新型低载钛负载型Z-N催化剂的一釜球磨法制备及催化烯烃聚合的研究
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摘要
Ziegler-Natta(Z-N)催化剂在整个聚烯烃的工业生产中起着主导作用,虽然它的发现已有50年的历史了,但由于Z-N催化剂的复杂性及多样性,许多问题依然有待解决,例如:如何改进Z-N催化剂的制备方法以调控催化剂中活性中心的种类及分布?聚合物链是如何增长的?一些特定体系的聚合动力学是如何的?等等诸多方面还不是很清楚,进一步弄清这些问题对开发具有独特结构和性能的聚烯烃材料具有深远的理论意义和重大的应用价值。
本论文发展了一种MgCl_2负载的低载钛Z-N催化剂的—釜球磨法制备新工艺,成功地制备了系列MgCl_2负载的低载钛Z-N催化剂:TiCl_4(0.4%)/MgCl_2和TiCl_4(0.8%)/MgCl_2。该制备方法工艺简单、操作方便、钛含量易控、稳定性好、易于工业化生产,所得催化剂催化丙烯聚合能获得应用领域广阔的新型低等规聚丙烯。用所制得的MgCl_2负载的低载钛Z-N催化剂催化丙烯聚合,发现较好的聚合条件为:钛含量0.8(wt)%;聚合温度40℃;[Al]/[Ti]=40。改变聚合条件,用此催化体系成功地制得了系列新型低等规及立体嵌段聚丙烯。将所得系列新型低等规及立体嵌段聚丙烯用作沥青改性,发现所得改性沥青的主要技术指标及经济指标达到或超过同类进口产品的指标,具有明显的应用前景。
聚丙烯的微结构主要取决于Z-N催化剂活性中心的性质及其分布。本论文采用多元Flory函数分峰拟合聚合产物分子量分布曲线的方法,研究了—釜球磨法制备的MgCl_2负载的低载钛Z-N催化剂的活性中心种类及分布,发现该催化体系中可能存在6种不同的聚合物链增长方式。对各种不同链增长方式所产生的聚合物的分子量Mi及所占的百分比f_i的模拟计算表明,计算值和实验值吻合得很好,这表明体系中存在6种链增长方式是可能的。
根据所得聚合物具有低等规及立体嵌段的微结构特点,本文提出了一种新的聚丙烯增长链受具有两种能够相互转换活性位的增长方式控制的模型,其中一种活性位服从对映体活性中心控制增长机理,另一种活性位服从链末端控制增长机理,两种活性位可转换,因而交替控制整条聚合物链的增长,并推导了在该链增长方式控制下聚合物链结构的五元组分布函数表达式。在此基础上,提出了采用—釜球磨法制备的MgCl_2负载的低载钛Z-N催化剂在催化丙烯聚合过程中聚合物链的增长模型,并用该模型模拟计算了所得聚合物的五元组分布,发现计算值与~(13)C-NMR实测值吻合得很好,这表明所建立的新模型是合理的。
基于—釜球磨法制备的MgCl_2负载的低载钛Z-N催化体系存在6种链增长方式,考虑再活化作用,本文建立了新的动力学模型:
当t 当t>t_0时:R_M=k_p~1M(ρ_(11)e~(λ_5(t-t_0))+ρ_(12)e~(λ_6(t-t_0))+ρ_(13))+k_p~2M(ρ_(14)e~(λ_5(t-t_0))+ρ_(15)e~(λ_6(t-t_0))+ρ_(16))+k_p~3M(ρ_(17)e~(λ_7(t-t_0))+ρ_(18)e~(λ_8(t-t_0))+ρ_(19))+k_p~4M(ρ_(20)e~(λ_7(t-t_0))+ρ_(21)e~(λ_8(t-t_0))+ρ_(22))
用此模型对实验数据进行拟合,发现计算值和实验值吻合得相当好,说明此模型是合理
Ziegler-Natta (Z-N) catalysts are an important class of commercial catalysts for the preparation of polyolefins. However, some problems such as how to improve the method of preparing the Z-N catalysts to control the type and distribution of active centers, propagating mechanism of the polymer chain and polymerization kinetic of some special catalyst systems still are unclear completely. It is of great theoretical significance and practical value to clear above metioned problems for development of new polymer material with special structures and properties.In this work, a new route for preparing MgCl_2-supported and low Ti-loading Z-N catalysts using a new one-pot ball milling method was developed, and a series of MgCl_2-supported and low Ti-loading Z-N catalysts, such as TiCl_4(0.4%)/MgCl_2 and TiCl_4(0.8%)/MgCl_2, were prepared successfully. This route is easy to be industrialized and the resultant catalysts can be employed in a study of propylene polymerization with AlEt_3 as cocatalyst. It was found that the resultant polymer had low isotactic and block microstructure, and can be widely used in many fields, for example, as additive for building top grade high way.The influence of polymerization temperature, catalyst concentration and [Al]/[Ti] molar ratio on catalytic activities and polymerization kinetics has been investigated. The results showed that the better polymerization conditions were: Ti-loading amount=0.8(wt)%, polymerization temperature =40°C, [Al]/[Ti]=30. Changing polymerization conditions, a series of novel low isotactic polypropylene and block polypropylene were prepared successfully. Using the resultant novel low isotactic polypropylene and block polypropylene as modifier for asphalt, it was found that