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.

LanguageEnglish (US)
Pages5885-5890
Number of pages6
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume48
Issue number24
DOIs
StatePublished - Dec 15 2010

Profile

Ring opening polymerization
Titanium
Polymerization
Monomers
Nuclear magnetic resonance
Catalysts
Kinetics
Extrusion
Polymers
Activation energy
Molecular weight
Oxygen
4-dioxanone

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. 2010 ; Vol. 48, No. 24. pp. 5885-5890
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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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