高等学校化学学报 ›› 2022, Vol. 43 ›› Issue (11): 20220353.doi: 10.7503/cjcu20220353
收稿日期:
2022-05-18
出版日期:
2022-11-10
发布日期:
2022-08-01
通讯作者:
陈涛
E-mail:tchen@ecust.edu.cn
基金资助:
CHANG Sihui1, CHEN Tao1,3(), ZHAO Liming2,3, QIU Yongjun2,3
Received:
2022-05-18
Online:
2022-11-10
Published:
2022-08-01
Contact:
CHEN Tao
E-mail:tchen@ecust.edu.cn
Supported by:
摘要:
采用疏水性1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF6)和亲水性1-丁基-3-甲基咪唑四氟硼酸盐 ([BMIM]BF4)两种咪唑类离子液体(IL)增塑聚丁内酰胺(PBL), 探讨了IL对PBL结晶性能及热性能的影响. 研究发现, 两种IL都会削弱PBL分子间氢键, 并抑制PBL晶体在(200)晶面的生长, 降低PBL结晶度. 当IL添加质量分数为5%时, 增塑膜熔点下降7~8 ℃. 与纯PBL膜相比, [BMIM]BF4增塑PBL膜热稳定性下降, 而[BMIM]PF6增塑PBL膜的热稳定性提高. [BMIM]PF6增塑PBL膜热分解过程的热动力学分析结果表明, 其热分解反应活化能为46.68 kJ/mol, 反应级数为1, 热分解最概然机理函数模型符合Mampel单行法则(一级), 即PBL受到热刺激后, 在聚合物和分解产物界面无规律成核, 反应核心具备反应活性, 随后反应逐步扩大, 直至结束.
中图分类号:
TrendMD:
常斯惠, 陈涛, 赵黎明, 邱勇隽. 离子液体增塑生物基聚丁内酰胺的热分解机理. 高等学校化学学报, 2022, 43(11): 20220353.
CHANG Sihui, CHEN Tao, ZHAO Liming, QIU Yongjun. Thermal Degradation Mechanism of Bio-based Polybutylactam Plasticized by Ionic Liquids. Chem. J. Chinese Universities, 2022, 43(11): 20220353.
Fig.2 Surface SEM images of PBL film(A) and PBL films plasticized by [BMIM]BF4(B, C) and [BMIM]PF6(D, E) with IL mass fraction of 3%(B, D) and 5%(C, E)
Sample | Mass fraction of IL* (%) | 2θ/(°) | d/nm | Xc(%) | |||
---|---|---|---|---|---|---|---|
(200) | (020) | (200) | (020) | ||||
PBL | 0 | 20.10 | 23.96 | 0.441 | 0.371 | 47.9 | |
[BMIM]BF4/PBL | 3 | 20.26 | 24.20 | 0.438 | 0.367 | 39.2 | |
5 | 20.56 | 24.46 | 0.432 | 0.364 | 35.0 | ||
[BMIM]PF6/PBL | 3 | 20.28 | 24.20 | 0.438 | 0.367 | 44.6 | |
5 | 20.34 | 24.32 | 0.436 | 0.366 | 35.7 |
Table 1 Crystallization properties of PBL films plasticized by ionic liquids
Sample | Mass fraction of IL* (%) | 2θ/(°) | d/nm | Xc(%) | |||
---|---|---|---|---|---|---|---|
(200) | (020) | (200) | (020) | ||||
PBL | 0 | 20.10 | 23.96 | 0.441 | 0.371 | 47.9 | |
[BMIM]BF4/PBL | 3 | 20.26 | 24.20 | 0.438 | 0.367 | 39.2 | |
5 | 20.56 | 24.46 | 0.432 | 0.364 | 35.0 | ||
[BMIM]PF6/PBL | 3 | 20.28 | 24.20 | 0.438 | 0.367 | 44.6 | |
5 | 20.34 | 24.32 | 0.436 | 0.366 | 35.7 |
Sample | Mass fractoin of IL(%) | T5/℃ | Tp/℃ | Tend/℃ | (dw/dt)max/(%?min-1) |
---|---|---|---|---|---|
PBL | 0 | 259 | 300 | 323 | 26 |
[BMIM]BF4/PBL | 3 | 245 | 287 | 311 | 24 |
