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Nonmigratory internal plasticization of poly(vinyl chloride) (PVC) is achieved by synthesis of poly(vinyl chloride)-co-poly(4,5-bis(2-ethylhexyl)-1-[6-prop-2enoyloxy)hexyl]-1H-1,2,3-triazole-4,5-dicarboxylate) [PVC-co-P(DEHT-HA)] copolymers via free radical polymerization (FRP). Optimization of the polymerization temperature, solvent, initiator, and vinyl chloride / acrylate (VC/DEHT-HA) monomer ratio were systematically investigated, and the corresponding glass transition temperatures (Tg) of the resultant copolymers determined. These internally plasticized copolymers were characterized by 1 H NMR, FTIR, SEC and DMTA. The Tg values of the PVC-co-P(DEHT-HA) copolymers range from -27 to 78 ºC, and the physical properties suggest that the P(DEHT-HA) and PVC segments are miscible.Thermogravimetric analysis shows that increasing the ratio of the monomer DEHT-HA to vinyl chloride increases the thermal stability. By varying the initial VC/DEHT-HA monomer ratio, one can tune the Tg of the resulting copolymer, making both the strategy and the polymer flexible.

A bio-based eutectic mixture (EM), composed of DL-menthol and 1-tetradecanol was investigated, for the first time, as the solvent for the homogeneous polymerization of different hydrophobic monomers, namely methyl acrylate...

Reversible deactivation radical polymerization of vinyl chloride (VC) by methyl (ethoxycarbonothioyl)­sulfanyl acetate (MEA)-mediated macromolecular design via the interchange of xanthate (MADIX) polymerization at ambient temperature is reported. The polymerization system was studied using two conventional radical initiators (having very distinct half-life times at room temperature). The system was optimized regarding the nature of the solvent, the monomer concentration, the polymerization temperature, and the target molecular weight. The kinetic data showed linear first-order kinetics, the linear evolution of molecular weights with conversion, and polymers with narrow molecular weight distributions (Đ ≈ 1.2 to 1.3) using a low temperature (30–42 °C) and cyclopentyl methyl ether (CPME) as a “green” solvent. The resulting MEA-terminated poly­(vinyl chloride) (PVC) was fully characterized by 1H nuclear magnetic resonance spectroscopy that revealed the existence of a very small fraction of structural defects and the presence of chain-end functional groups. “One-pot” chain extension (with VC) and “one-pot” block copolymerizations (with vinyl acetate − VAc and N-vinylcaprolactam − NVCL) experiments confirmed the “livingness” of the MEA-terminated PVC chains, giving access to different PVC-based block copolymers. Computational studies confirm the results of the solvent screen and suggest that changes to the initial MADIX leaving or stabilizing groups could improve control. The computational data were further confirmed using methyl 2-(4-methoxyphenoxycarbonothioylthio)­acetate. This work establishes a new green route to afford a wide range of new complex macrostructures including high-value materials based on PVC segments.

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