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A series of deuterated tri-block copolymers with the general structure d8-PMMA-POEGMA-d8-PMMA, with variation in d8-PMMA chain length, were synthesized using sequential controlled radical polymerization (ATRP). Solid polymer electrolytes (SPEs) were produced by blending tri-block copolymers and lithium bis(trifluoro methylsulfonate) (LiTFSI). Small-angle neutron scattering (SANS) was used to study...
Copper complexes bearing ligands based on tris(2-methylpyridyl)amine (TPMA) are leading catalysts in atom transfer radical polymerization (ATRP). In recent years, the TPMA structure has been finely modified to enhance the catalytic activity of the corresponding Cu complex. In this study, we report the synthesis of eight novel copper TPMA complexes, and the evaluation of the catalytic activity for...
The efficient formulation of layered gels that encompass both hydrophilic and hydrophobic domains could lead to novel materials with a range of vital functionalities. To facilitate the fabrication of these materials, we perform dissipative particle dynamics (DPD) simulations to model the formation of two-layered stackable gels where the gels are incompatible and their respective solvents are immiscible...
Novel, facile, and stable mediating agent (dithiobenzoic copper(II)) combining atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer (RAFT) characteristics was firstly designed by replacing the halogen of ATRP metal catalyst with thiocarbonyl carboxylic group of RAFT agent. As two kinds of mediating agents (ATRP activator and RAFT agent) may be formed in situ during...
In this study we achieved an efficient metal-catalyzed radical “miniemulsion” polymerization with ferrocene (FeCp2) as a cocatalyst in conjunction with a thermoresponsive PEG containing ruthenium catalyst for the polymerization of methacrylate monomers. The iron-cocatalysis worked well even in the miniemulsion similar to homogeneous solution system. The secondary catalytic cycle by ferrocene allows...
Core-shell like structured barium zirconium titanate-barium calcium titanate-poly(methyl methacrylate) [(Ba0.94Ca0.06)(Zr0.16Ti0.84)O3-PMMA] nanocomposites were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate (MMA) from the surface of BZT-BCT nanoparticles. X-ray diffraction patterns of pure polymer and BZT-BCT nanoparticles revealed their amorphous...
Topological polymers with T-shaped and H-shaped molecular architecture were built on the combination of atom transfer radical polymerization (ATRP) and UV-induced strain promoted azide-alkyne cycloaddition (SPAAC) reaction. In the presence of a cyclopropenone-masked dibenzocyclooctyne functionalized dibromo ATRP initiator, reactive polystyrene (PS) was synthesized to have a cyclopropenone-masked dibenzocyclooctyne...
Transparent and high permittivity films were prepared by melt pressing poly(methyl methacrylate) (PMMA)-grafted 7 nm barium titanate (BT) particles. PMMA chains with molecular weights of 32–40 kDa were grafted on BT particle surfaces at a density of 0.2–0.7 chains nm−1 through surface-initiated atom transfer radical polymerization of methyl methacrylate. This yielded BT/PMMA composites with BT volume...
This article describes two convenient methods for removing the ω-terminal bromine atom of well-defined soluble polymer supports prepared by atom transfer radical polymerization (ATRP). The targeted soluble supports are linear polystyrene chains that contain an acid-labile p-alkoxybenzyl ester linker (i.e. Wang linker) at their α-chain end. These polymers are synthesized by ATRP using a fluorenylmethoxycarbonyl...
An azobenzene liquid crystalline mesogen, 6-(4-((4-methoxyphenyl)diazenyl)phenoxy)hexyl methacrylate (MMAZO) was incorporated into a block copolymer with regioregular poly(3-hexylthiophene) (P3HT). The synthesis was performed by a combination of Grignard metathesis (GRIM) and atom transfer radical polymerization (ATRP) techniques. The composition of synthesized copolymers was determined from 1HNMR...
A series of bicyclic polystyrenes were prepared by combining atom transfer radical polymerization and click coupling reaction. To investigate effect of experimental parameters, bicyclic polymers were prepared by changing types of ligands for click chemistry, concentration of polymers and coupling agents, feed rate of polymers and coupling agents, concentration of catalyst, and types of coupling agents...
Ordered arrays of hollow carbon nanospheres and nanotubules were synthesized using polyacrylonitrile (PAN) as a carbon precursor and ordered mesoporous silicas with spherical pores (large-pore FDU-12) and cylindrical pores (ultra-large-pore SBA-15) as templates. PAN was grafted on the surface of the silica template using surface-initiated atom transfer radical polymerization (ATRP). The pore size...
Dibrominated poly(methyl acrylate) (BrPMABr) was prepared by atom transfer radical polymerization (ATRP), and this unpurified reaction mixture was used directly in a radical trap-assisted atom transfer radical coupling (RTA-ATRC) reaction to achieve cyclic PMA by intramolecular chain-end coupling. When the polymerization-to-cyclization crossover was performed as a one pot-two step sequence simply...
Halloysite nanotube (HNT) was functionalized with (3-Aminopropyl)triethoxysilane (APTES), alpha-bromoisobutyryl bromide (BiBB), and poly (N,N-dimethylaminoethyl methacrylate) (PDMAEMA) chains. Successful grafting of PDMAEMA by SI-ATRP method was evaluated by XPS, FTIR, TEM, and TGA. Pore volume studies were accomplished by BET, and XRD was used to study crystalline structure of nanotubes. PDMAEMA...
Two functional atom transfer radical polymerization (ATRP) initiators (I-2 and I-3) were developed bearing a cyclopropenone-masked dibenzocyclooctyne group. ATRP was then explored on three main kinds of monomers for radical polymerization including acrylates, styrenics, and methacrylates based on these novel initiators. By a standard ATRP protocol, the polymerization behavior demonstrated the living...
Photoinduced atom transfer radical polymerization (ATRP) has promising applications because it requires small amounts of transition metal catalysts and low temperatures, and can be extended to numerous monomers. We investigated the photoinduced ATRP of 2-methacryloyloxyethyl phosphorylcholine (MPC) in a polar medium and prepared block-type copolymers with a poly(MPC) segment. Polymerizations in methanol...
Niobium complex was successfully introduced into atom transfer radical polymerization (ATRP) system as a new kind of recyclable photocatalyst. The niobium complex acted as photocatalyst that could be activated by the photoredox reaction under visible light irradiation and ethyl 2-bromoisobutyrate (EBiB) was used as initiator. Successful ATRP polymerizations of acrylates were realized. The well-defined...
The dibenzocyclooctyne end functionalized agent 1 was designed as atom transfer radical polymerization (ATRP) initiator. The ATRP was then explored on three types of monomers widely used in free radical polymerization: methyl methacrylate, styrene, and acrylates (n-butyl acrylate and tert-butyl acrylate). The living polymerization behaviors were obtained for the methyl methacrylate and styrene monomers...
Monobrominated polystyrene (PStBr) chains were prepared using standard atom transfer radical polymerization (ATRP) procedures at 80 °C in THF, with monomer conversions allowed to proceed to approximately 40%. At this time, additional copper catalyst, reducing agent, and ligand were added to the unpurified reaction mixture, and the reaction was allowed to proceed at 50 °C in an atom transfer radical...
Dynamic polystyrene (d-PS) and poly(n-butyl acrylate) (d-PBA) with an acylhydrazone linkage at each chain center were synthesized by atom transfer radical polymerization (ATRP) of corresponding monomers using a bis-bromoisobutyrate initiator bearing one acylhydrazone bond. Kinetic studies demonstrated that the polymerization followed a first-order mechanism. When treated with trifluoroacetic acid...
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