侧基为磺酸根基团的聚丁二酸丁二醇酯共聚物的合成及应用研究

以丁二酸,富马酸和1,4-丁二醇为原料,通过溶液聚合的方法合成了一系列主链含有碳碳双键的不饱和脂肪族聚酯,聚(丁二酸丁二醇酯-共-富马酸丁二醇酯)P(BS-co-BF)s.以过量的Na HSO3为磺化试剂,合成了侧基为磺酸根基团的聚丁二酸丁二醇酯PBS共聚物P(BS-co-SBS)s.运用核磁共振氢谱(1HNMR),红外光谱(IR)和凝胶渗透色谱(GPC)表征了共聚物的化学结构及分子量.结合溶剂挥发和透析法研究了系列共聚物P(BS-co-SBS)s在水中的自组装行为.动态光散射(DLS)和透射电镜(TEM)的研究发现,系列共聚物P(BS-co-SBS)s均可自组装形成稳定的、具有核壳结构,表面带有负电荷的胶束(尺寸:103~165nm,PDI:0.187~0.264,zeta电位-35~-51 m V).载药和释药的结果显示,胶束对疏水药物阿霉素具有一定的缓释效果.     

爪形大分子柠檬酸-1,3-丁二醇-硬酯酸十六醇的合成、表征与降滤性质研究

以1，3-丁二醇、柠檬酸为原料，设计、合成了以1，3-丁二醇为核心的柠檬酸-1，3．丁二醇-柠檬酸（cBc）爪状物小分子；再用酯化反应依次与带有功能化集团的硬酯酸、十六醇接枝合成了多元酯类爪形大分子柠檬酸-1，3-丁二醇-柠檬酸-硬酯酸-十六醇（CBC-SH）．采用核磁共振、红外光谱对合成的两种化合物进行了结构表征，表明合成的CBC和CBC-SH与所设计的分子结构相吻合．元素分析确定了CBC和CBC-SH的化学组成依次为C16H22O14和C98H184O15．合成的CBC-SH溶于非极性的有机溶剂，不溶于水．将CBC-SH按600μg／g的加剂量添加到不同的轻柴油中，柴油的冷滤点可降低6℃．     

脂肪酶催化水解反应纯化α-生育酚琥珀酸酯

α-生育酚琥珀酸酯（α-tocopherol succinate）是天然维生素E的衍生物，它是由琥珀酸与α-生育酚的β-色酮环的6位羟基成酯而形成的化合物（图1），由于丧失了自由的羟基而不具有维生素E的抗氧化活性，在空气中较为稳定，因其可保护α-生育酚的6位羟基，使α-生育酚在储存和运输中稳定性增加，而广泛用于α-生育酚的运输和储存。     

聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯化学扩链反应

综述了用于聚对苯二甲酸乙二醇酯（ＰＥＴ）、聚对苯二甲酸丁二醇酯（ＰＢＴ）化学扩链反应的羧基加成型和羟基加成型扩链剂，以及缩合型扩链反应、羧基加成型扩链反应和羟基加成型扩链反应、羧羟基同时加成型扩链反应。讨论了扩链反应、反应特性和扩链产物的性能，并简要介绍了国内研究概况。参考文献２０篇。     

聚对苯二甲酸乙醇酯和聚对苯二甲酸丁二醇酯化学扩链反应

综述了用于聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯聚对苯二甲酸丁二醇酯化学扩链反应的羧基加成型和羟基加成型扩链剂，以及缩合型扩链反应，羧基加成型扩链反应和羟基加成型扩链反应、羟羟基同时加成型扩链反应。     

N-正辛基硼酸二乙醇胺酯催化合成2-羟基-4-正辛氧基二苯甲酮

N-正辛基硼酸二乙醇胺酯催化合成2-羟基-4-正辛氧基二苯甲酮;硼酸酯; 合成; 羟基正辛氧基二苯甲酮     

N-（5-氯-2-羟基苄基）氨基酸衍生物及其金属配合物的合成、表征及抑菌活性

以N-（5-氯-2-羟基苄基）氨基酸及其酯为配体,在室温下以水和甲醇为溶剂,采用分步法,以1∶1的摩尔比将配体与金属离子在弱碱性条件下混合,合成了20种未见报道的N-(5-氯-2-羟基苄基)氨基酸类金属配合物。 用核磁、红外和紫外光谱技术对其结构进行了表征。 证明在配合物中配体N-(5-氯-2-羟基苄基)氨基酸的羟基、胺基和羧基均参与了配位。 抑菌测试表明,N-(5-氯-2-羟基苄基)氨基酸类金属配合物的抑菌活性普遍高于其配体,尤其对白色念珠菌的抑菌效果更为明显,均高达100%。 对N-（5-氯-2-羟基苄基）席夫碱氨基酸酯的合成方法进行了优化,得到了较佳的合成工艺条件。     

