含磷苯并咪唑基铜配合物合成及阻燃环氧树脂的性能

兰州理工大学学报 ›› 2021, Vol. 47 ›› Issue (6): 66-73.

含磷苯并咪唑基铜配合物合成及阻燃环氧树脂的性能

杨保平^*,陈晓东,王念念,崔锦峰,郭军红

兰州理工大学石油化工学院, 甘肃兰州 730050

收稿日期:2020-12-07 出版日期:2021-12-28 发布日期:2021-12-28
通讯作者: 杨保平(1968-),男,甘肃兰州人,教授,博导.Email:yangbaoping2004@163.com
基金资助:
国家自然科学基金(02-061608)

Synthesis of phosphorus-containing benzimidazole-based copper complex and properties of flame-retardant epoxy resin

YANG Bao-ping, CHEN Xiao-dong, WANG Nian-nian, CUI Jin-feng, GUO Jun-hong

College of Petrochemical Technology, Lanzhou Univ. of Tech., Lanzhou 730050, China

Received:2020-12-07 Online:2021-12-28 Published:2021-12-28

摘要/Abstract

摘要： 为了改性环氧树脂阻燃性能,通过取代反应和缩合反应制备一种新型含磷/氮二元杂化物—磷酸4-(1H-苯并咪唑-2-基)-苯基酯二苯酯(PBIm),并作为有机官能团与乙酸铜-水合物反应合成含磷苯并咪唑基铜配合物阻燃剂PBIm-Cu,将其添加到环氧树脂(EP)中,制备阻燃环氧树脂复合材料(PBIm-Cu/EP).通过红外光谱、X-射线光电子能谱、核磁氢谱和核磁磷谱对阻燃剂PBIm和PBIm-Cu进行结构表征.采用热重分析仪(TGA)、极限氧指数测定仪(LOI)和锥形量热仪(CCA)测试复合材料的热稳定性和阻燃性能.PBIm-Cu质量分数为7%的PBIm-Cu/EP体系在垂直燃烧测试中通过了 V-1级,LOI增加到31.6%,并且,峰值放热速率(PHRR)、总热释放量(THR)和总排烟量(TSP)较纯EP分别降低64%,41%和43%,残重率达到了26.7%.SEM 结果显示:PBIm-Cu/EP材料燃烧后碳层表面光滑连续且致密.

关键词: 阻燃剂, 有机金属配合物, 环氧树脂, 阻燃性能

Abstract: In order to modify the flame retardant property of epoxy resin, a new type of phosphorous/nitrogen dihydric compound, phosphoric acid 4-(1H-benzoimidazol-2-yl)-phenyl ester diphenyl ester (PBIm), was prepared by substitution reaction and condensation reaction, and used as an organic functional group to react with copper acetate-hydrate to synthesize phosphorus-containing benzimidazole-based copper complex flame retardant PBIm-Cu. It was added to epoxy resin (EP) to prepare flame retardant epoxy resin composite (PBIm-Cu /EP). The structure of the flame retardants PBIm and PBIm-Cu was characterized by infrared spectroscopy, X-ray photoelectron spectroscopy, hydrogen nuclear magnetic spectrum and phosphorus nuclear magnetic spectrum. Thermogravimetric analyzer (TGA), limiting oxygen index (LOI) and cone calorimeter (CCA) were used to test the thermal stability and flame retardancy of composite materials. The PBIm-Cu/EP system with a PBIm-Cu mass fraction of 7% passed the V-1 level in the vertical combustion test, and the LOI was increased to 31.6%. Moreover, compared with pure EP, the peak heat release rate (PHRR), total heat release rate (THR) and total smoke exhaust rate (TSP) were decreased by 64%, 41% and 43%, respectively, and the residual weight rate reached 26.7%. SEM results show that the surface of the carbon layer after the combustion of PBIm-Cu/EP material is smooth, continuous and dense.

Key words: flame retardant, organometallic complex, epoxy resin, flame retardant properties

中图分类号:

O633.13

杨保平,陈晓东,王念念,崔锦峰,郭军红. 含磷苯并咪唑基铜配合物合成及阻燃环氧树脂的性能[J]. 兰州理工大学学报, 2021, 47(6): 66-73.

YANG Bao-ping, CHEN Xiao-dong, WANG Nian-nian, CUI Jin-feng, GUO Jun-hong. Synthesis of phosphorus-containing benzimidazole-based copper complex and properties of flame-retardant epoxy resin[J]. Journal of Lanzhou University of Technology, 2021, 47(6): 66-73.

