论文部分内容阅读
对Ni(naph)_2-(i-Bu)_2AlOAr-BF_3·OEt_2(Ni-AlOAr-B)体系催化丁二烯(Bd)聚合合成BR进行了研究,发现该体系中的Ni(Ⅰ)含量比国内已工业化的Ni-Al-B体系高。对8种AlOAr的研究表明,当—OAr_1为2,6-二叔丁基-4-甲苯氧基时,体系活性最高;且AlOAr_1/Ni=5-10(mol比)、AlOAr_1/B=0.3-1.0(mol比)时,可制得[η]为2.6dL/g左右、顺式-1,4含量大于96％、凝胶含量低于0.15％的BR;该体系的动力学方程为-d[Bd]/dt=αk_p[Bd][Cat],催化剂利用率为3.0％左右,链增长速度常数随聚合温度的升高而迅速增加,但活性中心寿命却缩短。
The catalytic synthesis of BR catalyzed by Ni (naph) _2- (i-Bu) _2AlOAr-BF_3 · OEt_2 (Ni-AlOAr-B) catalyzed polymerization of butadiene was investigated. It was found that the Ni (Ⅰ) Domestic industrialized Ni-Al-B system is high. The results of eight AlOAr studies show that the system has the highest activity when -OAr_1 is 2,6-di-tert-butyl-4-methylphenoxy, and AlOAr_1 / Ni = 5-10 (mol ratio) and AlOAr_1 / B = 0.3 -1.0 (molar ratio), BR with [η] of 2.6 dL / g, cis-1,4 content of more than 96% and gel content of less than 0.15% can be obtained. The kinetic equation of this system is - The catalyst utilization rate is about 3.0%, and the rate constant of chain growth rapidly increases with the increase of polymerization temperature, but the service life of the active center is shortened.