In this work temperature-triggered association and gel formation within aqueous solutions of a new family of cationic poly( N-isopropyl acrylamide) (PNIPAm) graft copolymers have been investigated. Five copolymers were synthesized using aqueous atom transfer radical polymerization (ATRP) involving a macroinitiator based on quaternarized N, N-dimethylaminoethyl methacrylate units (DMA+). The PDMA+) x - g-(PNIPAmn)y copolymers have x and y values that originate from the macroinitiator; values for n correspond to the PNIPAm arm length. The copolymer solutions exhibited temperature-triggered formation of nanometer-sized aggregates at the cloud point temperature, which was 33-34 degrees C. The aggregates were investigated using variable-temperature turbidity, hydrodynamic diameter, and electrophoretic mobility measurements. The aggregates were clearly evident using SEM and flowerlike or spherical morphologies were observed. Variable-temperature electrophoretic mobility measurements revealed that the zeta potentials of the aggregates increased with DMA+ content. A study of the effect of added NaNO3 showed that electrostatic interactions controlled the size of the aggregates. The concentrated graft copolymer solutions showed temperature-triggered gelation when the copolymer concentrations exceeded 5 wt %, Fluid-to-gel phase diagrams were constructed. It was found that electrostatic interactions also controlled the gelation temperature. A correlation was found between aggregate size and the minimum copolymer concentration needed to form a gel. A mechanism for the temperature-triggered structural changes leading to the formation of aggregates (in dilute solution) or gels (in concentrated solutions) is proposed.

In this work, temperature-triggered gelation of aqueous laponite dispersions containing a cationic poly(N-isopropylacrylamide) (PNIPAm) graft copolymer was investigated. The copolymer used was PDMA(+)(30)-g-(PNIPAm(210))(14) [Liu et al. Langmuir 2008, 24, 7099]. DMA(+) is quarternarized N,N-dimethylaminoethyl methacrylate. The presence of small concentrations of laponite enabled temperature-triggered gel formation to occur at low copolymer concentrations (e.g., 1 wt %). Dynamic rheological measurements of the gels showed that they had storage modulus values of up to 400 Pa when the total solid volume fraction (polymer and laponite) was only about 0.02. The storage modulus was dependent on both the temperature and the composition of the dispersion used for preparation. The key component that provided the temperature-triggered gels with their elasticity was found to be self-assembled nanocomposite (NC) sheets. These NC sheets spontaneously formed at room temperature upon addition of laponite to the copolymer solution. The NC sheets had lateral dimensions on the order of hundreds of micrometers and a thickness of a few micrometers. The NC sheets were present within the temperature-triggered gels and formed elastically effective chains. The NC sheets exhibited temperature-triggered contraction with a contraction onset temperature of 27 degrees C. A conceptual model is proposed to qualitatively explain the relationship between gel elasticity and dispersion composition.

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