协效剂对膨胀阻燃聚丙烯基木塑复合材料的阻燃增效研究

doi:10.11944/j.issn.1000-0518.2017.02.160189

摘要/Abstract

摘要：

赋予木塑复合材料(WPC)的阻燃性能成为近年来该领域国内外的研究热点之一。本文通过两轮正交试验,研究8种常见的协效剂对膨胀型阻燃剂(IFRs,m(聚磷酸铵,APP):m(季戊四醇,PER)=2:1)的阻燃增效作用,筛选出具有显著协效作用的协效剂组MgO/EG(可膨胀石墨)/SiO₂,其组成为m(MgO):m(EG):m(SiO₂)=1:5:5,其与IFRs的最佳配比为m(IFRs):m(MgO/EG/SiO₂)=1:0.18,得到性能良好的阻燃型聚丙烯基木塑复合材料。通过热重分析(TGA)和锥形量热分析(CONE)评价IFRs及协效剂组对聚丙烯(PP)基木塑复合材料(WPC)热稳定性能和阻燃性能的影响。结果表明,IFRs及MgO/EG/SiO₂的加入可以有效提高WPC的热稳定性,WPC/IFRs/MgO/EG/SiO₂ 600 ℃的残炭率达到22.42%。 WPC/IFRs的热释放速率峰(PHRR)、总热释放量(THR)和总烟释放量(TSP)相比于WPC分别降低了21.9%、8.7%和22%。 MgO/EG/SiO₂的加入可以进一步提高IFRs的阻燃效率,WPC/IFRs/MgO/EG/SiO₂的PHRR和THR相比于WPC分别降低了33.0%和13.8%。

关键词: 正交试验, 木塑复合材料, 膨胀型阻燃剂, 协效剂

Abstract:

Improving flame retardant properties of wood plastic composite material(WPC) has become one of the research hotspots of WPC in recent years. In this paper, the flame-retardant synergistic effects of eight kinds of synergists on intumescent flame retardants(IFRs, m(polyphosphate, APP):m(pentaerythritol, PER)=2:1) were studied by two rounds of orthogonal experiments. The synergist group MgO/EG(expandable graphite)/SiO₂with a significant synergistic flame retardant effect on the IFRs was obtained. The composition of MgO/EG/SiO₂is m(MgO):m(EG):m(SiO₂)=1:5:5, optimum proportion of m(IFRs):m(MgO/EG/SiO₂) is 1:0.18. The influence of IFRs and MgO/EG/SiO₂ on thermal stability and flame-retardant properties of polypropylene based wood-plastics composite(WPC) was evaluated by thermogravimetric analysis(TGA) and cone calorimetry analysis(CONE). The results show that adding IFRs and MgO/EG/SiO₂ to WPC can improve its thermal stability effectively, and the char residue of WPC/IFRs/MgO/EG/SiO₂ at 600 ℃ reaches to 22.42%. The peak heat release rate(PHRR), the total heat release(THR) and total smoke production release(TSP) of WPC/IFRs reduce by 19.0%, 8.7% and 22.1%, respectively, compared with WPC. MgO/EG/SiO₂ can further improve the flame retardant efficiency of IFRs, and the PHRR and THR of WPC/IFRs/MgO/EG/SiO₂ drop by 33.0% and 13.8%, respectively, compared with WPC.

Key words: orthogonal experiment, wood-plastics composite, intumescent flame retardants, synergist

朱德钦, 郑守扬, 生瑜. 协效剂对膨胀阻燃聚丙烯基木塑复合材料的阻燃增效研究[J]. 应用化学, 2017, 34(2): 195-203.

ZHU Deqin, ZHENG Shouyang, SHENG Yu. Flame-retardant Synergistic Effect of Synergists on Intumescent Flame-retardant Wood Flour-Polypropylene Composites[J]. Chinese Journal of Applied Chemistry, 2017, 34(2): 195-203.

