Synthesis and characterization of a series of star-branched poly(ε-caprolactone)s with the variation in arm numbers and lengths

A series of star-branched poly(ε-caprolactone)s (SPCLs) was synthesized with structural variation of the arm numbers and lengths through ring-opening polymerization under bulk condition. Arm numbers were varied to be 3, 4, and 6 by using multifunctional initiating cores such as trimethylol propane, pentaerythritol, and dipentaerythritol, respectively. The lengths of the poly(ε-caprolactone) arms were varied by controlling the molar ratio of monomer-to-initiating hydroxyl group molar ratio ([CL]₀/[-OH]₀=5, 10, 15). Molecular weights were determined by both ¹H NMR end-group analysis and MALDI-TOF mass spectrometry, which gave reasonably consistent values. On the contrary, the GPC method failed to give accurate values of molecular weight of SPCLs due to the discrepancy with the linear standard. The branching architecture of SPCLs was evaluated by the branching ratio, g, which is the ratio of the mean-square radius of SPCL to that of liner counterpart, linear poly(ε-caprolactone) (LPCL), which is of the same chemistry and having the same molecular weight. The radii of gyration of SPCLs and LPCLs were determined using small-angle X-ray scattering (SAXS) from the initial slopes of Zimm plots, represented as 1/I(q) vs q² with I(q) and q being the scattered intensity and scattering vector, respectively. The g values were observed to decrease with increasing arm numbers, indicating more compact molecular structure for SPCLs with higher arm numbers, while no such effect was observed for arm length variation. Thermal properties as well as the degree of crystallinity of SPCLs were found to be also dependent on structural variations. The melting points and the degradation temperatures were observed to increase with increasing arm lengths but with constant arm number. On the other hand, arm number variation with constant arm length gave no such changes to the thermal transitions of SPCLs. However, for the SPCLs with equivalent molecular weights, the degree of crystallinity was found to decrease with increasing arm numbers.     

Potential tissue implants from the networks based on 1,5-dioxepan-2-one and ε-caprolactone

The synthesis and characterization of degradable polymeric networks for biomedical applications was performed. Cross-linked films of poly(ε-caprolactone) (PCL) and poly(1,5-dioxepan-2-one) (PDXO) having various mole fractions of monomers and different cross-link densities were successfully prepared using 2,2′-bis-(ε-caprolactone-4-yl) propane (BCP) as cross-linking agent. Reaction parameters were carefully examined to optimise the film-forming conditions. Networks obtained were elastomeric materials, easy to cast and remove from the mould. Effect of CL content and cross-link density on the final properties of the polymer network was evaluated. High CL content or degree of cross-linking led to increase in Young's modulus and decrease in elongation at break. An increase in crystalline domains in films having a higher CL content was observed by optical microscopy. A greater thermal stability was observed in films having a high CL content. The hydrophilicity of the materials could be tailored by changing the CL content. The surface of the films became rougher with higher CL content.     

Crystallization and thermoelectric behavior of conductive-filler-filled poly(ε-caprolactone)/poly(vinyl butyral)/montmorillonite nanocomposites

Crystallization and thermoelectric properties of poly(ε-caprolactone) (PCL)/poly(vinyl butyral) (PVB)/montmorillonite (MMT) nanocomposites containing carbon black (CB) have been studied as a functions of a small amount of amorphous PVB content and a wide range of molecular weight of PVB. X-ray diffraction data of PCL/PVB/MMT nanocomposites indicates most of the swellable silicate layers are exfoliated and randomly dispersed into PCL/PVB system. The band spacings of PCL spherulites in PCL/PVB/MMT nanocomposites decrease with increasing PVB content, and this indicates that increasing the PVB content greatly shortens the period of lamellar twisting. The presence of 1 wt% MMT and higher molecular weight of PVB also shorten the period of PCL lamellar twisting. Nucleation and crystallization parameters, such as growth rate G and Avrami exponent n, can be determined by using POM and DSC isothermally crystallized at 41 °C. For samples with the same CB content, the intensity of positive temperature coefficient (PTC) (I_PTC, defined as the ratio of peak resistivity to resistivity at room temperature) of the nanocomposites was increased as the content and the molecular weight of PVB increases. The change of the PTC property related to the morphological difference (i.e. period of lamellar twisting) in the nanocomposites can be discussed.     

