Diblock and triblock copolymers of styrene and acetoxymethylstyrene by one‐pot ATRP

Abstract

We describe the synthesis of diblock and triblock copolymers by sequential atom transfer radical polymerization of styrene and acetoxymethylstyrene. Contrary to the usual block copolymerization involving isolation of the macroinitiator, a convenient one-pot procedure is developed. This is possible because of the preferential polymerization of acetoxymethylstyrene, even in the presence of residual styrene, as inferred from characterization of the intermediate polystyrenes and the block copolymers by size exclusion chromatography, 1 H NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, and GPEC techniques. The latent acetoxy functionalities in these block copolymers are shown to be easily unmasked to OOH and OBr functionalities, with the potential for block ionomers and dense graft architectures.

Smart “All Acrylate” ABA Triblock Copolymer Bearing Reactive Functionality via Atom Transfer Radical Polymerization (ATRP): Demonstration of a “Click Reaction” in Thermoreversible Property

“…It eliminates the stringent reaction of ionic polymerization but maintains versatility of ionic polymerization. Among different types of CRP, transition metal halide-catalyzed CRP, widely known as atom transfer radical polymerization (ATRP), is widely used to prepare different tailor-made polymers with complex architectures like block copolymers, star polymers, hyperbranched polymers, etc. − Interestingly, ATRP can be applied to a great variety of monomers, especially functional monomers which are very difficult to polymerize via ionic polymerizations. ATRP has been used to prepare different block copolymers based on acrylates .…”

Block Copolymer Synthesis via a Combination of ATRP and RAFT Using Click Chemistry

“…The second method is to isolate and purify the first polymer, also called the macroinitiator, for initiating the second monomer, known as the subsequent process. Later the second monomer is added without any additional initiator to obtain the block copolymer 2, 14–23. A schematic of the block copolymers formed from the sequential and the subsequent addition methods is shown in Figure 5.…”

“…An important issue with the subsequent addition method is the need for efficient re‐initiation of the second monomer using the first homopolymer as a macroinitiator. There are several instances available in literature where one chooses either the sequential or the subsequent method depending on the monomers to be polymerized 14–23. Since both methods have pros and cons, the coupling method may be an easier way to synthesize block copolymers.…”

“…Using controlled radical polymerization techniques, block and graft copolymers, star polymers, hyperbranched polymers, and dendrimers with well‐defined structures have been successfully synthesized 1, 5, 7, 13. Generally, block copolymers are made using controlled radical polymerization methods by either the subsequent or the sequential addition of monomers and there are many reports available 14–23. Block copolymers have also been made using dual functional initiators.…”

Synthesis of fluorinated diblock copolymer by ATRP and its application of PAVAc polymerization in ScCO2

“…It has been proven that a well‐controlled block copolymer can be synthesized by a sequential two‐step or one‐pot method without any transformation or protection of initiating sites. ATRP, one of the most robust CRP techniques, has been applied for the controlled polymerization of various monomers such as styrenes,2–4 acrylates,5–8 methacrylates,9–11 acrylamides,12, 13 and acrylonitrile 14–16. In addition, compared with other controlled radical polymerizations, the reaction condition of ATRP is relatively mild.…”