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Abstract Polylactide (PLA), a promising biodegradable and renewable polymer, finds many applications, particularly, used as biodegradable fiber in textile industry. The key is to improve its heat resistance. In this work, small amount of poly (D-lactide) (PDLA) was added firstly into poly (L-lactide) (PLLA) matrix to form stereocomplex polylactide (SC-PLA), which has much better heat resistance than that of PLLA matrix. Then two melting temperatures were adopted for fiber spinning, the one (210 °C) is far below the melting temperature of SC-PLA (i.e., 220–230 °C), and the other (225 °C) is close to the melting temperature of SC-PLA. The boiling water shrinkage and tensile strength of PLLA/PDLA fibers were investigated as function of PDLA content. It was found, the boiling water shrinkage could be largely reduced to as low as 5.6% and a satisfactory tensile strength (628 MPa) is achieved for fibers spun at 225 °C, compared with fibers spun at 210 °C (7.5% and 500 MPa, respectively), as the PDLA content is 3 wt%. SEM observation suggests a formation of nanofibrillar like SC-PLA structure as spun at 225 °C, while only spherical SC-PLA particles as spun at 210 °C. DSC result indicates that adding PDLA could largely enhance the crystallization rate of PLLA, but almost a constant crystallinity and SC-PLA content were observed for both spun fibers, disregarding the spinning temperatures. Herman's orientation parameters of spun fiber were obtained from 2D-WAXD, which suggests that fiber spun at 225 °C has higher orientation than that of fiber spun at 210 °C. Thus it can be concluded that the formation of nanofibrillar like SC-PLA and enhanced orientation degree contribute mainly to the improved heat resistance and tensile strength. This work presents a feasible and effective way to fabricate all-PLA-based fibers with the outstanding heat resistance by adding a small amount of PDLA and using a suitable spinning temperature. Graphical abstract Image 1 Highlights • The influence of spinning temperature on the orientation and properties of PLLA/PDLA fibers was depicted in detail. • A critical PDLA content of increasing PLLA/PDLA fibers' heat resistant and mechanical property was revealed.. • All-PLA-based fiber with outstanding heat resistance was manufactured by melt spinning process. [ABSTRACT FROM AUTHOR]

Abstract Recently, powder metallurgy inspired low-temperature (below the melting temperature) sintering has been proposed as an innovative technology for the processing of eco-friendly stereocomplex-type polylactide (SC-PLA) from its nascent powder, without triggering noticeable thermal degradation. The physicochemical performances of the obtained SC-PLA products are governed by the newly formed SC crystallites with a remarkable ability to weld the interfaces between adjacent powder particles, however, the insufficient interdiffusion of poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) chains across the interfaces makes it challenging to form sufficient amounts of new SC crystallites. In the present work, we describe a facile and robust strategy to address this challenge by coating a trace amount (e.g., 0.001 wt%) of disentangled carbon nanotubes (CNTs) on the SC-PLA particle surfaces. During the subsequent sintering, these interface-localized CNTs can function as efficient nucleating agent to substantially promote the SC crystallization of PLLA/PDLA chains on their surfaces and finally countless SC crystallites are formed to strongly weld the interfaces as welded joints. Accordingly, SC-PLA/CNTs products possessing superb heat/solvent resistances and mechanical strength have been fabricated. Impressively, with the introduction of 0.001 wt% CNTs, the tensile strength is significantly enhanced from 45.8 MPa to 67.2 MPa. Most importantly, there is a linear relationship between the tensile strength and the content of the CNTs induced SC crystallites. Overall, this wok could provide a practical guidance for the design and fabrication of high-performance SC-PLA products through low-temperature sintering assisted by nanofillers like CNTs. Graphical abstract Image 1 Highlights • SC-PLA products with superb performances has been fabricated by CNTs assisted low-temperature sintering. • The disentangled CNTs were coated on the surface of SC-PLA powder particles before sintering. • These CNTs can substantially promote SC crystallization across particle interfaces as nucleating agent. • Countless new SC crystallites are induced to strongly weld the interfaces and thus enhance the product performances. • The linear relationship between tensile strength and CNTs induced SC crystallites has been established. [ABSTRACT FROM AUTHOR]

