Synthesis and Thin Film Phase Behaviour of Functional Rod‐Coil Block Copolymers Based on Poly(<i>para</i>‐phenylenevinylene) and Poly(lactic acid)

Braun, Christoph H.; Schöpf, Benjamin; Ngov, Chheng; Brochon, Cyril; Hadziioannou, Georges; Crossland, Edward J. W.; Ludwigs, Sabine

doi:10.1002/marc.201100012

Cited by 11 publications

(7 citation statements)

References 62 publications

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“…On the basis of our knowledge, there has been no previous publication on the synthesis of a PLA‐NR diblock copolymer. The PLA‐based diblock copolymers have included PLA‐poly(ethylene glycol), PLA‐poly(ethylene oxide), PLA‐PS, and PLA‐poly(para‐phenylenevinylene) . NR has been chemically modified to obtain a hydroxyl terminated liquid rubber (a hydroxyl telechelic natural rubber, HTNR).…”

Section: Introductionmentioning

confidence: 99%

Bio‐based diblock copolymers prepared from poly(lactic acid) and natural rubber

Chumeka

Pasetto

Pilard

et al. 2014

J of Applied Polymer Sci

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New bio-based diblock copolymers were synthesized from poly(lactic acid) (PLA) and natural rubber (NR). NR polymer chains were modified to obtain hydroxyl telechelic natural rubber oligomers (HTNR). Condensation polymerization between PLA and HTNR was performed at 110 C during 24 or 48 h. The molecular weight of PLA and HTNR and the molar ratio PLA : HTNR were varied. The new ester linkage in the diblock copolymers was determined by 1 H-NMR. The molecular weight of the diblock copolymers determined from SEC agreed with that expected from calculation. The thermal behavior and degradation temperature were determined by DSC and TGA, respectively. The diblock copolymers were used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. PLA blended with the diblock copolymer showed higher impact strength, which was comparable to the one of a PLA/NR blend. The former blend showed smaller dispersed particles as showed by SEM images, indicating the increase in miscibility in the blend due to the PLA block. The compatibilization was effective in the blends containing 10 wt % of rubber. At a higher rubber content (>10 wt %), coalescence of the NR and diblock copolymer was responsible of the larger rubber diameter in the blends, which causes a decrease of the impact strength.

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Section: Introductionmentioning

confidence: 99%

Bio‐based diblock copolymers prepared from poly(lactic acid) and natural rubber

Chumeka

Pasetto

Pilard

et al. 2014

J of Applied Polymer Sci

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“…The homopolymers and assemblies are further evaluated using fluorescence spectroscopy. Although the complementary helices and coils do not exhibit fluorescence, the emission properties of PPV homopolymers and covalent block copolymers, as well as their aggregation-influenced properties are well documented. ,, The heterotelechelic PPV homopolymers exhibit emission maxima at 520 nm with a broad shoulder at 560 nm (Figure S-33). Both ABC triblock copolymers exhibit mainly relative changes in intensity compared to their parent PPV polymers.…”

Section: Resultsmentioning

confidence: 99%

“…Essential to this design is the development of a new functional initiator based upon Grubbs II; we realize this through an iterative cross-metathesis–ring-opening metathesis polymerization (CM-ROMP) strategy that installs an α-chain end upon the PPV. We choose PPV scaffolds for multiple reasons: (i) conjugated polymer frameworks serve as hosts for a variety of applications, ranging from electronics to sensing; − (ii) homopolymers and block copolymers featuring PPVs are well-studied in the context of optical properties and molecular structures; − and (iii) spectroscopic methodologies that can be used to explicitly investigate conjugated polymer folding motifs have recently emerged. ,, …”

Section: Methodsmentioning

confidence: 99%

“…Additionally, both assemblies support a hypsochromic shift in excitation (450 to 440 nm), likely owing to the disruption of interactions that normally dominate the PPV aggregated state. 46,48 For the helix−(antiparallel π-sheet)−helix upon both metal coordination and hydrogen bonding, we observe an overall decrease in fluorescence intensity (Figure S-39). These collective results suggest maintenance of the antiparallel π-sheets in the wake of assembly, while the complementary polymers successfully compete with the intrachain associations common in PPV-based scaffolds.…”

