二芳酮-可聚合胺紫外光引发1，6-己二醇二丙烯酸酯聚合的动力学研究

用Photo-DSC（光差热扫描）研究了一种可聚合胺助引发荆乙二醇-3-吗啡啉丙酸酯甲基丙烯酸酯（EGMPM）分别与二苯甲酮（BP）、4-（4-甲苯硫基苯基）苯基甲酮（BMS）、4-氯二苯甲酮（CBP）、4-氯甲基二苯甲酮（CMBP）、4-羟甲基二苯甲酮（HMBP）等二芳酮组成的光引发体系引发以1，6-己二醇二丙烯酸酯（HDDA）为单体的紫外光聚合动力学．考察二芳酮质量分数、聚合温度、光照强度对其光聚合动力学影响，并评价其引发效果；同时计算出了EGMPM／BP引发HDDA聚合体系的活化能．结果表明，二芳酮的质量分数增加时，反应达到最大反应速率的时间减少，单体的转化率也相应增加，单体聚合速率相应增大；相同质量分数（0．1％）的不同二芳酮，BMS体系达到最大反应速率的时间最短，单体转化率也最高；随着温度和光强的增加，单体最终转化率、最大反应速率增大，达到最大反应速率所需的时间减少．     

二苯酮-可聚合胺引发1，6-己二醇二丙烯酸酯的光聚合研究

以UV-Vis分光光度计法和Photo-DSC法分别研究了合成的3种可聚合胺类助引发剂DMPDA、EGDPM、EGMPM与二苯甲酮（BP）组成的引发体系的光化学初级过程及引发1，6-已二醇二丙烯酸酯（HDDA）的紫外光聚合动力学．考察了助引发剂胺的含量对BP的光化学初级过程和对引发HDDA光聚合动力学的影响，以及光强和温度对聚合动力学的影响．结果表明，随着胺含量的增加，BP的光化学初级反应速率增加，从而使体系的聚合反应速率增加．随着温度和光强的增加，单体最终转化率、最大反应速率增大，达到最大反应速率所需的时间减小．     

4-乙烯基-4’-甲氧基二苯甲酮的光聚合性能研究

用萃取法研究了4-乙烯基-4’-甲氧基二苯甲酮(4-VMBP)和二苯甲酮(BP)在固化膜中的残留量;用实时红外法研究了4-VMBP的光聚合动力学,考察了胺浓度、引发剂浓度、灯距、氧阻、固化方式对氨基丙烯酸酯6116固化时间的影响。结果表明4,-VCBP固化残留量比BP小一个数量级;4-VMBP和三乙醇胺(TEOA)匹配性最好;固化体系中4-VMBP和TEOA质量分数均为4%时较为合适;隔绝空气条件下,固化时间缩短;灯距从10 cm调到20 cm,固化时间延长2倍多;间歇固化时间是连续固化的2倍多。     

一种新型的复合型光引发剂的制备及其光聚合性质

利用4-羟基二苯甲酮（ HBP）,丙烯酰氯和吗啡啉为原料,合成了一种新型的复合型光引发剂（ BPMDO）,通过核磁共振氢谱和红外光谱来表征其结构。用实时红外光谱（ RT-IR）技术研究了光引发剂的浓度、不同单体对光聚合动力学的影响。结果表明, BPMDO是一种有效的光引发剂,随着引发剂浓度增大,单体转化率、引发速率增大,诱导期缩短。     

二苯甲酮环缩醛单组分光引发剂的合成与光聚合性能的研究

本文合成了一种新型二苯甲酮基复合光引发剂5-(4'-苯甲酰基苯甲氧基)-1,3-二氧苯并环戊烷(BPCH2BDO),利用FIR、1HNMR对其结构进行表征。并采用实时红外光谱研究了BPCH2BDO光引发剂引发丙烯酸酯类单体的光聚合行为。结果表明,该引发剂的最大吸收光谱在258 nm,随着紫外光照的进行,BPCH2BDO的最大吸收峰258 nm逐渐减少。当引发剂的浓度不断增大时,单体的反应速率和该体系的反应程度先增大后减小;随着光照强度增大,单体转化率和最大聚合速率都增大。BPCH2BDO与传统的光引发剂二苯甲酮/4-二甲基氨基苯甲酸乙酯(BP/EDAB)引发效率相当。     

