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  1. Article ; Online: Quo Vadis Carbanionic Polymerization?

    Ntetsikas, Konstantinos / Ladelta, Viko / Bhaumik, Saibal / Hadjichristidis, Nikos

    ACS polymers Au

    2022  Volume 3, Issue 2, Page(s) 158–181

    Abstract: Living anionic polymerization will soon celebrate 70 years of existence. This living polymerization is considered the mother of all living and controlled/living polymerizations since it paved the way for their discovery. It provides methodologies for ... ...

    Abstract Living anionic polymerization will soon celebrate 70 years of existence. This living polymerization is considered the mother of all living and controlled/living polymerizations since it paved the way for their discovery. It provides methodologies for synthesizing polymers with absolute control of the essential parameters that affect polymer properties, including molecular weight, molecular weight distribution, composition and microstructure, chain-end/in-chain functionality, and architecture. This precise control of living anionic polymerization generated tremendous fundamental and industrial research activities, developing numerous important commodity and specialty polymers. In this Perspective, we present the high importance of living anionic polymerization of vinyl monomers by providing some examples of its significant achievements, presenting its current status, giving several insights into where it is going (Quo Vadis) and what the future holds for this powerful synthetic method. Furthermore, we attempt to explore its advantages and disadvantages compared to controlled/living radical polymerizations, the main competitors of living carbanionic polymerization.
    Language English
    Publishing date 2022-12-22
    Publishing country United States
    Document type Journal Article ; Review
    ISSN 2694-2453
    ISSN (online) 2694-2453
    DOI 10.1021/acspolymersau.2c00058
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  2. Article ; Online: Microscopic Evidence for the Topological Transition in Model Vitrimers.

    Arbe, Arantxa / Alegría, Angel / Colmenero, Juan / Bhaumik, Saibal / Ntetsikas, Konstantinos / Hadjichristidis, Nikos

    ACS macro letters

    2023  Volume 12, Issue 11, Page(s) 1595–1601

    Abstract: In addition to the glass transition, vitrimers undergo a topological transition from viscoelastic liquid to viscoelastic solid behavior when the network rearrangements facilitated by dynamic bond exchange reactions freeze. The microscopic observation of ... ...

    Abstract In addition to the glass transition, vitrimers undergo a topological transition from viscoelastic liquid to viscoelastic solid behavior when the network rearrangements facilitated by dynamic bond exchange reactions freeze. The microscopic observation of this transition is elusive. Model polyisoprene vitrimers based on imine dynamic covalent bonds were synthesized by reaction of α,ω-dialdehyde-functionalized polyisoprenes and a tris(2-aminoethyl)amine. In these dynamic networks nanophase separation of polymer and reactive groups leads to the emergence of a relevant length scale characteristic for the network structure. We exploited the scattering sensitivity to structural features at different length scales to determine how dynamical and topological arrests affect correlations at segmental and network levels. Chains expand obeying the same expansion coefficient throughout the entire viscoelastic region, i.e., both in the elastomeric regime and in the liquid regime. The onset of liquid-like behavior is only apparent at the mesoscale, where the scattering reveals the reorganization of the network triggered by bond exchange events. The such determined "microscopic" topological transition temperature is compared with the outcome of "conventional" methods, namely viscosimetry and differential scanning calorimetry. We show that using proper thermal (aging-like) protocols, this transition is also nicely revealed by the latter.
    Language English
    Publishing date 2023-11-10
    Publishing country United States
    Document type Journal Article
    ISSN 2161-1653
    ISSN (online) 2161-1653
    DOI 10.1021/acsmacrolett.3c00586
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  3. Article: Noncovalent Supramolecular Diblock Copolymers: Synthesis and Microphase Separation.

    Bhaumik, Saibal / Ntetsikas, Konstantinos / Hadjichristidis, Nikos

    Macromolecules

    2020  Volume 53, Issue 15, Page(s) 6682–6689

    Abstract: Supramolecular block copolymers ( ...

    Abstract Supramolecular block copolymers (
    Language English
    Publishing date 2020-07-22
    Publishing country United States
    Document type Journal Article
    ZDB-ID 3436-8
    ISSN 0024-9297
    ISSN 0024-9297
    DOI 10.1021/acs.macromol.9b02326
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  4. Article: Synthesis and Characterization of Asymmetric A₁BA₂ Supramolecular Triblock Copolymers via Noncovalent Interactions: A Solution and Solid-State Study

    Bhaumik, Saibal / Shan, Wenpeng / Thomas, Edwin L. / Hadjichristidis, Nikos

    Macromolecules. 2021 Nov. 22, v. 54, no. 23

    2021  

    Abstract: We present the design, synthesis, and characterization of triple hydrogen-bond-forming precursors and their supramolecular triblock copolymers. Thymine end-functionalized polystyrene-b-polyisoprene (PS-b-PI-Thy) and diaminotriazine end-functionalized ... ...

    Abstract We present the design, synthesis, and characterization of triple hydrogen-bond-forming precursors and their supramolecular triblock copolymers. Thymine end-functionalized polystyrene-b-polyisoprene (PS-b-PI-Thy) and diaminotriazine end-functionalized polystyrene (PS-DAT) were successfully synthesized via anionic polymerization followed by suitable organic reactions and then solution-mixed to form supramolecular triblocks via hydrogen-bonding interactions. Three different types of asymmetric A₁-b-B-sb-A₂ supramolecular triblock copolymers were prepared by varying the molecular weight of the A₁-b-B diblock copolymers and A₂ homopolymers. Proton nuclear magnetic resonance spectroscopy was used for the detailed structural characterization of the polymers in solution, and gel permeation chromatography was used to determine the molecular weight and polydispersity index of all homopolymers and block copolymers. Additionally, transmission electron microscopy and small-angle X-ray scattering measurements were employed to assess the solid-state morphological structures of the supramolecular triple hydrogen-bond triblocks, the diblocks, and single hydrogen-bond mixtures of diblocks with homopolymers.
    Keywords composite polymers ; gel chromatography ; hydrogen bonding ; molecular weight ; nuclear magnetic resonance spectroscopy ; polymerization ; polystyrenes ; small-angle X-ray scattering ; thymine ; transmission electron microscopy
    Language English
    Dates of publication 2021-1122
    Size p. 10730-10739.
    Publishing place American Chemical Society
    Document type Article
    ZDB-ID 1491942-4
    ISSN 1520-5835 ; 0024-9297
    ISSN (online) 1520-5835
    ISSN 0024-9297
    DOI 10.1021/acs.macromol.1c01848
    Database NAL-Catalogue (AGRICOLA)

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