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J4  2011, Vol. 45 Issue (5): 907-913    DOI: 10.3785/j.issn.1008-973X.2011.05.022
化学工程、材料工程     
丁二醇活化氯化镁制备Ziegler-Natta
催化剂及其乙烯聚合
叶健,黄海波,张乐天,王靖岱,蒋斌波,阳永荣,廖祖维
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
Preparation of Ziegler-Natta catalyst by butanediol
activation and its ethylene polymerization
YE Jian, HUANG Hai-bo, ZHANG Le-tian, WANG Jing-dai, JIANG Bin-bo,
YANG Yong-rong, LIAO Zu-wei
Department of Chemical and Biological Engineering, State Key Laboratory of Chemical Engineering,
Zhejiang University, Hangzhou 310027, China
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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δ-MgCl2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.

Abstract:

MgCl2/THF/HO(CH2)4OH 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 δ-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.

出版日期: 2011-11-24
:  TQ 426.62  
基金资助:

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

通讯作者: 廖祖维, 男, 助理研究员.     E-mail: liaozw@zju.edu.cn
作者简介: 叶健(1987-), 男, 浙江丽水人, 硕士生. 从事烯烃聚合催化剂的研究.
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引用本文:

叶健,黄海波,张乐天,王靖岱,蒋斌波,阳永荣,廖祖维. 丁二醇活化氯化镁制备Ziegler-Natta
催化剂及其乙烯聚合[J]. J4, 2011, 45(5): 907-913.

YE Jian,HUANG Hai-bo,ZHANG Le-tian,WANG Jing-dai,JIANG Bin-bo,YANG Yong-rong. Preparation of Ziegler-Natta catalyst by butanediol
activation and its ethylene polymerization. J4, 2011, 45(5): 907-913.

链接本文:

https://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2011.05.022        https://www.zjujournals.com/eng/CN/Y2011/V45/I5/907

[1] SOZZANI P, BRACCO S, COMOTTI A, et al. Stoichiometric compounds of magnesium dichloride with ethanol for the supported ZieglerNatta catalysis: First recognition and multidimensional MAS NMR study [J]. Journal of the American Chemical Society, 2003, 125(42): 12881-12893.
[2] PUHAKKA E, PAKKANEN T T, PAKKANEN T A. Theoretical investigations on heterogeneous ZieglerNatta catalyst supports: stability of the electron donors at different coordination sites of MgCl2 [J]. Journal of Physical Chemistry A, 1997, 101(34): 6063-6068.
[3] 肖士镜, 余赋生. 烯烃配位聚合催化剂及聚烯烃 [M]. 北京工业大学出版社, 2002: 17-69.
[4] NOTOV D, PAVANELLO L, VIVIANI M, et al. A kinetic investigation of ethyl formate elimination from the [MgCl2(HCOOC2H5)2]n adduct using thermoanalytical data\
[J\]. Thermochimica Acta, 1991, 189(2): 223-233.
[5] NOTO V D, MARIGO A, VIVIANI M, et al. MgCl2supported ZieglerNatta catalysts: Synthesis and Xray diffraction characterization of some MgCl2Lewis base adducts [J]. Macromolecular Chemistry and Physics, 1992, 193(1): 123-131.
[6] NOTO V D, ZANNETTI R, VIVIANI M, et al. MgCl2supported ZieglerNatta catalysts: A structural investigation by Xray diffraction and Fouriertransform IR spectroscopy on the chemical activation process through MgCl2ethanol adducts [J]. Macromolecular Chemistry and Physics, 1992, 193(7): 1653-1663.
[7] NOTO V D, ZANNETTI R, VIVIANI M, et al. Magnesium chloridesupported catalysts for ZieglerNatta propene polymerization: Ethyl formate as internal base[J]. Macromolecular Chemistry and Physics, 1994, 195(10): 3395-3409.
[8] NOTO V D, BRESADOLA S. New synthesis of a highly active δMgCl2 for MgCl2/TiCl4/AlEt3 catalytic systems [J]. Macromolecular Chemistry and Physics, 1996, 197(11): 3827-3835.
[9] NOTO V D, FREGINESE D, MARIGO A, et al. High yield MgCl2supported catalysts for propene polymerization: Effects of ethyl propionate as internal donor on the activity and stereospecificity [J]. Macromolecular Chemistry and Physics, 1998, 199(4): 633-640.
[10] CHUNG J S, SONG I K, LEE W Y, et al. Morphology control of a MgCl2supported ZieglerNatta catalyst by the recrystallization method[J]. Macromolecular Chemistry and Physics, 1995, 196(4): 1205-1210.
[11] SHIN H W, CHUNG J S, SONG I K, et al. Temperature effect of TiCl4 impregnation of a recrystallized MgCl2 support on propene polymerization [J]. Macromolecular Chemistry and Physics, 1995, 196(11): 3765-3770.
[12] CHOI J H, CHUNGJ S, SHIN H W, et al. The effect of alcohol treatment in the preparation of MgCl2 support by a recrystallization method on the catalytic activity and isotactic index for propylene polymerization [J]. European Polymer Journal, 1996, 32(4): 405-410.
[13] MAGALHAES D N T, FILHO O D C, COUTINHO F M B. ZieglerNatta catalyst for ethylene and propylene polymerization supported on adducts of magnesium chlorides with methyl and ethyl alcohols [J]. European Polymer Journal, 1991, 27(8): 827-830.
[14] YANG C B, HSU C C, PARK Y S, et al. Infrared characterization of MgCl2 supported ZieglerNatta catalysts with monoester and diester as a modifier [J]. European Polymer Journal, 1994, 30(2): 205-214.
[15] FORTE M C, COUTINHO F M B. Highly active magnesium chloride supported ZieglerNatta catalysts with controlled morphology[J]. European Polymer Journal, 1996, 32(2): 223-231.
[16] YE Z Y, WANG L, FENG L F, et al. Novel spherical Ziegler–Natta catalyst for polymerization and copolymerization. I. Spherical MgCl2 support [J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2002, 40(18): 3112-3119.
[17] WANG L, YU H J, MaAZ L, et al. Preparation of novel MgCl2adduct supported spherical Ziegler–Natta catalyst for αOlefin polymerization[J]. Journal of Applied Polymer Science, 2006, 99(3): 945-948.
[18] GUPTA V K, RAVINDRANATHAN M. Studies of a supported titanium catalyst system using magnesium dichlo

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