Effect of phthalimide as an efficient nucleating agent on the crystallization kinetics of poly(lactic acid)

The effect of phthalimide compound on the nonisothermal and isothermal crystallization behavior of poly(lactic acid) (PLA) was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. It was found that the incorporation of a small amount of phthalimide promoted the crystallization of PLA significantly. The Avrami model was applied to analyze the isothermal crystallization kinetics. It was found that the Avrami exponent was higher for PLA/phthalimide blends than for neat PLA, indicating a heterogeneous nucleation mechanism. These results indicate that phthalimide may act as an efficient nucleating agent to improve the crystallization of PLA and expand its applications.     

Crystallization kinetics of virgin and processed poly(lactic acid)

Poly(lactic acid) (PLA) is an emerging material mainly because it can be synthesized from renewable resources and is thus environmentally and ecologically safe. The mechanical properties, above all the thermal resistance of PLA are determined by the crystalline content: the heat deflection temperature of crystalline PLA can reach 100 °C, whereas amorphous PLA loses mechanical properties at temperatures slightly higher than 60 °C. However, PLA has a low crystallization rate, so that after processing it remains mostly amorphous. This characteristic heavily limits the use of PLA for commercial applications. Many studies have been recently published on the crystallization kinetics of PLA. The effect of processing on this feature is however often neglected. In this work, the significance of processing on the crystallization kinetics of a commercial PLA was investigated. Two processing methods were explored: extrusion and injection moulding. The obtained materials, and the starting pellets of virgin polymer, were analyzed by calorimetry in order to obtain the crystallization kinetics. Two protocols were adopted to determine the crystallization rates during cooling from the melt or heating from the solid. The parameters of a kinetic equation were determined for all the materials and protocols adopted and it was thus possible to describe the evolution of crystallinity during heating and during cooling.     

Crystallization behavior of poly(lactic acid) with a self-assembly aryl amide nucleating agent probed by real-time infrared spectroscopy and X-ray diffraction

The effect of a self-assembly nucleating agent, N,N′,N″-tricyclohexyl-1,3,5-benzenetricarboxylamide (BTCA), on the crystallization behavior of poly(lactic acid) (PLA) was probed by time-resolved Fourier transform infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). The vibrational changes associated with inter- and intra-chain interactions during crystallization were monitored. In the initial period of crystallization, the order of intensity changes is as follows: 1458 cm⁻¹ > 1210 cm⁻¹ » 921 cm⁻¹, 1458 cm⁻¹ ∼ 1210 cm⁻¹ > 921 cm⁻¹, and 1458 cm⁻¹ ∼ 1210 cm⁻¹ ∼ 921 cm⁻¹ for neat PLA, PLAs containing 0.1 wt% and 0.3 wt% BTCA, respectively. This indicates that BTCA can accelerate both the formation of skeletal conformational-ordered structure and, especially, the 10₃ helix one. The incorporation of BTCA changes the crystallization mechanism but has no impact on the crystal form of PLA.     

Crystallization behavior of biodegradable poly(ethylene adipate) modulated by a benign nucleating agent: Zinc phenylphosphonate

Zinc phenylphosphonate (PPZn), a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly(ethylene adipate) (PEA) to investigate its effect on the crystallization behavior, crystallization kinetics and spherulite morphology of PEA. Upon addition of PPZn, the crystallization temperature and crystallinity of PEA in the non-isothermal crystallization process increased significantly. Analysis of crystallization kinetics by Avrami equation suggests that the crystallization time shortened greatly and crystallization rate increased markedly after addition of PPZn. In the presence of PPZn, the spherulite size decreased and spherulite density increased significantly. It suggests that PPZn is an efficient nucleating agent for the crystallization of PEA. The accelerated crystallization in the presence of PPZn is mainly attributed to the epitaxial nucleation of PEA crystals on the surface of PPZn crystals, that is, a perfect lattice matching between PEA crystal and PPZn crystal occurs.     

Crystallization kinetics and morphology of poly(lactic acid) with polysaccharide as nucleating agent

Journal of Thermal Analysis and Calorimetry - An ever-increasing concern about environmental pollution has spearheaded research into alternative biodegradable polymers. Currently, poly(lactic acid)...     

基于聚乙二醇结构调控高分子量聚乳酸立构复合体系的结晶行为

设计合成了梳形聚(聚乙二醇甲醚丙烯酸酯)(PPEGA)及其与聚乙二醇(PEG)的嵌段共聚物(PEG-b-PPEGA).通过与高分子量左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)共混探究了PEG不同的结构对PLA立构复合体系(sc-PLA)结晶的影响.结果 表明线形PEGA和PEG能与sc-PLA完全相容,两者均能促进...     

