聚乙烯亚胺修饰富勒烯的制备及其对聚丙烯热氧稳定性的影响

沈海峰; 邵胜栋; 王子路; 郭正虹

doi:10.13801/j.cnki.fhclxb.20200421.004

聚乙烯亚胺修饰富勒烯的制备及其对聚丙烯热氧稳定性的影响

doi: 10.13801/j.cnki.fhclxb.20200421.004

浙大宁波理工学院　高分子材料与共混实验室，宁波 315100

基金项目: 国家自然科学基金(51991355)

详细信息

通讯作者:
郭正虹，博士，副教授，研究方向为阻燃高分子复合材料　E-maill：guozhenghong@nit.zju.edu.cn

中图分类号: O631.2+1
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- 被引次数: 0
出版历程
- 收稿日期: 2019-12-05
- 录用日期: 2020-02-08
- 网络出版日期: 2020-04-22
- 刊出日期: 2020-11-15

Preparation of polyethyleneimine-decorated fullerene and its effect on thermal stability of polypropylene

Lab of Polymer Material and Engineering, NingboTech Zhejiang University, Ningbo 315100, China

摘要

摘要: 利用聚乙烯亚胺(PEI)分子中活泼的−NH−与富勒烯(C₆₀)结构中C=C键之间的加成反应，制备了PEI修饰C₆₀杂化物(C₆₀−PEI)，并采用FTIR、TEM等测试方法对C₆₀−PEI的分子结构和形态进行表征。采用熔融共混法制备了C₆₀−PEI/聚丙烯(PP)复合材料，并对其热性能和阻燃性能进行研究。热失重分析结果表明，C₆₀−PEI可以更有效地发挥C₆₀的自由基捕捉作用，对PP热稳定性的提高效果较C₆₀更明显；氧化诱导测试(OIT)结果表明，C₆₀−PEI/PP复合材料比C₆₀/PP复合材料具有更优异的抗氧性能；微型量热测试也表明，燃烧过程中C₆₀−PEI/PP复合材料比C₆₀/PP复合材料具有更低的热释放量。
- 富勒烯(C₆₀) /
- 自由基捕捉 /
- 热氧稳定性 /
- 氧化 /
- 聚丙烯(PP) /
- 复合材料
Abstract: The hybrid of polyethyleneimine-decorated fullrene (C₆₀−PEI) was synthesized by the addition reaction between active −NH− bonds in PEI and C=C bonds in C₆₀, and the molecular structure and morphology of C₆₀−PEI were characterized by FTIR and TEM. The C₆₀−PEI/polypropylene (PP) composite was prepared through the melt blending method and its thermal and flame retarded properties were studied. The thermogravimetric analysis results show that the thermal stability of the C₆₀-PEI/PP composite is significantly higher than the C₆₀/PP composite, because C₆₀−PEI can play the radical capture role of C₆₀ more effectively. The oxidation induced test (OIT) results show that the C₆₀−PEI/PP composite has higher anti-oxidative ability than the C₆₀/PP composite; the micro-calorimeter results also show that the heat release of the C₆₀−PEI/PP composite is obviously lower than the C₆₀/PP composite.
- fullerene(C₆₀) /
- trapping radicals /
- thermo-oxidative stability /
- oxidation /
- polypropylene(PP) /
- composites

HTML全文

图 1 C₆₀、PEI和C₆₀-PEI的FTIR图谱

Figure 1. FTIR spectra of C₆₀, PEI and C₆₀-PEI

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图 2 C₆₀-PEI的合成示意图

Figure 2. Schematic diagram of C₆₀-PEI synthesis

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图 3 C₆₀(a)和C₆₀-PEI (b)的TEM图像

Figure 3. TEM images of C₆₀(a) and C₆₀-PEI (b)

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图 4 C₆₀、PEI和C₆₀-PEI在N₂气氛下的TG曲线

Figure 4. TG curves of C₆₀, PEI and C₆₀-PEI in N₂

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图 5 PP、3C₆₀/PP、(3C₆₀+PEI)/PP、3C₆₀-PEI/PP和3PEI/PP复合材料空气气氛下的TG曲线

Figure 5. TG curves for PP, 3C₆₀/PP, (3C₆₀+PEI)/PP, 3C₆₀-PEI/PP and 3PEI/PP composites in air

