丙交酯开环聚合反应的新型有机催化剂

作为生物高分子降解材料,聚乳酸具有良好的生物相容性和生物降解性,已经广泛应用于包装材料、农用薄膜等环境领域和药物控制释放体系、医用缝合线、组织工程支架等医学领域。丙交酯开环聚合是制备聚乳酸的理想之选,其催化体系目前以金属催化剂为主,但金属离子在聚合物中的痕量残留和细胞毒性限制了聚乳酸在生物医学及微电子领域的应用,而有机催化剂能够克服这些缺点,是目前聚乳酸合成领域的研究热点。本文从不同的活化机理角度,阐述了近年来有机催化剂在合成聚乳酸中的研究进展,总结了各种催化体系在活性、结构可控性及选择性方面的特点,同时展望有机催化剂在开环聚合反应中所面临的机遇与挑战。     

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。     

基于聚乳酸的可降解形状记忆高分子的研究进展

综述了基于聚乳酸的可生物降解的形状记忆高分子材料的研究情况。首先介绍了形状记忆高分子材料的记忆效应、记忆机理,然后讨论了基于聚乳酸的三种类型的形状记忆高分子材料：单组份的聚乳酸类、聚乳酸共聚物类以及聚乳酸与无机物的复合材料,分别介绍了各种类型的形状记忆高分子材料的形状记忆性能和生物降解性能。最后,讨论了聚乳酸类记忆材料的应用情况,并对其研究前景和发展趋势进行了展望。     

生物医用PLA改性研究进展北大核心CSCD

聚乳酸(polylactic acid)材料是一种用途广泛的可生物降解高分子材料,已经成为生物医用材料中最受重视的材料之一。但是聚乳酸也存在许多缺陷,限制了其在医药领域的广泛应用。本文综述了聚乳酸疏水性强、细胞亲和性差、力学性能不足,降解产物造成局部酸性积累而导致机体发生无菌性炎症反应,缺乏修复、降解、吸收速度与细胞的增殖、组织修复速度匹配的系列产品,成本高,均聚物成孔性能差等缺陷,总结了近些年国内外针对以上各个缺陷做出的改进方案,并对聚乳酸医用改性的研究发展方向进行了展望。     

聚乳酸在生物医药领域的改性研究进展

聚乳酸类材料是一种用途广泛的生物降解高分子材料,已经成为生物医用材料中最受重视的材料之一。但由于聚乳酸本身的缺陷,限制了其在生物医学工程中的应用。对聚乳酸的改性工作就一直备受关注。本文综述了近几年聚乳酸生物降解材料的物理改性和化学改性研究进展,经改性后聚乳酸的力学性能、降解性能、亲水性能和生物活性得到有效改善,从而更好地满足了生物医用需要。     

生物可降解高分子材料及其在药物释放中的应用

综述了生物可降解高分子材料的发展情况及其在药物释放领域的应用 ,着重介绍了聚乳酸和聚己内酯的研究进展和应用     

羧甲基香菇多糖表面修饰的聚乳酸材料的表面性能研究

制备了香菇多糖羧甲基衍生物,再通过化学接枝方法利用共价键将羧甲基香菇多糖固定在氨基化聚乳酸基材表面,得到羧甲基香菇多糖化学接枝修饰的聚乳酸材料.此外,通过在氨基化聚乳酸基材表面进行羧甲基香菇多糖与壳聚糖的层层自组装,得到生物多糖层层自组装修饰的聚乳酸材料.采用扫描电子显微镜、水接触角测量仪、抗菌活性测试、溶血试验和血栓试验等方法对被修饰聚乳酸材料的表面性能和生物性能进行了分析和比较.结果表明采用2种表面修饰方法得到的羧甲基香菇多糖修饰的聚乳酸材料的亲水性、血液相容性以及对大肠杆菌抗菌活性得到改善.与化学接枝方法相比,经过羧甲基香菇多糖与壳聚糖层层自组装修饰的聚乳酸材料具有更好的亲水性、血液相容性和抗菌活性.     

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。     

生物基化工与材料产业技术的开发与探索

本文阐述了中国石油化工集团公司(中国石化)在生物基化工与材料领域的探索路径和发展战略,介绍了中国石化近年来在生物基单体、生物基材料与可降解材料等领域开展的创新实践及取得的阶段性成果,主要包括乳酸—聚乳酸、丁二酸/二元醇—生物可降解材料、长链二元酸—生物基尼龙以及生物质芳烃—聚对苯二甲酸乙二酯(PET)等技术领域.提出了建立生物基化工与材料科学技术平台、突破关键技术、发展新兴产业等建议.     

