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。     

聚对苯二甲酸-2,5-呋喃二甲酸乙二醇无规共聚酯的合成与表征

以对苯二甲酸、2,5-呋喃二甲酸(FDCA)和乙二醇为原料,钛酸四丁酯为催化剂,采用直接酯化法,通过改变对苯二甲酸与2,5-呋喃二甲酸摩尔比合成了一系列高分子量线性聚对苯二甲酸-2,5-呋喃二甲酸乙二醇无规共聚酯(PEFT).运用1H-NMR和13C-NMR表征并确立了共聚酯的结构,XRD结果显示该系列共聚酯在原生态状态下均为无定形聚集态结构,DSC结果表明该系列共聚酯只有一个玻璃化转变温度(73.3～84.2℃),介于PET和PEF之间,随着PEF含量的增加而增大.TGA结果显示该系列聚酯具有良好的热稳定性,起始热分解温度高于390℃,介于PET和PEF之间.拉伸测试结果表明共聚酯的组成对其力学性能有影响,其中PEFT-10,PEFT-70和PEFT-90的力学性能较好,优于PET.     

运用1H-NMR和13C-NMR研究聚对苯二甲酸-2,5-呋喃二甲酸乙二醇共聚酯（PEFT）的序列结构

采用直接酯化法,通过改变对苯二甲酸(PTA)与2,5-呋喃二甲酸(FDCA)的摩尔比,制备了一系列聚对苯二甲酸-2,5-呋喃二甲酸乙二醇共聚酯(PEFT)。运用1H-NMR和13C-NMR测试手段研究PEFT共聚酯的链结构。通过观察PEFT共聚酯链上乙二醇单元中氢原子和碳原子的化学位移及相应的4种信号的强度变化,计算出共聚酯的数均序列长度(L),无规度值(B)和共聚物的组成。通过Yamadera和Murano公式计算所得共聚酯无规度值B均接近于1,说明PEFT共聚酯为无规共聚物;PEF-block-PET嵌段共聚物B为0.577,PEF-blend-PET共混物的B为0;差示扫描量热仪(DSC)测试结果表明,0PEFT共聚酯均有一个玻璃化温度,进一步说明了PEFT共聚酯为无规共聚物。其中PTA∶FDCA的摩尔比为1∶1时,即PEFT-50,B值最大,基于1H-NMR谱图计算得B=1.012,13C-NMR谱图计算得B=1.028。上述结果表明,2,5-呋喃二甲酸与对苯二甲酸在与乙二醇的亲核取代反应中活性相近。     

新型成纤共聚酯

介绍了成纤共聚酯的研究工作主要是对聚对苯二甲酸乙二醇酯的研究、首先阐述了共聚单体的化学结构对共聚酯性能的影响。实验结果指出了经曲有限元 含有间）邻）位苯环结构和含柔性链结构的共聚是具有明显不同的物理例如,后者的玻璃化温度下降比前者大的多,前者的结昌速度减慢,而后乾的结晶速度加快。其次是阐述了共聚酯的物理性能对其纤维性能的影响,例如,玻璃化温度的降低有利于纤维染色性能的提高,含有柔性 的共聚酯玻璃化     

一种支氏液晶共聚酯的合成

在聚对苯二甲酸乙二醇酯与对羟基苯甲酸 (HBA)形成的共聚酯 (PET HBA)分子链中 ,引入具有分形结构的单体———三羟基苯 (TOP) ,以降低其熔点 ,改善加工性能 .考察乙酰化时间、缩聚时间、压力、TOP和HBA加入量对新型分形共聚酯的对数比浓粘度的影响规律 ,以及TOP和HBA加入量对新型分形共聚酯的熔点和液晶清亮点的影响 .TOP的加入能使PET HBA共聚酯的熔点下降 10℃以上 ,而液晶清亮点没有变化 ,拓宽了液晶区域     

