Under pressure: electrochemically-mediated atom transfer radical polymerization of vinyl chloride

Bon, Francesco De; Ribeiro, Diana Cunha; Abreu, Carlos M. R.; Rebelo, Rafael C.; Isse, Abdirisak Ahmed; Serra, Arménio C.; Gennaro, Armando; Matyjaszewski, Krzysztof; Coelho, Jorge F. J.

doi:10.1039/d0py00995d

Cited by 12 publications

(9 citation statements)

References 104 publications

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“…In a subsequent study, a 4- star -[PBA- block -PVC] was prepared using a similar protocol (Scheme ). More recently, electrochemically initiated ATRP (eATRP) and supplemental activator and reducing agent atom transfer radical polymerization (SARA–ATRP) with Cu(I) as activator have been evaluated in preparing similar 4- star -PVC . The 4- star -[PBA- block -PVC] formed by SET–RDRP was proposed as a potential plasticizer for PVC, and a patent was obtained .…”

Section: Introductionmentioning

confidence: 99%

“…40 More recently, electrochemically initiated ATRP (eATRP) and supplemental activator and reducing agent atom transfer radical polymerization (SARA−ATRP) with Cu(I) as activator have been evaluated in preparing similar 4-star-PVC. 59 The 4star-[PBA-block-PVC] formed by SET−RDRP was proposed as a potential plasticizer for PVC, and a patent was obtained. 60 However, there appear to be no published data for the 4-star-[PBA-block-PVC], or the 4-star-PVC, in this application.…”

Section: Introductionmentioning

confidence: 99%

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“All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization

Sun

Mi²,

et al. 2021

Macromolecules

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Xanthate-mediated RAFT polymerization has been used to prepare 3-star and 4-star-poly(vinyl chloride) (star-PVC) with a number average molar mass (M n ) in the range of 1 to 7 kg mol −1 . The T g of star-PVC reduces with molar mass and with the number of arms. The star-PVC have substantially lower glasstransition temperatures (T g ) than that of linear PVC of similar M n , with the T g of low-molar mass 4-star-PVC being −7.4 °C. The star-PVC are effective in lowering the T g of blends with commercial PVC when added at 10−30 wt % PVC. When added even at 10 wt %, they are effective in improving the ductility of PVC with an elongation at break (EB) of ∼350% (4-star-PVC) and ∼300% (3star-PVC) relative to commercial PVC, which is substantially higher than that for PVC conventionally plasticized with 30 wt % dioctyl phthalate under similar conditions (EB ∼160%). Importantly, the star-PVC, despite their low molar mass, do not migrate from the PVC blends when tested under standard conditions. The performance of the star-PVC as non-migratory plasticizers for PVC demonstrates the potential for an "all-PVC" flexible PVC.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization

Sun

Mi²,

et al. 2021

Macromolecules

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“…These include activators regenerated by electron transfer (ARGET) ATRP, [ 8–10 ] initiators for continuous activator regeneration (ICAR) ATRP, [ 11,12 ] supplemental activator and reducing agent (SARA) ATRP, [ 13–16 ] photochemically mediated ATRP (photoATRP), [ 17–21 ] mechanoATRP, [ 22–24 ] and electrochemically mediated ATRP ( e ATRP) ( Scheme a). [ 25–31 ] SARA ATRP exploits the comproportionation of Cu II and Cu 0 to (re)generate active Cu I catalyst species (Scheme 1b). A wide variety of monomers, from methyl acrylate (MA) to vinyl chloride (VC), have been polymerized by SARA ATRP.…”

Section: Methodsmentioning

confidence: 99%

Catalytic Halogen Exchange in Supplementary Activator and Reducing Agent Atom Transfer Radical Polymerization for the Synthesis of Block Copolymers

Bon

Abreu

Serra

et al. 2020

Macromol. Rapid Commun.

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Synthesis of block copolymers (BCPs) by catalytic halogen exchange (cHE) is reported, using supplemental activator and reducing agent Atom Transfer Radical Polymerization (SARA ATRP). The cHE mechanism is based on the use of a small amount of a copper catalyst in the presence of a suitable excess of halide ions, for the synthesis of block copolymers from macroinitiators with monomers of mismatching reactivity. cHE overcomes the problem of inefficient initiation in block copolymerizations in which the second monomer provides dormant species that are more reactive than the initiator. Model macroinitiators with low dispersity are prepared and extended to afford well‐defined block copolymers of various compositions. Combined cHE/SARA ATRP is therefore a simple and potent polymerization tool for the copolymerization of a wide range of monomers allowing the production of tailored block copolymers.

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“…Polymerizations of butyl acrylate, methyl methacrylate, and styrene in DMF and OEOMA in water yielded polymers with low dispersity and predictable molecular weights [48a] . This reactor was employed also for e ATRP of vinyl chloride, which is a gaseous monomer and needs a pressure resistant cell [48b] …”

Section: Electrochemically‐mediated Atrpmentioning

confidence: 99%

Electrochemistry for Atom Transfer Radical Polymerization

Isse

Gennaro

2021

The Chemical Record

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Atom Transfer Radical Polymerization (ATRP) is the most powerful and most employed technology of Controlled Radical Polymerization (CRP) to produce polymers with well‐defined architecture, that is, composition, topology, and functionality. Several hundreds of papers are published every year on ATRP processes, mainly based on empiric experimental procedures. Electrochemistry powerfully entered in the field of ATRP about 10 years ago, providing important contributions both to the further development of the process and to a better understanding of its mechanism. Five main issues took advantage of electrochemistry and/or its synergism with ATRP: i) understanding the mechanism of ATRP activation; ii) determination of thermodynamic parameters; iii) determination of activation and deactivation rate constants; iv) the SARA ATRP vs SET‐LRP dispute: the role of Cu0; v) electrochemically‐mediated ATRP.

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Under pressure: electrochemically-mediated atom transfer radical polymerization of vinyl chloride

Abstract: The stringent control over the polymerization of less activated monomers remains one major challenge for Reversible Deactivation Radical Polymerizations (RDRP), including Atom Transfer Radical Polymerization (ATRP). Electrochemically mediated ATRP (eATRP)...

Cited by 12 publications

References 104 publications

“All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization

“All-PVC” Flexible Poly(vinyl Chloride): Nonmigratory Star-Poly(vinyl Chloride) as Plasticizers for PVC by RAFT Polymerization

Catalytic Halogen Exchange in Supplementary Activator and Reducing Agent Atom Transfer Radical Polymerization for the Synthesis of Block Copolymers

Electrochemistry for Atom Transfer Radical Polymerization

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