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<p>In this work, furan-terminated polystyrene (FPS) and polyisoprene (FPI) building blocks with molecular weights ranging from 3000 to 5000 were synthesized via living anionic polymerization. A series of styrene-isoprene-styrene (SIS) block copolymers with thermoreversible structures (DASIS) were then prepared through the Diels-Alder (DA) reaction between the furan groups of FPS/FPI and N,N'-(1,4-phenylene)bismaleimide (BMI). The microstructure, dynamic bond formation and thermoreversibility of the as-synthesized polymers were characterized by 1H-NMR, FT-IR, DSC and other analytical techniques. The results demonstrated that DASIS block copolymers with molecular weights of 80000–130000 were successfully fabricated. Benefiting from the unique properties of dynamic DA bonds, the precise connection of building blocks to form macromolecules was achieved at a mild temperature of 60 °C, while the efficient dissociation and recovery of building blocks were realized at an elevated temperature of 150 °C, thus enabling the flexible regulation of the monomer ratio in DASIS. With the increase in the mass fraction of the PS phase in DASIS from the initial 20% to 50%, the elongation at break decreased significantly, whereas the Young’s modulus and tensile strength increased by 182.5% and 157.7%, respectively, which conforms to the basic law of the effect of the ratio of rigid to soft phases on the macroscopic properties in multiphase polymer systems. Furthermore, the Young’s modulus and tensile strength of the recycled DASIS remained above 90% of those of the pristine DASIS. This strategy provides a new insight into the precise synthesis of recyclable polymeric materials and exhibits great potential in the fields of polymer modification and elastomer applications.</p>

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Molecular structure design and modular synthesis of SIS building blocks with reversible structures

  • 期刊论文

  • 发表日期：

    2026年7月3日

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  • Peng Zheng,
  • Fan Yang,
  • Zhongfu Zhao,
  • Chunqing Zhang

摘要

In this work, furan-terminated polystyrene (FPS) and polyisoprene (FPI) building blocks with molecular weights ranging from 3000 to 5000 were synthesized via living anionic polymerization. A series of styrene-isoprene-styrene (SIS) block copolymers with thermoreversible structures (DASIS) were then prepared through the Diels-Alder (DA) reaction between the furan groups of FPS/FPI and N,N'-(1,4-phenylene)bismaleimide (BMI). The microstructure, dynamic bond formation and thermoreversibility of the as-synthesized polymers were characterized by 1H-NMR, FT-IR, DSC and other analytical techniques. The results demonstrated that DASIS block copolymers with molecular weights of 80000–130000 were successfully fabricated. Benefiting from the unique properties of dynamic DA bonds, the precise connection of building blocks to form macromolecules was achieved at a mild temperature of 60 °C, while the efficient dissociation and recovery of building blocks were realized at an elevated temperature of 150 °C, thus enabling the flexible regulation of the monomer ratio in DASIS. With the increase in the mass fraction of the PS phase in DASIS from the initial 20% to 50%, the elongation at break decreased significantly, whereas the Young’s modulus and tensile strength increased by 182.5% and 157.7%, respectively, which conforms to the basic law of the effect of the ratio of rigid to soft phases on the macroscopic properties in multiphase polymer systems. Furthermore, the Young’s modulus and tensile strength of the recycled DASIS remained above 90% of those of the pristine DASIS. This strategy provides a new insight into the precise synthesis of recyclable polymeric materials and exhibits great potential in the fields of polymer modification and elastomer applications.