无机填料对聚乳酸成型加工性能的影响

研究了滑石粉、硅藻土、白炭黑填充聚乳酸材料的热稳定性、熔化特性及流变行为等成型加工性能。结果表明,无机填料对复合材料的热稳定性几乎没有影响,但填料的加入使PLA冷结晶温度向低温方向移动,PLA及其填充体系熔体流变特性属假塑性流动行为,黏度随温度变化明显。     

聚乳酸降解性能研究进展

聚乳酸是典型的绿色塑料,因其良好的生物相容性、完全可降解性及生物可吸收性,是生物降解医用材料领域中最受重视的材料之一。本文介绍了聚乳酸的降解机理,着重对近年来有关聚乳酸降解性能的研究进行了综述。     

聚乳酸改性及成型加工研究进展

针对生物可降解材料聚乳酸的一些缺点,提出了几种改性的方法,并对聚乳酸成型加工常用的两种方法,即挤出成型和注射成型做了介绍,最后对聚乳酸的应用进行了展望.     

液压脉动注射成型聚乳酸力学性能及生物降解性能的研究

在不同振动工艺参数下,研究液压脉动注射成型对聚乳酸(PLA)制品力学性能、结晶性能及生物降解性能的影响.结果表明,与普通注射成型相比,液压脉动注射成型的PLA制品拉伸强度提高了10.6%,冲击强度提高了29.7%,结晶度提高了11.9%.在蛋白酶K催化降解下,其生物降解过程是从表面侵蚀到内部整体侵蚀的逐步演变过程,制品总降解速率比普通注射成型的小.     

聚乳酸/天然纤维复合材料成型加工研究进展

综述了天然纤维增强聚乳酸基复合材料的成型加工方法包括挤出成型、注射成型、模压成型,其中着重阐述了模压成型包括简单预混模压、层叠模压、纤网模压、缠绕模压等的工艺特点和潜在应用。     

聚乳酸生物复合材料降解性能的研究

研究了使用土埋法降解后,经聚乙二醇400改性前后的聚乳酸/热塑性淀粉复合材料其质量和力学性能的变化,进而分析聚乳酸生物复合材料的降解性能。结果表明:在改性前,样条的降解性能随着热塑性淀粉含量的增加而变得更好;经过PEG400改性后,样条的降解率随着PEG400含量的增加而增加,说明PEG400在一定程度上促进了复合材料的降解。     

可生物降解性高分子材料——聚乳酸

主要介绍了可生物降解高分子材料－聚乳酸的合成、基本性能,聚乳酸纤维和聚乳酸塑料的成型加工及主要用途。     

聚乳酸注塑加工技术

聚乳酸（PLA）以其良好的机械加工性能，优越的生物降解性能及植物原料来源，被誉为本世纪最具发展前景的绿色环保材料。随着聚乳酸使用范围的日益广泛，其加工技术也逐渐受到了产业界的重视，虽然可把聚乳酸当作一种通用树酯来对待，但是与其他通用树酯相比，聚乳酸的注塑加工过程仍然存在着一些独特之处。[编者按]     

聚乳酸的研究进展及其应用

综述了国内外关于生物可降解材料聚乳酸(PLA)的物理、化学与复合改性的研究进展,并介绍了其成型加工方法与应用领域。     

阻燃竹纤维增强聚乳酸复合材料降解性能的研究

以聚乳酸(PLA)为原料,乙酰柠檬酸三丁酯(ATBC)为增塑剂,利用竹纤维作为增强体,加入聚磷酸铵/淀粉/甲酰胺、双氰胺(APP/TS/FD)混合膨胀型阻燃剂,制备阻燃型竹纤维/PLA复合材料,通过分析土埋、热老化两种条件下,复合材料表面形貌、燃烧性能、热性能、吸水性能、力学性能的变化,研究竹纤维增强PLA复合材料的降解性能。研究表明,在热老化情况下,复合材料的力学性能变化更为明显,在80℃下热老化12天后复合材料的拉伸强度和弯曲强度分别降低了86.6%和77.1%,而土埋3个月后的拉伸强度和弯曲强度分别降低了71.9%和61.8%,处理前后复合材料的燃烧性能和热性能均无明显变化。     

聚L-乳酸的热性能研究

为了了解聚L-乳酸(PLLA)自身结构特点,更好地控制其成型加工过程,研究了PLLA的非等温结晶行为、熔融行为和热失重过程。结果表明:降温速率对PLLA的非等温结晶过程具有显著影响,在1℃/min的降温速率下,PLLA的结晶起始温度为121℃,结晶焓为3.363 J/g;PLLA的熔融双峰遵循熔融-再结晶的机理;PLLA热分解温度在300℃左右,且随升温速率的增加而增大。     