PET/HBA/TA/HQ四元共聚酯形态及相结构的研究

研制了一套蚀刻方法并对聚对苯二甲酸乙二醇酯/对羟基苯甲酸/对苯二甲酸/对苯二酚(PET/HBA/TA/HQ)体系的共聚酯液晶试样断面进行蚀刻,并用扫描电镜观察,发现此类共聚酯中存在两相结构.当PET摩尔分数小于50％时,分散相呈球状且富含PET,连续相富含全芳族链段;当PET摩尔分数等于或大于50％时,分散相和连续相结构发生颠倒,连续相富含PET,分散相球状粒子富含全芳族链段且为纤维状结构.因此可以断言,用熔融缩聚方法制备的PET/HBA/TA/HQ四元共聚酯不是无规共聚物,而是嵌段共聚物.     

HDI作为扩链剂合成含PLLA和PBS链段的聚酯氨酯

以数均分子量为6350g/mol端羟基聚L-乳酸(PLLA-OH)与10500g/mol端羟基聚丁二酸丁二酯(PBS-OH)为预聚物,六亚甲基二异氰酸酯(HDI)为扩链剂,通过熔融反应制备了分子量高达30×104g/mol的可完全生物降解聚酯氨酯(PEU).研究了异氰酸根(NCO)与羟基比例对扩链反应的影响.结果表明,当[NCO]/[OH]=1∶1时,扩链效果最好,PEU分子量最大;PEU分子量随着预聚物中PBS含量增大而提高.通过核磁共振谱(1H-NMR)确定了PEU的结构与组成,并对聚酯氨酯进行了凝胶渗透色谱(GPC)、差示扫描量热(DSC)、热重分析(TGA)以及拉伸性能测试.DSC结果显示,扩链后PEU的结晶主要由PBS链段产生,而PLLA链段几乎不结晶;TGA结果表明,PEU的热降解分两步进行,第一步为PEU中PLLA链段的热降解,第二段为其中PBS链段的降解;拉伸测试结果表明,PBS与PLLA的共聚能够制备拉伸强度与断裂伸长率优异的聚合物材料.     

聚酯-聚酯多嵌段共聚物的合成及其动态力学性能

聚酯-聚醚多嵌段共聚物的动态力学性能谱上有两个T_8,不宜做阻尼材料。本文报道聚对苯二甲酸乙二醇酯(PET)-端羟基聚己二酸乙二醇酯(PEA)共聚物(简称嵌段共聚酯),比聚醚-聚酯多嵌段共聚物有更好的相容性。我们研究了PEA的分子量,间苯二甲酸的用量对嵌段共聚酯的结晶度,以及结晶度对嵌段共聚酯的动态力学性能的影响。     

基于异甘露醇和间苯二甲酸的光学共聚酯的合成及性能表征

合成了聚(对苯二甲酸乙二醇酯-共-对苯二甲酸异甘露醇酯-共-间苯二甲酸乙二醇酯-共-间苯二甲酸异甘露醇酯)(PEIIT).通过差示扫描量热分析(DSC)、紫外-可见-近红外光谱(UV-Vis-NIR)、X射线衍射(XRD)、偏光显微镜(POM)球晶培养等分析方法研究了PEIIT的结晶性能、光学性能及热性能.阐述了增加四元共聚酯PEIIT中间苯二甲酸结构单元的含量可以有效降低其结晶度和结晶速率的具体机制.间苯二甲酸结构单元含量的增加使PEIIT链段运动过程中的空间位阻增大,结晶能力降低,其冷结晶温度逐渐升高,热结晶温度逐渐降低直至不再有热结晶现象产生.由于结晶程度的降低,PEIIT的雾度可以完全降为零,并且透光率可以达到90.7%.同时发现了造成PEIIT透光率降低的吸光因素,黄变程度增加使330~550 nm波长的蓝紫光被PEIIT吸收,导致其透光率受到影响.PEIIT的熔点受间苯二甲酸含量变化影响较大,但仍保持了良好的耐热分解性能.     

