Improving Environmental Stress Cracking Resistance of High-Density Polyethylene Grades by Comonomer Addition and Nanocomposite Approach.

The aim of this paper is to determine the effect of polymer density, correlated to the comonomer content, and nanosilica addition on the mechanical and Environmental Stress Cracking Resistance (ESCR) characteristics of high-density polyethylene (HDPE). In this regard, five HDPE samples with similar Melt Flow Index (MFI) and molar mass but various densities were acquired from a petrochemical plant. Two polymerization reactors work in series and differ only in the amount of 1-buene comonomer fed to the second reactor. To ascertain the microstructure of the studied samples, GPC and SSA (successive self-nucleation and annealing) analyses were accomplished. All samples resulted having similar characteristics but slightly various SCB/1000 C=7.26-9.74 (SCB=Short Chain Branching). Consequently, meanwhile studied HDPEs reveal similar notched impact and stress at yield values, the tensile modulus, stress-at-break, and elongation-at-break tend to demonstrate different results with the SCB content. More significantly, ESCR characteristic varied considerably with SCB/1000 C extent, so that higher amount of SCB acknowledged advanced ESCR. Notably, blending HDPE sample containing higher amount of SCB/1000 C, with 3 wt.% of chemically modified nanosilica enhanced ESCR characteristic by 40 %. DFT (Density Functional Theory) calculations unveiled the role of the comonomer, quantitatively by binding energies and qualitatively by Non Covalent Interaction (NCI) plots.

Silyl diol ester as a new selectivity control agent in MgCl2-supported Ziegler-Natta systems for propylene polymerization: catalyst structure and polymer properties.

In this study, bis(benzoyloxy)dimethylsilane (SDE) was developed as a non-phthalate selectivity control agent (internal donor (ID) and external donor (ED)) in MgCl2-supported Ziegler-Natta (ZN) systems. The impact of SDE as an ID was investigated in regards to chemical composition, morphology, adsorption behavior (using FTIR spectroscopy, WAXD and SEM studies) and the propylene polymerization performance of the catalyst. The results of the adsorption behavior of SDE revealed that SDE, while able to stabilize the electronically unsaturated surfaces of MgCl2 [(104) and (110)], has a rather high tendency to be absorbed on strongly acidic Mg ions at the corners of these crystals. The catalyst with optimum SDE content as an ID afforded a system with reasonable activity and isotacticity (even in the absence of ED) along with broader molecular weight distribution (PDI: 6.2-10) and greater flexural modulus than phthalate-based ZN systems. SDE was also used as a new ED in most widely used fourth- and fifth-generation catalyst systems. The results revealed that in fifth-generation catalyst systems, there was an increase in hydrogen response (>40%) along with an increase of activity without any change in the thermal properties of the final polymer in comparison to a conventional ED (alkoxy silane).