Quaterpolymerization of Ethylene,Propylene, Dicyclopentadiene,and Methylcyclopentadienyl-5-endo-norborn-2-enyl-methane

Abstract

The quaterpolymerization of methylcyclopentadienyl-5-endo-norborn-2-enyl-methane with ethylene, propylene, and either endo- or exo-dicyclopentadiene was studied by using the catalyst system VAcac₃-Et₂AlCl. The influence of catalyst and polyenes concentrations, catalyst modifiers, and other polymerization parameters on the general properties of quaterpolymers was investigated. The polymers obtained showed a random distribution of the comonomeric units and the ability to covulcanize with 1,4-cis-polyisoprene.     

Depth-resolved molecular structure and orientation of polymer thin films by synchrotron X-ray diffraction

An exemplary system suitable for optoelectronics applications, i.e. poly(3-hexylthiophene), hereinafter P3HT, deposited by spin casting onto silicon substrates functionalised by three selected molecules and then properly annealed, has been examined. Grazing Incidence X-ray Scattering (GIXS) measurements have been performed with 4-circle diffractometer, allowing for a fine control of sample axes movement.By choosing different grazing incident angles, diffraction patterns from different layers of polymeric thin films have been recorded. Both in-plane and out-of-plane geometries have been combined in order to obtain complementary structural information. In this way structural and orientational differences of the polymer along with the film thickness (?50 nm) have been highlighted. For all P3HT films spun on functionalized Si wafer, macromolecular layers close to the substrate surface give some evidence of higher order and orientation than those outmost the surface, and this behaviour is pronounced to a different extent depending on the functionalized molecules used. Contrariwise P3HT layers deposited onto bare Si wafer display reduced orientation and decreased crystallite size, especially at buried interface.     

Impact resistant resins based on olefinic terpolymers containing a system of conjugated double bonds—V. Influence of reaction solvent on the physico-chemical properties of ungrafted SAN and some technological properties of ATS resins

Radical induced grafting of styrene (S) and acrylonitrile (AN) on to an unsaturated ethylene-propylene based terpolymer (EPTM) in mixed solvents has been investigated. Molecular weight, molecular weight distribution, conversion of ungrafted poly(styrene-co-acrylonitrile) (SAN) with 25 w% of AN and its degree of graft on to EPTM have been reported as functions of composition of the toluene/η-heptane mixture used as solvent. Mechanical properties of ATS resins are strongly dependent on the degree of graft of SAN resins and the molecular parameters of the ungrafted SAN; both are influenced by toluene content in the solvent mixture.     

Multiscale Lattice Boltzmann Schemes with Turbulence Modeling

The viability of multiscale lattice Boltzmann schemes for the numerical simulation of turbulent flows is discussed and numerically demonstrated for turboaxial machine applications. The extension of boundary-fitting formulas based on wall functions is proposed, which enables the efficient computation of turbulent flows in complex curvilinear geometry using a simple Cartesian grid. Examples of two-dimensional turbulent flows in an axial compressor cascade are presented.     

Structure and morphology optimization of poly(3-hexylthiophene) thin films onto silanized silicon oxide

The influence of the preparation conditions, including substrate functionalization with common silanizers, onto structure/morphology of the overlying poly(3-hexylthiophene) thin films has been investigated by using both grazing incidence X-ray diffraction and atomic force microscopy. The factors determining the formation of spin-coated films suitable for applications in field effect transistors, i.e. concentration, spin-speed, and thermal treatment are addressed. We have established, by a tuning of the preparation and post-deposition treatments, the optimal conditions to get films with the required structural/morphologic features. Moreover we have shown that the macromolecules orient and organize at the interface zone (?10 nm from the interface) better than in the upper layers, i.e. far away from the interface.     

Model simulation studies of complex free radical reactions: The graft copolymerization of styrene and acrylonitrile onto ethylene-propylene-isopropylidendicyclopentadiene terpolymer

A kinetic analysis without steady approximation of the graft copolymerization of styrene-acrylonitrile onto ethylene- propylene-isopropylidendicyclopentadiene terpolymer (EP-IPDCP) is described. Some of the kinetic constants were experimentally determined. The grafting process is interpreted mainly in terms of the attack on EP-IPDCP by benzoyloxy radicals; phenyl radicals play a minor negative role by enhancing the rate of homopolymerization. A major contribution to the grafting yield is made by the propagation steps in graft polymerization and by crossed termination between grafted and ungrafted chains; of minor importance are the cross terminations between ungrafted growing chains and rubber radicals. The ole played by the solvent (benzene) and by saturated and unsaturated units in the EP-IPDCP chains is analyzed. Diffusion effects caused by the poor solvent compatibility of grafted and ungrafted chains were taken into account by allowing the termination and propagation rate constants to change in a controlled way during the reaction. The trapping of EP-IPDCP units caused by the aggregation of polymer particles seems to be indispensable to explain the decreasing trend of the grafting efficiency curve. Other information of interest pertains to the distribution of initiating radicals among the various competing reactions in the process and to the data of concentrations versus reaction time for reactants, products, and free radical intermediates. The results of a sensitivity analysis and the rate constants used in the calculations are given.     

Highly Emissive Nanostructured Thin Films of Organic Host–Guests for Energy Conversion

All‐organic nanostructured host–guest materials (see picture) show enhanced, tunable fluorescence due to a high concentration of dyes with controlled spatial and geometrical organization that allows controlled resonant energy transfer. Homogeneous films of deoxycholic acid host–guests, provide coatings that convert near‐UV light into blue light with an efficiency higher than that of the standard polymeric blends.

     

Grazing‐incidence X‐ray diffraction study of rubrene epitaxial thin films

The growth of organic semiconductors as thin films with good and controlled electrical performances is nowadays one of the main tasks in the field of organic semiconductor‐based electronic devices. In particular it is often required to grow highly crystalline and precisely oriented thin films. Here, thanks to grazing‐incidence X‐ray diffraction measurements carried out at the ELETTRA synchrotron facility, it is shown that rubrene thin films deposited by organic molecular beam epitaxy on the surface of tetracene single crystals have the structure of the known orthorhombic polymorph, with the (2 0 0) plane parallel to the substrate surface. Moreover, the exact epitaxial relationship between the film and the substrate crystalline structures is determined, demonstrating the presence of a unique in‐plane orientation of the overlayer.