Iranian Journal of Polymer Science and Technology
Year:2016 | Volume:29 | Issue:2|Papers Count:7

Different chemical components in traditional Ziegler–Natta catalytic system include: (1) titanium and vanadium containing compounds, mostly TiCl4, as an active centre, (2) trialkylaluminium-based Lewis acid compounds, especially triethylaluminium, as precatalyst and alkylating agent, and (3) inorganic compounds, specifically MgCl2 and silica, as catalyst supports. Besides these compounds, shortly after the first discovery of Ziegler-Natta catalysts, electron donors have been considered as the key components for MgCl2-supported Ziegler-Natta catalysts, as they improve the stereospecificity and activity of these types of catalysts. Most electron donor compounds have oxygen atom and only a few contain nitrogen atom in their structure. Starting from benzoate for third-generation Ziegler–Natta catalysts, the discovery of new donors has always updated the performance of Ziegler–Natta catalysts. Since the first discovery of these compounds numerous efforts have been devoted in both industry and academic laboratories, not only to discover new electron donors but also to understand their roles in Ziegler–Natta olefin polymerization and suitable MgCl2-alcohol adducts formation. This article reviews the history of such research and development efforts. The first part of the article describes the historical developments of catalyst, with a special focus on donors of industrial importance, followed by an account given on recent trends in the latest donors developed. The next part of the article covers the historical progress toward mechanistic understanding of how donors improve the performance of Ziegler–Natta catalysts and how they undergo decomposition by interaction with Lewis acidic species such as the AlEt3 and TiCl4.

The performance of poly (4-metyl-1-pentyne) as mixed matrix membrane (MMM) filled with MIL 53 particles was studied to separate mixtures of carbon dioxide and nitrogen. MIL 53 particles was added to the polymer matrix with 10, 20 and 30 weight percentages. The adsorption of CO2 and N2 gases by MIL 53 was evaluated and the adsorption data was analyzed by Langmuir equation. Structure and thermal/mechanical properties of prepared membranes were characterized by means of FTIR, SEM, TGA and elongation test. Moreover, the gas permeation properties of membranes were studied by measuring the permeation of pure CO2 and N2. Furthermore, for accurate understanding of the gas permeation properties of the membranes, diffusion and solution coefficient of gases in neat membrane and MMMs were calculated using modified time-lag method. The results from TGA analysis showed that the degradation temperature of MMMs was enhanced and increased to 348oC for membrane containing 30 wt% of MIL 53. The SEM images also illustrated a relatively uniform dispersion of particles with proper polymer/filler interfaces in the polymer matrix. The gas permeation results revealed that the permeability of both gases (especially CO2) increased with increasing MIL 53 loading, in which the permeability of CO2 increased from 98.74 Barrer in neat membrane to 217.65 Barrer in MMM containing 30 wt% filler. Moreover, calculation of CO2/N2 selectivity depicted that the selectivity enhanced from 16.66 to 22.70. Finally, the performance of MMMs was compared with Robeson’s upper bound in CO2/N2 separation and results showed that the MMM having 30 wt% of MIL 53 took over the Robeson bound.

A comprehensive study is launched to compare different simulation techniques for the mechanical behavior of steel cord/rubber composites. A brief literature review is first performed and then various developed computational methods are examined. Uncured pre-shaped steel cord/rubber specimens, collected from a tire factory, were cured with different cord angles. These test samples were tested under tensile and shear modes. In order to check the validity and accuracy of the different computational techniques, the samples were analyzed using both analytical and numerical procedures which were based on the finite element method. The results showed that the accuracy and convergence of the computational methods are highly dependent on the selected numerical approach, the angle between cord and direction of applied load and also the hyperelastic or hyperviscoelastic model used to describe the mechanical behavior of the rubbery part. None of these models could predict nonlinear behavior of the cord/rubber composites in shear mode. Therefore, developing new constitutive models for this purpose is necessary.

