Copper‐based reverse ATRP process for the controlled radical polymerization of methyl methacrylate
TL;DR: In this article, a series of copper-based reverse atom transfer radical polymerizations (ATRP) were carried out for methyl methacrylate (MMA) at same conditions (in xylene, at 80°C) using N,N,N′, N′-teramethylethylendiamine (TMEDA), N, N, n′,N-N′-N-pentamethyldiethylentriamine (PMDETA), 2-2′-bipyridine, and 4,4′-Di(
Abstract: A series of copper-based reverse atom transfer radical polymerizations (ATRP) were carried out for methyl methacrylate (MMA) at same conditions (in xylene, at 80°C) using N,N,N′,N′-teramethylethylendiamine (TMEDA), N,N,N′,N′,N′-pentamethyldiethylentriamine (PMDETA), 2-2′-bipyridine, and 4,4′-Di(5-nonyl)-2,2′-bipyridine as ligand, respectively. 2,2′-azobis(isobutyronitrile) (AIBN) was used as initiator. In CuBr2/bpy system, the polymerization is uncontrolled, because of the poor solubility of CuBr2/bpy complex in organic phase. But in other three systems, the polymerizations represent controlled. Especially in CuBr2/dNbpy system, the number-average molecular weight increases linearly with monomer conversion from 4280 up to 14,700. During the whole polymerization, the polydispersities are quite low (in the range 1.07–1.10). The different results obtained from the four systems are due to the differences of ligands. From the point of molecular structure of ligands, it is very important to analyze deeply the two relations between (1) ligand and complex and (2) complex and polymerization. The different results obtained were discussed based on the steric effect and valence bond theory. The results can help us deep to understand the mechanism of ATRP. The presence of the bromine atoms as end groups of the poly(methyl methacrylate) (PMMA) obtained was determined by 1H-NMR spectroscopy. PMMA obtained could be used as macroinitiator to process chain-extension reaction or block copolymerization reaction via a conventional ATRP process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007
Citations
More filters
TL;DR: In this paper, a general method for tuning the dispersity of polymers synthesized via atom transfer radical polymerization (ATRP) was described, and it was shown that adding varying amounts of phenylhydrazine (PH) to the ATRP of tert-butyl acrylate led to significant deviations in the reaction kinetics.
37 citations
TL;DR: In this article, the structural chemistry of copper(I) and copper(II) with a range of multidentate N-donor ligands employed in atom transfer radical polymerisation (ATRP) is illustrated and discussed in the context of both its solid state and solution structures.
27 citations
TL;DR: In this paper, the atom transfer radical polymerization (ATRP) of n-butyl acrylate (nBA) using initiators for continuous activator regeneration (ICAR) was successfully carried out in ionic liquid in the presence of a catalyst system of FeCl3·6H2O/succinic acid using 2-bromoisobutyrate as the initiator and 2,2′-azobisisobutyronitrile as the reducing agent.
Abstract: The atom transfer radical polymerization (ATRP) of n-butyl acrylate (nBA) using initiators for continuous activator regeneration (ICAR) was successfully carried out in ionic liquid in the presence of a catalyst system of FeCl3·6H2O/succinic acid using 2-bromoisobutyrate as the initiator and 2,2′-azobisisobutyronitrile as the reducing agent. The ICAR ATRP of nBA was proved a ‘living’/controlled polymerization such as a linear increase of molecular weights of polymers with monomer conversion and relatively narrow polydispersities (<1.25) when the conversion was beyond 30% and its kinetics in this system was investigated. The polymerization rate increased with temperature and the apparent activation energy was calculated to be 32.84 kJ mol−1. The chain extension experiment was carried out to confirm the controlled manner of the polymerization system. The resultant was characterized by nuclear magnetic resonance and gel permeation chromatography.
17 citations
TL;DR: In this article, an asymmetric Salen-type Schiff-base complex was obtained in the presence of salicylaldehyde due to the formation of intermediate {[Cu(L)(OAc)]}.
13 citations
TL;DR: In this paper, a series of mononuclear asymmetric Salen-type Schiff-base complexes [Cu(L n )] were obtained by the Cu(II)-templated approach in the presence of five salicylaldehyde derivatives, respectively.
13 citations
References
More filters
TL;DR: An extension of ATRA to atom transfer radical addition, ATRP, provided a new and efficient way to conduct controlled/living radical polymerization as mentioned in this paper, using a simple alkyl halide, R-X (X = Cl and Br), as an initiator and a transition metal species complexed by suitable ligand(s), M t n /L x, e.g., CuX/2,2'-bipyridine, as a catalyst.
