RAFT (Reversible addition-fragmentation chain transfer) crosslinking (co)polymerization of multi-olefinic monomers to form polymer networks

Moad, Graeme

doi:10.1002/pi.4767

Cited by 102 publications

(82 citation statements)

References 115 publications

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“…34 These researches aimed at the improvement of the performance of cathodes based on S-rich polymer networks, namely by increasing their conductivity and minimizing the PS shuttle effect. The production of sulfur/thiirane copolymers considering reversible addition-fragmentation chain transfer (RAFT) polymerization [35][36][37] in mild reaction conditions (e.g., temperature range 20-90 8C and in a presence of a solvent), leading to high S content (up to 80%) soluble polymeric materials [e.g., in toluene and tetrahydrofuran (THF)] was also recently reported in literature. 23 In the research here presented the synthesis of sulfur-rich polymer networks was carried out using the inverse vulcanization process in the presence of a RAFT agent.…”

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confidence: 99%

Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Almeida

Costa

Kadhirvel

et al. 2016

J of Applied Polymer Sci

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Novel results concerning the inverse vulcanization of sulfur using reversible addition-fragmentation chain transfer (RAFT) polymerization are here reported. It is shown that RAFT polymerization can be used to carry out this cross-linking process, with the additional possibility to extend the reaction time from a few minutes as with classical free radical polymerization (FRP) to several hours. Higher control on viscosity and processability of the synthesized networks, as well as, the implementation of semibatch feed policies during cross-linking are important advantages of the RAFT process here explored comparatively to the FRP inverse vulcanization. Using cyclic voltammetry, it was assessed the electrochemical activity of the synthesized sulfur-rich polymer networks. It is shown that the fundamental electrochemical activity of the elemental sulfur was preserved in the produced materials. Testing of electrochemical cells assembled with lithium in the anode and different sulfur based materials in the cathode, including the synthesized RAFT networks, is also shown. The results here presented highlight the new opportunities introduced by reversible-deactivation radical polymerization mechanisms on the control of the synthesis process and in the design of such advanced materials and show also that many potential derivatizing possibilities can be achieved.

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confidence: 99%

Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Almeida

Costa

Kadhirvel

et al. 2016

J of Applied Polymer Sci

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“…FTIR spectrum of the MAA-β-CD monomer (Figure 4a , in both spectra of the MIPs, represented the α-(1,4)-glucopyranose group of the β-CD structure [46]. due to the occurrence of covalent interaction between the carbon-carbon double bond from the monomer and the cross-linker molecules [9,28]. Furthermore, the carbonyl, methyl, and methylene groups, which demonstrated the strong absorption peaks, were permanently preserved in the MIPs.…”

Section: Characterization Of Raft-mips and Mipsmentioning

confidence: 99%

“…The reversible addition-fragmentation chain transfer (RAFT) polymerization process, which is a type of RDRP method [28], was selected for this study. Among RDRP methods, RAFT polymerization is the most versatile [29], especially in terms of providing living characteristics to the radical polymerization [30,31], making it compatible with almost all TRP monomers [32].…”

Section: Introductionmentioning

confidence: 99%

Effects of RAFT Agent on the Selective Approach of Molecularly Imprinted Polymers

2015

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Two types of reversible addition-fragmentation chain transfer molecularly imprinted polymers (RAFT-MIPs) were synthesized using different monomers, which were methacrylic acid functionalized β-cyclodextrin (MAA-β-CD) and 2-hydroxyethyl methacrylate functionalized β-cyclodextrin (HEMA-β-CD), via reversible addition-fragmentation chain transfer (RAFT) polymerization, and were represented as RAFT-MIP(MAA-β-CD) and RAFT-MIP(HEMA-β-CD), respectively. Both RAFT-MIPs were systematically characterized using Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), Brunauer-Emmett-Teller (BET), and rebinding experimental study. The results were compared with MIPs synthesized via the traditional radical polymerization (TRP) process, and were represented as MIP(MAA-β-CD) and MIP(HEMA-β-CD). Morphology results show that RAFT-MIP(MAA-β-CD) has a slightly spherical feature with a sponge-like form, while RAFT-MIP(HEMA-β-CD) has a compact surface. BET results show that the surface area of RAFT-MIP(MAA-β-CD) is higher than MIP(MAA-β-CD), while the RAFT-MIP(HEMA-β-CD) surface area is lower than that of MIP(HEMA-β-CD). Rebinding experiments indicate that the RAFT agent increased the binding capacity of RAFT-MIP(MAA-β-CD), but not of RAFT-MIP(HEMA-β-CD), which proves that a RAFT OPEN ACCESSPolymers 2015, 7 485 agent does not always improve the recognition affinity and selective adsorption of MIPs. The usability of a RAFT agent depends on the monomer used to generate potential MIPs.

