Synthesis of poly(vinyl acetate)-b-poly(vinyl chloride) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP)

Piette, Yasmine; Debuigne, Antoine; Bodart, Vincent; Willet, Nicolas; Duwez, Anne‐Sophie; Jérôme, Christine; Detrembleur, Christophe

doi:10.1039/c2py20965a

Cited by 28 publications

(13 citation statements)

References 48 publications

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“…Piette et al . performed cobalt‐mediated radical (co)polymerization (CMRP) of VC and VAc by using bis (acetylacetonato)cobalt [Co(acac) 2 ] as a controlling agent, and prepared PVAc‐ b ‐PVC and PVAc‐ b ‐P(VC‐ co ‐VAc) copolymers using PVAc‐Co(acac) 2 as the macroinitiator . However, the conversion of VC (or VC and VAc) is low (less than 30%) after 6 h of reaction, and MWD of PVC and block copolymers are wider.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Huang

Pan

Bao

2017

J of Applied Polymer Sci

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Reversible addition–fragmentation chain transfer miniemulsion (co)polymerizations of vinyl acetate (VAc) and vinyl chloride (VC) are conducted in the presence of a fluorinated xthanate (X1). VAc miniemulsion polymerization can be well controlled by X1, and PVAc with small polydispersity index (PDI, <1.20) are obtained. X1 also shows well mediative effect to VC‐VAc miniemulsion copolymerization, while the PDI of VC‐VAc copolymer is greater than that of PVAc since a chain transfer rate to VC is greater than that to VAc. PVAc‐b‐PVC copolymers are synthesized by VC miniemulsion polymerizations mediated by X1‐terminated PVAc. PDIs of PVAc‐b‐PVC copolymers are greater than that of PVAc and VC‐VAc random copolymers with close monomer compositions, and increase with the increase of VC conversion. This is caused by the increased chain transfer to monomer and the formation of monomer‐rich and polymer‐rich phases during the VC polymerization stage. As‐prepared PVAc‐b‐PVC copolymers exhibit a micro‐phase separated morphology. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45074.

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Section: Introductionmentioning

confidence: 99%

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Huang

Pan

Bao

2017

J of Applied Polymer Sci

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“…SET‐LRP and SET‐DTLRP of VC and chain extension of hydroxypropyl acrylate were also demonstrated to be reliable on a pilot scale . Besides SET‐LRP and SET‐DTLRP, only a few literatures have been reported on the CLRP of VC . Abreu et al have first realized the CLRP of VC via RAFT method by using dithiocarbonate cyanomethyl methyl(phenyl)carbamodithioate as RAFT agent and tetrahydrofuran (THF) as sovlent .…”

Section: Introductionmentioning

confidence: 99%

Solution and aqueous miniemulsion polymerization of vinyl chloride mediated by a fluorinated xanthate

Huang

Pan

Bao

2016

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

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Solution and aqueous miniemulsion polymerizations of vinyl chloride (VC) mediated by (3,3,4,4,5,5,6,6,7, 7,8,8,8-tridecafluorooctyl-2-((ethoxycarbonothioyl)thio) propanoate) (X1) were studied. The living characters of X1-mediated solution and miniemulsion polymerizations of VC were confirmed by polymerization kinetics. The miniemulsion polymerization exhibits higher rate than solution polymerization. Final conversions of VC in the reversible addition-fragmentation chain transfer (RAFT) miniemulsion polymerization reach as high as 87% and are independent of X1 concentration. Initiation process of X1-mediated RAFT miniemulsion polymerization is controlled by the diffusion-adsorption process of prime radicals. Due to the heterogeneity of polymerization environments and concentration fluctuation of RAFT agent in droplets or latex particles, PVCs prepared in RAFT miniemulsion exhibit relatively broad molecular weight distribution. Furthermore, chain extensions of living PVC (PVC-X) with VC, vinyl acetate (VAc), and N-vinylpyrrolidone (NVP) reveal that PVC-X can be reinitiated and extended, further confirming the living nature of VC RAFT polymerization. PVC-b-PVAc diblock copolymer is successfully synthesized by the chain extension of PVC-X in RAFT miniemulsion polymerization.

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“…Among the few Co complexes that have been successfully used for controlling the polymerization of VAc, Co(acac) 2 is the most efficient, enabling the production of well‐defined PVAc of high molar mass in the bulk and in aqueous based dispersed media . Recent publications highlight the high versatility of Co(acac) 2 as a controlling agent to mediate the radical polymerization of nonconjugated monomers including vinyl esters, N ‐vinylamides, N ‐vinyl imidazoliums and vinyl chloride, and conjugated monomers including acrylonitrile (AN) and acrylates, and to allow the synthesis of well‐defined copolymers of ethylene with VAc or AN …”

Section: Introductionmentioning

confidence: 99%

Cobalt-Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide

Kermagoret

Chau

Grignard

et al. 2016

Macromol. Rapid Commun.

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Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO2). CMRP of VAc is conducted using an alkyl-cobalt(III) adduct that is soluble in scCO2. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (Mn) are key parameters that affect the CMRP in scCO2. It is noticed that CMRP is controlled for Mn up to 10 000 g mol(-1), but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO2, is then successfully used to initiate the acrylonitrile polymerization. PVAc-b-PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO2 without the utilization of fluorinated comonomers or organic solvents.

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Synthesis of poly(vinyl acetate)-b-poly(vinyl chloride) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP)

Cited by 28 publications

References 48 publications

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Synthesis of random and block copolymers of vinyl chloride and vinyl acetate by RAFT miniemulsion polymerizations mediated by a fluorinated xanthate

Solution and aqueous miniemulsion polymerization of vinyl chloride mediated by a fluorinated xanthate

Cobalt-Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide

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