ⅣB、Ⅷ族金属配合物体系催化乙烯齐聚合成直链低碳α-烯烃的研究
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摘要
直链低碳α-烯烃是生产线性低密度聚乙烯和高密度聚乙烯的共聚单体，国内外的需求量大，但目前国内尚无乙烯齐聚法工业化生产α-烯烃。为了形成具有我国独立知识产权的技术，本文研究了ⅣB族和Ⅷ族金属配合物催化乙烯齐聚制备α-烯烃的反应。
探讨了(Ind)_ZrCl_2，(1-η~5-But-Ind)_2ZrCl_2，(η~5-4,7-Me_2-Ind)_2ZrCl_2与Et_2AlCl组成的催化体系对乙烯齐聚的催化作用，发现它们都具有中等的催化活性和较高的低碳α-烯烃选择性。当茚基上烷基取代基数增多，催化活性增加；茚基上取代基体积增大，低碳α-烯烃的选择性提高。考察了(η~5-4,7-Me_2-Ind)_2ZrR_2(R=Me、CH_2Ph，Ph)／Et_2AlCl体系对乙烯齐聚的催化作用。研究结果表明，(η~3-4,7-Me_2-Ind)_2ZrCl_2／Et_2AlCl催化体系的性能最好，在最佳反应条件下，催化活性为1714g／g·Zr·h, C_(4-10)烯烃选择性为97.6％，线性C_(4-10) α烯烃选择性为90.3％。
研究了(C_6H_(4-o-)R-N=C-C_6H_(4-o)-O-)_2ZrCl_2(R=Me、H、CL)/Et_2AlCl体系催化乙烯齐聚合成低碳α-烯烃的反应。发现催化剂的活性顺序为R=Me＞R=H＞R=Cl。在反应温度为120℃时，(C_6H_(4-o-)Me-N=C-C_6H_(4-o-)O-)_2ZrCl_2/Et_2AlCl的催化活性为5590g/g·Zr·h，(C_(4-10))~=的选择性为96.4％，1-C_(4-10)~=的选择性为91.2％。
研究了(dppe)MCl_2[M=Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)]／EAO体系对乙烯齐聚的催化作用。在反应温度为200℃时，(dppe)CoCl_2／EAO催化乙烯齐聚的活性为4021g／g·Co·h，C_(4-10)烯烃选择性为95.5％，1-C_(4-10)~=的选择性为为75.4％。(dPPP)MCl_2[M=Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)]／EAO也能催化乙烯齐聚。在相同的反应条件下，五元环比六元环金属配合物的催化活性稍高。
考察了在双齿膦配合物／EAO催化体系中加入三苯基膦和1，2-双(二苯基膦基)乙烷对乙烯齐聚活性和选择性的影响。
研究了二价金属配合物：(bipy)CoCl_2；(C_6H_4-o-R-N=C-C_6H_4-o-O-)_2M(M=Fe、Co)；(acac)_2Co与EAO组成的体系对乙烯齐聚的催化作用。结果表明，双齿氮的配合物催化活性最高。在反应温度为180℃时，催化活性为2441g／g·Co·h，低碳烯烃的选择性为95.9％。
对（＊po）＊CI＊白紫夕光谱牙穆乡 堡勺谱的 表亏，认为催化齐的活性。上心是
阳离子的Npo厂丫。采用半经验分于轨道P＊3方法计算了韩钻配合物的结构
和电荷参数，井与催化剂的催化性能相关联，也验证了催化活性中心的阴离于
性质。对于含有相同煎环的烷基任以SI化剂，具有相同的催化活性中。0。
Linear low carbon a-olefins are used primarily as comonomers for production of linear low-density polyethylene and high-density polyethylene. There are great, demands of comonomers in the world, but until now there is no modern a-olefin industry in our country. In this dissertation, the linear low carbon olefins have been synthesized using ethylene oligomerization catalyzed by. ⅦB and Ⅷ complexes.
The catalytic performance of (Ind)_2ZrCl_2, (n~(5)-l-But-Ind)_2ZrCl_2 (n~(5)-4,7-Me_2-Ind)_2ZrCl_2 complexes with EtiAlCl as co-catalyst has been studied. They displayed medium catalytic activity and high selectivity to low a-olefms. Introducing electron donor group into an indene ligand increased the catalytic activity, however the selectivity of linear low a-olefins was enhanced with the bulky group.
The ethylene oligomerization catalyzed by a series of alkyl coordinating zirconium complexes, such as (n~(5)-4,7-Me_2-Ind)_2ZrMe_2
(n~(5)-4,7-Me_2-Ind)_2Zr(CH_(2)Ph)_2 and (n_(5)-4,7-Me_2-Ind)_2ZrPh_2 with Et_2AlCl, was studied The results showed that (n~(5)-4,7-Me_2-Ind)_2ZrCl_2/ Et_2AlCl was the best one with the catalytic activity of 1714 g/g.Zr.h, selectivities of C~(=)_(4-10) and linear l-C~(=)_(4-10) are 97.6% and 90.3% respectively, on the optimal conditions.
