發(fā)布時(shí)間：2018-11-18 12:12

【摘要】：本研究致力于推動(dòng)國內(nèi)乙氧基鎂負(fù)載型聚乙烯催化劑的發(fā)展,以乙氧基鎂載體和催化劑制備技術(shù)為突破口,制備出了性能優(yōu)良乙氧基鎂負(fù)載型聚乙烯催化劑;在乙氧基鎂載體方面,公布了在二氧硅與癸烷的共同作用下可以制備大顆粒乙氧基鎂,同時(shí)少量的二氧化硅與癸烷能提高小粒徑乙氧基鎂顆粒的綜合性能,戊五醇能有效提高小粒徑乙氧基鎂顆粒的堆密度與流動(dòng)性能;在催化劑制備技術(shù)方面,公布了在工業(yè)小試的條件下,乙氧基鎂負(fù)載型聚乙烯催劑催化乙烯聚合,基本沒活性,但是通過預(yù)聚部分乙烯后,在28/45 (氫氣壓力:0.28 MPa,乙烯壓力:0.45 MPa)的條件下,催化劑催化乙烯聚合效率可達(dá)13700(g PE/g Cat)倍,添加多元素硅烷類給電子體后可將催化劑的催化效率提高至17000(gPE/gCat)倍。最佳制備條件:大顆粒乙氧基鎂制備:m(Mg): V(CH3CH2OH): m (二氧化硅)、V (癸烷)=1 g:30mL:0.2g:10mL時(shí),乙氧基鎂堆密度、流動(dòng)傾斜值tanδ、粒徑 d(0.5)及粒徑分布指數(shù)分別為 3.42 g·cm-3、0.719、158.9 μm、1.96,改用機(jī)械攪拌后可以制備的乙氧基鎂顆粒d(0.5)可達(dá)240 μm;小粒徑乙氧基鎂制備:m(Mg): V(CH3CH2OH): m(二氧化硅)、V(癸烷)=1 g:20 mL:0.05 g:2.5 mL 時(shí),磁力攪拌速率 1000 r.min-1 三次投料等條件下可以制得堆密度為0.469 g.c-3、流動(dòng)傾斜值tanδ為0.615、粒徑d(0.5)=26.9 μm的乙氧基鎂顆粒;催化劑制備:n(小粒徑乙氧基鎂):n(ED1)=1:0.25,m(小粒徑乙氧基鎂):V(TiCl4)=1 g:10 mL,滴鈦速率為 0.5 mL·(support(g)·h)-1,可制得d(0.5)的為26.1μm的類球形催化劑,催化劑通過乙烯預(yù)聚合0.2(g PE/gCat)倍后(催化劑預(yù)聚后,其中聚乙烯質(zhì)量含量為12-30%),在28/45 (氫氣壓力:0.28 MPa,乙烯壓力:0.45 MPa)的條件下,催化效率可達(dá)17000(g PE/g Cat)倍,聚合物熔融指數(shù)(5 kg)為11.7 g·(10 min)-1,聚合物熔點(diǎn)為133.75 ℃,結(jié)晶度為77.8%,數(shù)均分子量為4.9×104,重聚分子量為2.83×105,分子量分布為指數(shù)為6.9。本文為乙氧基鎂型催化劑的載體制備技術(shù)及催化劑制備技術(shù)提供了依據(jù),為乙氧基鎂負(fù)載型Ziegler-Natta催化劑的國產(chǎn)化做了準(zhǔn)備。
[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，

本文編號：2340012