一种自交联型阻燃剂的合成及对固态环氧树脂的性能

楼高波; 戴进峰; 刘丽娜; 傅深渊

doi:10.13801/j.cnki.fhclxb.20230629.003

一种自交联型阻燃剂的合成及对固态环氧树脂的性能

doi: 10.13801/j.cnki.fhclxb.20230629.003

楼高波^{1, 2},
戴进峰^{1, 2},
刘丽娜^{1, 2},
傅深渊^{1, 2, ,}

1.
浙江农林大学　化学与材料工程学院，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，杭州 311300

基金项目: 浙江省科技厅领雁项目(2022C03128)；浙江农林大学人才引进启动基金项目(2022LFR103)

详细信息

通讯作者:
傅深渊，博士，教授，博士生导师，研究方向为复合材料与胶黏剂　E-mail：fshenyuan@sina.com

中图分类号: TB322；TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2023-04-19
- 修回日期: 2023-06-10
- 录用日期: 2023-06-15
- 网络出版日期: 2023-06-29
- 刊出日期: 2024-02-01

Synthesis of a self-crosslinking flame retardant and its performance on solid epoxy resin

LOU Gaobo^{1, 2},
DAI Jinfeng^{1, 2},
LIU Lina^{1, 2},
FU Shenyuan^{1, 2
, ,}

1.
College of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, China
2.
National Engineering Research Center for the Comprehensive Utilization of Wood Resources, Zhejiang A&F University, Hangzhou 311300, China

Funds: Leading Geese Projects of Zhejiang Provincial Department of Science and Technology (2022C03128); Research Foundation of Talented Scholars of Zhejiang A & F University (2022LFR103)

摘要

摘要: 环氧树脂(EP)凭借其良好的化学稳定性、电气性能、粘接性能及机械强度，广泛地应用于国民生产和生活的各个领域。但其易燃的特性给人们的生命和财产安全带来了威胁，因此，对环氧树脂进行阻燃改性一直是人们的研究热点。以3-氨基酚、4-硝基邻苯二甲腈、4-甲酰苯硼酸及9, 10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料，分别通过取代、缩合和加成等反应合成了一种具有自交联能力的阻燃剂(DBPN)，并将其用于固态环氧树脂的阻燃，系统研究了环氧树脂复合材料的热稳定性、阻燃性能及阻燃机制。结果表明：添加6.4wt%的DBPN，环氧树脂的初始热分解温度由纯EP的372.6℃提前至351.5℃，这有利于在燃烧过程中提前形成阻隔性炭层，隔绝传质传热过程；其UL-94垂直燃烧测试由N.R提升至V-2级，热释放速率峰值(PHRR)、总热释放量(THR)、烟生成速率峰值(PSPR)和总烟释放量(TSP)则较纯EP分别下降了34.2%、29.5%、20.8%和17.8%；通过对残炭的分析，提出了环氧树脂复合材料的阻燃机制。该工作为新型无卤阻燃剂的制备提供了创新思路。
- 阻燃 /
- 合成 /
- 自交联 /
- 环氧树脂 /
- 机制
Abstract: Epoxy resin (EP) is widely used in various fields of national production and life due to its excellent chemical stability, electrical properties, adhesive properties, and mechanical strength. But its flammable properties pose a threat to people's lives and property safety, thus, the flame retardancy modification of epoxy resin has always been a research hotspot. Using 3-aminophenol, 4-nitrophthalonitrile, 4-formylphenylboronic acid, and 9, 10-dihydro-9-oxa-10-phosphazephenanthroline-10 oxide (DOPO) as raw materials, a self-crosslinking flame retardant (DBPN) was synthesized through substitution, condensation, including addition reactions, and was used for flame retardancy of solid epoxy resin. The thermal stability, flame retardancy, and flame retardancy mechanism of epoxy resin composites were systematically studied. The results show that adding 6.4wt%DBPN advance the initial thermal decomposition temperature of epoxy resin composite from 372.6℃ of neat epoxy resin (EP) to 351.5℃, which is conducive to the formation of a carbon layer barrier during the combustion process, isolating the mass and heat transfer processes. Its UL-94 vertical combustion test increased from N.R to V-2 level, with peak heat release rate (PHRR), total heat release (THR), peak smoke production rate (PSPR), and total smoke production (TSP) decreased by 34.2%, 29.5%, 20.8%, and 17.8%, respectively, compared to neat EP. The flame retardancy mechanism of epoxy resin composites was proposed through the analysis of residual carbon. This work provides innovative ideas for the preparation of new halogen-free flame retardants.
- flame retardancy /
- synthesis /
- self-crosslinking /
- epoxy resin /
- mechanism

HTML全文

图 1 3-氨基苯氧基邻苯二甲腈(3-APN)及阻燃剂 (4-(((3-(3, 4-二氰基苯氧基) 苯基) 氨基)(6-氧化二苯并 [c, e][1-2] 氧膦-6-基) 甲基) 苯基) 硼酸 (DBPN)的合成路线