Abstract: An extension of atom transfer radical addition, ATRA, to atom transfer radical polymerization, ATRP, provided a new and efficient way to conduct controlled/living radical polymerization. By using a simple alkyl halide, R-X (X = Cl and Br), as an initiator and a transition metal species complexed by suitable ligand(s), M t n /L x , e.g., CuX/2,2'-bipyridine, as a catalyst, ATRP of vinyl monomers such as styrenes and (meth)acrylates proceeded in a living fashion, yielding polymers with degrees of polymerization predetermined by Δ[M]/[I] 0 up to M n ≃ 10 5 and low polydispersities, 1.1 < M w /M n < 1.5. The participation of free radical intermediates was supported by analysis of the end groups and the stereochemistry of the polymerization. The general principle and the mechanism of ATRP are elucidated. Various factors affecting the ATRP process are discussed.
1,628 citations
TL;DR: In this article, a direct preparation of amphiphilic graft copolymers from commercial poly(vinylidene fluoride) (PVDF) using atom transfer radical polymerization (ATRP) is demonstrated.
Abstract: The direct preparation of amphiphilic graft copolymers from commercial poly(vinylidene fluoride) (PVDF) using atom transfer radical polymerization (ATRP) is demonstrated. Here, direct initiation of the secondary fluorinated site of PVDF facilitates grafting of the hydrophilic comonomer. Amphiphilic comb copolymer derivatives of PVDF having poly(methacrylic acid) side chains (PVDF-g-PMAA) and poly(oxyethylene methacrylate) side chains (PVDF-g-POEM) are prepared using this method. Surface segregation of PVDF-g-POEM additives in PVDF is examined as a route to wettable, foul-resistant surfaces on PVDF filtration membranes. Because of surface segregation during the standard immersion precipitation process for membrane fabrication, a PVDF/5 wt % PVDF-g-POEM membrane, having a bulk POEM concentration of 3.4 wt %, exhibits a near-surface POEM concentration of 42 wt % as measured by X-ray photoelectron spectroscopy (XPS). This membrane displays substantial resistance to BSA fouling compared with pure PVDF and wets...
417 citations
TL;DR: Macromolecular anchoring layer approach was used for preparation of an effective macroinitiator for the synthesis of grafted polymer layers by atom transfer radical polymerization (ATRP) initiated from the surface.
Abstract: Macromolecular anchoring layer approach was used for preparation of an effective macroinitiator for the synthesis of grafted polymer layers by atom transfer radical polymerization (ATRP) initiated from the surface. For the initial surface modification, a thin layer of poly(glycidyl methacrylate) (PGMA) was deposited on the surface of a silicon wafer. The ATRP macroinitiator was synthesized on the substrate surface by the reaction between epoxy groups of PGMA and carboxy functionality of bromoacetic acid (BAA). Variation of the time and temperature of the BAA deposition as well as PGMA layer thickness allowed control over the amount of BAA attached to the surface. The PGMA anchoring layer allowed the achievement of initiator surface density significantly higher than that reported for a self-assembled monolayer of ATRP initiators. Polymer brushes were synthesized on the PGMA/BAA-modified substrates by ATRP. Different surface concentrations of BAA were used in our grafting experiments to acquire knowledge ab...
133 citations
101 citations
TL;DR: In this article, a well defined poly(methyl methacrylate) (PMMA) with an α-hydrogen atom and an ω-chlorine atom as the end groups has been synthesized by bulk polymerization of MMA at 95 °C using a new initiation system, 1,1,2,2-tetraphenyl-1, 2-ethanediol (TPED)/FeCl3/PPh3.
Abstract: Well-defined poly(methyl methacrylate) (PMMA) with an α-hydrogen atom and an ω-chlorine atom as the end groups has been synthesized by bulk polymerization of MMA at 95 °C using a new initiation system, 1,1,2,2-tetraphenyl-1,2-ethanediol (TPED)/FeCl3/PPh3. The conversion of polymerization reached to ∼100%. The molecular weight of PMMA obtained was high and the polydispersity index was quite narrow (e.g., Mn = 171 800; Mw/Mn = 1.13). The polymerization of MMA exhibited some “living”/controlled radical polymerization characteristics. The mechanism of polymerization was proposed as a reverse atom transfer radical polymerization (ATRP). The presence of the hydrogen and the chlorine atoms as end groups of the PMMA obtained was determined by 1H NMR spectroscopy.
82 citations