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浙江大学学报(工学版)
浙江大学学报(工学版)  2020, Vol. 54 Issue (12): 2321-2328    DOI: 10.3785/j.issn.1008-973X.2020.12.006
机械工程、能源工程     
PC/ABS合金的气相/凝聚相协同阻燃作用
高顺(),郭正虹*()
浙大宁波理工学院 高分子材料与工程实验室，浙江 宁波 315100
Synergistic flame retardancy of gas phase and condensed phase of PC/ABS alloy
Shun GAO(),Zheng-hong GUO*()
Laboratory of Polymer Material and Engineering, NingboTech University, Ningbo 315100, China
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摘要：

分别选用2种不同阻燃机理的磷系阻燃剂，即以凝聚相阻燃为主的间苯二酚-双(二苯基磷酸酯) (RDP)和以气相阻燃为主的磷酸三苯酯(TPP)，采用熔融共混法制备聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯共聚物(ABS)阻燃合金. 通过垂直燃烧测试和锥形量热测试探究RDP/TPP复配对合金阻燃性能的影响，通过扫描电子显微镜(SEM)观察燃烧残炭的微观形貌. 以甲基丙烯酸甲酯-丁二烯-苯乙烯(MBS)为相容剂，通过拉伸性能和冲击性能测试探究MBS对阻燃合金的增韧增容效果，并以SEM观察MBS对合金相界面和相形态的影响. 结果表明，RDP的凝聚相阻燃和TPP的气相阻燃作用具有协同效果，可以在PC/ABS合金中促进磷酸盐结构生成，进而有助于体系生成更连续、致密的炭层.
关键词： PC/ABS;  气相;  凝聚相;  阻燃;  相容性    
Abstract:

Two kinds phosphorus flame retardants, resorcinol bis (diphenyl phosphate) (RDP) (mainly condensed phase flame retardant) and triphenyl phosphate (TPP) (mainly gaseous phase flame retardant), were selected to prepare flame retardant polycarbonate (PC) /acrylonitrile-butadiene-styrene copolymer (ABS) alloy by melt blending.The effects of RDP/TPP on the flame retardancy of the alloy were investigated by vertical combustion test and cone calorimetry. The micro morphology of the carbon residue was observed by scanning electron microscope (SEM). The toughening and compatibilizing effect of methyl methacrylate-butadiene-styrene (MBS) on the flame retardant alloy was studied by tensile and impact tests, and the effects of MBS on the phase interface and the morphology of the alloy were observed by SEM. Results show that the condensed phase flame retardant of RDP and the gas phase flame retardant of TPP have synergistic effect, which can promote the formation of phosphate structure in PC/ABS alloy, thus help the system to form a continuous and compact carbon layer.
Key words: PC/ABS    gas phase    condensed phase    flame retardant    compatibility
收稿日期: 2019-11-19 出版日期: 2020-12-31
CLC:  TB 324  
基金资助: 国家自然科学基金资助项目(51991355)
通讯作者: 郭正虹     E-mail: 2066453523@qq.com;guozhenghong@nit.zju.edu.cn
作者简介: 高顺(1995—)，女，硕士，从事PC/ABS合金阻燃改性研究. orcid.org/0000-0002-7747-7312. E-mail： 2066453523@qq.com
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高顺
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引用本文:

高顺,郭正虹. PC/ABS合金的气相/凝聚相协同阻燃作用[J]. 浙江大学学报(工学版), 2020, 54(12): 2321-2328.

Shun GAO,Zheng-hong GUO. Synergistic flame retardancy of gas phase and condensed phase of PC/ABS alloy. Journal of ZheJiang University (Engineering Science), 2020, 54(12): 2321-2328.

链接本文:

http://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2020.12.006    或    http://www.zjujournals.com/eng/CN/Y2020/V54/I12/2321

