Thermo‐responsive Poly(methyl methacrylate)‐<i>block</i>‐poly(<i>N</i>‐isopropylacrylamide) Block Copolymers Synthesized by RAFT Polymerization: Micellization and Gelation

Tang, Tian; Castelletto, Valeria; Parras, P.; Hamley, Ian W.; King, Stephen M.; Roy, Debashish; Perrier, Sébastien; Hoogenboom, Richard; Schubert, Ulrich S.

doi:10.1002/macp.200600309

Cited by 87 publications

(67 citation statements)

References 29 publications

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“…St [184] MMA [88] 323 [185] 40 [186] S S O O St [186] St-b-MAH [186] St-b-MAH-b-NIPAM [186] 41* [187,188] S S (MMA) [64,187,189] BA [187] EHA [188] St [190] TBAM [191] DEAM [187] DMAM [187] NAM [191] NIPAM [187,189] BA/St [192] EHA-b-MA [188] TBAM-b-NAM [191] DMAM/NAS [193] NAM-b-TBAM [191] 42* S S Ph CN MMA [194] 376 [195] 376-b-MMA [195] BA [196] MMA [189] NIPAM [189] MMA-b-NIPAM [189] MMA/283 [197] MMA/284 [197] St/2VP [198] St/348 [199] THPA-b-St [200] THPA-b-St/373 [201] 44 [202] [200] 47 [203] …”

Section: Choice Of Raft Agentsmentioning

confidence: 99%

“…This approach has been used to make inorganic (TiO 2 , SnO 2 or ZnO) nanorods [102] or CdSe/ZnS quantum dots [538] with PAA-b-PSt, [539] P(AEME-co-328-co-342) [278] or semiconductor (P364 or P365) arms, gold nanoparticles with PSt, [476] PSt-b-P2VP, [198] PDMAEMA, PAA, or PSt, [91] P(340-co-AM) or P(341-co-AM), [239] PPEGA-b-PNIPAM, [217] PMMAb-PNIPAM, [189] or P(DEGMA-co-tBA), P(DEGMA-co-tBA)-b-PGMA, PGMA, PSt [398] grafts, magnetic iron with PNIPAM grafts, [305] silver nanoparticles with PSt grafts, [409] chitosan with PAA grafts, [487] and silicon wafers with NIPAM grafts. [273] Silicon wafers and silica particles have also been modified with multiple layers of an amine-functional polymer, polyethyleneimine or poly(allylamine hydrochloride), respectively, and PAA-bPSSO3Na in a layer-by-layer assembly process.…”

Section: Grafting-to Processesmentioning

confidence: 99%

See 1 more Smart Citation

Living Radical Polymerization by the RAFT Process - A Second Update

Moad¹,

Rizzardo²,

Thang³

2009

Aust. J. Chem.

906

720

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This paper provides a second update to the review of reversible deactivation radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379-410). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669-692). This review cites over 500 papers that appeared during the period mid-2006 to mid-2009 covering various aspects of RAFT polymerization ranging from reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses and a diverse range of applications. Significant developments have occurred, particularly in the areas of novel RAFT agents, techniques for end-group removal and transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Choice Of Raft Agentsmentioning

confidence: 99%

Section: Grafting-to Processesmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process - A Second Update

Moad¹,

Rizzardo²,

Thang³

2009

Aust. J. Chem.

906

720

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“…The micellar solution forms a soft gel at a lower threshold copolymer concentration (8 wt %) than other systems. [7][8][9] This soft gel is reversibly converted into an optically clear hard gel by merely decreasing the pH value or increasing the temperature. The ordered packing of the CSC micelles and the fast response to pH value were investigated by small-angle neutron scattering (SANS) and rheological measurements.…”

mentioning

confidence: 99%

“…The G' values are very high, being from 5 to 100 times higher than the modulus of recently reported micellar gels. [8,22,23,30,31] In order to give credit to this mechanism, SANS scattering cross sections were recorded at neutral and decreasing pH values (Figure 2). [32] Fairly wide peaks are discerned at neutral pH (soft gel).…”

