Designing Unusual Polymer Topologies by Electrostatic Self-Assembly and Covalent Fixation

Oike, Hideaki; Imaizumi, Hiroyuki; Mouri, Takayuki; Yoshioka, Yuka; Uchibori, and Akiko; Tezuka, Yasuyuki

doi:10.1021/ja001736z

Cited by 226 publications

(327 citation statements)

References 34 publications

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“…For a first attempt to realize the ESA-CF method N-methyl pyrrolidinium groups (Scheme 42) were used. [148][149][150][151] However, the nucleophilic attack of the carboxylate anions did not only cleave the pyrrolidinium ring as hoped for, it also caused substitution at the methyl group (yielding methyl esters), whereby linear chains were formed. [148][149][150][151] This disadvantage was avoided, when the N-phenyl pyrrolidinium endgroup was used (R ¼ C 6 H 5 in Scheme 42).…”

Section: Cyclization Via Electrostatic Interactionsmentioning

confidence: 98%

“…[148][149][150][151][152][153][154][155][156][157][158][159][160][161][162][163][164] Characteristic for this approach is the combination of bifunctional polymer having positively charged electrophilic endgroups with the negatively charged ''b 2 '' or ''b 3 '' monomer typically the anion of a dicarboxylic or tricarboxylic acid. As illustrated in Schemes 41-43, the carboxylate anions react with the ammonium endgroups upon heating by formation of a covalend bond, namely an ester group.…”

Section: Cyclization Via Electrostatic Interactionsmentioning

confidence: 99%

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Cyclic polymers: Synthetic strategies and physical properties

Kricheldorf

2009

J. Polym. Sci. A Polym. Chem.

401

442

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Syntheses of cyclic polymers including cyclic homopolymers, cyclic block copolymers, sun-shaped polymers, and tadpole polymers are discussed on the basis of a differentiation between synthetic methods and synthetic strategies (e.g., polycondensation, ring-ring equilibration, or ring-expansion polymerization). Furthermore, all synthetic methods are classified as kinetically or thermodynamically controlled reactions. Characteristic properties of cyclic polymers such as smaller hydrodynamic volume, lower melt viscosities, and higher thermostabilities are compared to the properties of their linear counterparts. Furthermore, the nanophase separation of cyclic diblock copolymers is discussed.

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Section: Cyclization Via Electrostatic Interactionsmentioning

confidence: 98%

Section: Cyclization Via Electrostatic Interactionsmentioning

confidence: 99%

Cyclic polymers: Synthetic strategies and physical properties

Kricheldorf

2009

J. Polym. Sci. A Polym. Chem.

401

442

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“…One elegant method to form cyclic polymer with a wide variety of topologies has been through the Tezuka 40,73,126,127 electrostatic self-assembly and covalent fixation (ESA-CF) method as shown in Scheme 3. The first step is the preparation of cyclic ammonium (pyrrolidium) salt groups attached at the end-groups of a hydrophobic polymer.…”

Section: Highlight Wwwpolymerchemistryorg Journal Of Polymer Sciencementioning

confidence: 99%

Cyclic polymers: Methods and strategies

Jia

Monteiro

2012

J. Polym. Sci. A Polym. Chem.

264

243

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Cyclic polymers have different physical properties compared to their linear counterparts of the same molecular weight. These different properties could have potential impact in the production of new and exciting polymer products. For industry to commercialize such materials, cyclic polymers need to be made on large scales, have controlled molecular weight distributions, and have versatile chemical composition. This highlight article describes many of the synthetic methods and strategies for obtaining highly pure cyclic polymers, and presents kinetic attributes for some of the processes.

