Synthesis,structural characterization,and olefin polymerization behavior of vanadium(III) complexes bearing bidentate phenoxy‐phosphine ligands

Vanadium(III) complexes bearing phenoxy‐phosphine ligands ( 2a–g ) (2‐R₁‐4‐R₂‐6‐PPh₂‐C₆H₂O)VCl₂(THF)₂ ( 2a : R₁ = R₂ = H; 2b : R₁ = F, R₂ = H; 2c : R₁ = Ph, R₂ = H; 2d : R₁ = tBu, R₂ = H; 2e : R₁ = R₂ = Me; 2f : R₁ = R₂ = tBu; 2g : R₁ = R₂ = CMe₂Ph) were prepared from VCl₃(THF)₃ by treating with 1.0 equiv of the ligand in tetrahydrofuran (THF) in the presence of excess triethylamine (TEA). The reaction of VCl₃(THF)₃ with 2.0 equiv of the ligand in THF in the presence of excess TEA afforded vanadium(III) complexes bearing two phenoxy‐phosphine ligands ( 3c–f ). These complexes were characterized by FTIR and mass spectrum as well as elemental analyses. Structures of 2f and 3c were further confirmed by X‐ray crystallographic analyses. Complexes 2a–g and 3c–f were employed as the catalysts for ethylene polymerization under various reaction conditions. On activation with Et₂AlCl, these complexes exhibited high catalytic activities (up to 41.3 kg PE/mmol_V·h·bar) even at high temperature (70°C), and produced high molecular weight polymer with unimodal molecular weight distributions, indicating the polymerization took place in a single‐site nature. Complexes 3c–f displayed better thermal stability than the corresponding complexes 2a–g under similar conditions. In addition, copolymerizations of ethylene and 1‐hexene with precatalysts 2a–g were also explored in the presence of Et₂AlCl. Catalytic activity, comonomer incorporation, and properties of the resultant polymers can be controlled over a wide range by tuning catalyst structures and reaction parameters.© 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ethylene polymerizations,and the copolymerizations of ethylene with hexene or norbornene with highly active mono(β‐enaminoketonato) vanadium(III) catalysts

Five novel vanadium(III) complexes [PhN = C(R₂)CHC(R₁)O]VCl₂(THF)₂ ( 4a : R₁ = Ph, R₂ = CF₃; 4b : R₁ = t‐Bu, R₂ = CF₃; 4c : R₁ = CF₃, R₂ = CH₃; 4d : R₁ = Ph, R₂ = CH₃; 4e : R₁ = Ph, R₂ = H) have been synthesized and characterized. On activation with Et₂AlCl, all the complexes, in the presence of ethyl trichloroacetate (ETA) as a promoter, are highly active precatalysts for ethylene polymerization, and produce high molecular weight and linear polymers. Catalyst activities more than 16.8 kg PE/mmol_V h bar and weight‐average molecular weights higher than 173 kg/mol were observed under mild conditions. The copolymerizations of ethylene and norbornene or 1‐hexene with the precatalysts were also explored, which leads to high molecular weight copolymers with high comonomer incorporation. Catalyst activity, comonomer incorporation, and polymer molecular weight as well as polydispersity index can be controlled over a wide range by the variation of precatalyst structure and the reaction parameters such as Al/V molar ratio, comonomer feed concentration, and polymerization temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2038–2048, 2008     

Bis(β‐enaminoketonato) vanadium (III or IV) complexes as catalysts for olefin polymerization

