Biopolymer blends based on polylactic acid and polyhydroxy butyrate‐co‐valerate: Effect of clay on mechanical and thermal properties

Biodegradable polymer blends consisting of polylactic acid (PLA) and polyhydroxy butyrate‐co‐valerate (PHBV) have been prepared by melt mixing in a twin screw extruder and followed by injection molding technique. Cereplast PLA containing starch as an additive was used to make the blends. The effects of three different types of clay (montmorillonite, bentonite, and chemically modified bentonite) on the mechanical and thermal properties of the blends were studied. The ratio of PLA and PHBV (w/w) was maintained at 70:30 while the weight of clay was fixed at 1%. The addition of clay was found to result in a slight increase in tensile strength and modulus. Viscoelastic studies revealed that the damping property of the blends decreased with the addition of clay. This was attributed to the decreased segmental motion in the molecular chains. The morphology of the blends has been investigated by environmental scanning electron microscopy and a homogenous surface was observed for the blend containing montmorillonite. POLYM. COMPOS., 36:2042–2050, 2015. © 2014 Society of Plastics Engineer     

聚碳酸亚丙酯/聚乳酸共混物光照条件下的降解行为研究

研究了聚碳酸亚丙酯（PPC）/聚乳酸（PLA）共混物在光照条件下的降解性能,通过力学实验、质量变化、扫描电子显微镜（SEM）、衰减全反射红外光谱技术（ATR-FTIR）、高温凝胶渗透色谱（GPC）和热重分析（TG）分别研究了共混物力学性能、质量损失、表面微观形貌、化学结构、相对分子质量和热稳定性的变化规律。结果表明,100/0、70/30、50/50、30/70、0/100（质量比,下同）的PPC/PLA共混物光照56d时质量损失率为34.89%、40.50%、39.38%、29.6%和6.24%,共混物在14d时几乎损失所有的力学性能;光照56d后PPC和50/50的PPC/PLA共混物表面有明显的裂纹和孔洞,而PLA表面没有变化,光照时间越长,共混物表面越粗糙,降解程度越大;共混物的羟基指数（HI）和羰基指数（CI）在前21d不断增大,其中前14d比较明显;共混物在光照56d后相对分子质量降低,多分散性指数减小,分子量分布变窄;共混物失重5%的热分解温度（T-5%）和最大速率失重温度（TP）提高,而PPC的TP却降低。     

Toughness enhancement of poly(lactic acid) by melt blending with natural rubber

Rubber toughened poly(lactic acid) (PLA) was prepared by blending with natural rubber (NR)‐based polymers. The blends contained 10 wt % of rubber and melt blended with a twin screw extruder. Enhancement of impact strength of PLA was primarily concernced. This study was focused on the effect of rubber polarity, rubber viscosity and molecular weight on mechanical properties of the blends. Three types of rubbers were used: NR, epoxidized natural rubber (ENR25 and ENR50), and natural rubber grafted with poly(methyl methacrylate) (NR‐g‐PMMA). Effect of viscosity and molecular weight of NR, rubber mastication with a two‐roll mill was investigated. It was found that all blends showed higher impact strength than PLA and NR became the best toughening agent. Viscosity and molecular weight of NR decreased with increasing number of mastication. Impact strength of PLA/NR blends increased after applying NR mastication due to appropriate particle size. DMTA and DSC characterization were determined as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

不同构型聚乳酸共混体系的立构复合结晶研究进展

左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)在共混体系中可形成立构复合(sc)结晶,与聚乳酸(PLA)同质结晶材料相比,sc 结晶材料具有良好的耐热性和耐化学稳定性。因此,sc 结晶是改善PLA 综合性能的一种有效手段。但在PLLA/PDLA 共混体系中,存在各自的同质结晶与两者之间sc 结晶的竞争,所以制备高耐热sc 型PLA 材料的关键之一是理解其sc 结晶的形成条件与机理,进而调控和促进其sc 结晶程度。在PLLA/PDLA 共混物中,sc 结晶受聚合物化学结构、结晶与加工条件等诸多因素影响,其影响规律和机理较复杂。根据PLLA/PDLA共混物sc 结晶行为影响因素的不同,从聚合物分子量、立构规整性、共混比例、分子链拓扑结构、结晶方式与条件、加工助剂和其他组分加入6 个方面出发,详细综述了PLLA/PDLA 共混物sc 结晶及其sc 材料制备的研究进展,以期为高耐热生物基PLA 材料的加工制备提供指导。     

