Influence of reaction conditions on catalytic properties of rac-Et(2-MeInd)2ZrMe2/(2,6-tBu2PhO-)AliBu2 in ethylene-propylene copolymerization

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

Homogeneous Group IVB Catalysts of New Generations for Synthesis of Ethylene-Propylene-Diene Rubbers: A Mini-Review

Ethylene-propylene-diene rubbers (EPDM) are one of the most important polyolefin materials widely commercialized and used in various industries in recent years. The production of EPDM is based solely on catalytic coordination polymerization processes. The development of new catalysts and processes for the synthesis of EPDM has expanded the range of products and their manufacturing in terms of energy efficiency, processability, and environmental safety. This mini-review mainly analyzes patented data on the synthesis of EPDM on new-generation single-site catalytic systems based on Group IVB complexes including the systems commercialized by major manufacturers of EPDM. The advantages of these systems are evident in comparison with conventional vanadium systems introduced into production in the 1960s and used to date in the industrial synthesis of EPDM

Homogeneous Group IVB Catalysts of New Generations for Synthesis of Ethylene-Propylene-Diene Rubbers: A Mini-Review

Ethylene-propylene-diene rubbers (EPDM) are one of the most important polyolefin materials widely commercialized and used in various industries in recent years. The production of EPDM is based solely on catalytic coordination polymerization processes. The development of new catalysts and processes for the synthesis of EPDM has expanded the range of products and their manufacturing in terms of energy efficiency, processability, and environmental safety. This mini-review mainly analyzes patented data on the synthesis of EPDM on new-generation single-site catalytic systems based on Group IVB complexes including the systems commercialized by major manufacturers of EPDM. The advantages of these systems are evident in comparison with conventional vanadium systems introduced into production in the 1960s and used to date in the industrial synthesis of EPDM

Synthesis and Properties of Ethylene/propylene and Ethylene/propylene/5-ethylidene-2-norbornene Copolymers Obtained on Rac-Et(2-MeInd)2ZrMe2/Isobutylaluminium Aryloxide Catalytic Systems

Ethylene/propylene (E/P) and ethylene/propylene/5-ethylidene-2-norbornene (E/P/ENB) copolymers were obtained on rac-Et(2-MeInd)2ZrMe2 activated by a number of isobutylaluminium aryloxides: (2,6-tBu2PhO-)AliBu2 (1-DTBP) (2,6-tBu2,4-Me-PhO-)AliBu2 (1-BHT), (2,4,6-tBu2PhO-)AliBu2 (1-TTBP), (2,6-tBu2,4-Me-PhO-)2AliBu (2-BHT), (2,6-tBu2PhO-)2AliBu (2-DTBP), [(2-Me,6-tBu-C6H3O)AliBu2]2 (1-MTBP), [(2,6-Ph2-PhO)AliBu2]2 (1-DPP). This study shows how the structure of an activator influences catalytic activity and polymer properties, such as the copolymer composition, molecular weight characteristics, and thermophysical and mechanical properties. It has been shown that both the introduction of a bulky substituent in the para-position of the aryloxy group and the additional aryloxy group in the structure of an activator lead to a significant decrease in activity of the catalytic system in all studied copolymerization processes. Moreover, activation by bulkier aryloxides leads to lower levels of comonomer insertion and gives rise to higher molecular weight polymers. Broad or multiple endothermic peaks with different values of melting points are observed on the DSC curves of the copolymers obtained with different catalytic systems. The DSC of the thermally fractionated samples makes it possible to reveal the heterogeneity of the copolymer microstructure, which manifests itself in the presence of a set of lamellar crystallites of different thickness. The results also present the mechanical properties of the copolymers, such as the tensile strength (σ), elongation at break (ε), and engineering strain (EL). The synthesized E/P and E/P/ENB copolymers contain about 1–4 wt.% of the sterically hindered phenols obtained in situ as a residue of the hydrolyzed activators in the course of reaction quenching. This determines the increased thermooxidative stability of the copolymers