吡啶/喹啉单亚胺镍(Ⅱ)配合物的合成及液体聚丁二烯的制备
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摘要
金属配合物中引入侧臂软电子给体膦或硫是提高配合物催化性能的有效途径。本文合成了一系列吡啶/喹啉单亚胺NNP三齿Ni(Ⅱ)配合物(2a~2d),采用傅里叶变换红外光谱、元素分析及单晶衍射对配合物进行了表征。配合物2a为方形锥体构型,配合物2d为三角双锥构型。该系列配合物在倍半乙基氯化铝(EASC)活化下,催化合成了数均相对分子质量为4200~7700、顺-1,4结构的摩尔分数在74.5%~79.9%的液体聚丁二烯。催化活性随着聚合温度的升高而提高。在90℃时,催化体系仍有很高的聚合活性,聚丁二烯的收率达到85.9%,表明其具有高的热稳定性。
The introduction of side arm soft donors( S or P) is an efficient method to improve catalytic performance of the complexes. A series of NNP-tridentate nickel( Ⅱ) complexes bearing pyridyl/quinolylimine ligands( 2 a ~ 2 d) was synthesized and characterized by Fourier transform infrared spectroscopy( FTIR)and elemental analysis. X-ray diffraction analysis( XRD) reveals that complexes 2 a and 2 d adopt squarepyramidal and trigonal bipyramid geometries, respectively. Activated by ethylaluminum sesquichloride( EASC),all complexes are highly active for butadiene polymerization to afford liquid polybutadienes having number-average relative molecular masses of 4200 ~ 7700 and medium cis-1,4 mole fraction( 74. 5% ~79. 9%). The ligand has little influence on the catalytic behaviors. The catalytic activity increases with the increment of polymerization temperature,and the catalytic system still exhibits high activity even at 90 ℃,indicating high thermal stability of the generated active species.
The introduction of side arm soft donors( S or P) is an efficient method to improve catalytic performance of the complexes. A series of NNP-tridentate nickel( Ⅱ) complexes bearing pyridyl/quinolylimine ligands( 2 a ~ 2 d) was synthesized and characterized by Fourier transform infrared spectroscopy( FTIR)and elemental analysis. X-ray diffraction analysis( XRD) reveals that complexes 2 a and 2 d adopt squarepyramidal and trigonal bipyramid geometries, respectively. Activated by ethylaluminum sesquichloride( EASC),all complexes are highly active for butadiene polymerization to afford liquid polybutadienes having number-average relative molecular masses of 4200 ~ 7700 and medium cis-1,4 mole fraction( 74. 5% ~79. 9%). The ligand has little influence on the catalytic behaviors. The catalytic activity increases with the increment of polymerization temperature,and the catalytic system still exhibits high activity even at 90 ℃,indicating high thermal stability of the generated active species.
引文
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[2]Dai S Y,Chen C L.Direct Synthesis of Functionalized High-Molecular-Weight Polyethylene by Copolymerization of Ethylene with Polar Monomers[J].Angew Chem Int Ed,2016,55(42):13281-13285.
[3]Johnson L K,Killian C M,Brookhart M.New Pd(Ⅱ)-and Ni(Ⅱ)-Based Catalysts for Polymerization of Ethylene andα-Olefins[J].J Am Chem Soc,1995,117(23):6414-6415.
[4]Britovsek G J P,Gibson V C,Kimberley B S,et al.Novel Olefin Polymerization Catalysts Based on Iron and Cobalt[J].Chem Commun,1998,(7):849-850.
[5]Osakada K,Takeuchi D.Coordination Polymerization of Dienes,Allenes,and Methylenecycloalkanes[M].Springer Berlin heidelberg,2004,171:137-194.
[6]Yue E L,Zeng Y N,Zhang W J,et al.Highly Linear Polyethylenes Using the 2-(1-(2,4-Dibenzhydrylnaphthylimino)ethyl)-6-(1-(arylimino)ethyl)-pyridylcobalt Chlorides:Synthesis,Characterization and Ethylene Polymerization[J].Sci China Chem,2016,59(10):1291-1300.
