Metal- and Organo-Catalyzed Ring-Opening Polymerization of α-Methyl-Trimethylene Carbonate: Insights into the Microstructure of the Polycarbonate
Abstract
“Immortal” ring-opening polymerization (iROP) of rac -4-methyl-1,3-dioxan-2-one (α-methyl trimethylene carbonate, α-MeTMC) has been carried out using various catalysts combined with an alcohol acting as a co-initiator and a chain transfer agent. The Lewis acid Al(OTf) 3, the metallo-organic β-diiminate [(BDI)Zn(N(SiMe 3 ) 2 )] (BDI i Pr = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)-imino)-2-pentene) complex, or the organic bases, 2- tert -butylimino-2-diethylamino-1,3dimethylperhydro-1,3,2diazaphosphorine (BEMP), 1.5.7-triazabicyclo-[4.4.0]dec-5-ene (TBD) and 4- N, N -dimethylaminopyridine (DMAP), successfully afforded the corresponding poly(α-MeTMC)s with quite good control and activities. In comparison, at 110 °C, these same catalytic systems were more active toward the iROP of native TMC, whereas the iROP of the seven-membered analogue α-Me7CC generally featured a poorer control. The dissymmetry of α-MeTMC raises the question of catalyst selectivity in the ROP process. Detailed microstructural analyses of the poly(α-MeTMC)s using 1 H and 13 C NMR revealed (1) the preferential ring-opening at the most hindered oxygen–acyl O–C(O)O bond, i.e., closest to the α-Me substituent of the zinc-based system, in the iROP of α-MeTMC, possibly as a result of the favorable steric hindrance; (2) the absence of regioselectivity of the aluminum or guanidine catalyst systems. In addition, MALDI–ToF–MS analyses confirmed the expected α-hydroxy,ω-alkoxyester chain-ends in these polymers. DSC analyses revealed a glass transition temperature of the poly(α-MeTMC)s ( T g ≈ −17 °C) similar to that of poly(TMC)s.
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This zinc catalyst showed exceptionally high regioselectivity (<1% regio-defects) for the ROP of methyl-substituted cyclic carbonates.
“In addition, this catalyst showed exceptionally high regioselectivity (< 1% regio-defects) for the ROP of methyl-substituted cyclic carbonates.298”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [298]
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- Authors
- Brignou, P., Carpentier, J.-F., & Guillaume, S. M.
- Affiliations
- Centre National de la Recherche Scientifique (FR)
- Corresponding author
- Guillaume, Sophie M.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2011-06-15
- Volume
- 44
- Issue
- 13
- Pages
- 5127-5135
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2325943047
- Cited by
- 56
- References
- 22
- Citations by year
- 2026: 4 · 2025: 6 · 2024: 1 · 2023: 2 · 2022: 4 · 2021: 4 · 2020: 3 · 2019: 1 · 2018: 3 · 2017: 2 · 2016: 2 · 2015: 6 · 2014: 5 · 2013: 3 · 2012: 8
- FWCI
- 2.36
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- HAL (submittedVersion)
- 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, aluminum triflate, guanidine catalysts, regioselectivity, steric hindrance, glass transition temperature
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