分子间氢键的形成对聚丁二酸丁二酯结晶熔融及动态力学行为的影响

研究了含有酚羟基的小分子添加剂双酚A(BPA)对可生物降解高分子材料聚丁二酸丁二酯(PBS)的结晶、熔融及玻璃化转变的影响.研究表明在PBS中添加BPA,使PBS的结晶能力下降、熔点降低,这源于PBS与BPA通过氢键相互作用形成复合物,破坏了PBS的规整结晶结构.动态力学热分析表明,复合物的玻璃化转变温度随着BPA含量...     

Novel copolyesters containing naphthalene structure. II. Copolyesters prepared from 2,6-dimethyl naphthalate, 1,4-dimethyl terephthalate,and ethylene glycol

Copolyesters containing rigid segments (naphthalene and terephthalene) and flexible seg-ments (aliphatic diol) structure were synthesized from DMN/DMT/EG (2,6-dimethyl naphthalate/1,4-dimethyl terephthalate/ethylene glycol) ternary monomers with various mole ratios. Copolyesters having intrinsic viscosities of 0.52–0.65 dL/g were obtained by melt polycondensation in the presence of metallic catalysts. The effect of reaction tem-perature and time on the formation of the copolyesters was investigated to obtain an op-timum condition for copolyester manufacturing. The optimum condition for PNT (poly-ethylene naphthalate terephthalate) copolyester manufacturing is the transesterification under nitrogen atmosphere for 4 h at a temperature of 185±2°C followed by polymerization under 2 mm Hg for 2 h at a temperature of 280°C. Most copolyesters have better solubilities than poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) in various solvents. The effect of the starting mole ratio of DMN, DMT, and EG on the thermal properties of the resulted copolyesters was also investigated using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures of copolyesters were in the range of 70.7–115.2°C, and 10% weight loss in nitrogen were all above 426°C. © 1995 John Wiley & Sons, Inc.     

Thermally stimulated current and DSC studies of the broadened glass transition in liquid crystalline polymers

The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main T_g, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that T_g is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc.     

TRANSESTERIFICATION OF POLY(ETHYLENE TEREPHTHALATE) WITH POLY(ε-CAPROLACTONE)*

Transesterification of poly(ethylene terephthalate) (PET) with poly(ε-caprolactone) (PCL) was investigated bymeans of NMR spectroscopy, extraction experiments, differential scanning calorimetry (DSC) and phase contrast microscopy(PCM). The ~1H-NMR results show that transesterification takes place in the melt blends and leads to the formation of thePET-PCL copolyester with a chemical structure similar to ethylene terephthalate-ε-caprolactonc copolycster (TCL)synthesized directly from monomers. However, even in the blend that has been transesterified for 8 h, the random PET-PCLcopolyester, PET-PCL copolyester with long PET or long PCL segments and the unreacted PET and PCL homopolymersmay coexist. Due to the low mobility of PET and PCL chains and the high viscosity of the two macromolecules, thetransesterification proceeds with difficulty. Furthermore, PET is incompatible with PCL, the transesterification can onlyoccur at the interface or in the interfacial region between two phases, and finally the reaction can only reach a localequilibrium. These results indicate that in fact the transesterification in the melt blend between two incompatiblehomopolymers could not lead to the formation of completely random or typical block copolyesters.     

Hydrogen bonding effects in the glassy state of random copolyamides

The thermal behavior of random copolyamides which are used as model polymers with hydrogen bonds has been investigated by differential scanning calorimetry (DSC), x-ray diffraction, and infrared spectroscopy. The quenched copolyamides have only halo patterns in their x-ray diffraction photographs. A random copolymer of nylons 6, 66, and 610 (in a composition ratio of 3: 4: 3) was found to have 20% of unbonded amide groups immediately after quenching. When the sample was kept at the glass transition temperature (20°C), no change in x-ray diffraction was observed after the treatment. The free amide band in the infrared spectrum at 3450 cm^-1, however, was decreased in intensity by keeping the sample at the glass transition temperature. The transition peak height observed in a DSC curve also increased in the same experiment. Large glass transition peaks were found in DSC curves after annealing of the random copolyamides in the vicinity of the glass transition temperature. It is probable that the free amide groups in the amorphous chains were rearranged and formed new hydrogen bonds during the heat treatment at the glass transition temperature. Packing and restriction of the amorphous chains due to the increase in hydrogen bonding seemed to increase the height of the transition peak in a DSC curve. It is inferred from the above results that in the case of the random copolyamide, structures corresponding to a given enthalpy of the glassy state can be related to the number of hydrogen bonds.     

