Vinyl acetate living radical polymerization mediated by cobalt porphyrins: kinetic–mechanistic studies

Hsu, C. C.; Yang, Tsung‐Yao; Peng, Chi‐How

doi:10.1039/c4py00191e

Cited by 39 publications

(41 citation statements)

References 53 publications

(62 reference statements)

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“…However, the very high reactivity of the propagating radicals makes VAc one of the most challenging monomers for LRP, which usually results in relatively broad molecular weight distributions and limitation of controlled molecular weights for the resultant PVAcs. Up to now, various LRP methods have been applied for the polymerization of VAc, such as atom transfer radical polymerization (ATRP), degenerative transfer with alkyl iodides, iodine transfer radical polymerization, organotellurium‐mediated chain transfer polymerization, organostibine‐mediated chain transfer polymerization, cobalt‐mediated radical polymerization (CMRP), and reversible addition‐fragmentation chain transfer (RAFT) polymerization. Among the above polymerization methods, RAFT/MADIX (macromolecular design via the interchange of xanthates) was explored extensively .…”

Section: Introductionmentioning

confidence: 99%

Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

Chen

Zhao

Zhang

et al. 2015

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

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In this work, high molecular weight polyvinyl acetate (PVAc) (Mn,GPC = 123,000 g/mol, Mw/Mn = 1.28) was synthesized by reversible addition‐fragmentation chain transfer polymerization (RAFT) under high pressure (5 kbar), using benzoyl peroxide and N,N‐dimethylaniline as initiator mediated by (S)‐2‐(ethyl propionate)‐(O‐ethyl xanthate) (X1) at 35 °C. Polymerization kinetic study with RAFT agent showed pseudo‐first order kinetics. Additionally, the polymerization rate of VAc under high pressure increased greatly than that under atmospheric pressure. The “living” feature of the resultant PVAc was confirmed by 1H NMR spectroscopy and chain extension experiments. Well‐defined PVAc with high molecular weight and narrow molecular weight distribution can be obtained relatively fast by using RAFT polymerization at 5 kbar. © 2015 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym. Chem. 2015, 53, 1430–1436

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Section: Introductionmentioning

confidence: 99%

Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

Chen

Zhao

Zhang

et al. 2015

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

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“…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%

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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“…Particularly, cobalt complex mediated radical polymerization (CMRP) represented one of the most successful and efficient OMRP. [8][9] The sulfonated cobalt porphyrin complexes (TMPS)Co(II) were used to mediate the LRP of acrylic acid in water. [7] When vinyl acetate as monomer, (TMP)Co(II) was also an efficient mediator in living radical polymerization.…”

Section: Introductionmentioning

confidence: 99%

Dispersion polymerization of acrylamide with living character and controlled morphologies initiated and mediated by cobalt porphyrin

et al. 2016

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Dispersion polymerization of acrylamide (AM) catalyzed by cobalt porphyrin [Cobalt tetramethoxyphenylporphyrin, (TMOP)Co(II)] with the feature of living radical polymerization (LRP) in alcohol/water or dimethylformamide (DMF)/water was described. Well-defined polyacrylamide (PAM) uniform spherical particles with predetermined molecular weight and narrow polydispersity (Mw/Mn = 1.09-1.35) were obtained under mild thermal conditions. Linear first-order kinetics with different feeding ratio of AM and cobalt porphyrin were obtained and the number-average molecular weight (Mn) increased linearly with monomer conversion. However, little research has been reported on the (TMOP)Co(II) mediating a living radical dispersion polymerization of acrylamide. The effects of feeding ratio of monomer and cobalt porphyrin, the solvent, the time of polymerization as well as monomer concentration on the morphology of the spherical particles were investigated. There were the increasing trends in the particle size with increasing the concentration of monomer, the time of polymerization and feeding ratio of AM and cobalt porphyrin. The effects of the volume ratio of alcohol or DMF and water were also studied.

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Vinyl acetate living radical polymerization mediated by cobalt porphyrins: kinetic–mechanistic studies

Cited by 39 publications

References 53 publications

Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

Reversible addition‐fragmentation chain transfer polymerization of vinyl acetate under high pressure

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

Dispersion polymerization of acrylamide with living character and controlled morphologies initiated and mediated by cobalt porphyrin

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