水溶性光引发剂二苯甲酮氯化铵引发三丙二醇双丙烯酸酯光聚合动力学的研究

以4-羟基二苯甲酮、环氧氯丙烷和三甲胺盐酸盐为原料,通过2步反应,合成了一种水溶性光引发剂——氯化[2-羟基-3-(4-苯甲酰基苯氧基)-N,N,N-三甲基-1-丙铵](HBPCl)。其结构通过核磁共振氢谱(1H-NMR)和傅里叶红外光谱(FT-IR)得到了证实。研究了水溶性光引发剂HBPCl的紫外吸收和降解特性,并通过实时红外(RT-IR)研究了氢助剂含量、HBPCl浓度和光强对HBPCl引发的TPGDA光聚合动力学的影响。结果表明,HBPCl在285 nm处有最大紫外吸收峰,能够有效地引发单体聚合;另外,随着氢助剂含量、引发剂浓度和光强的增大,光聚合速率和单体最终转化率随之增大,诱导期被缩短。     

DPPH引发丙烯酸酯单体光聚合动力学研究

采用傅立叶红外光谱仪、核磁共振仪对阳离子光引发剂4-(苯硫基)苯基二苯基硫鎓六氟磷酸盐(DPPH)结构进行了表征,紫外光谱分析表明该引发剂在302nm处有最大紫外吸收。通过实时红外(RT-IR)对DPPH引发丙烯酸酯单体光聚合动力学过程进行了研究,考查了引发剂浓度、光强及不同官能度单体对双键转化率及聚合速率的影响。随引发剂浓度增加,最大转化速率先增大后减小,而光强增加,最大转化速率增加。单体官能度越高,双键转化率与最大转化速率越低,达最大转化速率的时间越长。     

樟脑醌／乙二醇-3-吗啡啉基丙酸酯甲基丙烯酸酯引发牙科复合树脂的光聚合动力学研究

采用Photo-DSC研究了樟脑醌（CQ）／乙二醇-3-吗啡啉基丙酸酯甲基丙烯酸酯（EGMPM）可见光引发牙科复合树脂聚合的动力学过程．考察了CQ浓度、EGMPM浓度以及光强对牙科修复复合树脂光聚合动力学的影响．结果表明：增加引发体系的浓度和增加光强都可以增加反应速率和转化率；同时实验结果验证了Rp∝（I0[CQ][EGMPM]）^1／2的动力学关系．     

不同链长杂化单体合成及光聚合性能研究

通过三步反应合成了三种不同链长的新型杂化单体。使用傅里叶红外光谱和核磁共振仪对相应产物进行了表征。同时使用傅里叶实时红外(FT-RTIR)对三种杂化单体的光聚合性能进行了研究。考察了引发剂种类、不同浓度光引发剂以及链长对杂化单体的光聚合性能的影响。结果表明,光引发剂硫钅翁盐的引发性能要优于碘钅翁盐,随着光引发剂浓度的增大,杂化单体双键及环氧基团的转化率都相应提高,随着链长的增长,相应单体中的双键的转化率降低,但是相应单体中环氧基团的转化率随之升高。     

基于α-羟烷基苯酮（HAPK）可聚合大分子光引发剂的合成及其引发三丙二醇双丙烯酸酯（TPGDA）光聚合动力学的研究

以α-羟烷基苯酮(HAPK)、甲苯-2,4-二异氰酸酯(TDI)、聚乙二醇600(PEG600)和丙烯酸-β-羟乙酯(HEA)为原料,通过3步反应,合成了一种可聚合大分子光引发剂:HAPK-TDI-PEG600-TDI-HEA(HTPTH).用IR对反应过程进行了监测.通过Photo-DSC研究了HTPTH引发三丙二醇双丙烯酸酯(TPG-DA)光聚合动力学,考察了光强、引发剂浓度对TPGDA光聚合动力学的影响.结果表明,随着引发剂浓度和光强的增大,最大反应速率对应的转化率、单体最终转化率、最大反应速率都增大,达到最大反应速率所需的时间减小.     

