含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含4，4＇－二羟基二苯砜结构的共聚酯

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含４，４＇－二羟基二苯砜结构的共聚酯董德文，池振国，倪玉山，丁孟贤（中国科学院长春应用化学研究所长春１３００２２）陈玉（东北师范大学分析测试中心长春１３００２４）关键词４，４＇－二羟基二苯酮，热致...     

含二羟基二苯酮系列热致液晶共聚酯的合成与表征──Ⅱ．含4，4＇－二羟基二苯酮，对苯二甲酸，对羟基苯甲酸，间苯二酚的共聚酯

采用直接熔融缩聚及固相聚合方法由４，４’－二羟基二苯酮（ＢＨＰ），对苯二甲酸（ＴＰ），对羟基苯甲酸（ＰＨＢＡ），间苯二酚（ＲＥＳ）成功地合成了四元共聚酯高分子，该聚酯的组成结构及性质由偏光显微镜、广角Ｘ－射线衍射、ＤＳＣ等手段进行表征，结果表明共聚酯具有向列型液晶特征．     

含二羟基二苯酮系列热致液晶共聚酯的合成与表征——Ⅱ.含4,4‘—二羟…

采用直接熔融缩聚及固相聚合方法由４，４’－二羟基二苯酮（ＢＨＰ），对苯二甲酸（ＴＰＡ），对羟基苯甲酸（ＰＨＢＡ），间苯二酚（ＲＥＳ）成功地合成了四元共聚酯高分子，该聚酯的组成结构及性质由偏光显微镜、广角Ｘ－射线衍射、ＤＳＣ等手段进行表征，结果表明共聚酯具有向列型液晶特征。     

含二羟基二苯酮热致液晶共聚酯的合成与表征（Ⅵ）──含二羟基二苯酮热致液晶共聚酯结晶结构的X射线衍射研究

以广角Ｘ－射线衍射（ＷＡＸＤ）对含二羟基二苯酮（ＢＨＰ）、对羟基苯甲酸（ＰＨＢＡ）、对苯二甲酸（ＴＰＡ）、问苯二酚（ＲＥＳ）的系列热致液品共聚酯进行了较为深入的研究，详细讨论了不同组成的共聚酯的结晶结构、结晶度、结晶颗粒大小等等。     

4,4’-对苯二甲酰基二氧二苯甲酸与脂二醇的共聚及液晶性能研究

以对苯二甲酸和对羟基苯甲酸为起始原料合成了液晶单体4，4’-对苯二甲酰二氧二苯甲酰氯（TOBC），用TOBC分别与癸二醇-1，10，己二醇-1，6，戊二醇-1，5，丁二醇-1，4和乙二醇进行缩聚反应，生成了一系列主链型热致液晶共聚酯。用DSC、热台偏光显微镜和X-射线衍射仪等对合成的共聚酯的液晶行为进行了表征，结果表明，合成的共聚酯均为向列型热致液晶，其液晶温度范围在20℃－68℃之间，并随着脂肪族二醇中亚甲基（CH2）单元的增加，共聚酯的熔融转变温度（Tm）和各向同性温度（Ti）均有规律的变化。表明主链型液晶共聚酯分子中柔性间隔基的大小对共聚酯的液晶性质有着明显的影响。     

含X-型二维液晶基元和反式-4,4''''-双(4-羟基苯基偶氮)二苯并-18-冠-6冠醚环的液晶共聚酯的合成与表征

以4,4＇-（α,ω-己二酰氧）二苯甲酰氯（M1）、2,5-二（对辛氧基苯甲酰氧基）氢醌（M2）和反式-4,4＇-双（4-羟基苯基偶氮）二苯并-18-冠-6（M3）为单体,通过溶液共缩聚反应,合成了一系列含X-型二维液晶基元和反式-4,4＇-双（4-羟基苯基偶氮）二苯并-18-冠-6冠醚环的主链型液晶共聚酯.共聚酯的分子量不高,[η]在0.37～0.25 dL/g之间.单体的化学结构通过IR、UV、H-NMR、MS和元素分析等方法确证.共聚酯的外观为黄色粉状固体,除CP9外,室温下不溶于CHCl3和THF溶剂.共聚酯的性质采用GPC、[η]、DSC、TG、WAXD和POM等方法进行了研究.发现所有的共聚酯加热到各自的熔融温度以上都能形成液晶态,在液晶态可以观察到近晶相的镶嵌织构或焦锥织构或破扇型织构和向列相的球粒织构或丝状织构或纹影织构.共聚酯的熔融温度（Tm）和各向同性温度（Ti）随共聚酯分子中反式-4,4＇-双（4-羟基苯基偶氮）二苯并-18-冠-6用量的改变呈规律性变化.WAXD研究进一步证实了共聚酯的液晶性.     