[7]Zhang Y F,Huang C B,Wang X X,et al.Highly Branched Unsaturated Polyethylenes Achievable Using Strained Iminocyclopenta[b]pyridyl-nickel Precatalysts[J].Polym Chem,2017,8(6):995-1005.
[8]Wang G,Jiang X B,Zhao W Z,et al.Catalytic Behavior of Co(Ⅱ)Complexes with 2-(Benzimidazolyl)-6-(1-(arylimino)ethyl)pyridine Ligands on Isoprene Stereospecific Polymerization[J].J Appl Polym Sci,2014,131(1):39703.
[9]Liu H,Jia X Y,Wang F,et al.Synthesis of Bis(N-arylcarboximidoylchloride)pyridine Cobalt(Ⅱ)Complexes and Their Catalytic Behavior for 1,3-Butadiene Polymerization[J].Dalton Trans,2013,42(37):13723-13732.
[10]LIU Heng,WANG Feng,ZHANG Xuequan,et al.Synthesis,Characterization of Bis(arylcarboximidoylchloride)pyridine Ni(Ⅱ)Complexes and Their Catalytic Behavior for the Synthesis of Liquid Polybutadiene[J].Chem J Chinese Univ,2014,35(6):1336-1342(in Chinese).刘恒,王凤,张学全,等.吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、表征及催化合成液体聚丁二烯[J].高等学校化学学报,2014,35(6):1336-1342.
[11]LIANG Tao,WENG Xuling,ZHANG Huiyi,et al.Progress in Research and Development of Diene Liquid Rubber[J].Polym Bull,2012,(4):11-16(in Chinese).梁滔,魏绪玲,张惠怡,等.双烯类液体橡胶的研究进展[J].高分子通报,2012,(4):11-16.
[12]CHENG Qian,LIANG Jizhao.Progress in in Research and Development of Polybutadiene Liquid Rubber[J].Spec Purp Rubber Prod,2013,34(4):72-76(in Chinese).程倩,梁基照.聚丁二烯液体橡胶及其研究进展[J].特种橡胶制品,2013,34(4):72-76.
[13]HAN Chao,LIU Heng,YANG Feng,et al.Pyrazolylimine Ni(Ⅱ)Complexes:Synthesis,Characterization,and Catalytic Behaviors for 1,3-Butadiene Polymerization[J].Chinese J Appl Chem,2015,32(8):909-915(in Chinese).韩超,刘恒,杨凤,等.吡唑亚胺镍配合物的合成、表征及催化1,3-丁二烯聚合[J].应用化学,2015,32(8):909-915.
[14]Spasyuk D,Gusev D G.Acceptorless Dehydrogenative Coupling of Ethanol and Hydrogenation of Esters and Imines[J].Organometallics,2012,31(15):5239-5242.
[15]Zhuang R,Liu H,Zhang X Q,et al.Highly Active Nickel(Ⅱ)and Palladium(Ⅱ)Complexes Bearing N,N,P Tridentate Ligand for Vinyl Addition Polymerization of Norbornene[J].Eur Polym J,2017,93:358-367.
[16]Appukuttan V,Zhang L,Ha C S,et al.Highly Active and Stereospecific Polymerizations of 1,3-Butadiene by Using Bis(benzimidazolyl)amine Ligands Derived Co(Ⅱ)Complexes in Combination with Ethylaluminum Sesquichloride[J].Polymer,2009,50(5):1150-1158.
[17]Ai P G,Chen L,Li B G,et al.Polymerization of 1,3-Butadiene Catalyzed by Cobalt(Ⅱ)and Nickel(Ⅱ)Complexes Bearing Imino-or Amino-pyridyl Alcohol Ligands in Combination with Ethylaluminum Sesquichloride[J].J Organomet Chem,2012,705:51-58.
[18]Wang B L,Gong D R,Zhang X Q,et al.Synthesis,Characterization and 1,3-Butadiene Polymerization Behaviors of Cobalt Complexes Bearing 2-Pyrazolyl-substituted 1,10-Phenanthroline Ligands[J].Appl Organomet Chem,2013,27(4):245-252.