Removable Biobased Waterborne Pressure-Sensitive Adhesives Containing Mixtures of Isosorbide Methacrylate Monomers.

Growing environmental concerns are enforcing sustainable recycling processes for glass substrates, especially bottles, where a fast cleaning and minimization of the use of solvents is desired. In this process, labels and adhesives are mostly removed by the addition of harsh reagents, alkaline solutions, or high temperature, increasing economic costs and harming the environment. Herein, high performance and biobased waterborne pressure-sensitive adhesives with fast removability in water have been developed using small percentages of isosorbide (derived from glucose)-based methacrylate monomers. Formulations containing 2-octyl acrylate and isobornyl methacrylate and small amounts (1 wt %) of these monomers not only yield stronger adhesive fibrils, but also promote a removability in water 6× faster than that of nonisosorbide-based counterparts. This waterborne isosorbide containing PSAs represents an alternative to current PSA formulations toward more sustainable glass recycling and reusing processes.

One-Pot Synthesis of Waterborne Polymeric Dispersions Stabilized with Alkali-Soluble Resins.

Alkali-soluble resins (ASRs) are a type of electrosteric emulsifiers of high interest because they can profitably improve the features of waterborne dispersions. In this work, they have been synthesized in-situ through a one-pot approach and they have been used as polymeric surfactants for a second emulsion polymerization step in the same reactor. This strategy provides some advantages compared to other polymerization techniques, like the intensification of the process and the absence of organic solvents. Their use can also further reduce the environmental impact of formulations for film-forming applications, since grafting reactions with the particles have been observed and quantified in relation with the synthetic parameters. These chemical linkages with the particles may reduce the leaching and the release of surfactants from polymeric films, for example in water-based coatings or adhesives. The systems have been also studied from the kinetics point of view, finding relevant differences with other electrosterically stabilized processes from the literature, as well as concerns the nucleation mechanism.

Fructose-Based Acrylic Copolymers by Emulsion Polymerization.

The exploration of a renewable resource for the preparation of waterborne copolymers was conducted. Low molar mass sugar resources were selected for their wide availability. A fructose-based monomer (MF) bearing a methacrylate radically polymerizable group was successfully synthesized. The latter was shown to be able to homopolymerize in emulsion. The high Tg of the resulting polymer (about 115 °C) makes it of particular interest for adhesive and coating applications where hard materials are necessary to ensure valuable properties. As a result, its incorporation in waterborne acrylic containing formulations as an equivalent to petrochemical-based methyl methacrylate was investigated. It was found that the bio-based monomer exhibited similar behavior to that of common methacrylates, as shown by polymerization kinetics and particle size evolution. Furthermore, the homogeneous incorporation of the sugar units into the acrylate chains was confirmed by a unique glass transition temperature in differential scanning calorimeter (DSC). The potential of MF for the production of waterborne copolymers was greatly valued by the successful increase of formulation solids content up to 45 wt %. Interestingly, polymer insolubility in tetrahydrofurane increased with time due to further reactions occurring in storage. Most likely, the partial deprotection of sugar units was the reason for the creation of hydrogen bonding and, thus, physically insoluble entangled chains. This behavior highlights opportunities to make use of hydroxyl groups either for further functionalization or, eventually, for achieving enhanced adhesion on casted substrates.

Synthesis of three different galactose-based methacrylate monomers for the production of sugar-based polymers.

Glycopolymers, synthetic sugar-containing macromolecules, are attracting ever-increasing interest from the chemistry community. Glycidyl methacrylate (GMA) is an important building block for the synthesis of sugar based methacrylate monomers and polymers. Normally, glycidyl methacrylate shows some advantages such as reactivity against nucleophiles or milder synthetic conditions such as other reactive methacrylate monomers. However, condensation reactions of glycidyl methacrylate with for instance protected galactose monomer leads to a mixture of two products due to a strong competition between the two possible pathways: epoxide ring opening or transesterification. In this paper, we propose two alternative routes to synthesize regiospecific galactose-based methacrylate monomers using the epoxy-ring opening reaction. In the first alternative route, the protected galactose is first oxidized to the acid in order to make it more reactive against the epoxide of GMA. In the second route, the protected sugar was first treated with epichlorohydrin followed by the epoxy ring opening reaction with methacrylic acid, to create an identical analogue of the ring-opening product of GMA. These two monomers were polymerized using conventional radical polymerization and were compared to the previously known galactose-methacrylate one. The new polymers show similar thermal stability but lower glass transition temperature (Tg) with respect to the known galactose methacrylate polymer.

Determination of the coalescence temperature of latexes by environmental scanning electron microscopy.

A new methodology for quantitative characterization of the coalescence process of waterborne polymer dispersion (latex) particles by environmental scanning electron microscopy (ESEM) is proposed. The experimental setup has been developed to provide reproducible latex monolayer depositions, optimized contrast of the latex particles, and a reliable readout of the sample temperature. Quantification of the coalescence process under dry conditions has been performed by image processing based on evaluation of the image autocorrelation function. As a proof of concept the coalescence of two latexes with known and differing glass transition temperatures has been measured. It has been shown that a reproducibility of better than 1.5 °C can be obtained for the measurement of the coalescence temperature.

Cross-linked network development in compatibilized alkyd/acrylic hybrid latex films for the creation of hard coatings.

Hybrids made from an alkyd resin and an acrylic copolymer can potentially combine the desired properties of each component. Alkyd/acrylic hybrid latex particles were synthesized via miniemulsion polymerization and used to create films at room temperature. Comparisons of the alkyd auto-oxidative cross-linking rates and the associated network development are made between two alkyd resins (with differing levels of hydrophilicity as measured by their acid numbers). The effects of increasing the compatibilization between the alkyd and the acrylic phase via functionalization with glycidyl methacrylate (GMA) are investigated. Magnetic resonance profiling and microindentation measurements reveal that film hardening occurs much faster in a GMA-functionalized alkyd hybrid than in the standard hybrid. The film's hardness increases by a factor of 4 over a 5-day period. The rate of cross-linking is significantly slower in nonfunctionalized alkyd hybrid films and when the more hydrophilic alkyd resin is used. Tensile deformation of the hybrid latex films reveals the effects of GMA functionalization and drier concentration in creating a denser cross-linked network. Modeling of the tensile deformation behavior of the hybrid films used a combination of the upper convected Maxwell model (to describe the viscoelastic component) and the Gent model (to describe the elastic component). The modeling provides a correlation between the cross-linked network formation and the resulting mechanical properties.

Evolving stresses in latex films as a function of temperature.

Latex films were dried on a flexible substrate, and the substrate deflection was monitored over time to give an averaged film stress-evolution profile. Films were dried at various temperatures below and above the minimum film-formation temperature of the latex dispersion. The effect of polymer rheology, which is a temperature-dependent parameter, on film formation, was investigated. The reliability of the Stoney model in predicting film stress from substrate curvature was also examined and compared to the Euler-Bernoulli model. It was shown that the linearized Stoney model was unsuitable for the larger measured stresses.

Improving water sensitivity in acrylic films using surfmers.

The water sensitivity of films obtained from high solids content acrylic latexes was investigated, with special focus on the role of the surfactant used in the synthesis step. The performance of films obtained from latexes stabilized by nonionic surfmers was compared to that of the acrylic latexes stabilized with conventional nonionic and anionic surfactants. It was seen that the latexes stabilized with reactive surfactants exhibited a remarkably better resistance to both water permeability and water vapor permeability and therefore enlarged the durability of the films. Atomic force microscopy images suggested that the defects created by surfactant migration in the latexes stabilized with conventional surfactants promoted the permeation of water by capillarity.