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.     

Effect of miscibility on mechanical and thermal properties of poly(lactic acid)/ polycaprolactone blends

Binary blends based on poly(lactic acid) (PLA) and polycaprolactone (PCL) were prepared by melt mixing in a twin‐screw co‐rotating extruder in order to increase the low intrinsic elongation at break of PLA for packaging applications. Although PLA and PCL show low miscibility, the presence of PCL leads to a marked improvement in the ductile properties of PLA. Various mechanical properties were evaluated in terms of PCL content up to 30 wt% PCL. In addition to tensile and flexural properties, Poisson's ratio was obtained using biaxial extensometry to evaluate transversal deformations when axial loads are applied. Very slight changes in the melt temperature and glass transition temperature of PLA are observed thus indicating the low miscibility of the PLA–PCL system. Field emission scanning electron microscopy reveals some interactions between the two components of the blend since the morphology is characterized by non‐spherical polycaprolactone drops dispersed into the PLA matrix. In addition to the improvement of mechanical ductile properties, PCL provides higher degradation rates of blends under conditions of composting for contents below 22.5% PCL. © 2016 Society of Chemical Industry     

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。     

Crystallization, hydrolytic degradation, and mechanical properties of poly (trimethylene terephthalate)/poly(lactic acid) blends

Crystallization, melting, hydrolytic degradation, and mechanical properties of poly(trimentylene terephthalate)/poly(lactic acid) (PTT/PLA) blends have been investigated. The blends show a single and composition-dependent glass-transition temperature (T _g) over the entire composition range, implying that these blends are fully miscible in the amorphous state. The observed T _g is found to increase with increasing PLA content and fitted well with the Gordon–Taylor equation, with the fitting parameter k being 0.91. The cold-crystallization peak temperature increases, while the melt-crystallization peak decreases with increasing the PLA content. Both the pure PTT and PTT/PLA blends cannot accomplish the crystallization during the cooling procedure and the recrystallization occurs again on the second heating. Therefore, on the thermogram recorded, there is exothermal peak followed by endothermal peak with a shoulder. However, to pure PLA, no crystallization takes place during cooling from the melt, therefore, no melting endothermic peak is found on the second heating curve. WAXD analysis indicates PLA and PTT components do not co-crystallize and the crystalline phase of the blends is that of their enriched pure component. With increasing PLA content, the hydrolytic degradation of the blend films increases, while both the tensile strength and the elongation at break of the blend films decrease. That is to say, the hydrolytic degradation of the PTT/PLA blends increases with the introduction of PLA at the cost of the decrease of the flexibility of PTT.     

Effects of thermoplastic poly(ether-ester) elastomer and bentonite nanoclay on properties of poly(lactic acid)

This work presented the influence of thermoplastic poly(ether-ester) elastomer (TPEE) and bentonite (BTN) on improving the mechanical and thermal properties of poly(lactic acid) (PLA). PLA was initially melt mixed with TPEE at six different loadings (5–30 wt%) on a twin screw extruder and then injection molded. The mechanical tests revealed an increasing impact strength and elongation at break with increasing TPEE loading, but a diminishing Young's modulus and tensile strength with respect to pure PLA. The blend at 30 wt% TPEE provided the optimum improvement in toughness, exhibiting an increase in the impact strength and elongation at break by 3.21- and 10.62-fold over those of the pure PLA, respectively. Scanning electron microscopy analysis illustrated a ductile fractured surface of the blends with the small dispersed TPEE domains in PLA matrix, indicating their immiscibility. The 70/30 (wt/wt) PLA/TPEE blend was subsequently filled with three loadings of BTN (1, 3, and 5 parts by weight per hundred of blend resin [phr]), where the impact strength, Young's modulus, tensile strength and thermal stability of all the blends were improved, while the elongation at break was deteriorated. Among the three nanocomposites, that with 1 phr BTN formed exfoliated structure and so exhibited the highest impact strength, elongation at break, and tensile strength compared to the other intercalated nanocomposites. Moreover, the addition of BTN was found to increase the thermal stability of the neat PLA/TPEE blend due to the barrier properties and high thermal stability of BTN.     

海水环境下聚碳酸亚丙酯/聚乳酸共混物的降解性能研究

研究了聚碳酸亚丙酯（PPC）/聚乳酸（PLA）共混物在海水环境下的降解性能,通过力学实验、扫描电子显微镜、衰减全反射红外光谱等分别研究了共混物的力学性能、表面微观形貌、化学结构等的变化规律。结果表明,随着降解时间的延长,10/90、30/70、50/50、70/30（质量比,下同）的PPC/PLA共混物的拉伸强度都不断增大,而断裂伸长率在30 d时急剧降低,此后几乎保持不变;海水作用下240 d后PPC和PLA表面都存在明显孔洞和缺陷,而50/50的PPC/PLA共混物表面没有明显的裂纹和孔洞;纯PPC和纯PLA的羟基指数、羰基指数以及乳酸指数都呈现不断增大的趋势,且在前30 d比较明显,而50/50的PPC/PLA共混物则几乎没有变化;共混物的质量损失主要体现在前30 d,且质量损失率几乎都小于10 %,降解程度较低;共混物失重5 %的热分解温度提高,而最大速率失重温度几乎没有变化。     

