Surface and thermomechanical characterization of polyurethane networks based on poly(dimethylsiloxane) and hyperbranched polyester

Two series of polyurethane (PU) networks based on Boltorn® hyperbranched polyester (HBP) and hydroxyethoxy propyl terminated poly(dimethylsiloxane) (EO-PDMS) or hydroxy propyl terminated poly(dimethylsiloxane) (HPPDMS), were synthesized. The effect of the type of soft PDMS segment on the properties of PUs was investigated by Fourier transform infrared spectroscopy (FTIR), contact angle measurements, surface free energy determination, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). The surface characterization of PUs showed existence of slightly amphiphilic character and it revealed that PUs based on HP-PDMS have lower surface free energy, more hydrophobic surface and better waterproof performances than PUs based on EO-PDMS. PUs based on HPPDMS had higher crosslinking density than PUs based on EO-PDMS. DSC and DMTA results revealed that these newlysynthesized PUs exhibit the glass transition temperatures of the soft and hard segments. DMTA, SEM and AFM results confirmed existence of microphase separated morphology. The results obtained in this work indicate that PU networks based on HBP and PDMS have improved surface and thermomechanical properties

Methacrylic Acid Based Polymer Networks with a High Content of Unfunctionalized Nanosilica: Particle Distribution, Swelling, and Rheological Properties

The poor stability and tendency to agglomerate of unfunctionalized nano-SiO₂ in the presence of ionic species presents a challenge for preparing poly­(methacrylic acid)/nano-SiO₂ nanocomposite (NC) hydrogels with desired strength and swelling capability. We proposed a facile and eco-friendly method for the preparation of PMAA/SiO₂ NC hydrogels using unfunctionalized silica nanoparticles (NPs) in the form of a suspension. SEM and TEM analyses showed that the NP distribution in the polymer matrix highly depended on the particle concentration. At lower concentrations (up to 13.9 wt %), the NPs were uniformly dispersed as single nanoparticles. With an increase in NP concentration, homogeneously dispersed nanoscale aggregates were formed, while a further increase in the silica concentration led to the formation of homogeneous structures consisting of mutually interacting nanosilica particles coated with PMAA. Swelling experiments confirmed that the silica NPs behaved as adhesive fillers that interacted with PMAA chains, causing the formation of a thin polymer layer strongly adsorbed at the particle interface. The thicknesses of the adsorbed polymer layer, as well as the swelling kinetic parameters, were strongly influenced by nanoparticle size and concentration. Combining nanosilica and PMAA in the form of a soft hydrogel network provided stabilization of the NPs and ensured better mechanical properties of the obtained NC hydrogels compared to pure polymer matrix. The optimal loadings, necessary to ensure the most improved dynamical-mechanical properties, were found in the case of the formation of homogeneously dispersed, nanosized silica aggregates in a PMAA matrix

Methacrylic Acid Based Polymer Networks with a High Content of Unfunctionalized Nanosilica: Particle Distribution, Swelling, and Rheological Properties

The poor stability and tendency to agglomerate of unfunctionalized nano-SiO2 in the presence of ionic species presents a challenge for preparing poly(methacrylic acid)/nano-SiO2 nanocomposite (NC) hydrogels with desired strength and swelling capability. We proposed a facile and eco-friendly method for the preparation of PMAA/SiO2 NC hydrogels using unfunctionalized silica nanoparticles (NPs) in the form of a suspension. SEM and TEM analyses showed that the NP distribution in the polymer matrix highly depended on the particle concentration. At lower concentrations (up to 13.9 wt %), the NPs were uniformly dispersed as single nanoparticles. With an increase in NP concentration, homogeneously dispersed nanoscale aggregates were formed, while a further increase in the silica concentration led to the formation of homogeneous structures consisting of mutually interacting nanosilica particles coated with PMAA. Swelling experiments confirmed that the silica NPs behaved as adhesive fillers that interacted with PMAA chains, causing the formation of a thin polymer layer strongly adsorbed at the particle interface. The thicknesses of the adsorbed polymer layer, as well as the swelling kinetic parameters, were strongly influenced by nanoparticle size and concentration. Combining nanosilica and PMAA in the form of a soft hydrogel network provided stabilization of the NPs and ensured better mechanical properties of the obtained NC hydrogels compared to pure polymer matrix. The optimal loadings, necessary to ensure the most improved dynamical-mechanical properties, were found in the case of the formation of homogeneously dispersed, nanosized silica aggregates in a PMAA matrix