热塑性树脂的增强：从原位复合材料到原位混杂复合材料

综述了两类增强的热塑性树脂的基本方面。一类是由原位形成的热致液晶聚合物微纤增强的原位复合材料。从实验上研究了获得有效增强效果的两个关键因素；致热液晶聚合物的基体树脂中的成纤，以及在液晶聚合物与基体树脂不相容共混物中的增容作用。另一类是由作者发明的原位混杂复合材料，这一类材料是用直径在两个数量级上的纤维和原位形成的微纤混杂增强的。     

离聚物在液晶聚合物与聚碳酸酯共混体系中的增容作用

离聚物在液晶聚合物与聚碳酸酯共混体系中的增容作用刘杰何嘉松（中国科学院化学研究所工程塑料国家重点实验室北京１０００８０）关键词增容作用，离聚物，热致液晶聚合物原位复合材料（Ｉｎ ｓｉｔｕｃｏｍｐｏｓｉｔｅ）是一种新兴的复合材料，是由热致液晶聚合...     

离聚物对含液晶聚合物聚砜体系的增容作用

离聚物对含液晶聚合物聚砜体系的增容作用刘杰，何嘉松（中国科学院化学研究所工程塑料国家重点实验室北京１０００８０）关键词增容作用，离子聚合物，热致液晶聚合物，高分子共混物，原位复合材料工程塑料与液晶聚合物（Ｌｒｙ）共混（形成所谓的原位复合材料）时在降低...     

热致液晶聚合物的可纺性与其在基体树脂中的成纤

热致液晶聚合物的可纺性与其在基体树脂中的成纤何嘉松，张洪志（中国科学院化学研究所工程塑料国家重点实验室北京１０００８０）关键词热致液晶聚合物，熔融可纺性，高分子共混物，原位复合，亚微米增强用热致液晶聚合物（ＴＬＣＰ）对热塑性树脂产生亚微米级增强作用的...     

塑料增强的新途径——热致液晶高聚物的增强作用

评价了热致液晶高聚物作为高性能成型材料的特点。综述了由增强性的热致液晶高聚物和热塑料聚合物基体组成的原位复合材料及其制备、结构和性能。也讨论了今后研究这一塑料增强新途径时要注意的诱导取向和相容性。     

静电纺丝法制备PAN/HNTs混杂纤维增强热塑性聚氨酯复合材料

静电纺丝方法制备了聚丙烯腈/埃洛石纳米管(PAN/HNTs)混杂纤维增强体,通过改变接收装置、热拉伸处理得到5种不同的PAN/HNTs混杂纤维增强体。采用浸渍法将5种增强体用于改性热塑性聚氨酯,得到PAN/HNTs/TPU复合材料。结果表明,PAN/HNTs混杂纤维增强体可显著提高复合材料的力学性能。将平板接收制备的PAN/HNTs混杂纤维增强体以及另外两种由1050r/m滚筒接收制备的PAN/HNTs混杂纤维增强体(前者不采用热拉伸,后者采用热拉伸),三者制成PAN/HNTs/TPU复合材料。与通过平板接收制备的复合材料相比,通过由1050r/m滚筒接收制备的两种复合材料性能要优于前者,相较于前者,其复合材料的拉伸强度分别增加了19%和43%,弹性模量分别增加了44%和122%,断裂伸长率分别增加了19%和24%。当定向接收的PAN/HNTs纤维膜的含量为5.6%时所得到的PAN/HNTs/TPU复合材料力学性能为最佳;通过热拉伸处理PAN/HNTs纤维膜,当含量为4.5%时,复合材料的力学性能为最佳。这种力学增强的主要原因是PAN/HNTs纤维与热塑性聚氨酯材料之间的相容性得到了改...     

聚芳醚酮与液晶聚酯多嵌段共聚物的合成表征

近年来,以热塑性聚合物为基体,热致液晶聚合物(TLCP)作为增强剂的高分子原位复合材料由于其具有优异的机械性能和优良的成型加工性能,已引起各国工作者的普遍关注和极大兴趣．然而由于自聚集和相分离作用的影响,大部分液晶聚合物与通常的热塑性聚合物基体基本不相容或弱相容,这对于提高原位复合材料的力学性能不利．     

