Visible‐Light‐Enabled Organocatalyzed Controlled Alternating Terpolymerization of Perfluorinated Vinyl Ethers

Abstract

Polymerizations of perfluorinated vinyl ethers (PFVEs) providea ni mportant category of fluoropolymers that have received considerable interests in applications.Inthis work, we report the development of an organocatalyzed controlled radical alternating terpolymerization of PFVEs and vinyl ethers (VEs) under visible-light irradiation. This method not only enables the synthesis of ab road scope of fluorinated terpolymers of lowdispersities and high chain-end fidelity,f acilitating tuning the chemical compositions by rationally choosing the type and/or ratio of comonomers,b ut also allows temporal control of chain-growth, as well as the preparation of avariety of novel fluorinated blockcopolymers. To showcase the versatility of this method, fluorinated alternating terpolymers have been synthesized and customized to simultaneously displayav ariety of desirable properties for solid polymer electrolyte design, creating new opportunities in high-performance energy storage devices.

Oxygen-Tolerant Alternating Copolymerization of Fluorinated Monomers and Vinyl Ethers at Mild Temperature

“…27 In addition, terpolymerization of fluorinated olefins (FOs) with two different vinyl ethers (VEs) can be achieved either in presence of a radical initiator 25 or under visible-light irradiation. 30 In this work, mild polymerization conditions were studied using TBB-MOPA as initiator with commercially available fluoroolefins (such as PMVE and HFP) and vinyl ethers [such as ethyl vinyl ether (EVE) and 2-(perfluorohexyl)ethyl vinyl ether (FAVE6)] monomers.…”

“…On the other hand, the acceptor–donor copolymerization of electron-withdrawing highly fluorinated olefins (FO), such as chlorotrifluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoromethyl vinylether with electron-donating vinyl ethers (VE), is known to lead to alternating poly­(FO- alt -VE) copolymers. − As a matter of fact, fluoroolefins, such as perfluoromethyl vinyl ether (PMVE) and hexafluoropropylene (HFP), have an electron-acceptor character ( e values for PMVE and HFP are 3.01 and 1.50, , respectively). Meanwhile, vinyl ethers are electron-donating (− 2.0 < e < −1.5). ,, Furthermore, both these families of monomers cannot be homopolymerized.…”

Degradable Vinyl Random Copolymers via Photocontrolled Radical Ring‐Opening Cascade Copolymerization**

“…[6,33] We reasoned that performing the copolymerization at lower temperatures would provide a key opportunity to modulate the reactivity ratios of vinyl comonomers. Therefore, we turned our attention to light-mediated polymerization techniques, as recent works have demonstrated that they are versatile tools to mediate controlled polymerization following radical, [34][35][36][37][38][39][40][41][42] cationic, [43][44][45][46][47] and metathesis pathways [48][49][50] at ambient temperature (Figure 1B). [51] In particular, we envisioned that the photoinduced electron/energy transferreversible addition/fragmentation chain transfer (PET-RAFT) polymerization developed by Boyer and coworkers [52][53][54][55][56] could be employed to mediate the radical ringopening cascade copolymerization (rROCCP) [57,58] of the macrocyclic allylic sulfone with acrylates or acrylamides (Figure 1C).…”

Development of High Throughput Photopolymerizations Using Micron‐Sized Ultrathin Metal‐Organic Framework Nanosheets

“…[1,2] The success of rapid synthesis and screening is inseparable from the development of oxygen tolerant reversible deactivation radical polymerization (RDRP) techniques as they allow multiple parallel polymerizations to be carried out in a low volume without prior deoxygenation. [3][4][5][6][7][8][9][10] Particularly, photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization was proved to enact high throughput polymerizations due to the mild energy input (from visible to near infrared light). [11][12][13] For instance, PET-RAFT polymerization was employed under visible light irradiation to fabricate 32 linear copolymers with different functionalities and block sequences for screening the optimal antimicrobial effects.…”