A Lutetium Allyl Complex That Bears a Pyridyl-Functionalized Cyclopentadienyl Ligand: Dural Catalysis on Highly Syndiospecific and cis-1,4-Selective (Co)Polymerizations of Styrene and Butadiene
文献类型：期刊论文
| 作者 | Jian, Zhongbao1,2; Tang, Shijia3; Cui, Dongmei1 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2010 |
| 卷号 | 16期号:47页码:14007-14015 |
| 关键词 | Allyl Ligands Cyclopentadienyl Ligands Lanthanides Polymerization Syndiotactic Polymers |
| ISSN号 | 0947-6539 |
| DOI | 10.1002/chem.201001634 |
| 英文摘要 | A novel linked-half-sandwich lutetium-bis(allyl) complex [(C(5)Me(4)CH(5)H(4)N)Lu(eta(3)-C(3)H(5))2] (1) attached by a pyridyl-functionalized cyclopentadienyl ligand was synthesized and fully characterized. Complex 1 in combination with [Ph(3)C][B(C(6)F(5))(4)] exhibited unprecedented dual catalysis with outstanding activities in highly syndiotactic (rrrr > 99%) styrene polymerization and distinguished cis-1,4-selective (99%) butadiene polymerization, respectively. Strikingly, this catalyst system exhibited remarkable activity (396 kg copolymer (mol(Lu) h)(-1)) for the copolymerization of butadiene and styrene. Irrespective of whether the monomers were fed in concurrent mode or sequential addition of butadiene followed by styrene, diblock copolymers were obtained exclusively, which was confirmed by a kinetics investigation of monomer conversion of copolymerization with time. In the copolymers, the styrene incorporation rate varied from 4.7 to 85.4 mol%, whereas the polybutadiene (PBD) block was highly cis-1,4-regulated (95%) and the polystyrene segment remained purely syndiotactic (rrrr > 99%). Correspondingly, the copolymers exhibited glass transition temperatures (T(g)) around -107 degrees C and melting points (T(m)) around 268 degrees C; typical values for diblock microstructures. Such copolymers cannot be accessed by any other methods known to date. X-ray powder diffraction analysis of these diblock copolymers showed that the crystallizable syndiotactic polystyrene (syn-PS) block was in the toluene delta clathrate form. The AFM micrographs of diblock copolymer showed a remarkable phase-separation morphology of the cis-1,4-PBD block and syn-PS block. This represents the first example of a lutetium-based catalyst showing both high activity and selectivity for the (co)polymerization of styrene and butadiene. |
| 语种 | 英语 |
| WOS记录号 | WOS:000286289700018 |
| 出版者 | WILEY-BLACKWELL |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/71055]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Cui, Dongmei |
| 作者单位 | 1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China 3.Jilin Univ, Sch Chem, Changchun 130012, Peoples R China |
| 推荐引用方式 GB/T 7714 | Jian, Zhongbao,Tang, Shijia,Cui, Dongmei. A Lutetium Allyl Complex That Bears a Pyridyl-Functionalized Cyclopentadienyl Ligand: Dural Catalysis on Highly Syndiospecific and cis-1,4-Selective (Co)Polymerizations of Styrene and Butadiene[J]. CHEMISTRY-A EUROPEAN JOURNAL,2010,16(47):14007-14015. |
| APA | Jian, Zhongbao,Tang, Shijia,&Cui, Dongmei.(2010).A Lutetium Allyl Complex That Bears a Pyridyl-Functionalized Cyclopentadienyl Ligand: Dural Catalysis on Highly Syndiospecific and cis-1,4-Selective (Co)Polymerizations of Styrene and Butadiene.CHEMISTRY-A EUROPEAN JOURNAL,16(47),14007-14015. |
| MLA | Jian, Zhongbao,et al."A Lutetium Allyl Complex That Bears a Pyridyl-Functionalized Cyclopentadienyl Ligand: Dural Catalysis on Highly Syndiospecific and cis-1,4-Selective (Co)Polymerizations of Styrene and Butadiene".CHEMISTRY-A EUROPEAN JOURNAL 16.47(2010):14007-14015. |
入库方式： OAI收割
来源：化学研究所
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