Effect of stereocomplex crystal on foaming behavior and sintering of poly(lactic acid) bead foams

Poly(lactic acid) (PLA) bead foams with stereocomplex (Sc)/α crystals were prepared by melt mixing and solid‐state foaming methods, independently. A systematic method was applied to evaluate the effect of Sc/α crystals on rheological properties and foaming behavior of PLA. The results indicated that the presence of Sc/α crystals affected the foaming behavior and the melt elasticity of PLA. Hence, the enhanced rheological properties of PLA had a significant effect on controlling the foaming behavior. As a result, PLA bead foam with an expansion ratio of 24‐fold was developed. And, the presence of Sc/α crystals could also facilitate the sintering behavior and broaden the sintering process window. Sintered PLA bead foam with finer cellular morphology and strong sintering effect was obtained by inducing an appropriate Sc/α crystalline structure. © 2018 Society of Chemical Industry     

Enhanced crystallization of poly(lactide) stereocomplex by xylan propionate

The effect of xylan propionate (XylPr) as a novel biomass‐derived nucleating agent on the poly(lactide) sterecomplex was investigated. Addition of XylPr to an enantiomeric blend of poly(l ‐lactide) (PLLA) and poly(d ‐lactide) (PDLA) was performed in either the solution state or molten state. The solution blend of PLLA/PDLA with XylPr was prepared by mixing equal volumes of 1 wt% XylPr/PLLA and 1 wt% XylPr/PDLA solutions in chloroform and precipitating in methanol. The solution blend with XylPr showed shorter half‐time crystallization than the solution blend without XylPr in isothermal crystallization between 80 and 140 °C, although homocrystallization occurred. Enhanced stereocomplex crystallization in the solution blend with XylPr was observed at 180 °C, where no crystallization occurred in the solution blend without XylPr. Addition of XylPr to PLLA/PDLA blend in the molten state was performed at 240 °C. Thereafter, the melt blend of PLLA/PDLA with or without XylPr was either quenched in iced water or isothermally crystallized directly from the melt. Isothermal crystallization of the melt‐quenched blend with XylPr gave a similar result to the solution blend with XylPr. In contrast, the melt‐crystallized blend with XylPr formed only stereocomplex crystals after crystallization above 140 °C. Furthermore, the melt‐crystallized blend with XylPr showed a higher crystallinity index and melting temperature than the melt‐crystallized blend without XylPr. This shows that XylPr promotes stereocomplex crystallization only when the blend of PLLA/PDLA with XylPr is directly crystallized from the molten state just after blending. © 2016 Society of Chemical Industry     

Spontaneous formation of polylactide stereocomplex microspheres containing metal ions

Linear poly(l ‐lactides) (PLLAs ) and poly(d ‐lactides) (PDLAs ) with M _n in the range 2000 ? 4300 containing a different number and placement of carboxyl groups were obtained via cationic ring‐opening polymerization and post‐polymerization functionalization. PLA stereoisomers (PLLA ‐(COOH )_x and PDLA ‐(COOH )_x , where x = 1 ? 3) were used for the investigation of stereocomplexation in solution performed in the presence of metal cations such as Ca²⁺, Mg²⁺, Zn²⁺, Fe³⁺. Spherical microparticles with a diameter in the range 0.7 ? 3.0 µm were obtained in all cases which was confirmed on the basis of scanning electron microscopy (SEM ) analysis. The microsphere size and homogeneity were analyzed depending on the stereocomplexation conditions and the molecular weight as well as the number of carboxyl end groups in the PLLA and PDLA used for stereocomplexation. The PLA microspheres obtained were analyzed by Fourier transform IR spectroscopy, wide angle X‐ray spectroscopy and energy‐dispersive X‐ray spectroscopy methods which confirmed the presence of metal cations inside. The application of regular microspheres with metal ions as drug delivery systems is considered. © 2016 Society of Chemical Industry     

Stereocomplex Crystallization Induced Significant Improvement in Transparency and Stiffness–Toughness Performance of Core-Shell Rubber Nanoparticles Toughened Poly(l-lactide) Blends

Toughening modification of poly(l -lactide) (PLLA) with rubber particles is often realized at the cost of transparency, mechanical strength, and modulus because high rubber loadings are generally required for toughening. In this work, a promising strategy to simultaneously improve the transparency and stiffness–toughness performance of poly(butyl acrylate)-poly(methyl methacrylate) (BAMMA) core-shell rubber nanoparticles toughened PLLA blends by utilizing the stereocomplex (SC) crystallization between PLLA and poly(d -lactide) (PDLA) is devised. The results reveal that the construction of SC crystallites in PLLA matrix via melt-mixing PLLA/BAMMA blends with PDLA can prevent BAMMA nanoparticles from aggregation and promote them to form network-like structure at lower contents. As a result, not only higher toughening efficiency with less rubber contents but also superior transparency is achieved in the PLLA/PDLA/BAMMA blends as compared with the PLLA/BAMMA ones where large aggregated BAMMA clusters are formed. Moreover, the outstanding reinforcement of SC crystallites network for PLLA can impart an enhanced tensile strength and modulus to PLLA/PDLA/BAMMA blends, thus improving the stiffness–toughness performance of PLLA/PDLA/BAMMA blends to a higher degree. This work demonstrates that SC crystallization is a promising solution to solve the contradiction between transparency and mechanical properties and then obtain superior comprehensive performances in rubber toughened PLLA blends.     

