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Thermoanalytical studies on an order-disorder transition resulting from supramolecular organization of hydrogen bond motifs in an unpolar (polymer-) matrix are reported. Functional groups having two potential sites for hydrogen bonding are located statistically along the polymer backbone. Multistep hydrogen bond formation leads to the formation of association chains whose lengths can be controlled by addition of monofunctional groups like in conventional stepgrowth polymers. The association chain length is estimated from the variation of transition enthalpy and 'melting' temperature.