聚对苯二甲酸丁二醇酯二聚体键离能的理论研究

采用密度泛函理论方法对聚对苯二甲酸丁二醇酯(PBT)二聚体的键离能进行了计算.为了选取较为精确的方法来计算PBT各个键的键离能,以与PBT具有相同的酯基官能团的乙酸乙酯为模型参照物.采用M062X, B3P86, M06, PBE0, wB97xD方法分别在基组6-31G(d), 6-311G(d), 6-311+G(d, p), 6-311++G(d, p), cc-pVDZ, cc-pVTZ水平下对乙酸乙酯的键离能进行计算.通过对比计算结果与iBonD数据库的乙酸乙酯实验测定值可知,M062X在基组6-311G(d)水平下计算结果与实验值最为接近.因此,本研究采用M062X方法在基组6-311G(d)水平下对聚对苯二甲酸丁二醇酯(PBT)二聚体的键离能进行计算.计算结果表明：在PBT的各键中C-C_arcmatic键的键离能最大,主链上的C-C键离能最小,为370.9 kJ/mol.其次就是C-O键,为404.6 kJ/mol.基于PBT键离能的计算结果,设计了3条PBT二聚体热降解过程可能形成的反应路径,分析了热解产物的形成机理.结果表明PBT二聚体热解过程可...     

对苯二甲酸乙二醇酯-ε-己内酯共聚酯中硬链段结晶特性研究

利用广角X射线衍射和傅里叶变换红外光谱研究了对苯二甲酸乙二醇酯-ε-己内酯(TCL)共聚酯中对苯二甲酸乙二醇酯(ET)硬链段的晶区结构和结晶特性。结果表明,在ET硬段含量较高的TCL共聚酯中,ET链段的结晶特性与纯的聚对苯二甲酸乙二醇酯(PET)基本相同。ET硬段晶区的尺寸和结晶度均随链段序列长度的减小而减小。     

对苯二甲酸乙二醇酯降解机理密度泛函的理论研究

采用密度泛函理论方法B3P86/6-31++G(d, p),对对苯二甲酸乙二醇酯一聚体降解反应机理进行了理论研究.设计了对苯二甲酸乙二醇酯一聚体纯热解、水解和醇解、水或醇作为催化剂降解过程的各种可能反应路径，对参与反应的各种中间体、过渡态及产物进行了几何结构优化和频率计算以获得热力学与动力学参数值.计算结果表明：当水或甲醇作为对苯二甲酸乙二醇酯热降解过程中的催化剂时，利用水或甲醇O-H中H提供到对苯二甲酸乙二醇酯一聚体主链酯键中O原子上形成对苯二甲酸，而乙烷基脱掉的H原子与水中羟基(-OH)或醇中甲氧基(-OCH₃)结合形成新的水或者甲醇，从而降低对苯二甲酸乙二醇酯热解过程中的反应能垒(251.4 kJ/mol→181.1 kJ/mol(甲醇)和187.5 kJ/mol(水));当水或甲醇作为对苯二甲酸乙二醇酯热降解过程中的反应物参与反应时，利用水或甲醇O-H中H提供到对苯二甲酸乙二醇酯一聚体主链乙烷基旁O原子上形成乙二醇，而水中羟基(-OH)或醇中甲氧基(-OCH₃)结合对苯二甲酸乙二醇酯一聚体主链羰基中C原子上形成对苯二甲酸或对苯二甲酸单...     

对苯二甲酸丁二酯-ε-己内酯多嵌段共聚物中硬链段的受限结晶

用差示扫描量热法（DSC）,广角X射线衍射（WAXD）,傅立叶变换红外光谱（FTIR）等技术研究了对苯二甲酸丁二酸－ε－己内酯多嵌段共聚物中硬链段的受限结晶。结果表明,PBT－PCL共聚酯中软硬链段在非晶区的混容性比较好,不同组成的样品均显示出一个玻璃化转变温度;对硬段含量超过50％的共聚物来说,硬链段可以结晶,而软链段不能结晶;由于硬链段的受限特点,BT硬链段的结晶受软链段的影响和制约,其结晶能力随硬段序列长度的增加而逐渐增大。     

聚对苯二甲酸乙二醇酯-双酚A型聚碳酸酯共混体系中聚合物伸直链晶体的形态分析

利用扫描电子显微镜(SEM)和原子力显微镜(AFM)等表征手段,研究了聚对苯二甲酸乙二醇酯-双酚A型聚碳酸酯(PET-PC)共混物的高压结晶样品。研究发现共混体系中存在具备不同形态特征的伸直链晶体,其中包括楔形晶体、弯曲晶体以及楔形弯曲晶体。通过对这些晶体的形态观察,揭示出体系中大尺寸聚酯伸直链单晶体的增厚生长首先要经历形成折叠链晶核的成核阶段,然后才是在酯交换反应和链滑移扩散两种机制共同作用下的等温增厚的链伸展过程。有助于深入理解PET-PC共混物中伸直链单晶体生长过程的本质因素,以便在类似聚合物体系中合成大尺寸的同类晶体。     

