Hydrolysis behavior of a precursor for bridged polysilsesquioxane 1,4-bis(triethoxysilyl)benzene: A 29Si NMR study

Hitomi Saito, Yuki Nishio, Manabu Kobayashi, Yoshiyuki Sugahara

    Research output: Contribution to journalArticle

    8 Citations (Scopus)

    Abstract

    The hydrolysis behavior of 1,4-bis(triethoxysilyl)benzene (BTB), a precursor of bridged polysilsesquioxane, was investigated with high-resolution 29Si nuclear magnetic resonance (29Si NMR) spectroscopy at ambient temperature in a system with BTB:ethanol:water:HCl = 1:10:x:0.8 × 10-4 (x = 3, 6 or 9). Signals due to hydrolyzed triethoxysilyl groups as well as unhydrolyzed triethoxysilyl groups [-Si(OEt)3, -Si(OEt)2(OH), -Si(OEt)(OH)2 and -Si(OH)3 (OEt = OCH2CH3)] formed four sub-regions based on the number of hydroxyl groups bound to a silicon atom. In addition, one silicon environment influenced the other silicon environment by an intra-molecular interaction between two silicon atoms, and each sub-region for monomeric species thus contained four signals. Based on the development of signal intensity, it is revealed that one of the two triethoxysilyl groups in BTB is hydrolyzed preferentially. Thus, when a triethoxysilyl group is hydrolyzed, the -Si(OH) x (OEt)3-x (x = 1, 2) groups formed undergo further hydrolysis, which is opposite to the tendency expected from the hydrolysis behavior of organotrialkoxysilanes under acidic conditions.

    Original languageEnglish
    Pages (from-to)51-56
    Number of pages6
    JournalJournal of Sol-Gel Science and Technology
    Volume57
    Issue number1
    DOIs
    Publication statusPublished - 2011 Jan

    Fingerprint

    Silicon
    Benzene
    hydrolysis
    Hydrolysis
    benzene
    Nuclear magnetic resonance
    nuclear magnetic resonance
    silicon
    Atoms
    Molecular interactions
    Hydroxyl Radical
    Nuclear magnetic resonance spectroscopy
    Ethanol
    magnetic resonance spectroscopy
    molecular interactions
    ambient temperature
    atoms
    polysilsesquioxane
    Water
    tendencies

    Keywords

    • Si NMR
    • Bridged polysilsesquioxane
    • Hydrolysis behavior
    • Intra-molecular interaction

    ASJC Scopus subject areas

    • Chemistry(all)
    • Condensed Matter Physics
    • Biomaterials
    • Ceramics and Composites
    • Electronic, Optical and Magnetic Materials
    • Materials Chemistry

    Cite this

    Hydrolysis behavior of a precursor for bridged polysilsesquioxane 1,4-bis(triethoxysilyl)benzene : A 29Si NMR study. / Saito, Hitomi; Nishio, Yuki; Kobayashi, Manabu; Sugahara, Yoshiyuki.

    In: Journal of Sol-Gel Science and Technology, Vol. 57, No. 1, 01.2011, p. 51-56.

    Research output: Contribution to journalArticle

    @article{7b40d3d888b5496ab35cfb7301a39ce5,
    title = "Hydrolysis behavior of a precursor for bridged polysilsesquioxane 1,4-bis(triethoxysilyl)benzene: A 29Si NMR study",
    abstract = "The hydrolysis behavior of 1,4-bis(triethoxysilyl)benzene (BTB), a precursor of bridged polysilsesquioxane, was investigated with high-resolution 29Si nuclear magnetic resonance (29Si NMR) spectroscopy at ambient temperature in a system with BTB:ethanol:water:HCl = 1:10:x:0.8 × 10-4 (x = 3, 6 or 9). Signals due to hydrolyzed triethoxysilyl groups as well as unhydrolyzed triethoxysilyl groups [-Si(OEt)3, -Si(OEt)2(OH), -Si(OEt)(OH)2 and -Si(OH)3 (OEt = OCH2CH3)] formed four sub-regions based on the number of hydroxyl groups bound to a silicon atom. In addition, one silicon environment influenced the other silicon environment by an intra-molecular interaction between two silicon atoms, and each sub-region for monomeric species thus contained four signals. Based on the development of signal intensity, it is revealed that one of the two triethoxysilyl groups in BTB is hydrolyzed preferentially. Thus, when a triethoxysilyl group is hydrolyzed, the -Si(OH) x (OEt)3-x (x = 1, 2) groups formed undergo further hydrolysis, which is opposite to the tendency expected from the hydrolysis behavior of organotrialkoxysilanes under acidic conditions.",
    keywords = "Si NMR, Bridged polysilsesquioxane, Hydrolysis behavior, Intra-molecular interaction",
    author = "Hitomi Saito and Yuki Nishio and Manabu Kobayashi and Yoshiyuki Sugahara",
    year = "2011",
    month = "1",
    doi = "10.1007/s10971-010-2323-5",
    language = "English",
    volume = "57",
    pages = "51--56",
    journal = "Journal of Sol-Gel Science and Technology",
    issn = "0928-0707",
    publisher = "Springer Netherlands",
    number = "1",

