摘要
环氧树脂是一种十分重要的传统材料,广泛应用胶黏剂、涂料以及复合材料等各个方面。但其阻燃性能差,限制了应用范围,因此,对其进行阻燃改性是研究的重点问题。由于磷元素阻燃效率高,且燃烧时放出的毒气少,对环境和人体友好,所以近年来得到了广泛的关注。
本文旨在合成一种高磷含量的环氧树脂,可以将其作为阻燃剂添加到普通环氧树脂中使用。采用甲基膦酸二甲酯(DMMP)、乙二醇(EG)为原料,先合成出不同分子链长的端羟基膦酸酯中间体,然后使此中间体与环氧氯丙烷(ECH)反应,合成出含磷环氧树脂,并分别研究了它们对普通环氧树脂的阻燃性能和力学性能的影响。具体内容如下：
利用DMMP和EG的酯交换缩聚反应,制得不同分子量的端羟基膦酸酯中间体,讨论了合成条件,并采用羟值滴定、红外(FTIR)、核磁(1H-NMR)方法表征了其结构。其中,反应条件为：合成温度为170-180℃,催化剂用量为原料总质量的1wt%,反应时间为5个小时。
将第一步得到的三种中间体与环氧氯丙烷反应,经过一个两步反应制得含磷环氧树脂。讨论了合成条件,并采用环氧值滴定、红外(FTIR)、核磁(1H-NMR)方法表征了其结构。其中,反应条件为：催化剂三氟化硼乙醚的用量为0.6ml,氢氧化钠溶液的质量分数为40%。
将合成产物添加到普通环氧树脂E-51中,考查了磷含量对树脂阻燃性和力学性能的影响,其中,当材料的磷含量为1.0%左右时,材料的极限氧指数都超过27.0,已成为阻燃材料,当磷含量为3.0%左右时,材料的极限氧指数最高可达32.0,阻燃效果优异；拉伸强度稍有降低,断裂伸长率提高。
Epoxy resin is a very important traditional material, and is widely used inadhesives, coatings and conmposites. But epoxy has a poor flame retardant,which limites its application, so it is very important to improve this property.As phosphorus-containing compounds produce few harmful gases, and theyare much effective, so organic phosphorus is paid more attention.In this paper, a novel phosphorus-containing epoxy resin is synthesized, whichcan be mixed with other epoxy resins as flame retardant. DMMP and EG werefirst used to synthesize intermediate, then ECH was employed as rawmaterials to synthesize phosphorus-containing epoxy resin. With differentmolar ratio of EG/DMMP, three kinds of products were obtained. Theirinfluences to epoxy resin were investigated.
Intermediate with different molecular weight were synthesized throughtransesterification of DMMP and EG. Synthetic technology was determined:temprature at170-180, the amount of catalyst was1wt%of the total massof raw materials, and the reaction time was5h. Structures of the intermediatewere confirmed by hydroxyl value titration, FTIR and1H-NMR.Three intermediate obtained in the first step were reacted with ECH to synthesize phosphorus-containing epoxy resin. Synthetic technology wasdetermined: the amount of catalyst was0.6ml, mass fraction of NaOH was40%, and temprature of ring-close reaction was30. Structures of productswere confirmed by epoxy value titration, FTIR and1H-NMR.
The synthesized phosphorus-containing epoxy resin was mixed withepoxy resin E-51, LOI, tensile strength and elongation of cured products weretested. When phosphorus content was3%, LOI of32.0could be reached,while tensile strength reduced slightly, but elongation increased.