聚己内酯与不同纤维素衍生物形成的共混体系的红外光谱研究

用傅里叶变换红外光谱研究了聚己内酯与硝基纤维素、乙基纤维素和纤维素氨基甲酸酯所形成的共混体系中组分间的相互作用。对羟基基团、羰基基团以及聚己内酯结晶相相关的吸收谱带分析表明 :随着纤维素结构单元上羟基被取代程度的增加 ,纤维素衍生物的自身氢键相互作用明显减弱 ,而与聚己内酯之间的相互作用得到加强。这种相互作用的加强 ,显著改变了聚己内酯的结晶行为 ,使其结晶能力减弱。     

用红外光谱谱带分离技术定量测定聚对苯二甲酸乙二酯的结构

聚对苯二甲酸乙二酯(PET)的结晶状态与其脂肪链的内旋转构象有关。在晶区中,脂肪链均处于反式构象;而在非晶区中,既有左右式构象,也有反式构象。对应于这些结构,在红外光谱中会有不同的谱带。由于红外光谱法是表征结晶高聚物结构的有效手段,所以如何测定PET的这些结构一直是光谱学家感兴趣的课题。但是用红外光谱     

用红外谱带分离技术研究单向拉伸聚对苯二甲酸乙二酯薄膜的取向

用谱带分离技术可将聚对苯二甲酸乙二酯红外光谱中的1020cm~(-1)谱带分解为1204.2、1021.5和1017.8cm~(-1)三条谱带。可分别表征该高聚物中的晶区反式构象、非晶区反式构象和左右式构象三种结构。通过对这三条谱带的二向色性的测量,不需其他物理手段配合即可直接比较在不同拉伸条件下的聚对苯二甲酸乙二酯薄膜中上述三种结构的取向行为。     

聚对苯二甲酸乙二酯表面等离子体改性

纤维表面等离子体改性在学术上、工艺上都是很有意义的工作,人们对此甚感兴趣[1,2].我们利用射频电容耦合辉光放电产生等离子体,用静电双探针测量等离子体的电子温度和离子密度,用热电偶测量气体温度.研究等离子体与聚对苯二甲酸乙二酿(PET)的作用,拍摄了等离子体与PET作用时的     

聚对苯二甲酸乙二酯的拉曼光谱特性

为了研究聚对苯二甲酸乙二酯(PET)分子拉曼振动模式的特性,采用拉曼光谱法对PET纤维的拉曼光谱特性进行研究,并对PET纤维分别进行酸、碱、盐处理,获得酸、碱、盐处理前后纤维的拉曼光谱,分析与比较了处理前后拉曼光谱的特性;同时,采用原子力显微镜对其形貌结构进行观察。结果表明,在200～1 750 cm-1范围,NaOH处理的PET纤维的拉曼光谱强度高于未经处理的PET纤维,当拉曼频移大于1 750 cm-1时,经碱处理的PET拉曼峰强度低于未经处理的PET拉曼峰强度,且荧光背景减弱,H₂SO₄处理的PET纤维强度显著低于未经处理的PET纤维,CuSO₄处理的PET纤维强度较未经处理的PET纤维的强度明显增高。原子力显微镜测结果表明,碱和PET纤维分子的相互作用使化学键断裂,分子结构发生改变,经NaOH处理后的PET纤维表面较未经处理的PET纤维表面更为粗糙,H₂SO₄处理的PET表面相对未经处理的PET纤维表面粗糙度降低,经CuSO₄处理的PET纤维表面比未经处理的PET纤维粗糙度增加。PET纤维的拉曼光谱与原子力显微镜结果相一致,表明拉曼光谱与原子力显微镜的结合有望成为高聚物物性的表征技术。     

The Composition,Sequence Analysis,and Crystallization Characterization of Poly(Trimethylene‐co‐Butylene Terephthalate) Copolymer

