高分子材料支化结构与流变性的联系串讲北大核心CSCD

高分子链结构为直链型或支化型以及高分子支链的形态、多寡和长度对材料的剪切黏度、黏流活化能、熔体破裂现象等流变性能有显著影响,且与高分子材料成型加工行为密不可分。本文以串讲方式讨论了高分子材料支化结构与流变性能之间的联系。理解、串并、归纳和总结高分子支化结构与流变性之间的联系有利于使学生更加深刻领会《聚合物流变学》课程中高分子材料结构与性能间的关系,串联高分子物理、聚合物流变学、高分子材料成型加工系列专业课程知识。     

试论高聚物结构与性能关系的三个层次

高分子物理的基本任务之一就是探求高聚物的结构与性能,揭示结构与性能之间的内在联系及其基本规律。高聚物结构与性能的关系应该包含3个层次:通过分子运动联系的"分子结构与材料性能"关系、通过产品设计联系的"凝聚态结构与制品性能"关系和通过凝聚态物理知识联系的"电子态结构与材料功能"关系。传统教材上仅讲授"结构与性能关系",有相当的局限性,需要在研究生阶段补充有关"凝聚态结构与制品性能"关系和"电子态结构与材料功能"关系的课程。     

《功能高分子材料》课堂教学方法的探索

功能高分子材料课堂教学过程涉及到大量高分子化学与高分子物理的基础知识,具有相辅相成的关系。在教学中如果能将高分子化学与物理知识与功能高分子材料的核心问题即"分子设计、结构与性能的关系",巧妙地衔接,紧密地结合,并有效地加以利用,不仅可以提高学生对该课程的重视度与学习兴趣,还可以加强教学效果,提升学生对专业知识的深层次理解与综合运用能力。本文结合这几年的教学实践,就如何利用功能高分子材料与高分子化学、高分子物理之间的联系以及后者对前者的辅助教学作用进行了阐述。     

高分子物理本科教学之我见

高分子物理是一门物理课,其内涵为高分子物质的结构、结构演变与各层次结构单元的运动规律,而非聚合物的"结构与性能"关系.这门课为解释结构与性能关系提供基础概念与理论,但不是"结构与性能"关系本身.这样的定位决定了高分子物理课不应采用系统教学法,而应当采用逻辑教学法,即从一个不证自明的公理(逻辑起点)出发,沿着一条主线,依次导出、建立全部理论体系.在高分子物理中,这个逻辑起点就是长链结构,主线就是熵弹性.故该门课程应按熵弹性这条主线展开.对现行高分子物理课程内容进行分析,大多数内容均可用熵弹性的主线串起来,另外少部分内容也与熵弹性有密切关系.应根据这两点对现行课程体系与教学方法进行改造,为课程各项内容之间建立逻辑关系,方便学生的学习与应用.     

对功能高分子课程教学的思考

功能高分子的设计思想是功能高分子课程的灵魂 ,它以高分子物理学所研究的结构与性能之间关系为基础。结构与性能之间的关系是贯穿功能高分子课程始末的主线。功能高分子材料有三种设计途径 ,即化学结构设计、聚集态结构设计和复合结构设计     

由橡胶材料看高分子物理知识点的综合运用

高分子物理是高等院校高分子材料与工程专业的一门重要的专业基础课。橡胶是一种具有优异性能的高分子材料,橡胶材料的结构与性能在很多方面综合了高分子物理的知识。在高分子物理课程的教学过程中,我们穿插了橡胶的一些具体实例,通过向学生介绍橡胶的结构、分子运动、性能以及交联,串联与橡胶材料相关的高分子物理知识点,以增强学生对这些知识点的感性认识,加强其对高分子物理基本概念和基础理论的掌握,取得了较好的教学效果。     

凝炼“高分子物理”本科教学内容的核

要较为深刻地认识聚合物,学习并掌握"高分子物理"课程是十分必要的。那么,在打基础的本科阶段,"高分子物理"究竟要教些什么?对此,本文提出"高分子物理"课程本科教学内容有其核心部分,即结构单元形成的长链因各种相互作用所呈现的不同微观结构和形态、外场作用下聚合物微观结构和形态的变化、宏观响应行为及其之间的关系。作者以为,采用涵盖基本内容的统编经典教材,授予学生一个基本的核和不断地自我学习的有效方法,可由此臻于对"高分子物理"较为深入的理解、恰当运用乃至于发扬光大。     

高分子物理课程知识体系的构建革新

高分子物理是高分子材料相关专业的专业基础课,内容丰富,章节间关系复杂,课程主线往往不容易把握。本文从运动对高聚物性质(性能)的决定性作用角度,提出了构建高分子物理课程知识体系的观点:在高分子结构部分,充实原子、键等部分作用的论述,完善高分子结构划分的层次;明确高分子不同结构层次都具有运动与变化能力的认知,重点突出不同高分子结构运动、变化的特征和规律;根据根据每一个结构层次运动特征,综合理解结构、结构的变化对高分子性能的影响。     