PET/PLA共混物相容性和结晶性能的研究

研究了相容剂钛酸四丁酯[Ti(OBu)4]含量、聚乳酸(PLA)含量对聚对苯二甲酸乙二醇酯(PET)/PLA共混物相容性的影响,探讨了共混物的熔融和结晶行为,并对其结晶形貌进行了观察。结果表明,Ti(OBu)4含量为PLA的4%(质量分数,下同)时,PET/PLA共混物的相容性良好,但当PLA含量超过30%时,共混物出现相分离;PLA的加入使PET的结晶峰变窄,结晶速率增加,且结晶峰温度向高温方向移动;PLA的加入使PET的晶粒尺寸大幅减小,晶粒数目大幅增加,结晶更加完善。     

Modification of poly (lactic acid) through the incorporation of gum rosin and gum rosin derivative: Mechanical performance and hydrophobicity

The modification of PLA by melt compound with gum rosin (GR) and pentaerythritol ester of GR (PEGR) was investigated by studying the mechanical and thermal performance, blends morphology, wettability, and water absorption. Standard testing specimens for characterization were made at a variate resin content of 5, 10, and 15 part per hundred resin (phr) and manufactured by injection molding. It was found that GR and PEGR had a lubricating effect in PLA polymeric chains, resulting in a remarkable increase of 790 and 193% in melt flow index with only 5 phr GR and PEGR contents, respectively. A significant change in more than 10° of increasing water contact angle was observed for PLA with 15 phr PEGR. Thermogravimetric analysis reveals that PEGR led to delayed PLA degradation/decomposition process to higher temperature, increasing the onset temperature (T_5%) in more than 7°C for PLA with 15 phr PEGR.     

Mechanical and thermal properties of wood fibers reinforced poly(lactic acid)/thermoplasticized starch composites

Thermoplasticized starch (TPS) filled poly(lactic acid) (PLA) blends are usually found to have low mechanical properties due to poor properties of TPS and inadequate adhesion between the TPS and PLA. The purpose of this study was to investigate the reinforcing effect of wood fibers (WF) on the mechanical properties of TPS/PLA blends. In order to improve the compatibility of wood with TPS/PLA blends, maleic anhydride grafted PLA (MA‐g‐PLA) copolymer was synthesized and used. TPS, TPS/PLA blends, and WF reinforced TPS/PLA composites were prepared by twin‐screw extrusion and injection molded. Scanning electron microscope and crystallinity studies indicated thermoplasticity in starch. WF at two different weight proportions, that is, 20% and 40% with respect to TPS content were taken and MA‐g‐PLA at 10% to the total weight was chosen to study the effect on mechanical properties. At 20% WF and 10% MA‐g‐PLA, the tensile strength exhibited 86% improvement and flexural strength exhibited about 106% improvement over TPS/PLA blends. Increasing WF content to 40% further enhanced tensile strength by 128% and flexural strength by 180% with respect to TPS/PLA blends. Thermal behavior of blends and composites was analyzed using dynamic mechanical analysis and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46118.     

