ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION - SYNTHESIS OF UNSATURATED POLYTHIOETHERS

被引:50
作者
OGARA, JE
PORTMESS, JD
WAGENER, KB
机构
[1] UNIV FLORIDA,DEPT CHEM,GAINESVILLE,FL 32611
[2] UNIV FLORIDA,CTR MACROMOLEC SCI & ENGN,GAINESVILLE,FL 32611
关键词
D O I
10.1021/ma00063a031
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A series of symmetrical alpha,omega-unsaturated thioethers have been polymerized under standard acyclic diene metathesis (ADMET) conditions. Poly(thio-3-hexene-1,6-diyl)(7), poly(thio-4-octene-1,8-diyl) (8), and poly(thio-5-decene-1,10-diyl)(9) were synthesized in bulk from the corresponding bis(alkenyl) sulfides (2, 3, and 4, respectively) in the presence of the catalyst Mo(CHCMe2Ph)(N-2,6-C6H3-i-Pr2)(OCMe(CF3)2)2 (5). Poly[(thio-5-decene-1,10-diyl)-co-(1-octenylene)] (10) was prepared from the copolymerization of bis-(5-hexenyl) sulfide (4) and 1,9-decadiene. The polymerizability of the alpha,omega-dienes appears to be a function of the number of methylene spacers between the sulfur moiety and the terminal olefin. In the case of the monomer diallyl sulfide (1), where one methylene spacer is present, no polymerization was observed in the bulk, but rapid cyclization to 2,5-dihydrothiophene (6) was observed in solution. All polymers were characterized by H-1 NMR, C-13 NMR, and IR spectroscopies as well as elemental analysis, GPC, TGA, and DSC. These results suggest that sulfur-containing polymers are now accessible via ADMET polymerization.
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页码:2837 / 2841
页数:5
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