Maleic Anhydride-Grafted PLA Preparation and Characteristics of Compatibilized PLA/PBSeT Blend Films

Poly(butylene sebacate-co-terephthalate) (PBSeT) is a biodegradable flexible polymer suitable for melt blending with other biodegradable polymers. Melt blending with a compatibilizer is a common strategy for increasing miscibility between polymers. In this study, PBSeT polyester was synthesized, and poly(lactic acid) (PLA) was blended with 25 wt% PBSeT by melt processing with 3–6 phr PLA-grafted maleic anhydride (PLA-g-MAH) compatibilizers. PLA-g-MAH enhanced the interfacial adhesion of the PLA/PBSeT blend, and their mechanical and morphological properties confirmed that the miscibility also increased. Adding more than 6 phr of PLA-g-MAH significantly improved the mechanical properties and accelerated the cold crystallization of the PLA/PBSeT blends. Furthermore, the thermal stabilities of the blends with PLA-g-MAH were slightly enhanced. PLA/PBSeT blends with and without PLA-g-MAH were not significantly different after 120 h, whereas all blends showed a more facilitated hydrolytic degradation rate than neat PLA. These findings indicate that PLA-g-MAH effectively improves PLA/PBSeT compatibility and can be applied in the packaging industry.     

三醋酸甘油酯增塑聚乳酸共混体系热力学及动态力学性质

用三醋酸甘油酯(TA c)增塑聚乳酸(PLA),研究了TA c对PLA力学性能的影响。当塑化剂添加到15%之后抗张强度从64M Pa下降到29.9M Pa,断裂伸长率同时从5.6%升高到243.1%,可以达到吹膜所要求的性质。用DSC和DM A研究了该共混体系的相容性,观察到随着TA c含量的增大,线性降低了PLA的Tg和Tm,并且塑化剂提高了分子链的迁移性,也使得体系的结晶度增大。在塑化剂含量为25%时,PLA已经被塑化剂所饱和,继续添加塑化剂可能会导致两相分离。     

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。     

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。     

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.     

Characterization of biodegradable polymers by inverse gas chromatography. III. Blends of amylopectin and poly(L‐lactide)

The morphology changes and surface thermodynamics of blends of amylopectin (AP)–poly(L ‐lactide) (PLA) were investigated over a wide range of temperatures and compositions using the inverse gas chromatography method. Twenty‐five solutes were selected such as alkanes, acetates, oxy, halogenated, and six‐member ring families. They provided a variety of specific interactions with the blends' surface. The morphology showed two regions, some others showed a de‐polymerization above 130°C. These zones enabled the estimation of T_g and T_m of AP, PLA, and the blends. Blending AP with PLA caused a decrease in AP's T_g value due to the reduction of the degree of crystallinity of the blend. Exothermic values of χ₂₃ were obtained indicating the compatibility of AP and PLA at all temperatures and weight fractions of AP–PLA. The miscibility was favored at 75%AP, only 25%AP–75%PLA composition influenced the degree of crystallinity. The dispersive component of the surface energy of the blends ranged from 16.09 mJ/m² for the pure AP as high as 58.36 mJ/m² at 110°C when AP was mixed with PLA in a 50–50% ratio. The surface energy was at its highest value when the composition was 75% of AP, in good agreement with χ₂₃ values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of starch thermoplastics modified with waterborne polyurethane from renewable resources

A waterborne polyurethane (PU) aqueous dispersion was synthesized from castor oil, and blended with thermoplastic starch (TPS) to obtain a novel biodegradable plastic with improved physical properties. The effect of PU content on the morphology, miscibility and physical properties of the resulting blends was well investigated by scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis and measurements of mechanical properties and water sensitivity. The research results show that the blends exhibit a higher miscibility when PU content is lower than 15 wt% due to the hydrogen bonding interaction between urethane groups and hydroxyl groups on starch, whereas obviously phase separation occurs in the blends with more than 15 wt% PU. Incorporating PU of 4-20 wt% in TPS results in the blends with improved Young's modulus (40-75 MPa), tensile strength (3.4-5.1 MPa), elongation at break (116-176%). Further, PU also plays an important role in improving the surface- and bulk-hydrophobicity and water resistance of the resulting blends.     

Molecular simulation and experimental studies of the miscibility of polylactic acid/polyethylene glycol blends

Computer simulation and experiments were performed to investigate the miscibility of PLA/PEG blends with different PEG concentrations. Flory-Huggins interaction (χ) parameter used to predict the miscibility for the blends was estimated by molecular dynamic simulation of fully atomistic model. The calculated χ parameter and radial distribution function suggest that the PLA and PEG blends are likely miscible at low PEG concentrations (10–30 wt%), but they become apparently immiscible at higher PEG content (>50 wt%). This result is consistent with density distribution of PLA and PEG beads calculated from dissipative particle dynamics simulation of coarse-grained model. To support the computational results, experiments based on differential scanning calorimetry (DSC) and rheometry were also performed. The DSC thermograms of 90:10, 80:20, and 70:30 (wt/wt) of PLA/PEG blends showed a single glass transition and PLA melting peak, indicating PLA/PEG is miscible over this composition. In rheometry, frequency (ω) dependence of storage moduli (G′) at low frequencies for 75:25 and 70:30 blends indicate that these samples are near the phase separation point.     

