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In this paper, we report atom transfer radical polymerization of N-isopropylacrylamide (NIPAAm) by an enzyme mimetic catalyst, that is, hematin of a ferriprotoporphyrin complex. The hematin-catalyzed polymerization of NIPAAm was carried out in the presence of an alkyl halide as an initiator and a reducing agent in DMF/H 2 O solvent. The reaction proceeded at room temperature and the M ...
Quasiliving atom transfer radical polymerization (ATRP) of non-fluorous monomers, styrene and n-butyl acrylate, was attempted in benzotrifluoride (BTF; α,α,α-trifluorotoluene, TFT), the simplest trifluoromethylated aromatic compound, as an alternative solvent to widely used polymerization media in ATRP and other radical polymerizations, such as benzene, toluene, xylene, diphenylether etc., with toxic,...
A series of polyrotaxane (PR)-based triblock copolymers comprising a PR middle block and poly(n-butyl methacrylate) (PBMA) flanked blocks were prepared via bulk ATRP of n-butyl methacrylate initiated with polypseudorotaxanes self-assembled from α-cyclodextrins (α-CDs) with 2-bromoisobutyryl terminated Pluronic 17R4 at 35 °C. Their structure was verified by 1 H NMR, FTIR, GPC, WXRD and TGA...
Polystyrene radicals were formed in the presence of NtBPN under a variety of reaction conditions and reactant ratios, forming polymer dimers of twice the molecular weight of the monobrominated polystyrene (PStBr) precursors. The polystyrene radicals were generated by the activation of the monohalogentated polystyrene precursors, prepared by atom transfer radical polymerization (ATRP). The extent of...
Poly(9-(2-(4-vinyl(benzyloxy)ethyl)-9H-carbazole)) (PVBEC) brushes, have been successfully prepared on the silicon surfaces via surface-initiated atom transfer radical polymerization (ATRP). Conductance switching at a voltage of about −2.1 V is observed in the memory device based on the PVBEC brushes. The fabricated device shows the good memory characteristics as the ON/OFF current ratio up to 10...
Herein novel polyrotaxanes (PRs) comprising γ-CDs and Pluronic F127 end-capped using poly(N-isopropylacrylamide) blocks were prepared via the atom transfer radical polymerization in aqueous medium at room temperature. The structure was characterized in detail by 1 H NMR, 2D NOESY NMR, FTIR, GPC, WXRD and DSC analyses. Solvent treatments were conducted on the resulting PRs via incubation in...
Poly(rotaxan)s of poly(ethylene glycol) and α-cyclodextrines (CD) block copolymers end-capped with poly(methyl methacrylate) chains were synthesized by atom transfer radical polymerization. The synthesized copolymers were characterized by 1 H NMR, 2D NOESY NMR, X-ray and Thermogravimetric analysis. Assuming a maximum relation of 2 CDs per ethyleneglycol unit, a coverage degree of 18% and 15%...
Surface-initiated atom transfer radical polymerization (si-ATRP) technique was successfully employed to modify Ni nanoparticles with polymer shells. ATRP initiators were covalently bonded onto Ni nanoparticle surfaces by a combination of ligand exchange and condensation reactions. Various kinds of polymers including poly(methyl methacrylate) (PMMA) and poly(n-isopropylacrylamide) (PNIPAM) were grafted...
This investigation reports the preparation of a series of well-defined Poly(methyl methacrylate)-b-poly(hexyl acrylate)-b-poly (methyl methacrylate) (PMMA-b-PHA-b-PMMA) triblock copolymers by Atom Transfer Radical Polymerization (ATRP). Their morphology, dynamic mechanical and tensile properties are thoroughly investigated. Phase separation is observed for all the above-mentioned triblock copolymers,...
A novel polymer electrolyte membrane was synthesized by radiation-induced grafting and consequent atom transfer radical polymerization (ATRP). First, bromine-containing perfluorinated grafts were prepared by radiation grafting of 2-bromotetrafluoroethyl trifluorovinyl ether (BrTFF) into a poly(ethylene-co-tetrafluoroethylene) (ETFE) film. Then, the bromine atoms in the ETFE-g-PBrTFF grafted films...
