Novel bis(benzoin) titanium catalyst for homo- and copolymerization of norbornene with ethylene: Synthesis, characterization and catalytic properties

Hu, Hao; Gao, Haiyang; Song, Keming; Liu, Feng-Shou; Long, Jieming; Zhang, Ling; Zhu, Fangming; Wu, Qing

doi:10.1016/j.polymer.2008.08.035

Cited by 22 publications

(15 citation statements)

References 54 publications

(64 reference statements)

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“…The copolymers with low NBE incorporation show apparent melting peaks (120 °C), which is a result of relatively long ethylene sequences. The melting temperatures of the copolymer are lower than those of the polyethylenes, which can be attributed to long PE sequences containing very low isolated NBE unit ((E) m N(E) n ) [9,30].…”

Section: Ethylene-norbornene Copolymerizationmentioning

confidence: 89%

“…Typically, an apparent decrease in catalytic activity can be observed at relatively high temperature due to thermal instability of the active species [31] and low ethylene solubility in solvent [32]. Previously, we reported that bis(benzoin) titanium catalyst exhibits the highest activity for ethylene polymerization at 30 °C, and higher temperature leads to a decrease in activity [30]. Apparently, bis(-alkyloxoimine) titanium catalyst has better thermal stability than bis(benzoin) titanium catalyst.…”

Section: Ethylene Homopolymerizationmentioning

confidence: 99%

“…Copolymerization data in Table 3 show that the copolymerization activity and NBE incorporation in the copolymer are affected by the quantities of charged NBE. Unlike bis (pyrrolide-imine) titanium catalysts [22,23], bis(-diketiminato) titanium catalysts [29], and bis(benzoin) titanium catalyst [30], as the quantities of charged NBE increases (and thereby the NBE/E molar ratio increases), the catalytic activity remains practically unchanged and then increases apparently. This result is likely to arise from good performance of bis(-alkyloxoimine) titanium catalyst for NBE polymerization.…”

Section: Ethylene-norbornene Copolymerizationmentioning

confidence: 99%

“…The signals are assigned according to the previous reports [10,20] and our results [29,30]. As shown in Figure 3(a), the spectrum of the copolymer containing 19% NBE units displays solely eight major peaks respectively at 29.9 ppm (successive E sequences), 30.4 ppm (isolated E + C5/C6), 30.9 ppm (C5/C6 + E sequence), 33.1 ppm (C7), 41.7, 42.2 ppm (C1/C4), 47.4 and 48.0 ppm (C2/C3), which are characteristics of the NBE units existing as alternating (ENEN) and isolated (ENEE) sequences.…”

Section: Ethylene-norbornene Copolymerizationmentioning

confidence: 99%

“…The dyad (NN), and triad (NNN) sequences of NBE were also determined in the microstructure of the copolymer because the electronegative alkoxide group makes the titanium center prone to be attacked by norbornene monomers [30]. In this paper, we synthesized a new [N,O] bis(-alkyloxoimine) titanium complex on the basis of the structure of bis(benzoin) titanium, and investigated its catalytic properties on homo-and copolymerization of ethylene and norbornene.…”

Section: Introductionmentioning

confidence: 99%

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High norbornene incorporation in ethylene-norbornene copolymerization with a bis(α-alkyloxoimine) titanium-MAO catalyst

Gao

2010

Sci. China Chem.

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A novel bis(-alkyloxoimine) titanium(IV) complex was synthesized and used as a catalyst precursor to catalyze homo-and copolymerization of ethylene and norbornene. The titanium complex activated with methylalumoxane exhibits good activities for the homopolymerizations of ethylene and norbornene under high temperature to produce high-molecular-weight linear polyethylene and vinyl-type polynorbornene, respectively. Ethylene-norbornene copolymers with high molecular weight can also be produced by this catalyst. The incorporation of norbornene from 0 to 76 mol% in the copolymers can be controlled by varying the charged norbornene. 13 C NMR analyses show that the microstructures of the ethylene-norbornene copolymers with low norbornene incorporation are predominantly alternated and isolated norbornene units, while those with high norbornene incorporation are random polymers containing long norbornene sequences.

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Section: Ethylene-norbornene Copolymerizationmentioning

confidence: 89%

Section: Ethylene Homopolymerizationmentioning

confidence: 99%

Section: Ethylene-norbornene Copolymerizationmentioning

confidence: 99%

Section: Ethylene-norbornene Copolymerizationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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High norbornene incorporation in ethylene-norbornene copolymerization with a bis(α-alkyloxoimine) titanium-MAO catalyst

Gao

2010

Sci. China Chem.

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Copolymerization of styrene and norbornene with β‐diketiminato nickel/methylaluminoxane catalytic system

Min-yu

et al. 2012

Applied Organom Chemis

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Styrene-norbornene (S-N) copolymerizations were carried out using b-diketiminato nickel complexes CH{C(CF 3 )NAr} 2 NiBr (Ar = 2,6-i Pr 2 C 6 H 3 , 1; Ar = 2,6-Me 2 C 6 H 3 , 2) in the presence of methylaluminoxane. The influence of the comonomer feed content and polymerization temperature on the conversion and composition of the copolymers with the catalytic system was investigated. An increase in the feed ratio of S/N led to an increase in the incorporated styrene content of the resulting copolymer. NMR characterization of the copolymers generated with the catalytic systems showed that the random S-N copolymers are produced. Differential scanning calorimetric determination of the copolymers shows higher T g values than polystyrene, and gel permeation chromatographic measurements have shown that the copolymers possess rather narrow molecular weight distributions, suggesting that the copolymerization take place at a single active site.

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Performance of a Bis(imine)Pyridine Iron Catalyst System in Ethylene/Norbornene Copolymerization with Zinc Diethyl

Pereira

Marques

2014

Macromolecular Symposia

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Summary Brookhart catalysts are widely used in ethylene polymerization to produce polymers with high molecular weight and crystallinity degree. In the present work, the performance of a bis(imine)pyridine iron catalyst and methylaluminoxane (MAO) as a catalytic system was evaluated for ethylene/norbornene copolymerization and the influence of adding zinc diethyl (DEZ) in the reaction medium was investigated. The results showed that the system was effective in copolymerization besides the low incorporation of norbornene in polymer chain, as indicated by multimodal profiles in DSC and high crystalline degree.

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Novel bis(benzoin) titanium catalyst for homo- and copolymerization of norbornene with ethylene: Synthesis, characterization and catalytic properties

Cited by 22 publications

References 54 publications

High norbornene incorporation in ethylene-norbornene copolymerization with a bis(α-alkyloxoimine) titanium-MAO catalyst

High norbornene incorporation in ethylene-norbornene copolymerization with a bis(α-alkyloxoimine) titanium-MAO catalyst

Copolymerization of styrene and norbornene with β‐diketiminato nickel/methylaluminoxane catalytic system

Performance of a Bis(imine)Pyridine Iron Catalyst System in Ethylene/Norbornene Copolymerization with Zinc Diethyl

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