Reverse orders of reactivities in the polymerization of cyclic esters using N 2 O 2 aluminium alkoxide complexes
Abstract
Three aluminium alkoxide complexes containing N(2)O(2) bis(phenoxy)-amine ligands were synthesized from reactions of the corresponding N(2)O(2) ligands with Al(O(i)Pr)(3) in toluene. Different amine side chains of the ligands included pyridine (1), CH(2)NMe(2) (2), and CH(2)NEt(2) (3). The related chloro aluminium analog (4) was prepared from a reaction between AlCl(3) and the potassium salt of the N(2)O(2) ligand having CH(2)NMe(2) side chain. X-Ray crystallography reveals that complexes 3 and 4 have a monomeric five-coordinate aluminium center. Complexes 1-3 catalyzed the polymerization of epsilon-caprolactone (epsilon-CL) at 70 degrees C in toluene with the relative reactivities of 1<2< 3. In contrary, only complex 1 was active for the polymerization of lactide under the same polymerization conditions. (1)H NMR spectroscopy shows that treatment of 2 with 1 equivalent of lactide afforded the ring-opened product L(2)Al-OCH(Me)C(O)OCH(Me)C(O)O(i)Pr. Electronic effects are believed to be responsible for the observed trend in the epsilon-CL polymerization rates. On the other hand, steric hindrance at the amine side chain is the main contributor to the observed rates of lactide polymerization.
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It has been reported that reaction rates of monomers can differ in the presence of other comonomers.
“It has been reported that the reaction rates of monomers can differ in the presence of other comonomers.12,13,81”
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- Authors
- Phomphrai, K., Chumsaeng, P., Sangtrirutnugul, P., Kongsaeree, P., & Pohmakotr, M.
- Affiliations
- Mahidol University (TH)
- Corresponding author
- Phomphrai, Khamphee
- ORCID
- Venue
- Dalton Trans.
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2010
- Volume
- 39
- Issue
- 7
- Pages
- 1865-1871
- ISSN
- 1477-9226 (ISSN-L)
- 1477-9234
- OpenAlex
- W2004710638
- Cited by
- 49
- References
- 22
- Citations by year
- 2025: 1 · 2024: 2 · 2023: 3 · 2022: 4 · 2021: 1 · 2020: 1 · 2019: 4 · 2018: 5 · 2017: 5 · 2016: 1 · 2015: 4 · 2014: 5 · 2013: 5 · 2012: 4
- FWCI
- 1.17
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Dalton Transactions (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Thailand Research Fund
- Commission on Higher Education
- Center of Excellence for Innovation in Chemistry
- 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
- cyclic ester polymerization, ε-caprolactone, lactide, ring-opening polymerization, catalytic activity, steric hindrance, electronic effects, pyridine ligands
- MeSH terms
- Aluminum, Cyclization, Esters, Models, Molecular, Nitrogen Oxides, Organometallic Compounds, Stereoisomerism, Molecular Structure, Crystallography, X-Ray
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