具有含-CH2-SiMe3部分的非桥连二茂铪的混合催化剂的制作方法

文档序号:20619704发布日期:2020-05-06 20:40阅读:来源:国知局

技术特征:

1.负载的催化剂体系,其包含:

第一非桥连的第4族茂金属化合物;

第二非桥连的茂金属化合物;

载体材料;和

活化剂;

其中所述第一非桥连的第4族茂金属化合物是式(a)所示的:

其中:

m*是hf;

r1、r2、r4和r5中的每个独立地是氢、烷氧基或者c1-c40取代或者未取代的烃基;

r3独立地是氢、烷氧基、c1-c40取代或者未取代的烃基、或者-r11-sir'3或者-r11-cr'3,其中r11是c1-c4烃基,和每个r'独立地是c1-c20取代或者未取代的烃基;

每个r6、r7、r8和r10独立地是氢、卤基、烷氧基或者c1-c40取代或者未取代的烃基;

r9是-r11-sir'3或者-r11-cr'3,其中r11和r'是上面所定义的;

每个x独立地是单价阴离子配体,或者两个x接合来形成金属环状物环,或者两个x接合来形成螯合配体、二烯配体或者烷叉基配体;

和所述第二非桥连的茂金属化合物是式(b)所示的:

cpmmx'q(b)

其中每个cp独立地是取代或者未取代的环戊二烯基、茚基或者芴基,m是锆,x'是卤基、氢基、烷基、烯基或者芳基烷基,和m=2或者3,q=0、1、2或者3,并且m+q之和等于所述过渡金属的氧化态,和每个cp和x'键合到m上。

2.根据权利要求1的负载的催化剂体系,其中式(a)的m*是hf或者zr,每个r1、r2、r3、r4和r5是c1-c20烷基,r9是-r11-sir'3或者-r11-cr'3,其中r11是ch2,和r'是c1-c20烷基或者芳基。

3.根据权利要求1或者2的负载的催化剂体系,其中式(b)的m是zr,cpm是取代的或者未取代的茚基,和r9是-r11-sir'3或者-r11-cr'3,其中r11是ch2,和r'是c1-c20烷基或者芳基。

4.根据权利要求1的负载的催化剂体系,其中所述第一非桥连的茂金属化合物是下面中的一种或多种:

