Research Progress of Pre - transition Metal Olefin Polymerization Catalyst for Salicylaldehyde Imine

Lulu Hou, Hongyu Ren, Baoli Guo


Salicylaldehyde imine transition metal catalyst is a kind of olefin polymerization catalyst which is widely used in the coordination of salicylaldehyde imine ligand and pre-transition metal. Salicylaldehyde imine ligands have the characteristics of easily insert different substituents via organic synthesize. Therefore, the regulation of the polymerization activity, polymerization product and product distribution can be achieved by changing the steric hindrance effect, electronic effect and the number of metal active sites which near the catalytic active center. The development status of the transition metal catalyst of salicylaldehyde imide was summarized in this paper. The influence of the ligand structure of salicylaldehyde imide transition metal catalyst on the catalytic performance which involved the high selectivity ethylene trimerization, ethylene / α-olefin, / Polar monomer copolymerization, ethylene polymerization production of ultra-high molecular weight polyethylene and many other areas of olefin polymerization was elaborated and providing references for further study and industrial applications of this catalyst.

Full Text:



Wang C, Friedrich S, Younkin T R, et al. Neutral nickel (II) -BasedPeople for the combination of production [J]. Organometallics, 1998,17: 3149-3151.

Pong F Y, Mandal S, Sen A. Steric and electronic effects in ethene /Norbornene copolymerization by neutral salicylaldiminato-ligated Palladium (II) catalysts [J]. Organometallics, 2014, 33:7044-7051.

Yao E, Wang J, Chen Z, et al. Homo and heteroligated Salicylaldiminato titanium complexes with different rap Ortho to the phenoxy oxygens for ethylene and ethylene / 1-hexene (Co) polymerization [J]. Macromolecules, 2014, 47: 8164-8170.

Matsui S, Tohi Y, Mitani M, et al. New bis (salicylaldiminato) Titanium complexes for ethylene polymerization [J]. Chem.Lett. , 1999: 1065-1066.

Damavandi S, Galland G B, Zohuri G H, et al. FI Zr-type catalysts For production (J). J. Polym. Res. , 2011,18:1059-1065.

Matsugi T, Fujita T. High-performance olefin polymerization Produce on the basis of a new catalyst design concept[J]. Chem. Soc. Rev. , 2008, 37: 1264-1277.

Breuil P A R, Magna L, Olivier-Bourbigou H. Role of homoge-neous catalysis in oligomerization of olefins: focus on selected

examples Based on group 4to group 10transition metal complexes[J]. Catal. Lett. , 2015, 145: 173-192.

Suzuki Y, Kinoshita S, Shibahara A, et al. Trimerization of ethylene To 1-hexene with titanium complexes bearing phenoxy-imine Ligands with pendant const combined with MAO [J]. Organometallics,2010,29: 2394-2396.

Zhang W, Sun W H, Redshaw C. Tailoring iron complexes for Ethylene oligomerization and / or polymerization [J]. Dalton Trans. , 2013, 42: 8988-8997.

Suttil J A, Shaw M F, McGuinness D S, et al. Synthesis of Ti (IV) complexes of donor-functionalised phenoxy-imine tridentates And their evaluation in ethylene oligomerisation and polymerisation[J]. Dalton Trans. , 2013, 42: 9129-9138.

Sattler A, Labinger J A, Bercaw J E. Highly selective clay Trimerization catalysis by a borane-activated titanium trimethyl Complex [J]. Organometallics, 2013, 32: 6899-6902.

Soshnikov I E, Semikolenova N V, Ma J, et al. Selective Trimerization by titanium complexes bearing phenoxy-imine Ligands: NMR and EPR spectroscopic studies of the compound intermediates[J]. Organometallics, 2014, 33: 1431-1439.

Pasha F A, Basset J M, Toulhoat H, et al. DFT study on the Impact of the methylaluminoxane cocatalyst in ethylene oligomerization Using a titanium-based catalyst [J]. Organometallics,2015, 34: 426-431.

Sattler A, Vander Velde D G, Labinger J A, et al. Lewis acid Promoted titanium alkylidene formation: off-cycle intermediates

Related to olefin trimerization catalysis [J]. J. Am. Chem. Soc. , 2014, 136: 10790-10800.

