Use of maleic anhydride compatibilization to improve toughness and other properties of polylactide blended with thermoplastic elastomers

Polylactide (PLA) being a very brittle biopolymer could be toughened by blending with thermoplastic elastomers such as thermoplastic polyurethane elastomer (TPU) and thermoplastic polyester elastomer (TPE); unfortunately, these blends are immiscible forming round domains in the PLA matrix. Therefore, the purpose of this study was to investigate the effects of using maleic anhydride (MA) compatibilization on the toughness and other properties of PLA blended with TPU and TPE. MA grafting on the PLA backbone (PLA‐g‐MA) was prepared separately by reactive extrusion and added during melt blending of PLA/thermoplastic elastomers. IR spectroscopy revealed that MA graft might interact with the functional groups present in the hard segments of TPU and TPE domains via primary chemical reactions, so that higher level of compatibilization could be obtained. SEM studies indicated that PLA‐g‐MA compatibilization also decreased the size of elastomeric domains leading to higher level of surface area for more interfacial interactions. Toughness tests revealed that Charpy impact toughness and fracture toughness (K_IC and G_IC) of inherently brittle PLA increased enormously when the blends were compatibilized with PLA‐g‐MA. For instance, G_IC fracture toughness of PLA increased as much as 166%. It was also observed that PLA‐g‐MA compatibilization resulted in no detrimental effects on the other mechanical and thermal properties of PLA blends. Copyright © 2014 John Wiley & Sons, Ltd.     

Simultaneously toughening and reinforcing poly(lactic acid)/thermoplastic polyurethane blend via enhancing interfacial adhesion by hydrophobic silica nanoparticles

This work focuses on satisfactorily toughening and reinforcing poly(lactic acid)/thermoplastic polyurethane (PLA/TPU) blend with low TPU content (10 wt%) using appropriate amounts of hydrophobic silica nanoparticles (SiO₂) via simple melt mixing. Both thermodynamic prediction and transmission electron microscopy micrographs demonstrate that most SiO₂ nanoparticles distribute at interfaces between the PLA and TPU phases. This improves interfacial adhesion between the phases, which is attributed to good bonding strength between the PLA and SiO₂ via hydrophobic interaction and formation of hydrogen bonds between the TPU and SiO₂. The PLA/TPU (90/10) ternary blend nanocomposite with 2 wt% SiO₂ exhibits obviously high impact strength (about 5.0 and 12.6 times that of the corresponding blend and PLA, respectively) and higher tensile strength than the blend and even the PLA. Crazing is the main reason for improved impact toughnesses of the blend nanocomposites. This work provides a simple and effective strategy to endow PLA/elastomer blends with optimum strength–toughness balance by adding appropriate amounts of nanoparticles.     

Biodegradability study of polylactic acid/ thermoplastic polyurethane blends

Blends with varied ratio of polylactic acid (PLA) and thermoplastic polyurethane (TPU) were prepared by melt blending. The PLA content in blends was 20, 40, 60 and 80 wt%. Samples of pure PLA and TPU that underwent the same thermal treatment were also prepared. Biodegradation was examined by respirometry. Pure TPU started to degrade immediately due to degradation of the low molecular weight plasticizer in the polymer. Pure PLA, on the other hand, exhibited an incubation period after which degradation progressed rapidly and was almost complete after 70 days. The degradation profile of the blends can be correlated to their morphology. Samples with a co-continuous morphology initially degrade at a higher rate than the rest of the samples due to the higher exposure of the TPU phase in these blends.     

Improvement in Toughness of Polylactide by Melt Blending with Bio-based Poly（ester）urethane

Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The miscibility, mechanical properties, phase morphology and toughening mechanism of the blend were investigated. Both DSC and DMTA results manifested that the addition of TPU elastomer not only accelerated the crystallization rate, but also increased the final degree of crystallinity, which proved that TPU has limited miscibility with PLA and has functioned as a plasticizer. All the blend samples showed distinct phase separation phenomenon with sea-island structure under SEM observation and the rubber particle size in the PLA matrix increased with the increased contents of TPU. The mechanical property variation of PLA/TPU blends could be quantitatively explained by Wu＇s model. With the variation of TPU, a brittle-ductile transition has been observed for the TPU/PLA blends. When these blends were under tensile stress conditions, the TPU particles could be debonded from the PLA matrix and the blends showed a high ability to induce large area plastic deformation before break, which was important for the dissipation of the breaking energy. Such mechanism was demonstrated by tensile tests and scanning electron microcopy （SEM） observations.     