Bis(β‐enaminoketonato) vanadium(III) complexes ( 2a–c ) [O(R₁)C?C(H)_xC(R₂)?NC₆H₅]₂VCl(THF) and the corresponding vanadium(IV) complexes ( 3a–c ) [O(R₁)C?C(H)_xC(R₂)? NC₆H₅]₂VO (R₁ = ? (CH₂)₄? , R₂ = H, x = 0, a ; R₁ = ? C₆H₅, R₂ = H, x = 1, b ; R₁ = ? C₆H₅, R₂ = ? C₆H₅, x = 1, c ) have been synthesized from VCl₃(THF)₃ and VOCl₂(THF)₂, respectively, by treating with 2.0 equivalent β‐enaminoketonato ligands in tetrahydrofuran. Structures of 2b and 3a–c were further confirmed by X‐ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et₂AlCl. Complexes 2a–c and 3a–c exhibited high catalytic activities (up to 23.76 kg of PE/mmol_V h bar), and afforded polymers with unimodal molecular weight distributions at 70 °C indicating the good thermal stability. The catalytic behaviors were influenced not only by the oxidation state of the catalyst precursors but also by the ligand structures. Complexes 2a–c and 3a–c were also effective catalyst precursors for ethylene/1‐hexene copolymerization. The influence of polymerization parameters such as reaction temperature, Al/V molar ratio and hexene feed concentration on the ethylene/hexene copolymerization behaviors have bee also investigated in detail. In addition, the agents such as AlMe₃, AlⁱBu₃, MeMgBr, MgCl₂, and ZnEt₂ were applied to control the molecular weight and molecular weight distribution modal. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3062–3072, 2010     

Ethylene/α‐olefin copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Copolymerizations of ethylene with α‐olefins (i.e., 1‐hexene, 1‐octene, allylbenzene, and 4‐phenyl‐1‐butene) using the bis(β‐enaminoketonato) titanium complexes [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ ( 1a : R₁ = CF₃, R₂ = CH₃; 1b : R₁ = Ph, R₂ = CF₃; and 1c : R₁ = t‐Bu, R₂ = CF₃), activated with modified methylaluminoxane as a cocatalyst, have been investigated. The catalyst activity, comonomer incorporation, and molecular weight, and molecular weight distribution of the polymers produced can be controlled over a wide range by the variation of the catalyst structure, α‐olefin, and reaction parameters such as the comonomer feed concentration. The substituents R₁ and R₂ of the ligands affect considerably both the catalyst activity and comonomer incorporation. Precatalyst 1a exhibits high catalytic activity and produces high‐molecular‐weight copolymers with high α‐olefin insertion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6323–6330, 2005     

Highly efficient ethylene/norbornene copolymerization by o‐Di(phenyl)phosphanylphenolate‐based half‐titanocene complexes

A series of o‐di(phenyl)phosphanylphenolate‐based half‐titanocene complexes CpTiCl₂[O‐2‐R¹‐4‐R²‐6‐(Ph₂P)C₆H₂] (Cp = C₅H₅, 2a : R¹ = R² = H; 2b : R¹ = F, R² = H; 2c : R¹ = Ph, R² = H; 2d : R¹ = SiMe₃, R² = H; 2e : R¹ = ^tBu, R² = H; 2f : R¹ = R² = ^tBu) have been synthesized in high yields (65–87%) by treating CpTiCl₃ with 1.0 equiv of the deprotonated ligands in THF. The ¹H and ³¹P NMR spectra indicated that the phosphorus is not coordinated to titanium in complexes 2a – c , but is coordinated to titanium in complexes 2d – f . Structures for 2c – f were further confirmed by X‐ray crystallography. Complex 2c is essentially a four‐coordinate tetrahedral geometry, whereas complexes 2d ‐ f adopt five‐coordinate distorted square–pyramid geometry around the titanium center. All complexes exhibited low to moderate activities toward homopolymerization of ethylene. Excitingly, they displayed excellent ability to copolymerize ethylene with norbornene, and catalytic activity was more than 100 times larger than that of ethylene homopolymerization in the case of Ph₃CB(C₆F₅)₄/ⁱBu₃Al as cocatalyst, affording the copolymers with high comonomer incorporations. Moreover, DFT calculations study had been performed to shed light on the active species and the fundamental role of NBE in improving the catalytic activity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013     

Quasi‐living copolymerization of ethylene with 1‐hexene by heteroligated (salicylaldiminato β‐enaminoketonato) titanium complexes

