增容剂改性PLA/PBAT共混物的制备及性能研究

研究了增容剂聚己内酯(PCL)和聚乙二醇(PEG)对聚乳酸(PLA)/己二酸丁二醇酯和对苯二甲酸丁二醇酯共聚物(PBAT)共混物的力学性能、热性能和断面微观形态的影响。结果表明,加入适量的增容剂可以增强两相界面的黏结力,提高共混物的力学性能;共混物的结晶峰值温度(Tc)降低,说明PLA与PBAT的相容性得到改善;共混物断面的扫描电子显微镜(SEM)表明,两相之间呈现良好的相容性。     

PLA/PCL共混物的制备及性能分析

采用熔融共混法制备了聚乳酸(PLA)/聚己内酯(PCL)共混物,探讨了PCL含量对共混物加工性能和力学性能的影响。结果表明,随着PCL含量的增加,共混物拉伸强度逐渐降低,断裂伸长率逐渐减小;冲击强度则先增加后减小,当PCL质量分数为15%时,达到最大。随后探讨了柠檬酸三丁酯(TBC)、聚乙二醇(PEG) 2种相容剂对聚乳酸/聚己内酯共混物的力学性能、热性能和断面微观结构形态的影响。结果表明,加入适量的增容剂可以增强两相界面的粘接力,改善共混物的力学性能;共混物的Tg和Tc均降低,说明PLA与PCL的相容性得到改善;共混物断面的SEM表明,分散相的粒径变小,两相之间呈现良好的的相容性。     

PLA/PBAT/纳米碳酸钙三元复合材料的微观形貌与性能

采用双螺杆挤出机制备了聚乳酸/己二酸-对苯二甲酸-丁二醇酯共聚物(PLA/PBAT)共混物和PLA/PBAT/纳米碳酸钙(PLA/PBAT/nano-CaCO_3)复合材料;通过差示扫描量热仪(DSC)、扫描电子显微镜(SEM)和微机电子万能试验机研究了PLA/PBAT共混物的微观结构、相容性、熔融与结晶行为及力学性能;不同含量的nano-CaCO_3对PLA/PBAT/nano-CaCO_3三元复合材料中PLA的熔融与结晶行为及复合材料力学性能的影响及nano-CaCO_3在PLA/PBAT共混物中的分布行为。DSC表明,与少量的PBAT共混后,PLA的结晶度提高;而加入nano-CaCO_3后,PLA的结晶温度降低;SEM表明,PLA与少量PBAT部分相容,且nano-CaCO_3选择性地分布在PBAT相中;力学性能测试表明,与PBAT共混后,PLA的韧性得到很大程度的改善,且nano-CaCO_3与PBAT起到了协同增韧的作用,冲击强度提高了162%;但nano-CaCO_3的加入量存在阈值,超过10%时,会使PLA/PBAT/nano-CaCO_3复合材料的拉伸强度下降。     

PLA/PBAT 共混体系相容性研究

采用熔融共混法制备了聚乳酸/聚己二酸-对苯二甲酸-丁二酯共聚物(PLA/PBAT)共混物,研究了不同含量的钛酸四丁酯(TBT)、过氧化苯甲酰(BPO)和乙酰化柠檬酸三丁酯(ATBC)对PLA/PBAT共混物(PLA/PBAT质量比为50/50)相容性的影响,同时,利用万能力学试验机、差示扫描量热仪及扫描电子显微镜对共混物的力学性能、热性能以及微观形态进行了表征。结果表明,相容剂BPO和TBT均能改善PLA/PBAT的相容性;当BPO、ATBC添加量分别为0.5份(质量份,下同)时,共混物的拉伸强度达到最大值,分别为39MPa和38MPa,使得材料刚性增加,但对材料韧性改善效果一般;当TBT添加量为0.5份时,共混物的断裂伸长率达到最大值263%,使得材料韧性提高。     

