可聚合型光引发剂4-丙烯酰氧基二苯甲酮的光聚合性能研究

以实时红外光谱（RT-IR）法研究了合成的4-丙烯酰氧基二苯甲酮（4-ABP）的光聚合动力学性质，考察了不同单体、不同引发剂和助引发剂浓度、不同光强对聚合性能的影响．以萃取法对比研究了4-ABP和二苯甲酮（BP）在固化膜中的的残留量．结果表明，4-ABP是一种非常有效的光引发剂．随着引发剂浓度和光强的增大，单体转化率、最大反应速率都增大，诱导期缩短．萃取实验表明4-ABP在固化膜中的残留量远低于BP．     

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。     

新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚的合成及光聚合性能研究

通过3步反应合成了一种新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚(POBGE)。使用傅立叶红外光谱和核磁共振仪对相应产物结构进行了表征。同时使用傅立叶实时红外(FT-RTIR)对该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,不同光照强度对杂化单体的光聚合性能的影响。结果表明,光引发剂硫鎓盐的引发性能要优于碘鎓盐,随着光引发剂浓度以及光照强度的增大杂化单体双键及环氧基团的转化率都相应提高。     

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。     

邻羟基环己基丙烯酸酯光聚合动力学研究

采用实时红外光谱技术(RTIR)研究了邻羟基环己基丙烯酸酯(HCA)光聚合反应动力学,探讨了光照强度、光引发剂种类和浓度对其光聚合动力学的影响,并与脂肪族羟基丙烯酸酯单体丙烯酸羟乙酯(HEA)进行了对比。结果表明,最终双键转化率和相对反应速率随光强增大而增加;光引发剂浓度对最终双键转化率和反应速率的影响随引发剂不同呈现不同规律;与HEA相比,HCA具有更高的反应活性,但最终双键转化率较低。     

2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪光引发剂的合成及其光聚合动力学性能研究

以对甲氧基苯甲腈和三氯乙腈为原料合成了光引发剂2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪(MBTT),通过傅里叶红外光谱仪、核磁共振仪和紫外吸收光谱对所合成的产物结构进行了表征.并利用实时红外(RT-IR)对该引发剂进行了光聚合反应动力学研究,考察了单体、引发剂浓度和光强对引发速率及单体转化率的影响.结果表明,MBTT是一种高效的紫外光引发剂,在引发剂用量为0.1%时光聚合的单体转化率就能达到90%;随着光强的增大,单体的双键转化率和最大反应速率都增大,诱导期缩短;双丙烯酸酯类单体的双键转化率比三丙烯酸酯类单体的双键转化率要高.     

新型紫外光产酸剂的合成及其光聚合动力学研究

以2-硝基噻吩,甲基磺酰氯及苯乙腈为原料合成了一种紫外光产酸剂(5-甲磺酸酯亚胺-5H-噻吩-2-亚基)-苯基-乙腈(MTPA),通过傅里叶红外光谱仪、核磁共振仪和紫外吸收光谱仪及热重分析对所合成的产物的结构和性能进行了表征,并利用实时红外(RT-IR)对该引发剂进行了光聚合反应动力学研究。考察了单体、产酸剂浓度对引发速率及单体转化率的影响。结果表明,在一定浓度范围内,随着引发剂浓度增大,聚合速率加快,最终的双键转化率也增高。     

PVC片材表面的光接枝亲水化处理

采用光接枝聚合方法对商品化PVC片材进行了表面亲水化处理。以二苯甲酮作引发剂 ,丙烯酸为接枝单体研究了反应过程中单体浓度、引发剂浓度、反应时间对亲水化效果的影响。衰减全反射红外光谱 (ATR FTIR)分析发现 ,在 15 5 5cm-1处出现COO-的特征峰 ,证明丙烯酸已经接枝到材料表面。随着反应时间的延长 ,接触角持续下降 ,3 0s以后趋于恒定 ,最低可达 3 3°。较低单体浓度下 ,均聚反应较弱 ,材料的亲水性要好于高单体浓度时的情况。同样 ,较低引发剂浓度时 ,引发剂的自屏蔽效应弱 ,有利于接枝反应 ,接触角要比高引发剂浓度条件下小     

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。     

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).     

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.     

Ultraviolet photopolymerization induced by a triazine derivative

2‐(3,4‐Methdioxyphenyl)‐4,6‐bis(trichloromethyl)‐ 1,3,5‐triazine (MBTTR) was used as a photoinitiator for the polymerization of acrylate monomer. Ultraviolet–visible absorption spectroscopy was used to investigate the photochemical behavior during the photophysical process. The photopolymerization kinetics were monitored by real‐time Fourier transform infrared spectroscopy. The polymerization rates of the acrylates were significantly higher than those of the methacrylates. When MBTTR induced the polymerization of trimethylolpropane triacrylate, there was an optimum polymerization rate and the final conversion was obtained at 0.1 wt % MBTTR. MBTTR was an inefficient photoinitiator for ethyl vinyl. The final conversions of tripropylene glycol diacrylate induced by MBTTR and triazine/1,3‐benzodioxole were similar. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

聚烷基酚聚氧乙烯醚型表面活性剂的表面性能分析

合成了一系列不同聚合度的聚烷基酚聚氧乙烯醚(HHL)型非离子表面活性剂。通过红外光谱,核磁共振等仪器对其结构进行表征,用表面张力法对不同聚合度的合成产物的表面性能进行研究,并对不同聚合度的表面活性剂的物理化学参数进行理论分析。结果表明:三聚烷基酚聚氧乙烯醚型非离子表面活性剂较相应单体的烷基酚聚氧乙烯醚表面活性剂,表面活性和吸附能力有较大的提升。     

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     

羧酸改性钛白粉促进光固化研究

采用油酸对商用二氧化钛进行表面改性,通过 X-射线光电子能谱仪（ XPS）、红外光谱（FT-IR）和 X射线粉末衍射分析（ XRD）对改性后的 TiO₂粒子进行了结构表征,并借助热重分析测定了改性剂的含量。采用光差示扫描量热法（ photo-DSC）研究了无机膜保护型 TiO₂、去包膜型 TiO₂、油酸改性 TiO₂和三甲基苯甲酰二苯基氧化膦（ TPO）对丙烯酸酯光聚合动力学的影响。结果表明：油酸改性的 TiO₂与无机膜保护的 TiO₂和去包膜的 TiO₂相比,能在空气中引发丙烯酸酯的光聚合,并能增强以 TPO为光引发剂的丙烯酸酯的光聚合,从而在相同固化效果下,可减少小分子光引发剂的添加,降低残留。本研究为后续紫外光（UV）固化白色涂料、油墨固化不完善等问题提供了解决途径。     

1,3-dioxane methylcoumarin as a novel photoinitiator for free radical polymerization

1,3-Dioxane methylcoumarin (DOMC), a novel photoinitiator (PI) for free radical polymerization, was synthesized and characterized. UV–vis absorption spectroscopy was used to investigate its photochemical behavior during the photophysical process. The photopolymerization kinetics of DOMC was studied by real-time infrared spectroscopy (FTIR). There was an optimum curing rate with the increase in DOMC concentration. Both the polymerization rate and final conversion increased with the increase in light intensity. DOMC was the most efficient PI for tripropylene glycol diacrylate (TPGDA) in different acrylate monomers. The kinetics study of TPGDA photopolymerization showed that DOMC was a more effective PI than benzophenone/ethyl-4-dimethylaminobenzoate. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012