Selective localization of nanoparticles at the interface of immiscible polymer blends has been witnessed as an efficient method to improve blend properties and even provide some added functionalities. Nevertheless, it is still a great challenge to achieve thermodynamically stable interface-localization of the nanoparticles mainly due to their low interfacial stabilities as well as high transfer speeds between the blend phases, especially for those with high aspect ratios. In this work, taking poly( l -lactide)/poly( d -lactide) grafted ethylene-acrylic ester copolymer/multi-walled carbon nanotubes (PLLA/EGD/MWCNTs) ternary composite as an example, we describe a new and facile strategy to address this challenge via anchoring high-aspect-ratio MWCNTs at the interface of PLLA/EGD blends using interface-localized stereocomplex (SC) crystallites as anchoring agents. During melt mixing of EGD with PLLA/MWCNTs mixture, such SC crystallites can be rapidly formed at the blend interface to prevent MWCNTs transferring from the thermodynamically unfavorable PLLA matrix into favorable EGD phase as physical barriers, and meanwhile some of these transferring MWCNTs could serve as nucleating agents to induce SC crystallization on their surfaces. As a result, many MWCNTs are firmly anchored at the blend interface by these SC crystallites. The anchored MWCNTs can not only function as effective interfacial enhancers to remarkably enhance interfacial strength and resulting impact toughness of PLLA/EGD blends but also enable the formation of electrical conductive pathway in the network-like PLLA/EGD blends at a much lower percolation threshold. This wok could offer a promising opportunity for preparing high-performance and multifunctional PLLA-based composites through controlling particle localization at the interface of immiscible PLLA blends with the aid of SC crystallization. [ABSTRACT FROM AUTHOR]

The performance of semicrystalline polymers is significantly dependent on the crystal morphology and lamellae orientation. In this work, the crystal superstructure and mechanical properties of polylactide (PLA) with different amounts of nucleating agent (tetramethylene-dicarboxylic dibenzoyl-hydrazide, TMC-306) were investigated. It was found that TMC-306 can be dissolved in PLA melt and re-crystallize into fibrils upon cooling. These fibrils can serve as nucleation templates to induce the crystallization of PLA on their surface, resulting in a large enhancement in crystallization rate. More importantly, PLA lamellae can grow perpendicular to the long axis of TMC-306 fibrils, inducing the formation of shish-calabash, shish-kebab and needle-like structures, depending on the concentration of TMC-306 used. Taking advantage of shear flow experienced in injection molding, TMC-306 fibrils tend to align in PLA melt along the shear flow direction, inducing the formation of highly orientated PLA lamellae in injection-molded articles. In this way, a simultaneous improvement in impact toughness, tensile strength and elongation at break is achieved. This work provides a good example of using a fibrous nucleating agent as a template to tailor the crystal morphology and lamellae orientation, thus achieving greatly enhanced properties for PLA. [ABSTRACT FROM AUTHOR]

In this work, influence of matrix crystallization on the electrical conductivity and mechanical properties of poly( l -lactide)/multiwalled carbon nanotubes (PLLA/MWCNTs) nanocomposites has been investigated. By introducing trace amount of nucleating agent (0.15 wt%) and controlling isothermal crystallization time (0.1–8 min) of PLLA matrix in a hot mould (130 °C), the injection molded bars of the nanocomposites with different matrix crystallinities (5–45%) were prepared. Interestingly, the electrical conductivity is found to be linearly increased with increasing matrix crystallinity for nanocomposites with low concentrations of MWCNTs (below the percolation threshold). This could be attributed to the volume exclusion effect and the straightening effect of MWCNTs provided by PLLA crystallization, as evidenced from SEM observations. However, matrix crystallization induced reconstruction of MWCNTs network cannot effectively enhance the electrical conductivity when the concentration of MWCNTs is high enough (above the percolation threshold). More interestingly, the reconstructed MWCNTs network shows a better reinforcement effect in the nanocomposites as compared with that initially formed in the amorphous matrix. [ABSTRACT FROM AUTHOR]

