多功能阻燃增韧剂对聚碳酸酯阻燃和力学性能的影响

高纳川; 高雪雨; 闫莉; 桑晓明

doi:10.13801/j.cnki.fhclxb.20230922.002

多功能阻燃增韧剂对聚碳酸酯阻燃和力学性能的影响

doi: 10.13801/j.cnki.fhclxb.20230922.002

高纳川^{1, 2},
高雪雨^{1, 2},
闫莉^{1, 2, ,},
桑晓明^{1, 2}

1.
华北理工大学　材料科学与工程学院，唐山 063210
2.
河北省无机非金属材料重点实验室，唐山市功能高分子材料重点实验室，唐山 063210

基金项目: 河北省自然科学基金(E2019209446)

详细信息

通讯作者:
闫莉，博士，副教授，硕士生导师，研究方向为高分子材料改性和功能化　E-mail: yl_dlut@126.com

中图分类号: TQ317；TB332
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出版历程
- 收稿日期: 2023-07-17
- 修回日期: 2023-09-04
- 录用日期: 2023-09-12
- 网络出版日期: 2023-09-23
- 刊出日期: 2024-05-15

Effect of multifunctional flame retardant tougheners on the flame retardant and mechanical properties of polycarbonates

GAO Nachuan^{1, 2},
GAO Xueyu^{1, 2},
YAN Li^{1, 2
, ,},
SANG Xiaoming^{1, 2}

1.
College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, China
2.
Key Laboratory of Functional Polymer Materials of Tangshan, Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, Tangshan 063210, China

Funds: Natural Science Foundation of Hebei Province (E2019209446)

摘要

摘要: 为了平衡聚碳酸酯(PC)的阻燃改性和力学改性效果，本文采用由种子乳液聚合自制的有机硅-含磷丙烯酸酯核壳结构的阻燃增韧剂(ACR)共混改性PC材料。当在PC中添加质量分数为4wt%的ACR时，4%ACR/PC的极限氧指数(LOI)可达31.7%，垂直燃烧测试达到UL-94 V-0级，锥形量热测试表明燃烧释热和烟释放总量分别降低了43.2%和20.5%；同时，4%ACR/PC保持了与纯PC相近的拉伸强度，且冲击强度提高了9.4%。热重-红外联用、拉曼光谱和燃烧后残余物扫描电镜分析表明，阻燃作用主要来自于磷-硅协同效应及磷元素对PC的催化成炭作用。冲击断面SEM图像显示，增韧作用体现在ACR核层有机硅橡胶可以吸收冲击能量，抑制或终止裂纹的产生。
- 阻燃 /
- 增韧 /
- 力学性能 /
- ACR /
- 聚碳酸酯 /
- 磷-硅协同
Abstract: In order to balance the effect of flame retardant modification and mechanical modification of polycarbonate (PC), the flame retardant toughening agent with silicone-phosphorus-containing acrylate core-shell structure (ACR) prepared by seed emulsion polymerization was used to modify PC materials in this paper. When 4wt%ACR was added to PC, the limiting oxygen index (LOI) of 4%ACR/PC could reach 31.7%, the vertical combustion test reached UL-94 V-0 level, and the cone calorimeter test showed that the combustion heat release and smoke density were reduced by 43.2% and 20.5%, respectively. At the same time, the tensile strength of 4%ACR/PC was similar to that of pure PC, and the impact strength was increased by 9.4%. Thermogravimetric-infrared spectroscopy, Raman spectroscopy and post-combustion residue scanning electron microscopy analysis showed that the flame retardant effect was mainly due to the synergistic effect of phosphorus-silicon and the catalytic charring effect of phosphorus on PC. The impact cross-section SEM images showed that the toughening effect is reflected in the fact that the ACR core layer silicone rubber can absorb impact energy and inhibit or terminate the generation of cracks.
- flame retardancy /
- toughening /
- mechanical properties /
- ACR /
- polycarbonate /
- phosphorus-silicon synergy

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图 1 丙烯酸酯(ACR)的合成路线

D4—Octamethylcyclotetrasiloxane; DBSA—Dodecylbenzenesulfonic acid; DEAMP—Diethyl methacrylate acrylate; DOPO-AA—9, 10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide acrylate; KH-570—γ-methacryloxypropyltrimethoxysilane

Figure 1. Synthesis route of acrylic resin (ACR)

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图 2 ACR、PC和ACR/PC的TGA (a) 和DTG (b) 曲线

Figure 2. TGA (a) and DTG (b) curves of ACR, PC and ACR/PC

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图 3 PC、ACR/PC材料的热释放速率(HRR) (a)、总释放热(THR) (b)、生烟速率(SPR) (c)和总生烟量(TSP) (d)曲线