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“…13 Moreover, a tricyclic polymer having a trefoil topology has been produced from the self-assembly consisting of three units of a linear telechelic precursor carrying a hexafunctional carboxylate counteranion (Scheme 6). …”

Section: Multicyclic Polymer Constructions By Electrostaticmentioning

confidence: 99%

“…5, 13 Linear or star telechelic precursors, such as poly(tetrahydrofuran, THF), poly(ethylene oxide), poly(styrene), and poly(dimethylsiloxane), obtainable through the living polymerization technique, and having moderately strained, 5-membered cyclic ammonium salt groups, carrying counteranions of appropriate nucleophilic reactivity, like carboxylates, have been employed as key polymer precursors. It is also notable that not only small (low molecular weight and water-soluble) but also large (polymeric and water-insoluble) carboxylates can be employed in this electrostatic self-assembly and covalent fixation process.…”

Section: Electrostatic Polymer Self--assembly and Covalent Fixation Fmentioning

confidence: 99%

Topological Polymer Chemistry in Pursuit of Elusive Polymer Ring Constructions

Adachi

Tezuka

2009

J. Synth. Org. Chem. Jpn.

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Current challenges and future perspectives of topological polymer chemistry have been reviewed. A variety of novel cyclic and multicyclic macromolecular topologies has now been realized by intriguing synthetic protocols. In particular, the electrostatic polymer self-assembly of telechelic precursors having cyclic ammonium salt groups accompanying polyfunctional carboxylate counteranions has been exploited in dilution to produce topologically significant, non-covalent constructions of a dynamic nature. The subsequent covalent conversion through the ring-opening or through the ring-emitting reaction of cyclic ammonium salt groups by carboxylate counteranions provides cyclic and multicyclic polymer products effectively. Furthermore, the metathesis condensation process with functional cyclic polymer precursors has been demonstrated as a promising synthetic means to construct a variety of complex polymer topologies. Scheme 1. Single and multicyclic polymer topologies (ring family tree).tive properties in comparison with conventional linear or branched polyethylenes. 7a The "end-biting" chain transfer to eliminate the initiator species is a key to producing stable ring polymers. However, the chain transfer occurs concurrently during the propagation, and the chain length distribution (MWD) of the polymer products could not be controlled rigorously. By this ring-expansion process using a bulky, dendronized monomer, a ring-shaped nano-object has also been produced. 7e Ring poly(sulfide)s, free of the initiator fragment and having controlled size distributions have also been reported, in which the repetitive insertion of thiirane, a three-membered cyclic sulfide monomer into the thioester unit of a cyclic initiator proceeds with the concurrent chain transfer by intermolecular ester exchange reactions.7f More recently, ring polyesters with narrow size distributions have been obtained by a zwitterionic ring-opening polymerization of cyclic lactones and lactides with an N-heterocyclic carbene initiator (Scheme 2).7g-i In this process, the "end-biting" chain transfer is assumed to take place after the rapid propagation to eliminate the initiator species. Furthermore, ring-expansion polymerization has been combined with the end-linking reaction for the practical synthesis of ring polymers of high molar mass (Scheme 2). 10Thus, a cyclic initiator of stannous dialkoxide has been employed for the ring-opening polymerization of e-caprolactone. By taking advantage of the living nature of this process, a few units of a photo-crosslinkable, acrylate-functionalized e-caprolactone derivative have subsequently been introduced. Thereafter the intramolecular photo-crosslinking of acrylic groups has been conducted under dilution, and the stannous dialkoxide initiator fragment has finally been removed by hydrolysis, to produce ring polymers free of the initiator fragments.10a By this process, a twin-tail tadpole polymer comprised of a ring and two outward branch segments, has also been prepared by the re-initiation of ring-ope...

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Designing Unusual Polymer Topologies by Electrostatic Self-Assembly and Covalent Fixation

Cited by 226 publications

References 34 publications

Cyclic polymers: Synthetic strategies and physical properties

Cyclic polymers: Synthetic strategies and physical properties

Cyclic polymers: Methods and strategies

Topological Polymer Chemistry in Pursuit of Elusive Polymer Ring Constructions

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