用于质子交换膜材料的侧链型磺化聚芳醚酮砜的光谱分析

采用直接缩聚的方法,通过调整氨基单体用量,合成出了系列带有不同氨基含量的聚芳醚酮砜(Am-PAEKS)聚合物,在聚合物侧链上进行后磺化接枝制备出了系列不同磺化度的侧链型磺化聚芳醚酮砜(S-SPAEKS),并且通过调整磺酸基团含量来控制聚合物的磺化度。通过红外光谱(FTIR)和氢核磁谱(1HNMR),对所合成的单体及其聚合物的结构进行了表征,S-SPAEKS红外光谱在1 239和1 060 cm-1处出现了磺酸基团中OSO的特征吸收峰,氢核磁谱中1.64 ppm处出现了处于烷基链中间位置的两个氢(—CH₂—CH₂—)化学位移,证明得到了S-SPAEKS聚合物。经热失重分析发现,聚合物中磺酸基团的脱落温度都高于240 ℃,聚合物主链降解温度都高于450 ℃。研究表明,该系列聚合物具有良好的热性能,可以用作质子交换膜材料。     

Intermolecular Hydrogen Bonding of Poly(Imino Imino Ketone Ketone)

Molecular dynamics calculations were made of the distance from the hydrogen atom of the imino group to the distance of the oxygen atom of the carbonyl group of poly(imino imino ketone ketone) (PIIKK). The results showed that theoretically there was hydrogen bond formation between the hydroxyl group and the carbonyl group of PIIKK. The existence of the hydrogen bonding between the polymer chains of PIIKK was confirmed by infrared spectrum analysis. Due to the existence of the hydrogen bonding, the glass transition temperature increased to 273°C from 143°C for poly(ether ether ketone) (PEEK).     

Rheological Behaviors and Properties of Poly (Ether Ether Ketone) In-Situ Blends: Effect of Chemical Structure of Added Thermotropic Liquid Crystalline Polyarylates

Abstract

Two kinds of thermotropic liquid crystalline polyesters (TLCP) with different chemical structures were used as flow modifiers during the melt spinning of poly (ether ether ketone). One of TLCPs, named PAT-S, was a kind of aromatic polyester synthesized from 4-acetoxybenzoicacid and 6-hydroxy-naphthoic acid, and the other one named, PEEKAR, was a block copolymer based on poly (ether ether ketene) (PEEK) oligomers and PAT-S oligomers. The effects of the chemical structures of the prepared TLCPs on the rheological behavior of the TLCP/PEEK blends were measured by rheological measurements, and then the structure and properties of the TLCP/PEEK in-situ blend fibers were studied by a series of methods, including differential scanning calorimetry (DSC), wide angle X-ray diffraction (WRXD), optical microscopy (OM), scanning electron microscopy (SEM), orientation degree tests, mechanical properties tests, etc. The results showed that the melt viscosity of PEEK could be effectively reduced by nearly 20% by adding a small amount of PEEKAR or PAT-S with the viscosity reducing effect of PEEKAR on PEEK being greater than that of PAT-S; this was mainly caused by the better compatibility between PEEK and PEEKAR because of the similar segment structures. The crystallinity of the PEEK fibers increased by nearly 50% with addition of both TLCPs, indicating that both the PEEKAR and PAT-S could serve as nucleating agent as well. The results from the morphology analysis clearly proved that PEEKAR had a better compatibility with the PEEK resin compared with PAT-S. The tensile strength of the PEEK fibers could be improved to some extent by adding PEEKAR, while it was obviously reduced after adding PAT-S.     

Crystal Morphology of High-Pressure Crystallized Bisphenol-A Polycarbonate

High-pressure crystallized bisphenol-A polycarbonate (BAPC) samples were investigated using wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The results showed that BAPC chain-extended crystals with c-axis thickness around 2.0 μm were developed through the melt crystallization. Furthermore, a high-crystallinity BAPC sample with a wide variety of microstructures was obtained by a stepwise double-heat treatment at high pressure. In the sample, individual spherulites can be easily exposed and isolated with selective etching, which results in open porous microspheres. These spheres provide the possibility to study the spherulite structure in three dimensions. The open porous microspheres may have functional applications, such as catalyst support and for other surface active materials.     

