Filling of poly(lactic acid) with native starch

Poly(lactic-acid) (PLA), a biodegradable polyester with excellent properties for different polymer applications, will play a major role in future markets for biodegradable polymers. But only if the currently very high price level can be reduced significantly to at least 4 $US/kg. Therefore, studies to fill poly(lactic acid) (PLA) with relative inexpensive native corn starch were conducted. Because PLA is a very brittle material with a glass transition point at 54°C, filling of PLA with native starch might seem unrealistic, as the brittleness is increased by the dispersed starch granules. To avoid this, low molecular weight poly(ethylene glycol) (PEG) is introduced into the PLA to enhance crystallization and to lower the glass transition temperature significantly under possible usage temperatures. The polymer that is modified in this way is then filled with native starch. The thermal behavior of the achieved di- or triblends is determined by means of differential scanning calorimetry (DSC) and the degradation behavior at high temperature has been looked at with the help of thermogravimetric analysis (TGA).     

Plasticizing polylactide—the effect of different plasticizers on the mechanical properties

Poly(lactide) (PLA), a biodegradable aliphatic polyester with excellent property profiles for different polymer applications, will play a major role in future markets for biodegradable polymers from renewable resources. PLA is a very brittle and stiff polymer with a glass transition temperature of around 58°C. The mechanical properties of PLA are comparable to those of polystyrene, with an elasticity modulus of 3500 MPa, a maximum tensile strength of 50 MPa, and an elongation at break of 4%. To introduce PLA into other applications requiring other mechanical property profiles, especially higher flexibility and higher impact resistance, it is necessary to use plasticizers. In this study the influence of several biocompatible plasticizer systems on the mechanical properties of PLA is determined. Poly(ethylene glycol), glucosemonoesters and partial fatty acid esters are introduced at 2.5, 5, and 10 wt% into polylactide. The mechanical properties, such as impact strength and the stress-strain-interrelationship of tensile tests, show changes, which are discussed.     

Ductile PLA modified with methacryloyloxyalkyl isocyanate improves mechanical properties

The majority of the biodegradable polymers in clinical use are composed of stiff materials that exhibit limited extendibility with unsuitably high Young’s modulus and low elongation at break values that make them non-optimal for various biomedical applications. Polylactide (PLA) is often used as a biomedical material because it is biodegradable, but the physical and mechanical properties of PLA need to be improved for biomedical applications. In order to improve the flexibility and strength of biodegradable PLA, various reaction conditions were studied. Urethane structure polymer materials were prepared; PLA was reacted with a small amount of methacryloyloxyethyl isocyanate (MOI) to obtain a ductile PLA with markedly improved mechanical properties. Elongation at break increased by 20 times when compared to neat PLA. Impact resistance (notched) improved 1.6 times. Thus, this modified PLA biodegradable polymer may have greater application as a biomedical material with increased mechanical properties.     

生物可降解聚乳酸基复合材料研究进展

生物可降解高分子材料的研究开发是解决石油基塑料对环境污染的有效方法之一。其中,聚乳酸（PLA）具有可完全生物降解、可加工、可再生、力学性能优良等特点,是代替石油基塑料的必然趋势。但是PLA的疏水性大、性脆、价格贵等缺点限制了其应用和发展。论文主要综述了近年来国内外有关聚乳酸与天然高分子共混、合成高分子共混改性的研究进展,介绍了加工工艺、表面处理、添加剂等对复合体系性能的影响。在现有研究成果的基础上,可以通过加入柔性高分子、表面活性剂、纤维等以改善复合材料的脆性、相容性以及强度,以推动聚乳酸基复合材料的广泛发展。     

Preparation of ductile PLA materials by modification with trimethyl hexamethylene diisocyanate

Polylactide (PLA) is biodegradable and has been useful in various biomedical applications. Since the majority of the biodegradable polymers in clinical use are rather stiff materials that exhibit limited extendibility with low elongation at break values, the physical and mechanical properties of PLA must be improved to allow for more biomedical applications. Poly(ester-urethane) structure polymer materials were prepared; PLA was reacted with a small amount of trimethyl hexamethylene diisocyanate to obtain ductile PLA with markedly improved mechanical properties. Elongation at break was increased by more than 20 times while maintaining relatively high tensile stress when compared to pristine PLA. Impact resistance (notched) improved 1.6 times. Thus, the modified PLA biodegradable polymers presented here may have greater application as a biomedical material due to its enhanced mechanical properties.     

