Towards understanding the increase in strength of thermotropic polyesters with heat treatment

Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc.     

聚十二烷二元酸酯及其共聚酯的合成

通过直接熔融缩聚法合成了一系列聚十二烷二元酸酯，用GPC、^1H—NMR、FTIR对产物进行了表征，并讨论了预聚酯合成时催化剂浓度和种类、预聚反应温度、预聚初始醇酸摩尔比对聚合反应的影响。结果表明，在所选的三个催化剂体系中，氮化亚锡二水合物与对甲苯磺酸复合催化剂的催化效果最好；最佳反应条件：n对甲苯横酯／n二元酸=0．0021～0．0032，反应温度为160～180℃，醇酸摩尔比范围为1．05—1.10。     

PET-HBT嵌段热致性液晶共聚酯的合成

液晶高分子材料具有相当高的强度和模量，被誉为当代超级工程塑料．以对羟基苯甲酸甲酯、1，4-丁二醇为主要原料，经熔融酯交换合成双-对羟基苯甲酸丁二醇酯(BBHB)；以四氯乙烷为溶剂，采用溶液缩聚法将过量的BBHB与对苯二甲酰氯(TPC)合成端基为BBHB的齐聚物(PHBT)；以对苯二甲酸二甲酯与乙二醇为原料，经熔融酯交换合成对苯二甲酸双β-羟乙酯(BHET)，然后采用溶液缩聚法将BHET与少量的TPC合成端基为TPC的齐聚物(PTET)；最后以PHBT与PTET为原料，以四氯乙烷为溶剂，采用溶液缩聚法合成目标共聚酯(PET-HBT)。研究了共聚酯的双折射现象及热行为；用偏光显微镜观察了试共聚酯的织态结构并用FTIR表征了共聚酯的微观结构．     

芳香族热致液晶聚（对羟基苯甲酸－对苯二甲酸双酚A酯）的流变性能

用Ｉｎｓｔｒｏｎ３２１１型毛细管流变仪研究了以对羟基苯甲酸（ＰＨＢ）、对苯二甲酸（ＴＰＡ）和双酚Ａ（ＢＰＡ）为单体合成的共聚芳酯液晶熔体的流变性能。结果表明，切变速率、熔体温度及ＰＨＢ链节含量对切粘度和结构粘度有很大的影响。切变速率在１０～１０３／Ｓ、温度２９５～３３０℃范围内，共聚酯粘流活化能△Ｅη为７４．５～２０５．１（ｋＪ／ｍｏｌ）。液晶熔体在剪切流中存在屈服应力τｏ，随温度升高τｏ值降低。在低温、低切变速率下，共聚酯熔体的弹性很小，甚至呈现挤出收缩现象。     

KINETICS OF NON-ISOTHERMAL CRYSTALLIZATION OF POLY (ETHYLENE TEREPHTHALATE) MODIFIED BY POLY (ETHYLENE GLYCOL)

The non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) modified by poly (ethlene glycol) (PEG) were determined by DSC. The dual linear regression method was used to evaluate the relationship between the reciprocal of t 1/2 ( the half life of crystallization) and the appropriate temperature variable. The parameters such as the activation energy (Ed) for transport, the equilibrium melting temperature (T_m~0),the nucleation parameter (ψ),themaximum crystallization temperature (T_(e, max)), and the kinetic crystallizability (G) for the copolyesters were obtained. The influence of the PEG content in PET chains on the parameters characterizing crystallization kinetics and crystallization thermodynamics was discussed.     

含柔性间隔基的热致液晶性共聚酯的结晶形态

采用偏光显微镜、扫描和透射电镜从不同层次的结构水平上研究了含柔性间隔基热致液晶性共聚酯的结晶形态。在偏光显微镜下观察到典型的负光性球晶形态,透射电镜揭示了球晶是由厚度为10nm并沿着径向生长的片晶结构所组成,分子链沿晶片厚度方向取向排列。并研究了分子链的刚性程度对热致聚芳酯结晶性质的影响。结果表明,分子链刚性越大其结晶性和球晶的完善性越高。     

Preparation and characterization of aliphatic/aromatic copolyesters based on 1,4-cyclohexanedicarboxylic acid

A series of biodegradable aliphatic/aromatic copolyesters, poly(butylene terephthalate)-co-poly(butylene cyclohexanedicarboxylate)-b-poly(ethylene glycol) (PTCG), were prepared by a two-step melt polycondensation method and characterized by means of GPC, FTIR, NMR, DSC, TGA, etc. The effects of aliphatic ester content on the physical, mechanical and thermal properties, as well as in vitro and in vivo degradation behaviors were investigated. The decrease in mechanical strength was observed with an increase in poly(butylene cyclohexanedicarboxylate) (PBC) molar fraction. DSC results showed one melting point and two glass transition temperatures in all samples, and the melting temperature was found to go down gradually as more cyclohexanedicarboxylic acid (CHDA) was added. During the in vitro and in vivo degradation processes, erosion of the surface was dominant as evidenced by scanning electron microscopic observations. The copolyesters containing many CHDA units were featured by the higher water uptake and faster degradation due to much richer amorphous phase within them.     

Determination of percolation threshold electroactivity and phase behavior study on conducting blends of thermotropic polyesters and polyaniline

The new thermotropic polyester/polyaniline (PIn/PAni) blends have been prepared by solution blend of synthesized liquid crystalline poly[4,4′‐bis (ω‐alkoxy) biphenylisophthalate]s having four and six methylene units in spacer (PI4 and PI6) with PAni doped with camphorsolfonic acid (CSA). The percolation threshold electroactivity of prepared blend films has been determined by cyclic voltammetry. The effect of the PAni concentration, solvent nature and polyester structure on the electroactivity of the blends has been investigated. The extremely low percolation threshold of prepared PIn/PAni‐CSA blends from dimethylformamide (DMF) and m‐cresol solution was 3% weight of PAni‐CSA. The amount of conducting polymer necessary to retard the formation of the liquid crystalline (LC) phase is up to 45% by weight. Phase behavior studies by differential scanning calorimetry and polarizing microscopy show that blends with 45% of conducting polymer are both liquid crystal and conductive. The morphology of the blends has been investigated by scanning electron microscopy. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and characterization of segmented liquid crystal poly(azoxy polyester-co-polyoxypropylene)

In this study a series of a segmented copolyester, poly(4,4′-dioxy-2,2′-dimethyl-azoxybenzene dodecanedioyl) (PMABD)-co-polyoxypropylene 400 (POP), was prepared. The chain length of PMABD studied (n) was varied from 7.8-18.2, and that of POP was unchanged. The intrinsic viscosity of the segmented copolyesters was 1.04-1.30, and the number average molecular weight obtained was 2.53 × 10⁴?3.49 × 10⁴ g/mol. The mesophase texture and thermal properties of the segmented copolyesters were measured as functions of n. It was found that the insert of flexible POP between those liquid crystalline domains of PMABD did affect thermotropic properties of PMABD. As the n value was 9.0 and 7.8 (or 7.4 and 8.6% by weight POP) the texture appeared as cholesteric-like oily streaks. The effect could not be attained by simply copolymerizing a mesogenic moiety with a pair of spacers of different lengths. The fluidity and domain structure of the flexible dodecanedioyl-POP-dodcanedioyl segments are taken into account for the obtained results. © 1995 John Wiley & Sons, Inc.