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 %。     

PLA/PBAT/OMMT生物基材料的制备及快速成型

对生物可降解材料聚乳酸(PLA)与聚己二酸对苯二甲酸丁二酯(PBAT)及有机蒙脱土(OMMT)材料进行共混,采用挤出成型制备PLA/PBAT/OMMT线材,再采用快速成型制备标准试样,通过对样件的力学性能、结晶行为、断面形貌和表观质量的测试和分析得出:纯PLA的拉伸强度和断裂伸长率分别为7.42MPa和1.8%,表现出硬而脆的特点;PLA/PBAT共混后,随着PBAT含量的增加,共混材料的断裂伸长率以及冲击强度不断提高,当PBAT含量为60%时,共混物的断裂伸长率达到405%,材料的冲击强度为31.11kJ/m2,约为纯PLA的11倍;而共混材料的拉伸强度表现出先增后减的趋势,当PBAT含量约为30%时,拉伸强度最佳,为37.08MPa;加入2%含量的OMMT后,共混材料的综合力学性能较之前又有不同程度的提高,其中拉伸强度以及冲击强度提升的较为明显;通过差示扫描量热和扫描电镜分析,PLA/PBAT共混体系为不相容体系,两相界面存在大量的孔洞,且结晶性能差,为半结晶聚合物,OMMT的加入使PLA/PBAT的两相界面变得模糊,极大地改善他们的相容性,而且还提高了共混物的结晶度;通过观察打印制件的表观质量,当PBAT的含量在30%左右,综合快速成型性能最佳。     

聚乳酸增韧改性研究

采用熔融共混法,将聚乳酸(PLA)分别与丁二醇-己二酸-对苯二甲酸共聚物(PBAT)、聚丁二酸丁二醇酯(PBS)及聚甲基乙撑碳酸酯(PPC)共混制备生物降解复合材料,并模压成型。研究了3种复合材料的拉伸性能、冲击性能及断面微观形貌。结果表明:PBAT、PBS和PPC均能提高PLA的断裂伸长率和冲击强度;与PBS和PPC相比,PBAT与PLA的相容性更好;随着PBAT含量的增加,增韧PLA材料的冲击强度逐渐上升,但PBAT与PLA的相容性逐渐变差。     

PBAT/PLA复合材料的制备及其微球发泡行为研究

采用熔融共混法制备了聚(己二酸丁二醇酯-对苯二甲酸丁二醇酯)/聚乳酸(PBAT/PLA)共混复合材料,并对PBAT/PLA共混体系的流变性能、结晶性能、力学性能、微观形貌以及发泡行为(热膨胀微球作为发泡剂)进行了表征。结果表明:随着PLA含量的增加,PBAT/PLA共混体系的非牛顿指数先减小后增大,其中当PLA含量为30%时达到最小值;PLA的引入改善了PBAT的结晶性能,且PBAT与PLA对彼此的晶型均无影响;随PLA含量的增加,PBAT/PLA共混体系的拉伸强度增大、断裂伸长率降低,其中当PLA含量为50%时,拉伸强度和断裂伸长率分别达到25.3 MPa和422.2%;PLA与PBAT的相容性差,当PLA含量为30%时,PLA/PBAT共混体系发生相分离;此外,当PLA含量为10%时,PBAT/PLA复合发泡材料的密度达到最小值0.34 g/cm~3。     

PBAT及增容剂含量对PLA/PBAT共混物结构和性能的影响

通过拉伸试验、扫描电子显微镜和差示扫描量热法分析,研究了聚己二酸-对苯二甲酸丁二酯(PBAT)用量对聚乳酸(PLA)/PBAT共混物拉伸性能、微观结构和热性能的影响。结果表明:PBAT能显著改善PLA韧性,增韧效果与PBAT相尺寸及两相间相互作用有关。当m(PLA)∶m(PBAT)=80∶20时,PLA/PBAT共混物的断裂拉伸应变提高约8倍。自制接枝共聚物增容剂能显著改善PLA与PBAT的相容性,提高两相间的相互作用。接枝共聚物增容剂最佳用量为6phr时,共混物断裂拉伸应变提高1倍多。     

PLA/PBAT/PDEGA共混物的制备北大核心

以聚己二酸二甘酯(PDEGA)为增塑剂,通过双螺杆挤出机制备了聚乳酸(PLA)/聚对苯二甲酸-己二酸-丁二酯(PBAT)/PDEGA共混物,并研究了PLA/PBAT/PDEGA共混物的热性能、结晶行为、力学性能、冲击断面形态、阻隔性能、流变性能和熔体强度。结果表明:加入PDEGA和PBAT,提高了PLA的冷结晶能力,并改善了PLA的柔韧性;PLA/PBAT/PDEGA共混物对水蒸气的阻隔性能受PDEGA和PBAT影响不大;加入PDEGA和PBAT,增强了共混物的流动性。     