Synthesis and photopolymerization characterization of a novel difunctional photoinitiator

A novel difunctional photoinitiator HBP‐TDI‐HBP based on 4‐hydroxybenzophenone (HBP) and toluene‐2,4‐diisocyanate (TDI) was synthesized and characterized by ¹H NMR and UV–Vis absorption spectroscopy. The kinetics of photopolymerization was studied by real‐time infrared spectroscopy. It showed that HBP‐TDI‐HBP was a more effective photoinitiator than benzophenone. When this photointiator and amine were used to efficiently initiate polymerization of acrylates and methacrylates, both rate of polymerization and final conversion increased with increase of HBP‐TDI‐HBP concentration, light intensity, and amine concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymeric amine bearing side-chain thioxanthone as a novel photoinitiator for photopolymerization

Novel polymeric photoinitator (PTX) was synthesized by introducing thioxanthone (TX) moieties to polymeric amine side-chain. Compared with low-mulecular weight model compound, PTX has similar UV-vis absorption and weaker fluorescence emission, and some radicals are trapped in the macromolecular coil cage. The kinetics for polymerization of trimethylolpropane triacrylate using PTX as photoinitiator was studied by photo-DSC. It shows that PTX is an efficient photoinitiator, and that PTX concentration and light intensity have similar effect on photopolymerization. The increase in PTX concentration and light intensity leads to the increase in the polymerization rate and the final conversion. The increase in temperature also results in the increase in the polymerization rate and final conversion, due to the enhanced molecular mobility and delay in vitrification at high temperature. At the late stage of polymerization, the reaction becomes more diffusion-controlled than that at early stage of polymerization.     

Synthesis and characterization of 4,4′-diacryloyloxybenzophenone

A copolymerizable type II photoinitiator 4,4′-diacryloyloxybenzophenone (DABP) based on 4,4′-dihydroxybenzophenone (DHBP) and acryloyl chloride was synthesized, and its structure was confirmed by ¹H NMR and real-time infrared spectroscopy. UV–vis absorption spectroscopy of DABP exhibited red-shifted maximal absorption as compared with benzophenone (BP). The kinetics of photopolymerization was studied by real-time infrared spectroscopy. It showed that DABP was a more effective photoinitiator than benzophenone. When this photointiator and amine was used to efficiently initiate polymerization of acrylates and methacrylates, both rate of polymerization and final conversion increased and the induction period was shortened with increase of amine concentration, DABP concentration and light intensity.     

Synthesis and photopolymerization kinetics of polymeric one‐component type II photoinitiator containing benzophenone moiety and tertiary amine

A polymeric one‐component type II photoinitiator (PDABPP) based on 4,4′‐dihydroxybenzophenone (DHBP), acryloyl chloride, and piperazine was synthesized, and its structure was confirmed by GPC and ¹H NMR. The photopolymerization kinetics of the photoinitiator was studied by real‐time infrared spectroscopy. It indicated that PDABPP was a more effective photoinitiator than that of benzophenone (BP)/triethylamine (TEA). The rate of polymerization and final conversion increased, and the induction period shortened with increase of PDABPP concentration, light intensity, and amine concentration. The kinetics of photopolymerization for tripropylene glycol diacrylate (TPGDA) incorporating PDABPP in the presence of different tertiary amines as the initiating system indicated that the PDABPP/TEA combination exhibited the highest polymerization rates among the PDABPP/amines combinations. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

High performance of the linked visible photoinitiator for free radical polymerization based on erythrosine B derivative

A novel erythrosine B derivative linked with a tertiary amine used as a visible light initiator for free radical polymerization was synthesized and characterized. For comparison, the free hydrophobic erythrosine B derivative was also synthesized and its combination with the tertiary amine was used as the separated two component photoinitiator. The linked initiator exhibited higher photoinitiator efficiency in high viscosity monomer than in low viscosity one, compared with the separated counterpart. Especially, when it was combined with iodonium salt, the further promotion of the photoinitiator efficiency was observed, compared with the separated three component system. It was found that as iodonium salt together with tertiary amine was continuously added to the formula with the linked initiator, the photoinitiator efficiency was dramatically enhanced compared with the same addition to the formula with the separated counterpart, revealing the application potential of the linked initiator. And the continuous addition of either the iodium salt or the tertiary amine to the formula only leaded to the small size increase of the photoinitiator efficiency. These results suggested that there existed an interdependent relationship between iodonium salt and tertiary amine in promoting the photoinitiator efficiency of the dye/amine/iodonium salt system. For these, the corresponding synergistic mechanism was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42361.     