Effect of wood flour as nucleating agent on the isothermal crystallization of poly(lactic acid)

The effect of wood flour (WF) as an efficient nucleating agent on the isothermal melt crystallization and isothermal cold crystallization behavior of poly(lactic acid) (PLA) was investigated by differential scanning calorimeter and polarized optical microscopy. It was found that the incorporation of 4 wt% WF promoted the crystallization of PLA about 4.2%. Polarized optical microscopy results showed the Maltese cross of the samples. The presence of the 4 wt% WF may increase the nucleation density, leading to the increase of the spherulites; however, the size of the spherulites decreased, and the structure became incomplete. The Avrami model was applied to analyze the isothermal crystallization kinetics. It is concluded that the addition of WF modified the crystallization process of PLA (the value of Avrami exponent changed). Various parameters, such as the crystallization half time and crystallization rate constant, reflect that 4 wt% WF significantly improves the crystallization process. The observations in this article indicate that WF is an efficient nucleating agent of PLA. Copyright © 2016 John Wiley & Sons, Ltd.     

聚乳酸成型加工过程中的熔体粘弹特性和结晶行为调控

聚乳酸(PLA)是目前合成生物可降解高分子材料中应用量最大的品种,可望逐渐部分取代聚烯烃而更广泛应用于各个领域。但PLA树脂结构决定的松弛特性导致其加工过程特殊的黏弹特性,使其熔体强度低、成型工艺特性不稳定并进而导致产品尺寸和性能不稳定。此外,PLA极低的结晶速率,使其在挤出和注射成型等较高冷却速率的实际加工条件下呈无定型态,进一步影响了其加工和使用性能。这些问题已成为PLA更大规模商品化应用的瓶颈。本文从通过调控PLA熔体加工过程的黏弹特性而提高其可加工性出发,综述近年来本课题组在PLA成型加工过程中熔体粘弹特性和结晶行为(结晶速率和结晶结构)调控方面的研究进展。     

Organically modified rectorite toughened poly(lactic acid): Nanostructures, crystallization and mechanical properties

To improve the toughness of PLA, poly(lactic acid) (PLA)/organically modified rectorite (OREC) nanocomposites were prepared via the melt-extrusion method. A partially exfoliated and partially intercalated structure was confirmed by WAXD and TEM. The crystallization behaviors of neat PLA and nanocomposite were studied by POM and DSC, and it was found that OREC had a great effect on the overall crystallization rate and spherulitic texture of PLA. The presence of OREC could toughen PLA greatly. For example, when 1 wt.% OREC was added, the elongation at break of the nanocomposite was increased to 210%. The toughening mechanism was analyzed through the observation of the inner structure of the tensile test bar using SEM.     

Crystallization kinetics and morphology of poly(vinylidene fluoride)/poly(ethylene adipate) blends

The miscibility, isothermal crystallization kinetics and morphology of the poly(vinylidene fluoride)(PVDF)/poly(ethylene adipate)(PEA) blends have been studied by differential scanning calorimetry(DSC), optical microscopy(OM) and scanning electron microscopy(SEM). A depression of the equilibrium melting point of PVDF was observed. From the melting point data of PVDF, a negative but quite small value of the interaction parameter ?PVDF-PEA is derived using the Flory-Huggins equation, implying that PVDF shows miscibility with PEA to some extent. Nonisothermal and isothermal crystallization kinetics suggest that the crystallization rate of PVDF decreases with increasing the amount of PEA, and a contrary trend was found when PEA crystallizes with the increase of the amount of PVDF. It was further disclosed that the blend ratio and crystallization temperature affect the texture of PVDF spherulites greatly, which determines the subsequent crystallization of PEA. At high temperatures, e.g. 150 ℃, the band spacing of PVDF spherulites increases with the addition of PEA content and the spherulitic structure becomes more open. In this case, spherulitic crystallization of PEA is not observed for all blend compositions. At low temperatures, e.g. 130 ℃, for the PEA-rich blends, the interpenetrated structures are eventually formed by the penetration of the spherulites of PEA growing within the pre-existing PVDF spherulites.     

