POLYMERIZATION OF ETHYLENE WITH UNSYMMETRIC 2,6-BIS(IMINO)PYRIDINE IRON(Ⅱ)COMPLEX

An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene polymerization and theeffects of polymerization conditions such as temperature, aluminum/iron molar ratio on the activity of catalyst and thecharacteristics of polyethylene were reported. The unsymmetric catalyst 1' has a good catalytic performance of 3.47×10~6 gPE·mol^(-1)·Fe·h^(-1) at 40℃ with aluminum/iron molar ratio = 2500. A dependence of catalyst activity on themethylaluminoxane (MAO) concentration and reaction temperature was found. The molecular weight (MW) of polyethylenewith broad dispersity is about 10~4-10~5 g/mol. The melting temperature and branching of polyethylenes vary with changingreaction temperature and aluminum/iron molar ratio.

Sum Frequency Spectroscopy Studies on Cell Membrane Fusion Induced by Divalent Cations

Cell membrane fusion is a fundamental biological process involved in a number of cellular living functions. Regarding this, divalent cations can induce fusion of the lipid bilayers through binding and bridging of divalent cations to the charged lipids, thus leading to the cell membrane fusion. However, the elaborate mechanism of cell membrane fusion induced by divalent cations is still needed to be elucidated.Here, surface/interface sensitive sum frequency generation vibrational spectroscopy(SFG-VS) and dynamic light scattering(DLS) were applied in this research to study the responses of phospholipid monolayer to the exposure of divalent metal ions i.e.Ca^(2+)and Mg^(2+). According to the particle size distribution results measured by DLS experiments, it was found that Ca^(2+)could induce inter-vesicular fusion while Mg^(2+)could not. An octadecyltrichlorosilane self-assembled monolayer(OTS SAM)-lipid monolayer system was designed to model the cell membrane for the SFG-VS experiment. Ca^(2+)could interact with the lipid POO_(2)^(-)head groups more strongly, resulting in cell membrane fusion more easily, in comparison with Mg^(2+). No specific interaction between the two metal cations and the C=O groups was observed. However, the C=O orientations changed more after Ca^(2+)-PO2-binding than Mg^(2+)mediation on lipid monolayer. Meanwhile, Ca^(2+)could induce dehydration of the lipids(which should be related to the strong Ca^(2+)-PO_(2)^(-)interaction), leading to the reduced hindrance for cell membrane fusion.

High Temperature Iron Ethylene Polymerization Catalysts Bearing N,N,N'-2-(1-(2,4-Dibenzhydryl-6-fluorophenylimino)ethyl)-6-(1-(arylphenylimino)ethyl)pyridines

The N,N,N'-ferrous chloride complexes,[2-{CMeN(2,4-(CHPh)_(2)-6-FC_(6)H_(2))}-6-(CMeNAr)C_(5)H_(3)N]FeCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3) Fe1,2,6-Et_(2)C_(6)H_(3)Fe2,2,6-^(i)Pr_(2)C_(6)H_(3) Fe3,2,4,6-Me_(3)C_(6)H_(2) Fe4 and 2,6-Et_(2)-4-MeC_(6)H_(2) Fe5),each possessing one N-2,4-dibenzhydryl-6-fluorophenyl group,were readily synthesized from their respective unsymmetrical bis(imino)pyridines,L1-L5.Structural identification of Fe2 highlighted the variation in the steric properties provided by the dissimilar N-aryl groups.Following pre-treatment with either MAO or MMAO,complexes Fe1-Fe5 all displayed,at an operating temperature of 80℃,high activities for ethylene polymerization with levels falling in the order:Fe4> Fe1> Fe5> Fe2> Fe3.Notably,Fe4/MAO displayed the highest activity of 1.94×10^(7) g_(PE)·mol_(Fe)^(-1)·h^(-1) of the study with only a modest loss in performance at 90℃.Generally,the resulting polyethylenes were highly linear(T_(m) range:122-132℃),narrowly disperse and of low molecular weight(M_(w) range:6.73-46.04kg·mol^(-1)),with the most sterically hindered Fe3 forming the highest molecular weight polymer of the series.End-group analysis by ^(1)H-and ^(13)CNMR spectroscopy revealed saturated alkyl(n-propyl and i-propyl) and unsaturated vinyl chain ends indicative of the role of both β-H elimination and chain transfer to aluminum as termination pathways.By comparison with previou sly reported iron precatalysts with similar tridentate ligand skeletons,it is evident that the introduction of a large benzhydryl group in combination with a fluorine as the ortho-substituents of one N-aryl group has the effect of enhancing thermal stability of the iron polymerization catalyst whilst maintaining appreciable polymer molecular weight.

