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.     

Miscibility and thermal and mechanical properties of melt‐mixed poly(lactic acid)/poly(trimethylene terephthalate)/(methyl methacrylate)‐butadiene‐styrene copolymer blends

This study examined the miscibility and mechanical properties of melt‐mixed poly(lactic acid) (PLA), poly (trimethylene terephthalate) (PTT), and PLA/PTT blend with 5–10 phr of methyl methacrylate‐butadiene‐styrene copolymer (MBS). The isothermal crystallization kinetics of the PTT blends were analyzed by using the Avrami equation. The Differential Scanning Calorimetry (DSC) and scanning electron microscope results indicated that the miscibility of the PLA/PTT blends was improved by adding 5–10 phr of MBS. Although PLA, with the addition of 10 phr of MBS, had lower tensile strength at yield and higher breaking elongation and impact strength than pure PLA, no improvement in these mechanical properties could be observed in PLA/PTT blends. This result is explained by assuming that the crystallization of PTT at the interface favors the disentanglement of MBS from the PTT domain. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Biodegradable polymer blends of poly(L‐lactic acid) and gelatinized starch

Gelatinized starches were prepared with various content of glycerol and were investigated in terms of the effect of the glycerol addition on characteristics of starch and its blends. Poly (L‐lactic acid) (PLA) with various ratios of linear/star shaped PLA and starch gelatinized with various ratios of water/glycerol were melt‐blended by using twin screw mixer. The blends were characterized by DSC thermal analysis, tensile test and morphological analysis. Gelatinization of starch was found to lead to destruction or diminution of hydrogen bonding in granules and a decrease of crystallinity of starch. DSC data showed that starch played a role as a nucleating agent and glycerol as plasticizer contributed to an improvement in crystallinity in PLA blends. When the content of starch increased, the size of spherulites in PLA blends was smaller and less regular. In the case of PLA/pure starch blends, the voids appeared, which were formed by the separation of starch particles from the matrix. But for PLA/gelainized starch blends, these voids were not observed. In the case of blends with linear PLA and starch gelatinized with water/glycerol ratio of 100/40, the greatest superiority of mechanical properties was shown and the toughness was improved compared with PLA/pure starch blends.     

PLA/PBS共混物增黏改性的研究

采用熔融反应共混法,通过引入过氧化二苯甲酰(BPO),对聚乳酸/聚丁二酸丁二醇酯(PLA/PBS)进行增黏改性。研究了该PLA/PBS反应共混物的流变性能、凝胶分数、热性能、力学性能和断面微观形貌。结果表明:随着BPO用量的增加,PLA/PBS反应共混物的转矩和凝胶分数均增大;PLA/PBS反应共混物的结晶性和熔点(Tm)随着BPO用量的增加而降低,且出现熔融双峰,当BPO用量增至1 phr时,熔融双峰消失,PLA和PBS间的相容性显著改善;随着BPO用量的增加,PLA/PBS反应共混物的断裂伸长率、拉伸强度、冲击强度均有所提高,而玻璃化转变温度(Tg)先降后升,体系的内耗则逐渐降低。     

Development and properties evaluation of bio‐based PLA/PLGA blend films reinforced with microcrystalline cellulose and organophilic silica

The preparation and properties of hybrid materials based on poly(lactic acid)/poly(lactic acid‐co‐glycolic acid) (PLA/PLGA) blends using microcrystalline cellulose (MCC) and organophilic silica (R972) as fillers have been investigated. Hybrid materials were manufactured by solution casting using chloroform as solvent to prepare films. R972 was incorporated in a ratio of 3 wt%, and MCC was added in ratios of 3, 5, or 7 wt% with respect to the weight of the polymeric matrix. Films were prepared with only MCC addition or with MCC and R972 combined. Properties of the films were evaluated by X‐ray diffraction (XRD), nuclear magnetic resonance, differential scanning calorimetry (DSC) and mechanical property measurements. The results show that each filler, when added individually or in combination, affects the structure and final properties of the films differently. MCC acts as a nucleating agent for the crystallization of the polymeric matrix. An increase in the MCC content increased the crystallinity of the films. This effect became more pronounced with silica addition. The domain distribution curves showed PLA/PLGA blends to be homogeneous, which was further confirmed by DSC. An improvement in the mechanical performance was observed with MCC addition, especially when silica was added together with cellulose. POLYM. ENG. SCI., 57:464–472, 2017. © 2016 Society of Plastics Engineers.     