Crystallization kinetics,morphology, and mechanical properties of novel poly(ethylene succinate-co-octamethylene succinate)

The crystallization kinetics, morphology and mechanical properties of a novel poly(ethylene succinate-co-octamethylene succinate) (PEOS) copolyester with 82 mol% ethylene succinate (ES) units and 18 mol% octamethylene succinate (OS) units, and its homopolymer poly(ethylene succinate) (PES) were extensively investigated. The glass transition temperature, cold crystallization peak temperature and melting point of PEOS are around −24, 47.5, and 80.5 °C, respectively. The Avrami equation was used to analyze the isothermal melt crystallization kinetics of PEOS and PES. They display the same crystallization mechanism, and PEOS crystallizes slower than PES at the same degree of supercooling. The spherulitic growth rates of PEOS and PES exhibit a bell shape within the investigated crystallization temperature range, with the crystallization regime transition temperature of PEOS being lower than that of PES. In addition, PEOS has high thermal stability and good mechanical properties.     

降解可控乳酸类聚合物

聚乳酸作为生物医用材料，其降解性能最为人们关注。根据降解性能的不同，其应用也有不同的用途。本文从共聚和共混两方面综述了聚乳酸在降解可控性方面研究的最新进展，对未来的工作进行了展望。     

Compatibilizing effects for improving mechanical properties of biodegradable poly (lactic acid) and polycarbonate blends

Mechanical, morphological and rheological properties of polycarbonate (PC) and poly (lactic acid) (PLA) blends with compatibilizers have been investigated. Three types of compatibilizers were used: poly(styrene-g-acrylonitrile)-maleic anhydride (SAN-g-MAH), poly(ethylene-co-octene) rubber-maleic anhydride (EOR-MAH) and poly(ethylene-co-glycidyl methacrylate) (EGMA). The maximum value of the mechanical properties such as impact and tensile strengths of the PC/PLA (70/30, wt%) blend before or after hydrolysis was observed when the SAN-g-MAH was used as a compatibilizer at the amount of 5 phr. From the interfacial tension between PC and PLA which was determined from the weighted relaxation spectra using Palierne emulsion model, minimum value of interfacial tension (0.08 mN/m) was observed when the SAN-g-MAH (5 phr) was used. From the morphological studies of the PC/PLA (70/30) blends, the PLA droplet size showed minimum (0.19 μm) at the 5.0 phr SAN-g-MAH. From the results of mechanical, morphological and rheological properties of the PC/PLA (70/30) blend, it is suggested that the SAN-g-MAH is the most effective compatibilizer to improve the mechanical strength of the PC/PLA (70/30) blends among the compatibilizers used in this study, especially at the amount of 5 phr.     

Chemical modification of poly(lactic acid) and its use as matrix in poly(lactic acid) poly(butylene adipate-co-terephthalate) blends

Poly(lactic acid), PLA, was chemically modified with maleic anhydride (MA) by reactive extrusion. The effect of this modification on molar mass (MM) and acidity was assessed by means of size-exclusion chromatography (SEC) and titration, respectively. PLA MM decreased in the presence of MA solely and of MA and peroxide. Reduction in MM was monitored by the increase in acidity. PLA blends containing poly(butylene adipate-co-terephthalate) (PBAT) were prepared through different mixing protocols, PLA/PBAT, PLA-g-MA/PBAT and PLA/PBAT/MA/peroxide (PLA/PBAT in situ). SEC results and rheological properties revealed reduction in MM and viscosity of the modified blends. PLA/PBAT presented increase in MM and bimodal MM distribution. The calculated interfacial tension was significantly lower for the modified blends, despite the lower average particle area of PLA/PBAT. Surprisingly, the modified blends presented higher yield strength than that predicted by the rule of mixtures, which might indicate interfacial reactions.     

Cooperativity length evolution during crystallization of poly(lactic acid)

Effects of stereoregularity and crystallization mode on the amorphous phase dynamics are investigated for poly(lactic acid) PLA. An isothermal crystallization from the melt and a cold crystallization are imposed. For each PLA, the cold crystallization leads to the appearance of a less perfect crystalline phase and to an important rigid amorphous fraction RAF content (35%), although only 10% of RAF is generated after crystallization from the melt. Temperature Modulated Differential Scanning Calorimetry is used to determine the Cooperative Rearranging Regions (CRR) size at the glass transition temperature in the mobile amorphous phase MAP. It is shown that the CRR size in the MAP is not modified by the appearance and the spherulite growth. For the intra-spherulite MAP, a confining effect is evidenced, causing an amorphous phase thickness decrease during crystallization, and inducing a drastic CRR size reduction.     

Biodegradation of poly(lactic acid) and its nanocomposites

PLA nanocomposites based on organically modified montmorillonites at 5% w/w loading were prepared by melt blending using an internal mixer and then degraded in a commercial compost. The addition of nanoclays was found to increase the PLA degradation rate, especially for the highest dispersed clay in the polymer matrix. Biodegradation by microorganisms isolated from the compost showed the bacterium Bacillus licheniformis as one of the responsible for PLA biodegradation in compost. It was also found that clays can influence the polymer bacterial degradation depending on their chemical structure and affinity of the bacterium towards the clay.     

