GAP基自修复粘结剂的制备及性能
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摘要
为了延长粘结剂的储存寿命,采用一步法将具有可自修复性能的双硫官能团引入叠氮粘结剂中,首次合成了具有自修复性能的聚叠氮缩水甘油醚(GAP)基自修复粘结剂。通过傅里叶红外光谱(FTIR)、X射线衍射(XRD)和光学显微镜对其结构和表面形貌进行表征,在此基础上,通过自修复前后拉伸强度的变化,考察了不同自修复温度和不同自修复时间下的自修复效率。结果显示:合成的GAP基自修复粘结剂具有聚氨酯结构,60℃下24 h后表面裂纹基本愈合完全。提高自修复温度和延长自修复时间,均有助于提高体系的自修复效率。同时随着交联剂质量分数的增加,自修复效率先提高后降低,其中交联剂质量分数为8%的配方,自修复效率可达98.2%,相对于自修复效率为61.7%的对比样,表明双硫官能团的引入能够提高体系的自修复效率。
To prolong the storage life of binder, the poly(glycidyl azide) ether(GAP)-based binders with self-healing performance were firstly synthesized by introducing disulfide functional group into an azide binder through an one-step method. Fourier transform infrared spectroscopy(FTIR), X-ray diffractometry(XRD) and optical microscopy were used to characterize its structure and surface topography characterization. On this basis, the self-healing efficiency under different self-healing temperature and different self-healing time was examined through the change of tensile strength before and after self-healing. Results show that the synthesized GAP-based self-healing binder has a polyurethane structure, the surface cracks of self-healing binder are completely healed after 24 h at 60℃. Increasing the temperature and prolonging the self-healing time are helpful to improve the self-healing efficiency. At the same time, the self-healing efficiency is firstly improved and then decreased with increasing mass fraction of the cross-linking agent, in which, the self-healing efficiency for the formula with a cross-linker mass fraction of 8%can reach 98%. Compared with control sample with the self-healing efficiency as 61.7%, which proves that the introduction of disulfide functional groups can improve the self-healing efficiency of the system.
To prolong the storage life of binder, the poly(glycidyl azide) ether(GAP)-based binders with self-healing performance were firstly synthesized by introducing disulfide functional group into an azide binder through an one-step method. Fourier transform infrared spectroscopy(FTIR), X-ray diffractometry(XRD) and optical microscopy were used to characterize its structure and surface topography characterization. On this basis, the self-healing efficiency under different self-healing temperature and different self-healing time was examined through the change of tensile strength before and after self-healing. Results show that the synthesized GAP-based self-healing binder has a polyurethane structure, the surface cracks of self-healing binder are completely healed after 24 h at 60℃. Increasing the temperature and prolonging the self-healing time are helpful to improve the self-healing efficiency. At the same time, the self-healing efficiency is firstly improved and then decreased with increasing mass fraction of the cross-linking agent, in which, the self-healing efficiency for the formula with a cross-linker mass fraction of 8%can reach 98%. Compared with control sample with the self-healing efficiency as 61.7%, which proves that the introduction of disulfide functional groups can improve the self-healing efficiency of the system.
引文
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[16]Xu Y,Chen D.A novel self‐healing polyurethane based on di‐sulfide bonds[J].Macromolecular Chemistry&Physics,2016,217(10):1191-1196.
[2]Amamoto Y,Otsuka H,Takahara A,et al.Self‐healing of co‐valently cross‐linked polymers by reshuffling thiuram disulfide moieties in air under visible light[J].Advanced Materials,2012,24(29):3975-3980.
[3]Jo Y Y,Lee A S,Baek K Y,et al.Thermally reversible self‐healing polysilsesquioxane structure‐property relationships based on Diels‐Alder chemistry[J].Polymer,2017,108(1):58-65.
[4]Huyang G,Debertin A E,Sun J.Design and development of self‐healing dental composites[J].Materials&Design,2016,94:295-302.
[5]Zhang Y,Ying H,Hart K R,et al.Malleable and recyclable poly(urea‐urethane)thermosets bearing hindered urea bonds[J].Advanced Materials,2016,28(35):7646-7651.
[6]Xu Y,Chen D.A novel self‐healing polyurethane based on di‐sulfide bonds[J].Macromolecular Chemistry and Physics,2016,217(10):1191-1196.
[7]An S Y,Noh S M,Nam J H,et al.Dual sulfide‐disulfide cross‐linked networks with rapid and room temperature self‐healabil‐ity[J].Macromolecular Rapid Communications,2015,36(13):1255-1260.
[8]Rekondo A,Martin R,Ruizdeluzuriaga A,et al.Catalyst‐free room‐temperature self‐healing elastomers based on aromatic disulfide metathesis[J].Materials Horizons,2014,1(2):237-240.
[9]杨一林,卢珣,王巍巍,等.热可逆自修复聚氨酯弹性体的制备及表征[J].材料工程,2017,45(8):1-8.YANG Yi‐lin,LU Xun,WANG Wei‐wei,et al.Preparation and characterization of thermally reversible self‐healing polyure‐thane elastomer[J].Journal of Materials Engineering,2017,45(8):1-8.
[10]Jian X,Hu Y,Zhou W,et al.Self‐healing polyurethane based on disulfide bond and hydrogen bond[J].Polymers for Advanced Technologies,DOI:10.1002/pat.4135.
[11]菅晓霞,郑启龙,胡义文,等.PBT弹性体力学性能及低温脆性研究[J].固体火箭技术,2017,40(2):189-193.JIAN Xiao‐xia,ZHENG Qi‐long,HU Yi‐wen,et al.Mechanical properties and low temperature embrittleness of PBT elastomer[J].Journal of Solid Rocket Technology,2017,40(2):189-193.
[12]王巍巍.热可逆自修复弹性体的制备、结构与性能研究[D].广州:华南理工大学,2015.WANG Wei‐wei.Studies on preparation,structure and proper‐ties of thermally reversible self‐healing elastomers[D].Guang‐zhou:South China University of Technology,2015.
[13]Lafont U,Van Z H,Van d Z S.Influence of cross‐linkers on the cohesive and adhesive self‐healing ability of polysul‐fide‐based thermosets[J].ACS Applied Materials&Interfaces,2012,4(11):6280-6288.
[14]Yang J X,Long Y Y,Pan L,et al.Spontaneously healable ther‐moplastic elastomers achieved through one‐pot living ring‐open‐ing metathesis copolymerization of well‐designed bulky mono‐mers[J].ACS Applied Materials&Interfaces,2016,8(19):12445-12455.
[15]菅晓霞,肖乐勤,左海丽,等.GAP基热塑性弹性体的合成及表征[J].含能材料,2008,16(5):614-617.JIAN Xiao‐xia,XIAO Le‐qin,ZUO Hai‐li,et al.Synthesis and characterization of GAP‐based thermoplastic elastomer[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2008,16(5):614-617.
[16]Xu Y,Chen D.A novel self‐healing polyurethane based on di‐sulfide bonds[J].Macromolecular Chemistry&Physics,2016,217(10):1191-1196.