Insights into Stereocomplexation of Poly(lactic acid) Materials: Evolution of Interaction between Enantiomeric Chains and Its Role in Conformational Transformation in Racemic Blends

Zhang, Meng; Fan, Xuezhong; Guo, Wenlong; Zhou, Haijun; Li, Zhaolei; Ma, Yu; Yan, Chao‐Guo; Dufresne, Alain

doi:10.1021/acsapm.2c00781

Cited by 10 publications

(4 citation statements)

References 63 publications

(81 reference statements)

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“…PLA is a simple polyester that has a flexible chain structure containing the C═O dipoles, and it could be divided into homochiral enantiomer‐packed homo‐crystals (HC) and stereocomplex crystals (SC). [ 23 ] In HC, the homochiral PLA chains crystallize separately, where the intermolecular interaction such as the weak C─H···O═C hydrogen bonds aligned them in an ordered arrangement. Differently, PLLA and PDLA chains in SC are packed alternately with the assistance of C─H···O═C hydrogen bonds and dipolar interactions between PLLA and PDLA chains.…”

Section: Resultsmentioning

confidence: 99%

Observation of Ferroelectric Lithography on Biodegradable PLA Films

Jiang,

Song,

et al. 2023

Advanced Materials

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Ferroelectric lithography, which can purposefully control and pattern ferroelectric domains in the micro‐/nanometer scale, has extensive applications in data memories, field‐effect transistors, race‐track memory, tunneling barriers, and integrated biochemical sensors. In pursuit of mechanical flexibility and light weight, organic ferroelectric polymers such as poly(vinylidene fluoride) (PVDF) have been developed; however, they still suffer from complicated stretching processes of film fabrication and poor degradability. These poor features severely hinder its applications. Here, we demonstrate the ferroelectric lithography on the biocompatible and biodegradable poly(lactic acid) (PLA) thin films at room temperature. The semi‐crystalline PLA thin film can be easily fabricated through the melt‐casting method, and the desired domain structures can be precisely written according to the predefined patterns. Most importantly, the coercive voltage (Vc) of PLA thin film is relatively low (lower than 30 V) and can be further reduced with the decrease of the film thickness. These intriguing behaviors combined with satisfying biodegradability make PLA thin film a desirable candidate for ferroelectric lithography and enable its future application in the field of bioelectronics and biomedicine. This work sheds light on further exploration of ferroelectric lithography on other polymer ferroelectrics as well as their application as nanostructured devices.This article is protected by copyright. All rights reserved

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Section: Resultsmentioning

confidence: 99%

Observation of Ferroelectric Lithography on Biodegradable PLA Films

Jiang,

Song,

et al. 2023

Advanced Materials

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“…24,30 Low-molecular-weight PHB can be well miscible with PLA and act as a nucleating agent to improve the crystallinity and rigidity of PLA. 31,32 On the other hand, poly(ε-caprolactone) (PCL) has a very low melting point (59−64 °C) and a low glass-transition temperature (−60 °C) resulting in low molecular interactions due to the high mobility of chain segments. PCL is generally presented in a rubber state, which gives it better flexibility.…”

Section: Introductionmentioning

confidence: 99%

“…PHB is a kind of linear semicrystalline biodegradable polymer, and its linear chain structure includes the amorphous phase and crystalline phase, in the crystallinity range of 50–80%, with good biocompatibility . Besides, PHB is harder and less flexible than conventional plastics, and rigidity and durability increase with increasing crystallinity. , Low-molecular-weight PHB can be well miscible with PLA and act as a nucleating agent to improve the crystallinity and rigidity of PLA. , On the other hand, poly(ε-caprolactone) (PCL) has a very low melting point (59–64 °C) and a low glass-transition temperature (−60 °C) resulting in low molecular interactions due to the high mobility of chain segments. PCL is generally presented in a rubber state, which gives it better flexibility. , Cellulose acetate (CA) can be used as a branched center to regulate the chain structure due to the abundant hydroxyl group on the surface. − …”

Section: Introductionmentioning

confidence: 99%

Designing of the Branched PDLA-Grafted Copolymers with Different Architectures through Cellulose Acetate as the Node for High-Performance Polylactide-Based Enantiomers

Wu,

Gao,

Guo

et al. 2024

Ind. Eng. Chem. Res.

