聚合物在压力下的流动诱导结晶

流动诱导聚合物结晶研究很少在压力场下开展,其原因是压力下流动诱导聚合物结晶对实验设备要求较高。然而,实际加工中不仅存在流动场,还有压力场。为此,作者课题组利用自制的装置对压力下流动诱导聚合物结晶开展了系统研究,发现其结晶行为与常压的流动诱导结晶有较大差别。等规聚丙烯(iPP)在压力和剪切场下可形成独特取向球形晶体形态。在短时间内(30min),iPP片晶可快速增厚,形成熔点接近平衡熔点的厚片晶(近180℃),其原因是在压力和流动场协同作用下,片晶增厚活化能快速减小。同时,从研究结果也获得了添加β成核剂的iPP体系在压力和流动场下形成β晶的窗口条件。对聚乳酸(PLA)的研究也发现了相似的片晶快速增厚规律。另外,在压力和流动场下,可直接从PLA熔体中获得可增韧PLA的β晶。研究成果为实际加工中的聚合物形态结构调控提供了理论和实验依据。     

高压结晶PET/PC共混体系中生长在伸直链晶体内部球晶形态的观察

自从Wundedich等报道聚乙烯（PE）在高压结晶时可以生成伸直链晶体以来,相继很多有关聚合物体系的高压结晶行为方面的研究已见报道．研究结果表明,聚合物在高压下经历相转变时可产生非常丰富的微观结构,而球晶及伸直链晶体是其中最常见的两种结晶形态．但是,所观察到的这两种聚合物晶体都是分别存在,且独立生长的．到目前为止,尚未见到关于高压下球晶可以在伸直链晶体内部存在的报道．     

聚合物流动诱导结晶研究进展

在外力作用下,半结晶聚合物的结晶形态、结晶动力学等与静态条件下相比,均发生了较大的变化,并继而影响到成型制品的性能.自上世纪六十年代人们从溶液中发现外力诱导结晶现象以来,相继开展了大量相关的理论和实验研究,提出了一些模型,随着测试手段的改进,流动诱导结晶研究取得了较大的进展,但仍存在许多争议.本文回顾了围绕聚合物流动诱导结晶所开展的工作,重点综述了流动诱导结晶形态变化、分子量及其分布、剪切速率、温度等因素对聚合物结晶动力学的影响,并指出了今后的研究方向.     

剪切均匀性对流动诱导等规聚丙烯结晶的影响

固定应变和最终应变速率,采用瞬时和缓慢2种电机加速方式对样品施加剪切,研究了流场加载模式对样品流变和结晶行为的影响.实验结果显示缓慢加速能够消除剪切过程中流场的非均匀性,使样品取向度增加,提高流场对聚合物熔体的作用效果.同时,流动诱导结晶对于加速时间有依赖性.对于速率为17.7 s-1的剪切,加速时间为1 s时,熔体流动均匀且流动诱导的晶体取向最强,短加速时间(0.5 s)和长加速时间(1.5 s)样品的流动诱导结晶效果都弱于加速时间为1 s的样品.但是,对于不同剪切速率,其对应的最优加速时间不同.对于流动诱导结晶来说,加速时间应当作为一个重要参数来考虑,其背后的真实物理含义还需要进一步研究来说明.     

成核剂及其完善剂对聚乳酸结晶行为的影响

通过POM、DSC以及流变测试系统考察了成核剂(PPZn)及其完善剂(E61)对PLA结晶形貌及其结晶能力的影响.POM结果表明PPZn和E61对PLA的结晶形态的影响随两者含量的变化而变化.加入低含量的PPZn可诱导PLA得到一定完善程度的球晶,而较高含量的PPZn能够诱导PLA基体得到针状晶体.通过添加少量E61可使在PPZn较高含量下的PLA针状晶体转变为球晶.但更高含量E61的添加却使PPZn的成核作用受到抑制,再次生成针状晶体,且E61含量越高,抑制作用越明显.DSC和流变测试进一步证明PPZn可显著提高PLA的结晶能力、有效地缩短基体结晶时间,而E61的添加对PLA的结晶速率影响不大.     

