The morphology,properties, and shape memory behavior of polylactic acid/thermoplastic polyurethane blends

Biodegradable polylactic acid (PLA) was compounded with thermoplastic polyurethane (TPU) by twin‐screw extrusion at weight ratios of 90/10, 80/20, 70/30, and 60/40. The blends were investigated based on their phase morphology, thermal and mechanical properties, and shape memory properties. The tensile results showed that PLA was successfully toughened by TPU. When the TPU content was 40%, the elongation‐at‐break increased to 400%. The SEM morphology showed that TPU was dispersed uniformly in the PLA matrix; DMA and DSC results indicated that the two polymers were immiscible. Most interestingly, it was found that the blends exhibited a shape memory behavior and, unlike most of the existing shape memory polymers (SMPs), the PLA/TPU blends could be deformed at room temperature without an extra heating and cooling step. During the deformation process, TPU acted as a toughening agent that prevented the PLA/TPU blends from breaking; thus, the temporary shape could be kept and internal stress was stored in the blends. Upon heating to above the glass transition temperature of PLA (about 60°C), the deformed parts regained their original shapes quickly along with the release of the stress. POLYM. ENG. SCI., 55:70–80, 2015. © 2014 Society of Plastics Engineers     

聚酰胺弹性体增韧聚乳酸改性研究

选用聚酰胺弹性体(聚酰胺和聚氧乙烯的共聚物,PAE)与聚乳酸(PLA)熔融共混进行增韧改性。结果表明,当PAE弹性体含量在20%～30%(质量分数,下同)之间时,共混体系发生脆韧转变,最大冲击强度达到67.6J/m,但拉伸强度和模量大幅度下降;PAE弹性体含量为5%～10%时共混体系的拉伸强度保持率最高,而且断裂伸长率提高近40倍,综合性能较好;虽然扫描电子显微镜照片显示共混体系为两相分离,但是差示扫描量热分析数据均表明,随着PAE弹性体含量的增加,共混体系的玻璃化转变温度和熔点发生相应变化,证明该共混体系为半溶混性,即两相间存在一定的相互作用;热失重分析数据显示,PAE弹性体在一定程度上提高了PLA的热降解温度。     

Enhancing mechanical and shape memory properties of polylactide/polyamide elastomer blends via reactive blending with a chain extender

The structure and properties of incompatible polylactide (PLA)/polyamide elastomer (PAE) blends were tailored by a chain extender specifically the styrene–glycidyl acrylate copolymer Joncryl ADR4368 (ADR). Various PLA/PAE/ADR blends with different compositions were prepared by melt blending, and their morphology, crystallization behavior, and mechanical and the shape memory properties were systematically investigated. The results showed a uniform dispersion of PAE particles in the PLA matrix for the PLA blends with a reduction in particle size upon the addition of ADR. The crystallization of PLA was retarded, which was confirmed by a decrease in the melt crystallization temperature and an increase in cold crystallization temperature in the PLA/PAE/ADR blends. Rheological analysis showed an improvement in the melt elasticity of the PLA/PAE binary blend due to the presence of ADR, possibly attributed to the formation of long-chain-branched copolymers at the interface. Notably, the PLA/PAE/ADR blend exhibited superior toughness, featuring an elongation at break of 288% and a notched impact strength of 37 kJ·m⁻², along with a high shape memory fixation rate and recovery rate when the ADR content was 1 wt%. Furthermore, the underlying toughening mechanism was elucidated. This work may offer an industrially scalable relevant model to fabricate high-performance PLA materials.     

Thermal,mechanical, and morphological properties of polylactic acid toughened with an impact modifier

Polylactic acid (PLA) was melt‐blended with different amount (0 to 50 wt %) of a commercially available ethylene acrylate copolymer impact modifier. PLA/impact modifier blends were prepared via an internal mixer and compression molded into test specimens. The thermal, mechanical, and morphological properties of the blends were investigated. The addition of impact modifier decreased the ability of PLA to crystallize and/or recrystallize. The degree of crystallinity of PLA decreased while the cold crystallization temperature shifted to higher temperatures with increasing the impact modifier content. PLA/impact modifier blends were partially miscible. This was confirmed by the dynamic mechanical analysis (DMA) tests. With increasing the impact modifier content, the blends showed some improvement in the elongation at break and notched impact strength indicating the toughening effects of the impact modifier. In contrast, the yield stress and tensile modulus decreased with the increase in the impact modifier content. Scanning electron microscopy (SEM) micrographs revealed that the toughening mechanisms among others involved shear yielding or plastic deformation of the PLA matrix induced by interfacial debonding between the PLA and the impact modifier domains. PLA with 30 wt % impact modifier showed comparable yield stress and tensile modulus and better elongation at break and impact strength (+90%) than those of polypropylene (PP). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123:2715–2725, 2012     

