Polymeric Composite Materials
Frontal Radical Homo- and Co-Polymerization of the Crystalline Powdery Monomers and Formation of Diverse Polymeric Disperse-Filled Composition Materials
Tech Area / Field
- CHE-IND/Industrial Chemistry and Chemical Process Engineering/Chemistry
- CHE-POL/Polymer Chemistry/Chemistry
- MAT-ELE/Organic and Electronics Materials/Materials
3 Approved without Funding
National Polytechnical University of Armenia, Armenia, Yerevan
- Institute of Structural Macrokinetics and Material Science, Russia, Moscow reg., Chernogolovka\nScientific Technological Center of Organic and Pharmaceutical Chemistry / Institute of Fine Organic Chemistry, Armenia, Yerevan
- Department of Chemistry, USA, OH, Cincinnati\nUniversity of Akron / Institute of Polymer Engineering, USA, OH, Akron\nRostok University, Germany, Rostock\nMichigan State University / Department of Physiology, USA, MI, East Lansing\nThe University of Akron, USA, OH, Akron
Project summaryBesides scientific the investigation of the processes of frontal polymerisation in the periodic and continuously working (continuous action) reactors has a practical importance as well, as an easy and energy saving method of formation of block and powdery filler polymeric articles in a single technological cycle:
Initiators polymer products,
where products can be obtained during the running period of the frontal polymerization, or after its finishing thus avoiding multi-phase and energy-consuming stages of polymer processing.
It seems, that when the stream of the initiators is directed perpendicular to the front of the polymerization it is easy to realise continuous process in the tubular reactors. Nevertheless, a strongly stretched jet of monomer liquid is formed, which - upon approaching to the end of the reactor - leaves the reactor without interaction because of the sticking of the polymeric mass to the walls of the reactor and the formation of the gradient of the stream velocities in the axial region of the reactor section. That is why, for the processes of frontal polymerization the type of the reactor, as well as its shape are determined by a series of accompanying processes (jet formation, gravitation mass transfer, etc.) the manifestations of which depend upon the aggregate condition of the used monomers and the products of the polymerization. Provisionally, in view of this, monomers used for frontal polymerization, can be pided into three classes:
1. Liquid monomers, whose polymers at the temperatures of heat waves are under the viscous-fluid condition;
2. Liquid or viscous-fluid (mono or multifunctional) monomers or oligomers, the polymers of which are in solid state at the heat wave temperatures;
3. Powdery crystalline monomers, the polymers of which are either in viscous-fluid or in solid state at the temperature of heat wave.
For the first two classes the macro-kinetic peculiarities of frontal polymerization are sufficiently elucidated in literature.
Nevertheless, there are no works mentioned in literature concerning the frontal polymerization of powdered monomers, although this particular class of monomers attracts the highest interest for the practical realisation of the methods of frontal polymerization in the tubular periodic and continuous action reactors as neither jet is formed nor other negative processes held there. Utilisation of fine powdery crystalline monomers during the frontal polymerization will enable to ply new energy- and resource-saving product-molding techniques by using homo- and co-polymers, as well as the powdery-filled polymeric compositions at the presence and absence of the external perturbing loads (mono-axial loading, centrifugal forces, pressing, dislocation deformation and complex displacements).
Acryl amid, derivatives of N-substituted,-dehydroamino acids, amyl amides of N-substituted,-de-hydro amino acids with various amino acid residues as well as metal-monomer complexes of the monomers with the nitrates of transition metals Co, Mn, Ba, Y, etc. will be used as examples of finely dispersed powdered monomer.
Powdered metal-containing monomer complexes were included in this project, as both the powdered metal-monomer complexes and their metal-polymers possess catalytic properties in the reactions of nitrile (CN) group reduction with sodium boron hydride,
Thus, the following investigations are presumed to carry within the Project framework:
1. Study of the peculiarities of the thermal and initiated frontal homo- and Co-Polymerization of the crystalline and powdery monomers in tubular reactors of periodic action both in the presence and in absence of external perturbations. Study of the synthesis of N-substituted,-dehydrated amino acids of allyl amides.
2. Study of the steady-state range of the stationary heat waves during frontal homo- and Co-Polymerization of the crystalline and powdery monomers both in presence and in absence of external perturbations. Synthesis of N-substituted,-dehydrated amino acids.
3. Investigation of the macro-kinetics of frontal homo- and Co-Polymerization of the powdery crystalline monomers (acryl amide, allyl amides, etc.) and the complexes of metal-monomers based on the nitrates of transition metals (Co, Mn, Li, Ba, etc.), and the synthesis of these complexes. Design of the installation of the frontal polymerization under perturbation, and modes for the loading of the samples. Study of the catalytic properties of the complexes of metal-containing monomers.
4. Investigation of the influence of addition of mineral and refractory powdery fillers on the radical frontal homo- and Co-Polymerization of the crystalline vinyl monomers. Frontal homo- and Co-Polymerization of metal-containing complexes under the impact of external perturbations. Study of the physical-mechanical properties of the block and filler materials. Investigation of the catalytic properties of the metal-containing monomers, as well as their selectivity.
5. Mathematical simulation of the processes of frontal polymerization: solution and analysis. Preparation of laboratory (pilot) installations for carrying out frontal polymerization of powdery crystalline monomers in the reactors of periodic and continuous action. Investigation of the influence of positive and negative gravitational loads on the propagation rate, on the structure and the limiting temperature of the heat waves. Investigation of the catalytic properties and selectivity of the metal-containing monomer’s complexes and metal-containing monomers in the reduction reaction of organic compounds by the sodium boron hydrides.
6. Investigation of the possibility of the formation of materials gradually changing in chemical composition, in nature and in filling rate, etc. (so-called gradient materials) under the impact of frontal polymerization in presence and absence of external perturbations. Investigation of the addition of gaseous additives on the foam-formation processes right after the completion of frontal polymerization of foamy polymers carried out under the impact of perturbations. Optimization of the processes of frontal polymerization held in laboratory installations with and without perturbations.
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