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.     

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     

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.     

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.     

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     

亚麻纤维增强立构聚乳酸复合材料的制备及界面改性

采用熔融共混及注塑成型法制得立构聚乳酸(sc-PLA)及亚麻纤维/立构聚乳酸(Flax/sc-PLA)复合材料,并通过差示扫描量热分析、动态力学分析、热重分析、扫描电镜、维卡软化温度及力学性能测试等方法研究了亚麻纤维增强及偶联剂六亚甲基二异氰酸酯(HMDI)界面改性对Flax/sc-PLA复合材料结构与性能的影响。结果表明:亚麻纤维的加入可有效提高sc-PLA的立构结晶度、耐热性以及力学性能,Flax/sc-PLA复合材料的立构结晶度由17.3%提高到24.9%,维卡软化温度由161.1℃升至195.7℃,拉伸强度也从57.4 MPa提高到62.5 MPa。通过HMDI界面改性可有效改善复合材料的界面相容性,使复合材料的拉伸强度进一步提高到70.4 MPa。此外,HMDI改性还提高了复合材料的热稳定性,其初始降解温度和动态储能模量G'均比未改性复合材料显著提高。     

Rapid stereocomplex formation of polylactide using supercritical fluid technology

It is generally believed that stereocomplex polylactide is a prospect for rigorous application in the future due to enhancement of the physical properties of its homopolymers. There have been many studies about the formation and characterization of this stereocomplex. However, we are the first to report that supercritical fluid technology can yield a high‐degree stereocomplex polylactide (ca 98%) in a relatively short time (1 min). “This method generated a dry product and feasible for polylactide with weight‐average molecular weight (Mw) up to 70 000–160 000 g mol^?1 or higher by modifying the material feed of the homopolymer.” The “feasible” term is used to explained that our system is suitable for stereocomplexation of the polylactide material with molecular weight 70 000–160 000 or above. We also discovered that modification of the material feed did not affect the properties of the stereocomplex polylactide generated. The process and outcome of this research indicate that supercritical fluid technology is suitable for a continuous stereocomplex polylactide formation process. Copyright © 2012 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