再谈“高分子物理”本科阶段教学内容

高分子的特殊性在于其长链结构,特殊的长链结构带来运动的特殊性。本文从"高分子物理"的定义是运动着的高分子物质和高分子物质的运动出发,确定高分子物理的定位是高分子物质的结构、结构演变和各层次结构单元的运动,围绕"高分子物理"的核心本质是长链状结构、长链状结构的演变及各层次长链结构的运动规律,针对本科阶段的任务和特点,阐述教学主要内容是结构和运动,附带相关性能,提出对现行教材内容和编排顺序的建议和想法。     

“高分子物理”及“高分子物理实验”2门精品课程的建设

"高分子物理"(在中国科学技术大学叫"高聚物的结构与性能")和"高分子物理实验"课是该校高分子科学与工程系本科生的必修课。为了讲好和全面建设这两门课,作者倡导并积极开展教学研究,发表39篇教学研究论文,作者把这些研究心得和成果及时引入教学中,先后编写和出版了十几本教材及教学参考书,教学质量不断提高,并逐步形成了有鲜明特色的教学,在国内高校产生了很好的影响。通过多方面的建设,2005年"高聚物的结构与性能"被评为国家级精品课程,2006年"高分子物理实验"被评为安徽省精品课程。     

Synergistic Covalent and Supramolecular Polymers for Mechanically Robust but Dynamic Materials

Nature has engineered delicate synergistic covalent and supramolecular polymers (CSPs) to achieve advanced life functions, such as the thin filaments that assist in muscle contraction. Constructing artificial synergistic CSP materials with bioinspired mechanically adaptive features, however, represents a challenging goal. Here, we report an artificial CSP system to illustrate the integration of a covalent polymer (CP) and a supramolecular polymer (SP) in a synergistic fashion, along with the emergence of notable mechanical and dynamic properties which are unattainable when the two polymers are formed individually. The synergistic effect relies on the peculiar network structures of the SP and CPs, which endow the resultant CSPs with overall improved mechanical performance in terms of the stiffness, strength, stretchability, toughness, and elastic recovery. Moreover, the dynamic properties of the SP, including self‐healing, stimuli‐responsiveness, and reprocessing, are also retained in the CSPs, thus leading to their application as programmable and tunable materials.     

Polymers with advanced structural and supramolecular features synthesized through topochemical polymerization

Polymers are an integral part of our daily life. Hence, there are constant efforts towards synthesizing novel polymers with unique properties. As the composition and packing of polymer chains influence polymer''s properties, sophisticated control over the molecular and supramolecular structure of the polymer helps tailor its properties as desired. However, such precise control via conventional solution-state synthesis is challenging. Topochemical polymerization (TP), a solvent- and catalyst-free reaction that occurs under the confinement of a crystal lattice, offers profound control over the molecular structure and supramolecular architecture of a polymer and usually results in ordered polymers. In particular, single-crystal-to-single-crystal (SCSC) TP is advantageous as we can correlate the structure and packing of polymer chains with their properties. By designing molecules appended with suitable reactive moieties and utilizing the principles of supramolecular chemistry to align them in a reactive orientation, the synthesis of higher-dimensional polymers and divergent topologies has been achieved via TP. Though there are a few reviews on TP in the literature, an exclusive review showcasing the topochemical synthesis of polymers with advanced structural features is not available. In this perspective, we present selected examples of the topochemical synthesis of organic polymers with sophisticated structures like ladders, tubular polymers, alternating copolymers, polymer blends, and other interesting topologies. We also detail some strategies adopted for obtaining distinct polymers from the same monomer. Finally, we highlight the main challenges and prospects for developing advanced polymers via TP and inspire future directions in this area.

This perspective showcases the potential of topochemical polymerization as an effective tool for synthesizing polymers with advanced molecular and supramolecular structures.     

高分子结构与性能关系原理-结构层次的意义

高分子结构是高分子性能的重要物质基础,对其结构进行合理的划分,有助于准确把握高分子物理知识体系的内在脉络。高分子结构层次的划分不仅要思考静态时特定质点在空间的堆砌特征,而且也要考虑结构出现运动或是变化的基本单元。按照质点尺度的不同,高聚物的结构可以分为单一高分子结构(链结构)、多个高分子结构(凝聚结构)和多种高分子结构(织态结构)三个主要层次。其中,化学因素所确定的链结构层次包括相对分子质量以及构造、构型等同分异构体形式;物理因素所确定的结构层次为高分子局部质点集合在空间的堆砌和排列;链段是容易被忽视、但又是最为重要的运动(变化)单元。     

高分子立构复合结晶的研究进展

立构复合结晶是高分子结晶中的一种普遍现象,也是不同高分子之间共结晶的特殊形式.互为立体异构高分子在共混物和立体嵌段共聚物中可形成立构复合结晶.由于这种独特的链凝聚结构,立构复合结晶材料与相应的同质结晶材料的性能显著不同,立构复合结晶通常可提高高分子材料的熔点、耐热性、结晶能力、结晶度、机械力学性能、耐溶剂性能等.通过立构复合结晶,可使一些非晶或难结晶的高分子转变为可结晶或高结晶度的状态,从而实现材料性能的转变.因此,互为立体异构高分子之间的立构复合结晶为聚合物材料的性能优化和调控提供了有效的途径.文献已报道了多类可立构复合结晶的聚合物体系,包括脂肪族聚酯、脂肪族聚碳酸酯、聚甲基丙烯酸酯、聚酰胺和聚酮等.本文根据聚合物化学结构的不同,针对文献已报道的可立构复合结晶的高分子体系,综述了其立构复合结晶的形成条件、结构特征与物理性质.     