茶碱晶体印迹聚合物

采用分子印迹的方法 ,以甲基丙烯酸为功能单体 ,双甲基丙烯酸乙二酯为交联剂 ,茶碱晶体为印迹物 ,采用光引发聚合的方式 ,制备了茶碱晶体印迹聚合物 .扫描电镜观察显示 ,聚合物表面用 0 1mol L盐酸溶液反复洗涤除去茶碱晶体后 ,可以在饱和茶碱溶液中诱导茶碱结晶的生成 ;而在同样条件下的咖啡因晶体印迹聚合物表面则没有相应的诱导结晶能力 .分析结果表明 ,茶碱和咖啡因在咪唑取代基上的微小差异可能是导致两者表现不同的主要原因 ,茶碱分子可以通过其咪唑环和相邻嘧啶环上的羰基以氢键或静电作用的方式与甲基丙烯酸的羧基产生分子识别所需的 3点协同相互作用 ,而结构相似的咖啡因则因其咪唑环上的取代基不同 ,无法满足识别所需的基本要求     

丙酮诱导聚碳酸酯的结晶行为

在298 K, 采用液相丙酮或26.5 kPa蒸气压的气相丙酮, 对双酚A聚碳酸酯(BAPC)的液相或气相诱导结晶行为进行研究. 实验结果表明, 在诱导结晶的起始阶段, 非晶态BAPC结晶能力得到极大的提高. 气相诱导BAPC结晶的结晶速度和结晶度均低于液相诱导结晶的结果. 广角X射线衍射(WAXD)测试结果表明, 与BAPC热结晶样品相比, 丙酮液相或气相诱导BAPC结晶生成的晶体具有完善度低、晶粒尺寸小、熔点低, 而结晶度高的结构特点. 采用扫描电子显微镜(SEM)分别对液相或气相丙酮诱导BAPC结晶样品表面形态进行了观察, 研究了不同诱导机制下BAPC的结晶生成球晶的形态与机制.     

超临界CO_2下的聚合物结晶形态和动力学研究现状北大核心CSCD

聚合物结晶一直以来是高分子凝聚态研究的热点,随着超临界流体尤其是超临界CO2(scCO2)在聚合物方面应用日益增加,对超临界条件下的聚合物结晶研究显得更加重要。scCO2在聚合物中溶解度较高,增塑效果好,能显著降低玻璃化温度(Tg)和熔点(Tm),改变聚合物的晶体形态,并对动力学过程产生较大影响。因此,聚合物在scCO2条件下结晶行为的深入研究,在实际应用中起着重要的指导作用。本文对scCO2作用下的链型、晶体形态、共混物特点和结晶动力学过程的研究现状进行综述。     

PET/PC共混体系的酯交换反应对其高压结晶行为的影响

利用转矩流变仪、DSC、SEM及WAXD等表征手段研究了PET/PC共混体系的酯交换反应对其高压结晶行为的影响.SEM观察表明,PET和PC熔混时的酯交换反应有利于PET/PC体系在高压结晶时生成厚度较大的伸直链晶体,且可以促进其高压下酯交换反应的发生.楔形伸直链晶体和弯曲伸直链晶体的存在证明链滑移扩散和酯交换反应两种机制对体系中聚酯伸直链晶体的增厚有贡献.拟合分峰法和War-ren-Averbach傅里叶分析法的计算结果表明,随PET/PC体系熔混时酯交换反应程度的增加,高压结晶共混物的结晶度降低,PET的平均微晶尺寸增大,点阵畸变平均值则减小,而微晶尺寸分布变宽.提出了在共聚物组分都具备结晶能力时,结晶诱导化学反应和化学反应诱导结晶两种过程在一定条件下可同时发生的观点.     

热致液晶共聚酯对聚丙烯结晶的诱导作用

用差示扫描量热法和光学解偏振法研究了热致液晶性芳香共聚酯与聚丙烯共混物的等温和非多温结晶行为.结果表明,这一热致液晶聚合物对聚丙烯结晶有诱导成核和加速作用.当共聚酯含量在2-5％之间时,聚丙烯的结晶速率最快.偏光显微镜的观察揭示出在聚丙烯熔体中原位形成的液晶聚合物微纤诱导了聚丙烯横穿晶的形成.     

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.     

