2004 Fiscal Year Final Research Report Summary
Development of New Type Polymerization Using Crystalline Media
| Project/Area Number |
14550832
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
高分子合成
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
MASAHITO Suzuki Tokyo Institute of Technology, Dept. of Org. & Polym. Mat., Associate Prof., 大学院・理工学研究科, 助教授 (20179253)
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| Project Period (FY) |
2002 – 2004
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| Keywords | Solid-State Polymerization / Polycondensation / Polyether / Saccharide / Polysaccharide / Highly Branched Polymer / Polysiloxane |
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| Research Abstract |
1) The oxidative coupling polymerization of 2,6-dihydroxynaphthalene to poly(2,6-dihydroxy-1,5-naphthylene) took place by grinding with FeCl_3/6H_2O without any solvent. Using the cocrystals with amines, especially bezylamine, promoted the polymerization giving the higher molecular weight (Mn=〜10000) polymer.
2) Arene dimethanol derivatives underwent solid-state polycondensation forming polyether. Typically, grinding and heating (100℃ under a N_2 flow) the crystals of dl-1,3-bis(hydroxyphenylmethyl)benzene with powder of camphorsulfonic acid (5 mol%) produced the polymer (Mn:〜40000). Interestingly, the reaction mixture was white powdery throughout the polymerization without any change in appearance. The diastereomeric isomers showed different polymerizability in the solid-state but the same in the solution.
3) Solid-state polycondensations of natural mono-and di-saccharides took place in the presence of H_3PO_4 (5 mol%) by heating at 110℃ under a N_2 flow, giving a highly branched polysa
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ccharide (Conv. 11〜84%, Mw=1400〜19,000, Mn=1200〜3700); the reaction mixture was powdery throughout the polymerization. Interestingly, α- and β-anomers showed different polymerization behavior ; the former was polymerized more slowly, however, they gave comparable molecular weight polymers. Sugar fluorides underwent powder-to-powder polycondensation without any catalyst at 110-160℃ under vacuum, giving highly branched polysaccharides (Conv.=40〜95%, Mw=1400〜20000). The cross-polarized optical microscopic images at 110℃ indicated that the crystal shape of α-glucosyl fluoride was unchanged before and after the polymerization in spite of producing the amorphous polymer. 4) Various silanediols and disiloxanediols produced cyclic oligosiloxanes or linear polysiloxane by the treatment with acid or base catalyst without any solvent. Interestingly, the copolymerization of the silanediols that afforded the cyclic oligosilane produced high molecular weight polysiloxanes (10^4〜10^5), which was also obtained from the disiloxanediols. Less
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Research Products
(8 results)
