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.     

2-甲基-3-甲苯基喹唑啉-4-酮盐酸盐的合成研究

以邻氨基苯甲酸为原料，以不同的中间体和不同的脱水剂对2-甲基-3-甲苯基喹唑啉-4-酮的合成进行研究比较，寻找较佳的合成路径。     

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.     

Assessment of Bonelike® graft with a resorbable matrix using an animal model

Synthetic bone grafts have been developed to provide an alternative to autografts and allografts. Bonelike® is a patented synthetic osteoconductive bone graft that mimics the mineral composition of natural bone. In the present preliminary animal studies a user-friendly version of synthetic bone graft Bonelike® have been developed by using a resorbable matrix, Floseal®, as a vehicle and raloxifene hydrochloride as a therapeutic molecule, that is known to decrease osteoclast activity and therefore enhanced bone formation. From histological and scanning electron microscopy evaluations, the use of Bonelike® associated with Floseal® and raloxifene hydrochloride showed that new bone was rapidly apposed on implanted granules and also that the presence of the matrix and therapeutic molecule does not alter the proven highly osteoconductivity properties of Bonelike®. Therefore, this association may be one step-forward for the clinical applications of Bonelike® scaffolds since it is much more easy-to-handle when compared to granular materials.     

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).     

单烷基取代苯基哌嗪衍生物的合成

单烷基取代苯基哌嗪衍生物是合成苯基哌嗪类化合物的重要中间体。以二乙醇胺为起始原料,在10℃滴加氯化亚砜,室温反应1 h,再于60℃反应5 h,经氯代反应制得β,β′-二氯代二乙胺盐酸盐,然后分别与2-甲基苯胺、4-叔丁基苯胺、4-甲基苯胺在130℃反应50 h,得2-甲基苯基哌嗪盐酸盐、4-叔丁基苯基哌嗪盐酸盐、4-甲基苯基哌嗪盐酸盐3个目标化合物,收率分别为78%、61%、67%。其结构经1HNMR、13CNMR、MS证实与目标化合物的结构一致。