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。     

Melt characteristics,mechanical, and thermal properties of blown film from modified blends of poly(butylene adipate‐co‐terephthalate) and poly(lactide)

Blown films from poly(butylene adipate‐co‐terephthalate) and poly(lactide) (PLA) blends were investigated. The blends were prepared in a twin‐screw extruder, in the presence of small amounts of dicumyl peroxide (DCP). The influence of DCP concentration on film blowing, rheological, mechanical, and thermal properties of the blends is reported in this article. Rheological results showed a marked increase in polymer melt strength and elasticity with the addition of DCP. As a consequence, the film homogeneity and the stability of the bubble were improved. The modified blend films, compared with the unmodified blend, showed an improvement in tensile strength and modulus with a slight loss in elongation. Fourier transform infrared and gel results revealed that chain scission and branching were more significant than crosslinking when the DCP loadings in the blends were not higher than 0.7%. A reduction in melt temperatures of PLA was observed due to difficulty in chain crystallization. The concentrations of DCP strongly affected the melting temperatures but had an insignificant effect on the decomposition behavior of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

过氧化物对PBS/PLA共混物反应性增容研究

通过加入过氧化二苯甲酰(BPO)和过氧化二异丙苯(DCP)进行反应性增容来改善其相容性,并通过扫描电子显微镜(SEM)、偏光显微镜(PLM)、动态力学性能测试(DMA)以及差示扫描量热分析仪(DSC)等方法对共混体系相容性及力学性能进行了表征及测试。实验结果表明,加入过氧化物BPO或DCP可以使共混体系相结构均匀细化,共混体系的相结构由未加入过氧化物时的海岛相转为双连续相结构,同时由DSC测试还可以明显看出共混体系形成了共晶结构,说明共混体系的相容性得到了显著提高。     

Bio-renewable precursor fibers from lignin/polylactide blends for conversion to carbon fibers

Lignin, a highly aromatic biopolymer extracted as a coproduct of wood pulping, was investigated as a suitable precursor for carbon fibers. Lignin was chemically modified and blended with poly(lactic acid) (PLA) biopolymer before melt spinning into lignin fibers. The chemical modification of raw lignin involved butyration to form ester functional groups in place of polar hydroxyl (–OH) groups, which enhanced the miscibility of lignin with PLA. Fine fibers were extracted and spooled continuously from lignin/PLA blends with an overall lignin concentration of 75 wt.%. The influence of chemical modification and physical blending of lignin with PLA on the resulting fiber was studied by analyzing the microstructure of the fibers using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The influence of blend composition on the phase behavior was studied by differential scanning calorimetry (DSC). The effect of composition on the mechanical properties was studied by tensile tests of the lignin/PLA blend fibers. The thermal stability and carbon yield of the blended fibers with different concentrations of lignin were characterized by thermogravimetric analysis (TGA). The microstructure analysis of carbon fibers produced from lignin/PLA blends revealed composition dependent microporous structures inside the fine fibers.     

Improvements in morphology,mechanical and thermal properties of films produced by reactive blending of poly(lactic acid)/natural rubber latex with dicumyl peroxide

The effect of dicumyl peroxide (DCP) as a free-radical cross-linking agent on the morphology, thermal and mechanical properties, and gas permeation of blown films prepared by reactive blending of poly(lactic acid) (PLA) and natural rubber latex was investigated. In comparison to the blown films without DCP, SEM micrographs revealed that the amount of debonded rubber domains from the cryofractured surface reduced considerably. This was when DCP at 0.003 phr was incorporated and the free radicals from thermally decomposed DCP reacted with PLA and NR chains, generating PLA–NR copolymers and cross-linked NR as confirmed by FTIR spectra. These PLA–NR copolymers acted as compatibilizers, which increased the strength at the PLA/NR interfaces, leading to the improvement in tensile strength, elongation at break, tensile toughness, impact strength, and tear strength. Although DCP did not influence the cold crystallization of PLA, TGA thermograms showed that thermal stability slightly increased owing to the enhanced interfacial adhesion. However, the addition of DCP at 0.005 and 0.010 phr resulted in a high content of cross-linked NR gel, by consuming the free radicals instead in copolymer formation. Therefore, the compatibilization efficiency was significantly reduced and the mechanical properties of reactive PLA/NR blown films finally dropped. Also, this poor interfacial adhesion facilitated the microvoid formation at the polymer–rubber interface as a result of mechanical stretching upon the film blowing process, increasing the permeation of water vapor and oxygen molecules. According to our study, it can be summarized that to optimize the morphology, mechanical properties, and gas permeation property of the free radical-assisted reactive blends, it is of great concern to carefully balance reactive compatibilizer formation and gel formation by adjusting the DCP content.     

