乙氧基镁载体化Ziegler-Natta催化剂及其催化乙烯预聚合初探
发布时间：2018-11-18 12:12
【摘要】：本研究致力于推动国内乙氧基镁负载型聚乙烯催化剂的发展,以乙氧基镁载体和催化剂制备技术为突破口,制备出了性能优良乙氧基镁负载型聚乙烯催化剂;在乙氧基镁载体方面,公布了在二氧硅与癸烷的共同作用下可以制备大颗粒乙氧基镁,同时少量的二氧化硅与癸烷能提高小粒径乙氧基镁颗粒的综合性能,戊五醇能有效提高小粒径乙氧基镁颗粒的堆密度与流动性能;在催化剂制备技术方面,公布了在工业小试的条件下,乙氧基镁负载型聚乙烯催剂催化乙烯聚合,基本没活性,但是通过预聚部分乙烯后,在28/45 (氢气压力:0.28 MPa,乙烯压力:0.45 MPa)的条件下,催化剂催化乙烯聚合效率可达13700(g PE/g Cat)倍,添加多元素硅烷类给电子体后可将催化剂的催化效率提高至17000(gPE/gCat)倍。最佳制备条件:大颗粒乙氧基镁制备:m(Mg): V(CH3CH2OH): m (二氧化硅)、V (癸烷)=1 g:30mL:0.2g:10mL时,乙氧基镁堆密度、流动倾斜值tanδ、粒径 d(0.5)及粒径分布指数分别为 3.42 g·cm-3、0.719、158.9 μm、1.96,改用机械搅拌后可以制备的乙氧基镁颗粒d(0.5)可达240 μm;小粒径乙氧基镁制备:m(Mg): V(CH3CH2OH): m(二氧化硅)、V(癸烷)=1 g:20 mL:0.05 g:2.5 mL 时,磁力搅拌速率 1000 r.min-1 三次投料等条件下可以制得堆密度为0.469 g.c-3、流动倾斜值tanδ为0.615、粒径d(0.5)=26.9 μm的乙氧基镁颗粒;催化剂制备:n(小粒径乙氧基镁):n(ED1)=1:0.25,m(小粒径乙氧基镁):V(TiCl4)=1 g:10 mL,滴钛速率为 0.5 mL·(support(g)·h)-1,可制得d(0.5)的为26.1μm的类球形催化剂,催化剂通过乙烯预聚合0.2(g PE/gCat)倍后(催化剂预聚后,其中聚乙烯质量含量为12-30%),在28/45 (氢气压力:0.28 MPa,乙烯压力:0.45 MPa)的条件下,催化效率可达17000(g PE/g Cat)倍,聚合物熔融指数(5 kg)为11.7 g·(10 min)-1,聚合物熔点为133.75 ℃,结晶度为77.8%,数均分子量为4.9×104,重聚分子量为2.83×105,分子量分布为指数为6.9。本文为乙氧基镁型催化剂的载体制备技术及催化剂制备技术提供了依据,为乙氧基镁负载型Ziegler-Natta催化剂的国产化做了准备。
[Abstract]:This research is devoted to promote the development of ethoxy magnesium supported polyethylene catalyst. The ethoxy magnesium supported polyethylene catalyst with excellent performance was prepared by using the ethoxy magnesium support and catalyst preparation technology as the breakthrough point. In the aspect of ethoxy magnesium carrier, it is reported that large particles of ethoxy magnesium can be prepared under the joint action of dioxosiloxane and decane, and a small amount of silica and decane can improve the comprehensive properties of small size ethoxy magnesium particles. Pentapentanol can effectively improve the bulk density and fluidity of small size magnesium ethoxy particles. In the aspect of catalyst preparation technology, ethylene polymerization catalyzed by ethoxy magnesium supported polyethylene catalyst was reported under the condition of industrial trial. However, after partial ethylene prepolymerization, after 28 / 45 (hydrogen pressure: 0. 28 MPa,) Under the condition of ethylene pressure: 0. 45 MPa), the catalytic efficiency of ethylene polymerization can reach 13700 (g PE/g Cat), and the catalytic efficiency of the catalyst can be increased to 17000 (gPE/gCat) after the addition of multi-element silane donor. The optimum preparation conditions are as follows: when the: m (Mg): V (CH3CH2OH): m (silica), V (decane is prepared by large particle ethoxy magnesium) = 1 g:30mL:0.2g:10mL, the bulk density of ethoxy magnesium, the flow tilt value tan 未, The particle size d _ (0.5) and the particle size distribution index were 3.42 g cm-3,0.719158.9 渭 m ~ (1.96), respectively. The d _ (0.5) of ethoxy magnesium particles prepared by mechanical stirring could reach 240 渭 m. Preparation of: m (Mg): V (CH3CH2OH): m (silica), V (decane with small particle size of ethoxy magnesium) = 1 g: 20 mL:0.05 g: 2.5 mL, Under the conditions of magnetic stirring rate of 1000 r.min-1, the agitation rate is 1000 r.min-1, the bulk density is 0.469 g 路c-3, the flow inclination value tan 未 is 0.615, and the particle size d (0.5) = 26.9 渭 m. : n (with small particle size of ethoxy magnesium (): n (ED1) = 1: 0.25m (): V (TiCl4 = 1 g: 10 mL,), the rate of