In this study, thermal analysis, infrared spectroscopy (near and mid) in conjunction with low field NMR, have been used to characterize the crosslinking reaction involving phenol formaldehyde resin ...and a crosslinking agent, hexamethylenetetramine (HMTA) used as adhesive in organic-inorganic composites. The strong hydrogen bonds in the resin and the completely crystalline HMTA (Tm = 280°C) severely hamper the crosslinking process. Yet the addition of a small amount of plasticizer can induce an efficient (> 50% increase) crosslinking reaction as compared to the system without plasticizer. The infrared spectroscopy clarifies the dissolution process of the crystalline crosslinker and the specific interactions needed to achieve miscibility of the reactants. The thermal analysis enabled us to follow the reaction as a function of temperature. The low field NMR with the T1 inverse recovery technique allowed us to monitor the crosslinking process directly. For the first time, it is now possible to identify the functionality of the plasticizer and correlate the degree of crosslinking achieved in order to assess the macroscopic cohesive strength needed for high performance adhesives.
A uniform dispersion of reactants is necessary to achieve a complete reaction involving multiple components. Utilizing a combination of infrared spectroscopy, thermal analysis and low field NMR, we ...have elucidated the role of three types of reactive plasticizers on the crosslinking reaction between hexamethylenetetramine and phenol formaldehyde resin. These two seemingly dissimilar reactants are responsible for the exceptionally high mechanical strength in a number of organic-inorganic composites. The efficiencies of the curing reaction and the achieved crosslinked structures are strongly dependent on the type of plasticizer employed. Infrared active vibrations are used to characterize the changing molecular structures of the individual reactants as a function of temperature. The T1 spin-lattice relaxation time measured using low field NMR is especially useful for the characterization of segmental dynamics of the chains in the formation of the extremely rigid crosslinked product. This study shows that the amount of crosslinking and the crosslinked structure can be very different for the three types of reactive plasticizers and also different in comparison to non-reactive plasticizers. We are also able to correlate the reactivity and functionality of the plasticizer to the crosslink density in the reacted product.
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