Olefin polymerization and copolymerization
Fengtao Li; Jing Wang; Xuelian He
Abstract
In this study, a titanium-based constrained geometry catalyst, [t-BuNSiMe2(Me4Cp)]TiMe2, was synthesized and activated with methylaluminoxane for ethylene-propylene random and block copolymerization. The catalyst exhibited optimal activity at 70°C, yielding random copolymer chains with trace amounts ...
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In this study, a titanium-based constrained geometry catalyst, [t-BuNSiMe2(Me4Cp)]TiMe2, was synthesized and activated with methylaluminoxane for ethylene-propylene random and block copolymerization. The catalyst exhibited optimal activity at 70°C, yielding random copolymer chains with trace amounts of long polyethylene crystalline segments. When the ethylene content fell below 35%, random copolymers failed to crystallize. The block copolymerization system achieved maximum catalytic activity at a reaction temperature of 50°C and an ethylene block duration of 10 minutes. Shorter ethylene block durations correlated inversely with enhanced catalytic activity, increased molecular weight (peaking at 2.88 × 105 g/mol), and a narrower molecular weight distribution. The predominant component comprised extended PPP segments, constituting over 50% of the total copolymer composition. Within the polymer chains, propylene monomers were primarily incorporated as PPP and PPE structural motifs. Moreover, a progressive decrease in [PPP] content was observed with increasing ethylene block duration, whereas [PPE] content exhibited the opposite trend. This inverse relationship suggested that PPP segments gradually transform into PPE configurations via ethylene monomer insertion. These findings demonstrated that product structure and properties can be effectively tuned by adjusting initial monomer feed ratios or the timing of monomer block introduction.
Olefin polymerization and copolymerization
Evgeny E Faingol'd; Stanislav L. Saratovskikh; Andrei N. Panin; Olga N. Babkina; Igor V. Zharkov; Artur T. Kapasharov; Nikita N. Lashmanov; Gennadii V. Shilov; Natalia M. Bravaya
Abstract
Ethylene-propylene copolymerization reactions were carried out using rac-Et(2-MeInd)2ZrMe2 catalyst and (2,6-tBu2PhO-)AliBu2 as activator under varying reaction conditions. We demonstrate that reaction conditions such as monomer concentration, Al/Zr molar ratio and solvent type (toluene and heptane) ...
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Ethylene-propylene copolymerization reactions were carried out using rac-Et(2-MeInd)2ZrMe2 catalyst and (2,6-tBu2PhO-)AliBu2 as activator under varying reaction conditions. We demonstrate that reaction conditions such as monomer concentration, Al/Zr molar ratio and solvent type (toluene and heptane) all have significant effect on activity of the system and copolymers composition. The decrease in reaction pressure from 11 to 3 atm leads to: a) 1.6-fold increase in specific activity (from 3030 to 4840 kg copolymer/(mol Zr•h•atm)), b) increase of Mn value from 38 to 89 kg/mol, and c) increase of ethylene content in copolymer from 87 to 92 mol %. The increase of ethylene/propylene molar ratio from 0.7 to 2 does not significantly affect activity but leads to the rise in the ethylene content in copolymer from 92 to 97 mol % and, correspondingly, to the increase of copolymer crystallinity from 43 to 48%. As a result, thermal and mechanical properties of the obtained polymers also change, according to the shifts in copolymers composition. The change in Al/Zr molar ratio is confirmed to have great effect on the catalytic activity of our systems. In a row of Al/Zr= 100, 150, 200, 300 mol/mol, the lowest activity of 80 and the highest one of 8550 kg copolymer/(mol Zr•h•atm) are observed at 100 and 150 molar ratios correspondingly. We have also demonstrated the ability of catalytic systems with isobutylaluminum aryloxide activators to operate in aliphatic medium (heptane). On another note, during the reaction quenching, aryloxide activator hydrolyzes the polymer infused with 2,6-di-tert-butylphenol antioxidant. This results in the increased resistance of copolymers to the thermal-oxidative degradation. The presence of 4 wt.% phenol in the copolymer leads to an increase in the 5% mass loss temperature by 67°C. Moreover, increasing the residual phenol content from 2 to 4 wt.% affects the mechanical properties of the copolymers: the elongation-at-break increases from 500 to 600%, and the tensile strength decreases from 10 to 8 MPa.
