Propylene slurry polymerization with a MgCl2-supported Ziegler-Natta catalyst containing internal electron donor was conducted after different durations of pre-contact of the catalyst with triethylaluminum cocatalyst....Propylene slurry polymerization with a MgCl2-supported Ziegler-Natta catalyst containing internal electron donor was conducted after different durations of pre-contact of the catalyst with triethylaluminum cocatalyst. The number of active centers([C*]/[Ti])was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and measuring sulfur content in the polymer. The pre-contact treatment caused selective deactivation of a part of active centers with low stereoselectivity and much lower activity in the initial stage of polymerization as compared with the polymerization run without the pre-contact stage. The active center concentration and polymerization activity decreased with prolonging of the pre-contact stage. The proportion of stereoselective active centers was increased by prolonging the pre-contact stage, so the isotacticity of produced polypropylene was enhanced. Release of active centers through catalyst particle fragmentation was significantly retarded, and the polymerization rate curve changed from decay type to induction type by the precontact treatment. In the induction period both non-stereoselective and stereoselective active centers were released and activated, resulting in gradual reduction of the polymer’s isotacticity in the first 5-10 min of polymerization. Selective deactivation of non-stereoselective active centers also took place in propylene polymerization using the catalyst without pre-contacting with the cocatalyst. In this case, the polymerization rate decayed with time after a short induction period of 2-5 min. Over reduction of the active center precursors with low stereoselectivity by triethylaluminum was considered as the reason for their deactivation during the pre-contact or the polymerization processes.展开更多
将由室内试验总结得到的岩石微观胶结模型嵌入离散元软件,对Lac du Bonnet花岗岩石进行预制单裂隙单轴压缩试验DEM数值模拟,分析了压缩过程中裂隙试样中应力的分布,并与理论计算结果进行对比分析,同时对各种断裂判据中裂纹起裂角的预测...将由室内试验总结得到的岩石微观胶结模型嵌入离散元软件,对Lac du Bonnet花岗岩石进行预制单裂隙单轴压缩试验DEM数值模拟,分析了压缩过程中裂隙试样中应力的分布,并与理论计算结果进行对比分析,同时对各种断裂判据中裂纹起裂角的预测值进行了适用性的对比分析。结果表明,离散元模拟试样破坏形态与试验结果相近;离散元分析得到的应力分布与理论解在定性上相似;当预制角度较小时,侧向应力都处于拉压状态;由于裂隙左右两端压应变的集中造成了裂隙上下面拉应变的产生,造成了裂隙周围特殊的应力分布;当裂隙角度较大时,应力集中现象已不明显,因而,理论值与试验值有偏差;在断裂判据中最大周应力准则和最大能量释放率准则得到的裂纹扩展角与室内试验与DEM结果中的数值较为吻合。展开更多
基金financially supported by the National Natural Science Foundation of China (No. 51773178)
文摘Propylene slurry polymerization with a MgCl2-supported Ziegler-Natta catalyst containing internal electron donor was conducted after different durations of pre-contact of the catalyst with triethylaluminum cocatalyst. The number of active centers([C*]/[Ti])was determined by quenching the polymerization with 2-thiophenecarbonyl chloride and measuring sulfur content in the polymer. The pre-contact treatment caused selective deactivation of a part of active centers with low stereoselectivity and much lower activity in the initial stage of polymerization as compared with the polymerization run without the pre-contact stage. The active center concentration and polymerization activity decreased with prolonging of the pre-contact stage. The proportion of stereoselective active centers was increased by prolonging the pre-contact stage, so the isotacticity of produced polypropylene was enhanced. Release of active centers through catalyst particle fragmentation was significantly retarded, and the polymerization rate curve changed from decay type to induction type by the precontact treatment. In the induction period both non-stereoselective and stereoselective active centers were released and activated, resulting in gradual reduction of the polymer’s isotacticity in the first 5-10 min of polymerization. Selective deactivation of non-stereoselective active centers also took place in propylene polymerization using the catalyst without pre-contacting with the cocatalyst. In this case, the polymerization rate decayed with time after a short induction period of 2-5 min. Over reduction of the active center precursors with low stereoselectivity by triethylaluminum was considered as the reason for their deactivation during the pre-contact or the polymerization processes.
文摘将由室内试验总结得到的岩石微观胶结模型嵌入离散元软件,对Lac du Bonnet花岗岩石进行预制单裂隙单轴压缩试验DEM数值模拟,分析了压缩过程中裂隙试样中应力的分布,并与理论计算结果进行对比分析,同时对各种断裂判据中裂纹起裂角的预测值进行了适用性的对比分析。结果表明,离散元模拟试样破坏形态与试验结果相近;离散元分析得到的应力分布与理论解在定性上相似;当预制角度较小时,侧向应力都处于拉压状态;由于裂隙左右两端压应变的集中造成了裂隙上下面拉应变的产生,造成了裂隙周围特殊的应力分布;当裂隙角度较大时,应力集中现象已不明显,因而,理论值与试验值有偏差;在断裂判据中最大周应力准则和最大能量释放率准则得到的裂纹扩展角与室内试验与DEM结果中的数值较为吻合。
