聚乳酸耐热改性的研究进展

聚乳酸(PLA)是一种兼具良好生物相容性、力学以及加工性能的生物基可降解脂肪族聚酯,因此,在医药、食品包装等领域得到广泛应用。然而,PLA结晶速率慢、所得制品结晶度低、耐热性差,严重制约了其在高温环境下的使用。本文综述了国内外聚乳酸耐热改性方面的研究进展,重点阐述通过化学共聚、交联、共混以及外场作用(热处理、拉伸)等手段提高PLA耐热性的方法,并对耐热聚乳酸材料的发展前景进行了展望。     

聚乳酸基生物可降解材料的相容性

随着能源危机和环境污染的日益严重,生物可降解塑料逐渐成为研究的趋势和热点。聚乳酸(PLA)具有良好的生物降解性、生物相容性、可再生性、高强度、易加工等优点,被认为是最有前途的生物降解聚合物之一。聚乳酸的延展性和冲击性能较差严重制约了PLA的应用,共混改性是一种经济有效的方法,从而解决其韧性不足的缺点。然而,PLA在热力学上与大多数聚合物不相容,为了获得性能优良的PLA共混材料,聚合物共混过程中需要加入一种有效的相容剂进行增容。近年来,PLA与不同聚合物共混时的相容性研究已取得一定进展,本文就其进展进行全面综述。     

聚乳酸改性壳聚糖及其在生物医学领域的应用北大核心CSCD

壳聚糖(CS)和聚乳酸(PLA)具有许多独特的性能,包括可生物降解性、良好的生物相容性,对人体无刺激、无毒,是一种绿色生物医药材料,具备潜在的应用价值。将二者单独用于医药领域优势不是很显著,而聚乳酸改性壳聚糖的产物及其衍生物能够很好地融合二者的优点,改性后能得到综合性能更好的生物医学复合材料。本文从聚乳酸改性壳聚糖的角度,综述了壳聚糖和聚乳酸的性质、改性原因、改性现状、改性产物的性能以及在医药领域的一些应用,重点介绍了改性产物在药物缓释方面的应用,并指出今后改性材料方面应注意的问题和发展趋势。     

环氧呋喃树脂反应性增容改性聚乳酸/淀粉复合材料的研究

研究了环氧呋喃树脂反应增容改性聚乳酸/淀粉复合材料,对索氏提取法得到的淀粉进行1H-NMR、FTIR、XPS和静态接触角测试表征.结果表明在熔融共混过程中环氧呋喃树脂(FER)与淀粉及聚乳酸(PLA)发生化学反应,从而起到反应性增容的作用.另外,利用SEM、万能材料试验机和DSC分别对复合材料的界面相容性、机械性能以及热性能进行了表征,结果表明FER能够显著改善PLA和淀粉之间的界面相容性,在保持PLA高强度高模量的基础上,显著提高了PLA/starch复合材料的综合机械性能和结晶性能.     

完全降解聚乳酸共混复合材料的研究进展

聚乳酸(PLA)是可完全生物降解的材料,广泛应用于包装、纺织、生物医用等领域。但其具有性脆,价格较高,疏水性大等缺点,限制了应用发展。近年来对聚乳酸共混改性已成为研究热点。根据共混组分的生物降解性,聚乳酸共混体系分为完全生物降解体系和部分生物降解体系。文中综述了近年来完全生物降解聚乳酸共混体系的研究,主要阐述了PLA/淀粉、PLA/天然纤维复合材料,并简要介绍了PLA/甲壳素、PLA/蛋白等PLA/天然高分子复合材料,以及PLA/PCL、PLA/PPC、PLA/PEO等PLA/合成高分子复合材料。     

聚乳酸立体复合物的结构与性能研究进展及展望北大核心CSCD

聚乳酸(PLA)类材料以其独特的生物相容性和生物可降解性备受关注。将其两种旋光对映体,即PLLA与PDLA共混,会产生一种具有更高熔点的立体复合物(sc-PLA),并能提高聚合物的结晶度、结晶速率以及耐热性,对于PLA类材料的开发和应用具有重要意义。本文从结晶机理、球晶形态、热稳定性和降解性能等方面综述了近年来有关sc-PLA结构与性能的研究进展,并对sc-PLA研究方向提出了作者的观点。     

