On the Morphological Behavior of ABC Miktoarm Stars Containing Poly(cis 1,4-isoprene), Poly(styrene), and Poly(2-vinylpyridine)

Sergey Chernyy*, Jyoti P. Mahalik, Rajeev Kumar, Jacob Judas Kain Kirkensgaard, Matthias M. L. Arras, Hyeyoung Kim, Lars Schulte, Sokol Ndoni, Gregory S. Smith, Kell Mortensen, Bobby G. Sumpter, Thomas P. Russell, Kristoffer Almdal

*Corresponding author for this work

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    Abstract

    Fundamental understanding of microphase separation in ABC miktoarm copolymers is vital to access a plethora of nonconventional morphologies. Miktoarm stars based on poly(cis 1,4-isoprene) (I), poly(styrene) (S), and poly(2-vinylpyridine) (V) are model systems, which allow systematic studies of the effects of composition, chemical microstructure, and temperature on the thermodynamics of microphase separation. Eleven ISV-x (I:S:V = 1:1:x, v:v:v) miktoarm copolymers were synthesized by anionic polymerization affording well-defined copolymers with a variable V arm. Equilibrium bulk morphologies of all samples, as evidenced by smallangle X-ray scattering, transmission electron microscopy (TEM), and self-consistent field theory, showed a systematic transition from lamellae (x ≈ 0–0.2) to [8.8.4] tiling (x ≈ 0.6–0.9) to cylinders inundulating lamellae (x ≈ 2–4) and, finally, to hexagonally packed core–shell cylinders (x ≈ 5–8). Chemical microstructure of the I arm [poly(cis 1,4-isoprene)] versus poly(3,4-isoprene) is shown to play important role in affecting morphological behavior. To reconcile differences between ISV-x star morphologies reported in the literature and those reported herein, even for the same composition, effects of the microstructure of I arm on the Flory–Huggins parameter between I and V arms were taken into account in a qualitative manner.
    Original languageEnglish
    JournalJournal of Polymer Science. Part B, Polymer Physics
    Volume56
    Issue number22
    Pages (from-to)1491-1504
    ISSN0887-6266
    DOIs
    Publication statusPublished - 2018

    Cite this

    Chernyy, Sergey ; Mahalik, Jyoti P. ; Kumar, Rajeev ; Kirkensgaard, Jacob Judas Kain ; Arras, Matthias M. L. ; Kim, Hyeyoung ; Schulte, Lars ; Ndoni, Sokol ; Smith, Gregory S. ; Mortensen, Kell ; Sumpter, Bobby G. ; Russell, Thomas P. ; Almdal, Kristoffer. / On the Morphological Behavior of ABC Miktoarm Stars Containing Poly(cis 1,4-isoprene), Poly(styrene), and Poly(2-vinylpyridine). In: Journal of Polymer Science. Part B, Polymer Physics. 2018 ; Vol. 56, No. 22. pp. 1491-1504.
    @article{2597d1f9bb1e4481949bda5509cfae43,
    title = "On the Morphological Behavior of ABC Miktoarm Stars Containing Poly(cis 1,4-isoprene), Poly(styrene), and Poly(2-vinylpyridine)",
    abstract = "Fundamental understanding of microphase separation in ABC miktoarm copolymers is vital to access a plethora of nonconventional morphologies. Miktoarm stars based on poly(cis 1,4-isoprene) (I), poly(styrene) (S), and poly(2-vinylpyridine) (V) are model systems, which allow systematic studies of the effects of composition, chemical microstructure, and temperature on the thermodynamics of microphase separation. Eleven ISV-x (I:S:V = 1:1:x, v:v:v) miktoarm copolymers were synthesized by anionic polymerization affording well-defined copolymers with a variable V arm. Equilibrium bulk morphologies of all samples, as evidenced by smallangle X-ray scattering, transmission electron microscopy (TEM), and self-consistent field theory, showed a systematic transition from lamellae (x ≈ 0–0.2) to [8.8.4] tiling (x ≈ 0.6–0.9) to cylinders inundulating lamellae (x ≈ 2–4) and, finally, to hexagonally packed core–shell cylinders (x ≈ 5–8). Chemical microstructure of the I arm [poly(cis 1,4-isoprene)] versus poly(3,4-isoprene) is shown to play important role in affecting morphological behavior. To reconcile differences between ISV-x star morphologies reported in the literature and those reported herein, even for the same composition, effects of the microstructure of I arm on the Flory–Huggins parameter between I and V arms were taken into account in a qualitative manner.",
    author = "Sergey Chernyy and Mahalik, {Jyoti P.} and Rajeev Kumar and Kirkensgaard, {Jacob Judas Kain} and Arras, {Matthias M. L.} and Hyeyoung Kim and Lars Schulte and Sokol Ndoni and Smith, {Gregory S.} and Kell Mortensen and Sumpter, {Bobby G.} and Russell, {Thomas P.} and Kristoffer Almdal",
    year = "2018",
    doi = "10.1002/polb.24733",
    language = "English",
    volume = "56",
    pages = "1491--1504",
    journal = "Journal of Polymer Science. Part B, Polymer Physics",
    issn = "0887-6266",
    publisher = "JohnWiley & Sons, Inc.",
    number = "22",

