Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides

Bradley Seurer, Vandana Vij, Timothy Haddad, Joseph M. Mabry, Andre Lee

    Research output: Contribution to journalArticle

    • 15 Citations

    Abstract

    Thermal transitions and reaction kinetics of polyhedral oligomeric silsesquioxane (POSS) with phenylethynylphthalimide (PEPI) moieties were investigated. Specifically, this study was designed to probe the influence of the POSS peripheries, types of spacer group in between the PEPI and the SiO 1.5 core, the architecture of the PEPI arrangement with respect to the SiO1.5 core, and the number of PEPI groups per cage on the thermal transitions and the cross-linking reaction of phenylethynyl. PEPI-POSS compounds with isobutyl peripheries exhibited lower melting temperatures as compared to those with phenyl periphery, consequently these isobutyl PEPI-POSS derivatives have a higher phenylethynyl reaction rate, although the onset of reaction temperature was not significantly affected. Changing the spacer group from propyl to phenyl causes an increase in the melting transition temperature along with a higher heat of fusion at melting; however, the more rigid phenyl spacer enables the PEPI-POSS to form a higher degree of crystallinity upon cooling. The more rigid phenyl spacer also initiates the polyene reactions at lower temperatures. For POSS with PEPI attached to either side of the cage, there are two isomers with respect to the SiO1.5 core. This mixture of two isomers inhibits the formation of crystallinity as compared with the "pendent" derivative where both PEPI groups come off from the same corner of POSS cage. Finally, it was found that these PEPI-POSS molecules have reaction kinetics and onset temperatures on par with organic hexafluorophenylethynyl oligoimides, which make these PEPI-POSS molecules excellent candidates as nanocomposite additives in high performance composite applications.

    Original languageEnglish (US)
    Pages (from-to)9337-9347
    Number of pages11
    JournalMacromolecules
    Volume43
    Issue number22
    DOIs
    StatePublished - Nov 23 2010

    Profile

    Hot Temperature
    Acetanilides
    Benin
    Reaction kinetics
    Temperature
    Cross Circulation
    Hematopoiesis
    Motor Activity
    Molecules
    Isomers
    Melting point
    Derivatives
    Accidental Falls
    Laryngeal Mucosa
    Octanols
    Amputees
    Agglutination Tests
    Pneumocystis Pneumonia
    Fusion reactions
    Composite materials

    ASJC Scopus subject areas

    • Organic Chemistry
    • Materials Chemistry
    • Polymers and Plastics
    • Inorganic Chemistry

    Cite this

    Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides. / Seurer, Bradley; Vij, Vandana; Haddad, Timothy; Mabry, Joseph M.; Lee, Andre.

    In: Macromolecules, Vol. 43, No. 22, 23.11.2010, p. 9337-9347.

    Research output: Contribution to journalArticle

    Seurer, Bradley; Vij, Vandana; Haddad, Timothy; Mabry, Joseph M.; Lee, Andre / Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides.

    In: Macromolecules, Vol. 43, No. 22, 23.11.2010, p. 9337-9347.

    Research output: Contribution to journalArticle

    @article{eb71d572e912415094fbe80edb3310d8,
    title = "Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides",
    abstract = "Thermal transitions and reaction kinetics of polyhedral oligomeric silsesquioxane (POSS) with phenylethynylphthalimide (PEPI) moieties were investigated. Specifically, this study was designed to probe the influence of the POSS peripheries, types of spacer group in between the PEPI and the SiO 1.5 core, the architecture of the PEPI arrangement with respect to the SiO1.5 core, and the number of PEPI groups per cage on the thermal transitions and the cross-linking reaction of phenylethynyl. PEPI-POSS compounds with isobutyl peripheries exhibited lower melting temperatures as compared to those with phenyl periphery, consequently these isobutyl PEPI-POSS derivatives have a higher phenylethynyl reaction rate, although the onset of reaction temperature was not significantly affected. Changing the spacer group from propyl to phenyl causes an increase in the melting transition temperature along with a higher heat of fusion at melting; however, the more rigid phenyl spacer enables the PEPI-POSS to form a higher degree of crystallinity upon cooling. The more rigid phenyl spacer also initiates the polyene reactions at lower temperatures. For POSS with PEPI attached to either side of the cage, there are two isomers with respect to the SiO1.5 core. This mixture of two isomers inhibits the formation of crystallinity as compared with the {"}pendent{"} derivative where both PEPI groups come off from the same corner of POSS cage. Finally, it was found that these PEPI-POSS molecules have reaction kinetics and onset temperatures on par with organic hexafluorophenylethynyl oligoimides, which make these PEPI-POSS molecules excellent candidates as nanocomposite additives in high performance composite applications.",
    author = "Bradley Seurer and Vandana Vij and Timothy Haddad and Mabry, {Joseph M.} and Andre Lee",
    year = "2010",
    month = "11",
    doi = "10.1021/ma101640q",
    volume = "43",
    pages = "9337--9347",
    journal = "Macromolecules",
    issn = "0024-9297",
    publisher = "American Chemical Society",
    number = "22",