引文
[1]Ellis, B. Chemistry and Technology of Epoxy Resin[M]. Blackie Academic&Professional: London, UK:1993
[2]Muriel Rakotomalala, Sebastian Wagner, Manfred Doring. Recent Developments in Halogen Free Flame Retardants for Epoxy Resins for Electrical and Electronic Applications[J]. Materials.2010,3:4300-4327
[3]张瑞鹏.阻燃环氧树脂体系的研究进展[J].科技信息,2010(26)：594
[4]王晨,夏英,侯传金,等.环氧树脂无卤阻燃化的研究[J].塑料制造,2011,(11)：53-56
[5]王红娟.含磷环氧树脂制备、表征与应用研究[D].南京：南京理工大学,2005
[6]Leisegang, E.C., Stephen, A.M. The Thermal Degradation In Vacuo of an Amine-Cured Epoxide Resin[J].Appl. Polym. Sci.1970,14:1961-1981
[7]Ulrike Braun. Influence of the oxidation state of phosphorus on the decomposition and fire behavioru of flame-retarded epoxy rersin composites [J]. Polymer,2006,47:8495-8508
[8]梁静.环氧值滴定ODOPB合成含磷菲环环氧树脂制备、表征及性能研究[D].南京：南京理工大学,2007
[9]张奎.萘基环氧树脂体系的合成与性能研究[D].广州：华南师范大学,2009
[10]Gannon J. Epoxy resins, in encyclopedia of chemical technology [J]. John Wiley&Sons, New York,1994:730
[11]李晶.防腐阻燃型玻璃鳞片/环氧涂料的性能研究[D].北京：北京化工大学,2009
[12]王德中.环氧树脂生产与应用[M].北京：化学工业出版社,2001：230
[13]王建祺等.无卤阻燃聚合物基础与应用[M].北京：科学出版社,2005
[14]欧育湘,陈宇,王筱梅.阻燃高分子材料[M].北京：国防工业出版社,2001：12-14
[15]谭壬海.含磷阻燃剂DOPO的合成及在环氧树脂中的应用[D].湘潭：湘潭大学,2008
[16]Vogt, J. Thermal analysis of epoxy-resins:Identification of decomposition products[J]. Thermochim. Acta1985,85:411-414
[17]Ming Gao, Weihong Wu, Fachao Wu. Thermal degradation and flame retardance of epoxy resins containing a microencapsulated flame retardant[J]. Journal of vinyl and additive technology,2012,18(1):40-45
[18]Lingang Liu, Xiao Wang, Shousheng Yang, et. al. Synthesis and application of novel arborescent monomolecular P-N intumescent flame retardant[J]. Acta chimica sinica,2012,70(2):190-194
[19]Jun Li, Hongfang Zhu, Li Juan, et. al. Thermal degradation behaviors of phosphorus-silicon synergistic flame-retardant copolyester[J]. Journal of applied polymer science,2011,122(3):1993-2003
[20]Dechao Sun, Youwei Yao. Synthesis of three novel phosphorus-containing flame retardants and their application in epoxy resins Polymer degradation and stability,2011,96(10):1720-1724
[21]Vandersall, H.L. Intumescent coating systems, their development and chemistry. J. Fire Flammabilitv1971,2:97-105
[22]Koennicke Daniela, Kuehn Alexandra, Mahrholz Thorsten, et. al. Polymer nanocomposites based on epoxy resin and ATH as a new flame retardant for CFRP: preparation and thermal characterisation[J]. Journal of materials science,2011,46(21):7046-7055
[23]杨宋,黄荣辉,李兴敏,等.超细氢氧化铝对无卤覆铜板性能的影响[J].铜箔与层压板,2010,(8)：27-30
[24]Bourbigot, S., Le Bras, M., Leeuwendal, R.et. al.. Recent advances in the use of zinc borates in flame retardancy of EVA. Polym[J]. Degrad. Stab.1999,64:419-425
[25]王海龙.热固/光固型磷系阻燃剂的合成及其性能研究[D].合肥：中国科学技术大学,2009
[26]Zhixiang Shi, Renli Fu, Simen Agathopoulos, et. al. Thermal conductivity and fire resistance of epoxy molding compounds filled with Si3N4and Al(OH)3[J]. Materials&design,2012,34:820-824
[27]Levchik, S.V., Levchik, G.F., Balanovich, A.I. et. al.. Mechanistic study of combustion performance and thermal decomposition behaviour of nylon6with added halogen-free fire retardants[J]. Polym. Degrad. Stab.1996,54:217-222
[28]刘玉桂,任元林.无卤环保型阻燃环氧树脂的研究进展[J].天津工业大学学报,2011,30(1)：74-78
[29]张英,都佳,郝文涛POSS改性环氧树脂的耐热性研究进展[J].塑料助剂,2011,(3)：17-22
[30]王铁飞,侯琳熙,刘燕.印制板粘胶剂阻燃性的研究进展[J].广东化工,2011,38(2)：64-65
[31]Wei Yao, Aijuan Gu, Guozheng Liang, et. al. Preparation and properties of hollow silica tubes/bismaleimide/diallylbisphenol A composites with improved toughness, dielectric properties, and flame retardancy[J]. Polymers for advanced technologies,2012,23(3):326-335
