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    低共熔溶剂改性聚丁内酰胺的结晶性能

    Crystallization Property of Polybutyrolactam Modified by Deep Eutectic Solvents

    • 摘要: 以氯化胆碱为氢键受体,尿素、草酸和甘油为氢键供体制备了氯化胆碱-尿素、氯化胆碱-草酸和氯化胆碱-甘油三种低共熔溶剂(DES),并用DES改性聚丁内酰胺(PBL)使其熔点降低。通过差示扫描量热、热重分析、红外光谱和X射线衍射研究了DES对PBL的热稳定性、熔点和结晶的影响,并分析了内在作用机理。利用拉伸测试法及熔融指数测定验证了DES对PBL力学性能及加工性能的影响。研究结果表明,氯化胆碱-尿素通过形成新的氢键抑制PBL (200)晶面生长,使结晶度降低了16.2%,从而使熔点降低至253 ℃。氯化胆碱-草酸通过草酸羧基与PBL的游离羰基形成氢键,氯化胆碱-甘油则以增塑作用为主,两者对PBL氢键的破坏作用有限,改性效果略差,结晶度分别降低了4.4%和1.9%,熔点分别降低了8 ℃和6 ℃。

       

      Abstract: Three deep eutectic solvents (DESs), choline chloride-urea (CU), choline chloride-oxalic acid (CO) and choline chloride-glycerol (CG) , were synthesized and utilized to modify polybutyrolactam (PBL) in order to lower its melting point. Differential scanning calorimetry, thermogravimetric analysis, infrared spectroscopy and X-ray diffraction were employed for investigating the effects of DES on the thermal stability, melting point and crystallization of PBL, as well as analyzing the underlying interaction mechanisms. Additionally, tensile testing and melt index measurements were conducted to verify the influence of DES on the mechanical and processing properties of PBL. CU partially disrupted the hydrogen bonds of PBL while forming new ones between NH groups on PBL and C=O on urea. This led to a distortion in the crystal lattice structure and parameters of PBL, resulting in a reduction in crystallinity by 16.2% along with a decrease in melting point from 265 ℃ to 253 ℃. CO distorted the lattice structure by forming new hydrogen bonds between oxalic acid carboxyl groups and free carbonyl groups on PBL, while CG primarily acted as a plasticizer; both had less influence on PBL hydrogen bonds compared to CU. As a result, they reduced crystallinity by only 4.4% and 1.9%, leading to decreases in melting point by 8 ℃ and 6 ℃ respectively. CU, the most effective DES, decreased the tensile strength of PBL by 3.5 MPa, increased the elongation at break by 15.6%, and lowered the melting temperature of PBL to below 32 5 ℃ with further addition of CU.

       

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