Use of crosslinking agent to produce high-performance PLA/EVA blends via reactive processing

Poly (lactic acid) (PLA) is one of the most currently investigated polymers due to its production from renewable sources and biodegradability. Being a brittle polymer, PLA has low toughness, limiting its use for commercial applications. Therefore, the present work aims to produce PLA blends, using the ethylene-vinyl acetate copolymer (EVA), dynamically vulcanized with dicumyl peroxide (DCP) as a crosslinking agent. A 70/30 mixture of PLA/EVA was produced with 0.2, 0.4, 0.6, 0.8, and 1.0 phr DCP. The produced blends were characterized by torque rheometry, melt flow index (MFI), gel content, thermogravimetry (TG), and differential scanning calorimetry (DSC). Tensile properties, impact strength, heat deflection temperature (HDT), and blends morphologies (SEM) were also studied. The presence of increased dynamically vulcanized systems with added DCP was verified through torque rheometry, MFI, and gel content. Substantial increases in the impact strength and elongation at break were observed in PLA/EVA/DCP, providing super-tough materials at 0.6, 0.8, and 1.0 phr of DCP, with impact strengths of 829.5, 860.3, and 890.2 J/m and elongation at break of 138.5, 146.8, and 120.4%, respectively. These results are promising when compared with engineering polymers and blends. This is probably due to in situ compatibilizer PLA-g-EVA, which resulted in a homogeneous morphology as evidenced by SEM images.     

PPO-g-MA对PPO/PA66共混物的原位增容作用

用傅里叶变换红外光谱证明了聚(2,6-二甲基-1,4-苯醚)(PPO)与马来酸酐(MA)在过氧化二异丙苯的作用下,采用熔融挤出法生成了PPO-g-MA。通过透射电子显微镜、扫描电子显微镜、Instron毛细管流变仪、力学性能试验机和Molau实验分别对不同PPO-g-MA用量的PPO/聚酰胺66(PA66)共混物的亚微相态、流变行为、力学性能进行了考察,结果表明,PPO-g-MA对PPO/PA66共混物起到了原位增容作用。     

Properties of coconut shell powder‐filled polylactic acid ecocomposites: Effect of maleic acid

Ecocomposites were produced by incorporating coconut shell powder (CSP) into polylactic acid (PLA) resin. The effect of filler content and chemical modification on the mechanical properties, thermal properties, and morphology of PLA/CSP ecocomposites were investigated. The addition of filler has decreased the tensile strength and elongation at break of PLA/CSP ecocomposites. However, tensile strength and modulus of elasticity of PLA/CSP ecocomposites were enhanced by maleic acid treatment. Meanwhile, glass transition temperature (T_g) and crystallinity (X_c) of PLA/CSP ecocomposites increased at 30 php of filler content and increased the presence of maleic acid (MA). However, the melting temperature (T_m) and crystallization temperature (T_c) were not significantly changed with the filler content and MA modification The thermal stability of PLA/CSP ecocomposites increased with the CSP content. The MA modification improved the thermal stability of PLA/CSP ecocomposites through better filler–matrix interaction. The improvement was confirmed by scanning electron microscope study. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Modification of wood flour/PLA composites by reactive extrusion with maleic anhydride

