Ambient temperature catalyst-free light-induced preparation of macrocyclic aliphatic polyesters

Josse, Thomas; Altintas, Ozcan; Oehlenschlaeger, Kim K.; Dubois, Philippe; Gerbaux, Pascal; Coulembier, Olivier; Barner‐Kowollik, Christopher

doi:10.1039/c3cc49067j

Cited by 38 publications

(44 citation statements)

References 24 publications

(10 reference statements)

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“…The apparent molecular weights estimated by GPC ( M n,GPC ) of C1–C3 ranged between 1660 and 6200 g mol −1 , with PDI values similar to their linear precursors. The M n,GPC (C x )/ M n,GPC (L x ) ( x = 1–3) values within 0.82–0.84 were roughly comparable to those reported for other cyclic polymers . To further reveal the formation of ring topology, typical samples L2 and C2 were chosen to perform MALDI‐TOF MS measurements (Figure S3, Supporting Information).…”

Section: Resultssupporting

confidence: 71%

“…The significant progress in living/controlled polymerization techniques allows facile construction of a variety of precisely controlled topological polymers . Among them, cyclic polymers prepared via ring‐closure and ring‐expansion techniques have attracted increasing attention due to the intriguing topological constraint and its impact on comprehensive properties . Because of reduced hydrodynamic volume, ring polymers lacking chain ends have a more compact structure as compared to their linear analogs with the same molecular weight (MW).…”

Section: Introductionmentioning

confidence: 99%

“…This study aims at synthesis and properties of cyclic PDMAs with low molecular weights via UV‐induced Diels–Alder click reaction . To this end, 3‐(2‐formyl‐3‐methylphenoxy)propyl 4‐(benzodithioyl)‐4‐cyanopentanoate (FBCP) mediated reversible addition–fragmentation chain transfer (RAFT) polymerization of DMA was employed to generate α‐orthoquinodimethane‐ω‐dithiobenzoate heterofunctionalized PDMA, and then followed by Diels–Alder reaction between two end groups to form cyclic PDMA (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis, Thermal Properties, and Thermoresponsive Behaviors of Cyclic Poly(2‐(dimethylamino)ethyl Methacrylate)s

Tang

Zhu

et al. 2016

Macromol. Rapid Commun.

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This study aims at physicochemical properties of thermo- and pH/CO2 -responsive cyclic homopolymers. Three examples of cyclic poly(2-(dimethylamino)ethyl methacrylate)s (PDMAs) are synthesized by combining the reversible addition-fragmentation chain transfer process and the Diels-Alder ring-closure reaction. After cyclization, the glass transition temperature significantly increases (ΔTg = 51.8-59.7 °C) due to the different configurational entropy and end groups, and the maximum decomposition temperature to lose the pendent groups is drastically decreased from 309 to 278 °C. Effects of polymerization degree, polymer concentration, additive of NaCl, and pH/CO2 on lower critical solution temperature behaviors of PDMA aqueous solutions are investigated. The cloud points (Tc ) of ring PDMAs are usually higher than their linear precursors, and the ΔTc values obtained under a fixed condition can reach up to 20.7 °C, revealing the crucial role of the topology effect. This study paves the way for unique properties and applications of smart cyclic polymers and their derivatives.

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Section: Resultssupporting

confidence: 71%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Thermal Properties, and Thermoresponsive Behaviors of Cyclic Poly(2‐(dimethylamino)ethyl Methacrylate)s

Tang

Zhu

et al. 2016

Macromol. Rapid Commun.

