欢迎登录材料期刊网

材料期刊网

高级检索

9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物简称DOPO,此种化合物及其衍生物在阻燃剂领域中因其低烟、低毒的特点而备受青睐。本文将DOPO、多聚甲醛、二乙醇胺反应合成出一种含氮含磷反应型DOPO类阻燃剂,对其结构进行了表征,并初步研究了这种物质在空气气氛中的耐热性能,结果表明,该产物在182.35℃开始分解,到700℃剩余7.22%。将其加入到聚氨酯中制备复合材料,在氮气气氛中进行热重测试,发现随着其用量加大,复合材料的初始分解温度先增高后降低,失重台阶的降解活化能也是先增加后降低,且都比纯粹聚氨酯的高,证明添加此种阻燃剂之后起到了一定的耐热效果,且当添加量为4%时综合性能最好;然后探讨了复合材料降解过程的机理。对4%添加量的复合材料在空气气氛中进行热重测试,发现其在227.2℃开始分解,主要有两大失重平台,分别失重26.01%和18.14%,在700℃时还剩余8.57%。

9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide( DOPO) and its derivatives are highly at-tracted because of its smokeless and toxicityless properties in the flame retardant field. A reactive nitrogen-phos-phorus-contained DOPO-based flame retardant was synthesized with DOPO,paraformaldehyde and diethanolamine. The structure has been characterized,and the thermal properties were studied. The results showed that this product begins to decompose in 182. 35℃,it remaining 7. 22% at 700℃. When it was added to the polyurethane,the com-posite materials were produced,according to their TGA results in nitrogen,we found that the decomposition tempera-ture of the composite material is firstly increased and then decreased,the same as their weightlessness stepped deg-radation activation energy,and they are all higher than pure polyurethane,so it was proved that this composite play a certain flame-retardant effect after adding such flame retardants in polyurethane,when its content is 4%,the best overall performance were get. Then the mechanism of the degradation process of the composite material was ex-plored. At last,the TGA results in air atmosphere was get when the dosage of this kind of flame retardant was 4%, we found that it decomposed at 227. 2℃, there are two weight loss platform, the weight loss were 26. 01% and 18. 14% respectively,the remaining was 8. 57% at 700℃.

