Preparation of High-Molecular-Weight Aliphatic Polycarbonates by Condensation Polymerization of Diols and Dimethyl Carbonate
Abstract
A synthetic strategy was developed for the condensation polymerization of aliphatic diols with dimethyl carbonate to produce high-molecular-weight aliphatic polycarbonates. In the first step, oligomers were formed bearing almost equal numbers of hydroxyl and methyl carbonate end-groups. In the second step, the condensation reaction was conducted at a high temperature (>180 °C) to connect the −OH and −OC(O)OCH 3 chain-ends while removing the generated methanol under reduced pressure. Small amounts of sodium alkoxide (0.02–0.5 mol %) were used as a catalyst. Using an anhydrous diol was crucial for increasing the reaction rate and also for obtaining reproducible results. In the second step, the pressure was gradually reduced and the temperature was optimized, in order to minimize side products. Using this strategy, high-molecular-weight poly(1,4-butylene carbonate) (PBC) and its copolymers incorporating various other diols (2–10 mol %) were prepared, with weight-average molecular weight ( M w ) of 100 000–200 000, in a short reaction time, totaling 6.5 h. This strategy was also effective for producing other high-molecular-weight aliphatic polycarbonates ( M w ∼ 200 000) using 1,6-hexanediol and cyclohexane-1,4-dimethanol. When the [−OH]/[−OCH 3 ] ratio of the oligomers generated in the first step deviated from ∼1, it was hard to attain such a high molecular weight.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The crystallinity and biodegradation rate of poly(alkylene carbonates) can be adjusted by employing diols with different chain lengths.
“The crystallinity and biodegradation rate of poly(alkylene carbonates) can be adjusted by employing diols with different chain lengths.215,216”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [215]
The two-stage procedure has enabled the synthesis of polyesters and polycarbonates with molecular weights over 50 kDa.
“This two-stage procedure has enabled the synthesis of polyesters and polycarbonates with molecular weights over 50 kDa.215,223”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [215]
Cites
Coates, G. W., & Moore, D. R. (2004) · Angewandte Chemie International Edition · doi:10.1002/anie.200460442 · Cited by 1,154 · see citing works
The synthesis of organic carbonates from carbon dioxide
Sakakura, T., & Kohno, K. (2009) · Chemical Communications · doi:10.1039/b819997c · Cited by 1,067 · see citing works
CO2 Copolymers from Epoxides: Catalyst Activity, Product Selectivity, and Stereochemistry Control
Lu, X., Ren, W., & Wu, G. (2012) · Accounts of Chemical Research · doi:10.1021/ar300035z · Cited by 654 · see citing works
A novel non-phosgene polycarbonate production process using by-product CO 2 as starting material
Fukuoka, S., Kawamura, M., Komiya, K., Tojo, M., Hachiya, H., Hasegawa, K., Aminaka, M., Okamoto, H., Fukawa, I., & Konno, S. (2003) · Green Chemistry · doi:10.1039/b304963a · Cited by 471 · see citing works
Construction of functional aliphatic polycarbonates for biomedical applications
Feng, J., Zhuo, R., & Zhang, X. (2011) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2011.07.008 · Cited by 358 · see citing works
A Highly Active and Recyclable Catalytic System for CO2/Propylene Oxide Copolymerization
Sujith, S., Min, J. K., Seong, J. E., Na, S. J., & Lee, B. Y. (2008) · Angewandte Chemie International Edition · doi:10.1002/anie.200801852 · Cited by 330 · see citing works
Self-citationWhat's new with CO2? Recent advances in its copolymerization with oxiranes
Darensbourg, D. J., & Poland, S. J. (2012) · Green Chemistry · doi:10.1039/c2gc35928f · Cited by 318 · see citing works
Kember, M. R., & Williams, C. K. (2012) · Journal of the American Chemical Society · doi:10.1021/ja307096m · Cited by 303 · see citing works
Kerres, J. A., Cui, W. L., & Reichle, S. (1996) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/(sici)1099-0518(19960915)34:12 · Cited by 205 · see citing works
Pêgo, A. P., Poot, A. A., Grijpma, D. W., & Feijen, J. (2001) · Journal of Biomaterials Science Polymer Edition · doi:10.1163/156856201744434 · Cited by 189 · see citing works
Nakano, K., Kobayashi, K., & Nozaki, K. (2011) · Journal of the American Chemical Society · doi:10.1021/ja203382q · Cited by 183 · see citing works
Cyriac, A., Lee, S. H., Varghese, J. K., Park, E. S., Park, J. H., & Lee, B. Y. (2010) · Macromolecules · doi:10.1021/ma101259k · Cited by 161 · see citing works
Self-citationSuriano, F., Coulembier, O., Hedrick, J. L., & Dúbois, P. (2010) · Polymer Chemistry · doi:10.1039/c0py00211a · Cited by 157 · see citing works
Zhu, W., Huang, X., Li, C., Xiao, Y., Zhang, D., & Guan, G. (2011) · Polymer International · doi:10.1002/pi.3043 · Cited by 142 · see citing works
Cobaltoporphyrin-Catalyzed CO2/Epoxide Copolymerization: Selectivity Control by Molecular Design
