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A network formation from an OH-functional star oligomer and two isocyanates (HDI and HDI-trimer) was investigated by changes in the critical molar ratio of OH groups $$(r_{\rm OH})_{\rm c}$$ as a function of dilution. The critical ratio $$(r_{\rm OH})_{\rm c}$$ is such critical excess of OH groups at which the critical conversion of NCO at the gel point groups reaches 100%. The dilution effect was interpreted by pronounced cyclization, which was higher in the case of the HDI-trimer compared with the HDI.

The new generation clear coats introduced in the automotive industry have improved scratch and mar resistance. It is believed that those properties are related to the introduction of new binder technologies leading to higher film cross-link densities. This was relatively easy to accomplish in the automotive industry because baking temperatures are well above the glass-transition temperature (Tg) of the final clear coat film. In car repair coatings, the cross-linking takes place under conditions where the intermediate and/or final film Tg values are above the curing temperature. Such formulations result in vitrification during the drying process, a transition during which chemical cure and solvent release are slowed down substantially. The chemical cure can be improved through more reactive and/or higher functional binders, but this shifts the gel point to shorter times in the drying cycle which may lead to more solvent entrapment, resulting in low film hardnesses and paint defects. This paper describes the overall properties of 2K-refinish clear coats based on linear versus branched, random and graft acrylic polyols. The authors will try to correlate overall properties with theoretical predictions and practical results.

Gel point conversions and equilibrium tensile moduli of polyester-based polyurethane networks were determined for different dilutions during network formation. Also, the limiting dilution beyond which the network was not formed at full conversion of functional groups was determined. It ranged between 92 and 94% of diluent. The scaling dependences against the reference states – the ring-free case and the limiting dilution case – showed that the excluded volume effects were operative and structural changes associated with cyclization affected the rates of both the intramolecular and the intermolecular reactions.

Cross-linking hydroxy-functional stars and copolymer precursors with a triisocyanate and associated structural changes were studied theoretically and experimentally. The model of network formation was based on the statistical generation of structures from units which were in different reaction states. The differences in gel point conversion and cross-link density were interpreted in terms of precursor functionality and functionality distribution, and differences in the reactivity of functional groups. Hydroxy-functional copolymer systems containing precursors of the same number-average functionality gel at lower conversions than stars which are monodispersed mainly due to functionality distribution. The structure of copolymers characteristic of several internal cross-links contributes more to the concentration of elastically-active network chains than stars with a single cross-link. Cyclization accompanies intermolecular cross-linking; its intensity is higher for copolymer systems compared with stars.

A model describing swelling changes of covalently crosslinked gels caused by unfolding of crosslinks of folded chains built-in in the gel matrix was proposed. By unfolding, a new interacting surface is exposed which may differ from the interacting sites of the gel polymer. Non-ionic as well as ionic interactions are considered. A certain force generated by the swelling pressure acts on the ends of the folded crosslinks and unfolding starts when this force exceeds a certain limiting value. The continuation or arrest of unfolding depends on whether the exposure of the new interacting surface decreases or increases this force. The unfolding process is considered to be irreversible but possible reversibility can be considered. This model relates to biohybrid gels in which the folded domain of the crosslink is composed of elements of the muscle protein titin. The model is based on the statistical-mechanical theory of swelling of crosslinked polymers. A change in external variables such as temperature or degree of ionization can cause an abrupt change in volume of the swollen gel (transition) within a certain range of parameters characterizing the gel and polymer-solvent interactions.

During formation of films from solutions of reactive polymers, crosslinking and solvent evaporation occur simultaneously but with different rates. If the film adheres to the substrate, the formed network shrinks only in the direction normal to the film surface and lateral strains develop. It was demonstrated theoretically that the lateral strain reduces the activity of the solvent in the film and thus lowers the evaporation rate.