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<p>Additive manufacturing via vat photopolymerization is heavily dependent on the performance of photocurable resins, where urethane acrylate oligomers (UAO) play a crucial role in determining the mechanical properties, curing behavior, and, therefore, printability of the photopolymer. This study investigates the structure–property relationships of a series of ten novel UAO, derived from 2,4-toluene diisocyanate, polyether triol, hydroxyethyl acrylate and benzyl, isoamyl, butyl, cyclohexyl and furfuryl alcohols. Through a controlled three-step synthesis, oligomers with varying functionality and structure were obtained and characterized using NMR, FTIR, and GPC. A decrease in acrylate functionality in the molecular structure resulted in lower polymerization rates and prolonged induction periods. At an identical acrylate functionality, aliphatic substituents, in contrast to aromatic ones, reduced viscosity and increased reactivity. In addition, the introduction of butyl substituents led to an approximately twofold increase in impact toughness. On the one hand, a decrease in acrylate functionality improved the flexural toughness in the greenbody state; on the other hand, it led to a decrease in toughness after postcuring. These findings provide a roadmap for designing tailored oligomers, bridging molecular architecture with application-specific performance in vat photopolymerization 3D printing.</p>

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UV curable urethane acrylates for 3D printing: the role of functionality and chemical structure in tuning viscosity, reactivity and mechanical properties

  • 期刊论文

  • 发表日期：

    2026年5月7日

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  • Yu. G. Rudenko,
  • D. A. Bazhanov,
  • R. R. Khasbiullin,
  • A. V. Shapagin,
  • N. V. Fedyakova,
  • M. V. Bermeshev,
  • P. P. Chapala

摘要

Additive manufacturing via vat photopolymerization is heavily dependent on the performance of photocurable resins, where urethane acrylate oligomers (UAO) play a crucial role in determining the mechanical properties, curing behavior, and, therefore, printability of the photopolymer. This study investigates the structure–property relationships of a series of ten novel UAO, derived from 2,4-toluene diisocyanate, polyether triol, hydroxyethyl acrylate and benzyl, isoamyl, butyl, cyclohexyl and furfuryl alcohols. Through a controlled three-step synthesis, oligomers with varying functionality and structure were obtained and characterized using NMR, FTIR, and GPC. A decrease in acrylate functionality in the molecular structure resulted in lower polymerization rates and prolonged induction periods. At an identical acrylate functionality, aliphatic substituents, in contrast to aromatic ones, reduced viscosity and increased reactivity. In addition, the introduction of butyl substituents led to an approximately twofold increase in impact toughness. On the one hand, a decrease in acrylate functionality improved the flexural toughness in the greenbody state; on the other hand, it led to a decrease in toughness after postcuring. These findings provide a roadmap for designing tailored oligomers, bridging molecular architecture with application-specific performance in vat photopolymerization 3D printing.