1,8-辛二酸改性热致液晶共聚酯的制备及其性能

以对羟基苯甲酸、对苯二甲酸和对苯二酚为共聚单体，经乙酰化和熔融缩聚两步法合成三元热致液晶共聚酯。引入长链脂肪族化合物1,8-辛二酸作为改性单体，按不同比例代替对苯二甲酸，制备了一系列含柔性链段的新型四元热致液晶共聚酯。通过傅里叶红外光谱(FT-IR)和核磁共振碳谱(¹³C-NMR)对共聚酯结构进行表征，采用差示扫描量热(DSC)和热失重分析(TGA)表征其热性能，采用偏光显微镜(POM)和X射线衍射(XRD)分析其液晶性能。研究表明，三元液晶共聚酯熔点达407℃，热稳定性优异。随着1,8-辛二酸含量增加，四元共聚酯熔点显著降至214℃，热稳定性较好，最大热分解温度达到428℃。该系列共聚酯显示了典型的向列型液晶织态结构。1,8-辛二酸的引入显著改善了液晶共聚酯的可加工性。     

新的含T－型二维液晶基元的液晶高分子的合成

采用低温溶液聚合方法，以Ｎ－（２，５－二羟基苯）亚甲基－４－取代苯胺和不同结构的二酰氯为单体，合成了两类新的高分子．聚合物的液晶行为用ＤＳＣ、偏光显微镜和Ｘ射线衍射进行了表征，发现其中一类为向列型热致液晶高分子，另一类则无液晶性．随单体结构的改变，聚合物的特性粘数、熔点（Ｔｍ）和液晶态的清亮点（Ｔｉ）均呈现规律性变化。     

一类可纺丝的全芳香热致性液晶共聚酯的合成和表征

利用Higashi芳香聚酯直接缩聚法的原理 ,采用一步混合投料直接缩聚的方法 ,以对羟基苯甲酸(PHB)、间苯二甲酸 (MPA)、4 ,4′ 二羟基二苯酮 (DHBP)和对苯二酚 (HQ)为单体原料 ,合成了全芳香共聚酯 .该合成方法反应条件温和 ,简单易控 ,产物分子量高 .用差热分析 (DSC)、热重分析 (TA)、偏光显微镜 (PLM)、广角X 射线衍射 (WAXD)等测试分析手段对共聚酯的热性能和液晶特性进行了表征 .研究结果表明 ,利用此方法合成所得的聚合物呈明显的向列型热致液晶特性 ,热稳定性高 ,并具有极易成纤的特点 ,有望成为一种可用于纺丝的全芳香热致液晶共聚酯材料     

4,4‘—对苯二甲酰基二氧二苯甲酸与酸二醇的共聚及液晶性能研究

以对苯二甲酸和对羟基苯甲酸为起始原料合成了液晶单体４,４’－对苯二甲酰地氧二苯甲酰氯（ＴＯＢＣ）,用ＴＯＢＣ分别与癸二醇－１,１０,己二醇－１,６,戊二醇－１,５,丁二醇－１,４和乙二醇进行缩聚反应,生成了一系列主链型热致液晶共聚酯。用ＤＳＣ、热台偏光显微镜和Ｘ－射线衍射仪等对合成的共聚酯的液晶行为进行了表征。结果表明,合成的共聚互均为向列型热致液晶,共液晶温度范围在２０℃￣６８℃之间,并随着脂肪     

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含4，4＇－二羟基二苯砜结构的共聚酯

hermotropic liquid crystalline copolyesters were synthsized from his(4-hydroxyphenyl) methanone (BHP), tereplithalic acid (TPA), p-hydroxybenzoic acid (PHB) and dihydroxydiphenyl sulfone(DPS). The properties of the copolyesters were characterized by polarized microscope with a hot stage, wide angle X-ray diffraction and differential scanning calorimetry. The results show that the copolyesters containing the BHP exhibit nematic liquid crystallinity.     

New polymer syntheses. LXVI. Copolyester of 4-hydroxybenzoic acid and 3-(4'-hydroxyphenoxy)benzoic acid or 4-(3'-hydroxyphenoxy)benzoic acid

Copolyesters of 4-hydroxybenzoic acid (HBA) and 3-(4'-hydroxyphenoxy)benzoic acid were prepared by two different procedures. Either the acetyl derivatives were polycondensed in bulk at temperatures up to 300°C or they were polycondensed in an inert reactions medium (Marlotherm-S) at 340°C. Two analogous series of copolyesters were synthesized from 4-acetoxybenzoic acid (4-HBA) and 4-(3'-acetoxyphenoxy)benzoic acid. The copolyesters were characterized by elemental analyses, inherent viscosities, ¹H- and ¹³C-NMR spectroscopy, WAXS and DSC measurements, and by optical microscopy. All copolyesters synthesized in solution were highly crystalline materials which were neither meltable nor soluble. Part of the copolyesters prepared by polycondensation in bulk were semi-crystalline, meltable, and soluble. The copolyester derived from 3-(4'-hydroxyphenoxy)benzoic acid proved to be thermotropic forming a nematic melt, whereas the isomeric copolyesters of 4-(3'-hydroxyphenoxy)benzoic acid only formed isotropic melts. © 1993 John Wiley & Sons, Inc.     

