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.     

可生物降解聚乳酸纳米复合材料的研究进展

聚乳酸具有良好的机械性能、热塑性、生物相容性和生物降解性等,广泛应用于可控释材料、生物医用材料、组织工程材料、合成纤维等领域.将填充剂以纳米尺度分散在聚乳酸基体中形成聚乳酸纳米复合材料,能显著提高聚乳酸的机械性、气体阻隔性能、热性能及生物降解性能,受到国内外学者及工业界的广泛关注.本文针对近年来在聚乳酸纳米复合材料的制备方法、结构表征与性能测试等方面取得的研究成果进行综述,并对今后的研究方向进行了展望.     

Preparation and biodegradation of clay composites of PLA

PurposePerspective applications of nanocomposites in biomedical applications are investigated in this work by producing intercalated dispersions of clays into a biodegradable polymer matrix. Poly(lactic acid) (PLA) was selected being produced from renewable resources and approved by the Food and Drug Administration for medical use.In order to improve PLA mechanical properties and to accelerate its degradation, different layered silicate nanoclays are added: montmorillonites and fluorohectorites, without or with organic modifiers. Preparation, characterization, mechanical properties and biodegradation in blood plasma are evaluated.ResultsNew biodegradable materials were obtained, with improved mechanical properties (Young modulus, Peak stress and Strain at break) and with increased degradation rate (weight loss and lactic acid release).     

Polylactide/graphite nanosheets/MWCNTs nanocomposites with enhanced mechanical, thermal and electrical properties

In this study, we have prepared a series of novel biodegradable polymer [polylactide (PLA)]-based nanocomposites using graphite nanosheets (GNs) and multi-walled carbon nanotubes (MWCNTs) by solution-blending technique and investigated their morphologies, structures, thermal stabilities, mechanical and dielectric properties, and electrical and thermal conductivities. Before preparation of the PLA/GNs/MWCNTs nanocomposites, the raw GNs used were endured a rapid expansion by thermal treatment. Temperature of this treatment had some obvious impacts on morphological changes of graphite nanosheets which were verified by means of scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. Resultant nanocomposites were characterized and evaluated by means of SEM, XRD, thermal conductivity measurements, tensile and impact tests, thermogravimetric analysis and dielectric measurements. Results obtained in this study indicated that thermal-expanded GNs in the presence of MWCNTs facilitate the formation of an appropriate conductive network in PLA matrix which resulted in a relatively low percolation threshold for thermal and electrical conductions of PLA/GNs/MWCNTs nanocomposites. Significant improvements in thermal and electrical conductivities, thermal stability and mechanical properties of PLA/GNs/MWCNTs nanocomposites obtained through the presence of both nanoparticles in PLA matrix were associated with their good co-dispersion and co-reinforcement effects. The macroscopic properties of nanocomposites were found to be strongly dependent on their components, concentrations, dispersion, and the resulted morphological structures.     

A review on degradation mechanisms of polylactic acid: Hydrolytic,photodegradative, microbial,and enzymatic degradation

Recently, thoughtful disagreements between scientists concerning environmental issues including the use of renewable materials have enhanced universal awareness of the use of biodegradable materials. Polylactic acid (PLA) is one of the most promising biodegradable materials for commercially replacing nondegradable materials such as polyethylene terephthalate and polystyrene. The main advantages of PLA production over the conventional plastic materials is PLA can be produced from renewable resources such as corn or other carbohydrate sources. Besides, PLA provides adequate energy saving by consuming CO₂ during production. Thus, we aim to highlight recent research involving the investigation of properties of PLA, its applications and the four types of potential PLA degradation mechanisms. In the first part of the article, a brief discussion of the problems surrounding use of conventional plastic is provided and examples of biodegradable polymers currently used are provided. Next, properties of PLA, and (Poly[L-lactide]), (Poly[D-lactide]) (PDLA) and (Poly[DL-lactide]) and application of PLA in various industries such as in packaging, transportation, agriculture and the biomedical, textile and electronic industry are described. Behaviors of PLA subjected to hydrolytic, photodegradative, microbial and enzymatic degradation mechanisms are discussed in detail in the latter portion of the article.     

