Synthesis of Branched Polymers by Means of Living Anionic Polymerization, 5. Synthesis of Star Polymers by Reactions of End-Functionalized Polystyrenes with Chloromethylphenyl Groups with Polymer Anions Consisting of Two Polymer Chains

Hirao, Akira; Tokuda, Yui; Morifuji, Kazushi; Hayashi, Mayumi

doi:10.1002/1521-3935(20010601)202:9<1606::aid-macp1606>3.0.co;2-m

Cited by 25 publications

(20 citation statements)

References 12 publications

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“…The use of this method enables the synthesis of well-defined star polymers with up to 64 arms. [51] Furthermore, the simple introduction of different polymers can lead to multifunctional stars [51][52][53][54][55][56][57][58].…”

Section: Synthesis Of Star-shaped Polymersmentioning

confidence: 99%

Sequential Reactions for Post-polymerization Modifications

Moldenhauer

Théato

2015

Multi-Component and Sequential Reactions in Polymer Synthesis

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Section: Synthesis Of Star-shaped Polymersmentioning

confidence: 99%

Sequential Reactions for Post-polymerization Modifications

Moldenhauer

Théato

2015

Multi-Component and Sequential Reactions in Polymer Synthesis

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“…[95][96][97][98] These benzyl halidefunctionalized polymers are used as polymeric coupling agents in the reaction of living anionic polymers.…”

Section: Synthesis Of Star Polymers Using Benzyl Halide-functionalizementioning

confidence: 99%

Precise Synthesis of Regular and Asymmetric Star Polymers and Densely Branched Polymers with Starlike Structures by Means of Living Anionic Polymerization

Hirao

Hayashi

Tokuda

et al. 2002

Polym J

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ABSTRACT:The subject of this review is to present new synthetic methodologies recently developed by us, which are applicable to both regular and asymmetric star polymers with well-defined architectures. The first methodology involves the coupling reaction of a variety of living anionic polymers of styrene, α-methylstyrene, isoprene, tert-butyl methacrylate, and ethylene oxide with novel chain-end-and in-chain-functionalized polymers with a definite number of benzyl halide moieties intentionally designed as polymeric coupling agents. In the second methodology, we propose a new concept based on iterative approach, with which star polymers can be successively and, in principle, unlimitedly synthesized by repeating the iterative reaction sequence. Finally, a convenient synthesis of densely branched polymers with starlike structures is presented by the quantitative coupling reaction of living anionic polymers with reactive benzyl halide-functionalized backbone polymers based on a grafting-onto method.KEY WORDS Star Polymer / Asymmetric Star Polymer / Living Anionic Polymerization / Iterative Methodology / Polymeric Coupling Agent / 1,1-Diphenylethylene Derivative / Star polymers are branched polymers in which more than three linear polymer chains are linked together at one end of each chain by a central core or a single branch. They have physical properties in bulk, melt, and solution quite distinct from linear analogues. For this reason, star polymers have been widely studied from both synthetic and theoretical points of view. [1][2][3][4][5][6][7][8][9] It is of course essential to use star polymers with welldefined structures for evaluating fundamental understanding regarding the effect of chain branching on such physical properties.At the present time, the most successful methodologies for the synthesis well-defined regular star polymers have been developed mainly based on coupling reactions of living anionic polymers of styrene and 1,3-dinene monomers with multifunctional chlorosilane compounds as electrophilic coupling agents. A variety of star polymers with a definite number of three to eighteen arms have been synthesized. [10][11][12][13][14][15][16][17][18][19] Furthermore, the successful syntheses of the 32-, 64-, and even 128-arm star polymers by using specially designed carbosilane dendrimers have been reported so far. 20,21 Currently, great attention has been paid to more complex asymmetric star polymers whose arms differ in molecular weight and chemical composition, since star polymers of this type are expected to exhibit interesting and unique physical performance originated from their † To whom correspondence should be addressed.branched architectures as well as heterophase structures. [22][23][24][25][26][27][28][29][30][31][32][33] Synthesis of asymmetric star polymers is generally more difficult than that of regular star polymers. In the synthesis of regular star polymers, for example, their arms can be simultaneously introduced by one reaction. On the other hand, two or more highyielding reactions...

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“…[10] Radical Coupling Reaction of Chain-End-Functionalized Polymers with DPE Moiety with Potassium Naphthalenide…”

Section: Synthesis Of Chain-end-functionalized Polymers With a Dpe Momentioning

confidence: 99%

“…[10] Our method involved two reaction steps. The first reaction step was to prepare the polymeric anion by a living linking reaction of a DPEchain-end-functionalized polymer with a living anionic polymer.…”

Section: Introductionmentioning

confidence: 99%