Study of poly(N,N-diethylacrylamide) nanogel formation by aqueous dispersion polymerization of N,N-diethylacrylamide in the presence of poly(ethylene oxide)-b-poly(N,N-dimethylacrylamide) amphiphilic macromolecular RAFT agents

Grazon, Chloé; Rieger, Jutta; Sanson, Nicolas; Charleux, Bernadette

doi:10.1039/c0sm01181a

Cited by 94 publications

(100 citation statements)

References 27 publications

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“…Nonetheless, the (RAFT) polymerization induced selfassembly and the factors which control what structure is formed have recently attracted considerable interest with studies on the phenomenon in emulsion polymerization, [354,381,400] dispersion polymerization [187,224,229,353,361,571] and non-aqueous dispersion polymerization. [394,397] Blanazs et al [187] have constructed a phase diagram for poly(288)-poly(HPMA).…”

Section: Raft Polymerization In Heterogeneous Mediamentioning

confidence: 99%

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Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Raft Polymerization In Heterogeneous Mediamentioning

confidence: 99%

“…BA BA TEGMA MBAm [355] [ 355] DMAm 132 DEAm MBAm [571] PEGMA-b-EGMA 173 BA TEGMA [355] PEGMA 97 EGMA TEGMA [353] NIPAm 138 St DVB [419] -158 397 EGDMA [584] -158 -DVB [626] MA 158 -DVB [626] -23 DMAEMA 422 [256] 354 145 St 423 [427] PFPA PFPA PFPA tBA 179 -424 [461] NIPAm 179 -424 [461] A See footnote B of Table 3. cleavable imine linkages (Scheme 27).…”

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confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…[30][31][32][33][34][35][36][37][38][39][40][41][42] For example, Charleux et al reported the preparation of crosslinked poly(N,N-diethylacrylamide) nanogels through aqueous dispersion RAFT polymerization in the presence of the amphiphilic poly(ethylene oxide)-b-poly(N,Ndimethylacrylamide) macro-RAFT agent. 30,31 It is found that the size and stability of the resultant nanogels are dependent strongly on the chain length of the macro-RAFT agent. An et al have reported the aqueous dispersion RAFT polymerization mediated with either linear poly(ethylene glycol) or graft poly(poly(ethylene glycol) methyl ether methacrylate) macro-RAFT agent.…”

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confidence: 99%

Aqueous RAFT polymerization of N‐isopropylacrylamide‐mediated with hydrophilic macro‐RAFT agent: Homogeneous or heterogeneous polymerization?

Wang¹,

Li²,

Su³

et al. 2013

J. Polym. Sci. A Polym. Chem.

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Aqueous RAFT polymerization of N-isopropylacrylamide (NIPAM) mediated with hydrophilic macro-RAFT agent is generally used to prepare poly(N-isopropylacrylamide) (PNI-PAM)-based block copolymer. Because of the phase transition temperature of the block copolymer in water being dependent on the chain length of the PNIPAM block, the aqueous RAFT polymerization is much more complex than expected. Herein, the aqueous RAFT polymerization of NIPAM in the presence of the hydrophilic macro-RAFT agent of poly(dimethylacrylamide) trithiocarbonate is studied and compared with the homogeneous solution RAFT polymerization. This aqueous RAFT polymerization leads to the well-defined poly(dimethylacrylamide)-b-poly(N-isopropylacrylamide)-b-poly(dimethylacrylamide) (PDMA-b-PNIPAM-b-PDMA) triblock copolymer. It is found, when the triblock copolymer contains a short PNIPAM block, the aqueous RAFT polymerization undergoes just like the homogeneous one; whereas when the triblock copolymer contains a long PNIPAM block, both the initial homogeneous polymerization and the subsequent dispersion polymerization are involved and the two-stage ln ([M] o /[M])-time plots are indicated. The reason that the PNIPAM chain length greatly affects the aqueous RAFT polymerization is discussed. The present study is anticipated to be helpful to understand the chain extension of thermoresponsive block copolymer during aqueous RAFT polymerization.

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“…Both our group 15,[17][18][19][20][21][22][23][24][25][26] and other workers [9][10][11][12][13][29][30][31][32][33][34][35][36] have reported that chain extension of a RAFT macro-CTA under dispersion polymerization conditions leads to the formation of a range of diblock copolymer nano-objects in either aqueous or alcoholic media. In the present study, we demonstrate the versatility and 75 broad applicability of this approach by extending such PISA formulations to include non-polar media (e.g.…”

mentioning

confidence: 99%

“…For example, RAFT aqueous dispersion polymerization has been utilized to grow a waterinsoluble core-forming block from a water-soluble stabilizer block in order to prepare a range of sterically-stabilized diblock copolymer nanoparticles. [9][10][11][12][13][14] Spherical morphologies are most 35 commonly obtained, [9][10][11][12][13] but systematic variation of the block copolymer composition coupled with a detailed knowledge of the block copolymer phase diagram also allows access to higher order morphologies such as worms [14][15][16] and vesicles. [17][18][19][20][21][22][23][24][25][26] In most cases good blocking efficiencies and reasonably low final 40 polydispersities (e.g.…”

Section: Introductionmentioning

confidence: 99%

RAFT dispersion polymerization in non-polar solvents: facile production of block copolymer spheres, worms and vesicles in n-alkanes

et al. 2013

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ABSTRACT. Well-defined poly(lauryl methacrylate-benzyl methacrylate) (PLMA-PBzMA) diblock copolymer nanoparticles are prepared in n-heptane at 90°C via reversible addition-fragmentation chain transfer (RAFT) polymerization. Under these conditions, the PLMA macromolecular chain transfer agent (macro-CTA) is soluble in n-heptane, whereas the growing PBzMA block quickly becomes insoluble. Thus this dispersion polymerization formulation leads to polymerization-induced self-assembly (PISA). 10Using a relatively long PLMA macro-CTA with a mean degree of polymerization (DP) of 37 or higher leads to the formation of well-defined spherical nanoparticles of 41 to 139 nm diameter, depending on the DP targeted for the PBzMA block. In contrast, TEM studies confirm that using a relatively short PLMA macro-CTA (DP = 17) enables both worm-like and vesicular morphologies to be produced, in addition to the spherical phase. A detailed phase diagram has been elucidated for this more asymmetric diblock 15 copolymer formulation, which ensures that each phase can be targeted reproducibly.1 H NMR spectroscopy confirmed that high BzMA monomer conversions (> 97 %) were achieved within 5 h, while GPC studies indicated that reasonably good blocking efficiencies and relatively low diblock copolymer polydispersities (M w /M n < 1.30) were obtained in most cases. Compared to prior literature reports, this allmethacrylic PISA formulation is particularly novel because: (i) it is the first time that higher order 20 morphologies (e.g. worms and vesicles) have been accessed in non-polar solvents and (ii) such diblock copolymer nano-objects are particularly relevant to potential boundary lubrication applications for engine oils.

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Study of poly(N,N-diethylacrylamide) nanogel formation by aqueous dispersion polymerization of N,N-diethylacrylamide in the presence of poly(ethylene oxide)-b-poly(N,N-dimethylacrylamide) amphiphilic macromolecular RAFT agents

Cited by 94 publications

References 27 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

Aqueous RAFT polymerization of N‐isopropylacrylamide‐mediated with hydrophilic macro‐RAFT agent: Homogeneous or heterogeneous polymerization?

RAFT dispersion polymerization in non-polar solvents: facile production of block copolymer spheres, worms and vesicles in n-alkanes

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