Herein, near‐infrared (NIR) photocontrolled iodide‐mediated reversible‐deactivation radical polymerization (RDRP) of methacrylates, without an external photocatalyst, was developed using an alkyl iodide (e.g., 2‐iodo‐2‐methylpropionitrile) as the initiator at room temperature. This example is the first use of a series of special solvents containing carbonyl groups (e.g., 1,3‐dimethyl‐2‐imidazolidinone) as both solvent and catalyst for photocontrolled RDRP using long‐wavelength (λmax=730 nm) irradiation. The polymerization system comprises monomer, alkyl iodide initiator, and solvent. Well‐defined polymers were synthesized with excellent control over the molecular weights and molecular weight distributions (Mw/Mn<1.21). The living features of this system were confirmed by polymerization kinetics, multiple controlled “on‐off” light switching cycles, and chain extension experiments. Importantly, the polymerizations proceeded successfully with various barriers (pork skin and A4 paper), demonstrating the advantage of high‐penetration NIR light.
Amphiphilic poly(poly(ethylene glycol)methyl ether methacrylate)-b-poly(methyl methacrylate) (PPEGMA-b-PMMA) diblock copolymer nanoparticles were successfully synthesized via polymerization-induced self-assembly (PISA) at 70 °C in a continuous tubular reactor.
Photocontrolled iodine-mediated
reversible-deactivation radical
polymerization (RDRP) is a facile and highly efficient access to precision
polymers. Herein, a facile photocontrolled iodine-mediated green RDRP
strategy was successfully established in water by using 2-iodo-2-methylpropionitrile
(CP-I) as the initiator and water-soluble functional monomers including
poly(ethylene glycol) methyl ether methacrylate (PEGMA), 2-hydroxyethyl
methacrylate (HEMA), and 2-hydroxypropyl methacrylate (HPMA) as the
model monomers under blue-light-emitting diode (LED) irradiation at
room temperature. Well-defined polymers (PPEGMA, PHEMA, PHPMA) with
narrow polydispersities (1.09–1.21) were obtained, and amphiphilic
block copolymers which can form nanospheres in situ in water (PPEGMA-b-poly(benzyl methacrylate) (PPEGMA-b-PBnMA) and PPEGMA-b-PHPMA) were prepared.
To explore the role of water in our polymerization, control experiments
were successfully carried out by using oil-soluble monomer methyl
methacrylate (MMA) with the help of trace amounts of water. Notably,
the green solventwaterhas an additionally positive
effect in accelerating the polymerization and makes our polymerization
system an environmentally friendly polymerization system. Therefore,
this simple strategy conducted in the presence of water enables the
green preparation of well-defined water-soluble or water-insoluble
polymers and clean synthesis of amphiphilic copolymer nanoparticles in situ.
A series of hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) macroinitiators and stabilizers are synthesized in methanol through in situ photo-controlled bromine-iodine transformation living radical polymerization, where ethyl α-bromophenylacetate (EBPA) is the initial initiator and is converted to an iodo-type initiator in the presence of NaI. The subsequent photo-controlled polymerization-induced self-assembly (photo-PISA) process is achieved by adding a second monomer, hydrophobic benzyl methacrylate (BnMA), under irradiation with blue light emitting diode (LED) light at room temperature. The effect of the target degree of polymerization (DP) of PPEGMA, PBnMA, as well as the solids content on the self-assembly behavior of block copolymer PPEGMA-b-PBnMA is evaluated by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS) characterization. Resulting uniform spherical micelles and vesicle aggregates are observed.
A facile and clean strategy for synthesizing unimodal polymethacrylates with narrow dispersity (Đ < 1.10) is successfully developed by a near‐infrared (NIR) light‐emitting diode (LED) light (λmax = 740 nm)‐controlled in situ bromine–iodine transformation reversible‐deactivation radical polymerization system without the use of NIR dyes and expensive catalysts. In this system, alkyl iodide ethyl α‐iodophenylacetate (EIPA) initiator is generated in situ by the nucleophilic substitution reaction between an alkyl bromide compound ethyl α‐bromophenylacetate and sodium iodide (NaI). At the same time, excessive NaI is also acted as a highly active catalyst by forming halogen bonds with terminal iodine of the polymer chains in this system to make it capable of precisely synthesizing polymethacrylates with narrow dispersities (Đ = 1.03–1.10). In addition, the strong penetration ability of NIR LED light is illustrated by the successful polymerization even through 11 pieces of A4 paper.
An iron-mediated reverse ATRP of methyl methacrylate (MMA) is successfully carried out in water in the absence of any dispersants, using a water-soluble 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50) as the initiator and the stabilizer, and using an oil-soluble N,N-butyldithiocarbamate ferrum (Fe(S2 CN(C4 H9 )2 )3 ) as the catalyst without adding any additional ligands. Micron-sized PMMA particles with UV light-sensitive -S2 CN(C4 H9 )2 end group are obtained, and monomer droplet nucleation and suspension polymerization mechanism are proposed. Polymerization results demonstrated typical "living"/controlled characteristics of ATRP: first-order polymerization kinetics, linear increase of molecular weights with monomer conversion and narrow molecular weight distributions for the resultant PMMA particles. NMR spectroscopy and chain-extension experiments under UV light irradiation confirm the attachment and livingness of UV light-sensitive -S2 CN(C4 H9 )2 group in the chain end.
The performance of functional polymer nanomaterials is a vigorously discussed topic in polymer science. We devoted ourselves to investigating polymer nanomaterials based on near-infrared (NIR) fluorescence imaging and polymer prodrug in this study. Aza-boron dipyrromethene (BODIPY) is an important organic dye, having characteristics such as environmental resistance, light resistance, high molar extinction coefficient, and fluorescence quantum yield. We incorporated it into our target monomer, which can be polymerized without changing its parent structure in a polar solvent and copolymerized with water-soluble monomer to improve the solubility of the dye in an aqueous solution. At the same time, the hydrophobic drug camptothecin (CPT) was designed as a prodrug monomer, and the polymeric nanoparticles (NPs) with NIR fluorescence imaging and prodrug were synthesized in situ in reversible addition-fragmentation chain transfer (RAFT)-mediated aqueous dispersion polymerization. The dynamic light scattering (DLS) and transmission electron microscopy (TEM) revealed the final uniform size of the dual-functional polymeric NPs morphology. The dual-functional polymeric NPs had a strong absorption and emission signal in the NIR region (>650 nm) based on the fluorescence tests. In consideration of the long-term biological toxicity, confocal laser scanning microscopy (CLSM) results indicated that the dual-functional NPs with controlled drug content exhibited effective capability of killing HeLa cells. In addition, in vivo imaging of the dual-functional NPs was observed in real time, and the fluorescent signals clearly demonstrated the dynamic process of prodrug transfer.
RAFT copolymerization of a phosphorus-containing monomer with α-hydroxy phosphonate PHMA and MMA was successfully conducted and the resultant well-defined copolymer material shows good superior flame-retardant properties and hydrophilicity.
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