A detailed kinetic study of the RAFT polymerization of a bi-substituted acrylamide derivative: influence of experimental parameters

Favier, Arnaud; Charreyre, Marie‐Thérèse; Pichot, Christian

doi:10.1016/j.polymer.2004.10.055

Cited by 68 publications

(94 citation statements)

References 60 publications

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“…Clearly, this is very similar with the typical RAFT polymerization under homogeneous condition. 57 However, it should be pointed out that the m-R/I ratio in the present aqueous RAFT polymerization may not be the real value, because only part of the V-50 initiator, the half-life time of which at 56 C is 10 h, is decomposed under the present polymerization conditions (in 15 min and at 60 C). Figure 3(A) shows the GPC traces of the PDMA-b-PNIPAM-b-PDMA triblock copolymer synthesized at the three cases with different m-R/I values, from which monomodal traces with slight shoulder at the higher molecular weight side (less elution time) are observed.…”

Section: The Effect Of the Molar Ratio Of Macro-raft Agent To Initiatmentioning

confidence: 82%

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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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Section: The Effect Of the Molar Ratio Of Macro-raft Agent To Initiatmentioning

confidence: 82%

“…56,57 Generally, RAFT polymerization under high R/I values runs slow and affords well-controlled RAFT polymerization. 56 Table 1.…”

Section: The Effect Of the Molar Ratio Of Macro-raft Agent To Initiatmentioning

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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“…[48,49,148,188,193,194] Furthermore, in cases where Z is a very strong stabilizing group (e.g., phenyl), several kinetic studies have suggested that the IR may be stable at room temperature, although no direct evidence has been reported to date. [14,96,189,292] IRs, usually considered as non-propagating radicals, are key compounds in a RAFT polymerization. On the one hand, if their concentration and stabilization are significant, a polymerization rate retardation is observed relative to a conventional free radical polymerization.…”

Section: Vinyl Esters and Othersmentioning

confidence: 99%

“…[9,43,74] It may also contribute to the occurrence of an induction period at the beginning of the polymerization as is sometimes observed. [252,292,380] On the other hand, IRs may potentially undergo some radical reactions (termination, possibly propagation and transfer) (Scheme 7). [30] Irreversible termination reactions onto IR (more likely for the smaller and the more stabilized species) contribute to the polymerization rate retardation [43,187,188] and lead to the formation of sulphur-containing by-products, which may further act as irreversible transfer agents.…”

Section: Vinyl Esters and Othersmentioning

confidence: 99%

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Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process

Favier

Charreyre

2006

Macromol. Rapid Commun.

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433

346

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Summary: Reversible addition‐fragmentation chain transfer (RAFT) polymerization is a recent and very versatile controlled radical polymerization technique that has enabled the synthesis of a wide range of macromolecules with well‐defined structures, compositions, and functionalities. The RAFT process is based on a reversible addition‐fragmentation reaction mediated by thiocarbonylthio compounds used as chain transfer agents (CTAs). A great variety of CTAs have been designed and synthesized so far with different kinds of substituents. In this review, all of the CTAs encountered in the literature from 1998 to date are reported and classified according to several criteria : i) the structure of their substituents, ii) the various monomers that they have been polymerized with, and iii) the type of polymerization that has been performed (solution, dispersed media, surface initiated, and copolymerization). Moreover, the influence of various parameters is discussed, especially the CTA structure relative to the monomer and the experimental conditions (temperature, pressure, initiation, CTA/initiator ratio, concentration), in order to optimise the kinetics and the efficiency of the molecular‐weight‐distribution control.

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Toward New Materials Prepared via the RAFT Process: From Drug Delivery to Optoelectronics?

Favier

Lambert

Charreyre

2008

Handbook of RAFT Polymerization

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IntroductionThe development of controlled/living ionic and radical polymerization techniques during the last decades represents a major breakthrough in polymer chemistry and polymer science. Since these techniques lead to the synthesis of a wide range of tailor-made macromolecular architectures, significant improvements are expected in the current or future application fields of polymers. The industrial impact will however depend on the versatility and applicability of each technique, and of course on the extra cost for the final product.In this context, controlled radical polymerizations (CRP) and especially the reversible addition-fragmentation chain transfer (RAFT) process [1-3] have attracted a lot of attention since they combine the advantages of conventional radical polymerization and living ionic polymerizations. Conventional radical polymerizations are cost-effective techniques, easy to process with a low sensitivity to water and oxygen and applicable to a wide range of monomers. In addition, CRP techniques result in a very efficient control over molecular weight (MW), molecular-weight distribution (MWD), microstructure, chain-end functionality and macromolecular architecture.As shown in the previous chapters of this handbook, the RAFT process appears as one of the most interesting CRP techniques. First, RAFT polymerization is very similar to conventional radical polymerization since it only requires the addition of a chain-transfer agent (CTA) in the medium. Second, RAFT is a very versatile process able to control the (co)polymerization of a large variety of monomers leading to a virtually unlimited macromolecular design library.As a consequence, RAFT polymerization is a well-suited and promising technique to prepare high-performance polymers for a wide range of applications. Indeed, an efficient control at the macromolecular level is a very important step to control and improve the macroscopic properties of the final materials ( Fig. 13.1).

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A detailed kinetic study of the RAFT polymerization of a bi-substituted acrylamide derivative: influence of experimental parameters

Cited by 68 publications

References 60 publications

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

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

Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process

Toward New Materials Prepared via the RAFT Process: From Drug Delivery to Optoelectronics?

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