从单分子到分子聚集态科学

有机光电功能材料的宏观性能不仅只依赖于基元分子自身的理化性质,还取决于其分子聚集行为和聚集态结构。在特定的聚集态结构中,分子间弱相互作用的加和与协同,可促进体系性能的拓展与质变,获得超越分子本征属性的功能。这凸显出当前化学研究逐步从关注单分子向分子聚集态科学转变,体现出分子聚集态研究的重要性。本文借助有机室温磷光性能对分子聚集态结构的高度灵敏性与响应性,系统探讨了分子聚集态结构的形成规律与核心影响因素。以此为基础,进一步拓展分子聚集态研究的应用领域,包括力致发光、有机二阶非线性光学、力致变色、有机发光二极管等,从静态调控到动态刺激响应(刺激源：力、热、光、电场等),从单一结构到多组分体系与器件,同时,确立了各种有机光功能材料的优势分子聚集形式,提出了聚集态调控的有效策略与研究思路,阐述了光电功能材料体系设计与合成的可控性与预见性。     

线性脂环族聚酰胺化学结构对其力学和光学性能的影响

以重复单元结构不同的3种线性脂环族聚酰胺(LATPA)材料为研究对象,通过核磁共振谱、红外光谱、热分析、X射线衍射等技术,研究了链结构单元的侧基、端基对材料聚集态结构的影响,并对比研究了不同聚集态结构材料的宏观力学性能和光学透明性差异,建立了链结构、聚集态结构与力学性能、光学性能的关系.研究发现,侧基带来的大空间位阻降...     

分子基材料聚集态结构的场发射性质研究

场发射在扫描电子显微镜、平面显示器、压力传感器、加速度传感器以及电子束可寻址记忆器件等许多领域中得到了广泛的应用,分子基材料由于其结构和能带可设计,性质可调和柔性易加工等显著特点,被认为是新一代的场发射材料。本文综述了近年来分子基材料聚集态结构的场发射性质研究的新进展,特别是分子基材料的结构和聚集态形貌和尺寸对场发射性质的影响以及通过对分子基材料的杂化优化其场发射的性质,展望了分子基材料聚集态结构场发射的应用前景和发展趋势。     

抗冲共聚聚丙烯结构研究进展

综述了已广泛应用于汽车及家电行业的抗冲共聚聚丙烯结构的研究进展,重点介绍了抗冲共聚聚丙烯组成、链结构及聚集态结构的研究方法及研究进展。阐述了典型抗冲共聚聚丙烯的组成、链结构及聚集态结构,总结了研究抗冲共聚物组成、链结构以及聚集态结构的研究方法。同时还回顾了聚合工艺条件对抗冲共聚聚丙烯的组成及链结构的影响规律以及组成及链结构对材料聚集态相结构的影响规律。最后重点回顾了异质多相体系的组成、链结构及聚集态相结构与性能之间的关系,展望了抗冲共聚聚丙烯领域的某些可能发展方向。     

透射电子显微镜在聚合物不同层次结构研究中的应用

聚合物材料的性能与功能取决于各级结构,其中化学结构决定材料的基本功能与性能,而不同层次聚集态结构能够改变材料的性能和赋予材料特殊功能,如高取向超高分子量聚乙烯的模量比相应非取向样品提高3个数量级,聚偏氟乙烯的β和γ结晶结构则能赋予其压电、铁电等特殊功能.因此,明确聚合物不同层次聚集态结构的形成机制、实现各层次结构的精准...     

高聚物的力学性能

力学性能,从其应用的广泛程度来说,是高聚物最重要的一种性能。三大合成材料:塑料、纤维、橡胶的应用都离不开它们的力学性能。从高分子物理的角度研究力学性能的目的是弄清高聚物力学性能的一般规律和特点以及结构(链结构、聚集态结构)和力学性能间的相互关系。这种相互关系包括了结构因素对力学性能的影响以及力学作用对高聚物结构(主要是聚集态结构)的影响。     

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     

先进功能分子体系的设计与组装——从低维到多维

在设计、合成功能分子基元的基础上,综合考虑能量、结构和性质匹配的原则及小尺度下复杂的物理化学现象等关键科学问题,建立了自组装新方法,发展了尺寸与结构可控的分子聚集态结构材料定向、定维自组装技术,构建了大面积、高有序分子聚集态结构材料.并研究了有序异质和同质结构以及表界面问题,特别是界面活性、界面连接等关键科学问题.证明了分子聚集态材料中的性质和性能与形貌、尺寸和维数的强烈依赖关系.从合成化学新的视角出发,建立了合成碳的新同素异形体——石墨炔的新方法,并研究了石墨炔在信息技术、电子、能源、催化以及光电等领域的应用.这些研究对化学、材料科学、物理学、微电子学等基础科学研究以及基于这些学科的交叉研究具有重大的科学意义.     

