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Mechanistic aspects on molecular structure formation of polymeric networks from diisocyanates with amidine compounds
Abstract:Polymeric networks are produced by step‐growth polyaddition and co‐polyaddition reactions of 1‐ethylimidazoline in combination with various diisocyanates. Five aromatic, two aliphatic diisocyanates and a polyurethane prepolymer are used as particular reactant in N,N‐dimethylformamide as solvent at room temperature. Obviously, 1‐ethylimidazoline can serve as trifunctional monomer, which enables a crosslinking reaction with diisocyanates. Molecular structure elements of the polymeric networks were studied by solid state 13C‐NMR spectroscopy revealing that detailed molecular structure formations are determined whether aromatic or aliphatic diisocyanates are used. Quantum chemical calculations were used as supporting method to elucidate the complex reaction cascades. Hence, it can be shown that beside 3:1 stoichiometric structures 2:1 based structures are formed as well. These structures are observed as kinetically controlled products only when aromatic diisocyanate monomers are used. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 977–985
Keywords:addition polymerization  amidine  blocked isocyanate  differential scanning calorimetry (DSC)  isocyanate  polymer network  step‐growth polymerization  theory and modeling  resins
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