N-金刚烷基芳氧亚胺锆配合物的合成及其催化乙烯聚合
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摘要
以3-叔丁基-5-甲氧基水杨醛和金刚烷胺为原料,合成了两个水杨醛亚胺配体(1,2)及相应的锆络合物(3,4),并用MS、1H NMR和13C NMR等方法表征了配体及络合物。在甲基铝氧烷(MAO)助催化下,研究了络合物催化乙烯聚合性能。(3)在70℃时催化乙烯聚合活性为18. 1 kg PE/mmol·Zr·h,而(4)在30℃时催化乙烯聚合活性达到23. 8 kg PE/mmol·Zr·h,络合物催化所得聚乙烯的粘均分子量在3. 8×104%18. 9×104g/mol之间。红外谱图结果表明,聚合物以乙烯基封端,DSC测试表明聚乙烯的熔点分别为130℃和133℃,GPC测试聚乙烯的分子量分布为7. 6。
Salicylaldehyde imine ligands(1,2) and corresponding bis(phenoxy-imine) zirconium complexes(3,4) have been synthesized by using 3-tert-butyl-5-methoxy salicylaldehyde and adamantyl amine as the starting material. Both ligands and complexes were characterized by mass spectrum,1 H NMR and13 C NMR spectroscopy. In the presence of MAO as a cocatalyst,the catalytic performances of ethylene polymerization catalyzed by complexes were studied. Complex(3) exhibited ethylene polymerization activity of18. 1 kg of PE/mmol of Zr·h at 70 ℃,while complex(4) displayed good activity of 23. 8 kg of PE/mmol of Zr·h at 30 ℃,affording the polyethylene with a viscosity average molecular weight between 3. 8 × 104~ 18. 9 × 104 g/mol. The infrared spectra indicated that the polymer was terminated with vinyl group.DSC curves suggested that the melting point of polyethylene were 130 ℃ and 133 ℃ respectively. The GPC measurement showed that the molecular weight distribution of polyethylene was 7. 6.
Salicylaldehyde imine ligands(1,2) and corresponding bis(phenoxy-imine) zirconium complexes(3,4) have been synthesized by using 3-tert-butyl-5-methoxy salicylaldehyde and adamantyl amine as the starting material. Both ligands and complexes were characterized by mass spectrum,1 H NMR and13 C NMR spectroscopy. In the presence of MAO as a cocatalyst,the catalytic performances of ethylene polymerization catalyzed by complexes were studied. Complex(3) exhibited ethylene polymerization activity of18. 1 kg of PE/mmol of Zr·h at 70 ℃,while complex(4) displayed good activity of 23. 8 kg of PE/mmol of Zr·h at 30 ℃,affording the polyethylene with a viscosity average molecular weight between 3. 8 × 104~ 18. 9 × 104 g/mol. The infrared spectra indicated that the polymer was terminated with vinyl group.DSC curves suggested that the melting point of polyethylene were 130 ℃ and 133 ℃ respectively. The GPC measurement showed that the molecular weight distribution of polyethylene was 7. 6.
引文
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[19] Li Y,Zhang Y,Li Q,et al. Synthesis of novel chain-endfunctionalized polyethylenes via thiol-ene click chemistry[J]. Macromolecular Chemistry&Physics,2015,216(5):569-581.
[2]邓杰义,仇文辉.聚乙烯(PE)管材的应用现状及发展趋势[J].广东化工,2017,44(13):137-138.
[3]卢丹亚.高密度聚乙烯管材专用料的市场应用探讨[J].橡塑技术与装备,2016(10):38-39.
[4]刘显圣,吕崇福,孙颖,等.聚乙烯催化剂研究进展[J].精细石油化工进展,2013,14(6):44-48.
[5]张强.新型非桥连茂金属配合物的合成、表征及催化烯烃聚合性质研究[D].长春:吉林大学,2016.
[6] Kenyon P,Mecking S. Pentafluorosulfanyl substituents in polymerization catalysis[J]. J Am Chem Soc,2017,139(39):13786-13790.
[7] Chen Z,Allen K E,White P S,et al. Synthesis of branched polyethylene with “Half-Sandwich”pyridine-imine nickel complexes[J]. Organometallics,2016,35(11):1756-1760.
[8] Ryken S A,Schafer L L. N,O-chelating four-membered metallacyclic titanium(IV)complexes for atom-economic catalytic reactions[J]. Acc Chem Res,2015,48(9):2576-2586.
[9] Connor E F,Younkin T R,Henderson J I,et al. Linear functionalized polyethylene prepared with highly active neutral Ni(II)complexes[J]. Journal of Polymer Science Part A Polymer Chemistry,2002,40(16):2842-2854.
[10] Weiser M S,Wesolek M,Mülhaupt R. The synthesis and X-ray structure of a phenoxyimine catalyst tailored for living olefin polymerisation and the synthesis of ultra-high molecular weight polyethylene and atactic polypropylene[J]. Journal of Organometallic Chemistry,2006,691(13):2945-2952.
[11] Saito J,Mitani M,Matsui S,et al. A new titanium complex having two phenoxy-imine chelate ligands for ethylene polymerization[J]. Macromolecular Chemistry&Physics,2002,203(1):59-65.
[12] Makio H,Kashiwa N,Fujita T. FI Catalysts:a new family of high performance catalysts for olefin polymerization[J].Advanced Synthesis&Catalysis,2002,344(5):477-493.
[13] Ishii S I,Saito J,Mitani M,et al. Highly active ethylene polymerization catalysts based on titanium complexes having two phenoxy-imine chelate ligands[J]. Journal of Molecular Catalysis A Chemical,2002,179(1/2):11-16.
[14] Makio H,Terao H,Iwashita A,et al. FI Catalysts for olefin polymerization——A comprehensive treatment[J]. Chemical Reviews,2011,111(3):2363-2449.
[15] Matoishi K,Nakai K,Nagai N,et al. Value-added olefinbased materials originating from FI catalysis:Production of vinyl-and Al-terminated PEs,end-functionalized PEs,and PE/polyethylene glycol hybrid materials[J]. Catalysis Today,2011,164(1):2-8.
[16] Oleinik I I,Oleinik I V,Zaitsev D E,et al. Design of postmetallocene catalytic systems of arylimine type for olefin polymerization:Synthesis of(N-aryl)salicylaldimines containing pent-4-enyloxy group and their complexes with titanium(IV)dichloride[J]. Russian Journal of Organic Chemistry,2014,50(2):191-199.
[17] Francis P S,Jr R C C,Elliott J H. Fractionation of polyethylene[J]. Journal of Polymer Science,1958,31(123):453-466.
[18]谢侃,陈冬梅,蔡霞. PE微观结构的红外光谱实用表征[J].合成树脂及塑料,2005,22(1):48-52.
[19] Li Y,Zhang Y,Li Q,et al. Synthesis of novel chain-endfunctionalized polyethylenes via thiol-ene click chemistry[J]. Macromolecular Chemistry&Physics,2015,216(5):569-581.