Facile Synthesis of ABC and CBABC Multiblock Copolymers of Styrene, tert-Butyl Acrylate, and Methyl Methacrylate via Room Temperature ATRP of MMA

Abstract

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‘,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 M n, M w, 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.

RETRACTED ARTICLE: Microstructure of poly(vinyl acetate)-block-poly(methyl acrylate-co-methyl methacrylate) block terpolymers. 2D NMR and thermal study

“…13 C NMR and DEPT-135 Studies of the Block Terpolymer: Figure 1 [33][34][35][36] The carbons of C-Cl (6), CHCl (7), and C-Cl 2 (8) groups in the block terpolymer resonate at 69, 70, and 77 ppm. 22 The peaks at 60 and 39 ppm corresponding to methylene carbons in terpolymer chain end (9) and neighbor of the C- …”

“…[1][2][3][4][5][6][7][8] Among the several block copolymers and terpolymers with controlled structures which were synthesized via ATRP, [9][10][11][12][13][14][15][16][17][18][19][20] good agreement between the molecular structures and morphological, thermal, electrical, mechanical, and transport properties have been observed.…”

Hydrated Clay for Catalyst Removal in Copper Mediated Atom Transfer Radical Polymerization

“…Under appropriate conditions, these monomers undergo ATRP at ambient temperature and produce controlled molecular weight polymers with narrow molecular weight distributions (MWD). [34,35] In order to understand the effect of Na-clay in ATRP, the polymerization of BnMA and MMA was performed in the presence of hydrated Na-clay in anisole at 25 8C (Table 1). Accordingly, the polymerization of BnMA was performed in the presence of Na-clay staturated with moisture (moist clay, H 2 O/clay % 10 wt.-%) using ethyl-2-bromoisobutyrate (BrEiB) as an initiator, CuBr as a catalyst and…”

Novel Telechelic 2-Methyl-2-Bromopropionate Terminated Polyurethane Macroinitiator for the Synthesis of ABA type Tri-block Copolymers through Atom Transfer Radical Polymerization of Methyl Methacrylate

“…Similar type curves have been reported in case of ATRP. [47][48][49] However, it is interesting to note that MWD decreases with increasing conversion which indicates that the controlled incorporation nature of MMA units take place as the conversion increases. The controlled polymerization nature of the present system can also be understood from the less deviation between M n,GPC and M n,th in Figure 2.…”