Juan C. Sánchez-Díaz

Increasing Solid Content in Latexes of Polyacrylamide Nanoparticles Made by Semi-continuous Inverse Heterophase Polymerization

The synthesis of polyacrylamide nanoparticles by semi-continuous inverse heterophase polymerization as a function of feeding rate of monomer aqueous solution is reported here. In this process, a concentrated acrylamide aqueous solution is dosed semi-continuously at various rates over an AOT-toluene solution containing the initiator. Our results indicate that particle size and the viscosimetric molar masses diminish as the dosing rate is slowed down and that smaller particles, as well as lower molar masses, are obtained compared to those produced by batch and semi-continuous microemulsion polymerizations, employing the same concentration of surfactant. Moreover, higher polymer/surfactant ratios are higher compared to those obtained in batch microemulsion polymerization and similar or slightly higher than that in semi-continuous microemulsion polymerization.

Effect of Particle Size on the Swelling and Compression Modulus of Nanostructured Polyacrylamide Hydrogels

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.

Temperature and pH-Responsive Polyacrylamide/Poly(Acrylic Acid) Interpenetrating Polymer Network Nanoparticles

ABSTRACT 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 pKa 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.

Thermoresponsive poly(N-isopropylacrylamide) nanogels/poly(acrylamide) nanostructured hydrogels

ABSTRACT Here we report the preparation and characterization of nanostructured thermo-responsive poly(acrylamide) (PAM)-based hydrogels. The addition of slightly crosslinked poly(N-isopropylacrylamide) (PNIPA) nanogels to AM reactive aqueous solution produces nanostructured hydrogels that exhibit a volume phase transition temperature (TVPT). Their swelling kinetics, TVPTs and mechanical properties at the equilibrium-swollen state (Heq) are investigated as a function of the concentration of PNIPA nanogels in the nanostructured hydrogels. Nanostructured hydrogels with PNIPA nanogels/AM mass ratios of 20/80 and above exhibit higher Heq and longer time to reach the equilibrium swelling than those of the conventional PAM hydrogels. However, the PNIPA nanogels possess thermo-responsive character missing in conventional PAM hydrogels. The TVPT of nanostructured hydrogels depends on PNIPA nanogel content but their elastic and Young moduli are larger than those of conventional hydrogels at similar swelling ratios. Swelling kinetics, TVPT, and mechanical properties are explained in terms of the controlled in-homogeneities introduced by the PNIPA nanogels during the polymerization.