现代纺织技术2026，Vol.34Issue(1)：21-31,11.DOI:10.12477∕j.att.202412056
多嵌段反应性聚氨酯材料的微相结构对其强韧性能的影响机制
Influence mechanism of microphase structure on the strength and toughness properties of multi-block reactive polyurethane materials
摘要
Abstract
With the advancement of the"dual carbon"goals(carbon peaking and carbon neutrality),environmental friendliness has emerged as one of the pivotal directions in the development of materials science.Reactive polyurethane(RPU)has garnered widespread application in fields such as high-performance coatings,elastomers,and synthetic leathers,owing to its excellent weather resistance,chemical stability,and mechanical properties achieved through a highly cross-linked molecular structure under solvent-free conditions.Compared with traditional solvent-based and waterborne polyurethane systems,RPU demonstrates significant advantages in reducing volatile organic compound(VOC)emissions and improving production efficiency.However,the mechanical properties of polyurethanes often face a trade-off between strength and toughness:an increase in strength typically leads to a decline in toughness,thereby elevating the risk of brittle fracture.This issue becomes particularly pronounced under solvent-free synthesis routes,where the lack of solvent's fluidity and processing convenience exacerbates the challenge. This paper proposed an innovative approach:in a solvent-free system,a rigid-flexible integrated silicone polyurethane(Six-RPU)system was constructed through a two-component in situ polymerization strategy.Polydimethylsiloxane(PDMS),polytetramethylene ether glycol(PTMEG),and castor oil(CO)were selected as the soft segments,while hexamethylene diisocyanate(HMDI),binaphthol(BIONL),and 1,4-butanediol(1,4-BDO)were chosen as the hard segments.This strategy aims to synthesize Six-RPU materials that possess both high rigidity and high toughness. Contact angle measurements revealed that with the introduction of 15%PDMS into the polyurethane main chain,the hydrophilicity of Six-RPU underwent a significant transformation to hydrophobicity,with the hydrophobicity angle reaching 117.3°.Furthermore,the Si-O layer formed during the thermal degradation of PDMS significantly increased the high-temperature char yield of RPU,as confirmed by TGA tests.The rigid network formed between the flexible Si—O—Si soft segments provided by PDMS and the binaphthyl hard segments constructed a robust and complementary structure,successfully achieving outstanding mechanical properties that harmonized rigidity and flexibility.Mechanical tensile test results indicated that,compared to Si0%-RPU,the tensile strength of Si15%-RPU increased from 26.6 MPa to 30.8 MPa,the elongation at break rose from 550.4%to 704.1%,and the toughness escalated from 56.3 MJ/m3 to 138.8 MJ/m3.Through characterization analyses such as AFM,XRD,and DSC,the formation mechanism of the rigid-flexible structure and microstructure were further elucidated:PDMS disrupted the ordered stacking of hard segments through multiple hydrogen bonding interactions with the hard segments and its inherent incompatibility with them,thereby promoting ordered microphase separation and the formation of a more stable two-phase structure.This,in turn,optimized the mechanical properties and microstructure of the polyurethane.关键词
多嵌段/反应性聚氨酯/微相分离/强韧性Key words
multi-block/reactive polyurethane/microphase separation/strength and toughness分类
化学化工引用本文复制引用
赵锦标,段慧敏,朱彦,杨浩,姚连琪,戚栋明,黄志超..多嵌段反应性聚氨酯材料的微相结构对其强韧性能的影响机制[J].现代纺织技术,2026,34(1):21-31,11.基金项目
浙江省自然科学基金公益项目(LGG22E030011) （LGG22E030011）
浙江省博士后科研项目择优资助项目(ZJ2024033) （ZJ2024033）
绍兴市基础公益项目(2023A11007) （2023A11007）
浙江理工大学绍兴柯桥研究院博士后项目(KYY2023002B) （KYY2023002B）