A series of heteroligated (salicylaldiminato)(β‐enaminoketonato)titanium complexes [3‐Bu^t‐2‐OC₆H₃CH = N(C₆F₅)] [PhN = C(R₁)CHC(R₂)O]TiCl₂ [ 3a : R₁ = CF₃, R₂ = ^tBu; 3b : R₁ = Me, R₂ = CF₃; 3c : R₁ = CF₃, R₂ = Ph; 3d : R₁ = CF₃, R₂ = C₆H₄Ph(p ); 3e : R₁ = CF₃, R₂ = C₆H₄Ph(o ); 3f : R = CF₃, R₂ = C₆H₄Cl(p ); 3g : R₁ = CF₃; R₂ = C₆H₃Cl₂(2,5); 3h : R₁ = CF₃, R₂ = C₆H₄Me(p )] were investigated as catalysts for ethylene (co)polymerization. In the presence of modified methylaluminoxane as a cocatalyst, these complexes showed activities about 50%–1000% and 10%–100% higher than their corresponding bis(β‐enaminoketonato) titanium complexes for ethylene homo‐ and ethylene/1‐hexene copolymerization, respectively. They produced high or moderate molecular weight copolymers with 1‐hexene incorporations about 10%–200% higher than their homoligated counterpart pentafluorinated FI‐Ti complex. Among them, complex 3b displayed the highest activity [2.06 × 10⁶ g/mol_Ti?h], affording copolymers with the highest 1‐hexene incorporations of 34.8 mol% under mild conditions. Moreover, catalyst 3h with electron‐donating group not only exhibited much higher 1‐hexene incorporations (9.0 mol% vs. 3.2 mol%) than pentafluorinated FI‐Ti complex but also generated copolymers with similar narrow molecular weight distributions (M _w/M _n = 1.20–1.26). When the 1‐hexene concentration in the feed was about 2.0 mol/L and the hexene incorporation of resultant polymer was about 9.0 mol%, a quasi‐living copolymerization behavior could be achieved. ¹H and ¹³C NMR spectroscopic analysis of their resulting copolymers demonstrated the possible copolymerization mechanism, which was related with the chain initiation, monomer insertion style, chain transfer and termination during the polymerization process. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2787–2797     

Synthesis of novel zirconium complexes bearing mono‐Cp and tridentate Schiff base [ONO] ligands and their catalytic activities for olefin polymerization

A series of novel zirconium complexes {R²Cp[2‐R¹‐6‐(2‐CH₃OC₆H₄N?CH)C₆H₃O]ZrCl₂ ( 1 , R¹ = H, R² = H, 2 : R¹ = CH₃, R² = H; 3 , R¹ = ^tBu, R² = H; 4 , R¹ = H, R² = CH₃; 5 , R¹ = H, R² = n‐Bu)} bearing mono‐Cp and tridentate Schiff base [ONO] ligands are prepared by the reaction of corresponding lithium salt of Schiff base ligands with R²CpZrCl₃·DME. All complexes were well characterized by ¹H NMR, MS, IR and elemental analysis. The molecular structure of complex 1 was further confirmed by X‐ray diffraction study, where the bond angle of Cl? Zr? Cl is extremely wide [151.71(3)°]. A nine‐membered zirconoxacycle complex Cp(O? 2? C₆H₄N?CHC₆H₄‐2? O)ZrCl₂ ( 6 ) can be obtained by an intramolecular elimination of CH₃Cl from complex 1 or by the reaction of CpZrCl₃·DME with dilithium salt of ligand. When activated by excess methylaluminoxane (MAO), complexes 1–6 exhibit high catalytic activities for ethylene polymerization. The influence of polymerization temperature on the activities of ethylene polymerization is investigated, and these complexes show high thermal stability. Complex 6 is also active for the copolymerization of ethylene and 1‐hexene with low 1‐hexene incorporation ability (1.10%). Copyright © 2006 John Wiley & Sons, Ltd.     

