纳米SiO<sub>2</sub>与间苯二酚-双(二苯基磷酸酯)对聚碳酸酯-ABS合金的协同阻燃机制

高顺; 郭正虹

doi:10.13801/j.cnki.fhclxb.20200311.002

纳米SiO₂与间苯二酚-双(二苯基磷酸酯)对聚碳酸酯-ABS合金的协同阻燃机制

doi: 10.13801/j.cnki.fhclxb.20200311.002

高顺,
郭正虹^,

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: TB324
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- 被引次数: 0
出版历程
- 收稿日期: 2019-12-28
- 录用日期: 2020-02-02
- 网络出版日期: 2020-03-12
- 刊出日期: 2020-11-15

Synergistic flame retardant mechanism of nano SiO₂ and resorcinol bis(diphenylphosphate) on polycarbonate-ABS blends

GAO Shun,
GUO Zhenghong^,

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

摘要

摘要: 选用以凝聚相阻燃机制为主的间苯二酚-双(二苯基磷酸酯)(RDP)作为阻燃剂，纳米SiO₂为协效剂，以熔融共混法制备了聚碳酸酯(PC)-丙烯腈-丁二烯-苯乙烯共聚物(ABS)阻燃合金。通过垂直燃烧(UL94)和锥形量热测试(Cone)探究了纳米SiO₂与RDP复配对PC-ABS合金阻燃性能和燃烧行为的影响。采用SEM观察燃烧残炭的微观形貌，用EDS分析炭层表面元素含量的变化，进一步探究了纳米SiO₂与RDP在PC-ABS凝聚相中的协效阻燃机制。通过拉伸性能和冲击性能测试研究纳米SiO₂与RDP复配对PC-ABS合金力学性能的影响及甲基丙烯酸甲酯-丁二烯-苯乙烯(MBS)对PC-ABS合金的增韧增容作用。结果表明，纳米SiO₂与RDP可以在凝聚相中形成Si—O—P化合物，对PC-ABS合金的燃烧炭层起到增强作用，从而改善PC-ABS合金的阻燃性能；适量MBS的加入可以提高PC-ABS合金的冲击强度和断裂伸长率，但会降低其阻燃性能。
- 聚碳酸酯(PC) /
- 丙烯腈-丁二烯-苯乙烯共聚物(ABS) /
- 纳米SiO₂ /
- 阻燃 /
- 凝聚相 /
- 力学性能
Abstract: The flame retardant polycarbonate (PC)-acrylonitrile-butadiene-styrene (ABS) blends was prepared by melt blending with resorcinol bis(diphenylphosphate) (RDP) (mainly based on condensed phase flame retardant mechanism) and nano SiO₂ as the synergist. The effects of nano SiO₂ and RDP on the flame retardancy and combustion behavior of PC-ABS blends were investigated by vertical combustion (UL94) and cone calorimetry (Cone). SEM was used to observe the micro morphology of burning carbon residue, and EDS was used to analyze the change of element content on the surface of carbon layer, so as to further explore the synergistic flame retardant mechanism of nano SiO₂ and RDP in the condensed phase of PC-ABS. The effects of nano SiO₂ and RDP on the mechanical properties of PC-ABS blends and the toughening and compatibilizing effects of methyl methacrylate-butadiene-styrene (MBS) on the blends were studied by tensile and impact tests. The results show that nano SiO₂ and RDP can form Si—O—P compound in the condensed phase, which can enhance the combustion carbon layer, thus improving the flame retardancy of PC-ABS blends; The impact strength and elongation at break of the PC-ABS blends can be increased with the addition of MBS, but the flame retardancy can be decreased.
- polycarbonate (PC) /
- acrylonitrile-butadiene-styrene (ABS) /
- nano SiO₂ /
- flame retardant /
- condensed phase /
- mechanical property

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图 1 SiO₂-RDP/(PC-ABS)阻燃合金的热释放速率、质量损失、总热释放量、总生烟量、烟释放速率、CO生成率和CO₂生成率的曲线

Figure 1. Heat release rate, mass loss, total heat release, total smoke release, smoke production rate, volume fraction of CO and volume fraction of CO₂ curves of SiO₂-RDP/PC-ABS flame retardant blends

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图 2 10RDP/(PC-ABS)((a)~(c))、1SiO₂-10RDP/(PC-ABS)((d)~(f))和1SiO₂/(PC-ABS)((g)~(i))阻燃合金的燃烧残炭形貌

Figure 2. Morphologies of char residues of 10RDP/(PC-ABS)((a)–(c)), 1SiO₂-10RDP/(PC-ABS)((d)–(f)) and 1SiO₂/(PC-ABS)((g)–(i)) flame retardant blends

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图 3 10RDP/(PC-ABS)(a)、1SiO₂-10RDP/(PC-ABS)(b)和1SiO₂/(PC-ABS)(c)阻燃合金燃烧残炭的SEM图像

