Thermosets from Step-Polymerization Mechanism

As explained in See. 7.1, epoxy networks have been and are still the subject of controversy. This is mainly based on the particular interpretation of results obtained using microscopy techniques. On the contrary, results obtained with small-angle neutron scattering (SANS) proved that typical diepoxy iiamine networks were homogeneous (Wu and Bauer, 1985). 

In addition, from thermal and thermomechanical measurements, it is found that typical epoxy-amine networks exhibit one glass transition temperature, Tg, and one sharp well-defined relaxation peak. The same techniques were used for crosslinked polyurethanes based on triol and diisocyanate or diol and triisocyanate (Andrady and Sefcik, 1983). Similar conclusions to those found for epoxy-amine networks were attained. 

It can be stated that networks based on a simple formulation (one monomer reacting with a comonomer), obtained from the step-polymerization process will exhibit a homogeneous structure. This is the case for epoxy-amine networks (the most studied) and polyurethane networks that have been used very often as ideal networks for structure-property correlations. 

2 But the Step-Polymerization Process Can Also Induce Inhomogeneities 

In this case of three-monomer polyurethane synthesis, there is no thermodynamic driving force for phase separation. The formation of clusters is fully controlled by the initial composition of the system, the reactivity of functional groups, and the network formation history (one or two stages, macrodiol or triol reacted with diisocyanate first, etc.). 

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Abstract Polymers are macromolecules derived by the combination of one or more chemical units (monomers) that repeat themselves along the molecule. The lUPAC Gold Book defines a polymer as A molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass. Several ways of classification can be adopted depending on their source (natural and synthetic), their structure (linear, branched and crosslinked), the polymerization mechanism (step-growth and chain polymers) and molecular forces (Elastomers, fibres, thermoplastic and thermosetting polymers). In this chapter, the molecular mechanisms and kinetic of polymer formation reactions were explored and particular attention was devoted to the main polymerization techniques. Finally, an overview of the most employed synthetic materials in biomedical field is performed. 

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