Early Metal Di(pyridyl) Pyrrolide Complexes with Second Coordination Sphere Arene−π Interactions: Ligand Binding and Ethylene Polymerization

Early metal complexes supported by hemilabile, monoanionic di(pyridyl) pyrrolide ligands substituted with mesityl and anthracenyl groups were synthesized to probe the possibility of second coordination sphere arene−π interactions with ligands with potential for allosteric control in coordination chemistry, substrate activation, and olefin polymerization. Yttrium alkyl, indolide, and amide complexes were prepared and structurally characterized; close contacts between the anthracenyl substituents and Y-bound ligands are observed in the solid state. Titanium, zirconium, and hafnium tris(dimethylamido) complexes were synthesized, and their ethylene polymerization activity was tested. In the solid state structure of one of the Ti tris(dimethylamido) complexes, coordination of Ti to only one of the pyridine donors is observed pointing to the hemilabile character of the di(pyridyl) pyrrolide ligands

Olefin Polymerization by Dinuclear Zirconium Catalysts Based on Rigid Teraryl Frameworks: Effects on Tacticity and Copolymerization Behavior

Toward gaining insight into the behavior of bimetallic catalysts for olefin polymerization, a series of structurally related binuclear zirconium catalysts with bisamine bisphenolate and pyridine bisphenolate ligands connected by rigid teraryl units were synthesized. Anthracene-9,10-diyl and 2,3,5,6-tetramethylbenzene-1,4-diyl were employed as linkers. Bulky Si^iPr_3 and SiPh_3 substituents were used in the position ortho to the phenolate oxygen. Pseudo-C_s and C_2 symmetric isomers are observed for the binuclear complexes of bisamine bisphenolate ligands. In general, binuclear catalysts show higher isotacticity compared to the monozirconium analogues, with some differences between isomers. Amine bisphenolate-supported dizirconium complexes were found to be moderately active (up to 1.5 kg mmol_(Zr)^(–1) h^(–1)) for the polymerization of 1-hexene to isotactically enriched poly-1-hexene (up to 45% mmmm) in the presence of stoichiometric trityl or anilinium borate activators. Moderate activity was observed for the production of isotactically enriched polypropylene (up to 2.8 kg mmol_(Zr)^(–1) h^(–1) and up to 25.4% mmmm). The previously proposed model for tacticity control based on distal steric effects from the second metal site is consistent with the observed behavior. Both bisamine bisphenolate and pyridine bisphenolate supported complexes are active for the production of polyethylene in the presence of MAO with activities in the range of 1.1–1.6 kg mmol_(Zr)^(–1) h^(–1) and copolymerize ethylene with α-olefins. Little difference in the level of α-olefin incorporation is observed between mono- and dinuclear catalysts supported with the pyridine bisphenolate catalysts. In contrast, the size of the olefin affects the level of incorporation differently between monometallic and bimetallic catalysts for the bisamine bisphenolate system. The ratio of the incorporation levels with dinuclear vs mononuclear catalysts decreases with increasing comonomer size. This effect is attributed to steric pressure provided by the distal metal center on the larger olefin in dinuclear catalysts

In-Reactor Polypropylene Functionalization-The Influence of Catalyst Structures and Reaction Conditions on the Catalytic Performance

To unravel the relationship between silylene-bridged metallocene catalyst structures and polymerization conditions and their effect on the performance in in-reactor functionalization of polypropylene, the behaviors of rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MMAO, rac-Me2Si(Ind)2ZrCl2, rac-Me2Si(2-Me-4-Ph-Ind)2HfCl2, and rac-Me2Si(Ind)2HfCl2 in propylene/aluminum alkyl-passivated 10-undecen-1-ol copolymerization were compared. Kinetic analysis revealed higher catalytic activities for zirconocenes compared to analogous hafnocenes. Both the zirconocene and hafnocene with substituted indenyl ligands afforded a higher molecular weight capability, improved stereo-selectivity, and enhanced ability to incorporate functionalized comonomers compared to their non-substituted congeners. An in-depth study of polypropylene functionalization using the best performing catalyst system, rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MMAO, at temperatures ranging from 40 to 100 °C, revealed a linear inversely proportional correlation of polymerization temperature with functionalized comonomer reactivity (↑Tp → ↓ r1), copolymer molecular weight (↑Tp → ↓Mn), and melting temperature (↑Tp → ↓Tm). While performing well under standard laboratory polymerization conditions, rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2/MMAO showed limited molecular weight and stereo-selectivity capabilities under high-temperature (130-150 °C) solution process conditions. Although immobilization of rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 onto silica, allowing it to be used under industrially relevant slurry and gas-phase conditions, led to an active catalyst, it failed to incorporate any functionalized comonomer

Early Metal Di(pyridyl) Pyrrolide Complexes with Second Coordination Sphere Arene−π Interactions: Ligand Binding and Ethylene Polymerization

Early metal complexes supported by hemilabile, monoanionic di(pyridyl) pyrrolide ligands substituted with mesityl and anthracenyl groups were synthesized to probe the possibility of second coordination sphere arene−π interactions with ligands with potential for allosteric control in coordination chemistry, substrate activation, and olefin polymerization. Yttrium alkyl, indolide, and amide complexes were prepared and structurally characterized; close contacts between the anthracenyl substituents and Y-bound ligands are observed in the solid state. Titanium, zirconium, and hafnium tris(dimethylamido) complexes were synthesized, and their ethylene polymerization activity was tested. In the solid state structure of one of the Ti tris(dimethylamido) complexes, coordination of Ti to only one of the pyridine donors is observed pointing to the hemilabile character of the di(pyridyl) pyrrolide ligands

