Double Crystallization and Phase Separation in Polyethylene—Syndiotactic Polypropylene Di-Block Copolymers

Crystallization and phase separation in the melt in semicrystalline block copolymers (BCPs) compete in defining the final solid state structure and morphology. In crystalline–crystalline di-block copolymers the sequence of crystallization of the two blocks plays a definitive role. In this work we show that the use of epitaxial crystallization on selected crystalline substrates allows achieving of a control over the crystallization of the blocks by inducing crystal orientations of the different crystalline phases and a final control over the global morphology. A sample of polyethylene-block-syndiotactic polypropylene (PE-b-sPP) block copolymers has been synthesized with a stereoselective living organometallic catalyst and epitaxially crystallized onto crystals of two different crystalline substrates, p-terphenyl (3Ph) and benzoic acid (BA). The epitaxial crystallization on both substrates produces formation of highly ordered morphologies with crystalline lamellae of sPP and PE highly oriented along one direction. However, the epitaxial crystallization onto 3Ph should generate a single orientation of sPP crystalline lamellae highly aligned along one direction and a double orientation of PE lamellae, whereas BA crystals should induce high orientation of only PE crystalline lamellae. Thanks to the use of the two selective substrates, the final morphology reveals the sequence of crystallization events during cooling from the melt and what is the dominant event that drives the final morphology. The observed single orientation of both crystalline PE and sPP phases on both substrates, indeed, indicates that sPP crystallizes first onto 3Ph defining the overall morphology and PE crystallizes after sPP in the confined interlamellar sPP regions. Instead, PE crystallizes first onto BA defining the overall morphology and sPP crystallizes after PE in the confined interlamellar PE regions. This allows for discriminating between the different crystalline phases and defining the final morphology, which depends on which polymer block crystallizes first on the substrate. This work also shows that the use of epitaxial crystallization and the choice of suitable substrate offer a means to produce oriented nanostructures and morphologies of block copolymers depending on the composition and the substrates.

Influence of Starch Content on the Thermal and Viscoelastic Properties of Syndiotactic Polypropylene/Starch Composites

In this study, syndiotactic Polypropylene/Starch (sPP/starch) composites were prepared using a solution mixing technique. The thermal characterization was performed using Differential Scanning Calorimetry (DSC), and the melting point was measured for all polymer composites. The thermal degradation temperature was measured using thermal gravimetric analysis. The viscoelastic measurements were performed using the Atomic Rheometric Expansion System (ARES). Both melting point and thermal degradation temperatures were found to decrease with increasing starch content. Moreover, the elastic modulus was found to decrease when the starch content increased.

Highly conductive anion exchange membranes based on polymer networks containing imidazolium functionalised side chains

Two novel types of anion exchange membranes (AEMs) having imidazolium-type functionalised nanofibrous substrates were prepared using the facile and potentially scalable method. The membranes’ precursors were prepared by graft copolymerization of vinylbenzyl chloride (VBC) onto syndiotactic polypropylene (syn-PP) and polyamide-66 (PA-66) nanofibrous networks followed by crosslinking with 1,8-octanediamine, thermal treatment and subsequent functionalisation of imidazolium groups. The obtained membranes displayed an ion exchange capacity (IEC) close to 1.9 mmol g–1 and ionic (OH-) conductivity as high as 130 mS cm–1 at 80 °C. This was coupled with a reasonable alkaline stability representing more than 70% of their original conductivity under accelerated degradation test in 1 M KOH at 80 °C for 360 h. The effect of ionomer binder on the performance of the membrane electrode assembly (MEA) in AEM fuel cell was evaluated with the optimum membrane. The MEA showed a power density of as high as 440 mW cm−2 at a current density is 910 mA cm−2 with diamine crosslinked quaternized polysulfone (DAPSF) binder at 80 °C with 90% humidified H2 and O2 gases. Such performance was 2.3 folds higher than the corresponding MEA performance with quaternary ammonium polysulfone (QAPS) binder at the same operating conditions. Overall, the newly developed membrane was found to possess not only an excellent combination of physico-chemical properties and a reasonable stability but also to have a facile preparation procedure and cheap ingredients making it a promising candidate for application in AEM fuel cell.

Synthesis, structure and properties of copolymers of syndiotactic polypropylene with 1-hexene and 1-octene

Incorporation of long branches, such as 1-hexene or 1-octene, in syndiotactic polypropylene gives novel elastomeric materials, whose crystallization behavior and elastic properties can be easily tailored through tuning of the branches concentration.

Effect of sPP Content on Electrical Tree Growth Characteristics in PP-Blended Cable Insulation

This paper aims at investigating the electrical tree characteristics of isotactic polypropylene (iPP)/syndiotactic polypropylene (sPP) blends for thermoplastic cable insulation. PP blended samples with sPP contents of 0, 5, 15, 30, and 45 wt% are prepared, and electrical treeing experiments are implemented under alternating current (AC) voltage at 50, 70, and 90 °C. Experimental results show that with the incorporation of sPP increasing to 15 wt%, the inception time of electrical tree increases by 8.2%. The addition of sPP by 15% distinguishes an excellent performance in inhibiting electrical treeing, which benefits from the ability to promote the fractal dimension and lateral growth of branches. Further increase in sPP loading has a negative effect on the electrical treeing resistance of blended insulation. It is proved by DSC and POM that the addition of sPP promotes the heterogeneous crystallization the of PP matrix, resulting in an increasing density of interfacial regions between crystalline regions, which contains charge carrier traps. Charges injected from an electrode into a polymer are captured by deep traps at the interfacial regions, thus inhibiting the propagation of electrical tree. It is concluded that the modification of crystalline morphology by 15 wt% sPP addition has a great advantage in electrical treeing resistance for PP-based cable insulation.