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。     

Characterization of poly(lactic acid)s with reduced molecular weight fabricated through an autoclave process

Poly(lactic acids) (PLAs) with different molecular weights (MWs) were prepared by autoclaving a commercial PLA for different time periods. The harvested PLAs were characterized by different techniques. Gel permeation chromatography results showed that the MW of PLA decreased with increasing autoclaving time. The Mark–Houwink parameters for PLA in dichloromethane at 25 °C were determined for the first time. The melting endotherms, revealed by differential scanning calorimetry, were observed for the 60 and 120 min-autoclaved PLAs (cf. PLA60 and PLA120) but hardly detected for the original and 30 min-autoclaved PLA (PLA30). The PLA120 exhibited higher crystallinity than that of PLA60. Thermogravimetric analysis showed that the activation energy for thermal degradation decreased from 186 kJ mol⁻¹ to 140 kJ mol⁻¹ for original PLA and PLA120. The hydrophilicity of the PLA increased, indicating higher number of COOH groups, with increasing autoclaving time, as revealed by the contact angle measurement. Rheological data showed that the complex viscosity and storage modulus of PLA decreased with increasing autoclaving time due to the decreasing MW. Unlike original PLA and PLA30, PLA60 and PLA120 exhibited Newtonian fluid behavior at all test frequencies.     

Increased expansion ratio,cell density,and compression strength of microcellular poly(lactic acid) foams via lignin graft poly(lactic acid) as a biobased nucleating agent

Green and renewable foaming poly(lactic acid) (PLA) represents one of the promising developments in PLA materials. This study is the first to use the lignin graft PLA copolymer (LG‐g‐PLA) to improve the foamability of PLA as a biobased nucleating agent. This agent was synthesized via ring‐opening polymerization of lignin and lactide. The effects of LG‐g‐PLA on cell nucleation induced by the crystallization, rheological behavior, and foamability of PLA were evaluated. Results indicated that LG‐g‐PLA can improve the crystallization rate and crystallinity of PLA, and play a significant nucleation role in the microcellular foam processing of PLA. LG‐g‐PLA improved the foam morphology of PLA, obtaining a reduced and uniform cell size as well as increased expansion ratio and cell density. With the addition of 3 wt% LG‐g‐PLA content, the PLA/LG‐g‐PLA foams increased the compressive strength 1.6 times than that of neat PLA foams. The improved foaming properties of PLA via a biobased nucleating agent show potential for the production and application of green biodegradable foams.     

Effect of Carboxylic Acid Nucleating Agent on Crystallization and Mechanical Properties of PLA/PBS Blends

Poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends were prepared using a carboxylic acid salt as nucleating agent (NA). The effect of NA on the crystallization kinetics of PLA and PLA/PBS blend was investigated using a differential scanning calorimeter, a polarized optical microscope and a wideangle X-ray diffractometer. The crystallization rate of PLA component in PLA/PBS blends is increased effectively by NA through fast nucleation and growth rate of PLA α'-form crystal, which is confirmed by isothermal crystallization behavior of PLA/PBA/NA composites. The isothermal crystallization results also show that the incorporation of NA induces heterogeneous nucleation mechanism in PLA component. The increased number of crystal nuclei hinders the increase of average grain size of PLA component in composites but contributes to a higher crystallinity of both PLA and PBS components in PLA/PBS blends. Finally, the mechanical properties and dynamic mechanical properties of PLA/PBS/NA composites are improved because of the increased crystallinity, which are superior to that of PLA/PBS blend.     

In vitro degradation behaviour of non-porous ultra-fine poly(glycolic acid)/poly(l-lactic acid) fibres and porous ultra-fine poly(glycolic acid) fibres

The in vitro degradation behaviour of non-porous ultra-fine poly(glycolic acid)/poly(l-lactic acid) (PGA/PLA) fibres and porous ultra-fine PGA fibres was investigated. The non-porous ultra-fine PGA/PLA fibres were prepared by electrospinning of a PGA/PLA solution in 1,1,1,3,3,3-hexafluoro-2-propanol and the porous ultra-fine PGA fibres were obtained from them via selective removal of PLA with chloroform. Since PLA has a lower degradation rate than PGA, the degradation rates of the ultra-fine PGA/PLA fibres decreased with increasing content of PLA. The porous ultra-fine PGA fibres were degraded in vitro in the order of non-porous PGA > P-PGA/PLA(90/10) > P-PGA/PLA(70/30) > P-PGA/PLA(50/50) > P-PGA/PLA(30/70) due to autocatalytic hydrolysis.     

