Synthesis of Acrylate and Methacrylate Block Copolymers Using Atom Transfer Radical Polymerization

Abstract

The synthesis of di- and triblock copolymers, involving methyl methacrylate (MMA), butyl acrylate, and methyl acrylate, using copper-based atom transfer radical polymerization (ATRP) is reported. It was found that poly(MMA) macroinitiator is able to initiate the ATRP of acrylic monomers. However, for polyacrylates to effectively initiate the ATRP of MMA, the end group should be a bromine atom and the catalyst CuCl; that is, halogen exchange should take place. ABA-type triblock copolymers, where B = poly(butyl acrylate) and A = poly(methyl methacrylate), were synthesized by growing the center block first using a difunctional initiator and then adding MMA to the ends.

Novel polymers based on atom transfer radical polymerization of 2‐methoxyethyl acrylate

“…Ethyl 2-bromoisobutyrate that is known as an efficient initiator for methacrylates 10,13,[21][22][23][24] under various ATRP conditions was employed for the MEA polymerization with Cu(I)Br catalysis utilizing different ligands. In addition, both temperature and solvents were screened to establish the most efficient polymerization conditions as seen from Table 1.…”

“…However, this macroinitiator was prepared with Cu(I)Cl as catalyst to improve the ATRP characteristics. 11,23 Thus, some halogen exchange is expected 24 and the total macroinitiator halogen efficiency is most likely higher than 50% when some growing chains contain Cl atoms. This will probably also account for different propagation rates resulting in higher polydispersity.…”

Association Behavior of Poly(methacrylic acid)-block-poly(methyl methacrylate) in Aqueous Medium: Potentiometric and Laser Light Scattering Studies

“…Using tBMA as a macroinitiator to block copolymerize with MMA may result in the broadening of the molecular weight distribution due to difference in the initiation rates. In addition, it has been reported that Cl end groups are poor initiator for the MMA monomer 14 . Bearing this in mind, we synthesised P(tBMA)-Br using CuBr as a catalyst, similar to that reported by Davis et al for tert-butyl acrylate 15 .…”

Solution Behavior of Temperature‐Responsive Molecular Brushes Prepared by ATRP

“…Halogen exchange was employed by using a CuCl catalyst along with the bromine-containing macroinitiator to facilitate well-controlled polymerizations and reduce the rate of propagation with respect to initiation. [21] Molecular weight distributions remained relatively narrow throughout the polymerizations ( Table 1). The true molecular weights of these highly-branched polymers are significantly higher than those measured from gel permeation chromatography (GPC) calibrated with linear standards.…”