LIQUID CRYSTALLINE BEHAVIOR OF AROMATIC COPOLYAMIDE IN CONCENTRATED SULPHURIC ACID

The liquid crystalline behavior of anisotropic solutions in 100% sulphuric acid ofaromatic copolyamide obtained by low-temperature solution copolycondensation of tere-phthalic acid chloride (TPC), p-phenylene diamine (PPD) and 4, 4'-diamino-diphenylether(DAPE) has been studied by optical microscopy and X-ray diffeaction. The effects ofinherent viscosity, concentration of copolyamide in sulphuric acid, the content of the thirdmonomer (DAPE) and sequence distribution of copolyamide on the critical concentration,isotropic temperature, phase diagram and texture of liquid crystal were investigated. Theschlieren texture was observed and the results of X-ray diffraction indicate that the con-centrated solutions of copolyamide exhibit nematic liquid crystalline behavior.     

STUDY ON THE BLENDS OF NYLON 66 AND LIQUID CRYSTALLINE POLYESTERS

Blends of polyamide (Nylon 66) with two different kinds of liquid crystalline polyesters were studied in all the composition range. Homogeneous samples were obtained by coprccipitation from 2 wt%. solution of blends. The thermal properties, crystallinity and morphology of these blends were studied by using DSC, polarizing microscopy, and scanning electron microscopy. The phase transition and morphology of the blends are markedly-influenced by the composition of liquid crystalline polyesters. The mechanical behaviour of PHB/HNA-Nylon 66 blend was improved. although polyamidc (Nylon 66)with the liquid crystalline polyesters were incompatible, but a rather strong interaction between the polymers did exist.     

PREPARATION AND ELECTROCHEMICAL CHARACTERISTICS OF POLYMER ELECTROLYTE MEMBRANES BASED ON SAN/PVDF-HFP BLENDS

A copolymer of poly(acrylonitrile-co-styrene) (SAN) was synthesized via an emulsion polymerization method. Novel polymer electrolyte membranes cast from the blends of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), SAN and fumed silica (SiO2) are microporous and can be used in polymer lithium-ion batteries. The membrane shows excellent characteristics such as high ionic conductivity and good mechanical strength when the mass ratio between SAN and PVDF-HFP and SiO2 is 3.5/31.5/5. The ionic conductivity of the membrane soaked in a liquid electrolyte of 1 mol/L LiPF6/EC/DMC/DEC is 4.9×10-3 S cm-1 at 25℃. The membrane is electrochemical stable up to 5.5 V versus Li /Li in the liquid electrolyte. The influences of SiO2 content on the porosity and mechanical strength of the membranes were studied. Polymer lithium-ion batteries based on the membranes were assembled and their performances were also studied.     

PREPARATION AND SURFACE PROPERTIES OF ACRYLIC COPOLYMERS CONTAINING FLUORINATED MONOMERS

A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.     

PREPARATION AND CHARACTERIZATION OF POLY[STYRENE-co-4-(2-PHENYLTHIOETHYLTHIOMETHYL)STYRENE]

Sulfur-containing monomers have received special interest from researchers because of their outstanding opticalperformance. Using the reaction between 2-phenylthioethyl-1-mercaptan and p-chloromethylstyrene, a new vinyl monomer4-(2-phenylthioethylthiomethyl)styrene (PTETMSt) was synthesized. Its structure was characterized by FT-IR and NMR.Copolymerization of styrene and PTETMSt was investigated. The data show that poly(styrene-co-PTETMSt) has higher refractive index, lower density and percentage of water absorption. The copolymer can be used on optical materials.     

STUDY OF GRAFTING COPOLYMER OF STYRENE AND 2,2,6,6-TETRAMETHYL-4-PIPERIDINYL METHACRYATE ONTO POLYPROPYLENE DURING HEATING

The grafting of copolymer of styrene and 2, 2, 6, 6-tetramethyl-4-piperidinyl methacrylate onto polypropylene during heating was studied by IR and ESR. It is found that the graft reaction is going through the stable free radical > NO mechanism.     

EVIDENCE FOR THERMOTROPIC LIQUID CRYSTALLINITY OF A FUSIBLE POLYDIACETYLENE

The thermotropic liquid crystalline behavior of a fusible polydiacetylene has beenstudied by using polarizing optical microscopy and wide angle X-ray diffraction. It wasfound that the typical threaded texture can exhibit in the melt and the banded texture canbe observed when applied a gentle shear to the melt. The results indicate that thispolydiacetylene is really a thermotropic liquid crystalline polymer.     