高压对溶液中聚左旋乳酸单晶生长的影响

采用高压技术实现了500 MPa下聚左旋乳酸(PLLA)在稀薄二甲苯溶液中的单晶生长,采用透射电子显微镜、拉曼光谱和红外光谱对样品的结晶形态和结构进行了表征,考察了高压对聚左旋乳酸单晶生长行为的影响。结果表明,在相同的结晶温度和时间下,高压结晶PLLA的单晶仍为α-型晶体,但单晶尺寸明显大于常压样品;高压环境下PLLA分子链在晶核两端的生长扩散速率不同,容易形成非对称的菱晶形态;高压影响PLLA晶体中分子链的构象分布;在单晶生长期,高压诱导有利于PLLA晶体成核,但不利于单晶生长。     

Micellization Process in Poly(Ether Urethane) Solutions

Poly(ether urethane)s containing different hard segments were investigated by viscometry, fluorescence spectra, polarizing optical microscopy, and scanning electron microscopy. The polarity dependence of the vibrational structure of the pyrene emission spectrum indicated the formation of aggregates at concentrations that are significantly below the critical concentrations that define the separation of dilute‐semidilute domains. Unlike the sample with 4,4'‐methylene diphenylene diisocyanate, the sample with 2,4‐tolylene diisocyanate in hard segments gives a fluorescence spectra in which the pyrene excimer appears. Supermolecular structures associated with the form of spherulites or of spherical micelles were detected by scanning electron microscopy. The results are discussed in correlation with viscometric data and optical microscopy.     

Nonisothermal Crystallization of Recycled Poly(Ethylene Terephthalate)/Poly(Ethylene Octene) Blends

Recycled poly(ethylene terephthalate) (r-PET) was blended with poly(ethylene octene) (POE) and glycidyl methacrylate grafted poly(ethylene octene) (mPOE). The nonisothermal crystallization behavior of r-PET, r-PET/POE, and r-PET/mPOE blends was investigated using differential scanning calorimetry (DSC). The crystallization peak temperatures (T _p ) of the r-PET/POE and r-PET/mPOE blends were higher than that of r-PET at various cooling rates. Furthermore, the half-time for crystallization (t _1/2 ) decreased in the r-PET/POE and r-PET/mPOE blends, implying the nucleating role of POE and mPOE. The mPOE had lower nucleation activity than POE because the in situ formed copolymer PET-g-POE in the PET/mPOE blend restricted the movement of PET chains. Non-isothermal crystallization kinetics analysis was carried out based on the modified Avrami equation, the Ozawa equation, and the Mo method. It was found that the Mo method provided a better fit for the experimental data for all samples. The effective energy barriers for nonisothermal crystallization of r-PET and its blends were determined by the Kissinger method.     

高压结晶PET/PC共混体系中大尺寸聚合物伸直链晶体的形态观察

 大尺寸聚合物伸直链晶体在低维体系物理学的研究中具有不可替代的重要作用。但以往高压合成的聚合物伸直链晶体,尺寸较小且合成时间过长,使其作用至今未能显现。加入10%（质量分数）聚碳酸酯（PC）于聚对苯二甲酸乙二醇酯（PET）中,在研究PET/PC共混体系高压结晶行为的过程中快速合成了大量生长厚度超过100 μm 的聚合物伸直链晶体,并采用扫描电子显微镜对其进行了深入研究。研究表明,高压结晶PET/PC共混体系中存在不同类型的大尺寸伸直链晶体：完善的伸直链晶体、沿平行或垂直于C轴方向发生断裂的伸直链晶体、内聚能密度较大而发生内聚破裂的伸直链晶体、不同断裂方式下呈不同形态的楔形状伸直链晶体以及弯曲的伸直链晶体。同时对不同形态伸直链晶体的形成机理作了阐述。     

Size-Frustrated Thickening Growth of Extended-Chain Crystals in a Poly (Ethylene Terephthalate)/Bisphenol A Polycarbonate Blend Under High Pressure

High-pressure crystallized blend samples of poly (ethylene terephthalate)/bisphenol A polycarbonate (PET/BAPC) were investigated with scanning electron microscopy (SEM), confocal laser micro-Raman spectroscopy, and a standard general area detector diffraction system (GADDS) X-ray micro-diffraction system. The results showed that long time annealing at high pressure could result in extended-chain polymer single crystals with thicker lamellae. However, the large size of such crystals was also found to frustrate their thickening growth along the c-axis thickness, as demonstrated by the observation of a novel wrinkled crystal. The winkled crystals with different morphologies were thought to be formed as the compromise between the kinetic pathway and the thermodynamic driving force during the size-frustrated thickening growth of the large polymer crystals. Further observations revealed that environmental confinement was the main factor responsible for the creation of the wrinkled structures in polymer extended-chain crystals. The present study may promote understanding of the fundamental nature of the crystal thickening in these binary polyester blends.     