Morphology and properties of super-toughened bio-based poly(lactic acid)/poly(ethylene-co-vinyl acetate) blends by peroxide-induced dynamic vulcanization and interfacial compatibilization

Super-toughened poly(lactic acid) (PLA)/poly(ethylene-co-vinyl acetate) (EVA) blends were prepared via 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD) induced dynamic vulcanization and in situ interfacial compatibilization. The effects of AD on the morphology and properties of PLA/EVA blends were studied using a Brabender torque rheometer, gel content test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC) thermogravimetric analysis (TGA) and mechanical properties test. The torque and gel content demonstrated that EVA and PLA was successfully vulcanized in the presence of free radicals obtained by the decomposition of the 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD). Additionally, the gel content results indicated that, compared with PLA, EVA is more aggressive with free radicals. The SEM revealed that a relatively uniform phase morphology and good interfacial compatibilization were achieved in the dynamically vulcanized PLA/EVA/AD blends. The interfacial reaction and compatibilization between the component polymers resulted in the formation of super-toughened PLA/EVA blended materials.     

Co-continuous phase structure formed in melt processing inducing shear bands to prevent crack propagation: Significant improvement in impact toughness of PMMA

High toughened polymeric materials have a wide application in many fields. Poly(methyl methacrylate) (PMMA) is a typical brittle polymer and it has been difficult to prepare high toughened PMMA material for a long time. To work on this issue, co-continuous phase structure was devised in PMMA/chlorinated polyethylene (CPE) blends through controlling the interfacial tension and viscosity in this work, resulting in the pronounced enhancement of impact toughness. The notched impact strength of co-continuous blends with 40 wt% CPE was up to 28.5 kJ/m², increased by 26 times compared with pure PMMA. Selective extraction experiments, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) showed that the CPE network was thin and weak when CPE addition was low, but became dense and strong once the content was more than 20 wt%. Two toughening mechanisms, i.e. cavitation and shear yielding, were put forward based on the micrographs of impact-fractured surfaces and double-notch four-point-bending test. This work may broaden the application prospects of PMMA and provide a new strategy to prepare high toughened polymeric materials through fabricating co-continuous in polymer blends.     

Toughening polylactide by dynamic vulcanization with castor oil and different types of diisocyanates

Dynamic vulcanization of polylactide (PLA) with castor oil (CO) and three different diisocyanates, namely 4,4′-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI), was performed to study the effect of diisocyanate type on the vulcanization process and on the morphology as well as mechanical properties of the PLA/CO-based polyurethane blends. The reactivity of the three diisocyanate followed the order of MDI > HDI > IPDI when reacting with castor oil. Interfacial compatibilization between PLA and the CO-based polyurethane occurred when the less reactive HDI and IPDI was used. Among all the blends, PLA/CO-IPDI showed the finest morphology and the best toughening efficiency. Incorporation of 20 wt% CO-IPDI increased the elongation at break and notched impact strength of PLA by 47.3 and 6.6 times, respectively. Cavitation induced matrix plastic deformation was observed as the toughening mechanism for the PLA blends with CO-based polyurethane. The effect of CO-IPDI content on the morphology and mechanical properties of PLA was studied in detail. The particle size of dispersed CO-IPDI and the elongation at break increased gradually, the tensile strength and Young's modulus decreased gradually, while the impact strength first increased and then decreased with increasing CO-IPDI content from 5 to 30 wt%. The maximum impact strength appeared for the blends with 20 wt% CO-IPDI.     

Morphology and performance of unsaturated polyester nanocomposites modified with organoclay and thermoplastic polyurethane

<正>Unsaturated polyester(UPR)/thermoplastic polyurethane(TPU)/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hybrids of styrene monomers and organoclay at ambient temperature.The crosslinking reaction eventually occurred through the unsaturated polyester prepolymer and styrene monomer.The morphology of the composites was investigated by scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The results show that the impact strength of UPR/TPU/organoclay nanocomposites increases obviously;the cure shrinkage decreases markedly,the glass transition temperature is enhanced and an elastic response to the deformation is prominent at the temperature above 10℃.     

