Narrow Polydispersity Block Copolymers by Free-Radical Polymerization in the Presence of Macromonomers

Krstina, Julia; Moad, Graeme; Rizzardo, Ezio; Winzor, Catherine L.; Berge, Charles T.; Fryd, Michael

doi:10.1021/ma00119a034

Cited by 209 publications

(212 citation statements)

References 4 publications

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“…[31] We also reported that living characteristics (narrow polydispersities, block synthesis) could be achieved with the use of macromonomer RAFT agents in emulsion polymerization of methacrylate monomers in 1995 (the acronym RAFT was not used at that time). [34,35] Living radical polymerization using thiocarbonylthio RAFT agents was first described in a patent published in 1998. [14] The first paper and conference reports describing the process also appeared in 1998.…”

Section: History Of Raftmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

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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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Section: History Of Raftmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

Self Cite

2,134

1,894

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“…[135][136][137] Macromonomer RAFT polymerization has been reviewed within larger reviews on catalytic chain transfer (CCT). [138,139] Similarities between the chemistry of RAFT polymerization and that seen in formation and reaction of acrylate mid chain radicals were highlighted in a recent publication.…”

Section: Macromonomer Raft Polymerizationmentioning

confidence: 99%

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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“…Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization [18,19] is arguably the most versatile among these techniques with respect to temperature [20], solvent [21], and monomer choice [22], and can be used to synthesize a wide variety of polymeric structures [23]. It proceeds via a degenerative chain transfer mechanism, which induces equilibrium between propagating macroradicals and dormant polymeric RAFT agents carrying dithio moieties [24] and has already been successfully employed to produce multiblock copolymers by stepwise addition of monomers to the polymerization [25,26].…”

Section: Introductionmentioning

confidence: 99%

Multiblock Copolymers of Styrene and Butyl Acrylate via Polytrithiocarbonate-Mediated RAFT Polymerization

Ebeling

Vana

2011

Polymers

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Abstract:When linear polytrithiocarbonates as Reversible Addition-Fragmentation chain Transfer (RAFT) agents are employed in a radical polymerization, the resulting macromolecules consist of several homogeneous polymer blocks, interconnected by the functional groups of the respective RAFT agent. Via a second polymerization with another monomer, multiblock copolymers-polymers with alternating segments of both monomers-can be prepared. This strategy was examined mechanistically in detail based on subsequent RAFT polymerizations of styrene and butyl acrylate. Size-exclusion chromatography (SEC) of these polymers showed that the examined method yields low-disperse products. In some cases, resolved peaks for molecules with different numbers of blocks (polymer chains separated by the trithiocarbonate groups) could be observed. Cleavage of the polymers at the trithiocarbonate groups and SEC analysis of the products showed that the blocks in the middle of the polymers are longer than those at the ends and that the number of blocks corresponds to the number of functional groups in the initial RAFT agent. Furthermore, the produced multiblock copolymers were analyzed via differential scanning calorimetry (DSC). This work underlines that the examined methodology is very well suited for the synthesis of well-defined multiblock copolymers.

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Narrow Polydispersity Block Copolymers by Free-Radical Polymerization in the Presence of Macromonomers

Cited by 209 publications

References 4 publications

Living Radical Polymerization by the RAFT Process

Living Radical Polymerization by the RAFT Process

Living Radical Polymerization by the RAFT Process – A Third Update

Multiblock Copolymers of Styrene and Butyl Acrylate via Polytrithiocarbonate-Mediated RAFT Polymerization

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