Efficient synthesis of narrowly dispersed amphiphilic double-brush copolymers through the polymerization reaction of macromonomer micelle emulsifiers at the oil–water interface

Li, Heng; Han, Moonsik; Gao, Yong; Li, Huaming; Chen, Daoyong

doi:10.1039/c6py00705h

Cited by 27 publications

(20 citation statements)

References 54 publications

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“…Gao et al prepared poly(methyl methacrylate)-block-poly(N,N-dimethyl acrylamide) (PMMA-b-PDMA) diblock macromonomers that had a methacryloyl group at the junction of the two blocks for grafting through polymerization. 152 The diblock macromonomer could first form micelles in the aqueous phase, then stabilize o/w Pickering emulsions (a mixture of ndecanol and toluene as the oil phase) with the hydrophobic cores and hydrophilic shells extending into oil and aqueous phases and the methacryloyl groups residing at the boundary, as shown in Fig. 10.…”

Section: Bottlebrush Polymersmentioning

confidence: 99%

Polymers with advanced architectures as emulsifiers for multi-functional emulsions

Russell

2021

Mater. Chem. Front.

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Section: Bottlebrush Polymersmentioning

confidence: 99%

Polymers with advanced architectures as emulsifiers for multi-functional emulsions

Russell

2021

Mater. Chem. Front.

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“…Such a DGBCP is a synthetically challenging target, as it requires the insertion of a backbone into the middle of the B block of the A- b -B- b -C triblock copolymer and controlling its position. We note that previously reported DGBCPs carry either two identical side chains or A and C chains (without B) synthesized via different polymerization mechanisms, which do not allow the introduction of B blocks. − …”

Section: Introductionmentioning

confidence: 92%

Self-Assembly of Monolayer Vesicles via Backbone-Shiftable Synthesis of Janus Core–Shell Bottlebrush Polymer

Nam

Kim

et al. 2019

Macromolecules

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We report the self-assembly of monolayer vesicles from Janus core–shell bottlebrush polymers. A route was developed to synthesize doubly grafted bottlebrush copolymers (DGBCPs) possessing A-b-B and B′-b-C side chains on a single repeating unit. Graft-through ring-opening metathesis polymerization of a norbornene moiety installed by single unit monomer insertion allowed us to place the backbone on any repeating unit of the core (B and B′) block. By decorating each core chain end with different chains via reversible addition–fragmentation chain transfer polymerization, we can obtain nanoobjects with an asymmetric B core and a phase-separated A/C shell. We demonstrate that polystyrene-branch-polystyrene′ and polylactide-b-polystyrene-branch-polystyrene′-b-poly(n-butyl acrylate) macromonomers can be successfully synthesized and polymerized to produce DGBCPs in high yields (81–94% conversion) with an absolute molar mass of 149–395 kg mol–1 and a dispersity of 1.18–1.38. In a solvent slightly more selective to A than C, self-assembly of monolayer vesicles with diameter of <100 nm was observed by transmission electron microscopy. Dissipative particle dynamics simulations suggest that increasing the backbone length and moving the backbone toward the B′/C interface increases the backbone bending energy and favors a lower curvature. The spontaneous curvature appears to prefer a particular layer radius, avoiding bilayer formation.

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“…Besides ROMP, free radical polymerizations of macromonomers by a Pickering emulsion template at an oil–water interface was employed to prepare Janus bottlebrush polymers via grafting‐through approach. [ 54 ] By using ATRP of methyl methacrylate (MMA) and RAFT of N , N ‐dimethylacrylate (DMA), poly(methyl methacrylate)‐ block ‐poly( N,N ‐dimethylacrylate) (PMM‐ b ‐PDMA) was synthesized as the precursor of macromonomer. After the esterification reaction, vinyl group was attached to form the amphiphilic macromonomer of MA–PMMA‐ b ‐PDMA ( Figure ).…”