Peculiar crystallization kinetics of biodegradable poly(lactic acid)/poly(propylene carbonate) blends

Binary blends of poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) were found to display a peculiar crystallization kinetics. The two biodegradable polymers were blended by melt mixing, to obtain binary blends at various compositions. Temperature‐modulated calorimetry and dynamic‐mechanical analysis indicated that the blend components are partially miscible, and display two separate glass transitions, at temperatures intermediate to those of the plain polymers. Electron microscopy analysis disclosed the morphology of PLA/PPC blends, made of PPC‐rich particles finely dispersed within the PLA‐rich matrix. The possible establishment of interactions between the functional groups of the two polymers upon melt mixing has been hypothesized as the reason for partial miscibility and compatibility of the two biodegradable polymers. The PLA/PPC blends display good mechanical properties, with enhanced performance at rupture compared with plain PLA. Most importantly, the addition of PPC affects also the crystallization kinetics of PLA, since the more mobile PPC chains favor diffusion of the stiffer PLA chain segments towards the growing crystals, which fastens the spherulite growth rate of PLA. Such positive influence of an amorphous polymer on crystal growth rate has been demonstrated here for the first time in blends that display phase‐separation in the melt. POLYM. ENG. SCI., 55:2698–2705, 2015. © 2015 Society of Plastics Engineers     

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     

Preparation and characterization of polylactide/thermoplastic konjac glucomannan blends

In this article, a new degradable thermoplastic konjac glucomannan (TKGM) was synthesized by graft copolymerization of vinyl acetate and methyl acrylate onto konjac glucomannan (KGM). Melt blending of polylactide (PLA) and TKGM has been performed in an effort to improve the processing and comprehensive mechanical properties of PLA and TKGM without compromising its degradability and biocompatibility. The miscibility, processing rheology, phase morphology, thermal properties, interaction, crystallization and mechanical properties of PLA/TKGM blends were investigated in detail. The thermal processing property of PLA/TKGM blend (60/40) was quite close to low density polyethylene (LDPE). As observed from the tan δ curves in dynamic mechanical analysis, all of the blends exhibit a single glass transition over the entire composition range, indicating that the blends were thermodynamically miscible. The TKGM exhibited a relatively broad endothermic peak at around 120 °C, which was lower than that of KGM. And an obvious glass-transition behavior was obtained around 26.6 °C. Furthermore, the PLA/TKGM blend (60/40) had a very high elongation at break of 234.8%, while the tensile strength remained as high as 36.5 MPa. And the PLA/TKGM blend (20/80) resulted in an even greater ductility with an elongation at break of 520.5% as compared with 14.1% for pure PLA. A substantial increase in the non-notched impact strength was also observed with the PLA/TKGM blend (20/80) demonstrating two times the impact strength of pure PLA.     

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。     

PPC与IPDI原位聚合增韧聚乳酸

以聚碳酸亚丙酯多元醇(PPC)和异佛尔酮二异氰酸酯(IPDI)为反应性增韧单体,在熔融共混过程中原位聚合生成聚氨酯(PU)增韧相,制备了新型增韧PLA/PU材料。通过FTIR、万能电子试验机、TG、DSC、SEM测试研究了单体用量对PLA共混物加工性、相容性及韧性的影响规律。结果表明:随着增韧单体用量的增加,共混物中PLA组分的冷结晶温度(Tc)和玻璃化转变温度(Tg)降低;当n(NCO)/n(OH)=1/1,PPC用量为30%时,共混物的断裂伸长率和冲击强度比纯PLA分别增加71.8倍和15.6倍;原位聚合物对PLA有较好的增韧效果。     

Synergistic effect of compatibilizer and cloisite 30B on the functional properties of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/polylactide blends

Blends of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and polylactide (PLA) with different PHBV/PLA weight ratios (100/0, 75/25, 50/50, 25/75, 0/100) were prepared by melt compounding. To improve the miscibility between the two components of the blend, low amount of compatibilizing agent (5 wt%), obtained by grafting maleic anhydride onto PHBV, was used. When compared with the uncompatibilized blends, the compatibilizer presence induces a greater interfacial adhesion. The effect of Cloisite 30B (C30B) on the blend morphology and the blend properties was also investigated. The morphology of the different blends as well as the evolution of their material properties were discussed in terms of the nanoclay and compatibilizing agent contents. A synergistic effect of compatibilizer and C30B was highlighted leading to an improved miscibility of the two blend components. The resulting properties were correlated with the morphology observed for the different blends. POLYM. ENG. SCI., 54:2239–2251, 2014. © 2013 Society of Plastics Engineers