Rapid Self-healing and Strong Adhesive Elastomer via Supramolecular Aggregates from Core-shell Micelles of Silicon Hydroxyl-functionalized cis-Polybutadiene

• Published in: Chinese journal of polymer science Vol. 41; no. 1; pp. 84 - 94
• Main Authors: Zheng, Ying-Ying, Zhu, Han, Tan, Yi, Liu, Feng-Yi-Qi, Wu, Yi-Xian
• Format: Journal Article
• Language: English
• Published: Singapore Springer Nature Singapore 2023; Springer Nature B.V
• Subjects: Adhesive strength; Aggregates; Characterization and Evaluation of Materials; Chemical bonds; Chemistry; Chemistry and Materials Science; Condensed Matter Physics; Copolymerization; Damping; Elastomers; Hexanes; Hydrogen bonding; Industrial Chemistry/Chemical Engineering; Micelles; Nanoparticles; Neodymium; Polybutadiene; Polymer Sciences; Research Article; Room temperature; Self healing materials; Silanes; Silicon dioxide; Steel columns; Amphiphilicity; Core-shell micelles; Polybutadiene; Supramolecular aggregates
• ISSN: 0256-7679; 1439-6203
• DOI: 10.1007/s10118-022-2808-z

Liquid trimethoxy silane-functionalized cis-polybutadiene ( cis -PB-Si(OMe) 3 ), possessing number-average molecular weights of cis -PB segments ( M n,PB ) ranging from 1800 g/mol to 5400 g/mol, with cis -1,4 content of ca. 80% and high functionality (>96%) could be synthesized by coordination copolymerization of living cis -PB chain ends with ethenyltrimethoxy-silane with neodymium-based catalytic system. The silicon hydroxyl-functionalized cis-polybutadiene ( cis -PB-Si(OH) 3 )-based micelles in water have been achieved by in situ hydrolysis of cis -PB-Si(OMe) 3 in hexane/water mixture (pH=6.8) at 70 °C and by sequential removal of residue hexane. The size of the above micelles with soft elastic cis -PB cores could be remarkably enlarged by loading SiO 2 nanoparticles on their surfaces via hydrogen bonding interaction. Giant supramolecular long chain aggregates or networks formed by hydrogen bonding interaction and possible O—Si—O chemical bonds between cis -PB-Si(OH) 3 -based micellar surfaces had relatively large size and thus precipitated from water after several months of storage, leading to production of cis -PB-Si(OH) 3 solid elastomer with extremely low T g at −107.0 °C. The left cis -PB-Si(OH) 3 -based micelles in water with relatively small size gradually formed the water-insoluble cis -PB-Si(OH) 3 -based supramolecular aggregates or networks. The cis -PB-Si(OH) 3 -based supramolecular elastomer exhibited excellent self-healing property within 60 s at 25 °C. The elastomer (20 mg) in a joint of 25 mm × 30 mm (2.7 mg/cm 2 ) provided very strong adhesion for two pieces of glass and the bound glass keep unchanged at room temperature for 98 h even hung with 100 g of steel column below. The cis -PB-Si(OH) 3 -based supramolecular elastomer would have potential applications in adhesives, self-healing materials, damping materials and elastic materials.