负载型茂金属催化剂催化乙烯淤浆聚合  

Supported metallocene catalysts for ethylene slurry polymerization

作　　者：花紫阳 郭建双 李建龙 赖春波 李雪坤 王原 HUA Ziyang;GUO Jianshuang;LI Jianlong;LAI Chunbo;LI Xuekun;WANG Yuan(State Key Laboratory of Polyolefins and Catalysis,Shanghai 200062,China;Shanghai Research Institute of Chemical Industry Co.,Ltd.,Shanghai 200062,China;Shanghai Key Laboratory of Catalysis Technology for Polyolefins,Shanghai 200062,China;Guangxi Key Laboratory of Green Chemical New Materials and Safety Technology,Qinzhou 545322,Guangxi,China)

机构地区：[1]聚烯烃催化技术与高性能材料国家重点实验室,上海200062 [2]上海化工研究院有限公司,上海200062 [3]上海市聚烯烃催化技术重点实验室,上海200062 [4]广西绿色化工新材料与安全技术重点实验室,广西钦州545322

出　　处：《精细化工》2025年第3期603-610,共8页Fine Chemicals

基　　金：广西科技重大专项项目(桂科AA23062020)。

摘　　要：以聚甲基铝氧烷(MAO)、双(正丁基环戊二烯基)二氯化锆为金属源,活化硅胶为载体,制备了两种不同Al、Zr质量分数的硅胶负载茂金属催化剂cat1和cat2。采用FTIR、激光粒度仪、电感耦合等离子体发射光谱仪(ICP-OES)对催化剂的化学组成和粒径分布进行了测试。考察了聚合温度、聚合时间对催化剂催化乙烯淤浆聚合活性和聚乙烯黏均相对分子质量(M_(v))的影响。通过DSC和流变分析法对聚乙烯的缠结度进行了表征。结果表明,cat1的Al、Zr质量分数分别为21.26%、0.70%,cat2的Al、Zr质量分数分别为7.37%、0.20%。cat1和cat2催化乙烯聚合动力学具有显著差异,在聚合温度为70和60℃时,cat1、cat2催化乙烯聚合活性分别达到9200、5140 gPE/gcat,M_(v)分别为3.20×10^(5)、3.70×10^(5)。cat1催化乙烯活性较为平稳,催化剂寿命长(8 h),整体活性较高;cat2制备的低M_(v)树脂具有明显的解缠结特性。同时,树脂的缠结度随着M_(v)的增加而增大。Two types of silica gel supported metallocene catalysts,cat1 and cat2,with different Al and Zr mass fractions,were prepared using polymethylaluminoxane(MAO)and bis(n-butylcyclopentadienyl)zirconium dichloride as metal sources,and activated silica gel as carrier,and characterized by FTIR,laser particle size analyzer,inductively coupled plasma emission spectroscopy(ICP-OES)for analyses on chemical composition and particle size distribution.The effects of polymerization temperature and time on the catalytic performance of cat1 and cat2 for ethylene slurry polymerization and the viscosity-average relative molecular mass(M_(v))of polyethylene were analyzed,while the entanglement degree of polyethylene was characterized by DSC and rheological analysis.The results showed that cat1 had an Al and Zr mass fraction of 21.26%and 0.70%,while cat2 had 7.37%and 0.20%,respectively.Catalysts cat1 and cat2 exhibited significant differences in the catalytic kinetics for ethylene polymerization.At polymerization temperatures of 70 and 60℃,the catalytic activity of cat1 and cat2 for ethylene polymerization reached 9200 and 5140 gPE/gcat,respectively.The M_(v)of polyethylene was 3.20×10^(5)and 3.70×10^(5),respectively.Catalyst cat1 showed relatively stable catalytic activity for ethylene,long catalyst life(8 h),and overall high activity.The low M_(v)polyethylene prepared by cat2 exhibited significant entanglement removal properties.Meanwhile,the entanglement degree of the polyethylene increased with the increase of M_(v).

关 键 词：茂金属催化剂 聚乙烯 淤浆聚合 黏均相对分子质量 缠结度 

分 类 号：TQ316.314[化学工程—高聚物工业] TQ325.12