聚乳酸微纳复合泡孔的结构与性能研究

通过熔融共混制备聚乳酸（PLA）/聚（己二酸丁二酯?对苯二甲酸丁二酯）（PBAT）共混物。以环氧扩链剂（CE）为相容剂，研究了CE含量对共混物的流变行为、结晶行为的影响，并研究了CE含量为5份的共混物在冷结晶温度下的发泡行为以及泡沫的拉伸性能。结果表明，共混体系的相容性、结晶速率随着CE含量的增加而增加、可发性提高，在添加了5份CE的共混物中得到了微纳复合泡孔，泡孔密度达到10¹³ 个/cm³，相对于PLA泡沫，共混物泡沫的断裂伸长率提高了40 %。     

聚乳酸/聚己二酸对苯二甲酸丁二酯合共混体系发泡行为研究

采用多环氧基团增容剂制备了聚乳酸/聚己二酸对苯二甲酸丁二酯(PLA/PBAT)共混物,研究了增容剂含量对于PLA/PBAT共混体系的结晶和流变性能的影响。并采用高压釜发泡的方法进行PLA/PBAT共混物的间歇发泡,研究增容剂对发泡材料泡体结构的影响。结果表明,增容剂加入后会降低其绝对结晶度,以及显著改善PLA/PBAT共混体系的熔体弹性,提高其可发性;增容剂可以有效地改善共混体系的泡体结构,降低共混物发泡密度,提高其发泡倍率。     

EVA熔体流动速率对PLA/EVA共混物性能的影响

通过熔融共混法制备了聚乳酸（PLA）/乙烯-乙酸乙烯酯共聚物（EVA）共混物,采用SEM、DSC、旋转流变仪等研究了VA质量分数为28%,熔体流动速率（MFR）不同的EVA对PLA/EVA共混物性能的影响。结果表明,EVA熔体流动速率越小,其在PLA基体中分散越均匀,EVA颗粒粒径也越小。共混物的结晶度随EVA熔体流动速率的增大而增大,但PLA的玻璃化转变温度（Tg）基本不受EVA的影响。PLA/EVA共混物的复数黏度和储能模量均随EVA的熔体流动速率的增高而减小。力学性能测试结果表明,当EVA的质量分数为15%时,PLA的断裂伸长率明显升高,冲击强度约是纯PLA的2倍。     

Morphology,rheology, crystallization behavior,and mechanical properties of poly(lactic acid)/poly(butylene succinate)/dicumyl peroxide reactive blends

The reactive blends were prepared by the blending of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) in the presence of dicumyl peroxide (DCP) as a radical initiator in the melt state. The gel fractions, morphologies, crystallization behaviors, and rheological and mechanical properties of the reactive blends were investigated. Some crosslinked/branched structures were formed according to the rheological measurement and gel fraction results, and the crosslinked/branched structures played the role of nucleation site for the reactive blends. The PLA–PBS copolymers of the reactive blends acted as a compatibilizer for the PLA and PBS phases and, hence, improved the compatibility between the two components. Moreover, it was found that the reactive blends showed the most excellent mechanical properties as the DCP contents were 0.2 and 0.3 phr. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39580.     

Toughness improvement of poly(lactic acid) with poly(vinyl propionate)-grafted natural rubber

Natural rubber (NR) grafted with poly(vinyl propionate) (NR-g-PVP) was prepared by emulsion polymerization. The monomer content was set at 5, 10, 20, and 30 wt%. The chemical structure of NR-g-PVP was confirmed by ¹H-NMR and FTIR techniques. The grafting parameters of purified NR-g-PVP were evaluated. Binary (PLA/NR and PLA/NR-g-PVP) and ternary (PLA/NR/NR-g-PVP) blends were prepared by melt blending using a twin-screw extruder. The percentage of grafted PVP on NR affected morphology, thermal and mechanical properties of the blends. In binary blends, 5% grafting showed the greatest improvement of toughness and ductility with PLA, whereas there was no improvement in the mechanical properties of PLA/NR blend from using NR-g-PVP as a compatibilizer. The mechanical properties of the blends are related to mutual compatibility of the components. Good interfacial adhesion and proper particle size of NR were the key factors contributing to mechanical properties.     

