磷氮阻燃剂GAP-DOPO的合成及其对环氧树脂阻燃性能

Synthesis of A New Phosphorus-nitrogen Flame Retardant GAP-DOPO and Its Flame Retardant Performance for Epoxy Resin

以3-氨基苯酚、戊二醛及9,10-2H-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料,制备了一种磷氮阻燃剂1,5-双(3-羟基苯氨基)-1,5-双{二苯并[c,e][1,2]氧杂膦-6-氧化物}戊烷(GAP-DOPO),对中间体1,5-双(3-羟基苯基亚胺基)戊烷(GAP)和GAP-DOPO的物料配比、溶剂用量、反应温度和反应时间进行了单因素考察,GAPDOPO的最佳合成条件为:n(GAP)∶n(DOPO)=1.0∶2.1,溶剂用量为GAP质量的10倍,反应温度为90℃,反应时间为6 h。通过FTIR、~1HNMR与TGA对阻燃剂的结构及热性能进行了表征;将GAP-DOPO用于阻燃环氧树脂(E-51),制备了3种阻燃环氧树脂复合材料EP1、EP2和EP3,并用TGA、SEM对复合材料的热性能及残炭结构进行了表征,使用垂直燃烧测试仪对试样进行了燃烧测试。结果表明:当w(GAP-DOPO)=30%时,EP3可通过UL94 V-0级测试;TGA结果显示,在800℃(N_2氛围)下,EP3残炭率为21.5%,与纯环氧树脂的16.3%相比,提高了31.9%;SEM结果表明:阻燃剂的加入能够明显改善环氧树脂燃烧后残炭形貌,GAP-DOPO能够提高环氧树脂的阻燃性能。

A new phosphorus-nitrogen flame retardant [1,5-bis（ 3-hydroxyphenyl） amino-1,5-bisdibenzo [c,e][1,2]oxaphosphine-6-oxide pentane,denoted as GAP-DOPO] was prepared with 3-aminophenol,glutaraldehyde and 9,10-2H-9-oxa-10-phospaphenanthrene-10-oxide（ DOPO） as raw materials. Ratio of raw materials,dosage of solvent,reaction temperature and reaction time of intermediate GAP and GAP-DOPO were investigated by using single-factor test. Yield of GAP-DOPO was maximum when n（ GAP） ∶ n（ DOPO） = 1. 0 ∶ 2. 1,m（ solvent） ∶ m（ GAP） = 10 ∶ 1,reaction temperature was 90 ℃ and reaction time was 6 h. Its structure and thermal properties were characterized by means of FTIR,1HNMR and TGA. And then as-prepared GAP-DOPO was added into epoxy resin（ EP） and cured products（ EP1、EP2 and EP3） were obtained. The thermal properties of cured products were investigated by TGA and the structure of carbon residue was characterized by SEM,The results indicated that when the added amount of GAP-DOPO was w（ GAP-DOPO） = 30%,the cured EP3 can meet the standard of UL94 V-0 class. TGA measurement showed that the carbonresidue rate of EP3 reached 21. 5% at 800 ℃（ N2 atmosphere）,which was an improvement of 31. 9%compared with that of pure EP（ 16. 3%）. And SEM result revealed that the addition of GAP-DOPO can obviously improve the carbon residue morphology after combustion,and GAP-DOPO can enhance the flame retardant properties of epoxy resin.