Figure 3. SEM images of char residues of 10RDP/(PC-ABS)(a), 1SiO₂-10RDP/(PC-ABS)(b) and 1SiO₂/(PC-ABS)(c) flame retardant blends

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图 4 1SiO₂-10RDP/(PC-ABS)阻燃合金燃烧残炭表面的P元素(a)和Si元素(b)分布

Figure 4. P distribution(a) and Si distribution(b) of char residues of 1SiO₂-10RDP/(PC-ABS) flame retardant blends

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图 5 SiO₂-RDP-MBS/(PC-ABS)阻燃合金的力学性能

Figure 5. Mechanical properties of SiO₂-RDP-MBS/(PC-ABS) flame retardant blends

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图 6 PC-ABS ((a)、(b))、10RDP/(PC-ABS) ((c)、(d))、1SiO₂-10RDP/(PC-ABS) ((e)、(f))和1SiO₂-10RDP-20MBS/(PC-ABS)((g)、(h))阻燃合金缺口冲击断面的SEM图像

Figure 6. SEM images of notched impact cross section of PC-ABS ((a),(b)), 10RDP/(PC-ABS) ((c),(d)), 1SiO₂-10RDP/(PC-ABS) ((e),(f)) and 1SiO₂-10RDP-20MBS/(PC-ABS) ((g),(h)) flame retardant blends

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表 1 SiO₂-间苯二酚-双(二苯基磷酸酯)-甲基丙烯酸甲酯-丁二烯-苯乙烯/(聚碳酸酯-丙烯腈-丁二烯-苯乙烯共聚物)(SiO₂-RDP-MBS/(PC-ABS))阻燃合金配比

Table 1. Formulations of SiO₂-resorcinol bis(diphenylphosphate)-methyl methacrylate-butadiene-styrene/(polycarbonate-acrylonitrile-butadiene-styrene)(SiO₂-RDP-MBS/(PC-ABS)) flame retardant blends wt%

Sample	PC	ABS	RDP	SiO₂	PTFE	MBS
10RDP/(PC-ABS)	62.7	26.9	10	—	0.4	—
0.5SiO₂-10RDP/(PC-ABS)	62.4	26.7	10	0.5	0.4	—
1SiO₂-10RDP/(PC-ABS)	62.0	26.6	10	1	0.4	—
2SiO₂-10RDP/(PC-ABS)	61.3	26.3	10	2	0.4	—
3SiO₂-10RDP/(PC-ABS)	60.6	26.0	10	3	0.4	—
4SiO₂-10RDP/(PC-ABS)	59.9	25.7	10	4	0.4	—
5SiO₂-10RDP/(PC-ABS)	58.9	25.2	10	5	0.4	—
6SiO₂-10RDP/(PC-ABS)	58.5	25.1	10	6	0.4	—
7SiO₂-10RDP/(PC-ABS)	57.8	24.8	10	7	0.4	—
1SiO₂/(PC-ABS)	69.0	29.6	—	1	0.4	—
1SiO₂-10RDP-5MBS/(PC-ABS)	58.5	25.1	10	1	0.4	5
1SiO₂-10RDP-10MBS/(PC-ABS)	55.0	23.6	10	1	0.4	10
1SiO₂-10RDP-15MBS/(PC-ABS)	51.5	22.1	10	1	0.4	15
1SiO₂-10RDP-20MBS/(PC-ABS)	48.0	20.6	10	1	0.4	20
1SiO₂-10RDP-25MBS/(PC-ABS)	44.5	19.1	10	1	0.4	25
Note: PTFE—Polytetrafluoroethylene.

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表 2 SiO₂-RDP-MBS/(PC-ABS)阻燃合金的垂直燃烧 (UL94) 测试结果

Table 2. Vertical combustion (UL94) results of SiO₂-RDP-MBS/(PC-ABS) flame retardant blends

Sample	t₁/s	t₂/s	t₁+t₂/s	Dripping	UL94
10RDP/(PC-ABS)	12.1	20.3	32.4	N	V-1
0.5SiO₂-10RDP/(PC-ABS)	21.4	24.5	45.9	N	V-1
1SiO₂-10RDP/(PC-ABS)	3.1	8.9	12.0	N	V-0
2SiO₂-10RDP/(PC-ABS)	11.3	31.4	42.7	N	V-1
3SiO₂-10RDP/(PC-ABS)	16.8	26.1	42.9	N	V-1
4SiO₂-10RDP/(PC-ABS)	25.7	38.7	64.4	N	V-1
5SiO₂-10RDP/(PC-ABS)	>30.0	>60.0	>60.0	Y	No-rating
6SiO₂-10RDP/(PC-ABS)	>30.0	>60.0	>60.0	Y	No-rating
7SiO₂-10RDP/(PC-ABS)	>30.0	>60.0	>60.0	Y	No-rating
1SiO₂/(PC-ABS)	>30.0	>60.0	>60.0	N	No-rating
1SiO₂-10RDP-5MBS/(PC-ABS)	16.2	24.5	40.7	N	V-1
1SiO₂-10RDP-10MBS/(PC-ABS)	31.3	50.4	81.7	N	V-2
1SiO₂-10RDP-15MBS/(PC-ABS)	>30.0	>60.0	>60.0	Y	No-rating
1SiO₂-10RDP-20MBS/(PC-ABS)	>30.0	>60.0	>60.0	Y	No-rating
1SiO₂-10RDP-25MBS/(PC-ABS)	>30.0	>60.0	>60.0	Y	No-rating
Notes: t₁—Self-extinguishing time after the first ignition; t₂—Self-extinguishing time after the second ignition;Y—Yes; N—No.