Thermal,mechanical, and rheological properties of polylactide/poly(1,2‐propylene glycol adipate)

Polylactide (PLA) was melt blended with poly(1,2‐propylene glycol adipate) (PPA) in a Thermo‐Haake mixer. 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. PPA lowered the glass transition temperature and increased the ability of PLA to cold crystallization. With the increase in PPA content (5–25 wt%), the blends showed decreased tensile strength and Young's modulus; however, impact strength and elongation‐at‐break along were dramatically increased due to the plastic deformation. Morphological results of PLA/PPA blends showed that PPA was good compatible with PLA. The plasticization effect of PPA was also manifested by the lowering of dynamic storage modulus and viscosity in the melt state of the blends compared with neat PLA. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Toughening of polylactide with epoxy-functionalized methyl methacrylate–butyl acrylate copolymer

Glycidyl methacrylate-functionalized methyl methacrylate–butyl acrylate (GACR) core–shell structure copolymers were synthesized to toughen polylactide (PLA). With an increase in GACR content, the PLA/GACR blends showed decreased tensile strength and modulus; however, the elongation at break and the impact strength were significantly increased compared with that of PLA. The brittle fracture of neat PLA was gradually transformed into ductile fracture by the addiction of GACR. From dynamic mechanical analysis, the rigidity of the PLA/GACR blends was decreased with the increase of GACR content. The addition of GACR decreased the degree of crystallinity of PLA. The GACR was found to aggregate to form clusters with size increasing with increasing GACR content by transmission electron microscope analysis. The clusters dispersed in PLA matrix uniformly. It was found that PLA demonstrated large area, plastic deformation (shear yielding) and cavities in the blend upon being subjected the tensile and impact tests, which was an important energy-dissipation process and led to a toughened and transparent blend.     

EVM/PLA共混发泡材料泡孔结构和性能的研究

以乙烯-醋酸乙烯酯橡胶(EVM)和聚乳酸(PLA)共混物为基体材料,经模压发泡制备了共混发泡材料。研究了EVM/PLA不同共混比、硫化剂(DCP)、发泡剂(AC)和白炭黑用量以及不同发泡时间对EVM/PLA共混物发泡材料泡孔结构和物理机械性能的影响。结果表明,随PLA组分的减少,白炭黑和DCP用量的增加,泡孔逐渐减小,均匀度增加,孔壁增厚,材料的密度、拉伸强度和拉断伸长率呈升高趋势,发泡倍率呈降低趋势。随发泡剂AC用量的增加,泡孔壁变薄,平均泡孔尺寸变化不大,材料的密度、拉伸强度和拉断伸长率呈降低趋势,发泡倍率增加。随硫化时间的延长,泡孔尺寸变小,孔壁增厚、发泡倍率逐渐下降,拉伸强度先增大后减少,拉断伸长率先下降后上升。     

PLA/PPC/OMMT纳米复合材料的结构与性能研究

采用双螺杆挤出机制备了聚乳酸（PLA）/聚碳酸亚丙酯（PPC）共混物和PLA/PPC/有机改性蒙脱土（OMMT）纳米复合材料,采用偏光显微镜、差示扫描量热仪和力学性能试验机等对共混物和纳米复合材料的相态结构、熔融与结晶行为和力学性能等进行了研究。结果表明,在PPC含量低于30 %时,随着PPC含量的增加,PLA/PPC和PLA/PPC/OMMT体系中PLA的玻璃化转变温度（Tg）均降低,在PPC含量为50 %时出现了明显的相分离;随着PPC含量的增加,PLA/PPC的冲击强度增大;OMMT的含量小于1.5 %时,PLA/PPC/OMMT体系的结晶度、拉伸强度、断裂伸长率和冲击强度均随OMMT含量的增加而增大。     

Morphology and properties of the biosourced poly(lactic acid)/poly(ethylene oxide‐b‐amide‐12) blends