    }

    TY - JOUR

    T1 - Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides

    AU - Seurer,Bradley

    AU - Vij,Vandana

    AU - Haddad,Timothy

    AU - Mabry,Joseph M.

    AU - Lee,Andre

    PY - 2010/11/23

    Y1 - 2010/11/23

    N2 - Thermal transitions and reaction kinetics of polyhedral oligomeric silsesquioxane (POSS) with phenylethynylphthalimide (PEPI) moieties were investigated. Specifically, this study was designed to probe the influence of the POSS peripheries, types of spacer group in between the PEPI and the SiO 1.5 core, the architecture of the PEPI arrangement with respect to the SiO1.5 core, and the number of PEPI groups per cage on the thermal transitions and the cross-linking reaction of phenylethynyl. PEPI-POSS compounds with isobutyl peripheries exhibited lower melting temperatures as compared to those with phenyl periphery, consequently these isobutyl PEPI-POSS derivatives have a higher phenylethynyl reaction rate, although the onset of reaction temperature was not significantly affected. Changing the spacer group from propyl to phenyl causes an increase in the melting transition temperature along with a higher heat of fusion at melting; however, the more rigid phenyl spacer enables the PEPI-POSS to form a higher degree of crystallinity upon cooling. The more rigid phenyl spacer also initiates the polyene reactions at lower temperatures. For POSS with PEPI attached to either side of the cage, there are two isomers with respect to the SiO1.5 core. This mixture of two isomers inhibits the formation of crystallinity as compared with the "pendent" derivative where both PEPI groups come off from the same corner of POSS cage. Finally, it was found that these PEPI-POSS molecules have reaction kinetics and onset temperatures on par with organic hexafluorophenylethynyl oligoimides, which make these PEPI-POSS molecules excellent candidates as nanocomposite additives in high performance composite applications.

    AB - Thermal transitions and reaction kinetics of polyhedral oligomeric silsesquioxane (POSS) with phenylethynylphthalimide (PEPI) moieties were investigated. Specifically, this study was designed to probe the influence of the POSS peripheries, types of spacer group in between the PEPI and the SiO 1.5 core, the architecture of the PEPI arrangement with respect to the SiO1.5 core, and the number of PEPI groups per cage on the thermal transitions and the cross-linking reaction of phenylethynyl. PEPI-POSS compounds with isobutyl peripheries exhibited lower melting temperatures as compared to those with phenyl periphery, consequently these isobutyl PEPI-POSS derivatives have a higher phenylethynyl reaction rate, although the onset of reaction temperature was not significantly affected. Changing the spacer group from propyl to phenyl causes an increase in the melting transition temperature along with a higher heat of fusion at melting; however, the more rigid phenyl spacer enables the PEPI-POSS to form a higher degree of crystallinity upon cooling. The more rigid phenyl spacer also initiates the polyene reactions at lower temperatures. For POSS with PEPI attached to either side of the cage, there are two isomers with respect to the SiO1.5 core. This mixture of two isomers inhibits the formation of crystallinity as compared with the "pendent" derivative where both PEPI groups come off from the same corner of POSS cage. Finally, it was found that these PEPI-POSS molecules have reaction kinetics and onset temperatures on par with organic hexafluorophenylethynyl oligoimides, which make these PEPI-POSS molecules excellent candidates as nanocomposite additives in high performance composite applications.

    UR - http://www.scopus.com/inward/record.url?scp=78651280728&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=78651280728&partnerID=8YFLogxK

    U2 - 10.1021/ma101640q

    DO - 10.1021/ma101640q

    M3 - Article

    VL - 43

    SP - 9337

    EP - 9347

    JO - Macromolecules

    T2 - Macromolecules

    JF - Macromolecules

    SN - 0024-9297

    IS - 22

    ER -