组成 wB /%
PC ABS RDP TPP PTFE1） MBS
1）注：PTFE作为抗滴落剂存在，每组配方都是相同份数
PC/ABS 70.0 30.0 ? ? ? ?
PC/ABS/10TPP 62.7 26.9 ? 10 0.4 ?
PC/ABS/10RDP 62.7 26.9 10 ? 0.4 ?
PC/ABS/（8RDP+2TPP） 62.7 26.9 8 2 0.4 ?
PC/ABS/（6RDP+4TPP） 62.7 26.9 6 4 0.4 ?
PC/ABS/（5RDP+5TPP） 62.7 26.9 5 5 0.4 ?
PC/ABS/（4RDP+6TPP） 62.7 26.9 4 6 0.4 ?
PC/ABS/（2RDP+8TPP） 62.7 26.9 2 8 0.4 ?
PC/ABS/（6RDP+4TPP）/5MBS 59.2 25.4 6 4 0.4 5
PC/ABS/（6RDP+4TPP）/10MBS 55.7 23.9 6 4 0.4 10
PC/ABS/（6RDP+4TPP）/15MBS 52.2 22.4 6 4 0.4 15
表 1  阻燃PC/ABS合金配比表
组成 $\overline {{t_1}} $/s $\overline {{t_2}} $/s $\overline {{t_1}} $+ $\overline {{t_2}} $/s UL 94等级
PC/ABS >30.0 >60.0 >60.0 无等级
PC/ABS/10TPP 16.4 26.2 42.6 V-1
PC/ABS/10RDP 12.1 20.3 32.4 V-1
PC/ABS/（8RDP+2TPP） 14.3 17.2 31.5 V-1
PC/ABS/（6RDP+4TPP） 3.3 6.7 10.0 V-0
PC/ABS/（5RDP+5TPP） 2.1 4.2 6.3 V-0
PC/ABS/（4RDP+6TPP） 4.1 5.1 9.2 V-0
PC/ABS/（2RDP+8TPP） 12.1 15.2 27.3 V-1
PC/ABS/（6RDP+4TPP）/5MBS 8.9 9.3 18.2 V-0
PC/ABS/（6RDP+4TPP）/10MBS 26.4 28.9 55.3 V-1
PC/ABS/（6RDP+4TPP）/15MBS >30.0 >60.0 >60.0 无等级
表 2  阻燃PC/ABS合金UL 94测试结果
组成 tign /s tPHRR /s PHRR /
（kW·m?2） 		THR /
（MJ·m?2） 		AEHC /
（MJ·kg?1） 		ASEA /
（m2·kg?1） 		CHR /% FGI /
（kW·m?2·s?1） 		FPI /
（m2·s·kW?1）
PC/ABS/10RDP 41.5±0.5 155.0±5.0 444.8±22.3 68.2±0.4 19.9±0.1 1048.1±35.8 6.86±0.03 2.87 0.093
PC/ABS/（6RDP+4TPP） 40.5±1.5 157.5±2.5 422.1±20.4 65.8±1.1 19.4±0.3 1123.4±15.9 6.70±0.08 2.68 0.096
PC/ABS/10TPP 40.1±3.0 150.0±1.0 445.5±3.4 67.6±0.1 19.5±0.2 1102.3±6.7 4.68±1.06 2.97 0.090
表 3  阻燃PC/ABS合金在辐射强度为50 kW/m2下的锥形量热测试结果
图 1  锥形量热燃烧残炭的形貌图片
图 2  燃烧残炭的扫描电镜图片
组成 xB /%
C O P Si
PC/ABS/10RDP 79.44 18.02 2.54 0.00
PC/ABS/（6RDP+4TPP） 75.95 21.06 2.95 0.04
PC/ABS/10TPP 88.92 10.12 0.96 0.00
表 4  锥形量热燃烧残渣的X射线能谱仪分析数据
组成 a /（kJ·m?2） σb /MPa εb /% Et /MPa
PC/ABS 41.7±5.3 51.1±2.4 27.8±8.1 853.1±104.4
PC/ABS/10RDP 8.6±2.4 51.4±2.8 19.2±5.1 838.7±146.2
PC/ABS/10TPP 10.4±1.8 46.6±2.9 21.2±11.9 736.1±123.5
PC/ABS/（6RDP+4TPP） 7.1±0.8 49.7±3.4 17.1±4.2 863.6±175.9
PC/ABS/（5RDP+5TPP） 6.9±0.9 48.8±1.7 15.5±3.4 689.7±123.2
PC/ABS/（4RDP+6TPP） 5.1±0.7 49.5±1.2 19.1±3.2 970.2±111.3
PC/ABS/（6RDP+4TPP）/5MBS 10.7±1.5 43.1±3.5 10.8±0.7 649.6±197.5
PC/ABS/（6RDP+4TPP）/10MBS 27.6±2.8 38.3±3.3 14.8±4.4 722.2±116.5
PC/ABS/（6RDP+4TPP）/15MBS 33.5±1.2 33.9±2.4 25.8±7.3 465.6±74.6
表 5  阻燃PC/ABS合金的缺口冲击强度、拉伸强度、断裂伸长率和弹性模量测试结果
图 3  缺口冲击断面的扫描电镜图片
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