Tetrahydrofurfuryl methacrylate (THFMA), a heterocyclic monomer was polymerized by ambient temperature Atom Transfer Radical Polymerization (AT ATRP) using CuX/PMDETA/EBiB system. THFMA was found to undergo very rapid polymerization, in bulk. For a target DP &gt; 200, bulk polymerization results in cross-linking as evidenced by (CH2)n,wag peaks (IR spectroscopy). Atom Transfer Radical copolymerization (ATRcP) of THFMA with MMA was performed and the reactivity ratios were calculated from the copolymer composition, as determined by 1H NMR, using Fineman-Ross and Kelen-Tudos methods. The reactivity ratios determined for ATRP were found to be significantly different from the literature values for conventional free radical polymerization (CFRP). This may be due to the coordination of copper catalytic system with the oxygen atom of the tetrahydrofurfuryl group that could lead to the variation in reactivity ratios. 1H NMR evidence for catalyst-monomer interaction is also provided. © 2009 Elsevier Ltd. All rights reserved.

R. Dhamodharan

Department Of Chemistry

AMBIENT TEMPERATURE ATRP

Ambient temperatures

ATOM TRANSFER RADICAL COPOLYMERIZATION

Bulk polymerization

Catalytic system

CONVENTIONAL FREE-RADICAL POLYMERIZATION

COPOLYMER COMPOSITIONS

HETEROCYCLIC MONOMERS

IR spectroscopy

KELEN-TUDOS METHOD

Methyl methacrylates

Oxygen atom

RAPID POLYMERIZATION

REACTIVITY RATIO

TETRAHYDROFURFURYL

TETRAHYDROFURFURYL METHACRYLATE

TETRAHYDROFURFURYL METHACRYLATES

Acrylic monomers

Atoms

catalysis

CATALYSTS

Copolymerization

Esters

Free radical polymerization

Free radicals

Monomers

nuclear magnetic resonance

Oxygen

Polymers

Temperature

ATOM TRANSFER RADICAL 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

European Polymer Journal

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.

Journal of Polymer Science, Part A: Polymer Chemistry

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

An extract prepared from inexpensive, drumstick leaves having natural transition metals in ppm levels was exploited as a catalyst for a well-controlled synthesis of poly(N-isopropylacrylamide) and poly(methyl acrylate).

Polymer Chemistry

Natural catalyst mediated ARGET and SARA ATRP of N-isopropylacrylamide and methyl acrylate

A binol ester initiator was used as a bifunctional ATRP initiator in combination with PMDETA/copper bromide catalyst system in DMF to synthesize n-butyl acrylate macroinitiator at 50° C. The resulting macroinitiator was used for a detailed investigation of the ATRP of methyl methacrylate (MMA) with CuCl/N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) catalyst system in anisole at 30° C. Thus, the MMA polymerization is shown to proceed with first order kinetics, with predicted molecular weight and narrow polydispersity indices. Gel permeation chromatography (GPC) and NMR were used for the characterization of the polymers synthesized. Copyright © Taylor & Francis, Inc.

Journal of Macromolecular Science - Pure and Applied Chemistry

Synthesis and characterization of block copolymers, of P(MMA-b-n-BA-b-MMA) via ambient temperature ATRP of MMA

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.

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

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.

Macromolecules

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

Macromolecular Chemistry and Physics

Atom-Transfer Radical Copolymerization of Furfuryl Methacrylate (FMA) and Methyl Methacrylate (MMA): A Thermally-Amendable Copolymer

Journal of Polymer Science Part A: Polymer Chemistry

A tailor-made polymethacrylate bearing a reactive diene in reversible diels-alder reaction

Ambient temperature Atom Transfer Radical copolymerization of tetrahydrofurfuryl methacrylate and methyl methacrylate: Reactivity ratio determination

Journal	European Polymer Journal
ISSN	00143057
Open Access	No