聚酯纤维布混杂增强环氧树脂可钻复合材料的制备与性能研究

采用聚酯纤维布与碳纤维、Kevlar纤维分别混杂增强环氧树脂,制备满足油田开发的可钻桥塞用高性能复合材料。分别采用液体芳胺(DETDA)与固体芳胺(DDM)作为固化剂,两种材料有着相近的玻璃化转变温度和力学强度。以DETDA固化的树脂基体中,活性环氧稀释剂用量增加,拉伸强度变化不大,但材料的弹性模量在10%稀释剂用量时,达到最大值;树脂交联密度1000/Mc为2.35时,材料的模量和拉伸强度都处于相对较大值。聚酯纤维/Kevlar纤维和聚酯纤维/碳纤维混杂增强环氧树脂复合材料的模量和强度,分别随着Kevlar纤维和碳纤维含量的增加而增加,有碳纤维的复合材料拉伸强度增加较大,断裂伸长率相对较小。实验显示:聚酯纤维混杂增强复合材料具有较好的可钻性,在钻压为1.5吨,钻速为32转/分的条件下,磨铣速度为4 mm·min~(-1)。     

全芳香族热致液晶聚合物与热塑性树脂聚砜的原位复合材料

用自制的四种全芳香族热致液晶聚合物ＢＰ ＬＣＰ、ＢＰＭ ＬＣＰ、ＢＰＡ ＬＣＰ、ＢＰＳ ＬＣＰ与热塑性树脂聚砜（ＰＳＦ）熔融共混，制备了一系列原位复合材料．研究了所得材料的微观形态、热性能、力学性能等，结果显示：四种液晶聚合物中，ＢＰ ＬＣＰ，ＢＰＳ ＬＣＰ在所用加工条件下可在ＰＳＦ中取向成纤，而且这两种共混物断面上存在皮 核效应；ＢＰＭ ＬＣＰ和ＢＰＡ ＬＣＰ未成纤，均以球状存在于ＰＳＦ中．这四种液晶聚合物与ＰＳＦ的相容性较差，各共混物的Ｔｇ均分别接近于二纯组分的Ｔｇ值，ＳＥＭ照片上明显的相界面也能说明以上问题．液晶聚合物对ＰＳＦ有增强作用，但增强效果不很显著，这可能是二者相容性较差所致     

热致液晶聚合物对短玻璃纤维增强聚丙烯加工性、结构与性能的改善

<正> 短切玻璃纤维增强的热塑性复合材料具有加工简便,生产周期短,可以反复加工等优点,因此得到了广泛应用。但短切玻璃纤维会给加工成型带来困难,主要在于纤维对加工设备的磨损,以及由于纤维的加入增大了熔体的粘度等。如果提高加工温度来降低粘度又会导致高聚物降解。几年前Kiss和Isayev提出用热致液晶聚合物(TLCP)的刚性棒状分子链作增强剂与被增强基体熔融共混,在加工中TLCP原位形成增强纤维,形成原位复合材料。原位复合材料中由于TLCP的流变性质,使其共混物的加工粘度     

In Situ fibril formation of thermotropic liquid crystal polymer in polyesters blends

Polymer blends based on poly(ethylene 2,6‐naphthalate) (PEN) and poly‐(ethylene terephthalate) (PET) reinforced with a thermotropic liquid crystal polymer (TLCP) were prepared using a melt blending process. Polymer blends consisting of conventional cheap polyester with a small quantity of expensive TLCP are of interest from an economic point of view. The shear viscosity of the TLCP and polyester blends decreased with increasing shear rate and depended on TLCP content. The lower values of the structural viscosity index for the TLCP and polyester blends were attributed to the formation of fibrillar TLCP structures having elongated fibrils in the polyester matrix. The TLCP/PEN blends exhibited long TLCP fibrils that had smaller average diameters and narrower distributions of the diameter compared with those of the TLCP/PET blends. The higher shear force and lower viscosity ratio observed may favor the in situ TLCP fibril formation in the polyester matrix. The viscosity ratio was the most crucial factor in controlling the morphology of the TLCP phase in the TLCP and polyester blends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3600–3610, 2005     

Properties of a carbon filled cyclic olefin copolymer

This article investigates electrical conductivity and rheological aspects of cyclic olefin copolymer (COC) composites containing both carbon fiber (CF) and carbon black (CB) at various concentrations. The different formulations of carbon filled COC were compression molded in such a manner that the formed circular sheets exhibited preferred in‐plane filler orientation. Through‐plane and in‐plane conductivity were measured by 2‐probe and 4‐probe methods, respectively, while an ARES rheometer in dynamic mode was employed to measure the storage modulus and complex viscosity. It was found that formulations with CF:CB ratios around 3 and where the CB content was close or below its critical percolation concentration resulted in higher electrical conductivity while maintaining the viscosity of the composite at a level acceptable for polymer processing machinery. For those composites containing both fillers, collaborative associations between the CB and CF fillers were found in the established percolating network structure, producing measured conductivities which exceeded the estimated values by the additive rule by up to sixfold. An empirical expression to handle hybrid filler systems is proposed in this work based on the standard percolation model. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1808–1820, 2007     

粘度比对刚性链高分子与柔性链高分子共混物微结构的影响

粘度比对刚性链高分子与柔性链高分子共混物微结构的影响何嘉松,卜文胜,张洪志,许向青（中国科学院化学研究所,北京,１０００８０）（化工部北京化工研究院,北京,１０００１３）关键词高分子共混物,热致液晶聚合物,聚合物加工影响柔性链高分子与柔性链高分子共混...     

