Hydrogen-bonded supramolecular polymer networks

The strong dimerizing, quadruple hydrogen-bonding ureido-pyrimidone unit is used to obtain reversible polymer networks. A new synthetic route from commercially available starting materials is described. The hydrogen-bonding ureido-pyrimidone network is prepared using 3(4)-isocyanatomethyl-1-methylcyclohexyl-isocyanate (IMCI) in the regioselective coupling reaction of multi-hydroxy functionalized polymers with isocytosines. 1H- and 13C-NMR, IR, MS, and ES-MS analysis, performed on a model reaction using butanol, demonstrated the formation of the hydrogen-bonding ureido-pyrimidone unit in a yield of more than 95%. The well-defined, strong hydrogen-bonding ureido-pyrimidone network is compared with a traditional covalently bonded polymer network, a multi-directional hydrogen-bonded polymer network based on urea units, and a reference compound. The advantage of the reversible, hydrogen-bonded polymer networks is the formation of the thermodynamically most favorable products, which show a higher “virtual” molecular weight and shear modulus, compared to the irreversible, covalently bonded polymer network. The properties of the ureido-pyrimidone network are unique; the well-defined and strong dimerization of the ureido-pyrimidone unit does not require any additional stabilization such as crystallization or other kinds of phase separation, and displays a well-defined viscoelastic transition. The ureido-pyrimidone network represents the first example of a truly reversible polymer network showing these features. Furthermore, the ureido-pyrimidone dimerization is strong enough to construct supramolecular materials possessing acceptable mechanical properties.