Mechanical,morphological, thermal properties and hydrolytic degradation behavior of polylactic acid/polypropylene carbonate blends prepared by solvent casting

The preparation of polylactic acid (PLA) and polypropylene carbonate (PPC) blend films by using the solvent casting method is to improve the properties of pure PLA. The blends' mechanical and thermal properties, morphological as well as hydrolytic degradation behavior are evaluated. The tensile test proved that the increase of PPC from 0 wt% to 75 wt% could improve the elongation of pure PLA when the graph showed a significant increase of the elongation from 10% to 1000%. Scanning Electron Microscopy (SEM) supported the significant increase in elongation of the blends when it shows a definite phase separation in 75/25 PLA/PPC, where 25% of PPC has formed islands in the PLA matrix. Differential scanning calorimetry indicates the partial miscibility of the blends where two peaks of the glass transition temperature moved towards each other when the amount of PPC increases. Fourier transform infrared (FTIR) spectroscopy revealed a possible intermolecular interaction between two polymers, which affects the miscibility of the blends. Finally, the hydrolytic degradation test indicates that the degradation started from the PLA phase and the blends' degradation rate decrease as wt% of PPC increase.     

EVA增韧聚乳酸的性能研究

对乙烯-醋酸乙烯共聚物(EVA)增韧聚乳酸(PLA)体系的力学、热学和结晶性能进行了研究,并分析了增塑剂邻苯二甲酸二辛酯(DOP)对PLA/EVA增韧体系性能的影响。结果表明,PLA/EVA的质量比为80/20时,二元共混体系的力学性能最佳;PLA/EVA/DOP的质量比为80/20/8时,三元共混体系的力学性能最佳;EVA对PLA的T_g、T_m和结晶度影响不大,但DOP会使T_g和T_m降低,而结晶度得到很大提高;偏光显微镜观察结果也证实了DOP的加入有利于PLA的结晶。     

Structures and properties of injection‐molded biodegradable poly(lactic acid) nanocomposites prepared with untreated and treated multiwalled carbon nanotubes

Structural, mechanical, thermal, and electrical properties of low‐loaded (0?1.5 wt%), untreated, and treated (with heat and nitric acid) multiwalled carbon nanotubes (MWCNTs)/poly (lactic acid) (PLA) nanocomposites have been studied. Among all synthesized composites, acid‐treated 1.0 wt% MWCNTs reinforced PLA shows superior tensile strength and modulus to those shown by other samples. All nanocomposites including the pure PLA exhibit the orthorhombic β‐form crystalline structure with low degree of crystallization, as demonstrated by X‐ray diffraction study. Differential scanning calorimetry (DSC) of injection molded samples, respectively, reveals an enhancement of PLA crystallinity by 8% and 14% for untreated and treated nanotubes, relating to the observed improvement in mechanical properties. Nanocomposites show double melting behavior when crystallized nonisothermally by DSC, whilst the pure PLA shows single melting character. Thermogravimetric analysis discloses that the MWCNTs‐loaded sample degraded faster than PLA. Surface resistivity of the nanocomposites is found to be dropped drastically by a factor of 10¹³ with a low loading of MWCNTs (1.5 wt%). A detailed discussion and correlation of the observed structures and properties are presented in this study. POLYM. ENG. SCI., 54:317–326, 2014. © 2013 Society of Plastics Engineers     

Reactive compatibilization of poly(l‐lactide)/poly(butylene succinate) blends through polyester maleation: from materials to properties

