Facile Synthesis of a High Molecular Weight Amphiphilic Aramid–ROMP Block Copolymer

Badoux, Michael; Drechsler, Susanne; Pal, Subhajit; Kilbinger, Andreas F. M.

doi:10.1021/acs.macromol.7b01989

Cited by 8 publications

(9 citation statements)

References 43 publications

(95 reference statements)

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“…Hence, in the case of a BCP, signals corresponding to different blocks but correlating to the same diffusivity prove that the blocks are indeed connected. [63][64][65][66] A decrease in the diffusion coefficient in comparison with the homopolymers or macroinitiator allows for a qualitative evaluation of an increase in the molecular weight. Loo et al exploited DOSY analysis for mapping the actual molecular weight distribution.…”

Section: Alternative Methods For Molecular Weight Determinationmentioning

confidence: 99%

The block copolymer shuffle in size exclusion chromatography: the intrinsic problem with using elugrams to determine chain extension success

2021

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Section: Alternative Methods For Molecular Weight Determinationmentioning

confidence: 99%

The block copolymer shuffle in size exclusion chromatography: the intrinsic problem with using elugrams to determine chain extension success

2021

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“…The spherical or rodlike micelles’ number depended on poly(ethylene glycol) length in nonpolar solvents. The schematic self-assembly behavior of the block copolymer is shown in Figure 3 A. Badoux et al [ 34 ] prepared an amphiphilic aramid–ROMP block copolymer which self-assembled into large ribbonlike aggregates up to 50 nm in thickness and 300 nm in length ( Figure 3 B). Kataoka et al [ 35 ] reported the gelation of monodisperse diblock copolymers of poly( N -octyl m -benzamide) with poly( p -benzamide) or poly( m -benzamide).…”

Section: Self-assembly Of Pptamentioning

confidence: 99%

“…Copyright 2010 American Chemical Society (Washington, DC, USA). ( B ) TEM pictures and schematic self-assembly behavior of amphiphilic aramid–ROMP block copolymer [ 34 ]. Copyright 2017 American Chemical Society.…”

Section: Figurementioning

confidence: 99%

Recent Advances in Self-Assembly and Application of Para-Aramids

Xie

Yang

et al. 2022

Molecules

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Poly(p-phenylene terephthalamide) (PPTA) is one kind of lyotropic liquid crystal polymer. Kevlar fibers performed from PPTA are widely used in many fields due to their superior mechanical properties resulting from their highly oriented macromolecular structure. However, the “infusible and insoluble” characteristic of PPTA gives rise to its poor processability, which limits its scope of application. The strong interactions and orientation characteristic of aromatic amide segments make PPTA attractive in the field of self-assembly. Chemical derivation has proved an effective way to modify the molecular structure of PPTA to improve its solubility and amphiphilicity, which resulted in different liquid crystal behaviors or supramolecular aggregates, but the modification of PPTA is usually complex and difficult. Alternatively, higher-order all-PPTA structures have also been realized through the controllable hierarchical self-assembly of PPTA from the polymerization process to the formation of macroscopic products. This review briefly summarizes the self-assembly methods of PPTA-based materials in recent years, and focuses on the polymerization-induced PPTA nanofibers which can be further fabricated into different macroscopic architectures when other self-assembly methods are combined. This monomer-started hierarchical self-assembly strategy evokes the feasible processing of PPTA, and enriches the diversity of product, which is expected to be expanded to other liquid crystal polymers.

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“…On top of this, it has been demonstrated that PLA is a suitable substitute for many commodity plastics synthesized from petroleum derivatives which makes it a good target for commercial applications. − PLA is industrially produced from the ROP of lactide (LA), a transformation requiring high temperatures and the intervention of an efficient catalyst. , Despite the continuous efforts to implement sustainable catalysis in its production, the current synthetic pathway requires metal catalysts, the most widespread example being tin octoate (SnOct 2 ), employed because of its excellent thermal stability and high activity even at low catalyst loading. However, the subsequent removal of SnOct 2 is arduous, which regularly compromises the applicability of PLA and generates environmental issues at the end of the useful life of the plastic when it is left to biodegrade. − In addition, at the industrial level, concerns have been raised due to upcoming regulations limiting the use of tin-based catalysts …”

Section: Introductionmentioning

confidence: 99%

Stereoretention in the Bulk ROP of l-Lactide Guided by a Thermally Stable Organocatalyst

et al. 2021

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Polylactide (PLA) has emerged as one of the most promising bio-based alternatives to petroleum-based plastics, mainly because it can be produced from the fermentation of naturally occurring sugars and because it can be industrially compostable. In spite of these benefits, the industrial ring-opening polymerization (ROP) of l -lactide (L-LA) still requires the use of highly active and thermally stable metal-based catalysts, which have raised some environmental concerns. While the excellent balance between activity and functional group compatibility of organic acid catalysts makes them some of the most suitable catalysts for the metal-free ROP of L-LA, the majority of these acids are highly volatile and subject to decomposition at high temperature, which limits their use under industrially relevant conditions. In this work we exploit the use of a nonstoichiometric acid–base organocatalyst to promote the solvent-free and metal-free ROP of L-LA at elevated temperatures in the absence of epimerization and transesterification. To do so, a stable acidic complex was prepared by mixing 4-(dimethylamino)pyridine (DMAP) with 2 equiv of methanesulfonic acid (MSA). Both experimental and computational results indicate that DMAP:MSA (1:2) not only is highly thermally stable but also promotes the retention of stereoregularity during the polymerization of L-LA, leading to PLLA with a molar mass of up to 40 kg mol –1 and a chiral purity in excess of 98%. This result provides a new feature to exploit in organocatalyzed polymerization and in the design of new catalysts to facilitate the path to market.

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Facile Synthesis of a High Molecular Weight Amphiphilic Aramid–ROMP Block Copolymer

Cited by 8 publications

References 43 publications

The block copolymer shuffle in size exclusion chromatography: the intrinsic problem with using elugrams to determine chain extension success

The block copolymer shuffle in size exclusion chromatography: the intrinsic problem with using elugrams to determine chain extension success

Recent Advances in Self-Assembly and Application of Para-Aramids

Stereoretention in the Bulk ROP of l-Lactide Guided by a Thermally Stable Organocatalyst

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