The effects of concentration and size of polyacrylamide (PAM) nanoparticles on the swelling behavior and compression modulus of nanostructured polyacrylamide hydrogels are examined here. These hydrogels are made by free radical polymerization in an aqueous solution of acrylamide and a crosslinking agent containing dispersed crosslinked PAM nanoparticles of different sizes, previously made by inverse emulsion or microemulsion polymerization. Faster swelling rate and larger equilibrium swelling are observed as particle content increases or the nanoparticle size diminishes. The compression modulus depends on the concentration and size of the disperse nanoparticles: it is larger for hydrogels containing smaller particles at similar concentrations, and it increases as the nanoparticle concentration augments. Moreover, the nanostructured hydrogels have larger compression modulus than those of the conventional ones having similar swelling.

Nanoemulsions of water, Brij 56 and hexyl methacrylate (with a small amount of squalene as hydrophobe or costabilizer) were made by the phase inversion temperature (PIT) method and then polymerized. In the absence of squalene, the nanoemulsions destabilized within minutes; however with squalene, the nanoemulsions were kinetically stable for at least several hours, which is long enough to carry out the reactions, with diameters of narrow size distribution in the range from 32 to 44 nm, depending on the surfactant concentration. Polymerizations, carried out a 20°C using a par redox, were extremely fast (ca. 100% conversion in less than 5 min) yielding polymer particles of ca. 40 nm, which were similar to the original nanoemulsion droplets (ca. 35 nm), indicating that the nanoemulsion droplets act as templates, and that squalene diminishes substantially monomer diffusion between reacting and non-reacting monomer droplets. Molar masses were high and alike to those produced by microemulsion polymerization of this monomer, suggesting that chain transfer to monomer is the main termination mechanism.

The synthesis, by two sequential inverse microemulsion polymerizations, of interpenetrating polymer networks (IPN) formed by polyacrylamide (PAM) and poly(acrylic acid) (PAA) and their response to changes in pH and temperature are reported here. The temperature and pH responses of the IPN nanoparticles are compared with those of polyacrylamide and random copolymers of polyacrylamide and poly(acrylic acid) P(AM-co-AA) nanoparticles also made by inverse microemulsion polymerization. We found that only the IPN nanogels exhibited a sharp swelling increase with temperature associated with its Upper Consolute Solution Temperature, driven by hydrogen bonding interactions, and with pH, driven by electrostatic repulsions of the PAA carboxylic groups, especially at pHs larger than the pK_a of the PAA. The ς-potentials of the PAM, P(AM-co-AA) and IPN nanogels were measured as a function of pH and temperature, to determine the effects of these two variables, which in turn, affected the swelling of the nanogels. Field emission scanning electron microscopy revealed that the IPN nanogels were spheroidal with sizes similar to those determined by dynamic light scattering.

The synthesis and characterization of copolymers of n-Butyl Acrylate (BA) and Poly(ethylene glycol) dimethacrylate (PEGDMA) were realized by microemulsion. In this synthesis, the relation of PEGDMA 10, 20, 30, 40 and 50% wt with respect to BA was changed. The copolymers obtained were characterized by the determination of conversions (gravimetry), infrared spectroscopy: Fourier transform (FTIR), dynamic light scattering (DLS), thermogravimetry (TGA) and differential scanning calorimetry (DSC). The results confirmed the synthesis of BA-co - PEGDMA copolymers by the identification of characteristic FTIR bands and which determined the glass transition temperature of the copolymers. The conversions were found in the range of 85% to 90%. Within the stability of the produced latex, it was observed that at 10% and 30% wt. of PEGDMA the systems were stable, but when more PEGDMA was added up 40% to 50% wt., the system became unstable. The stability of produced latexes depends on the PEGDMA contents and this must be less than 30% wt.; meanwhile the PEGDMA content greater than 30% wt. leads to unstable latexes, forming clots. Copolymers showed single glass transition temperatures between -53.37°C and -16.58°C, depending on the composition of PEGDMA in the copolymers. Resulting in the different arrangements of units of PEGDMA along in the chain affected the thermal properties of the final copolymers.

The design of nanocomposites with the potential for drug delivery is a topic of great interest. In this work, the synthesis of nanocomposites of poly(methacrylic acid) (PMAA) grafted onto carbon nanotubes (CNTs) functionalized with poly(amidoamine) (PAMAM) dendrimer by semicontinuous heterophase polymerization SHP, at three different methacrylic acid (MAA) dosing rates, is reported. SHP is a polymerization technique poorly used to prepare nanocomposites containing CNTs and has the potential to produce more ordered alkyl methacrylic polymer chains, which could favor the obtaining of a homogenous nanocomposite. For the nanocomposites synthesized, a lowest addition rate monomer-starved condition was reached. Analysis by X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) demonstrate that functionalized CNTs are grafted onto the PMAA matrix. The ability of prepared nanocomposites to deliver hydrocortisone was evaluated by ultraviolet-visible spectroscopy (UV-Vis). The hydrocortisone release profiles of pure PMAA and of their nanocomposites prepared at the lowest monomer fed rate were fitted with Higuchi and Korsmeyer–Peppas models, successfully. Functionalized CNTs have a crucial role to induce an effective release of hydrocortisone from the prepared nanocomposites.