Synthesis of biodegradable and flexible,polylactic acid based,thermoplastic polyurethane with high gas barrier properties

Polylactic acid (PLA) has the beneficial properties of good mechanical strength, biodegradability and biocompatibility, and these properties make it suitable for use as an environmentally friendly packaging material. However, its use has been limited by its brittleness and poor stability. In this work, we successfully developed an efficient synthesis scheme to improve the mechanical properties, flexibility and gas barrier properties of PLA‐based polymers. Four different PLA‐based thermoplastic polyurethane (PLAPU) polymers were synthesized through the reaction of PLA diol with hexamethylene diisocyanate, followed by chain extension with polycaprolactone (PCL) diol. The relative compositions of the hard PLA and the soft PCL diols in the PLAPU polymers were controlled systematically to optimize the physical properties of the polymers. For example, increasing the content of PCL resulted in higher molecular weight PLAPU polymers that had increased tensile strengths and elongations at break, but their moduli were decreased. At the optimized PLA:PCL ratio of 1:3, the PLAPU polymer had an excellent elongation at break of 1053% with a relatively high Young's modulus of 51.8 MPa. In addition, the gas barrier properties of the PLAPUs were significantly enhanced depending on the molecular weight and PCL content of the polymers. To demonstrate the feasibility of using PLAPU polymers for biodegradable packaging materials, hydrolytic degradation tests were performed in phosphate buffer solution, and the PLAPU polymers were degraded gradually at rates that depended on the content of PCL in the polymers. This optimized PLAPU polymer exhibited excellent flexibility and gas barrier property, as well as high elongation, demonstrating its potential utility as packaging materials. © 2013 Society of Chemical Industry     

Polylactic acid blends: The future of green,light and tough

Polylactic acid (PLA) is a biobased product and a compostable aliphatic polyester that has been studied for use in several applications over the last decade. Many properties of PLA, such as strength, stiffness, and gas permeability, have been found to be comparable to those of traditional petrochemical-based polymers. However, PLA-based materials exhibit a number of limitations for specific applications, such as slow biodegradation rate, high cost, and low toughness. The modification of PLA using the polymer blending technique to achieve suitable properties for different applications has been receiving significant attention over the past few years. Hence, the aim of this work is to summarize the current developments regarding the preparation and properties of PLA polymer blends. In this review, the recent advances in PLA preparation are broadly introduced. In addition, the miscibility and compatibilization strategies of PLA polymer blends are discussed. The preparations and characterizations of PLA blends with both biodegradable and non-biodegradable polymers are outlined. Finally, the biodegradation, mechanical properties, and potentiality of PLA blends are presented.     

Recent advances in stereocomplexation of enantiomeric PLA-based copolymers and applications

Poly(lactic acid) or poly(lactide) (PLA) is a biodegradable and biocompatible thermoplastic polymer, being derived from renewable resources such as corn and sugar cane. The building block of PLA, lactic acid is chiral and the polymerization of lactic acids (or lactides) leads to isotatic, syndiotatic and atactic/heterotactic PLA primary structures. The stereoselective interaction between two complementary enantiomeric PLLA and PDLA has led to enhanced physical properties such as mechanical properties, thermal resistance and hydrolytic stability compared with the parent polymers. Progress in controlled and/or living polymerization techniques combined with other new synthetic methodologies has facilitated the preparation of PLA-based copolymers with complex architectures such as diblock, triblock, multiblock, star-shape block, comb-shape block and various PLA-grafted structures. The utilization of stereocomplexation strategy to these newly developed copolymers has opened avenues to access a variety of new materials with unique characteristics, including novel chemical functionalities, bioactivities, and smart (responsive to external stimulus) properties tailored for specific applications. This review presents recent advancements in the synthesis of PLA-based block/graft copolymers having complex architectures, with emphasis on the enhanced material performances induced by PLA stereocomplex formation. The origin of the enhanced thermal mechanical property observed in PLA stereocomplex is first discussed. The strong interaction resulted from stereocomplexation in PLA based copolymers could be exploited not only for fabrication of advanced therapeutic delivery carriers and tissue engineering devices, but also for stabilizing colloidal systems in microparticles, micelles and hydrogels, that further broaden the applications of PLA that could not have been attained with single PLLA or its copolymers. The stereocomplexation could also be used to tailor the interface interactions between fillers and PLA matrix that lead to higher strength and toughness of PLA.     

Poly(lactic acid) mass transfer properties

Poly(lactic acid) (PLA), a biodegradable and compostable polymer, is gaining market acceptance and has been extensively investigated. The versatility of PLA has led to its broad and different applications in medical, agriculture, and food packaging fields. Similar to other polymers, PLA is permeable to gases, vapors and organic compounds. Thus, the mass transfer properties of PLA can influence its suitability for end-use applications. Here, we present a comprehensive, systematic, and critical review of more than 300 papers published since 1990 reporting the mass transfer properties of PLA, which include permeability, diffusion and solubility to gases, water vapor and organic vapors, along with migration of chemical compounds from PLA. Overall, PLA provides moderate barrier to gases, water vapor, and organic compounds. Barrier enhancement can be achieved through modifications such as blending with other polymers and formation of composite structures. Most of the mass transfer parameters reported in the literature are based on two-phase mobile amorphous and crystalline fractions, omitting the role of the restricted amorphous fraction, which can lead to unclear comprehension of PLA barrier properties as well as what affects those properties. Additional research is needed to address this shortcoming. This review provides an in-depth analysis of PLA mass transfer and a foundation for future research and commercial development.     