The melt blending of poly(l ‐lactide) (PLLA) with biodegradable poly(butylene succinate) (PBS) is considered with a view to fine‐tuning its mechanical properties and its degradability. For this purpose, both maleic‐anhydride‐grafted PLLA (PLLA‐g‐MA) and maleic‐anhydride‐grafted PBS (PBS‐g‐MA) were prepared and used as reactive compatibilizers. The influence of PBS melt viscosity on the morphology and mechanical properties of PLLA/PBS blends was studied. Interestingly, the blending of low viscosity PBS with PLLA allows PLLA to be toughened while the use of high viscosity PBS led to PLLA/PBS blends exhibiting co‐continuous morphology. The nanostructure of the co‐continuous blends may be tuned through the joint action of organo‐modified clays and reactive compatibilizers. The effect of PBS on PLLA degradability was also investigated. The accelerated weathering testing of blends reveals that such combination of biodegradable polymers allows their degradability rate to be tailored. It is found that the addition of 20 wt% PBS to PLLA allows the molar mass loss fraction to be doubled after 425 h of testing. © 2014 Society of Chemical Industry     

Compatibilization method applied to the chitosan‐acid poly(L‐lactide) solution

We are testing the compatibilization of the chitosan/PLA blends by addition of diisocyanate and at studying the effect of several MDI concentrations (0.5 and 2.5% of the global blend mass, w/w). To evaluate the MDI efficiency as a compatibilizer of chitosan/PLA blends, we worked with the following methods: IRTF spectra with higher peak at 1558 cm⁻¹ is due to the  NH bonds that exist in urea and urethane, thermal properties shows that the temperature of the endothermic peaks of the chitosan/PLA blends with MDI is very close to the temperature of pure chitosane and SEM micrography shows that MDI addition decreases the PLA particles size in the chitosan mixture; they also comply with the compatibilization theory. After that the mechanical properties have been characterized: we can notice that the MDI compatibilized chitosan/PLA blends have a higher Young's modulus than the noncompatibilized blends. we are showed that the use of 0.5% MDI is not enough sufficient to obtain a compatibilization, because a part of the MDI can be consumed by water. The addition of MDI increases the performance of the mechanical properties of the blends. Therefore, with this compatibilization, we could obtain some chitosan/PLA blends that would be water‐resistant and that would also keep their mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the shape of dispersed particles on the thermal and mechanical properties of biomass polymer blends composed of poly(L‐lactide) and poly(butylene succinate)

The structure and properties of binary blends composed of poly(lactic acid) (PLA) and fibrous poly(butylene succinate) (PBS), which were prepared by an uniaxial stretching operation in the molten state, were studied and compared with those of blends having spherical particles of PBS in a continuous PLA phase. We found from electron microscope observation that PBS nanofibers with a large aspect ratio were generated in the stretched samples. Enlargement of the surface area of the PBS particles, which showed nucleating ability for PLA, led to a high degree of crystallization and enhanced the cold crystallization in the heating process. Moreover, the PBS fibers in the stretched samples had a dominant effect on the mechanical properties in the point range between the glass‐transition temperature of PLA and the melting temperature of PBS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚乳酸/聚乙醇酸共混合金界面改性研究

用熔融共混挤出法制备了不同配比的聚乳酸(PLA)/聚乙醇酸(PGA)共混合金,并分别加入环氧型扩链剂ADR 4370F进行对比分析,通过拉伸性能测试、弯曲性能测试、缺口冲击强度测试、扫描电子显微镜(SEM)和差示扫描量热(DSC)仪研究了共混合金力学性能、相容性和结晶性能。结果表明:与纯PLA和纯PGA相比,PLA/PGA共混合金的相容性差,导致力学性能降低,纯PLA、纯PGA和70%PLA/30%PGA合金的拉伸强度、弯曲强度、断裂伸长率和缺口冲击强度分别为58.6 MPa,123.5 MPa,8.52%,9.0 J/m;91.9 MPa,157.6 MPa,7.9%,5.2 J/m;41.2 MPa,91.2 MPa,3.8%,2.0 J/m。PLA和PGA可以互相加快结晶速度,加入环氧型扩链剂可以改善合金的相容性,上述四个力学性能可相应提高到49.2 MPa,96.0 MPa,4.5%,4.3 J/m,而且降低了PLA和PGA的结晶度。另外,向PLA中加入1%PGA时,PGA可以充当PLA的成核剂,使PLA的冷结晶温度降低10℃左右,结晶度提高1.3%。     

Formulation‐properties versatility of wood fiber biocomposites based on polylactide and polylactide/thermoplastic starch blends