Preliminary results indicated that ethylene oligomerization was catalyzed by (C_6H_4-0-R-N=C-C_6H_4-0-O-)_2ZrCl_2(R=-Me, -H, -Cl)/Et_2AlCl. The effect of R in complexes has the following order: R=Me > R=H > R=Cl. The best catalyst war: (C6H4-o-Me-N=C-C6H4-o-O-)2ZrCl2/Et2AlCl with the catalytic activity of 5590p/ g-Zr-h, and the selectivities of C4-io~ and linear l-C4-io~ up to 96.4% and 91.2%.
The catalytic behavior of (dppe)MCl2(M= Fe( II), Co(II) , Ni( II) )/EAO k. ethylene oligomerization has been studied. The results showed that these catalytic systems have medium catalytic activity and high selectivity to low carbon olefins. The catalytic activity of (dppe)CoCl_2/EAO was 4021 g / g.Co. h with the selectivity of 95.5% to C_(4-10)lefins and 75.4% to linear C_(4-10) a-olefms at 200℃. The catalytio
systems of (dppp)FeCl_2, (dppp)CoCl_2 and (dppp)NiCl_2 with EAO displayed the similar behavior, but the catalytic activity of the complex with a six-membered ring was slightly lower than that with a five-membered ring under the same reaction conditions.
The effect of adding of Ph_3P or dppe as a third-component for the catalytic system of (dppe)MCl_2/EAO (M= Fe(Ⅱ) , Co(Ⅱ) > Ni(Ⅲ) on ethylene oligomerization has been studied.
The catalytic performance of (bipy)CoCl_2, (C_6H_4-o-R-N=C-C_6H_4-o-O-)_2M (M= Fe,Co) and (acac)_2Co with EAO as co-catalyst for ethylene oligomerization has been studied. The results showed that the catalytic activity of (bipy)CoCl_2/EAO was 2441g/g.Co.h, which is the highest one with selectivity of 95.9% to C_(4-10) olefins at 1807
The catalytic center of (dppe)FeCl_2/EAO was characterized by UV and Mossbauer spectrum. The information of cationic (dppe)Fe+Et has been observed. The construction data of zirconocenes were investigated by molecular mechanics and molecular orbital models, and were correlated to the catalytic performance. A cationic mechanism of ethylene oligomerization was suggested.
探讨了(Ind)_ZrCl_2，(1-η~5-But-Ind)_2ZrCl_2，(η~5-4,7-Me_2-Ind)_2ZrCl_2与Et_2AlCl组成的催化体系对乙烯齐聚的催化作用，发现它们都具有中等的催化活性和较高的低碳α-烯烃选择性。当茚基上烷基取代基数增多，催化活性增加；茚基上取代基体积增大，低碳α-烯烃的选择性提高。考察了(η~5-4,7-Me_2-Ind)_2ZrR_2(R=Me、CH_2Ph，Ph)／Et_2AlCl体系对乙烯齐聚的催化作用。研究结果表明，(η~3-4,7-Me_2-Ind)_2ZrCl_2／Et_2AlCl催化体系的性能最好，在最佳反应条件下，催化活性为1714g／g·Zr·h, C_(4-10)烯烃选择性为97.6％，线性C_(4-10) α烯烃选择性为90.3％。
研究了(C_6H_(4-o-)R-N=C-C_6H_(4-o)-O-)_2ZrCl_2(R=Me、H、CL)/Et_2AlCl体系催化乙烯齐聚合成低碳α-烯烃的反应。发现催化剂的活性顺序为R=Me＞R=H＞R=Cl。在反应温度为120℃时，(C_6H_(4-o-)Me-N=C-C_6H_(4-o-)O-)_2ZrCl_2/Et_2AlCl的催化活性为5590g/g·Zr·h，(C_(4-10))~=的选择性为96.4％，1-C_(4-10)~=的选择性为91.2％。
研究了(dppe)MCl_2[M=Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)]／EAO体系对乙烯齐聚的催化作用。在反应温度为200℃时，(dppe)CoCl_2／EAO催化乙烯齐聚的活性为4021g／g·Co·h，C_(4-10)烯烃选择性为95.5％，1-C_(4-10)~=的选择性为为75.4％。(dPPP)MCl_2[M=Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)]／EAO也能催化乙烯齐聚。在相同的反应条件下，五元环比六元环金属配合物的催化活性稍高。
考察了在双齿膦配合物／EAO催化体系中加入三苯基膦和1，2-双(二苯基膦基)乙烷对乙烯齐聚活性和选择性的影响。
研究了二价金属配合物：(bipy)CoCl_2；(C_6H_4-o-R-N=C-C_6H_4-o-O-)_2M(M=Fe、Co)；(acac)_2Co与EAO组成的体系对乙烯齐聚的催化作用。结果表明，双齿氮的配合物催化活性最高。在反应温度为180℃时，催化活性为2441g／g·Co·h，低碳烯烃的选择性为95.9％。
对（＊po）＊CI＊白紫夕光谱牙穆乡 堡勺谱的 表亏，认为催化齐的活性。上心是
阳离子的Npo厂丫。采用半经验分于轨道P＊3方法计算了韩钻配合物的结构
和电荷参数，井与催化剂的催化性能相关联，也验证了催化活性中心的阴离于
性质。对于含有相同煎环的烷基任以SI化剂，具有相同的催化活性中。0。
Linear low carbon a-olefins are used primarily as comonomers for production of linear low-density polyethylene and high-density polyethylene. There are great, demands of comonomers in the world, but until now there is no modern a-olefin industry in our country. In this dissertation, the linear low carbon olefins have been synthesized using ethylene oligomerization catalyzed by. ⅦB and Ⅷ complexes.
