Федеральное государственное бюджетное учреждение науки
Новосибирский институт органической химии им. Н.Н. Ворожцова
Сибирского отделения Российской академии наук

В журнале Polymers   (IF=3,426) опубликована статья с участием  д.х.н. И.И. Олейника и к.х.н. И.В. Олейник

 Post-functionalization of narrowly dispersed PE waxes generated using tuned N,N,N'-cobalt ethylene polymerization catalysts substituted with ortho-cycloalkyl groups

Hongyi Suo, Irina V.Oleynik, Ivan I.Oleynik, Gregory A.Solan, Yanping Ma, Tongling Liang, Wen-Hua Sun

Polymer, Volume 213, 20 January 2021, 123294




Six structurally related bis(arylimino)trihydroquinolyl-cobalt (II) chloride complexes [2-(ArNdouble bondCCH3)-8-(ArN)-5,6,7-C9H8N]CoCl2 (Ar = 2-(C5H9)-6-MeC6H3 Co1, 2-(C6H11)-6-MeC6H3 Co2, 2-(C8H15)-6-MeC6H3 Co3, 2-(C5H9)-4,6-Me2C6H2 Co4, 2-(C6H11)-4,6-Me2C6H2 Co5, 2-(C8H15)-4,6-Me2C6H2 Co6), distinguishable by the ring size of the ortho-cycloalkyl substituent and type of para-R group, have been synthesized and characterized. A distorted square pyramidal geometry is a feature of the molecular structure of Co4 with the two ortho-cyclopentyl groups located on neighboring N-aryl groups trans-configured. Compounds Co1 – Co6, on activation with methylaluminoxane (MAO) or modified MAO (MMAO), proved highly productive catalysts for ethylene polymerization at 60 °C [up to 17.1 × 106 g (PE) mol−1(Co) h−1 for cyclopentyl-containing Co4/MAO]; even at 90 °C significant activity was attainable (up to 6.75 × 106 g (PE) mol−1(Co) h−1). Strictly linear polyethylene waxes of low molecular weight (ca. 1.50 kg mol−1), narrow dispersity (Mw/Mn range: 1.1–2.4) and incorporating high levels of vinyl end-groups were generated. Post-functionalization of these PE waxes by epoxidation, thiol-ene addition and cross-olefin metathesis to form e-PE, PE-S-CH2CH2NH2·HCl and PE-MMA, respectively, has been demonstrated. For comparative purposes, [2-(ArNdouble bondCCH3)-8-ArN-5,6,7-C9H8N]CoCl2 (Ar = 2,4,6-Me3C6H2 Coo-Me, 2-(Ph2CH)-4,6-Me2C6H2 Coo-CHPh2) have also been prepared and evaluated as polymerization catalysts.


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