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In this work, poly(D-lactic acid) (PDLA) multiblock copolymers with a branched structure were designed by a twostep coupling strategy. First, polyhydroxybutyrate (PHB), poly(ε-caprolactone) (PCL), and PDLA blocks were subsequently introduced by coupling to prepare a linear PDLA block copolymer (PDLA-rB), and PDLA-rB was then grafted on a cellulose acetate (CA) chain to get the CA-g-PDLA-rB copolymer (CA-rB-PDLA). PDLA-rB and CA-rB-PDLA copolymers were blended with commercial poly(L-lactic acid) (PLLA) to form the stereocomplex crystals (SCs) of poly(lactic acid) enantiomers and reduce the inherent brittleness of PLLA. For PLLA/PDLA-rB blends, the PHB-PCL block in the multiblock copolymer acts as a plasticizer to promote HC crystallization; the crystallinity increased from 17 to 17.9%. Compared with the linear blends, a higher SC crystallinity is probably attributed to the formation of the favorable interdigitation between polymer chains. Moreover, the branched chains introduced more PHB-PCL blocks and promoted the formation of multiple heterogeneous nucleation spots, which plays a role in accelerating the crystallization kinetics of HCs. The PLLA/CA-rB-PDLA blends also exhibited a greatly improved tensile toughness. With CA-rB-PDLA-5.0 loading, the strain at break of PLLA/CA-rB-PDLA was increased 4 times. Scanning electron microscopy investigation revealed that the formation of dense cavities and fibrous network structure can resist local strain, resulting in high toughness. It is further proved by tan delta (δ) curves that the great improvement in toughness of the PLLA/CA-rB-PDLA blends is attributed to its high crystallinity. These results revealed that branched structures play a significant role in improving the crystallization and mechanical properties of PLLA.

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“…In the present work, oxygen and water vapor barrier properties of SCPLA with α, α′, and SC crystals were examined, different polymorphisms were obtained by annealing at selective temperatures, and the impact of polymorphism on amorphous phases and the barrier performances were discussed. Due to faster nucleation of SC than HC, − most SCPLA products hold polymorphisms of exclusive SC crystals, SC + α crystals, or SC + α′ crystals. Thus, this study holds fundamental insights and practical relevance for growing real-world applications of SCPLA-based materials.…”

Section: Introductionmentioning

confidence: 99%

Modulating Barrier Properties of Stereocomplex Polylactide: The Polymorphism Mechanism and Its Relationship with Rigid Amorphous Fraction

Chen,

Auras,

Kirkensgaard

et al. 2023

ACS Appl. Mater. Interfaces

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The barrier properties of semicrystalline polymers are crucial for their performance and their use as packaging materials. This work uncovers the mechanism of polymorphism modification (α, α′ and stereocomplex-crystals) and its combined effect on the oxygen and water vapor barrier properties of semicrystalline stereocomplex polylactide (SCPLA). A polymorphic selective filler-type nucleator was employed to eliminate the temperature effect on the development of polymorphism and rigid amorphous fraction (RAF), allowing correlations of barrier properties with different crystal forms and RAF combinations under the same amorphous composition (SCPLA). The oxygen and water vapor barrier performances strongly correlated with crystallinity and crystal form but were not monotonically related to the RAF quantity. The study proposes that the chain conformation of intermediate phases between the crystalline and amorphous phases differs with the associated crystal forms, thereby leading to different RAF “qualities” and contributing to different gas diffusion and solubility coefficients of the amorphous regions. RAF’s per unit excess free volume may be varied with crystal forms, for instance: α′ ≫ SC > α. Therefore, SCPLA with α′ crystals exhibited high oxygen and water vapor permeabilities. Those with high SC and α crystals showed similar barrier behaviors governed by Henry’s law dissolution and followed a linear “two-phase” relationship with total crystallinity.

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Insights into Stereocomplexation of Poly(lactic acid) Materials: Evolution of Interaction between Enantiomeric Chains and Its Role in Conformational Transformation in Racemic Blends

Cited by 10 publications

References 63 publications

Observation of Ferroelectric Lithography on Biodegradable PLA Films

Observation of Ferroelectric Lithography on Biodegradable PLA Films

Designing of the Branched PDLA-Grafted Copolymers with Different Architectures through Cellulose Acetate as the Node for High-Performance Polylactide-Based Enantiomers

Modulating Barrier Properties of Stereocomplex Polylactide: The Polymorphism Mechanism and Its Relationship with Rigid Amorphous Fraction

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