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.     

聚乳酸/聚丁二酸丁二醇酯共混物的研究

通过熔融共混制备了聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)共混物,采用扫描电子显微镜、差示扫描量热仪、旋转流变仪对其相容性、热性能和黏度等进行了研究,并研究了PBS的加入对PLA力学性能的影响。结果表明,PLA和PBS之间是部分相容的,PBS的少量添加并不影响PLA的拉伸强度,且其冲击强度随着PBS含量的增加呈先上升后下降的趋势,当PBS含量为10份时,共混物的冲击强度最好;与纯PLA相比,共混物的黏度有所增加,且随着PBS含量的增加,共混物的黏度逐渐增大;PBS的添加起到异相成核作用,促进了PLA的结晶。     

The effect of poly(butylene succinate) content on the structure and thermal and mechanical properties of its blends with polylactide

Poly(butylene succinate) (PBS) and polylactide (PLA) were blended in a co‐rotating twin‐screw extruder with various contents of PBS from 0 to 100 wt%. The effect of PBS content on the thermal and mechanical properties of PBS/PLA blends was investigated by using DSC, softening point measurements, a Charpy impact test and tensile testing. The Fourier transform infrared spectra showed that the polymers are immiscible, but the addition of PBS could modify the PLA structure in PBS/PLA blends by changing the content of amorphous and crystalline phases. In addition, the cold crystallization temperature of PLA in blends decreases in comparison with pure PLA, which shows that PBS could have a plasticizing effect on PLA. This is confirmed by the results of DSC analysis. The mechanical properties of the blends depend on the percentage of PBS addition. Typically, the mechanical properties of PBS/PLA blends are intermediate between the properties of the polyesters from which they are obtained. However, in some cases unexpected changes in mechanical properties of the blends were observed. For example, the elongation at break for a PBS/PLA blend containing 10 wt% PLA is higher than for pure PBS. © 2019 Society of Chemical Industry     

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。     

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。     

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。     

PEG、PPG改性PLA材料的性能研究

采用熔融共混法用聚乙二醇(PEG)对生物可降解材料聚乳酸(PLA)进行改性,研究了PEG的相对分子质量对共混体系热性能和力学性能的影响,对比了相同相对分子质量的PEG和聚丙二醇(PPG)由分子结构差异对共混体系性能的影响。结果表明,PEG的相对分子质量为2 000时,改性效果最好;相同相对分子质量的PEG改性效果优于PPG。     

Preparation and property testing of polymer blends of poly(lactic acid) and poly(butylene succinate) plasticised with long-chain fatty acids

This study investigates the influence of three fatty acids (lauric acid, palmitic acid, and stearic acid) on biodegradable polymer blends based on poly(lactic acid) (PLA) and poly(butylene succinate) (PBS), containing different weight ratios (100:0, 100:2, and 100:4) of fatty acids on the transparency, mechanical properties, morphology, contact angle, and water vapour permeability. All of the blends were pressed into thin films and tested. The experimental results showed that the properties of the samples varied with chain length and amounts of the fatty acids. Thus, it could be concluded that use of fatty acids opens up new ways for the plasticisation of PLA/PBS blends for use as new bioplastics.     

扩链剂TMP-6000对聚乳酸/聚（3-羟基丁酸-co-3 -羟基戊酸酯）共混物性能的影响

以扩链剂TMP-6000为增容剂,采用熔融共混制备了聚乳酸（PLA）和聚（3羟基丁酸co3羟基戊酸酯）（PHBV）复合材料,研究了TMP-6000对PLA/PHBV复合材料的结晶行为、微观结构、力学性能的影响。结果表明,无定形PLA的加入抑制了PHBV的结晶,TMP-6000的加入使得PLA/PHBV复合材料的结晶能力变弱,提高了PLA的冷结晶温度,且当TMP-6000含量为0.5 %（质量分数,下同）时,PLA的冷结晶峰开始消失,且适量的TMP-6000使得PHBV的玻璃化转变温度（Tg）升高;TMP-6000的加入使得PHBV均匀分散于PLA基体中,且当TMP-6000含量为0.7 %时,PLA与PHBV的相容性最好;TMP-6000的加入显著提高了PLA/PHBV复合材料的分子量;TMP-6000提高了PLA与PHBV之间的结合力,提高了复合材料的拉伸强度,但断裂伸长率有稍微地降低。     

Poly (ethylene oxide) (PEO) influence on mechanical,thermal, and degradation properties of PLA/PBSeT blends

Poly (lactic acid) (PLA) is an important biodegradable plastic with unique properties. However, its widespread application is hindered by its low miscibility and suboptimal degradation properties. To overcome these limitations, we investigated the mechanical, thermal, and degradation properties of PLA and poly (butylene sebacate-co-terephthalate) (PBSeT) blends in the presence of poly (ethylene oxide) (PEO). Specifically, this study aimed to identify the effects of PEO as a compatibilizer and hydrolysis accelerator in PLA/PBSeT blends. PLA (80%) and PBSeT (20%) were melt blended with various PEO contents (2–10 phr), and their mechanical, thermal, and hydrolytic properties were analyzed. All PEO-treated blends exhibited a higher elongation at break than that of the control sample, and the tensile strength was slightly reduced. In the PEO 10% sample, the elongation at break increased to 800% of that of the control sample. Differential scanning chromatography (DSC) analysis confirmed that when PEO was added to the PLA/PBSeT blends, the two glass transition temperatures (T_g) narrowed, resulting in improved miscibility of PLA and PBSeT. In addition, the hydrolytic degradation of the PLA/PBSeT/PEO blend accelerated as the PEO content increased. It was confirmed that PEO can act as a compatibilizer and hydrolysis-accelerating agent for PLA/PBSeT blends.     

