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Synthesis of methyl methacrylate and N ‐aryl itaconimide block copolymers via atom‐transfer radical polymerization
Author(s) -
Anand Vishal,
Agarwal Seema,
Greiner Andreas,
Choudhary Veena
Publication year - 2005
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/pi.1776
Subject(s) - polymer chemistry , atom transfer radical polymerization , methyl methacrylate , copolymer , glass transition , dispersity , polymerization , monomer , differential scanning calorimetry , materials science , aryl , poly(methyl methacrylate) , methacrylate , chemistry , polymer , organic chemistry , alkyl , physics , thermodynamics
The paper describes the synthesis of block copolymers of methyl methacrylate (MMA) and N ‐aryl itaconimides using atom‐transfer radical polymerization (ATRP) via a poly(methyl methacrylate)–Cl/CuBr/bipyridine initiating system or a reverse ATRP AIBN/FeCl 3 ·6H 2 O/PPh 3 initiating system. Poly(methyl methacrylate) (PMMA) macroinitiator, ie with a chlorine chain‐end (PMMA‐Cl), having a predetermined molecular weight ( M n = 1.27 × 10 4 g mol −1 ) and narrow polydispersity index (PDI = 1.29) was prepared using AIBN/FeCl 3 ·6H 2 O/PPh 3 , which was then used to polymerize N ‐aryl itaconimides. Increase in molecular weight with little effect on polydispersity was observed on polymerization of N ‐aryl itaconimides using the PMMA‐Cl/CuBr/Bpy initiating system. Only oligomeric blocks of N ‐aryl itaconimides could be incorporated in the PMMA backbone. High molecular weight copolymer with a narrow PDI (1.43) could be prepared using tosyl chloride (TsCl) as an initiator and CuBr/bipyridine as catalyst when a mixture of MMA and N ‐( p ‐chlorophenyl) itaconimide in the molar ratio of 0.83:0.17 was used. Thermal characterization was performed using differential scanning calorimetry (DSC) and dynamic thermogravimetry. DSC traces of the block copolymers showed two shifts in base‐line in some of the block copolymers; the first transition corresponds to the glass transition temperature of PMMA and second transition corresponds to the glass transition temperature of poly( N ‐aryl itaconimides). A copolymer obtained by taking a mixture of monomers ie MMA: N ‐( p ‐chlorophenyl) itaconimide in the molar ratio of 0.83:0.17 showed a single glass transition temperature. Copyright © 2005 Society of Chemical Industry