MA modified wood flour/PLA composites were prepared by one‐step reactive extrusion, in which wood flour and poly(lactic acid) (PLA) were used as raw material, maleic anhydride (MA) was used as modifier, and dicumyl peroxide (DCP) was used as initiator. The influences of MA concentration on the morphology, thermal stability, rheological, and mechanical properties of the composites were studied. The addition of MA improved the compatibility of the composites significantly. The thermal and rheological results showed that with the increase of the concentration of MA, the thermal stability of the composites decreased, the storage modulus and complex viscosity of the composites also decreased. The MA modified composites had an enhanced mechanical strength compared to the unmodified one. As the concentration of the MA increased, the tensile and flexural strength of the composites first increased and then decreased, and reached a maximum when the concentration of MA was 1 wt %. The MA modified composites showed a better water resistance than the unmodified ones. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43295.     

Tailoring the morphology and properties of poly(lactic acid)/poly(ethylene)‐co‐(vinyl acetate)/starch blends via reactive compatibilization

Poly(lactic acid)/poly(ethylene‐co‐vinyl acetate)/starch (PLA/EVA/starch) ternary blends were prepared by multi‐step melt processing (reactive extrusion) in the presence of maleic anhydride (MA), benzoyl peroxide and glycerol. The effects of MA and glycerol concentration on the morphology and properties of the PLA/EVA/starch blends were studied using scanning electron microscopy, transmission electron microscopy, atomic force microscopy, the Molau experiment, dynamic mechanical thermal analysis and differential scanning calorimetry etc. The plasticization and compatibilization provided a synergistic effect to these blends accompanied by a significant reduction in starch particle size and an increase in interfacial adhesion. Starch was finely dispersed in the ternary blends with a dimension of 0.5 ? 2 µm. Furthermore, EVA‐coated starch or a starch‐in‐EVA type of morphology was observed for the reactively compatibilized PLA/EVA/starch blends. The EVA with starch gradually changed into a co‐continuous phase with increasing MA concentration. Consequently, the toughness of the blends was improved. Since property stability of starch is an issue, the tensile properties of these blends were measured after different storage times and the blends showed good property stability. Copyright © 2012 Society of Chemical Industry     

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.     

Improving the toughening in poly(lactic acid)‐thermoplastic cassava starch reactive blends

Poly(lactic acid) (PLA), a physical blend of PLA and thermoplastic cassava starch (TPCS) (PLA‐TPCS), and reactive blends of PLA with TPCS using maleic anhydride as compatibilizer with two different peroxide initiators [i.e., 2,5‐bis(tert‐butylperoxy)‐2,5‐dimethylhexane (L101) and dicumyl peroxide (DCP)] PLA‐g‐TPCS‐L101 and PLA‐g‐TPCS‐DCP were produced and characterized. Blends were produced using either a mixer unit or twin‐screw extruder. Films for testing were produced by compression molding and cast film extrusion. Morphological, mechanical, thermomechanical, thermal, and optical properties of the samples were assessed. Blends produced with the twin‐screw extruder resulted in a better grade of mixing than blends produced with the mixer. Reactive compatibilization improved the interfacial adhesion of PLA and TPCS. Scanning electron microscopy images of the physical blend showed larger TPCS domains in the PLA matrix due to poor compatibilization. However, reactive blends revealed smaller TPCS domains and better interfacial adhesion of TPCS to the PLA matrix when DCP was used as initiator. Reactive blends exhibited high values for elongation at break without an improvement in tensile strength. PLA‐g‐TPCS‐DCP provides promising properties as a tougher biodegradable film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46140.     

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     

Dynamic vulcanization of recycled milk pouches (LDPE–LLDPE) and EPDM blends using dicumyl peroxide