(cp)(3-ch2-sime3-cp)hfme2;(mecp)(3-ch2-sime3-cp)hfme2;(etcp)(3-ch2-sime3-cp)hfme2;(prcp)(3-ch2-sime3-cp)hfme2;(bucp)(3-ch2-sime3-cp)hfme2;(bzcp)(3-ch2-sime3-cp)hfme2;(3-ch2-sime3-cp)2hfme2;(me3cp)(3-ch2-sime3-cp)hfme2;(me4cp)(3-ch2-sime3-cp)hfme2;(me5cp)(3-ch2-sime3-cp)hfme2;(1-me,3-bu-cp)(3-ch2-sime3-cp)hfme2;(1-me,3-ph-cp)(3-ch2-sime3-cp)hfme2;(me4cp-pr)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-sime3-cp)hfme2;(2-me,3-ch2-sime3-ind)2hfme2;(2-et,3-ch2-sime3-ind)2hfme2;(2-pr,3-ch2-sime3-ind)2hfme2;(2-bu,3-ch2-sime3-ind)2hfme2;(2-ph,3-ch2-sime3-ind)2hfme2;(3-ch2-sime3-ind)2hfme2;(3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(3-me-ind)(3-ch2-sime3-cp)hfme2;(3-et-ind)(3-ch2-sime3-cp)hfme2;(3-pr-ind)(3-ch2-sime3-cp)hfme2;(3-bu-ind)(3-ch2-sime3-cp)hfme2;(cp)(3-ch2-sime3-ind)hfme2;(mecp)(3-ch2-sime3-ind)hfme2;(etcp)(3-ch2-sime3-ind)hfme2;(prcp)(3-ch2-sime3-ind)hfme2;(bucp)(3-ch2-sime3-ind)hfme2;(me3cp)(3-ch2-sime3-ind)hfme2;(me4cp)(3-ch2-sime3-ind)hfme2;(me5cp)(3-ch2-sime3-ind)hfme2;(1-me,3-bu-cp)(3-ch2-sime3-ind)hfme2;(1-me,3-ph-cp)(3-ch2-sime3-ind)hfme2;(cp)(3-ch2-sime3-cp)hfme2;(mecp)(3-ch2-sime3-cp)hfme2;(etcp)(3-ch2-sime3-cp)hfme2;(prcp)(3-ch2-sime3-cp)hfme2;(bucp)(3-ch2-sime3-cp)hfme2;(bzcp)(3-ch2-sime3-cp)hfme2;(3-ch2-sime3-cp)2hfme2;(me2cp)(3-ch2-sime3-cp)hfme2;(me3cp)(3-ch2-sime3-cp)hfme2;(me4cp)(3-ch2-sime3-cp)hfme2;(me5cp)(3-ch2-sime3-cp)hfme2;(et2cp)(3-ch2-sime3-cp)hfme2;(et3cp)(3-ch2-sime3-cp)hfme2;(et4cp)(3-ch2-sime3-cp)hfme2;(et5cp)(3-ch2-sime3-cp)hfme2;(pr2cp)(3-ch2-sime3-cp)hfme2;(pr3cp)(3-ch2-sime3-cp)hfme2;(pr4cp)(3-ch2-sime3-cp)hfme2;(pr5cp)(3-ch2-sime3-cp)hfme2;(bu2cp)(3-ch2-sime3-cp)hfme2;(bu3cp)(3-ch2-sime3-cp)hfme2;(bu4cp)(3-ch2-sime3-cp)hfme2;(bu5cp)(3-ch2-sime3-cp)hfme2;(bz2cp)(3-ch2-sime3-cp)hfme2;(bz3cp)(3-ch2-sime3-cp)hfme2;(bz4cp)(3-ch2-sime3-cp)hfme2;(bz5cp)(3-ch2-sime3-cp)hfme2;(etme4cp)(3-ch2-sime3-cp)hfme2;(prme4cp)(3-ch2-sime3-cp)hfme2;(bume4cp)(3-ch2-sime3-cp)hfme2;(pnme4cp)(3-ch2-sime3-cp)hfme2;(hxme4cp)(3-ch2-sime3-cp)hfme2;(bzme4cp)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-sime2ph)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-sime2ph)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-simeph2)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-siph3)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-sime2cy)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-simecy2)(3-ch2-sime3-cp)hfme2;(me4cp-ch2-sicy3)(3-ch2-sime3-cp)hfme2;(etme3cp)(3-ch2-sime3-cp)hfme2;(prme3cp)(3-ch2-sime3-cp)hfme2;(bume3cp)(3-ch2-sime3-cp)hfme2;(bzme3cp)(3-ch2-sime3-cp)hfme2;(me3cp-ch2-sime3)(3-ch2-sime3-cp)hfme2;(me3cp-ch2-sime2ph)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-simeph2)(3-ch2-sime3-cp)hfme2;(me3cp-ch2-siph3)(3-ch2-sime3-cp)hfme2;(me3cp-ch2-sime2cy)(3-ch2-sime3-cp)hfme2;(me3cp-ch2-simecy2)(3-ch2-sime3-cp)hfme2;(me3cp-ch2-sicy3)(3-ch2-sime3-cp)hfme2;(meetcp)(3-ch2-sime3-cp)hfme2;(meprcp)(3-ch2-sime3-cp)hfme2;mebucp)(3-ch2-sime3-cp)hfme2;(bzmecp)(3-ch2-sime3-cp)hfme2;(etprcp)(3-ch2-sime3-cp)hfme2;(etbucp)(3-ch2-sime3-cp)hfme2;(bzetcp)(3-ch2-sime3-cp)hfme2;(prbucp)(3-ch2-sime3-cp)hfme2;(bzprcp)(3-ch2-sime3-cp)hfme2;(bubzcp)(3-ch2-sime3-cp)hfme2;(cp)(3-ch2-sime2ph-cp)hfme2;(mecp)(3-ch2-sime2ph-cp)hfme2;(etcp)(3-ch2-sime2ph-cp)hfme2;(prcp)(3-ch2-sime2ph-cp)hfme2;(bucp)(3-ch2-sime2ph-cp)hfme2;(bzcp)(3-ch2-sime2ph-cp)hfme2;(3-ch2-sime2ph-cp)2hfme2;(me2cp)(3-ch2-sime2ph-cp)hfme2;(me3cp)(3-ch2-sime2ph-cp)hfme2;(me4cp)(3-ch2-sime2ph-cp)hfme2;(me5cp)(3-ch2-sime2ph-cp)hfme2;(et2cp)(3-ch2-sime2ph-cp)hfme2;(et3cp)(3-ch2-sime2ph-cp)hfme2;(et4cp)(3-ch2-sime2ph-cp)hfme2;(et5cp)(3-ch2-sime2ph-cp)hfme2;(pr2cp)(3-ch2-sime