Polypropylene and poly(ethylene‐co‐1‐octene) effective synthesis with diamine‐bis(phenolate) complexes: Effect of complex structure on catalyst activity and product microstructure

A series of group 4 metal complexes bearing amine‐bis(phenolate) ligands with the amino side‐arm donor: (μ‐O)[Me₂N(CH₂)₂N(CH₂‐2‐O‐3,5‐tBu₂‐C₆H₂)₂ZrCl]₂ ( 1a ), R₂N(CH₂)₂N(CH₂‐2‐O‐3‐R¹‐5‐R²‐C₆H₂)₂TiCl₂ (R = Me, R¹, R² = tBu ( 2a ), R = iPr, R¹, R² = tBu ( 2b ), R = iPr, R¹ = tBu, R² = OMe ( 2c )), and Me₂N(CH₂)₂N(CH₂‐2‐O‐3,5‐tBu₂‐C₆H₂)(CH₂‐2‐O‐C₆H₄)TiCl₂ ( 2d ) are used in ethylene and propylene homopolymerization, and ethylene/1‐octene copolymerization. All complexes, upon their activation with Al(iBu)₃/Ph₃CB(C₆F₅)₄, exhibit reasonable catalytic activity for ethylene homo‐ and copolymerization giving linear polyethylene with high to ultra‐high molecular weight (600·× 10³–3600·× 10³ g/mol). The activity of 1a /Al(iBu)₃/Ph₃CB(C₆F₅)₄ shows a positive comonomer effect, leading to over 400% increase of the polymer yield, while the addition of 1‐octene causes a slight reduction of the activity of the complexes 2a‐2d . The complexes with the NMe₂ donor group ( 2a , 2d , 1a ) display a high ability to incorporate a comonomer (up to 9–22 mol%), and the use of a bulkier donor group, N(iPr)₂ ( 2b , 2c ), results in a lower 1‐octene incorporation. All the produced copolymers reveal a broad chemical composition distribution. In addition, the investigated complexes polymerized propylene with the moderate ( 1a , 2a ) to low ( 2b‐2d ) activity, giving polymers with different microstructures, from purely atactic to isotactically enriched (mmmm = 28%). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2467–2476     

Vanadium(III) complexes containing phenoxy–imine–thiophene ligands: Synthesis,characterization and application to homo‐ and copolymerization of ethylene

A set of vanadium(III) complexes, namely {SNO}VCl₂(THF)₂ ( 2a , SNO = thiophene‐(N═CH)‐phenol; 2b , SNO = 5‐phenylthiophene‐(N═CH)‐phenol; 2c , SNO = 5‐phenylthiophene‐(N═CH)‐4‐tert ‐butylphenol; 2d , SNO = 5‐methylthiophene‐(N═CH)‐phenol; 2e , SNO = 5‐methylthiophene‐(N═CH)‐4‐tert ‐butylphenol; 2f , SNO = 5‐methylthiophene‐(N═CH)‐2‐methylphenol; 2g , SNO = 5‐methylthiophene‐(N═CH)‐4‐fluorophenol), were synthesized by reaction of VCl₃(THF)₃ with phenoxy–imine–thiophene proligands ( 1a – g ). All vanadium(III) complexes were characterized using elemental analysis and infrared and electron paramagnetic resonance spectroscopies. Upon activation with methylaluminoxane (MAO), vanadium precatalysts 2a – g proved active in the polymerization of ethylene (213.6–887.2 kg polyethylene (mol[V])⁻¹⋅h⁻¹), yielding high‐density polyethylenes with melting temperatures in the range 133–136 °C and crystallinities varying from 28 to 41%. The 2e/ MAO catalyst system was able to copolymerize ethylene with 1‐hexene affording poly(ethylene‐co ‐1‐hexene)s with melting temperatures varying from 126 to 102 °C and co‐monomer incorporation in the range 3.60–4.00%.     