新型光引发剂修饰蒙脱土及其光固化环氧丙烯酸酯纳米复合材料的制备和表征

通过4-溴甲基二苯甲酮与二甲基正十八胺反应合成长链型季铵盐光引发剂苯甲酰苄基二甲氨基十八烷基溴化铵,插层修饰蒙脱土;通过层间引发聚合的方法光固化制备环氧丙烯酸酯/蒙脱土纳米复合材料。XRD和TEM分析结果表明,蒙脱土在光固化复合材料中已得到插层和部分剥离;T0GA及力学性能测试结果表明,环氧丙烯酸酯/蒙脱土光固化纳米材料的热稳定性、拉伸强度、弹性模量及断裂伸长率得到了显著提高。     

Benzodioxoles as alternative coinitiators for radical polymerization in a model‐dental adhesive resin

This study evaluated the effectiveness of benzodioxole derivatives as coinitiators of radical polymerization in a model‐dental adhesive resin. To compose the adhesive resin, a monomer mixture based on 50 wt % of Bis‐GMA, 25 wt % of TEGDMA, and 25 wt % of HEMA was used. Camphorquinone (CQ) 1 mol % was used as a photoinitiator to initiate polymerization. 1,3‐Benzodioxole (BDO) and piperonyl alcohol (PA) were used as coinitiators at 0.25, 0.5, 1, 2, 4, 8, and 16 mol % level. In addition, tertiary amine, ethyl 4‐dimethylamino benzoate (EDAB) was used as coinitiator in the control group. Some physical, chemical, and mechanical properties of the polymer formed in the experimental adhesives were evaluated using the kinetics of polymerization, sorption and solubility, flexural strength, and elastic modulus tests. The results indicated that BDO and PA were effective coinitiators in the photoinitiator system based on CQ. Comparisons between the benzodioxoles derivative coinitiators and EDAB showed similar performance in the kinetics of polymerization and flexural strength. For water sorption and solubility evaluation, BDO and PA demonstrated significantly more sorption of water and less solubility than the EDAB control group. The findings suggest that BDO and PA were feasible alternatives to conventional amine as coinitiator. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Benzophenone-di-1,3-dioxane as a novel initiator for free radical photopolymerization

Benzophenone-di-1,3-dioxane (BP-DDO), a novel photoinitiator for free radical polymerization, was synthesized and characterized. The photopolymerization kinetics of BP-DDO was studied by real-time infrared spectroscopy (FT-IR). When this photointiator was used to efficiently initiate polymerization of acrylates and methacrylates, there was an optimum cure rate with the increase in BP-DDO concentration. Both the polymerization rate and final conversion increased with the increase in light intensity. The kinetics study of photopolymerization of TMPTA showed that BP-DDO was a more effective photoinitiator than benzophenone and benzophenone/ethyl-4-dimethylaminobenzoate (EDAB).     

Inhibition of premature polymerization of cationically polymerizable low viscosity systems

Photocurable inkjet inks based on cationically curable materials are a promising new technology with many advantages and some problems yet to be solved. One of the latter is the long-term stability of liquid inks. Reactive monomers are stable in the dark at room temperature for a long time. When a photoinitiator (iodonium salt) is added, premature gelation takes place within several days, depending on the temperature. Tertiary amine, hindered amine, hindered phenol, a quinone derivative, a sulphur-based antioxidant, beta-carotene and their selected mixtures were tested as potential inhibitors of premature cationic polymerization by being subjected to accelerated ageing at higher temperatures. The influence of additives on photoinitiated polymerization was studied by means of FTIR spectroscopy. The inhibition effect of additives was ascertained by monitoring the changes in viscosity during long-term temperature exposition as well. The system used for the study was a model system containing a cycloaliphatic epoxide monomer, oxetane monomers and a diaryliodonium salt photoinitiator. Amines, in contrast to antioxidants, proved to be effective as premature polymerization inhibitors.