SYNTHESES OF STYRENE-METHYL METHACRYLATE BLOCK COPOLYMER BY POLYAZOAMIDE AS INITIATOR

Polyazoamide(PAA) was used as initiator to prepare block copolymer P(MMA-b-St) byfree radical polymerization. The fraction of block copolymer was about 50%. The structureof the block-copolymer was characterized by IR and the results of ~1H-NMR and GPCshowed that the content of the block and the molecular weight (M_w) of the prepolymerand block copolymer could be controlled by varying the mol ratio of styrene/PAA andMMA/prepolymer. DSC and TEM results revealed that the block copolymer has twoseparated glass transition temperatures and phase separation within the domain structure.     

EFFECT OF DRAWING ON MORPHOLOGY,STRUCTURE AND MECHANICAL PROPERTIES OF BLENDS OF A LIQUID CRYSTALLINE POLYMER AND MODIFIED POLY(PHENYLENE OXIDE)

Polymer strands with various draw ratios of a thermotropic liquid crystalline polymer(LCP) and modified poly(phenylene oxide) were prepared by drawing the melts leaving aslit die in open air. The morphology, structure and mechanical properties of the resultingstrands were studied as a function of LCP content and draw ratio. It was found that thethermal and mechanical properties of the matrix phase did not change dramatically withthe amount of LCP and draw ratio, but the orientation of LCP phase could be increasedwith draw ratio. The mechanical properties of the strands could be improved by moderatelydrawing the melts. Wide angle X-ray diffraction suggested that the improvement in tensilestrength of the strands was due to the resultant fibrillation of LCP phase and enhancedmolecular orientation. Morphological observation indicated that excessive drawing of thestrands could lead to the break down of the microfibrils of LCP and thus resulted in thedecrease of mechanical strength.     

PREPARATION AND CELL COMPATIBILITY OF FUNCTIONALIZED BIODEGRADABLE POLY(DL-LACTIDE-co-RS-β-MALIC ACID

In order to create a functionalized biodegradable polymer for vascular tissue engineering application,poly(DL- lactide-co-RS-β-malic acid)(PDLLMAc)was synthesized.PDLLMAc was obtained after hydrogenolysis of poly(DL- lactide-co-RS-β-benzyl malolactonate)(PDLLMA),which was from the ring-opening polymerization of DL-lactide(DLLA) and RS-β-benzyl malolactonate(MA)using stannous octoate as catalyst.The copolymers were characterized by ~1H-NMR, FTIR,GPC and DSC.The tensile strength and water uptake of the copolymers were measured.In copolymerization,the proportion of MA in the derived copolymers was lower than that in the feeding dose,a consequence of its lower reactivity. The molecular weight of the copolymers decreased with increasing MA content.The protective benzyl groups were completely removed in hydrogenolysis.The glass transition temperature(T_g)of the protected copolymers decreased with increasing MA content.The mechanical strength test showed that the tensile strength of PDLLMA decreased while elongation increased with MA content increasing,and the tensile strength increased and elongation decreased with increasing malic acid content in PDLLMAc for the formation of hydrogen bonding.The water uptake showed that more hydrophilic malic acid adsorbed more water in PDLLMAc.In order to test the reactivity of functional pendant groups,bioactive RGD peptide was immobilized on the functionalized polymer film surface and smooth muscle cells(SMCs)were cultured on it. The results showed that the functionalized copolymer was biocompatible and could be potentially applied in vascular tissue engineering.     

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis,monomer reactivity ratios,thermal properties,and liquid crystalline behavior

Copolymers of a liquid crystalline monomer, 2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene (MPCS), with St and MMA were prepared by free radical polymerization at low conversion in chlorobenzene with 2,2′‐azobisisobutyronitrile (AIBN) as initiator. The copolymers of poly(MPCS‐co‐St) and poly(MPCS‐co‐MMA) were characterized by ¹H NMR and GPC. The monomer reactivity ratios were determined by using the extended Kelen–Tudos (EKT) method. Structural parameters of the copolymers were obtained from the possibility statistics and monomer reactivity ratios. The influence of MPCS content in copolymers on the glass transition temperatures of copolymers was investigated by DSC. The thermal stabilities of the two copolymer systems increased with an increase of the molar fraction of MPCS in the copolymers. The liquid crystalline behavior of the copolymers was also investigated using DSC and POM. The results revealed that the copolymers with high MPCS molar contents exhibited liquid crystalline behaviors. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2666–2674, 2005     