titanium dropping is 0.5 mL (support (g) h) -1. A spherical catalyst with d (0.5) of 26.1 渭 m was prepared. The catalyst was prepared by ethylene prepolymerization (0.2 (g PE/gCat) times) (the mass content of polyethylene was 12-30% after the pre-polymerization of the catalyst). Under the conditions of 28 / 45 (hydrogen pressure: 0.28 MPa, ethylene pressure: 0.45 MPa), the catalytic efficiency is 17000 (g PE/g Cat), and the melt index (5 kg) of the polymer is 11.7g (10 min) -1. The melting point of the polymer is 133.75 鈩，
本文编号：2340012
[Abstract]:This research is devoted to promote the development of ethoxy magnesium supported polyethylene catalyst. The ethoxy magnesium supported polyethylene catalyst with excellent performance was prepared by using the ethoxy magnesium support and catalyst preparation technology as the breakthrough point. In the aspect of ethoxy magnesium carrier, it is reported that large particles of ethoxy magnesium can be prepared under the joint action of dioxosiloxane and decane, and a small amount of silica and decane can improve the comprehensive properties of small size ethoxy magnesium particles. Pentapentanol can effectively improve the bulk density and fluidity of small size magnesium ethoxy particles. In the aspect of catalyst preparation technology, ethylene polymerization catalyzed by ethoxy magnesium supported polyethylene catalyst was reported under the condition of industrial trial. However, after partial ethylene prepolymerization, after 28 / 45 (hydrogen pressure: 0. 28 MPa,) Under the condition of ethylene pressure: 0. 45 MPa), the catalytic efficiency of ethylene polymerization can reach 13700 (g PE/g Cat), and the catalytic efficiency of the catalyst can be increased to 17000 (gPE/gCat) after the addition of multi-element silane donor. The optimum preparation conditions are as follows: when the: m (Mg): V (CH3CH2OH): m (silica), V (decane is prepared by large particle ethoxy magnesium) = 1 g:30mL:0.2g:10mL, the bulk density of ethoxy magnesium, the flow tilt value tan 未, The particle size d _ (0.5) and the particle size distribution index were 3.42 g cm-3,0.719158.9 渭 m ~ (1.96), respectively. The d _ (0.5) of ethoxy magnesium particles prepared by mechanical stirring could reach 240 渭 m. Preparation of: m (Mg): V (CH3CH2OH): m (silica), V (decane with small particle size of ethoxy magnesium) = 1 g: 20 mL:0.05 g: 2.5 mL, Under the conditions of magnetic stirring rate of 1000 r.min-1, the agitation rate is 1000 r.min-1, the bulk density is 0.469 g 路c-3, the flow inclination value tan 未 is 0.615, and the particle size d (0.5) = 26.9 渭 m. : n (with small particle size of ethoxy magnesium (): n (ED1) = 1: 0.25m (): V (TiCl4 = 1 g: 10 mL,), the rate of titanium dropping is 0.5 mL (support (g) h) -1. A spherical catalyst with d (0.5) of 26.1 渭 m was prepared. The catalyst was prepared by ethylene prepolymerization (0.2 (g PE/gCat) times) (the mass content of polyethylene was 12-30% after the pre-polymerization of the catalyst). Under the conditions of 28 / 45 (hydrogen pressure: 0.28 MPa, ethylene pressure: 0.45 MPa), the catalytic efficiency is 17000 (g PE/g Cat), and the melt index (5 kg) of the polymer is 11.7g (10 min) -1. The melting point of the polymer is 133.75 鈩，
本文编号：2340012
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