Formulation and characterization of compatibilized poly(lactic acid)‐based blends and their nanocomposites with silver‐loaded kaolinite

Biodegradable polymer nanocomposites have been developed in this study as materials for use in the packaging of moisture‐sensitive products. Poly(lactic acid) (PLA) was the main component of the nanocomposites with poly(butylene adipate‐co‐terephthalate) (PBAT) as flexibility enhancer. Tetrabutyl titanate was also added as a compatibilizer to enhance the interfacial affinity between PLA and PBAT by inducing the formation of some PLA/PBAT via transesterification during the melt blending process, thereby improving the mechanical properties of the blends. Silver‐loaded kaolinite synthesized via chemical reduction was also incorporated into the compatibilized blends for further property improvement. Herein, we report a novel biodegradable quaternary nanocomposite system with intercalated‐exfoliated clay dispersion that was uniquely achieved by increasing the interlamellar space between kaolinite layers through silver nanoparticle insertion. The resultant nanocomposites containing as little as 4 phr modified clay reduced the elongation at break from 213.0 ± 5.85% to 53.8 ± 1.81%, enhanced thermal stability (initial decomposition temperature increased from 378 °C to 399 °C) and exhibited a water vapor permeability reduction of 41.85%. On the basis of these properties, the developed nanocomposites are considered to be promising candidates for use in bio‐packaging applications to replace non‐biodegradable and petro‐based plastics. © 2014 Society of Chemical Industry     

熔融插层法制备聚乳酸/有机蒙脱土纳米复合材料及其性能研究

以新疆地产蒙脱土和聚乳酸为原料,通过熔融插层的方法制备了聚乳酸(PLA)/有机蒙脱土（OMMT）纳米复合材料。分别采用X射线衍射仪、扫描电子显微镜、透射电子显微镜、热重分析仪等对复合材料的微观结构、形貌及热稳定性进行了表征和分析。研究表明,PLA大分子链已经插入OMMT片层间,层间距明显增大,形成PLA/OMMT纳米复合材料,体系的相容性良好。PLA/OMMT纳米复合材料的热失重曲线移向高温端,其热分解温度提高。PLA/OMMT纳米复合材料的熔点、维卡软化点、冲击强度、拉伸强度、热稳定性均比PLA基体有明显的提高。PLA/OMMT纳米复合材料的降解性初步研究表明其是一种良好的生物可降解环保塑料。     

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.     

An overview of the recent advances in polylactide-based sustainable nanocomposites

The article reports recent advances in reference to the existing literature and presents a knowledge gap and potential solution ideas for polylactide (PLA) nanocomposites as sustainable materials. Various types of nanoparticles have been used for the development of PLA nanocomposites; however, this work focuses on PLA nanocomposites of nanoclay, nanocelluloses, carbon nanotube, and graphene. By providing a wholistic overview of the fundamental knowledge pertaining to PLA, and covering all critical aspects related to processing, characterization, and applications of PLA nanocomposites, this review provides a direction for future developments in the field of PLA nanocomposites suitable for various advanced applications, which is still scarce in the literature, including review articles. Moreover, the effects of dispersion/distribution of various types of nanoparticles on the degradation characteristics and special properties, such as cytocompatibility, electrical conductivity, and antimicrobial properties, of PLA nanocomposites are critically reviewed with regard to the nature of nanoparticles used for nanocomposite formation. In summary, this review provides new insight into the design and formulation of advanced PLA nanocomposites for a wide range of applications as sustainable materials.     

Fabrication and characterization of biodegradable poly(lactic acid)/layered silicate nanocomposites

In this study biocompatible/biodegradable poly(lactic acid) (PLA)/layered silicate nanocomposites (PLSNs) were successfully prepared by the intercalation of PLA polymer into organically modified layered silicate through the solution mixing process. Both X‐ray diffraction data and transmission electron microscopy images of PLSNs indicate most of the swellable silicate layers were disorderedly intercalated into the PLA matrix. Mechanical properties of the 0.1 wt% silicate‐containing fabricated nanocomposites performed by dynamic mechanical analysis have significant improvements in the storage modulus when compared to that of neat PLA matrix. Adding more layered silicates into PLA matrix induced a decrease in the mechanical properties of PLSNs, probably due to the presence of a large dimension of porosity in the fabricated nanocomposites. POLYM. ENG. SCI., 45:1615–1621, 2005. © 2005 Society of Plastics Engineers     

生物降解聚乳酸合金最新进展及展望

系统论述了生物降解聚乳酸(PLA)合金复合材料的最新研究进展,着重介绍了聚乳酸合金中有巨大商用潜力的完全生物基降解高分子合金体系:PLA/淀粉合金、PLA/纤维素合金、PLA/聚ε-己内酯合金、PLA/聚酰胺合金、PLA/聚羟基脂肪酸酯合金、PLA/壳聚糖合金及PLA/稀土多元复合材料等。并提出利用稀土离子独特的4f电子亚层能级的空轨道与聚乳酸生物基复合材料中的羰基、羟基等含氧官能团配位来改善聚乳酸合金复合材料的综合性能,这为设计开发新型稀土-聚乳酸复合材料提供了新的思路,为聚乳酸产业化进程提供新的契机。     

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.     

