@article { ISI:000232612200002, title = {Novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate}, journal = {Journal of Polymer Science Part A-Polymer Chemistry}, volume = {43}, number = {21}, year = {2005}, month = {NOV}, pages = {4996-5008}, publisher = {WILEY-BLACKWELL}, type = {Article}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

A tridentate ligand, BPIEP: 2,6-bis[1-(2,6-diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/{\textquoteright}{\textquoteright}living{\textquoteright}{\textquoteright} radical polymerization of MXU at 90 degrees C in toluene as solvent, (CuBr)-Br-I as catalyst, and ethyl-2-bromoisobutyrate (EBiB) as initiator resulting in well-defined polymers with polydispersities M-W/M-n \<= 1.23. The rate of polymerization follows first-order kinetics, k(app) = 3.4 x 10(-5) s(-1), indicating the presence of low radical concentration ([P*] \<= 10(-8)) throughout the reaction. The polymerization rate attains a maximum at a ligand-to-metal ratio of 2:1 in toluene at 90 degrees C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (M-n,M-SEC) increased linearly with conversion and were found to be higher than predicted molecular (M-n,M-Cal). However, the polydispersity remained narrow, i.e., \<= 1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed. with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33\%, v/v) gave PDI of 1.22 (Mn = 8500) in 48 h whereas, at 50 degrees C the PDI is 1.18 (Ma = 10,300), which is achieved in 23 h. The plot of In kapp versus 1/T gave an apparent activation energy of polymerization as (Delta E-app(not equal)) 58.29 KJ/mol and enthalpy of equilibrium (Delta H-eq(0)) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. (c) 2005 Wiley Periodicals, Inc.

}, keywords = {2, 6-bis [1-(2, 6-diisopropyl phenylimino) ethyl] pyridine (BPIEP), Activation energy, apparent rate constant, Atom transfer radical polymerization (ATRP), diphenylether, ethyl-2-bromoisobutyrate (EBiB), methyl methacrylate, polydispersity index (PDI), Toluene}, issn = {0887-624X}, doi = {10.1002/pola.20973}, author = {Mittal, A. and Sivaram, S.} } @article { ISI:000259651700007, title = {Hydrated clay for catalyst removal in copper mediated atom transfer radical polymerization(a)}, journal = {Macromolecular Rapid Communications}, volume = {29}, number = {18}, year = {2008}, month = {SEP}, pages = {1538-1543}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {PO BOX 10 11 61, D-69451 WEINHEIM, GERMANY}, abstract = {

A simple method has been described to remove catalyst from the copper mediated atom transfer radical polymerization (ATRP) of benzyl methacrylate and methyl methacrylate in anisole at 25 degrees C using hydrated natural clay (sodium montmorillonite, Na-clay). The method consists of (1) addition of hydrated clay (CU(I/)clay approximate to 5 wt.-\%) either during or after the polymerization, (2) oxidation of catalyst complex by exposing the terminated reaction mixture in air, and (3) filtration to obtain catalyst free polymer solution. A strong coordination of CuBr-ligand complex onto hydrated clay (10 wt.-\%

}, keywords = {Atom transfer radical polymerization (ATRP), Catalysts, clay, selectivity, synthesis}, issn = {1022-1336}, doi = {10.1002/marc.200800240}, author = {Munirasu, Selvaraj and Deshpande, Ashwini and Baskaran, Durairaj} } @article { ISI:000285326300001, title = {New ATRP initiator for synthesis of cyclic carbonate-terminated poly(methyl methacrylate)}, journal = {Reactive \& Functional Polymers}, volume = {70}, number = {12}, year = {2010}, month = {DEC}, pages = {931-937}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

A new ATRP initiator, viz, 2-oxo-1,3-dioxolan-4-yl-(methyl-2-bromo-2-methylpropanoate) (ODMBMP) was synthesized by the reaction of commercially available glycerol carbonate with 2-bromoisobutyrylbromide and was used to carry out ATRP reactions of methyl methacrylate (MMA) in the presence of copper chloride/N,N{\textquoteright},N{\textquoteright},N{\textquoteright}{\textquoteright}N{\textquoteright}{\textquoteright}-pentamethyldiethylenetriamine to afford low molecular weight (M(n)(GPC) = 1750-7550) cyclic carbonate-terminated poly(methyl methacrylate)s with relatively narrow molecular weight distribution (M(w)/M(n) = 1.16-1.30). Poly(methyl methacrylate)s having higher molecular weight (M(n)(GPC) = 18,250 and 44,130) could also be synthesized using ODMBMP as the ATRP initiator. The kinetic studies of bulk ATRP of MMA showed a linear relationships between both In[M](o)/[M(t)] vs time and molecular weight vs conversion indicating controlled/living polymerization. The presence of cyclic carbonate functionality in poly(methyl methacrylate)s was confirmed by FUR. (1)H NMR, and (13)C NMR spectroscopy. The reactivity of cyclic carbonate group was demonstrated by a model reaction using n-propyl amine and the results showed quantitative conversion to hydroxyl urethane group. (C) 2010 Elsevier Ltd. All rights reserved.