High-Performanceα-Diimine Nickel Complexes for Facile Access of PE Elastomers with Exceptional Material Properties

For practicable elastomeric polyethylene,achieving high catalyst thermal stability and activity,along with precise control of polymer properties such as branching density,molecular weights,and distribution,is crucial but challenging.In this study,two sets of symmetricalα-diimine nickel complexes,each comprising four nickel bromide or chloride complexes,were synthesized and investigated their performance for ethylene polymerization under various reaction conditions.Upon activation with either Et2AlCl or MMAO cocatalysts,these complexes displayed not only high activity but also generated high molecular weight polyethylenes with controlled polydispersity and a substantial number of branches.The catalyst with the least steric hindrance displayed the remarkable high activity(up to 1.2×10^(7) g·mol^(-1)·h^(-1)).Notably,nickel bromides demonstrated higher activity compared to their chloride counterparts.The investigation into the effect of reaction temperature on catalytic performance revealed that NiBrMe-MMAO system displayed high thermal stability(activity up to 2.51×10^(6) g·mol^(-1)·h^(-1) at 100℃)and consistently yielded high polymer molecular weights with narrow polydispersity over a broad temperature range of 30-100℃.Of significant note,mechanical analysis of the resulting polyethylene demonstrated excellent ultimate tensile strength and high strain at break.Particularly,the polyethylene sample prepared at 100℃exhibited ultimate tensile strength up to 10 MPa with 1863%maximum strain at break and a strain recovery of up to 54.9%after ten cycles at a fixed strain of 300%,indicating excellent material properties of prepared thermoplastic polyethylene elastomers(TPE).

Recent Progress on Transition Metal （Fe, Co, Ni, Ti and V） Complex Catalysts in Olefin Polymerization with High Thermal Stability

The design and synthesis of transition metal complexes with high thermal stability in olefin polymerization have become more and more important in order to meet the need of industrial application.This review focuses on the transition metal complex catalyst with high thermal stability containing different structures,including the backbone of bis（imino）pyridine,a-diimine and other types of ligands.Besides the catalytic activity,the influence of reaction temperature on the molecular weight and molecular weight distribution of the obtained polymer was also described.The plausible mechanism on the stability of catalysts at high temperature was proposed,which may give guidance to design catalyst with good thermal stability.

Highly linear polyethylenes using the2-(1-(2,4-dibenzhydrylnaphthylimino)ethyl)-6-(1-(arylimino)ethyl)-pyridylcobalt chlorides: synthesis, characterization and ethylene polymerization

The series of 2-（1-（2,4-dibenzhydrylnaphthylimino）ethyl）-6-（1-（arylimino）ethyl）pyridine derivatives and their cobalt chlorides （Col-Co5） were synthesized and fully characterized. The representative complexes Co2 and Co3 were confirmed by single crystal X-ray diffraction analyses, indicating pseudo-square-pyramidal geometry around the cobalt centre. All cobalt complexes, activated with either methylaluminoxane （MAO） or modified methylaluminoxane （MMAO）, exhibited high activities towards ethylene polymerization, and produced polyethylenes with high molecular weight and highly linear feature as well as unimodal distribution.

Investigating the Effects of Para-methoxy Substitution in Sterically Enhanced Unsymmetrical Bis(arylimino)pyridine-cobalt Ethylene Polymerization Catalysts

A group of five bis(arylimino)pyridine-cobalt(Ⅱ)chloride complexes,[2-{(2,6-(Ph_(2)CH)_(2)-4-MeOC_(6)H_(2))N=CMe}-6-(ArN=CMe)C_5 H_(3)N]CoCl_(2)(Ar=2,6-Me_(2)C_(6)H_(3)Co1,2,6-Et_(2)C_(6)H_(3)Co2,2,6-iPr_(2)C_(6)H_(3)Co3,2,4,6-Me_(3)C_(6)H_(2)Co4,2,6-Et_(2)-4-MeC_(6)H_(2)Co5),each containing one N-4-methoxy-2,6-dibenzhydrylphenyl group and one smaller sterically/electronically variable N-aryl group,have been synthesized in good yield(>71%)from the corresponding neutral terdentate nitrogen-donor precursor,L1-L5.All complexes have been characterized by^(1)H-NMR and FTIR spectroscopy with the former highlighting the paramagnetic nature of these cobaltous species and the unsymmetrical nature of the chelating ligand.The molecular structures of Co3 and Co4 emphasize the steric differences of the two inequivalent N-aryl groups and the distorted square pyramidal geometry about the metal centers.In the presence of MAO or MMAO,Co1-Co5 collectively displayed high activities for ethylene polymerization producing high molecular weight polyethylenes that,in general,exhibited narrow dispersities(M_w/M_n values:2.12-4.07).Notably,the least sterically hindered Co1 when activated with MAO was the most productive(6.92×10^(6)g_(PE)·mol^(-1)_((Co))·h^(-1))at an operating temperature of60℃.Conversely,the most sterically hindered Co3/MMAO produced the highest molecular weight polyethylene(M_w=6.29×10^(5)g·mol^(-1)).All the polymers displayed high linearity as demonstrated by their melting temperatures(>130℃)and their~1 H-and^(13)C-NMR spectra.By comparison of Co1 with its para-methyl,-chloro and-nitro counterparts,the presence of the para-methoxy substituent showed the most noticeable effect of enhancing the thermal stability of the catalyst.

