Multifunctionalized acrylates

Another approach for the synthesis of networks relies on the polycondensation of multifunctionalized polyesters with the appropriate multifunctionalized agent, provided that one of the partner is at least tri-functionalized. Toward this end, several reaction have been reported, such as the Michael addition of amines onto acrylates [184], the coupling of ketones and oxyamines [185], the click copper(II)-catalyzed azide-alkyne cycloaddition [186], and esterification reactions [25, 159, 187]. Interestingly, if esterification reactions are used, the crosslinks are then degradable. 

Moreover, a study has been made on the effect of fluorine substitution in the MBH reaction of various fluorocarbonyl partners with acrolein, methyl vinyl ketone, ethyl acrylate and acrylonitrile. Multifunctionalized fluorinated allyl alcohols were prepared from amine-sensitive aldehydes and olefins by balancing their reactivities. When the olefin is capable of reacting with itself in the presence of an amine e.g. acrolein), the electrophile has to be very reactive as well e.g. fluoral) to obtain a modest to good yield of MBH products. The reaction of a moderately reactive olefin e.g. ethyl acrylate or acrylonitrile) and a very reactive electrophile e.g. fluoral) resulted in self-reaction of the electrophile or very low yield of the allylic alcohol product. 

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