光敏树脂固化机理研究

本文探讨了高新技术──快速成型技术中关键材料:光敏树脂的光固化机理。着重分析了光敏预聚物和光敏引发剂的光交联固化机理,并对光固化过程进行了讨论。     

杂化溶胶改性紫外光固化胶粘剂的研究

 以自制的杂化溶胶对紫外光固化丙烯酸酯胶粘剂进行改性，得到了具有高粘接强度，对丙酮、乙醇、氯仿等具有明显的耐溶剂性的紫外光固化胶粘剂。实验发现：活性稀释剂中含有较多的羟基、羧基时，此胶粘剂对玻璃的粘接强度较高；胶层粘接力随杂化溶胶用量的增加先增大，后减小，当杂化溶胶中的固体质量为光敏树脂的60％时，胶粘剂的剪切强度达到最大（12MPa）。     

Z箍缩动态黑腔负载装配用胶粘剂

由于Z箍缩动态黑腔负载中的低密度聚合物泡沫柱具有多孔结构和极低的力学强度,在装配过程中对胶粘剂有一定的特殊要求。实验以聚氨酯丙烯酸酯为主体树脂,丙烯酸异冰片酯为活性单体,配以光引发剂和偶联剂制得了适用于低密度泡沫粘接用的紫外光固化胶粘剂。测试表明,所研制的胶粘剂的体积收缩率仅为2.25%,且具有较高的固化速率和适当的粘接强度,能够满足稳固、快速装配的要求。通过对粘接界面的观测发现,胶粘剂在诊断孔内没有明显的扩散,且在低密度致密结构泡沫中的扩散厚度较小,均匀性好。     

NVP在全息聚合物分散液晶光栅中的反应动力学研究

为了提高全息聚合物分散液晶(简称HPDIC)光栅的衍射效率并得到良好的光栅表面形貌,在制备光栅的反应体系中添加了具有吡咯烷酮结构的单官能度小分子NVP,并进一步阐述了NVP对HPDLC光栅在反应动力学方面的影响.分析表明,NVP的添加显著增加了预聚单体的聚合速率,并且能使原本被困在聚合物网络当中的双键继续发生反应,从而大大提高了反应体系的双键转化率;另外,NVP的添加使得光栅的相分离更加彻底,在获得良好的表面形貌的同时也增大了光栅的折射率调制度,从而提高了HPDLC光栅的衍射效率.总之,在添加了NVP之后,体系的聚合速率和预聚单体的反应度都大大提高,从而使得光栅的表面形貌和衍射效率也得到较大的改善和提高,衍射效率提高到96.36%.     

n-GaN肖特基势垒光敏器件的电子辐照效应

本文主要研究了n型GaN肖特基紫外光敏器件(包括GaN肖特基势垒紫外探测器,GaN肖特基二极管)的电子辐照效应和失效机理,以及辐照后二极管对不同波长光的光敏特性的变化。从实验中观测到,随着辐照注量的不断增加,GaN光敏器件的击穿电压明显减小,反向漏电流逐渐增大。证实了辐照后Au/GaN间产生的界面态是引起GaN肖特基势垒光敏器件辐照失效的原因。另外,在研究辐照效应对GaN肖特基二管光敏特性的影响时观测到,经过一定剂量的辐照后,GaN肖特基二管能探测到380nm的紫外光和可见光,而在辐照以前,它是探测不到的。这说明辐照效应将导致肖特基势垒光敏器件对较长波长的吸收,使得UV探测器中可见光成分的背景噪声增加。     

聚丙烯/有机改性蒙脱土纳米复合材料的光氧化降解研究

研究了聚丙烯/有机改性蒙脱土(OMMT)纳米复合材料在365 nm紫外光辐照下的光氧化降解过程中的结构变化。主要利用红外光谱方法进行表征。在辐照初期(紫外光辐照时间小于11 h),复合体系的光氧化降解速率大于纯聚丙烯体系;随着辐照时间的延长(大于11 h),复合体系的光氧化降解速率小于纯聚丙烯体系。主要原因是蒙脱土既有光屏蔽作用,又有加速光氧化降解的作用,这两种作用共存,但在辐照初期,催化光降解作用占主导地位,随着辐照时间延长,光屏蔽作用占主导。蒙脱土的含量对聚丙烯的光氧化降解速率也存在影响。另外,蒙脱土的加入对聚丙烯光氧化降解产物也产生影响,羧酸类及酸酐类产物增多,酯类产物减少。     

新型腰果酚基不饱和树脂的结构及其紫外光固化行为的红外光谱研究

以天然产物腰果酚为原料,利用其酚羟基与环氧基的反应活性,通过开环醚化反应制备了两种腰果酚基不饱和树脂单体。通过傅里叶红外光谱研究了合成过程中主要活性基团的变化,结合核磁共振氢谱及凝胶渗透色谱分析进一步确定了合成树脂单体的分子结构,并利用红外光谱法对树脂单体的紫外光固化行为进行了研究,且对其光固化物进行了热重分析。研究表明：分子结构分析确认了目标产物的成功合成,树脂单体的分子结构以及不饱和双键含量对树脂的固化速度和固化物的热稳定性有着重要影响,两种单体在30 s内均已基本达到最高固化水平,光固化物的主分解初始温度均可达到350 ℃以上。     