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图 6 PP、3C₆₀/PP、(3C₆₀+PEI)/PP、3C₆₀-PEI/PP和3PEI/PP复合材料空气气氛下的DTG曲线

Figure 6. DTG curves for PP, 3C₆₀/PP, (3C₆₀+PEI)/PP, 3C₆₀-PEI/PP and 3PEI/PP composites in air

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图 7 PP、3C₆₀/PP、(3C₆₀+PEI)/PP和3C₆₀-PEI/PP复合材料180℃的氧化诱导时间(OIT)曲线

Figure 7. Oxidation induced time (OIT) curves of PP, 3C₆₀/PP, (3C₆₀+PEI)/PP and 3C₆₀-PEI/PP composites at 180℃

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图 8 PP、3C₆₀/PP、(3C₆₀+PEI)/PP和3C₆₀-PEI/PP复合材料的热释放率曲线

Figure 8. Heat release rate curves of PP, 3C₆₀/PP, (3C₆₀+PEI)/PP and 3C₆₀-PEI/PP composites

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表 1 富勒烯/聚丙烯(C₆₀/PP)和C₆₀-聚乙烯亚胺(PEI)/PP复合材料的配方

Table 1. Composition of fullrene/polypropylene(C₆₀/PP) and C₆₀-polyethyleneimine(PEI)/PP composites

Sample	PP	1C₆₀/PP	2C₆₀/PP	3C₆₀/PP	1C₆₀-PEI/PP	2C₆₀-PEI/PP	3C₆₀-PEI/PP	(3C₆₀+PEI)/PP
PP/wt%	100	99	98	97	99	98	97	97
C₆₀/wt%	—	1	2	3	—	—	—	2.75
C₆₀-PEI/wt%	—	—	—	—	1	2	3	—
PEI/wt%	—	—	—	—	—	—	—	0.25

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表 2 C₆₀/PP和C₆₀-PEI/PP复合材料空气气氛下的TG测试结果

Table 2. TG test results of C₆₀/PP and C₆₀-PEI/PP composites in air

Sample	PP	1C₆₀/ PP	2C₆₀/PP	3C₆₀/PP	1C₆₀-PEI/PP	2C₆₀-PEI/PP	3C₆₀-PEI/PP	(3C₆₀+PEI)/PP
T_onset/℃	266.1	285.5	293.5	303.9	293.2	296.7	312.0	271.3
T_max/℃	381.2	397.8	400.0	417.5	399.2	404.6	427.5	396.8
Residue at 800^oC/wt%	0.3	1.3	0.7	1.2	0.6	0	0	0.4
Notes: T_onset—Initial degradation temperature; T_max—Maximum degradation temperature.

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表 3 PP、3C₆₀/PP、(3C₆₀+PEI)/PP和3C₆₀-PEI/PP复合材料180℃的OIT测试结果

Table 3. OIT test results of PP, 3C₆₀/PP, (3C₆₀+PEI)/PP and 3C₆₀-PEI/PP composites at 180℃

Sample	PP	3C₆₀/PP	(3C₆₀+PEI)/PP	3C₆₀-PEI/PP
t_max/min	35.5	37.4	32.5	48.5
OIT/min	5.8	10.2	2.6	17.5
ΔH/(J·g⁻¹)	6 119	5 176	5 088	3 909
Notes: t_max—Time corresponding to maximum oxidant speed; ΔH—Enthalpy.

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表 4 PP、3C₆₀/PP、(3C₆₀+PEI)/PP和3C₆₀-PEI/PP复合材料微型量热测试结果

Table 4. Micro-calorimeter test results of PP, 3C₆₀/PP, (3C₆₀+PEI)/PP and 3C₆₀-PEI/PP composites

Sample	PP	3C₆₀/PP	(3C₆₀+PEI)/PP	3C₆₀-PEI/ PP
PHRR/(W·g⁻¹)	1 176	1 003	1 173	880
THR/(kJ·g⁻¹)	41.9	39.8	42.8	37.5
T_p/℃	486	488	487	489
Notes: PHRR—Peak of heat release rate; THR—Total heat release; T_p—Temperature to PHRR.

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