Studies on microgels. 5. Synthesis of microgels via living free radical polymerisation

Abrol, Simmi; Caulfield, Marcus J.; Qiao, Greg G.; Solomon, David H.

doi:10.1016/s0032-3861(01)00023-4

Cited by 68 publications

(46 citation statements)

References 12 publications

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“…The so called 'arm-first' process [221,222] involves making a living polymer then using this to initiate (co)polymerization of a di-(or higher) functional monomer which forms a crosslinked core (Scheme 30). The methodology has been used to make star-shaped molecules using NMP or ATRP.…”

Section: Microgelsmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,146

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: Microgelsmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,146

1,894

View full text Add to dashboard Cite

show abstract

“…applications, [8][9][10][11][12][13][14][15] such as information storage materials, optical fiber coatings, ophthalmic lenses and biomedical materials. Conventional free radical polymerizations of multifunctional monomers have been widely used to synthesize polymer networks and the polymerization mechanisms and kinetics have been extensively studied both experimentally and theoretically.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Behavior of Atom Transfer Radical Polymerization of Dimethacrylates

Zhang

Cheng

et al. 2006

Macro Chemistry & Physics

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Summary: The reaction behavior and kinetics of the atom transfer radical polymerization (ATRP) of poly(ethylene glycol) dimethacrylates (PEGDMA) were studied with respect to polymerization rate, vinyl conversion and the development of a crosslinked network. The polymerization rates were much slower than the corresponding conventional free radical polymerizations with the ATRP systems exhibiting milder autoacceleration. The linear relationship of the semi‐logarithmic kinetic plot of ln([M]0/[M]) vs. time did not provide good evidence for any living nature of the system because of the combined effects of diffusion controlled radical deactivation and diffusion controlled monomer propagation. The influence of the spacer length (CH2CH2O)x between the vinyl moieties of the dimethacrylates on the polymerization kinetics was examined. The polymerization rate and final vinyl conversion increased as value of x decreased from 14 to 9 to 4. These increases in rate and conversion were caused by a more rigid network structure with shorter spacer lengths, and thus more restricted diffusion of the catalyst/ligand complexes that impeded the radical deactivation. The effect of temperature on the polymerization rate and final vinyl conversion were also investigated.Apparent rate constants versus vinyl conversions for the ATRP of PEGDMA with the different spacer lengths at 100 °C.magnified imageApparent rate constants versus vinyl conversions for the ATRP of PEGDMA with the different spacer lengths at 100 °C.

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“…Initially, a few divinyl molecules are added to the living polymer chain ends to form short block copolymers, and they then react with each other to form highly cross-liked cores, which leads to the formation of star-shaped polymers. The polymerizations used in this technique include living anionic polymerization, [10] stable free radical polymerization (SFRP), [11][12][13] atom transfer radical polymerization (ATRP), [14][15][16] and reversible addition fragmentation chain transfer (RAFT). [17][18][19][20] Briefly, the controlled radical polymerizations of divinyl monomers or monovinyl monomers in good solvents using macro initiators or living polymer chains produce star-shaped polymers or block copolymers, respectively.…”

Section: Introductionmentioning

confidence: 99%

One‐Pot Synthesis of Micelles with a Cross‐Linked Poly(acrylic acid) Core

Zheng

Pan

2006

Macro Chemistry & Physics

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Summary: Stable micelles with polystyrene (PS) as a shell and cross‐linked poly[(acrylic acid)‐co‐(ethylene glycol diacrylate)] as a core have been successfully prepared by reversible addition fragmentation chain transfer (RAFT) copolymerization of acrylic acid and ethylene glycol diacrylate in a selective solvent with PS‐SC(S)Ph as a RAFT agent. For the preparation of stable micelles, the RAFT polymerizations are carried out in different solvents: benzene, cyclohexane, and mixtures of tetrahydrofuran and cyclohexane. The monomer/PS‐SC(S)Ph molar ratio and molecular weight of the macro‐RAFT agent, PS‐SC(S)Ph, influence the RAFT polymerization and the formation of micelles.Block copolymerization in selective solvent with the RAFT agent.magnified imageBlock copolymerization in selective solvent with the RAFT agent.

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Studies on microgels. 5. Synthesis of microgels via living free radical polymerisation

Cited by 68 publications

References 12 publications

Living Radical Polymerization by the RAFT Process

Living Radical Polymerization by the RAFT Process

Kinetic Behavior of Atom Transfer Radical Polymerization of Dimethacrylates

One‐Pot Synthesis of Micelles with a Cross‐Linked Poly(acrylic acid) Core

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