2ph-cp)hfme2;(pr3cp)(3-ch2-sime2ph-cp)hfme2;(pr4cp)(3-ch2-sime2ph-cp)hfme2;(pr5cp)(3-ch2-sime2ph-cp)hfme2;(bu2cp)(3-ch2-sime2ph-cp)hfme2;(bu3cp)(3-ch2-sime2ph-cp)hfme2;(bu4cp)(3-ch2-sime2ph-cp)hfme2;(bu5cp)(3-ch2-sime2ph-cp)hfme2;(bz2cp)(3-ch2-sime2ph-cp)hfme2;(bz3cp)(3-ch2-sime2ph-cp)hfme2;(bz4cp)(3-ch2-sime2ph-cp)hfme2;(bz5cp)(3-ch2-sime2ph-cp)hfme2;(etme4cp)(3-ch2-sime2ph-cp)hfme2;(prme4cp)(3-ch2-sime2ph-cp)hfme2;(bume4cp)(3-ch2-sime2ph-cp)hfme2;(bzme4cp)(3-ch2-sime2ph-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-sime2ph-cp)hfme2;(me4cp-ch2-sime2ph)(3-ch2-sime2ph-cp)hfme2;(me4cp-ch2-simeph2)(3-ch2-sime2ph-cp)hfme2;(me4cp-ch2-siph3)(3-ch2-sime2ph-cp)hfme2;(me4cp-ch2-sime2cy)(3-ch2-sime2ph-cp)hfcl2;(me4cp-ch2-simecy2)(3-ch2-sime2ph-cp)hfcl2;(me4cp-ch2-sicy3)(3-ch2-sime2ph-cp)hfme2;(etme3cp)(3-ch2-sime2ph-cp)hfme2;(prme3cp)(3-ch2-sime2ph-cp)hfme2;(bume3cp)(3-ch2-sime2ph-cp)hfme2;(bzme3cp)(3-ch2-sime2ph-cp)hfme2;(me3cp-ch2-sime3)(3-ch2-sime2ph-cp)hfme2;(me3cp-ch2-sime2ph)(3-ch2-sime2ph-cp)hfme2;(me3cp-ch2-simeph2)(3-ch2-sime2ph-cp)hfme2;(me3cp-ch2-siph3)(3-ch2-sime2ph-cp)hfme2;(me3cp-ch2-sime2cy)(3-ch2-sime2ph-cp)hfme2;(me3cp-ch2-simecy2)(3-ch2-sime2ph-cp)hfme2;(me3cp-ch2-sicy3)(3-ch2-sime2ph-cp)hfme2;(meetcp)(3-ch2-sime2ph-cp)hfme2;(meprcp)(3-ch2-sime2ph-cp)hfme2;(mebucp)(3-ch2-sime2ph-cp)hfme2;(bzmecp)(3-ch2-sime2ph-cp)hfme2;(etprcp)(3-ch2-sime2ph-cp)hfme2;(etbucp)(3-ch2-sime2ph-cp)hfme2;(bzetcp)(3-ch2-sime2ph-cp)hfme2;(prbucp)(3-ch2-sime2ph-cp)hfme2;(bzprcp)(3-ch2-sime2ph-cp)hfme2;(bubzcp)(3-ch2-sime2ph-cp)hfme2;(cp)(3-ch2-simeph2-cp)hfme2;(mecp)(3-ch2-simeph2-cp)hfme2;(etcp)(3-ch2-simeph2-cp)hfme2;(prcp)(3-ch2-simeph2-cp)hfme2;(bucp)(3-ch2-simeph2-cp)hfme2;((bzcp)(3-ch2-simeph2-cp)hfme2;(3-ch2-simeph2-cp)2hfme2;(me2cp)(3-ch2-simeph2-cp)hfme2;(me3cp)(3-ch2-simeph2-cp)hfme2;(me4cp)(3-ch2-simeph2-cp)hfme2;(me5cp)(3-ch2-simeph2-cp)hfme2;(et2cp)(3-ch2-simeph2-cp)hfme2;(et3cp)(3-ch2-simeph2-cp)hfme2;(et4cp)(3-ch2-simeph2-cp)hfme2;(et5cp)(3-ch2-simeph2-cp)hfme2;(pr2cp)(3-ch2-simeph2-cp)hfme2;(pr3cp)(3-ch2-simeph2-cp)hfme2;(pr4cp)(3-ch2-simeph2-cp)hfme2;(pr5cp)(3-ch2-simeph2-cp)hfme2;(bu2cp)(3-ch2-simeph2-cp)hfme2;(bu3cp)(3-ch2-simeph2-cp)hfme2;(bu4cp)(3-ch2-simeph2-cp)hfme2;(bu5cp)(3-ch2-simeph2-cp)hfme2;(bz2cp)(3-ch2-simeph2-cp)hfme2;(bz3cp)(3-ch2-simeph2-cp)hfme2;(bz4cp)(3-ch2-simeph2-cp)hfme2;(bz5cp)(3-ch2-simeph2-cp)hfme2;(etme4cp)(3-ch2-simeph2-cp)hfme2;(prme4cp)(3-ch2-simeph2-cp)hfme2;(bume4cp)(3-ch2-simeph2-cp)hfme2;(pnme4cp)(3-ch2-simeph2-cp)hfme2;(hxme4cp)(3-ch2-simeph2-cp)hfme2;(bzme4cp)(3-ch2-simeph2-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-simeph2-cp)hfme2;(me4cp-ch2-sime2ph)(3-ch2-simeph2-cp)hfme2;(me4cp-ch2-simeph2)(3-ch2-simeph2-cp)hfme2;(me4cp-ch2-siph3)(3-ch2-simeph2-cp)hfme2;(me4cp-ch2-sime2cy)(3-ch2-simeph2-cp)hfme2;(me4cp-ch2-simecy2)(3-ch2-simeph2-cp)hfme2;(me4cp-ch2-sicy3)(3-ch2-simeph2-cp)hfme2;(etme3cp)(3-ch2-simeph2-cp)hfme2;(prme3cp)(3-ch2-simeph2-cp)hfme2;(bume3cp)(3-ch2-simeph2-cp)hfme2;(bzme3cp)(3-ch2-simeph2-cp)hfme2;(me3cp-ch2-sime3)(3-ch2-simeph2-cp)hfme2;(me3cp-ch2-sime2ph)(3-ch2-simeph2-cp)hfme2;(me3cp-ch2-simeph2)(3-ch2-simeph2-cp)hfme2;(me3cp-ch2-siph3)(3-ch2-simeph2-cp)hfme2;(me3cp-ch2-sime2cy)(3-ch2-simeph2-cp)hfme2;(me3cp-ch2-simecy2)(3-ch2-simeph2-cp)hfme2;(me3cp-ch2-sicy3)(3-ch2-simeph2-cp)hfme2;(meetcp)(3-ch2-simeph2-cp)hfme2;(meprcp)(3-ch2-simeph2-cp)hfme2;(mebucp)(3-ch2-simeph2-cp)hfme2;(bzmecp)(3-ch2-simeph2-cp)hfme2;(etprcp)(3-ch2-simeph2-cp)hfme2;(etbucp)(3-ch2-simeph2-cp)hfme2;(bzetcp)(3-ch2-simeph2-cp)hfme2;(prbucp)(3-ch2-simeph2-cp)hfme2;(bzprcp)(3-ch2-simeph2-cp)hfme2;(bubzcp)(3-ch2-simeph2-cp)hfme2;(cp)(3-ch