聚乙烯交联过程结构演化的流变学研究

采用耐压等级分别为35kV及110kV的两种不同商业化可交联聚乙烯(XLPE)电缆料为研究模型,考察其化学交联过程中结构演化与线性黏弹响应的关系.研究结果表明,流变学方法可敏感表征较低温度、较长时间下XLPE交联过程的结构演化.随着交联温度的升高,体系预交联时间缩短,而黏弹特性的变化速率不变;交联导致体系弹性和黏性均增加,但弹性增加幅度远大于黏性增加幅度.比较两种样品交联过程的流变行为,发现随着交联反应的进行,两者的黏性增长速率基本一致,但35kV电缆料样品的弹性增长略大.采用低频率区域(频率末端区)的动态储能模量(G′),计算体系交联点之间的平均分子量(Mc),以表征样品的交联密度.同时用常规的溶胀平衡法研究了两种电缆料Mc与交联时间的依赖关系.     

硫酸铜含量对硫酸铜与丁腈橡胶之间配位交联反应的影响

利用丁腈橡胶(NBR)的可配位侧基——腈基(—CN)与金属盐硫酸铜(CuSO4)的铜离子(Cu2+)之间的配位反应制备了一种配位交联CuSO4/NBR.影响该配位交联反应的因素众多,如热压温度、热压时间、增塑剂等等,考察了CuSO4含量对其的影响.通过X射线光电子能谱(XPS)、动态力学分析(DMA)、差示扫描量热分析(DSC)等手段对CuSO4与NBR之间的配位交联反应进行了分析,并对所得配位交联的CuSO4/NBR进行了交联密度及力学性能的测试.结果发现,随CuSO4含量的不断增加,CuSO4与NBR的配位交联程度逐渐增强,且所得配位交联CuSO4/NBR显示出从典型橡胶到韧性塑料再到脆性塑料的力学转变特性.另外,通过扫描电子显微镜(SEM)及X射线能谱仪(EDX)对材料的微观结构进行了分析,发现CuSO4在聚合物基体中不仅充当交联剂的角色,而且还起着增强填料的作用.     

Crosslinking investigation of polybutadiene thermal degradation by carbon-13 nuclear magnetic resonance

Thermal degradation of polybutadiene (PBD) in anaerobic atmosphere at 250 °C had been studied by carbon-13 nuclear magnetic resonance spectroscopy (¹³C NMR) before complete crosslinking. In this investigation four types of low molecular weight PBD with different 1,2-vinyl isomer content had been chosen, then pure and mixed samples of PBD were heated in different time periods. ¹³C NMR spectra showed that two kinds of crosslinking mechanisms occur that both of them produce methyl groups. The first mechanism is a reaction between 1,2-vinyl isomers of two PBD chains, and the second one occurs between 1,2-vinyl isomer of one chain via methylene carbon of cis or trans isomer in another chain. Also ¹³C NMR results showed that the presence of 1,2-vinyl isomer in the PBD structure is necessary and without it none of the mentioned reactions will occur. Furthermore isomers sequence is another important parameter which affects crosslinking. Results show that cis or trans isomer which is not adjacent to 1,2-vinyl isomer does not take part in crosslinking reaction. Moreover such cis or trans isomer can take part in second mechanism of crosslinking that 1,2-vinyl isomer was attached from head to cis or trans isomer, thus in this arrangement of isomers second mechanism of crosslinking will become dominant rather than first mechanism of crosslinking.     

Investigation of antioxidant and electron beam radiation effects on the thermal oxidation stability of low-density polyethylene

Effect of various antioxidants on the thermal oxidation stability of LDPE and X-LDPE has been investigated. To achieve this purpose, miscellaneous commercial grade antioxidants such as Irganox 1010, Irganox1076, Irgafos168, Irganox B225, and Chimassorb 944 were selected. Then, formulations based on different content of antioxidant were prepared. The samples were crosslinked by exposure to electron beam irradiation. To assess the thermal oxidation stability of samples, oxidation induction time (OIT) test was accomplished on both the irradiated and unirradiated specimens. Ageing tests were carried out in order to evaluate the thermal oxidation stability of irradiated X-LDPE. The results indicate that Irganox 1010 is the most effective antioxidant amongst the selected ones, concerning thermal oxidation stability of LDPE, before and after aging test.     

