中文版 | English
Title

Norbornene Monomer Effects and Mechanistic Insights in Binuclear Nickel-Catalyzed Olefin Chain Walking Copolymerizations

Author
Corresponding AuthorZhou, You-Yun; Tang, Yong
Publication Years
2023-09-18
DOI
Source Title
ISSN
2155-5435
Volume13Issue:19
Abstract
Chain walking is a unique process in late transition metal-catalyzed ethylene (alpha-olefin) polymerizations and can be modulated to achieve control over polyolefin branch type, density, topology, branch stereochemistry, and so on, most of which are unattainable without chain walking. Introducing a second monomer could perturb the chain walking process and afford copolymers with unique microstructures. Here, we report the effects of norbornene (NBE) monomer, which is ring strained and cannot undergo chain walking, in binuclear Ni complex-catalyzed ethylene or alpha-olefin chain walking copolymerization, and have observed significantly reduced molecular weight, promoted chain transfer, suppressed branching, and the appearance of characteristic olefinic end groups versus their respective homopolymerizations. In contrast, the M-w of the NBE copolymers was reduced by 8.6, 9.4, and 16.4 times for ethylene, propylene, and 1-hexene, respectively. The chain transfer was confirmed by significantly increased chains/catalyst numbers in the copolymerizations, by 15.4, 85.1, and 27.1 times versus homopolymerizations, respectively. While various alkyl branches were generated in ethylene and alpha-olefin homopolymerization, their NBE copolymers showed much reduced branch density and predominant long chain branches. Olefinic end groups also appeared, predominantly norbornyl-linked vinyl (V-N) for ethylene copolymer, alkyl-linked vinyl (V-E), and vinylene for both propylene and 1-hexene copolymers, suggesting beta-H elimination/transfer after ethylene enchainment or propylene/1-hexene 2,1-enchainment. The copolymers' glass transitions could be broadly tuned from 109 to 326 C-degrees with linear relationships against the NBE content and the slopes depending on the monomer type and reaction temperature, indicating a random and uniform distribution of the enchained comonomer. Furthermore, the mechanistic scenarios for the distinctive NBE monomer effects on chain walking, chain growth, and chain transfer were proposed based on DFT studies, confirming the experimental findings.
Keywords
URL[Source Record]
Indexed By
Language
English
SUSTech Authorship
Corresponding
Funding Project
National Natural Science Foundation of China["U19B6001","22101041"] ; Southern University of Science and Technology Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; National Key R&D Program of China[2021YFA1501700]
WOS Research Area
Chemistry
WOS Subject
Chemistry, Physical
WOS Accession No
WOS:001070763400001
Publisher
Data Source
Web of Science
Citation statistics
Document TypeJournal Article
Identifierhttp://kc.sustech.edu.cn/handle/2SGJ60CL/582945
DepartmentShenzhen Grubbs Institute
理学院_化学系
Affiliation
1.Sichuan Univ, Coll Polymer Sci & Engn, State Key Lab Polymer Mat Engn, Chengdu 610065, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
5.Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China
First Author AffilicationShenzhen Grubbs Institute;  Department of Chemistry;  Southern University of Science and Technology
Corresponding Author AffilicationShenzhen Grubbs Institute;  Department of Chemistry;  Southern University of Science and Technology
First Author's First AffilicationShenzhen Grubbs Institute
Recommended Citation
GB/T 7714
Qu, Bingxin,Zhao, Yanan,Song, Ping,et al. Norbornene Monomer Effects and Mechanistic Insights in Binuclear Nickel-Catalyzed Olefin Chain Walking Copolymerizations[J]. ACS CATALYSIS,2023,13(19).
APA
Qu, Bingxin.,Zhao, Yanan.,Song, Ping.,Gao, Yanshan.,Zhou, You-Yun.,...&Tang, Yong.(2023).Norbornene Monomer Effects and Mechanistic Insights in Binuclear Nickel-Catalyzed Olefin Chain Walking Copolymerizations.ACS CATALYSIS,13(19).
MLA
Qu, Bingxin,et al."Norbornene Monomer Effects and Mechanistic Insights in Binuclear Nickel-Catalyzed Olefin Chain Walking Copolymerizations".ACS CATALYSIS 13.19(2023).
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