Nitroxide mediated controlled synthesis of glycidyl methacrylate-rich copolymers enabled by SG1-based alkoxyamines bearing succinimidyl ester groups

Synthesis of Stimuli-responsive, Water-soluble Poly[2-(dimethylamino)ethyl methacrylate/styrene] Statistical Copolymers by Nitroxide Mediated Polymerization

“…The results of the DMAEMA/styrene statistical copolymerizations demonstrated that NHS-BlocBuilder was not only an effective initiator for synthesizing DMAEMA-rich copolymers, but also simplifies polymerization procedures and provides opportunities for further functionalization of the copolymers. Our group earlier noticed similar performance for NHS-BlocBuilder controlled copolymerizations of glycidyl methacrylate with styrene [38].…”

“…The combination of NHS-BlocBuilder with DMAEMA-rich feeds was envisioned to enable the development of a water-soluble PDMAEMA with LCST behavior that could also later be conjugated to biological compounds or other amine-containing materials. Further, NMP with NHS-BlocBuilder will be tested to see if no additional free SG1 nitroxide was required, as has recently been shown for other methacrylate-rich feeds [38]. The following study details results concerning the NMP synthesis of DMAEMA-rich copolymerizations (kinetics, level of control and livingness of the copolymers) followed by the responses of the copolymers to temperature and pH changes in aqueous media.…”

“…Vinas et al synthesized the first NHS-functionalized initiator for NMP using BlocBuilder [37]. The NHS-BlocBuilder (Scheme 1(b)) has been used to effectively control the homopolymerization of styrene and n-butyl acrylate, as well as statistical copolymerization of glycidyl methacrylate and styrene without aid of additional free SG1 nitroxide [37,38].…”

Thermo-responsive, UV-active poly(phenyl acrylate)-b-poly(diethyl acrylamide) block copolymers

“…In this study, we first demonstrate the homopolymerization of PA using a succinimidyl functional unimolecular alkoxyamine initiator (NHS-BlocBuilder [30,31], Figure 1) followed by the synthesis of a PPA-b-P(DEAAm) block copolymer and the characterization of its thermo-responsive behavior. A series of PPA homopolymers were synthesized at either 90 or 110°C, using NHS-BlocBuilder with 0 or 15 mol% additional SG1 relative to NHSBlocBuilder.…”

Synthesis of Narrow Molecular Weight Distribution Norbornene-Lactone Functionalized Polymers by Nitroxide-Mediated Polymerization: Candidates for 193-nm Photoresist Materials

“…The successful control of methacrylates with SG1 was not achieved until Nicolas et al demonstrated that with a small amount of styrene or acrylonitrile as the controlling co-monomer, the polymerization of methyl methacrylate (MMA) could be effectively controlled with relatively low dispersity and the ability to re-initiate a second batch of monomer [11][12][13]. Following this, NMP has been shown to be an effective and robust method for the synthesis of a variety of poly(methacrylate)s with a small amount of controlling co-monomers, such as styrene [14,15], 9-(4-vinylbenzyl)-9H-carbazole (VBK) [16], sodium 4-styrene sulfonate [17] and 2-vinylpyridine (2VP) [18] using the SG1-based BlocBuilder unimolecular initiator. Furthermore, NMP is able to provide tight control over the molecular weight distribution and excellent retention of chain end fidelity in bulk [9,19], aqueous (mini)emulsion [20][21][22] and ionic liquids [23,24].…”