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The dependence of morphology of the poly(imide siloxane)s (PISs) on the solubility parameter of unmodified polyimides and the molecular weight and content of ␣,-bis(3-aminopropyl) polydimethylsiloxane (APPS) has been studied. The effect of the morphology on the mechanical properties is also under investigation. The domain formation in the PISs with the APPS molecular weight M n ϭ 507 g/mol is not found until the mol ratio of APPS/PIS Ն 0.5% in the pyromellitic dianhydride/p-phenylene diamine (PMDA/p-PDA)-based PISs, and at a mol ratio Ն 2.7% in the 3,3Ј,4,4Ј-benzophenone tetracarboxylic dianhydride/2,2Ј-bis[4-(3-aminophenoxy) phenyl] sulfone (BTDA/m-BAPS)-based PISs. As the APPS M n ϭ 715 g/mol, the critical APPS concentrations of the domain formation in both types of PISs are equal to 0.1 and 1.1%, respectively. The critical concentration is equal to 0.6% in the BTDA/m-BAPS-based PIS film with the APPS M n ϭ 996 g/mol. The isolated siloxane-rich phase in the BTDA/m-BAPS-based PISs becomes a continuous phase as the mol ratio of APPS/PIS Ն 7.7, 10.0, and 16.6% as the APPS M n ϭ 996, 715, and 507 g/mol, respectively. Dynamic Mechanical Analysis (DMA) shows two T g s in the PIS films having phase separation: one at Ϫ118 ϳ -115°C, being the siloxane-rich phase, the other at 181-244°C, being the aromatic imide-rich phase. The SEM micrographs show a significant deformation on the fractured surfaces of the BTDA/m-BAPS-based PIS films with a continuous siloxane-rich phase. This phenomenon of plastic deformation is also observed in the tensile tests at Ϫ118°C and at room temperature. The highest elongation in the PIS films is found at the critical siloxane content of the continuous siloxane-rich phase formation.
The dependence of morphology of the poly(imide siloxane)s (PISs) on the solubility parameter of unmodified polyimides and the molecular weight and content of ␣,-bis(3-aminopropyl) polydimethylsiloxane (APPS) has been studied. The effect of the morphology on the mechanical properties is also under investigation. The domain formation in the PISs with the APPS molecular weight M n ϭ 507 g/mol is not found until the mol ratio of APPS/PIS Ն 0.5% in the pyromellitic dianhydride/p-phenylene diamine (PMDA/p-PDA)-based PISs, and at a mol ratio Ն 2.7% in the 3,3Ј,4,4Ј-benzophenone tetracarboxylic dianhydride/2,2Ј-bis[4-(3-aminophenoxy) phenyl] sulfone (BTDA/m-BAPS)-based PISs. As the APPS M n ϭ 715 g/mol, the critical APPS concentrations of the domain formation in both types of PISs are equal to 0.1 and 1.1%, respectively. The critical concentration is equal to 0.6% in the BTDA/m-BAPS-based PIS film with the APPS M n ϭ 996 g/mol. The isolated siloxane-rich phase in the BTDA/m-BAPS-based PISs becomes a continuous phase as the mol ratio of APPS/PIS Ն 7.7, 10.0, and 16.6% as the APPS M n ϭ 996, 715, and 507 g/mol, respectively. Dynamic Mechanical Analysis (DMA) shows two T g s in the PIS films having phase separation: one at Ϫ118 ϳ -115°C, being the siloxane-rich phase, the other at 181-244°C, being the aromatic imide-rich phase. The SEM micrographs show a significant deformation on the fractured surfaces of the BTDA/m-BAPS-based PIS films with a continuous siloxane-rich phase. This phenomenon of plastic deformation is also observed in the tensile tests at Ϫ118°C and at room temperature. The highest elongation in the PIS films is found at the critical siloxane content of the continuous siloxane-rich phase formation.
Polyimide/silica hybrids were produced by a sol‐gel process and were examined in terms of their morphology, dynamic‐mechanical properties and mechanical performances. Two types of morphology were obtained by tailoring the composition of the precursor solution mixture, i.e. phase‐ separated or co‐continuous systems. These morphologies were found to exhibit considerably different properties. In particular, co‐continuous nanocomposite systems were found much more effective in suppressing molecular relaxation processes than micron sized particulate hybrids. The latter systems, on the other hand, exhibited enhanced ductility and fracture toughness
Conventional crosslinked photopolymers possess permanent network structures, which cannot be remolded/recycled and generally discarded as waste after use. Research has begun to incorporate dynamic bonds into crosslinked photopolymers to make them reprocessable/recyclable, however, previous studies typically require tedious pre‐syntheses to obtain photoreactive building blocks that contain desired dynamic linkages/functionalities. In this study, we report a simple, one‐step, and scalable synthesis of chemically recyclable crosslinked thiol‐ene photopolymers that contain dynamic disulfide bonds from commercially available building blocks. Specifically, liquid polysulfides containing both reactive thiol end groups and internal disulfide bonds, together with multifunctional alkenes, are selected as the building blocks to simultaneously incorporate disulfide bonds during network formation via thiol‐ene photopolymerization. The incorporated dynamic disulfide bonds allow these thiol‐ene networks to be chemically recycled into photoreactive thiol oligomers through base‐catalyzed thiol‐disulfide exchange reactions. The resulting thiol oligomers can be effectively reused, together with the original multifunctional alkenes, for the next‐generation syntheses of crosslinked thiol‐ene photopolymers with chemical compositions and material properties that are nearly identical to those of the originally crosslinked sample. This chemical recycling process can be repeated many (infinite in theory) times to produce recycled thiol‐ene photopolymer networks with full property retention. Overall, the unique chemistry demonstrated in this study could potentially provide a route towards a circular economy of crosslinked photopolymers.
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