Half-Metallocene Titanium(IV) Phenyl Phenoxide for High Temperature Olefin Polymerization: Ortho-Substituent Effect at Ancillary o-Phenoxy Ligand for Enhanced Catalytic Performance
DC Field | Value | Language |
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dc.contributor.author | Kim, Tae-Jin | - |
dc.contributor.author | Kim, Sung-Kwan | - |
dc.contributor.author | Kim, Beom-Jun | - |
dc.contributor.author | Hahn, Jong Sok | - |
dc.contributor.author | Ok, Myung-Ahn | - |
dc.contributor.author | Song, Jong Hee | - |
dc.contributor.author | Shin, Dae-Ho | - |
dc.contributor.author | Ko, Jaejung | - |
dc.contributor.author | Cheong, Minserk | - |
dc.contributor.author | Kim, Jin | - |
dc.contributor.author | Won, Hoshik | - |
dc.contributor.author | Mitoraj, Mariusz | - |
dc.contributor.author | Srebro, Monika | - |
dc.contributor.author | Michalak, Artur | - |
dc.contributor.author | Kang, Sang Ook | - |
dc.date.accessioned | 2021-06-23T15:03:35Z | - |
dc.date.available | 2021-06-23T15:03:35Z | - |
dc.date.created | 2021-01-21 | - |
dc.date.issued | 2009-09 | - |
dc.identifier.issn | 0024-9297 | - |
dc.identifier.uri | https://scholarworks.bwise.kr/erica/handle/2021.sw.erica/40884 | - |
dc.description.abstract | A series of mono- or dialkyl/lphenyl o-substituted phenoxy ligands in half-metallocene titanium(IV) complexes wits examined to determine the structure-catalytic activity relationship in high temperature olefin polymerization. Five different types of polymerization catalysts with different Cp/Cp* and mono- or disubstituted symmetric/asymmetric alkyl/phenyl phenoxide ancillary ligands were compared. This series wits examined for ethylene homopolymerization after activation with Ph3CB(C6F5)(4) and mMAO-7 at high temperatures (140 degrees C). Type 4 complexes of compounds 15-18 [33.0-39.0 kg/(mmol of Ti.h)] showed much higher catalytic activity than those found in types 1-3 and 5 [3.6-27.6 kg/(mmol of Ti.h)], and among the type 4 complexes, the Cp*/2-phenylphenoxy combination of compound 18 [39 kg/(mmol of Ti.h)] Surpassed the Cp*/2-alkyl ligand systems of compounds 15-17 [33.0-36.0 kg/(mmol of Ti.h)]. The revolving nature of the phenoxy ligand around the Ti-O-C axis was identified by the NOSEY correlation peaks between the methyl protons of Cp* and protons of ancillary phenyl phenoxy ligand in compound 18. The conformational flexibility of the phenyl phenoxy ligand was further confirmed by a series of temperature-dependent ROSEY experiments based oil the optimization of two conformational structures related by this rotation. Rotational barriers of 4.3 and 6.6 kcal/mol were estimated from theoretical DFT studies. DFT calculations of the transition states for ethylene insertion and termination were carried out for representative examples of types 4 (15,16, 18), 3 (10,12), and 1 (3) catalysts as well as the constrained geometry catalyst (CGC) its a reference. The preference for back-side insertion was a unique feature of the monosubstituted type 4 catalysts. The type 4 catalysts showed significant activities for ethylene/1-octene copolymerization affording high molecular weight poly(ethylene-co-1-octene)s (M-w = 107 000-164 000) with unimodal molecular weight distributions (M-w/M-n = 2.08-4.15). The activity increased in the order of type 3 [90-132 kg/(mmol of Ti.h), in toluene, ethylene 30 atm, 1-octene 8 mL, 140 degrees C, 10 min.] < CGC (222) < type 4 (228-354). Among the type 4 series, compound 18 showed the best performance, reaching an activity of 354 kg/(mmol of Ti.h). The polymer density of 0.9148 g/mL for compound 18 was lower than that found in CGC (0.9154 g/mL), indicating higher I-octene incorporation, which was further confirmed by an analysis of the C-13 NMR spectra of the polymers (18, 2.73 mol % and CGC, 2.55 mol %). | - |
dc.language | 영어 | - |
dc.language.iso | en | - |
dc.publisher | American Chemical Society | - |
dc.title | Half-Metallocene Titanium(IV) Phenyl Phenoxide for High Temperature Olefin Polymerization: Ortho-Substituent Effect at Ancillary o-Phenoxy Ligand for Enhanced Catalytic Performance | - |
dc.type | Article | - |
dc.contributor.affiliatedAuthor | Won, Hoshik | - |
dc.identifier.doi | 10.1021/ma901219a | - |
dc.identifier.scopusid | 2-s2.0-70349931821 | - |
dc.identifier.wosid | 000269699400016 | - |
dc.identifier.bibliographicCitation | Macromolecules, v.42, no.18, pp.6932 - 6943 | - |
dc.relation.isPartOf | Macromolecules | - |
dc.citation.title | Macromolecules | - |
dc.citation.volume | 42 | - |
dc.citation.number | 18 | - |
dc.citation.startPage | 6932 | - |
dc.citation.endPage | 6943 | - |
dc.type.rims | ART | - |
dc.type.docType | Article | - |
dc.description.journalClass | 1 | - |
dc.description.isOpenAccess | N | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Polymer Science | - |
dc.relation.journalWebOfScienceCategory | Polymer Science | - |
dc.subject.keywordPlus | D(0)F(N) TRANSITION-METALS | - |
dc.subject.keywordPlus | FOCK-SLATER CALCULATIONS | - |
dc.subject.keywordPlus | ETHYLENE POLYMERIZATION | - |
dc.subject.keywordPlus | CONSTRAINED GEOMETRY | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURE | - |
dc.subject.keywordPlus | UNIFIED VIEW | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | CYCLOPENTADIENYL | - |
dc.subject.keywordPlus | APPROXIMATION | - |
dc.subject.keywordPlus | ACTIVATION | - |
dc.subject.keywordAuthor | APPROXIMATION | - |
dc.subject.keywordAuthor | CONSTRAINED GEOMETRY | - |
dc.subject.keywordAuthor | D(0)F(N) TRANSITION-METALS | - |
dc.subject.keywordAuthor | CRYSTAL-STRUCTURE | - |
dc.subject.keywordAuthor | COMPLEXES | - |
dc.subject.keywordAuthor | KAMINSKY-TYPE CATALYSTS | - |
dc.subject.keywordAuthor | UNIFIED VIEW | - |
dc.subject.keywordAuthor | CYCLOPENTADIENYL | - |
dc.subject.keywordAuthor | FOCK-SLATER CALCULATIONS | - |
dc.subject.keywordAuthor | ETHYLENE POLYMERIZATION | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/ma901219a | - |
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