Degradation of polypropylene impact-copolymer during processing

The effect of processing on molecular structure and properties of polypropylene impact-copolymer (ICPP) was investigated. It was confirmed that multiple extrusions induced changes in molecular weight resulting in increased MFI and decreased long-term thermooxidation stability. In terms of mechanical properties only impact strength well reflected the processing history. Tensile and flexural properties remained almost unchanged. The sizes of rubbery domains observed by SEM exhibited only minimum changes. The results of SSA and TREF techniques provided further data helping to elucidate the phenomena in rubbery phase. Based on indirect indications one could conclude that while typical polypropylene degradation resulting in chain backbone cleavage took place in the PP homopolymer phase, the rubbery phase containing EPR and PE homopolymer underwent a certain extent of crosslinking.     

Binding assays with streptavidin-functionalized superparamagnetic nanoparticles and biotinylated analytes using fluxgate magnetorelaxometry

Binding assays based on the magnetorelaxation of superparamagnetic nanoparticles as markers are presented utilizing a differential fluxgate system. As ligand and receptor, streptavidin and biotin, respectively, are used. Superparamagnetic nanoparticles are functionalized with streptavidin and bound to two types of biotinylated analytes: agarose beads and bovine serum (BSA) proteins. The size difference of the two analytes causes a different progress of the reaction. As a consequence, the analysis of the relaxation signal is carried out dissimilarly for the two analytes. In addition, we studied the reaction kinetics of the two kinds of analytes with the fluxgate system.     

Structural effects on thermal properties and morphology in XLPE

This study investigated the morphological, thermal and mechanical changes with increasing crosslink density for two low density polyethylenes (LDPE). A reference LDPE was compared with an LDPE containing a higher number of vinyl groups that was introduced via a copolymerisation with a diene. During crosslinking, two reactions simultaneously occur in the copolymer, i.e. a reaction of the vinyl groups and combination crosslinking. After crosslinking with a low amount of peroxide, the majority of the crosslinks originate from reacted vinyl groups in the LDPE containing the higher number of vinyl groups, whereas the crosslinks in the reference LDPE originate from combination crosslinking, thus leading to different crosslinked structures for the two polymers. The melt temperature, crystallisation temperature, and degree of crystallinity were measured using a Differential Scanning Calorimeter. Thermal fractionation studies and morphology studies were also made. The Differential Scanning Calorimetry results show a decrease in those properties for both materials along with a concurrent change in the morphology when the crosslink density increased. The results deviate slightly between the materials.     

Photodegradation of PEEK sheets under tensile stress

The photochemical reaction of poly(ether ether ketone) (PEEK) sheets under tensile loads has been investigated. Two types of UV irradiation tests were carried out in a vacuum environment: with and without a cooling apparatus. Chemical structures, thermal properties, and mechanical properties were measured to clarify photo-deterioration. Chemical analysis based on Fourier Transform Infrared Spectrometry (FT-IR) and X-ray Photoelectron Spectroscopy (XPS) showed photochemical scission caused by UV exposure. Thermal properties, measured by Differential Scanning Calorimetry (DSC), indicated that a crosslinking reaction occurred during the radiation tests. Tensile properties of PEEK sheets after UV radiation clearly showed a tendency to embrittlement affected not only by crosslinking but also by the orientation of molecular chains resulting from the temperature rise of the specimens. Furthermore, applied tensile stress during exposure accelerated molecular scission and disturbed the crosslinking effects of the tensile properties.     

硅氮聚合物交联剂交联的室温硫化硅橡胶的热稳定性

利用硅氮聚合物作交联剂使双组分缩合型室温硫化硅橡胶在不需要催化剂存在下硫化，通过对硫化胶老化后的热失重、交联密度和力学性能的测定，表明这种硫化胶的耐温性能由２００℃提高到３５０℃．对硫化胶的降解动力学研究表明：降解反应活化能由７０ＫＪ／ｍｏｌ提高到３３０ＫＪ／ｍｏｌ，这是由于消除了端基引发的主链降解．     

PVA/PVP互穿网络膜的渗透蒸发性质(Ⅱ)

用4,4′-双叠氮-2,2′-二磺酸钠(DAS)和戊二醛对聚乙烯吡咯烷酮(PVP)和聚乙烯醇(PVA)依次进行光化学交联和化学交联,制备了具有互穿网络结构的渗透蒸发膜.研究了它们用于醇、酮和醚等有机溶剂脱水的渗透蒸发性质.结果表明,对于大多数有机溶剂,随着共混膜中PVP含量的增加,膜的渗透性明显提高,而膜的选择性有所下降.但用于THF脱水时,膜的选择性和渗透性均随着PVP含量的增加而增加.交联使膜的力学性能得到改善