Precise Synthesis of Bottlebrush Block Copolymers from ω-End-Norbornyl Polystyrene and Poly(4-<i>tert</i>-butoxystyrene) via Living Anionic Polymerization and Ring-Opening Metathesis Polymerization

Yu, Yong‐Guen; Chae, Chang‐Geun; Kim, Myung-Jin; Seo, Ho‐Bin; Grubbs, Robert H.; Lee, Jae‐Suk

doi:10.1021/acs.macromol.7b02447

Cited by 54 publications

(57 citation statements)

References 49 publications

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“…The kinetic behaviors of macromonomer ROMP have been widely studied with a variety of functional groups in the macromonomer 74–77. The reactions usually follow pseudo first‐order kinetics in monomer to generate linear relationships between ln([ M ] 0 /[ M ]) versus time and M n as a function of % conversion.…”

Section: Resultsmentioning

confidence: 99%

“…Since the controlled polymerization of NB‐DMAEA‐C6‐Br 14 to varied DPs was demonstrated, amphiphilic bottlebrush block copolymerization was examined by utilizing NB‐PDMAEA‐C6‐Br 14 and a polystyrene MM, NB‐PS 17 . NB‐PS MMs have been widely polymerized by ROMP to yield well‐defined bottlebrush block copolymers using a variety of anchor norbornene groups 41,71,76. In this work, a NB‐PS MM with the same anchor group as the quaternary ammonium MMs was prepared from RAFT polymerization to obtain a 17 DP MM (2000 g mol −1 ).…”

Section: Resultsmentioning

confidence: 99%

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Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting‐Through Ring‐Opening Metathesis Polymerization

Senkum

Gramlich

2020

Macro Chemistry & Physics

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Cationic bottlebrush homopolymers are polymerized using a grafting‐through approach by ring‐opening metathesis polymerization (ROMP) to afford well‐defined polymers. Quaternary ammonium macromonomers (MMs) are prepared by quaternizing tertiary amine MMs synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The quaternary ammonium MMs undergo ROMP to target molecular weights (Mn = 30 000–100 000 g mol−1) and a low dispersity (Đ = 1.10–1.30). Halide‐ligand exchange between the third generation Grubbs catalyst (G3) and halide counter ions (bromide and iodide ions) of MMs changes the catalyst activity throughout ROMP, causing it to deviate from pseudo‐first order kinetic behavior; however, the polymerization still follows controlled behavior without significant catalyst termination. Increasing steric bulk of the MMs decreases the polymerization rate as well. Amphiphilic block copolymers are synthesized by sequential polymerization of quaternary ammonium MMs and polystyrene (PS) MMs. Using a PS macroinitiator affords block copolymers with lower Đ values as compared to the less active cationic macroinitiator.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting‐Through Ring‐Opening Metathesis Polymerization

Senkum

Gramlich

2020

Macro Chemistry & Physics

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“…[ 96,97 ] They also contributed ultrahigh molecular weight bottlebrush block copolymers based on the macromonomers via anionic polymerization. [ 26,27 ] Teo, Xia and co‐workers [ 94 ] reported an efficient one‐pot synthesis of macromonomers via nitroxide radical coupling of a norbornene moiety to the chain end of various polymers from atom transfer radical polymerization (ATRP). Matson and co‐workers [ 77 ] and Pitsikalis and co‐workers [ 98 ] prepared polylactide (PLA) and poly(caprolactone) (PCL) grafts via ROP.…”

Section: Design and Synthesis Of Janus Bottlebrush Polymersmentioning

confidence: 99%

“…According to the architecture, bottlebrush polymers are basically classified into homo‐, [ 16,17 ] block‐, [ 18,19 ] random‐, core–shell‐, [ 20,21 ] and Janus‐types [ 22,23 ] (Figure 1B). Self‐assembly of bottlebrush polymers in bulk, [ 24–27 ] in solution, [ 28–30 ] and at the interfaces [ 31,32 ] features the unique microstructures and varied applications (Figure 1C).…”

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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“…An approach utilizing macromonomers or macrocycles was used for the synthesis of multiblock copolymers with random or sequence-controlled structure [66]. The ROMP is also suitable for the synthesis of bottle-brush block copolymers, in which linear or branched side chains are densely grafted to a linear backbone, being easily functionalized for recognition, imaging, and drug delivery in aqueous media [4–6 67]. They have a low tendency to entangle and can rapidly self-assemble in selective solvents even at very low concentrations forming large-domain microstructures.…”

Section: Reviewmentioning

confidence: 99%

Olefin metathesis in multiblock copolymer synthesis

Gringolts

Denisova

Финкельштейн

et al. 2019

Beilstein J. Org. Chem.

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Multiblock copolymers constitute a basis for an emerging class of nanomaterials that combine various functional properties with durability and enhanced mechanical characteristics. Our mini-review addresses synthetic approaches to the design of multiblock copolymers from unsaturated monomers and polymers using olefin metathesis reactions and other ways of chemical modification across double C=C bonds. The main techniques, actively developed during the last decade and discussed here, are the coupling of end-functionalized blocks, sequential ring-opening metathesis polymerization, and cross metathesis between unsaturated polymers, or macromolecular cross metathesis. The last topic attracts special interest due to its relative simplicity and broad opportunities to tailor the structure and hence the properties of the copolymer products. Whenever possible, we analyze the structure–property relations for multiblock copolymers and point to their possible practical applications.

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Precise Synthesis of Bottlebrush Block Copolymers from ω-End-Norbornyl Polystyrene and Poly(4-tert-butoxystyrene) via Living Anionic Polymerization and Ring-Opening Metathesis Polymerization

Cited by 54 publications

References 49 publications

Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting‐Through Ring‐Opening Metathesis Polymerization

Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting‐Through Ring‐Opening Metathesis Polymerization

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

Olefin metathesis in multiblock copolymer synthesis

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