Structure,properties and interfacial interactions in poly(lactic acid)/polyurethane blends prepared by reactive processing

Polyurethane elastomers are promising candidates for the impact modification of PLA producing blends for example for biomedicine. Poly(lactic acid) (PLA)/polyurethane elastomer (PU) blends were prepared by reactive processing and physical blending as comparison. The blends were characterized by a number of techniques including microscopy (scanning electron microscopy, SEM, and atomic force microscopy, AFM), rotational viscometry, thermal (dynamic mechanical analysis, DMA), and mechanical (tensile) measurements. The analysis and comparison of the structure and properties of physical and reactor blends proved the successful coupling of the phases. Coupling resulted in more advantageous structure and superior mechanical properties compared to those of physical blends as confirmed by morphology, macroscopic properties and the quantitative estimation of interfacial interactions. Structural studies and the composition dependence of properties indicated the formation of a submicron, phase-in-phase structure which positively influenced properties at large PU contents. The results strongly support that reactive processing is a convenient, cost-effective and environmentally friendly technique to obtain blends with superior properties.     

Physico-Mechanical Properties of Biodegradable Rubber Toughened Polymers

Summary: In this study, blends of poly(lactic acid) (PLA) with poly(butylene adipate-co-terephthalate) (PBAT) were studied for their mechanical and thermal properties as a function of the PBAT content. Tensile testing, impact testing, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMTA) and scanning electron microscopy (SEM) were used to characterize the blends. It was observed that PLA/PBAT blends maintained quite high modulus and tensile strength compared to pure PLA. Small amounts of PBAT improved the elongation at break and the impact resistance showing a debonding effect typical of rubber toughened systems.     

Structure and blood compatibility of highly oriented poly(lactic acid)/thermoplastic polyurethane blends produced by solid hot stretching

Highly oriented poly(lactic acid) (PLA)/thermoplastic polyurethane (TPU) blends were fabricated through solid hot stretching technology in an effort to improve the mechanical properties and blood biocompatibility of PLA as blood‐contacting medical devices. It was found that the tensile strength and modulus of the blends can be improved dramatically by stretching. With the increase of draw ratio, the cold crystallization peak became smaller, and the glass transition and the melting peak moved to high temperature, while the crystallinity increased, and the grain size of PLA decreased, indicating of the stress‐induced crystallization during drawing. The oriented blends exhibited structures with longitudinal striations which indicate the presence of micro‐fibers. TPU phase was finely and homogeneously dispersed in the PLA, and after drawing, TPU domains were elongated to ellipsoid. The introduction of TPU and orientation could enhance the blood compatibility of PLA by prolonging kinetic clotting time, and decreasing hemolysis ratio and platelet activation. Copyright © 2013 John Wiley & Sons, Ltd.     

A polymer network based on thermoplastic polyurethane and ethylene-propylene-diene elastomer via melt blending: morphology, mechanical properties, and rheology

Blends of thermoplastic polyurethane (TPU) and ethylene-propylene-diene elastomer (EPDM) were prepared via a melt blending, and morphology, mechanical properties, and rheology were studied. Scanning electron microscopy (SEM) micrographs demonstrated that a network of EPDM domain was formed in TPU matrix, and became finer and more perfect with addition of 8 wt% EPDM into TPU. Dynamic mechanical analysis (DMA) and Fourier transformed infrared spectroscopy (FTIR) investigation indicated that EPDM was thermodynamically miscible with the soft segments of TPU and incompatible with the hard segments. The formation of the network was resulted from the competition of compatible and incompatible segments of TPU with EPDM. The tensile strength and elongation at break achieved a significant improvement with addition of EPDM, and obtained the optimum values of 39.21 MPa and 2659%, respectively, when EPDM content was 8 wt%. PEO-g-MA as a compatibilizer was employed to improve the compatibilization between EPDM and the hard segments of EPDM, and consequently, the network became finer and more perfect. The evaluation of rheological properties revealed that the introduction of EPDM into TPU resulted in a reduction of the viscosity at high shear rate and a decrease of the flow activation energy; thus the processability of the blends was improved.     

