Combination of Ring-Opening Polymerization and “Click Chemistry”: Toward Functionalization and Grafting of Poly(ε-caprolactone)
Abstract
A straightforward strategy is proposed for the derivatization of poly(ε-caprolactone) (PCL). First, statistical copolymerization of α-chloro-ε-caprolactone (αClεCL) with ε-caprolactone (εCL) was initiated by 2,2-dibutyl-2-stanna-1,3-dioxepane (DSDOP). In a second step, pendent chlorides were converted into azides by reaction with sodium azide. Finally, duly substituted terminal alkynes were reacted with pendent azides by copper-catalyzed Huisgen's 1,3-dipolar cycloaddition, thus a “click” reaction. According to this strategy, pendent hydroxyl and acrylate groups and atom transfer radical polymerization (ATRP) initiators were successfully attached to PCL. Similarly, amphiphilic graft copolymers were prepared by cycloaddition of an alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents of the copolyester. The dependence of the grafting yield on the experimental conditions of the “click” reaction, i.e., temperature, solvent, and catalyst, was investigated. This strategy is very versatile because a large variety of aliphatic polyesters can be easily synthesized from a single precursor, easily prepared from commercially available compounds, merely by changing the alkyne involved in the Huisgen's 1,3-dipolar cycloaddition. Last but not least, PCL subsituted by azide groups does not have to be isolated after substitution of chlorides by sodium azide, and the “click” reaction can be carried out in a “one-pot” process.
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?
PCL-g-PEO were synthesized by reaction of an alkyne end-group of PEO with poly(αN3εCL-co-εCL); grafting efficiency was approximately 30%, in line with yield reported for ATRA, and no degradation was detected.
“PCL-g-PEO were also synthesized by reaction of an alkyne end-group of PEO (ω-alkyne-PEO) with poly(αN 3 εCL-co-εCL).The grafting efficiency was approximately 30% in line with the yield reported for ATRA.Importantly, no degradation was detected.”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [153]
The cycloaddition was complete in THF when poly(αN3εCL) homopolymer (Mn=46,000; Mw/Mn=1.6) was reacted with propargyl benzoate.
“Indeed, the aforementioned cycloaddition was complete in THF when poly(αN 3 εCL) homopolymer (Mn=46,000 ; Mw/Mn=1.6) was reacted with propargyl benzoate.”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [153]
In a representative example, poly(αClεCL-co-εCL) (Mn=22,000; Mw/Mn=1.5) was reacted with 5 equivalents of sodium azide in DMF at room temperature overnight; then 5 equivalents of propargyl benzoate were added and the click reaction was quantitative at 35 °C for 3 h; a slight increase in polydispersity index was observed (Mw/Mn=1.7).
“In a representative example, poly (αClεCL-co-εCL) (Mn=22,000 ; Mw/Mn= 1.5) was reacted with 5 equivalents of sodium azide in DMF at room temperature overnight.5 equivalents of propargyl benzoate were then added to the reaction mixture, and the “click” reaction was quantitative at 35 °C for 3 h.A slight increase in the polydispersity index was observed (Mw/Mn= 1.7).”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [153]
Cycloaddition of both propargyl benzoate mediated by CuI and triethylamine and 3-dimethylaminoethyl-1-propyne mediated by CuI turned out to be quantitative with no significant degradation.
“Cycloaddition of both propargyl benzoate mediated by Cul and triethylamine (NEt 3 ) and 3-dimethylaminoethyl-1-propyne mediated by Cul turned out to be quantitative with no significant degradation [153] (Scheme 16).”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [153]
Polycationic polyesters were prepared by using N,N,N-triethylammonium propargyl bromide as the alkyne reagent.
“Indeed, polycationic polyesters were prepared by using N,N,N-triethylammonium propargyl bromide as the alkyne reagent.”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [153]
Poly(αClεCL-co-εCL) can be quantitatively converted into azides, followed by click reaction with functional alkynes.