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表 3 SiO₂-RDP/(PC-ABS)阻燃合金的锥形量热测试结果

Table 3. Cone data for SiO₂-RDP/(PC-ABS) flame retardant blends

Sample	10RDP/(PC-ABS)	1SiO₂-10RDP/(PC-ABS)	1SiO₂/(PC-ABS)
t_ign/s	41.5±0.5	42.0±1.0	38.5±0.5
t_PHRR/s	155.0±5.0	167.5±2.5	70±0.1
PHRR/(kW·m⁻²)	444.8±22.3	379.1±5.4	566.1±16.8
THR/(MJ·m⁻²)	68.2±0.4	70.4±1.5	92.0±1.3
AHRR/(kW·m⁻²)	135.9±2.1	142.7±0.6	224.3±2.3
AMLR/(g·s⁻¹)	0.060±0.001	0.062±0.002	0.082±0.002
AEHC/(MJ·kg⁻¹)	19.9±0.1	20.4±0.6	24.5±0.4
ASEA/(m²·kg⁻¹)	1 048.1±35.8	1 068.0±15.1	838.2±45.4
ACOY/(kg·kg⁻¹)	0.146±0.001	0.156±0.002	0.083±0.001
ACO₂Y/(kg·kg⁻¹)	1.383±0.001	1.382±0.014	1.738±0.041
TSR/(m²·m⁻²)	3 592.1±102.9	3 682.1±85.3	3 156.6±182.8
CHR/%	6.86±0.03	6.94±0.53	5.76±0.98
FGI/(kW·m⁻²·s⁻¹)	2.87	2.26	8.09
FPI/(m²·s·kW⁻¹)	0.093	0.110	0.068
Notes: PHRR—Peak heat release rate; THR—Total heat release at 600 s; AHRR—Average heat release rate; AMLR—Average mass loss rate; AEHC—Average effective heat of combustion; ASEA—Average specific extinction area; ACOY—Average yield of CO; ACO₂Y—Average yield of CO₂; TSR—Total smoke release; CHR—Char residue; FGI—Fire spread index; FPI—Fire performance index; t_ign—Time to ignition; t_PHRR—Time to PHRR.

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表 4 10RDP/(PC-ABS)、1SiO₂-10RDP/(PC-ABS)和1SiO₂/(PC-ABS)阻燃合金锥形量热测试后残炭的EDS分析

Table 4. EDS analysis of char residues of 10RDP/(PC-ABS), 1SiO₂-10RDP/(PC-ABS) and 1SiO₂/(PC-ABS) flame retardant blends after Cone tests

Sample	Element/at%
Sample	C	O	P	Si
1SiO₂/(PC-ABS)	83.89	16.09	—	0.03
10RDP/(PC-ABS)	79.44	18.02	2.54	—
1SiO₂-10RDP/(PC-ABS)	54.17	36.71	7.24	1.88

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表 5 SiO₂-RDP-MBS/(PC-ABS)阻燃合金的缺口冲击强度、拉伸强度、断裂伸长率和弹性模量

Table 5. Izod impact strength、tensil strength、elongation at break and tensile modulus of SiO₂-RDP-MBS/(PC-ABS) flame retardant blends

Sample	Izod impact strength/(kJ·m⁻²)	Tensile strength/MPa	Elongation at break/%	Tensile modulus/MPa
10RDP/(PC-ABS)	8.6±2.4	51.4±2.8	19.2±5.1	838.7±146.2
1SiO₂-10RDP/(PC-ABS)	6.0±1.1	50.9±3.7	18.6±3.1	893.2±168.4
1SiO₂-10RDP-5MBS/(PC-ABS)	8.1±0.6	47.8±2.4	14.9±3.1	372.2±366.1
1SiO₂-10RDP-10MBS/(PC-ABS)	13.1±3.5	39.8±2.9	25.1±6.8	504.1±84.6
1SiO₂-10RDP-15MBS/(PC-ABS)	15.4±1.5	36.9±2.9	37.9±5.8	406.2±178.5
1SiO₂-10RDP-20MBS/(PC-ABS)	26.8±3.5	32.3±3.3	29.1±4.1	414.9±105.9
1SiO₂-10RDP-25MBS/(PC-ABS)	23.1±0.9	27.7±2.6	24.5±8.1	468.1±149.1

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