三［（S）-α，α-二（4-甲基苯基）-2-吡咯烷甲醇］膦酰胺催化链状酮酯化合物的不对称还原反应

报道了三［（S）-α,α-二（4-甲基苯基）-2-吡咯烷甲醇］膦酰胺催化剂催化链状酮酯化合物的不对称还原反应。 研究发现,该方法对碳链长为5~11的链状酮酯具有较好的催化效果,在物质的量分数为5%手性膦酰胺催化作用下,产物手性羟基酯化合物的收率最高可达89%,对映体过量（ee）值最高可达95%。 此方法为手性链状羟基酯衍生物的合成提供了新选择。     

聚酰胺的合成——N-羟基-5-降冰片烯-2,3-双甲酰亚胺的双活性酯与脂族二胺间在温和条件下的缩聚反应

<正> 在合成聚酰胺的研究中,关于由N-羟基化合物O,O′-双酰基衍生物与二元胺在温和条件下合成聚酰胺的报道较少。Overberger及ebenda首先研究了N-羟基丁二酰亚胺的双活性酯及N-羟基邻苯二甲酰亚胺的双活性酯与派嗪间的缩聚反应。Ueda、Imai等则报道了另两类活性双酯,如1-羟基苯并三氮唑的双活性酯及O,O′-间苯二甲酰双肟与二元胺间的缩聚合成聚酰胺的结果。     

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．     

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.     

聚对苯二甲酸二甲酯/聚2,5-呋喃二甲酸二甲酯嵌段聚酯的合成与表征

以生物基单体2,5-呋喃二甲酸、乙二醇为原料合成聚2,5-呋喃二甲酸乙二醇酯(PEF)。采用熔融酯交换法以PEF聚酯部分取代聚对苯二甲酸乙二醇酯(PET),制备了系列PET-b-PEF嵌段共聚酯。通过核磁共振仪(NMR)、差示扫描量热仪(DSC)、热失重仪(TGA)、X射线衍射仪(XRD)等技术手段表征了共聚酯的结构和性能。结果表明,该系列共聚酯的玻璃化转变温度(Tg)在75.8~80.3℃之间,且随着PEF链段质量分数的增加,PET-b-PEF嵌段共聚酯的Tg先降低后升高,结晶度和熔融温度逐渐降低。当PEF链段含量高于15%时,共聚酯没有结晶峰。该系列共聚酯具有良好的热稳定性,起始分解温度在392.2~407.9℃之间,与所制备的PET起始分解温度403.3℃接近。且当共聚酯中PEF链段含量低于15%时,起始分解温度均在407℃左右,优于PET的热稳定性。     

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.     

含4，4＇－二羟基二苯酮热致液晶四元共聚酯的合成与表征

含４，４＇－二羟基二苯酮热致液晶四元共聚酯的合成与表征董德文，韩平，倪玉山，丁孟贤，韩伟（中国科学院长春应用化学研究所长春１３００２２）（吉林化工学院化工系吉林）关键词　热致液晶，共聚酯，向列型，二羟基二苯酮关于热致液晶芳香族聚酯的研究已有大量的报道...     

Thermal Properties and Crystallinity of Thermotropic Liquid Crystalline Copolyesters Prepared from Poly(ethylene terephtalate) (PET) and Rigid Aromatic Units

A series of copolyesters were synthesized by melt‐polycondensation reaction of poly(ethylene terephtalate) (PET) with various proportions of equimolar compositions of p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA) and terephtalic acid (TPA). Viscosity, liquid crystallinity, thermal properties, degree of crystallinity and thermal stabilitiy of these copolyesters were investigated by Ubbelohde viscometer, hot‐stage polarized light microscopy (PLM), differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD) and thermogravimetric analysis (TGA), respectively. On the basis of viscosity measurement, it was observed that intrinsic viscosity values of the copolyesters are increased regularly with increasing amounts of aromatic units (p‐ABA, HQDA and TPA) in the polymer chain. Thermotropic liquid crystalline behavior was observed in the copolyesters containing over 50 mol% of rigid p‐ABA/HQDA/TPA aromatic units. DSC analysis of the anisotropic copolyesters revealed broad and weak endotherms associated with the nematic phases, and the melting temperatures were found to be in the processable region. As the mol% of PET in the polymer chain increased, the specific enthalpies of fusion and the degree of crystallinity of the copolyesters were also increased regularly.     