高风电渗透率下考虑需求侧管理策略的智能微电网调度方法

提出了一种高风电渗透率下考虑需求侧管理策略的智能微电网调度方法。首先,考虑经济、环境成本指标、清洁能源就地消纳量以及可中断负荷和可转移负荷策略,建立了多目标优化调度模型。然后,引入ε约束法生成Pareto前沿解集,利用归一化方法求出最优折衷解。最后,基于24节点配电系统对所提方法进行分析验证。算例结果表明:建立的多目标优化模型能够有效提升清洁能源的消纳率,提高调度方案经济性,同时有效降低发电污染排放。采用的需求侧管理策略能够有效平抑负荷波动,达到削峰填谷的目的。     

A Facile Approach toward Thermoplastic Triple-Shape Memory Polymers

In this work, a ternary blend of polyolefin elastomer (POE), lauric acid (LA), and poly(ε-caprolactone) (PCL) with triple-shape memory effect (triple-SME) is reported. LA and PCL exhibit distinct thermal transitions and construct two reversible switching networks capable of fixing and releasing different temporary shapes under a mild condition. The ternary blend shows excellent triple-shape memory properties and good toughness. Besides, the permanent shape can be reconfigured by a simple thermal treatment. These particular features make the novel blend a competitive candidate for diverse applications. And the creative combination of crystalline small molecule and semicrystalline polymer expands the freedom for producing triple-shape memory polymers (triple-SMPs).     

纤维素醋酸酯接枝己内酯的聚合研究

以冰醋酸为溶剂,浓硫酸为催化剂,将取代度为2 4的二醋酸纤维素水解为取代度为1 4的醋酸纤维素(CA)。以此醋酸纤维素为接枝骨架,ε 己内酯(ε CL)为接枝单体,在辛酸亚锡的引发下,合成了醋酸纤维素/聚己内酯接枝共聚物(CA g PCL)。研究了反应物纯度、原料配比、引发剂与单体摩尔比、反应时间、反应温度对单体转化率(C%)、接枝率(G%)、接枝效率(GE%)的影响。结果表明,当反应温度为140℃,单体ε 己内酯与醋酸纤维素的质量比为4∶1,引发剂辛酸亚锡与单体ε 己内酯的摩尔比为0 005,反应时间为16h,C%,GE%和G%分别为46 8%,65 2%和122 1%。     

生物防腐剂ε-聚赖氨酸的稳定性

研究了ε-聚赖氨酸（ε-PL）在不同温度、pH、盐离子浓度条件下的稳定性及ε-PL适宜的贮存条件．结果表明：争PL在121℃处理60min仍具有优良的热稳定性;在pH4．0～7．5时ε-PL相对抑菌活性高于95％,但在pH8．0-9．0时其相对抑菌活性下降约15％;Na^＋,NH4^＋、Mg^2＋对ε-PL的相对抑菌活性无影响;而Ag^＋、Fe^2＋、Cu^2＋浓度大于0．8mol／L时,这些盐离子对供试菌的毒害作用显著于争PL的抑菌作用.ε-PL适宜的贮存条件是避光、低温,其稳定率大于97％．     

Crystallization behavior of polymer/montmorillonite nanocomposites. Part II. Intercalated poly(ε-caprolactone)/montmorillonite nanocomposites

The combination of surfactant modified montmorillonite (MMT) silicate layers, poly(ε-caprolactone) (PCL) and the adopted melt processing procedure results in intercalated nanocomposites in which the silicate layers act as nucleating agents for the crystallization of the PCL matrix and by which in turn the overall crystallization rate increases. At a sufficiently high MMT concentration and degree of supercooling the polymer-swollen silicate layer stacks disturb crystal growth, resulting in a decrease in the overall crystallization rate. Simultaneous, time resolved, synchrotron small and wide angle X-ray scattering experiments reveal that—when the retarding effect is absent at a sufficiently high temperature—the final semicrystalline structures of pure PCL and its nanocomposites are identical. The poorer nucleation in the case of pure PCL, however, results in a time wise smearing of primary and secondary crystallization whereas in the nanocomposites these events are well separated due to a nucleation induced, efficient and rapid primary crystallization. Secondary crystallization involves the insertion of new lamellar crystals in between the already existing ones.     

基于改进鲸鱼优化算法的血液供应链网络多目标鲁棒优化设计

为解决血液供应链网络设计中的不确定性问题,建立了一种血液供应链网络多目标鲁棒优化设计模型。首先,针对带有5个节点的血液供应链网络,建立考虑安全库存的、目标为成本最小、存储时间最短的优化函数,并采用ε约束、Pareto最优和鲁棒优化方法对已建模型进行处理,将多目标问题转化为单目标鲁棒问题;其次,对原有鲸鱼优化算法（WOA）进行改进,引入差分算法的交叉和变异理念,增强了搜索能力并改善了局限性,从而得到差分鲸鱼优化算法（DWOA）,并采用此算法对处理后的模型求解。通过数值实例,验证当测试问题相同时,优化模型在需求短缺方面比确定模型的短缺量平均少76%。因此,所提优化模型在应对需求短缺时更具优势;通过仿真对比分析图像,得出DWOA相比WOA、粒子群优化（PSO）算法和遗传算法（GA）中断时间更短并且成本更低。