Effects of thermoplastic polyurethane on the properties of poly(lactic acid)/organo‐montmorillonite nanocomposites based on novel vane extruder

Polylactic acid (PLA)/organo‐montmorillonite (OMMT) nanocomposites toughened with thermoplastic polyurethane (TPU) were prepared by melt‐compounding on a novel vane extruder (VE), which generates global dynamic elongational flow. In this work, the mechanical properties of the PLA/TPU/OMMT nanocomposites were evaluated by tensile, flexural, and tensile tests. The wide‐angle X‐ray diffraction and transmission electron microscopy results show that PLA/TPU/OMMT nanocomposites had clear intercalation and/or exfoliation structures. Moreover, the particles morphology of nanocomposites with the addition of TPU was investigated using high‐resolution scanning electronic microscopy. The results indicate that the spherical TPU particles dispersed in the PLA matrix, and the uniformity decreased with increasing TPU content (≤30%). Interestingly, there existed abundant filaments among amount of TPU droplets in composites with 30 and 40 wt% TPU. Furthermore, the thermal properties of the nanocomposites were examined with differential scanning calorimeter and dynamic mechanical analysis. The elongation at break and impact strength of the PLA/OMMT nanocomposites were increased significantly after addition of TPU. Specially, Elongation at break increased by 30 times, and notched impact strength improved 15 times when TPU loading was 40 wt%, compared with the neat PLA. Overall, the modified PLA nanocomposites can have greater application as a biodegradable material with enhanced mechanical properties. POLYM. ENG. SCI., 54:2292–2300, 2014. © 2013 Society of Plastics Engineers     

New polylactide-layered silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and melt rheology

Our continuing research on the preparation, characterization, materials properties, and biodegradability of polylactide (PLA)-layered silicate nanocomposites has yielded results for PLA-montmorillonite nanocomposites. Montmorillonite modified with trimethyl octadecylammonium cation was used as an organically modified layered silicate for the nanocomposites preparation. The internal structure of the nanocomposites in the nanometer range has been established by using wide-angle X-ray diffraction and transmission electron microscope analyses. All the nanocomposites exhibited superior improvement of practical materials properties such as storage modulus, flexural modulus, flexural strength, heat distortion temperature, and gas barrier property as compared to that of neat PLA. The biodegradability of neat PLA and a representative nanocomposite was also studied under compost, and the rate of biodegradation of neat PLA significantly increased after nanocomposites preparation. The melt rheology of neat PLA and various PLACNs was also studied.     

可生物降解聚合物基纳米复合材料降解性能研究进展

可生物降解聚合物中的层状硅酸盐纳米复合材料,可极大提高其力学性能,但同时会影响到材料的降解速率。研究纳米填料对可生物降解聚合物降解速率的影响及降解机理的变化,可拓宽其应用领域。综述聚乳酸(PLA)、淀粉、聚己内酯(PCL)、纤维素、聚羟基烷脂肪酸酯(PHA)、聚琥珀酸丁二醇酯(PBS)等可生物降解聚合物基层状硅酸盐纳米复合材料制备及降解性能研究现状及进展。     

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。     

Inorganic silica functionalized with PLLA chains via grafting methods to enhance the melt strength of PLLA/silica nanocomposites

