C-13-NMR SPECTROSCOPY OF POLY(BETA-SUBSTITUTED BETA-PROPIOLACTONE)S - TACTICITY RECOGNITION IN 1,5-SUBSTITUTED POLYMER SYSTEM AND STEREOSPECIFIC CONTACT OF SHIFT-REAGENT

被引:39
作者
IIDA, M [1 ]
HAYASE, S [1 ]
ARAKI, T [1 ]
机构
[1] OSAKA UNIV,FAC SCI,DEPT POLYMER SCI,TOYONAKA,OSAKA 560,JAPAN
关键词
D O I
10.1021/ma60063a012
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
13C-NMR spectroscopy has been found to be effective for observing the dyad tacticity in poly(β-substituted β-propiolactone)s, a 1, 5-substituted polymer system which had been difficult to investigate by 1H-NMR spectroscopy. Although the dyad resonances have very similar chemical shifts, 13C-NMR spectroscopy provides a useful diagnosis for polymer stereoregularity. Addition of a shift reagent, Eu(DPM)3, is helpful for the polymers whose tacticity separation in the 13C NMR is insufficient. The lanthanide-induced shift occurs stereospecifically, resulting in a stronger low-field shift for meso-dyad signals than for racemic dyad signals. The stereospecificity may be caused by small differences in the pseudocontact angle xi of the Eu ion with the meso and racemic-dyad units in the polymer chain. In the poly-β-esters the carbon atoms sensitive to tacticity recognition include the carbonyl carbon and main chain methylene carbon atoms, whereas the methine carbon is insensitive. © 1978, American Chemical Society. All rights reserved.
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页码:490 / 493
页数:4
相关论文
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