1989 Fiscal Year Final Research Report Summary
Design, Synthesis, and Characterization of Novel Sulfur-Containing Polyacetylenes
Project/Area Number |
63550686
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Research Category |
Grant-in-Aid for General Scientific Research (C)
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Allocation Type | Single-year Grants |
Research Field |
高分子合成
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Research Institution | KYOTO UNIVERSITY |
Principal Investigator |
MASUDA Toshio Kyoto University, Polymer Chemistry, Associate Professor, 工学部, 助教授 (60026276)
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Project Period (FY) |
1988 – 1989
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Keywords | Substituted Polyacetylene / Sulfur-Containing Polymer / 1-n-Alkylthio-1-propyne / 1-Methylthio-1-alkyne / Transition-Metal Catalyst / Polymer Synthesis / Molecular Design / Functional Polymer |
Research Abstract |
The present project has dealt with the molecular design of novel sulfur-containing- polyacetylenes, the exploitation of methods for synthesizing high molecular weight polymers, and the characterization of the polymers obtained. The results are summarized as follows: 1. Synthesis and Properties of Poly(1-n-alkylthio-1-propynes) 1-n-Alkylthio-l-propynes (CH_3CXICSR; R = Me, Et, n-Bu, n-C_6H_<13>, n-C_8H_<17>, and n-C_<10>H_<21>) polymerized in good yields (50 - 80%) in toluene at 80 ゚C in the presence of MoCl_5-Ph_3SiH(1:2) catalyst. The corresponding W, Nb and Ta catalysts were effective. The product possessed weight-average molecular weights (M^^-___w up to 1x10^5 - 2x10^5, higher than any other sulfur-containing polyacetylenes so far synthesized. Spectroscopic data supported the polymer structure, (-CCH_3=CSR-)_n. Except poly(1-methylthio-1-propyne), the present polymers totally dissolved in common solvents such as toluene and CHCl_3. They were colorless, film-forming, thermally fairly stable in air, electrically insulating, and moderately permeable to gases. 2. Polymerization of 1-Methylthio-1-alkynes and Polymer Properties Polymerization of 1-methylthio-1-alkynes (MeSCXICR; R = Et, n-Bu, n-C_6H_<13>, and n-C_8H_<17>) was studied by use of transition metal catalysts. A 1:2 mixture of MoCl_5 and Ph_3SiH provided polymers having M^^-___w over 1x10^5 in 30 - 50% yields from these monomers. The length of the alkyl group hardly affected the polymerization. The monomer, MeSCXIC-n-C_6H_<13>, showed low reactivity in homopolymerization, but higher reactivity than that of MeCXIC-n-C_5H_<11> in copolymerization. Poly(1-methylthio-1-alkynes) were colorless solids, and those with long alkyl pendants (R = n-C_6H_<13>, n-C_8H_<17>) were soluble in various organic solvents. The present polymers were thermally more stable than poly(2-alkynes), the corresponding hydrocarbon polymers. Further, polymerization of several sulfur-containing aromatic acetylenes was examined.
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Research Products
(4 results)