Direct synthesis of functional novolacs and their polymer reactions

We report the direct synthesis of new functional novolacs having allyl ether (4) or bromoalkyl groups (5 and 6) in the side chain by the addition-condensation of allyl phenyl ether (1), 1-bromo-2-phenoxyethane (2) or 1-bromo-4-phenoxybutane (3) with formaldehyde. The structure of these novolacs was confirmed by Fourier transform infrared, (1)H NMR and (13)C NMR spectra. The number-average molecular weights (M(n)) of the obtained polymers were found to be similar to 1000-3000. In the case of the polymerization of 1 with formaldehyde using hydrated sulfuric acid as a catalyst, Claisen condensation did not occur with the polymerization; therefore, pure allylated novolac (4) without a phenol moiety was obtained. Thus, in this process, phenol formaldehyde condensation proceeded under such conditions that the functional group was not affected. These polymers (4-6) have considerable potential as reactive polymers in the field of materials science. Their applications are as follows: (i) a key reaction of a latent curing system: thermal stimuli-induced Claisen rearrangement of allylated novolac to generate phenolic hydroxyl groups; (ii) vinyl ether-modified novolac (7) prepared by 1-bromoethoxy-group-modified novolac; and (iii) an amphiphilic graft-shaped polymer prepared by bromoalkyl-group-modified novolac-initiated ring-opening polymerization of 2-methyl-2-oxazoline. Polymer Journal (2010) 42, 443-449; doi:10.1038/pj.2010.26; published online 14 April 2010