Tandem RAFT-ATRP Synthesis of Polystyrene–Poly(Methyl Methacrylate) Bottlebrush Block Copolymers and Their Self-Assembly into Cylindrical Nanostructures

Bolton, Justin; Rzayev, Javid

doi:10.1021/mz200003j

Cited by 86 publications

(78 citation statements)

References 29 publications

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“…An example of this is shown in Scheme 31. [628] Grafting-through Processes This approach requires attaching monomer functionality to the substrate which may be:…”

Section: Grafting-from Processesmentioning

confidence: 99%

“…Formation of block-bottle brush polymer by tandem ATRP-RAFT. [628] Grafting through polymerization of MMA, St, and tBA with 2-((phenylcarbonothioyl)thio)acetic acid 61 as RAFT agent to gold or ITO surfaces functionalized with 454 by electrodeposition. The RAFT agent 61 is a poor RAFT agent and does not provide control over MMA polymerization, yet free poly(MMA) obtained under these conditions was reported to have a very narrow dispersity.…”

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confidence: 99%

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Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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“…An example of this is shown in Scheme 31. [628] Grafting-through Processes This approach requires attaching monomer functionality to the substrate which may be:…”

Section: Grafting-from Processesmentioning

confidence: 99%

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confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…There are examples of poly(MAM 1 )‐ b ‐poly(MAM 2 ) block copolymers prepared by the combining of ATRP and RAFT in a tandem process. One such example was described by Rzayer et al . They described an elegant synthesis of a polystyrene−poly(methyl methacrylate) bottlebrush block copolymer with asymmetric branches that was synthesized by grafting from asymmetrical backbone containing a block copolymer of poly(solketal methacrylate) (PSM) and poly(2‐(bromoisobutyryl)ethyl methacrylate) (PBIEM).…”

Section: Transformations From Atrpmentioning

confidence: 99%

Section: Transformations From Atrpmentioning

confidence: 99%

Polymer Synthesis with More Than One Form of Living Polymerization Method

Guo

Choi

Feng

et al. 2018

Macromol. Rapid Commun.

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Controlled radical polymerization (CRP) or controlled/living radical polymerization has revolutionized the polymer industry as a tool for the preparation of a wide variety of polymers. This process enables the preparation of polymers with good control of molecular weight, narrow polydispersity, and a range of architectures including block and graft copolymers, star polymers, and other functional polymers. The mechanistic transformation reaction provides a great opportunity to tune chemical and physical properties of copolymers. It can be applied to combine different homopolymers using post‐modification techniques or by the use of a dual initiator, allowing the combination of mechanistically distinct polymerization reactions. This review will cover CRP transformations including the synthesis of block copolymers with both linear structures (AB, ABA, (AB) n , multiblocks, etc.) and branched macromolecular architectures (graft, miktoarm star, and dendritic‐like), which are obtained by a combination of more than one form of living polymerization reaction.

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“…Such 'brush-like' polymers [45][46][47][48] have been studied in detail by various research groups, including Sheiko and Matyjaszewski, [49][50][51][52][53][54][55][56][57][58][59][60][61][62][63] and by the groups of Grubbs, [64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80] Bowden, [81][82][83][84][85] Wooley, [86][87][88][89][90][91] and others. [92][93][94][95]…”

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confidence: 99%

Synthesis of block polymer miktobrushes

et al. 2013

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Well defined m-A(BC) n 'miktobrush' terpolymers were synthesized utilizing the alternating radical copolymerization of two hydrophobic and incompatible macromonomer (MM) building blocks; a maleimide (MI) end functionalized poly(methyl-caprolactone) block (MI-PMCL) or 'C' and a styrene (Sty) end functionalized poly(perfluoro propylene oxide) block (Sty-PFPO) or 'F'. Polymerizations were mediated by a poly(ethylene oxide) (PEO) functionalized reversible addition-fragmentation chain transfer (RAFT) agent (PEO-CTA) or 'O' to control the chain growth of the MMs from the O block to form O(CF) n ''miktobrush'' terpolymers. The synthesis of a range of well defined m-O(CF) n terpolymers with various compositions was achieved by changing the feed of MMs. All building blocks and brush polymers were characterized by nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC) and elemental analyses. This new strategy offers a powerful route towards a block polymer architecture that can enable the formation of multi-domain hierarchical nanostructures with features on multiple length scales due to the incompatibility and unique connectivity of the building blocks incorporated.Block polymers can spontaneously self-assemble into welldefined nanostructures in block selective solvents and in the bulk, offering a powerful 'bottom up' approach towards precisely engineered materials for many diverse applications including; microelectronics, 1 tissue engineering, 2 drug delivery and water purification. 3 The increased understanding of self-assembled block polymers with varied architectures is of both fundamental and technological importance. 4 Towards this goal, AB diblock copolymers have been studied in depth. 5-7 Adding more blocks and functional groups to AB diblock copolymers increases architectural and functional complexity and can lead to more exotic self-assembled morphologies. 8,9 For instance, in a solvent selective for the A block, an ABC triblock terpolymer will form 'multicompartment micelles' whereby the two solvophobic (and incompatible) B and C blocks will produce two separate nanoscopic core domains. 10,11 If the chemistry of the microphase separated domains (B and C) is sufficiently different, multicompartment micelles can facilitate the storage of distinct small molecules within their separate core domains, thus enabling simultaneous storage and delivery of multiple incompatible payloads. 12 Linear ABC terpolymers, 13-19 linear BAC or ACB terpolymers, 20 side chain grafted ABC terpolymers or 'polysoaps', 21-23 miktoarm star m-ABC terpolymers, 24-30 and blends of block polymers 31-36 have been pursued as multicompartment micelle systems by various research groups. In each case, the connection point of the solvophobic B and C chains relative to the solvophilic corona forming block, A influences the micelle morphology to a great extent, although factors such as the solvophobicity and overall terpolymer composition play important roles. 5,11 In m-ABC terpolymers, three mutually immiscible blocks are...

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Tandem RAFT-ATRP Synthesis of Polystyrene–Poly(Methyl Methacrylate) Bottlebrush Block Copolymers and Their Self-Assembly into Cylindrical Nanostructures

Cited by 86 publications

References 29 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

Polymer Synthesis with More Than One Form of Living Polymerization Method

Synthesis of block polymer miktobrushes

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