Biosourced poly(lactic acid) (PLA) blends with different content of poly(ethylene oxide‐b‐amide‐12) (PEBA) were prepared by melt compounding. The miscibility, phase structure, crystallization behavior, mechanical properties, and toughening mechanism were investigated. The blend was an immiscible system with the PEBA domains evenly dispersed in the PLA matrix. The PEBA component suppressed the nonisothermal melt crystallization of PLA. With the addition of PEBA, marked improvement in toughness of PLA was achieved. The maximum for elongation at break and impact strength of the blend reached the level of 346% and 60.5 kJ/m², respectively. The phase morphology evolution in the PLA/PEBA blends after tensile and impact tests was investigated, and the corresponding toughening mechanism was discussed. It was found that the PLA matrix demonstrates obvious shear yielding in the blend during the tensile and impact tests, which induced energy dissipation and therefore lead to improvement in toughness of the PLA/PEBA blends. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Mechanical,rheological, and crystallinity properties of polylactic acid/polyethylene glycol-polydimethylsiloxane copolymer blends by melt blending

Polylactic acid (PLA) is high in strength and modulus, but its applications are limited partly due to its inherent brittleness. It is difficult to keep the toughness and transparency of modified PLA without damaging its tensile strength and crystallinity. To improve the properties of PLA, polyethylene glycol-polydimethylsiloxane copolymer (PEG-PDMS) was incorporated to PLA via melt blending. By incorporating only 5 wt% of PEG-PDMS into PLA matrix, the elongation at break of the blends increased from 6% to 58% and the tensile strength was found to be 48.8 MPa. Differential scanning calorimetry demonstrated that the crystallinity of PLA/5%PEG-PDMS blends reached 33.5%. At the same time, the energy storage modulus (G) and complex viscosity (η*) of the blends had been improved. UV–vis test showed the light transmittance of the PLA/5%PEG-PDMS blends was slightly decreased. The toughened materials are sufficient to cope with the challenges brought by complex environments, achieving an efficient toughening effect.     

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 %。     

Toughening polylactide with epoxidized styrene–butadiene impact resin: Mechanical,morphological, and rheological characterization

Styrene–butadiene impact resin (SBC) was chosen as the toughening agent to improve the tensile toughness of polylactide (PLA). Epoxidized SBC (ESBC) with different epoxidation degree were prepared by epoxidation using in situ peroxoformic acid method and a series of PLA/SBC(ESBC) blends were prepared by melt blending. The elongation at break of the PLA/ESBC blends was greatly improved, which was reflected in the slight decrease in the tensile strength and tensile modulus. Moreover, the tensile strength and tensile modulus were not significantly affected by the epoxidation degree of ESBC. For example, the incorporation of ESBC28.8% (30 wt %) to PLA caused an obvious increment of elongation at break from 3.5% of pure PLA to 305.0%, while the tensile modulus and tensile strength decreased to 80 and 78% of pure PLA, respectively. Scanning electron microscopy observations of cryo‐fractured surface morphology and particle size analysis demonstrated that the compatibility of the PLA/ESBC blends was improved significantly compared to PLA/SBC blend. PLA/ESBC(70/30) blends exhibited shear‐thinning behavior over the range of the studied shear rate. With an increase in shear rate, the non‐Newtonian index of the blends decreased gradually. Furthermore, the flow behavior of PLA/ESBC(70/30) blends was more sensitive to the shear rate than pure PLA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46058.     

SEBS-g-MAH增韧聚乳酸的性能研究

采用哈克密炼机制备了聚乳酸(PLA)与马来酸酐接枝苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚弹性体(SEBS-g-MAH)的共混物,并对共混物的力学性能、流变性能和微观结构进行了分析。结果表明,共混物的拉伸强度随着SEBS-g-MAH含量的增加而下降,断裂伸长率随着SEBS-g-MAH含量的增加而增大。当SEBS-g-MAH的含量为30 %时,共混物的冲击强度提高了2.5倍,共混物的韧性得到提高。随着SEBS-g-MAH含量的增加,PLA熔体黏度的变化趋势与SEBS-g-MAH越来越相似,即熔体黏度随着频率的增大而下降。扫描电镜分析表明,MAH基团改善了两相间的界面作用,增韧作用明显。     

聚乳酸／聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混材料3D打印线材改性研究

采用熔融共混法制备聚乳酸／聚（3?羟基丁酸?co?3?羟基戊酸酯）（PLA/PHBV），以及分别添加苯乙烯?甲基丙烯酸缩水甘油酯共聚物（ADR）、柠檬酸三丁酯（TBC）的共混物PLA/PHBV/ADR和PLA/PHBV/TBC，通过注塑和熔融沉积成型（FDM）技术制备了标准测试样条，研究了添加ADR和TBC后对PLA/ PHBV共混材料及三维（3D）打印样品热学性能和力学性能的影响。结果表明，PHBV结晶度均降低，加入ADR的注塑样品断裂伸长率最大提高到32 %，加入TBC的注塑样品拉伸强度和冲击强度提高，断裂伸长率提高到2.8 %；加入ADR的3D打印制品拉伸强度降低，断裂伸长率提高，添加TBC的3D打印制品相容性得到了明显的提升，通过扫描电子显微镜（SEM）观察无明显的颗粒相，拉伸强度在改性前后无明显变化。     