Synthesis and characterization of biodegradable poly(butylene succinate-co-butylene fumarate)s

A series of aliphatic biodegradable polyesters modified with fumaric residues was synthesized by transesterification in the melt of dimethyl succinate, dimethyl fumarate and 1,4-butanediol. The amount of unsaturation, originating from the fumaric acid residues in the polyesters chains was varied from 5 to 20 mol%. The molecular structure and composition of the polyesters were determined by ¹H NMR spectroscopy. The effects of the content of fumaric residues on the thermal and thermo-oxidative properties of the synthesized polyesters were investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis. The degree of crystallinity was determined by DSC and wide angle X-ray scattering. The degrees of crystallinity of the unsaturated copolyesters were reduced, while the melting temperatures were higher in comparison to poly(butylene succinate). Biodegradation of the synthesized copolyesters was estimated in enzymatic degradation tests using a buffer solution with Rhizopus arrhizus lipase at 37 °C. Although the degree of crystallinity of the copolyesters decreases slightly with increasing unsaturation, the biodegradation is not enhanced suggesting that not only the chemical structure and molecular stiffness but also the morphology of the spherulites has an influence on the biodegradation properties. The highest biodegradability was observed for the copolyesters containing 5 and 10 mol% of fumarate units.     

非晶聚对苯二甲酸乙二酯的制备与表征

通过单体酯交换法和聚 2 ,6 萘二甲酸乙二酯 (PEN)与低分子量PET酯交换的方法分别合成了一系列NPA/TPA/EG和IPA/TPA/EG共聚酯 .随着NPA或IPA单元含量的增加 ,等温结晶速度迅速降低 ,共聚物的结晶性降低甚至非晶化 .由NMR分析得知单体酯交换法与聚合物酯交换法得到的共聚酯NPA/TPA/EG序列分布相近 ,链结构都接近完全无规 .由DSC结果分析 ,随共聚单体含量的增加 ,熔点和熔融热降低 ,结晶度也随之降低 .当NPA或IPA含量达到 2 0 %时 ,可以得到非晶的共聚酯 (APET) .本文还对共聚物组成与结晶温度的关系进行了表征     

New polymer syntheses. CIX. Biodegradable,alternating copolyesters of terephthalic acid,aliphatic dicarboxylic acids,and alkane diols

Copolyesters with an alternating sequence of terephthalic acid and aliphatic dicarboxylic acids were prepared with three different methods. First, dicarboxylic acid dichlorides were reacted with bis(2‐hydroxyethyl)terephthalate (BHET) in refluxing 1,2‐dichlorobenzene. Second, the same monomers were polycondensed at 0–20 °C in the presence of pyridine. Third, dicarboxylic acid dichlorides and silylated BHET were polycondensed in bulk. Only this third method gave satisfactory molecular weights. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry revealed that the copolyesters prepared by the pyridine and silyl methods might have contained considerable fractions of cyclic oligoesters and polyesters despite the absence of transesterification and backbiting processes. The alternating sequences and thermal properties were characterized with ¹H NMR spectroscopy and differential scanning calorimetry measurements, respectively. In agreement with the alternating sequence, all copolyesters proved to be crystalline, but the crystallization was extremely slow [slower than that of poly(ethylene terephthalate)]. A second series of alternating copolyesters was prepared by the polycondensation of silylated bis(4‐hydroxybut‐ yl)terephthalate with various aliphatic dicarboxylic acid dichlorides. The resulting copolyesters showed significantly higher rates of crystallization, and the melting temperatures were higher than those of the BHET‐based copolyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3371–3382, 2001     

Synthesis of high‐molecular‐weight aliphatic–aromatic copolyesters from poly(ethylene‐co‐1,6‐hexene terephthalate) and poly(L‐lactic acid) by chain extension

A series of aliphatic–aromatic multiblock copolyesters consisting of poly(ethylene‐co‐1,6‐hexene terephthalate) (PEHT) and poly(L ‐lactic acid) (PLLA) were synthesized successfully by chain‐extension reaction of dihydroxyl terminated PEHT‐OH prepolymer and dihydroxyl terminated PLLA‐OH prepolymer using toluene‐2,4‐diisoyanate as a chain extender. PEHT‐OH prepolymers were prepared by two step reactions using dimethyl terephthalate, ethylene glycol, and 1,6‐hexanediol as raw materials. PLLA‐OH prepolymers were prepared by direct polycondensation of L ‐lactic acid in the presence of 1,4‐butanediol. The chemical structures, the molecular weights and the thermal properties of PEHT‐OH, PLLA‐OH prepolymers, and PEHT‐PLLA copolymers were characterized by FTIR, ¹H NMR, GPC, TG, and DSC. This synthetic method has been proved to be very efficient for the synthesis of high‐molecular‐weight copolyesters (say, higher than M_w = 3 × 10⁵ g/mol). Only one glass transition temperature was found in the DSC curves of PEHT‐PLLA copolymers, indicating that the PLLA and PEHT segments had good miscibility. TG curves showed that all the copolyesters had good thermal stabilities. The resulting novel aromatic–aliphatic copolyesters are expected to find a potential application in the area of biodegradable polymer materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5898–5907, 2009     

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．