参考文献

[1] Shui-Yu Lu;Ian Hamerton .Recent developments in the chemistry of halogen-free flame retardant polymers[J].Progress in Polymer Science,2002(8):1661-1712.
[2] 梁晓峰,权英,邵有林,梁彤祥.氢氧化镁基有机无机复合阻燃剂的制备[J].科技导报,2006(07):82-84.
[3] Ding J P;Tao Z Q;Fan L;Yang S Y .Preparation and characterization of flame retardant epoxy res-ins based on phosphorus-containing biphenyl-type phenolic resin[J].E-POLYMERS,2010,122:1-13.
[4] Liancheng Yang;Longhe Xu;Zaizhou Tao .Palladium-Catalyzed Arylation of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with Halogen-Substituted Phenols[J].Phosphorus, Sulfur, and Silicon and the Related Elements,2009(12):3175-3181.
[5] Yana Bykov;Sebastian Wagner;Olaf Walter .Synthesis of NewDibenzo[c.e][1,2]oxaphosphorine 2-oxideContaining Diols Based on Diethanolamine[J].Heteroatom Chemistry,2012(2):146-153.
[6] Lin C H;Lin H T;Chang S L;Hu Y M .Phosphor-us-containing benzoxazine-based bisphenols,de-rivatives thereof,and preparing method for the same[P].US,20110257347A1,2011.
[7] Lin C H;Taso Y R;Hsieh C W;Lee H H Su F H Tu A P Hwang K Y .Novel Phosphorus-based oxazine compounds and preparation method and the same[P].US,20090171120A1,2008.
[8] Lin C H;Lin T L;Chang C W;Hwang K Y Tu A P Su F H .Novel Phosphorus-containing com-pounds and their preparing process and use[P].US,20090258997A1,2008.
[9] Johannes Artner;Michael Ciesielski;Olaf Walter .A Novel DOPO-Based Diamine as Hardener and Flame Retardant for Epoxy Resin Systems[J].Macromolecular materials and engineering,2008(6):503-514.
[10] Xin Wang;Yuan Hu;Lei Song;Weiyi Xing;Hongdian Lu .Thermal degradation mechanism of flame retarded epoxy resins with a DOPO-substitued organophosphorus oligomer by TG-FTIR and DP-MS[J].Journal of analytical & applied pyrolysis,2011(1):164-170.
[11] Wang, X.;Hu, Y.;Song, L.;Xing, W.;Lu, H.;Lv, P.;Jie, G. .Flame retardancy and thermal degradation mechanism of epoxy resin composites based on a DOPO substituted organophosphorus oligomer[J].Polymer: The International Journal for the Science and Technology of Polymers,2010(11):2435-2445.
[12] Perez RM;Sandler JKW;Altstadt V;Hoffmann T;Pospiech D;Ciesielski M;Doring M .Effect of DOP-based compounds on fire retardancy, thermal stability, and mechanical properties of DGEBA cured with 4,4 '-DDS[J].Journal of Materials Science,2006(2):341-353.
[13] Lin, C.H.;Chang, S.L.;Wei, T.P. .High-T_g transparent poly(ether sulfone)s based on phosphinated bisphenols[J].Macromolecular chemistry and physics,2011(5):455-464.
[14] 田立云.无溶剂聚氨酯复合粘合剂研究[J].塑料包装,2011(01):38-40.
[15] 石红翠,贾金兰,毛祖秋,郭晓勇.打印涂层用聚氨酯胶粘剂的合成[J].涂料工业,2011(01):21-23.
[16] 许春华.聚氨酯胎面--复合橡胶轮胎技术进展[J].中国橡胶,2011(09):11-12.
[17] 刘益军.阻燃聚氨酯泡沫垫圈[J].聚氨酯工业,1999(01):39.
[18] M. Boutin;J. Lesage;C. Ostiguy;J. Pauluhn;M.J. Bertrand .Identification of the isocyanates generated during the thermal degradation of a polyurethane car paint[J].Journal of analytical & applied pyrolysis,2004(2):791-802.
[19] Parsons NS;Lam MH;Hamilton SE;Hui F .A preliminary investigation into the comparison of dissolution/digestion techniques for the chemical characterization of polyurethane foam.[J].Science & justice: journal of the Forensic Science Society,2010(4):177-181.
[20] M. Dressier;S. Reinsch;R. Schadrack .Burnout behavior of ceramic coated open cell polyurethane (PU) sponges[J].Journal of the European Ceramic Society,2009(16):3333-3339.
[21] V.S. Dagostin;D.L. Golcalves;C.B. Pacheco;W.B. Almeida;I.P. Thome;C.T. Pich;M.M.S. Paula;L. Silva;E. Angioletto;M.A. Fiori .Bactericidal polyurethane foam mattresses: Microbiological characterization and effectiveness[J].Materials science & engineering. C, Biomimetic and supramolecular systems,2010(5):705-708.
[22] M.C. Swinton;W. Maref;M. T. Bomberg;M. K. Kumaran;N. Normandin .In situ performance evaluation of spray polyurethane foam in the exterior insulation basement system (EIBS)[J].Building and environment,2006(12):1872-1880.
[23] 胡荣祖;高胜利;赵凤起.热分析动力学[M].北京:科学出版社,2008:81-82,63-64.
[24] 闪海威,陈栋华,唐万军.MC2O4(M=Mn、Fe、Co、Ni、Cu、Zn)的热力学及其热分析动力学[J].物理化学学报,2005(09):1001-1005.
[25] 张伟南,袁誉洪,李丽清,陈栋华.二水草酸锌脱水的热分解动力学研究[J].物理化学学报,2004(01):33-37.
[26] 李靖华;张桂恩.固体热分解反应动力学的研究(Ⅰ)一水合草酸钾脱水过程的动力学[J].河南师范大学学报(自然科学版),1991(03):40-45.
[27] 李靖华;张桂恩;王革命 等.二水合草酸锰脱水过程的机理函数判别和动力学研究[J].河南师范大学学报(自然科学版),1992,20:79-83.
[28] 相益信,冯绍华,冯厂.聚氨酯/三聚氰胺甲醛树脂复合泡沫热降解动力学研究[J].聚氨酯工业,2011(03):22-25.
上一张 下一张
上一张 下一张
计量
  • 下载量()
  • 访问量()
文章评分
  • 您的评分:
  • 1
    0%
  • 2
    0%
  • 3
    0%
  • 4
    0%
  • 5
    0%