Poly(lactic acid)/coplasticized thermoplastic starch blend: Effect of plasticizer migration on rheological and mechanical properties

Polylactic acid (PLA) and thermoplastic starch (TPS) are known as bio‐based and biodegradable thermoplastic polymers that can be used in different applications owing to their inherent physical and mechanical properties. In order to reduce the higher costs of PLA and tuning its physical and mechanical properties suitable for short life packaging applications, blending of PLA with the TPS, more economical biodegradable polymer, has been considered in academic and industrial researches. However, melt blending of PLA with TPS without compatibilization process caused some drawbacks such as coarsening morphology and declining mechanical properties and ductility because of thermodynamic immiscibility, which may restrict its usage in packaging applications. Subsequently, our approach in this research is compatibilization of PLA/TPS blends by utilization of primary well tuning of TPS formulation with a combination of sorbitol and glycerol plasticizers. In this work, the wide composition range of melt mixed PLA/TPS blends was prepared using a laboratory twin screw extruder. The effects of microstructure on the rheological and mechanical properties of PLA/TPS blends were studied using different methods such as scanning electron microscopy (SEM) images, contact angle, oscillatory shear rheological measurements, and tensile and impact strength mechanical tests. The rheological and mechanical properties were interpreted according to the morphological features and considering the possibility of plasticizer migration from TPS to PLA phase during melt blending. Reduction in complex viscosity and storage modulus of PLA matrix samples indicates the improved melt processability of blends. Finally, in comparison with mechanical results reported in literature, our simple approach yielded the blends with elastic modulus and ductility comparable with those of chemically compatibilized PLA/TPS blends.     

Thermogravimetric analysis and differential scanning calorimetric studies on nanoclay-filled TPU/PP blends

Thermal stability of ester-thermoplastic polyurethane (TPU)/polypropylene (PP) and ether-TPU/PP blends was evaluated by thermogravimetric studies. Thermal studies were made as a function of blend ratio. Effects of compatibilization using MA-g-PP and nanoclay addition on thermal stability were evaluated. Mass loss at 400 °C was found to decrease with increasing PP content were determined. Finally the compatibility and crystallization behavior of the blends were studied by differential scanning calorimetry. Compared to the ether-TPU blend nanocomposites, the ester-TPU blends showed better compatibility and thermal stability.     

Facile fabrication of organically modified boron nitride nanosheets and its effect on the thermal stability,flame retardant,and mechanical properties of thermoplastic polyurethane

Although hexagonal boron nitride (h‐BN) has presented a potential prospect in polymer composite fields, undesirable interfacial interaction with polymer matrix that generates serious aggregation of nanomaterials has suppressed its enhancement effect. Moreover, the chemically inert surface of h‐BN also makes the commonly used approach that improves the interfacial interaction between nanofillers and polymeric matrix invalid. Herein, the functionalized modification of chemically inert h‐BN was successfully fabricated by the adsorption of cetyl‐trimethylammonium bromide, with electrostatic interactions. The obtained h‐BN (cetyl‐trimethylammonium bromide‐BN) was well characterized by systematic tests and then added into thermoplastic polyurethane (TPU) matrix. The inclusion of functionalized h‐BN can dramatically improve thermal stability, flame retardant, and mechanical properties of TPU composites. With the incorporation of as low as 4.0 wt% nanofillers, maximal value of heat release rate and total heat release of TPU were reduced by 57.5% and 17.8%, compared with those of pure TPU, respectively. Moreover, tensile strength of TPU composite with a loading of 2.0 wt% was increased by 79.3% in comparison with that of neat TPU. The facile functionalized approach of chemically inert h‐BN paves the way for promising applications of h‐BN in the development of flame retardant polymer materials.     

Morphology and properties of biodegradable poly (lactic acid)/poly (butylene adipate-co-terephthalate) blends with different viscosity ratio

Phase morphology exerts a tremendous influence on the properties of polymer blends. The development of the blend morphology depends not only on the intrinsic structure of the component polymers but also on extrinsic factors such as viscosity ratio, shearing force and temperature in the melt processing. In this study, various poly (butylene adipate-co-terephthalate) (PBAT) materials with different melt viscosity were prepared, and then poly (lactic acid) (PLA)/PBAT blends with different viscosity ratio were prepared in a counter-rotating twin-screw extruder under constant processing conditions. The influence of viscosity ratio on the morphology, mechanical, thermal and rheological properties of PLA/PBAT (70/30 w/w) blends was investigated. The experimental results showed that the morphology and properties of PLA/PBAT blends strongly depended on the viscosity ratio. Finer size PBAT phase were observed for viscosity ratio less than 1 (λ < 1) compared to samples with λ > 1. It was found that the interfacial tensions of PLA and PBAT were significantly different when the viscosity ratio was changed, the lowest interfacial tensions (0.12 mN/m) was obtained when the viscosity was 0.77. Additionally, the maximal tensile strength in PLA/PBAT blends were obtained when the viscosity ratio was 0.44, while the maximal impact properties were obtained when the viscosity ratio was 1.95.     