The viability of thermomechanical recycling of post‐consumer milk pouches (blend of low‐density polyethylene (LDPE) and linear low‐density polyethylene (LLDPE)) and its scope for suitable engineering applications were investigated. The effects of blending with ethylene‐propylene‐diene monomer (EPDM) rubber and subsequent curing using dicumyl peroxide (DCP) on the macromolecular structure and properties of recycled polyethylene (PE) blends were studied. The crosslinking efficiency of recycled PE/EPDM blends and possible thermooxidative degradation of recycled polymer upon peroxide curing was assessed using torque and gel content measurements along with infrared spectroscopic analysis. Both the torque and gel content of the blends varied with DCP crosslinking reactions and also were affected by oxidative degradation. In view of the electrical application area of this recycled blend material, the dielectric breakdown strength and volume resistivity were measured. The mechanical performance and thermal stability of recycled PE/EPDM blends improved with progressive crosslinking by DCP but deteriorated somewhat at higher DCP dose. Scanning electron microscopy showed good interface bonding between recycled polymer and dispersed EPDM phase in the cured blends compared to the non‐cured blends. Copyright © 2007 Society of Chemical Industry     

Mechanical properties and morphological changes of poly(lactic acid)/polycarbonate/poly(butylene adipate‐co‐terephthalate) blend through reactive processing

The mechanical properties and morphological changes of poly(lactic acid) (PLA), polycarbonate (PC), and poly(butylene adipate‐co‐terephthalate) (PBAT) polymer blends were investigated. Several types of blend samples were prepared by reactive processing (RP) with a twin‐screw extruder using dicumyl peroxide (DCP) as a radical initiator. Dynamic mechanical analyses (DMA) of binary polymer blends of PC/PBAT indicated that each component was miscible over a wide range of PC/PBAT mixing ratios. DMA of PLA/PBAT/PC ternary blends revealed that PBAT is miscible with PC even in the case of ternary blend system and the miscibility of PLA and PBAT can also be modified through RP. As a result, the tensile strain and impact strength of the ternary blends was increased considerably through RP, especially for PLA/PBAT/PC = 42/18/40 (wt/wt/wt) with DCP (0.3 phr). Scanning electron microscopy (SEM) analysis of the PLA/PBAT/PC blends revealed many small spherical island phases with a domain size of approximately 0.05–1 μm for RP, whereas it was approximately 10 μm without RP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Partial replacement of NR by GTR in thermoplastic elastomer based on LLDPE/NR through using reactive blending: Its effects on morphology,rheological, and mechanical properties

Attempts have been made to use different amount of ground tire rubber (GTR) powder as a partial substitute for natural rubber (NR) in thermoplastic elastomer based on linear low‐density polyethylene (LLDPE, 60 wt%) and NR (40wt%). Maleic anhydride (MA) and dicumyl peroxide (DCP) were used, during melt mixing of the compound, to modify GTR and vulcanize the rubber phases of the blends. Morphology of the blends was studied by scanning electron microscopy and rheological behavior investigated through rheomechanical spectroscopy. Mechanical properties of the blends were also measured, and the effect of GTR concentration on properties was evaluated. Obtained results showed that modification of GTR with MA and using DCP in the blends containing GTR improves the bonding between GTR and matrix. This leads to a distinctive rheological behavior and enhances tensile strength and elongation at break compared to its corresponding simple blend. It can be said that using of MA and DCP during melt mixing of thermoplastic elastomers based on LLDPE/NR containing GTR, concludes to a better dispersion of GTR and formation of morphology similar to that of a dynamic vulcanized thermoplastic elastomer, which improves interfacial bonding between phases and causes a dramatically increase in mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Toughening modification of PLLA/PBS blends via in situ compatibilization

Biodegradable polymer blends consisting of poly(L ‐lactic acid) (PLLA) and poly(butylene succinate) (PBS) were prepared in the presence of dicumyl peroxide (DCP). The effects of DCP content on the mechanical properties, thermal and rheological behavior, phase morphology as well as the toughening mechanism of the blends were investigated. The notched Izod impact strength of PLLA/PBS (80/20) blend significantly increased after the addition of 0.05–0.2 phr DCP, but the strength and modulus monotonically decreased with increasing DCP content. PBS acted as a nucleating agent at the environmental temperature below its melting temperature and accelerated the crystallization rate of PLLA but had little effect on its final degree of crystallinity. The degree of crystallinity of PBS and the cold crystallization ability of PLLA gradually reduced with increasing DCP content. The addition of DCP induced an increase in viscosity of the blends at low frequencies as well as finer dispersion of PBS particles and better interfacial adhesion between PLLA and PBS, indicating the in situ compatibilization occurred between the two components. The optical clarity of PLLA/PBS blends was significantly improved after the addition of DCP, which was in accordance with the crystallization behavior and phase structure of the blends. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Properties of grafted wood flour filled poly (lactic acid) composites by reactive extrusion