聚丁二酸丁二醇酯与氯醚弹性体协同增韧改性聚乳酸多元共混体系

以来源于可再生资源聚丁二酸丁二醇酯(PBS)和氯醚橡胶(ECO)作为聚乳酸(PLA)的增韧改性剂,通过熔融共混的方法制备了PLA/PBS/ECO三元共混体系。动态力学分析和扫描电子显微镜结果表明,ECO促进了PBS和PLA之间的相容性。力学性能测试表明,ECO与PBS可实现对聚乳酸基体的协同增韧: PLA/PBS/ECO(70/20/10)显示出最优的拉伸性能,断裂伸长率高达270%;PLA/PBS/ECO(70/10/20)的冲击强度提高至23.7 kJ/m²,是纯聚乳酸的12倍。结合形态结构和冲击断面形貌分析表明ECO的存在可起到增容/增韧双重作用, 与柔性PBS产生良好的协同效应,有效改善聚乳酸材料的韧性。我们的研究表明,构造PLA-柔性生物聚酯和生物基弹性体多元共混体系是一种获得高性能生物基材料简单高效的手段。     

聚乳酸立体复合物的结构与性能研究进展及展望

聚乳酸(PLA)类材料以其独特的生物相容性和生物可降解性备受关注。将其两种旋光对映体,即PLLA与PDLA共混,会产生一种具有更高熔点的立体复合物(sc-PLA),并能提高聚合物的结晶度、结晶速率以及耐热性,对于PLA类材料的开发和应用具有重要意义。本文从结晶机理、球晶形态、热稳定性和降解性能等方面综述了近年来有关sc-PLA结构与性能的研究进展,并对sc-PLA研究方向提出了作者的观点。     

生物可降解聚乳酸的改性及其应用研究进展

综述了近年来国内外关于生物可降解材料聚乳酸(PLA)通过共聚、共混、增塑和复合等方法得到聚乳酸改性材料的研究进展,以及对其在生物医学领域、纺织领域和包装领域中的应用作了广泛而深入的总结和评述,并预示了聚乳酸材料的研究开发前景。     

功能化聚乳酸微球改性聚乳酸膜片表面及其细胞相容性

以两亲三嵌段共聚物PEO PPO PEO及其氨基酸、多肽RGD衍生物作为微球制备过程中的表面稳定剂 ,低分子量的聚乳酸作为成核材料 ,采用o w乳液溶剂挥发法制备得到表面含不同氨基酸的聚乳酸微球 ,荧光标记手段证明了氨基酸存在于微球的表面 ;利用溶胀嵌入固定法将微球固定到具有生物惰性聚乳酸膜片表面 ,制备得到了具有良好稳定性的微球改性聚乳酸生物惰性膜片 ;成骨细胞相容性测试表明 ,氨基酸尤其是多肽RGD在生物惰性聚乳酸表面的引入能较大程度地提高聚乳酸生物惰性表面的细胞相容性 ,能较好地诱导细胞行为如细胞粘附、增殖等过程的发生 ,为实现对细胞行为的诱导控制提供了一种新途径 .     

Characterization of Magnesium-Polylactic Acid Films Casted on Different Substrates and Doped with Diverse Amounts of CTAB

Polylactic acid (PLA) is a good candidate for the manufacture of polymeric biodegradable biomaterials. The inclusion of metallic particles and surfactants solves its mechanical limitations and improves its wettability, respectively. In this work, cetyltrimethylammonium bromide (CTAB) and magnesium particles have been incorporated into PLA films to evaluate the changes produced in the polymeric matrix cast on glass and silicone substrates. For this purpose, the surface of the films has been characterized by means of contact angle measurements and ToF-SIMS. Depth profiles and SEM images of the cross sections of the films have also been obtained to study their morphology. The results show that the CTAB in the polymer matrix with and without magnesium improves the wettability of the films, making them more suitable for cell adhesion. The higher the hydrophilicity, the higher the surfactant concentration. The depth profiles show, for the first time, that, depending on the surfactant concentration and the presence of Mg, there is a layer-like distribution near the surface where, in addition to the CTAB + PLA mixture, a surfactant exclusion zone can be seen. This new structure could be relevant in in vitro/in vivo situations when the degradation processes remove the film components in a sequential form.     

