We report the preparation and structural and mechanical characterization of a tough supramolecular hydrogel, based exclusively on hydrophobic association. The system consists of a multiblock, segmented copolymer of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dimer fatty acid (DFA) building blocks. A series of copolymers containing 2K, 4K, and 8K PEG were prepared. Upon swelling in water, a network is formed by self-assembly of hydrophobic DFA units in micellar domains, which act as stable physical cross-link points. The resulting hydrogels are noneroding and contain 75–92 wt % of water at swelling equilibrium. Small-angle neutron scattering (SANS) measurements showed that the aggregation number of micelles ranges from 2 × 102 to 6 × 102 DFA units, increasing with PEG molecular weight. Mechanical characterization indicated that the hydrogel containing PEG 2000 is mechanically very stable and tough, possessing a tensile toughness of 4.12 MJ/m3. The high toughness, processability, and ease of preparation make these hydrogels very attractive for applications where mechanical stability and load bearing features of soft materials are required.
In this work we present the synthesis of poly(1,2-butylene oxide) (PBO) functionalized with the complementary hydrogen bond forming groups 2,4-diaminotriazine (DAT) and thymine. PBO is a rubbery polymer. Due to its semi-polar nature PBO is expected to suppresses non-directed cluster formation of the supramolecular groups but not influence their directed interactions. For the synthesis of backbone functionalized polymers we developed a procedure which allowed randomly copolymerizing BO with 1,2-epoxy-7-octene using anionic ring opening polymerization with potassium tert-butanolate as initiator. The vinyl groups were converted to OH-groups by oxidation. In addition, PBO with one alcoholic end group was obtained by homopolymerization of BO. For the variant with OH-groups at both chain ends a procedure was developed which was based on the cleavage of the tert-butyl initiator group. In all the polymers the alcohol groups were basically quantitatively transformed into NH 2 -groups.DAT and thymine functionalities were attached to the NH 2 -groups again in almost quantitative conversion. All reaction steps were monitored by 1 H-NMR using pyridine-d 5 as solvent. This method allowed determining the conversions of the different synthesis steps with high precision. The materials were examined in linear rheology in order to study the effect of the hydrogen-bonds on the dynamics of the resulting supramolecular structures. The results corroborate the exclusive existence of directed interactions between the supramolecular groups.
Abstract:In this work an investigation of the hydrogen bonding mechanism in a transiently branched comb-like polymer system in the melt is reported. The system under investigation consists of a polybutylene oxide (PBO)-based backbone, randomly functionalized with thymine (thy) groups, in combination with shorter PBO graft chains, end-functionalized with diaminotriazine (DAT) groups. The functional groups are able to associate through hydrogen bonding. The hetero-complementary association of these groups leads to the formation of a transiently branched comb-like polymer system. Since recently virtually exclusive heterocomplementary association could be observed in the supramolecular association of telechelically-modified oligomeric PEG chains, here we aim to extend the supramolecular assembly mechanism towards branched structures. The present work combines Small Angle Neutron Scattering (SANS) experiments on a selectively labeled system with macroscopic dynamics measured in linear rheology response. The association of thy-and DAT-modified components was studied as a function of temperature and composition. The scattering function reveals the formation of a block copolymer and can be exclusively attributed to heterocomplementary association of the hydrogen bonding groups. Scattering functions of nonfunctionalized blends are also reported as references and evidence the change in the microstructure induced by the hetero-complementary association. All scattering profiles were described by means of the Random Phase Approximation (RPA) formalism from which the average aggregation number i.e. comb arm functionality and the equilibrium association constant could be determined directly in the melt state as a function of temperature. On the other hand, rheological measurements were performed in the melt state to study the influence of the reversible bonds on the macroscopic dynamics of the polymer system. The rheology data are in good agreement with the SANS results and confirm the transient comb-like branched architecture. The supramolecular association exhibits characteristic bonding times of the groups in the order of 1 s at -25 °C and therefore makes the thy-DAT pair an ideal candidate for the development of responsive materials that combine permanent and transient linkages for novel applications and self-healing properties.