Composites of poly(lactic acid) with wood flour which was grafted by melt extruding with methyl acrylate in the presence of benzoyl peroxide (BPO) were investigated. The modification of filler (WF-g-PMA) was carried out to enhance the filler-matrix interactions, while the treated component was characterized by infrared spectrum. Properties of binary (PLA/WF, PLA/WF-g-MA) composites were analyzed as a function of the grafting monomer amount by scanning electron microscopy, differential scanning calorimeter, thermogravimetric analysis, water absorption and mechanical tests. Compared with the untreated system (PLA/WF), all treated composites showed higher interfacial compatibility as a result of chemical bonding between WF and grated monomer. All composites showed higher tensile modulus and lower strength and elongation at break as compared to pure PLA; grafting modification with methyl acrylate led to an increased stiffness and decreased water absorption of the composites because of an enhanced filler-matrix interfacial compatibility.     

Improved Performance of Environmentally Friendly Blends of Biobased Polyethylene and Kraft Lignin Compatibilized by Reactive Extrusion with Dicumyl Peroxide

In this work, different contents (0.25, 0.50, 0.75, and 1 phr) of dicumyl peroxide (DCP) are incorporated into the bio-based high-density polyethylene (bioPE)/kraft lignin (KL) blends with a composition of 80 and 20 wt%, respectively with the aim of improving overall performance. The samples are obtained by reactive extrusion and injection-molding process, and then their overall performance is assessed by tensile tests, thermal analysis, optical and surface appearance, and wettability studies. The obtained mechanical properties confirm the successful interaction between bioPE and KL due to the addition of organic peroxide, which plays a key role in compatibilization. In particular, bioPE/KL blends with 1 phr of DCP achieve an increase in elongation at break of about 300% together with a noticeable increase in the impact strength of about 29% higher than the uncompatibilized bioPE/KL blend, while the tensile modulus decreases 42%. In addition, images obtained by field emission scanning electron microscopy show that the presence of DCP in the blends enhances better dispersion of KL into the bioPE matrix. The wettability analysis indicates that KL and DCP affect the hydrophobicity of the neat bioPE. Therefore, the resultant blends can be considered as potential sustainable polymers with balanced properties.     

Morphology,thermal, and dynamic mechanical properties of poly(lactic acid)/sisal whisker nanocomposites

Sisal whiskers were used as biobased nanofillers to prepare poly(lactic acid) (PLA)‐based nanocomposites. The whiskers were prepared from sisal fibers via sulfuric acid hydrolysis. Freeze drying of the aqueous whisker suspension was carried out to obtain loosely packed dry sisal whiskers. The nanocomposites were prepared by melt mixing, followed by hot melt pressing. The effect of the freeze drying of the nanofibers, the treatments of the samples with maleic anhydride (MA)/dicumyl peroxide (DCP) and with DCP, and the premixing of the powdered components on the dispersion of the whiskers in the PLA matrix and on the morphology, as well as the thermal and dynamic mechanical properties, of the resultant nanocomposites were investigated. Transmission electron microscopy micrographs show that the acid hydrolysis has led to separation of the whiskers, which had an approximate length and diameter of 195 and 15 nm, respectively. The TEM images of the nanocomposites show similar dispersion of the whiskers in the PLA matrix, whether untreated or MA/DCP or DCP treated. It was found that the crystallization behavior of the PLA matrix changed somewhat depending on whether the samples were treated or not. The thermogravimetric analysis results show a slight decrease in the thermal stabilities of the untreated and the MA/DCP‐treated nanocomposite samples compared to that of the neat PLA, whereas the DCP treatment slightly improved the thermal stability of the nanocomposites. The storage modulus of the nanocomposites increased over the investigated temperature region, and the incorporation of sisal whiskers reduced the intensity of the glass transition at 67°C. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers