Effect of nucleation mechanism on complex poly(L‐lactide) nonisothermal crystallization process,part 2: Crystallization kinetics analysis

In the first part of this article, we reported the crystalline memory effect on the nonisothermal crystallization of poly(L ‐lactide). The experiments were carried out by using polymer single crystals growth from dilute solution as standard starting material. In this article (Part II), we have analyzed in detail the effect of the melting condition on the overall crystallization kinetics by applying the Nakamura‐Avrami model to DSC results. The absence or the low concentration of foreign infusible heterogeneous nuclei in our system allowed us to exalt the self‐nuclei role in polymer crystallization, to follow their concentration decrease during the melting process and to find the limiting melting temperature for their disappearance. Below such a temperature, a stable equilibrium number of self‐nuclei was observed, probably deriving from ordered structures, persisting in the melt, and originated from the single crystals thickening process during the polymer dynamic melting in the DSC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

可反应性纳米二氧化硅对聚乳酸结晶行为的影响

通过熔融共混法制备了聚乳酸（PLLA）／可反应性纳米二氧化硅（RNS）复合材料,用透射电子显微镜观察RNS在PLLA基体中的分散情况,用差示扫描量热仪（DSC）和X射线衍射仪（XRD）对复合材料的非等温结晶行为进行了研究,并利用Jeziomy法和Mo法对复合材料的非等温结晶动力学进行分析。结果表明,RNS在PLLA中分散均匀,RNS的加入虽不会改变PLLA的晶型,但RNS与PLLA之间的相互作用及其异相成核能力会对聚乳酸基体的结晶速率和结晶度产生影响,导致材料结晶过程发生变化。     

Construction of functional aliphatic polycarbonates for biomedical applications

Aliphatic polycarbonates are one important kind of biodegradable polymers and have been commonly used as integral components of engineered tissues, medical devices and drug delivery systems. As far as the biomedical application is concerned, traditional aliphatic polycarbonates usually suffer from the strong hydrophobicity, deficient functionality, and insufficient compatibility with cell/organs. Consequently, the application is quite limited in scope. Due to the imparted appealing properties, aliphatic polycarbonates bearing specifically designed functional/reactive groups attract great interest from researchers in the recent years. The present review outlines the development up to date concerning the design and biomedical application of functional aliphatic polycarbonates, with an emphasis on their ring-opening (co)polymerization preparation.     

High-Impact PLA in Compatibilized PLA/PCL Blends: Optimization of Blend Composition and Type and Content of Compatibilizer

In this work, the effectiveness of seven commercial compatibilizers is tested in polylactide (PLA)/poly(ε-caprolactone) (PCL) blends with different compositions to obtain a high-impact PLA. None of the compatibilizers is effective for 90/10 and 80/20 PLA/PCL compositions, as no improvement of the impact strength is observed. For the 70/30 composition, compatibilizers having glycidyl methacrylate (GMA) and acrylate groups in their structure are proved the most effective, as the morphological change towards co-continuity induced by them leads to significant impact strength improvements (of ≈345% and 90% with respect to the neat PLA and the noncompatibilized PLA/PCL 70/30 blend, respectively). The 70/30 PLA/PCL composition, as it shows the best balance of properties, and the best compatibilizer (ElvaloyPTW) are chosen to carry out the optimization of the compatibilizer content. It is found that adding 6 phr to the blend results in highly toughened and ductile blends while maintaining a high modulus and yield strength values. Larger compatibilizer contents lead to even higher impact strength values, but the low-strain mechanical properties are notably reduced. Thus, in this work, a simple and easily scalable method to produce high-impact PLA is shown, as it implies the compounding of three commercially available components without involving any toxic solvents.     

Preparation of core–shell type nanoparticles of diblock copolymers of poly(L‐lactide)/poly(ethylene glycol) and their characterization in vitro

Core–shell type nanoparticles of poly(L ‐lactide)/poly(ethylene glycol) (LE) diblock copolymer were prepared by a dialysis technique. Their size was confirmed as 40–70 nm using photon correlation spectroscopy. The ¹H‐NMR analysis confirmed the formation of core–shell type nanoparticles and drug loading. The particle size, drug loading, and drug release rate of the LE nanoparticles were slightly changed by the initial solvents that were used. The drug release behavior of LE core–shell type nanoparticles showed an initial burst during the first 12 h and then a sustained release until 100 h. The degradation behavior of LE block copolymer nanoparticles was divided into three phases: the initial rapid degradation phase, the stationary phase, and the rapid degradation phase until complete degradation. It was suggested that lidocaine release kinetics were predominantly governed by the diffusion mechanism in the initial burst phase and after that by both of the diffusion and degradation mechanisms. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2625–2634, 2002     