“Riva et al. described that poly(αClεCL-co-εCL) can be quantitatively converted into azides, followed by “click” reaction with functional alkynes (Scheme 16) [153].”
From Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆ (2008) · cites this paper as [153]
Cites
Gautier, S., D'Aloia, V., Halleux, O., Mazza, M., Lecomte, P., & Jérôme, R. (2003) · Journal of Biomaterials Science, Polymer Edition · doi:10.1163/15685620360511146 · Cited by 49 · see citing works
Self-citationRiva, R., Rieger, J., Jérôme, R., & Lecomte, P. (2006) · Journal of Polymer Science Part A: Polymer Chemistry · doi:10.1002/pola.21674 · Cited by 48 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆
JEROME, C., & LECOMTE, P. (2008) · Advanced Drug Delivery Reviews · doi:10.1016/j.addr.2008.02.008 · Cited by 590 · see citing works
Self-citationFunctional aliphatic polyesters for biomedical and pharmaceutical applications
Seyednejad, H., Ghassemi, A. H., van Nostrum, C. F., Vermonden, T., & Hennink, W. E. (2011) · Journal of Controlled Release · doi:10.1016/j.jconrel.2010.12.016 · Cited by 425 · see citing works
Recent Developments in Ring-Opening Polymerization of Lactones
Lecomte, P., & Jérôme, C. (2011) · Advances in Polymer Science · doi:10.1007/12_2011_144 · Cited by 163 · see citing works
Self-citationYu, Y., Chen, C.-K., Law, W.-C., Weinheimer, E., Sengupta, S., Prasad, P. N., & Cheng, C. (2014) · Biomacromolecules · doi:10.1021/bm401471p · Cited by 134 · see citing works
Santoro, O., Zhang, X., & Redshaw, C. (2020) · Catalysts · doi:10.3390/catal10070800 · Cited by 111 · see citing works
Design of reversibly core cross-linked micelles sensitive to reductive environment
Cajot, S., Lautram, N., Passirani, C., & Jérôme, C. (2011) · Journal of Controlled Release · doi:10.1016/j.jconrel.2011.03.026 · Cited by 76 · see citing works
Self-citationContribution of click chemistry to the synthesis of antimicrobial aliphatic copolyester
Riva, R., Lussis, P., Lenoir, S., Jérôme, C., Jérôme, R., & Lecomte, P. (2008) · Polymer · doi:10.1016/j.polymer.2008.03.008 · Cited by 57 · see citing works
Self-citationSun, L., Shen, L., Zhu, M., Dong, C., & Wei, Y. (2010) · Journal of Polymer Science Part A: Polymer Chemistry · doi:10.1002/pola.24255 · Cited by 40 · see citing works
- Authors
- Riva, R., Schmeits, S., Jérôme, C., Jérôme, R., & Lecomte, P.
- Affiliations
- University of Liège (BE)
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2007-01-17
- Volume
- 40
- Issue
- 4
- Pages
- 796-803
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2089394496
- Cited by
- 253
- References
- 2
- Citations by year
- 2026: 3 · 2025: 4 · 2024: 6 · 2023: 2 · 2022: 7 · 2021: 6 · 2020: 4 · 2019: 9 · 2018: 6 · 2017: 7 · 2016: 10 · 2015: 13 · 2014: 15 · 2013: 16 · 2012: 24
- FWCI
- 16.04
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- ORBi (University of Liège) (submittedVersion)
- Funders
- Fonds De La Recherche Scientifique - FNRS
- Fonds pour la Formation à la Recherche dans l’Industrie et dans l’Agriculture
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemistry › Organic Chemistry › Click Chemistry and Applications
- Keywords
- polycaprolactone, ring-opening polymerization, click chemistry, copper-catalyzed azide-alkyne cycloaddition, sodium azide, graft copolymers, amphiphilic copolymers, poly(ethylene oxide), hydroxyl end groups, one-pot synthesis, aliphatic polyesters
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
