Nomadic Molecular Key‐Driven Instantaneous Covalent Reconstruction Enables Ultrahigh Impact‐Stiffening Polymeric Armor

X Xiao‐Yun Li (The Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) State Key Laboratory of Advanced Polymer Materials College of Chemistry Sichuan University Chengdu China) F Fu‐Rong Zeng (State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China) J Jian‐Wen Ma (State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China) H Hao Chen L Lei He (State Key Laboratory of Chemical Resource Engineering) S Shi‐Qiang Chen (The Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) State Key Laboratory of Advanced Polymer Materials College of Chemistry Sichuan University Chengdu China) B Bo‐Wen Liu (State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China) Y Yu‐Zhong Wang (Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Key Laboratory of Advanced Polymer Materials Engineering National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu China) H Hai‐Bo Zhao (State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China)

Abstract

ABSTRACT Impact‐stiffening materials hold great promise in safeguarding human safety and apparatus integrity, serving as intelligent armor to mitigate transient impact and damage. However, high activation strain/rate, stiffening hysteresis, and inefficient energy dissipation of current materials pose significant challenges for matching extreme events. Herein, we report a nomadic molecular key‐driven ultrahigh impact‐stiffening strategy that leverages strain‐rate‐sensitive and covalent‐active molecules to trigger covalent reconstruction and nanodomain agglomeration within polymers. Our design employs poly(styrene‐thioctic acid) (PSTx) with a few thioctic acids (TA) as a critical stiffening key, in which disulfide/hydrogen bonds form energy‐dissipating multi‐networks, while phenyls act as precursors for physical crosslinking. Distinct from conventional mechanisms, force‐activated TA functions as a molecular key that rapidly induces covalent crosslinking and phenyl nanodomain resembling, effectively “locking” networks and blunting cracks to achieve efficient impact‐resistance. PSTx exhibits ultralow relaxation time (15.8 ms), exceptional stiffening response (2925 times), and stretchability over 4000%. Even at low strains/rates of 2000 s −1 , it achieves high modulus (5.8 GPa), record strength (84.3 MPa), and excellent energy dissipation (12.4 MJ/m 3 ), yielding 97% impact‐force reduction. PSTx is processable into various wearable composites with outstanding impact force attenuation (+957%) and puncture resistance (+360%). This work resolves challenges of activation thresholds and stiffening hysteresis in impact‐stiffening materials, providing a molecular key‐switchable paradigm for intelligent systems.

Article Details

Volume / Issue Vol. 38, Issue 17
Published March 01, 2026
ISSN 0935-9648
Publisher Unknown Publisher

Journal Info

Advanced Materials

Unknown Publisher

ISSN: 0935-9648 Physical Sciences

Authors (9)

X

Xiao‐Yun Li

The Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) State Key Laboratory of Advanced Polymer Materials College of Chemistry Sichuan University Chengdu China

F

Fu‐Rong Zeng

State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China

J

Jian‐Wen Ma

State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China

H

Hao Chen

L

Lei He

State Key Laboratory of Chemical Resource Engineering

S

Shi‐Qiang Chen

The Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) State Key Laboratory of Advanced Polymer Materials College of Chemistry Sichuan University Chengdu China

B

Bo‐Wen Liu

State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China

Y

Yu‐Zhong Wang

Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Key Laboratory of Advanced Polymer Materials Engineering National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu China

H

Hai‐Bo Zhao

State Key Laboratory of Advanced Polymer Materials Collaborative Innovation Center for Eco‐Friendly and Fire‐Safety Polymeric Materials (MoE) National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University Chengdu 610064 China