A series of poly(trimethylene‐co‐butylene terephthalate) (PTBT) copolymers were prepared by direct esterification followed by polycondensation. The composition and sequence distribution of the copolymers were investigated by nuclear magnetic resonance (NMR). The results demonstrate that the synthesized PTBT copolymers are block copolymers and the content of poly(butylene terephthalate) (PBT) units incorporated into the copolymers is always less than that in the polymerization feed. The 1,4‐butanediol consumption by a side reaction leads to a relatively lower content of PBT units in the resultant copolymers. At the same time, the PBT and poly(trimethylene terephthalate) (PTT) sequence length distributions in the copolymers are different. The PBT segments favor a longer sequence length than do the PTT segments in their corresponding enriched copolymers. The crystallization rate of the copolymers becomes lower than the homopolymers, especially for PTT‐enriched copolymers. Compared with the PTT segment, the presence of PBT segments in the copolymers seems to accelerate crystallization. A wide‐angle X‐ray diffraction (WAXD) analysis indicates PTT and PBT units do not co‐crystallize. The reduced melting temperatures of the copolymers may be attributed to a smaller lamellar thickness and lateral size due to short sequence lengths.     

Poly(butylene terephthalate)/phenoxy blends: Synergistic behavior in mechanical properties

The mechanical properties of miscible poly(butylene terephthalate) (PBT)/poly (hydroxy ether of bisphenol A) (phenoxy) blends obtained by melt mixing have been studied by means of the tensile test. The crystallinity of the blends has been studied by means of DSC and density measurements. A synergistic behavior, principally in the break properties, at high PBT contents in the blends is observed. As can be seen from the torque and density data, this synergistic behavior is related with the high level of miscibility which seems to exist at high PBT contents compared with that of the high phenoxy content region.     

Crystallization kinetics of copoly(ester imide)s derived from PBT,trimellitic anhydride,and aliphatic diamines

The crystallization kinetics of copoly(ester imide)s based on poly(butylene terephthalate) (PBT), trimellitic anhydride, and diaminobutane (PEI-4), resp. diaminohexane (PEI-6) or diaminoethane (PEI-2) are investigated by means of time-resolved x-ray scattering employing synchrotron radiation. The PEI-4 and PEI-6 copolymers exhibit a remarkably high degree of crystallinity, which can be attributed to the formation of mixed crystals in the co-PEI-4 and to blockiness in the case of co-PEI-6. Whereas the pure PEI-4 forms large negatively birefringent spherulites, the co-PEI-4 and the PEI-6 homo- and copolymers form much smaller superstructures like axialites or ellipsoids. In the co-PEI-4 and co-PEI-6, the rate of crystallization is slower compared to the homopolymers due to the incorporation of the respective comonomer unit. The PEI-4 forms a second crystal modification upon drawing and subsequent crystallization, probably with a monoclinic unit cell. The PEI-6 crystallizes faster than PEI-4 due to the improved flexibility of the longer diamine component. In contrast, the crystallization of PEI-2 and its copolymers takes several hours and the equimolar co-PEI-2 remains completely amorphous.     

Poly(butylene terephthalate) Toughening with Butadiene-Epoxy-Functionalized Methyl Methacrylate Core–Shell Copolymer

Butadiene glycidyl methacrylate-functionalized-methyl methacrylate (PB-g-MG) core–shell copolymer was used to toughen poly(butylene terephthalate) (PBT). Fourier transform infrared (FTIR) spectra and torque tests showed that compatibilization reactions took place between the carboxyl and/or hydroxyl groups of PBT and the epoxy groups of PB-g-MG. Phase morphology results showed that the PB-g-MG core–shell particles dispersed in the PBT matrix uniformly. The addition of PB-g-MG significantly improved the mechanical properties of PBT. The elongation at break and the impact strength increased with the increase of PB-g-MG content. SEM results showed that the shear yielding properties of the PBT matrix was the main toughening mechanism. The relationship between complex viscosity and angular frequency of the PBT/PB-g-MG blends indicated that the melt viscosity was higher than that of pure PBT.     

POLY(ETHER-BLOCK-SULFONATED ESTER)COPOLYMERS. I. PHASE STRUCTURE AND PHYSICAL PROPERTIES*

The physical properties and a microphase-separated structure of multiblockcopolymers based on flexible segments of poly(1,4-oxytetramethylene)(PTMO) and rigid crystalline segments of poly(butylene terephthalate) (PBT) modified by ionic units were studied. Ionic copolymers were characterizedby limiting viscosity number, melt flow index, and tensile property measurements. The mechanical behavior of ionic poly(ether-block-sulfonated ester)(PESE) copolymers can be compared to that of conventional hard-soft thermoplasticelastomers. The phase structure was studied using differential scanningcalorimetry (DSC). Clearly, the DSC results show that the ionic unitsin the polyester segments have no significant influence on the microphaseseparation structure of PESE. A small reduction of the degree of crystallinitywith increasing content of ionic groups in the polyester rigid segments wasobserved. This results from the effect of ionic forces caused by incorporationof ionic units in the polyester segments.

