Microcapsules (MCs) containing isocyanate compounds for use as self-healing materials in waterborne polyurethane coatings have been synthesized, in the presence of modified Novolac resins. With ...modification of Novolac resin, it is succeeded partial or total protection (Benzylation and Acetylation) of its hydroxyl groups. The idea here is to use a protected Novolac resin as the organic substrate for the encapsulation of the less reactive Isophorone isocyanate (IPDI) while the more reactive one, Methylene diphenyl diisocyanate (MDI), is used for the shell formation. Based on that strategy microcapsules of different morphologies and sizes were obtained, depending on the agitation conditions, as revealed using SEM and optical microscopy. Selective extraction was performed to determine the amount of the less reactive isocyanate (IPDI) stored inside the capsules through FTIR-ATR spectroscopy and isocyanate titration as well as the stability of IPDI inside the capsules over time. As determined, microcapsules based on Acetyl-modified Novolac resin encapsulated 96 wt% of IPDI monomer; this amount is about five and ten times higher than that encapsulated in MCs based on by Benzyl-modified Novolac resin or unprotected Novolac resin, respectively. At the same time, MCs based on Acetyl-modified Novolac resin were stable, maintaining approximately 80 % of the initial isocyanate content after two months of storage under inert conditions. Finally, the self-healing ability of the microcapsules was tested by adding selected IPDI-loaded microcapsules in waterborne polyurethane dispersions. It was proven that the Acetyl-modified Novolac-based MCs showed efficient healing behavior, in the absence of any catalyst, on the polyurethanes’ surfaces when scratched artificially.
•Two derivatives of Novolac resin through benzylation and acetylation were prepared•Novolac-based microcapsules (MCs) loaded with isocyanates (IPDI) were synthesized•High IPDI loading and stability has been found for acetyl-modified Novolac MCs•MCs can be well incorporated into waterborne polyurethane films•Acetyl-modified Novolac-based MCs were proved efficient self-healing materials
The encapsulation of active components is currently used as common methodology for the insertion of additional functions like self-healing properties on a polymeric matrix. Among the different ...approaches, polyurea microcapsules are used in different applications. The design of polyurea microcapsules (MCs) containing active diisocyanate compounds, namely isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI), is explored in the present work. The polyurea shell of MCs is formed through the interfacial polymerization of oil-in-water emulsions between the highly active methylene diphenyl diisocyanate (MDI) and diethylenetriamine (DETA), while the cores of MCs contain, apart from IPDI or HDI, a liquid Novolac resin. The hydroxyl functionalities of the resin were either unprotected (Novolac resin), partially protected (Benzyl Novolac resin) or fully protected (Acetyl Novolac resin). It has been found that the formation of MCs is controlled by the MDI/DETA ratio, while the shape and size of MCs depends on the homogenization rate applied for emulsification. The encapsulated active compound, as determined through the titration of isocyanate (NCO) groups, was found to decrease with the hydroxyl functionality content of the Novolac resin used, indicating a reaction between NCO and the hydroxyl groups. Through the thorough investigation of the organic phase, the rapid reaction (within a few minutes) of MDI with the unprotected Novolac resin was revealed, while a gradual decrease in the NCO groups (within two months) has been observed through the evolution of the Attenuated Total Reflectance-Fourier-Transform Infrared (ATR-FTIR) spectroscopy and titration, due to the reaction of these groups with the hydroxyl functionalities of unprotected and partially protected Novolac resin. Over longer times (above two months), the reaction of the remaining NCO groups with humidity was evidenced, especially when the fully protected Acetyl Novolac resin was used. HDI was found to be more susceptible to reactions, as compared with IPDI.
