The ability to do very rapid bulk atom transfer radical polymerization (ATRP) of benzyl methacrylate using a CuX/PMDETA complex at room temperature was demonstrated in this study. The experimental conditions required to synthesize low- and high-molecular-weight poly(benzyl methacrylate) with low polydispersity are reported here. The controlled/living nature of the polymerization was demonstrated through kinetic studies, and chain-extension studies. © 2004 Wiley Periodicals, Inc.

R. Dhamodharan

Department Of Chemistry

Benzene

catalysis

Chromatographic analysis

Copper

Fourier transform infrared spectroscopy

Interfaces (materials)

Mixtures

Molecular weight

Monomers

Polystyrenes

Reaction kinetics

Solutions

Synthesis (chemical)

ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

LIGHT EMITTING POLYMERS

Polydispersity

POLYFLUORENE

POLYOXADIAZOLE

Free radical polymerization

Polymerization

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

Journal of Polymer Science, Part A: Polymer Chemistry

Controlled and very rapid ambient temperature polymerization of tert-butyl acrylate (tBA) via atom transfer radical polymerization (ATRP) and single electron transfer living radical polymerization (SET-LRP) conditions is reported. Two initiators, one that would generate a secondary radical and another that would generate a primary radical, upon activation, are used. A very active catalyst CuBr/Me 6TREN was found to initiate rapid polymerization whether it was the primary or the secondary initiator. The polymerization was well controlled and very rapid. The initiator that produces secondary initiating site is found to result in more rapid polymerization than the one that produces primary initiating site. To explore the possibility of rapid ambient temperature polymerization through the SET-LRP mechanism, the polymerization was also carried out in the presence of DMSO. It was found that the polymerization was much faster compared to the bulk ATRP, without loss of control. Styrene was block copolymerized from PtBA macroinitiators and vice versa. In both the cases, block copolymers with controlled molecular weights were obtained. The tBA block of the polymer was selectively hydrolyzed to get amphiphilic block copolymers. This amphiphilic block copolymer was found to be useful in preparing stable cadmium sulfide (CdS) nanoparticulate dispersion. © 2011 Wiley Periodicals, Inc.

Controlled radical polymerization of tert-butyl acrylate at ambient temperature: Effect of initiator structure and synthesis of amphiphilic block copolymers

We demonstrate, for the first time, the synthesis of model poly(benzyl methacrylate) [P(BnMA)] brushes of very high thickness (>300 nm) on silicon wafer. P(BnMA) brush is also synthesized from the surface of silica nanoparticles, from a covalently anchored initiator monolayer, using ambient temperature ATRP. The kinetic studies and block copolymerization from the surface anchored P(BnMA)-Br macroinitiator showed that the polymerization was controlled in nature. AFM, ellipsometry, and water contact angle were used for the characterization of the polymer brush. The grafting density of the P(BnMA) brush, formed by immersion in a dilute monomer solution, was relatively less (∼11% less) in comparison to that obtained by immersion in neat monomer under similar conditions. The P(BnMA)-Br macroinitiator brushes were used to synthesize P(BnMA-b-S) diblock copolymer brushes by the ATRP of styrene at 95 °C. The P(BnMA-b-S) brushes showed stimulus response to a selective solvent and various nanopatterns were observed according to the composition of the block copolymer. © 2011 American Chemical Society.

Langmuir

Synthesis and morphological study of thick benzyl methacrylate-styrene diblock copolymer brushes

Isobornyl methacrylate (IBMA), a bulky hydrophobic methacrylate, undergoes very fast polymerization, in bulk, with Cu(I)Br/N,N,N′,N″,N″- pentamethyldiethylenetriamine (PMDETA)/ethyl-2-bromoisobutyrate system, at ambient temperature. IBMA also undergoes a spontaneous initiator-free polymerization, at ambient temperature, with Cu(I)Br/PMDETA catalytic system in dimethyl sulfoxide-water mixtures. The rate of the polymerization is seen to increase with the water content up to 80 mol % of water. A possible intervention of air in initiation is proposed. The active Cu(0) formed by the disproportionation of Cu(I) species in aqueous medium probably plays a vital role for a possible air-initiation of IBMA via single electron transfer-living radical polymerization (SET-LRP) mechanism. A high tolerance level to water under SET-LRP conditions is demonstrated. The poly(IBMA) samples obtained exhibit low molecular weight distributions (1.1-1.3). Similar behavior was not observed with other common methacrylates such as methyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. © 2011 Wiley Periodicals, Inc.