Polymer crystallization in complex conditions. Towards more realistic modelling of industrial processes

Crystallization plays an important role in processing many industrial polymers. Crystallinity controls mechanical and sorptional properties of solid materials and strongly affects rheological properties of polymer melts and solutions. Therefore, realistic modeling of technological processes involving crystallizable polymers (melt spinning, film blowing, injection molding, etc.) requires that crystallization in the course of processing is taken into account. In contrast to idealized laboratory conditions usually applied in academic studies, crystallization in processing conditions covers wide range of rapidly changing temperatures and pressures. Simple models of non‐isothermal, and stress‐induced crystallization kinetics are discussed. Consideration of crystallization in the computer model of melt spinning reveals new effects, absent in earlier models, in which crystallization was ignored.     

Mechanical properties of recycled polymers

Modifications of structure and morphology of the polymers induced by the thermomechanical stress (or by the presence of water for some polymers) during reprocessing can cause a drastic deterioration of mechanical properties of the recycled material. The property - reprocessing relationships are an important tool to determine not only the properties of the recycled polymers but also the strategies to use (processing conditions, stabilizers, fillers, compatibilizers, etc) in order to obtain recycled polymers with good mechanical properties. In this work, typical behaviour of some mechanical properties as a function of the number of reprocessing operations is discussed and correlated with their structure and morphology. The influences of the type of apparatus and of the processing conditions are also considered.     

The characterization of polymer deformation by rheo-optical fourier-transform infrared spectroscopy

The mechanical properties of polymeric materials are of considerable importance to their engineering applications. Apart from the chemical structure and the thermal history, molecular orientation has a major influence on the mechanical properties of a polymer. The increased need for more detailed data and a better understanding of the mechanisms involved in polymer deformation has led to the search for new experimental techniques to characterize transient structural changes during mechanical processes. With the advent of rapid-scanning Fourier - transform infrared (FTIR) spectroscopy, simultaneous vibrational spectroscopic and mechanical (so-called rheo-optical) measurements during the deformation of polymers have emerged as a very informative probe for the study of deformation and relaxation phenomena in polymer films in the late seventies and have since then been applied to obtain data on strain-induced crystallization and orientational and conformational changes during mechanical treatment of a wide variety of polymers.     

Combining X-ray scattering with dielectric and calorimetric experiments for monitoring polymer crystallization

In order to understand nucleation; crystallization and other phase transitions in polymers, polymer based composites, or in liquid crystals simultaneous experiments with a combination of different methods are useful. Due to different sample geometry, contact faces with the sample holder, and thermal conditions it is usually difficult to compare the results of several individual experiments. As an important supplement to the classical techniques for studying crystallization like X-ray scattering, or differential scanning calorimetry, measurements which test molecular mobility like dielectric or mechanical spectroscopy are of interest during isothermal and non-isothermal crystallization. From such simultaneous experiments one can learn about the existence of pre-ordered structures before formation of crystals, as detected by DSC or X-ray scattering.In this contribution we present the development of a device for simultaneous measurements of electrical properties and X-ray scattering intensities, which was extended to a microcalorimeter and allows measuring thermal properties like heat capacity and thermal conductivity additionally at the same time and at the same sample volume.     

Backbone flexibility on conjugated polymer's crystallization behavior and thin film mechanical stability

Extensive efforts have been made to develop flexible electronics with conjugated polymers that are intrinsically stretchable and soft. We recently systematically investigated the influence of conjugation break spacers (CBS) on the thermomechanical properties of a series n-type naphthalene diimide-based conjugated polymer and found that CBS can significantly reduce chain rigidity, melting point, as well as glass transition temperature. In the current work, we further examined the influence of CBS on the crystallization behaviors of PNDI-C3 to C6, including isothermal crystallization kinetics, crystal polymorphism and subsequently time-dependent modulus, in a holistic approach using differential scanning calorimetry, X-ray scattering, polarized optical microscopy, atomic force microscopy, and pseudo-free-standing tensile test. Results demonstrate that increasing the length of CBS increases the crystallization half-time by 1 order of magnitude from PNDI-C3 to PNDI-C6 from approximately 10³ to 10⁴ s. The crystallization rate shows a bimodal dependence on the temperature due to the presence of different polymorphs. In addition, crystallization significantly affects the mechanical response, a stiffening in the modulus of nearly three times is observed for PNDI-C5 when annealed at room temperature for 12 h. Crystallization kinetic is also influenced by molecular weight (MW). Higher MW PNDI-C3 crystallizes slower. In addition, an odd–even effect was observed below 50°C, odd-number PNDI-Cxs (C3 and C5) crystallize slower than the adjacent even-numbered PNDI-Cxs (C4 and C6). Our work provides an insight to design flexible electronics by systematically tuning the mechanical properties through control of polymer crystallization by tuning backbone rigidity.     