The catalytic performance of (Ind)_2ZrCl_2, (n~(5)-l-But-Ind)_2ZrCl_2 (n~(5)-4,7-Me_2-Ind)_2ZrCl_2 complexes with EtiAlCl as co-catalyst has been studied. They displayed medium catalytic activity and high selectivity to low a-olefms. Introducing electron donor group into an indene ligand increased the catalytic activity, however the selectivity of linear low a-olefins was enhanced with the bulky group.
The ethylene oligomerization catalyzed by a series of alkyl coordinating zirconium complexes, such as (n~(5)-4,7-Me_2-Ind)_2ZrMe_2
(n~(5)-4,7-Me_2-Ind)_2Zr(CH_(2)Ph)_2 and (n_(5)-4,7-Me_2-Ind)_2ZrPh_2 with Et_2AlCl, was studied The results showed that (n~(5)-4,7-Me_2-Ind)_2ZrCl_2/ Et_2AlCl was the best one with the catalytic activity of 1714 g/g.Zr.h, selectivities of C~(=)_(4-10) and linear l-C~(=)_(4-10) are 97.6% and 90.3% respectively, on the optimal conditions.
Preliminary results indicated that ethylene oligomerization was catalyzed by (C_6H_4-0-R-N=C-C_6H_4-0-O-)_2ZrCl_2(R=-Me, -H, -Cl)/Et_2AlCl. The effect of R in complexes has the following order: R=Me > R=H > R=Cl. The best catalyst war: (C6H4-o-Me-N=C-C6H4-o-O-)2ZrCl2/Et2AlCl with the catalytic activity of 5590p/ g-Zr-h, and the selectivities of C4-io~ and linear l-C4-io~ up to 96.4% and 91.2%.
The catalytic behavior of (dppe)MCl2(M= Fe( II), Co(II) , Ni( II) )/EAO k. ethylene oligomerization has been studied. The results showed that these catalytic systems have medium catalytic activity and high selectivity to low carbon olefins. The catalytic activity of (dppe)CoCl_2/EAO was 4021 g / g.Co. h with the selectivity of 95.5% to C_(4-10)lefins and 75.4% to linear C_(4-10) a-olefms at 200℃. The catalytio
systems of (dppp)FeCl_2, (dppp)CoCl_2 and (dppp)NiCl_2 with EAO displayed the similar behavior, but the catalytic activity of the complex with a six-membered ring was slightly lower than that with a five-membered ring under the same reaction conditions.
The effect of adding of Ph_3P or dppe as a third-component for the catalytic system of (dppe)MCl_2/EAO (M= Fe(Ⅱ) , Co(Ⅱ) > Ni(Ⅲ) on ethylene oligomerization has been studied.
The catalytic performance of (bipy)CoCl_2, (C_6H_4-o-R-N=C-C_6H_4-o-O-)_2M (M= Fe,Co) and (acac)_2Co with EAO as co-catalyst for ethylene oligomerization has been studied. The results showed that the catalytic activity of (bipy)CoCl_2/EAO was 2441g/g.Co.h, which is the highest one with selectivity of 95.9% to C_(4-10) olefins at 1807
The catalytic center of (dppe)FeCl_2/EAO was characterized by UV and Mossbauer spectrum. The information of cationic (dppe)Fe+Et has been observed. The construction data of zirconocenes were investigated by molecular mechanics and molecular orbital models, and were correlated to the catalytic performance. A cationic mechanism of ethylene oligomerization was suggested.
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