[32]Ka Zhang, Minmin Shen, Kun Wu. Comparative study on flame retardancy and thermal degradation of phosphorus-and silicon-containing epoxy resin composites [J]. Journal of polymer research,2011,18(6):2061-2070
[33]Tingting zhang, Weiwei Men, Ying Liu, Zaijun Lu. Synthesis and characterization of polybenzoxazine containing phosphorus [J]. Chinese and materials science,2012,30,(2):250-257
[34]Dan Yu, Kleemeier Malte, Guangmei Wu, et. al. Phosphorus and silicon containing low-melting organic-inorganic glasses improve flame retardancy of epoxy/clay composites [J]. Macromolecular materials and engineering,2011,296(10):952-964
[35]卢林刚,李铃,舒仲俊,等.无卤磷系阻燃环氧树脂的制备及阻燃性能[J].高分子材料科学与工程,2010,26(5)：158-161
[36]王国建,黄演.透明膨胀型防火涂料国内外研究进展[J].材料导报A：综述篇,2011,25：58-63
[37]Xueqing Liu; Jiyan Liu; Shan Sun. A new type of flame retarded epoxy resin based on metal phosphinates[A]. In:Polymers&polymer composites[C]. Jinnan:1st International Congress on advanced materials,2011,20:151-154
[38]白向鸽,陈连喜,黄世帅.阻燃型胺类环氧树脂固化剂的研究进展[J].粘接,2011(5)：73-76
[39]Huan Liu, Kai Xu, Hualun Cai, et. al. Thermal properties and flame retardancy of novel epoxy based on phosphorus-modified Schiff-base[J]. Polymers for advanced technologies,2012,23(1):114-121
[40]Xin Zhao, Yajie Lei, Rui Zhao, Jiachun Zhong, Xiaobo Liu. Preparation and properties of halogen-free flame-retarded phthalonitrile-epoxy blends [J]. Journal of applied polymer science,2012,123(6):3580-3586
[41]XileiChen, Chuanmei Jiao, Shaoxiang Li, et. al. Flame retardant epoxy resins from bisphenol-A epoxy cured with hyperbranched polyphosphate ester [J]. Journal of polymer research,2011,18(6):2229-2237
[42]蔡少君,范敦贵,刘学清,等.2-甲基-2,5-二氧-1,2-氧磷杂环戊烷阻燃及固化环氧树脂研究[J].2011,25(11)：86-89
[43]Meenakshi K. Shree, Sudhan E. Pradeep Jaya, Kumar S. Ananda, et. al. Development and characterization of novel DOPO based phosphorus tetraglycidyl epoxy nanocomposites for aerospace applications [J]. Progress in organic coatings,2011,72(3):402-409
[44]钱立军,叶龙健,韩鑫磊,等.基于磷杂菲基团化合物的构建与性能[J].化学进展,2010,22(9)：1776-1783
[45]Hou Chien Chang, Hung Tse Lin, Ching Hsuan Lin. Benzoxazine-based phosphinated bisphenols and their application in preparing flame-retardant, low dielectric cyanate ester thermosets[J]. Polymer Chemistry,2012,3(4):970-978
[46]Chen Zhang, Junyi Huang, Shumei Liu, et. al. The synthesis and properties of a reactive flame-retardant unsaturated polyester resin from a phosphorus-containing diacid[J]. Polymers for advanced technologies,2011,22(12):1768-1777
[47]Ciesielski, M., Diederichs, J., Doring, M., Schafer, A. Advanced Flame-Retardant Epoxy Resins for Composite Materials. In Fire and Polymers V. Materials and Concepts for Fire Retarancy; Wilkie, C.A., Morgan, A.B., Nelson, G.L., Eds.; ACS:Washington, DC, USA,2009:174-190
[48]Chunshan Wang, Ching Hsuan Lin. Synthesis and properties of phosphorus-containing epoxy resins by novel method[J].1999,37:3903-3909
[49]王宝仁,杨连成DOPO衍生物在阻燃环氧树脂中的应用研究进展[J].化工新型材料2010,38(3)：51-54
[50]Wenchao Zhang, Xiangmei Li, Rongjie Yang. Novel flame retardancy effects of DOPO-POSS on epoxy resins[J]. Polymer degradation and stability,96(12):2167-2173
[51]Lijun Qian, Longjian Ye, Yong Qiu, et. al. Thermal degradation behavior of the compound containing phosphaphenanthrene and phosphazene groups and its flame retardant mechanism on epoxy resin[J]. Polymer,2011,52(24):5486-5493
[52]陶志强,丁佳培,宋涛,等.DOPO衍生物阻燃性能研究[J].宇航材料工艺,2011,(1)：89-92
[53]Xiaodong Wang, Qiang Zhang. Synthesis, characterization, and cure properties of phosphorus-containing epoxy resins for flame retardance[J]. European Polymer Journal,2004,40:385-395
