RAFT-mediated emulsion polymerization of vinyl acetate: a challenge towards producing high molecular weight poly(vinyl acetate)

Zhao, Funian; Mahdavian, Ali Reza; Teimouri, Mohammad Bagher; Daniels, Eric S.; Klein, A.; El‐Aasser, M. S.

doi:10.1007/s00396-012-2640-z

Cited by 21 publications

(12 citation statements)

References 52 publications

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“…An S-(2-phenylethyl) substituted xanthate had no effect on the polymerization of VAc [72], due to the lack of stabilization of the primary 2-phenylethyl radical. Similarly use of a methyl 3-propionyl leaving group [109] in emulsion polymerization of VAc did not lead to control of molecular weight, although retardation of the polymerization was observed.…”

Section: Methodsmentioning

confidence: 94%

“…Best control was obtained using dithiocarbamate 7. A more recent study [109] used an unusual dithiocarbamate RAFT agent carrying a primary methyl 3-propionyl leaving group (4, Scheme 10). Addition of the RAFT agent to emulsion polymerizations of VAc resulted in retardation of the polymerization kinetics, confirming its involvement in the reaction.…”

Section: Heterogeneous Polymerizationsmentioning

confidence: 99%

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RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

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This article is the first comprehensive review on the study and use of vinyl ester monomers in reversible addition fragmentation chain transfer (RAFT) polymerization. It covers all the synthetic aspects associated with the definition of precision polymers comprising poly(vinyl ester) building blocks, such as the choice of RAFT agent and reaction conditions in order to progress from simple to complex macromolecular architectures. Although vinyl acetate was by far the most studied monomer of the range, many vinyl esters have been considered in order to tune various polymer properties, in particular, solubility in supercritical carbon dioxide (scCO 2 ). A special emphasis is given to novel poly(vinyl alkylate)s with enhanced solubilities in scCO 2 , with applications as reactive stabilizers for dispersion polymerization and macromolecular surfactants for CO 2 media. Other miscellaneous uses of poly(vinyl ester)s synthesized by RAFT, for instance as a means to produce poly(vinyl alcohol) with controlled characteristics for use in the biomedical area, are also covered.

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Section: Methodsmentioning

confidence: 94%

Section: Heterogeneous Polymerizationsmentioning

confidence: 99%

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

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“…Although several works report experimental results for VAc RAFT polymerizations, the production of PVAc in a controlled manner, with high molecular weight average and narrow polydispersity (

{\overset{true‾}{M}}_{normalw} / {\overset{true‾}{M}}_{normaln}

< 1.3) remains a challenge . This is related mainly to the tendency of VAc radicals to get involved in chain‐transfer (to monomer and polymer) and chain‐termination reactions, which also lead to development of inhibitory effects in both conventional and RAFT polymerizations .…”

Section: Resultsmentioning

confidence: 99%

Reversible Addition-Fragmentation Chain Transfer Polymerization of Vinyl Acetate in Bulk and Suspension Systems

Oliveira

Barbosa

Nele

et al. 2014

Macromol. React. Eng.

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Suspension and bulk polymerizations of vinyl acetate (VAc) are performed in several experimental conditions, using cyanomethyl methyl(phenyl) carbamodithioate as the chain transfer agent (CTA). The polymerization kinetics are monitored in batch for bulk polymerizations, showing an inhibitory period at the beginning of the reaction runs, despite the particular experimental conditions used. More accurate control over the molecular properties of the synthesized poly(vinyl acetate) (PVAc) is achieved when high concentrations of CTA are used. Similar experimental conditions are applied to prepare PVAc particles via suspension polymerization of VAc in the presence of small amounts of CTA. It is possible to produce spherical particles with a narrow particle size distribution and predominant spherical morphology. Although the reactions yield low control over the molecular weight properties, it is possible to use the synthesized particles as macro-CTAs and promote chain extension reactions to extend the chain length of the PVAc.

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“…At present, the reversible addition–fragmentation chain‐transfer (RAFT) emulsion radical polymerization technique can enable the polymerization of nonpolar and polar monomers, such as styrene, butadiene, (meth)acrylate, acrylonitrile, γ‐methyl‐α‐methylene‐γ‐butyrolactone, and vinyl acetate . Meanwhile, RAFT emulsion polymerization has a much stronger designability for block copolymers because of its tolerance toward a wide range of monomers.…”

Section: Introductionmentioning

confidence: 99%

Use of short isobornyl methacrylate building blocks to improve the heat and oil resistance of thermoplastic elastomers via RAFT emulsion polymerization

Yuan

Chen

et al. 2017

J of Applied Polymer Sci

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Triblock copolymer (TCP)-based thermoplastic elastomers (TPEs) were designed via reversible addition-fragmentation chain-transfer emulsion polymerization. Short isobornyl methacrylate (IM) building blocks in the two ends of molecular chain were incorporated to guarantee the mechanical properties of the TPEs at high temperature (i.e., heat resistance) because of the high glasstransition temperature (T g ) of poly(isobornyl methacrylate) (PIM; 180 8C). The microphase separation, tensile properties at different temperatures, dynamic mechanical properties, oil resistance, and thermal stability of the TPEs were extensively characterized. The TPEs had distinct microphase separation with a wide inter-T g interval (150-185 8C). The tensile strength and elongation at break of the TPEs decreased with increasing temperature from 25 to 100 8C because of the reduced interactions in the phase domain. Even so, the TPEs had a high elongation at break beyond 200% and little change in the tensile strength even at 100 8C together with a wide quasi-platform stage between the T g values in dynamic mechanical analysis; this indicated good heat resistance. Meanwhile, the TPEs had an enhanced oil resistance and a thermal stability higher than 300 8C. These TCP-based TPEs with heat and oil resistance broaden the application potential in practical fields.

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RAFT-mediated emulsion polymerization of vinyl acetate: a challenge towards producing high molecular weight poly(vinyl acetate)

Cited by 21 publications

References 52 publications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

Reversible Addition-Fragmentation Chain Transfer Polymerization of Vinyl Acetate in Bulk and Suspension Systems

Use of short isobornyl methacrylate building blocks to improve the heat and oil resistance of thermoplastic elastomers via RAFT emulsion polymerization

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