}, keywords = {Atom transfer radical polymerization (ATRP), cyclic carbonate, functional polymers, poly(methyl methacrylate)}, issn = {1381-5148}, doi = {10.1016/j.reactfunctpolym.2010.08.005}, author = {Palaskar, Dnyaneshwar V. and Sane, Prakash S. and Wadgaonkar, Prakash P.} } @article { ISI:000293939800014, title = {Synthesis of bis-allyloxy functionalized polystyrene and poly (methyl methacrylate) macromonomers using a new ATRP initiator}, journal = {European Polymer Journal}, volume = {47}, number = {8}, year = {2011}, month = {AUG}, pages = {1621-1629}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A new bis-allyloxy functionalized ATRP initiator, viz, 4,4-bis (4-(allyloxy) phenyl) penty1-2-bromo-2-methylpropanoate was synthesized starting from commercially available 4,4-bis (4-hydroxyphenyl) pentanoic acid. Atom transfer radical polymerization of styrene in bulk and that of methyl methacrylate in anisole using CuBr/N,N,N{\textquoteright},N{\textquoteright},N {\textquoteleft}{\textquoteright}-pentamethyldiethyl-enetriamine system was carried out. The kinetic study of styrene polymerization showed controlled polymerization behavior. Bis-allyloxy functionalized well-defined polystyrene (M(n)(GPC): 13,600-28,250, PDI: 1.07-1.09) and poly (methyl methacrylate) (M(n)(GPC): 10,100-18,450, PDI: 1.23-1.34) macromonomers were obtained. The presence of allyloxy functionality was confirmed by (1)H NMR spectroscopy. The reactivity of allyloxy functionality was demonstrated by carrying out organic reactions such as addition of bromine and hydrosilylation on polystyrene macromonomer. Polystyrene macromonomer with bis-allyloxy functionality was transformed into bis-epoxy functionalized polystyrene macromonomer using 3-chloroperoxybenzoic acid. (C) 2011 Elsevier Ltd. All rights reserved.

}, keywords = {Allyloxy end-functional polymer, Atom transfer radical polymerization (ATRP), Macromonomers, Poly (methyl methacrylate), Polystyrene}, issn = {0014-3057}, doi = {10.1016/j.eurpolymj.2011.05.012}, author = {Sane, Prakash S. and Palaskar, Dnyaneshwar V. and Wadgaonkar, Prakash P.} } @article {45509, title = {New approach for the synthesis of miktoarm star polymers through a combination of thiol-epoxy {\textquoteleft}{\textquoteleft}click{\textquoteright}{\textquoteright} chemistry and ATRP/Ring-opening polymerization techniques}, journal = {Journal of Polymer Science Part A-Polymer Chemistry}, volume = {57}, year = {2019}, month = {JAN }, pages = {146-156}, type = {Article}, abstract = {

A new approach was developed for synthesis of certain A(3)B(3)-type of double hydrophilic or amphiphilic miktoarm star polymers using a combination of {\textquoteleft}{\textquoteleft}grafting onto{\textquoteright}{\textquoteright} and {\textquoteleft}{\textquoteleft}grafting from{\textquoteright}{\textquoteright} methods. To achieve the synthesis of desired miktoarm star polymers, acetyl protected poly(ethylene glycol) (PEG) thiols (M-n = 550 and 2000 g mol(-1)) were utilized to generate A(3)-type of homoarm star polymers through an in situ protective group removal and a subsequent thiol-epoxy {\textquoteleft}{\textquoteleft}click{\textquoteright}{\textquoteright} reaction with a tris-epoxide core viz. 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl ether. The secondary hydroxyl groups generated adjacent to the core upon the thiol-epoxy reaction were esterified with alpha-bromoisobutyryl bromide to install atom transfer radical polymerization (ATRP) initiating sites. ATRP of N-isopropylacrylamide (NIPAM) using the three-arm star PEG polymer fitted with ATRP initiating sites adjacent to the core afforded A(3)B(3)-type of double hydrophilic (PEG)(3)[poly(N-isopropylacrylamide)] (PNIPAM)(3) miktoarm star polymers. Furthermore, the generated hydroxyl groups were directly used as initiator for ring-opening polymerization of epsilon-caprolactone to prepare A(3)B(3)-type of amphiphilic (PEG)(3)[poly(epsilon-caprolactone)](3) miktoarm star polymers. The double hydrophilic (PEG)(3)(PNIPAM)(3) miktoarm star polymers showed lower critical solution temperature around 34 degrees C. The preliminary transmission electron microscopy analysis indicated formation of self-assembly of (PEG)(3)(PNIPAM)(3) miktoarm star polymer in aqueous solution. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 146-156

}, keywords = {Atom transfer radical polymerization (ATRP), miktoarm star polymers, ring-opening polymerization (ROP), thermoresponsive, thiol-epoxy}, issn = {0887-624X}, doi = {10.1002/pola.29278}, author = {Gadwal, Ikhlas and Wadgaonkar, Prakash P. and Ichake, Amol B. and Mane, Shivshankar R.} }