碳纤维/双马树脂预浸料体系的固化动力学

给出了以等温固化航空航天工业用预浸料和纯树脂的固化动力学模型的研究 .树脂基体是改性的BMI树脂 ,增强相是碳纤维 (T70 0 12S) .用n级反应模型分析了一系列差示扫描量热法 (DSC)的试验数据 .无论是纯树脂或是预浸料 ,固化温度越高 ,固化速率就越大 .达到峰值以后 ,固化速率降低比较快 ,导致预浸料体系的总反应热低 .纤维的存在明显影响树脂的固化反应 ,预浸料体系固化动力学参数和纯树脂的参数有显著差异 .增强纤维约束了树脂基体固化过程中的分子运动能力 ,降低了体系的固化程度 ,但没有改变树脂的固化机理 .     

邻甲酚醛环氧丙烯酸光敏树脂的合成研究

用丙烯酸对邻甲酚醛环氧树脂进行改性,合成了邻甲酚醛环氧丙烯酸光敏树脂(OCAFEE),考察了反应温度、催化剂种类和反应时间对丙烯酸转化率的影响,并提出最佳反应条件.在烯丙基/环氧基的摩尔比为0.3:1时,温度控制在95C,采用N,N-二甲苯胺作为催化剂(用量为1%),反应3h后,丙烯酸转化率可达到98.80%.     

可聚合型溶致液晶单体3,4,5-三(11-十一烷氧丙烯酰氧基)苯甲酸钠的自组装及紫外光固化性能

以3,4,5-三羟基苯甲酸为原料,依次经过酯化、醚化、酰氯化和钠盐化四步反应合成一种可聚合型溶致液晶单体3,4,5-三(11-十一烷氧丙烯酰氧基)苯甲酸钠,并对其结构进行了傅里叶变换红外与1H核磁表征. 在室温下研究了该单体在水中的自组装行为,组装体结构通过偏光显微镜与X射线衍射仪进行表征. 研究表明,单体与水比例为80:20时可自组装为层状(La)相,92:8时组装为反六方(H_II)相,这与临界堆积参数的理论计算相吻合,表明单体浓度是影响组装体结构的重要因素. 在组装的基础上研究了含不同光引发剂的溶致液晶体系的双键转化率及固化后组装体结构的保留. 经实时红外表征及溶胶-凝胶法的验证发现在光强为30 mW/cm²的365 nm下曝光30 min,含引发剂Darocur2959的溶致液晶体系双键转化率可达78%. 聚合之后La相与H_II相的纳米结构都得到了保留.     

Production of tung oil epoxy resin using low frequency high power ultrasound

Epoxy resins made from vegetable oils are an alternative to synthesize epoxy resins from renewable sources. Tung oil is rich in α -eleostearic fatty acid, which contains three double bonds producing epoxy resins with up to three epoxy groups per fatty acid. This work studied the production of tung oil epoxy resin using hydrogen peroxide as an oxidizing agent and acetic and formic acid as percarboxylic acid precursors, applying low frequency high power ultrasound. This study evaluated the effects of ultrasound power density, hydrogen peroxide concentration, acetic acid concentration, and formic acid concentration on the yield into epoxy resin, selectivity, and by-products formation. Application of ultrasound was carried out using a 19 kHz probe ultrasound (horn ultrasound) with a 1.3 cm diameter titanium probe, 500 W nominal power, 2940 W L⁻¹ maximum effective power density applied to the reaction mixture. Ultrasound technology yielded up to 85% of epoxy resin in 3 h of reaction. The use of formic acid resulted in a slightly lower oil conversion than acetic acid but with a much higher selectivity towards epoxidized tung oil. However, using acetic acid resulted in the production of high-value by-products, such as 2-heptenal and 2,4-nonadienal. The ultrasound-assisted epoxidation showed to be particularly efficient when applied to oils containing conjugated double-bonds.     

Photo-differential Scanning Calorimetry Study on Photopolymerization of Polyacrylate/E7 Liquid Crystal Blends

Photo-differential scanning calorimetry (photo-DSC) was used to investigate the cure kinetics of a photo-initiated polymerization of tripropylene glycol diacrylate (TPGDA) monomers mixed with a eutectic liquid crystal mixture, E7, chosen due to its significant optical properties. The thermal photo-polymerization reactions were performed in isothermal mode in order to identify and evaluate the different thermal effects occurring during the photo-polymerization reaction under UV light. The results obtained help to better understand the curing mechanisms as well as the kinetics of the curing reactions. The isothermal photo-DSC provided complex thermograms showing the presence of two thermal effects: an exothermic heat (positive activation energy) generated during the conversion of monomers and an endothermic heat produced by the UV lamp. The latter phenomenon was observed in our previous work and was associated to the heating of the polymer dispersed liquid crystals (PDLC) material by the UV irradiation lamp. The dependence of photopolymerization on the time and intensities of the curing UV light were investigated. The results showed that the high intensity UV light heats the material and slows the process of phase separation which, in turn, affects the electro-optical properties of the material under study. The photo DSC results also revealed that the heating of the system was insignificant and can, therefore, be neglected, for materials exposed to UV radiation with an irradiation time of 5?seconds and a low intensity of 13.80?mW/cm².     

