Disulfide bond and free radical copolymerization endow TPU with reversible cross-linking properties
Wenxin Gan, Hanyu Xue, Hongyi Lin, Renjin Gao, Yuchi Zhang, Liwei Wang, Jiuping Rao
Vol. 19., No.3., Pages 311-325, 2025
DOI: 10.3144/expresspolymlett.2025.22
DOI: 10.3144/expresspolymlett.2025.22
GRAPHICAL ABSTRACT

ABSTRACT
Cross-linking frequently enhanced the mechanical properties of linear polymeric materials; however, it also resulted in the transition from thermoplastic to thermosetting materials, which posed issues from an environmental perspective. Thermoplastic polyurethane (TPU) elastomers were extensively applied across various industries. To improve the mechanical properties of TPU while preserving its environmental benefits, this study integrated radical copolymerization technology to develop a reversible crosslinked TPU. Specifically, the linear polyurethane molecular chains were crosslinked using diallyl disulfide (DADS) as a functional cross-linking monomer. Through radical copolymerization reactions, reversible crosslinks formed from disulfide bonds were created between the linear polyurethane molecular chains, yielding a self-healing reversible crosslinked thermoplastic polyurethane (DSTPU). The study showed that DSTPU could self-heal and dissolve under UV light and alkaline N,N-dimethylformamide (DMF) conditions, achieving 82.2% self-healing efficiency at 3 phr DADS. It dissolved into fine particles in alkaline DMF. Disulfide bonds in DSTPU enhanced cross-linking, boosting 19% oxygen permeability, thermal conductivity (0.218 W/(m·K)), and mechanical properties like tensile stress (11.18 MPa), force (134.13 N), and elongation (548%). These bonds also enhanced aging resistance, cutting ΔYI to 6.0%.
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Thermoplastic
vulcanizates (TPVs) were prepared by blending natural rubber (NR) and
polypropylene (PP) using dynamic sulfur curing systems with varying
accelerator/sulfur ratios: 0.5/2.5, 1.5/1.5, and 2.5/0.5 phr, categorized as
conventional (CV), semi-efficient (semi-EV), and efficient (EV). The onset of
dynamic vulcanization closely corresponded with scorch time in statically cured
NR compounds. Mixing torque decreased over time, reflecting reversion patterns
in static curing. The CV system exhibited the highest reversion tendency due to
polysulfide linkage breakdown, forming stronger but shorter crosslinks. Dynamic
vulcanization induced higher reversion than static curing, influenced by shear
and extensional forces. Curing systems caused crosslinking rates, reversion,
and crosslink density and distribution variations. Unlike statically cured NR,
PP-extracted TPVs exhibited an inverse trend in total crosslink densities and
distributions; TPVs primarily comprised shorter crosslinks with opposed total
crosslink densities ranked EV > semi-EV > CV. This trend is strongly
correlated with superior mechanical strength, toughness, storage modulus,
viscosity, and rubber elasticity in the EV-cured TPV. EV system also had the
smallest vulcanized NR domains in the PP matrix.