it had evident effects to improve the properties of asphalt.In this work, the complex GPC data of polypropylene synthesized by MgCl_2-supported and low Ti-loading Z-N catalyst were analyzed using the method of fitting the molecular weight distribution (MWD) curves with multiple Flory-Schulz functions. It was found that these MWD curves could be actually fitted with 6 Flory-Schulz most-probable distributions with different position and area, which showed that it was a reasonable suggestion that there exist six types propagating way of the polymer chain in the polymerization system.Based on microstructure character of obtained polypropylene, we developed a new two-site propagating model: the polymer chain propagates at two-site which can intertransform. Site-1 obeys the enantiomorphic-site model while site-2 follows the chained-end growing dependent model, and the propagation of the polymer chain are controlled by the site-1 and site-2 alternately. The theoretical expressions of the pentad intensities of the polypropylene based on this new propagating model were deduced. A novel multi-active-centers propagating model in the propylene polymerization catalyzed by MgCl_2-supported and low Ti-loading Z-N catalysts prepared using a new one-pot ball milling method was also proposed. After simulating the pentad
intensities of the resultant polypropylene using multi-active-centers model, it was found that the calculated results from this new model could satisfactorily account for the experimental data, which showed the proposed model is plausible and reasonable.Based on six types propagating way of the polymer chain in the MgCl2-supported and low Ti-loading Z-N catalysts prepared using one-pot ball milling method, a polymerization kinetics model was proposed as following:When tto: RM = *;M(Ai^('-'"> + pl2e*<^ + Pu) + k]M^e^ + p^'^ + pj-* + Pl9) + klM(p2Oe^ + p2]e?'-'-> + p22)Applying this kinetics model, the good agreement between the experimental data and the fitting profiles was achieved, which indicated the proposed model is reasonable.Molecular weight and its distribution of the polyethylene have extensively effects to the product properties. And so it is of great significance to adjust the molecular weight distribution of the polyethylene for developing novel kinds of polyethylene with high properties. In this work, MgCb/SiC^—bi-supported Z-N catalysts were prepared using the one-pot ball milling method and were employed in ethylene polymerization with AlEt3 as cocatalyst. The results showed that by changing the molar ratios of two component of supports in the catalysts and polymerization temperature, the molecular weight and molecular weight distribution of the resultant polyethylene could be widely adjusted.The copolymerizations of ethylene/ct-olefin catalyzed by the catalysts prepared using the one-pot ball milling method were studied. A series of copolymer with various content of hexane and dodecene were synthesized successfully. It was found that these catalyst systems had stable kinetic curves and the content of co-monomer in the resultant copolymer could be widely adjusted, which showed that these catalysts might be useful to commercial preparation of polyolefins.
