Facile, Controlled, Room-Temperature RAFT Polymerization of <i>N</i>-Isopropylacrylamide

Convertine, Anthony J.; Ayres, Neil; Scales, Charles W.; Lowe, Andrew B.; McCormick, Charles L.

doi:10.1021/bm049825h

Cited by 233 publications

(219 citation statements)

References 35 publications

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“…The critical temperature was also found to be controllable, as expected, through changes in the pendant group (oxyethylene and alkyl groups) of the monomer and through the random copolymerization of such monomers. 60,64 Until recently, this polymer was the only living polymer system that exhibited such sharp phase separation, with the exception of PEO [69][70][71][72][73][74] and recently reported poly(N-isopropylacrylamide) [poly (NIPAM)]. [3][4][5][6] The latter, known to behave in a similar manner, could not be obtained by living polymerization; therefore, vinyl ethers with oxyethylene side groups held the advantage of living polymerization over poly(NIPAM).…”

Section: Synthesis and Self-association Of Stimuli-responsive Polymersmentioning

confidence: 99%

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Aoshima

Yoshida

Kanazawa

et al. 2007

J. Polym. Sci. A Polym. Chem.

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Our recent extensive research on Lewis acid catalysts with a weak base for the cationic polymerization of vinyl ethers led to unprecedented living reaction systems: fast living polymerization within 1-3 s; a wide choice of metal halides containing Al, Sn, Fe, Ti, Zr, Hf, Zn, Ga, In, Si, Ge, and Bi; and heterogeneously catalyzed living polymerization with Fe 2 O 3 . The use of added bases for the stabilization of the propagating carbocation and the appropriate selection of Lewis acid catalysts were crucial to the success of such new types of living polymerizations. In addition, the base-stabilized living polymerization allowed the quantitative synthesis of star-shaped polymers with a narrow molecular weight distribution via polymerlinking reactions and the precision synthesis and self-assembly of stimuli-responsive block copolymers.

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Section: Synthesis and Self-association Of Stimuli-responsive Polymersmentioning

confidence: 99%

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Aoshima

Yoshida

Kanazawa

et al. 2007

J. Polym. Sci. A Polym. Chem.

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“…AA, [99] EA, [99] BA, [100] AA-b-EA, AA-b-S [99] BAM, [99] NIPAM [104] NC CH 2 CH 2 CO 2 H 64 CH 3 (CH 2 ) 11 -S---MMA [15] -A See footnotes A-D in Table 2. coefficients. [46,52] Transfer coefficients in RAFT polymerization can also be estimated by analyzing the dependence of the molecular-weight distribution on monomer/RAFT agent conversion.…”

mentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,134

1,894

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This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC( S)SR] by a mechanism of reversible addition-fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

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“…At present, living radical polymerization, such as atom transfer radical polymerization (ATRP) [14,16,23] and reversible addition-fragmentation chain transfer (RAFT) polymerization [36][37][38], has been used for the synthesis of PNIPAM with well-defined architecture. For instance, Stöver and coworkers reported the synthesis of narrow-disperse PNIPAM by ATRP in alcohols, using alkyl chloride as initiator in conjunction with CuCl/tris (2-(dimethylamino)-ethyl)amine (Me 6 TREN) as the catalyst [14].…”

Section: Introductionmentioning

confidence: 99%

Well-defined poly(N-isopropylacrylamide) with a bifunctional end-group: synthesis, characterization, and thermoresponsive properties

Liu

Liao

Yang

et al. 2012

Designed Monomers and Polymers

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(2013) Well-defined poly(N-isopropylacrylamide) with a bifunctional end-group: synthesis, characterization, and thermoresponsive properties, Designed Monomers and Polymers, 16:5, 465-474, DOI: 10.1080/15685551.2012 In this study, well-defined poly(N-isopropylacrylamide) (PNIPAM) with a bisalkyne end-group was synthesized by reversible addition-fragmentation chain transfer polymerization using 2-(2-(ethylthiocarbonothioylthio)-2-methylpropanoyl-oxy)ethyl 3,5-bis(prop-2-ynyloxy) benzoate (EMEB) as the chain transfer agent. The molecular weight and polydispersity index of polymer was determined by gel permeation chromatography (GPC). The linear increase in molecular weight with conversion, unimodal, and almost symmetrical peak in GPC trace together with low polydispersity indicated the controlled polymerization process of NIPAM mediated by EMEB. Subsequently, the Cu(I)-catalyzed [3 + 2] Huisgen cycloaddition between the end-group of polymer and azide derivatives was carried out to produce PNIPAM, in which the bisfunctional end-group was modified with phenyl, octyl, amido, and hydroxyl groups. After completing the click reaction, the structure of the polymer was characterized carefully by Fourier transform infrared spectroscopy (FTIR), 1 H NMR, and Matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS), indicating the complete consumption of alkyne end-groups. In addition, almost no change in molecular weight as well as the polydispersity was observed by comparison with the GPC traces of polymers before and after click reaction. The cloud point temperatures (T cp s) of the resulting PNIPAM derivatives in aqueous solution were investigated in detail by dynamic light scattering. The results showed that the values of T cp were ranged from 22 to 38°C, which depended largely on end-groups as well as the polymer molecular weights.

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Facile, Controlled, Room-Temperature RAFT Polymerization of N-Isopropylacrylamide

Cited by 233 publications

References 35 publications

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Living Radical Polymerization by the RAFT Process

Well-defined poly(N-isopropylacrylamide) with a bifunctional end-group: synthesis, characterization, and thermoresponsive properties

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