Spectroscopic analysis of post drawing relaxation in poly(lactic acid) with oriented mesophase

Uniaxial deformation of amorphous poly(lactic acid) (PLA) film was performed at 60 °C (around the glass transition temperature). The deformed samples revealed a strain-induced mesophase, and its fraction and thermal stability increased with draw strain. Further annealing was performed in situ at constant length, at the drawing temperature for the films drawn to strains of 100% and 230%. Interestingly, the orientation of amorphous phase relaxed more rapidly for the 100% sample compared with the 230% one. This could be ascribed to the constraint effect of mesophase on the amorphous chains. In addition, the chains of mesophase relaxed slightly for the 100% sample while it retained high orientation for the 230% sample. Meanwhile, the mesophase fraction decreased, and the trend was more significant for the sample drawn to 100%. These effects can be ascribed to the melting of mesophase and the different thermal stabilities of the mesophases.     

Properties of immiscible and ethylene-butyl acrylate-glycidyl methacrylate terpolymer compatibilized poly (lactic acid) and polypropylene blends

Poly(lactic acid) (PLA) and polypropylene (PP) blends of various proportions were prepared by melt-compounding. The miscibility, phase morphology, thermal behavior, and mechanical and rheological properties of the blends were investigated. The blends were immiscible systems with two typical morphologies, spherical droplet and co-continuous, and could be obtained at various compositions. Complex viscosity, storage modulus and loss modulus depend on the PP content. Thermal degradation of all blends led to two weight losses, for PLA and PP. The incorporation of PP improved the thermal stability of the blend. The effect of compatibilizer (ethylene-butyl acrylate-glycidyl methacrylate terpolymer, EBA-GMA) on the morphology and mechanical properties of 70/30 w/w PLA/PP blends was investigated. The tensile strength of these blends reached a maximum for 2.5 wt% EBA-GMA, and impact strength increased with increasing EBA-GMA content, suggesting that EBA-GMA is an effective compatibilizer for PLA/PP blends.     

Solid state polymerization of poly(lactic acid): Some fundamental parameters

Poly(lactic acid) (PLA) was submitted to solid state polymerization (SSP) in a fixed bed reactor under nitrogen flow, so as to examine technique efficiency for increasing the molecular weight and hence permitting the reduction of the melt polymerization residence times. In order to use a suitable starting material, SSP prepolymers of low and medium molecular weight were first prepared through solid state hydrolysis of commercial PLA grade under acidic and alkaline conditions. During these degradation runs, hydrolysis involved the random scission of ester groups in the polymer backbone, while the relevant kinetics and the resulting thermal properties were also examined. In a subsequent step, the prepolymers obtained were subjected to SSP at three temperatures, approximately 2.5–25.0 °C below their melting point. The process achieved an increase of up to 1.7 times the initial molecular weight, however, with different trends depending on the prepolymer characteristics, reaction temperature and time, as well as the pH of the hydrolysis medium. In addition to molecular weight build up, the effect of the SSP process on end product thermal properties was also investigated.     

Compatibility and phase structure of binary blends of poly(lactic acid) and glycidyl methacrylate grafted poly(ethylene octane)

This work study is the compatibility, phase structure, and component interaction of poly(lactic acid) (PLA) and glycidyl methacrylate grafted poly(ethylene octane) (GMA-g-POE denoted as mPOE) blend by Fourier transform infrared (FTIR) spectra, dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and wide-angle X-ray diffraction (WAXD), respectively. All the binary blend compositions exhibit two distinct glass transition temperatures corresponding to the mPOE-rich and PLA-rich phases, respectively. Moreover, these two peaks approach each other with increasing mPOE content, indicating partial compatibility between the PLA and mPOE. Chemical reactions between the end carboxyl groups of the PLA and epoxy groups of the mPOE are considered as the driving force of the enhanced compatibility. They lead to an increase in viscosity of the blends and a decrease in the structural symmetry of PLA. This result brings about a decrease in the spherulite growth rate and the degree of crystallinity. Glass transition temperature (T_g) depression of mPOE is attributed to the negative pressure imposed on the dispersed rubber phase, resulting from differential contraction due to the thermal shrinkage mismatch upon cooling from the melt state. The negative pressure in the dispersed particles, in turn, would cause a dilational effect for the matrix ligament between the particles, and therefore increases the ductility and toughness of PLA.