[54]Tsung-Han Ho, Hann-Jang Hwang, Jeng-Yueh Shieh et.al. Thermal and physical properties of flame-retardant epoxy resins containing2-(6-oxido-6H-dibenz<1,2>oxaphosphorin-6-yl)-1,4-naphthalenediol and cured with dicyanate ester[J]. Polymer Degradation and Stability,2008,93:2077-2083
[55]Seibold, S.; Schafer, A.; Walter, O.; Doring, M. Phosphorus-containing terephthaldialdehyde adducts-Structure determination and their application as flame retardants in epoxy resins. J. Appl. Polym. Sci.2008,108:264-271
[56]王昱,罗炎,张桢.阻燃型DOPO马来酸酐改性的环氧树脂研究[J].绝缘材料,2010,43(3)：20-28
[57]Xia, X.N.; Lu, Y.B.; Zhou, X.; Xiong, Y.Q.; Zhang, X.H.; Xu, W.J. Synthesis of novel phosphorous-containing biphenol,2-(5,5-dimethyl-4-phenyl-2-oxy-1,3,2-dioxaphosphorin-6-yl)-1,4-benzenediol and its application as flame-retardant in epoxy resin. Appl. Polym. Sci.2006,102:3842-3847
[58]夏新年,张小华,陈义红等.新型含磷阻燃环氧树脂的合成与表征[J].化工进展,2007,26(1)：56-59
[59]Chun-Shan Wang, Jeng-Yueh Shieh. Synthesis and properties of epoxy resins containing bis(3-hydroxyphenyl)phenyl phosphate[J]. European Polymer Journal,2000,36:443-452
[60]Liping Gao, Deyi Wang, YuzhongWang, et.al. A flame-retardant epoxy resin based on a reactive phosphorus-containing monomer of DODPP and its thermal and its thermal and flarne-retardant properties [J]. Polymer Degradation and Stability,2008,93(7):1308-1315
[61]刘继延,刘学清,石红.亚瞵酸酯环氧树脂的合成及性能[J].中国塑料,2011,25(5)：85-89
[62]M Jose'Alco'n, Gemma Ribera, Marina Galia'et.al. Synthesis, characterization and polymerization of isobutylbis(glycidylpropylether) phosphine oxide[J]. Polymer,2003,44:7291-7298
[63]李昕,欧育湘.双环笼状磷酸酯阻燃环氧树脂的燃烧行为研究[J].北京理工大学学报.2001,21(3)：388-391
[64]姜兴三,邱桂花,于名讯PEPA阻燃环氧树脂的性能研究[J].工程塑料应用,2009,37(6)：9-12
[65]钱立军,叶龙健,许国志,等.具有磷杂菲和磷腈双效官能团的新型阻燃助剂的合成及表征[J].化工新型材料,2010,38(8)：48-50
[66]Mustapha El Gouri, Abderrahim El Bachiri, Salah Eddine Hegazi, Mohamed Rafik, Ahmed El harfi. Thermal degradation of a reactive flame retardant based on cyclotriphosphazene and its blend with DGEBA epoxy resin[J]. Polymer Degradation and stability,2009,94:2101-2106
[67]秦强强.磷腈阻燃剂的合成及对环氧树脂的阻燃应用[D].北京：北京化工大学,2011
[68]Geeta Durga, Anudeep Kumar Narula. Synthesis and characterization of diamide-diimide-diamines based on p-amino benzoic acid and their curing and thermal behavior with epoxy blends containing phosphorus/silicon in the main chain [J]. Journal of applied polymer science,2012,124(5):3685-3694
[69]Zhenjie Wei, Weiqu Liu, Hongjing Li. Properties of phosphorus-containing organic silicon/epoxy hybrid resin[J]. Acta polymerica sinica,2012,(2):148-153
[70]Xin Wang; Yuan Hu; Lei Song. Preparation, flame retardancy, and thermal degradation of epoxy thermosets modified with phosphorous/nitrogen-containing glycidyl derivative [J]. Polymers for advanced technologies,2012,23(2):190-197
[71]Zongyue Yang, Bin Fei, Xiao wen Wang, et. al. A novel halogen-free and formaldehyde-free flame retardant for cotton fabrics[J]. Fire and materials,2012,36(1):31-39
[72]张卡,吴昆,张延奎,等.新型磷硅改性环氧树脂阻燃性能研究[J].热固性树脂,2011,26(6)：8-11
[73]王政芳,刘伟区,胡朝辉,等.含磷有机硅氧烷改性环氧树脂酚醛固化体系性能研究[J].中国塑料,2010,24(2)：42-46
[74]魏振杰,刘伟区,李宏静,等.含磷有机硅杂化环氧树脂固化体系性能研究[J].高分子学报,2012,(2)：148-153
[75]周晓.新型氮系/磷系阻燃环氧树脂的合成及性能研究[D].长沙：湖南大学,2006
[76]M Jose'Alco'n, Gemma Ribera, Marina Galia et.al. Synthesis, characterization and polymerization of isobutylbis(glycidylpropylether) phosphine oxide[J]. Polymer,2003,44:7291-7298
[77]张兴宏.高性能含氮阻燃环氧树脂/固化剂的合成、固化反应及结构性能与应用研究[D].杭州：浙江大学,2006
[78]Jiajun Ma; Junxiao Yang; YawenHuang. Aluminum-organophosphorus hybrid nanorods for simultaneously enhancing the flame retardancy and mechanical properties of epoxy resin[J]. Journal of materials chemistry,2012,22(5):2007-2017