Bruno Grassl

pH-triggered reversible sol–gel transition in aqueous solutions of amphiphilic gradient copolymers

We demonstrate the possibility of reversible pH-controlled sol–gel transition in aqueous solution of associating amphiphilic triblock copolymer poly(styrene-grad-acrylic acid)-b-poly(acrylic acid)-b-poly(styrene-grad-acrylic acid), (PS-grad-PAA)-b-PAA-b-(PS-grad-PAA), synthesized vianitroxide-mediated (NM) radical copolymerization. The presence of pH-sensitive co-monomer units of the acrylic acid in the terminal blocks ensures the dynamic nature of the styrene-rich hydrophobic nano-domains which are formed at low pH. At small polymer concentrations the association triggered by lowering the pH gives rise to flower-like micelles stabilized by partially ionized PAA coronae. The pH-controlled association was monitored by DLS-titration and manifested in the evolution of a correlation peak in the SANS spectra. The resulting copolymer aggregates were visualized by TEM, which confirmed the spherical shape of the dense styrene-rich domains. Above the micelle overlap concentration a decrease in pH provokes macroscopic gelation. Here the styrene-reach domains perform as cross-links in the transient network. The pH-triggered sol-to-gel transition is manifested in an abrupt and strong (up to 3 orders of magnitude) increase in the zero-shear viscosity and in a characteristic change in the frequency dependence of the storage and loss moduli. The discovered effect can be used for efficient pH-control of the rheological properties of aqueous solutions.

Synthesis and pH- and salinity-controlled self-assembly of novel amphiphilic block-gradient copolymers of styrene and acrylic acid

A novel type of amphiphilic ionic copolymer comprising a hydrophilic poly(acrylic acid) (PAA) block and an amphiphilic poly(acrylic acid)-grad-poly(styrene) (PAA-grad-PS) copolymer block was synthesized using a one step direct nitroxide-mediated polymerization (NMP). A strong influence of the macroinitiator on the values of the reactivity ratios of the co-monomers is confirmed by 1H NMR. The aggregation behaviour of the copolymers in the aqueous medium was studied by small-angle neutron scattering (SANS) and dynamic light scattering (DLS) and by transmission electron microscopy (TEM) in a wide range of pHs and ionic strengths. It has been demonstrated that PAA-b-(PAA-grad-PS) copolymers are soluble in alkaline water at room temperature without the special experimental procedures (addition of co-solvent, heating, etc.) that are usually required for solubilisation of classical PAA-b-PS diblock copolymers. The self-assembly of the PAA-b-(PAA-grad-PS) copolymers into nano-scale aggregates at low/moderate pH and/or high ionic strength was demonstrated by SANS and DLS experiments. The SANS spectra for the copolymer solution exhibit a correlation peak pointing to the formation of micelles with repulsive coronae. TEM images indicate that the micelles have an approximately spherical shape and exhibit a wide size distribution. Our results prove, that in contrast to “frozen” aggregates formed by PAA-b-PS copolymers in aqueous media, the micelles of PAA-b-(PAA-grad-PS) amphiphilic copolymers exhibit “dynamic” pH-responsive properties, i.e. they can reversibly change their aggregation number upon a variation in the pH or salinity of the solution.

Hydrogel nanocomposites as pressure-sensitive adhesives for skin-contact applications

This study investigates the effects of monodisperse polystyrene nanoparticle fillers on the network formation, rheological properties and adhesion performance of hydrogel nanocomposites based on polyacrylamide and poly(acrylamide-hydroxyethyl methacrylate). We demonstrated a simultaneous increase in elasticity and tack of these humid composite materials. A 1H-NMR kinetic study showed quasi-total conversion of these monomers during the polymerization–reticulation process and the formation of inhomogeneities within the hydrogel network structure due to the difference in reactivity ratios of the comonomers: acrylamide (AM) and hydroxyethyl methacrylate (HEMA)(rAM = 0.41 ± 0.01 and rHEMA = 7.4 ± 0.3). The rheological properties of these materials were found to be affected by their chemical composition (HEMA content, presence of nanoparticles and heterogeneities). We investigated the adhesion properties of our materials using a probe test tack. Measurements were carried out on a human skin substitute to compare with metal and investigate the potential use of these hydrogel nanocomposites as dermatological patches. The adhesion energy was found to be related to the chemical composition and rheological properties of the hydrogels, as well as to the surface properties of both the adhesive and the substrate.

Rapid and quantitative determination of critical micelle concentration by automatic continuous mixing and static light scattering.

We present the rapid and quantitative characterization of ionic, non-ionic and zwitterionic surfactants based upon the combination of an automatic continuous mixing technique and static light scattering. Collection and subsequent analysis of data are both rapid and semiautomatic, which increases precision, sensitivity, and range of applicability while substantially decreasing the amount of manual intervention required by the investigator. By treating the continuous data, the entire data set may be rapidly analyzed in the context of the closed association model to determine the critical micelle concentration cmc and aggregation number Nag of a detergent; these technique are comparable in the scope and resolution currently obtainable from other conductimetric, fluorescence and surface tension techniques.