聚乳酸（PLA）的合成及应用进展

聚乳酸是近年来广泛应用，生物相容性和生物可降解性能良好的生物材料。综述了聚乳酸的合成，聚合机理以及应用等方面研究的最新进展，对未来的工作进行了展望。     

聚乳酸接枝共聚改性的研究进展

聚乳酸是目前最具竞争力的生物降解高分子材料,但也存在脆性过大、亲水性差、售价太高等明显缺点。本文综述了近年来以聚乳酸为主链进行的接枝聚合反应。聚乳酸接枝物的合成,能够明显改善聚乳酸的表面性能。而且可以在聚乳酸与其他高分子材料的共混体系中发挥明显的增容作用,为新型聚乳酸共混物的制备提供了可能性。     

Preparation of poly(β-hydroxybutyrate) and poly(lactide) hollow spheres with controlled wall thickness

In recent years, polymer microcapsules have attracted more and more attention because of their specific properties and applications in encapsulation and drug delivery. Great effort has been made to investigate the preparation methods, structure controls as well as the property designs for the polymer microcapsules. In this work, we reported an effective route for the preparation of poly(β-hydroxybutyrate) (PHB) and poly(lactic acid) (PLA) hollow spheres with controlled wall thickness, which involves the graft polymerization of the biodegradable polymers from the surface of silica spheres followed by removing the template cores. Nuclear magnetic resonance spectroscopy (NMR), thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscope (TEM) have been used to prove the structure of the hollow sphere and the intermediates. The result reveals that with the increase of reaction time the wall thickness of the hollow sphere will increase gradually.     

低毒金属配合物催化丙交酯开环聚合研究进展

可生物降解材料聚丙交酯主要通过丙交酯开环聚合反应制备,金属配合物催化剂由于具有结构易调变、催化活性高和立体选择性等优点,成为丙交酯开环聚合反应中应用最多的催化剂。近年来,低毒金属配合物催化剂引起了人们的极大关注。本文详细评述了低毒锂、钠、钾、钙、镁和锌配合物催化剂的最新研究进展,重点阐述了配体类型、配体上不同取代基的结构、电子效应对催化剂催化性能的影响,分析了溶剂对配合物在溶液中的状态以及对单体的配位、插入和聚合反应的影响。本文还对该领域发展趋势进行了展望,随着对低毒金属配合物催化丙交酯开环聚合机理研究的深入,未来将从配体结构设计出发,开发催化活性更高、性能更好的配合物催化剂,进而制得高质量的聚丙交酯。     

Influence of biodegradable materials in the recycled polystyrene

Polystyrene (PS) is one of the commonly used polymer in food packaging, that is why it generates a large amount of residual PS: because of the need of reduce environmental damage that occurs, it is common to recycle this polymer. Recycling of PS may be affected by the introduction of biodegradable polymer in industrial food. For this reason we have studied the influence that generates small amounts of biodegradable polymer (PLA, PHB, and TPS) in the recycled PS properties. The recycled PS and biodegradable polymers blends were evaluated by measuring the Vicat softening temperature, melt flow index, Fourier transformed infrared spectroscopy, and mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41161.     

Peculiar crystallization kinetics of biodegradable poly(lactic acid)/poly(propylene carbonate) blends

Binary blends of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) were found to display a peculiar crystallization kinetics. The two biodegradable polymers were blended by melt mixing, to obtain binary blends at various compositions. Temperature‐modulated calorimetry and dynamic‐mechanical analysis indicated that the blend components are partially miscible, and display two separate glass transitions, at temperatures intermediate to those of the plain polymers. Electron microscopy analysis disclosed the morphology of PLA/PPC blends, made of PPC‐rich particles finely dispersed within the PLA‐rich matrix. The possible establishment of interactions between the functional groups of the two polymers upon melt mixing has been hypothesized as the reason for partial miscibility and compatibility of the two biodegradable polymers. The PLA/PPC blends display good mechanical properties, with enhanced performance at rupture compared with plain PLA. Most importantly, the addition of PPC affects also the crystallization kinetics of PLA, since the more mobile PPC chains favor diffusion of the stiffer PLA chain segments towards the growing crystals, which fastens the spherulite growth rate of PLA. Such positive influence of an amorphous polymer on crystal growth rate has been demonstrated here for the first time in blends that display phase‐separation in the melt. POLYM. ENG. SCI., 55:2698–2705, 2015. © 2015 Society of Plastics Engineers     

