聚乳酸/DMSO增塑淀粉复合材料的制备与表征

采用聚乳酸分别和纯淀粉及二甲基亚砜(DMSO)塑化淀粉进行共混制备了淀粉/聚乳酸复合材料,通过力学性能测试,DSC测试,TG分析及SEM观察发现淀粉含量增加,材料力学性能降低,而经DMSO塑化淀粉共混物虽然其拉伸强度等力学性能降低,但冲击强度和弯曲应变均提高,且复合材料结晶度有较大提高,DMSO质量分数为3%时,复合材料的冷结晶温度降低9.4℃,熔融温度降低2.2℃。纯淀粉和聚乳酸共混复合材料呈现明显的两相结构,加入DMSO之后,界面黏结加强,呈现均相特征。     

From microstructure to mechanical properties of compatibilized polylactide/thermoplastic starch blends

Bio‐degradable polymer blends of polylactic acid/thermoplastic starch (PLA/TPS) were prepared via direct melt blending varying order of mixing of ingredients fed into the extruder. The effect of interface interactions between PLA and TPS in the presence of maleic anhydride (MA) compatibilizer on the microstructure and mechanical properties was then investigated. The prepared PLA/TPS blends were characterized by scanning electron microscopy, differential scanning calorimetry (DSC), tensile, and rheological measurements. Morphology of PLA/TPS shows that the introduction of MA into the polymer matrix increases the presence of TPS at the interface region. DSC results revealed the reduction of glass transition temperature of PLA with contributions from both TPS and MA. The crystallization temperature was decreased by the addition of MA leading to reduction of overall crystallization of PLA/TPS blend. The mechanical measurements show that increasing MA content up to 2 wt % enhances the modulus of PLA/TPS more than 45% compared to the corresponding blends free of MA compatibilizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44734.     

Comparison of sorbitol and glycerol as plasticizers for thermoplastic starch in TPS/PLA blends

This article investigates the structure and properties of thermoplastic starch/PLA blends where the TPS phase is plasticized by sorbitol, glycerol, and glycerol/sorbitol mixtures. The blends were prepared using a twin‐screw extruder where starch gelatinization, water removal, and dispersion of TPS into a PLA matrix were carried out sequentially. The plasticizers were added to starch in the first stage of the extruder to allow complete starch gelatinization. The PLA was added at mid‐extruder and thoroughly mixed with the TPS. The plasticizer concentration was varied from 30 to 42% and the TPS content was varied from 27 to 60% on a weight basis. In all investigated blends, the PLA formed the continuous phase and the TPS was the dispersed phase. The viscosity, blend morphology, tensile mechanical properties as well as the thermal properties of the materials were measured. It was found that the glycerol/sorbitol ratio has an important effect on the blend properties. Finer blend morphologies, higher tensile strength and modulus but lower crystallization rate were found for the sorbitol plasticized blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical,thermal, and biodegradability properties of PLA/modified starch blends

Three different kinds of modified starch (MS) were prepared as fillers to assess the compatibility between them and poly(lactic acid) (PLA) resin. The blends were prepared by incorporating 15 wt% of the MS into PLA using a twin‐screw extruder. Through morphology analysis, it can be seen that the dispersion state of MS granules was greatly different. Investigations of thermal behavior indicated that the addition of MS decreased thermal properties which found expression in the decrease of melting temperature and vicat softening temperature (VST). But thermal stability of PLA/maleic anhydride grafted starch (MA‐g‐ST) was slightly higher than those of other blends. PLA/MA‐g‐ST blend exhibited the highest notched impact strength, elongation at break, and tensile strength, which means MA‐g‐ST was suitable as a filler improving the toughness of PLA. It was also proved that biodegradability rate of blends increased dramatically and reached up to 1.80, 1.89, 1.44 g day⁻¹ after 60 days, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

The effect of MBS on the heat resistant,mechanical properties,thermal behavior and rheological properties of PLA/EVOH blend

