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材料研究学报  2015, Vol. 29 Issue (2): 88-94    DOI: 10.11901/1005.3093.2014.363
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聚合填充法制备铁/二氧化硅/聚乙烯复合颗粒
顾玉彬,杨勇,黄正梁(),蒋斌波,包崇龙,王靖岱,阳永荣
化学工程联合国家重点实验室 浙江大学化学工程与生物工程学院 杭州 310027
Preparation of Fe/SiO2/PE Composites Through Polymerization Filling Technique
Yubin GU,Yong YANG,Zhengliang HUANG(),Binbo JIANG,Chonglong BAO,Jingdai WANG,Yongrong YANG
State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
引用本文:

顾玉彬,杨勇,黄正梁,蒋斌波,包崇龙,王靖岱,阳永荣. 聚合填充法制备铁/二氧化硅/聚乙烯复合颗粒[J]. 材料研究学报, 2015, 29(2): 88-94.
Yubin GU, Yong YANG, Zhengliang HUANG, Binbo JIANG, Chonglong BAO, Jingdai WANG, Yongrong YANG. Preparation of Fe/SiO2/PE Composites Through Polymerization Filling Technique[J]. Chinese Journal of Materials Research, 2015, 29(2): 88-94.

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摘要: 

以用溶胶凝胶法制备的Fe/SiO2复合颗粒作为载体负载二氯二茂锆(Cp2ZrCl2), 用聚合填充法催化乙烯聚合制备了Fe/SiO2/PE复合颗粒。用扫描电镜、X射线能谱分析、红外光谱、电感耦合等离子体光谱仪、热重分析仪和激光粒度分析仪、凝胶渗透色谱等手段对复合颗粒进行了分析和表征。结果表明, Fe/SiO2复合颗粒外层SiO2包覆完整, 可用作Cp2ZrCl2的载体; Fe/SiO2/Cp2ZrCl2催化剂体系在乙烯聚合过程中显示出较高的活性, 可聚合得到Fe/SiO2/PE复合颗粒; 催化活性组分在聚合过程中不会从Fe/SiO2复合颗粒上脱离, 生成的聚乙烯在载体表面包覆良好; Fe/SiO2/PE复合颗粒在聚合过程中出现了明显的团聚; Fe/SiO2/Cp2ZrCl2催化剂颗粒和Fe/SiO2/PE复合颗粒的形状均不规则, 两者之间有复制效应; 改变聚合时间和聚合压力可调节Fe/SiO2/PE复合颗粒中的Fe含量; 用Fe/SiO2/Cp2ZrCl2催化剂催化乙烯聚合得到的聚乙烯, 分子量分布较窄。
关键词 ： 无机/有机复合材料,  Fe/SiO2/PE复合颗粒,  聚合填充,  茂金属催化剂    
Abstract：

Fe/SiO2composites were prepared by sol-gel method firstly and further on which zirconcene dichloride (Cp2ZrCl2) was deposited to prepare a catalyst Fe/SiO2/Cp2ZrCl2. Then particulates of Fe/SiO2/PE composites were produced by polymerization filling technique with ethylene and the Fe/SiO2/Cp2ZrCl2 catalysit. The obtained Fe/SiO2/PE composite particles were characterized by scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDX), infrared spectroscopy(IFR), inductively coupled plasma spectroscopy(ICP), thermal gravimetric analysis(TGA) and laser particle size analyzer, respectively. The results show that the Fe core was perfectly coated by a SiO2 layer for the Fe/SiO2 composites, which could act well as a supporter for the deposition of Cp2ZrCl2. The Fe/SiO2/Cp2ZrCl2 catalyst showed a high activity for the ethylene polymerization process. PE chains grew and attached on the Fe/SiO2/Cp2ZrCl2 composites gradually, until the Fe/SiO2 composites were entirely coated. Moreover, the Fe/SiO2/PE particles were found to agglomerate significantly during ethylene polymerization. Both the Fe/SiO2/Cp2ZrCl2 catalysts and Fe/SiO2/PE composites had irregular shapes, and the latter tended to duplicate the shape of the former. The Fe content in the Fe/SiO2/PE composites can be adjusted by varying the time and pressure of the polymerization process. Finally, the range of the molecular mass distribution of the PEs produced by this process is narrow.
Key words： inorganic/organic composites    Fe/SiO2/PE composites    polymerization filling technique    metallocenes catalysts
收稿日期: 2014-07-17     
基金资助:* 国家自然科学基金21406194, 高等学校博士学科点专项科研基金20130101110063, 国家重点基础研究发展计划2012CB720500, 浙江省自然科学基金青年基金LQ13B060002资助项目。
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顾玉彬
杨勇
黄正梁
蒋斌波
包崇龙
王靖岱
阳永荣

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https://www.cjmr.org/CN/10.11901/1005.3093.2014.363      或      https://www.cjmr.org/CN/Y2015/V29/I2/88

图1  Fe/SiO2复合颗粒的扫描电镜照片
图2  Fe/SiO2复合颗粒的EDX谱图
Batch Temperature /℃ Reaction time/min Al/Zr molar ratio Pressure /MPa Productivity/ (kgPE/molZrhMPa) Fe/SiO2 content/% Fe content/%
1 40 10 4055 0.6 1467.5 24.31 7.15
2 40 10 4055 0.8 3453.5 8.04 2.36
3 40 15 4055 0.8 2272.5 7.30 2.14
表1  不同聚合条件下Fe/SiO2/Cp2ZrCl2催化剂的活性以及Fe含量
图3  Fe/SiO2/PE复合颗粒的生成路径
图4  Fe/SiO2/Cp2ZrCl2催化剂和Fe/SiO2/PE复合颗粒的扫描电镜照片
图5  Fe/SiO2/Cp2ZrCl2催化剂的粒径分布
图6  Fe/SiO2/PE复合颗粒粒径分布曲线
图7  Fe/SiO2/Cp2ZrCl2催化剂粒径分布和Fe/SiO2/PE复合颗粒的归一化粒径分布对比
图8  Fe/SiO2和Fe/SiO2/PE复合颗粒的红外光谱
图9  吸附在磁铁上的Fe/SiO2/PE复合颗粒
图10  Fe/SiO2/PE复合颗粒的热重分析
图11  Fe/SiO2/PE复合颗粒中PE的分子量分布曲线
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