2-siph3-cp)hfme2;(mecp)(3-ch2-siph3-cp)hfme2;(etcp)(3-ch2-siph3-cp)hfme2;(prcp)(3-ch2-siph3-cp)hfme2;(bucp)(3-ch2-siph3-cp)hfme2;(bzcp)(3-ch2-siph3-cp)hfme2;(3-ch2-siph3-cp)2hfme2;(me2cp)(3-ch2-siph3-cp)hfme2;(me3cp)(3-ch2-siph3-cp)hfme2;(me4cp)(3-ch2-siph3-cp)hfme2;(me5cp)(3-ch2-siph3-cp)hfme2;(et2cp)(3-ch2-siph3-cp)hfme2;(et3cp)(3-ch2-siph3-cp)hfme2;(et4cp)(3-ch2-siph3-cp)hfme2;(et5cp)(3-ch2-siph3-cp)hfme2;(pr2cp)(3-ch2-siph3-cp)hfme2;(pr3cp)(3-ch2-siph3-cp)hfme2;(pr4cp)(3-ch2-siph3-cp)hfme2;(pr5cp)(3-ch2-siph3-cp)hfme2;(bu2cp)(3-ch2-siph3-cp)hfme2;(bu3cp)(3-ch2-siph3-cp)hfme2;(bu4cp)(3-ch2-siph3-cp)hfme2;(bu5cp)(3-ch2-siph3-cp)hfme2;(bz2cp)(3-ch2-siph3-cp)hfme2;(bz3cp)(3-ch2-siph3-cp)hfme2;(bz4cp)(3-ch2-siph3-cp)hfme2;(bz5cp)(3-ch2-siph3-cp)hfme2;(etme4cp)(3-ch2-siph3-cp)hfme2;(prme4cp)(3-ch2-siph3-cp)hfme2;(bume4cp)(3-ch2-siph3-cp)hfme2;(bzme4cp)(3-ch2-siph3-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-siph3-cp)hfme2;(me4cp-ch2-sime2ph)(3-ch2-siph3-cp)hfme2;(me4cp-ch2-simeph2)(3-ch2-siph3-cp)hfme2;(me4cp-ch2-siph3)(3-ch2-siph3-cp)hfme2;(me4cp-ch2-sime2cy)(3-ch2-siph3-cp)hfme2;(me4cp-ch2-simecy2)(3-ch2-siph3-cp)hfme2;(me4cp-ch2-sicy3)(3-ch2-siph3-cp)hfme2;(etme3cp)(3-ch2-siph3-cp)hfme2;(prme3cp)(3-ch2-siph3-cp)hfme2;(bume3cp)(3-ch2-siph3-cp)hfme2;(bzme3cp)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-sime3)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-sime2ph)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-simeph2)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-siph3)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-sime2cy)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-simecy2)(3-ch2-siph3-cp)hfme2;(me3cp-ch2-sicy3)(3-ch2-siph3-cp)hfme2;(meetcp)(3-ch2-siph3-cp)hfme2;(meprcp)(3-ch2-siph3-cp)hfme2;(mebucp)(3-ch2-siph3-cp)hfme2;(bzmecp)(3-ch2-siph3-cp)hfme2;(etprcp)(3-ch2-siph3-cp)hfme2;(etbucp)(3-ch2-siph3-cp)hfme2;(bzetcp)(3-ch2-siph3-cp)hfme2;(prbucp)(3-ch2-siph3-cp)hfme2;(bzprcp)(3-ch2-siph3-cp)hfme2;(bubzcp)(3-ch2-siph3-cp)hfme2;(cp)(3-ch2-sicyme2-cp)hfme2;(mecp)(3-ch2-sicyme2-cp)hfme2;(etcp)(3-ch2-sicyme2-cp)hfme2;(prcp)(3-ch2-sicyme2-cp)hfme2;(bucp)(3-ch2-sicyme2-cp)hfme2;(bzcp)(3-ch2-sicyme2-cp)hfme2;(3-ch2-sicyme2-cp)2hfme2;(me2cp)(3-ch2-sicyme2-cp)hfme2;(me3cp)(3-ch2-sicyme2-cp)hfme2;(me4cp)(3-ch2-sicyme2-cp)hfme2;(me5cp)(3-ch2-sicyme2-cp)hfme2;(et2cp)(3-ch2-sicyme2-cp)hfme2;(et3cp)(3-ch2-sicyme2-cp)hfme2;(et4cp)(3-ch2-sicyme2-cp)hfme2;(et5cp)(3-ch2-sicyme2-cp)hfme2;(pr2cp)(3-ch2-sicyme2-cp)hfme2;(pr3cp)(3-ch2-sicyme2-cp)hfme2;(pr4cp)(3-ch2-sicyme2-cp)hfme2;(pr5cp)(3-ch2-sicyme2-cp)hfme2;(bu2cp)(3-ch2-sicyme2-cp)hfme2;(bu3cp)(3-ch2-sicyme2-cp)hfme2;(bu4cp)(3-ch2-sicyme2-cp)hfme2;(bu5cp)(3-ch2-sicyme2-cp)hfme2;(bz2cp)(3-ch2-sicyme2-cp)hfme2;(bz3cp)(3-ch2-sicyme2-cp)hfme2;(bz4cp)(3-ch2-sicyme2-cp)hfme2;(bz5cp)(3-ch2-sicyme2-cp)hfme2;(etme4cp)(3-ch2-sicyme2-cp)hfme2;(prme4cp)(3-ch2-sicyme2-cp)hfme2;(bume4cp)(3-ch2-sicyme2-cp)hfme2;(bzme4cp)(3-ch2-sicyme2-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-sicyme2-cp)hfme2;(me4cp-ch2-sicyme2ph)(3-ch2-sicyme2-cp)hfme2;(me4cp-ch2-simeph2)(3-ch2-sicyme2-cp)hfme2;(me4cp-ch2-siph3)(3-ch2-sicyme2-cp)hfme2;(me4cp-ch2-sime2cy)(3-ch2-sicyme2-cp)hfme2;(me4cp-ch2-simecy2)(3-ch2-sicyme2-cp)hfme2;(me4cp-ch2-sicy3)(3-ch2-sicyme2-cp)hfme2;(etme3cp)(3-ch2-sicyme2-cp)hfme2;(prme3cp)(3-ch2-sicyme2-cp)hfme2;(bume3cp)(3-ch2-sicyme2-cp)hfme2;(bzme3cp)(3-ch2-sicyme2-cp)hfme2;(me3cp-ch2-sime3)(3-ch2-sicyme2-cp)hfme2;(me3cp-ch2-sime2ph)(3-ch2-sicyme2-cp)hfme2;(me3cp-ch2-simeph2)(3-ch2-sicyme2-cp)hfme2;(me3cp-ch2-siph3)(3-ch2-sicyme2-cp)hfme2;(me3cp-ch2-sime2cy)(3-ch2-sicyme2-cp)hfme2;(me3cp-ch2