DMSO—Dimethyl sulfoxide

Figure 1. Synthesis route of 3-aminophenoxyphthalonitrile (3-APN) and (4-(((3-(3, 4-2-cyano phenoxy) phenyl) amino) (6-diphenyl oxide and [c, e] [1-2] oxygen phosphine-6-) methyl) phenyl) boric acid (DBPN)

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图 2 3-氨基酚(a)、4-硝基邻苯二甲腈(b)及3-APN (c)的¹H NMR图谱

Figure 2. ¹H NMR spectra of 3-aminophenol (a), 4-nitrophthalonitrile (b) and 3-APN (c)

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图 3 3-APN和DBPN的红外图谱

Figure 3. FTIR spectra of 3-APN and DBPN

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图 4 9, 10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO) (a)和DBPN(b)的³¹P NMR图谱

Figure 4. ³¹P NMR spectra of 9, 10-dihydro-9-oxa-10-phosphazephenanthroline-10 oxide (DOPO) (a) and DBPN (b)

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图 5 3-APN和DBPN在N₂氛围下的热重测试

Figure 5. Thermogravimetric analysis of 3-APN and DBPN under N₂ atmosphere

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图 6 3-APN和DBPN的DSC曲线

Figure 6. DSC curves of 3-APN and DBPN

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图 7 阻燃剂DBPN的自交联聚合机制

Figure 7. Self-crosslink polymerization reaction mechanism of flame retardant DBPN

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图 8 环氧树脂(EP)复合材料在N₂氛围下的热重测试

Figure 8. Thermogravimetric analysis of epoxy resin (EP) composites under N₂ atmosphere

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图 9 纯EP及EP/6.4wt%DBPN复合材料在垂直燃烧测试(UL-94)中的实时图像

Figure 9. Real-time photos of neat EP and EP/6.4wt%DBPN composites under vertical burning test (UL-94)

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图 10 纯EP及其复合材料的热释放速率 (HRR) (a)、总热释放 (THR) (b)、烟释放速率 (SPR) (c)、总烟释放 (TSP) (d)、CO释放速率 (COP) (e) 及CO₂释放速率 (CO₂P) 曲线 (f)

Figure 10. Heat release rate (HRR) (a), total heat release (THR) (b), smoke production rate (SPR) (c), toal smoke production (TSP) (d), CO production (COP) (e) and CO₂production (CO₂P) curves (f) vs time for the neat EP and EP composites

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图 11 纯EP ((a), (a1))、EP/6.4wt%3-APN ((b), (b1))、EP/6.4wt%DBPN ((c), (c1)) 锥形量热测试后的残炭数码照片及对应的SEM图像；(d) EP/6.4wt%DBPN残炭的元素Mapping

Figure 11. Digital photos and corresponding SEM images for residual char of neat EP ((a), (a1)), EP/6.4wt%3-APN ((b), (b1)), EP/6.4wt%DBPN ((c), (c1)); (d) EDS mapping for EP/6.4wt%DBPN

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表 1 不同环氧树脂(EP)体系的配比

Table 1. Epoxy resin (EP) systems with different proportioning

Sample	E12/g	3-APN/g	DBPN/g	DCD/g	2-MI/g
Neat EP	100	0	0	2.5	0.5
EP/6.4wt%3-APN	100	7	0	2.5	0.5
EP/6.4wt%DBPN	100	0	7	2.5	0.5
Notes: E12—Epoxy resin with an epoxy value of 0.12; DCD—Dicyanodiamide; 2-MI—2-Methylimidazole.

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表 2 EP复合材料在N₂氛围下的TGA数据

Table 2. TGA data of EP composites under N₂ atmosphere

Sample	T_5%/℃	T_max/℃	^*Y_c/wt%
Neat EP	372.6	433.5	11.0
EP/6.4wt%3-APN	365.8	428.0	13.4
EP/6.4wt%DBPN	351.5	435.0	12.4
Notes: T_5%—Onset degradation temperature; T_max—Maximum decompsoition temperature; Y_c—Char yield at 800℃.

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表 3 纯EP及其复合材料的锥形量热数据

Table 3. Cone calorimeter data of neat EP and EP composites

Sample	T_PHRR/s	PHRR/ (kW·m⁻²)	THR/ (MJ·m⁻²)	PSPR/ (m²·s⁻¹)	TSP/m²	PCOP/ (g·s⁻¹)	PCO₂P/ (g·s⁻¹)	FIGRA/ (kW·m⁻²·s⁻¹)
Neat EP	139±4	1095±29	117.6±2.2	0.24±0.013	23.1±2.1	0.0326±0.0006	0.695±0.010	7.9
EP/6.4wt%3-APN	131±5	936±21	112.4±1.9	0.16±0.011	20.0±1.9	0.0282±0.0005	0.542±0.009	7.4
EP/6.4wt%DBPN	104±3	729±19	82.9±1.6	0.19±0.012	19.0±1.4	0.0301±0.0005	0.374±0.007	7.0
Notes: T_PHRR—The time to PHRR; PHRR—Peak heat release rate; THR—Total heat rate; PSPR—Peak smoke production rate; TSP—Total smoke production; PCOP—Peak CO production; PCO₂P—Peak CO₂ production; FIGRA—Fire growth rate.

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