ICCAS OpenIR
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
Jian, Zhongbao1,2; Tang, Shijia3; Cui, Dongmei1
2010
Source PublicationCHEMISTRY-A EUROPEAN JOURNAL
ISSN0947-6539
Volume16Issue:47Pages:14007-14015
AbstractA 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.
KeywordAllyl Ligands Cyclopentadienyl Ligands Lanthanides Polymerization Syndiotactic Polymers
DOI10.1002/chem.201001634
Indexed BySCI ; IC
Language英语
WOS IDWOS:000286289700018
PublisherWILEY-BLACKWELL
Citation statistics
Cited Times:61[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/71056
Collection中国科学院化学研究所
Corresponding AuthorCui, Dongmei
Affiliation1.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
Recommended Citation
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.
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