Poly(<scp>l</scp>-lactic acid) with Segmented Perfluoropolyether Enchainment

Haynes, D.M.; Naskar, Amit K.; Singh, Akhilesh Kumar; Yang, Chih‐Chao; Burg, Karen J. L.; Drews, Michael J.; Harrison, Graham M.; Smith, Dennis W.

doi:10.1021/ma0712192

Cited by 40 publications

(31 citation statements)

References 25 publications

(40 reference statements)

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“…87 Also, for a series of LFL triblock polymers (L = poly(L-lactide), F = perfluoropolyether, M n,F = 500 g mol −1 ), as the polylactide composition increased from 5 to 20 wt %, the mechanical response transitioned from ductile to brittle; the authors claimed this occurred because the overall molecular weight of the polymer decreased. 89 Thus, it appears that a ductile response of PLA-b-rubbery-b-PLA triblocks relies on the combined effect of rubber toughening from the midblock with entangled lactide chains that provide additional reinforcement in the bulk phase.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis and Rheology of Branched Multiblock Polymers Based on Polylactide

2016

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To improve the toughness and processability of poly(lactic acid) (PLA), a branched multiblock polymer was prepared from D,L-lactide and ε-decalactone. A hydroxy telechelic four-arm star poly(ε-decalactone)−poly(D,L-lactide) diblock was synthesized using sequential ring-opening transesterfication polymerization (ROTEP) and coupled using a substoichiometric amount of sebacoyl chloride to obtain a segmented multiblock with a comb-like architecture. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) revealed that this branched multiblock was microphase separated but lacked long-range order. Unlike a linear multiblock of similar mass, the branched material demonstrated significant extensional hardening in the disordered state, suggesting much improved processability in polymer processing methods that require fast elongational flows. Additionally, the branched multiblock material exhibited remarkable tensile toughness. This simple synthetic approach allows for simultaneous control of mechanical and rheological properties using a single macromolecular architecture to address key practical issues with PLA.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis and Rheology of Branched Multiblock Polymers Based on Polylactide

2016

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“…Non‐degradable mid‐blocks have also been used to make tough PLA triblock copolymers with a higher content of PLA than the polyester mid‐block materials. The polymerization of l ‐lactide has been initiated off an α,ω‐hydroxyl‐terminated poly(tetrafluoroethylene oxide‐ co ‐difluoromethylene oxide) (PFPE) to yield an ABA triblock (PLA‐ b ‐PFPE‐ b ‐PLA) (Figure ) . When a copolymer with 5 wt% PFPE was fashioned into a fiber, the elongation to break of the material was around 300% as compared to 10% for the PLLA homopolymer.…”

Section: Nanometer‐scale Pla Toughening Approachesmentioning

confidence: 99%

Toughening Polylactide with Phase‐Separating Complex Copolymer Architectures

Gramlich

2014

Macro Chemistry & Physics

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Polylactide (PLA) is a commercially produced potentially sustainable plastic that holds promise to replace petroleum‐sourced materials. Unfortunately, the brittle nature of PLA limits its current utility to disposable packaging. Melt blends of PLA and a rubbery material can rubber toughen the plastic, but often require the addition of a compatibilizer and generate opaque materials. Current efforts explore using block and graft copolymers with a majority PLA block and minority rubbery block that phase separate on the nanometer length scale to rubber toughen PLA. With these complex architectures, the polymer matrix, the minor rubbery component, and the compatibilizer are present in one molecule. Many block and graft copolymers rely on non‐sustainable rubbery blocks, which limits the sustainability of these materials. Recent work has utilized polyisoprene (PI) as the sustainable backbone for PLA graft copolymers. Post‐polymerization functionalization and copolymerization of PI provides a method to create fully sustainable PLA/PI graft copolymers that phase separate on the nanometer‐scale to make potentially tough, sustainable plastics.

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“…PLLA presents outstanding bioresorbability and biocompatibility, but PLLA is brittle (9). Polymeric materials with adjustable degradation and mechanical properties were obtained through blending or copolymerization (10)(11)(12)(13). During the last decades, many researches have been focused on producing both random (14)(15)(16) and block (17)(18)(19)(20)(21)(22) copolymers from e-CL and LLA to provide copolymers with desirable properties.…”

Section: Introductionmentioning

confidence: 99%

Benzo-12-crown-4 modifiedN-heterocyclic carbene for organocatalyst: Synthesis, characterization and degradation of block copolymers of ϵ-caprolactone withL-lactide

Wang

Niu

Jiang

et al. 2016

Journal of Macromolecular Science, Part A

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A set of poly(L-lactide)-poly(e-caprolactone) diblock copolymers (AB) and poly(L-lactide)-poly(e-caprolactone)-poly(L-lactide) triblock copolymers (ABA) with predictable molecular weights and relatively narrow distributions were synthesized by ring-opening polymerization of successively added e-caprolactone (e-CL) and L-lactide (LLA) using 4-methyl benzo-12-crown-4 imidazol-2-ylidene as catalyst. The effects of polymerization conditions, such as reaction time, temperature, monomer/catalyst molar ratio and monomer concentration on the copolymerization have been discussed in detail. The resulting copolymers were characterized by 1 H-NMR, 13 C-NMR, IR, GPC and DSC methods which confirmed the successful synthesis of block copolymers of LLA and e-CL. Hydrolytic degradation of the polymers showed that the PLLA-PCL-PLLA copolymer exhibited faster degradation as compared with the PCL homopolymer in alkaline medium at 37 C.

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Poly(l-lactic acid) with Segmented Perfluoropolyether Enchainment

Cited by 40 publications

References 25 publications

Synthesis and Rheology of Branched Multiblock Polymers Based on Polylactide

Synthesis and Rheology of Branched Multiblock Polymers Based on Polylactide

Toughening Polylactide with Phase‐Separating Complex Copolymer Architectures

Benzo-12-crown-4 modifiedN-heterocyclic carbene for organocatalyst: Synthesis, characterization and degradation of block copolymers of ϵ-caprolactone withL-lactide

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