Synthesis of Poly(vinyl acetate) Molecular Brushes by a Combination of Atom Transfer Radical Polymerization (ATRP) and Reversible Addition−Fragmentation Chain Transfer (RAFT) Polymerization

Nese, Alper; Kwak, Yungwan; Nicolaÿ, Renaud; Barrett, Michael J.; Sheiko, Sergei S.; Matyjaszewski, Krzysztof

doi:10.1021/ma1004698

Cited by 52 publications

(55 citation statements)

References 41 publications

(77 reference statements)

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“…[166] [420] NIPAm-b-DMAm [420] Thiol-ene Cellulose 156 EA [629] NIPAm [629] DCC/DMAP PLA Poly(MMA-co-TMSEMA) 136 NIPAm [630] Alkyne-azide 'click' C Poly(TMSEMA) 226 VAc [631] DCC/DMAP C Loprodyne (hydroxylated nylon-6,6 membrane) 121 NIPAm [382] DIC/DMAP Polypropylene 89 AA [632] AA-b-Am [632] UV initiator grafted to surface, used in AA polymerization in presence of 89. Am grafted Divinylbenzene microspheres 11 312 [166] RAFT agent attached by single unit monomer insertion.…”

Section: Grafting-from Processesmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(¼S)SR) by a mechanism of reversible addition-fragmentation chain transfer ( Chem. 2009Chem. , 62, 1402. This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Grafting-from Processesmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process – A Third Update

2012

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“…This rather low apparent M n in GPC was also observed for PPXEM-g -PVAc molecular brushes by Nese et al, in which they found M n,NMR = 1 880 000 and M n,GPC = 315 000. [ 22 ] The second peak in the GPC trace at t top = 14.16 min ( M n = 11 500) might originate from the brush-like structure and/or interactions of the chlorine groups of the polymer side chains with the column. The PPXEM-g -PVClAc precursor bottlebrush was hydrolyzed under mild conditions using THF/MeOH/K 2 CO 3 at room temperature to yield PPXEM-g -PVA (Scheme 1 ).…”

Section: Preparation Of Ppxem Macro-ctamentioning

confidence: 99%

“…Nese et al developed an effi cient procedure to prepare molecular brushes of VAc and other vinyl ester monomers, using a combination of atom-transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. [ 22,23 ] However, the PVAc side chains of the molecular brush could not be hydrolyzed to prepare PVA bottlebrushes due to the presence of multiple ester bonds.…”

Section: Introductionmentioning

confidence: 99%

Influence of Polymer Chain Architecture of Poly(vinyl alcohol) on the Inhibition of Ice Recrystallization

Olijve

Hendrix

Voets

2016

Macromol. Chem. Phys.

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Poly(vinyl alcohol) (PVA) is a water‐soluble synthetic polymer well‐known to effectively block the recrystallization of ice. The effect of polymer chain architecture on the ice recrystallization inhibition (IRI) by PVA remains unexplored. In this work, the synthesis of PVA molecular bottlebrushes is described via a combination of atom‐transfer radical polymerization and reversible addition‐fragmentation chain‐transfer polymerization. The facile preparation of the PVA bottlebrushes is performed via the selective hydrolysis of the chloroacetate esters of the poly(vinyl chloroacetate) (PVClAc) side chains of a PVClAc precursor bottlebrush. The IRI efficacy of the PVA bottlebrush is quantitatively compared to linear PVA. The results show that even if the PVA chains are densely grafted onto a rigid polymer backbone, the IRI activity of PVA is maintained, demonstrating the flexibility in PVA polymer chain architecture for the design of synthetic PVA‐based ice growth inhibitors.

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“…Matyjaszewski et al synthesized a macroRAFT agent (poly(2-((2-ethylxanthatepropanoyl)oxy)ethyl methacrylate, PXPEM) by attaching xanthate chain transfer agents onto each monomeric unit of poly (2-hydroxyethyl methacrylate) (PHEMA) prepared by ATRP. Polymerization of VAc [152] or sequential polymerizations of NVP and VAc [153] in the presence of PXPEM allowed the formation of molecular brushes (Figure 3). Scheme 17.…”

Section: Scheme 16 Strategy For the R And Z-designed Pvac Combsmentioning

confidence: 99%

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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Synthesis of Poly(vinyl acetate) Molecular Brushes by a Combination of Atom Transfer Radical Polymerization (ATRP) and Reversible Addition−Fragmentation Chain Transfer (RAFT) Polymerization

Cited by 52 publications

References 41 publications

Living Radical Polymerization by the RAFT Process – A Third Update

Living Radical Polymerization by the RAFT Process – A Third Update

Influence of Polymer Chain Architecture of Poly(vinyl alcohol) on the Inhibition of Ice Recrystallization

RAFT Polymerization of Vinyl Esters: Synthesis and Applications

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