Spontaneous Cu(I)Br-PMDETA-mediated polymerization of isobornyl methacrylate in heterogeneous aqueous medium at ambient temperature

Poly(benzyl methacrylate)-magnesium phyllosilicate nanocomposites were synthesized using a novel in situ intercalative ambient temperature atom transfer radical polymerization (ATATRP). The organic moiety in the synthesized magnesium phyllosilicate was modified to initiate ATRP, in the presence of Cu(I)/PMDETA. Exfoliation was achieved and this process was rapid. The anchoring efficiency of the polymer chains on the organically modified phyllosilicate increased with silicate loading. This route to nanocomposite preparation is expected to be general and viable, and superior in comparison to the melt mixing route which did not result in the formation of a nanocomposite in these systems. © 2010 Elsevier B.V.

Applied Clay Science

Synthesis of poly (benzyl methacrylate)/Mg-phyllosilicate nanocomposites by surface-initiated ambient temperature ATRP

The arborescent polystyrene (APS) is used as a precursor to form ordered honeycomb-like microstructured template through self-assembly of water molecules at the air-solution interface via breath-figure mechanism. The APS is synthesized by successive cycles of functionalization (bromination) of polystyrene and grafting reactions via ambient temperature ATRP using the graft-from-graft approach. The resulting polymer film self-assembles to a micrometer-sized honeycomb-like arrangement. The morphology is investigated using AFM and SEM. © 2009 American Chemical Society.

Macromolecules

Arborescent polystyrene via ambient temperature ATRP: Toward ordered honeycomb microstructured templates

A detailed investigation of the atom transfer radical polymerization of methyl methacrylate (MMA) with the ethyl 2-bromoisobutyrate (2-EiBBr)/CuBr/N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) catalyst system in anisole was performed at 30 °C. The number-average molecular weight of the PMMA was observed to increase gradually and linearly while the polydispersity index (PDI) remained narrow throughout the reaction time. The summary of these studies showed that PMMA with molecular weight up to 105 g/mol could be synthesized in a controlled fashion at room temperature. The new route developed was utilized to demonstrate the facile synthesis of ABC and CBABC multiblock copolymers of styrene, tert-butyl acrylate (tBA), and MMA. For this, the starting blocks of AB and BAB were synthesized by coupling different ATRP methods reported. The end-block consisting of PMMA was synthesized by the ATRP of MMA using the CuCl/PMDETA catalyst system (halogen exchange) with anisole as the solvent at room temperature. Gel permeation chromatography (GPC) was used to determine the Mn, Mw, and PDI of the polymers synthesized. The PDI of all the block copolymers is found to be low (1.1-1.4). 1H NMR spectroscopy was used to determine the chemical composition of the block copolymers. Additional evidence for the blocky nature was also gained from FT-IR and thermal analysis.

Facile synthesis of ABC and CBABC multiblock copolymers of styrene, tert-butyl acrylate, and methyl methacrylate via room temperature ATRP of MMA

The atom-transfer radical polymerization of methyl methacrylate at room temperature starting from monolayers of initiators, which are covalently anchored to silicon substrates, is described. The control of layer thickness and molecular weight, a constant graft density, and a narrow molecular weight distribution of the polymers produced provide evidence for a controlled surface-initiated polymerization, and dense surface-attached polymer brushes on the SiO2 surfaces are obtained under mild reaction conditions.

Macromolecular Rapid Communications

Controlled growth of PMMA brushes on silicon surfaces at room temperature

Journal of the American Chemical Society

Tailored Synthesis of Structurally Defined Polymers by Organotellurium-Mediated Living Radical Polymerization (TERP): Synthesis of Poly(meth)acrylate Derivatives and Their Di- and Triblock Copolymers

High Molecular Weight PMMA by ATRP

Atom Transfer Radical Polymerization of Hydroxy-Functional Methacrylates at Ambient Temperature: Comparison of Glycerol Monomethacrylate with 2-Hydroxypropyl Methacrylate

Very Rapid Copper-Mediated Atom Transfer Radical Polymerization of Benzyl Methacrylate at Ambient Temperature

Journal	Data powered by TypesetJournal of Polymer Science, Part A: Polymer Chemistry
Publisher	Data powered by TypesetJohn Wiley and Sons Inc.
ISSN	0887624X
Open Access	No