Preparation of Polylactide Composite with Excellent Flame Retardance and Improved Mechanical Properties

Despite the good biodegradable and mechanical properties, poly(lactic acid) still suffers from a highly inherent flammability, which restricts its applications in the electric and automobile fields. In order to improve the flame retardancy of PLA, in this work, melamine polyphosphate (MPP) and zinc bisdiethylphosphinate (ZnPi) were firstly incorporated into PLA, and the synergistic effect of them on flame retardance of PLA was investigated using limiting oxygen index (LOI), UL-94 vertical measurement, scanning electron microscopy (SEM) and cone calorimeter tests etc. The results showed that PLA composite with 15 wt% of MPP/ZnPi (3:2) had the best flame-retardant efficiency with LOI value of 30.1 and V0 rating in UL-94 tests, which was far better than using MPP or ZnPi alone. What is more, although a wide range of flame retardants have been developed to reduce the flammability, so far, they normally compromise the mechanical properties of PLA. On the premise of maintaining good flame-retardant performance, we improved the toughness of flame-retardant PLA composite, and the impact strength of flame-retardant PLA composite was more than tripled (8.08 kJ/m²) by adding thermoplastic urethanes (TPU). This work offers an innovative method for the design of the unique integration of extraordinary flame retardancy and toughening reinforcement for PLA materials.     

Investigation on the thermo-mechanical properties and thermal stability of polylactic acid tissue engineering scaffold material

Thermogravimetric analysis and dynamic mechanical analysis were combined with scanning electron microscopy to analyze the thermo-mechanical properties and thermal stability of polylactic acid (PLA) foams fabricated using a solvent-free solid-state gas foaming method. The dependence of decomposition time and the lifetime on the PLA cell size was evaluated based on the thermal decomposition kinetic analyses. The results show that PLA specimens with larger cell sizes can be made at lower saturation gas pressures, which will ensure that the fabricated PLA foams have a shorter decomposition time, better flexibility, and are more satisfactory for medical requirements of tissue engineering scaffold (TES) material. The current work may help to optimize the PLA foaming parameters and precisely design PLA foams with different decomposition times according to specific TES requirements of different organ structures.     

聚乳酸接枝葡聚糖共聚物的合成及其体外降解行为的研究

研究了聚乳酸接枝葡聚糖梳型共聚物的合成 ,以及共聚物的结构特征、亲水性能及降解行为的表征 .结果表明由于亲水性葡萄糖单元组分的引入以及共聚物的梳型结构特征 ,聚乳酸接枝葡聚糖共聚物的亲水性明显优于相应的线型聚乳酸 ,而且降解速度也明显加快 .由于这类梳型结构的聚多糖 聚酯共聚物综合了聚多糖细胞亲和性好和聚酯生物降解速率可调节性的特点 ,因此有望成为一类优良的细胞支架材料 .     

Research progress in the heat resistance,toughening and filling modification of PLA

Due to its high strength, high modulus, excellent clarity, good biodegradability and biocompatibility, poly(lactic acid) (PLA), a bio-based thermoplastic polyester, has evolved into a competitive commodity material with potential to replace conventional petrochemical-based polymers. However, the wide applications of PLA have been hampered by its native drawbacks, such as low heat distortion temperature (HDT), inherent brittleness and relatively high cost. In recent years, researchers have devoted to breaking above-mentioned bottleneck and attempted to extend the application of PLA. This review will summarize recent work about the modification of PLA, especially focusing on enhancing HDT, toughening and reducing cost.     

Sensitive determination of rhodamine 110-labeled monosaccharides in glycoprotein by capillary electrophoresis with laser-induced fluorescence detection

Rhodamine 110 (Rho110) has been used in the highly sensitive analysis of monosaccharides, as it reacts with the reducing carbonyl group of the saccharides. The monosaccharide derivatives were investigated by capillary electrophoresis with laser-induced fluorescence detection. The derivatization was performed at 90 °C for 30 min for all monosaccharides. The derivatized monosaccharides were separated using 200 mM borate (pH 10.5) as running buffer within 20 min. The fluorescence intensities of Rho110-derivatives were significantly decreased by the presence of excess reducing agent, but were greatly increased by the addition of potassium hexacyanoferrate(III). The concentration and mass detection limits for monosaccharides were in the range of 1.4–2.8 nM and 36–70 amol, respectively. We have applied this derivatization method to the analysis of the composition of monosaccharides in glycoproteins (ribonuclease B, fetuin, and erythropoietin) following their subjection to strong acid hydrolysis. The results from these analyses were in good agreements with the reported values established previously.     