聚乳酸（PLA）／己二酸-对苯二甲酸-丁二酯共聚物（PBAT）／乙酰化柠檬酸三丁酯（ATBC）共混物的结晶行为

采用熔融共混法制备聚乳酸（PLA）／己二酸-对苯二甲酸-丁二酯共聚物（PBAT）／乙酰化柠檬酸三丁酯（ATBC）共混物。用差示扫描量热仪（DSC）和偏光显微镜（POM）分析了乙酰化柠檬酸三丁酯（ATBC）对共混物PLA结晶行为的影响。结果表明当PLA／PBAT含量为80／20（质量比）时,随着ATBC量的增加,PLA的Tg、Tc和Tm降低,结晶度提高,球晶生长速率增加。     

Morphologies and mechanical properties of polylactide blends with medium chain length poly(3‐hydroxyalkanoate) and chemically modified poly(3‐hydroxyalkanoate)

Blends of bacterial poly(3‐hydoroxyalkanoate) (PHA) with a medium‐length side chain and polylactide (PLA), and blends of the chemically modified PHA (ePHA) with PLA, were prepared. The morphologies, some physical properties, and thermal behavior of the blends based on PLA were investigated by electron microscopies, testing machines, and a differential scanning calorimeter, respectively. A blend of uncrystallized rubbery second components, PHA and ePHA, produced an increase in the impact toughness of the PLA blends in contrast to a decrease in the tensile strength value. PHA, especially, with an inserted epoxy group side chain was more effective in improving the morphology and the physical properties than PHA. The ePHA particles existed in the PLA domain as a dispersed phase having a size of 0.1–1 μm. The results of the biodegradation test demonstrated that the PLA blends still maintained their biodegradability and were more accessible to hydrolysis and microbial attack, resulting in a greater weight loss than the pure PLA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2363–2369, 2004     

Tributyl citrate oligomers as plasticizers for poly (lactic acid): thermo-mechanical film properties and aging

Poly (lactic acid), PLA, is a biodegradable thermoplastic that can be produced from renewable resources. The polymer is of interest for production of films for packaging applications. However, plasticization of PLA is required in order to obtain films with sufficient flexibility. PLA was blended with tributyl citrate (TbC) and two oligomers of TbC that were synthesized by transesterification of tributyl citrate (TbC) and diethylene glycol (DEG). Dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were used to investigate the dynamic mechanical and thermal properties of the blends. All the plasticizers investigated decreased the glass transition temperature of PLA, and the reduction was the largest with the plasticizer having the lowest molecular weight. The PLA matrix became saturated with plasticizer at a certain concentration and phase separation occurred; the higher the molecular weight of the plasticizer, the lower the saturation concentration. Aging of the blends at room temperature for several months induced partial phase separation in the material. It was observed that the morphological stability of the blends was enhanced when the plasticizer concentration was reasonably low, i.e. 10-15 wt%.     

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.     

Effects of moisture content and heat treatment on the physical properties of starch and poly(lactic acid) blends

Starch, a hydrophilic renewable polymer, has been used as a filler for environmentally friendly plastics for about 2 decades. Starch granules become swollen and gelatinized when water is added or when they are heated, and water is often used as a plasticizer to obtain desirable product properties. The objective of this research was to characterize blends from starch and poly(lactic acid) (PLA) in the presence of various water contents. The effects of processing procedures on the properties of the blends were also studied. Blends were prepared with a lab‐scale twin‐screw extruder, and tensile bars for mechanical testing were prepared with both compression and injection molding. Thermal and mechanical properties of the blends were analyzed, and the morphology and water absorption of the blends were evaluated. The initial moisture content (MC) of the starch had no significant effects on its mechanical properties but had a significant effect on the water absorption of the blends. The thermal and crystallization properties of PLA in the blend were not affected by MC. The blends prepared by compression molding had higher crystallinities than those prepared by injection molding. However, the blends prepared by injection molding had higher tensile strengths and elongations and lower water absorption values than those made by compression molding. The crystallinities of the blends increased greatly with annealing treatment at the PLA second crystallization temperature (155°C). The decomposition of PLA indicated that PLA was slightly degraded in the presence of water under the processing temperatures used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3069–3082, 2001     

Reactive compatibilization of PLA/PBS bio-blends via a new generation of hybrid nanoparticles

