Institute of Organic Chemistry and Macromolecular Chemistry, Heinrich‐Heine‐University Duesseldorf, Duesseldorf, Germany
Abstract:
Hydroxyalkylation of N‐vinylcaprolactam (NVCL) in α‐position via ring‐opening reaction of propylene oxide and ε‐caprolactone, respectively, yields in precursors for multifunctional NVCL derivatives. Homo‐ and copolymers of hydroxyfunctionalized NVCL derivatives, synthesized by free radical mechanism, are further investigated regarding their thermoresponsive behavior. Esterification of hydroxypropylated NVCL derivative with methacrylic anhydride is carried out yielding a versatile bifunctional cross‐linker. Networks are obtained either via free radical polymerization of the cross‐linker or anionic polymerization of only the methacrylic function and subsequent polymer analogous cross‐linking of the vinylic side groups. The rheological behavior during and after curing is investigated by oscillatory rheology. Furthermore, N‐vinylcaprolactam anion is used as an initiator for the anionic ring‐opening polymerization of ε‐caprolactone. Copolymerization of poly(ε‐caprolactone) macromonomer with NVCL yields graft copolymers. A polymerizable thermotropic liquid crystalline (LC) derivative is prepared by coupling cholesteryl chloroformate to NVCL. The thermal behavior of LC derivative is investigated by differential scanning calorimetry and polarized light microscopy.