This work focuses on improve the mechanical properties of poly(lactic acid)/poly(ethylene-co-vinyl alcohol) (PLA/EVOH) blend and simultaneously remained a high Vicat softening temperature (VST) using appropriate contents of methyl methacrylate–butadiene–styrene copolymer (MBS) via simple melt blending. The effects of MBS on the heat resistant, mechanical properties, thermal properties and rheological behavior were examined in detail with various techniques. The VST of neat PLA significantly increased to 159 °C from 66.8 °C after blending with 50 wt% EVOH. However, the VST was gradually decreased with increasing MBS content but were still much higher than that of neat PLA. On the basis of the tensile and impact tests results, PLA/EVOH/MBS blends showed a considerably higher elongation at break and impact strength. For all PLA/EVOH/MBS blends, the thermal stability was increased compared than that of PLA/EVOH blend without MBS. With increasing MBS content, the complex viscosity and storage modulus of PLA/EVOH blend increased, especially at low frequencies, indicating that MBS enhanced the chain entanglement in the PLA/EVOH matrix. In addition, the results Han curves and Cole–Cole plots indicated that the relaxation time was increased when MBS was added.     

异氰酸酯对聚乳酸/热塑性聚氨酯共混物性能的影响

以4,4^′-二苯基甲烷二异氰酸酯（MDI）为反应增容剂，采用熔融共混法制备了不同MDI含量的聚乳酸/热塑性聚氨酯（PLA/TPU）共混物，采用傅里叶变换红外光谱仪（FTIR）、万能试验机、冲击试验机、扫描电子显微镜（SEM）、差示扫描量热仪（DSC）和旋转流变仪对共混物力学性能、微观形态、热性能和流变性能进行了研究。结果表明：MDI可以有效改善共混物的力学性能，当MDI质量分数为1%时，共混物力学性能最佳，缺口冲击强度为40.0kJ/m²，断裂伸长率为214.1%，与未加MDI的共混物相比，分别增加了4.3倍和5.8倍，拉伸强度稍有下降（47.6MPa）；SEM表明，MDI的加入提高了共混物的相容性，加入MDI后，共混物的断面由海-岛结构变为核-壳包覆结构，相界面作用力增强；DSC测试表明，共混物的玻璃化转变温度、冷结晶温度和熔融温度随着MDI含量的增加而升高；流变测试表明，MDI质量分数的增加，共混物呈现更显著的剪切变稀行为，推测共混反应机理为：MDI质量分数的增加，体系内依次发生PLA的扩链、支化和TPU的交联。     

Preparation and characterization of thermoplastic starch/PLA blends by one‐step reactive extrusion

In the presence of dicumyl peroxide, the compatibility of thermoplastic dry starch (DTPS)/poly(lactic acid) (PLA) blends, using maleic anhydride (MA) as compatibilizer, was investigated. The plasticization of starch and its compatibilizing modification with PLA was accomplished in a single‐screw extruder by one‐step reactive extrusion. In the presence of MA, the plasticization of starch in DTPS/PLA blends could be improved and homogeneous DTPS/PLA blends could be achieved as observed using scanning electron microscopy. Tensile tests showed that the tensile strength of compatibilized DTPS/PLA blends was about 40.5 MPa higher than that of the original composites. Differential thermal analysis indicated that the glass transition temperature of DTPS and PLA became closer in the presence of MA than the blend without any additions, which suggested the compatibility between DTPS and PLA was improved. In addition, Fourier transform infrared spectroscopy proved that MA improved the interaction between DTPS and PLA. At the same time, the blend became more thermally stable as shown by thermogravimetric analysis results. A novel decomposition peak at about 450 °C was detected in the compatibilized blend, which was higher than those observed for DTPS and PLA. Finally, a rheological study suggested that MA could improve the fluidity of DTPS/PLA blends. Copyright © 2007 Society of Chemical Industry     

MDI作为聚乳酸/木薯淀粉共混物交联剂的研究

用木薯淀粉作(Tapioca)为聚乳酸(PLA)的填充剂,以4,4-二苯基甲烷二异氰酸酯(MDI)为界面兼容剂,通过密炼机共混,用DSC测试热力学性质,以及SEM分析断面形态。当MDI含量为0.5%时共混PLA70Tapioca30的抗张强度由38.2MPa提高到61.0MPa。     