液晶聚酯与环氧嵌段共聚物的合成及表征

近年来 ,人们利用高分子液晶作为热固性环氧树脂的改性剂 ,不仅可以提高环氧树脂的韧性和强度 ,而且可以改善其热性能 ,为制备高性能的环氧树脂提供了一条新的途径[1,2 ] .目前报道所使用的液晶聚合物大多为液晶聚酯[3 ] 或液晶性聚氨酯[4] ,这些液晶聚合物与环氧树脂由于存在相容性不好的问题 ,给其实际应用带来了困难 .为了改善二者的相容性 ,本文采用溶液法合成了末端带有反应活性基团的聚酯型液晶聚合物 ,将它再与双酚Ａ环氧预聚物反应 ,制得了高分子液晶环氧嵌段共聚物 ,其合成路线如下 :2ＨＯＣＯＯＣＨ3+ ＨＯ(ＣＨ2 ) 6 ＯＨ　　Ｈ…     

端不饱和羧基环氧丙烷聚醚与苯乙烯共聚物的微相分离

用端乙烯基液体聚合物作单体可制得各种多嵌段多相聚合物.本文在端不饱和羧基环氧丙烷液体聚醚与苯乙烯共聚物互溶性研究的基础上,对分子运动进行了进一步的研究.用膨胀仪、红外、应力-应变和DSC确定和测定其中的组分分离运动,阐述组分分离对互溶性的影响.     

具有预期结构的苯乙烯与丙烯酸丁酯接枝共聚物的合成与表征

通过苯乙烯 (St)与 4 对氯甲基苯乙烯 (CMS)进行氮氧稳定自由基共聚合反应 ,合成了二元共聚物P(St co CMS) ,并以此共聚物引发丙烯酸丁酯进行原子转移自由基聚合 ,成功地合成了结构明晰的以聚苯乙烯为主链、聚丙烯酸丁酯为支链的接枝共聚物 ,研究了共聚合反应动力学 .P(St co CMS)和接枝共聚物的结构通过1 H NMR得到确认 ,并表征了接枝共聚物平均侧链数目和平均侧链长度     

长侧基甲壳型液晶高分子的合成及性质研究

设计并合成了一系列尾链为不同长度烷氧基的长侧基甲壳型液晶高分子聚[2,5-二(4 ′-烷氧基联苯氧羰基)苯乙烯]( PnCbiPCS,n=4,6,8,10,14).这些聚合物都具有良好的热稳定性.偏光显微镜及一维和二维广角X射线衍射等研究结果表明PnCbiPCS这一系列聚合物均能形成稳定的近晶A相结构,所对应的层间距随...     

ATOM TRANSFER RADICAL POLYMERIZATION OF 2,5-BIS[（4-HEXYLOXYPHENYL）OXYCARBONYL]STYRENE

A side-on liquid crystalline monomer, 2,5-bis[(4-hexyloxyphenyl)oxycarbonyl]styrene) (HPCS), was successfully polymerized via atom transfer radical polymerization (ATRP). The polymerization was catalyzed by CuBr/PMDETA in chlorobenzene at 90℃ with (1-bromoethyl)benzene as the initiator. The polymers have narrow MWD. It is the second example of mesogen-jacketed liquid crystalline polymer (MJLCP) prepared by ATRP.     

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.     

甲基丙烯酸丁酯和苯乙烯的原子转移自由基共聚

研究了甲基丙烯酸丁酯（ＢＭＡ）和苯乙烯（Ｓ）这两种不同极性单体的原子转移自由基嵌段共聚和无规共聚,得到了实测分子量与理论分子量相近,分子量分布较窄的嵌段共聚物和无规共聚物．聚合过程中分子量和单体转化率成比例增加,多分散性指数变化不大．用１Ｈ ＮＭＲ法测定共聚组成,Ｋｅｌｅｎ Ｔｕｄｏｓ法计算竞聚率．得到ｒＳｔ＝０９１,ｒＢＭＡ＝０３２．     

助催化剂对N催化剂催化乙烯-苯乙烯共聚反应的影响

研究了N催化剂分别与助催化剂AlEt3和Et2 AlOAlEt2 结合 ,在给电子体二苯基二甲氧基硅烷 (DDS)存在下 ,催化乙烯和苯乙烯共聚合反应 ,考察了Al Ti摩尔比对共聚反应的影响 .共聚产物经过丁酮 (MEK)和四氢呋喃 (THF)连续抽提 ,表明共聚产物包括无规聚苯乙烯 ,乙烯 苯乙烯共聚物和乙烯均聚物 .乙烯 苯乙烯共聚物分别用1 3C NMR、DSC和GPC进行表征 ,结果表明 ,助催化剂不仅对N催化剂的聚合活性有影响 ,而且对共聚产物中各级份的重量比例也有显著影响 ;特别是对乙烯 苯乙烯共聚物中苯乙烯的含量、熔点 (Tm)和玻璃化转变温度 (Tg)有明显的影响 .