Ethylene polymerization and ethylene/hexene copolymerization with vanadium(III) catalysts bearing heteroatom‐containing salicylaldiminato ligands

A series of novel vanadium(III) complexes bearing heteroatom‐containing group‐substituted salicylaldiminato ligands [RN?CH(ArO)]VCl₂(THF)₂ (Ar = C₆H₄, R = C₃H₂NS, 2a ; C₇H₄NS, 2c ; C₇H₅N₂, 2d ; Ar = C₆H₂tBu₂ (2,4), R = C₃H₂NS, 2b ) have been synthesized and characterized. Structure of complex 2c was further confirmed by X‐ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et₂AlCl. Complexes 2a–d exhibited high catalytic activities (up to 22.8 kg polyethylene/mmol_V h bar), and affording polymer with unimodal molecular weight distributions at 25–70 °C in the first 5‐min polymerization, whereas produced bimodal molecular weight distribution polymers at 70 °C when polymerization time prolonged to 30 min. The catalyst structure plays an important role in controlling the molecular weight and molecular weight distribution of the resultant polymers produced in 30 min polymerization. In addition, ethylene/hexene copolymerizations with catalysts 2a–d were also explored in the presence of Et₂AlCl, which leads to the high molecular weight and unimodal distributions copolymers with high comonomer incorporation. Catalytic activity, comonomer incorporation, and polymer molecular weight can be controlled over a wide range by the variation of catalyst structure and the reaction parameters, such as comonomer feed concentration, polymerization time, and polymerization reaction temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3573–3582, 2009     

Ethylene polymerization of the new titanium complexes bearing a phosphine oxide‐bridged bisphenolato ligand

A series of novel titanium(IV) complexes combining a phosphine oxide‐bridged bisphenolato ligand TiCl₂{2,2′‐O?P‐R₃ (4‐R₂‐6‐R₁‐C₆H₂O)₂}(THF) ( 6a : R₁ = tBu, R₂ = H, R₃ = Ph; 6b : R₁ = Ph, R₂ = H, R₃ = Ph; 6c : R₁ = R₂ = tBu, R₃ = Ph; 6d : R₁ = R₂ = cumyl, R₃ = Ph; 6e : R₁ = tBu, R₂ = H, R₃ = PhF₅) were prepared by the reaction of corresponding bisphenolato ligands with TiCl₄ in THF. X‐ray analysis reveals that complex 6a adopts distorted octahedral geometry around the titanium center. These catalysts were performed for ethylene polymerization in the presence of modified methyaluminoxane (MMAO). The effects of reaction parameters on ethylene polymerization behaviors, such as cocatalyst concentration, polymerization temperature, and reaction time were studied in detail. In general, these new complexes exhibited high catalytic activity, good temperature tolerance, and long lifetime for ethylene polymerization. The resulting polymers possess high molecular weight, unimodal distribution, and linear structure. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7062–7073, 2008     

α‐olefin homopolymerization and ethylene/1‐hexene copolymerization catalysed by novel ansa‐group IV complexes/MAO system

The catalytic properties of a set of ansa‐complexes (R‐Ph)₂C(Cp)(Ind)MCl₂ [R = ^tBu, M = Ti ( 3 ), Zr ( 4 ) or Hf ( 5 ); R = MeO, M = Zr ( 6 ), Hf ( 7 )] in α‐olefin homopolymerization and ethylene/1‐hexene copolymerization were explored in the presence of MAO (methylaluminoxane). Complex 4 with steric bulk ^tBu group on phenyl exhibited remarkable catalytic activity for ethylene polymerization. It was 1.6‐fold more active than complex 11 [Ph₂C(Cp)(Ind)ZrCl₂] at 11 atm ethylene pressure and was 4.8‐fold more active at 1 atm pressure. The introduction of bulk substituent ^tBu into phenyl groups not only increased the catalytic activity greatly but also enhanced the content of 1‐hexene in ethylene/1‐hexene copolymerization. The highest 1‐hexene incorporation was 25.4%. In addition, 4 was also active for propylene and 1‐hexene homopolymerization, respectively, and low isotactic polypropylene (mmmm = 11.3%) and isotactic polyhexene (mmmm = 31.6%) were obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

