Novel amphiphilic polymer conetworks (APCNs) were prepared via end group cross-linking. To this end, poly(2-methyloxazoline) (PMOx), poly(2-butyloxazoline) (PBuOx), and the triblock copolymers PMOx-b-PBuOx-b-PMOx were synthesized by cationic ring-opening polymerization in varying block lengths and telechelically modified with N,N -bis(2-aminoethyl)ethylendiamine (TREN). First the cross-linking with 1,4-dibromo-2-butene (DBB) was established for the homopolymers. The swelling of those matches the theoretical value for full cross-linking, indicating that in this way “near perfect” networks could be obtained. Mixtures of the homopolymers and the triblock copolymers were cross-linked with DBB to give APCNs with similar polymer segments but different network topology. AFM showed that all formed APCNs are nanophase separated with slight structural differences in the nanostructures when comparing conetworks with similar composition but different cross-linking strategies. The more drastic difference between APCNs of different topologies was found in their swelling characteristics, which clearly proves the influence of conetwork structure on their properties.

Nanoporous and macroporous templates were simultaneously infiltrated from both of their opposite surfaces using model polymers labeled with fluorescent probes or bearing probe molecules detectable by energy-dispersive X-ray spectroscopy by precursor wetting. Face-to-face wetting with polymeric solutions resulted in partial mixing of both components, leading to tubular nanostructures characterized by a longitudinal composition gradient. Mixing of the components infiltrated from the opposite surfaces could be prevented by face-to-face wetting with polymeric melts, leading to the formation of tubular components predominantly consisting of the pure components that were separated by sharp interfaces.

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