Anderson, C. E., Vagin, S. I., Xia, W., et al. (2012) · Macromolecules · doi:10.1021/ma301205g · Cited by 118 · see citing works
Nishioka, K., Goto, H., & Sugimoto, H. (2012) · Macromolecules · doi:10.1021/ma301696d · Cited by 95 · see citing works
Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions
Naik, P. U., Refes, K., Sadaka, F., Brachais, C., Boni, G., Couvercelle, J., Picquet, M., & Plasseraud, L. (2012) · Polymer Chemistry · doi:10.1039/c2py20056b · Cited by 75 · see citing works
Pokharkar, V (1995) · Polymer · doi:10.1016/00323-8619(59)9302b- · Cited by 73 · see citing works
Yamamoto, Y., Kaihara, S., Toshima, K., et al. (2009) · Macromolecular Bioscience · doi:10.1002/mabi.200900039 · Cited by 67 · see citing works
Controlled Lipase-Catalyzed Synthesis of Poly(hexamethylene carbonate)
Jiang, Z., Liu, C., Xie, W., & Gross, R. A. (2007) · Macromolecules · doi:10.1021/ma070665m · Cited by 65 · see citing works
Brignou, P., Guillaume, S. M., Roisnel, T., Bourissou, D., & Carpentier, J. (2012) · Chemistry - A European Journal · doi:10.1002/chem.201200336 · Cited by 63 · see citing works
Thermal degradation mechanism of poly(butylene carbonate)
Zhu, W., Li, C., Zhang, D., Guan, G., Xiao, Y., & Zheng, L. (2012) · Polymer Degradation and Stability · doi:10.1016/j.polymdegradstab.2012.06.029 · Cited by 50 · see citing works
Synthesis of linear aliphatic polycarbonate macroglycols using dimethylcarbonate
Foy, E., Farrell, J. B., & Higginbotham, C. L. (2008) · Journal of Applied Polymer Science · doi:10.1002/app.28887 · Cited by 44 · see citing works
Multistage melt polymerization of bisphenol‐A and diphenyl carbonate to polycarbonate
Kim, Y., & Choi, K. Y. (1993) · Journal of Applied Polymer Science · doi:10.1002/app.1993.070490501 · Cited by 43 · see citing works
Kricheldorf, H. R., & Mahler, A. (1996) · Polymer · doi:10.1016/0032-3861(96)00288-1 · Cited by 42 · see citing works
Zhu, W., Zhou, W., Li, C., Xiao, Y., Zhang, D., Guan, G., & Wang, D. (2011) · Journal of Macromolecular Science Part A · doi:10.1080/15226514.2011.586264 · Cited by 39 · see citing works
Liu, C., Jiang, Z., Decatur, J. D., Xie, W., & Gross, R. A. (2011) · Macromolecules · doi:10.1021/ma102899c · Cited by 31 · see citing works
Feng, Y. X., Yin, N., Li, Q. F., et al. (2008) · Industrial & Engineering Chemistry Research · doi:10.1021/ie070759k · Cited by 30 · see citing works
Thermal degradation mechanism of poly(butylene carbonate)
朱文祥, & 李春成 (2012) · Cited by 28 · see citing works
Reactions of Phosphines with Cyclic Carbonate Esters
Keough, P. T., & Grayson, M. (1962) · The Journal of Organic Chemistry · doi:10.1021/jo01052a082 · Cited by 20 · see citing works
(2010) · Filtration Industry Analyst · doi:10.1016/s1365-6937(10)70074-5 · Cited by 6 · see citing works
India Interprets Drug Patenting
TREMBLAY, J.-F. (2012) · Chemical & Engineering News · doi:10.1021/cen-09019-bus1 · Cited by 2 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Catalysis as an Enabling Science for Sustainable Polymers
Zhang, X., Fevre, M., Jones, G. O., & Waymouth, R. M. (2018) · Chemical Reviews · doi:10.1021/acs.chemrev.7b00329 · Cited by 936 · see citing works
Direct Copolymerization of CO2 and Diols
Tamura, M., Ito, K., Honda, M., Nakagawa, Y., Sugimoto, H., & Tomishige, K. (2016) · Scientific Reports · doi:10.1038/srep24038 · Cited by 122 · see citing works
Gregory, G. L., Ulmann, M., & Buchard, A. (2015) · RSC Advances · doi:10.1039/c5ra07290e · Cited by 87 · see citing works
Chen, Z., Hadjichristidis, N., Feng, X., & Gnanou, Y. (2016) · Polymer Chemistry · doi:10.1039/c6py00783j · Cited by 44 · see citing works
Zhang, J., Zhu, W., Li, C., Zhang, D., Xiao, Y., Guan, G., & Zheng, L. (2015) · RSC Advances · doi:10.1039/c4ra10466h · Cited by 40 · see citing works
Bian, S., Pagan, C., Andrianova “Artemyeva”, A. A., & Du, G. (2016) · ACS Omega · doi:10.1021/acsomega.6b00278 · Cited by 38 · see citing works
Sun, J., Aly, K. I., & Kuckling, D. (2017) · RSC Advances · doi:10.1039/c7ra01317e · Cited by 34 · see citing works
- Authors
- Park, J. H., Jeon, J. Y., Lee, J. J., Jang, Y., Varghese, J. K., & Lee, B. Y.
- Affiliations
- Ajou University (KR)
- Corresponding author
- Lee, Bun Yeoul
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2013-04-16
- Volume
- 46
- Issue
- 9
- Pages
- 3301-3308
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2319976091
- Cited by
- 158
- References
- 32
- Citations by year
- 2026: 10 · 2025: 11 · 2024: 12 · 2023: 13 · 2022: 15 · 2021: 6 · 2020: 7 · 2019: 17 · 2018: 15 · 2017: 20 · 2016: 12 · 2015: 10 · 2014: 6 · 2013: 4
- FWCI
- 4.07
- 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
- aliphatic polycarbonates, polycondensation, dimethyl carbonate, aliphatic diols, high molecular weight, 1,6-hexanediol, copolymers, methanol removal
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