Poly(butylene succinate) (PBS) is a worthy biodegradable thermoplastic polyester for blending along with other biopolymers, especially with poly (lactic acid) (PLA), to overcome its inadequacies in mechanical and thermal characteristics. Since binary blends of PLA and PBS showed that they are incompatible, compatibilization is required. In this work, multi-epoxide polyhedral oligomeric silsesquioxane (Glycidyl POSS) was added to PLA and PBS using the melt blending method to make them compatible. The blends were prepared at different weight ratios having different amounts of compatibilizer. SEM analysis showed that the Glycidyl POSS impacted the interfacial adhesion and other properties of PLA and PBS blends. Noticeable improvements in mechanical properties were revealed by tensile and impact test results. Tensile strength and Young's modulus were improved when epoxy-POSS was added up to 1 and 3 wt% into ternary blends, but further increasing POSS concentrations resulted in lower values. FTIR analysis showed a strong interaction between the epoxide group of POSS and the end groups of PBS or PLA. The thermal properties of samples were analyzed using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. The shifts in glass transition temperatures of the PLA phase towards lower values appeared in DSC, confirming the enhanced compatibility of PLA and PBS. Also, the reinforcing ability of the POSS inorganic core structure impacted the thermal stability of the blends.     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

Morphology,mechanical properties,and durability of poly(lactic acid) plasticized with Di(isononyl) cyclohexane‐1,2‐dicarboxylate

Di(isononyl) cyclohexane‐1,2‐dicarboxylate (DINCH) was used as a new plasticizer for poly(lactic acid) (PLA), and the effects of DINCH and tributyl citrate ester (TBC) on the morphology, mechanical and thermal properties, and durability of PLA were compared. DINCH has limited compatibility with PLA, leading to PLA/DINCH blends with phase separation in which DINCH forms spherical dispersed phase. TBC is compatible with PLA and evenly distributed in PLA. Plasticized PLA with 10 and 20 phr DINCH have a constant glass transition temperature (T_g) of 50°C and are stiff materials with high elongation at break and impact strength. TBC could significantly decrease the T_g and increase the crystallinity of PLA, and PLA/TBC (100/20) blend is a soft material with a T_g of 24°C. The durability of plasticized PLA was characterized by weight loss measurement under water immersion, mechanical properties, and thermal analysis. The results reveal that PLA/DINCH blends have better water resistance and aging resistance properties than PLA/TBC blends, which is attributed to the relatively high hydrophobicity of DINCH and high T_g of PLA/DINCH blends. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

The morphology,properties, and shape memory behavior of polylactic acid/thermoplastic polyurethane blends

Biodegradable polylactic acid (PLA) was compounded with thermoplastic polyurethane (TPU) by twin‐screw extrusion at weight ratios of 90/10, 80/20, 70/30, and 60/40. The blends were investigated based on their phase morphology, thermal and mechanical properties, and shape memory properties. The tensile results showed that PLA was successfully toughened by TPU. When the TPU content was 40%, the elongation‐at‐break increased to 400%. The SEM morphology showed that TPU was dispersed uniformly in the PLA matrix; DMA and DSC results indicated that the two polymers were immiscible. Most interestingly, it was found that the blends exhibited a shape memory behavior and, unlike most of the existing shape memory polymers (SMPs), the PLA/TPU blends could be deformed at room temperature without an extra heating and cooling step. During the deformation process, TPU acted as a toughening agent that prevented the PLA/TPU blends from breaking; thus, the temporary shape could be kept and internal stress was stored in the blends. Upon heating to above the glass transition temperature of PLA (about 60°C), the deformed parts regained their original shapes quickly along with the release of the stress. POLYM. ENG. SCI., 55:70–80, 2015. © 2014 Society of Plastics Engineers     

Influence of phthalic anhydride and bioxazoline on the mechanical and morphological properties of biodegradable poly(lactic acid)/poly[(butylene adipate)‐co‐terephthalate] blends

