Thermoresponsive properties of poly(acrylamide-<i>co</i>-acrylonitrile)-based diblock copolymers synthesized (by PISA) in water

Audureau, Nicolas; Coumes, Fanny; Nguyen, Thi Phuong Thu; Ménager, Christine; Stoffelbach, François; Rieger, Jutta

doi:10.1039/d0py00895h

Cited by 21 publications

(26 citation statements)

References 84 publications

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“…In summary, PEG 113 -PHBA x nano-objects are clearly much more thermoresponsive than their isomeric PEG 113 -PHPMA x counterparts and other structure-directing blocks. 42,94 This observation is expected to be important for the rational design of thermoresponsive diblock copolymer nano-objects for potential biomedical applications.…”

Section: Resultsmentioning

confidence: 99%

Shape-shifting thermoreversible diblock copolymer nano-objects via RAFT aqueous dispersion polymerization of 4-hydroxybutyl acrylate

2021

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Section: Resultsmentioning

confidence: 99%

Shape-shifting thermoreversible diblock copolymer nano-objects via RAFT aqueous dispersion polymerization of 4-hydroxybutyl acrylate

2021

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“…[19,20] It is generally obtained by free radical polymerization (FRP) or reversible deactivation radical polymerization (RDRP)-in particular through reversible addition fragmentation chain transfer (RAFT)-of Am and AN in organic solvents [14] or in water. [21] Uchiyama and Otsuka et al [18] reported that-in addition to hydrogen bonds between the Am units [14,22] -dipole−dipole interactions between the cyano groups in the AN units are a major driving force for the UCST behavior. Due to a difference in reactivity of both comonomers, [23] the Am/AN composition and distribution in the polymer chains depend however greatly on the polymerization technique, and therefore the cloud point (T CP ) is sensitive to the polymerization conditions.…”

Section: Introductionmentioning

confidence: 99%

RAFT‐Polymerized N‐Cyanomethylacrylamide‐Based (Co)polymers Exhibiting Tunable UCST Behavior in Water

Audureau

Veith

Coumes

et al. 2021

Macromol. Rapid Commun.

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In this present work, the synthesis of a new family of upper critical solution temperature (UCST)-thermoresponsive polymers based on N-cyanomethylacrylamide (CMAm) is reported. It is demonstrated that the thermally initiated reversible addition fragmentation chain transfer (RAFT) polymerization of CMAm conducted in N,N-dimethylformamide (DMF) is well controlled. The homopolymer presents a sharp and reversible UCST-type phase transition in pure water with a very small hysteresis between cooling and heating cycles. It is demonstrated that the cloud point (T CP ) of poly(N-cyanomethylacrylamide) (PCMAm) is strongly molar mass dependent and shifts toward lower temperatures in saline water. Moreover, the transition temperature can be tuned over a large temperature range by copolymerization of CMAm with acrylamide or acrylic acid. The latter copolymers are both thermoresponsive and pH responsive. Interestingly, by this strategy sharp and reversible UCST-type transitions close to physiological temperature can be reached, which makes the copolymers extremely interesting candidates for biomedical applications.

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“…Since 2012, the UCST-behavior of poly(acrylamideco-acrylonitrile) (P(Am-co-AN)) [7], a neutral statistical copolymer of acrylamide and acrylonitrile, has been revealed and since then it has been largely studied for numerous applications [12][13][14][15][16]. While it had been generally synthesized by free radical polymerization in DMSO solution, Ferji et al [17] and some of us [18] demonstrated recently that well defined P(Am-co-AN) copolymers can be synthesized directly in water, using the reversible addition-fragmentation chain transfer (RAFT) radical polymerization. Furthermore, we demonstrated that it was possible to synthesize in situ P(Am-co-AN) based block copolymer nanoparticles using the polymerization-induced self-assembly (PISA) process in water [18].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Temperature-Responsive N-Cyanomethylacrylamide-Containing Diblock Copolymer Assemblies in Water

et al. 2021

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We have previously demonstrated that poly(N-cyanomethylacrylamide) (PCMAm) exhibits a typical upper-critical solution temperature (UCST)-type transition, as long as the molar mass of the polymer is limited, which was made possible through the use of reversible addition-fragmentation chain transfer (RAFT) radical polymerization. In this research article, we use for the first time N-cyanomethylacrylamide (CMAm) in a typical aqueous dispersion polymerization conducted in the presence of poly(N,N-dimethylacrylamide) (PDMAm) macroRAFT agents. After assessing that well-defined PDMAm-b-PCMAm diblock copolymers were formed through this aqueous synthesis pathway, we characterized in depth the colloidal stability, morphology and temperature-responsiveness of the dispersions, notably using cryo-transmission electron microscopy (cryo-TEM), dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and turbidimetry. The combined analyses revealed that stable nanometric spheres, worms and vesicles could be prepared when the PDMAm block was sufficiently long. Concerning the thermoresponsiveness, only diblocks with a PCMAm block of a low degree of polymerization (DPn,PCMAm < 100) exhibited a UCST-type dissolution upon heating at low concentration. In contrast, for higher DPn,PCMAm, the diblock copolymer nano-objects did not disassemble. At sufficiently high temperatures, they rather exhibited a temperature-induced secondary aggregation of primary particles. In summary, we demonstrated that various morphologies of nano-objects could be obtained via a typical polymerization-induced self-assembly (PISA) process using PCMAm as the hydrophobic block. We believe that the development of this aqueous synthesis pathway of novel PCMAm-based thermoresponsive polymers will pave the way towards various applications, notably as thermoresponsive coatings and in the biomedical field.

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Thermoresponsive properties of poly(acrylamide-co-acrylonitrile)-based diblock copolymers synthesized (by PISA) in water

Abstract: In this present work, we report the synthesis of UCST-thermoresponsive diblock copolymers using reversible addition fragmentation chain transfer (RAFT) polymerization in aqueous media. First, statistical poly(acrylamide-co-acrylonitrile) copolymers, P(AAm-co-AN), with various...

Cited by 21 publications

References 84 publications

Shape-shifting thermoreversible diblock copolymer nano-objects via RAFT aqueous dispersion polymerization of 4-hydroxybutyl acrylate

Shape-shifting thermoreversible diblock copolymer nano-objects via RAFT aqueous dispersion polymerization of 4-hydroxybutyl acrylate

RAFT‐Polymerized N‐Cyanomethylacrylamide‐Based (Co)polymers Exhibiting Tunable UCST Behavior in Water

Synthesis and Characterization of Temperature-Responsive N-Cyanomethylacrylamide-Containing Diblock Copolymer Assemblies in Water

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