Unique Crystallization Behavior of Poly(L-lactic acid) Nucleated by Stereocomplex with Different Fine Structure

Effect of the addition of poly(D-lactic acid) (PDLA) as stereocomplex (SC) on crystallization behavior of poly(L-lactic acid) (PLLA) had been systemically investigated. The result indicated that the inclusion of PDLA with higher MW into PLLA exhibited lower t _1/2 and showed accelerated crystallization behavior. Meanwhile, SC formed in blends with higher MW of PDLA exhibited enhanced nucleation activity. In combination with both DSC and WAXD analysis, it was believed that nucleation process was more related to the crystalline size of SC. The result in this study would provide guidance for the application of SC as nucleating agent for the PLA-based products.     

聚乳酸/纳米二氧化钛复合材料的制备及其性能研究

以纳米二氧化钛对聚L-乳酸进行共混改性,并对所得PLLA/TiO2复合材料的结构与性能进行了分析表征。实验结果表明,所得复合材料处于无定型态,退火处理后结晶,TiO2不改变PLLA基体结晶的α晶型,但结晶衍射峰强度随TiO2添加量增加而减弱。TiO2对PLLA基体的结晶性能和熔融行为影响较小,表明TiO2对PLLA的异相成核作用有限。     

Kinetics of crystal nucleation of poly(L-lactic acid)

The kinetics of crystal nucleation of poly(L-lactic acid) (PLLA) has been analyzed by fast scanning chip calorimetry in a wide temperature range between 313 and 383 K, that is, between temperatures about 30 K below and 40 K above the glass transition temperature. The relaxed melt was rapidly cooled to the analysis temperature and subsequently aged between 10⁻¹ and 10⁴ s, to permit formation of nuclei. The number of formed crystal nuclei has been probed by analysis of the crystallization rate at 393 K. The nucleation rate is maximal at 370–375 K and decreases monotonously with decreasing temperature in the analyzed temperature range. The observation of a monomodal dependence of the nucleation rate on temperature points to predominance of a single nucleation mechanism in the analyzed temperature range, regardless nucleation occurs in the glassy or devitrified amorphous phase. The collected data suggest that nuclei formation at ambient temperature requires a waiting time longer than about 10⁸ s. The performed study is considered as a quantitative completion of nucleation-rate data available for PLLA only at temperatures higher than 360 K, suggesting that the nucleation mechanism is independent on temperature in the analyzed temperature range between 313 and 383 K.     

Unique Homo-Crystallization and Melting Behavior of Poly(L-lactic acid): Influence of Stereocomplex with Varied Structure

Homo-crystallization and melting behavior of poly(L-lactic acid) (PLLA) with poly(D-lactic acid) (PDLA) (≤10 wt.%) was studied. The different thermal history had been applied to exert structural variation on stereocomplex (SC). The PLLA/PDLA blend showed different crystallization and melting behavior when cooled from 250°C or 200°C. Double melting peaks were observed after the blend was cooled from 250°C. SC annealing at different temperatures exhibited significant effect for melt-crystallization of PLLA. Influence of initial melting condition before cooling was also investigated. The cold crystallization of amorphous blend initially was studied and some novel results had been observed.     

The relationship between solubility and nucleating effect of organic nucleating agent in poly(L-lactic acid)

N,N′-bis(benzoyl) hexanedioic acid dihydrazide (BHAD), and N,N′-bis(benzoyl) terephthalic acid dihydrazide (BTAD) were synthesized as the organic nucleating agents for poly(L-lactic acid) (PLLA). These two organic compounds exhibited different nucleating effect to PLLA. When the concentration was very low, BTAD was able to nucleate PLLA, while BHAD was not. When the concentration was adequate, BHAD showed better nucleating effect than BTAD. The experiments showed that, BHAD had the ability of dissolving into PLLA melt matrix, while BTAD was insoluble in PLLA. The optical microscope images revealed the quite different PLLA crystal morphologies nucleated by BHAD and BTAD. As BTAD could not dissolve in PLLA melt, it only induced a mass of small grain crystals of PLLA, the morphology of which is the same as neat PLLA. BHAD had relatively different nucleation and crystallization behaviors. Upon heating, BHAD could partially or totally dissolve in PLLA melt, which depended on the final heating temperature and its concentration. Upon cooling, BHAD separated from PLLA matrix and formed needle like or dendritic structures. Moreover, totally dissolved BHAD could finally exhibit dendritic structures, which had an excellent nucleation effect to PLLA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46851.     