参考文献

[1]	Jeencham R,Suppakarn N,Jarukumjorn K. Effect of Flame Retardants on Flame Retardant, Mechanical, and Thermal Properties of Sisal Fiber/Polypropylene Composites[J]. Compos Part B,2014,56(1):249-253.
[2]	Bras M L,Duquesne S,Fois M,et al.Intumescent Polypropylene/Flax Blends:A Preliminary Study[J]. Polym Degrad Stab,2005,88(1):80-84.
[3]	Zhou L,Guo C G,Li L P. Influence of Ammonium Polyphosphate Modified with 3-(Methylacryloxyl) Propyltrimethoxy Silane on Mechanical and Thermal Properties of Wood Flour-Polypropylene Composites[J]. J Appl Polym Sci,2011,122(2):849-855.
[4]	Laoutid F,Bonnaud L,Alexandre M,et al.New Prospects in Flame Retardant Polymer Materials:From Fundamentals to Nanocomposites[J]. Mater Sci Eng,2009,63(3):100-125.
[5]	Wu Z P,Hu Y C,Shu W Y. Effect of Ultrafine Zinc Borate on the Smoke Suppression and Toxicity Reduction of a Low-density Polyethylene/Intumescent Flame-retardant System[J]. J Appl Polym Sci,2010,117(1):443-449.
[6]	Nie S B,Song L,Bao C L,et al.Synergistic Effects of Ferric Pyrophosphate(FePP) in Intumescent Flame-retardant Polypropylene[J]. Polym Adv Technol,2011,22(6):870-876.
[7]	DU Jianxin,HAO Jianwei,WANG Jianqi. An Investigation of Synergism Between SiO2, Al2O3 and PP/APP/PER IFR System[J]. Polym Mater Sci Eng,2004,20(1):165-167(in Chinese). 杜建新,郝建薇,王建祺. SiO2和Al2O3对PP/APP/PER膨胀阻燃体系的协同作用[J]. 高分子材料科学与工程,2004,20(1):165-167.
[8]	Zhu H F,Zhu Q L,Li J,et al.Synergistic Effect Between Expandable Graphite and Ammonium Polyphosphate on Flame Retarded Polylactide[J]. Polym Degrad Stab,2011,96(2):183-189.
[9]	Gao S L,Li B,Bai P,et al.Effect of Polysiloxane and Silane-modified SiO2 on a Novel Intumescent Flame Retardant Polypropylene System[J]. Polym Adv Technol,2011,22(12):2609-2616.
[10]	Ye L,Zhang Y J,Wang S H,et al.Synergistic Effects and Mechanism of ZnCl2 on Intumescent Flame-retardant Polypropylene[J]. J Therm Anal Calorim,2014,115(2):1065-1071.
[11]	Ma Z L,Fan C R,Lyu G Y,et al.Synergy of Magnesium and Calcium Oxides in Intumescent Flame-retarded Polypropylene[J]. J Appl Polym Sci,2012,125(5):3567-3574.
[12]	Lin M,Li B,Li Q F,et al.Synergistic Effect of Metal Oxides on the Flame Retardancy and Thermal Degradation of Novel Intumescent Flame-retardant Thermoplastic Polyurethanes[J]. J Appl Polym Sci,2011,121(4):1951-1960.
[13]	Ren Q,Zhang Y,Li J,et al.Synergistic Effect of Vermiculite on the Intumescent Flame Retardance of Polypropylene[J]. J Appl Polym Sci,2011,120(2):1225-1233.
[14]	Chen X Y,Sun T,Cai X F. The Investigation of Intumescent Flame-retarded ABS Using Zinc Borate as Synergist[J]. J Therm Anal Calorim,2014,115(1):185-191.
[15]	Zhou R M,Lai X J,Li H Q,et al.Enhancement of Wollastonite on Flame Retardancy and Mechanical Properties of PP/IFR Composite[J]. Polym Compos,2014,35(1):158-166.
[16]	NIE Qin,ZHANG Jiahuan,CHEN Si,et al.Effect of Modified Sepiolite and Metal Oxides on the Combustion of Intumescent Flame Retardant PP[J]. China Plast Ind,2012,40(3):108-111,121(in Chinese). 聂芹,张佳欢,陈思,等. 改性海泡石与金属氧化物对膨胀阻燃 PP 燃烧性能的影响[J]. 塑料工业,2012,40(3):108-111,121.
[17]	WU Na,YANG Rongjie,HAO Jianwei,et al.Synergistic Effect of Metal Oxides on Intumescent Flame-Retardant PP Systems[J]. Acta Polym Sin,2009,(12):1205-1210(in Chinese). 吴娜,杨荣杰,郝建薇,等. 金属氧化物对聚丙烯膨胀阻燃体系阻燃性能的影响[J]. 高分子学报,2009,(12):1205-1210.
[18]	LI Linjie. Study on Smoke Movement in Vertical Shaft of High-rise Building and Flame Behavior in the Fire Compartment[D]. Hefei:University of Science and Technology of China,2014(in Chinese). 李林杰. 高层建筑竖向通道内烟气输运规律及着火房间火行为特性研究[D]. 合肥:中国科学技术大学,2014.
[19]	Li B,He J M. Investigation of Mechanical Property, Flame Retardancy and Thermal Degradation of LLDPE-wood-fibre Composites[J]. Polym Degrad Stab,2004,83(2):241-246.