A new polythiourethane thermosetting system based on a diisocyanate and a trithiol was studied. After characterization of the reactive species, two critical temperatures, namely T g∞ (maximum glass transition temperature of the thermosetting system) and gel T g (T g of the material at the gel point), were determined. The conversion at gel point was also determined and compared to the theoretical prediction. Two different characteristics of the evolution of a reactive system, T g and conversion x as a function of time, were related. This is of particular interest for understanding the curing process, especially when non-isothermal cure schedules are used. Viscoelastic and plastic properties were investigated, with the aim of establishing connections between the chemical structure and properties through detailed analysis of the polymer chain motions (β and α relaxations). Measurements of the storage modulus at the rubbery plateau and of the critical strain intensity factor K Ic complete the study.
Cloud-point curves of blends of poly(methyl methacrylate) (PMMA) with a series of oligodiols based on a bisphenol A nucleus and short branches of poly(ethylene oxide) or poly(propylene oxide) (BPA-EO or BPA-PO), and with PEO and PPO oligomers, were obtained using a light transmission device. Experimental results were fitted with the Flory-Huggins model using an interaction parameter depending on both temperature and composition. For PMMA/PEO and PMMA/PPO blends, the miscibility increased when increasing the size of the diol, due to the significant decrease in the entropic and enthalpic terms contributing to the interaction parameter. This reflected the decrease in the selfassociation of solvent molecules and in the contribution of terminal OH groups to the mismatching of solubility parameters. For PMMA/BPA-EO blends, a decrease of the entropic contribution to the interaction parameter when increasing the size of the oligodiol was also found. However, the effect was counterbalanced by the opposite contribution of combinatorial terms leading to cloud-point curves located in approximately the same temperature range. For PMMA/BPA-PO blends, the interaction parameter exhibited a very low value. In this case, the effect of solvent size was much more important on combinatorial terms than on the interaction parameter, leading to an increase in miscibility when decreasing the oligodiol size.For short BPA-PO oligodiols no phase separation was observed. The entropic contribution of the interaction parameter exhibited an inverse relationship with the size of the oligodiols, independent of the nature of the chains bearing the hydroxyls and the type of OH groups (primary or secondary). This indicates that the degree of self-association of solvent molecules through their OH terminal groups, was mainly determined by their relative sizes.
Poly(methyl methacrylate) and random copolymers of methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMA) containing 7.5, 15, or 20 wt % DMA were dissolved in a stoichiometric mixture of m-xylylene diisocyanate and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, precursors of a polythiourethane network. Phase separation, which took place during polymerizations at 60, 90, and 120 8C, exhibited a lower critical solution temperature behavior. The cloud-point conversions, which were determined by the iodometric titration of free thiol groups of samples chilled in ice at the cloud point, increased with the weight fraction of DMA in the random copolymer. This could be used to control the cloud-point conversion and determine the characteristic size of the dispersed domains. A thermodynamic analysis was performed with the Flory-Huggins equation, taking into account the polydispersities of both the thermoplastic and thermoset polymers and using an interaction parameter depending on the temperature and on the three binary interaction energies. A reasonable fitting of the experimental curves was obtained with negative values for the interaction energies of the MMA-thermoset and DMA-thermoset pairs and with a positive value for the MMA-DMA pair.
Poly[Styrene-b-Butadiene-b-(Methyl Methacrylate)], SBM triblock copolymers have been incorporated in different polyurethane, PU formulations in order to prepare nanostructured materials. Macrodiols used for PU synthesis were based on a central bisphenol A, BPA unit with two hydroxylterminated oligo(oxypropylene), BPA-PO x or oligo(oxyethylene), BPA-EO chains with varying lengths. The initial solubility of the three blocks and the rheological behavior of the solutions in macrodiols and also in two diisocyanates, isophorone diisocyanate, IPDI, and 1,3-xylylene diisocyanate, XDI have been first characterized. The PMMA block is the most soluble and its role during the reaction is to stabilize the initial nanostructure or to control the reaction-induced microphase separation. Block copolymers can be dissolved first in the macrodiol, or preferably in the diisocyanate. With BPA-PO x and low SBM content (less than 10 wt %), transparent linear or crosslinked PU with well dispersed triblock nanoparticles have been prepared, depending on the molar mass of the macrodiol and on the concentration of diblock SB impurities present in the triblock. For high SBM concentrations (> 50 wt %), a twin screw extruder had to be used for the blending. Under well-defined conditions, transparent linear PUs and linear segmented polyurethane-ureas have been prepared. This study confirms that for designing a nanostructured material from a reactive mixture with a triblock additive, one block, called "the nanostructuring block" has to remain soluble up to the end of the reaction.
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