Synthesis of amphiphilic homopolymers with high chain end functionality by SET–LRP

Abstract

Single electron transfer‐living radical polymerization (SET–LRP) of two amphiphilic acrylates, 2‐methoxyethyl acrylate up to [M]0/[I]0 = 1,000 and di(ethylene glycol) 2‐ethylhexyl ether acrylate up to [M]0/[I]0 = 200, is accomplished with good control of molecular weight and molecular weight distribution in 2,2,2‐trifluoroethanol at 25 °C using hydrazine activated Cu(0) wire as catalyst, methyl 2‐bromopropionate as initiator, and Me6‐TREN as ligand. The chain end functionality of the resulting polymers has been analyzed by MALDI‐TOF spectrometry to demonstrate the synthesis of perfect or near‐perfect chain‐end functional amphiphilic homopolymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 294–303

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

“…1,2,26,37,38,47 It is important to mention that from many LRP methods that provide polymers with narrow molecular weight distribution, only SET-LRP generates polymers with both narrow molecular weight distribution and quantitative or near quantitative chain-end functionality. 6,7,[48][49][50][51]57,[71][72][73][74][75][76][77] Narrow molecular weight distribution is an important feature of the polymers prepared by LRP but the most significant structural parameter of these polymers is the quantitative or near quantitative chain-end functionality combined with narrow molecular weight distribution. Chain-end functionality is the major parameter of a polymer that allows the construction of complex architectures such as multiple block copolymers, 64,73,[76][77][78][79] and dendrimers by iterative synthesis.…”

“…56 Most monomers used in SET-LRP can often mediate this disproportionation but do not always dissolve Cu(II)X 2 limiting its usefulness under certain conditions. 10,46,57 The catalyst most frequently employed in SET-LRP is Cu(0) in the form of powder 2,4,12,58 including powder generated by the disproportionation of Cu(I)X in a large diversity of solvents, 12 wire, 12,64,69 activated wire [59][60][61][62] and tubes. 63,64 Almost all initiators employed in other metal catalyzed LRP such as alkyl halides, 65,66 sulfonyl halides, 33,48,65,[67][68][69] N-halides 2,70 can be used as such or modified to become soluble for SET-LRP in various media including H 2 O.…”

Fabrication of cross-linked fluorescent polymer nanoparticles and their cell imaging applications

“…These organic dyes were rst reported by Tang et al in 2001 and were called aggregation induced emission (AIE) dyes. The physical method is mainly to encapsulate the AIE dyes with biocompatible amphiphilic polymers to afford FPNs; [25][26][27] nevertheless, dye leakage or surface coating detachment is the main obstacle in this non-covalent system. [14][15][16][17][18][19] Recently, many kinds of AIE dye based FPNs have been rapidly developed and have received much attention owing to their facile processability, good solubility, high emission efficiency in the aggregated states, etc.…”

Photo‐Induced atom transfer radical polymerization with nanosized α‐Fe2O3 as photoinitiator

“…ATRP is compatible with a great variety of monomers, and it gives polymeric materials with excellent control. [13][14][15][16] Recently, photoinduced ATRP have been attractive since the polymerizations were controlled through turning on/off light. To overcome these drawbacks, some new techniques were developed: initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP), [5][6][7][8] activators regenerated by electron transfer in atom transfer radical polymerization (ARGET ATRP) [9][10][11][12] and single-electron transfer living radical polymerization (SET LRP).…”

“…To overcome these drawbacks, some new techniques were developed: initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP), [5][6][7][8] activators regenerated by electron transfer in atom transfer radical polymerization (ARGET ATRP) [9][10][11][12] and single-electron transfer living radical polymerization (SET LRP). [13][14][15][16] Recently, photoinduced ATRP have been attractive since the polymerizations were controlled through turning on/off light. [17][18][19][20][21][22] In addition, the amount of catalysts is reduced to ppm levels.…”