本论文发展了一种MgCl_2负载的低载钛Z-N催化剂的—釜球磨法制备新工艺,成功地制备了系列MgCl_2负载的低载钛Z-N催化剂:TiCl_4(0.4%)/MgCl_2和TiCl_4(0.8%)/MgCl_2。该制备方法工艺简单、操作方便、钛含量易控、稳定性好、易于工业化生产,所得催化剂催化丙烯聚合能获得应用领域广阔的新型低等规聚丙烯。用所制得的MgCl_2负载的低载钛Z-N催化剂催化丙烯聚合,发现较好的聚合条件为:钛含量0.8(wt)%;聚合温度40℃;[Al]/[Ti]=40。改变聚合条件,用此催化体系成功地制得了系列新型低等规及立体嵌段聚丙烯。将所得系列新型低等规及立体嵌段聚丙烯用作沥青改性,发现所得改性沥青的主要技术指标及经济指标达到或超过同类进口产品的指标,具有明显的应用前景。
聚丙烯的微结构主要取决于Z-N催化剂活性中心的性质及其分布。本论文采用多元Flory函数分峰拟合聚合产物分子量分布曲线的方法,研究了—釜球磨法制备的MgCl_2负载的低载钛Z-N催化剂的活性中心种类及分布,发现该催化体系中可能存在6种不同的聚合物链增长方式。对各种不同链增长方式所产生的聚合物的分子量Mi及所占的百分比f_i的模拟计算表明,计算值和实验值吻合得很好,这表明体系中存在6种链增长方式是可能的。
根据所得聚合物具有低等规及立体嵌段的微结构特点,本文提出了一种新的聚丙烯增长链受具有两种能够相互转换活性位的增长方式控制的模型,其中一种活性位服从对映体活性中心控制增长机理,另一种活性位服从链末端控制增长机理,两种活性位可转换,因而交替控制整条聚合物链的增长,并推导了在该链增长方式控制下聚合物链结构的五元组分布函数表达式。在此基础上,提出了采用—釜球磨法制备的MgCl_2负载的低载钛Z-N催化剂在催化丙烯聚合过程中聚合物链的增长模型,并用该模型模拟计算了所得聚合物的五元组分布,发现计算值与~(13)C-NMR实测值吻合得很好,这表明所建立的新模型是合理的。
基于—釜球磨法制备的MgCl_2负载的低载钛Z-N催化体系存在6种链增长方式,考虑再活化作用,本文建立了新的动力学模型:
当t
用此模型对实验数据进行拟合,发现计算值和实验值吻合得相当好,说明此模型是合理
Ziegler-Natta (Z-N) catalysts are an important class of commercial catalysts for the preparation of polyolefins. However, some problems such as how to improve the method of preparing the Z-N catalysts to control the type and distribution of active centers, propagating mechanism of the polymer chain and polymerization kinetic of some special catalyst systems still are unclear completely. It is of great theoretical significance and practical value to clear above metioned problems for development of new polymer material with special structures and properties.In this work, a new route for preparing MgCl_2-supported and low Ti-loading Z-N catalysts using a new one-pot ball milling method was developed, and a series of MgCl_2-supported and low Ti-loading Z-N catalysts, such as TiCl_4(0.4%)/MgCl_2 and TiCl_4(0.8%)/MgCl_2, were prepared successfully. This route is easy to be industrialized and the resultant catalysts can be employed in a study of propylene polymerization with AlEt_3 as cocatalyst. It was found that the resultant polymer had low isotactic and block microstructure, and can be widely used in many fields, for example, as additive for building top grade high way.The influence of polymerization temperature, catalyst concentration and [Al]/[Ti] molar ratio on catalytic activities and polymerization kinetics has been investigated. The results showed that the better polymerization conditions were: Ti-loading amount=0.8(wt)%, polymerization temperature =40°C, [Al]/[Ti]=30. Changing polymerization conditions, a series of novel low isotactic polypropylene and block polypropylene were prepared successfully. Using the resultant novel low isotactic polypropylene and block polypropylene as modifier for asphalt, it was found that it had evident effects to improve the properties of asphalt.In this work, the complex GPC data of polypropylene synthesized by MgCl_2-supported and low Ti-loading Z-N catalyst were analyzed using the method of fitting the molecular weight distribution (MWD) curves with multiple Flory-Schulz functions. It was found that these MWD curves could be actually fitted with 6 Flory-Schulz most-probable distributions with different position and area, which showed that it was a reasonable suggestion that there exist six types propagating way of the polymer chain in the polymerization system.Based on microstructure character of obtained polypropylene, we developed a new two-site propagating model: the polymer chain propagates at two-site which can intertransform. Site-1 obeys the enantiomorphic-site model while site-2 follows the chained-end growing dependent model, and the propagation of the polymer chain are controlled by the site-1 and site-2 alternately. The theoretical expressions of the pentad intensities of the polypropylene based on this new propagating model were deduced. A novel multi-active-centers propagating model in the propylene polymerization catalyzed by MgCl_2-supported and low Ti-loading Z-N catalysts prepared using a new one-pot ball milling method was also proposed. After simulating the pentad
intensities of the resultant polypropylene using multi-active-centers model, it was found that the calculated results from this new model could satisfactorily account for the experimental data, which showed the proposed model is plausible and reasonable.Based on six types propagating way of the polymer chain in the MgCl2-supported and low Ti-loading Z-N catalysts prepared using one-pot ball milling method, a polymerization kinetics model was proposed as following:When t
引文
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