Isothermal Crystallization and Melting Behavior of Composites Composed of Poly(L-lactic Acid) and Poly(glycolic Acid) Fibers

Several composites of poly (L-lactic acid) (PLLA) with poly (glycolic acid) (PGA) fibers were prepared. The isothermal crystallization kinetics and melting behavior of PLLA and all of the composites were characterized by using differential scanning calorimetry. The experimental data were processed by using the Avrami equation. The relative parameters, such as the Avrami exponent and half-time crystallization, revealed that PGA fibers had positive effects on the crystallization of PLLA, but these effects had only a minimal dependence on the PGA fiber content. Moreover, at low isothermal crystallization temperatures (85°C～110°C), recrystallization during the heating scan was observed, which could lower the melting point of the samples to a certain extent.     

Molecular Simulations of Physical and Chemical Properties of Poly(Imino Ketone)s

Six kinds of poly(imino ketone)s (PIKs) with different structures were designed, involving different ratios of carbonyl and imino groups, and the insertion of two types of bulky groups in the main chain. Under 3D periodic boundary conditions, simulations of physical and chemical properties for PIKs with six different structures on the molecular level, including fractional free volume (FFV) and melt density, solubility, and glass transition temperature, were carried out.     

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.     

Rheological Behavior of Blends of Poly(Phenylene Sulfide) with a Thermotropic Liquid Crystalline Aromatic Poly(Ether Ester)

A new type of thermotropic liquid crystalline aromatic poly(ether ester) (PEE) was prepared from 1,3-bis(4′-carboxyphenoxy)benzene, 1,4-diacetoxybenzene, and p-acetoxybenzoic acid through a melt transesterification process. The rheological behavior of blends of poly(phenylene sulfide) (PPS) with PEE was studied using a high-pressure capillary rheometer with the shear rate range of 50 s^?1 to 3000 s^?1. The results show that according to the range of shear rate, the flow curves of PEE/PPS blends can be divided into three zones: a first shear-thinning zone (n < 1, “n” represents non-Newtonian indexes), a shear-thickening zone (n > 1), and a second shear-thinning zone (n < 1), and the former two zones are more obvious with the increase of PEE content or elevated temperature. In the second shear-thinning zone, the PPS melt is close to a Newtonian fluid at high temperature and high shear rate; meanwhile the non-Newtonian behavior of the PPS melt at high temperature is enhanced with the addition of PEE. The apparent viscosity of PPS melts sharply dropped after adding PEE, especially at relatively low temperature and low shear rate. The curve of apparent viscosity vs. shear rate starts to flatten out after adding PEE, suggesting that the addition of PEE lowers the sensitivity of PPS to shear rate. As the content of PEE increases, the activation energy of the viscous flow, ΔE_η, of PPS decreases, which means that adding PEE weakens the temperature sensitivity of the apparent viscosity of the PPS melt. It can clearly be seen that the addition of PEE is beneficial to the processing of PPS.     

The Surface Wettability and Adhesion of Poly(Ester Urethane)s and Poly(Ether Urethane)s

In this study the wetting characteristics of untreated and plasma-treated polyurethane thin films were investigated. The degree of wettability was investigated by measuring the contact angle formed between a liquid drop and the solid surface. The work of adhesion, interfacial free energy, spreading coefficient, and Girifalco–Good's interaction parameter changed significantly for plasma-treated polyurethane films. Both complete and partial wetting were analyzed from the spreading coefficient of liquid drops on the solid substrate.     

