We demonstrate a concept to prepare thermally cross-linked nanostructured phenolic resins
based on self-organization. Novolac, containing hexamethyltetramine (HMTA) as a curing agent, is blended
with poly(2-vinylpyridine)-block-poly(isoprene), P2VP-block-PI, where the block length of P2VP has been
selected to be sufficiently high to allow the mutually hydrogen-bonded novolac and P2VP, including HMTA,
to be contained in the same microphase-separated domains. The novolac-containing domains have
subsequently been cross-linked by thermal curing. By tailoring the block lengths, we demonstrate lamellar,
cylindrical, and spherical cross-linked phases using transmission electron microscopy. The concept opens
simple schemes to modify properties of common phenolic thermosets.
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