Section: Design and Synthesis Of Janus Bottlebrush Polymersmentioning

confidence: 99%

“…Design, synthesis, and self‐assembly of Janus bottlebrush polymers have arouse much interest in polymer chemistry and material science. [ 54,55 ] In general, Janus bottlebrush polymers could be prepared via backbone‐first [ 50 ] (grafting‐to and grafting‐from) or side‐chain‐first [ 56 ] (grafting‐through) strategy. Most of Janus bottlebrush polymers were reported via grafting‐through approach.…”

Section: Introductionmentioning

confidence: 99%

Design, Synthesis, and Self‐Assembly of Janus Bottlebrush Polymers

Chen

Zhu

et al. 2020

Macromol. Rapid Commun.

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in solution, [28-30] and at the interfaces [31,32] features the unique microstructures and varied applications (Figure 1C). Janus bottlebrush polymers are a class of special molecular brushes, which have two incompatible side chains on the same repeating unit of the backbone. [33] "Janus" is the god in ancient Roman religion and myth with two faces looking to the past and the future. [34] In scientific community, the phrases containing Janus, such as "Janus nanoparticles," [35-38] "Janus beads," [39,40] and "Janus polymerization," [41-43] indicate something consisting of counterparts. [44-46] The design of Janus bottlebrush polymers was inspired by Janus particles. [35,47-49] The characteristic of Janus bottlebrush polymers is that the repeating unit of the backbone possesses two immiscible side chains. [50-52] Core-shell bottlebrush polymers with block copolymers as the side chains are usually not Janus-type unless the block side chains are unsymmetrical. [6] An emerging Janus core-shell bottlebrush polymer has been developed by transferring the side chains from homo polymers to two different block copolymers. [53] Design, synthesis, and self-assembly of Janus bottlebrush polymers have arouse much interest in polymer chemistry and material science. [54,55] In general, Janus bottlebrush polymers could be prepared via backbone-first [50] (grafting-to and graftingfrom) or side-chain-first [56] (grafting-through) strategy. Most of Janus bottlebrush polymers were reported via grafting-through approach. Macromonomers are first designed and subsequently polymerizations occur to form the backbone. [23] Backbonefirst route also allows for the synthesis of Janus bottlebrush polymers by using combined grafting-to and grafting-from approach. [57] The special unsymmetrical architectures enable Janus bottlebrush polymers to achieve ideal phase separation in bulk, [58,59] in solution, [52] and at the interface. [32] The preorganized interface can promote self-assembly process and avoid the distorted phase separation. [32,33] The self-assembly of Janus bottlebrush polymers achieves small domain size and tunable bulk property, [58,59] which is challenging for the traditional linear or bottlebrush polymers. [60,61] Therefore, Janus bottlebrush polymers have great potential applications in nanolithography, [58] photonic crystals, [62] biomedicine, [53] surfactants, [63] etc. The big families of bottlebrush polymers have been nicely reviewed by Grubbs and co-workers, [64] Müllner and coworkers, [65-67] Rzayev and co-workers, [7] Verduzco and coworkers, [6] and Matyjaszewski and co-workers [2]. As a young but significant class, Janus bottlebrush polymers have achieved remarkable advances in recent years. Therefore, this review attempts to focus on Janus bottlebrush polymers, covering Janus bottlebrush polymers are a class of special molecular brushes, which have two immiscible side chains on the repeating unit of the backbone. The characteristic architectures of Janus bottlebrush polymers enable unique selfassembly properties and br...

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Efficient synthesis of narrowly dispersed amphiphilic double-brush copolymers through the polymerization reaction of macromonomer micelle emulsifiers at the oil–water interface

Cited by 27 publications

References 54 publications

Polymers with advanced architectures as emulsifiers for multi-functional emulsions

Polymers with advanced architectures as emulsifiers for multi-functional emulsions

Self-Assembly of Monolayer Vesicles via Backbone-Shiftable Synthesis of Janus Core–Shell Bottlebrush Polymer

Design, Synthesis, and Self‐Assembly of Janus Bottlebrush Polymers

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