基于移动核磁共振仪的聚乙烯聚集态结构的非侵入检测

采用移动核磁共振仪(MObile Universal Surface Explorer,NMR-MOUSE)快速、非侵入地检测聚乙烯(PE)粉料和管材料的聚集态结构。NMR-MOUSE仅需几秒钟就可以完成聚集态结构检测。本文首先建立了CPMG序列数据分析方法,用于描述PE的结晶相含量、无定形相含量、界面相含量以及各相区的横向弛豫时间,进而用于分析相同牌号不同厂家的PE粉料聚集态结构中各相区的的微小差异以及受力变形的PE管材不同位点的聚集态结构。结果表明,基于表征各相区链段运动性差异的NMR-MOUSE可实现PE聚集态结构的在线检测。     

聚合物产品工程:面向高性能高分子材料的化学工程新拓展

化学产品工程是化学工程学科的新拓展,其核心研究内容是化学品结构的精确定制.聚合物产品具有复杂的多层次结构,其中分子结构和分子的聚集态结构是决定聚合物性能的最主要结构层次.聚合过程可在很大程度上决定聚合物的分子结构和聚集态结构.近年来,本研究组在活性聚合机理和共聚动力学研究的基础上,针对各种链结构目标,建立了半连续聚合过程的模型化方法和操控聚合过程的计算机程序,实现了多种聚合产物分子结构的精确定制,制备了一些全新的高性能或特殊性能的聚合物.同时,通过反应器内合金化方法和活性界面细乳液聚合的方法尝试进行了聚合物原生聚集态结构的定制.本文综述了上述研究工作,并对未来研究的发展进行了展望.     

The influence of nano‐PS particle on structure evolution and electrical properties of PP/PS

The polypropylene‐g‐polystyrene (PP‐g‐PS) copolymers with different grafting ratios are used as compatibilizers to control the size of polystyrene (PS) particles at nanometer scale in polypropylene (PP) matrix. Then the PP/PS insulating nanocomposites (containing 10 wt % PS calculated from PS and PP‐g‐PS) are manufactured. With the increase in grafting ratio of PP‐g‐PS, the size of PS particle is reduced and the interfacial adhesion is enhanced. Meanwhile, the dielectric properties, DC breakdown strength and volume resistivity are increased with the decreasing of PS particle size. The spherulite size of PP is decreased and the boundary between crystals and amorphous regions is blurred or even disappears due to the presence of PS nanoparticles. This evolution of PP structure is attributed to the serious entanglements of PP and PS molecular chains. Finally, the correlation between morphological structure and electrical properties is ultimately established based on the in‐depth understanding of the molecular chain movement, crystal structure, and phase morphology. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 706–717     

Morphology and Properties of Particulate Filled Polymers

Although the structure of particulate filled polymers is usually thought to be very simple, often structure related phenomena determine their properties. Segregation occurs only when long flow paths and large particles are used in production. The occurrence and extent of aggregation depend on the relative magnitude of attractive and separating forces, which prevail during the homogenization of the composite; the balance of adhesive and shear forces determines structure. Fillers of small particle size always aggregate, usually leading to decreased strength and especially low impact resistance. Anisotropic particles (talc, mica, short fibers) are orientated during processing. ESR is a relatively simple technique for the estimation of orientation and orientation distribution, which are determined by processing conditions, i.e. flow pattern, shear conditions, mold filling rates, cooling conditions, etc. The orientation of the particles strongly affects composite stiffness and strength. In practice, often several factors simultaneously influence the properties of products prepared from particulate filled polymers. Separation of the effects of the influencing factors is difficult, although such knowledge would help to control composite properties. The structure and properties of injection and compression moulded PP composites containing CaCO₃ or talc differs considerably from each other. The aggregation of CaCO₃, the nucleating effect and the orientation of talc affect product properties. The latter are also influenced by the skin-core structure developing during injection molding as well as by the orientation of the polymer. An example is discussed in this paper, which facilitates the identification of the effect of these factors with the help of a simple model and indicates a way in which product properties can be controlled.     