热致液晶共聚酯的熔融行为及结晶结构研究

采用ＤＳＣ及ＷＡＸＤ手段对含对羟基苯甲酸热致液晶共聚酯的相变行为及结晶结构进行了初步研究。结果表明，聚合物中存在两种同属于正交晶系的不同堆积形态结晶结构，在相变上表现为双重熔融峰。     

热致液晶性聚合物——含萘环主成分为对羟基苯甲酸的全芳香族共聚酯

由对乙酰氧基苯甲酸、对苯二酚二乙酯、2,6-萘二甲酸及间苯二甲酸四种单体通过熔融缩聚反应,合成了全芳香族四组分共聚酯。在一定的组成范围内,共聚酯熔体有很好的液晶性。本文重点讨论了聚合物的组成与性质的关系,热谱特征和液晶相行为。     

Effect of Polycondensation Reaction Conditions on the Properties of Thermotropic Liquid‐Crystalline Copolyester

In this study a range of wholly aromatic copolyesters based on kink m‐acetoxybenzoic acid (m‐ABA) monomer (33 mol%) and equimolar‐linear p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA) and terephthalic acid (TPA) monomers (67 mol%) have been synthesized by melt polycondensation reaction process at 280°C and 260°C for different time intervals. Characterization of copolyesters were performed by solution viscosity measurement, wide–angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), hot‐stage polarized light microscopy, proton‐nuclear magnetic resonance analysis (¹H‐NMR). According to the results obtained, copolyesters showed thermotropic liquid crystalline behavior in an appropriate temperature range. The copolyesters were prepared in high yields. It was observed that the intrinsic viscosities of the copolyesters are increased regularly with increasing polymerization time and temperature. All the copolyesters were soluble in a trifluoroacetic acid/dichloromethane (30:70 v/v) except the copolyesters which were synthesized at 280°C in 5 h. According to the WAXD results; the degree of crystallinity of copolyesters were found to be between 5–15%. DSC and hot stage polarized light microscopy results showed that all the copolyesters are melt processable and a significant molecular interaction exist in a very broad temperature range (160°C and 165°C) in the nematic mesophase. The T_g values are increased with an increasing polycondensation reaction time and temperature and they were observed between 93–126°C. Fibers prepared by a hand‐spinning technique from the polymer melt exhibit well‐developed fibrillar structure parallel to the fiber axis.     

PREPARATION AND PROPERTIES OF POLY （LACTIC ACID-CO-GLYCOL TEREPHTHALIC ACID） COPOLYESTER

To obtain a kind of biodegradable polymer material with satisfactory properties, a new biodegradable copolyester poly(lactic acid-co-glycol terephthalate) (PETA), was synthesized from three monomers of lactic acid, glycol and terephthalic acid. The resulting copolyesters, PETA, were characterized by FT-IR, 1H-NMR, DSC, TGA and by the ways of weight loss rate to characterize their biodegradability. The findings in this work indicated that, the TmS and TdS of copolyesters PETA increased with increasing contents of the terephthalic acid units. From the biodegradation tests in natural soil, boiling water, acid buffer solution and alkali buffer solution, it was shown that the biodegradability of copolyesters PETA decreased with increasing contents of the terephthalic acid units.     

PREPARATION AND PROPERTIES OF POLY(LACTIC ACID-CO-GLYCOL TEREPHTHALIC ACID)COPOLYESTER

1. INTRODUCTIONThe amount of industrial and municipal waste has been increasing all over the world. Therefore, the design and development of materials capable of being degraded into safe components under specific environmental conditions have become incre…     

热致性共聚酯液晶的研究——以双酚-对苯二甲酸酯为间隔段

热致性共聚酯液晶由于具有优异的热、机械及加工等性能,引起人们对其应用及基础研究的重视。本实验室曾对以不同长度碳链为软间隔段的共聚酯进行了研究,在产物介晶单元含量不高(约20％)时即可表现出明显液晶性。本文选用以双酚A(BPA)或双酚S(BPS)-对苯二甲酸酯为间隔段进行了研究。     

Novel poly(butylene succinate-co-lactic acid) copolyesters: Synthesis, crystallization, and enzymatic degradation

A series of aliphatic biodegradable poly(butylene succinate-co-dl-lactide) (PBSLA) copolyesters were synthesized with the aim of improving the degradation rate of poly(butylene succinate) (PBS) by incorporation of dl-oligo(lactic acid) (OLA) into the PBS molecular chains. The composition and sequential structure of the aliphatic copolyesters were investigated by proton nuclear magnetic resonance (¹H NMR) spectroscopy. The crystallization behaviors, the crystal structure and morphology of the copolyesters were investigated by using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarizing optical microscopy (POM), respectively. The results indicate that the crystallization of the copolyesters was restricted by the incorporation of lactide (LA) units, which further tuned the mechanical properties of the copolyesters. The copolyesters could form complete spherulites and exhibit the same crystal structure as that of PBS. Enzymatic study indicated that the copolyesters with higher content of LA units degraded faster, and the degradation began in the amorphous regions and then in the crystalline regions. The morphology and the resulting degradation products of the copolyesters were investigated by scanning electron microscopy (SEM) and ¹H NMR analysis during the degradation process.