Dramatic electronic effect of fluoro substituents on the olefin polymerization activity of mono β‐diiminato titanium complexes

A series of new mono β‐diiminato titanium complexes [(N(Ar)C(CH₃))₂ CH]TiCl₃ ( 3a : Ar = 2.6‐F₂C₆H₃; 3b : Ar = C₆F₅; 3c : Ar = 2.6‐Me₂C₆H₃) have been synthesized and characterized. The crystal structure of 3a revealed that the β‐diiminato ligand in our complex is more close to the η²‐coordination mode with little delocalization of the double bonds, which is different from the strong delocalization in the ligands of η⁵‐coordinated (Tolnacnac)TiCl₃ and η²‐coordinated (Dipnacnac)ZrCl₃. The significant electronic effects of fluoro‐substituents on the olefin polymerization activity of mono β‐diiminato titanium complexes were found. Titanium complexes with fluorine‐containing β‐diiminato ligands, on activation with MMAO, are extremely active catalysts for polymerization of ethylene. The activity of copolymerization of ethylene and 1‐hexene is higher than homopolymerization of ethylene and increases with the increase of 1‐hexene concentrations, which show the positive “comonomer effect.” The molar percentage of 1‐hexene incorporation and polymer microstructures can also be modulated by the initial comonomer concentrations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 211–217, 2008     

Ethene homopolymerization and copolymerization with 1‐hexene for all methyl‐substituted (RnC5H5−n)2ZrCL2/MAO catalytic systems: Effects of split methyl substitution

Ethene homopolymerization and copolymerization with 1‐hexene were catalyzed by methyl‐substituted cyclopentadienyl (Cp) zirconium dichlorides, (R_n C₅H_5−n)₂ZrCl₂ (R_n = H, Me, 1,2‐Me₂, 1,3‐Me₂, 1,2,3‐Me₃, 1,2,4‐Me₃, Me₄, or Me₅), and methylaluminoxane. The polymers were characterized with Fourier transform infrared, nuclear magnetic resonance, gel permeation chromatography, and differential scanning calorimetry techniques. Generally, an increasing number of methyl substituents on the Cp ligand results in lower 1‐hexene incorporation in the copolymer. The two catalysts with split methyl substitution (R_n = 1,3‐Me₂ and R_n = 1,2,4‐Me₃) show a higher comonomer response than their disubstituted and trisubstituted counterparts (R_n = 1,2‐Me₂ and R_n = 1,2,3‐Me₃). They even incorporate more 1‐hexene than R_n = H and R_n = Me. These findings are qualitatively in agreement with the results of a theoretical study based on density functional calculations. The presence of comonomer does not influence the termination reactions after the insertion of ethene. There is more frequent termination after each hexene insertion with increasing comonomer incorporation except for the two catalysts with split methyl substituents. The termination probability per inserted comonomer is highest for the less substituted catalysts. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3161–3172, 2000     

Ethylene polymerization by the chromium catalysts based on bidentate [O,PO] or [S,P] ligands

Novel chromium catalysts based on bidentate phenoxy‐phosphinoyl (HO‐2R₁‐4R₂‐6(Ph₂P?O)C₆H₂: R₁ = R₂ = H, 3a ; R₁ = tBu, R₂ = H, 3b ; R₁ = R₂ = tBu, 3c ; R₁ = R₂ = cumyl, 3d ; R₁ = anthracenyl, R₂ = H, 3e ) and thiophenol‐phosphine (HS‐2R₁‐4R₂‐6(Ph₂P)C₆H₂: R₁ = R₂ = H, 4a ; R₁ = SiMe₃, R₂ = H, 4b ) were prepared and characterized. Treatment with modified methyaluminoxane, these catalysts displayed moderate to high‐catalytic activities for ethylene polymerization. The activities of them were higher than those of the corresponding catalysts based on bidentate phenoxy‐phosphine ligands. Both the coordinated donors and the ortho‐substituent of the ligands played an important role in improving catalytic activity. The effects of reaction parameters, such as cocatalyst and Al/Cr molar ratio as well as reaction temperature, on ethylene polymerization behaviors were investigated in detail for two favorable catalytic systems, 3b /CrCl₃(thf)₃ and 4b /CrCl₃(thf)₃. Catalyst 4b /CrCl₃(thf)₃ displayed higher catalytic activity and better temperature tolerance for ethylene polymerization than 3b /CrCl₃(thf)₃. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 311–319, 2010     

