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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Cycloheptyl-fused N, N, N '-chromium catalysts with selectivity for vinyl-terminated polyethylene waxes: thermal optimization and polymer functionalization
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Cycloheptyl-fused N, N, N '-chromium catalysts with selectivity for vinyl-terminated polyethylene waxes: thermal optimization and polymer functionalization

机译:环蟾熔融N,N,N' - 具有选择性对乙烯基封端的聚乙烯蜡的选择性:热优化和聚合物官能化

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摘要

Five chromium(iii) chloride complexes, [2-{(Ar)N=CMe}-9-{N(Ar)}C10H10N]CrCl3 (Ar = 2,6-Me(2)C(6)H(3)Cr1, 2,6-Et(2)C(6)H(3)Cr2, 2,6-i-Pr(2)C(6)H(3)Cr3, 2,4,6-Me(3)C(6)H(2)Cr4, 2,6-Et-2-4-MeC(6)H(2)Cr5), each chelated by a sterically and electronically different cycloheptyl-fused N,N,N'-bis(imino)pyridine, have been synthesized by the reactions of CrCl3(THF)(3) with the corresponding ligand (L1/L1'-L5/L5'). The molecular structure of Cr2 highlights both the steric properties exerted by the inequivalent N-2,6-ethylphenyl groups and the puckering of the fused cycloheptyl ring; a distorted octahedral geometry is conferred about the metal center. On activation with methylaluminoxane (MAO) or modified MAO (MMAO), Cr1-Cr5 displayed their optimal activity for ethylene polymerization at temperatures between 70 and 80 degrees C with the least sterically demanding Cr1 proving the most productive (1.44 x 10(7) g (PE) per mol (Cr) per h). The polyethylenes formed are of low molecular weight (M-w range: 0.66-3.56 kg mol(-1)) with narrow molecular weight distributions and display high levels of end-group unsaturation. Furthermore, the amenability of these vinyl-terminated polyethylenes to undergo functionalization via epoxidation has been demonstrated.
机译:五种铬(III)氯化物配合物,[2 - {(Ar)n = Cme} -9- {n(Ar)} C10H10N] C1Cl 3(Ar = 2,6-Me(2)C(6)H(3) CR1,2,6-ET(2)C(6)H(3)Cr2,2,6-I-Pr(2)C(6)H(3)CR3,2,4,6-ME(3) C(6)H(2)CR4,2,6-ET-2-4-MEC(6)H(2)CR5),每次螯合在空间和电子不同的循环庚基稠合N,N,N'-BIS (亚氨基)吡啶,通过CRCl3(THF)(3)与相应配体的反应合成(L1 / L1'-L5 / L5')合成。 CR2的分子结构突出了不等价N-2,6-乙基苯基和熔融环庚绒铃的褶皱的施加的空间。令金属中心赋予扭曲的八面体几何形状。在用甲基铝氧烷(MAO)或改性的MAO(MMAO)的活化,CR1-CR5在70至80℃的温度下显示出它们的最佳活性,最低限度的CR1证明最有生产力(1.44 x 10(7)g (PE)每摩尔(CR))。形成的聚乙烯具有低分子量(M-W的范围:0.66-3.56kg摩尔(-1)),分子量分布窄,显示出高水平的末端组不饱和度。此外,已经证明了这些乙烯基封端的聚乙烯的易于性通过环氧化经历官能化。

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