Visible-Light-Induced Living Radical Polymerization (LRP) Mediated by (salen)Co(II)/TPO at Ambient Temperature

Zhao, Youliang; Zhang, Shuailin; Wu, Zhenqiang; Liu, Xu; Zhao, Xianyuan; Peng, Chi‐How; Fu, Xuefeng

doi:10.1021/acs.macromol.5b01149

Cited by 41 publications

(35 citation statements)

References 61 publications

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“…The mechanism of cobalt‐mediated radical polymerization includes C/LRP and CCTP is thus proposed as Scheme . In most cases, both C/LRP and CCTP mediated by cobalt complexes start from the reaction of cobalt(II) complexes and radicals to form the organo‐cobalt(III) species, resulting in an induction period . C/LRPs directly initiated by organo‐cobalt(III) species, which was synthesized from cobalt(II) complex in advance, do not have induction period .…”

Section: Resultsmentioning

confidence: 99%

“…Particularly, the comparison of Co II (TMP) and Co II (acac) 2 is one of interest to polymer scientists because they have totally different coordinating atoms, configuration, and spin state. Although the use of Co II (salen*), a cobalt complex with square planar O,N,N,O‐coordinated environment [Scheme (e)], as a mediator in C/LRP provided a reference between Co II (TMP) and Co II (acac) 2 from the aspect of coordinating atoms, the influence of configuration, and spin state of the cobalt complexes to the C/LRP is still ambiguous.…”

Section: Introductionmentioning

confidence: 99%

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Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

Chen

et al. 2019

Journal of Polymer Science

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A series of cobalt(II) phenoxy‐imine complexes (CoII(FI)2) have been synthesized to mediate the radical polymerization of vinyl acetate (VAc) and methyl acrylate (MA) to evaluate the influence of chelating atoms and configuration to the control of polymerization. The VAc polymerizations showed the properties of controlled/living radical polymerization (C/LRP) with complexes 1a and 3a, but the catalytic chain transfer (CCT) behaviors with complexes 2a, 1b, 2b, and 3b. The control of VAc polymerization mediated by complex 1a could be improved by decreasing the reaction temperature to approach the molecular weights that not only linearly increased with conversions but also matched the theoretical values and relatively narrow molecular weight distributions. The catalytic chain transfer polymerizations (CCTP) mediated by complexes 2a, 1b, 2b, and 3b were characterized by Mayo plots and the polymer chain end double bonds were observed by 1H NMR spectra. The tendency toward C/LRP or CCTP in VAc polymerization mediated by CoII(FI)2 could be determined by the ligand structure. Cobalt complex coordinated by the ligand with more steric hindered and less electron‐donating substituents favored the controlled/living radical polymerization. In contrast, the efficiency of CCT process could be enhanced by less steric hindered, more electron‐donating ligands. The controlled/living radical polymerization of MA, however, could not be achieved by the mediation of these cobalt(II) phenoxy‐imine complexes. Associated with the results of polymerization mediated by other cobalt complexes, this study implied that the configuration and spin state of cobalt complexes were more critical than the chelating atoms to the control behavior of radical polymerization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 101–113

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

Chen

et al. 2019

Journal of Polymer Science

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“…The external activation methods to RDRPs include photochemical, thermochemical, electrochemical and mechanical forces, and so on. Among them, as a more environmentally friendly external methods, visible light is the most ideal stimulus due to its low energy consumption, high performance and safe operation, it also could reversibly trigger the growth of polymer chains by simply switching the light “on” or “off.” So far, a lot of photoinduced RDRPs have been developed including atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer polymerization (RAFT), ring‐opening metathesis polymerization (ROMP), iodine mediated polymerization (IMP), and cobalt mediated radical polymerization (CMRP) …”

Section: Introductionmentioning

confidence: 99%

Visible‐light induced RAFT polymerization of styrenic monomers with aromatic aldehydes as organophotoredox catalysts

Yang

Zhang

Chen

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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A photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) polymerization of p‐methylstyrene (p‐MS) and styrene (St) with 2‐(dodecylthiocarbonothioylthio)‐2‐methylpropionic acid as the chain transfer agent (CTA) and aromatic aldehydes, including 4‐cyanobenzaldehyde (PC1), 2,4‐dimethoxy benzaldehyde, and 4‐methoxy benzaldehyde, as organic photocatalysts has been demonstrated via irradiation with 23 W compact fluorescent lamps. The kinetics of the polymerizations shows first order with respect to monomer conversions. Linear evolution of the Mn of the produced polymers with the monomer conversion is observed. Meanwhile, the as‐prepared polymers are of relatively narrow polydispersity (PDI = Mw/Mn). For instance, the polymerization of p‐MS shows living polymerization features using PC1 within a range of solvents. Especially, the Mn of PpMS increased from about 2100 to 12,700 g/mol with the monomer conversion from 8% to 52% in tetrahydrofuran. The controlled polymerization of St is also observed under optimal reaction conditions. However, the Mn discrepancy between the experimental readings and theoretical calculations is greater at the monomer conversions greater than 40% and the PDI increased gradually over the monomer conversion. This is probably because that CTA is strongly sensitive to the light irradiation with wave range around its characteristic absorption wavelength, leading to significant decomposition of CTA moieties during the RAFT polymerization. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2072–2079

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“…In the last few years, visible light mediated living radical polymerization techniques have been widely investigated . In particular, photocatalyst mediated polymerizations, such as photoinduced electron/energy transfer reversible addition–fragmentation chain transfer (PET‐RAFT) and photoinduced atom transfer radical polymerization, are rapidly emerging as promising tool in polymerizing a wide range of monomers with a high degree of control over the molecular weight and molecular weight distributions (Scheme ) .…”

Section: Introductionmentioning

confidence: 99%

Polymerization of a Photocleavable Monomer Using Visible Light

Bagheri

Yeow

Arandiyan³

et al. 2016

Macromol. Rapid Commun.

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The polymerization of the photocleavable monomer, o-nitrobenzyl methacrylate (NBMA), is investigated using photoinduced electron/energy transfer reversible addition-fragmentation chain transfer polymerization. The polymerizations under visible red (λ max = 635 nm, 0.7 mW cm(-2) ) and yellow (λ max = 560 nm, 9.7 mW cm(-2) ) light are performed and demonstrate rational evidence of a controlled/living radical polymerization process. Well-defined poly(o-nitrobenzyl methacrylate) (PNBMA) homopolymers with good control over the molecular weight and polymer dispersity are successfully synthesized by varying the irradiation time and/or targeted degree of polymerization. Chain extension of a poly(oligo(ethylene glycol) methyl ether methacrylate) macro-chain transfer agent with NBMA is carried out to fabricate photocleavable amphiphilic block copolymers (BCP). Finally, these self-assembled BCP rapidly dissemble under UV light suggesting the photoresponsive character of NBMA is not altered during the polymerization under yellow or red light. Such photoresponsive polymers can be potentially used for the remote-controlled delivery of therapeutic compounds.

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Visible-Light-Induced Living Radical Polymerization (LRP) Mediated by (salen)Co(II)/TPO at Ambient Temperature

Cited by 41 publications

References 61 publications

Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

Visible‐light induced RAFT polymerization of styrenic monomers with aromatic aldehydes as organophotoredox catalysts

Polymerization of a Photocleavable Monomer Using Visible Light

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