A Highly Efficient Initiator for the Ring-Opening Polymerization of Lactides and ε-Caprolactone: A Kinetic Study
Abstract
A trinuclear zinc alkoxide [{(BDI-OMe)Zn(μ-OBn)} 2 Zn(μ-OBn) 2 ] ( 1 ) and a homoleptic zinc complex [(BDI-OMe) 2 Zn] ( 2 ) have been prepared by the addition of benzyl alcohol to a mixture of BDI-OMe-H with Et 2 Zn. Compound 1 has been employed as an initiator for ring-opening polymerization of lactides and ε-caprolactone. The highly efficient initiator of the zinc complex shown in the polymerization process enabled us to synthesize the PLA at ambient temperature, yielding PLA with well molecular control and narrow molecular weight distribution in a very short period of time. The polymerization kinetics were studied with [LA] 0 /[ 1 ] = 200/1 and [LA] 0 = 0.5 M at 25 °C. Experimental results indicate a second-order dependency on [LA] ( k obs = 0.033 M -1 s -1 ). Moreover, a first-order dependency in [ 1 ] is indicated of k obs vs [Initiator], with a slope equal to the first-order rate constant k = 12.2 M -2 s -1 . Furthermore, the heterotactic PLA with Pr up to 83% can be achieved in a mixed solvent of CH 2 Cl 2 and THF at −35 °C. However, according to polymerization kinetic studies of CL, a first-order dependency on [CL] and [ 1 ] is observed for ROP of ε-caprolactone.
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Especially with catalysts based on Al, Mg and Zn, the rate of homopolymerisation of CL is often much faster than that of (l-LA)2.
“Especially with catalysts based on Al, Mg and Zn, the rate of homopolymerisation of CL is often much faster than that of (l-LA)2.82”
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- Authors
- Chen, H.-Y., Huang, B.-H., & Lin, C.-C.
- Affiliations
- National Chung Hsing University (TW)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2005-05-28
- Volume
- 38
- Issue
- 13
- Pages
- 5400-5405
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2064824669
- Cited by
- 166
- References
- 52
- Citations by year
- 2026: 2 · 2025: 3 · 2024: 3 · 2023: 4 · 2022: 7 · 2021: 9 · 2020: 2 · 2019: 6 · 2018: 3 · 2017: 5 · 2016: 10 · 2015: 10 · 2014: 9 · 2013: 13 · 2012: 13
- FWCI
- 4.43
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemical Engineering › Process Chemistry and Technology › Carbon dioxide utilization in catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- ring-opening polymerization, lactide, ε-caprolactone, poly(L-lactic acid), trinuclear zinc complex, polymerization kinetics, second-order kinetics, molecular weight distribution, ambient temperature polymerization
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