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Cycloheptyl-fused NNO-ligands as electronically modifiable supports for M(II) (M=Co, Fe) chloride precatalysts; probing performance in ethylene oligo-/polymerization
Bariashir, Chantsalnyam1,2,3,4; Wang, Zheng1,2,3,4; Du, Shizhen1,2; Solan, Gregory A.1,2,5; Huang, Chuanbing1,2,3,4; Liang, Tongling1,2; Sun, Wen-Hua1,2,3,4,6
2017-12-15
Source PublicationJOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume55Issue:24Pages:3980-3989
AbstractThe N,N,O-cobalt(II), [2,3-{C4H8C(NAr)}:5,6-{C4H8C(O)}C5HN]CoCl2 (Ar=2,6-(CHPh2)(2)-4-MeC6H2 Co1, 2,6-(CHPh2)(2)-4-EtC6H2 Co2, 2,6-(CHPh2)(2)-4-ClC6H2 Co3, 2,6-(CHPh2)(2)-4-FC6H2 Co4) and N,N,O-iron(II) complexes, [2,3-{C4H8C(NAr)}:5,6-{C4H8C(O)}C5HN]FeCl2 (Ar=2,6-(CHPh2)(2)-4-MeC6H2 Fe1, 2,6-(CHPh2)(2)-4-EtC6H2 Fe2, 2,6-(CHPh2)(2)-4-ClC6H2 Fe3, 2,6-(CHPh2)(2)-4-FC6H2 Fe4), each containing one sterically enhanced but electronically modifiable N-2,6-dibenzhydryl-4-R-2-phenyl group, have been prepared by a one-pot template approach using ,-dioxo-2,3:5,6-bis(pentamethylene)pyridine, the corresponding aniline along with the respective cobalt or iron salt in acetic acid. Distorted square pyramidal geometries are a feature of the molecular structures of Co1-Co4. Upon activation with MAO or MMAO, Co1-Co4 show good activities (up to 2.2 x 10(5) g mol(-1)(Co) h(-1)) affording short chain oligomers (C-4-C-30) with good -olefin selectivity. By contrast, Fe1-Fe4, in the presence of MMAO, displayed moderate activities (up 10.9 x 10(4) g(PE) mol(-1)(Fe) h(-1)) for ethylene polymerization forming low-molecular-weight linear polymers (up to 13.0kgmol(-1)) incorporating saturated n-propyl and i-butyl chain ends. For both cobalt and iron, the precatalysts incorporating the more electron withdrawing 4-R-2-substituents [Cl (Co3/Fe3), F (Co4/Fe4)] deliver the best catalytic activities, while with cobalt, these types of substituents additionally broaden the oligomeric distribution. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3980-3989
KeywordCoordination Polymerization Alpha-imino-oxo-2 Metal-organic Catalysts 3:5 Oligomers 6-bis(Pentamethylene)Pyridine Polyethylene
Indexed BySCI
Language英语
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/39100
Collection工程塑料实验室
Affiliation1.Chinese Acad Sci, Key Lab Engn Plast, Inst Chem, Beijing 100190, Peoples R China
2.Chinese Acad Sci, Beijing Natl Lab Mol Sci, Inst Chem, Beijing 100190, Peoples R China
3.Univ Chinese Acad Sci, CAS Res Educ Ctr Excellence Mol Sci, Beijing 100049, Peoples R China
4.Univ Chinese Acad Sci, Int Sch, Beijing 100049, Peoples R China
5.Univ Leicester, Dept Chem, Univ Rd, Leicester LE1 7RH, Leics, England
6.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Gansu, Peoples R China
Recommended Citation
GB/T 7714
Bariashir, Chantsalnyam,Wang, Zheng,Du, Shizhen,et al. Cycloheptyl-fused NNO-ligands as electronically modifiable supports for M(II) (M=Co, Fe) chloride precatalysts; probing performance in ethylene oligo-/polymerization[J]. JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY,2017,55(24):3980-3989.
APA Bariashir, Chantsalnyam.,Wang, Zheng.,Du, Shizhen.,Solan, Gregory A..,Huang, Chuanbing.,...&Sun, Wen-Hua.(2017).Cycloheptyl-fused NNO-ligands as electronically modifiable supports for M(II) (M=Co, Fe) chloride precatalysts; probing performance in ethylene oligo-/polymerization.JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY,55(24),3980-3989.
MLA Bariashir, Chantsalnyam,et al."Cycloheptyl-fused NNO-ligands as electronically modifiable supports for M(II) (M=Co, Fe) chloride precatalysts; probing performance in ethylene oligo-/polymerization".JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 55.24(2017):3980-3989.
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