Toughened PLA-<i>b</i>-PCL-<i>b</i>-PLA triblock copolymer based biomaterials: effect of self-assembled nanostructure and stereocomplexation on the mechanical properties

Mulchandani, Neha; Masutani, Kazunari; Kumar, Sachin; Yamane, Hideki; Sakurai, Shinichi; Kimura, Yoshiharu; Katiyar, Vimal

doi:10.1039/d1py00429h

Cited by 23 publications

(15 citation statements)

References 83 publications

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“…Another option for PLA toughening involves the synthesis of polymeric architectures with alternative repeating block units composed of PLA as a major segment and immiscible polymers to offer ductility, such as diblocks, triblocks, terpolymers, and graft copolymers, − which can also be achieved by nanoscale phase separation. In particular, multiblock copolymers, which were derived from ABA triblocks with a hard A phase (PLA or PLLA block) connected by a soft or rubbery B segment as a bridge, have demonstrated emerging and enhanced mechanical properties, including elastomeric and toughening performance.…”

Section: Introductionmentioning

confidence: 99%

Semicrystalline-Glassy Multiblock Copolymers via Mechanochemical Synthesis toward Tough Poly(lactide)

Hong

Jeong

Yuk

et al. 2022

ACS Sustainable Chem. Eng.

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A series of semicrystalline-glassy (poly(amide11)–poly(lactide)) n (PA11–PLA) n multiblock copolymers with >97% renewable carbon content were developed for tough PLA. The resulting copolymers exhibited superior mechanical performance, comparable to those of commercial PA11 and PLA. Amine-terminated PA11 with a M n,NMR of 12 kg mol–1 was prepared by bulk self-condensation and subsequently capped with only one LA molecule through mechanochemical ball milling, to produce HO–LA–PA11–LA–OH. After adding Sn(Oct)2, unreacted LA was propagated in one-pot by ring-opening polymerization to make PLA–PA11–PLA with a f PLA of 0.5–0.8. The hydroxyl-telechelic triblocks were also coupled with diisocyanate by ball milling to manufacture (PA11–PLA) n multiblocks. The well-defined molecular structures demonstrated controlled PA11 and PLA lengths. Thermal analysis determined the phase separation of PA11 and PLA based on T g,PLA (48–56 °C) and T m,PA11 (183–186 °C) and confirmed the two transitions of thermal degradation (T d). SAXS profiles of the multiblocks also verified their microphase-separated morphologies. The temperature dependence of χ for the PA11–PLA system, χPA11–PLA = (426.00 ± 4.81)/T – (0.90 ± 0.01), simply represented as 0.24 and 0.13 at 100 and 140 °C, was estimated using the T ODT values obtained from the DMA of three symmetric PLA–PA11–PLA triblocks with a f PLA of 0.5. The resulting semicrystalline-glassy multiblocks showed superior tensile characteristics, merging PLA-originated initial modulus and yield stress (E = 758–903 MPa and σyield = 57–63 MPa), and a PA11-derived toughening even with strain hardening (εb = 380–500%, σb = 40–51 MPa, and γ = 124–171 MJ m–3). These results show promising potential for polymeric materials with sustainability and strength-toughness balance.

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Section: Introductionmentioning

confidence: 99%

Semicrystalline-Glassy Multiblock Copolymers via Mechanochemical Synthesis toward Tough Poly(lactide)

Hong

Jeong

Yuk

et al. 2022

ACS Sustainable Chem. Eng.

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“…1 Compared with blends composed of their respective block counterparts, block copolymers can achieve miscibility at the molecular level. 2 Ordered nanostructures self-assembled from copolymers can be used to tailor properties in photovoltaic, electrical, and optical applications. 3 Repulsive interaction (χN) and volume fraction play key roles in the formation of nanostructures.…”

