van M Martin Duin

Solid-State Modification of Polypropylene (PP): Grafting of Styrene on Atactic PP

Grafting of unsaturated vinyl monomers onto polypropylene (PP) is a convenient route to develop new polymeric materials with synergistic properties. Particular attention must be paid to the formation of graft copolymer relative to the formation of homopolymer, since the final properties are dependent both on the dispersion of the new polymer into the iPP matrix, which is controlled by the degree of grafting, as well as on the chemical nature of the in-situ formed polymer chains. In the present work the grafting reaction of styrene on atactic PP (aPP), considered as good model system for the more studied solid-state modification of isotactic PP (iPP), has been investigated in the presence of two different radical initiators in order to get a first insight into the grafting reactions onto PP. Several grafting reactions were carried out by changing the chemical compositions of the starting polymerization mixture, whose homogeneity was accurately investigated by Raman spectroscopy. Infrared-spectroscopy (FT-IR) was used for qualitative and quantitative characterization of the reaction product. A quantitative separation procedure, based on the concept of selective solvent extraction, has been established which enables the determination of the grafting efficiency (Φ) as well as the exact chemical composition of the final product. Finally, all products were characterized by means of Differential Scanning Calorimetry (DSC) in order to study their thermal behaviour.

Thermoreversible Crosslinking of Maleated Ethylene/Propylene Rubber Using Ionic Interactions, Hydrogen Bonding and a Combination Thereof

Abstract Maleated ethylene/propylene copolymer (MAn-g-EPM) was thermoreversibly crosslinked using different routes, i.e. ionic interactions (ionomers), hydrogen bonding and a combination thereof. Microphase separation into polar MAn-rich aggregates occurs for MAn-g-EPM and all crosslinked materials, which act as physical crosslinks. The crosslink density does not change upon modification, but the strength of the aggregates is significantly increased, resulting in improved mechanical properties. All materials except the potassium ionomer with high degree of neutralization (DN) could be remolded into homogeneous and smooth films without chemical changes, indicating that the crosslinks are truly thermoreversible. A comparison of the mechanical properties, i.e. tensile properties and compression set at room temperature, for the different crosslinking routes showed that the poorest properties are obtained for hydrogen-bonded materials. The potassium ionomer with high DN has the best properties by far, but is d...

Characterization of the morphology of co-extruded, thermoplastic/rubber multi-layer tapes.

Tapes with alternating semi-crystalline thermoplastic/rubber layers with thicknesses varying from 100 nm up to several microm were prepared by multi-layer co-extrusion. The variation in layer thickness was obtained by varying the thermoplastic/rubber feed ratio. A systematic study on the use of various microscopy techniques to visualize the morphology of the layered systems is presented. The relatively large length scales and the sample preparation make optical microscopy (OM) unsuitable to study the morphology of the multi-layer tapes. Although excellent contrast between the thermoplastic and rubber layers can be obtained, the usually applied, relatively large magnifications limit the use of transmission electron microscopy (TEM) and atomic force microscopy (AFM) to small sample areas. The large range of applicable magnifications makes scanning electron microscopy (SEM) the most suitable technique to study the morphology of the multi-layer tapes. The sample preparation for SEM with a secondary electron (SE) detector is often based on the removal of one of the components, which may induce changes in the morphology. SEM with a back-scattered electron (BSE) detector is a very convenient method to study the morphology over a wide range of length scales, where the contrast between the different layers can be enhanced by chemical staining. Finally, the nucleation behavior (homogeneous versus heterogeneous) of the semi-crystalline layers, as probed by differential scanning calorimetry (DSC), provides valuable information on the layered morphology. The use of relatively straightforward DSC measurements shows a clear advantage with respect to the discussed microscopy techniques, since no sample preparation is required and relatively large samples can be studied, which are more representative for the bulk.