Successive Synthesis of Multiarmed and Multicomponent Star‐Branched Polymers by New Iterative Methodology Based on Linking Reaction between Block Copolymer In‐Chain Anion and α‐Phenylacrylate‐Functionalized Polymer

Ito, Shotaro; Goseki, Raita; Manners, Ian; Ishizone, Takashi; Hirao, Akira

doi:10.1002/macp.201500148

Cited by 15 publications

(5 citation statements)

References 71 publications

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“…Multiarm star polymers containing linear polymeric chains emanating as “arms” from a central branching point, or core, represent one of the simplest branched topologies with spherical shape, high functionality, low viscosity, and dense structure and provide properties and functions as compared to their linear analogs with similar molecular weight . Until recently, the living ionic polymerization procedures mostly anionic polymerization were the only system for the preparation of the multiarm star polymers . Without a doubt, the introduction of living radical polymerization (LRP) routes has enabled the synthesis of multiarm star polymers with a cross‐linked core from a wide range of monomers under less stringent reaction conditions with good control over dispersity .…”

Section: Introductionmentioning

confidence: 99%

Heterofunctionalized Multiarm Star Polymers via Sequential Thiol-para-Fluoro and Thiol-Ene Double “Click” Reactions

Çakır

Tunca

Hızal

et al. 2016

Macromol. Chem. Phys.

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The successful postfunctionalization of multiarm star polystyrene (PS) with pentafluorophenyl and allyl moieties at the periphery is demonstrated employing modular thiol‐para‐fluoro and photoinduced radical thiol‐ene double “click” reactions, respectively. α‐Fluoro and α‐allyl functionalized PS (α‐fluoro‐PS and α‐allyl‐PS) are in situ prepared by atom transfer radical polymerization of styrene and their mixture is used as macroinitiator in a crosslinking reaction with divinyl benzene (DVB) yielding (fluoro‐PS)m–polyDVB–(allyl‐PS)m multiarm star polymer. It is found that the multiarm star polymer includes nearly identical number of arms possessing pentafluorophenyl and allyl moieties at the periphery. The obtained multiarm star polymer is then reacted with 1‐propanethiol through thiol‐para‐fluoro “click” reaction to give (propyl‐PS)m–polyDVB–(allyl‐PS)m multiarm star polymer, which is subsequently reacted with N‐acetyl‐l‐cysteine methyl ester via radical thiol‐ene “click” reaction in order to give well‐defined heterofunctionalized (propyl‐PS)m–polyDVB–(cysteine‐PS)m multiarm star polymer, with higher molecular weight and narrow molecular weight distribution. Multiarm star polymers are characterized by using viscotek triple detection gel permeation chromatography, 1H, and 19F NMR.

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Section: Introductionmentioning

confidence: 99%

Heterofunctionalized Multiarm Star Polymers via Sequential Thiol-para-Fluoro and Thiol-Ene Double “Click” Reactions

Çakır

Tunca

Hızal

et al. 2016

Macromol. Chem. Phys.

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“…Importantly, for the methodology developed in this study, all the living anionic polymers derived from the methacrylate monomers and 2-VP with less nucleophilicities are readily introduced as either the graft or the main chain by reacting each of them with the PA reaction site. Furthermore, since highly reactive living anionic PS, PI, and PB have already been reported to react with the PA reaction site based on our previous studies, − these polymer segments are also used in the graft copolymer synthesis. Thus, the developed methodology becomes more general and versatile than those already reported for the synthesis of exact graft copolymers. − , …”

Section: Discussionmentioning

confidence: 99%

“…All the materials and measurements in this study were reported in our previous papers , and described in the Supporting Information.…”

Section: Experimental Sectionmentioning

confidence: 99%

Precise Synthesis of New Exactly Defined Graft Copolymers Made up of Poly(alkyl methacrylate)s by Iterative Methodology Using Living Anionic Polymerization

