合成了2个含吡啶亚甲基修饰芴配体的二价稀土金属有机配合物[η5∶η1-(C5H4NCH2C13H8)]2LnⅡ[Ln=Yb(1),Eu(2)],发现其对甲基丙烯酸甲酯聚合具有高的催化活性.研究了配合物1,2作为单一组分催化剂催化甲基丙烯酸甲酯聚合的性能,结果表明,温度、溶剂、催化剂和单体的物质的量比对催化剂的活性、聚合物分子量的分布及规整度有明显影响.
Organolanthanide complexes with 2-pyridylmethyl substituted fluorenyl ligand [η5 ∶η1-(C5 H4 NCH2C13H8 )]2 LnⅡ [ Ln= Yb(1), Eu(2)] were found to be highly efficient catalysts for polymerization of methyl methacrylate(MMA). The activities of complexes 1 and 2 as single-component catalysts in catalyzing MMA polymerization were examined. Results show that the temperatures, solvents and the catalyst/MMA monomer mole ratios have influences on the catalytic activities of catalysts, the molecular weight and the stereoregularity of polymers.
参考文献
[1] | Kawaoka A M;Marks T J .Organolanthanide-catalyzed synthesis of phosphine-terminated polyethylenes scope and mechanism[J].Journal of the American Chemical Society,2005,127(17):6311. |
[2] | Yunjie Luo;Jens Baldamus;Zhaomin Hou .Scandium Half-Metallocene-Catalyzed Syndiospecific Styrene Polymerization and Styrene-Ethylene Copolymerization: Unprecedented Incorporation of Syndiotactic Styrene-Styrene Sequences in Styrene-Ethylene Copolymers[J].Journal of the American Chemical Society,2004(43):13910-13911. |
[3] | Fanny Bonnet;Anna C.Hillier;Philip Mountford;Anna Collins;Stuart R.Dubberley .Lanthanide mono(borohydride) complexes of diamide-diamine donor ligands:novel single site catalysts for the polymerisation of methyl methacrylate[J].Dalton transactions: An international journal of inorganic chemistry,2005(3):421-423. |
[4] | Gamer MT;Rastatter M;Roesky PW;Steffens A;Glanz M .Yttrium and lanthanide complexes with various P,N ligands in the coordination sphere: Synthesis, structure, and polymerization studies[J].Chemistry: A European journal,2005(10):3165-3172. |
[5] | Shaowu Wang;Shaoyin Wang;Shuangliu Zhou;Gaosheng Yang;Wei Luo;Nan Hu;Zhihong Zhou;Hai-Bin Song .Synthesis, characterization, and catalytic activity of divalent organolanthanide complexes with new tetrahydro-2H-pyranyl-functionlized indenyl ligands[J].Journal of Organometallic Chemistry,2007(10):2099-2106. |
[6] | Sheng EH.;Wang SW.;Yang GS.;Zhou SL.;Cheng L.;Zhang KH.;Huang ZX. .A new heteroatom coordination promoted homolysis of the Yb-N bond. Synthesis and structural characterization of a new class of ytterbium(II) and ytterbium(III) complexes with amido and indenyl ligands and catalytic activities of ytterbium(II) complex[J].Organometallics,2003(4):684-692. |
[7] | Wang SW.;Zhou SL.;Sheng EH.;Xie MH.;Zhang KH.;Cheng L.;Feng Y.;Mao LL.;Huang ZX. .Homolysis of the Eu-N bond. Synthesis, structural characterization, and catalytic activity of novel europium(II) complexes[J].Organometallics,2003(17):3546-3552. |
[8] | Wang S W;Feng Y;Mao L L et al.Homolysis of the LnN bond:Synthesis,characterization and catalytic activity of organolanthanide(Ⅱ) complexes with 2-pyridylmethyl and 3-pyridylmethyl-functionalized indenyl ligands[J].Journal of Organometallic Chemistry Library,2006,691(06):1265. |
[9] | Molander G A;Romero J A C .Lanthanocene catalysts in selective organic synthesis[J].Chemical Reviews,2002,102(06):2161. |
