的发展趋势。     

紫外光固化水性光引发剂的研究现状及进展

水性紫外光固化技术是一种绿色环保的技术,而水性光引发剂是紫外光固化水性体系中的重要组成部分。本文综述了水性均裂碎片型光引发剂(包括水性安息香衍生物类和水性苯乙酮衍生物类)以及水性氢转移型光引发剂(包括水性蒽醌类、水性硫杂蒽酮类、水性二苯乙二酮类和水性二苯甲酮类)的性能及研究现状,指出水性光引发剂发展的主要方向是水性大分子光引发剂和水性可聚合光引发剂。     

聚氨酯型高分子硫杂蒽酮光引发剂的制备及性能研究

通过三种二异氰酸酯、2-（2,3-二羟基）丙氧基硫杂蒽酮（HPTX）及N-甲基二乙醇胺(MDEA)进行逐步聚合反应,将硫杂蒽酮结构及共引发剂胺结构引入到同一高分子链上,得到侧链含有硫杂蒽酮,主链含有共引发剂胺的聚氨酯型高分子光引发剂。傅立叶红外变换光谱和核磁共振氢谱证实了高分子光引发剂的结构。紫外光谱证实了高分子链的结构对硫杂蒽酮单元的最大紫外吸收几乎没有影响。用光致差示量热计（photo-DSC）研究聚氨酯型高分子光引发剂引发聚氨酯丙烯酸酯树脂（PUA）的光聚合反应,发现PU-IMTX是本文合成的引发剂中引发PUA光聚合最有效的光引发剂。     

含共引发剂胺的聚氨酯型高分子光引发剂的制备及性能研究

通过异佛尔酮二异氰酸酯（IPDI）、2-（2,3-二羟基）丙氧基硫杂蒽酮（HPTX）及N取代的二乙醇胺进行逐步聚合反应,将硫杂蒽酮结构及共引发剂胺结构都引入到同一高分子链上,得到侧链含有硫杂蒽酮、主链含有共引发剂胺的聚氨酯型高分子光引发剂（PU-IBTX、Pu—IMTX和Pu．IPTX）。傅立叶红外变换光谱和核磁共振氢谱证实了高分子光引发剂的结构。紫外光谱证实了高分子链的结构对硫杂蒽酮单元的最大紫外吸收几乎没有影响。用光致差示量热计研究聚氨酯型高分子光引发剂引发聚氨酯丙烯酸酯（PUA）树脂的光聚合反应,结果表明,Pu—IPTX是引发PUA光聚合最有效的光引发剂。     

含共引发剂胺的聚酯型高分子光引发剂的制备及其性能研究

为克服小分子光引发剂的固有缺陷,通过2-(2,3-二羟基)丙氧基硫杂蒽酮(HPTX)、二酰氯及N-甲基二乙醇胺(MDEA)进行逐步聚合反应,将硫杂蒽酮结构及共引发剂胺结构都引入到同一个高分子链上,制备了侧链含有硫杂蒽酮,主链含有共引发剂胺的聚酯型高分子光引发剂。傅里叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)证实了高分子光引发剂的结构。紫外光谱(UV-Vis)证实了高分子的结构对硫杂蒽酮单元的最大紫外吸收几乎没有影响。用光致差示扫描量热仪(photo-DSC)研究聚酯型高分子光引发剂引发聚酯丙烯酸酯树脂(PEA)的光聚合反应,结果表明:高分子光引发剂的主链结构对其引发效率有着显著的影响。     

Effect of photosensitive groups on the photoefficiency of polymeric photoinitiators

The purpose of this paper is to determine the effect of photosensitive groups contained in the main chain of polymeric photoinitiator on photopolymerization. Through polycondensation of toluene-2,4-diisocyanate (TDI), different diamines and N-phenyldiethanolamine (PDEA), three novel polymeric photoinitiators containing in-chain benzophenone (BP) and coinitiator amine were synthesized in comparison with the corresponding side-chain ones. FT-IR, ¹H NMR and GPC analyses confirm the structures of all polymers. UV-Vis spectra showed that the maximal absorption and the molar extinction coefficient of polymeric photoinitiator can be greatly improved by the electron donating groups and the imino nitrogen that directly link to BP structure. The photopolymerization of trimethylolpropane triacrylate (TMPTA) and PU prepolymer, initiated by these polymeric photoinitiators, was studied by photo-DSC. The results indicate that the location of photosensitive group has an important effect on the photoefficiency of polymeric photoinitiators. The efficiency order of polymeric photoinitiators comprising in-chain BP is different from that of the side-chain ones: PUIBA-s and PUIBA-n are the most efficient for TMPTA and PU prepolymer, respectively.     

