烷基铝对球形MgCl_2负载的茂金属催化剂催化乙烯聚合的影响

以甲基铝氧烷(MAO)为助催化剂的茂金属催化剂虽然具有催化活性高、分子量分布窄、聚合物化学组成均匀等优点,但其极高的Al/Zr比和聚合物颗粒形态差等缺点限制了其工业化应用,因此对茂金属催化剂的负载化成为近年来的研究热点.在众多的载体中,球形MgCl2是研究得很少的一类载体,文献中曾采用先负载主催化剂茂金属配合物,聚合时再加入助催化剂MAO的方法1],由于加入的MAO与主催化剂的络合能力很强,会使部分载上的主催化剂溶解下来,成为均相聚合2,3],导致聚合物颗粒形态差,且粘釜现象严重.我们则采用相反的思路,即先将助催化剂MAO负载在球形MgCl2上,制得MgCl2/MAO,在聚合前再将MgCl2/MAO与EtInd]2ZrCl2混合陈化,并立即在少量烷基铝活化下引发乙烯聚合4],实验结果表明,该催化剂聚合活性高、聚合物的颗粒形态好、且不粘釜,是一种新型的载体催化剂.由于烷基铝的加入可使催化剂的活性大幅度提高,所以本文将烷基铝也称作助催化剂,来研究其对该载体催化剂催化乙烯聚合的影响.

THE EFFECT OF ALKYLALUMINUM ON SPHERICAL MgCl2 SUPPORTED METALLOCENE CATALYST FOR ETHYLENE POLYMERIZATION

Spherical MgCl 2 supported metallocene catalyst was prepared by supporting MAO on carrier which was prepared from MgCl 2 ·n EtOH.Ethylene polymerization was carried out by addition of MAO/MgCl 2,different metallocenes and alkylaluminum,in the absence of soluble MAO.It shows high activity for ethylene polymerization at lower Al/Zr(Al/Zr=45).The effect of concentration of Al( i Bu) 3 on polymerization activities and activation of Et(Ind) 2ZrCl 2 were studied.Kinetic behavior of ethylene polymerization on spherical MgCl 2 supported metallocene catalyst was investigated,which indicated the polymers obtained by reaction could affect the diffusion of ethylene in hexane under the experiment condidtion.Different aluminium alkyls have great impact on the whole polymerization behavior,and the relative reactivity decreases in the following order:Al( i Bu) 3>AlEt 3>AlMe 3>AlEt 2Cl,in which Al( i Bu) 3 shows the highest catalytic activity (5 78×10 7 g PE/mol\|Zr·h).