FTIR和^(13)C-NMR研究球笼烯钕系聚丁二烯链结构

Determination of polybutadiene chain structure synthesized with C60(fullerens)-neodymium catalyst by FTIR and 13C-NMR

用ＦＴＩＲ和１３Ｃ－ＮＭＲ法测定了Ｎｄ（ｎａｐｈ）３－Ａｌ（ｉ－Ｂｕ）３－Ｃ６０衍生物催化体系及添加Ｃ６０合成的聚丁二烯的链节含量。结果表明，球笼烯钕系聚丁二烯的顺－１，４链节达９８．８％，反－１，４链节为０．８％；当添加的Ｃ６０用量为Ｃ６０／Ｂｄ＝１．６×１０－４（摩尔比）时，顺－１，４链节降至９３．６％，反－１，４链节升至４．６％，反－１，４链节ＩＲ特征吸收峰较普通钕系聚丁二烯向高频移动了６ｃｍ－１，这表明Ｃ６０分子与Ｂｄ共同参与了向活性中心竞争配位过程。

The chain contents of polybutadiene synthesized with Nd(naph)3-Al(i-Bu)3-C60 derivative catalytic system as well as adding C60 into it were determined by FTIR and 13C-NMR.The results showed that the content of cis-1,4 chain of polybutadiene obtained was 98.8%, the content of trans-1,4 chain was only 0.8%.The chain content of cis-1,4 decreased to 93.6%,whereas the trans-1,4 increased to 4.6% when C60 was added to the catalytic system with the mole ratio of C60/Bd 1.6×10-4 .The characteristic absorption peak of trans-1,4 chain shifted from 967 cm-1 to 973 cm-1 which indicated C60 and Bd all took part in the coordination process accessing to the active center.