Surface structure analysis of stabilized iron particles by XPS with chemical derivatization

The surface structure of iron particles stabilized by oleic acid and unsaturated alcohol, isophytol, was studied by XPS and chemical derivatization. It was shown that there are hydroxyl groups, iron carboxylate complexes, and iron complexes coordinated with alcohol groups in the proportion one part metal to one part ligand on the outer surface of the stabilizing coating. The formation of stabilizing layers based on unsaturated compounds leads to the conversion of double bonds, resulting in the polymerization of oleic acid and isophytol in condensed close-packed self-organizing stabilizing layers on the surface of iron particles.     

Paraloid文物保护材料光老化的红外光谱研究

Paraloid(乳胶粘合剂)是一系列丙烯酸树脂的商品名称,是文物保护领域中最常用的保护材料之一,主要用于文物的加固、封护和粘接,适用文物材质范围非常广泛。其中以Paraloid B-72最具代表性,在国内外的文物保护中被大量使用,相关的应用案例、性能评价及其老化机理研究都有较多报道,而Paraloid系列的其他产品却鲜有关注,在国内应用较少,老化性能研究尚未开展工作。该研究系统评价了Paraloid B-72, Paraloid B-44, Paraloid B-48N和Paraloid B-67的光老化性能,采用红外光谱跟踪紫外辐照3 864 h过程中Paraloid材料分子结构变化,对光老化机理进行了深入解析和半定量评测。结果显示,4种Paraloid系列丙烯酸树脂材料中,B-72老化前后颜色和光泽度均没有发生明显变化,B-48N和B-67老化前后色差较大,B-44光泽度降低最多。丙烯酸树脂老化过程中高分子材料内部发生断链反应以及一定程度的交联反应,表现在主要官能团吸收的减弱和羰基指数(CI)的增加。根据主要官能团吸收峰CO相对强度的半定量分析结果反映出,B-72的光稳定性最好,...     

乙烯基酯树脂光固化的拉曼光谱研究

文章利用理论计算(DFT,密度泛函理论)和实验两种方法得到了乙烯基酯树脂的拉曼光谱.通过对比分析,再结合相关文献,对其光谱的振动模式进行初步的指认,拉曼光谱中苯环平面内的变形振动在1598 cm-1、C=C的伸缩振动和C=O的伸缩振动分别在1628 cm-1和1702 cm-1.3007 cm-1和3062cm-1的振动归属于=C-H的伸缩振动和苯环上C-H的伸缩振动,而-C-H的伸缩振动在2800 cm-1~3000 cm-1.并且对比了可见光固化树脂固化前后的拉曼光谱图,可见光固化树脂的固化,主要由于1630cm-1C=C的交联反应产生.     

红外和CD光谱的HSA糖基化反应产物结构和反应进程分析

用干法制备糖基化产物。人血清白蛋白(HSA)与葡萄糖质量比1∶1,溶解混和均匀,经48 h冷冻干燥,根据不同反应时间得到20个样本。旨在联合多光谱学技术(紫外、荧光、近红外、红外和圆二色光谱(CD光谱))分析人血清白蛋白糖基化前后二级三级结构和官能团的变化信息,以及分析不同反应时间对HSA糖基化产物结构特性的影响。实验结果表明：HSA与葡萄糖在干热条件下极易发生糖基化反应;随反应时间延长,蛋白质紫外吸收强度减弱,内源荧光吸收强度增强,糖基化反应增强,美拉德反应程度提高,蛋白质二级三级结构相应发生变化。反应到140 min左右时,美拉德反应前期糖基化反应完全,生成Amadori产物,进一步加热反应到220 min左右,反应进入中后期,开始生成醛酮类物质,反应到280 min左右,蛋白质氨基酸与羰基化合物发生脱羧、脱氨反应。     

The scaling behavior of the molecular parameters of the hyperbranched polymers made by self-condensing vinyl polymerization

The hyperbranched polymers can be made by self-condensing vinyl polymerization without gelation transition. The average molecular weights, as well as the average sizes, can reach infinite values as the reaction is quantitatively completed, and the scaling forms of the molecular parameters should exist. In the paper, based on a recursion formula, the scaling form of the number fraction distribution and the number of the n-mers are given analytically as the conversion of double bonds is near 1. The mean square radius of gyration for very large hyperbranched polymers is calculated explicitly to give a scaling exponent. Finally, a scaling relation associated with the fractal dimension and the polydispersity exponent is given clearly.