丁二醇活化氯化镁制备Ziegler-Natta催化剂及其乙烯聚合  

Preparation of Ziegler-Natta catalyst by butanediol activation and its ethylene polymerization

作　　者：叶健[1] 黄海波[1] 张乐天[1] 王靖岱[1] 蒋斌波[1] 阳永荣[1] 廖祖维[1] 

机构地区：[1]浙江大学化学工程与生物工程学系,化学工程联合国家重点实验室,浙江杭州310027

出　　处：《浙江大学学报（工学版）》2011年第5期907-913,共7页Journal of Zhejiang University：Engineering Science

基　　金：国家自然科学基金重大资助项目(20776124,20736011);国家高技术研究发展计划资助项目(2007AA030208)

摘　　要：采用1,4-丁二醇作为沉淀剂,析出溶解于四氢呋喃(THF)中的MgCl2,制备得到具有新型结构的MgCl2/THF/HO(CH2)4OH化合物.该化合物经过三乙基铝(TEA)处理得到MgCl2.nTHF.mAl(OR)3载体,负载TiCl4后得到了高活性的Ti-Mg催化剂.采用X-射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、感应耦合等离子体发射光谱(ICP)、核磁共振(NMR)和氮气吸附法等手段对其结构进行表征,发现所制得的载体呈现-δMgCl2晶型,催化剂具有较大的比表面积和较高的钛质量分数(5.79%).乙烯聚合结果表明,催化剂活性较高,每克Ti单位时间单位反应压力下可制得聚乙烯47.38 kg,即47.38 kg.g-1.h-1.10-5Pa-1,且具有缓慢衰减型动力学曲线.聚合产物具有较宽的分子量分布(MWD=9.02).加氢后产物的分子量分布变窄(MWD=6.81),但随氢气体积分数的增加变化不大.MgCl2/THF/HO（CH2 ）4 OH adduct with a novel structure was synthesized by using 1,4-butanediol to precipitate MgCl2 from tetrahydrofuran solution. The resulting adduct was treated by triethylaluminum（TEA） and activated MgCl2 · nTHF · mAl（OR）3 support was obtained. Highly active catalyst for ethylene polymerization was prepared by impregnating TICl4 on this support. The synthesized support and catalyst was characterized by XRD, FT-IR, ICP, NMR and nitrogen adsorption method. The characterization results demonstrated that the support was in the crystal form of 3-MgCl2, and the catalyst showed high surface area and titanium mass fraction（5.79%）. The ethylene polymerization results indicated the catalyst had high catalytic activity. 47.38 kg polyethylene （PE） · could be produced by one gram of Titanium under unit time and unit pressure, namely, 47.38 kg·g^-1·h^-1·10^-5Pa^-1. A slow declined kinetic curve of the catalyst was observed in polymerization. Moreover, the molecular weight distribution （MWD） of polyethylene produced by this catalyst was broad （MWD= 9.02）. The MWD was narrowed in the presence of hydrogen, and changed slightly with increasing hydrogen volume fraction.

关 键 词：氯化镁 1 4-丁二醇 四氢呋喃 乙烯聚合 氢调 

分 类 号：TQ426.62[化学工程]