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“…de ketal-containing, [21][22][23][24][25][26][27][28] dimethacrylate cross-linker to accomplish the star interconnection and/or the formation of the star core. Although the polymerizations could have been performed using a controlled radical polymerization method, [29] such as atom transfer radical polymerization or reversible addition-fragmentation radical polymerization, a type of living oxyanionic polymerization, group transfer polymerization (GTP) [30][31][32][33][34][35] was used instead. GTP is suited for the polymerization of methacrylates up to medium molecular weights, with the important advantages of operability at room temperature and very fast kinetics, requiring only 5-10 min per polymerization step.…”

Section: Introductionmentioning

confidence: 99%

Networks Based on “Core‐First” Star Polymers End‐Linked Using a Degradable Ketal Cross‐Linker: Synthesis, Characterization, and Cleavage

Kepola

Patrickios

2017

Macro Chemistry & Physics

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out of every cross-linking core (crosslinking node functionality) is characterized by a rather broad distribution. We also developed a variation of this method, requiring only a monofunctional initiator, in which star polymers are first prepared using either the "arm-first" or the "corefirst" strategy, followed again by the addition of cross-linker to interconnect the stars to a quasimodel network. [4] Thus, our above-described methods represent a compromise between ease of synthesis and structural control, employing a onepot sequential procedure to yield polymer networks with a good control in the elastic chain length but less control in the core functionality.In the past 20 years, we developed many quasimodel polymer network families, based on end-linked linear chains or star copolymers. In addition to purely hydrophobic and hydrophilic homopolymer systems, more complex ones were also developed, most notable of which were the amphiphilic systems, combining both hydrophobic and hydrophilic segments. [5][6][7] Amphiphilic polymer conetworks (APCNs) self-assemble in water, phase separating at the nanoscale, and yielding hydrophilic and hydrophobic domains of nanoscopic dimensions, as well as a huge interfacial area between the nano phases. These attributes endow APCNs with a great utility in a variety of applications, including uses as the material for soft contact lenses, [8] matrices for drug delivery [9] and tissue engineering, [10] and porous scaffolds for phase transfer (bio)catalysis. [11] Other complex quasimodel polymer network systems we developed include polyampholytic ones, [12,13] comprising positively and negatively ionizable polymer segments, [14,15] and double-hydrophilic ones, comprising both hydrophilic polymer segments, of which one was ionizable and the other nonionic. [16,17] Another important development within quasimodel polymer networks was the introduction of degradability, either through a degradable cross-linker [18] or through a degradable bifunctional initiator, [19] with the latter being more demanding than the former, arising from the difficulties associated with the synthesis, purification, and the stability of degradable bifunctional initiators.In the present manuscript, we report the preparation, characterization, and cleavage of degradable quasimodel poly mer networks based on interconnected "core-first" star [20] poly(methyl methacrylate)s (polyMMAs), using a degradable, Group Transfer PolymerizationSequential group transfer polymerization of cross-linker, monomer (methyl methacrylate), and cross-linker again is used to prepare cleavable polymer networks based on interconnected "core-first" star polymers. By employing a degradable and a nondegradable cross-linker, four networks are prepared. While cleavage of the degradable cross-linker residues leads to complete polymer network dissolution, the degradation products do not always display the expected molecular weight features. These products are the expected in the case of the network prepared using only the degradable cross-li...

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RAFT (Reversible addition-fragmentation chain transfer) crosslinking (co)polymerization of multi-olefinic monomers to form polymer networks

Cited by 102 publications

References 115 publications

Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Electrochemical activity of sulfur networks synthesized through RAFT polymerization

Effects of RAFT Agent on the Selective Approach of Molecularly Imprinted Polymers

Networks Based on “Core‐First” Star Polymers End‐Linked Using a Degradable Ketal Cross‐Linker: Synthesis, Characterization, and Cleavage

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