苯基次磷酸盐离聚物/聚磷酸铵协效阻燃增韧改性聚乳酸

通过将双端羟基的聚己内酯(PCL)、聚乳酸(PLA)预聚物以及苯基次磷酸离子盐扩链得到一种含苯基次磷酸盐的离子共聚物,将其与聚磷酸铵(APP)复合用于协同改性聚乳酸,离聚物中苯基次磷酸盐结构与APP具有优异的协同阻燃PLA的作用,同时该离聚物中PLA与苯基次磷酸盐结构有效提升了APP在PLA中的分散能力,最后该离聚物中PCL柔性链段有效改善了PLA的韧性,最终得到更高效阻燃性能且韧性也较好改善的PLA/PCLA-PIU/APP复合材料.一方面,离聚物中苯基次磷酸盐结构与APP协同有效促进了PLA的成炭,形成更连续致密的炭层从而阻隔可燃气体的释放,达到更好的阻燃效果.锥形量热、残炭的扫描电子显微镜(SEM)、能谱分析(EDS)、拉曼光谱等测试证实了这一结果,与纯PLA以及仅使用APP的PLA/APP相比,PLA/PCLA-PIU/APP的热释放速率与总热释放均降低,同时残炭的石墨化程度更高,形成了更为致密的炭层.另一方面,力学性能测试结果表明,离聚物中PCL柔性链段的存在使得与APP复合改性后的PLA的韧性相比纯PLA和PLA/APP有较大的提升;SEM测试表明,离聚物中PLA与苯基次磷酸盐结构起到增容作用,提升了APP在PLA中的分散性.     

Influences of poly(lactic acid)‐grafted carbon nanotube on thermal,mechanical, and electrical properties of poly(lactic acid)

Poly(lactic acid)‐grafted multiwalled carbon nanotubes (MWNT‐g‐PLA) were prepared by the direct melt‐polycondensation of L ‐lactic acid with carboxylic acid‐functionalized MWNT (MWNT‐COOH) and then mixed with a commercially available neat PLA to prepare PLA/MWNT‐g‐PLA nanocomposites. Morphological, thermal, mechanical, and electrical characteristics of PLA/MWNT‐g‐PLA nanocomposites were investigated as a function of the MWNT content and compared with those of the neat PLA, PLA/MWNT, and PLA/MWNT‐COOH nanocomposites. It was identified from FE‐SEM images that PLA/MWNT‐g‐PLA nanocomposites exhibit good dispersion of MWNT‐g‐PLA in the PLA matrix, while PLA/MWNT and PLA/MWNT‐COOH nanocomposites display MWNT aggregates. As a result, initial moduli and tensile strengths of PLA/MWNT‐g‐PLA composites are much higher than those of neat PLA, PLA/MWNT, and PLA/MWNT‐COOH, which stems from the efficient reinforcing effect of MWNT‐g‐PLA in the PLA matrix. In addition, the crystallization rate of PLA/MWNT‐g‐PLA nanocomposites is faster than those of neat PLA, PLA/MWNT, and PLA/MWNT‐COOH, since MWNT‐g‐PLA dispersed in the PLA matrix serves efficiently as a nucleating agent. It is interesting that, unlike PLA/MWNT nanocomposites, surface resistivities of PLA/MWNT‐g‐PLA nanocomposites did not change noticeably depending on the MWNT content, demonstrating that MWNTs in PLA/MWNT‐g‐PLA are wrapped with the PLA chains of MWNT‐g‐PLA. Copyright © 2008 John Wiley & Sons, Ltd.     

Significant enhancement of crystallization kinetics of polylactide in its immiscible blends through an interfacial effect from comb-like grafted side chains

A significant enhancement in isothermal crystallization kinetics of biodegradable polylactide (PLA) in its immiscible blends can be accomplished through blending it with a comb-like copolymer. PLA was blended with poly(ethylene glycol) methyl ether acrylate (PEGA) and poly[poly(ethylene glycol) methyl ether acrylate] (PPEGA, a comb-like copolymer), respectively. The results measured from phase contrast optical microscopy (PCOM) and differential scanning calorimetry (DSC) indicate that PLA and PEGA components are miscible, whereas PLA and PPEGA components are immiscible. The study of crystallization kinetics for PLA/PEGA and PLA/PPEGA blends by means of polarized optical microscopy (POM) and DSC indicates that both PEGA and PPEGA significantly increase the PLA spherulitic growth rates, G, although PLA/PPEGA blends are immiscible and the glass transition temperatures of PLA only have slight decreases. PPEGA component enhances nucleation for PLA crystallization as compared with PEGA component owing to the heterogeneous nucleation effect of PPEGA at the low composition of 20 wt%, while PLA crystallization-induced phase separation for PLA/PEGA blend might cause further nucleation at the high composition of 50 wt%. DSC measurement further demonstrates that isothermal crystallization kinetics can be relatively more enhanced for PLA/PPEGA blends than for PLA/PEGA blends. The “abnormal” enhancement in G for PLA in its immiscible blends can be explained by local interfacial interactions through the densely grafted PEGA side chains in the comb-like PPEGA, even though the whole blend system (PLA/PPEGA blends) represents an immiscible one.     