具有包藏结构的三元聚丙烯纳米复合材料结构与性能关系的研究

制备了一种新型聚丙烯 丁苯橡胶 纳米碳酸钙三元纳米复合材料 .研究结果显示 ,复合材料中的大多数纳米碳酸钙粒子被包藏在丁苯橡胶中 ,并与之共同形成分散于聚丙烯树脂中的分散相 ,这种聚丙烯纳米复合材料具有高刚性、高韧性、高耐热性和高的结晶速率 .系统研究了成核剂苯甲酸钠的加入和纳米碳酸钙的用量对该类纳米复合材料相态结构、结晶形态和结晶动力学的影响 ,以及具有包藏结构的分散相粒径和PP中β晶含量对材料性能的影响 .结果表明 ,苯甲酸钠的加入和纳米碳酸钙用量的提高均可使体系中分散相粒径减小 ,结晶速率加快 ,进而使材料的韧性、刚性和耐热性提高 .     

尼龙-6和尼龙-6合金的球晶结构与破坏性能的研究

成型冷却速度即结晶速度对单纯尼龙 ６和尼龙 ６合金的拉伸破坏性能具有不同的影响．结晶速度慢，球晶尺寸大，单纯尼龙 ６的拉伸破坏强度高，破坏形变和破坏能量减小；尼龙 ６／热塑性聚酰胺弹性体／增容剂合金不仅拉伸破坏强度高，而且破坏形变和破坏能量都有所增加．研究表明，虽然球晶尺寸影响尼龙 ６的破坏性能，但球晶的性质即球晶的界面上和片晶 片晶间的非晶部分结构、微小分散粒子的空洞化及相与相之间的界面结合强度是影响尼龙 ６破坏性能的主要因素．     

纳米刚性微粒与橡胶弹性微粒同时增强增韧聚丙烯的研究

通过力学性能测试、动态力学试验、ＤＳＣ 分析以及材料断面形貌与结构分析等手段,对以纳米二氧化硅（ＳｉＯ２） 为刚性微粒、以三元乙丙橡胶（ＥＰＤＭ） 为弹性微粒组成的聚丙烯（ＰＰ）／ 纳米ＳｉＯ２／ＥＰＤＭ 的同时增强增韧效果进行了研究．结果显示,上述两种微粒可同时大幅度提高ＰＰ 的韧性、强度和模量,当ＰＰ／ 纳米ＳｉＯ２／ＥＰＤＭ 为８０／３／２０ 时,两种微粒体现较明显的协同增韧效应．纳米ＳｉＯ２ 可提高ＰＰ 的结晶温度和结晶速度,并使球晶细化．纳米ＳｉＯ２ 刚性微粒在ＰＰ连续相中以微粒团聚体形态分布,构成团聚体的平均微粒数约为６ ～７ ,其与ＰＰ基体表现出较强的结合牢度．ＰＰ／ 纳米ＳｉＯ２／ＥＰＤＭ 的综合性能已接近或达到工程塑料的性能．     

PP-g-MAH对聚丙烯/滑石粉复合材料的性能影响

研究了两种马来酸酐接枝聚丙烯（PP-g-MAH）在不同含量时对聚丙烯（PP）/滑石粉复合材料的力学性能、雾化性能和线性膨胀系数的影响.结果表明,接枝物的加入能提高复合材料的拉伸性能、冲击性能和弯曲性能,但随着含量的增加拉伸强度、冲击强度和弯曲强度及弯曲模量有所降低.在含量相同时,接枝物1对冷凝组份的影响更小.复合材料的线性膨胀系数随接枝物含量的增加先减小后增加.     