Synthesis and rheological properties of hydrophobically modified polyacrylamides with lateral chains of poly(propylene oxide) oligomers

Hydrophobically modified polyacrylamides (HMPAM) were synthesized by aqueous micellar copolymerization using poly(propylene glycol) monomethacrylate, PPGMA, as hydrophobic monomer and sodium dodecyl sulfate, SDS, as surfactant. The hydrophobic monomer to surfactant ratio was varied during micellar synthesis to obtain different hydrophobic block lengths. It was found that the rheology of HMPAM/SDS solutions depends both on the ratio of PPGMA to surfactant and on the concentration of surfactant used in the micellar copolymerization. Also, the rheological behavior of the copolymer solutions was studied as a function of SDS addition and temperature. In the presence of SDS, an increase in zero-shear viscosity was observed that depended on polymer and surfactant concentration. At the highest SDS concentration, the copolymer did not reach the viscosity value exhibited by the solution without surfactant. In the presence of surfactant, HMPAM solutions exhibited a small thermo-thickening behavior when the temperature increases from 25 to 50 degrees C. Our rheological results evidence that the properties of HMPAM aqueous solution as a function of temperature, are a consequence of the rheological response of both components within the copolymer chain, i.e., hydrophilic (acrylamide) and lateral lower critical solution temperature (LCST) sequences (PPO).

Saponins: A Renewable and Biodegradable Surfactant From Its Microwave-Assisted Extraction to the Synthesis of Monodisperse Lattices

Synthetic surfactants are widely used in emulsion polymerization, but it is increasingly desirable to replace them with naturally derived molecules with a reduced environmental burden. This study demonstrates the use of saponins as biodegradable and renewable surfactants for emulsion polymerization. This chemical has been extracted from soapnuts by microwave assisted extraction and characterized in terms of surfactant properties prior to emulsion polymerization. The results in terms of particle size distribution and morphology control have been compared to those obtained with classical nonionic (NP40) or anionic (SDS) industrial surfactants. Microwave-extracted saponins were able to lead to latexes as stable as standard PS latex, as shown by the CMC and CCC measurements. The saponin-stabilized PS particles have been characterized in terms of particle size and distribution by Dynamic Light Scattering and Asymmetrical Flow Field Flow Fractionation. Monomodal and monodispersed particles ranging from 250 to 480 nm in terms of diameter with a particle size distribution below 1.03 have been synthesized.

Multielement molecular size fractionation in crude oil and oil residue by size exclusion microchromatography with high resolution inductively coupled plasma mass spectrometric detection (HR ICP MS)

Microchromatography using permeation through gels with the increasing exclusion limit (5000, 400000 and 20000000 Da) was combined with high resolution (R = 4000) ICP MS to measure the distribution of Co, Cr, Fe, Ni, S, Si, V and Zn as a function of the molecular mass fraction of crude oil and oil vacuum distillation residue. The accuracy of the simultaneous multielement determination was verified by the µflow-injection-ICP MS analysis of certified reference materials (wear-metals in lubricating oils: SRM 1084a and SRM 1085b). The method allowed the acquisition of chromatograms with high sensitivity competitive existing methods, showing element- and sample origin-dependent morphology.

Determination of the macromolecular dimensions of hydrophobically modified polymers by micellar size exclusion chromatography coupled with multiangle light scattering.

The present work demonstrates that the use of a nonionic surfactant in the mobile phase together with light scattering coupled to size exclusion chromatography (SEC) provides an accurate determination of macromolecular dimensions of hydrophobically modified water-soluble polymer and polyelectrolyte, i.e., weight-average molar mass M(w) and polydispersity I(p). This method, called micellar SEC, is based on the dissociation of the aggregates in aqueous solution and the formation of mixed micelles between the surfactant and the polymer hydrophobic groups. The methodology and its application are presented for synthetic sulfonated polyacrylamides (5 and 20 mol %) modified with three hydrophobic alkyl side groups (C8, C12, and C18) and with Triton X-100 as a nonionic surfactant and are discussed according to the associativity of polymers. The results are compared to those obtained by classical SEC in 0.1 M NaNO(3) and by static light scattering in formamide solution.

Size characterization of the associations between carbon nanotubes and humic acids in aqueous media by asymmetrical flow field-flow fractionation combined with multi-angle light scattering

This work focuses on the influence of humic acids (HAs) on the fate of carbon nanotubes (CNTs) in aqueous media. This influence was demonstrated by mixing CNT powder with HAs in aqueous solution in varying concentrations. The aqueous media containing HAs and CNTs were size-characterized by asymmetrical flow field-flow fractionation (AsFlFFF) coupled with multi-angle light scattering (MALS). This coupling yielded information concerning the size distribution of single- and multi-walled CNTs (SWCNTs and MWCNTs) and HAs under different physico-chemical conditions that can occur in environmental water. HAs can disperse individual CNTs in aqueous media. However, the difference in the physical structure between SWCNTs and MWCNTs leads to significant differences in the quantity of HA that can adsorb onto the nanotube surface and in the stability of the CNT/HA complex. Compared with MWCNTs, SWCNTs suspended in HAs are less affected by changing ionic strength with respect to stability and the amount suspended.

Microwave‐Assisted Syntheses in Recyclable Ionic Liquids: Photoresists Based on Renewable Resources

The copoly(2-oxazoline) pNonOx80-stat-pDc=Ox20 can be synthesized from the cationic ring-opening copolymerization of 2-nonyl-2-oxazoline NonOx and 2-dec-9′-enyl-2-oxazoline Dc=Ox in the ionic liquid n-hexyl methylimidazolium tetrafluoroborate under microwave irradiation in 250 g/batch quantities. The polymer precipitates upon cooling, enabling easy recovery of the polymer and the ionic liquid. Both monomers can be obtained from fatty acids from renewable resources. pNonOx80-stat-pDc=Ox20 can be used as polymer in a photoresist (resolution of 1 μm) based on UV-induced thiol–ene reactions.