聚乳酸／PBAT共混物的制备及其性能研究

用熔融挤出法制备了聚乳酸饼苯二甲酸-己二酸-1，4-丁二醇三元共聚酯（PLA／PBAT）共混物，研究了聚乳酸／PBAT共混物的力学性能、热性能以及相容性。结果表明：共混物的冲击强度及断裂伸长率随着PRAT含量的增加而增大，在PBAT含量为30％时，断裂伸长率最大，达到9％，PBAT的加入降低了共混物的拉伸、弯曲性能，但在添加量较少的情况下（如5％和10％），拉伸、弯曲性能下降不大。退火处理极大的提高了材料的维卡软化温度。当PBAT含量较高时，共混物的断面可以明显的观察到不相容的两相结构。     

扩链剂增容PLA/PBAT共混物流变性能

通过熔融共混法制备了Joncryl ADR 4370F扩链剂增容聚乳酸/聚对苯二甲酸/己二酸丁二酯(PLA/PBAT)共混物,采用旋转流变仪分别研究了扩链剂和PBAT含量对PLA/PBAT共混物动态流变行为的影响。通过动态应变扫描确定了PLA/PBAT共混物的线性黏弹区,应变选取1%;PLA/PBAT共混物的储能模量和损耗模量随着角频率的增加而增大,但复数黏度却降低,共混物熔体呈现剪切变稀行为,是典型的假塑性流体流动特征;随着扩链剂和PBAT含量的增加,共混物的储能模量、损耗模量和复数黏度增大;Han曲线分析表明,扩链剂的加入改善了共混物的相容性;动态时间扫描表明,时间对纯PLA和PBAT的储能模量基本没有影响,PLA/PBAT共混物的储能模量随时间的延长而降低,扩链剂和PBAT含量不同,使得时间对共混物储能模量的影响不同。     

PPC/PBAT共混复合材料性能的研究

采用双螺杆挤出机制备了聚碳酸亚丙酯/聚对苯二甲酸-己二酸丁二酯共混复合材料(PPC/PBAT)。考察了PPC、扩链剂和增塑剂用量对该共混材料力学性能和流变性能的影响。研究结果表明:在PPC/PBAT共混体系中,随PPC用量的增加,拉伸强度逐渐提高,而断裂伸长率和熔体流动速率(MFR)不断降低;而扩链剂二苯基甲烷二异氰酸酯(MDI)的引入,改善了PPC与PBAT的相容性,且随着MDI用量的增加,共混材料的拉伸强度和断裂伸长率呈增加趋势,而MFR则持续降低;另外,当体系中加入增塑剂柠檬酸三丁酯后,随其用量的增加,PPC/PBAT共混材料的拉伸强度降低,而断裂伸长率和MFR持续提高。     

Rheological and mechanical behavior of non-spherical poly(lactic acid) particles embedded poly(butylene adipate-co-terephthalate) blend

In this study, the poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate)(PBAT) blend is investigated to improve rheological and mechanical performances of PBAT based on rheological, mechanical, and thermal behavior analyses. The multi-step mixing method is developed to fabricate the blend with non-spherical morphology. In the multi-step mixing method, blends with a wide composition range (25/75–75/25) are mixed with additional PBAT at a mixing temperature between the melting temperatures of PBAT and PLA to produce the PBAT blend embedded with non-spherical PLA particles (10 wt%). The embedding of non-spherical PLA particles in PBAT increases the resistance against deformation, resulting in strain hardening behavior and an increase in the yield strength as well as the tear resistance of the PBAT. The presence of stiff PLA particles enhances the crystallization behavior of PBAT, meaning that polymer chains may interpenetrate. The findings of this study suggest that the multi-step mixing method is beneficial for embedding non-spherical PLA particles into a PBAT matrix, which in turn facilitates the maintenance of good interfacial adhesion to increase the melt strength, yield strength, and tear resistance.     

增容剂DT对PLA/PBAT共混物性能的影响

以不饱和酯类化合物(DT)为增容剂,通过双螺杆挤出机反应性挤出制备聚乳酸(PLA)/聚己二酸对苯二甲酸丁二酯(PBAT)共混物。采用扫描电子显微镜、旋转流变仪、偏光显微镜、差示扫描量热仪、热重分析仪和万能试验机讨论DT对共混物相容性、结晶性能、热失重以及力学性能的影响。结果表明,适量的DT增加了两相之间界面黏结,有效改善了PLA和PBAT之间相容性;当DT添加量为0.3 %（质量分数,下同）时,断裂伸长率增加了46.3 %,冲击强度显著增加,冲击试样未完全断裂。     

