聚合物功能梯度材料的研究现状与展望

功能梯度材料(FGM)是一种全新的非均质复合材料.聚合物梯度材料(PGM)是基体材料为高分子材料的一类功能梯度材料,因其独特的形态结构、奇特的功能和潜在的应用价值,已逐渐引起了人们的高度重视.本文综述了国内外聚合物功能梯度材料的研究现状,介绍了PGM的概念、分类、制备方法、表征方法及应用等,并对PGM未来的研究进行了展望.     

Mechanically reinforced chitosan/cellulose nanocrystals composites with good transparency and biocompatibility

Chitosan/cellulose nanocrystals(CS/CNCs) composites were prepared with different contents of CNCs. Due to the homogeneous dispersion of CNCs and the strong interfacial interactions resulting from hydrogen bonding between CS chains and CNCs, the transparency of CS is well retained and the overall mechanical properties of CS are significantly improved. Furthermore, because both CS and CNCs are biocompatible materials, cell proliferation test shows that the obtained composites are noncytotoxic and can potentially meet safety requirements of biomedical applications. These advantages pave the way of potential applications of CS in the field of commercial plastics and encourage the use of CS as environmentfriendly material and biomedical material.     

Towards high molecular weight poly(bisphenol a carbonate) with excellent thermal stability and mechanical properties by solid-state polymerization

Poly(bisphenol A carbonate) (BPA-PC) was post-polymerized by solid-state polymerization (SSP) after supercritical CO₂-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry (DSC), Ubbelohde viscosity method and gel permeation chromatography (GPC). The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles (2 mm) increased from 1.9 × 10⁴ g/mol to 2.8 × 10⁴ g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.     

聚丙烯的结晶形态调控与高性能化

聚丙烯作为目前最重要的通用塑料之一,对其进行高质化改性具有重大的现实意义.基于聚丙烯的同质多晶态行为,加入成核剂进行β结晶改性是改善聚丙烯韧性和热稳定性的有效方式.过去的研究主要关注结晶度、β晶含量等对性能的影响.而近年来我们提出通过调控聚丙烯的β结晶形态来实现其高性能化的新思路,并开展了卓有成效的研究工作:(1)利用小分子成核剂的溶解性及自组装影响聚丙烯的结晶行为,获得了如球晶、横晶、花瓣状晶等形态,实现了对β结晶形态的有效调控;(2)特定的结晶形态能够使聚丙烯的韧性显著增加,并且热变形温度进一步提高,证实结晶形态会对宏观性能发挥重要作用;(3)β结晶形态调控有利于获得更佳的成孔均匀性与高的孔隙率,对制备高品质锂电池隔膜有明显的指导意义.结晶形态调控可望成为实现结晶性聚合物高性能化与功能化通行的、高效的策略.     

Preparation of nylon MXD6/EG/CNTs ternary composites with excellent thermal conductivity and electromagnetic interference shielding effectiveness

In this article,hybrid fillers with different dimensions,namely,2-dimensional (2-D) expanded graphite (EG) and 1-dimensional (1-D) multi-walled carbon nanotubes (CNTs),were added to aromatic nylon MXD6 matrix via melt-blending,to enhance its thermal and electrical conductivity as well as electromagnetic interference shielding effectiveness (EMI SE).For ternary composites of MXD6/EG/CNTs,the electrical conductivity reaches up nine orders of magnitude higher compared to that of the neat MXD6 sample,which tumed the polymer-based composites from an insulator to a conductor,and the thermal conductivity has been enhanced by 477％ compared with that of neat MXD6 sample.Meanwhile,the EMI SE of ternary composite reaches ～50 dB at the overall filler loading of only 18 wt％.This work can provide guidance for the preparation of polymer composites with excellent thermal and electrical conductivity via using hybrid filler.     

Fabrication of electrospun PVDF nanofibers with higher content of polar <Emphasis Type="Italic">β</Emphasis> phase and smaller diameter by adding a small amount of dioctadecyl dimethyl ammonium chloride

In this work, the effect of dioctadecyl dimethyl ammonium chloride (DDAC, a kind of alkyl ammonium salt) on polar β phase content and the diameter of electrospun PVDF nanofibers was investigated for the first time. Our experimental results show that the diameter of the electrospun PVDF nanofiber could be largely reduced and the content of polar β phase also become dominant immediately by just adding a little amount of DDAC. When the mass fraction of DDAC reached 4%, the content of polar β phase increased by about 39.1% compared with PVDF nanofibers without DDAC. Besides, the crystallinity of PVDF nanofibers also increased with the addition of DDAC. Based on the results, the possible mechanism of cooperative effect between electrospinning and DDAC on fiber diameter and formation of β phase in PVDF was discussed.     

基于TVAR模型的人民币汇率的价格传递效应

利用门限向量自回归模型对人民币有效汇率的价格传递效应进行了研究,分析了不同的通货膨胀环境对人民币汇率传递效应的影响.以通货膨胀率作为门限值变量,并以0.001 175和0.006 118为门限值进行实证分析.得到汇率传递效应在不同的通货膨胀环境下显著性存在差异,在高通货膨胀下汇率对国内价格的传递效应是显著的,然而在低通货膨胀下是不显著的.考虑了汇率传递对国内价格的非线性性,进而更加准确的验证了通货膨胀与汇率传递的相关性.     

高分子加工制品的多层次结构控制——从传统加工到定构加工

现代高分子材料加工所倡导的高性能化、功能化、多用途性、节能低碳等对加工制品内部多层次结构控制提出了非常高的要求.与传统高分子加工方法所注重评价加工参数变量对形态结构的影响不同,本文提出的定构加工方法学是通过特殊外场作用使得形态结构更利于调控,其特点是由外场作用决定的多层次结构;所获得的加工制品具有比常规加工更优异的宏观性能.两个典型的定构加工实例,聚丙烯/β成核剂注塑制品中形成类似竹子的仿生结构以及嵌段共聚物SIS微相分离结构与宏观力学性能关系,表明定构加工在调控制品最终多层次结构上的突出优势.定构加工代表着未来高分子加工发展的重要方向.     

青霉噻唑酸表面分子印迹聚合物的制备及其吸附性能的考察

针对青霉素药物及乳制品中致敏杂质青霉噻唑酸(PEOA)的特异性分离分析,采用表面印迹聚合法,以青霉噻唑酸为模板分子,制备青霉噻唑酸分子印迹聚合物(PEOA-MIPs)。通过静态吸附、吸附动力学及选择性实验考察其吸附性能,结果显示PEOA-MIPs对青霉噻唑酸有特异的识别能力和快速的传质速率,饱和吸附量为122.78 mg/g,静态吸附和吸附速率分别符合Langmuir模型和准二级动力学方程,表明MIPs的吸附是以化学吸附为主的单分子层吸附。利用扫描电镜(SEM)、红外光谱(FT-IR)和热重分析(TGA)对聚合物进行表征,结果显示聚合物成功接枝在硅胶表面,并具有良好的热稳定性。PEOA-MIPs对PEOA具有特异的识别能力,可用作萃取介质,为建立快速分离分析致敏杂质青霉噻唑酸的方法提供基础。