1,2-丁二醇共聚对聚对苯二甲酸乙二醇酯结晶行为及力学性能的影响

为了探索生物基乙二醇中的1,2-丁二醇(1,2-BDO)作为共聚单体对生物基聚对苯二甲酸乙二醇酯(PET)的结晶行为和力学性能的影响。 本文合成了生物基PET均聚物和不同1,2-BDO共聚单元摩尔分数的系列生物基PET共聚物(共聚单体摩尔分数分别为2.0%、2.7%和5.6%),并采用傅里叶变换红外光谱仪(FTIR)、差示扫描量热仪(DSC)和力学测试等技术手段研究了其结晶行为和力学性能。 结果表明,随着1,2-BDO共聚单元摩尔分数的增加,PET共聚物的熔融温度、结晶速率及结晶度均明显降低,表明1,2-BDO共聚单体的引入破坏了PET分子链的规整性,阻碍了PET链段的结晶。 PET材料的拉伸强度随着1,2-BDO共聚单元摩尔分数的增加而降低,而弯曲强度和弯曲模量略有升高。     

Reactive compatibilization of polyamide‐6 (PA 6)/polybutylene terephthalate (PBT) blends by a multifunctional epoxy resin

A multifunctional epoxy resin has been demonstrated to be an efficient reactive compatibilizer for the incompatible and immiscible blends of polyamide‐6 (PA 6) and polybutylene terephthalate (PBT). The torque measurements give indirect evidence that the reaction between PA and PBT with epoxy has an opportunity to produce an in situ formed copolymer, which can be as an effective compatibilizer to reduce and suppress the size of the disperse phase, and to greatly enhance mechanical properties of PA/PBT blends. The mechanical property improvement is more pronounced in the PA‐rich blends than that in the PBT‐rich blends. The fracture behavior of the blend with less than 0.3 phr compatibilizer is governed by a particle pullout mechanism, whereas shear yielding is dominant in the fracture behavior of the blend with more than 0.3 phr compatibilizer. As the melt and crystallization temperatures of the base polymers are so close, either PA or PBT can be regarded as a mutual nucleating agent to enhance the crystallization on the other component. The presence of compatibilizer and in situ formed copolymer in the compatibilized blends tends to interfere with the crystallization of the base polymers in various blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 23–33, 2000     

Quadruple‐shape‐memory effect of TPI/LDPE/HDPE composites

Shape‐memory polymers are important smart materials with potential applications in smart textiles, medical devices, and sensors. We prepared trans‐1,4‐polyisoprene, low‐density polyethylene (LDPE), and high‐density polyethylene (HDPE) shape‐memory composites using a simple mechanical blend method. The mechanical, thermal, and shape‐memory properties of the composites were studied. Our results showed that the shape‐memory composites could memorize 3 temporary shapes, as revealed by the presence of broad melting transition peaks in the differential scanning calorimetry curves. In the trans‐1,4‐polyisoprene/LDPE/HDPE composites, the cross‐linked network and the crystallization of the LDPE and HDPE portions can serve as fixed domains, and all crystallizations can act as reversible domains. We proposed a schematic diagram to explain the vital role of the cross‐linked network and the crystallization in the shape‐memory process.     

聚对苯二甲酰对苯二胺对尼龙-6共混改性的影响

<正> 聚对苯二甲酰对苯二胺(PPTA)是一种棒状的刚性高分子,由它的液晶溶液可制得高强度、高模量、耐高温纤维,这种纤维可作为增强剂以制备高性能的复合材料。若将刚性链高分子以近于分子水平分散到柔性链高分子中,可期望得到性能良好的分子复合材