Figure 3. Heat release rate (HRR) (a), total heat release (THR) (b), smoke produce rate (SPR) (c) and total smoke production (TSP) (d) curves for PC, ACR/PC

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图 4 PC、ACR/PC材料锥形量热测试后的残炭俯视(a)和正视(b)数码图像

Figure 4. Top view digital (a) and front view digital (b) of photographs for residual carbon after cone calorimetry testing of PC, ACR/PC materials

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图 5 PC、ACR/PC锥形量热测试后残炭的SEM和EDS能谱图

Figure 5. SEM and EDS spectra of residual carbon after PC and ACR/PC cone calorimetry tests

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图 6 PC、ACR/PC锥形量热测试后残炭的拉曼图谱

I_D/I_G—Intensity ratio of D and G peaks

Figure 6. Raman spectra of residual carbon after PC and ACR/PC cone calorimetry tests

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图 7 PC、ACR/PC锥形量热测试后残炭的红外图谱

Figure 7. Infrared spectra of residual carbon after PC and ACR/PC cone calorimetry tests

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图 8 PC、4%ACR/PC的三维TG-IR图((a), (b))和不同温度下热解产物的红外图谱((c), (d))

Figure 8. 3D TG-IR maps of PC, 4%ACR/PC ((a), (b)) and IR spectra of pyrolysis products at different temperatures ((c), (d))

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图 9 PC、ACR/PC的应力-应变曲线

Figure 9. Stress-strain curves of PC, ACR/PC

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图 10 PC、ACR/PC材料冲击断面的SEM图像

Figure 10. SEM images of impact section of PC, ACR/PC materials

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表 1 ACR/聚碳酸酯(PC)复合材料的配方表

Table 1. Formulation sheet for ACR/polycarbonate (PC) composites

Sample	PC/wt%	ACR/wt%
PC	100	—
1%ACR/PC	99	1
2%ACR/PC	98	2
4%ACR/PC	96	4

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表 2 PC、ACR/PC的UL-94和极限氧指数(LOI)

Table 2. UL-94 and limiting oxygen index (LOI) for PC, ACR/PC

Sample	UL-94				LOI/%
Sample	t₁/t₂	Dripping	Ignition	Rating	LOI/%
PC	17/9	Yes	Yes	V-2	25.8
1%ACR/PC	13/4	Yes	No	V-1	26.3
2%ACR/PC	6/3	No	No	V-0	27.6
4%ACR/PC	1/1	No	No	V-0	31.7
Notes: t₁—First afterflame time; t₂—Second afterflame time.

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表 3 ACR、PC、ACR/PC的TGA和DTG数据

Table 3. TGA and DTG data for ACR, PC, ACR/PC

Sample	T_d5%/℃	T_d10%/℃	T_d50%/℃	T_Max/℃	Char residue/wt%
ACR	375	418	482	476	36.4
PC	496	506	528	526	26.2
1%ACR/PC	495	505	530	525	25.6
2%ACR/PC	485	495	515	513	26.1
4%ACR/PC	492	497	517	512	28.8
Notes: T_d5%—5wt% mass loss temperature; T_d10%—10wt% mass loss temperature; T_d50%—50wt% mass loss temperature; T_Max—Maximum mass loss temperature.

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表 4 PC、ACR/PC的锥形量热数据

Table 4. Cone calorimetry data for PC, ACR/PC

Sample	TTI/s	t_p/s	pHRR/(kW·m⁻²)	THR/(MJ·m⁻²)	Av-EHC/(MJ·kg⁻¹)	Char residue/wt%	TSP/m²
PC	165	280	165	15.5	6.2	17.5	7.3
1%ACR/PC	116	271	145	13.6	6.4	18.6	6.3
2%ACR/PC	112	258	125	12.1	5.0	20.2	6.1
4%ACR/PC	102	275	73	8.8	4.3	26.1	5.8
Notes: TTI—Ignition time, ±1 s; pHRR—Peak heat release rate, ±2 kW·m^–2; t_p—Peak time corresponding to the heat release rate, ±1 s; THR—Total heat release, ±0.5 MJ·m^–2; Av-EHC—Average effective heat of combustion, ±0.1 MJ·kg^–1; TSP—Total smoke production, ±0.1 m².

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表 5 PC、ACR/PC的力学性能测试结果

Table 5. Mechanical property test results of PC, ACR/PC

Sample	Tensile strength/MPa	Impact strength/(J·m⁻¹)
PC	69.7±1.5	6.4±0.1
1%ACR/PC	69.8±1.4	8.5±0.1
2%ACR/PC	69.1±1.7	7.6±0.2
4%ACR/PC	68.4±1.3	7.0±0.1

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