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<p>This study introduces a targeted synthesis and comprehensive evaluation for optimizing the composition of hot-melt polyurethane reactive adhesives (HMPUR) by methodically varying the soft segment of the polyester polyol (PSPO) and evaluating the distinct effects of amine- versus hydroxyl-functionalized chain extenders. Three PSPOs (synthesized from succinic, adipic, and dodecanedioic acid) were formulated with either ethylenediamine (EDA) or 1,4-butanediol (BDO), due to the fundamental differences in their chemical reactivity. The structure-property relationships of the adhesives, formulated with varying polyester polyols and chain extenders, were systematically investigated using analytical techniques including differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), proton nuclear magnetic resonance (<sup>1</sup>H NMR), melt viscometry, lap shear testing, and isocyanate titration. EDA-based adhesives have consistently demonstrated superior crosslinking efficiency, resulting in significantly enhanced mechanical performance and faster cure kinetics. The PSPO-1_EDA formulation exhibits a cure time of 8.5&#xa0;h. In contrast, BDO formulations exhibited greater flexibility and lower processing viscosity. The longest-chain polyol, PSPO-3, was found to be the most high-performing, achieving the highest lap shear strength of 2.0&#xa0;MPa when coupled with EDA, a result attributed to its ability to form highly ordered hard domains (ΔH<sub>m</sub> = 31&#xa0;mJ/mg). This research highlights the critical importance of polyol chain length and chain extender chemistry in decoupling mechanical strength from processing characteristics, providing a clear pathway for tailoring HMPUR formulations to meet diverse industrial demands.</p>

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Engineering high-performance reactive hot-melt polyurethanes: the role of chain extenders in modulating polyester polyols properties

  • 期刊论文

  • 发表日期：

    2026年8月5日

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  • Arash Dehghanian,
  • Kurosh Rad-Moghadam

摘要

This study introduces a targeted synthesis and comprehensive evaluation for optimizing the composition of hot-melt polyurethane reactive adhesives (HMPUR) by methodically varying the soft segment of the polyester polyol (PSPO) and evaluating the distinct effects of amine- versus hydroxyl-functionalized chain extenders. Three PSPOs (synthesized from succinic, adipic, and dodecanedioic acid) were formulated with either ethylenediamine (EDA) or 1,4-butanediol (BDO), due to the fundamental differences in their chemical reactivity. The structure-property relationships of the adhesives, formulated with varying polyester polyols and chain extenders, were systematically investigated using analytical techniques including differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), proton nuclear magnetic resonance (1H NMR), melt viscometry, lap shear testing, and isocyanate titration. EDA-based adhesives have consistently demonstrated superior crosslinking efficiency, resulting in significantly enhanced mechanical performance and faster cure kinetics. The PSPO-1_EDA formulation exhibits a cure time of 8.5 h. In contrast, BDO formulations exhibited greater flexibility and lower processing viscosity. The longest-chain polyol, PSPO-3, was found to be the most high-performing, achieving the highest lap shear strength of 2.0 MPa when coupled with EDA, a result attributed to its ability to form highly ordered hard domains (ΔHm = 31 mJ/mg). This research highlights the critical importance of polyol chain length and chain extender chemistry in decoupling mechanical strength from processing characteristics, providing a clear pathway for tailoring HMPUR formulations to meet diverse industrial demands.