SYNTHESIS AND CHARACTERIZATION OF FLUORO-SUBSTITUTED β-ENAMINOKETONATO TITANIUM COMPLEXES AND THEIR CATALYTIC BEHAVIOR OF REGIOSELECTIVE ETHYLENE/CYCLOPENTADIENE COPOLYMERIZATION
Special Issue: Coordination Polymerization of Olefins|Updated:2023-01-03
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SYNTHESIS AND CHARACTERIZATION OF FLUORO-SUBSTITUTED β-ENAMINOKETONATO TITANIUM COMPLEXES AND THEIR CATALYTIC BEHAVIOR OF REGIOSELECTIVE ETHYLENE/CYCLOPENTADIENE COPOLYMERIZATION
Chinese Journal of Polymer ScienceVol. 31, Issue 4, Pages: 574-582(2013)
Affiliations:
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
Yan-guo Li, Miao Hong, Gui-bao Zhang, et al. SYNTHESIS AND CHARACTERIZATION OF FLUORO-SUBSTITUTED β-ENAMINOKETONATO TITANIUM COMPLEXES AND THEIR CATALYTIC BEHAVIOR OF REGIOSELECTIVE ETHYLENE/CYCLOPENTADIENE COPOLYMERIZATION[J]. Chinese Journal of Polymer Science, 2013, 31(4): 574-582. DOI: 10.1007/s10118-013-1249-0.
DOI:
Yan-guo Li, Miao Hong, Gui-bao Zhang, et al. SYNTHESIS AND CHARACTERIZATION OF FLUORO-SUBSTITUTED β-ENAMINOKETONATO TITANIUM COMPLEXES AND THEIR CATALYTIC BEHAVIOR OF REGIOSELECTIVE ETHYLENE/CYCLOPENTADIENE COPOLYMERIZATION[J]. Chinese Journal of Polymer Science, 2013, 31(4): 574-582. DOI: 10.1007/s10118-013-1249-0.DOI:
SYNTHESIS AND CHARACTERIZATION OF FLUORO-SUBSTITUTED β-ENAMINOKETONATO TITANIUM COMPLEXES AND THEIR CATALYTIC BEHAVIOR OF REGIOSELECTIVE ETHYLENE/CYCLOPENTADIENE COPOLYMERIZATION
The ethylene/cyclopentadiene (CPD) copolymerization behavior by using fluoro-substituted bis(
β
-enaminoketonato) titanium complexes [FC
6
H
4
NC(CH
3
)CHCO(CF
3
)]
2
TiCl
2
(
1a−1c
) has been investigated in detail. Upon utilizing MMAO as a cocatalyst
complexes
1a−1c
exhibit high catalytic activities
affording the copolymers with high molecular weight and unimodal molecular weight distribution. Compared with non-substituted complex [C
6
H
5
NC(CH
3
)CHCO(CF
3
)]
2
TiCl
2
(
1
)
complexes
1a−1c
can produce the copolymers with CPD incorporation adjusted in a wide range due to the enhancement of electrophilicity of metal center caused by introducing electron-withdrawing groups. Especially complex
1c
bearing fluorine at the
para
-position of
N
-aryl moiety provides the highest CPD incorporation
which is nearly two times (18.5 mol%) higher than the non-substituted complex
1
(8.9 mol%) under the same conditions. The highest CPD incorporation up to 24.6 mol% can be easily achieved using this complex.
1
H- and
13
C-NMR spectra demonstrate that these fluoro-substituted complexes possess regioselective nature with exclusive 1
2-insertion fashion
and alternating ethylene-CPD sequence can be detected at high CPD incorporation.
关键词
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