One‐pot, facile synthesis of well‐defined molecular brush copolymers by a tandem RAFT and ROMP, “Grafting‐through” strategy

Li, Ang; Ma, Jun; Sun, Guorong; Zhou, Li; Cho, Sangho; Clark, Corrie; Wooley, Karen L.

doi:10.1002/pola.25954

Cited by 47 publications

(54 citation statements)

References 63 publications

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“…[39][40][41][42][43] Following this seeded RAFT polymerization, a new block is introduced into the pre-prepared AB diblock copolymer nano-objects just as similarly as those in the graftthrough strategy to afford triblock copolymer nano-objects. 44 Recently, we have prepared ABA triblock copolymer corecorona particles following this seeded RAFT polymerization in the presence of the AB diblock copolymer nanoparticles. 42,43 It is found that the hydrodynamic diameter (D h ) of the ABA triblock copolymer core-corona particles increases with the polymerization degree (DP) of the newly introduced A block.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of multicompartment nanoparticles of a triblock terpolymer by seeded RAFT polymerization

Gao

et al. 2015

Polym. Chem.

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Seeded RAFT polymerization is proposed to prepare multicompartment nanoparticles of the poly(N,Ndimethylacrylamide)-b-polystyrene-b-poly(4-vinylpyridine) (PDMA-b-PS-b-P4VP) triblock terpolymer, which contain a polystyrene (PS) core, discrete poly(4-vinylpyridine) (P4VP) microphases on the PS core, and a solvated poly(N,Ndimethylacrylamide) (PDMA) corona. Following this seeded RAFT polymerization, the seed nanoparticles of poly(N,Ndimethylacrylamide)-b-polystyrene are initially prepared through dispersion RAFT polymerization, and then the P4VP block is introduced onto the seed nanoparticles by seeded RAFT polymerization to prepare the corona-core nanoparticles of PDMA-b-PS-b-P4VP containing a PS core and a mixed corona of P4VP and PDMA. When the corona-core nanoparticles of PDMA-b-PS-b-P4VP are dispersed in water, the P4VP chains, which are segregated by the neighboring PDMA chains, deposit onto the PS core to form the discrete P4VP microphases on the PS core, and they convert into multicompartment nanoparticles. It is found that the size of the P4VP microphases on the PS core increases with the polymerization degree of the P4VP block. This seeded RAFT polymerization is believed to be a valid method to prepare block copolymer multicompartment nanoparticles.Scheme 2. Seeded RAFT polymerization to synthesize the corona-core nanoparticles of PDMA-b-PS-b-P4VP containing a mixed corona.

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Section: Methodsmentioning

confidence: 99%

Synthesis of multicompartment nanoparticles of a triblock terpolymer by seeded RAFT polymerization

Gao

et al. 2015

Polym. Chem.

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“…As a result of the high reactivity of Ru catalysts, polymerization of MMs proceeds at a fast rate, even at low norbonenyl concentrations [157]. Furthermore, the ring strain of the norbonenyl functionality is released after polymerization, which provides an additional thermodynamic driving force for the graftingthrough polymerization process.…”

Section: Grafting-through Approachmentioning

confidence: 99%

Synthetic Strategies towards Well‐Defined Complex Polymeric Architectures through Covalent Chemistry

Ren

Qiao

2014

Chemie Ingenieur Technik

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Macromolecular architecture is a key factor determining the materials properties of polymers. Exploration of novel structural arrangements has become a viable means to develop advanced functional nanomaterials. Recent developments in polymer chemistry have forged robust synthetic platforms for innovative polymeric materials with highly regulated structures, functionalities, and compositions. This review summarizes the latest synthetic strategies for well-defined polymer architectures through covalent chemistry, with the focus on four main types of well-defined macromolecular constructs.

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“…ROMP also has demonstrated a wide functional group tolerance to produce well‐defined bottlebrush block copolymers with MMs carrying heteroatom functional groups through sequential ROMP 43–46. Well‐controlled MMs are needed for well‐defined bottlebrush polymers and they have been synthesized from a variety of techniques, which suppress side reactions of norbornene incorporation, such as reversible addition‐fragmentation chain transfer (RAFT) polymerization,47–49 atom transfer radical polymerization (ATRP),50–52 living anionic polymerization (LAP),53,54 ring‐opening polymerization (ROP),55 and other types of polymerizations 56,57. Thus, a wide library of potential MMs exist to create new bottlebrush block copolymers.…”

Section: Introductionmentioning

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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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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One‐pot, facile synthesis of well‐defined molecular brush copolymers by a tandem RAFT and ROMP, “Grafting‐through” strategy

Cited by 47 publications

References 63 publications

Synthesis of multicompartment nanoparticles of a triblock terpolymer by seeded RAFT polymerization

Synthesis of multicompartment nanoparticles of a triblock terpolymer by seeded RAFT polymerization

Synthetic Strategies towards Well‐Defined Complex Polymeric Architectures through Covalent Chemistry

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

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