Preparation and properties of biodegradable poly (lactic acid)/ethylene butyl acrylate glycidyl methacrylate blends via novel vane extruder

ABSTRACT

In this work, poly (lactic acid) (PLA) and elastomer ethylene-butyl acrylate-glycidyl methacrylate terpolymer (EBA-GMA) containing epoxy groups were melt-blended using a novel vane extruder. The solid-state ¹³C nuclear magnetic resonance spectra (¹³C-NMR) and the Fourier-transform infrared (FTIR) spectroscopy proved that epoxy groups of EBA-GMA reacted with the carboxylic acid or hydroxyl groups of PLA during melt blending, resulting in a grafted structure which improved the interfacial adhesion of PLA/EBA-GMA blends. The phase morphology, mechanical and thermal properties were investigated to identify the effect of EBA-GMA weight fraction on the properties of PLA/EBA-GMA blends. Thermogravimetric analysis revealed that the incorporation of EBA-GMA improved the thermal stability of PLA. The impact strength of the annealed PLA80/20EBA-GMA binary blend increased up to ten times compared without annealing process.     

Poly(lactic acid)/low‐density polyethylene blends and its nanocomposites based on sepiolite

Poly(lactic acid) (PLA) nanocomposite ternary blends based on unmodified sepiolite were prepared by melt blending using a corotating twin‐screw extruder. Two grafted polymers were used as compatibilizer agents, in an effort to increase the PLA tensile toughness. The influence of incorporating a low‐cost commodity low‐density polyethylene, as dispersed phase to the composites on thermal degradation, and rheological and tensile properties was studied. The morphology of the blends and composites was determined through transmission and scanning electron microscopy techniques. Results showed that the compatibilized blends prepared without clay have higher thermal degradation susceptibility and tensile toughness than those prepared with sepiolite and significant changes in complex viscosity and melt elasticity values were observed between them. The nanocomposite blends exhibited similar thermal degradation, lower tensile strength, and Young's modulus values and increased elongation at break and tensile toughness, complex viscosity, and storage modulus compared with those of the nanocomposite of PLA. These results are related to the clay dispersion, to the type of morphology of the different blends, to the localization of the sepiolite in the different phases, the thermomechanical degradation of the PLA matrix phase during melt blending and the grafting degree of the compatibilizers used. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

不同分子量PCL增韧PLA的结构与性能

采用两种不同分子量的聚(ε-己内酯)(PCL)(粘均分子量60 000和3 000)与聚乳酸(PLA)在175℃下共混10 min制备PLA/PCL共混物。通过动态流变、扫描电子显微镜(SEM)和力学性能等研究了PLA/PCL共混物的结构和性能。动态流变显示,在PCL低含量(质量分数小于15%)时,PCL与PLA是相容的,质量分数为15%时PCL与PLA表现出明显的相分离行为。SEM显示,随着PCL含量的增加,PCL相的尺寸变大;低分子量PCL(L-PCL)的相尺寸明显大于高分子量PCL(H-PCL),而且相形态不是规则的球状。随着PCL含量的增加,共混物的拉伸强度下降,而断裂伸长率增加。当H-PCL质量分数为8.3%时,PLA/H-PCL共混物的断裂伸长率为137.32%。当H-PCL质量分数为15%时,其断裂伸长率高达232.76%。在添加相同含量PCL时,PLA/H-PCL共混物的拉伸强度高于PLA/L-PCL;而PCL质量分数8%时,共混物的断裂伸长率相差不多,当PCL质量分数大于8%时,PLA/H-PCL共混物的断裂伸长率明显比PLA/L-PCL共混物的高。     