Section: Introductionmentioning

confidence: 99%

Facile Method for the Synthesis of PCL-b-PA6-b-PCL Using Amino-Terminated PA6 as a Macroinitiator and Its Characterization

et al. 2022

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Polyesteramides have attracted much attention due to their intriguing properties. However, the synthesis of di- or triblock polyesteramides based on polyamide 6 (PA6) remains challenging owing to their harsh reaction conditions. In this work, we introduced a new strategy to synthesize poly(ε-caprolactone)-block-PA6-block-poly(ε-caprolactone) (PCL-b-PA6-b-PCL) in a mild way. A series of well-designed copolymers were characterized by gel permeation chromatography, 1H, DOSY, and 13C NMR, and their crystallization and melting behavior, degradation rate, and compatibilization effect on PA6/PCL blends were found to be strongly composition dependent. Interestingly, the copolymers exhibited diverse spherulite morphologies, including curving stems and banded spherulites, which also correlated with the different relative content of PA6. Besides, PA6 nanodomains could act as physical cross-linking points to improve the tensile strength and Young’s modulus of PCL. This work fills the synthesis gap of well-defined PA6-based triblock polyesteramides, providing new materials for material modification and elucidation of some basic scientific questions.

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“…To develop biomedical material with ideal performance, such as both mechanics and efficacy matching the healing times of the lesion, there are lots of modifications routes, such as blending, copolymerization, grafting, long-chain branching, and so forth, to enhance material properties. [9][10][11][12][13][14][15] Among them, copolymerization is an effective way in which the sequence structure of copolymer chains can be designed to improve the toughness of material and regulate its degradation rate. 5,16,17 The copolymerization of PLLA with other monomers has drawn attention over the past few decades, and common monomers include ethylene glycol, glycolide (GA) and ε-caprolactone.…”

Section: Introductionmentioning

confidence: 99%

“…PLLA stents or fibers exposed to in vivo conditions begin to degrade after approximately 12 months, 8 a quite long period of time. To develop biomedical material with ideal performance, such as both mechanics and efficacy matching the healing times of the lesion, there are lots of modifications routes, such as blending, copolymerization, grafting, long‐chain branching, and so forth, to enhance material properties 9–15 . Among them, copolymerization is an effective way in which the sequence structure of copolymer chains can be designed to improve the toughness of material and regulate its degradation rate 5,16,17 .…”

Section: Introductionmentioning

confidence: 99%

Structure, properties, and in vitro degradation behavior of biodegradable poly(L‐lactic acid)‐trimethylene carbonate‐glycolide terpolymer

Xia

Zhang

et al. 2022

J of Applied Polymer Sci

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For biodegradable medical implants, it is critical to match the degradation rate of the material with the lesion healing rate of the tissue defect. Here, we report the synthesis of poly(L-lactic acid) (PLLA)-trimethylene carbonate (TMC)glycolide (GA) terpolymers with various monomer feeding ratios of L-lactide, TMC, and GA. The terpolymers were prepared through ring-opening polymerization with the purpose to improve degradation and mechanical properties of the terpolymers for biomedical applications. The influence of various GA contents in PLLA-TMC-GA terpolymers on the chain structure and their in vitro degradation performances were evaluated by using gel permeation chromatography, differential scanning calorimetry, X-ray diffraction, 1 H nuclear magnetic resonance, and tensile tests. Compared with pure PLLA, the degradation rate of terpolymers increased with the increase of GA content, because GA segments, which have a faster hydrolysis rate, not only effectively disrupt the regularity of LLA segment, but also increase the probability of chains scission during the degradation process. In a 28-week long degradation study, the mass loss of PLLA-TMC-GA terpolymers was about 36%, which is a faster rate than reported for pure PLLA. Therefore, it is possible to tailor the copolymer chain structures by varying the ratio of GA in the terpolymer to balance its degradation rate with body's lesion healing rate.

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Toughened PLA-b-PCL-b-PLA triblock copolymer based biomaterials: effect of self-assembled nanostructure and stereocomplexation on the mechanical properties

Abstract: The current research unfolds the effect of block lengths, microdomain morphology and stereocomplexation on the mechanical properties of PLA-b-PCL-b-PLA triblock copolymers where PCL is involved to improve the poor extensibility of PLA.

Cited by 23 publications

References 83 publications

Semicrystalline-Glassy Multiblock Copolymers via Mechanochemical Synthesis toward Tough Poly(lactide)

Semicrystalline-Glassy Multiblock Copolymers via Mechanochemical Synthesis toward Tough Poly(lactide)

Facile Method for the Synthesis of PCL-b-PA6-b-PCL Using Amino-Terminated PA6 as a Macroinitiator and Its Characterization

Structure, properties, and in vitro degradation behavior of biodegradable poly(L‐lactic acid)‐trimethylene carbonate‐glycolide terpolymer

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