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。     

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     

含液晶聚合物的原位复合材料中界面相容性的改善策略

综述了近年来含液晶聚合物的原位复合材料中增容技术的一些进展,主要了四种增容技术,即加入具有增容作用的第三组分;在分散相液晶聚合物的主链上引入与基体树脂主链中相同或相似的单元,酯交换反应和多元共混技术,简要描术字原位复合材料的发展趋势。     

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...     

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...     

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。     

热致型液晶共聚与聚烯烃的原位复合

用热致型液晶共聚酯作为成纤材料、聚烯烃为基体进行复合，在复合中引入界面改性剂。对共混体的熔体流动性、基体聚合物的结晶性能进行了研究，对两相界面结合原位复合材料的力学性能进行了分析测试。     

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...     

热塑性/热固性聚合物共混体系研究——乙炔端基砜/聚砜共混物的动态固化动力学

近年来,半互穿聚合物网络(SIPN)概念被用来研制能结合热塑性聚合物的加工性和热固性聚合物的高温性能的大分子体系,用于复合材料耐高温树脂基体。例如:乙炔端基酰亚胺低聚物与热塑性聚酰亚胺基SIPN,线性聚酰亚胺与热固性双马来酰亚胺基SIPN以及热塑性树脂与双腈基SIPN已有报道。研究结果表明共混物起到协同作用,易于加工并具有优异的性能。乙炔端基砜(ATS)树脂具有与聚砜树脂相类似的结构,被认为在将来代替环氧用于高性能粘合剂和复合材料树脂基体的候选者之一。其另     

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     

Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP

H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.     

Synthesis of a novel liquid crystal rod–coil star block copolymer consisting of poly(methyl methacrylate) and poly{2,5‐bis[(4‐methoxy‐phenyl)oxycarbonyl] styrene} via atom transfer radical polymerization

A bromine capped star‐shaped poly(methyl methacrylate) (S‐PMMA‐Br) was synthesized with CuBr/sparteine/PT‐Br as a catalyst and initiator to polymerize methyl methacrylate (MMA) according to atom transfer radical polymerization (ATRP). Then, with S‐PMMA‐Br as a macroinitiator, a series of new liquid crystal rod–coil star block copolymers with different molecular weights and low polydispersity were obtained by this method. The block architecture {coil‐conformation of the MMA segment and rigid‐rod conformation of 2,5‐bis[(4‐methoxyphenyl)oxycarbonyl] styrene segment} of the four‐armed rod–coil star block copolymers were characterized by ¹H NMR. The liquid‐crystalline behavior of these copolymers was studied by differential scanning calorimetry and polarized optical microscopy. We found that the liquid‐crystalline behavior depends on the molecular weight of the rigid segment; only the four‐armed rod–coil star block copolymers with each arm's M_n,_GPC of the rigid block beyond 0.91 × 10⁴ g/mol could form liquid‐crystalline phases above the glass‐transition temperature of the rigid block. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 733–741, 2005     

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     

甲壳型液晶高分子研究进展与展望

简要介绍了甲壳型液晶高分子的模型理论, 概述了当前国内外对甲壳型液晶高分子设计、 液晶相态、 性质及基于甲壳型液晶高分子的嵌段共聚物体系的设计和自组装性质等研究进展, 展望了今后的研究方向.     

Synthesis of a novel hybrid liquid‐crystalline rod–coil diblock copolymer

A series of novel rod–coil diblock copolymers on the basis of mesogen‐jacketed liquid‐crystalline polymer were successfully prepared by atom transfer radical polymerization from the flexible polydimethylsiloxane (PDMS) macroinitiator. The hybrid diblock copolymers, poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene}‐block‐polydimethylsiloxane, had number‐average molecular weights (M_n's) ranging from 9500 to 30,900 and relatively narrow polydispersities (≤1.34). The polymerization proceeded with first‐order kinetics. Data from differential scanning calorimetry validated the microphase separation of the diblock copolymers. All block copolymers exhibited thermotropic liquid‐crystalline behavior except for the one with M_n being 9500. Four liquid‐crystalline diblock copolymers with PDMS weight fractions of more than 18% had two distinctive glass‐transition temperatures. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1799–1806, 2003     

