Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After dec...Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After decades of research,recent developments in a variety of high-performance catalytic systems have shown that this field is on the brink of industrialization.This review summarizes representative olefin-polar monomer coordination copolymerization catalyst systems that may be suitable for industrial polyolefin production via homogeneous solution-phase processes or heterogeneous gas-phase/slurry-phase processes.展开更多
Metal catalyzed olefin hydrosilylation and metal mediated olefin polymerization are both of great academic and industrial importance, In this article, these two aspects are combined to prepare silicon- functionalized ...Metal catalyzed olefin hydrosilylation and metal mediated olefin polymerization are both of great academic and industrial importance, In this article, these two aspects are combined to prepare silicon- functionalized polyolefin materials, First, pyridine-diimine cobalt-catalyzed dehydrogenative silylations of various terminal olefins with alkylsilanes lead to the formation of a variety of allylsilanes at high yields, Then, the allylsilanes are copolymerized with ethylene using an α-diimine nickel catalyst, leading to the formation of branched polyolefins with high molecular weight and moderate comonomer incorporation. This subsequent catalytic process is an efficient strategy for the synthesis of silicon-functionalized polyolefins using widely available and inexpensive starting materials.展开更多
Ethylene/norbornene(NBE)copolymers are the most representative and widely-used cyclic olefin copolymers(COCs).Higher NBE content in COCs leads to higher transparency,glass transition temperature and mechanical strengt...Ethylene/norbornene(NBE)copolymers are the most representative and widely-used cyclic olefin copolymers(COCs).Higher NBE content in COCs leads to higher transparency,glass transition temperature and mechanical strength,but also makes the COC more brittle and therefore hampers its end uses.In this study,to improve the brittleness of COCs while maintaining their high strength,heat-resistant and transparency,bimodal distributed COCs have been prepared via two selective catalysts reactive blending in one pot.The shape of the molecular weight distribution curves of the obtained COCs could be easily controlled by adjusting the proportion of the two catalysts.These COCs maintained high glass transition temperature,balanced tensile performance,high transparency.展开更多
Two new half-sandwich zirconium(IV) complexes bearing salicylaldimine ligands of the type Cp*Zr[2-tBu-4-R-6-(CH=NiPr)C6H2O]C12[R=H(1), tBu(2)] were prepared by the reaction of Cp*ZrC13 with the corresponding...Two new half-sandwich zirconium(IV) complexes bearing salicylaldimine ligands of the type Cp*Zr[2-tBu-4-R-6-(CH=NiPr)C6H2O]C12[R=H(1), tBu(2)] were prepared by the reaction of Cp*ZrC13 with the corresponding lithium of salicylaldimine ligands 2-tBu-4-R-6-(CH=NiPr)C6H2OLi[R=H(LiLa), tBu(LiLb)]. Com- plexes 1 and 2 were characterized by 1H NMR, BC NMR spectroscopy and elemental analysis. When activated with AliBu3 and Ph3CB(C6F5)4, both complexes 1 and 2 exhibited reasonable catalytic activities for ethylene polymeriza- tion, producing polyethylenes with moderate molecular weight. Complexes 1 and 2 also exhibited reasonable catalyt- ic activities for ethylene copolymerization with 1-hexene, producing poly(ethylene-co-l-hexene)s with moderate molecular weight and reasonable 1-hexene content.展开更多
基金supported by the National Key R&D Program of China(grant no.2021YFA1501700)the National Natural Science Foundation of China(grant nos.52025031,22001004,52373002,U1904212,and 52203016).
文摘Studies on transition-metal catalyzed olefin-polar monomer coordination copolymerization and their resulting polar-functionalized polyolefin materials have attracted attention from both academia and industry.After decades of research,recent developments in a variety of high-performance catalytic systems have shown that this field is on the brink of industrialization.This review summarizes representative olefin-polar monomer coordination copolymerization catalyst systems that may be suitable for industrial polyolefin production via homogeneous solution-phase processes or heterogeneous gas-phase/slurry-phase processes.
基金supported by the National Natural Science Foundation of China(21690071 and 51522306)
文摘Metal catalyzed olefin hydrosilylation and metal mediated olefin polymerization are both of great academic and industrial importance, In this article, these two aspects are combined to prepare silicon- functionalized polyolefin materials, First, pyridine-diimine cobalt-catalyzed dehydrogenative silylations of various terminal olefins with alkylsilanes lead to the formation of a variety of allylsilanes at high yields, Then, the allylsilanes are copolymerized with ethylene using an α-diimine nickel catalyst, leading to the formation of branched polyolefins with high molecular weight and moderate comonomer incorporation. This subsequent catalytic process is an efficient strategy for the synthesis of silicon-functionalized polyolefins using widely available and inexpensive starting materials.
基金subsidy provided by the National Natural Science Foundation of China(No.U1510124).
文摘Ethylene/norbornene(NBE)copolymers are the most representative and widely-used cyclic olefin copolymers(COCs).Higher NBE content in COCs leads to higher transparency,glass transition temperature and mechanical strength,but also makes the COC more brittle and therefore hampers its end uses.In this study,to improve the brittleness of COCs while maintaining their high strength,heat-resistant and transparency,bimodal distributed COCs have been prepared via two selective catalysts reactive blending in one pot.The shape of the molecular weight distribution curves of the obtained COCs could be easily controlled by adjusting the proportion of the two catalysts.These COCs maintained high glass transition temperature,balanced tensile performance,high transparency.
基金Supported by the National Natural Science Foundation of China(No.21204082).
文摘Two new half-sandwich zirconium(IV) complexes bearing salicylaldimine ligands of the type Cp*Zr[2-tBu-4-R-6-(CH=NiPr)C6H2O]C12[R=H(1), tBu(2)] were prepared by the reaction of Cp*ZrC13 with the corresponding lithium of salicylaldimine ligands 2-tBu-4-R-6-(CH=NiPr)C6H2OLi[R=H(LiLa), tBu(LiLb)]. Com- plexes 1 and 2 were characterized by 1H NMR, BC NMR spectroscopy and elemental analysis. When activated with AliBu3 and Ph3CB(C6F5)4, both complexes 1 and 2 exhibited reasonable catalytic activities for ethylene polymeriza- tion, producing polyethylenes with moderate molecular weight. Complexes 1 and 2 also exhibited reasonable catalyt- ic activities for ethylene copolymerization with 1-hexene, producing poly(ethylene-co-l-hexene)s with moderate molecular weight and reasonable 1-hexene content.