Thermal,mechanical and rheological properties of poly (lactic acid)/epoxidized soybean oil blends

Summary  Poly(lactic acid) (PLA) was melt blended with epoxidized soybean oil (ESO) in an internal mixer and thermal, mechanical and rheological properties of the blends were investigated by means of differential scanning calorimetry, dynamic mechanical analysis, tensile test and small amplitude oscillatory shear rheometry. ESO lowered glass transition temperature and increased the ability of PLA to cold crystallization. The blend exhibited improved elongation-at-break along with a plastic deformation. The plasticization effect by ESO was also manifested by the lowering of dynamic storage modulus and viscosity in the melt state of the blends compared with neat PLA.     

Mechanical properties of poly(lactic acid) and wheat starch blends with methylenediphenyl diisocyanate

Poly(lactic acid) (PLA) and wheat starch are biodegradable polymers derived from renewable sources. A previous study showed that thermally blending starch and PLA in the presence of methylenediphenyl diisocyanate (MDI) enhanced the mechanical properties of the blends. In this work, blends of PLA with various levels of wheat starch and MDI were hot mixed at 180°C then hot‐pressure molded at 175°C to form test specimens. The blends were characterized for mechanical properties, fracture microstructure, and water absorption. Pure PLA had a tensile strength of 62.7 MPa and elongation of 6.5%. The blend with 45% wheat starch and 0.5 wt % MDI gave the highest tensile strength of about 68 MPa with about 5.1% elongation. The blend with 20% starch and 0.5 wt % MDI had the lowest tensile strength of about 58 MPa with about 5.6% elongation. Dynamic mechanical analysis showed that storage modulus increased and tan δ decreased as starch level increased, but almost leveled off when starch level reached 45% or higher. Water absorption of the blends increased significantly with starch content. Yet the blend, if water proofed on its surface, has potential for short‐term disposable applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1257–1262, 2002; DOI 10.1002/app.10457     

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     

Mechanical and thermal properties of poly(lactic acid)/starch blends with dioctyl maleate

Poly(lactic acid) (PLA)/starch blends were prepared blending with dioctyl maleate (DOM). DOM acted as a compatibilizer at low concentrations (below 5%), and markedly improved tensile strength of the blend. However, DOM functioned as a plasticizer at concentrations over 5%, significantly enhancing elongation. Compatibilization and plasticization took place simultaneously according to the analysis of, for example, mechanical properties and thermal behavior. With DOM as a polymeric plasticizer, thermal loss in the blends was not significant. Water absorption of PLA/starch blends increased with DOM concentration. DOM leaching in an aqueous environment was inhibited. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1697–1704, 2004     

不同淀粉类型TPS/PBS共混体系的形貌与黏弹行为

引言自20世纪70年代以来,随着环保意识的不断增强以及石油资源的日益枯竭,生物质基高分子材料的研究价值日益凸显[1-3]。其中淀粉由于来源广泛、价格低廉以及完全生物降解引起了人们的广泛关注[4-5]。     

改性淀粉/LLDPE共混体系生物降解材料性能的研究

将自制接枝改性淀粉与LLDPE、玉米淀粉以及另外两种相容剂进行共混。通过对共混体系的形态结构、力学性能、流变性能、热性能以及对共混物薄膜的生物降解性能等的研究说明:复合相容剂MAH-g-PE+LA-g-starch的加入改善了淀粉和LLDPE的相容性,使得共混物体系具有适宜的拉伸强度及断裂伸长率;LLDPE/淀粉/(MAH-g-PE+LA-g-starch)共混物薄膜具有很好的生物降解性能。     