Synthesis and characterization of poly(L‐lactide)‐poly(ethylene glycol) multiblock copolymers

Poly(L‐lactide)‐poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. The reaction was carried out under mild conditions, using dicyclohexylcarbodiimide as the coupling agent and dimethylaminopyridine as the catalyst. The resulting copolymers were characterized by various analytical techniques, such as GPC, viscometry, ¹H‐NMR, FTIR, DSC, X‐ray diffractometry, and contact angle measurement. The results indicated that these copolymers presented outstanding properties pertinent to biomedical use, including better miscibility between the two components, low crystallinity, and hydrophilicity. Moreover, the properties of the copolymers can be modulated by adjusting the block length of the two components or the reaction conditions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1729–1736, 2002; DOI 10.1002/app.10580     

Crystallization and phase separation in blends of high stereoregular poly(lactide) with poly(ethylene glycol)

The effect of cooling rate on crystallization and subsequent aging of high stereoregular poly(lactide) (PLA) blended with poly(ethylene glycol) (PEG) was studied by thermal analysis and by direct observation of the solid state structure with atomic force microscopy (AFM). Blending with PEG accelerated crystallization of PLA. When a PLA/PEG 70/30 (wt/wt) blend was slowly cooled from the melt, PLA crystallized first as large spherulites followed by crystallization of PEG. The extent of PLA crystallization depended on the cooling rate, however, for a given blend composition the PEG crystallinity was proportional to PLA crystallinity. The partially crystallized blend obtained with a cooling rate of 30 °C min⁻¹ consisted of large spherulites dispersed in a homogeneous matrix. The blend was not stable at ambient temperature. With time, epitaxial crystallization of PEG on the edges of the spherulites depleted the surrounding region of PEG, which created a vitrified region surrounding the spherulites. Further from the spherulites, the homogeneous amorphous phase underwent phase separation with formation of a more rigid PLA-rich phase and a less-rigid PEG-rich phase. Decreasing the amount of PEG in the blend decreased the crystallization rate of PLA and increased the nucleation density. The amount of PLA crystallinity did not depend on blend composition, however, PEG crystallinity decreased to the extent that PEG did not crystallize in a PLA/PEG 90/10 (wt/wt) blend.     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

Effects of plasma treatment on biocompatibility of poly[(L‐lactide)‐co‐(ϵ‐caprolactone)] and poly[(L‐lactide)‐co‐glycolide] electrospun nanofibrous membranes

Poly[(l ‐lactide)‐co ‐(? ‐caprolactone)] (PLCL) and poly[(l ‐lactide)‐co ‐glycolide] (PLGA) copolymers are widely used in neural guide tissue regeneration. In this research, the surface modification of their hydrophilicity was achieved using plasma treatment. Attachment and proliferation of olfactory ensheathing cells on treated electrospun membranes increased by 26 and 32%, respectively, compared to the untreated PLCL and PLGA counterparts. Cells cultivated on both the PLCL and PLGA membranes showed high viability (>95%) and healthy morphologies with no evidence of cytotoxic effects. Cells grown on treated electrospun fibres displayed significant increases in mitochondrial activity and reductions in membrane leakage when compared to untreated samples. The results suggested that plasma treatment of the surface of the polymers enhanced both cell viability and growth without incurring any cytotoxic effects. © 2017 Society of Chemical Industry     

希夫碱镍金属催化对L-丙交酯的开环聚合

该文合成了3种希夫碱镍金属催化剂:NiL1〔乙二胺缩香草醛Ni(Ⅱ)〕、NiL2〔邻苯二胺缩3,5-二叔丁基水杨醛Ni(Ⅱ)〕、NiL3(1S,2S-二苯基乙二胺缩水杨醛Ni(Ⅱ)),并用1HNMR、X-ray单晶衍射等方法对新合成的催化剂NiL3进行了表征。以NiL1为催化剂通过单因素分析,选择合适的L-LA(左旋丙交酯)本体开环聚合条件,在该聚合条件下,对比不同配体结构特点的催化剂NiL1、NiL2、NiL3的催化聚合效果,结果表明,催化剂配体结构中引入供电子基团甲氧基有利于提高催化剂活性;配体结构中在金属活性中心周围增大位阻效应有利于得到相对分子质量(简称分子量,下同)分布较窄的聚合产物。