[10] | Zhang, L.;Xia, J.;Li, Q.;Li, X.;Wang, S. .Fast synthesis of hydrazine and Azo derivatives by oxidation of rare-earth-metal-nitrogen bonds[J].Organometallics,2011(3):375-378. |
[11] | Lijun Zhang;Shaowu Wang;Shuangliu Zhou;Gaosheng Yang;Enhong Sheng .Cannizzaro-Type Disproportionation of Aromatic Aldehydes to Amides and Alcohols by Using Either a Stoichiometric Amount or a Catalytic Amount of Lanthanide Compounds[J].The Journal of Organic Chemistry,2006(8):3149-3153. |
[12] | Peter M.Zeimentz;Jun Okuda;Benjamin R.Elvidge;Stefan Arndt .Cationic Organometallic Complexes of Scandium,Yttrium,and the Lanthanoids[J].Chemical Reviews,2006(6):2404-2433. |
[13] | Trifonov A A;Fedorova E A;Fukin G K et al.Bridging μ-η5:η4-coordination of an indenyl ligand and reductive coupling of diazabutadienes in the assembly of di-and tetranuclear mixed-valent ytterbium indenyldiazabutadiene complexes[J].Chemistry-A European Journal,2006,12(10):2752. |
[14] | Dietrich H M;Grove H;Anwander R et al.Multiple C-H bond activation in group 3 chemistry:Synthesis and structural characterization of an yttrium-aluminum-methine cluster[J].Journal of the American Chemical Society,2006,128(43):1458. |
[15] | Miao, H;Wang, SW;Zhou, SL;Wei, Y;Zhou, ZH;Zhu, H;Wu, SH;Wang, H .Synthesis, characterization of some organolanthanide complexes containing 2-pyridylmethyl substituted fluorenyl ligand and catalytic activity of organolanthanide(II) complexes[J].Inorganica Chimica Acta,2010(7):1325-1331. |
[16] | Sheng E H;Zhou S L;Wang S W.Homolysis of the Ln-N(Ln=Yb,Eu) bond-Synthesis,structure,and cataly-tic activity of ytterbium(Ⅱ) and europium(Ⅱ) complexes having(dimethylamino) propyl-and (dimethylamino) ethylfunctionalized indenyl ligands[J].European Journal of Inorganic Chemistry,2004(14):2923. |
[17] | Zhou SL;Wang SW;Sheng EH;Zhang LJ;Yu ZY;Xi XB;Chen GD;Luo W;Li Y .Synthesis, characterization, and catalytic activity of some neodymium(III), ytterbium(II), and europium(II) complexes with pyrrolidinyl- and piperidinyl-functionalized indenyl ligands[J].European journal of inorganic chemistry,2007(11):1519-1528. |
[18] | Bovey F A;Mirau P A.NMR of polymers[M].San Diego:academic Press,1996 |
[19] | Nakamura H.;Yasuda H.;Maruo T.;Kanehisa N.;Kai Y.;Nakayama Y. .Alternative eta(5)- and eta(6)-bonding modes for bis(fluorenyl)lanthanide complexes by reactions with AlR3 and succesive addition of THF[J].Organometallics,2000(25):5392-5399. |
[20] | Wei Y;Yu ZY;Wang SW;Zhou SL;Yang GS;Zhang LJ;Chen GD;Qian HM;Fan JX .Synthesis, characterization and catalytic activity of organolanthanide(II) complexes with heterocyclic-functionalized fluorenyl ligands[J].Journal of Organometallic Chemistry,2008(13):2263-2270. |
[21] | Boffa L S;Novak B M .Bimetallic samarium(Ⅲ) initiators for the living polymerization of methacrylates and lactones.A new route into telechelic,triblock,and "link-functionalized" polymers[J].Macromolecules,1994,27(23):6993. |
[22] | Knjazhanski SY.;Cadenas G.;Bulychev BM.;Elizalde L. .Polymerization of methyl methacrylate with alane complexes of bivalent lanthanidocenes[J].Journal of Organometallic Chemistry,1998(1/2):33-40. |
- 下载量()
- 访问量()
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%