mentioning

confidence: 99%

Fast Multiresponsive Micellar Gels from a Smart ABC Triblock Copolymer

et al. 2007

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Self-assembly of block copolymers in a solvent selective for one block is at the origin of unique behaviors of micellar particles, such as stimuli responsiveness. [1][2][3][4] ABC triblock copolymers are very versatile precursors of micelles, whose internal structure is dictated by the constitutive blocks and their sequential arrangement. Accordingly, smart materials can be contemplated, including multiresponsive ones. Herein, we report on pH-and temperature-sensitive gels formed by an amphiphilic ABC triblock copolymer, polystyrene-bpoly(2-vinylpyridine)-b-poly(ethylene oxide). The selfassembly of this copolymer into core-shell-corona (CSC) micelles [5,6] is observed in N,N-dimethylformamide upon addition of water. The micellar solution forms a soft gel at a lower threshold copolymer concentration (8 wt %) than other systems. [7][8][9] This soft gel is reversibly converted into an optically clear hard gel by merely decreasing the pH value or increasing the temperature. The ordered packing of the CSC micelles and the fast response to pH value were investigated by small-angle neutron scattering (SANS) and rheological measurements.Block copolymers consist of two or more chemically different polymer chains covalently bonded at their chain ends to form one single linear macromolecule.[10] The freeenergy-driven micellization of these copolymers takes place in a selective solvent, that is, a nonsolvent for one block and a good solvent for another. This self-association phenomenon is based on the phase separation of the insoluble blocks, which is, however, restricted to the nanometric scale by a surrounding shell of soluble blocks. Depending on the nature, length, and number of constitutive blocks and their interaction with the solvent, a variety of nanoobjects can be formed in dilute solutions, ranging from typical core-shell nanospheres [11][12][13] to cylinders, [12,14] vesicles, [12,15,16] and tubules, [16] as well as multilayered (onion), [5,17] non-centrosymmetric ("Janus"), and segregated structures. [18,19] Quite importantly, although less extensively studied, higher levels of organization can be observed, that is, assembly into clusters, networks, and gels. Stimulus-triggered aggregation of micelles has been reported for ABA triblock copolymers in a solvent selective for the B block, [9,[20][21][22][23][24] with special attention paid to the well-known polyoxyalkylene-type ABA copolymers (mainly Pluronics). [9,20,21] Among other responsive systems, Armes and coworkers synthesized biocompatible ABA triblocks, where A is poly(N-isopropylacrylamide) and B is poly(2-methacryloyloxyethyl phosphorylcholine).[24] Because of the thermosensitivity of the outer A blocks, micellization and ultimately gelation occurred above a lower critical solution temperature (LCST) of 37 8C. In recent years, increasing attention was paid to sol-to-gel transitions exhibited by multitalented ABC terpolymers. In addition to the synthesis of several isomers of a triblock terpolymer (ABC, BAC, and ACB) by Patrickios and co-workers that were...

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“…There is a vast amount of literature available on the synthesis of PNIPAAm via RAFT polymerization including reports on block copolymers of PNIPAAm with N,N-dimethylacrylamide, [58,59] methacrylic acid, [60] methyl methacrylate, [61] benzyl methacrylate, [62] styrene, [63] tert-butyl methacrylate, [63] 4-vinylbenzoic acid, [64] N-acryloyl glucoseamine, [65] acrylic acid, [66] 2-(diethylamino)ethyl methacrylate, [67] 2-(dimethylamino)ethyl methacrylate, [68] and ionic monomers such as N-(3-aminopropyl)methacrylamide hydrochloride, [69] phosphorylcholine, [70,71] and sodium 2-(acrylamido)-2-methylpropanesulfonate. [72] For a full review the reader is refereed to a compendium of water soluble polymers prepared by RAFT polymerization.…”

Section: Micelles From Block Copolymersmentioning

confidence: 99%

Hairy Core–Shell Nanoparticles via RAFT: Where are the Opportunities and Where are the Problems and Challenges?

Stenzel

2009

Macromol. Rapid Commun.

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The preparation of hairy core-shell nanoparticles including (crosslinked) micelles, unimolecular micelles such as star polymers with block structures in each arm and surface grafted nanoparticles such as inorganic particles via the RAFT process are discussed. The RAFT process is certainly a highly versatile process. However, it should not be forgotten that RAFT polymerization is a process, i.e., superimposed on a conventional free radical process. Furthermore, the livingness of the process is dependent on the accessibility of the RAFT group, which can be hampered in certain approaches such as star synthesis and surface grafting from nanoparticles. Nevertheless, the RAFT process is a versatile toolbox that offers good solutions to a range of problems in the preparation of hairy nanoparticles.

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Thermo‐responsive Poly(methyl methacrylate)‐block‐poly(N‐isopropylacrylamide) Block Copolymers Synthesized by RAFT Polymerization: Micellization and Gelation

Cited by 87 publications

References 29 publications

Living Radical Polymerization by the RAFT Process - A Second Update

Living Radical Polymerization by the RAFT Process - A Second Update

Fast Multiresponsive Micellar Gels from a Smart ABC Triblock Copolymer

Hairy Core–Shell Nanoparticles via RAFT: Where are the Opportunities and Where are the Problems and Challenges?

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