Ziegler-Natta催化剂制备超高相对分子质量聚1-辛烯
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摘要
选取了取代基不同的1,3-二醇酯作为Ziegler-Natta催化剂的内给电子体,在硅油中催化1-辛烯聚合,利用GPC考察了聚合条件对催化剂性能的影响。实验结果表明,低温下聚合得到的聚1-辛烯的相对分子质量在10~6以上,符合作为减阻剂的聚α-烯烃的要求。在制备超高相对分子质量聚1-辛烯时,催化剂的浓度不能太高,尽量使聚合速率缓慢以提高聚合物的相对分子质量。在一定范围内提高铝钛摩尔比能有效提高催化剂活性,但会造成聚1-辛烯相对分子质量的下降。适当降低反应体系温度能提高聚1-辛烯的相对分子质量,但不宜过低。以1,3-二醇酯为内给电子体的Ziegler-Natta催化剂在-10℃左右制备超高相对分子质量聚1-辛烯较适宜。
Ziegler-Natta catalysts with 1,3-glycol esters having different substituents as internal electron donors were used to catalyze the polymerization of 1-octene in silicone oil,and the effects of polymerization conditions on the performance of the catalyst were investigated by GPC. The results showed that the poly(1-octene) prepared at a low temperature,of which the relative molecular weight was above 10~6,could meet the requirement on poly(alpha-olefin) as a drag reducing agent. When the super-high M_W poly(1-octene) was prepared,light concentration of the catalyst was preferred to make the polymerization rate slow as much as possible so as to increase the M_W of the polymer. Raising the Al/Ti molar ratio within a certain range could effectively improve the activity of the catalyst,but would cause reduction of the M_W of the poly(1-octene). Appropriately reducing the temperature of the reduction system could increase the M_W of the poly(1-octene). The temperature,however,should not be too low. Moreover,a temperature around-10 ℃ would be the best for preparation of super-high relative molecular weight poly(1-octene) in the presence of the Ziegler-Natta catalysts with 1,3-glycol esters as the internal electron donors.
Ziegler-Natta catalysts with 1,3-glycol esters having different substituents as internal electron donors were used to catalyze the polymerization of 1-octene in silicone oil,and the effects of polymerization conditions on the performance of the catalyst were investigated by GPC. The results showed that the poly(1-octene) prepared at a low temperature,of which the relative molecular weight was above 10~6,could meet the requirement on poly(alpha-olefin) as a drag reducing agent. When the super-high M_W poly(1-octene) was prepared,light concentration of the catalyst was preferred to make the polymerization rate slow as much as possible so as to increase the M_W of the polymer. Raising the Al/Ti molar ratio within a certain range could effectively improve the activity of the catalyst,but would cause reduction of the M_W of the poly(1-octene). Appropriately reducing the temperature of the reduction system could increase the M_W of the poly(1-octene). The temperature,however,should not be too low. Moreover,a temperature around-10 ℃ would be the best for preparation of super-high relative molecular weight poly(1-octene) in the presence of the Ziegler-Natta catalysts with 1,3-glycol esters as the internal electron donors.
引文
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[2]Mowla D,Naderi A.Experimental study of drag reduction by a polymeric additive in slug two-phase flow of crude oil and air in horizontal pipes[J].Chem Eng Sci,2006,61(5):1549-1554.
[3]杨玉琴,郑文耀,李秀贞,等.输油管道用聚α-烯烃类减阻剂的研究进展[J].信息记录材料,2012,13(6):26-31.
[4]马玄,岳前升,吴洪特,等.国内外水力压裂减阻剂研究进展及展望[J].中外能源,2014,19(12):32-36.
[5]Wang Yo,Yu Bo,Zakin J L,et al.Review on drag reduction and its heat transfer by additives[J].Doi:10.1155/2011/478749.
[6]刘长圣,李惠萍,胡子昭,等.长链α-烯烃本体聚合制备油溶性减阻剂的研究[J].当代化工,2011,40(11):1133-1136.
[7]邢文国,张长桥,于萍,等.Polymerization mechanism ofα-linear olefin[J].化学物理学报,2010,23(1):39-44.
[8]Echevskaya L,Matsko M,Nikolaeva M,et al.Kinetic features of hexane-1 polymerization over supported titaniummagnesium catalyst[J].Macromol React Eng,2015,8(9):666-672.
[9]中国石油化工股份有限公司北京化工研究院.用于烯烃聚合反应的催化剂组分及其催化剂:1453298 A[P].2003-11-05.
[10]洪定一.聚丙烯——原理、工艺与技术[M].北京:中国石化出版社,2002.
[11]Kaminsky W.Polyolefins:50 Years after Ziegler and Natta I[M].Heidelberg:Springer,2013:99-134.
[12]Yang Hongrui,Zhang Letian,Zang Dandan,et al.Effects of alkylaluminum as cocatalyst on the active center distribution of1-hexene polymerization with Mg Cl2-supported Ziegler–Natta catalysts[J].Catal Commun,2015,62:104-106.
[13]Natta G,Pasquon I.The kinetics of the stereospecific polymerization ofα-olefins[J].Adv Catal,1959,11:1-66.
[14]Soga K,Shiono T.Ziegler-Natta catalysts for olefin polymerizations[J].Prog Polym Sci,1997,22(7):1503-1546.
[15]Li Hongbo,Li Liting,Marks T J,et al.Catalyst/cocatalyst nuclearity effects in single-site olefin polymerization.Significantly enhanced 1-octene and isobutene comonomer enchainment in ethylene polymerizations mediated by binuclear catalysts and cocatalysts[J].J Am Chem Soc,2003,125(36):10788-10789.