Section: Journal Of the American Chemical Societymentioning

confidence: 99%

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Supramolecular Multiblock Copolymers Featuring Complex Secondary Structures

et al. 2017

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This contribution introduces main-chain supramolecular ABC and ABB'A block copolymers sustained by orthogonal metal coordination and hydrogen bonding between telechelic polymers that feature distinct secondary structure motifs. Controlled polymerization techniques in combination with supramolecular assembly are used to engineer heterotelechelic π-sheets that undergo high-fidelity association with both helical and coil-forming synthetic polymers. Our design features multiple advances to achieve our targeted structures, in particular, those emulating sheet-like structural aspects using poly(p-phenylenevinylene)s (PPVs). To engineer heterotelechelic PPVs in a sheet-like design, we engineer an iterative one-pot cross metathesis-ring-opening metathesis polymerization (CM-ROMP) strategy that affords functionalized Grubbs-II initiators that subsequently polymerize a paracyclophanediene. Supramolecular assembly of two heterotelechelic PPVs is used to realize a parallel π-sheet, wherein further orthogonal assembly with helical motifs is possible. We also construct an antiparallel π-sheet, wherein terminal PPV blocks are adjacent to a flexible coil-like poly(norbornene) (PNB). The PNB is designed, through supramolecular chain collapse, to expose benzene and perfluorobenzene motifs that promote a hairpin turn via charge-transfer-aided folding. We demonstrate that targeted helix-(π-sheet)-helix and helix-(π-sheet)-coil assemblies occur without compromising intrinsic helicity, while both parallel and antiparallel β-sheet-like structures are realized. Our main-chain orthogonal assembly approach allows the engineering of multiblock copolymer scaffolds featuring diverse secondary structures via the directional assembly of telechelic building blocks. The targeted assemblies, a mix of sequence-defined helix-sheet-coil and helix-sheet-helix architectures, are Nature-inspired synthetic mimics that expose α/β and α+β protein classes via de novo design and cooperative assembly strategies.

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“…Alternatively, Müllen and co‐workers demonstrated that end‐functionalized (hydroxymethyl)polyfluorene acts as an initiator in an anionic polymerization of oxirane to give a polyethylene glycol‐appended rod coil, featuring an oligofluorene block containing 2–6 repeat units 6. Very recently Ludwigs and co‐workers,7 starting from hydroxymethyl‐substituted poly[2,5‐di(2′‐ethylhexyloxy)‐1,4‐phenylene‐vinylene], attached a flexible poly(lactic acid) block to give rod coils with attractive mesoscopic lamellar structures as evidenced by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Overall though, the synthesis of rod‐coil block copolymers is not trivial.…”

Section: Introductionmentioning

confidence: 99%

Poly(para‐phenylene vinylene) and Polynorbornadiene Containing Rod‐Coil Block Copoylmers via Combination of Acyclic Diene Metathesis and Ring‐Opening Metathesis Polymerization

Porz

Mäker

Brödner

et al. 2013

Macromol. Rapid Commun.

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Poly(para-phenylene vinylene) (PPV) and its derivatives are important semiconducting polymers for organic electronics. Herein, an alkene metathesis approach to obtain PPVs is reported. Tri(iso propyl)silyl-substituted norbornadienes are employed as solubilizing agents. As PPV precursors divinylbenzene is used for acyclic diene metathesis and paracyclophane diene for a ring-opening metathesis polymerization-type approach. The resulting polymers are analyzed by gel permeation chromatography (GPC), UV-vis, fluorescence, and nuclear magnetic resonance (NMR) spectroscopy. All of the polymers show good solubility in common solvents.

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Synthesis and Thin Film Phase Behaviour of Functional Rod‐Coil Block Copolymers Based on Poly(para‐phenylenevinylene) and Poly(lactic acid)

Cited by 11 publications

References 62 publications

Bio‐based diblock copolymers prepared from poly(lactic acid) and natural rubber

Bio‐based diblock copolymers prepared from poly(lactic acid) and natural rubber

Supramolecular Multiblock Copolymers Featuring Complex Secondary Structures

Poly(para‐phenylene vinylene) and Polynorbornadiene Containing Rod‐Coil Block Copoylmers via Combination of Acyclic Diene Metathesis and Ring‐Opening Metathesis Polymerization

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