In-situ poly(butylene adipate-co-terephthalate)/soy protein concentrate composites: Effects of compatibilization and composition on properties

In this study, soy protein concentrate (SPC) was blended as plastic with poly(butylene adipate-co-terephthalate) (PBAT). An extra amount of water was added to SPC prior to compounding to ensure that SPC behaved like a plastic during mixing. Because of the extensive crosslinking and agglomeration during compounding and the fact that most water was evaporated after drying the compounds, the SPC phase was not able to flow like a plastic in the subsequent processing. Therefore, the compounds became in-situ formed composites. The effects of SPC content and compatibilizer on the morphological, rheological, tensile and dynamic mechanical properties of PBAT/SPC blends were studied. Using maleic anhydride grafted PBAT as compatibilizer resulted in fine domain sizes and good dispersion of SPC and hence improved tensile and dynamic mechanical properties. In the presence of compatiblizer, the formation of percolated SPC network structure was observed at high SPC concentrations, subsequently, resulted in drastic changes in rheological properties, mechanical and dynamic mechanical properties of the blends.     

聚乳酸/马来酸酐接枝线形低密度聚乙烯合金的制备及其发泡行为研究

通过熔融共混法制备聚乳酸（PLA）/马来酸酐接枝线形低密度聚乙烯（PE-LLD-g-MAH）合金,使用差示扫描量热仪、旋转流变仪、扫描电子显微镜、偏光显微镜等仪器研究了不同PE-LLD-g-MAH含量的PLA合金的结晶性能、流变性能、断面形貌及发泡性能等。结果表明,随着PE-LLD-g-MAH含量的增加,PLA/PE-LLD-g-MAH合金的冷结晶温度大幅提高和流变性能明显改善,样品断面出现了明显的“海岛”结构,发泡样品的泡孔尺寸逐渐减小,泡孔密度增加。     

Effect of triphenyl phosphite as a reactive compatibilizer on the properties of poly(L-lactic acid)/poly(butylene succinate) blends

Reactive blending is an innovative method for the improvement of compatibility of polymer blend. In this work, poly ( _L-lactic acid) and poly (butylene succinate) (PLLA/PBS) blends were prepared by melt blending to ameliorate the toughness of PLLA. Triphenyl phosphite (TPP) was introduced into the PLLA/PBS blends (80/20 by weight) to enhance their compatibility via reactive blending. The effects of TPP on the morphology and properties of PLLA/PBS blends were studied systematically. The increased torque during melt blending demonstrated that the compatibilizer successfully reacted with PLLA and PBS. The mechanical properties of the blends were exceedingly improved only with 0.5 wt% TPP. A reduction tendency of size of the dispersed phase was observed due to the improvement of compatibility. The DSC and DMA results indicate that the T _g of PLLA decreased at a slow rate with the increasing content of TPP. This work provided a simple approach for preparing a kind of high toughed PLLA material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48646.     

Morphology development,melt linear viscoelastic properties and crystallinity of polylactide/polyethylene/organoclay blend nanocomposites

Polylactide/polyethylene blends (PLA/PE) and their nanocomposites were prepared via the melt blending process. The effects of organoclay, compatibilizer (PE‐g‐MA), and PE content on morphology, linear viscoelastic properties of the melt and cold crystallization of the samples have been studied. The Palierne model is applied to predict the rheological behavior of unfilled blends. It implies that there is a quantitative agreement between model and experimental data for low PE content blend. From WAXD and the rheological behavior, it is shown that organoclay exhibits a higher extent of intercalation and dispersion in PLA/PE/organoclay nanocomposite than in PLA/organoclay nanocomposite. The DSC results present that the addition of compatibilizer into blend nanocomposite increases cold crystallization temperature of PLA by about 3°C. This can be explained by the role of compatibilizer in transfer of a part of organoclay from PLA matrix to droplets resulting in increase of PLA chain mobility and, therefore, slightly greater cold crystallization temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41300.     