Toughness enhancement of polylactide with low amounts of poly (butylene adipate-co-terephthalate) through in situ reactive compatibilization

Polylactide (PLA) was melt blended with low amounts of poly (butylene adipate-co-terephthalate) (PBAT) using a simple reactive extrusion process herein, aiming to address the inherent brittleness of PLA without significantly compromising its stiffness. PLA/PBAT (90/10) blends with a small amount of peroxide (0.02 phr) and a second crosslinker agent triallyl isocyanurate (TAIC) were produced to explore the structure-performance relationship evolution in reactive extrusion. The results showed that the PLA blend with an appropriate amount of TAIC (i.e., 0.3 phr) exhibited a remarkable increase in elongation at break, reaching as high as 96%. The sample with high elongation also demonstrated a high stiffness, boasting a Young's modulus of 2.4 GPa and a yield strength of 43 MPa. It was evident that the combination of enhanced compatibility and optimized homogeneous PBAT phase size of approximately 0.6 μm worked synergistically to enhance the toughness of PLA. Conversely, higher TAIC contents resulted in over-crosslinking, despite considerable improvements in compatibility. This study offers a versatile, scalable, and practical method to prepare fully biodegradable PLA blends with high toughness.     

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.     

The Potential Use of Epoxy-POSS as a Reactive Hybrid Compatibilizers for PLA/PBAT Blends: “Effect of PBAT Molecular Weight and POSS Type”

This article focuses on the effect of molecular weight of poly(butylene adipate-co-terephthalate) (PBAT) on the immiscible poly(lactic acid) (PLA)/PBAT blends compatibilized with epoxidized polyhedral oligomeric silsesquioxanes (Epoxy-POSSs) having different numbers of epoxy groups per molecule. Mechanical, thermomechanical, thermal, rheological, and morphological properties of the blends were investigated as a function of PBAT molecular weight and epoxy-POSS type. Mechanical tests revealed that all epoxy-POSS types significantly improved the performance of the blends containing low-molecular-weight PBAT. On the other hand, epoxy-POSS with three epoxy functional groups (TriEpPOSS) and Epoxy-POSS with multiple-epoxy functional groups (MuEpPOSS) only slightly improved the performance of blends with high-molecular-weight PBAT. Thermomechanical and thermal test results supported that the compatibilization effects of the epoxy-POSSs were more prominent in the PLA/PBAT blends with low-molecular-weight PBAT due to the observation of the shifts in the glass transition temperatures of the PLA phase. According to the rheological results, the addition of epoxy-POSSs increased the interactions between the PLA and PBAT phases much more effectively in the PLA/PBAT with low-molecular-weight PBAT. The dispersed phase size of the PBAT further decreased in the low-molecular-weight PLA/PBAT blend system due to the enhanced compatibility much better. POLYM. ENG. SCI., 60: 398–413, 2019. © 2019 Society of Plastics Engineers     

E-BA-GMA三嵌段共聚物对PLA/PBAT体系的增韧改性研究

研究了乙烯-丙烯酸正丁酯-甲基丙烯酸缩水甘油酯三嵌段共聚物(E-BA-GMA)作为增韧剂对聚乳酸(PLA)/对苯二甲酸、己二酸、1,4-丁二醇三元共聚酯(PBAT)共混物的力学性能、流动性能、热性能和断面形貌的影响。结果表明:E-BA-GMA的环氧官能团与PBAT/PLA体系的端羧基和端羟基发生反应,使得PBAT与PLA的相容性得到改善,共混物的冲击性能得到了明显的提高;E-BA-GMA的加入导致结晶温度向低温方向偏移和结晶度下降。     

PBAT/PLA薄膜的制备及性能研究

将聚乳酸（PLA）和聚对苯二甲酸-己二酸-丁二醇酯（PBAT）共混制备成共混材料,探讨了不同PLA含量对材料性能的影响。结果表明,PBAT/PLA共混材料中,随着PLA含量的增加,拉伸强度先降低后升高,当PLA含量为90 %时,拉伸强度达到60.12 MPa,而其断裂伸长率从703 %降低至8 %,由韧性材料逐渐转变为脆性材料;PLA含量为30 %时,性能变化出现拐点;PLA含量为50 %时出现明显相分离,且PLA的加入可以加速PBAT材料的结晶,使结晶温度由38 ℃提高至82 ℃;PBAT/PLA共混材料在PLA含量低于70 %时,都可以实现较好的吹膜过程,且薄膜材料的拉伸强度为39.59 MPa,断裂伸长率不低于137 %。