~1H和^(19)F NMR研究镍系催化丁二烯聚合中醇类对BF_3·OEt_2的增溶作用

~1H AND ^(19)F NMR STUDIES ON THE SOLUBILIZATION OF ROH-BF_3OEt_2 IN NICKEL SYSTEM CATALIZING THE POLYMERIZATION OF BUTADIENE

在镍系催化丁二烯聚合中,助催化剂BF_3·OEt_2在加氢汽油中溶解性差,往往形成非均相体系,因而降低了催化剂体系的稳定性和氟的利用率。我们曾研究了A1(i-Bu)_3分别与丙醇、丁醇、戊醇,己醇、辛醇、壬醇、癸醇和十六醇按等摩尔交换,制得A1(i-Bu)_2OR作助催化剂,观察Al/B与催化活性的关系,发现以十六醇为最好,Al/B在0.25—0.95聚合活性较高,超出此限活性迅速下降。为了进一步提高Al/B,采用了向镍催化体系添加醇的方法。聚合实验证实了该法可提高氟的利用率。测定醇-硼体系的~1HNMR,证实了醇-硼分子间形成了氟-氢氢键。

The solubility of BF3OEt2 in hydrogenated gasoline was improved greatly by means of premixing BF3OEt2 with C3H17OH in nickel catalyst system, so that the effeciency of fluorine in the system was increased markedly. It is confirmed that there was a intermolecular hydrogen bond between alcohol and BF3OEt2 molecules by using 1H NMR, which was a vital factor to lead the solubilization of BF3OEt2 in hydrogenated gasoline. Otherwise, the caculation formula of the chemical shift ofproton in hydroxy, 1H = xipi,was suggested in hydrogen bond system.