Reduction of the elongation at break of thermoplastic polyolefins through melt blending with polylactide and the influence of the amount of compatibilizers and the viscosity ratios of the blend components on phase morphology and mechanics

The objective of this work is the synthesis of a polypropylene/ethylene‐propylene‐rubber (TPO)/polylactide (PLA)/compatibilizer (PVM) blend to reduce the elongation at break of TPO by blending TPO with brittle PLA. Three TPO types with different viscosities were melt blended with PLA and an ethylene/n‐butylacrylate/glycidyl methacrylate terpolymer (PVM) as reactive compatibilizer. All blends had a constant PLA amount of 30 wt%. Two parameters were varied in the experiments, viscosity of the TPO types, and amount of PVM used in the blends. Both parameters played important roles in reducing the nominal elongation at break compared to pure TPO foils and influencing the phase morphology of extruded blend foils. The nominal elongation at break could be reduced by 100‐150% through blending TPO with PLA and PVM. Characterization regarding the blend morphology, especially the size and shape of the dispersed PLA phase in the TPO matrix was done by Environmental Scanning Electron Microscopy (ESEM) images. Investigations of the morphology showed that size and shape of dispersed PLA phases are dependent on the viscosity ratios of the blend components and on the amount of compatibilizer in the blend. AFM images of the polymer blends reveal soft rubbery layers around the dispersed PLA phases. POLYM. ENG. SCI., 56:905–913, 2016. © 2016 Society of Plastics Engineers     

环氧化杜仲胶增韧改性聚乳酸的性能

采用熔融共混法将环氧化杜仲胶(EEUG)用于聚乳酸(PLA)的增韧改性,制备了具有良好韧性的全生物基PLA/EEUG共混物,考察了EEUG用量对共混物的热性能、动态力学性能、力学性能及微观形貌等的影响.结果表明,PLA/EEUG共混物为典型的两相不相容体系.EEUG的加入限制了PLA分子链的运动,导致PLA的结晶度下降...     

丙烯酸酯接枝改性天然橡胶增韧聚乳酸

通过在天然橡胶(NR)分子链上接枝甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA),制备了三种丙烯酸酯接枝改性NR:NR-g-PMMA,NR-g-PBA和NR-g-(PMMA,PBA)。采用核磁共振氢谱对三种接枝物进行了化学结构鉴定。将接枝改性后的NR和未改性的NR与PLA采用哈克密炼机熔融共混,分别制备了PLA/NR,PLA/NR-gPMMA,PLA/NR-g-PBA和PLA/NR-g-(PMMA,PBA)共混物,研究了接枝改性NR和未改性NR含量对共混物力学性能和热性能的影响。各共混物的拉伸弹性模量和拉伸强度均随接枝改性NR和未改性NR含量的增加而降低,断裂伸长率和缺口冲击强度随接枝改性NR和未改性NR含量的增加而提高。其中,PLA/NR-g-PBA共混物的断裂伸长率和缺口冲击强度比其它共混物提高的幅度大,当NR-g-PBA的质量分数为5%时,PLA/NR-g-PBA共混物的断裂伸长率达到78%,缺口冲击强度为5.2 k J/m2,而纯PLA的断裂伸长率仅为7.7%,缺口冲击强度为2.5 k J/m2,说明NR接枝分子柔顺性较高的BA更有利于促进其与PLA共混物的韧性提高。热分析结果表明,PLA/NR-gPBA共混物的热稳定性相比于纯PLA也有所提高。     

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。     

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。     

聚乳酸（PLA）／三醋酸甘油酯（TAc）的结晶性能研究

用三醋酸甘油酯（TAc）增塑聚乳酸（PLA）,研究了TAc对PLA在不同温度结晶时的结晶性能的影响。随着TAc的添加,PLA的结晶度与其球晶生长速率逐渐增加,断裂伸长率增大,抗张强度降低。TAc的最佳添加量为25％。研究不同温度等温结晶时PLA/TAc的机械性能以及晶体形态的影响,发现结晶温度升高,PLA/TAc的球晶生长速率减小,抗张强度增大,断裂伸长率降低。