High-Pressure Analysis of the Multiple Melting Endotherms of Poly(ethylene succinate) and Poly(butylene succinate)

The origin of the multiple melting peaks in two linear polyesters, poly(ethylene succinate) (PES) and poly(butylene succinate) (PBS), of isothermally crystallized samples was investigated by differential scanning calorimetry (DSC) at atmospheric pressure and high-pressure differential thermal analysis (HP-DTA) at elevated pressures. In PES, the DSC melting curves showed three endothermic peaks at slow heating rates, which decreased to two with increasing heating rates. The HP-DTA curves showed that the area (qualitative) and peak height of the high-temperature peak decreased with increasing pressure and merged with the low-temperature peak at pressures above 450 MPa. This behavior supported the melting, recrystallization, and remelting model for the observed multiple melting endotherms. In PBS, the DSC melting curves were similar to those seen in PES. The HP-DTA curves were also similar to PES up to 400 MPa, but above this pressure the area and the peak height of the high-temperature peak and the temperature difference between the high- and low-temperature peaks remained unchanged. This observation suggested that the two peaks in PBS were due to the melting of two populations of crystals with different lamellar thickness originally present in the sample. The multiple melting behavior in isothermally crystallized PBS is proposed to incorporate both the melting of two populations of crystals and melting, recrystallization, and remelting.     

Stretch-Induced Shish-Kebabs in Rubbery Poly(L-Lactide)

The oriented crystallization in stretched rubbery poly(L-lactide) has been studied with the aid of in-situ rheo-Fourier transform infrared spectroscopy (FTIR) measurements and morphological observations. The oriented segments that survived after stretching are first transformed into shish structure composed of helical sequences via intra-chain conformational ordering and propagation, followed by the transverse growth of kebabs from the coiled chains in the surrounding matrix. Moreover, the formation of shish structure and kebabs shows different dependences on the stretching temperature as a result of different controlling molecular processes.     

Phase Ordering and Crystallization Kinetics in Ultrathin Poly(ethylene oxide)/Poly(methyl methacrylate) Blend Films

Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane.     

用纳米压痕法分析溶剂对聚醚醚酮(PEEK)力学性能的影响

Poly (ether ether ketone)(PEEK) is a high-performance semi-crystalline thermoplastic polymer.Exposure of the polymeric surface to solvents can have a strong effect like softening/swelling of polymeric network or dissolution.In this study,nano-indentation analysis was performed to study the effect of acetone on the surface mechanical properties of PEEK using different exposure time.The experiments were performed with a constant loading rate (10 nm/s) to a maximum indentation displacement (1000 nm).A 30-second hold segment was included at the maximum load to account for any creep effects followed by an unloading segment to 80% unloading.The indentation hardness and the elastic modulus were computed as a continuous function of the penetration displacement in the continuous stiffness mode (CSM) indentation.The experimental data showed that the peak load decreased from ~5.2 mN to ~1.7 mN as exposure time in solvent environment increased from 0 to 18 days.The elastic modulus and the hardness of PEEK samples also displayed a decreasing trend as a function of exposure time in the solvent environment.Two empirical models were used to fit the experimental data of hardness as a function of exposure time which showed a good agreement with the experimental values.     

Miscibility and Hydrogen Bonding Interactions in Blends of Poly(hydroxyether ketone) and Poly(4-vinyl pyridine)

The influence of silica nanoparticles on the tensile properties of poly(ethylene terephthalate)(PET) fibers was investigated. The results showed that mechanical properties of PET fibers were improved through nano‐silica incorporation. Two maxima of the modulus‐strain curves of PET/silica nanocomposites (PETS) fibers are always higher than those of pure PET (PET0) fibers. The results of microstructure investigations suggested that the amorphous orientation factor of PETS fibers is higher than that of PET0 fibers. It is suggested that the increase of amorphous orientation factor contributed to the improvement of tensile properties of PET fibers. Considering the difference in modulus‐strain curves of PET0 and PETS fibers, it is believed that the addition of nanoparticles not only improved the amorphous orientation factor but also changed the load units of PET fibers when strained, which also resulted in the improvement of tensile properties.     

聚芳醚非共轭性电致发光材料与器件

由单体Ma[2,5-二(2-乙基-己氧基)-1,4-双-{2,2-[5-(对-氟代苯基)]-1,3,4-噁二唑基}苯]分别与三组分单体(双酚A、砜代双酚A或混合的双酚A)在N,N-二甲基乙酰胺／甲苯／碳酸钾的催化下于165℃进行亲核取代聚合反应得到淡黄色的固体,进一步纯化后得到含噁二唑杂环的聚芳醚型非共轭的新型有机电致发光材料PE1、PE2、PE3。引入双侧链取代基增强了该类材料的溶解性能,通过控制反应条件及调节聚合温度获得了高收率的聚合产物。分别测得其化学物理性能,制备了聚合物PE1、PE2、PE3的简单结构器件(ITO／polymer／Ca／Ag),首次获得了该类材料单层器件的蓝色有机电致发光,且该类材料具有较优良的热稳定性。