Thermal Behavior of Poly（trimethylene-co-ethylene terephthalate）

Poly (trimethylene-co-ethylene terephthalate) with various compositions of diol has been synthesized. The crystallization of copolyesters with high comonomer content was observed by both wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). It was found that the copolyesters become less crystallizable with the involvement of the comonomer, the crystals of crystallizable copolyesters come from PIT or PET homopolymers. The glass transition temperature (Tg) of the copolyester increases with increasing PET component in the copolyester, and the relationship between Tg and composition obey both Fox equation and additiv elaw, the former is better in describing this relationship.     

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     

Synthesis of High Performance Thiophene–Aromatic Polyesters from Bio-Sourced Organic Acids and Polysaccharide-Derived Diol: Characterization and Degradability Studies

In this work, the feasibility of replacing petroleum-based poly(ethylene terephthalate) (PET) with fully bio-based copolyesters derived from dimethyl 2,5-thiophenedicarboxylate (DMTD), dimethyl 2,5-dimethoxyterephthalate (DMDMT), and polysaccharide-derived 1,6-hexanediol (HDO) was investigated. A systematic study of structure-property relationship revealed that the properties of these poly(thiophene–aromatic) copolyesters (PHS(20–90)) can be tailored by varying the ratio of diester monomers in the reaction, whereby an increase in DMTD content noticeably shortened the reaction time in the transesterification step due to its higher reactivity as compared with DMDMT. The copolyesters had weight-average molar masses (Mw) between 27,500 and 38,800 g/mol, and dispersity Đ of 2.0–2.5. The different polarity and stability of heterocyclic DMTD provided an efficient mean to tailor the crystallization ability of the copolyesters, which in turn affected the thermal and mechanical performance. The glass transition temperature (T_g) could be tuned from 70–100 °C, while the tensile strength was in a range of 23–80 MPa. The obtained results confirmed that the co-monomers were successfully inserted into the copolyester chains. As compared with commercial poly(ethylene terephthalate), the copolyesters displayed not only enhanced susceptibility to hydrolysis, but also appreciable biodegradability by lipases, with weight losses of up to 16% by weight after 28 weeks of incubation.     

Broadened glass transition in a liquid-crystalline polymer studied by thermally stimulated currents,AC dielectric,dynamic mechanical,and DSC methods

Thermally stimulated currents (TSC), a. c. dielectric, dynamic mechanical (DMTA), and differential scanning calorimetry (DSC) methods were used to study the glass transition in a thermotropic liquid-crystalline copolyester. All the techniques were consistent in the determination of the main glass transition temperature. Using the high sensitivity of the TSC thermal sampling method, it was shown that cooperative glass transition-like relax-ations occur down to 100°C below the main glass transition. DSC was sensitive only to a broadening of the glass transition to about ca. 30°C, so it was concluded that the thermal sampling method is sensing a very small fraction of cooperatively relaxing species which cannot be detected by DSC. Ac dielectric measurements and DMTA also indicated that the glass transition was broad, but difficulties with overlapping transitions prevented quantitative determination of the breadth of the glass transition. The results suggest that the broad glass transition, in this mostly amorphous LCP, is due to chemical heterogeneity of the copolyester chain. Other evidence indicates that the broadening is not due to the oriented nature of the glassy state. Some discussion is presented concerning how the heterogeneous nature of the LCP glass leads to compensation of the Arrhenius curves obtained by the thermal sampling method. © 1993 John Wiley & Sons, Inc.