This article discusses the interrelation between formulation, processing, and properties of biocomposites composed of a bioplastic reinforced with wood fibers. Polylactide (PLA) and polylactide/thermoplastic starch blends (PLA/TPS) were used as polymeric matrices. Two grades of PLA, an amorphous and a semicrystalline one, were studied. TPS content in the PLA/TPS blends was set at 30, 50, and 70 wt%. Two types of wood fiber were selected, a hardwood (HW) and a softwood (SW), to investigate the effect of the fiber type on the biocomposite properties. Finally, the impact of different additives on biocomposite properties was studied with the purpose to enhance the bioplastic/wood fiber adhesion and, therefore, the final mechanical performance. The biocomposites containing 30 wt% of wood fibers were obtained by twin‐screw extrusion. The properties of the biocomposites are described in terms of morphology, thermal, rheological, and mechanical properties. Furthermore, the biocomposites were tested for humidity and water absorption and biodegradability. An almost 100% increase in elastic modulus and 25% in tensile strength were observed for PLA/wood fiber biocomposite with the best compatibilization strategy used. The presence of the TPS in the biocomposites at 30 and 50 wt% maintained the tensile strength higher or at least equal as for the virgin PLA. These superior tensile results were due to the inherent affinity between the matrices and wood fibers improved by the addition of a combination of coupling and a branching agent. In addition to their outstanding mechanical performance, the biocomposites showed high biodegradation within 60 days. POLYM. ENG. SCI., 54:1325–1340, 2014. © Her Majesty the Queen in Right of Canada 2013 ¹      

表面改性CNF对PBS/PLA共混物的湿热老化行为的影响

以硅烷偶联剂KH550对纳米纤维素(CNF)进行表面改性,利用双螺杆挤出机熔融共混制备一系列聚丁二酸丁二醇脂(PBS)/CNF母粒改性聚乳酸(PLA)复合材料,并在湿热老化试验箱中进行老化试验。通过扫描电子显微镜、广角X射线衍射仪、差示扫描量热仪、偏光显微镜等对复合材料的结晶和力学性能进行测试。结果表明,CNF可作为异相成核剂改善PLA的结晶行为,使PLA的结晶度提高;改性后,PBS/CNF复合母粒与PLA基体之间的相容性有较大改善;老化36 h后,PLA/PBS/CNF-KH550复合材料结晶进一步完善,其结晶度、拉伸强度和断裂伸长率较老化前分别提高了28.15 %、5.54 %和8.23 %。     

A new biodegradable blends prepared from polylactide and hyaluronic acid

In this article, the biodegradable polylactide/hyaluronic acid (PLA/HA) composites were prepared by a melt blending method. In addition, the acrylic acid grafted polylactide (PLA-g-AA) was studied as an alternative to PLA. The samples were characterized by a fourier transform infrared (FTIR) spectroscopy, a nuclear magnetic resonance (NMR), a differential scanning calorimetry (DSC), an Instron mechanical tester, and a scanning electron microscopy (SEM). As the result, due to the poor compatibility between PLA and HA, the mechanical properties of PLA/HA composites were worse than PLA. Much better dispersion and homogeneity of HA in the polymer matrix could be obtained when PLA-g-AA was used in place of PLA in the composite. The PLA-g-AA/HA composites could obviously improve the mechanical properties of PLA/HA ones, and the former provided a plateau tensile strength at break when the HA content was up to 20 wt%. Furthermore, the PLA-g-AA/HA was more easily processed than the PLA/HA because the former had lower viscosity than the latter, as they were molten. Biodegradation tests of blends were also studied under the enzymatic environment, and the result showed that the mass of blends reduced by about the HA content within 4 weeks.     

