Recent Advances in
            <scp>ADMET</scp>
            Polycondensation Chemistry

Berda, Erik B.; Wagener, Kenneth B.

doi:10.1002/9783527603978.mst0430

Cited by 11 publications

(13 citation statements)

References 55 publications

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“…56 Additionally, Altintas et al reported a polymer folded by two different orthogonal hydrogen bonding dimers. Combining SCNP synthesis techniques with advanced polymer syntheses that control monomer sequence or functional group placement such as work by Perrier, 12 Lutz, 14 and Whittaker, 73 or well-defined step-growth chemistry such as ADMET, 13 provides possibilities that could take the current state of the art one step closer to the structural precision found in natural folded macromolecules. 63 Outlook Surveying the literature it becomes clear that SCNP synthesis using a singular covalent chemistry as an intra-chain crosslink, and even the use of dynamic covalent chemistry or various supramolecular interactions is a well developed, proven technique.…”

Section: Multiple Intra-chain Interactionsmentioning

confidence: 99%

“…Recent advances in contemporary controlled polymerization chemistry allow the synthesis of multiblock polymers with narrow molecular weight distributions 12 or materials with controlled monomer sequences 13,14 by step-growth and chain-growth methods. Tertiary structure is permitted by a pristine primary structure, a quality that is currently inaccessible in synthetic polymers.…”

Section: Introductionmentioning

confidence: 99%

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A brief user's guide to single-chain nanoparticles

et al. 2015

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In this review we outline the various methods that have been explored to synthesize architecturally defined nanoparticles from discrete polymer chains, summarize the methods of characterization that are required to prove their formation and probe their morphology, and introduce a number of potential applications that are being explored currently. Given the small size of the nanostructures produced by these methods and the relative ease with which they can be tailored to specific end use applications it is likely such efforts will intensify in the coming years. So far, simple chemistry has been utilized and high-level characterization and modeling studies have been applied to understand the process by which these particles form and how they behave, both in the bulk and in solution. Although impossible to predict where this work will lead, we hope this "user's guide" will prove useful to the community as research on singlechain nanoparticles continues to evolve.From left to right:

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Section: Multiple Intra-chain Interactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A brief user's guide to single-chain nanoparticles

et al. 2015

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“…Acyclic diene metathesis (ADMET) polymerization has been a promising method for synthesis of high molecular weight poly(2,5-dialkylphenylene-1,4-vinylene)s (PPVs), PFVs, and poly( N -alkylcarbazole-2,7-vinylene)s. − This is because the approach affords defect (impurities such as halogen sulfur, etc., and/or regio-/stereoirregularity, cross-linking, etc.) free, stereoregular ( all - trans ) materials which are difficult from those by adopting the conventional condensation (dehalogenation–condensation, etc.)…”

Section: Introductionmentioning

confidence: 99%

Effects of End-Groups on Photophysical Properties of Poly(9,9-di-n-octylfluorene-2,7-vinylene)s Linked with Metalloporphyrins: Synthesis and Time-Resolved Fluorescence Spectroscopy

et al. 2017

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A series of poly(9,9-di-n-octyl-fluorene-2,7-vinylene)s (PFVs) containing metalloporphyrins at the chain ends with different conjugation lengths (ca. average 8 or 24 FV repeat units), PFV-[Por(M)]2, have been prepared by olefin metathesis of the vinyl chain ends in PFVs (prepared by acyclic diene metathesis polymerization by ruthenium–carbene catalysts) using molybdenum–alkylidene catalyst (reagent) followed by Wittig-type cleavage with formyl porphyrin containing different metal ions [Zn(II), Cu(II), Ni(II), and Pt(II)]. Effects of the metalloporphyrins on photophysical properties of PFVs were studied by means of time-resolved fluorescence spectroscopy. The fluorescence spectral profile from PFV moiety in all the polymers with end-porphyrins was almost identical to that of the reference PFV. However, fluorescence quantum yields were remarkably lower, depending upon the central metal ion and the chain length. The observed reduction of the quantum yields is ascribed to intramolecular energy transfer to the end-groups as well as enhancement of intersystem crossing within the PFV unit. In the zinc derivative, PFV(High)-[Por(Zn)]2, fluorescence from zinc porphyrin was also observed with a higher fluorescence quantum yield. It was found that radiative rate constant in zinc porphyrin moiety was enhanced about 3 times, suggesting specific interaction between the PFV and the porphyrin. On the other hand, time-resolved fluorescence signals of PFV moiety in all the PFV end-modified by metalloporphyrins decay with two or more components without any change of spectral profile. A model in which the excitation is localized in several pieces of FV units is proposed.

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“…These precise polyethylenes are synthesized via acyclic diene metathesis (ADMET) polymerization, − a technique that provides remarkable control over polymer microstructure but remains challenging to scale up to industrially relevant levels of production. To capitalize on the attractive properties discovered in ADMET polymers, more scalable synthetic routes are desired.…”

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confidence: 99%

High Morphological Order in a Nearly Precise Acid-Containing Polymer and Ionomer

et al. 2017

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Linear polyethylenes with functional groups at precise intervals along the backbone possess a number of remarkable properties, but the current synthetic methods that produce these precise polymers are difficult to scale up beyond the laboratory setting. When evaluating alternative synthetic routes, a critical question is how precise must the polymer microstructure be to achieve the properties of interest? As a first step in answering this question, we present morphological characterization of a nearly precise polymerthat is, an acid-containing polymer wherein the acid groups are separated by either n or n + 1 methylene groups. We find that the size scale and uniformity of the amorphous morphologies of the nearly precise acid-containing polymer and its sodium-neutralized ionomer are essentially indistinguishable from the precise polymers based on X-ray scattering. Meanwhile, the nearly precise polymer is strikingly distinct from a pseudorandom copolymer with similar average composition. This result suggests that the properties of nearly precise polymers could likewise be quite similar to truly precise polymers and beckons future work to explore their properties.

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Recent Advances in ADMET Polycondensation Chemistry

Abstract: The sections in this article are Introduction Functionalized Polyethylenes Linear Ethylene/Vinyl Ether Copolymers Linear Ethylene/Acrylic Acid Copolymers Phosphonic Acid‐Functionalized Polyethylenes Functional Polymers and Materials via ADMET … Show more

Cited by 11 publications

References 55 publications

A brief user's guide to single-chain nanoparticles

A brief user's guide to single-chain nanoparticles

Effects of End-Groups on Photophysical Properties of Poly(9,9-di-n-octylfluorene-2,7-vinylene)s Linked with Metalloporphyrins: Synthesis and Time-Resolved Fluorescence Spectroscopy

High Morphological Order in a Nearly Precise Acid-Containing Polymer and Ionomer

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