Direct synthesis of functional novolacs and their polymer reactions

作者：Konishi Gen ichi^*; Tajima Takatsugu; Kimura Tsuyoshi; Tojo Yusuke; Mizuno Kazuhiko; Nakamoto Yoshiaki

来源：Polymer Journal, 2010, 42(6): 443-449.

DOI：10.1038/pj.2010.26

• allyl phenyl ether
• Claisen condensation
• graft polymerization
• novolac
• phenolic resin
• polycondensation
• polymer reaction

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

• 出版日期2010-6