Marcelo D. Failla

Rheological and barrier properties of nanocomposites of HDPE and exfoliated montmorillonite

Polyethylene (PE)/clay nanocomposites were prepared by melt mixing using PE grafted with maleic anhydride (PEg) as compatibilizer. Concentrations between 2 and 15 wt% of an organophilic montmorillonite (MMT) and concentration ratios of 1:1, 2:1 and 3:1 of PEg/MMT were employed. The materials were characterized using X-ray diffraction, scanning electron microscopy (SEM) and thermogravimetry. The SEM images show that the presence of PEg results in a large degree of exfoliation at all clay concentrations. For 5 wt% MMT, the best degree of exfoliation is obtained for a 2:1 ratio of PEg/MMT. This ratio results in higher increase in the elastic modulus, mainly at low frequencies, with respect to that of the corresponding matrix. As the clay concentration increases, for a 2:1 ratio of PEg/MMT, the dynamic moduli increase showing pseudo solid-like behavior at clay concentrations higher than 8 wt%. Moreover, the nanocomposites show rheological properties that are affected by annealing at 200°C signaling further exfoliation or improved platelet and tactoid distributions. The oxygen permeability of PE decreases gradually with the clay concentration, reaching a maximum reduction of ∼30% for 15 wt% MMT.

Chemical modification of styrene–butadiene–styrene co-polymer by grafting of N-carbamyl maleamic acid

A styrene–butadiene–styrene (SBS) block co-polymer was functionalized using different amounts of N-carbamyl maleamic acid (NCMA) and benzoyl peroxide as initiator. NCMA, which is a bifunctional monomer, was synthesized in our laboratories. The concentration of NCMA used in the functionalization of SBS ranged from 0.5 to 3% (w/w) based on the co-polymer mass. Benzoyloxy radicals generated from the thermal decomposition of benzoyl peroxide initiated the grafting reaction. The concentration of the initiator was kept constant at 0.076% (w/w). FT-IR spectroscopy was used to determine the amount of NCMA effectively grafted onto the SBS. The maximum amount of monomer grafted was about 0.3% (w/w) when the SBS was modified with 1% (w/w) NCMA. The effect of grafting on the surface properties and the adhesion to polyurethane adhesive of the modified SBS were evaluated. Contact angle values were obtained using liquid droplets. When the concentration of the NCMA used in the grafting reaction was 1% (w/w), the contact angles with water on original and modified SBS were 95° and 77°, respectively. Adhesion properties were evaluated by standard peel tests employing a commercial polyurethane adhesive. The modified SBS having the largest amount of NCMA displayed a T-peel strength value 5-times higher than the corresponding value measured with the original SBS.

Chemical modification of styrene–butadiene–styrene (SBS) rubber by reactive grafting with maleic anhydride

A procedure to increase the adhesion of block styrene-butadiene-styrene (SBS) rubber consisting of the reactive grafting with maleic anhydride (MA) in the presence of an organic peroxide radical initiator is proposed. The influence of the reactive grafting on the surface properties of SBS has been studied with special emphasis on the improvement of the adhesion to polyurethane adhesive. The grafting of MA onto SBS was carried out in the presence of different concentrations of 2,5-dimethyl-2,5-di(tertbutyl peroxy) hexane (DBPH) as initiator to generate oxygen radicals by thermal decomposition, which induce the grafting reaction. The modification process was performed in the molten state using a Brabender mixer to premix the reactants and a hot press to initiate the functionalizing reaction. ATR-IR and XPS spectroscopies were employed to verify the grafting of MA on SBS. The changes in wettability on the modified SBS rubber were determined by contact angle measurements. Adhesion properties were evaluated from T-peel tests of SBS rubber/polyurethane adhesive joints. Reasonable extents of MA grafting on SBS were obtained (evidenced by the presence of a weak carbonyl vibration at 1700 cm-1 in the ATR-IR spectra and by the carbon- oxygen band at a binding energy of 287.0 eV in the XPS spectra). The higher the DBPH amount, the higher the MA amount grafted onto the SBS surface. The maximum grafting level was obtained using 2 wt% MA. Grafted species seemed to be mainly concentrated on the surface of the SBS-molded sheets. The wettability of the modified rubber increased with respect to the original polymer, new carbon-oxygen moieties were created and the C/O ratio increased. A noticeable enhancement in peel strength values was observed, which was ascribed to the creation of interfacial interactions between the polyurethane and the SBS rubber surfaces.

Effect of montmorillonite on the crystallization and thermal degradation of poly(propylene-co- ethylene-co-1-butene) nanocomposites

Polymeric nanocomposites based on poly(propylene-co-ethylene-co-1-butene) (PEBC) were elaborated by melt mixing using an organophilic montmorillonite (o-MMT) and maleated PEBC (PEBCg) as compatibilizer. The effect of clay concentration, PEBCg:o-MMT ratio, and grafting degree of the compatibilizer were studied. X-ray diffraction and scanning electron microscopy show formation of partially intercalated structures in all compatibilized composites with well-distributed small tactoids. According to the differential scanning calorimetry results, the anhydride groups of the compatibilizer have a marginal nucleating effect, while the o-MMT causes a slight decrease in the crystallization temperature of the polymer. PEBC presents the largest activation energy of crystallization (Eα), while the composites show lower Eα than their matrices. It is also observed that the rate of degradation of PEBC is not affected by the presence of PEBCg. The nanoclay, on the other hand, retards the decomposition process of the polymeric matrix in about 40°C and augments its rate of degradation approximately four times.

Efficiency of Different Chain-Linking Agents in the Synthesis of Long-Chain Branched Polypropylene: Molecular, Thermal, and Rheological Characterization

ABSTRACT Long-chain branched polypropylenes were synthesized from a maleic anhydride grafted polypropylene (PPg). Different levels of branching were generated by reactive processing using four chain-linking agents: glycerol, 1,4-butanediol, 1,4-phenylenediamine, and the epoxy resin bisphenol-A diglycidyl ether. The results from Fourier transform infrared and size-exclusion chromatography confirm the grafting of the chain-linking agents onto grafted polypropylene and the generation of long-chain branches. In addition, the rheological and morphological results show that 1,4-phenylenediamine produces the largest increment of branching at significantly lower concentrations than the other chain-linking agents. Moreover, 1,4-phenylenediamine gives place to branched polypropylenes with narrower distribution of molecular structures. GRAPHICAL ABSTRACT