Poly(lactic acid) (PLA)/poly[(butylene adipate)‐co‐terephthalate] (PBAT) blends were fabricated by melt blending, with 2,2′‐(1,3‐phenylene)bis(2‐oxazoline) (BOZ) and phthalic anhydride (PA) used as compatibilizers. It was found that a small amount of BOZ or PA greatly increased the elongation at break of the PLA/PBAT blends without sacrificing their high tensile strength. Scanning electron microscopy results revealed that the PBAT particles became finer and were uniformly dispersed in the matrix when the compatibilizers were incorporated, which indicated that the interfacial bonding and compatibilization between PLA and PBAT were improved in the presence of the compatibilizers. Compared with PLA/PBAT blends, the molecular weight of PLA/PBAT/PA/BOZ blends was increased due to chain‐extending reactions. Differential scanning calorimetry results suggested PBAT decreased the crystallization rate and crystallinity of PLA in the blends. Moreover, the glass transition temperature of PBAT was further decreased when the compatibilizers were used. © 2013 Society of Chemical Industry     

PLA—SPP共聚物的合成及其在SPI／PLA共混中的应用

以辛酸亚锡为催化剂,合成出丙交酯-大豆多肽共聚物（PLA-SPP）,并对其进行红外及核磁共振光谱表征。研究了大豆蛋白（SPI）与聚乳酸（PLA）的共混工艺,考察了PLA-SPP共聚物对SPI/PLA共混体系的影响,发现该共聚物能有效地增加两者的相容性,当共聚物的含量为5%时,共混物的相容性明显改善;样品断面扫描电镜（SEM）照片显示,其微观结构明显变得均匀,两相分散较好。DSC结果显示,共聚物的加入增大了PLA与SPI间的作用力,并阻碍了PLA相的结晶行为。同时,加入共聚物后,共混物的耐水性也得到了明显提高。     

Hydrolytic stability of polylactide and poly(methyl methacrylate) blends

The hydrolytic stability of polylactide/poly(methyl methacrylate) (PLA/PMMA) blends prepared using a twin‐screw extrusion process was investigated. The effects of hydrolysis were monitored in neutral and alkaline media at 80 °C by tracking the changes in molecular weight distribution, weight loss, water uptake, and crystallization behavior. The crystallinity of PLA in blends prior to hydrolysis was shown to be largely hindered by the presence of PMMA. However, PLA recrystallized rapidly during hydrolysis. The PMMA in the blends was shown to provide increased hydrolytic and structural stability to the blends. In the neutral medium, the presence of PMMA delayed and reduced the weight loss but did not significantly affect PLA degradation kinetics. On the other hand, in the alkaline medium, the weight loss rate was strongly decreased in presence of PMMA and the kinetics of degradation was shown to be depend on PMMA content. The microstructure of these blends throughout the hydrolysis process was also examined by scanning electron microscopy. A porous structure, with interconnected pores in the 20–50 nm range, was developed due to the selective removal of PLA. Based on these morphological observations, erosion mechanism of PLA/PMMA blends was discussed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45991.     

Effect of Chain-Extenders on the Properties and Hydrolytic Degradation Behavior of the Poly(lactide)/Poly(butylene adipate-co-terephthalate) Blends

Biodegradable poly(lactide)/poly(butylene adipate-co-terephthalate) (PLA/PBAT) blends were prepared by reactive blending in the presence of chain-extenders. Two chain-extenders with multi-epoxy groups were studied. The effect of chain-extenders on the morphology, mechanical properties, thermal behavior, and hydrolytic degradation of the blends was investigated. The compatibility between the PLA and PBAT was significantly improved by in situ formation of PLA-co-PBAT copolymers in the presence of the chain-extenders, results in an enhanced ductility of the blends, e.g., the elongation at break was increased to 500% without any decrease in the tensile strength. The differential scanning calorimeter (DSC) results reveal that cold crystallization of PLA was enhanced due to heterogeneous nucleation effect of the in situ compatibilized PBAT domains. As known before, PLA is sensitive to hydrolysis and in the presence of PBAT and the chain-extenders, the hydrolytic degradation of the blend was evident. A three-stage hydrolysis mechanism for the system is proposed based on a study of weight loss and molecular weight reduction of the samples and the pH variation of the degradation medium.