Discussion of paper by H. Watanabe, Y. Matsumiya and Y. Kwon, entitled 'Dynamics of rouse chains undergoing head-to-head association and dissociation: Difference between dielectric and viscoelastic relaxation'
The improvement of mechanical properties of polymer-based nanocomposites is usually obtained through a strong polymer–silica interaction. Most often, precipitated silica nanoparticles are used as filler. In this work, we study the synergetic effect occurring between dual silica-based fillers in a styrene-butadiene rubber (SBR)/polybutadiene (PBD) rubber matrix. Precipitated Highly Dispersed Silica (HDS) nanoparticles (10 nm) have been associated with spherical Stöber silica nanoparticles (250 nm) and anisotropic nano-Sepiolite. By imaging filler at nano scale through Scanning Transmission Electron Microscopy, we have shown that anisotropic fillers align only in presence of a critical amount of HDS. The dynamic mechanical analysis of rubber compounds confirms that this alignment leads to a stiffer nanocomposite when compared to Sepiolite alone. On the contrary, spherical 250 nm nanoparticles inhibit percolation network and reduce the nanocomposite stiffness.
In this study, the evolution of the scattering function of silica-filled styrene-butadiene copolymer rubbers (SBRs) under a continuous uniaxial strain cycle is investigated in situ with a complementary mechanical analysis. The microscopic hierarchical arrangement of aggregating nanofiller particles in the rubber matrix is determined by ultrasmall-angle X-ray scattering (USAXS) at different strain stages up to 100%. The application of strain during the collection of the scattering images allows a unique correlation of the evolution of the microstructure with a macroscopic deformation. Industrially mixed filled rubber compounds are investigated in the absence of ZnO, typically used as a curing activator and strongly contributing to the scattering function, to relate the scattering function and its evolution to the unambiguous contribution of the silica fillers. The effect of the deformation is reflected in the two-dimensional (2D) scattering patterns as well as in the sectorially averaged intensities along the principal axes of the deformation tensor. A scattering model, based on fractal concepts, is applied to the orientation-dependent intensities, allowing a quantitative correlation between the external strain and the induced structural changes on a 10−100 nm length scale. The singular role of the initial preferential orientation of the silica clusters is investigated in this work due to a direct correlation between the initial states of the clusters and the stress−strain behavior of the rubbery system. Conclusions on the observed hysteresis could be drawn by the combination of microscopic and macroscopic observations.
In silica–rubber based nanocomposites, a single organo-silicon is often used to compatibilize and covalently link silica to rubber. In this work, we have investigated the impact, at micro- and macroscales, of the decoupling of the hydrophobization and the coupling activity of silane by pretreating silica with two different silane chemistries. The first one, a mercaptosilane, is the coupling agent that promotes a covalent link between silica and rubber during the sulfur-mediated vulcanization reaction. The second one, an alkylsilane, aims to improve the silica dispersion. For both kind of silanes, we have varied the chain length and studied at macroscale the dynamic mechanical properties through the key indicators that are E ′′ as loss modulus, E ′ as storage modulus, and their respective ratio tan δ. The shorter silanes combination yielded an improvement in terms of wet grip indicators with tan δ at 0 °C increasing from 0.205 to 0.237 while maintaining rolling resistance indicators at the same level. We have evaluated the impact of the silane chemistry onto the cross-linking reactivity within the fabricated rubber-based nanocomposites by using moving-dye rheometer measurements (MDR). By purposely using atomic force microscopy (AFM), we have studied the silica dispersion in the matrix and the rubber/silica interface and provided the rationale explanation of the mechanical properties observed at the macroscale. AFM observation pointed out the existence of a soft interface around silica fillers when long alkylsilanes were used. We infer that this interface impacts the polymer–filler dynamic and subsequently affects the mechanical properties of the composite material.
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