The internal plasticization of PVC by displacement of chlorine with phthalate-based thiol additives, that is, the covalent attachment of the plasticizer to the PVC chain, is described for the first time. Using this methodology, a good plasticization efficiency is achieved although flexibility is reduced compared with that of commercial PVC-phthalate systems. However, the migration is completely suppressed. This approach may open new ways to the preparation of flexible PVC with permanent plasticizer effect and zero migration.

A synthetic approach for the preparation and linkage of functionalized plasticizer molecules to PVC is described. The synthesis of this four-step procedure is economically and ecologically viable because it is based on trichlorotriazine as inexpensive starting material; the reactions can be carried out one-pot with quantitative yields and without need of final purification of the products. The approach is furthermore highly versatile and allows for the preparation of a large number of different plasticizers with properties that may be adjusted to a broad range of applications from highly flexible to semirigid.

A porous polymer containing a fluorophenylphenanthroimidazole core was easily prepared via one-pot Suzuki–Miyaura cross-coupling reactions under microwave heating. These new metal-free polymers have demonstrated heterogeneous photocatalytic activity toward aza-Henry reaction with reasonable recyclability. Their preparation require a minimal workup to build porous networks with control over the apparent surface area and pore volume from suitable molecular building blocks containing 2-(1H-phenanthro­[9,10-d]­imidazol-2-yl)-3,5-difluorophenol (PhIm-2F), as rigid and multitopic node, which afforded a conjugated porous polymer (CPP-PhIm-2F). A series of fluorinated ligands have shown their capability in the preparation of soluble and supported cationic Ru­(bpy)2(F-phenanthroimidazole) complexes by reaction with Ru­(bpy)2Cl2 and demonstrating a beneficial effect of two fluorine atoms on the photocatalytic effect.

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We report on the attachment of polymer monolayers or surface-attached, polymer networks onto SiO2 and/or polymer surfaces using thermo- and photoreactive α-diazoester groups. In the prior case, the α-diazoester groups are introduced into the system in the form of self-assembled monolayers of appropriately functionalized silanes. The monolayer decorated substrates are coated by polymer films and the α-diazoester groups in the monolayer are activated by heat or irradiation with UV-light. Upon activation, they cleave off nitrogen and the resulting carbene intermediates insert into C-H bonds of neighboring polymer chains. As a result of this binding process, surface-attached monolayers of the deposited polymer are obtained. When the polymers themselves carry such reactive moieties, the photo- or thermal activation leads to cross-linking of the polymers and thin surface-attached polymer networks result from the same process. The formation of the surface-attached layer is studied as a function of activation conditions, especially the temperature and the wavelength of the light used in the process.

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Summary:The sol-gel synthesis of organic-inorganic hybrids based on triethoxysilaneterminated poly(ethylene oxide) and tetraethylorthosilicate was monitored in-situ using three spectroscopic methods (FTIR/ATR, Raman, NIR). These spectroscopic methods allow in-situ monitoring of the evolution of hybrid materials starting from the modification of the polymer and the early steps of hydrolysis up to the network formation. By application of 29 Si solid-state NMR spectroscopy the assignment and quantification of the Raman bands to different end groups and different cross-linking states was made. The sol-gel reaction was also followed by in-line NIR spectroscopy. A multivariate data analysis was accomplished to obtain a conversion-time curve. Furthermore, we investigated spin-coated films on wafers using FTIR transmission spectroscopy.