参考文献

[1] WAN J T,LI C,BU Z Y,et al.A comparative study of epoxy resin cured with a linear diamine and a branched polyamine [J].Chemical Engineering Journal,2012,188:160-172.
[2] GU H B,MA C,GU J W,et al.An overview of multifunctional epoxy nanocomposites [J].Journal of Materials Chemistry C,2016,4(25):5890-5906.
[3] WANG R,ZHUO D X,WANG Z X,et al.A novel nanosilica/graphene oxide hybrid and its flame retarding epoxy resin with simultaneously improved mechanical,thermal conductivity,and dielectric properties [J].Journal of Materials Chemistry A,2015,3(18):9826-9836.
[4] JIN F L,LI X,PARK S J,et al.Synthesis and application of epoxy resins:A review [J].Journal of Industrial and Engineering Chemistry,2015,29:1-11.
[5] LI A J,XU W Z,CHEN R,et al.Fabrication of zeolitic imidazolate frameworks on layered double hydroxide nanosheets to improve the fire safety of epoxy resin [J].Composites Part A- Applied Science and Manufacturing,2018,112:558-571.
[6] DAI J Y,PENG Y Y,TENG N,et al.High-performing and fire-resistant biobased epoxy resin from renewable sources [J].ACS Sustainable Chemistry & Engineering,2018,6(6):7589-7599.
[7] CUI J F,ZHANG Y B,WANG L R,et al.Phosphorus-containing Salen-Ni metal complexes enhancing the flame retardancy and smoke suppression of epoxy resin composites [J].Journal of Applied Polymer Science,2020,137(21):48734.
[8] NAIK A D,BOURBIGOT S,BELLAYER S,et al.Salen complexes as fire protective agents for thermoplastic polyurethane:deep electron paramagnetic resonance spectroscopy investigation [J].ACS applied materials & interfaces,2018,10(29):24860-24875.
[9] CAO Z H,ZHANG Y,ZHAO L P,et al.Improving the flame retardancy and mechanical properties of high-density polyethylene-g-maleic anhydride with a novel organic metal phosphonate [J].Journal of Analytical and Applied Pyrolysis,2013,102:154-160.
[10] LIAO D J,XU Q K,MCCABE R W,et al.Ferrocene-based nonphosphorus copolymer:synthesis,high-charring mechanism,and Its application in fire retardant epoxy resin [J].Industrial & Engineering Chemistry Research,2017,56:12630.
[11] LEI L,SHAN J,HU J,et al.Co-curing effect of imidazole grafting graphene oxide synthesized by one-pot method to reinforce epoxy nanocomposites [J].Composites Science & Technology,2016,128(18):161-168.
[12] CHENG J,WANG J,YANG S,et al.Benzimidazolyl-substituted cyclotriphosphazene derivative as latent flame-retardant curing agent for one-component epoxy resin system with excellent comprehensive performance [J].Composites Part B Engineering,2019,177:107440.
[13] TIAN L,LI X,WANG L,et al.Synthesis and characterization of an efficient flame retardant based on aromatic ring and phosphate ester for epoxy resin [J].Polymer Engineering and ence,2019,59:E406-E413.
[14] ZHANG Q Q,YANG S,WANG J,et al.A DOPO based reactive flame retardant constructed by multiple heteroaromatic groups and its application on epoxy resin:curing behavior,thermal degradation and flame retardancy [J].Polymer Degradation and Stability,2019,167:10-20.
[15] HUO S,WANG J,YANG S,et al.Synthesis of a DOPO-containing imidazole curing agent and its application in reactive flame retarded epoxy resin [J].Polymer Degradation and Stability,2019,159:79-89.
[16] SEMYONOV O,LYSSENKO K A,SAFIN D A.Copper(II) acetate structures with benzimidazole derivatives [J].Inorganica Chimica Acta,2019,448:238-245.
[17] YANG S,ZHANG Q,HU Y.Synthesis of a novel flame retardant containing phosphorus,nitrogen and boron and its application in flame-retardant epoxy resin [J].Polymer Degradation and Stability,2016,133:358-366.
[18] LIN X B,DU S L,TAN Y,et al.Semi-aromatic Polyamide Flame-retarded by Modified Red Phosphorus and BM@Al-PPi Hybrid with High Temperature Resistance [J].Acta Polymerica Sinica,2016,11:1522-1528.
[19] YOU Y G,CHENG Z Q,PENG H,et al.Synthesis and performance of a novel nitrogen-containing cyclic phosphate for intumescent flame retardant and its application in epoxy resin [J].Journal of Applied Polymer Science,2015,132:41859.
[20] WANG J,MA C,WANG P,et al.Ultra-low phosphorus loading to achieve the superior flame retardancy of epoxy resin [J].Polymer Degradation and Stability,2018,149(MAR):119-128.