    }

    TY - JOUR

    T1 - Hydrolysis behavior of a precursor for bridged polysilsesquioxane 1,4-bis(triethoxysilyl)benzene

    T2 - A 29Si NMR study

    AU - Saito, Hitomi

    AU - Nishio, Yuki

    AU - Kobayashi, Manabu

    AU - Sugahara, Yoshiyuki

    PY - 2011/1

    Y1 - 2011/1

    N2 - The hydrolysis behavior of 1,4-bis(triethoxysilyl)benzene (BTB), a precursor of bridged polysilsesquioxane, was investigated with high-resolution 29Si nuclear magnetic resonance (29Si NMR) spectroscopy at ambient temperature in a system with BTB:ethanol:water:HCl = 1:10:x:0.8 × 10-4 (x = 3, 6 or 9). Signals due to hydrolyzed triethoxysilyl groups as well as unhydrolyzed triethoxysilyl groups [-Si(OEt)3, -Si(OEt)2(OH), -Si(OEt)(OH)2 and -Si(OH)3 (OEt = OCH2CH3)] formed four sub-regions based on the number of hydroxyl groups bound to a silicon atom. In addition, one silicon environment influenced the other silicon environment by an intra-molecular interaction between two silicon atoms, and each sub-region for monomeric species thus contained four signals. Based on the development of signal intensity, it is revealed that one of the two triethoxysilyl groups in BTB is hydrolyzed preferentially. Thus, when a triethoxysilyl group is hydrolyzed, the -Si(OH) x (OEt)3-x (x = 1, 2) groups formed undergo further hydrolysis, which is opposite to the tendency expected from the hydrolysis behavior of organotrialkoxysilanes under acidic conditions.

    AB - The hydrolysis behavior of 1,4-bis(triethoxysilyl)benzene (BTB), a precursor of bridged polysilsesquioxane, was investigated with high-resolution 29Si nuclear magnetic resonance (29Si NMR) spectroscopy at ambient temperature in a system with BTB:ethanol:water:HCl = 1:10:x:0.8 × 10-4 (x = 3, 6 or 9). Signals due to hydrolyzed triethoxysilyl groups as well as unhydrolyzed triethoxysilyl groups [-Si(OEt)3, -Si(OEt)2(OH), -Si(OEt)(OH)2 and -Si(OH)3 (OEt = OCH2CH3)] formed four sub-regions based on the number of hydroxyl groups bound to a silicon atom. In addition, one silicon environment influenced the other silicon environment by an intra-molecular interaction between two silicon atoms, and each sub-region for monomeric species thus contained four signals. Based on the development of signal intensity, it is revealed that one of the two triethoxysilyl groups in BTB is hydrolyzed preferentially. Thus, when a triethoxysilyl group is hydrolyzed, the -Si(OH) x (OEt)3-x (x = 1, 2) groups formed undergo further hydrolysis, which is opposite to the tendency expected from the hydrolysis behavior of organotrialkoxysilanes under acidic conditions.

    KW - Si NMR

    KW - Bridged polysilsesquioxane

    KW - Hydrolysis behavior

    KW - Intra-molecular interaction

    UR - http://www.scopus.com/inward/record.url?scp=79751536607&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=79751536607&partnerID=8YFLogxK

    U2 - 10.1007/s10971-010-2323-5

    DO - 10.1007/s10971-010-2323-5

    M3 - Article

    AN - SCOPUS:79751536607

    VL - 57

    SP - 51

    EP - 56

    JO - Journal of Sol-Gel Science and Technology

    JF - Journal of Sol-Gel Science and Technology

    SN - 0928-0707

    IS - 1

    ER -