Polymeric Michler's ketone photoinitiators: The effect of chain flexibility

Through introducing Michler's ketone (MK) moiety and diglycidyl ether monomers of different molecular chain into the same polymeric chain, polymeric photoinitiators of different chain flexibility, PMKPR, PMKPG and PMKPP were synthesized. These polymeric photoinitiators possess the similar characteristic UV–vis absorption of parent MK, and their photobleaching behavior is similar. The T_g of PMKPR, PMKPG and PMKPP is 58.1 °C, −24.9 °C and −12.5 °C, respectively. Three types of monomer with different functionality, phenoxy ethyleneglycol acrylate (AMP-10G), 2,2-bis[4-(acryloxypolyethoxy) phenyl]propane (A-BPE-10) and trimethylopropane triacrylate (TMPTA), were chosen to be initiated by these photoinitiators. The result indicates the chain structure of photoinitiators has significant influence on the polymerization of monomers. PMKPG is the most efficient polymeric photoinitiator for initiating the polymerization of AMP-10G and A-BPE-10, while PMKPP is the most efficient for TMPTA.     

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.     

Polymeric systems bearing side-chain 2,6-dimethylbenzoyldiphenylphosphinoxide moieties for UV curable coatings: Synthesis and photoinitiation activity

Polymeric photoinitiators with pendant 2,6-dimethylbenzoyldiphenylphosphinoxide moieties were prepared by reacting the hompolymer of 4-acryloyloxy-2,6-dimethyl benzoic acid, and its copolymers with n-butyl acrylate with thionyl chloride followed by methoxydiphenylphosphine. These polymeric systems were characterized and their photoinitiation activity checked in the UV curing of a standard acrylic mixture, by irradiation both at 330 and over 380 nm, the latter conditions being applied to simulate a TiO₂-pigmented coating formulation. The results were compared with those obtained by using the low molecular weight analog 2,4,6-trimethylbenzoyldiphenylphosphinoxide and previously prepared polymeric systems based on the benzoyldiphenylphosphinoxide moiety. The stability to light and to hydrolytic conditions of the polymeric photoinitiators with respect to the model compound was also tested. The results obtained are discussed and related to the structural requirements of these systems. © 1995 John Wiley & Sons, Inc.     

Polymeric photoinitiators bearing side-chain acyldiphenylphosphinoxide moieties for uv surface coatings

Polymeric photoinitiators bearing side-chain acyldiphenylphosphinoxide moieties have been prepared by reacting poly(methacryloyl chloride) and methacryloyl chloride/methyl methacrylate copolymers with methoxydiphenylphosphine. The activity of the above polymeric systems has been checked in the UV curing of both clear and pigmented coating formulations and compared with that of the low molecular weight analog pivaloyldiphenyl-phosphinoxide. The stability to light and to different hydrolitic conditions of the polymeric photoinitiators with respect to pivaloyldiphenylphosphinoxide has also been tested. The data concerning activity and stability are discussed in terms of structural features of the above systems. © 1993 John Wiley & Sons, Inc.     

Polymeric photoinitiators bearing side-chain benzoyldiphenylphosphinoxide moieties for UV curable coatings

Polymeric photoinitiators bearing side-chain benzoyldiphenylphosphinoxide moieties have been prepared by reacting poly(4-vinylbenzoic acid) or 4-vinylbenzoic acid/methyl methacrylate copolymers with thionyl chloride followed by methoxydiphenylphosphine. The activity of the above polymeric systems has been checked in the UV curing of the acrylic clear-coating formulation HDDA/BA and compared with that of the low molecular weight model 4-isoprophylbenzoyldiphenylphosphinoxide. The stability to light and to hydrolytic conditions of the polymeric photoinitiators with respect ot the model has also been tested. The results obtained are discussed in terms of composition and structural features of these systems. © 1994 John Wiley & Sons, Inc.     

水溶性光引发剂及研究进展

水溶性光引发剂既具有良好的引发光聚合反应的能力,又有优良的水溶性,属自由基型引发剂,其按结构可分为芳酮类、稠环芳烃类、聚硅烷类、酰基膦酸盐类、偶氮类及金属有机配合物类,其中芳酮类中的硫杂蒽酮类光引发剂是近年来光引发剂研究的热点.介绍了水溶性光引发剂(WSP)的研究背景、现状及进展,分别途述了这些典型的光引发剂的结构特性、光化学行为等,并对其前景进行了展望.