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“…RAFT/Diels-Alder reaction 21 , ring opening polymerization (ROP)/Diels-Alder reaction 22 , ROP/CuAAC 23 , and ROP/thiolene reaction 24 . Based on these combinations, a variety of cyclic polymers has been prepared including polystyrenics 8,10,13,15,[17][18][19]21 , polymethacrylates 11,16,21 , polyacrylates 14,21 , polyacrylamides 12,20,21 and polyesters [22][23][24] .…”

Section: Introductionmentioning

confidence: 99%

A ring-closure method for preparing cyclic polymers from unconjugated vinyl monomers

et al. 2015

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A unique ring-closure method was developed specifically focusing on the preparation of cyclic polymers derived from unconjugated vinyl monomers, which was established on the combination of reversible addition−fragmentaƟon chain transfer polymerization (RAFT)/macromolecular design via the interchange of xanthate (MADIX) and light-induced strain promoted azide-alkyne cycloaddition (SPAAC) reaction. By virtue of a specifically designed xanthate agent 1 as the reversible chain transfer agent to polymerize the unconjugated vinyl monomers, well-defined telechelic polymers were produced by RAFT/MADIX polymerization technique bearing the cyclopropenone-masked dibenzocyclooctyne and azide end groups. Under UV irradiation on a highly diluted solution of the resultant linear polymer precursors, the dibenzocyclooctyne end group was quantitatively released from cyclopropenone-masked dibenzocyclooctyne, which intramolecularly reacted with azide end group in situ to ring-close the linear polymers and produce the corresponding cyclic polymers based on the SPAAC click reaction. In addition, this novel ring-closure method produced the cyclic polymer chain with a cleavable S-C(S)O bond within the xanthate group, which facilitated the resultant cyclic polymers to be efficiently cleaved back to their linear counterparts under a mild aminolysis or reduction reaction condition.A unique ring-closure method was developed specifically focusing on the preparation of cyclic polymers derived from unconjugated vinyl monomers by combining RAFT/MADIX living polymerization technique and UV-induced SPAAC click reaction.

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“…The ring‐closure methods have been developed as one of the main synthetic strategies for preparing variously well‐defined cyclic polymers . To date, most of the known successful ring‐closure methods could be categorized as the unimolecular heterodifunctional/homodifunctional approach . In this approach, the telechelic linear polymer precursors with complementarily reactive terminals were ring‐closed in highly dilute solution to produce the corresponding cyclic polymers.…”

Section: Introductionmentioning

confidence: 99%

Efficient Homodifunctional Bimolecular Ring‐Closure Method for Cyclic Polymers by Combining RAFT and Self‐Accelerating Click Reaction

Sun

et al. 2017

Macromol. Rapid Commun.

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An efficient metal-free homodifunctional bimolecular ring-closure method is developed for the formation of cyclic polymers by combining reversible addition-fragmentation chain transfer (RAFT) polymerization and self-accelerating click reaction. In this approach, α,ω-homodifunctional linear polymers with azide terminals are prepared by RAFT polymerization and postmodification of polymer chain end groups. By virtue of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DBA) as small linkers, well-defined cyclic polymers are then prepared using the self-accelerating double strain-promoted azide-alkyne click (DSPAAC) reaction to ring-close the azide end-functionalized homodifunctional linear polymer precursors. Due to the self-accelerating property of DSPAAC ring-closing reaction, this novel method eliminates the requirement of equimolar amounts of telechelic polymers and small linkers in traditional bimolecular ring-closure methods. It facilitates this method to efficiently and conveniently produce varied pure cyclic polymers by employing an excess molar amount of DBA small linkers.

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Ambient temperature catalyst-free light-induced preparation of macrocyclic aliphatic polyesters

Cited by 38 publications

References 24 publications

Synthesis, Thermal Properties, and Thermoresponsive Behaviors of Cyclic Poly(2‐(dimethylamino)ethyl Methacrylate)s

Synthesis, Thermal Properties, and Thermoresponsive Behaviors of Cyclic Poly(2‐(dimethylamino)ethyl Methacrylate)s

A ring-closure method for preparing cyclic polymers from unconjugated vinyl monomers

Efficient Homodifunctional Bimolecular Ring‐Closure Method for Cyclic Polymers by Combining RAFT and Self‐Accelerating Click Reaction

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