离子络合物改性二维云母环氧树脂复合材料的制备及性能

doi:10.16085/j.issn.1000-6613.2023-1476

化工进展 ›› 2024, Vol. 43 ›› Issue (9): 5142-5156.DOI: 10.16085/j.issn.1000-6613.2023-1476

• 材料科学与技术 • 上一篇

离子络合物改性二维云母环氧树脂复合材料的制备及性能

楼高波¹^,²(), 姚潇翎³, 倪静雯¹, 傅深渊¹^,², 刘丽娜¹^,²()

^1.浙江农林大学化学与材料工程学院，浙江杭州 311300
^2.浙江农林大学国家木质资源综合利用工程技术研究中心，浙江杭州 311300
^3.湖州万马高分子材料有限公司，浙江湖州 313100

收稿日期:2023-08-23 修回日期:2023-10-12 出版日期:2024-09-15 发布日期:2024-09-30
通讯作者: 刘丽娜
作者简介:楼高波（1993—），男，博士，讲师，研究方向为复合材料与胶黏剂。E-mail：1142673814@qq.com。
基金资助:
浙江省科技厅领雁项目(2022C03128);浙江省自然科学基金探索项目(Y21C160015);浙江农林大学人才引进启动基金(2022LFR103)

Preparation and properties of two-dimensional mica epoxy resin composite modified by ion complex

LOU Gaobo¹^,²(), YAO Xiaoling³, NI Jingwen¹, FU Shenyuan¹^,², LIU Lina¹^,²()

^1.College of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, Zhejiang, China
^2.The National Engineering Research Center for the Comprehensive Utilization of Wood Resources, Zhejiang A&F University, Hangzhou 311300, Zhejiang, China
^3.Huzhou Wanma Polymer Materials Co. , Ltd. , Huzhou 313100, Zhejiang, China

Received:2023-08-23 Revised:2023-10-12 Online:2024-09-15 Published:2024-09-30
Contact: LIU Lina

摘要/Abstract

摘要：

为了实现环氧树脂（EP）的高性能化，将插层法得到的二维云母纳米片（MNs）与增韧型阻燃剂甲基膦酸-癸二胺离子络合物（MPA-DAD）复合，制备了一种环氧树脂多功能改性材料MNs@MPA-DAD。通过力学、UL-94、极限氧指数（LOI）、热重、锥形量热以及摩擦磨损等测试研究了MNs@MPA-DAD对环氧树脂复合材料的性能影响。结果表明：MPA-DAD中的离子键可充当牺牲键，耗散能量提升韧性。相较于纯EP，添加质量分数8%的MNs@MPA-DAD，环氧树脂复合材料的拉伸和弯曲韧性分别提高了302%和268%。二维的MNs可以作为物理屏障，抑制材料燃烧过程中热量和氧气的传递过程，与MPA-DAD协同发挥阻燃机制。EP/8%MNs@MPA-DAD的极限氧指数由纯EP的20.4%提高至28.9%，残炭率由8.9%提升至14.3%，UL-94测试通过了V-0级别，热释放速率峰值（PHRR）和总热释放（THR）分别降低了34.0%和19.7%。MNs@MPA-DAD能够产生均匀的润滑转移层，减少摩擦热的产生，避免熔化磨损，进而提高环氧树脂的耐磨性。EP/8%MNs@MPA-DAD的磨损面积较纯EP降低了76.6%。

关键词: 纳米材料, 复合材料, 力学性能, 阻燃, 耐磨

Abstract:

In order to achieve high performance of epoxy resin (EP), two-dimensional mica nanosheets (MNs) obtained by intercalation method were combined with toughening flame retardant methyl phosphonate-decanediamine ionic complex (MPA-DAD), and a multifunctional EP modified material MNs@MPA-DAD was prepared. The influence of MNs@MPA-DAD on the properties of EP composites was investigated by mechanical test, UL-94, limiting oxygen index (LOI), thermogravimetric, cone calorimetric and friction and wear test. The results exhibited that the ionic bond in MPA-DAD can act as a sacrificial bond and dissipate energy to improve toughness. Compared with neat EP, the tensile and flexural toughness of EP composites increased by 302% and 268%, respectively, when 8%MNs@MPA-DAD was added. Two-dimensional MNs could be used as a physical barrier to inhibit the transfer of heat and oxygen in the combustion process of materials, and played a synergistic flame retardancy mechanism with MPA-DAD. The limiting oxygen index of EP/8%MNs@MPA-DAD was increased from 20.4% (neat EP) to 28.9%, and the residues at 800℃ was increased from 8.9% to 14.3%. UL-94 test passed the V-0 level, and the peak heat release rate (PHRR) and total heat release (THR) were reduced by 34.0% and 19.7%, respectively. MNs@MPA-DAD could produce a uniform lubricating transfer layer, reduced friction heat generation, avoided melting wear and improved the wear resistance of epoxy resin. The wear area of EP/8%MNs@MPA-DAD was 76.6% lower than that of neat EP.