胆固醇-聚(D,L-乳酸)的制备及软骨细胞相容性研究

依据胆固醇对细胞膜良好的热力学亲和力及可以调节细胞膜磷脂双分子层的结构和动态行为的生理学的特点,采用本体聚合的方法制备了胆固醇-聚(D,L-乳酸),经GPC,1H-NMR分析证明产物分子量与理论分子量有较好的一致性,证明了聚合物的分子量可以通过调节D,L-丙交酯和胆固醇的量来控制.软骨细胞粘附率、增殖率以及3-(4,5-二甲基噻唑)-2,5-二苯基四氮唑溴盐(MTT)细胞活性的观测结果表明相比纯聚乳酸,胆固醇-聚乳酸明显促进了细胞的粘附与生长.通过激光共聚焦显微镜观察细胞形貌结果显示相比胆固醇-聚乳酸表面,纯聚乳酸表面的细胞数量较少且大多团聚没有正常铺展,而胆固醇-聚乳酸表面的软骨细胞则分布均匀,铺展充分.以上结果证明了胆固醇的存在有利于软骨细胞的生长和粘附,预示着胆固醇-聚乳酸在软骨组织工程以及其他相关的生物医疗领域有着广阔的应用前景.     

直接法共聚改性聚乳酸研究新进展

聚乳酸(PLA)是一种重要的生物降解材料.广泛应用于生物医学、纤维、塑料等领域.为了改善PLA的性能,人们进行了大量的共聚改性研究.其中,直接从乳酸出发不经丙交酯中间体路线的共聚改性方法,因其简单易行、经济实用,越来越引起科学家的重视.针对直接法共聚改性聚乳酸物中物质种类的不同,结合本课题组的一些乳酸直接熔融共聚研究工...     

Implantation of multiscale silk fibers on poly (lactic acid) fibrous membrane for biomedical applications

Despite that poly (lactic acid) (PLA) has satisfactory biodegradation in vivo, its application in biomedicine is restricted due to its unsatisfactory cytocompatibility. Silk fiber (SF) has outstanding biocompatibility and silk fibroin protein obtained from silk by degumming has good hydrophilicity. Therefore, combining the PLA and silk can improve hydrophilicity of PLA to apply as biomedical materials. In this study, different concentrations of sodium hypochlorite (NaClO) were used to separate the silk to obtain multiscale silk fibers (MSFs), which were implanted into the PLA electrospun fibrous membranes (EFMs). The morphology and structure of silk fibers separated by different concentrations of NaClO were studied by Zetasizer Nano ZS, UV spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. Moreover, the biocompatibility of the surface-modified PLA composite membranes by MSFs was investigated by cell cultivation and proliferation. The results showed that the surface-modified PLA EFMs through MSF bundles obtained from NaClO split silk exhibited a certain improvement on PLA hydrophilicity and enhancement on cellular compatibility, which could have a broad prospect in the practical application of biomedical materials.     

Polylactide compositions. II. Correlation between morphology and main properties of PLA/calcium sulfate composites

Starting from calcium sulfate (gypsum) as fermentation by‐product of lactic acid production process, high performance composites have been produced by melt‐blending polylactide (PLA, L/D isomer ratio of 96:4) and β‐anhydrite II (AII) filler, that is, calcium sulfate hemihydrate previously dehydrated at 500 °C. Characterized by attractive mechanical and thermal properties due to good filler dispersion throughout the polyester matrix, these composites are interesting for potential use as biodegradable rigid packaging. Physical characterization of selected composites filled with 20 and 40 wt % AII has been performed and compared to processed unfilled PLA with similar amorphous structure. State of dispersion of the filler particles and interphase characteristic features have been investigated using light microscopy (LM) and scanning electron microscopy (SEM). Addition of AII did not decrease PLA thermal stability as revealed by thermogravimetry analyses (TGA) and allowed reaching a slight increase of PLA crystallizability during melt crystallization and upon heating from the glassy, amorphous state (DSC). It was found by thermomechanical measurements (DMTA) that the AII filler increased pronouncedly storage modulus (E′) of the composites in comparison with PLA in a broad temperature range. The X‐ray investigations showed stable/unchanged crystallographic structure of AII during processing with molten PLA and in the composite system. The notable thermal and mechanical properties of PLA–AII composites are accounted for by the good filler dispersion throughout the polyester matrix confirmed by morphological studies, system stability, and favorable interactions between components. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2770–2780, 2007