Abstract: Enhancing matrix crystallization has been demonstrated to be an effective method to simultaneously improve the impact toughness and heat resistance of poly(l-lactide) (PLLA) modified with flexible polymers, such as poly(ε-caprolactone) (PCL). Unfortunately, increasing PLLA matrix crystallinity alone cannot guarantee the enhancement of impact toughness in most cases, so other structural parameters should be considered. In this work, taking PLLA/PCL (80/20) blend as an example, the combined roles of matrix crystallization and impact modifier particle size in the toughening have been investigated. PLLA matrix crystallinity was controlled by adding a highly effective nucleating agent and PCL particle size was tailored by varying processing conditions while maintaining constant interfacial adhesion. It is interesting to find that toughening is efficient only if matrix crystallinity and particle size are well matched. With the significant increase of matrix crystallinity, an evident decrease of optimum particle size for toughening PLLA has been identified for the first time. Therefore, suitable particle size is the precondition for highly crystalline matrix to work effectively in the toughening because only small particles (0.3–0.5 μm) are effective in trigger shear yielding mechanism of the matrix needed for good toughness, whereas relatively large particles (0.7–1.1 μm) are only capable of toughening amorphous matrix effectively by initiating multiple crazing of the matrix. Importantly, our findings can be used to well explain the reason for the different roles of matrix crystallization in the toughening of different PLLA blends reported in the literature. Furthermore, the heat resistance of the blend with a highly crystalline matrix is much better than that of the blend with an amorphous one as expected. This work could not only provide a new insight into the synergistic roles of matrix crystallization and modifier particle size in the toughening of PLLA but also set up a universal framework for designing high-performance PLLA products with both good impact toughness and high heat resistance. [Copyright &y& Elsevier]

Abstract: The effect of fabrication method on the properties of hierarchical 3D TiO2 nanostructures was investigated by employing and developing both hydrothermal method and calcination method to synthesize hierarchical 3D TiO2 nanorod spheres in this study. A comprehensive comparison in terms of morphologies, crystallization, specific surface areas, light absorption capabilities, and photoluminescence spectrum was conducted between 3D TiO2 nanorod spheres synthesized via hydrothermal method and that synthesized via calcination method. A better photocatalytic activity was demonstrated over the TiO2 nanorod spheres synthesized through calcination method. This was ascribed to the better crystallization and monodispersion of the hierarchical 3D TiO2 nanorod spheres resulted from the calcination method; thus rendering it with more superior characteristics such as larger specific surface area, enhanced light absorption capability and faster transfer of electrons which suppress the recombination of photogenerated electrons and holes. This study is thus significant not only in promoting the development of hierarchical 3D TiO2 nanorod spheres via different methods, but also in revealing the effect of fabrication method on the photocatalytic activity of hierarchical 3D TiO2 nanorod spheres. The calcination method is proposed to be a facile and promising method for scale-up production of the hierarchical 3D TiO2 nanorod spheres with high photocatalytic activity for efficient pollutants degradation. [Copyright &y& Elsevier]

Abstract: In this work, we investigated the epitaxial crystallization and its determinant factor in the blends of high density polyethylene (HDPE) and a low crystallizable propylene-ethylene random copolymer (PPR) during injection molding. For PPR dominated blend (blended with 30 wt.% HDPE), epitaxial growth of HDPE on the PPR crystals can be achieved, as demonstrated by two-dimensional wide-angle X-ray diffraction and small-angle X-ray scattering measurements, though the crystallization of PPR was far behind that of HDPE component under quiescent conditions. In-situ shear infrared experiments indicated that PPR crystallized in advance mainly due to larger crystallization window and flow-induced crystallization acceleration. As for the blend with 70 wt.% HDPE, however, one could not observe epitaxy. Shear-induced crystallization of HDPE hindered its epitaxial growth. Once the formation of shish-kebab of HDPE was activated, the epitaxial growth would be suppressed to a large extent. [Copyright &y& Elsevier]

Stereocomplex (SC) crystallization can prominently improve the physico-chemical properties of poly(l -lactide)/poly(d -lactide) (PLLA/PDLA) blends, yielding a novel polylactide (PLA) material. However, the predominant formation of SC crystals in the melt-processing of high-molar-mass (high-MW, >100 kg/mol) enantiomeric PLA blends remains a huge challenge due to the competition between SC crystallization and homocrystallization. Herein, double-grafted copolymer having both PLLA and PDLA side chain has been designed and synthesized as an efficient crystallization promoter for the harvest of SC crystals in the high-MW PLLA/PDLA blends. The results show that, with the addition of such a copolymer, the blends can preferentially crystallize into SC crystals in both isothermal and non-isothermal conditions. Promisingly, the SC crystals can be exclusively formed by adding only small amounts (e.g., 0.5 wt%) of the copolymer, without the formation of any homocrystals. This interesting observation can be interpreted by the crucial role of the unique copolymer in suppressing the phase separation of the opposite PLA enantiomers upon melting as an efficient compatibilizer and then encouraging the generation of alternatingly arranged PLLA/PDLA chain clusters favored for SC nucleation and crystal growth. These findings provide new inspiration for the development of high-performance PLA with desirable SC crystallizability. [Display omitted] [ABSTRACT FROM AUTHOR]