Key words: nanomaterials, composites, mechanical properties, flame retardant, wear resistant

中图分类号:

TB322

楼高波, 姚潇翎, 倪静雯, 傅深渊, 刘丽娜. 离子络合物改性二维云母环氧树脂复合材料的制备及性能[J]. 化工进展, 2024, 43(9): 5142-5156.

LOU Gaobo, YAO Xiaoling, NI Jingwen, FU Shenyuan, LIU Lina. Preparation and properties of two-dimensional mica epoxy resin composite modified by ion complex[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5142-5156.

图/表 22

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样品	E12/g	双氰胺/g	2-甲基咪唑/g	改性剂
纯EP	100	2.5	0.5	—
EP/8%MPA-DAD	100	2.5	0.5	8.9g MPA-DAD
EP/8%GM@MPA-DAD	100	2.5	0.5	8.9g GM@MPA-DAD
EP/8%MNs@MPA-DAD	100	2.5	0.5	8.9g MNs@MPA-DAD

样品	E12/g	双氰胺/g	2-甲基咪唑/g	改性剂
纯EP	100	2.5	0.5	—
EP/8%MPA-DAD	100	2.5	0.5	8.9g MPA-DAD
EP/8%GM@MPA-DAD	100	2.5	0.5	8.9g GM@MPA-DAD
EP/8%MNs@MPA-DAD	100	2.5	0.5	8.9g MNs@MPA-DAD

样品	拉伸强度 /MPa	拉伸模量 /MPa	拉伸韧性 /MJ·m^-3	弯曲强度 /MPa	弯曲模量 /GPa	弯曲韧性 /MJ·m^-3	冲击强度 /kJ·m^-2
纯EP	46.40±1.28	2522±56	0.42±0.08	69.13±2.11	2.71±0.13	1.11±0.09	6.01±1.40
EP/8%MPA-DAD	54.91±2.21	1875±102	4.69±0.18	82.61±2.37	2.30±0.09	7.89±0.18	10.24±1.73
EP/8%GM@MPA-DAD	50.84±1.92	1827±78	1.21±0.13	82.67±1.98	2.37±0.08	6.14±0.11	10.58±2.13
EP/8%MNs@MPA-DAD	52.13±1.74	1939±95	1.69±0.09	80.14±2.08	2.27±0.05	4.08±0.13	9.42±1.34

样品	拉伸强度 /MPa	拉伸模量 /MPa	拉伸韧性 /MJ·m^-3	弯曲强度 /MPa	弯曲模量 /GPa	弯曲韧性 /MJ·m^-3	冲击强度 /kJ·m^-2
纯EP	46.40±1.28	2522±56	0.42±0.08	69.13±2.11	2.71±0.13	1.11±0.09	6.01±1.40
EP/8%MPA-DAD	54.91±2.21	1875±102	4.69±0.18	82.61±2.37	2.30±0.09	7.89±0.18	10.24±1.73
EP/8%GM@MPA-DAD	50.84±1.92	1827±78	1.21±0.13	82.67±1.98	2.37±0.08	6.14±0.11	10.58±2.13
EP/8%MNs@MPA-DAD	52.13±1.74	1939±95	1.69±0.09	80.14±2.08	2.27±0.05	4.08±0.13	9.42±1.34

样品	T_onset/℃	T_max/℃	Y_c/%
纯EP	375.0	437.7	8.9
EP/8%MPA-DAD	311.8	394.3	13.0
EP/8%GM@MPA-DAD	309.7	394.8	13.4
EP/8%MNs@MPA-DAD	321.2	399.3	14.3

离子络合物改性二维云母环氧树脂复合材料的制备及性能

Preparation and properties of two-dimensional mica epoxy resin composite modified by ion complex

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参考文献 32

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样品	UL-94			LOI/%
样品	（t₁/t₂）/s	熔滴	等级	LOI/%
纯EP	>30	有	NR	20.4±0.3
EP/8%MPA-DAD	4.9/1.1	无	V-0	29.0±0.3
EP/8%GM@MPA-DAD	7.5/2.1	无	V-0	28.6±0.3
EP/8%MNs@MPA-DAD	5.3/2.1	无	V-0	28.9±0.3

样品	TTI/s	T_PHRR/s	PHRR/kW·m^-2	THR/MJ·m^-2	PSPR/m²·s^-1	TSP/m²	FIGRA/kW·m^-2·s^-1
纯EP	62±2	139±4	1095±29	117.6±2.2	0.24±0.013	23.1±2.3	7.9
EP/8%MPA-DAD	54±2	109±3	746±27	88.4±1.5	0.22±0.008	22.7±1.1	6.8
EP/8%GM@MPA-DAD	53±3	120±3	783±24	98.0±2.0	0.22±0.010	21.6±2.0	6.5
EP/8%MNs@MPA-DAD	53±1	143±4	723±19	94.4±1.7	0.22±0.011	22.3±1.7	5.1

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