-simecy2)(3-ch2-sicyme2-cp)hfme2;(me3cp-ch2-sicy3)(3-ch2-sicyme2-cp)hfme2;(meetcp)(3-ch2-sicyme2-cp)hfme2;(meprcp)(3-ch2-sicyme2-cp)hfme2;(mebucp)(3-ch2-sicyme2-cp)hfme2;(bzmecp)(3-ch2-sicyme2-cp)hfme2;(etprcp)(3-ch2-sicyme2-cp)hfme2;(etbucp)(3-ch2-sicyme2-cp)hfme2;(bzetcp)(3-ch2-sicyme2-cp)hfme2;(prbucp)(3-ch2-sicyme2-cp)hfme2;(bzprcp)(3-ch2-sicyme2-cp)hfme2;(bubzcp)(3-ch2-sicyme2-cp)hfme2;(cp)(3-ch2-sicy2me-cp)hfme2;(mecp)(3-ch2-sicy2me-cp)hfme2;(etcp)(3-ch2-sicy2me-cp)hfme2;(prcp)(3-ch2-sicy2me-cp)hfme2;(bucp)(3-ch2-sicy2me-cp)hfme2;(bzcp)(3-ch2-sicy2me-cp)hfme2;(3-ch2-sicy2me-cp)2hfme2;(me2cp)(3-ch2-sicy2me-cp)hfme2;(me3cp)(3-ch2-sicy2me-cp)hfme2;(me4cp)(3-ch2-sicy2me-cp)hfme2;(me5cp)(3-ch2-sicy2me-cp)hfme2;(et2cp)(3-ch2-sicy2me-cp)hfme2;(et3cp)(3-ch2-sicy2me-cp)hfme2;(et4cp)(3-ch2-sicy2me-cp)hfme2;(et5cp)(3-ch2-sicy2me-cp)hfme2;(pr2cp)(3-ch2-sicy2me-cp)hfme2;(pr3cp)(3-ch2-sicy2me-cp)hfme2;(pr4cp)(3-ch2-sicy2me-cp)hfme2;(pr5cp)(3-ch2-sicy2me-cp)hfme2;(bu2cp)(3-ch2-sicy2me-cp)hfme2;(bu3cp)(3-ch2-sicy2me-cp)hfcl2;(bu4cp)(3-ch2-sicy2me-cp)hfcl2;(bu5cp)(3-ch2-sicy2me-cp)hfcl2;(bz2cp)(3-ch2-sicy2me-cp)hfme2;(bz3cp)(3-ch2-sicy2me-cp)hfme2;(bz4cp)(3-ch2-sicy2me-cp)hfcl2;(bz5cp)(3-ch2-sicy2me-cp)hfcl2;(etme4cp)(3-ch2-sicy2me-cp)hfcl2;(prme4cp)(3-ch2-sicy2me-cp)hfme2;(bume4cp)(3-ch2-sicy2me-cp)hfme2;(bzme4cp)(3-ch2-sicy2me-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-sicy2me-cp)hfme2;(me4cp-ch2-sime2ph)(3-ch2-sicy2me-cp)hfme2;(me4cp-ch2-simeph2)(3-ch2-sicy2me-cp)hfme2;(me4cp-ch2-siph3)(3-ch2-sicy2me-cp)hfme2;(me4cp-ch2-sime2cy)(3-ch2-sicy2me-cp)hfme2;(me4cp-ch2-simecy2)(3-ch2-sicy2me-cp)hfme2;(me4cp-ch2-sicy3)(3-ch2-cy2me-cp)hfme2;(etme3cp)(3-ch2-sicy2me-cp)hfme2;(prme3cp)(3-ch2-sicy2me-cp)hfme2;(bume3cp)(3-ch2-sicy2me-cp)hfme2;(bzme3cp)(3-ch2-sicy2me-cp)hfme2;(me3cp-ch2-sime3)(3-ch2-sicy2me-cp)hfme2;(me3cp-ch2-sime2ph)(3-ch2-sicy2me-cp)hfme2;(me3cp-ch2-simeph2)(3-ch2-sicy2me-cp)hfme2;(me3cp-ch2-siph3)(3-ch2-sicy2me-cp)hfme2;(me3cp-ch2-sime2cy)(3-ch2-sicy2me-cp)hfme2;(me3cp-ch2-simecy2)(3-ch2-sicy2me-cp)hfme2;(me3cp-ch2-sicy3)(3-ch2-sicy2me-cp)hfme2;(meetcp)(3-ch2-sicy2me-cp)hfme2;(meprcp)(3-ch2-sicy2me-cp)hfme2;(mebucp)(3-ch2-sicy2me-cp)hfme2;(bzmecp)(3-ch2-sicy2me-cp)hfme2;(etprcp)(3-ch2-sicy2me-cp)hfme2;(etbucp)(3-ch2-sicy2me-cp)hfme2;(bzetcp)(3-ch2-sicy2me-cp)hfme2;(prbucp)(3-ch2-sicy2me-cp)hfme2;(bzprcp)(3-ch2-sicy2me-cp)hfme2;(bubzcp)(3-ch2-sicy2me-cp)hfme2;(cp)(3-ch2-sicy3-cp)hfme2;(mecp)(3-ch2-sicy3-cp)hfme2;(etcp)(3-ch2-sicy3-cp)hfme2;(prcp)(3-ch2-sicy3-cp)hfme2;(bucp)(3-ch2-sicy3-cp)hfme2(bzcp)(3-ch2-sicy3-cp)hfme2;(3-ch2-sicy3-cp)2hfme2;(me2cp)(3-ch2-sicy3-cp)hfme2;(me3cp)(3-ch2-sicy3-cp)hfme2;(me4cp)(3-ch2-sicy3-cp)hfme2;(me5cp)(3-ch2-sicy3-cp)hfme2;(et2cp)(3-ch2-sicy3-cp)hfme2;(et3cp)(3-ch2-sicy3-cp)hfme2;(et4cp)(3-ch2-sicy3-cp)hfme2;(et5cp)(3-ch2-sicy3-cp)hfme2;(pr2cp)(3-ch2-sicy3-cp)hfme2;(pr3cp)(3-ch2-sicy3-cp)hfme2;(pr4cp)(3-ch2-sicy3-cp)hfme2;(pr5cp)(3-ch2-sicy3-cp)hfme2;(bu2cp)(3-ch2-sicy3-cp)hfme2;(bu3cp)(3-ch2-sicy3-cp)hfme2;(bu4cp)(3-ch2-sicy3-cp)hfme2;(bu5cp)(3-ch2-sicy3-cp)hfme2;(bz2cp)(3-ch2-sicy3-cp)hfme2;(bz3cp)(3-ch2-sicy3-cp)hfme2;(bz4cp)(3-ch2-sicy3-cp)hfme2;(bz5cp)(3-ch2-sicy3-cp)hfme2;(etme4cp)(3-ch2-sicy3-cp)hfme2;(prme4cp)(3-ch2-sicy3-cp)hfme2;(bume4cp)(3-ch2-sicy3-cp)hfme2;(bzme4cp)(3-ch2-sicy3-cp)hfme2;(me4cp-ch2-sime3)(3-ch2-sicy3-cp)hfme2;(me4cp-ch2-sime2ph)(3-ch2-sicy3-cp)hfme2;(me4cp-ch2-simeph2)(3-ch2-sicy3-cp)hfme2;(me4cp-ch2-siph3)(3-ch2-sicy3-cp)hfme2;(me4cp-ch2-sime2cy)(3-ch2-sicy3-cp)hfme2;(me4cp-ch2-simecy2)(3-ch2-sicy3-cp)hfme2;(me4cp-ch2-sicy3)(3-ch2-sicy3-cp)hfme2;(etme3cp)(3-ch2-sicy3-cp)hfme2;(prme3cp)(3-ch2-sicy3-cp)hfme2