Effect of different biopolymers and polymers on the mechanical and permeation properties of extruded PHBV cast films

The biopolymer poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a promising material for packaging applications but its high brittleness is challenging. To address this issue, PHBV was blended with nine different biopolymers and polymers in order to improve the processing and mechanical properties of the films. Those biopolymers were TPS, PBAT, a blend of PBAT + PLA, a blend of PBAT + PLA + filler, PCL and PBS, and the polymers TPU, PVAc, and EVA. The extruded cast films were analyzed in detail (melting temperature, crystallinity, mechanical properties, permeation properties, and surface topography). A decrease in crystallinity and Young's modulus and an increase in elongation at break and permeability were observed with increasing biopolymer/polymer concentration. In PHBV‐rich blends (≥70 wt % PHBV), the biopolymers/polymers PCL, PBAT, and TPU increased the elongation at break while only slightly increasing the permeability. Larger increases in the permeability were found for the films with PBS, PVAc, and EVA. The films of biopolymer/polymer‐rich blends (with PBAT, TPU, and EVA) had significantly different properties than pure PHBV. A strong effect on the properties was measured assuming that at certain biopolymer/polymer concentrations the coherent PHBV network is disrupted. The interpretation of the permeation values by the Maxwell–Garnett theory confirms the assumption of a phase separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46153.     

Mechanical properties, morphology, and crystallization behavior of blends of poly(l-lactide) with poly(butylene succinate-co-l-lactate) and poly(butylene succinate)

The blends of poly(l-lactide) (PLLA) with poly(butylene succinate) (PBS) and poly(butylene succinate-co-l-lactate) (PBSL) containing the lactate unit of ca. 3 mol% were prepared by melt-mixing and subsequent injection molding, and their mechanical properties, morphology, and crystallization behavior have been compared. Dynamic viscoelasticity and SEM measurements of the blends revealed that the extent of the compatibility of PBSL and PBS with PLLA is almost the same, and that the PBSL and PBS components in the blends with a low content of PBSL or PBS (5-20 wt%) are homogenously dispersed as 0.1−0.4 μm particles. The tensile strength and modulus of the blends approximately followed the rule of mixtures over the whole composition range except that those of PLLA/PBS 99/1 blend were exceptionally higher than those of pure PLLA. All the blends showed considerably higher elongation at break than pure PLLA, PBSL, and PBS. Differential scanning calorimetric analysis of the blends revealed that the isothermal and non-isothermal crystallization of the PLLA component is promoted by the addition of a small amount of PBSL, while the addition of PBS was much less effective.     

原位反应法制备聚乳酸/聚氨酯共混物及性能

以聚乳酸（PLA）、聚四氢呋喃醚二醇（PTMG）和液化4,4′-二苯基甲烷二异氰酸酯（L-MDI）为原料,通过原位反应法制备了PLA/聚氨酯（PU）共混物,研究了PLA/PU共混物的反应原理、力学性能、断面形貌、动态流变性能以及结晶性能。结果表明,在原位反应中有微交联结构PU生成,且伴随着PLA的扩链和枝化反应;PLA/PU共混物的韧性得到显著提高,当PU含量为30 %（质量分数,下同）时,共混物的断裂伸长率、断裂韧性和缺口冲击强度分别达到230 %、134.13 MJ/m3和34.19 kJ/m2,较纯PLA分别增加了16.6、8.1和11.1倍,此时拉伸强度仍保持在较高水平（49.7 MPa）;纯PLA和PLA/PU共混物熔体均为假塑性流体,共混物具有更高的储能模量和复数黏度;PLA/PU共混物比纯PLA的结晶速率高,晶体完善程度高。     

Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/ polycaprolactone blends

Binary blends based on poly(lactic acid) (PLA) and polycaprolactone (PCL) were prepared by melt mixing in a twin‐screw co‐rotating extruder in order to increase the low intrinsic elongation at break of PLA for packaging applications. Although PLA and PCL show low miscibility, the presence of PCL leads to a marked improvement in the ductile properties of PLA. Various mechanical properties were evaluated in terms of PCL content up to 30 wt% PCL. In addition to tensile and flexural properties, Poisson's ratio was obtained using biaxial extensometry to evaluate transversal deformations when axial loads are applied. Very slight changes in the melt temperature and glass transition temperature of PLA are observed thus indicating the low miscibility of the PLA–PCL system. Field emission scanning electron microscopy reveals some interactions between the two components of the blend since the morphology is characterized by non‐spherical polycaprolactone drops dispersed into the PLA matrix. In addition to the improvement of mechanical ductile properties, PCL provides higher degradation rates of blends under conditions of composting for contents below 22.5% PCL. © 2016 Society of Chemical Industry     

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。