Synthesis and characterization of poly(lactic acid) based graft copolymers

This review summarizes recent developments in the preparation and characterization of grafting of poly(lactic acid) or polylactide (PLA). PLA is the most expansively researched and utilized biodegradable, biocompatible, compostable, recyclable and renewable thermoplastic polyester. The graft copolymers of PLA have been synthesized and characterized by different spectroscopic techniques, including FTIR spectra and NMR data. The graft copolymers of PLA have been analyzed critically by taking different monomers/polymers; such as chitosan, cellulose, starch, polyethylene glycol, vinyl based polymers, lignin, dextran, methyl methacrylate, maleic anhydride and graphene oxide. In the first part of this review, the grafting of PLA and applications of grafted PLA has been discussed briefly. The second part, the major objective of this paper, focuses on the synthesis and characterization of different PLA based graft copolymers. For few cases, where useful properties, such as high molecular weight, narrow PDI, or stereocontrol, have been observed, a more detailed examination of the graft copolymers is provided.     

Maleic Anhydride-Grafted PLA Preparation and Characteristics of Compatibilized PLA/PBSeT Blend Films

Poly(butylene sebacate-co-terephthalate) (PBSeT) is a biodegradable flexible polymer suitable for melt blending with other biodegradable polymers. Melt blending with a compatibilizer is a common strategy for increasing miscibility between polymers. In this study, PBSeT polyester was synthesized, and poly(lactic acid) (PLA) was blended with 25 wt% PBSeT by melt processing with 3–6 phr PLA-grafted maleic anhydride (PLA-g-MAH) compatibilizers. PLA-g-MAH enhanced the interfacial adhesion of the PLA/PBSeT blend, and their mechanical and morphological properties confirmed that the miscibility also increased. Adding more than 6 phr of PLA-g-MAH significantly improved the mechanical properties and accelerated the cold crystallization of the PLA/PBSeT blends. Furthermore, the thermal stabilities of the blends with PLA-g-MAH were slightly enhanced. PLA/PBSeT blends with and without PLA-g-MAH were not significantly different after 120 h, whereas all blends showed a more facilitated hydrolytic degradation rate than neat PLA. These findings indicate that PLA-g-MAH effectively improves PLA/PBSeT compatibility and can be applied in the packaging industry.     

聚乳酸的合成及催化剂研究进展

聚乳酸是目前最具有发展前景的具有生物相容性的可降解高分子塑料,其合成过程得到了广泛的研究。介绍了聚乳酸2种重要合成途径,间接聚合即开环聚合可以得到高相对分子质量且性质优良的产物,但是合成过程复杂,需要纯化步骤;直接聚合流程简单,产物相对分子质量较低,但直接聚合产物可以通过扩链法和固相缩聚这2种后缩聚方法,或者是共沸缩聚得到性质与开环聚合产物相媲美的产物,因此是降低聚乳酸生产成本的有效方法。此外,综述了合成阶段使用的各类催化剂,并指出开发新型无毒且高效的非金属催化剂是今后的发展趋势。     

生物可降解聚乳酸/层状硅酸盐纳米复合材料的研究进展

生物可降解聚乳酸是一种具有广泛应用前景的环境友好型的生物高分子材料,但是其力学性能、热稳定性能不稳定.利用层状硅酸盐的特殊结构,以各种有机改性的层状硅酸盐为添加物,通过原位插层聚合、溶液插层、熔融插层和剥离.吸附等方法制备生物可降解聚乳酸/层状硅酸盐纳米复合材料,其力学性能、热稳定性、生物降解性等均有显著提高,其展现出极其广阔的应用前景.本文概述了近年来生物可降解聚乳酸/层状硅酸盐纳米复合材料的制备、结构、性能和应用等方面的研究进展,并且对各种制备方法进行了分析比较.     

可完全生物降解的聚乳酸共混体系研究进展

综述了国内外以聚乳酸（PLA）为基础的完全生物降解共混体系的研究进展,主要包括不同光学活性的PLA共混、PLA与脂肪族聚脂共混、PLA与天然高分子共混、PLA与聚己内酯共混、PLA与聚乙二醇共混、PLA与聚乙烯醇共混以及PLA与聚乙烯基吡咯烷酮共混等。目前的研究表明,将PLA与另一种完全生物降解组分共混,通过不同组分分子间的相互作用,使PLA材料在保持环境友好性的同时提高了力学性能、增加了韧性、并降低了生产成本等,从而扩展了PLA在工程塑料领域和包装等领域的应用。