Comparative Polymerization Activity of EPM and EPDM Using VCI4 Homogenous Ziegler-Natta Catalyst and Characterization of EPDM Obtained

Copolymerization of ethylene/propylene (EPM) and terpolymerization of ethylene/propylene/5-ethylidene-2-nor-bornene (ENB) were carried out using VCl4 based Ziegler-Natta catalyst. Triisobutylaluminum (TIBA) was used as a cocatalyst while CHCl3 and CCl4 were used as promoters. Effects of [Al]/[V] ratio, temperature, promoters and ENB concentration, relative pressure of P/E, H2 concentration and polymerization time on polymerization behavior were studied. The highest productivity of the catalyst was obtained at [Al]/[V] ratio of 8–10. Increasing the [Al]/[V] ratio increased Et% and Tg and decreased ENB% of the EPDM (ethylene / propylene / diene) obtained. Activity of the catalyst system was higher for EPM than EPDM. ENB concentration affected polymer yield. Increasing ENB from 5 ml/Lit solvent to 10 ml /Lit solvent increased productivity of the catalyst; however, higher concentration decreased the EPDM polymer yield. Addition of ENB increased Et% of the EPDM. Polymerization of EPDM was carried out at temperatures of 25 °C to 75 °C. The highest productivity was obtained at ∼ 50 °C. At reaction temperature of ∼ 55 °C, Et% and ENB% were 65.5% and 9%, respectively. Rp/time profiles were decay types for both EPM and EPDM production. Et% of EPDM increased with polymerization time, while an inverse result was obtained for ENB%. Addition of CHCl3 to 3 ml /lit solvent increased productivity of the catalyst. However, addition of CCl4 did not have such effect on the yield of the polymer obtained. Effect of relative pressure of P/E=1.25:1 to 0.89:1 on EPDM polymerization was studied. Addition of ethylene relative pressure increased Et% and increased Tg of the EPDM obtained. The lowest Tg of the EPDM obtained was −39 °C. A compound made with the EPDM showed good thermal stability.