Organoclay/thermotropic liquid crystalline polymer nanocomposites. III. Effects of fully exfoliated organoclay on morphology,thermal, and rheological properties

A fully exfoliated organoclay in thermotropic liquid crystalline polymer (TLCP) based nanocomposite was prepared by a method combining ultrasonication, centrifugation, solution casting, and heat‐shearing separation. Morphological study showed that the organoclays of 15–25 nm in size dispersed uniformly in TLCP with fully exfoliated structures. The organoclays formed molecular level interactions with TLCP molecules. The interactions did not affect the liquid crystallinity and mesophase structure of TLCP, but they affected the thermal stability and thermal properties of TLCP, increasing the thermal stability and shifting the transition temperatures to the higher ends. Mechanical rheology investigations in the linear viscoelastic region showed that with the exfoliated organoclay in TLCP, more obvious pseudosolidlike behavior appeared in the terminal region. The rigidity of TLCP was enhanced by the presence of the exfoliated organoclay with percolated structures in the TLCP matrix. In steady shear tests, the nanocomposite had the similar shear viscosity and N1 (the first normal stress difference) to those of TLCP in the steady state condition. Percolated structures were easily destroyed by sufficient shear strain and the exfoliated organoclays were oriented along the shear direction, even assisting the neighboring TLCP molecules to align in the flow direction, resulting in a decrease of viscosity and an increase of the N1 slope. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 712–720, 2010     

聚醚砜/热致液晶高分子原位复合材料的结构与性能

<正> 国际上关于热致液晶高分子(TLCP)原位复合材料的报道始于80年代,原位复合增强材料的增强形式不是在树脂加工前实际存在的,而是在加工过程中形成的,原位复合的方法是将TLCP掺入树脂基体,使其在特定的流场和应力场作用下,诱导取向并形成徽     

Bulk rigid-rod molecular composites of articulated rod copolymers with thermoplastic pendants

Bulk rigid-rod molecular composites were successfully obtained by powder consolidation of a copolymer containing both the reinforcing rigid-rod segments and the thermoplastic matrix. By chemically linking the reinforcing segments and the matrix molecule, the copolymer was designed to minimize phase separation in the molecular composite. The copolymer was an articulated rigid-rod poly(p-phenylenebenzobisthiazole), aPBT, with an aromatic poly(ether ketone), mPEK, thermoplastic pendant grafted at the points of articulation. The copolymer powder was pre-formed and compression molded at an elevated temperature, which resulted in bulk rigid-rod molecular composites with three-dimensionally isotropic properties. Compared to the neat mPEK homopolymer, significant increases in glass transition temperature T_g and tensile properties have been realized for the aPBT-g(mPEK) copolymers with low rod content. Taking into account the aspect ratio of the aPBT, the bulk rigid-rod molecular composite showed a tensile modulus as predicted by the Halpin-Tsai equation. In addition, x-ray scattering revealed minimal rod aggregation. However, for the copolymer of higher rod content, significant phase separation was observed in the copolymer powder, which resulted in a decrease in T_g as well as reinforcement efficiency of the bulk rigid-rod molecular composite as compared to those derived from the copolymers of low rod content. © 1992 John Wiley & Sons, Inc.     

Correlation of the minor-phase orientation to the flow-induced morphological transitions in thermotropic liquid crystalline polymer/PBT blends

Immiscible blends of thermotropic liquid crystalline polymers (TLCP) and a flexible polymer matrix show viscosity reductions and extensive fiber formation under certain flow conditions. Here we study these phenomena by directly examining the TLCP component's molecular orientation and the dispersed phase morphology. The rheology and morphology of blends of polybutylene terephthalate and a thermotropic copolyester (HX-8000 series, DuPont) at concentrations varying from 5 to 30 wt % of TLCP are characterized. It is found that the blends show viscosity reduction as well as stable fiber formation at shear rates dependent on the TLCP content. Wide-angle X-ray scattering is performed to measure the degree of molecular orientation of the TLCP phase. A deconvolution scheme isolates the scattering from the TLCP in the blends and a molecular model enables extracting an experimental orientation factor. It was found that a highly microfibrillated TLCP phase is coupled with an increase in the TLCP molecular orientation to values close to the pure TLCP at similar processing conditions. Further, the microfibrillated TLCP phase is found to be stable within the testing time. Current hypotheses about fiber formation in immiscible blends are tested against the experimental observations. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1769–1780, 1998