Incorporating amylopectin in poly(lactic acid) by melt blending using poly(ethylene‐co‐vinyl alcohol) as a thermoplastic carrier. (I) morphological characterization

In this study, the possibility of using a biodegradable grade of thermoplastic poly(ethylene‐co‐vinyl alcohol) with high (71 mol %) vinyl alcohol (EVOH‐29), as a carrier to incorporate the renewable and biodegradable component amylopectin (AP) into poly(lactic acid) (PLA) through melt blending, was investigated. The effect of using a plasticizer/compatibilizer (glycerol) in the blend systems was also investigated. In a first step, the EVOH/AP blends were produced and thereafter, in a second step, these were mixed with PLA. In this first study, the blend morphology was investigated using optical microscopy, scanning electron microscopy and Raman imaging spectroscopy and the thermal properties were measured by differential scanning calorimetry. Despite the fact that EVOH and AP are both highly polar, their blends were immiscible. Still, the blends exhibited an excellent phase dispersion on a micron level, which was enhanced further by the addition of glycerol. A good phase dispersion was finally observed by incorporation of the latter blends in the PLA matrix, suggesting that the proposed blending route can be successfully applied for these systems. Finally, the Differential scanning calorimetry (DSC) data showed that the melting point of EVOH dropped in the EVOH/AP blends, but the properties of the PLA phase was still relatively unaffected as a result of blending with the above components. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The effect of epoxide content on compatibility of poly(lactic acid)/epoxidized natural rubber blends

The objective of this work was to determine the effect of the epoxide content in epoxidized natural rubber (ENR) on the miscibility and compatibility with poly(lactic acid) (PLA) in prepared PLA/ENR blends. PLA was blended with 10 wt% of ENRs (epoxidized at 10, 15, 20, and 25 mol%). The presented study showed that the in situ graft copolymer, PLA-g-ENR, was formed during melt blending in the blends containing 10 and 15 mol% ENR. This work is the initial study showing the presence of PLA-g-ENR in the blends by ¹H-NMR and ¹³C-NMR. PLA-g-ENR acted as a compatibilizer, producing a partially miscible blend, indicated by an inward shift of the α-transition temperatures of PLA and ENR in the blends. PLA-g-ENR also greatly reduced the particle size of ENR and increased the impact strength, tensile strength, and elongation at break of the blends. The epoxide content of ENR changed deformation mechanisms of the blends.     

不同PETG对PS/PETG共混物相态结构的影响

采用转矩流变仪制备了聚苯乙烯/聚对苯二甲酸-乙二醇-1,4-环己烷二甲醇酯(PS/PETG)共混物和PS/改性PETG（PETG-M）共混物。采用旋转流变仪和熔体流动速率测定仪测定了PS、PETG和PETG-M的流变性能;采用扫描电子显微镜观测了共混物的相态结构。结果表明,随着PETG和PETG-M含量的提高,PS/PETG共混物和PS/PETG-M中PETG和PETG-M分散相颗粒平均粒径都增大,分散相颗粒密度都减小,在含量相同的情况下,PETG-M的分散相颗粒平均粒径小于PETG,PETG-M的分散相颗粒密度高于PETG,PETG-M的分散相粒径分布宽度更窄。     

The synthesis of poly (lactic acid)-fulvic acid graft polymer and its effect on the crystallization and performance of poly (lactic acid)

ABSTRACT

The poly (lactic acid)-fulvic acid graft polymer (PLA-FA) was synthesized with lactic acid and fulvic acid (FA). The optimum parameters were determined by orthogonal experiment. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy exhibited that FA was successfully grafted onto PLA. Then, PLA/PLA-FA composites were prepared with PLA-FA as fillers by melt blending. The structure characterization and performance tests demonstrated that PLA-FA effectively enhanced the comprehensive performance of PLA composites. The rheological analysis demonstrated that PLA-FA had plasticization effect. The non-isothermal crystallization kinetics demonstrated that PLA-FA promoted the crystallization rate of PLA composites, improving toughness of PLA composites.     

