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本文介绍在有醋酸酐存在时采用乙酰基四氟硼酸盐CH_3COBF_4为催化剂进行四氢呋喃(THF)聚合反应;讨论了THF聚合及链转移的反应机理,发现醋酸酐对聚合速度有明显的影响。计算出0℃,6℃和15℃时的表观聚合反应速度常数K_p 分别为3.59,5.11和11.53×10~(-3)/mol·s;表观链转移速度常数K_(tr)分别为2.03,3.95和8.23×10~(-3)/mol·s;表观聚合反应活化能E_p 和链转移反应活化能E_(tr)分别为51.2和61.3 kJ/mol。
In this paper, the polymerization of tetrahydrofuran (THF) with acetyl tetrafluoroborate CH_3COBF_4 as catalyst was introduced in the presence of acetic anhydride. The reaction mechanism of THF polymerization and chain transfer was discussed. It was found that acetic anhydride had a significant effect on the polymerization rate. The apparent polymerization rate constant K_p at 0 ℃, 6 ℃ and 15 ℃ were calculated to be 3.59, 5.11 and 11.53 × 10 -3 / mol · s, respectively. The apparent chain transfer rate constant K tr was 2.03, 3.95 and 8.23 × 10 -3 / mol · s respectively. The activation energies E_p and E_ (tr) of the apparent polymerization were 51.2 and 61.3 kJ / mol, respectively.