Kirillov E, Roisnel T, Razavi A, et al. Chromium (III) complexes Of sterically crowded bidentante (ONR) and tridentate (ONNR) Naphthoxy-imine ligands: syntheses, structures, and use in Ethylene oligomerization [J]. Organometallics, 2009, 28: 2401-2409.

Suzuki Y, Kinoshita S, Shibahara A, et al. Transition metal Complex compounds, olefin oligomerization groups containing The compounds, and processes for producingrene oligomers using The carriers: US, 8258361 [P]. 2012-09-04.

Terao H, Iwashita A, Ishii S, et al. Ethylene / norbornene Copolymerization behavior of bis (phenoxy-imine) Ti complexes Combined with MAO [J]. Macromolecules, 2009, 42: 4359-4361. [18] Terao H, Iwashita A, Matsukawa N, et al. Ethylene and Ethylene / α-olefin (co) polymerization behavior of bis (phenoxyimine)Ti catalysts: significant means effects on activity andComonomer incorporation [J]. ACS Catal. , 2011,1: 254-265.

Terao H, Ishii S, Mitani M, et al. Ethylene / polar monomer copolymerization behavior of bis (phenoxy-imine) Ti complexes:Formation of polar monomer shares [J]. J. Am. Chem.Soc. , 2008, 130: 17636-17637.

Zhang X, Liu Z, Yi J, et al. Copolymerization of ethylene with Acrylonitrile promoted by novel nonmetallocene animals with Phenoxy-imine ligands [J]. J. Polym. Sci. Part A: Polym.Chem. , 2012, 50: 2068-2074.

Huang W, Sun X, Ma H, et al. Ethylene homopolymerization And ethylene / 1-hexene copolymerization catalysed by mixed Salicylaldiminato cyclopentadienyl zirconium complexes [J]. Inorg. Chim. Acta, 2010, 363: 2009-2015.

Liu K, Yao G, Wu W, et al. New half-sandwich zirconium (IV)Complexes containing salicylaldimine ligands: synthesis,

characterizationsAnd catalytic properties [J]. Chem. Res. Chin.Univ. , 2014, 30: 825-830.

Han S, Yao E, Qin W, et al. Binuclear heteroligated titanium Catalyst based on phenoxyimine ligands: synthesis,

characterization, And ethylene (co) polymerization [J]. Macromolecules,2012, 45: 4054-4059.

Aguilar M, Martin S, Vega J, et al. Processability of a Metallocene-catalyzed linear PE improved by blending with a Small amount of UHMWPE [J]. J. Polym. Sci. Part B: Polym.Phys. , 2005, 43: 2963-2971.

Makio H, Kashiwa N, Fujita T. FI hosts: a new family of High performance catalysts for binerals [J]. Adv.Synth. Catal. , 2002,

: 477-493.

[Matoishi K, Nakai K, Nagai N, et al. Value-added olefin-based Materials originating from FI catalysis: production of vinyl-and

Al-terminated PEs, end-functionalized PEs, and PE / polyethylene Glycol hybrid materials [J]. Catal. Today, 2011, 164: 2-8.

Weiser M S, Wesolek M, Mülhaupt R. The synthesis and X-ray Structure of a phenoxyimine catalyst tailored for living olefin polymerisation And the synthesis of ultra-high molecular weight polyethylene And atactic polypropylene [J]. J. Organomet. Chem. , 2006,691: 2945-2952.

Wang Y, Fan H, Jie S, et al. Synthesis and characterization of Titanium (IV) complexes bearing end functionalized biphenyl: efficient Catalysts for synthesizing high molecular weight polyethylene[J]. Inorg. Chem. Commun , 2014, 41: 68-71.

[Liu W, Zhang K, Fan H, et al. Living copolymerization of Ethylene / 1-octene with fluorinated FI-Ti catalyst [J]. J. Polym. Sci. Part A: Polym. Chem. , 2013, 51: 405-414.

Guo S, Fan H, Bu Z, et al. Synthesis of ultrahigh-molecularweight Ethylene-1-hexene copolymers with high hexene content Via living polymerization with fluorinated bis (phenoxy-imine) titanium (IV) [J]. Macromol. Rapid Commun , 2015, 36: 286-291.



  • There are currently no refbacks.

Creative Commons License

This site is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.