Importance of Low-Temperature Melt-Mixing on the Construction of Stereocomplex Crystallites with Superior Nucleation Efficiency in Asymmetric Poly(l-lactide)/Poly(d-lactide) Blends

The nucleation efficiency (NE) of stereocomplex crystallites (SCs) formed in asymmetric poly(L-lactide)/poly(D-lactide) (PLLA/PDLA) blends is generally unsatisfactory because the competition between stereocomplexation and chain mixing involved in the melt-mixing process can cause low formation efficiency and even severe aggregation of SCs. Herein, it is attempted to achieve high-efficient formation of finely dispersed SCs particles by designing a unique melt-mixing procedure, where the mixing of PLLA with 0.75 wt% PDLA is first performed at elevated temperatures (far above the melting temperature of SCs) to allow the homogeneous mixing of PLLA/PDLA chains and then at a low temperature (slightly above that of homocrystallites) to permit the full stereocomplexation of the premixed chains. It is found that the SCs formed in the blends exhibit unexpectedly low NEs (e.g., 54.5%), much inferior to that (73.6%) in the counterpart without undergoing premixing. This is because the introduction of premixing leads to a remarkable deterioration in the amount of SCs particles formed, despite decreased particle size, highlighting that the direct mixing at low temperatures of 170–180 °C (about 20–30 °C lower than that used in common melt-processing of PLA) is more effective for the construction of SCs with superior NE. The mechanisms for these striking findings are discussed.     

Crystalline,Thermal, and Biodegradable Properties of Poly(L-Lactic Acid)/Poly(D-Lactic Acid)/POSS Melt Blends

A ternary nanocomposite consisting of poly(L-lactic acid) (PLLA), poly(D-lactic acid) (PDLA), and epoxy cyclohexyl polyhedral oligomeric silsesquioxane (e-POSS) was prepared by reactive blending method. Scanning electron microscopy revealed that the feeding of three compositions in batches, i.e., PDLA incorporation at different times, was more beneficial for the even dispersion of POSS in matrix. POSS introduction improved the homocrystallinity and stereocomplex of the blends. Rheological properties and heat resistance were enhanced, which indicated potential extensive application of PLLA-based materials. The optimization of degradation stability in saline buffer was attributed to the various hydrophobic properties of blends caused by POSS structure.     

Multi-Level Information Encryption/Decryption of Fluorescent Hydrogels Based on Spatially Programmed Crystal Phases

The growing urgence of information protection promotes continuously the development of information-encryption technique. To date, hydrogels have become an emerging candidate for advanced information-encryption materials, because of their unique stimulus responsiveness. However, current methods to design multi-level information-encrypted hydrogels usually need sophisticated chemistry or experimental setup. Herein, a novel strategy is reported to fabricate hydrogels with multi-level information encryption/decryption functions through spatially programming the polymorphic crystal phases. As homocrystalline and stereocomplex crystal phases in fluorescent hydrogels have different solvent stabilities, the transparency and fluorescence of the hydrogels can be regulated, thereby enabling the multi-level encryption/decryption processes. Moreover, the structural origins behind these processes are discussed. It is believe that this work will inspire future research on developing advanced information-encryption materials upon programming the polymer crystal structure.     

Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

The effect of polylactic acid (PLA)/poly‐d‐lactide stereocomplex on the thermal and mechanical properties of various PLA/rubber blends

This study investigated the effect of polylactic acid (PLA)/poly‐d ‐lactide (PDLA) stereocomplex (ST) on the improvement of the mechanical and thermal properties of various rubber‐toughened PLAs. In this work, natural rubber (NR), synthetic polyisoprene rubber (IR), silicone rubber (SI), acrylic rubber (ACM), acrylic core–shell rubber (CSR), thermoplastic copolyester (TPE) and thermoplastic polyurethane (TPU) were chosen as the toughening agents. 5 wt% PDLA was melt‐blended with PLA to form ST crystals in the presence of 15 wt% rubber in an internal mixer at 180 °C and 50 rpm. It was found that the melting temperature of ST crystal (T_m,sc) and the impact strength of ST/rubber blends were strongly correlated with the rubber domain size. For the blends of ST with compatible rubbers (ACM, CSR, TPE and TPU), the rubber domain sizes tended to be smaller with higher T_m,sc and higher impact strength than the blends with incompatible rubbers (NR, IR and SI). However, the presence of ST crystals in PLA/incompatible rubber blends, especially the blends with NR and IR, led to a significant increase in the rubber domain size and plunges in tensile toughness and impact strength. On the other hand, the presence of these crystals in PLA/compatible blends did not change the rubber size or the impact strength significantly compared with those without ST crystals except in the case of ST/ACM, which resulted in a large increase in the impact strength. Among all rubber types, CSR provided the highest impact strength for both the PLA and ST systems. © 2019 Society of Chemical Industry     

不同构型聚乳酸共混体系的立构复合结晶研究进展

左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)在共混体系中可形成立构复合(sc)结晶,与聚乳酸(PLA)同质结晶材料相比,sc 结晶材料具有良好的耐热性和耐化学稳定性。因此,sc 结晶是改善PLA 综合性能的一种有效手段。但在PLLA/PDLA 共混体系中,存在各自的同质结晶与两者之间sc 结晶的竞争,所以制备高耐热sc 型PLA 材料的关键之一是理解其sc 结晶的形成条件与机理,进而调控和促进其sc 结晶程度。在PLLA/PDLA 共混物中,sc 结晶受聚合物化学结构、结晶与加工条件等诸多因素影响,其影响规律和机理较复杂。根据PLLA/PDLA共混物sc 结晶行为影响因素的不同,从聚合物分子量、立构规整性、共混比例、分子链拓扑结构、结晶方式与条件、加工助剂和其他组分加入6 个方面出发,详细综述了PLLA/PDLA 共混物sc 结晶及其sc 材料制备的研究进展,以期为高耐热生物基PLA 材料的加工制备提供指导。