Biosynthesized poly(3-hydroxybutyrate- co -3-hydroxyhexanoate) (PHBHHx) has emerged as a promising biodegradable polymer with a great potential to compete with traditional petroleum-based plastics, however, the poor crystallization ability makes it challenge to transform into high-performance products via common melt-processing methods. Herein, we demonstrate that N,N′ -dicyclohexyl-2,6-naphthalenedicarboxamide (TMB) can serve as an efficient nucleating agent to significantly enhance the crystallization and resulting storage stability of PHBHHx. The results indicate that PHBHHx with small amounts of TMB (0.3–0.5 wt%) can crystallize completely even under a rapid cooling rate of 100 °C/min and the isothermal crystallization time is greatly reduced. As a result, the crystallinity of the injection-molded PHBHHx products is increased from 24.5 % to 39.5 %, without secondary crystallization after being stored at room temperature for 6 h. The products exhibit superior dimensional stability and the post-shrinkage can be decreased to as low as 0.1 %. Our work offers a feasible method to develop high-performance PHBHHx materials with remarkably enhanced crystallization ability. [ABSTRACT FROM AUTHOR]

Stereocomplex-type polylactide (SC-PLA) has recently emerged as an up-and-coming engineering Bio-plastic because the SC crystallization between enantiomeric poly(l -lactide) (PLLA) and poly(d -lactide) (PDLA) can substantially enhance the heat resistance and hydrolytic stability. Unfortunately, it is exceedingly challenging for high-molecular-weight PLLA/PDLA blends to preferentially crystallize into SC crystals (SCs) during melt processing and the concomitant formation of homocrystals (HCs) causes a significant deterioration in physio-chemical properties of final products. Herein, a dibenzoylhydrazide compound has been utilized as an efficient nucleating agent (NA) for the SC crystallization of PLLA/PDLA blends. The results indicate that, in both non-isothermal and isothermal crystallizations, the SC crystallization is markedly promoted with the incorporation of 0.2–1.5 wt% NA. Specially, the enantiomeric blends with relatively high amounts (≥0.5 wt%) of NA are found to exclusively crystallize into SCs without any HCs formation. Meanwhile, the NA can accelerate the SC crystallization and reduce the crystal size. The preferential SC crystallization should be associated with the hydrogen-bonding interactions between PLAs and NA molecules, which could lower barriers for the nucleation and crystal growth of SCs. Our work provides a facile yet powerful strategy for the preparation of high-performance SC-PLA materials with exceptional SC crystallization ability. [Display omitted] • TMC can act as an efficient NA to promote the SC crystallization of PLLA/PDLA blends. • Exclusive formation of SCs is achieved after adding 0.5 wt% TMC into the blends. • The crystallization is greatly accelerated due to the increase in nucleation density. • The hydrogen bonding between TMC and PLA is responsible for the enhanced SC formation. • A facile strategy has been proved to develop SC-PLA with exceptional crystallizability. [ABSTRACT FROM AUTHOR]

Recently, stereocomplex-type polylactide (SC-PLA) has generated growing interest because the unique SC crystals can provide drastic improvement in the heat/chemical resistances and durability of bio-derived and biodegradable PLA, exhibiting great potential to compete with some petroleum-derived engineering plastics in diverse applications. However, SC-PLA suffers from poor melt memory effect as well as significant thermal degradation after being completely melted at temperatures above 250 °C, which make it challenging to converse SC-PLA into useful products using versatile melt-processing technologies. With these challenges in mind, in this work, we propose a facile and practical strategy to fabricate SC-PLA products with exceptional thermomechanical properties through low-temperature melt-processing of SC-PLA powder with a bimodal melting temperature distribution. The results show that the melting temperature (T m) bimodality makes SC-PLA powder able to be easily injection molded at a relatively low temperature of 210 °C (between the two T m s) due to the selective melting of the low- T m SC-PLA component (SC- l PLA, ca. 20–40 wt%), indicating a good melt-processability. Meanwhile, the high- T m SC-PLA (SC- h PLA) component can directly deliver its desirable properties to the injection molded SC-PLA products. More importantly, during the injection molding process, the unmelted SC- h PLA particles can also induce the exclusive SC crystallization of the SC- l PLA melt as nucleating agent and greatly amplify the shear stress imposed on the melt as "rigid particles", finally generating numerous oriented SC structure in the SC- l PLA. Consequently, the injection molded SC- h PLA/SC- l PLA products exhibit impressively high tensile strength (74.3 MPa) and Vicat softening temperature (211.6 °C). Overall, this work presents an effective guidance for achieving desirable melt-processability of SC-PLA without sacrificing its thermomechanical properties and provides an industrial processing route towards high-performance SC-PLA products. Image 106841 • SC-PLA products were fabricated by low-temperature melt-processing of bimodal SC-PLA powder. • The melting temperature bimodality plays a key role in achieving balanced melt-processability and product performance. • The SC- l PLA component can provide the powder with good low-temperature melt-processability. • The SC- h PLA component can endow the melt-processed products with exceptional thermomechanical performance. • SC- h PLA induced exclusive SC formation and crystal orientation can also contribute to the enhanced performance. [ABSTRACT FROM AUTHOR]