;(bume3cp)(3-ch2-sicy3-cp)hfme2;(bzme3cp)(3-ch2-sicy3-cp)hfme2;(me3cp-ch2-sime3)(3-ch2-sicy3-cp)hfme2;(me3cp-ch2-sime2ph)(3-ch2-sicy3-cp)hfme2;(me3cp-ch2-simeph2)(3-ch2-sicy3-cp)hfme2;(me3cp-ch2-siph3)(3-ch2-sicy3-cp)hfme2;(me3cp-ch2-sime2cy)(3-ch2-sicy3-cp)hfme2;(me3cp-ch2-simecy2)(3-ch2-sicy3-cp)hfme2;(me3cp-ch2-sicy3)(3-ch2-sicy3-cp)hfme2;(meetcp)(3-ch2-sicy3-cp)hfme2;(meprcp)(3-ch2-sicy3-cp)hfme2;(mebucp)(3-ch2-sicy3-cp)hfme2;(bzmecp)(3-ch2-sicy3-cp)hfme2;(etprcp)(3-ch2-sipcy-cp)hfme2;(etbucp)(3-ch2-sicy3-cp)hfme2;(bzetcp)(3-ch2-sicy3-cp)hfme2;(prbucp)(3-ch2-sicy3-cp)hfme2;(bzprcp)(3-ch2-sicy3-cp)hfme2;(bubzcp)(3-ch2-sicy3-cp)hfme2;(2-me,3-ch2-sime3-ind)2hfme2;(2-et,3-ch2-sime3-ind)2hfme2;(2-pr,3-ch2-sime3-ind)2hfme2;(2-bu,3-ch2-sime3-ind)2hfme2;(2-ph,3-ch2-sime3-ind)2hfme2;(2-bz,3-ch2-sime3-ind)2hfme2;(2-me,3-ch2-sime2ph-ind)2hfme2;(2-et,3-ch2-sime2ph-ind)2hfme2;(2-pr,3-ch2-sime2ph-ind)2hfme2;(2-bu,3-ch2-sime2ph-ind)2hfme2;(2-ph,3-ch2-sime2ph-ind)2hfme2;(2-bz,3-ch2-sime2ph-ind)2hfme2;(2-me,3-ch2-simeph2-ind)2hfme2;(2-et,3-ch2-simeph2-ind)2hfme2;(2-pr,3-ch2-simeph2-ind)2hfme2;(2-bu,3-ch2-simeph2-ind)2hfme2;(2-ph,3-ch2-simeph2-ind)2hfme2;(2-bz,3-ch2-simeph2-ind)2hfme2;(2-me,3-ch2-siph3-ind)2hfme2;(2-et,3-ch2-siph3-ind)2hfme2;(2-pr,3-ch2-siph3-ind)2hfme2;(2-bu,3-ch2-siph3-ind)2hfme2;(2-ph,3-ch2-siph3-ind)2hfme2;(2-bz,3-ch2-siph3-ind)2hfme2;(2-me,3-ch2-sicyme2-ind)2hfme2;(2-et,3-ch2-sicyme2-ind)2hfme2;(2-pr,3-ch2-sicyme2-ind)2hfme2;(2-bu,3-ch2-sicyme2-ind)2hfme2;(2-ph,3-ch2-sicyme2-ind)2hfme2;(2-bz,3-ch2-sicyme2-ind)2hfme2;(2-me,3-ch2-sicy2me-ind)2hfme2;(2-et,3-ch2-sicy2me-ind)2hfme2;(2-pr,3-ch2-sicy2me-ind)2hfme2;(2-bu,3-ch2-sicy2me-ind)2hfme2;(2-ph,3-ch2-sicy2me-ind)2hfme2;(2-bz,3-ch2-sicy2me-ind)2hfme2;(2-me,3-ch2-sicy3-ind)2hfme2;(2-et,3-ch2-sicy3-ind)2hfme2;(2-pr,3-ch2-sicy3-ind)2hfme2;(2-bu,3-ch2-sicy3-ind)2hfme2;(2-ph,3-ch2-sicy3-ind)2hfme2;(2-bz,3-ch2-sicy3-ind)2hfme2;(2-me,3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(2-et,3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(2-pr,3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(2-bu,3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(2-pn,3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(2-hx,3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(2-ph,3-ch2-sime3-ind)(3-ch2-sime3-cp)hfme2;(2-me,3-ch2-sime2ph-ind)(3-ch2-sime3-cp)hfme2;(2-et,3-ch2-sime2ph-ind)(3-ch2-sime3-cp)hfme2;(2-pr,3-ch2-sime2ph-ind)(3-ch2-sime3-cp)hfme2;(2-bu,3-ch2-sime2ph-ind)(3-ch2-sime3-cp)hfme2;(2-pn,3-ch2-sime2ph-ind)(3-ch2-sime2ph-cp)hfme2;(2-hx,3-ch2-sime2ph-ind)(3-ch2-sime3-cp)hfme2;(2-ph,3-ch2-sime2ph-ind)(3-ch2-sime3-cp)hfme2;(2-me,3-ch2-simeph2-ind)(3-ch2-sime3-cp)hfme2;(2-et,3-ch2-simeph2-ind)(3-ch2-sime3-cp)hfme2;(2-pr,3-ch2-simeph2-ind)(3-ch2-sime3-cp)hfme2;(2-bu,3-ch2-simeph2-ind)(3-ch2-sime3-cp)hfme2;(2-pn,3-ch2-simeph2-ind)(3-ch2-sime2ph-cp)hfme2;(2-hx,3-ch2-simeph2-ind)(3-ch2-sime3-cp)hfme2;(2-ph,3-ch2-simeph2-ind)(3-ch2-sime3-cp)hfme2;(2-me,3-ch2-siph3-ind)(3-ch2-sime3-cp)hfme2;(2-et,3-ch2-siph3-ind)(3-ch2-sime3-cp)hfme2;(2-pr,3-ch2-siph3-ind)(3-ch2-sime3-cp)hfme2;(2-bu,3-ch2-siph3-ind)(3-ch2-sime3-cp)hfme2;(2-pn,3-ch2-siph3-ind)(3-ch2-sime2ph-cp)hfme2;(2-hx,3-ch2-siph3-ind)(3-ch2-sime3-cp)hfme2;(2-ph,3-ch2-siph3-ind)(3-ch2-sime3-cp)hfme2;(2-me,3-ch2-sicyme2-ind)(3-ch2-sime3-cp)hfme2;(2-et,3-ch2-sicyme2-ind)(3-ch2-sime3-cp)hfme2;(2-pr,3-ch2-sicyme2-ind)(3-ch2-sime3-cp)hfme2;(2-bu,3-ch2-sicyme2-ind)(3-ch2-sime3-cp)hfme2;(2-pn,3-ch2-sicyme2-ind)(3-ch2-sime2ph-cp)hfme2;(2-hx,3-ch2-sicyme2-ind)(3-ch2-sime3-cp)hfme2;(2-ph,3-ch2-sicyme2-ind)(3-ch2-sime3-cp)hfme2,及其烷基或者卤基形式,其中me2是用bz2、et2、ph2、cl2、br2或者i2替代的。

