Synthesis, aqueous solution behavior and self-assembly of a dual pH/thermo-responsive fluorinated diblock terpolymer

Falireas, Panagiotis G.; Ladmiral, Vincent; Améduri, Bruno

doi:10.1039/d0py01515f

Cited by 12 publications

(10 citation statements)

References 76 publications

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“…While fluoropolymers oftentimes exhibit outstanding hydrophobicity and chemical inertness, the incorporation of gem -CF 3 /OH could dramatically improve the hydrophilicity and pH responsiveness due to decreased p K a of hydroxyls, as influenced by the strong electron-withdrawing geminal CF 3 substituents. Such materials are highly interesting for applications as chemically amplified and pH-responsive polymeric materials . Taking PCF 3 VB- co -PVAc copolymers as examples (Figure A), when silicon surfaces were coated with PCF 3 VB- co -PVAc of different fractions of gem -CF 3 /B ( F CF 3 VB = 0.49 in Figure B, F CF 3 VB = 0.79 in Figure C), two substrates exhibit similar contact angles for water (85 and 86°).…”

Section: Investigations On Water Contact Anglesmentioning

confidence: 99%

Facile Access to gem-Trifluoromethyl/Boron-Functionalized Polymers via Free-Radical Copolymerization and Cotelomerization

et al. 2022

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Functional fluoropolymers are important for various applications due to the integrated characteristics of functional groups and fluorocarbon segments. Herein, we developed (1) thermally initiated and visible-light-initiated copolymerization of (trifluoromethyl)vinyl boronic esters (CF3VBs) and unconjugated alkenes (18 examples, including vinyl ethers, esters, and amides), enabling the efficient synthesis of a broad scope of fluoropolymers in 71–92% yield and variable fractions of gem-CF3/B substituents (F CF3VB = 0.26–0.84) at different molar masses (M n = 5.2–33.4 kDa) and (2) visible-light-initiated cotelomerization of CF3VB and unconjugated alkenes with p-tolyl disulfide as a telogen (M n = 3.6–13.0 kDa). Reactivity ratios for copolymerization were determined by the Meyer–Lowry method at 65 °C (for BVE: r CF3VB = 1.254, r BVE = 0.006; for VAc: r CF3VB = 0.235, r VAc = 0.042; for NVP: r CF3VB = 1.067, r NVP = 0.063). The achieved high fractions of CF3VBs in copolymers are also confirmed by density functional theory (DFT) calculation results. Through post-polymerization modifications, gem-CF3/B units could transform into various copolymers and terpolymers with geminal functionalities (e.g., gem-CF3/OH, gem-CF3/vinyl, gem-CF3/furan). The increase of geminal functionalities enables clearly amplified chemical responsiveness toward pH variation, as demonstrated by fluoropolymers with gem-CF3/OH.

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Section: Investigations On Water Contact Anglesmentioning

confidence: 99%

Facile Access to gem-Trifluoromethyl/Boron-Functionalized Polymers via Free-Radical Copolymerization and Cotelomerization

et al. 2022

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“…Recently, Falireas et al reported the synthesis of dual pH-/temperature-responsive fluorinated block copolymers based on an alternating poly(VAc- alt -2-trifluoromethacrylic acid) sequence and poly(DMA) and poly( N -isopropylacrylamide) (PNIPAM) blocks (Scheme ).…”

Section: Sequence Regulation In Synthetic Fluoropolymersmentioning

confidence: 99%

“… a (a) Preparation of alternating poly(MAF-TBE- alt -VAc) macroCTA; (b) hydrolysis of poly(MAF-TBE- alt -VAc) into poly(MAF- alt -VOH); (c) synthesis of poly(MAF-TBE- alt -VAc)- b -PDMA; (d) obtained poly(MAF-TBE- alt -VAc)- b -PNIPAM; and (e) hydrolysis of poly(MAF-TBE- alt -VAc)- b -PNIPAM into P(MAF- alt -VOH)- b -PNIPAM. Reproduced with permission from ref . Copyright 2021 Royal Society of Chemistry. …”

Section: Sequence Regulation In Synthetic Fluoropolymersmentioning

confidence: 99%

Well-Defined Fluorinated Copolymers: Current Status and Future Perspectives

et al. 2021

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Well-defined fluoropolymers exhibit unique properties such as excellent oil and water repellency, satisfactory thermal stability, low refractive index, and low surface energy.The origin of these properties is attributed to the presence of strong electronegative and low polarizable Fluorine atom in the backbone of such polymers which leads to a strong C F bond (with a high bond dissociation energy of 485 kJ mol −1 ). Due to these features, these polymers have found applications as functional coatings, thermoplastics, biomedical items, separators and binders for Li-ion batteries, fuel cell membranes, piezoelectric devices, high quality wires and cables, etc. Usually, fluoropolymers are synthesized by conventional radical (co)polymerization of fluoroalkenes which leads to the production of (co)polymers with ill-defined end group, uncontrolled molar mass, and high dispersity values. In the last two decades, significant developments of various reversible deactivation radical polymerization (RDRP) techniques have helped the design of macromolecular architectures (including block, graft, star, dendrimers) on demand. However, for relevant new applications, well-defined fluoropolymers with well-defined macromolecular architectures (e.g. block copolymers as thermoplastic elastomers and electroactive polymers or graft copolymers for fuel cell membranes) are required.Several RDRP methods developed in the last couple of decades have paved the way for the synthesis of (co)polymers with well-defined molar mass, dispersity, chain end-functionality and

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“…They however readily copolymerize with more electron-rich olefins such as vinyl acetate for example. [80][81][82] Falireas et al 83 recently prepared amphiphilic diblock terpolymers composed of a PNIPAM or PDMA (DMA = N, N,-dimethyl acrylamide) hydrophilic block and an hydrophobic poly(MAF-TBE-alt VAc) block (MAFTBE = tertbutyl-2-trifluoromethacrylate) via sequential RAFT polymerization. Hydrolysis of the ester groups produced double hydrophilic diblock terpolymers endowed with pHresponsiveness (and also thermoresponsiveness for the PNIPAM-based BCP).…”

Section: -(Trifluoromethyl)acrylic Acid and Its Ester (Maf)mentioning

confidence: 99%

Solution self-assembly of fluorinated polymers, an overview

et al. 2021

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Synthesis, aqueous solution behavior and self-assembly of a dual pH/thermo-responsive fluorinated diblock terpolymer

Abstract: The synthesis of fluorinated dual-responsive block terpolymers via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization is presented. The resulting block terpolymers consist of a hydrophobic block which comprises an alternating...

Cited by 12 publications

References 76 publications

Facile Access to gem-Trifluoromethyl/Boron-Functionalized Polymers via Free-Radical Copolymerization and Cotelomerization

Facile Access to gem-Trifluoromethyl/Boron-Functionalized Polymers via Free-Radical Copolymerization and Cotelomerization

Well-Defined Fluorinated Copolymers: Current Status and Future Perspectives

Solution self-assembly of fluorinated polymers, an overview

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