一种热致液晶聚酰胺嵌段共聚物的合成及其表征

以聚三乙二醇双(4-羧苯)醚(PEG3)、邻联甲苯胺和己内酰胺为单体,通过共缩聚的方法合成了一种嵌段共聚物,聚酰胺-酰胺.采用红外光谱仪、核磁、偏光显微镜、差热分析和广角X光衍射对其结构及性能进行了表征.研究表明,这种嵌段共聚物具有液晶性;与缩聚得到的热致聚酰胺液晶(TLCP)相比,共缩聚得到的热致聚酰胺液晶(TLCP-N6)热力学性能发生了改变,在很宽的温度范围内呈向列相,并且在一定条件下可形成固化诱导条带织构和剪切条带织构.     

热塑性聚酯醚液晶弹性体的合成与表征

液晶聚酯醚嵌段共聚物是一类新型的高分子材料,已有较多研究［１～３］．当共聚物中软、硬段比例适当,在一定温度范围内,这类液晶聚合物可能出现高弹性．但系统报道聚酯醚液晶弹性体的工作并不多．Ｌｅｎｚ［２］报道得到了类似橡胶的低强度、低模量和高伸长率的液晶弹...     

Miscibility and crystallization kinetics in blends of poly(ethylene terephtalate) and thermotropic liquid crystal polyesters

Binary blends of poly(ethylene terephtalate) (PET) and thermotropic liquid crystal polyester (TLCP) have been prepared by both solution and melt blending methods. The TLCPs utilized were Vectra (Hoechst Celanese), TR-4, a TLCP synthesized in our laboratory, and a block copolymer consisting of three TR-4 units followed by three PET units. The phase behavior of the blends was studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and optical microscopy. The results show that none of the blends is miscible, but significant interactions exist between the PET phase and the TLCP phase in the case of TR-4 and TR-4 block copolymer blends. These interactions lead to a different nucleation mechanism in these blends compared to that in PET/Vectra.     

SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTALLINE MULTI-BLOCK COPOLYMERS,POLY[1,6-BIS(4-OXYBENZOYL-OXY)HEXANE TEREPHTHALATE]-b-BISPHENOL A POLYCARBONATE

A series of liquid crystalline multi-block copolymers poly [1,6-bis(4-oxybenzoyl-oxy)hexaneterephthalate]-b-bisphenol A polycarbonate (PHTH-6-b-PC) with different segment lengths were synthesizedin tetrachloroethane by solution polycondensation in which hydroxyl terminated PC and acyl chlorideterminated PHTH-6 were used. It is found that block copolymers with high molecular weight and well-defined structures were obtained. All the block copolymers exhibit a nematic liquid crystalline texture.     

Blends of a thermotropic liquid‐crystalline polymer and a poly(butylene terephthalate)/organoclay nanocomposite

Blends were synthesized via the melt blending of a thermotropic liquid‐crystalline polymer (TLCP) and a poly(butylene terephthalate) (PBT) hybrid containing 2 wt % organoclay. A TLCP was also synthesized with side groups based on a nematic liquid‐crystalline phase. The blends of TLCPs with PBT hybrids were melt‐spun with different concentrations of the liquid‐crystalline polymer and different draw ratios (DRs) to produce monofilaments. Regardless of the TLCP concentration in the hybrids, transmission electron microscopy photographs proved that the clay layers of the organoclay were intercalated and partially exfoliated in the PBT matrix. At DR = 1, the maximum enhancement in the ultimate tensile strength was observed for blends containing 8% TLCP, and the tensile strength decreased with further increases in the TLCP concentration. The initial modulus monotonically increased with increasing TLCP concentration. When DR increased from 1 to 44, the increased stretching caused the tensile property to decrease significantly, debonding to occur, and voids to form. These trends with increasing DR were observed in all the systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3667–3676, 2004