Effect of octa(epoxycyclohexyl) POSS on thermal,rheology property,and foaming behavior of PLA composites

Foams of poly(lactic acid) (PLA)/octa(epoxycyclohexyl) polyhedral oligomeric silsesquioxanes (ePOSS) composite were prepared by melt‐mixing and solid‐state foaming methods. A systematic and accurate method was applied to evaluate the effects of epoxy‐based POSS on the structure of dispersion, thermal behavior, and rheological properties of PLA composites. The application of secondary electron–electron back‐scattered diffraction technique was used to observe the cellular micromorphology and micro‐phase dispersion in composite foams, simultaneously. The results indicated that secondary dispersion of POSS aggregates occurred in foaming process. The enhanced melt elasticity, dispersity of POSS, and crystallization morphology of PLA/POSS composite had a significant effect on the controlling foaming behavior. Thus, a homogeneous and finer cellular morphology of PLA/POSS composite foam with high expansion ratio was obtained with a proper content of POSS in the composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46399.     

环氧类增容剂反应增容PLA/PBAT共混体系的研究

以环氧类增容剂(REC)为增容剂,采用双螺杆挤出机熔融共混制备聚乳酸(PLA)/聚对苯二甲酸己二酸丁二醇酯(PBAT)共混物。研究了增容剂对共混体系微观结构、力学性能和热性能的影响。结果表明,添加适量REC可以提高PLA与PBAT的相容性,改善PLA/PBAT共混体系的综合力学性能;REC用量为1.4份时共混体系呈现出良好的相容性,此时共混物冲击强度由268 kJ/m2增加到621 kJ/m2、断裂伸长率提高由222 %增加到357 %。     

PPC-MA/PETG共混型生物降解材料的结构与性能研究

采用熔融共混法制备了马来酸酐(MA)封端聚碳酸亚丙酯(PPC)和聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)的共混物(PPC-MA/PETG),采用套管上吹法将共混物吹塑成膜.通过差示扫描量热仪(DSC)、热失重分析(TGA)及扫描电子显微镜(SEM)等手段系统地研究了共混物的热、力学性能及形貌.结果表明:PPC-MA/PETG共混物为部分相容体系;MA封端PPC可以提高PPC的热分解温度(T-5%),PETG与PPC-MA共混进一步提高了PPC的热性能;当PETG含量低时,PETG作为岛相分散在PPC基体中,随着含量的增加,共混物将发生"海-岛"结构转变成"海-海"结构;共混物薄膜的力学性能较纯PPC大幅增强,从4.7MPa提高到16.93MPa.PPC-MA与PETG共混可以获得力学性能较好的膜材料,改善PPC材料的缺陷,在包装、生物医用材料等领域具有广阔的应用前景.     

Preparation,structure-property relationships of zinc oxide pillared organic layered double hydroxides and its effect on the performance of poly (lactic acid)

Zinc oxide pillared organic layered double hydroxides (ZnO-LDHs-S) were synthesized with sodium dodecyl sulfate (SDS) via a intercalation method. Meanwhile, the properties of ultraviolet (UV) absorbance and antibacterial of ZnO-LDHs-S were investigated. To improve the performances of poly (lactic acid) (PLA), PLA/ZnO-LDHs-S nanocomposites were prepared by melt blending using ZnO-LDHs-S as nucleating agent. Structure and properties of PLA/ZnO-LDHs-S nanocomposites were investigated by Fourier transform infrared spectra, transmission electron microscopy, mechanical properties testing, differential scanning calorimetry, polarized optical microscopy and rheological analysis. It was shown that the introduction of ZnO-LDHs-S improved the comprehensive performance of PLA.