Controlled Synthesis and Properties of Cyclic Polymers

Deffieux, Alain; Borsali, Rédouane

doi:10.1002/9783527631421.ch21

Cited by 31 publications

(35 citation statements)

References 108 publications

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“…In polymer science, synthetic methodologies have advanced significantly over the last two decades [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17]. As a result, there are several synthetic strategies for producing cyclic topological polymers [6,7,8,9,10,11,12,13,14,15,16,17]. Nevertheless, these synthetic methods are still facing key challenges such as the minimization of side reactions and the resulting byproducts, and improvement of workup processes for providing highly pure cyclic polymers while retaining high yields.…”

Section: Introductionmentioning

confidence: 99%

Micelle Structure Details and Stabilities of Cyclic Block Copolymer Amphiphile and Its Linear Analogues

2019

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In this study, we investigate structures and stabilities of the micelles of a cyclic amphiphile (c-PBA-b-PEO) composed of poly(-n-butyl acrylate) (PBA) and poly(ethylene oxide) (PEO) blocks and its linear diblock and triblock analogues (l-PBA-b-PEO and -l-PBA--b-PEO-b-PBA) by using synchrotron X-ray scattering and quantitative data analysis. The comprehensive scattering analysis gives details and insights to the micellar architecture through structural parameters. Furthermore, this analysis provides direct clues for structural stabilities in micelles, which can be used as a good guideline to design highly stable micelles. Interestingly, in water, all topological polymers are found to form ellipsoidal micelles rather than spherical micelles; more interestingly, the cyclic polymer and its linear triblock analog make oblate-ellipsoidal micelles while the linear diblock analog makes a prolate-ellipsoidal micelle. The analysis results collectively inform that the cyclic topology enables more compact micelle formation as well as provides a positive impact on the micellar structural integrity.

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Section: Introductionmentioning

confidence: 99%

Micelle Structure Details and Stabilities of Cyclic Block Copolymer Amphiphile and Its Linear Analogues

2019

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“…The absence of chain ends restricts their topologies and endows them a variety of physical properties that significantly distinguish them from their linear precursors and branched or star polymers [1]. For example, cyclic polymers have smaller hydrodynamic volumes and lower viscosity than their linear precursors [2,3]. Cyclic polymers cannot creep in the conventional sense in rheological studies [4][5][6].…”

Section: Introductionmentioning

confidence: 99%

“…However, the synthesis of well-defined cyclic polymers is still a challenge in polymer science [2]. Only few of cyclic polymers with controlled size and narrow molecular weight distribution are synthesized by the end-to-end chain-coupling of α,ω-heterodifunctional linear chains in highly dilute reaction conditions [3,11,12]. Living polymerization appears to be a special technique suitable to reach this goal.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of cyclic polystyrene via a combination of intramolecular coupling and ATRP

Shi

Yan

et al. 2012

J Polym Res

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Cyclic polystyrene with narrow molecular weight distribution was synthesized by intramolecular coupling of α-carboxyl-ω-butylamino heterotelechelic polystyrene using 2-chloro-1-methylpyridinium and triethylamine as the catalyst in highly dilute solution. The linear precursor α-carboxyl-ω-butylamine polystyrene was first prepared by atom transfer radical polymerization using 4-(chloromethyl) benzoic acid as the initiator and followed by nucleophilic substituted with n-butylamine. The results of IR, 1 H NMR, and gel permeation chromatography revealed that highly pure cyclic polystyrene was synthesized via a combination of intramolecular coupling and atom transfer radical polymerization, and can be isolated easily by column chromatography on silica gel using ethyl acetate as the eluant.

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“…Considerable attention has been paid to the cyclic polymers because of their unique properties derived from the absence of chain-ends. It is well known that cyclic polymers possess smaller hydrodynamic volumes, higher glass transition temperatures, and lower intrinsic viscosities and consequently exhibit different properties compared to their linear/star analogues . Among the two general strategies for synthesizing cyclic polymers, the ring expansion technique , affords the synthesis of high-purity, high molecular weight cyclic polymers but faces severe limitations concerning the variety of monomers that can be used, poor control over molecular weight, and broad polydispersity.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Self-Assembly of Well-Defined Star and Tadpole Homo-/Co-/Terpolymers

et al. 2019

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Tadpole polymers are excellent candidates to explore how architecture can influence self-assembly because they combine two topologies in the same molecule (ring polymer as the head and linear polymer as the tail). In this work, we synthesize well-defined tadpole homo-/co-/terpolymers derived from the appropriate chemical modification reactions of the corresponding 3-miktoarm star homo-/co-/ terpolymers via anionic polymerization, high vacuum techniques, and chlorosilane chemistry in combination with the Glaser coupling reaction. The 3-miktoarm star homo-/ co-/terpolymers bear two arms with t-butyl dimethylsiloxypropyl functional end-groups, whereas after deprotection, the ωhydroxyl chain-ends were modified to alkyne moieties. The dialkyne star polymers in the presence of Cu(I)Br and N,N,N′,N″,N″-pentamethyldiethylenetriamine were then transformed to well-defined tadpole homo-/co-/terpolymers. We employed strongly immiscible blocks to enable characterization using electron microscopy and X-ray scattering to explore how the molecular topology influences the self-assembled bulk-state microdomain morphologies.

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Controlled Synthesis and Properties of Cyclic Polymers

Cited by 31 publications

References 108 publications

Micelle Structure Details and Stabilities of Cyclic Block Copolymer Amphiphile and Its Linear Analogues

Micelle Structure Details and Stabilities of Cyclic Block Copolymer Amphiphile and Its Linear Analogues

Synthesis of cyclic polystyrene via a combination of intramolecular coupling and ATRP

Synthesis and Self-Assembly of Well-Defined Star and Tadpole Homo-/Co-/Terpolymers

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