Glass transition temperature of cyclic polystyrene and the linear counterpart contamination effect

Gao, Lingfeng; Oh, Joongsuk; Tu, Yingfeng; Chang, Taihyun; Li, Christopher Y.

doi:10.1016/j.polymer.2019.03.018

Cited by 52 publications

(40 citation statements)

References 45 publications

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“…2 However, the molecular weight dependence of the T g for rings has been found to decrease, increase, or remain unaltered with the decreasing molecular weight, depending on the polymer type and the ring purity. [32][33][34] For instance, macrocyclic poly(dimethylsiloxane) showed increasing T g values with the decreasing molecular weight, 35,36 in agreement with the theoretical model of Di Marzio and Guttman. 37 In contrast, macrocycles of polystyrene, 38 poly(2-vinylpyridine), 38 poly(α-methylstyrene), 38 poly (2-vinylnaphthalene), 38 poly( phenylmethylsiloxanes), 39 and poly(glycidyl phenyl ether) 40 exhibited decreasing T g values with the decreasing molecular weight.…”

Section: Papersupporting

confidence: 85%

Synthesis of macrocyclic poly(ethylene oxide)s containing a protected thiol group: a strategy for decorating gold surfaces with ring polymers

et al. 2019

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Section: Papersupporting

confidence: 85%

Synthesis of macrocyclic poly(ethylene oxide)s containing a protected thiol group: a strategy for decorating gold surfaces with ring polymers

et al. 2019

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“…[114] As polymers are characterized by a very close structure-property relationship, in solution as well as in bulk, the elimination of these impurities is crucial when determining the properties of cyclic polymers. [2,[115][116][117] The most traditional technique used to get rid of these impurities is the preparative SEC. In fact, because of its limited conformational freedom, a cyclic polymer will present a lower hydrodynamic volume when compared to its linear analogue.…”

Section: Elimination Of Cyclization Byproductsmentioning

confidence: 99%

“…[ 114 ] As polymers are characterized by a very close structure–property relationship, in solution as well as in bulk, the elimination of these impurities is crucial when determining the properties of cyclic polymers. [ 2,115–117 ]…”

Section: Advances In the Synthesis Of Cyclic Polymersmentioning

confidence: 99%

Cyclic polymers: Advances in their synthesis, properties, and biomedical applications

Liénard

Winter

Coulembier

2020

Journal of Polymer Science

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Since the time first synthetic macrocycles were observed as academic curiosities, great advances have been made. Thanks to the development of controlled polymerization processes, new catalytic systems and characterization techniques during the last decades, well-defined cyclic polymers are now readily accessible. This further permits the determination of their unique set of properties, mainly due to their lack of chain ends, and their use for industrial applications can now be foreshadowed. This review aims to give an overview on the recent progresses in the field of ring polymers to this day. The current state of the art of the preparation of cyclic polymers, the challenges related to it such as the purification of the samples and the scalability of the synthetic processes, the properties arising from the cyclic topology and the potential use of cyclobased polymers for biomedical applications are as many topics covered in this review.

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“…Cyclic polymers, with topological restrictions caused by their cyclic architecture, exhibit fascinating properties in comparison with their linear counterparts: smaller hydrodynamic volumes, higher glass‐transition temperatures, lower melt viscosity, better application in gene delivery, and so on . Typically, two main strategies, “ring closure” and “ring expansion,” can be used to construct cyclic polymers .…”

Section: Methodsmentioning

confidence: 99%

Efficient Heterodifunctional Unimolecular Ring‐Closure Method for Cyclic Polymers by Combining RAFT and SuFEx Click Reactions

Liu

Zhang

Liu

et al. 2019

Macromol. Rapid Commun.

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A novel ring‐closure strategy for cyclic polymers by combining reversible addition–fragmentation chain transfer polymerization (RAFT) and the sulfur(VI)‐fluoride exchange (SuFEx) click reaction is presented. Herein, a new heterodifunctional trithiocarbonate RAFT agent, 2‐((tert‐butyldimethylsilyl)oxy)ethyl (4‐(fluorosulfonyl)benzyl) carbonotrithioate (TBDMS‐FSBCT), containing both tert‐butyldimethylsilyl ether and sulfonyl fluoride moieties, is developed. The polymerization behavior of TBDMS‐FSBCT is first demonstrated by a standard RAFT polymerization procedure for two types of vinyl monomers, N‐isopropylacrylamide (NIPAAm) (conjugated vinyl monomer) and N‐vinylpyrrolidone (NVP) (unconjugated vinyl monomer). The tert‐butyldimethylsilyl ether and sulfonyl fluoride groups at the α and ω positions of the obtained linear polymer precursors (L‐PNIPAAm and L‐PVP) are verified by 1H, 13C, and 19F NMR spectra. Subsequent intramolecular SuFEx click cyclization of the α,ω‐heterofunctionalized linear precursors in air at room temperature conveniently yields the corresponding cyclic polymers (C‐PNIPAAm and C‐PVP). Overall, this is the first report on the preparation of cyclic polymers based on the SuFEx reaction under ambient conditions. It is envisioned that the approach may open an avenue for the formation of cyclic polymers.

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Glass transition temperature of cyclic polystyrene and the linear counterpart contamination effect

Cited by 52 publications

References 45 publications

Synthesis of macrocyclic poly(ethylene oxide)s containing a protected thiol group: a strategy for decorating gold surfaces with ring polymers

Synthesis of macrocyclic poly(ethylene oxide)s containing a protected thiol group: a strategy for decorating gold surfaces with ring polymers

Cyclic polymers: Advances in their synthesis, properties, and biomedical applications

Efficient Heterodifunctional Unimolecular Ring‐Closure Method for Cyclic Polymers by Combining RAFT and SuFEx Click Reactions

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