Crystalline Hetero‐Stereocomplexed Polycarbonates Produced from Amorphous Opposite Enantiomers Having Different Chemical Structures

Stereocomplexation is the stereoselective interaction between two opposite enantiomeric polymers through an interlocked orderly assembly. Most studies focus on the stereocomplex formation from the crystalline opposite enantiomers having the identical structure; nevertheless, rare examples were reported regarding the crystalline stereocomplexes from enantiomeric polymers having different chemical structures. Herein we show a strategy for polymer orderly assembly through the formation of crystalline hetero‐stereocomplexed polymeric materials by the cocrystallization of amorphous isotactic polycarbonates with different chemical structures and opposite configurations. The behaviors in the crystalline state are significantly different from that of the component enantiomeric polymers or their homo‐stereocomplexes. This study is expected to open up a new way to prepare various semicrystalline materials having a wide variety of physical properties and degradability.     

Fluorocarbon associative polymers

Fluorocarbon associative polymers modified along the backbone or at the extremities by hydrophobic groups are reviewed with respect to their association and rheological properties in aqueous solutions. Above a threshold concentration corresponding to the formation of a reversible network structure, the solutions behave as physical gels. In this review, it is shown that the viscoelasticity of fluorocarbon associative polymer gels is enhanced with respect to that of hydrocarbon analogues. For polymers substituted at the extremities (telechelics), significant progresses have been made in recent years concerning the microstructure, the phase behavior and the rheology of the gel state. Telechelics in solutions are forming multiconnected structures, which dynamical features are in good agreement with those of transient network models.     

聚合物在受限层空间中的形态结构演变及相关性能研究进展

自然界中的层状有序结构如强韧的贝壳、树木等,往往带来优异的性能或特殊的功能。作为仿生材料学在高分子加工成型技术中的应用,聚合物微纳层共挤出技术是通过特殊的流道设计对聚合物熔体进行多次强制分割叠加,来制备高性能交替多层聚合物材料的新方法。层倍增器单元对熔体的多重力场作用,为多相多组分体系形态的原位调控提供了可能。而通过两相交替层状排布形成的受限层空间和丰富的层界面不仅赋予了材料独特的力学、光电、阻隔等性能,还为聚合物结晶调控提供了理想的研究模型。本文简要综述了近年来在层倍增过程中聚合物的形态结构演变及其对相关性能影响方面的研究进展。     

非晶态与晶态的压电热电铁电高聚物

本文综述了晶态与非晶态两类高聚物的压电性,热释电性和铁电性。这些现象近年来研究得愈来愈广泛。文中以聚氯乙烯作为非晶态高聚物的例子;以PVDF及其共聚物,还有尼龙11作为晶态高聚物的例子。按照偶极子模型,高聚物一般假定需具备四个条件,就可显示出较大的压电性,热释电性和铁电性。本文探讨了上述高聚物的结构与性能,这些对识别材料是很重要的。最后,列举了PVDF及其它材料的压电常数,热释电系数和介电常数,以供读者参考。     

Synthesis,characterization and recent developments of liquid crystalline polymers

Recent developments of polymer liquid crystals (PLCs) are reviewed. The virial expansion method of Onsager and the lattice model used by Flory to appreciate the most relevant parameters in establishing mesomorphic behavior in polymeric systems are presented. These and other theoretical predictions are confirmed by numerous experiments. Both lyotropic (polymer solutions) and thermotropic (polymer melts) types of PLCs are considered with emphasis placed on the latter. The general properties of mesophases formed by such polymers are surveyed and some chemical structures capable of producing mesophases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthetic routes, the effects of polymer structure on physical properties, and applications of two major classes of lyotropic systems (polypeptides, polyamides) and of a range of potentially important thermotropic polymers are discussed.     

Application of vibrational spectroscopy for the analysis of polymer composites

Various examples of filled elastomeric networks will illustrate the potential of Fourier-transform infrared spectroscopy for a better understanding of the properties of elastomeric composite materials which are two-phase materials. The addition of an inorganic component to polymers leads to improvements in various physical and mechanical properties. These improvements are the result of a complex interplay between the properties of the individual constituent phases : the polymer, the filler and the interfacial region. Infrared spectroscopy has been used to characterize the interface in the isotropic state and also under uniaxial extension.