Mechanical, thermal and rheological properties of e-beam crosslinked ethylene octene copolymer

Ethylene-octene copolymer (EOC) with high octene content (45 wt.%) was crosslinked via electron beam irradiation at different dosages (30, 60, 90, and 120 kGy). Effect of irradiation dosage on thermal and mechanical properties was studied. When compared to low density polyethylene, EOC exhibited higher degree of crosslinking reflected in increased gel content, higher elastic modulus (G'), and lower tanδ obtained by rheology measurement at 150 °C. Crosslinking caused improvement in high temperature creep and also in elastic properties at room and elevated temperatures. Differential scanning calorimetry revealed that e-beam irradiation has caused a gradual reduction in crystallinity and a presence of a fraction with higher melting temperature. In the case of EOC, as the extent of crosslinking increased, stress at break showed an increasing trend whereas irradiation dosage had an inverse effect on elongation at break which could be aroused from the formation of crosslink networks. Radiation dosage has positive effect on thermal stability estimated by thermogravimetric analysis. After 30 min of thermal degradation at 220 °C, slightly higher C=O peak for crosslinked sample was found by Fourier transform infrared spectroscopy while for room temperature samples no C=O peak was detected. © 2022 Society of Plastics Engineers. All rights reserved

High temperature mechanical properties of peroxide cross-linked ethylene-octene copolymer

Ethylene-octene copolymer (EOC) was cross-linked by dicumyl peroxide (DCP). Thermoplastic vulcanizate (TPV) based on polypropylene (PP)/EOC-DCP was prepared by dynamic vulcanization. Gel content was noted. Tensile creep properties of these samples at elevated temperatures (70- 200°C) were studied. Residual strain after 100% and 200% elongation were examined. EOC cross-linked with lower peroxide levels underwent creep failure easily at lower temperatures even with small loads. EOC with 0.6 wt. % of DCP was found to be the strongest even at higher temperatures and lower temperatures with heavier loads

Effect of octene content on thermal and mechanical properties of crosslinked ethylene-octene copolymers

Two ethylene-octene copolymers (EOC - with octene wt.% of 20 and 35) were crosslinked using dicumyl peroxide (DCP). Crosslinking studies were done using rubber process analyzer (RPA) at 150-200 °C range. Highest s'max (maximum elastic torque) was found for EOC-20 with low octene content, always. High-octene EOC underwent more degradation. From dynamic mechanical analysis (DMA), storage modulus (M') and glass transition temperature (Tg) were found decreasing with increasing octene content. Differential scanning calorimetry (DSC) revealed the inverse effect of octene content on crystallinity and melting point. For high-octene EOC, increased β-scission has resulted in the poorer crosslinking and inferior properties

Creep and Dynamic mechanical analysis studies of peroxide-crosslinked ethylene-octene copolymer

An ethylene-octene copolymer (EOC) (45 wt% octene) is crosslinked using dicumyl peroxide (DCP). Differential scanning calorimetry (DSC) reveals a very low melting temperature (50 °C). The network density is evaluated by gel content. While 0.2-0.3 wt% of peroxide leads only to a molecular weight increase (samples completely dissolved in xylene), 0.4-0.6 wt% of peroxide caused network formation. High-temperature creep was measured at 70, 120, and 200 °C at three stress levels. At 200 °C and above 0.6 wt% of peroxide, degradation due to chain scission is observed by rubber process analyzer (RPA) and is again supported by creep measurements. Residual strain at 70 °C is found to improve with increasing peroxide level. Dynamic mechanical analysis (DMA) reveals a strong influence of peroxide content on storage modulus and tan δ, in particular in the range 30-200 °C

Effect of octene content on peroxide crosslinking of ethylene-octene copolymers

Various ethylene-octene copolymers were crosslinked by dicumyl peroxide. Octene content was 16, 20, 30, 35 and 38 wt% and melt flow index was 1 or 3 g/10 min. The concentration of dicumyl peroxide was 0.3, 0.5 and 0.7 wt%. Crosslinking was analyzed by a rubber process analyzer in the temperature range 150-200 °C. Cross-linkability was evaluated from the real part modulus s'max versus peroxide level plots as the slope of the line. With decreasing octene content and increasing melt flow index the crosslinkability increased. This was confirmed also by tan δ analysis. The network density was measured by the gel content. A higher gel content was found for melt flow index 3 and low octene content. The melting points Tm and the crystallinities were evaluated by DSC. © 2012 Society of Chemical Industry

Study on the influence of electron beam irradiation on the thermal, mechanical, and rheological properties of ethylene-octene copolymer with high comonomer content

Ethylene-octene copolymer (EOC) was irradiated using electron beam irradiation at different dosages (30, 60, 90, and 120 kGy). Effect of irradiation dosage on thermal and mechanical properties was studied. When compared to low density polyethylene, EOC exhibited higher degree of crosslinking reflected in increased gel content, higher elastic modulus (G′), and lower tan δ obtained by rheology measurement at 150°C. Crosslinking caused improvement in high-temperature creep and room temperature and also elevated temperature elastic properties. Differential scanning calorimetry revealed that e-beam irradiation has caused a gradual reduction in crystallinity and a presence of a fraction with higher melting temperature. In the case of EOC, as the extent of crosslinking increased, stress at break showed an increasing trend whereas irradiation dosage had an inverse effect on elongation at break. Radiation dosage has positive effect on thermal stability estimated by thermogravimetric analysis. After 30 min of thermal degradation at 220°C, slightly higher C=O peak for crosslinked sample was found by Fourier transform infrared spectroscopy while for room temperature samples no C=O peak was detected. © 2012 Wiley Periodicals, Inc