5 | 242 | 287 | 323 | 17 | |
[BMIM]PF6/PBL | 3 | 248 | 302/321 | 335 | 17/18 |
5 | 255 | 306/322 | 336 | 18/20 |
Table 2 Thermal degradation temperatures of PBL films plasticized by ionic liquids
Sample | Mass fractoin of IL(%) | T5/℃ | Tp/℃ | Tend/℃ | (dw/dt)max/(%?min-1) |
---|---|---|---|---|---|
PBL | 0 | 259 | 300 | 323 | 26 |
[BMIM]BF4/PBL | 3 | 245 | 287 | 311 | 24 |
5 | 242 | 287 | 323 | 17 | |
[BMIM]PF6/PBL | 3 | 248 | 302/321 | 335 | 17/18 |
5 | 255 | 306/322 | 336 | 18/20 |
α | Linear equation | r2 | E/(kJ?mol-1) | ln(A/min-1) |
---|---|---|---|---|
0.1 | y=-2028.60x+8.12 | 0.92336 | 36.93 | 20.28 |
0.2 | y=-2130.90x+8.23 | 0.96923 | 38.79 | 21.24 |
0.3 | y=-2015.80x+7.72 | 0.97304 | 36.70 | 20.58 |
0.4 | y=-1979.83x+7.48 | 0.97176 | 36.04 | 20.42 |
0.5 | y=-2008.97x+7.46 | 0.97946 | 36.57 | 20.67 |
0.6 | y=-2102.62x+7.66 | 0.98175 | 38.28 | 21.35 |
0.7 | y=-2163.43x+7.74 | 0.98715 | 39.39 | 21.79 |
0.8 | y=-2224.59x+7.84 | 0.99000 | 40.50 | 22.27 |
Average | 37.90 | 21.07 |
Table 3 Thermal kinetic parameters of PBL plasticized by 5% mass fraction of [BMIM]PF6 obtained by Ozawa method
α | Linear equation | r2 | E/(kJ?mol-1) | ln(A/min-1) |
---|---|---|---|---|
0.1 | y=-2028.60x+8.12 | 0.92336 | 36.93 | 20.28 |
0.2 | y=-2130.90x+8.23 | 0.96923 | 38.79 | 21.24 |
0.3 | y=-2015.80x+7.72 | 0.97304 | 36.70 | 20.58 |
0.4 | y=-1979.83x+7.48 | 0.97176 | 36.04 | 20.42 |
0.5 | y=-2008.97x+7.46 | 0.97946 | 36.57 | 20.67 |
0.6 | y=-2102.62x+7.66 | 0.98175 | 38.28 | 21.35 |
0.7 | y=-2163.43x+7.74 | 0.98715 | 39.39 | 21.79 |
0.8 | y=-2224.59x+7.84 | 0.99000 | 40.50 | 22.27 |
Average | 37.90 | 21.07 |
No. | Mechanism | g(α) | r2 | E/(kJ?mol-1) | ln(A/min-1) |
---|---|---|---|---|---|
1 | Avrami?Erofeev Equation | 0.99809 | 19.46 | 3.78 | |
2 | Avrami?Erofeev Equation | 0.99831 | 27.64 | 7.22 | |
3 | Avrami?Erofeev Equation | 0.99838 | 31.73 | 8.91 | |
4 | Mampel power law(first order) | 0.99852 | 44.00 | 13.88 | |
5 | Avrami?Erofeev Equation | 0.99861 | 68.55 | 23.60 | |
6 | Avrami?Erofeev Equation | 0.99866 | 93.10 | 33.19 | |
7 | Avrami?Erofeev Equation | 0.99870 | 142.19 | 52.18 | |
8 | Avrami?Erofeev Equation | 0.99872 | 191.28 | 71.04 |
Table 4 Thermal kinetic parameters in different mechanisms using C-R method
