Radical Addition–Fragmentation Chemistry and RAFT Polymerization

Moad, G.; Rizzardo, E.; Thang, San H.

doi:10.1016/b978-0-12-803581-8.01349-7

Cited by 7 publications

(13 citation statements)

References 550 publications

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“…15,16 Depending on the structure, these agents can be categorized into reversible (RAFT) and irreversible agents. 17 Especially agents, which undergo an irreversible mechanism, are expedient in radical photopolymerization as they maintain the high reactivity of the methacrylic polymerization opposed to RAFT agents. Common structural features of AFCT agents are a carbon−carbon double bond with an adjacent activating group (A, e.g., ester moiety), a particular central atom (Y, e.g., carbon atom), and a leaving group (L, e.g., tosyl moiety).…”

Section: ■ Introductionmentioning

confidence: 99%

“…The propagating radical attacks the reactive double bond and forms an intermediate radical which undergoes β-scission to form a leaving group radical (Figure 1). There are numerous substance classes thoroughly investigated as AFCT agents such as allyl sulfides, 18,19 allyl sulfones, 20,21 halides, 20 or phosphonates, 20 and an extensive review on addition−fragmentation chemistry was published by Moad et al 17 It is noteworthy that a vast majority of leaving groups are based on heteroatoms, while carbon-based leaving groups are solely found in activated vinyl ethers as AFCT agents. 22 These vinyl ethers (VE) contain an oxygen atom as center atom and thus show an irreversible character through the formation of a ketone.…”

Section: ■ Introductionmentioning

confidence: 99%

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Ester-Activated Vinyl Ethers as Chain Transfer Agents in Radical Photopolymerization of Methacrylates

et al. 2019

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The regulation of multifunctional methacrylates to yield tough photopolymers is a widely researched topic, whereby addition−fragmentation chain transfer (AFCT) agents represent one viable class of additives. Vinyl ethers have been described as potent AFCT agents in radical polymerization but are unexamined in network formation via photopolymerization. In this article, we present a sterically hindered vinyl ether as AFCT agent for methacrylate networks, which shows enhanced acid stability opposed to vinyl ethers described in the literature. After synthesis and confirmation of the efficient regulation in a monofunctional system, the reactivity and mechanical properties in a difunctional methacrylate were evaluated. An increase in double bond conversion, significantly lower shrinkage stress, and high toughness were assessed and substantiated the great potential of this compound in photopolymerizable resins.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Ester-Activated Vinyl Ethers as Chain Transfer Agents in Radical Photopolymerization of Methacrylates

et al. 2019

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“…The RAFT process is widely used in the construction of diverse polymeric structures for HRHMIs. RAFT was developed by CSIRO in 1998, [ 34 ] and is known for its experimental simplicity, [ 56 ] compatibility with wide range of monomers, [ 57 ] controllability of the polymeric architectures, [ 56 ] freedom from transition metals, [ 57 ] compatibility with many solvents (water included), [ 58,59 ] and facile modification of the end group. [ 60 ] Unlike NMP and ATRP, which use a reversible capping agent to provide the dormant state, RAFT uses reversible chain transfer.…”

Section: Synthetic Techniquesmentioning

confidence: 99%

Polymer Chemistry for Haptics, Soft Robotics, and Human–Machine Interfaces

Schara

Blau

Church

et al. 2021

Adv Funct Materials

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Progress in the field of soft devices—that is, the types of haptic, robotic, and human‐machine interfaces (HRHMIs) in which elastomers play a key role—has its basis in the science of polymeric materials and chemical synthesis. However, in examining the literature, it is found that most developments have been enabled by off‐the‐shelf materials used either alone or as components of physical blends and composites. A greater awareness of the methods of synthetic chemistry will accelerate the capabilities of HRHMIs. Conversely, an awareness of the applications sought by engineers working in this area may spark the development of new molecular designs and synthetic methodologies by chemists. Several applications of active, stimuli‐responsive polymers, which have demonstrated or shown potential use in HRHMIs are highlighted. These materials share the fact that they are products of state‐of‐the‐art synthetic techniques. The progress report is thus organized by the chemistry by which the materials are synthesized, including controlled radical polymerization, metal‐mediated cross‐coupling polymerization, ring‐opening polymerization, various strategies for crosslinking, and hybrid approaches. These methods can afford polymers with multiple properties (i.e., conductivity, stimuli‐responsiveness, self‐healing, and degradable abilities, biocompatibility, adhesiveness, and mechanical robustness) that are of great interest to scientists and engineers concerned with soft devices for human interaction.

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“…The polymer synthesis made use of the RAFT method [69][70][71][72][73], which is a powerful technique based on degenerative radical exchange to implement what is known as "reversible deactivation radical polymerization" (RDRP) [74]. In addition, carrying out the synthesis in water allows implementation of the "polymerization-induced self-assembly" (PISA) principle [75][76][77].…”

Section: Synthesis and Characterization Of The Nanoreactors Nixantphomentioning

confidence: 99%

Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation

et al. 2020

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A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 °C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO)2] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.

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Radical Addition–Fragmentation Chemistry and RAFT Polymerization

Cited by 7 publications

References 550 publications

Ester-Activated Vinyl Ethers as Chain Transfer Agents in Radical Photopolymerization of Methacrylates

Ester-Activated Vinyl Ethers as Chain Transfer Agents in Radical Photopolymerization of Methacrylates

Polymer Chemistry for Haptics, Soft Robotics, and Human–Machine Interfaces

Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation

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