Access to Ultra-High-Molecular Weight Poly(ethylene) and Activity Boost in the Presence of Cyclopentene With Group 4 Bis-Amido Complexes.
Access to Ultra-High-Molecular Weight Poly(ethylene) and Activity Boost in the Presence of Cyclopentene With Group 4 Bis-Amido Complexes.
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在环戊烯与第 4 族双酰胺复合物存在下获得超高分子量聚乙烯并提高活性
DOI：
10.1002/cplu.201300378
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发表时间：
2014
期刊：
影响因子：
3.4
通讯作者：
M. R. Buchmeiser
中科院分区：
文献类型：
--
作者：
G. V. Narayana;G. Xu. D. Wang;W. Frey;M. R. Buchmeiser
ZrIVcomplexes of the type [Me2Si{(NR)(6‐{2‐(diethylboryl)phenyl}pyridyl‐2‐yl‐N)}ZrCl2⋅thf] (R=tBu (4), adamantyl (7 a); thf=tetrahydrofuran), [Me2Si{(NAd)(6‐{2‐(diphenylboryl)phenyl}pyridyl‐2‐yl‐N)}ZrCl2] (Ad=adamantyl (7 b)), the nonbridged half‐titanocene complexes of the type [(N‐{6‐(2‐diethylborylphenyl)pyrid‐2‐yl}‐NR)Cp′TiCl2] (R=Me, Cp′=C5H5(12), Cp′=C5Me5(13)), and the titanium(IV)‐based metallocene‐type complex [bis{N‐(6‐{2‐(diethylboryl)phenyl}pyrid‐2‐yl)NMe}TiCl2] (14) have been synthesized. The structures of complexes7 b,12, and13were determined by single‐crystal X‐ray diffraction analysis. In solution, complex4slowly rearranges to [Me2Si{(N‐tBu)(6‐{2‐(diethylboryl)phenyl}pyridyl‐2‐yl‐N)}2Zr] (4 a), the structure of which was unambiguously confirmed by single‐crystal X‐ray crystallography. Similarly, reaction of HfCl4with Me2Si({RNLi}{6‐[2‐(diethylboryl)phenyl]pyridyl‐2‐ylNLi}) yielded the corresponding HfIVcomplexes [Me2Si{(NR)(6‐{2‐(diethylboryl)phenyl}pyridyl‐2‐ylN)}2Hf] (R=tBu (8) and Ad (9)). Upon activation of these complexes with methylalumoxane (MAO), complexes4,7 a, 7 b, and12–14showed activities up to 750 kg of polyethylene (PE)/molcat.bar h in the homopolymerization of ethylene (E), producing mainly linear PE (high‐density PE, HDPE) with molecular weights in the range of 1 800 000<Mn<4×106g mol−1. In the copolymerization of E with cyclopentene (CPE), the polymerization activities of complexes4,7 a, and7 bcan be enhanced by a factor of 140 up to 7500 kg PE/molcat.bar h, which produced PE‐co‐poly(CPE) containing 3.5 mol % of CPE. This dramatic increase in polymerization activity for E in the presence of CPE can be attributed to an involvement of CPE in the polymerization process rather than to solvent polarity.
ZrIVcomplexes of the type [Me2Si{(NR)(6‐{2‐(diethylboryl)phenyl}pyridyl‐2‐yl‐N)}ZrCl2⋅thf] (R=tBu (4), adamantyl (7 a); thf=tetrahydrofuran), [Me2Si{(NAd)(6‐{2‐(diphenylboryl)phenyl}pyridyl‐2‐yl‐N)}ZrCl2] (Ad=adamantyl (7 b)), the nonbridged half‐titanocene complexes of the type [(N‐{6‐(2‐diethylborylphenyl)pyrid‐2‐yl}‐NR)Cp′TiCl2] (R=Me, Cp′=C5H5(12), Cp′=C5Me5(13)), and the titanium(IV)‐based metallocene‐type complex [bis{N‐(6‐{2‐(diethylboryl)phenyl}pyrid‐2‐yl)NMe}TiCl2] (14) have been synthesized. The structures of complexes7 b,12, and13were determined by single‐crystal X‐ray diffraction analysis. In solution, complex4slowly rearranges to [Me2Si{(N‐tBu)(6‐{2‐(diethylboryl)phenyl}pyridyl‐2‐yl‐N)}2Zr] (4 a), the structure of which was unambiguously confirmed by single‐crystal X‐ray crystallography. Similarly, reaction of HfCl4with Me2Si({RNLi}{6‐[2‐(diethylboryl)phenyl]pyridyl‐2‐ylNLi}) yielded the corresponding HfIVcomplexes [Me2Si{(NR)(6‐{2‐(diethylboryl)phenyl}pyridyl‐2‐ylN)}2Hf] (R=tBu (8) and Ad (9)). Upon activation of these complexes with methylalumoxane (MAO), complexes4,7 a, 7 b, and12–14showed activities up to 750 kg of polyethylene (PE)/molcat.bar h in the homopolymerization of ethylene (E), producing mainly linear PE (high‐density PE, HDPE) with molecular weights in the range of 1 800 000<Mn<4×106g mol−1. In the copolymerization of E with cyclopentene (CPE), the polymerization activities of complexes4,7 a, and7 bcan be enhanced by a factor of 140 up to 7500 kg PE/molcat.bar h, which produced PE‐co‐poly(CPE) containing 3.5 mol % of CPE. This dramatic increase in polymerization activity for E in the presence of CPE can be attributed to an involvement of CPE in the polymerization process rather than to solvent polarity.
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{[(2,4,6-Me3C6H2NCH2CH2)2NMe]ZrR} 型阳离子中的 CH 键活化以及产生 1-己烯活性聚合催化剂的简单溶液
DOI：
--
发表时间：
2001
期刊：
影响因子：
--
作者：
R. Schrock;and Peter J. Bonitatebus;Yann Schrodi
通讯作者：
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影响因子：
5.4
作者：
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DOI：
--
发表时间：
1996
期刊：
影响因子：
--
作者：
S. Tinkler;R. Deeth;D. Duncalf;A. Mccamley
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带有 6-[2-(二乙基硼基)苯基]吡啶-2-基基序的第 4 族二甲基亚甲硅基双酰胺配合物：合成及其在环状烯烃与乙烯的串联开环复分解/乙烯基插入共聚中的应用。
影响因子：
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作者：
Y. Zou;Dongren Wang;K. Wurst;Christa Kühnel;I. Reinhardt;U. Decker;V. Gurram;Sebnem Camadanli;M. Buchmeiser
通讯作者：
M. Buchmeiser
影响因子：
16.6
作者：
Buchmeiser, Michael R.;Camadanli, Sebnem;Reinhardt, Ingrid
通讯作者：
Reinhardt, Ingrid