乙酸乙酯改性Ziegler-Natta催化剂用于乙烯聚合研究
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摘要
以乙酸乙酯(EAC)为内给电子体对乙烯淤浆聚合用钛系Ziegler-Natta催化剂进行改性,并与未改性的催化剂进行了对比。通过激光粒度仪和扫描电子显微镜分析了催化剂的颗粒大小、粒径分布和颗粒形态;采用傅里叶变换红外光谱、X射线衍射等方法分析了EAC与氯化镁和四氯化钛的相互作用;通过乙烯淤浆聚合的方法评价了不同EAC含量催化剂的活性和聚合反应动力学行为等。结果表明:n(EAC)∶n(Mg)=0.15时,催化剂活性可达39.72 kg/g,且具有颗粒形态好和反应动力学平稳等特点。
The titanium-based Ziegler-Natta catalysts were modified by ethyl acetate(EAC) as internal donors and compared with the unmodified catalysts. The particle size and its distribution and morphology of the catalysts were analyzed by laser particle size analyzer and scanning electron microscope. The interaction between EAC and magnesium chloride and titanium tetrachloride in catalyst preparation was analyzed by Fourier transform infrared spectroscope and X-ray diffractometer. The activities and polymerization kinetics of the catalysts in different amount of EAC were compared. The result indicate that when the molar ratio of EAC to Mg is 0.15,the activity of the catalysts reaches 39.72 kg/g. The particle morphology of the catalysts is excellent and kinetics is stable.
The titanium-based Ziegler-Natta catalysts were modified by ethyl acetate(EAC) as internal donors and compared with the unmodified catalysts. The particle size and its distribution and morphology of the catalysts were analyzed by laser particle size analyzer and scanning electron microscope. The interaction between EAC and magnesium chloride and titanium tetrachloride in catalyst preparation was analyzed by Fourier transform infrared spectroscope and X-ray diffractometer. The activities and polymerization kinetics of the catalysts in different amount of EAC were compared. The result indicate that when the molar ratio of EAC to Mg is 0.15,the activity of the catalysts reaches 39.72 kg/g. The particle morphology of the catalysts is excellent and kinetics is stable.
引文
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[16]秦金来,陈新,张文平,等.BCES催化剂在CX工艺装置上的工业应用[J].石油化工,2013,42(6):656-660.
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[4]Renata D S C,Jaqueline D S O,Luciana B R,et al.Ziegler-Natta catalyst based on MgCl2/Clay/ID/TiCl4 for the synthesis of spherical particles of polypropylene nanocomposites[J].J Nanosci Nanotechnol,2018,18(7):5124-5132.
[5]张磊,王世波,周俊领,等.高活性高氢调性能乙烯聚合用Ziegler-Natta催化剂[J].石油化工,2016,45(8):936-939.
[6]邹海潇,周剑,孙龙,等.乙烯淤浆聚合Ziegler-Natta催化剂的制备及性能[J].石化技术与应用,2014,32(3):209-213.
[7]王超群,范娟娟,牛磊,等.内给电子体在气相PE催化剂中作用的研究[J].化学工程师,2010(6):10-12;29.
[8]中国石油化工股份有限公司,中国石油化工股份有限公司北京化工研究院.用于乙烯聚合反应的催化剂组分及其催化剂:中国,101633704[P].2011-12-28.
[9]三井化学株式会社.乙烯聚合用固体状钛催化剂成分、乙烯聚合用催化剂以及乙烯的聚合方法:中国,101983211[P].2011-03-02.
[10]周俊领,李秉毅.酯类给电子体对球形PE催化剂活性的影响[J].石油化工,2016,45(5):548-551.
[11]张韬毅,周俊领,郭子芳.硼酸酯类给电子体在淤浆法制备PE催化剂中的应用[J].石油化工,2013,42(6):632-635.
[12]郎笑梅,姜涛,张怀志.一种乙烯均聚合与共聚合的制备方法:中国,101775086A[P].2010-7-14.
[13]Munoz E A,Hernandez J G,Gallardo J A.Catalytic activity and control of the nascent morphology of polyethylenes obtained with first and second generation of Ziegler-Natta catalysts[J].J Appl Polym Sci,1984,4(29):1187-1202.
[14]Vito D N,Silvano B.New synthesis of a highly activeδ-MgCl2for MgCl2/TiCl4/AlEt3 catalytic systems[J].Macromol Chem Phys,1996,11(197):3827-3835.
[15]Song B G,Ihm S K.The role of two different internal donors(phthalate and 1,3-diether)on the formation of surface structure in MgCl2-supported Ziegler-Natta catalysts and their catalytic performance of propylene polymerization[J].J Appl Polym Sci,2014,131(15):40536-40542.
[16]秦金来,陈新,张文平,等.BCES催化剂在CX工艺装置上的工业应用[J].石油化工,2013,42(6):656-660.