5.根据权利要求1-4任一项的负载的催化剂体系,其中所述第二非桥连的茂金属化合物是式cpacpbzrx′n所示的,其中cpa和cpb可以每个独立地选自环戊二烯基配体和与环戊二烯基等瓣的配体,cpa和cpb任一或者二者可以包含杂原子,和cpa和cpb任一或二者可以是取代的;x′可以是任何离去基团;和其中n是0,1或者2。

6.根据权利要求1-5任一项的负载的催化剂体系,其中所述第二非桥连的茂金属化合物选自:

双(环戊二烯基)二氯化锆,双(环戊二烯基)二甲基锆,双(正丁基环戊二烯基)二氯化锆,双(正丁基环戊二烯基)二甲基锆,双(五甲基环戊二烯基)二氯化锆,双(五甲基环戊二烯基)二甲基锆,双(五甲基环戊二烯基)二氯化铪,双(五甲基环戊二烯基)二甲基锆,双(1-甲基-3-正丁基环戊二烯基)二氯化锆,双(1-甲基-3-正丁基环戊二烯基)二甲基锆,双(1-甲基-3-苯基环戊二烯基)二氯化锆,双(1-甲基-3-苯基环戊二烯基)二甲基锆,双(1-甲基-3-正丁基环戊二烯基)二氯化铪,双(1-甲基-3-正丁基环戊二烯基)二甲基锆,双(茚基)二氯化锆,双(茚基)二甲基锆,双(四氢-1-茚基)二氯化锆,双(四氢-1-茚基)二甲基锆,(正丙基环戊二烯基)(五甲基环戊二烯基)二氯化锆,(正丙基环戊二烯基)(五甲基环戊二烯基)二甲基锆,外消旋/内消旋-双(1-乙基茚基)二氯化锆,外消旋/内消旋-双(1-乙基茚基)二甲基锆,外消旋/内消旋-双(1-甲基茚基)二氯化锆,外消旋/内消旋-双(1-甲基茚基)二甲基锆,外消旋/内消旋-双(1-丙基茚基)二氯化锆,外消旋/内消旋-双(1-丙基茚基)二甲基锆,外消旋/内消旋-双(1-丁基茚基)二氯化锆,外消旋/内消旋-双(1-丁基茚基)二甲基锆,内消旋-双(1-乙基茚基)二氯化锆,内消旋-双(1-乙基茚基)二甲基锆,(1-甲基茚基)(五甲基环戊二烯基)二氯化锆,和(1-甲基茚基)(五甲基环戊二烯基)二甲基锆,及其烷基或者卤基形式,其中所述二甲基是用bz2、et2、ph2、br2或者i2替代的。