Crystallization and flame‐retardant properties of polylactic acid composites with polyhedral octaphenyl silsesquioxane

To develop environmental‐friendly and flame‐retarded polymer composites, bio‐based polylactic acid (PLA) was loaded with thermally stable polyhedral octaphenyl silsesquioxane (OPS). Pure PLA and PLA/OPS composites with the OPS of 1, 3, 5, and 10 wt% were prepared by extrusion and injection molding, respectively. The scanning electron microscopy (SEM), polarized optical microscope (POM), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and thermal gravimetric analysis (TGA) were used to analyze the dispersion of the OPS in the PLA matrix and the effects of OPS on the crystallization and thermal stability properties of PLA/OPS composites, respectively. Limited oxygen index (LOI) and cone calorimeter (CONE) measurements were used to study flame retardancy of PLA and PLA/OPS composites. In order to study the flame‐retardant mechanism, the char residues were investigated by SEM, Fourier transform infrared spectra (FTIR), and X‐ray photoelectron spectroscopy (XPS). TGA‐FTIR was used to analyze the gaseous products of their thermal decomposition. The results show that the OPS particles were submicron in the PLA and could increase the crystallization rate of PLA and form small‐sized secondary α‐form crystalline compared with the pure PLA spherulite. The PLA and OPS decomposed individually in the PLA/OPS composites by TGA. According to the LOI tests, the PLA with the OPS loading exhibited very small reduction of LOI. However, the CONE tests indicated that the OPS could improve the flame retardancy of the PLA by means of low peak heat release rate and average heat release rate. It was obtained that the degree and type of the PLA crystalline for the pure PLA and PLA/OPS affect their flame retardancy. In the max thermal decomposition stage of PLA and PLA/OPS, their gaseous products were similar; at high temperatures, the PLA/OPS produced simple and clear gaseous products of PLA with solid SiO₂ in the gas phase.     

聚乳酸/壳聚糖纳米纤维结构形成的影响条件及其生物矿化活性

以二氧六环/冰醋酸为溶剂体系,采用相分离法制备了聚乳酸(PLA)/壳聚糖(CS)复合纳米纤维结构的组织工程支架,探讨了不同CS含量、不同凝胶温度及不同分子量对PLA/CS复合支架纳米纤维结构的影响以及支架的生物活性。结果表明,凝胶温度对PLA/CS复合材料的纳米纤维结构影响较大,且随着温度的降低,结构的微观尺寸也逐渐增大,从纳米级上升到普通的尺寸结构;CS含量对PLA/CS复合支架的基体结构影响不大;实验范围内PLA分子量对PLA/CS复合支架的纳米纤维结构有重要影响:分子量大的样品,较易得到PLA/CS复合纳米纤维结构的材料,而分子量小的样品则不能得到纳米纤维结构。另外,生物矿化实验表明CS的添加有利于PLA/CS复合材料生物活性的提高。     

Crystallization,Mechanical and Flame-retardant Properties of Poly(lactic acid) Composites with DOPO and DOPO-POSS

Poly(lactic acid)(PLA) composites with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and DOPOcontaining polyhedral oligomeric silsesquioxane(DOPO-POSS) were prepared via melting extrusion and injection molding. The crystallization, mechanical, and flame-retardant properties of PLA/DOPO and PLA/DOPO-POSS were investigated by differential scanning calorimetry(DSC), X-ray diffraction(XRD), tensile testing, thermogravimetric analysis(TGA), limiting oxygen index(LOI),and cone calorimeter test. The DSC results showed that the DOPO added could act as a plasticizer as reflected by lower glass transition temperature and inhibited crystallization of part of the PLA; the DOPO-POSS acted like a filler in the PLA matrix and slightly improved the crystallinity of the PLA matrix. The XRD and DSC analyses indicated that the PLA composites by cold molding injection were amorphous, and the PLA composites following a heat treatment in an oven at 120 °C for 30 min achieved crystallinity. All the PLA and its composites after heat treatment had improved mechanical properties. The thermogravimetric analysis(TGA) tests showed that the PLA,DOPO and DOPO-POSS decomposed separately in the PLA/DOPO and PLA/DOPO-POSS, respectively. The cone calorimeter tests offered clear evidence that addition of the DOPO-POSS resulted in an evident reduction of 25% for the peak of heat release rate(p-HRR).It was also confirmed that the crystalline flame-retardant PLA composites after heat treatment had better flame retardant properties than the amorphous PLA composites prepared by the cold molding.