Polyaniline/thermoplastic polyurethane blends: Preparation and evaluation of electrical conductivity

Conducting polymer blends whose undiluted components have different properties are promising materials for specific applications and have attracted interest in recent years. The aim of this study was to obtain and evaluate the electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid (PAni.DBSA)/polyurethane thermoplastic (TPU) blends. The PAni.DBSA was synthesized from DBSA-aniline (DBSAn) salt through an emulsion polymerization in tetrahydrofurane (THF) or in the presence of polyurethane thermoplastic solution, resulting in pure PAni.DBSA or PAni.DBSA/TPU blends. Blends of PAni.DBSA/TPU were also prepared through casting, at room temperature, after dissolving both components in THF as a common solvent. The insulator-conductor transition was very sharp and the percolation threshold was lower than 2.7 wt% of PAni.DBSA. The electrical conductivity of PAni.DBSA/TPU blends, prepared by both methods, reached maximum values at a PAni.DBSA concentration of 40 wt%, close to the value observed for the undiluted conducting polymer. However, for a PAni.DBSA content lower than 30 wt%, the electrical conductivity was dependent on the blend preparation method. Blends were characterized by infrared spectroscopy, thermogravimetric analysis (TG) and optical microscopy. The electrical conducting characteristics of the PAni.DBSA/TPU blends prepared using different procedures indicate a high potential for their successful application in electrical processes.     

环氧基团功能化弹性体增韧聚乳酸的性能

以2种不同结构的弹性体乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯(POE-g-GMA)和乙烯-丙烯酯甲酯-甲基丙烯酯缩水甘油酯三元共聚物(E-MA-GMA)增韧聚乳酸(PLA), 研究了接枝型与嵌段型弹性体的结构对聚乳酸增韧效果的影响. 结果表明, 接枝型聚合物POE-g-GMA与基体PLA之间具有良好的界面相互作用, 当POE-g-GMA的质量分数为15%时, 共混体系的缺口冲击强度为72.4 kJ/m², 而E-MA-GMA的质量分数为15%时, 共混体系的缺口冲击强度为32.4 kJ/m², 结果表明, 接枝型聚合物POE-g-GMA增韧效果明显优于嵌段型E-MA-GMA.     

玻璃纤维对碳纳米管填充聚合物/热塑性聚氨酯共混体系导电性能的影响

研究了表面带有环氧基团的玻璃纤维(GF)对聚丙烯(PP)/热塑性聚氨酯(TPU)/多壁碳纳米管(MWCNT)、 聚甲基丙烯酸甲酯(PMMA)/TPU/MWCNT和聚乳酸(PLA)/TPU/MWCNT体系导电性能的影响. 研究结果表明, 未添加GF时, 由于MWCNTs选择性地分布在TPU分散相中, PP/TPU/MWCNT, PMMA/TPU/MWCNT和PLA/TPU/MWCNT材料的导电性能很差; 加入20%的GF使3个体系的电阻率均大幅度下降, 最高下降约13个数量级, 表明填充GF是一种具有普适性的改善以TPU为分散相的共混体系导电性能的有效方法. GF使体系电阻率降低的机理主要是形成了TPU包覆GF结构, 该结构可以看作长径比较高的导电棒, 可以有效协助导电通路的构建; 同时GF还起到了体积占位的作用, 提高了体系中导电组分在基体中的有效浓度.     

Property correlations for dynamically cured rice husk ash filled epoxidized natural rubber/thermoplastic polyurethane blends: Influences of RHA loading

Novel thermoplastic vulcanizates based on thermoplastic polyurethane (TPU) and epoxidized natural rubber (ENR) were prepared with rice husk ash (RHA) filler. Therefore, two major renewable resource materials (i.e., ENR and RHA) were exploited. Influences of RHA loading on mechanical, morphological, thermal and dynamic properties of dynamically cured ENR/TPU blends were investigated. It was found that the RHA showed good dispersion and was mainly localized in the ENR phase. Increasing the RHA loading led to the formation of larger ENR domains dispersed in the TPU matrix. Also, migration of the RHA particles from ENR to TPU phases was observed, resulting in reduced strength properties. It was found that the RHA acted as a nucleating agent in the TPU matrix and could accelerate the crystallization of TPU. Additionally, stress relaxation of the blends was evaluated by temperature stress scanning relaxation (TSSR). Higher relaxation stresses or raised relaxation curves were observed with increased RHA loadings in the dynamically vulcanized ENR/TPU blends.