Precise Synthesis of High Generation Dendrimer-Like Star-Branched Polymers and Their Applications
| Project/Area Number |
18350060
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Polymer chemistry
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
HIRAO Akira Tokyo Institute of Technology, Graduate School of Science and Engineering, Professor (00111659)
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| Co-Investigator(Kenkyū-buntansha) |
SUGIYAMA Kenji Tokyo Institute of Technology, Graduate School of Science and Engineering, Assistant Professor (20282840)
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| Project Period (FY) |
2006 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥17,050,000 (Direct Cost: ¥15,700,000、Indirect Cost: ¥1,350,000)
Fiscal Year 2007: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000)
Fiscal Year 2006: ¥11,200,000 (Direct Cost: ¥11,200,000)
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| Keywords | Dendrimer-Like Star-Branched Polymer / Branched Polymer / Living Anionic Polymerization / Dendrimer-Like Star-Branched Block Copolymer / Iterative Methodology / Functional Polymer / Amphiphilic Polymer / Functional Group Transnformation / ブロック共重合体 / ポリメチルメタクリレート / 分岐構造 / 分岐ブロック共重合体 / 世代数 / 繰り返し反応 |
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| Research Abstract |
Dendrimer-like star-branched polymers have been synthesized by developing a novel methodology which involves two basic reactions: (1) linking reaction of α-functionalized living anionic polymers with benzyl bromide-functionalized polymers and (2) transformation reaction to benzyl bromides. The two reactions proceeded quantitatively several times, resulting in the formation of high-generation dendrimer-like star-branched polymers up to seventh generation. The resulting polymer (7th generation) is a really huge macromolecule possessing two million in molecular weight and a narrow molecular weight distribution (Mw/Mn =1.02) and comprising 508 polymer segments with 512 termini. Highly dense polymers consisting of four branches at each junction have also succeeded in synthesizing the polymers up to the third generation. The attempt to synthesize the 4th generation polymer was not successful possibly due to the steric hindrance. Other functional polymer segments have been successfully introduced into the outermost layers of dendrimer-like star-branched polymers. They involve poly(2-vinylpyridine), poly(tert-butyl methacrylate), poly(3-perfluorobutylpropyl methacrylate), and poly(2,3-dihydroxypropyl methacrylate), respectively. By introducing such segments, basic, acidic, ionic, hydrophobic and lipophobic, water-soluble characters could be provided to the polymers. Furthermore, the introduction of methacrylate polymers having liquid crystalline, chirality, and thermoresponsive characters were also successful. Their functional polymers have been examined in detail with respect to such functionalities. The shapes of the dendrimer-like star-branched polymers have been measured by SAXS and found to be ellipsoidal shapes rather than spherical ones. AFM structural imaging of the dendrimer-like star-branched polymers has been realized. The structures based on synthetic methodology as well as internal branching points could be clearly observed for the first time.
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Report
(3 results)
Research Products
(90 results)
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[Journal Article] Complex macromolecular chimeras2008
Author(s)
A., Karatzas, H., Iatrou, N., Hadjichristidis, K., Inoue, K., Sugiyama, A., Hirao
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Journal Title
Biomacromolecules 41(in press)
Description
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[Journal Article] Synthesis and Characterization of Model 3-Mikroarm Star Copolymers of Poly(dimethylsiloxane) and Poly(2-vinylpyridine) (PDMS)2(P2VP)2006
Author(s)
P. G., Fragouli, H., Iatrou, N., Hadjichristidis, T., Sakurai, A., Hirao
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Journal Title
J. Polym. Sci., Part A : Polymer Chemistry 44
Pages: 614-619
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Synthesis of Well-Defined Miktoarm Star Polymers of Poly(dimethylsiloxane) by Combining Chlorosilane and Benzyl Chloride Linking Chemistry2006
Author(s)
Panagiota, Fragouli, Hermis, Iatrou, Nikos, Hadjichristidis, T., Sakurai, Y., Matsunaga, A., Hirao
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Journal Title
J. Polym. Sci., Part A : Polymer Chemistry 44
Pages: 6587-6599
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Review : Precise Synthesis of Well-Defined Dendrimer-Like Star-Branched Polymers by Iterative Methodology based on Living Anionic Polymerization2006
Author(s)
A., Hirao, K., Sugiyama, Y., Tsunoda, A., Matsuo, T., Watanabe
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Journal Title
J. Polym. Sci., Part A : Polymer Chemistry 44
Pages: 6659-6687
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] End-Functionalization of PS by Malto-oligosaccharide Generating Aggregation-Tunable Polymeric Reverese Micelle2006
Author(s)
A.Narumi, Y.Miura, I.Otsuka, S.Yamase, Y.Kitajyo, T.Satoh, A.Hirao, N.Kaneko, H.Kaga, T.Kakuchi
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Journal Title
J. Polymer. Sci., Polymer Chemistry 44
Pages: 4864-4879
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[Presentation] Synthesis of water-soluble block copolymers and star-branched block copolymers comprised of thermosensitive segments and studies of their thermo-responsive properties2007
Author(s)
Takahumi, NAKAYAMA, Reiko, INUSHIMA, Yuji, TSUNODA, Kenji, SUGIYAMA, Takashi, ISHIZONE, Akira, Hirao, Main, DEFFIEUX, Stephane, CARLOTTI
Organizer
56th SPSJ Annual Meeting
Place of Presentation
Kyoto
Year and Date
2007-05-30
Description
「研究成果報告書概要(欧文)」より
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[Presentation] Successive Synthesis of Hyperbranched Poly(methyl methacrylate)s (PMMA) by Iterative Methodology Based on the Addition Reaction of a-phenylacryloylated PMMA with Living Anionic PMMA2007
Author(s)
Yosuke, MATSUNAGA, Takumi, WATANABE, Akira, HIRAO, Kenawy, EL-REFAIE, Ree, MOONHOR, Alain DEFFIEUX
Organizer
56th SPSJ Annual Meeting
Place of Presentation
Kyoto
Year and Date
2007-05-30
Description
「研究成果報告書概要(欧文)」より
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[Presentation] Precise synthesis of watersoluble star branched polymers2006
Author(s)
1, 1-Diphenylethylene Derivative Besed on Living Anionic Polymerization., Reiko, INUSHIMA, Takumi, WATANABE, Kenji, SUGIYAMA, Takashi, ISHIZONE, Akira, HIRAO, Main, DEFFIEUX
Organizer
55th SPSJ Annual Meeting
Place of Presentation
Nagoya
Year and Date
2006-05-26
Description
「研究成果報告書概要(欧文)」より
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[Presentation] Synthesis of Well-defined Water-soluble Star Polymers containing Poly(N,N-diethylacrylamide) Arms by Anionic Polymerization2006
Author(s)
Manabu, UENO, Maria, ITO, Akira, MATSUO, Akira, HIRAO, Takashi, ISHIZONE
Organizer
55th SPSJ Annual Meeting
Place of Presentation
Nagoya
Year and Date
2006-05-25
Description
「研究成果報告書概要(欧文)」より
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