Dinuclear Nickel(Ⅱ) Chlorides Bearing N,N′-bis(5,6,7-trihydroquinolin-8-ylidene)-[1,1′-biphenyl]-4,4′-diamines: Synthesis and Ethylene Polymerization

5,6,7-Trihydroquinolin-8-one was condensed with the corresponding benzidine to give N,N′-bis（5,6,7-trihydroquinolin-8-ylidene）-[1,1′-biphenyl]-4,4′-diamine derivatives（L1–L3）. The ligands were reacted with two equivalents of Ni Cl2·6H2O in a mixture of Et OH and CH2Cl2 to afford the corresponding dinickel（II） chloride complexes（Ni1-Ni3）. The organic compounds were completely characterized, whilst the bi-metallic complexes were characterized by FTIR spectra and elemental analysis. These nickel complexes exhibited high activities towards ethylene polymerization in the presence of either MAO or Me2AlCl, maintaining a high activity over a prolonged period. The obtained polyethylenes were confirmed as having low molecular weights by GPC analysis.

Fusing Carbocycles of Inequivalent Ring Size to a Bis(imino)pyridine-Iron Ethylene Polymerization Catalyst: Distinctive Effects on Activity, PE Molecular Weight, and Dispersity

The 4,6-bis(arylimino)-1,2,3,7,8,9,10-heptahydrocyclohepta[b]quinoline-iron(II)chlorides(aryl=2,6-Me_(2)C_(6)H_(3) Fe1;2,6-Et_(2)C_(6)H_(3) Fe_(2);2,6-i-Pr_(2)C_(6)H_(3) Fe_(3);2,4,6-Me3C_(6)H_(2) Fe4;and 2,6-Et_(2)-4-Me_(2)C_(6)H_(2) Fe_(5))have been prepared in good yield by a straightforward one-pot reaction of 2,3,7,8,9,10-hexahydro-1H-cyclohepta[b]quinoline-4,6-dione,FeCl_(2)·4H_(2)O,and the appropriate aniline in acetic acid.All ferrous complexes have been characterized by elemental analysis and FT-IR spectroscopy.In addition,the structure of Fe_(3) has been determined by single crystal X-ray diffraction,which showed the iron center to adopt a distorted square pyramidal geometry with the saturated sections of the fused six-and sevenmembered carbocycles to be cis-configured.In combination with either MAO or MMAO,Fe1–Fe5 exhibited exceptionally high activities for ethylene polymerization(up to 15:86×10^(6) g(PE)mol^(−1)(Fe)h^(−1) at 40℃(MMAO)and 9:60×10^(6) g(PE)mol^(−1)(Fe)h^(−1) at 60℃(MAO))and produced highly linear polyethylene(HLPE,Tm≥128℃)with a wide range in molecular weights;in general,the MMAO-promoted polymerizations were more active.Irrespective of the cocatalyst employed,the 2,6-Me_(2)-substituted Fe1 and Fe4 proved the most active while the more sterically hindered 2,6-i-Pr_(2) Fe_(3) the least but afforded the highest molecular weight polyethylene(Mw:65.6–72.6 kg mol^(-1)).Multinuclear NMR spectroscopic analysis of the polymer formed using Fe4/MMAO at 40℃ showed a preference for fully saturated chain ends with a broad bimodal distribution a feature of the GPC trace(Mw/Mn=13:4).By contrast,using Fe4/MAO at 60℃ a vinyl-terminated polymer of lower molecular weight(Mw=14:2 kg mol^(−1))was identified that exhibited a unimodal distribution(Mw/Mn=3:8).Moreover,the amount of aluminoxane cocatalyst employed,temperature,and run time were also found to be influential on the modality of the polymer.

New family of single-component Ni catalysts for ethylene polymerization to high and ultrahigh molecular weight polyethylene

Since the milestone discovery of Ni(II)salicylaldiminate catalysts by Grubbs and co-workers[1],nickel(II)complexes with N,N-and N,O-donor ligands have strengthened their lead in the search for highly active platforms for olefins homo-and copolymerization with various co-monomers,including those with polar groups,to achieve polymers with precisely controlled microstructures[2,3].