This contribution
describes the synthesis of 3-alkyl-1-vinylimidazolium
bromide ionic liquid monomers (ILMs), ion exchange with bis(trifluoromethane)sulfonimide
anion (NTf2
–), and their radical polymerization
to a homologous series of poly(ionic liquid)s (PILs) containing an
imidazolium ion substituted with alkyl chains of different lengths
(C2(n=7–11)). Owing to the presence
of a long alkyl chain, all the ILMs show crystalline phases whose
melting point and melting enthalpy increase sharply with increasing
alkyl chain length, and those parameters decrease upon replacing Br– with a NTf2
– anion. In
addition to the solid crystalline phase, the ILMs with a Br– ion only show liquid crystalline mesophases above the melting of
solid crystals. The corresponding PILs are semicrystalline in nature
due to crystallizable alkyl side chain showing similar chain length
and counteranion-dependent melting behaviors with poor crystallinity
compared to those of ILMs. The formation of strong birefringent crystals
of various morphologies including Maltese-cross and ring-banded spherulites
is observed for ILMs. However, the corresponding PILs with a Br– ion show crystals with fibrillar morphology with weak
birefringence, but surprisingly such fibrils are not observed for
PILs with a NTf2
– ion. The influence
of structural modulations of ILMs and their corresponding PILs on
their ionic conductivities is also investigated. Moreover, PILs with
a Br– ion exhibit an upper critical solution temperature
(UCST)-type turbid-to-transparent phase transition in CHCl3 with tunable cloud point as observed from turbidity and calorimetric
measurements. Such a thermoresponsive solution phase behavior is totally
absent for PILs when Br– is replaced with a NTf2
– ion.