The low melt strength greatly limits the application of PLA as biodegradable package materials produced by film blowing method. Modified silica nanoparticles are introduced into PLA matrix to solve this problem in this study. To build Poly (l-lactide) nanocomposites successfully, two kinds of convenient and efficient methods are conducted to synthesize well-defined topological PLLA grafted SiO₂ nanoparticle. One is the ring-opening of l-lactide (Grafting from), and another is nucleophilic addition reaction (Grafting to). The structure, molecular weight of grafted PLLA chains, grafting density, and the thermal decomposition behavior of the nanoparticles prepared by different methods are characterized. By varying the contents of the initiator SiO₂ and the molecular weight of the reacted PLA chains, high density-low molecular weight PLLA grafted SiO₂ are obtained in “grafting from” while high molecular weight-low grafting density PLLA grafted SiO₂ are synthesized in “grafting to”. It is exactly in good agreement with the theoretic model. The spatial distribution of nanoparticles as well as the interaction force between nanoparticles and matrix is critical important to structuring bionanocomposites with desirable properties. So the two kinds of synthesized nanoparticles are introduced into PLA matrix in our contribution to evaluate these two factors, respectively. The TEM and SEM results both reveal the uniform dispersion of nanoparticles after modified. While the extension and shear rheology results show that the long grafted chains covalently connected on the surface of the silica via “grafting to” contribute more to enhance the melt strength of PLA. Meanwhile, stabilized PLA nanocomposites films with modified silica via “grafting to” method are successfully blown base on these researches. The research in this work constitutes a robust way to design melt-strengthen PLA/SiO₂ nanocomposites.     

Nanocomposites of halloysite and polylactide

Naturally occurred halloysite (Hal) nanotubes compounded with polylactide (PLA) via melt mixing formed biodegradable and biocompatible clay polymer nanocomposites (CPN). The hydrogen bonding interactions between Hal and PLA were confirmed by Fourier transform infrared spectroscopy (FTIR). The modulus, strength and toughness of the Hal-PLA nanocomposites were substantially higher than those of neat PLA. Storage modulus and glass transition temperature of the Hal-PLA nanocomposites also increased with Hal loading as observed by dynamic mechanical analysis. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results showed that Hal was uniformly dispersed and oriented in the CPN. X-ray diffraction (XRD) of the CPN showed the absence of Hal reflection at around 20°, indicating interactions of the PLA molecular chains in the interlayer space of Hal. Hal could nucleate PLA, leading to the decreased cold crystallization temperature and increased crystallinity. The vicat softening temperature and the degradation temperature of the CPN increased with Hal loading. Owing to the high performance and biocompatibility of the CPN, the prepared Hal-PLA nanocomposites had potential applications in biodegradable plastic and biomedical areas.     

Mechanical and thermal properties of thermoplastic polyurethane‐toughened polylactide‐based nanocomposites

The crystallinity and mechanical and thermal properties of polylactide (PLA)‐based biodegradable‐engineered plastic nanocomposites were determined. The nanocomposites were composed of thermoplastic polyurethane (TPU)‐toughened PLA, Talcum (Talc) and organic modified clay (montmorillonite; OMC). The tensile and flexural tests showed that PLA blended with 10 wt% TPU, 4 wt% Talc powder and 2 wt% OMC had the highest modulus and strength without a loss of elongation. The heat distortion temperature (HDT) tests demonstrated that the thermally treated PLA‐based nanocomposites had an HDT of nearly double the HDT for untreated specimens. An analysis of the polymer using scanning electron microscopy demonstrated that the incorporation of inorganic fillers altered the heterogeneous morphology of the PLA/TPU blend. This study investigated the feasibility of using PLA‐based nanocomposites for practical use, including applications in the automotive and furniture industries. POLYM. COMPOS., 35:1744–1757, 2014. © 2013 Society of Plastics Engineers     

Interface compatibility and mechanisms of improved mechanical performance of starch/poly(lactic acid) blend reinforced by bamboo shoot shell fibers

Bamboo shoot shell fibers (BSSFs)/starch/poly(lactic acid) (PLA) ternary composites were prepared by blending BSSFs to starch/PLA matrices for the purpose of expanding BSSFs applications to enhance starch/PLA composites and creating a new low-cost biodegradable composite. The effects of BSSFs content (0–40 wt %) on the physical–mechanical properties were tested and interface compatibility and its mechanism to mechanical performance of BSSFs/starch/PLA composites were characterized by SEM-EDS, TG. The results showed that the mechanical strength, surface wettability, and water absorption of the composites continued improving when the BSSFs content increased from 0% to 20 wt %. However, mechanical modulus increased with increase in BSSFs content. The results of fracture microstructure and thermal property exhibited a good interfacial compatibility at low content of BSSFs and an interface debonding at high content of BSSFs. These investigations indicated that the BSSFs reinforcement to the composite is not consistent with interface compatibility of the ternary composites. The composites should be considered as a kind of green and low-cost biodegradable materials to replace traditional single-phase or multiphase materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47899.