Ethylene polymerization and ethylene/hexene copolymerizaion with vandium catalysts bearing thiophenolphosphine ligands

Vanadium(Ⅲ) complexes bearing thiophenol-phosphine ligands (2a-2b) (2-R-6-PPh2-C6H2S) VCl2(THF)2 (2a: R=H; 2b: R=Me3Si) were prepared from VCl3(THF)3 by treating with 1.0 equiv of the ligand in tetrahydrofuran in the presence of excess triethylamine. The two complexes were characterized by FTIR and mass spectra as well as elemental analyses. On activation with Et2AlCl, these complexes exhibited high catalytic activities (up to 22.1 kg PE/(mmolV·h·bar)) even at high temperature (70℃), and produced high molecular weight polymers with unimodal molecular weight distributions, indicating the polymerization took place in a single-site nature. This result may be attributed to benefits of introduction of second-row donor atoms for adjusting charge density of the vanadium centers. In addition, these complexes also exhibited high catalytic activities for ethylene/1-hexene copolymerization. Catalytic activity, comonomer incorporation and polymer molecular weight can be controlled in a wide range by the variation of catalyst structure and the reaction parameters such as Al/V molar ratio, comonomer feed concentration and polymerization reaction temperature.     

Copolymerization of ethylene and cyclopentene with bis(β‐enaminoketonato) titanium complexes

The copolymerizations of ethylene and cyclopentene with bis(β‐enaminoketonato) titanium complexes {[(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂; R₁ = CF₃ and R₂ = CH₃ for 1a , R₁ = Ph and R₂ = CF₃ for 1b ; and R₁ = t‐Bu and R₂ = CF₃ for 1c } activated with modified methylaluminoxane (MMAO) as a cocatalyst were investigated. High‐molecular‐weight copolymers with cis‐1,2‐cyclopentene units were obtained. The catalyst activity, cyclopentene incorporation, polymer molecular weight, and polydispersity could be controlled over a wide range through the variation of the catalyst structure and reaction parameters, such as the Al/Ti molar ratio, cyclopentene feed concentration, and polymerization reaction temperature. The complex 1b /MMAO catalyst system exhibited the characteristics of a quasi‐living ethylene polymerization and an ethylene–cyclopentene copolymerization and allowed the synthesis of polyethylene‐block‐poly(ethylene‐co‐cyclopentene) diblock copolymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1681–1689, 2005     

High molar mass ethene/1‐olefin copolymers synthesized with acenaphthyl substituted metallocene catalysts

The influence of ligand structure on copolymerization properties of metallocene catalysts was elucidated with three C₁‐symmetric methylalumoxane (MAO) activated zirconocene dichlorides, ethylene(1‐(7, 9)‐diphenylcyclopenta‐[a]‐acenaphthadienyl‐2‐phenyl‐2‐cyclopentadienyl)ZrCl₂ ( 1 ), ethylene(1‐(7, 9)‐diphenylcyclopenta‐[a]‐acenaphthadienyl‐2‐phenyl‐2‐fluorenyl)ZrCl₂ ( 2 ), and ethylene(1‐(9)‐fluorenyl‐(R)1‐phenyl‐2‐(1‐indenyl)ZrCl2 ( 3 ). Polyethenes produced with 1 /MAO had considerable, ca. 10% amount of trans‐vinylene end groups, resulting from the chain end isomerization prior to the chain termination. When ethene was copolymerized with 1‐hexene or 1‐hexadecene using 1 /MAO, molar mass of the copolymers varied from high to moderate (531–116 kg/mol) depending on the comonomer feed. At 50% comonomer feed, ethene/1‐olefin copolymers with high hexene or hexadecene content (around 10%) were achievable. In the series of catalysts, polyethenes with highest molar mass, up to 985 kg/mol, were obtained with sterically most crowded 2 /MAO, but the catalyst was only moderately active to copolymerize higher olefins. Catalyst 3 /MAO produced polyethenes with extremely small amounts of trans‐vinylene end groups and relatively low molar mass 1‐hexene copolymers (from 157 to 38 kg/mol) with similar comonomer content as 1 . These results indicate that the catalyst structure, which favors chain end isomerization, is also capable to produce high molar mass 1‐olefin copolymers with high comonomer content. In addition, an exceptionally strong synergetic effect of the comonomer on the polymerization activity was observed with catalyst 3 /MAO. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 373–382, 2008     

