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Chinese Journal of Materials Research  2015, Vol. 29 Issue (6): 453-462    DOI: 10.11901/1005.3093.2014.641
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Synthesis of a Series Novel Titanium Complexes with Salicylaldimine Ligands and Their Catalytic Performance for Ethylene Polymerization
Zhengzai CHENG1,2,**(),Weixing ZHANG1,Kai GONG1,Ye CONG1,Hongxiang CHEN1,Wenbing LI1,2
1. Institute of Chemical Engineering and Technology, Wuhan University of Science and Technology,Wuhan 430081, China
2. Hubei Province Key Laboratory of Coal Conversion and New Carbon Materials, Wuhan 430081, China
Cite this article: 

Zhengzai CHENG,Weixing ZHANG,Kai GONG,Ye CONG,Hongxiang CHEN,Wenbing LI. Synthesis of a Series Novel Titanium Complexes with Salicylaldimine Ligands and Their Catalytic Performance for Ethylene Polymerization. Chinese Journal of Materials Research, 2015, 29(6): 453-462.

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Abstract  

Four salicylaldimine ligands (called after 5, 6, 7 and 8 respectively) and their titanium complexes containing bis(phenoxy-imine) ligands, namely [O-C6H4-ortho-CH=N-2, 6-(i-Pr)2-C6H3]2TiCl2 (called after 13), [O-(5-NO2)-C6H3-ortho-CH= N-2, 6-(i-Pr)2-C6H3]2TiCl2 (called after 14), [O-(3, 5-di-Br)-C6H2-ortho-CH=N-2, 6-(i-Pr)2-C6H3]2TiCl2 (called after 15) and [O-(3, 5-di-C(CH3)3)- C6H2-ortho-CH=N-2, 6-(i-Pr)2-C6H3]2TiCl2 (called after 16) have been synthesized with salicylaldehyde and TiCl4 as raw materials. The prepared ligands and complexes were characterized by means of 1H-NMR and elemental analyses as well as mass spectra. After activated with methyaluminoxane (MAO), the complexes 13-16 become efficient catalysts for ethylene polymerization in methylbenzene. Under the conditions of T= 60℃, P=2.0 MPa and n(MAO)/n(cat)=1500∶1, the catalytic activities for the activated complexes 14-16 reached 1022.73-1302.27 gPE / (mmolTihMPa), which were much higher than that for the activated complex 13. The prepared polyethylene possessed a viscosity-average molecular weight in a rang of 19266-44754 measured by viscometry and a molecular weight distribution Mw /Mn in a rang of 1.88-2.12 measured by Gel Permeation in Chromatography. Among others the activated complex 15 displays the highest activity for ethylene polymerization under the same conditions. The characterization by 13C-NMR and DSC showed that the polymer synthesized with catalyst of the activated complex 15 was actually a kind of linear and crystalline polyethylene.
Key words:  organic polymer materials      titanium complex      catalyst      ethylene polymerization      phenoxy-imine ligands      activity     
Received:  01 November 2014     
Fund: *Supported by Natural Science Foundation of China No. 20803054, Natural Science Foundation of Hubei Province No. 2014CFB812 and Open Fund Project Funded by Hubei Province Key Laboratory of Coal Conversion and New Carbon Materials No. WKDM201302.
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Zhengzai CHENG
Weixing ZHANG
Kai GONG
Ye CONG
Hongxiang CHEN
Wenbing LI

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https://www.cjmr.org/EN/10.11901/1005.3093.2014.641     OR     https://www.cjmr.org/EN/Y2015/V29/I6/453

Fig.1  Synthetic route for ligands 5-8
Fig.2  Synthetic route for complexes 13-16
Fig.3  Ethylene polymerization experiment unit
Fig.4  1H NMR spectrum of complex 14
Fig.5  1H NMR spectrum of complex 15
Entry Complex PE(g) Activity (gPE/(mmolTihMPa)) Mv M.P(℃)d
1a — 0 0 — —
3c 13 0.53 120.45 19408 128.77
5c 14 5.42 1231.82 45226 133.82
6b 15 0 0 — —
7c 15 5.73 1302.27 35957 132.64
9c 16 4.50 1022.73 28902 131.49
Table 1  Ethylene polymerization for complexes 13-16
Time / min Polymer yield / g
Complex 13 Complex 14 Complex 15 Complex 16
15 0.10 1.24 1.34 1.05
30 0.23 2.63 2.77 2.13
45 0.39 4.05 4.28 3.30
60 0.53 5.42 5.73 4.50
75 0.59 6.50 6.84 5.44
90 0.60 7.55 8.03 6.31
105 0.61 7.79 8.16 6.42
120 0.61 7.80 8.17 6.44
Table 2  Effect of reaction time on the ethylene polymerization
Complex Mw Mv Mp Mn Mz Mw /Mn
13 20879 19266 18146 11079 32943 1.88
14 49319 44754 41937 23252 86256 2.12
15 38515 35108 33201 18434 65753 2.09
16 29677 27339 27116 15153 47093 1.96
Table 3  Polymer characterization results determined by GPC c
Fig.6  DSC curves of polymers sample
Fig.7  13C-NMR of PE produced by 15/MAO catalyst system
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