Recently, we proposed a novel strategy for fabricating high-performance stereocomplex-type polylactide (SC-PLA) products through low-temperature (180–210 °C, lower than the melting temperature of SC crystallites) sintering from its nascent powder, without serious thermal degradation involved in the conventional melt processing at higher temperatures. During the sintering, some poly( l -lactide) (PLLA) and poly( d -lactide) (PDLA) chains from adjacent powdery particles can interdiffuse across the interfaces and subsequently co-crystallize into new SC crystallites capable of welding the interfaces. The interfacial strength is dominated by the content of the newly-formed SC crystallites, however, the fast cocrystallization of PLLA/PDLA chains could hinder their sufficient interdiffusion at the interfaces and thus only limited interface-localized SC crystallites could be formed. In this work, we attempt to substantially promote the chain interdiffusion via depressing the cocrystallization rate. To do this, SC-PLA nascent powders with different optical purities of the lactate units were prepared, and the role of optical purity in directing the chain interdiffusion and cocrystallization has been investigated. Very interestingly, we demonstrate that decreasing optical purity (from 99.5 to 96%) is favorable for the formation of numerous SC crystallites at the interfaces because the lowering of cocrystallization rate enables more PLLA/PDLA chains to interdiffuse sufficiently before their cocrystallization. As a result, SC-PLA products with superior heat resistance have been fabricated by the sintering of low-optical-purity SC-PLA powder. These fascinating findings could not only provide new understanding on the low-temperature sintering mechanism of SC-PLA powders but also greatly expand the possibilities for the fabrication of SC-PLA products with superb properties. [ABSTRACT FROM AUTHOR]

Abstract: As a part of serial work about the application of tetra-needle-shaped zinc oxide whisker (T-ZnOw) in polymer composites, this work is focused on the crystallization and tensile fracture behaviors of T-ZnOw/polyamide 6 (T-ZnOw/PA6) composites. Our results show that the addition of T-ZnOw improves the composites tensile strength greatly. For virgin PA6, the stress–strain curve exhibits double-yielding phenomenon. Surface modified T-ZnOw reinforced PA6 composites exhibit higher yield stress and smaller strain-to-fracture compared with virgin PA6. The morphologies of tensile-fractured surfaces show that, addition of T-ZnOw changes the fracture mode from crazing–tearing/brittle fracture mode of virgin PA6 into fibrillation/brittle fracture mode of PA6 composites. Especially, the fracture process of T-ZnOw in composites during the tensile test has been characterized by scanning electronic microscope (SEM) and the corresponding reinforcement mechanism has been discussed. [Copyright &y& Elsevier]

Abstract: In this work, multi-walled carbon nanotubes were successfully chemically modified by maleic anhydride (f-MWCNTs), and the f-MWCNTs were melt compounded with poly(ethylene terephthalate) (PET) by using a twin-screw extruder to prepare nanocomposites. The effects of f-MWCNTs on the crystallization behavior of PET nanocomposites were studied via DSC and POM. The results show the apparent nucleation effect of f-MWCNTs in PET crystallization. The cold-crystallization peak temperature decreases with the increase of f-MWCNTs during the heating process. On the other hand, the addition of f-MWCNTs can greatly enhance the melt-crystallization peak temperature of PET when it is cooled from the melt. The nonisothermal crystallization kinetics of PET with f-MWCNTs was analyzed by different methods and the results also prove that the f-MWCNTs clearly accelerate the crystallization process of PET. [Copyright &y& Elsevier]