7.根据权利要求1-6任一项的负载的催化剂体系,其中所述载体材料的表面积是10m2/g-700m2/g和平均颗粒直径是10μm-500μm。

8.根据权利要求1-7任一项的负载的催化剂体系,其中所述载体材料选自二氧化硅,氧化铝,二氧化硅-氧化铝及其组合。

9.根据权利要求1-8任一项的负载的催化剂体系,其中所述载体材料是氟化的或者硫酸化的。

10.权利要求9的负载的催化剂体系,其中所述载体材料的氟浓度是0.6wt%-3.5wt%,基于该载体材料的重量。

11.根据权利要求1-10任一项的负载的催化剂体系,其中所述活化剂包含铝氧烷或者非配位阴离子。

12.根据权利要求1-11任一项的负载的催化剂体系,其中所述活化剂是甲基铝氧烷。

13.根据权利要求1-12任一项的负载的催化剂体系,其中所述载体是二氧化硅铝酸盐,并且用夺电子阴离子例如氟离子或者硫酸根处理。

14.根据权利要求1-13任一项的负载的催化剂体系,其中所述夺电子阴离子处理的载体用烷基铝处理。

15.根据权利要求1-14任一项的负载的催化剂体系,其中所述夺电子阴离子处理的载体用烷基铝处理,并且基本上没有甲基铝氧烷或者非配位阴离子。

16.根据权利要求1-15任一项的负载的催化剂体系,其中式(b)所示的非桥连的茂金属化合物作为至少两种异构体存在于所述催化剂体系中。

17.根据权利要求1-16任一项的负载的催化剂体系,其中所述活化剂包含下面中的一种或多种:n,n-二甲基苯铵四(全氟萘基)硼酸盐,n,n-二甲基苯铵四(全氟联苯基)硼酸盐,n,n-二甲基苯铵四(全氟苯基)硼酸盐,n,n-二甲基苯铵四(3,5-双(三氟甲基)苯基)硼酸盐,三苯基碳正离子四(全氟萘基)硼酸盐,三苯基碳正离子四(全氟联苯基)硼酸盐,三苯基碳正离子四(3,5-双(三氟甲基)苯基)硼酸盐,三苯基碳正离子四(全氟苯基)硼酸盐,[me3nh+][b(c6f5)4-],1-(4-(三(五氟苯基)硼酸根)-2,3,5,6-四氟苯基)吡咯烷鎓;[me3nh+][b(c6f5)4-],1-(4-(三(五氟苯基)硼酸根)-2,3,5,6-四氟苯基)吡咯烷鎓,四(五氟苯基)硼酸钠,四(五氟苯基)硼酸钾,4-(三(五氟苯基)硼酸根)-2,3,5,6-四氟吡啶鎓,四(全氟苯基)铝酸钠,四(五氟苯基)钾和n,n-二甲基苯铵四(全氟苯基)铝酸盐。

18.聚合烯烃单体的方法,其包括将一种或多种烯烃单体与权利要求1-17任一项的负载的催化剂体系接触。

19.权利要求18的方法,其中所述烯烃单体的聚合形成了线性低密度聚乙烯。

20.生产乙烯α-烯烃共聚物的方法,其包括:如下将乙烯和至少一种c3-c20α-烯烃聚合:将乙烯和至少一种c3-c20α-烯烃与权利要求1-17任一项的负载的催化剂在至少一个气相反应器中,在0.7-70bar的反应器压力和20℃-150℃的反应器温度下接触,来形成乙烯α-烯烃共聚物。

21.乙烯α-烯烃共聚物,其是通过将乙烯,至少一种c3-c20α-烯烃和权利要求1-17任一项的负载的催化剂在至少一个气相反应器中接触来获得的,该共聚物的密度是0.890g/cc或者更大,熔体指数是0.1-80g/10min,和mw/mn值是1-15。

22.权利要求21的共聚物,其中所述共聚物的密度是0.900-0.940g/cc。

23.权利要求17的共聚物,其中所述共聚物的mw/mz是2-3。

24.权利要求22或者23任一项的共聚物,其中所述共聚物的mw值是50000-250000g/mol和mw/mn值是2.5-12.5。

25.生产乙烯α-烯烃共聚物的方法,其包括:如下聚合乙烯和至少一种c3-c20α-烯烃:将乙烯和至少一种c3-c20α-烯烃与权利要求1-17任一项的负载的催化剂在至少一个淤浆相反应器中在0.7-70bar的反应器压力和60℃-130℃的反应器温度下接触,来形成乙烯α-烯烃共聚物。

26.乙烯α-烯烃共聚物,其是通过将乙烯,至少一种c3-c20α-烯烃和权利要求1-17任一项的负载的催化剂在至少一个淤浆相反应器中接触来获得的,该共聚物的密度是0.890g/cc或者更大,熔体流动指数是0.1g/10min-80g/10min,和mw/mn是2.5-12.5。

27.乙烯α-烯烃共聚物,其是通过将乙烯,至少一种c3-c20α-烯烃和权利要求1-17任一项的负载的催化剂在至少一个气相反应器中接触来获得的,该共聚物的密度是0.890g/cc或者更大,熔体流动指数是0.1g/10min-80g/10min,和mw/mn是2.5-12.5,和rci,m是100-200和cdr-2m是1.5-2.5。

28.乙烯α-烯烃共聚物,其是通过将乙烯,至少一种c3-c20α-烯烃和权利要求1-17任一项的负载的催化剂在至少一个气相反应器中接触来获得的,该共聚物的密度是0.890g/cc或者更大,熔体流动指数是0.1g/10min-80g/10min,mw/mn是2.0-5.0,mz/mw是2-3,rci,m是30-100和cdr-2m是1-2。


技术总结
本发明提供了负载的催化剂体系及其使用方法。具体地,所述催化剂体系包括非桥连的茂金属化合物,结构不同于该第一非桥连的茂金属化合物的另外的非桥连的茂金属化合物,载体材料和活化剂。所述催化剂体系可以用于制备聚烯烃。

技术研发人员:M·W·赫尔特卡普;L·G·麦卡洛;M·S·贝多雅;D·F·森德斯;C·J·哈兰;吕清泰;S·库普斯瓦米
受保护的技术使用者:埃克森美孚化学专利公司
技术研发日:2018.06.22
技术公布日:2020.05.05
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