Biodegradable Blends Prepared from Polycaprolactone and Poly(glutamic acid): Structure,Thermal Properties,and Biodegradability

Biodegradable polycaprolactone/poly(glutamic acid) (PCL/PGA) blends were prepared by a melt blending method. Additionally, acrylic acid-grafted polycaprolactone (PCL-g-AA) was studied as an alternative to PCL. The samples were characterized using Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), an Instron mechanical tester, and scanning electron microscopy (SEM). Because of poor compatibility between PCL and PGA, the mechanical properties of PCL/PGA blends were worse than of PCL alone. The PCL-g-AA/PGA blends had obviously improved mechanical properties over PCL/PGA ones, and the former provided a plateau tensile strength at break when the PGA content was up to 20 wt%. Biodegradation tests of blends were also conducted in a soil environment; the results showed that the mass of blends declined by about the PGA content within 4 weeks.     

Effects of molten poly(3-hydroxybutyrate) on crystalline morphology in stereocomplex of poly(L-lactic acid) with poly(D-lactic acid)

Effects of poly(3-hydroxybutyrate) (PHB) on crystalline morphology of stereocomplexing capacity of poly(L- and D-lactic acid) (PLLA and PDLA) were studied by differential scanning calorimetry (DSC), polarizing-light optical microscopy (POM), atomic-force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). When crystallized at high T_c (130 °C or above), morphology transition of stereocomplexed PLA (sc-PLA) occurs from original well-rounded Maltese-cross spherulites to dendritic form in blends of high PHB contents (50 wt.% or higher), where PHB acts as an amorphous species. Microscopy characterizations show that morphology of sc-PLA in PHB/sc-PLA blends crystallized at T_c = 170 °C no longer retain original complexed Maltese-cross well-rounded spherulites; instead, the spherulites are disintegrated and restructured into two types of dendrites: (1) edge-on feather-like dendrites (early growth) and (2) flat-on wedge-like crystal plates (later growth) by growing along different directions and exhibiting different optical brightness. The concentration and/or distribution of amorphous PHB at the crystal growth front, corresponding to variation of the slopes of spherulitic growth rates, is a factor resulting in alteration and restructuring of the sc-PLA spherulites in the blends. Despite of spherulite disintegration, WAXD result shows that these two PHB-induced dendrites still retain the original unit cells of complexes, and thus these two new dendrites are sc-PLA.     

熔融缩聚法合成高分子量聚L-乳酸

以L-乳酸为原料,采用分步除水、丙交酯回流、优选催化剂等工艺,通过熔融缩聚法制备了高分子量聚L-乳酸(PLLA),研究了脱水产物、反应装置、催化剂、聚合工艺等对产物分子量、产率及色泽的影响,并对产物分子结构进行了表征。在加装丙交酯回流装置后,以Sn(Ot)2/SnC l2.2H2O/TSA为催化剂,在170℃,反应12h所得PLLA黏均分子量(Mη)可达10.6万,产率为76%。     

Superstructure and mechanical properties of poly(L-lactic acid) microfibers prepared by CO2 laser-thinning

Poly(L-lactic acid) (PLLA) microfibers were obtained by a carbon dioxide (CO₂) laser-thinning method. A laser-thinning apparatus used to continuously prepare microfibers was developed in our laboratory; it consisted of spools supplying and winding the fibers, a continuous-wave CO₂-laser emitter, a system supplying the fibers, and a traverse. The laser-thinning apparatus produced PLLA microfibers in the range of 100-800 m min⁻¹. The diameter of the microfibers decreased as the winding speed increased, and the birefringence increased as the winding speed increased. When microfibers, obtained through the laser irradiation (at a laser power of 8.0 W cm⁻²) of the original fiber supplied at 0.4 m min⁻¹, were wound at 800 m min⁻¹, they had a diameter of 1.37 μm and a birefringence of 24.1×10⁻³. The draw ratio calculated from the supplying and winding speeds was 2000×. The degree of crystal orientation increased with increasing the winding speed. Scanning electron microscopy showed that the microfibers obtained with the laser-thinning apparatus had smooth surfaces not roughened by laser ablation that were uniform in diameter. The PLLA microfiber, which was obtained under an optimum condition, had a Young's modulus of 5.8 GPa and tensile strength of 0.75 GPa.