Despite of its enormous application potential as a prominent engineering bioplastic, the processing of the stereocomplex-type polylactide (SC-PLA) formed from poly(l -lactide)/poly(d -lactide) (PLLA/PDLA) blends into useful products remains challenging. Recently, low-temperature sintering has emerged as a feasible and promising processing technology towards transparent highly-crystalline SC-PLA products. During the sintering of SC-PLA nascent powder, the interfaces between adjacent particles could be bound together through SC crystallization of interdiffused PLLA and PDLA chains across the interfaces. However, the massive generation of the interface-localized SC crystallites is significantly impaired by the insufficient chain interdiffusion resulting from the rapid SC crystallization. In this work, miscible poly(methyl methacrylate) (PMMA) is adopted to substantially promote the chain interdiffusion by fundamentally diminishing the SC crystallization rate. Intriguingly, we find that the crystallization of PLLA/PDLA chains is greatly decelerated with the incorporation of PMMA and thus more enantiomeric PLA chains could interdiffuse through the interfaces before their crystallization. Moreover, the PMMA is also favorable for the particle wetting of the densified nascent powders, which makes it easier for the enantiomeric chains to interdiffuse across the interfaces. The promoted chain interdiffusion leads to an evident increase in the number of the newly-generated SC crystallites and resulting interfacial weld strength. Consequently, the sintered SC-PLA products possessing superior thermomechanical properties and markedly enhanced hydrolytic resistance have been fabricated by incorporating 9 wt% PMMA, without compromising transparency. These findings could bode well for the industrial fabrication and applications of SC-PLA products. Image 1 • PMMA has been used to improve the low-temperature sintering of SC-PLA nascent powder. • The PMMA can promotes the interdiffusion of PLLA/PDLA chains across the particle interfaces. • Both the decelerated crystallization and enhanced particle wetting contribute to the promotion of the chain interdiffusion. • Sufficient amounts of interface-localized SC crystallites are generated to achieve mechanically robust interfaces. • The obtained SC-PLA products have superior thermomechanical properties, transparency, and hydrolytic stability. [ABSTRACT FROM AUTHOR]

Stereoblock copolymerization is regarded an appealing strategy to substantially enhance the melt stability (i.e., the survival ability of the intermolecular collaboration between poly(l -lactide) (PLLA) and poly(d -lactide) (PDLA) upon melting) of high-molecular-weight (high-MW) stereocomplex-type polylactide (SC-PLA), however it usually suffers from complicated synthetic procedures and even impaired sustainability. Herein, solid-state transesterification (SST) has been devised as a facile and robust route to prepare unique multi-stereoblock PLA copolymers with outstanding melt stability and unexpectedly strong crystallizability from commercial available linear high-MW PLLA/PDLA (50/50) blends. The SST was performed through low-temperature (i.e., 180 °C) melt-blending of PLLA and PDLA in the presence of trace amounts (0.03–0.035 wt%) of catalysts, where the enantiomeric PLA chains could rapidly co-crystallize into solid-state SC crystallites upon melting and subsequently the hetero-chain transesterification reaction occurs exclusively in the mobile amorphous phase of the pre-formed SC crystallites. As a result, multiblock-like PLLA- b -PDLLA- b -PDLA copolymers with long crystallizable PLLA and PDLA blocks are in-situ generated. The results show that high-content SC crystallites can be exclusively formed in the melt-crystallization of the copolymers even at high cooling rates (e.g., 40 °C/min) and low temperatures (e.g., 140 °C). More interestingly, the presence of the non-crystallizable PDLLA blocks not only does not disturb the SC crystallizability of the enantiomeric PLA blocks, as evidenced by the same high crystallinity and melting temperature as those of starting PLLA/PDLA blends, but also increase the crystallization rate by stabilizing the clusters of ordered PLLA/PDLA segments in the copolymer melt. Overall, these findings could open a new pathway to develop melt-processible all SC-PLA for engineering applications. Image 1 • Unique stereoblock PLA copolymers are prepared via solid-state transesterification (SST). • The SST was performed during low-temperature melt-blending of high-MW PLLA and PDLA. • SC crystallites rapidly formed are subjected to hetero-chain reaction in the amorphous phase. • Multiblock-like PLLA- b -PDLLA- b -PDLA copolymers with long crystallizable blocks are in-situ generated. • The obtained copolymers possess outstanding melt stability and strong crystallizability. [ABSTRACT FROM AUTHOR]