    }

    On the Morphological Behavior of ABC Miktoarm Stars Containing Poly(cis 1,4-isoprene), Poly(styrene), and Poly(2-vinylpyridine). / Chernyy, Sergey; Mahalik, Jyoti P. ; Kumar, Rajeev ; Kirkensgaard, Jacob Judas Kain; Arras, Matthias M. L. ; Kim, Hyeyoung ; Schulte, Lars; Ndoni, Sokol; Smith, Gregory S. ; Mortensen, Kell; Sumpter, Bobby G. ; Russell, Thomas P.; Almdal, Kristoffer.

    In: Journal of Polymer Science. Part B, Polymer Physics, Vol. 56, No. 22, 2018, p. 1491-1504.

    Research output: Contribution to journalJournal articleResearchpeer-review

    TY - JOUR

    T1 - On the Morphological Behavior of ABC Miktoarm Stars Containing Poly(cis 1,4-isoprene), Poly(styrene), and Poly(2-vinylpyridine)

    AU - Chernyy, Sergey

    AU - Mahalik, Jyoti P.

    AU - Kumar, Rajeev

    AU - Kirkensgaard, Jacob Judas Kain

    AU - Arras, Matthias M. L.

    AU - Kim, Hyeyoung

    AU - Schulte, Lars

    AU - Ndoni, Sokol

    AU - Smith, Gregory S.

    AU - Mortensen, Kell

    AU - Sumpter, Bobby G.

    AU - Russell, Thomas P.

    AU - Almdal, Kristoffer

    PY - 2018

    Y1 - 2018

    N2 - Fundamental understanding of microphase separation in ABC miktoarm copolymers is vital to access a plethora of nonconventional morphologies. Miktoarm stars based on poly(cis 1,4-isoprene) (I), poly(styrene) (S), and poly(2-vinylpyridine) (V) are model systems, which allow systematic studies of the effects of composition, chemical microstructure, and temperature on the thermodynamics of microphase separation. Eleven ISV-x (I:S:V = 1:1:x, v:v:v) miktoarm copolymers were synthesized by anionic polymerization affording well-defined copolymers with a variable V arm. Equilibrium bulk morphologies of all samples, as evidenced by smallangle X-ray scattering, transmission electron microscopy (TEM), and self-consistent field theory, showed a systematic transition from lamellae (x ≈ 0–0.2) to [8.8.4] tiling (x ≈ 0.6–0.9) to cylinders inundulating lamellae (x ≈ 2–4) and, finally, to hexagonally packed core–shell cylinders (x ≈ 5–8). Chemical microstructure of the I arm [poly(cis 1,4-isoprene)] versus poly(3,4-isoprene) is shown to play important role in affecting morphological behavior. To reconcile differences between ISV-x star morphologies reported in the literature and those reported herein, even for the same composition, effects of the microstructure of I arm on the Flory–Huggins parameter between I and V arms were taken into account in a qualitative manner.

    AB - Fundamental understanding of microphase separation in ABC miktoarm copolymers is vital to access a plethora of nonconventional morphologies. Miktoarm stars based on poly(cis 1,4-isoprene) (I), poly(styrene) (S), and poly(2-vinylpyridine) (V) are model systems, which allow systematic studies of the effects of composition, chemical microstructure, and temperature on the thermodynamics of microphase separation. Eleven ISV-x (I:S:V = 1:1:x, v:v:v) miktoarm copolymers were synthesized by anionic polymerization affording well-defined copolymers with a variable V arm. Equilibrium bulk morphologies of all samples, as evidenced by smallangle X-ray scattering, transmission electron microscopy (TEM), and self-consistent field theory, showed a systematic transition from lamellae (x ≈ 0–0.2) to [8.8.4] tiling (x ≈ 0.6–0.9) to cylinders inundulating lamellae (x ≈ 2–4) and, finally, to hexagonally packed core–shell cylinders (x ≈ 5–8). Chemical microstructure of the I arm [poly(cis 1,4-isoprene)] versus poly(3,4-isoprene) is shown to play important role in affecting morphological behavior. To reconcile differences between ISV-x star morphologies reported in the literature and those reported herein, even for the same composition, effects of the microstructure of I arm on the Flory–Huggins parameter between I and V arms were taken into account in a qualitative manner.

    U2 - 10.1002/polb.24733

    DO - 10.1002/polb.24733

    M3 - Journal article

    VL - 56

    SP - 1491

    EP - 1504

    JO - Journal of Polymer Science. Part B, Polymer Physics

    JF - Journal of Polymer Science. Part B, Polymer Physics

    SN - 0887-6266

    IS - 22

    ER -