Copolymerization of ethylene with 1‐hexene promoted by novel multi‐chelated non‐metallocene complexes with imine bridged imidazole ligand

A series of novel bridged multi‐chelated non‐metallocene catalysts is synthesized by the treatment of N,N‐imidazole, N,N‐dimethylimidazole, and N,N‐benzimidazole with n‐BuLi, 2,6‐dimethylaniline, and MCl₄ (M = Ti, Zr) in THF. These catalysts are used for copolymerization of ethylene with 1‐hexene after activated by methylaluminoxane (MAO). The effects of polymerization temperature, Al/M molar ratio, and pressure of monomer on ethylene copolymerization behaviors are investigated in detail. These results reveal that these catalysts are favorable for copolymerization of ethylene with 1‐hexene featured high catalytic activity and high comonomer incorporation. The copolymer is characterized by ¹³C NMR, WAXD, GPC, and DSC. The results confirm that the obtained copolymer features broad molecular weight distribution (MWD) about 33–35 and high 1‐hexene incorporation up to 9.2 mol %, melting temperature of the copolymer depends on the content of 1‐hexene incorporation within the copolymer chain and 1‐hexene unit in the copolymer chain isolates by ethylene units. The homopolymer of ethylene has broader MWD with 42–46. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 417–424, 2010     

Ethylene homopolymerizaton and copolymerizaton by vanadium(III) complexes containing tridentate or tetradentate iminopyrrolyl ligands

Iminopyrrolyl vanadium(III) complexes 2a–b bearing tridentate ligands [C₄H₃NCH?NC₆H₄L]VCl₂(THF) [L = 2‐P(C₆H₅)₂ ( 2a ), 2‐SMe ( 2b )] and complexes 2c–d with tetradentate ligands [(C₄H₃NCH?N)₂R]VCl(THF) [R = 1,2‐C₆H₄ ( 2c ), 1,2‐C₂H₄ ( 2d )] have been synthesized in high yields. With diethylaluminium chloride as a cocatalyst, complexes 2a–d were investigated as efficient catalysts for ethylene polymerization under various reaction conditions, and exhibited high catalytic activity and remarkable thermal stability. With these complexes, high molecular weight polymers with unimodal molecular weight distributions were obtained, indicating that the polymerization reaction took place in a single‐site nature. Ethylene/1‐hexene copolymerizations were also investigated in the presence of Et₂AlCl. Both increasing ligand denticity and introducing softer atom into the sidearm of the ligands significantly influenced catalytic activity, comonomer incorporation, and the molecular weights of the resultant polymers, suggesting that both the steric and the electronic effects of the ligands played an important role in adjusting chain propagation and transfer rate. The chain transfer mechanisms involved in the copolymerization process were investigated by carefully analyzing the microstructure of the copolymers. The signals of vinyl, disubstituted and tri‐substituted vinylene double bond end groups were detected in the copolymer obtained by 2a /Et₂AlCl system but not in those by 2b–c /Et₂AlCl systems, indicating that bulky electron‐donating group, ? P(C₆H₅)₂, may lead to those unusual transfer reactions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011