新型水杨醛亚胺钛配合物的合成及催化乙烯聚合<sup>*</sup>

doi:10.11901/1005.3093.2014.641

材料研究学报

2015, Vol. 29

Issue (6): 453-462 DOI: 10.11901/1005.3093.2014.641

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新型水杨醛亚胺钛配合物的合成及催化乙烯聚合^*

程正载^1,²(

),张卫星¹,龚凯¹,丛野¹,陈红祥¹,李文兵^1,²

1. 武汉科技大学化学工程与技术学院武汉 430081
2. 煤转化与新型炭材料湖北省重点实验室武汉 430081

Synthesis of a Series Novel Titanium Complexes with Salicylaldimine Ligands and Their Catalytic Performance for Ethylene Polymerization

Zhengzai CHENG^1,^2,^**(

),Weixing ZHANG¹,Kai GONG¹,Ye CONG¹,Hongxiang CHEN¹,Wenbing LI^1,²

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

引用本文:

程正载,张卫星,龚凯,丛野,陈红祥,李文兵. 新型水杨醛亚胺钛配合物的合成及催化乙烯聚合^*[J]. 材料研究学报, 2015, 29(6): 453-462.
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[J]. Chinese Journal of Materials Research, 2015, 29(6): 453-462.

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摘要:

以价廉的水杨醛和TiCl₄为主要原料, 合成了四种水杨醛亚胺配体(5-8)及含(双苯氧基亚胺)配体的钛配合物[O-C₆H₄-ortho-CH=N-2, 6-(i-Pr)₂-C₆H₃]₂TiCl₂(13), [O-(5-NO₂)-C₆H₃-ortho-CH=N-2, 6-(i-Pr)₂-C₆H₃]₂TiCl₂(14), [O-(3, 5-di-Br)-C₆H₂-ortho-CH=N-2, 6-(i-Pr)₂-C₆H₃]₂TiCl₂(15)和[O-(3, 5-di-C(CH₃)₃)-C₆H₂-ortho-CH= N-2, 6-(i-Pr)₂-C₆H₃]₂TiCl₂(16)。用MS、¹H- NMR和元素分析等手段表征了配体5-8分子结构, 用¹H-NMR和元素分析表征了配合物13-16的分子结构。经MAO (甲基铝氧烷) 活化后, 钛配合物 (13-16) 在甲苯溶剂中能有效催化乙烯聚合。在60℃, 2.0 MPa及助催化剂与主催化剂摩尔比n(MAO)/n(cat)=1500∶1条件下钛配合物(14-16)催化乙烯聚合活性为1022.73-1302.27 gPE/(mmolTihMPa)), 远高于无取代水杨醛亚胺钛配合物(13)。所得聚乙烯粘均分子量(粘度法)为19266-44754, GPC测定分子量分布M_w/M_n为1.88-2.12。具有最高活性的催化剂15催化乙烯聚合得到的聚合物样品, 经¹³C-NMR和DSC的表征, 结果表明为线型结晶聚乙烯。

关键词 ：有机高分子材料, 钛配合物, 催化剂, 乙烯聚合, 苯氧基亚胺配体, 活性

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 TiCl₄as 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 19266-44754measured by viscometry and a molecular weight distribution M_w/M_n 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

收稿日期: 2014-11-01

基金资助:^*国家自然科学基金20803054, 湖北省自然科学基金2014CFB812和煤转化与新型炭材料湖北省重点实验室开放基金WKDM201302资助项目。

作者简介: 程正载

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https://www.cjmr.org/CN/10.11901/1005.3093.2014.641 或 https://www.cjmr.org/CN/Y2015/V29/I6/453

图1 配体5-8的合成路线

图2 配合物13-16的合成路线

图3 乙烯聚合装置

图4 配合物14的核磁氢谱图

图5 配合物15的核磁氢谱图

表1 配合物13-16催化乙烯聚合结果

表2 反应时间对乙烯聚合的影响

表3 GPC c聚合表征结果

图6 催化所得聚乙烯的DSC升温曲线(10℃/min)

图7 配合物15在MAO催化体系下的聚乙烯产品的碳谱图

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