Molecular structure formation as function of the catalytic process during the simultaneous twin polymerization of a hexadienyloxy-functionalized twin monomer with 2,2′-spirobi[4H-1,3,2-benzodioxasiline]
| Autor: | Rico John, Andreas Seifert, Stefan Spange, Katja Schreiter, Kevin Nagel, Judith Streif |
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| Rok vydání: | 2019 |
| Předmět: |
Polymers and Plastics
Chemistry Organic Chemistry 02 engineering and technology Nuclear magnetic resonance spectroscopy Tetracyanoethylene 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Catalysis chemistry.chemical_compound Monomer Polymerization Polymer chemistry Materials Chemistry Molecule 0210 nano-technology Ternary operation Hybrid material |
| Zdroj: | Polymer. 173:215-225 |
| ISSN: | 0032-3861 |
| Popis: | The 2-[(2E,4E)-hexa-2,4-dienyloxy]-2-methyl-4H-1,3,2-benzodioxasiline twin monomer (HD-TM) has been used in simultaneous twin polymerization (STP) with 2,2′-spirobi[4H-1,3,2-benzodioxasiline] (Spiro) to prepare ternary hybrid materials, where in contrast thermally induced twin polymerization of HD-TM alone failed. Depending on the used catalyst, organic-inorganic hybrid materials consisting of silica, phenolic resin and differently functionalized polysilsesquioxane are generated, as confirmed by solid-state NMR spectroscopy. During the thermally induced STP, DA reactions take place between hexadienyloxy groups and intermediately liberated ortho-quinone methide (oQM) from Spiro. If the HD-TM concentrations are too high, the polymerization process is inhibited by trapping the oQM, which is necessary for the phenolic resin formation. Base-catalyzed STP delivers phenolic resins and hexadienyloxy-functionalized polysilsesquioxanes structures (HDPS) which can be post-derivatized with tetracyanoethylene to a DA-adduct. Acid-catalyzed STP partly leads to a cleavage of the hexadienyl group from the silicon monomer, generating highly condensed inorganic networks. Thus, the hexadienyloxy group serves both as reactant and as an internal molecular probe, allowing statements about mechanistic processes and reactive species during the STP. |
| Databáze: | OpenAIRE |
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