No. | Mechanism | g(α) | r2 | E/(kJ?mol-1) | ln(A/min-1) |
---|---|---|---|---|---|
1 | Avrami?Erofeev Equation | 0.99809 | 19.46 | 3.78 | |
2 | Avrami?Erofeev Equation | 0.99831 | 27.64 | 7.22 | |
3 | Avrami?Erofeev Equation | 0.99838 | 31.73 | 8.91 | |
4 | Mampel power law(first order) | 0.99852 | 44.00 | 13.88 | |
5 | Avrami?Erofeev Equation | 0.99861 | 68.55 | 23.60 | |
6 | Avrami?Erofeev Equation | 0.99866 | 93.10 | 33.19 | |
7 | Avrami?Erofeev Equation | 0.99870 | 142.19 | 52.18 | |
8 | Avrami?Erofeev Equation | 0.99872 | 191.28 | 71.04 |
No. | Mechanism | E/(kJ·mol-1) | Theoretical n | Calculated n | Relative error |
---|---|---|---|---|---|
1 | Avrami?Erofeev Equation | 19.46 | 1/2 | 0.38 | -24% |
2 | Avrami?Erofeev Equation | 27.64 | 2/3 | 0.54 | -19% |
3 | Avrami?Erofeev Equation | 31.73 | 3/4 | 0.62 | -17% |
4 | Mampel power law(first order) | 44.00 | 1 | 0.86 | -14% |
5 | Avrami?Erofeev Equation | 68.55 | 3/2 | 1.34 | -10% |
6 | Avrami?Erofeev Equation | 93.10 | 2 | 1.82 | -9% |
7 | Avrami?Erofeev Equation | 142.19 | 3 | 2.79 | -7% |
8 | Avrami?Erofeev Equation | 191.28 | 4 | 3.75 | -6% |
Table 5 Reaction orders of PBL plasticized by 5% mass fraction of [BMIM]PF6 using Crane method
No. | Mechanism | E/(kJ·mol-1) | Theoretical n | Calculated n | Relative error |
---|---|---|---|---|---|
1 | Avrami?Erofeev Equation | 19.46 | 1/2 | 0.38 | -24% |
2 | Avrami?Erofeev Equation | 27.64 | 2/3 | 0.54 | -19% |
3 | Avrami?Erofeev Equation | 31.73 | 3/4 | 0.62 | -17% |
4 | Mampel power law(first order) | 44.00 | 1 | 0.86 | -14% |
5 | Avrami?Erofeev Equation | 68.55 | 3/2 | 1.34 | -10% |
6 | Avrami?Erofeev Equation | 93.10 | 2 | 1.82 | -9% |
7 | Avrami?Erofeev Equation | 142.19 | 3 | 2.79 | -7% |
8 | Avrami?Erofeev Equation | 191.28 | 4 | 3.75 | -6% |
Method | r2 | E/(kJ?mol-1) | ln(A/min-1) |
---|---|---|---|
Ozawa | >0.92300 | 37.90 | 21.07 |
Coats?Redfern | 0.99852 | 44.00 | 13.88 |
Satava | 0.99878 | 46.68 | 3.75 |
Table 6 Thermal kinetic parameters obtained by different methods
Method | r2 | E/(kJ?mol-1) | ln(A/min-1) |
---|---|---|---|
Ozawa | >0.92300 | 37.90 | 21.07 |
Coats?Redfern | 0.99852 | 44.00 | 13.88 |
Satava | 0.99878 | 46.68 | 3.75 |
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