Cited by 95biodegradable polymer synthesis and propertiesOrganometallic Complex Synthesis and CatalysisCarbon dioxide utilization in catalysis

Synthesis and Structural Studies of Heterobimetallic Alkoxide Complexes Supported by Bis(phenolate) Ligands: Efficient Catalysts for Ring-Opening Polymerization of l -Lactide

Chen, Hsuan-Ying, Liu, Mei-Yu, Sutar, Alekha Kumar, Lin, Chu-Chieh·2010·Inorganic Chemistry

Abstract

A series of heterobimetallic titanium(IV) complexes [LTi(O(i)Pr)(mu-O(i)Pr)(2)Li(THF)(2)], [LTi(O(i)Pr)(mu-O(i)Pr)(2)Na(THF)(2)], [LTi(mu-O(i)Pr)(2)Zn(O(i)Pr)(2)], and [LTi(mu-O(i)Pr)(2)Mg(O(i)Pr)(2)] (where L = bidentate bisphenol ligands) have been synthesized and characterized including a structural determination of [L(1)Ti(mu(2)-O(i)Pr)(2)(O(i)Pr)Li(THF)(2)] (1a). These complexes were investigated for their utility in the ring-opening polymerization (ROP) of l-lactide (LA). Polymerization activities have been shown to correlate with the electronic properties of the substituent within the bisphenol ligand. In contrast to monometallic titanium initiator 1e, all the heterobimetallic titanium initiators (Ti-Li, Ti-Na, Ti-Zn, and Ti-Mg) show enhanced catalytic activity toward ring-opening polymerization (ROP) of l-LA. In addition, the use of electron-donating methoxy or methylphenylsulfonyl functional ligands reveals the highest activity. The bisphenol bimetallic complexes give rise to controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number-average molecular weight. The polymerization kinetics using 2c as an initiator were also studied, and the experimental results indicate that the reaction rate is first-order with respect to both monomer and catalyst concentration with a polymerization rate constant, k = 81.64 M(-1) min(-1).

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Crossref · 10.1021/ic901938e

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Authors
Chen, H.-Y., Liu, M.-Y., Sutar, A. K., & Lin, C.-C.
Affiliations
  • National Chung Hsing University (TW)
  • Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan, Republic of China
Corresponding author
Lin, Chu-Chieh
Venue
Inorganic Chemistry
Published
2009-12-16
Volume
49
Issue
2
Pages
665-674
ISSN
  • 0020-1669 (ISSN-L)
  • 1520-510X
OpenAlex
W1967491248
Cited by
95
References
85
Citations by year
2026: 1 · 2024: 4 · 2023: 3 · 2022: 5 · 2021: 3 · 2020: 8 · 2019: 2 · 2018: 6 · 2017: 8 · 2016: 11 · 2015: 7 · 2014: 6 · 2013: 14 · 2012: 8
FWCI
2.49
Type
journal article
Language
en
Open access
closed
Locations
  • Inorganic Chemistry (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
  • Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
Keywords
ring-opening polymerization, L-lactide, poly(L-lactic acid), controlled ring-opening polymerization, polymerization kinetics, polymerization rate constants, ligand electronic effects, polymerization activity
MeSH terms
Catalysis, Dioxanes, Models, Molecular, Phenols, Polyesters, Titanium, Molecular Structure

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