Rapid ring-opening polymerization of 1,4-dioxan-2-one initiated by titanium alkoxides

Jian Bing Zeng, Madhusudhan Srinivansan, Yi Dong Li, Ramani Narayan, Yu Zhong Wang

    Research output: Contribution to journalArticle

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    Abstract

    Ring-opening polymerization of 1,4-dioxan-2-one in bulk was initiated by three titanium alkoxides, titanium dichlorodiisopropoxide (TiCl 2(OiPr)2), titanium chlorotriisopropoxide (TiCl(OiPr) 3), and titanium tetraisopropoxide (Ti(OiPr)4). The results indicate that the polymerization rate increased with number of OiPr groups in the initiator. High conversion of monomer (90%) and high molecular weight (11.9 × 104 g/mol) of resulting polymer can be achieved in only 5 min at 60 °C with Ti(OiPr)4 as an initiator. Analysis on nuclear magnetic resonance (NMR) spectra suggests the initiating sites for TiCl2(OiPr)2, TiCl(OiPr)3, and Ti(OiPr) 4 to be 1.9, 2.6, and 3.8, respectively. Coordination-insertion mechanism for the polymerization via cleavage of the acyl-oxygen bonds of the monomer was proved by NMR investigation. Kinetic studies indicate that polymerization initiated by Ti(OiPr)4 followed a first-order kinetics, with an apparent activation energy of 33.7 kJ/mol. It is noteworthy that this value is significantly lower than earlier reported values with other catalysts, namely La(OiPr)3 (50.5 kJ/mol) and Sn(Oct)2 (71.8 kJ/mol), which makes it an attractive catalyst for reactive extrusion polymerization.

    Original languageEnglish (US)
    Pages (from-to)5885-5890
    Number of pages6
    JournalJournal of Polymer Science, Part A: Polymer Chemistry
    Volume48
    Issue number24
    DOIs
    StatePublished - Dec 15 2010

    Profile

    Titanium
    Polymerization
    Ring opening polymerization
    Monomers
    Nuclear magnetic resonance
    Catalysts
    Kinetics
    Afferent Loop Syndrome
    Aerospace Medicine
    Dapsone
    Automation
    Extrusion
    Activation energy
    Molecular weight
    Oxygen
    Polymers
    Dextrothyroxine
    African Swine Fever

    Keywords

    • biocompatibility
    • biodegradable
    • poly(1,4-dioxan-2-one)
    • ring-opening polymerization
    • titanium alkoxide

    ASJC Scopus subject areas

    • Materials Chemistry
    • Polymers and Plastics
    • Organic Chemistry

    Cite this

    Rapid ring-opening polymerization of 1,4-dioxan-2-one initiated by titanium alkoxides. / Zeng, Jian Bing; Srinivansan, Madhusudhan; Li, Yi Dong; Narayan, Ramani; Wang, Yu Zhong.

    In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 48, No. 24, 15.12.2010, p. 5885-5890.

    Research output: Contribution to journalArticle

    Zeng, Jian Bing; Srinivansan, Madhusudhan; Li, Yi Dong; Narayan, Ramani; Wang, Yu Zhong / Rapid ring-opening polymerization of 1,4-dioxan-2-one initiated by titanium alkoxides.

    In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 48, No. 24, 15.12.2010, p. 5885-5890.

    Research output: Contribution to journalArticle

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    abstract = "Ring-opening polymerization of 1,4-dioxan-2-one in bulk was initiated by three titanium alkoxides, titanium dichlorodiisopropoxide (TiCl 2(OiPr)2), titanium chlorotriisopropoxide (TiCl(OiPr) 3), and titanium tetraisopropoxide (Ti(OiPr)4). The results indicate that the polymerization rate increased with number of OiPr groups in the initiator. High conversion of monomer (90%) and high molecular weight (11.9 × 104 g/mol) of resulting polymer can be achieved in only 5 min at 60 °C with Ti(OiPr)4 as an initiator. Analysis on nuclear magnetic resonance (NMR) spectra suggests the initiating sites for TiCl2(OiPr)2, TiCl(OiPr)3, and Ti(OiPr) 4 to be 1.9, 2.6, and 3.8, respectively. Coordination-insertion mechanism for the polymerization via cleavage of the acyl-oxygen bonds of the monomer was proved by NMR investigation. Kinetic studies indicate that polymerization initiated by Ti(OiPr)4 followed a first-order kinetics, with an apparent activation energy of 33.7 kJ/mol. It is noteworthy that this value is significantly lower than earlier reported values with other catalysts, namely La(OiPr)3 (50.5 kJ/mol) and Sn(Oct)2 (71.8 kJ/mol), which makes it an attractive catalyst for reactive extrusion polymerization.",
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    AU - Wang,Yu Zhong

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    AB - Ring-opening polymerization of 1,4-dioxan-2-one in bulk was initiated by three titanium alkoxides, titanium dichlorodiisopropoxide (TiCl 2(OiPr)2), titanium chlorotriisopropoxide (TiCl(OiPr) 3), and titanium tetraisopropoxide (Ti(OiPr)4). The results indicate that the polymerization rate increased with number of OiPr groups in the initiator. High conversion of monomer (90%) and high molecular weight (11.9 × 104 g/mol) of resulting polymer can be achieved in only 5 min at 60 °C with Ti(OiPr)4 as an initiator. Analysis on nuclear magnetic resonance (NMR) spectra suggests the initiating sites for TiCl2(OiPr)2, TiCl(OiPr)3, and Ti(OiPr) 4 to be 1.9, 2.6, and 3.8, respectively. Coordination-insertion mechanism for the polymerization via cleavage of the acyl-oxygen bonds of the monomer was proved by NMR investigation. Kinetic studies indicate that polymerization initiated by Ti(OiPr)4 followed a first-order kinetics, with an apparent activation energy of 33.7 kJ/mol. It is noteworthy that this value is significantly lower than earlier reported values with other catalysts, namely La(OiPr)3 (50.5 kJ/mol) and Sn(Oct)2 (71.8 kJ/mol), which makes it an attractive catalyst for reactive extrusion polymerization.

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