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Fluorinated polymers are important materials that are widely used in many areas. Herein, we report the development of a metal-free photocontrolled radical polymerization of semifluorinated (meth)acrylates with a new visible-light-absorbing organocatalyst. This method enabled the production of a variety of semifluorinated polymers with narrow molar-weight distributions from semifluorinated trithiocarbonates or perfluoroalkyl iodides. The high performance of "ON/OFF" control and chain-extension experiments further demonstrate the utility and reliability of this method. Furthermore, to streamline the preparation of semifluorinated polymers, a scalable continuous-flow approach has been developed. Given the broad interest in fluorinated materials and photopolymerization, we expect that this method will facilitate the development of advanced materials with unique properties.

Covalent functionalization of azide-modified SiO(2) with well-defined, alkyne-terminated poly(N-isopropylacrylamide) was accomplished by the Cu(I)-catalyzed [3 + 2] Huisgen cycloaddition. The alkyne-terminated RAFT chain transfer agent was first synthesized, and then the alkyne-terminated thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) with different molecular weights were synthesized by the RAFT of NIPAM monomer. The polymerization kinetics and the evolution of number-average molecular weights (M(n)), and polydispersities (M(w)/M(n)), with monomer conversions were investigated. A copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) "grafting to" method was used to attach thermoresponsive polymers onto the exterior surface of SiO(2) nanoparticles which produced relatively high grafting density. The as-synthesized hybrid nanoparticles showed thermoresponsive behavior and were characterized by FTIR, XPS, TGA, DLS, and TEM, etc.

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A well-defined thermoresponsive poly(ethylene glycol)-block-poly(N-isopropylacrylamide)-block-poly(ε-caprolactone) (PEG(43)-b-PNIPAM(82)-b-PCL(87)) triblock copolymer was synthesized by combination of atom transfer radical polymerization (ATRP), ring-opening polymerization (ROP), and click chemistry. The synthesis included the four steps, and all the structures of the polymers were determined. The thermoresponsive triblock copolymer can disperse in water at room temperature to form core-shell-corona micelles with the hydrophobic PCL block as core, the thermoresponsive PNIPAM block as shell, and the hydrophilic PEG block as corona. At temperatures above the lower critical solution temperature (LCST) of the PNIPAM block, the PNIPAM chains gradually collapse on the PCL core to shrink the size and change the structure of the resultant core-shell-corona micelles with temperature increasing.

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Ultra‐high‐molecular‐weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible‐deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain‐transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible‐light irradiation. In situ chain‐end extensions from UHMW polymers facilitated the synthesis of well‐defined block copolymers, revealing the excellent chain‐end fidelity achieved by this method.

Remarkably improved dielectric properties including high-k, low loss, and high breakdown strength combined with promising mechanical performance such as high flexibility, good heat, and chemical resistivity are hard to be achieved in high-k dielectric composites based on the current composite fabrication strategy. In this work, a family of high-k polymer nanocomposites has been fabricated from a facile suspension cast process followed by chemical cross-linking at elevated temperature. Internal double bonds bearing poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE-DB)) in total amorphous phase are employed as cross-linkable polymer matrix. α-SiC particles with a diameter of 500 nm are surface modified with 3-aminpropyltriethoxysilane (KH-550) as fillers for their comparable dielectric performance with PVDF polymer matrix, low conductivity, and high breakdown strength. The interface between SiC particles and PVDF matrix has been finely tailored, which leads to the significantly elevated dielectric constant from 10 to over 120 in SiC particles due to the strong induced polarization. As a result, a remarkably improved dielectric constant (ca. 70) has been observed in c-PVDF/m-SiC composites bearing 36 vol % SiC, which could be perfectly predicted by the effective medium approximation (EMA) model. The optimized interface and enhanced compatibility between two components are also responsible for the depressed conductivity and dielectric loss in the resultant composites. Chemical cross-linking constructed in the composites results in promising mechanical flexibility, good heat and chemical stability, and elevated tensile performance of the composites. Therefore, excellent dielectric and mechanical properties are finely balanced in the PVDF/α-SiC composites. This work might provide a facile and effective strategy to fabricate high-k dielectric composites with promising comprehensive performance.