Synthesis of oligomer vinyl acetate with different topologies by RAFT/MADIX method and their phase behaviour in supercritical carbon dioxide

Zhang, Shoucun; Chen, Keping; Liang, Liyun; Tan, Bien

doi:10.1016/j.polymer.2013.07.045

Cited by 16 publications

(14 citation statements)

References 37 publications

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“…In between these extremes, a wide range of R-groups may be employed to good effect, including esters of 1-acetyl [86][87][88][89][90]108,[110][111][112][113], 2-propionyl [3][4][5][6][7][8][9]30,31,34,66,69,70,[80][81][82]85,89,91,107,[114][115][116][117][118][119][120][121][122][123] and 2-methyl-2-propionyl [67,91], 2-acetic acid [124], 2-propionic acid [106,114,125], t-butyl [106], cyanomethyl [67,102], benzyl …”

Section: Methodsmentioning

confidence: 99%

“…In a subsequent paper [69] the authors compared the R-group approach to the Z-group approach in VAc polymerization and concluded that the R-group approach afforded better-defined star polymers, and was the only way to obtain star-shaped PVA after hydrolysis of the star PVAc, as the Z-group approach would result in hydrolysis of the core of the star shaped polymer. Recently the Z-group approach has been used by Zhang et al [122] to synthesize PVAc oligomers with different topologies, to study their behavior in scCO 2 .…”

Section: Controlled Architectures: Stars Hyperbranched and End-functmentioning

confidence: 99%

“…At higher molecular weights, these differences were less marked as the influence of the terminal group was weaker. Additionally, topology effects were studied and revealed the positive impact of branching on the solubility of PVAc [122].…”

Section: Co 2 -Philic Polymers and Surfactantsmentioning

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: 99%

Section: Controlled Architectures: Stars Hyperbranched and End-functmentioning

confidence: 99%

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RAFT Polymerization of Vinyl Esters: Synthesis and Applications

et al. 2014

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“…Since that, the branch effect on solubility of CO 2 -philes had attracted a lot of research attentions. Tan et al [33] synthesized a series of PVAc with different topologies using RAFT polymerization with Z-core xanthates, where the xanthate groups served as the core of the transfer agent. Their results showed that the PVAc with more arms had higher solubility in CO 2 at about 3500 g/mol.…”

Section: Introductionmentioning

confidence: 99%

Effect of molecular weight on CO2-philicity of poly(vinyl acetate) with different molecular chain structure

Zhang

et al. 2016

The Journal of Supercritical Fluids

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The low molecular weight, topological structure and end group removal are expected to enhance the CO 2-philicity of poly(vinyl acetate) (PVAc), which is of great interest for expanding CO 2 applications as a green solvent. This work aims at investigating the effect of molecular weight (M n) of PVAc with different molecular chain structure on the CO 2-philicity through dissolution behavior measurement and molecular modeling. Well-defined 3-armed and 4-armed R-core PVAc was synthesized by RAFT polymerization, and then the corresponding xanthate groups were removed. The CO 2-philicity of multi-armed PVAc was found to be inferior to that of linear one at low M n. With increasing the M n from 1000 to 7000 g/mol, the cloud point pressures (P c) of multi-armed PVAc first decreased, reached a minimum at a given M n , and then increased, which was different from the variation trend of the P c of linear PVAc versus M n. In addition, removal of the xanthate groups could effectively enhance the CO 2-philicity of PVAc, especially at low M n. Moreover, the molecular dynamics (MD) simulations on the interactions in polymer/CO 2 systems indicated that the multi-armed structure had different effects on the compatibility with CO 2 at different M n. At low M n , the polymer-polymer interaction was the main driving force deciding the CO 2-philicity due to the significant difference in different molecular chain structures. At high M n , multi-armed structure enhanced the CO 2-philicity due to the synergistic effect of moderate polymer-polymer interaction and large polymer-CO 2 interaction. The appropriate molecular chain structure could be selected to enhance the CO 2-philicity of PVAc at a certain M n .

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“…And New vinyl ester copolymers poly (vinyl butyrate) (PVBu) and poly (vinyl octanoate) (PVOc) had been designed for use as stabilizers for dispersion polymerization in scCO 2 [28]. Tan et al synthesized the oligomer vinyl acetate with different topologies and functional oligo(vinyl acetate) bearing bipyridine moieties by RAFT/MADIX method [29,30]. Johnston et al developed the nonionic hydrocarbon surfactants and investigated the morphology and stability of CO 2 -inwater foams [31].…”

Section: Introductionmentioning

confidence: 99%