Recyclability Studies on Poly(lactic acid)/Poly(butylene succinate-co-adipate) (PLA/PBSA) Biobased and Biodegradable Films

Poly(lactic acid)/poly(butylene succinate-co-adipate) (PLA/PBSA) blends are found promising for film packaging applications because of their flexibility, resistance, and compostability. Industrially extruded granules and films based on PLA and containing different amounts of PBSA are reprocessed through mini-extrusion, to simulate recycling, and tested in terms of their melt flow rate as a function of PBSA content. Moreover, pure PLA commercial granules and the film produced extruding the PLA/PBSA 60/40 blend are reprocessed several times by injection molding and characterized in terms of melt flow rate, mechanical properties, thermal properties, and color as a function of injection molding cycles. The variation in melt fluidity and thermo-mechanical properties is negligible up to 3 injection molding cycles for both pure PLA granules and PLA/PBSA blend. In the case of blend the change in color (yellowing and darkening) is more evident and slight local compositional change in injection molded items can be evidenced as well as a slight decrease in PBS crystallinity as a function of injection molding cycles. Nevertheless, in applications where these aspects are not critical, these materials can be recycled by extrusion or injection molding before being composted, thus prolonging their life cycle and storing carbon in them as longer as possible.     

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.     

PBS/PBAT共混型全生物降解材料的制备及其性能研究

通过熔融共混法制备了聚丁二酸丁二醇酯（PBS）/聚己二酸对苯二甲酸丁二酯（PBAT）共混物,用熔体流动速率法、扫描量热法、X射线衍射、扫描电镜法及力学性能测试等手段研究了PBS/PBAT共混物的熔体流动性、结晶性能、力学性能以及共混物相容性。结果表明,随着PBAT含量的增加,PBS/PBAT共混体系的拉伸强度先升高后降低,断裂伸长率不断提高,冲击强度先降低后提高;当PBAT含量为20 %（质量分数,下同）时,与纯PBS相比,断裂伸长率提高10倍,冲击强度提高82 %,而拉伸强度仅仅降低6 %。     

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。     

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 %。     

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。     

The effect of poly(ethylene glycol) as plasticizer in blends of poly(lactic acid) and poly(butylene succinate)

The effect of polyethylene glycol (PEG) on the mechanical and thermal properties of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends was examined. Overall, it was found that PEG acted as an effective plasticizer for the PLA phase in these microphase‐separated blends, increasing the elongation at break in all blends and decreasing the T_g of the PLA phase. Significant effects on other properties were also observed. The tensile strength and Young's modulus both decreased with increasing PEG content in the blends. In contrast, the elongation at break increased with the addition of PEG, suggesting that PEG acted as a plasticizer in the polymer blends. Scanning electron microscope images showed that the fracture mode of PLA changed from brittle to ductile with the addition of PEG in the polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43044.     

Morphology evolution of poly(lactic acid) during in situ reaction with poly(butylenesuccinate) and ethylene-methyl acrylate-glycidyl methacrylate: The formation of a novel 3D star-like structure

Morphology control of polymer alloys is an attractive topic for investigators due to its ability to improve the performance of products for years. However, it is hard to control the morphology of immiscible polymer blends during melt processing. Herein, we studied the morphology evolution of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) with the inclusion of ethylene-methyl acrylate-glycidyl methacrylate (EGMA). Scanning electron microscopy of both cryo-fractured and etched cryo-fractured samples indicates that the in situ reaction among PLA, PBS, and EGMA can induce the morphology change and result in a novel 3D star-like structure. Rheology behaviors of the samples under different angular frequencies were used to validate the formation of 3D networks in the samples. Tensile stiffness reinforcements at both room temperature and high temperature were provided through dynamic mechanical analysis. In addition, a 10-fold improvement in impact strength is also monitored by the unnotched impact test to indicate the superior toughening effect. Furthermore, the crystalline behavior and thermal properties of the blends were also studied. It is believed that our work not only gives a deeper understanding of the reaction-induced morphology evolution of the PLA/PBS/EGMA blends but also reveals an avenue toward morphology control by melt processing.     

不同膨胀型阻燃剂改性聚丙烯/聚乳酸复合材料

用两种不同的膨胀型氮磷阻燃剂(IFR1和IFR2)阻燃改性聚丙烯(PP)/聚乳酸(PLA)复合材料。结果表明:两种阻燃剂在PP/PLA基体中都具有良好的分散性和界面粘合性。阻燃剂的加入降低了材料的力学性能,而含有25%阻燃剂的PP/PLA复合材料就能到达垂直燃烧试验(UL-94)的V0等级。燃烧过程中阻燃剂通过在材料表面形成致密的炭层来提高材料的阻燃性,其中IFR1对PP/PLA体系的阻燃改性效果更好。从力学性能和阻燃效果的双重考虑,质量含量25%的阻燃剂适合于PP/PLA材料的阻燃改性。