Extremely Active Ethylene Tetramerization Catalyst Avoiding the Use of MAO

DC Field Value Language
dc.contributor.advisor이분열-
dc.contributor.author박희수-
dc.date.accessioned2022-11-29T02:32:01Z-
dc.date.available2022-11-29T02:32:01Z-
dc.date.issued2020-02-
dc.identifier.other29906-
dc.identifier.urihttps://dspace.ajou.ac.kr/handle/2018.oak/19504-
dc.description학위논문(석사)--아주대학교 일반대학원 :분자과학기술학과,2020. 2-
dc.description.tableofcontentsAbstract Ⅰ 1. Introduction 1 2. Results and Discussion 2 2.1 Preparation of [(PNP)CrCl2]+[B(C6F5)4]– 2 2.2 Preparation of the PNP ligand bearing various -SiR3 substituents 12 2.3 Oligomerization studies with [(PNP)CrCl2]+[B(C6F5)4]– 13 3. Conclusions 15 4. Experimental Section 16 4.1 General remarks 16 4.2 Synthesis of ligands and complexes 16 4.3 Ethylene oligomerization 24 4.4 X-Ray crystallography 24 5. Reference 25 6. Supporting information 29-
dc.language.isoeng-
dc.publisherThe Graduate School, Ajou University-
dc.rights아주대학교 논문은 저작권에 의해 보호받습니다.-
dc.titleExtremely Active Ethylene Tetramerization Catalyst Avoiding the Use of MAO-
dc.title.alternativePark Hee soo-
dc.typeThesis-
dc.contributor.affiliation아주대학교 일반대학원-
dc.contributor.alternativeNamePark Hee soo-
dc.contributor.department일반대학원 분자과학기술학과-
dc.date.awarded2020. 2-
dc.description.degreeMaster-
dc.identifier.localId1138539-
dc.identifier.uciI804:41038-000000029906-
dc.identifier.urlhttp://dcoll.ajou.ac.kr:9080/dcollection/common/orgView/000000029906-
dc.subject.keyword1-octene production-
dc.subject.keywordPNP ligand derivative-
dc.subject.keywordchromium catalyst-
dc.subject.keywordethylene tetramerization-
dc.description.alternativeAbstractCritical issues raised in the Sasol's original ethylene tetramerization catalyst composed of Cr(acac)3, iPrN(PPh2)2 and MMAO (modified-methylaluminoxane) are the use of expensive MMAO, low working temperature around 60 °C, and generation of PE side product. Generation of polyethylene, though its amount is small, also poses a critical problem that is often referred to as 'fouling' of the operation of the continuous commercial process. In this work, we disclosed an upgraded catalytic system that avoids the use of MAO solving the issues. In precedent trials to prepare the catalyst precursors, [(PNP)CrCl2]+[B(C6F5)4]–-type species, the main product isolated was inactive bis(PNP)-CrIII complex ([(PNP)2CrCl2]+[B(C6F5)4]–). The targeted mono(PNP)-CrIII complex was obtained from CrCl3(THF)3, [PhN(H)Me2]+[B(C6F5)4]–, and iPrN[P(C6H4-p-Si(nBu)3]2 (2). The bulky (nBu)3Si-substituents in 2 play a crucial role, preventing the formation of the inactive bis(PNP)-CrIII species and hindering the rotation around P-N bonds to block demetallation process. The prepared species [2-CrCl2]+[B(C6F5)4]– combined with iBu3Al was extremely active (> 6000 Kg/g-Cr/h), worked well at a high temperature up to 90 °C, and generated a negligible amount of PE (0.03 wt%). The extremely active [2-CrCl2]+[B(C6F5)4]– was also prepared by simply reacting 2 and [CrCl2(NCCH3)4]+[B(C6F5)4]–. Screening the performance with a series of iPrN[P(C6H4-p-SiR3]2 (R3Si- = (nBu)3Si-, iPr3Si-, Et3Si-, Me3Si-, Et2(iPr)Si-, Me2(iPr)Si-, and Me2(1-octyl)Si-) further supported that bulky R3Si-substiuents are crucial not only to gain the extremely high activities but also to minimize generation of the problematic side product PE even at a high temperature.-
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Graduate School of Ajou University > Department of Molecular Science and Technology > 3. Theses(Master)
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