2015

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An iterative methodology using living anionic polymerization with a 1,1-diphenylethylene disubstituted with trimethylsilyl (TMS) and tert-butyldimethylsilyl (TBS) ethers has been developed in order to synthesize new exactly defined graft copolymers made up of poly(alkyl methacrylate)s. During each reaction sequence, the TMS and TBS ethers were transformed into α-phenyl acrylate (PA) functions one by one at the different reaction stages. The first PA function derived from the TMS ether was utilized to introduce the graft chain, while the main chain with the TMS and TBS ethers was introduced via the second PA function derived from the TBS ether. Thus, the same chain-end functionalities (both TMS and TBS ethers) were reintroduced after construction of the graft unit. In practice, the reaction sequence involving "the introduction of the graft chain" and "the introduction of the main chain with the two silyl ethers" was iterated three times, leading to the synthesis of poly(benzyl methacrylate) (PBnMA)-exact graf tpoly(methyl methacrylate) (PMMA) with three PMMA graft chains. Similarly, the synthesis of PBnMA-exact graf t-poly(2vinylpyridine) (P2VP) with two P2VP graft chains was successfully carried out. With the use of the α,ω-chain-enddifunctionalized PBnMA as the starting material, two graft units could be constructed at the same time by iterating the reaction sequence once. The graft copolymers with up to six graft chains were obtained by only three repeated reaction sequences. Thus, the reaction steps could be significantly reduced. The graft copolymers synthesized in this study were perfectly controlled in structure from a viewpoint of the following three parameters defining the structure of the graft copolymer: (1) molecular weight of the main chain, (2) molecular weights of the graft chains, and (3) number and placement of the graft chains. Furthermore, these three parameters can also be intentionally changed as required.

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“…Very recently, a new and improved methodology has been proposed, as illustrated in Scheme 2 [ 49 , 50 , 51 , 52 ]. The key of this methodology is to utilize two functionalities, X 1 and X 2 , which can be deprotected in turn to separately convert to the first and second Y reaction sites.…”

Section: Macromolecular Architecture Syntheses By Iterative Methodmentioning

confidence: 99%

Precise Synthesis of Macromolecular Architectures by Novel Iterative Methodology Combining Living Anionic Polymerization with Specially Designed Linking Chemistry

et al. 2017

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This article reviews the development of a novel all-around iterative methodology combining living anionic polymerization with specially designed linking chemistry for macromolecular architecture syntheses. The methodology is designed in such a way that the same reaction site is always regenerated after the polymer chain is introduced in each reaction sequence, and this "polymer chain introduction and regeneration of the same reaction site" sequence is repeatable. Accordingly, the polymer chain can be successively and, in principle, limitlessly introduced to construct macromolecular architectures. With this iterative methodology, a variety of synthetically difficult macromolecular architectures, i.e., multicomponent µ-star polymers, high generation dendrimer-like hyperbranched polymers, exactly defined graft polymers, and multiblock polymers having more than three blocks, were successfully synthesized.

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Successive Synthesis of Multiarmed and Multicomponent Star‐Branched Polymers by New Iterative Methodology Based on Linking Reaction between Block Copolymer In‐Chain Anion and α‐Phenylacrylate‐Functionalized Polymer

Cited by 15 publications

References 71 publications

Heterofunctionalized Multiarm Star Polymers via Sequential Thiol-para-Fluoro and Thiol-Ene Double “Click” Reactions

Heterofunctionalized Multiarm Star Polymers via Sequential Thiol-para-Fluoro and Thiol-Ene Double “Click” Reactions

Precise Synthesis of New Exactly Defined Graft Copolymers Made up of Poly(alkyl methacrylate)s by Iterative Methodology Using Living Anionic Polymerization

Precise Synthesis of Macromolecular Architectures by Novel Iterative Methodology Combining Living Anionic Polymerization with Specially Designed Linking Chemistry

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