The components’ content of foams, based on thermoplastic/thermoset blends, was studied by reaction extrusion method. For this purpose, a co-rotating twin screw extruder was designed and assembled. A high pressure-high temperature vessel was used in which the pressure could be dropped quickly. The foaming was carried out at saturation pressure of 68 bar in 2 s at 170oC. The results showed that the poly (vinyl chloride) /polyurethane (100/0) sample absorbed up to 8.09 % CO2 gas and produced foams with a cell average of 6 μm and a cell density of 6×109 cell/cm3.In the blend ratios of 90.10, 80.20, 70.30, 60.40 and 50/50, up to 4% by weight of CO2 gas was absorbed and no suitable foams were produced. Since the amount of gas diffusivity in the polyurethane was more than that in poly (vinyl chloride), the amount of gas leakage was equally increased by increases in polyurethane content, therefore there was no sufficient absorbed gas available for foam formation. It should be noted that the swelling caused by gas evolution is reduced due to the cross-linking structure which is highly resistant against the volume expansion. During the foaming step, the cross-linking density should be high enough to prevent viscous flow failure but not to the extent to initiate brittle failure in expanding bubbles. Therefore, it can be perceived that the optimum crosslinking density associated with the maximum foam expansion ratio could be achieved when the other processing parameters were fixed.

In recent years, fabrication of polymeric antibacterial wound dressing has gained most attention in controlling wound infections. Silk is also a member of the broad family of protein-based polmers. The silk produced by the lepidopteran insect Bombyx mori is a highly accepted material due to its long history as a very valuable textile fiber. Recently, additional applications have been developed for silk, mainly in the field of biotechnology. Regarding its importance in wound healing, silk fabric was incorporated with ciprofloxacin, as an antibiotic, on its surface coated with electro-spun PVA/ciprofloxacin nanofibers. Before coating, degumming was carried out using autoclave technique and properties of the silk fabric, before and after degumming process, was investigated by SEM, FTIR, mechanical properties and moisture absorbance measurement. The results of all analyses showed a reduction in fibers diameter, mechanical strength and moisture absorption after degumming process. Electrospinning condition was optimized and diameter of the nanofibers, with and without drug, was measured before coating. The results showed that addition of the drug increased electrical conductivity of electrospinning solution and resulted in finer nanofibers. Antibacterial test was performed using "disk diffusion method" withEscherichia coli (EC) and Staphylococcus aureus (SA) bacteria to compare the antibacterial properties of degummed and non-degummed silk fabrics alone and coated with nanofibers. Measurement of bacterial inhibition zone diameter showed no antibacterial activity for degummed and non-degummed silk fabrics alone. However, the sample coated with PVA/ciprofloxacin showed antibacterial activity. The antibacterial property for SA in both cases was the same, but for EC, the antibacterial activity of degummed silk fabric was more than that of non-degummed material.

Polyvinyl-based cross-linkers are most frequently used for internal crosslinking of hydrogels, while non-vinyl cross-linkers are used for surface crosslinking of hydrogels by reactions between the pendant groups of hydrogel and functional groups of cross-linkers. The type of internal or external cross-linking of hydrogels strongly affects their final properties. The type of internal or external cross-linking of hydrogels strongly affects the final properties of the products. In this research, the superabsorbent polymers (SAPs) based on partially neutralized acrylic acid (AA-NaAA) were synthesized by solution polymerization, using a series of new multifunctional cross-linkers such as polyethylene glycol diglycidyl ether (PEGDGE-300), ethylene glycol diglycidyl ether (EGDGE), 1, 4-butane diol (BDO) and [3- (2, 3-epoxypropoxy) -propyl] -trimethoxysilane (GPS) in the presence of ammonium persulfate-tetramethyl ethylene diamine (APS/TMEDA) as initiator.The molecular structures of PEGDGE and GPS hydrogels were detected by FTIR and EDX analyses. The type and concentration of cross-linkers were studied in relation to hydrogels’ free swelling capacity in distilled water and 0.9 wt% NaCl solution and their absorbency under load (AUL) and resulting rheological behavior. The result showed that the order of free swelling capacity in the hydrogels synthesized by these four cross-linkers was GPS>PEGDGE>EGDGE>BDO. In a constant free absorbency capacity (about 200 g/g), the cross-linked PEGDGE showed the highest amount of AUL. Furthermore, the rheological results showed the higher swollen gel strength in this hydrogel and confirmed the AUL result. The swelling properties of non-vinyl cross-linkers strongly depended on drying temperature, and hydrogels cured at different temperatures exhibited different rheological properties achieved by a constant amount of cross-linker. The use of non-vinyl cross-linker is a new approach to synthesize hydrogels without any polyvinyl-based cross-linkers.