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.

R. Dhamodharan

Department Of Chemistry

Ayothi Ramakrishnan

AMBIENT TEMPERATURE POLYMERIZATION

ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

BIFUNCTIONAL INITIATORS

BINOL ESTERS

Methyl methacrylates

N-BUTYL ACRYLATES

Triblock copolymers

CATALYSTS

Copper compounds

Esters

Free radical polymerization

Gel permeation chromatography

Nuclear magnetic resonance spectroscopy

Reaction kinetics

Synthesis (chemical)

THERMOPLASTIC ELASTOMERS

Block copolymers

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

Synthesis and Characterization of Block Copolymers of P(MMA‐b‐n‐BA‐b‐MMA) via Ambient Temperature ATRP of MMA

Journal of Macromolecular Science - Pure and Applied Chemistry

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.

European Polymer Journal

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

Well defined graft copolymers are prepared by "grafting from" atom transfer radical polymerization (ATRP) at room temperature (30°C). The experiments were aimed at grafting methacrylates and styrene at latent initiating sites of polystyrene. For this purpose, the benzylic hydrogen in polystyrene was subjected to allylic bromination with Af-bromosuccinimide and azobisisobutrylnitirle to generate tertiary bromide ATRP initiating sites (Br-C-PS). The use of Br-C-PS with lesser mol % of bromide initiating groups results in better control and successful graft copolymerization. This was used to synthesize a series of new graft copolymers such as PS-g-PBnMA, PS-g-PBMA, PS-g-GMA, and PS-g-(PMMA-b-PtBA) catalyzed by CuBr/PMDETA system, in bulk, at room temperature. The polymers are characterized by GPC, NMR, FTIR, TEM, and TGA. Graft copolymerization followed by block polymerization enabled the synthesis of highly branched polymer brush, in which the grafting density can be adjusted by appropriate choice of bromide concentration in the polystyrene. © 2007 Wiley Periodicals, Inc.

Journal of Polymer Science, Part A: Polymer Chemistry

Grafting of methacrylates and styrene on to polystyrene backbone via a "grafting from" ATRP process at ambient temperature

Novel bifunctional initiators [1,1′-Bi-2-naphthol bis(2-bromo-2-methylpropionate); (R)-, (S)-, and racemic-] were synthesized from the esterification of 1,1′-bi-2-naphthol and used as initiators in atom transfer radical polymerization (ATRP) in conjunction with N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA), and copper (I) bromide or copper (I) chloride. The initiators synthesized were completely characterized by UV, FTIR, NMR, and Mass spectroscopies. A detailed investigation of the ATRP of methyl methacrylate (MMA) with the bifunctional initiators (BBiBN) along with CuBr or CuCl/PMDETA catalyst system in anisole was carried out at 30°. Thus, MMA polymerization is shown to proceed with first-order kinetics, with predicted molecular weight, and narrow polydispersity indices. The ATRP of glycidyl methacrylate (GMA) and tert-butyl acrylate (tBA) were also performed with BBiBN initiator in conjunction with CuBr/PMDETA catalyst system. The polymerization of GMA was carried out at 30°C, but tBA was polymerized at 60°C. Gel permeation chromatography (GPC), FTIR, NMR, UV spectroscopies, and TGA were used for the characterization of the polymers synthesized. © 2004 Wiley Periodicals, Inc.

ATRP of methyl methacrylate using a novel binol ester-based bifunctional initiator

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

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

Polymer

Atom transfer radical polymerization of methyl acrylate from a multifunctional initiator at ambient temperature

Journal of Polymer Science Part A: Polymer Chemistry

Atom transfer radical polymerization ofn-butyl acrylate from silica nanoparticles

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

Journal	Journal of Macromolecular Science - Pure and Applied Chemistry
ISSN	10601325
Open Access	No