聚合物熔体界面扩散理论与研究方法

本文结合与聚合物加工过程密切相关的界面扩散问题,从动力学和热力学两方面综述了与聚合物界面互扩散相关的基础理论.结合在聚合物界面扩散方面的研究进展,系统介绍了聚合物熔体界面扩散的常用研究方法.对其中的流变学方法的原理及进展作了重点论述,该方法不仅可以有效表征聚合物熔体界面扩散的动力学过程,进一步从分子动力学角度发展并完善聚合物扩散理论,而且对于聚合物加工成型过程的界面结构设计和性能优化起到关键的指导作用.本文最后提出了聚合物熔体界面扩散研究中存在的问题并对其前景进行了展望.     

Crystallization kinetics and the fine morphological evolution of poly(ethylene oxide)/ionic liquid mixtures

The overall crystallization kinetics and spherulite morphologies of miscible poly(ethylene oxide)(PEO)/1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_6]) mixtures were studied by differential scanning calorimetry(DSC),polarized optical microscopy(POM) and rheological measurements. The finer crystal structures were further detected by wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS). Crystallization of PEO is largely suppressed by [BMIM][PF_6] addition especially at higher ionic liquid(IL) concentrations above 20 wt%. Both the overall crystallization rate and the spherulite growth decrease with the increase of IL content and crystallization temperature; however, the crystallization mechanism keeps unchanged as evidenced by the similar Avrami exponent n and WAXD results. The addition of [BMIM][PF_6] could induce more nuclei to some extent, but the induction time of crystallization is evidently prolonged,and a linear to non-linear transition of the spherulite growth(R ∝ t to R ∝ t~(1/2)) can be observed. At higher IL concentration,the spherulite texture changes apparently from particular serrated to branch surface due to the diffusion-controlled growth and the dilution effect, which also as a main factor contributes to the increasing trend of the long period of crystals.     

相态结构对聚氧化乙烯/丁二腈/高氯酸锂复合电解质室温电导率的影响

采用聚氧化乙烯(PEO)、丁二腈和高氯酸锂(LiClO4)的复合电解质体系, 制备了一系列不同配比的PEO/SN/LiClO4复合电解质, 对其室温电性能和相态结构进行了表征, 并探讨了相态结构对室温电导率的影响.     

乙烯-乙烯醇共聚物/碳纳米管复合发泡材料的电磁屏蔽性能研究

选用高机械强度和耐气候性乙烯-乙烯醇共聚物(EVOH)作为基体,添加高效导电填料多壁碳纳米管(MWCNTs),同时为了进一步提高材料性能,添加了聚醚多元醇(EOPO)与4,4’-二苯基甲烷二异氰酸(MDI)的共聚物.采用绿色环保的超临界二氧化碳发泡法制备EVOH/MDI-g-EOPO/MWCNTs纳米复合发泡材料,结果表明在EVOH/MDI-g-EOPO/MWCNTs复合材料中引入多孔结构,利用多层界面反射-吸收电磁波,比电磁屏蔽性能提升270%.通过调控MWCNTs体积含量与泡孔结构,当MWCNTs体积含量达到2.7 wt%时,EVOH/MDI-g-EOPO/MWCNTs复合发泡材料在X波段(9～12 GHz)表现出优异的比电磁屏蔽效能(41.76 dB·cm³/g).     

混合离子液体对聚甲基丙烯酸甲酯分子链缠结及松弛行为的影响

首先通过两步法合成了具有双咪唑环阳离子结构的离子液体(DIL),并将其与单咪唑环离子液体(MIL)进行混合以调控黏度变化,混合离子液体(ILs)的黏度符合对数混合规则且随温度变化呈现Arrhenius型流体行为.进一步通过动态流变、示差扫描量热(DSC)、电化学测试等方法研究了混合离子液体中DIL比例对聚甲基丙烯酸甲酯(PMMA)链缠结和松弛行为的影响,并讨论了PMMA/ILs体系热稳定性、玻璃化转变及离子电导率等的变化.结果表明,DIL独特的双咪唑环结构可与PMMA分子形成更多相互作用位点,从而导致凝聚缠结的形成,很大程度上限制了PMMA分子链的运动和松弛.随DIL含量增加,PMMA/ILs体系的松弛时间、热分解温度、玻璃化转变温度等参数均呈增大趋势,但其离子电导率有所损失,这与DIL较大的分子尺寸和运动能力有关.     

基于聚乙二醇结构调控高分子量聚乳酸立构复合体系的结晶行为

设计合成了梳形聚(聚乙二醇甲醚丙烯酸酯)(PPEGA)及其与聚乙二醇(PEG)的嵌段共聚物(PEG-b-PPEGA).通过与高分子量左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)共混探究了PEG不同的结构对PLA立构复合体系(sc-PLA)结晶的影响.结果 表明线形PEGA和PEG能与sc-PLA完全相容,两者均能促进...     

长链支化聚乳酸的多重松弛行为

在辐照法制备长链支化聚乳酸(LCB-PLA)的基础上,采用凝胶渗透色谱-多角度激光光散射联用(SEC-MALLS)表征了LCB-PLA的支化结构,利用动态流变学方法考察了PLA的黏弹松弛行为,计算得到了线型及支化PLA在较宽时间范围内完整的加权松弛时间谱.结果表明,由于长支链的引入及支链长度的增加,导致LCB-PLA松弛时间谱加宽,松弛时间增长,并呈现多重松弛行为.提出了一种计算长链支化聚合物支链长度的方法,可以定量表征LCB-PLA的支链长度以及长支链的分子量.     

Crosslinking kinetics of polyethylene with small amount of peroxide and its influence on the subsequent crystallization behaviors

Crosslinking reactions of high density polyethylene with low peroxide concentrations ranging from 0.1 wt% to 1.0 wt% at temperatures of 170, 180 and 190 ° C were monitored by rheological measurements. A critical gel forms at the peroxide concentration of 0.2 wt%, where the transition from long chain branching generation to crosslinking network formation could occur. Rheokinetics of crosslinking can be fitted well by Ding-Leonov's model. The curing rate k_2 at the earlier stage exhibits about 3 times acceleration per 10 °C with increasing temperature, while the equilibrium modulus G′ at the fully cured stage is almost independent of temperature. Influences of crosslinking on the subsequent crystallization behaviors were detected by DSC measurements. Above the critical gel concentration, crystallization is largely retarded as evidenced by the lower crystallization temperature Tc and crystallinity X_c due to the network formation. The secondary crystallization valley located at the temperature near 80 °C can be observed above the critical concentration, which becomes more evident with the increasing peroxide concentration and curing temperature. This phenomenon provides another evidence of crystallization retardation by the crosslinking network.     

网络结构对多层聚乙烯共混物界面扩散行为的影响

通过溶液法制备超高分子量聚乙烯(UHMWPE)/乙烯-己烯共聚物(PEH)共混物,采用动态流变学方法研究了UHMWPE/PEH共混物多层膜在熔点以上的界面扩散行为,结合Double-Reptation理论计算得到了UHMWPE/PEH共混物多层膜的自扩散系数.研究表明UHMWPE在浓度c=1.0 wt%以上可以在PEH基体中形成网络结构.UHMWPE/PEH共混物多层膜界面扩散不符合严格的菲克扩散定律,扩散系数具有时间依赖性.扩散曲线显示扩散过程在到达平台值之前分为2个区域,区域I接近于菲克扩散;然而由于引入UHMWPE,区域II扩散显著偏离菲克扩散行为,特别是当UHMWPE在PEH基体中形成网络结构以后,偏离菲克扩散行为更加显著.