New Chemistries for Degradable Pressure-Sensitive Adhesive Networks.

With the increasing use of pressure-sensitive adhesives (PSAs) in various industries, there is a need for greater sustainability, particularly in developing polymer materials from renewable resources, as well as the reuse and recycling of materials to reduce environmental impact, reduce waste, or extend their life. Here, we outlined the required properties of PSAs which are governed by the molecular parameters (molecular weights, dispersities, molecular weight between entanglement, molecular weight between cross-links and gel content) of polymer materials which subsequently define the physical properties (storage and loss moduli, glass transition temperature) that are required for good performance in peel, tack and shear tests. The sustainable approach discussed here is the development of degradable polymer materials featuring selectively degradable linkages in the backbone. This provides a viable alternative for the design of PSAs that could overcome the 'stickies' problem and make the recycling of glass and cardboard more efficient.

Degradable, Ultraviolet-Crosslinked Pressure-Sensitive Adhesives Made from Thioester-Functional Acrylate Copolymers.

Pressure-sensitive adhesives (PSAs) are made from soft, irreversibly lightly crosslinked polymers. Even after removal from surfaces, they retain insoluble networks which pose problems during the recycling of glass and cardboard. Herein, degradable PSAs are presented that provide the required performance in use but have networks that can be degraded after use. A series of copolymers was prepared through radical copolymerization of n-butyl acrylate, 4-acryloyloxy benzophenone (ABP) photo-crosslinker, and dibenzo[c,e]oxepin-5(7H)-thione (DOT) to provide degradable backbone thioesters. The optimum tack and peel strengths were found for molar contents of 0.05 mol% ABP and 0.25 mol% DOT. Degradation of the backbone thioesters through aminolysis or thiolysis led to the full dissolution of the networks, loss of adhesive properties of films (decreases in the measured tack and peel strengths), and the quick detachment of model labels from a substrate. Inclusion of DOT into PSAs offers a viable route toward degradable and recyclable packaging labels.

Diffusiophoresis-Driven Stratification in Pressure-Sensitive Adhesive Films from Bimodal Waterborne Colloids.

The uses of pressure-sensitive adhesives (PSAs) are wide ranging, with applications including labels, tapes, and graphics. To achieve good adhesion, a PSA must exhibit a balance of viscous and elastic properties. Previous research has found that a thin, elastic surface layer on top of a softer, dissipative layer resulted in greater tack adhesion compared with the single layers. Superior properties were achieved through a bilayer obtained via successive depositions, which consume energy and time. To achieve a multilayered structure via a single deposition process, we have stratified mixtures of waterborne colloidal polymer particles with two different sizes: large poly(acrylate) adhesive particles (ca. 660 nm in diameter) and small poly(butyl acrylate) (pBA) particles (ca. 100 nm). We used two types of pBA within the particles: either viscoelastic pBA without an added cross-linker or elastic pBA with a fully cross-linked network. Stratified surface layers of deuterium-labeled pBA particles with thicknesses of at least 1 µm were found via elastic recoil detection and qualitatively verified via the analysis of surface topography. The extent of stratification increased with the evaporation rate; films that were dried slowest exhibited no stratification. This result is consistent with a model of diffusiophoresis. When the elastic, cross-linked pBA particles were stratified at the surface, the tack adhesion properties made a transition from brittle failure to tacky. For pBA without an added cross-linker, all adhesives showed fibrillation during debonding, but the extent of fibrillation increased when the films were stratified. These results demonstrate that the PSA structure can be controlled through the processing conditions to achieve enhanced properties. This research will aid the future development of layered or graded single-deposition PSAs with designed adhesive properties.

How Particle Deformability Influences the Surfactant Distribution in Colloidal Polymer Films.

The distribution of surfactants in waterborne colloidal polymer films is of significant interest for scientific understanding and defining surface properties in applications including pressure-sensitive adhesives and coatings. Because of negative effects on appearance, wetting, and adhesion, it is desirable to prevent surfactant accumulation at film surfaces. The effect of particle deformation on surfactant migration during film formation was previously investigated by Gromer et al. through simulations, but experimental investigations are lacking. Here, we study deuterium-labeled sodium dodecyl sulfate surfactant in a poly(butyl acrylate) latex model system. The particle deformability was varied via cross-linking of the intraparticle polymer chains by differing extents. The cross-linker concentration varied from 0 to 35 mol % in the copolymer, leading to a transition from viscoelastic to elastic. Ion beam analysis was used to probe the dry films and provide information on the near-surface depth distribution of surfactant. Films of nondeformable particles, containing the highest concentration of cross-linker, show no surfactant accumulation at the top surface. Films from particles partially deformed by capillary action show a distinct surfactant surface layer (ca. 150 nm thick). Films of coalesced particles, containing little or no cross-linker, show a very small amount of surfactant on the surface (ca. 20 nm thick). The observed results are explained by considering the effect of cross-linking on rubber elasticity and applying the viscous particle deformation model by Gromer et al. to elastically deformed particles. We find that partially deformed particles allow surfactant transport to the surface during film formation, whereas there is far less transport when skin formation acts as a barrier. With elastic particles, the surfactant is carried in the water phase as it falls beneath the surface of packed particles. The ability to exert control over surfactant distribution in waterborne colloidal films will aid in the design of new high-performance adhesives and coatings.

Azide Photochemistry in Acrylic Copolymers for Ultraviolet Cross-Linkable Pressure-Sensitive Adhesives: Optimization, Debonding-on-Demand, and Chemical Modification.

Pressure-sensitive adhesives (PSAs) are usually made from viscoelastic, high-molecular-weight copolymers, which are fine-tuned by adjusting the comonomer ratios, molecular weights, and cross-link densities to optimize the adhesion properties for the desired end-use. To create a lightly cross-linked network, an ultraviolet (UV) photoinitiator can be incorporated. Here, we present the first use of perfluorophenylazide chemistry to control precisely a polyacrylate network for application as a PSA. Upon UV irradiation, the highly reactive nitrene from the azide moiety reacts with nearby molecules through a C-H insertion reaction, resulting in cross-linking via covalent bonding. This approach offers three benefits: (1) a means to optimize adhesive properties without the addition of an external photoinitiator; (2) the ability to switch off the tack adhesion on demand via a high cross-linking density; and (3) a platform for additional chemical modification. A series of poly(n-butyl acrylate-co-2,3,4,5,6-pentafluorobenzyl acrylate) or poly(PFBA-co-BA) copolymers were synthesized and modified post-polymerization into the photo-reactive poly(n-butyl acrylate-co-4-azido-2,3,5,6-tetrafluorobenzyl acrylate) [azide-modified poly(PFBA-co-BA)] with various molar contents. When cast into films, the azide-modified copolymers with a high azide content achieved a very high shear resistance after UV irradiation, whereas the tack and peel adhesion decreased strongly with the increase in azide content, indicating that excessive cross-linking occurred. These materials are thus photo-switchable. However, in the low range of azide content, an optimum probe tack adhesion energy was obtained in films with a 0.3 mol % azide content, where a long stress plateau (indicating good fibrillation) with a high plateau stress was observed. An optimum peel adhesion strength was achieved with 0.5 mol % azide. Thus, the adhesion was finely controlled by the degree of cross-linking of the PSA, as determined by the azide content of the copolymer chain. Finally, as a demonstration of the versatility and advantages of the material platform, we show an azide-aldehyde-amine multicomponent modification of the azide copolymer to make a dye-functionalized film that retains its adhesive properties. This first demonstration of using azide functionality has enormous potential for functional PSA design.