     

Influence of Blend Composition on Crystallization of Poly(L-Lactic Acid)/Poly (Ethylene Oxide) Crystalline/Crystalline Blends

The effect of blend composition on crystallization morphology and behavior of a crystalline/crystalline blend, poly(l-lactic acid) (PLLA)/poly(ethylene oxide) (PEO), during slow, non-isothermal crystallization was studied by polarized light microscopy (PLM) connected with a hot-stage and differential scanning calorimetry (DSC). The results showed that all of the PLLA/PEO blends produced spherulites which gradually became bigger and looser, as well as coarser, with the increment of the PEO content, indicating that the PEO crystals was resided in the interlamellar or interfibrillar (between clusters of commonly oriented lamellae) regions of the PLLA spherulites. In the (25/75) and (10/90) blends, the nucleation and growth processes of the PEO spherulites could be clearly observed in the pre-existing PLLA spherulites. The onset crystallization temperature and the melting point of one component decreased with increasing the content of the other one owing to the good miscibility of the two components in the non-crystalline state and the interaction between their macromolecules, indicating that the crystallization of each component was influenced by the other one.     

CRYSTALLIZATION IN PARTIALLY MOLTEN ORIENTED BLENDS OF POLYCONDENSATES AS REVEALED BY X-RAY STUDIES*

Oriented fibers or films of binary polymer blends from polycondensates were investigated by two-dimensional (2D) wide-angle X-ray scattering (WAXS) during the finishing process of microfibrillar reinforced composite (MFC) preparation, that is, heating to a temperature between the melting temperatures of the two components, isothermal annealing, and subsequent cooling. It is shown that the crystallization behavior in such MFC from polycondensates depends not only on the blend composition, but also on thermal treatment conditions. Poly(ethylene terephthalate)/polyamide 12 (PET/PA12), poly(butylene terephthalate)/poly(ether ester) (PBT/PEE), and PET/PA6 (polyamide 6) composites were prepared in various compositions from the components. Materials were investigated using rotating anode and synchrotron X-ray source facilities. The effect of the annealing time on the expected isotropization of the lower melting component was studied in the PET/PA6 blend. It was found that PA6 isotropization took place after 2 h; shorter (up to 30 min) and longer (up to 8 h) melt annealing results in oriented crystallization due to different reasons. In PET/PA12 composites, the effect of PA12 transcrystallization with reorientation was confirmed for various blend compositions. The relative strength of the effect decreases with progressing bulk crystallization. Earlier presumed coexistence of isotropic and highly oriented crystallites of the same kind with drawn PBT/PEE blend was confirmed by WAXS from a synchrotron source.

     

Isothermal Melt Crystallization Kinetics for Poly(Trimethylene Terephthalate)/Poly(Butylene Terephthalate) Blends

The kinetics of isothermal melt crystallization of poly(trimethylene terephthalate) (PTT)/poly(butylene terephthalate) (PBT) blends were investigated using differential scanning calorimetry (DSC) over the crystallization temperature range of 184–192°C. Analysis of the data was carried out based on the Avrami equation. The values of the exponent found for all samples were between 2.0 and 3.0. The results indicated that the crystallization process tends to be two‐dimensional growth, which was consistent with the result of polarizing light microscopy (PLM). The activation energies were also determined by the Arrhenius equation for isothermal crystallization. The values of ΔE of PTT/PBT blends were greater than those for PTT and PBT. Lastly, using values of transport parameters common to many polymers (U*=6280 J/mol, T _∞=T _g – 30), together with experimentally determined values of T _m ⁰ and T _g, the nucleation parameter, K _g, for PTT, PBT, and PTT/PBT blends was estimated based on the Lauritzen–Hoffman theory.     

Synthesis of Poly(butylene terephthalate)/Attapulgite Nanocomposites by In-Situ Polymerization and Its Crystallization Behavior

Poly(butylene terephthalate) (PBT)/attapulgite (AT) nanocomposites were prepared via in-situ polymerization without pre-modification of AT. By this method, PBT chains were successfully grafted onto the surface of AT, which was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. Scanning electron microscope examination indicated the uniform dispersion of AT nanoparticles in PBT matrix. The crystallization behavior of PBT/AT nanocomposites was investigated by X-ray diffraction patterns, differential scanning calorimetry, and step-scan differential scanning calorimetry. The non-isothermal crystallization processes were analyzed with the Avrami, Ozawa, and Mo methods. Crystallization activation energies of the samples were also determined by the Kissinger method. The results indicated that AT could act as a heterogeneous nucleating agent in PBT crystallization and lead to an acceleration of crystallization, while AT also acted as a physical hindrance to retard the transport of polymer chains to the growing crystals.