低乙烯含量共聚聚丙烯链结构和相结构与应力应变行为的关系

研究了两种典型的低温抗冲共聚聚丙烯(ICPP)的应力应变行为及温度依赖性,其低温应力应变行为揭示ICPP具有优异的低温抗冲性能和综合力学性能的结构本质.从初始弹性模量、屈服应力及断裂伸长随温度变化所显示的变化规律进一步确认了两种ICPP的序列结构特征和相结构特征.断裂伸长变化显示了乙丙橡胶相的增韧作用,屈服应力变化显示了分散相对基质结合紧密程度的影响,弹性模量则与基质的结晶状况和结晶形态有着比较密切的关系,同时也与乙丙橡胶相和聚丙烯基质的玻璃化转变温度密切相关.     

Photopolymerization and toughening performance in polypropylene of hyperbranched polyurethane acrylate

A novel UV-curable hyperbranched polyurethane acrylate (HUA) was synthesized and found to polymerize rapidly in the presence of 5 wt.% benzophenone in N₂ under UV exposure. The photopolymerization kinetics of HUA was studied by differential photocalorimetry (DPC). Its toughening effect for polypropylene (PP) was investigated by tensile and impact tests of the UV irradiated PP/HUA blends. The morphological structures and thermal behavior were determined by polarized optical microscopy, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The obtained results demonstrate that (1) the maximum photopolymerization rate increases with raising temperature up to 140 °C, whereas decreases at above 150 °C. The activation energy of 19 kJ mol⁻¹ for the photopolymerization was obtained at below 140 °C from the Arrhenius plot, while it is negative at above 150 °C. (2) The incorporation of 5 wt.% HUA greatly improved the notched impact strength of PP matrix with a slight improvement in the tensile strength and without obvious decline in breaking elongation. These results correlate well with SEM observation. (3) During the UV irradiation of PP/HUA blends, PP can be crosslinked/grafted with the cured HUA particles, resulting in the increase of the impact strength of PP matrix. (4) The cured HUA particles in the PP/HUA blends act as heterogeneous nucleation agent for PP, which results in the decrease of spherulite size and less perfection of PP crystals.     

Annealing of Oriented PP/PE Double-layer Film within the Melting Range of PE: the Role of Partial Melting and Self-nucleation

Due to the mechanical stability of the PP layer, the oriented PP/PE double-layer film with a row-nucleated crystalline structure can be annealed at a higher temperature than the PE monolayer film. In this work, the effects of annealing temperature within the melting range of PE on the crystalline structure and properties of PP/PE double-layer films were studied. When the annealing temperature is between 100 and 130 °C, below the melting point of PE, the crystallinity, the long period, lateral dimension and orientation of the lamellae in the PE layer increase with the annealing temperature due to the melting of thin lamellae and the self-nucleated effect of partially-melted melts during annealing. With the annealing temperature further increasing to 138 °C, near the melting ending point of PE, since the lamellae melt completely and the melt memory becomes weak during annealing, some spherulite structures are formed in the annealed sample, resulting in a decrease of orientation. In contrast, the annealing only causes the appearance of a low-temperature endothermic plateau in the PP layer. The improved size and orientation of lamellar structure in the PE layer increase the pore arrangement and porosity of the stretched PP/PE microporous membrane. This study successfully applies the self-nucleation effect of partially-melted polymer melt into the practical annealing process, which is helpful to guide the production of high-performance PP/PE/PP lithium batteries separator and the annealing process of other multilayer products.

     

动态固化聚丙烯/环氧树脂共混物的研究

将动态硫化技术应用于热塑性树脂 热固性树脂体系 ,制备了动态固化聚丙烯 (PP) 环氧树脂共混物 .研究了动态固化PP 环氧树脂共混物中两组分的相容性、力学性能、热性能和动态力学性能 .实验结果表明 ,马来酸酐接枝的聚丙烯 (PP g MAH)作为PP和环氧树脂体系的增容剂 ,使分散相环氧树脂颗粒变细 ,增加了两组分的界面作用力 ,改善了共混物的力学性能 .与PP相比 ,动态固化PP 环氧树脂共混物具有较高的强度和模量 ,含 5 %环氧树脂的共混物拉伸强度和弯曲模量分别提高了 30 %和 5 0 % ,冲击强度增加了 15 % ,但断裂伸长率却明显降低 .继续增加环氧树脂的含量 ,共混物的拉伸强度和弯曲模量增加缓慢 ,冲击强度无明显变化 ,断裂伸长率进一步降低 .动态力学性能分析 (DMTA)表明动态固化PP 环氧树脂共混物是两相结构 ,具有较高的储能模量 (E′)