聚乳酸／醋酸淀粉共混物性能形态研究

采用双螺杆挤出机制备聚乳酸（PLA）／醋酸淀粉（AS）复合材料,研究不同螺杆结构和加工次数对复合材料流变-性能-形态的影响。测试结果表明：通过螺杆Ⅱ、二次挤出后的复合材料的力学性能最优,As含量为60％的复合材料拉伸强度达到27．91MPa。动态流变和SEM的结果表明采用螺杆Ⅱ可以提高PLA与As的共混效果。本文也考察了AS含量对复合材料的力学性能和动态流变性能的影响,结果表明当AS质量含量从45％提高到70％时,复合材料的拉伸强度从36．7MPa降低到16．4MPa;其复数黏度和储能模量则随着AS含量的增加而增加。     

苹果酸对聚乳酸/热塑性淀粉共混物结构与性能的影响

将天然淀粉用甘油改性后制得了热塑性淀粉(TPS),再通过熔融共混法制备了聚乳酸(PLA)/TPS共混物。通过SEM、TG、DSC分析和拉伸性能、吸水性能、流变性能测试,研究了苹果酸对TPS和PLA/TPS共混物结构和性能的影响。结果表明:苹果酸能促进淀粉酸解,使TPS分散相尺寸减小,在PLA基体中的分布更加均匀;苹果酸能提高PLA/TPS共混物的拉伸性能;苹果酸对PLA/TPS共混物的玻璃化转变温度、熔融温度及冷结晶温度影响较小;少量的苹果酸可降低PLA/TPS共混物的吸水率。     

The morphology,rheological, and mechanical properties of wood flour/starch/poly(lactic acid) blends

An entirely biosourced blend composed of poly(lactic acid) (PLA), starch, and wood flour (WF) was prepared by a co‐extruder with glycerol as a plasticizer. The morphology, rheological properties, and mechanical properties of the WF/starch/PLA blends were comprehensively analyzed. The results showed that with the decrease of the starch/WF ratio, the morphology experienced a large transformation, and the compatibility of the blends was found to be superior to other blends, with a starch/wood flour ratio of 7/3. The dynamic mechanical thermal analysis (DMA) results demonstrated the incompatibility of the components in WF/starch/PLA blends. Following the decrease of the starch/WF ratio, the storage modulus (G″) and the complex viscosity (η*) of the blends increased. The mechanical strength first increased, and then decreased with the increase of the WF concentration. The water absorption results showed that the water resistance of the blends was reduced with the lower starch/WF ratio. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44743.     

聚乳酸/尼龙11/氯醚弹性体三元共混体系结构与性能研究

以生物基尼龙11(PA11)和氯醚橡胶(ECO)作为聚乳酸(PLA)的增韧和耐热改性剂,通过熔融共混的方法制备了PLA/PA11/ECO三元共混体系,并系统表征了体系的相容性、形貌结构、热行为及物理性能.PA11的存在改善了共混体系组分之间相容性.连续相PA11能有效提高PLA基体的维卡软化温度至160 ℃以上.PLA...     

In situ compatibilization of maleated thermoplastic starch/polyester melt‐blends by reactive extrusion

This article concerns the utilization of maleated thermoplastic starch (MTPS) in the reactive extrusion melt‐blending with poly(butylene adipate‐co‐terephthalate) (PBAT) in blown film applications. First, MTPS was prepared from cornstarch with glycerol (plasticizer) and maleic anhydride (MA; esterification agent). MTPS was then melt‐blended with PBAT in a subsequent downstream extrusion operation. The effects of both polyester and MA contents were studied on the physicochemical parameters of melt‐blends. For high polyester fractions (>60 wt%), PBAT‐g‐MTPS graft copolymers were obtained through transesterification reactions. They were promoted by the MA‐derived acidic moieties grafted onto the starch backbone as shown by selective Soxhlet extraction experiments and FTIR analyses. At lower polyester content, no significant reaction occurred more likely due to an inversion in the phase morphology between both components. Tensile properties of PBAT‐g‐MTPS graft copolymer containing 70 wt% polyester were much higher as the TPS/PBAT melt‐blend modified with MA. This can be explained by a finer morphology of the dispersed phase in the continuous PBAT matrix, and an increased interfacial area for the grafting reaction as attested by morphological studies. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

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 %。