A new titanium alkoxide, Ti[OCH 2 CCl 3 ] 4 , designed to combine the ring-opening polymerization (ROP) of ɛ-caprolactone and atom transfer radical polymerization (ATRP) of n-butyl acrylate, was synthesized through the ester-exchange reaction of titanium n-propoxide and 2,2,2-trichloroethanol. The mechanism and kinetics of Ti[OCH 2 CCl 3 ] 4 initiated...
In this work, a series of amphiphilic diblock copolymers bearing strong push–pull type azo chromophores was synthesized through post-polymerization azo-coupling reaction scheme. The copolymers (P(CNAZO m -b-MAA n )), composed of 2-(N-ethyl-N-(4-(4′-cyanophenylazo)-phenyl)amino)ethyl methacrylate (CNAZO) and methacrylic acid (MAA) blocks, were obtained through four-step reactions. Firstly,...
Atom transfer radical polymerization (ATRP) was used to prepare thermosensitive cationic block copolymers of (3-acrylamidopropyl)-trimethylammonium chloride (AMPTMA) and N-isopropylacrylamide (NIPAAM) with different block lengths. By using ethyl-2-chloropropionate (ECP) as initiator and CuCl/CuCl 2 /tris(2-dimethylaminoethyl)amine (Me 6 TREN) catalytic system in DMF:water 50:50 (v/v)...
A polymerizable l-phenylalanine-derived monomer (N′-octadecyl-N α [4-(acryloyloxy)-butanoyl]-l-phenylalanineamide (3)) has been newly synthesized and characterized. We reported an advanced approach to molecular shape recognitive hybrid materials that involves immobilization of radical initiator on mesoporous silica particles (average diameter, pore size and surface area are 4μm, 12nm, and...
A novel strategy for the preparation of main-chain polyrotaxanes with lengthily tunable PHEMA as outer bulky stoppers was described in the present study. Polypseudorotaxanes made from the self-assemblies of a distal 2-bromoisobutyryl end-capped PEG with a varying amount of α-CDs in aqueous media were used as macroinitiators in situ to initiate the ATRP of HEMA catalyzed by Cu(I)Br/PMDETA at room temperature...
Isotactic polypropylene (iPP)–polystyrene (PS) and iPP–poly(methyl methacrylate) (PMMA) multiblock copolymers were synthesized by atom transfer radical coupling (ATRC) of PS–iPP–PS and PMMA–iPP–PMMA triblock copolymers obtained by atom transfer radical polymerization (ATRP) of styrene (St) and methyl methacrylate (MMA), respectively, using α,ω-dibromoisobutyrateoligopropylene (iPP–Br) as a bifunctional...
Branching atom transfer radical polymerization (ATRP) of styrene and acrylonitrile was attempted in the presence of divinylbenzene targeting toward soluble branched copolymer. The kinetics and the development of branching with monomer conversion were studied in detail. Gas chromatography (GC), gel permeation chromatography (GPC) coupled with multi-angle laser light scattering (MALLS), proton nuclear...
Atom transfer radical polymerization (ATRP) of acrylonitrile (AN) with ethyl 2-bromoisobutyrate (EBiB) as the initiator was firstly approached in the absence of any ligand in three novel ionic liquids, 1-methylimidazolium acetate ([mim][AT]), 1-methylimidazolium valerate ([mim][VT]) and 1-methylimidazolium caproate ([mim][CT]), respectively. All the polymerizations in the ionic liquids proceeded in...
Dendritic–linear–dendritic triblock copolymers composed of linear polystyrene (PSt) and poly(amidoamine) dendrons have been successfully synthesized. Two bromines-terminated PSt with M n =13,000 was prepared by atom transfer radical polymerization (ATRP) using α,α′-dibromo-p-xylene as initiator. Then the terminal bromines at both ends of PSt chains were replaced by one imine group of piperazine...
The feasibility of high-pressure atom transfer radical polymerization (ATRP) for synthesizing well-defined polymers of extraordinarily high molecular weights was demonstrated. ATRP of methyl methacrylate (MMA) under pressures up to 500MPa was investigated at 60°C. The addition of a small amount of a Cu(II)Cl 2 /ligand complex along with the general benefits of high pressure of enhancing propagation...
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