透明含磷环氧树脂的制备及其阻燃性能  

Preparation and Flame-Retardant Performance of Transparent Flame-Retardant Epoxy Resins Containing Phosphorus

作　　者：李亮[1,2] 蔡再生 LI Liang;CAI Zaisheng(School of Pharmacy,Y ancheng Polytechnic College,Yancheng,Jiangsu 224005,China;College of Chemistry,Chemical Engineering and Biotechnology,Donghua Universily,Shanghai 201620,China)

机构地区：[1]盐城工业职业技术学院,药品与健康学院,江苏盐城224005 [2]东华大学,化学化工与生物工程学院,上海201620

出　　处：《塑料》2020年第5期58-63,共6页Plastics

基　　金：江苏省高等学校自然科学研究面上项目(19KJD430009);盐城工业职业技术学院自然科学课题(ygy1702)。

摘　　要：以9,10-二氢-9-氧代-10-磷杂菲-10-氧化物(DOPO)、水杨醛、4,4’-二氨基二苯砜(DDS)为主要原料,合成了一种含磷氮环氧树脂固化添加剂DSD,固化后制备出了一系列EP-DSD阻燃环氧树脂。采用傅里叶变换衰减全反射红外光谱法(ATR-FTIR)、核磁共振(NMR)等测试方法对DSD的化学结构进行了表征。极限氧指数(LOI)和UL 94测试结果表明,当DSD含量为9%时,LOI值达到35.4%,达到了UL 94的V-0级,此时EP-DSD复合环氧树脂具有较短的续燃时间和较好的阻燃性能。在残炭的SEM照片中,观察到了一个膨胀、致密且多孔的炭层。热重分析结果表明,EP-DSD热固性材料的提前分解,使最大失重率降低,残炭量分别提高至空气气氛下的3.98%及氮气气氛下的22.87%。热裂解分析表明,裂解过程中产生了含磷分子,在气相中抑制了燃烧自由基反应。拉伸测试结果表明,EP-DSD复合树脂的拉伸强度提高至88.83 MPa,但断裂延伸率下降。在凝聚相中,促进了膨胀、致密炭层的形成及残炭量的提高;在气相中,含磷分子抑制了燃烧自由基反应,提高了EP-DSD复合环氧树脂的阻燃性能。A flame retardant additive defined as DSD was successfully synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide( DOPO),4,4’-diaminodiphenyl sulfone( DDS) and salicylaldehyde. DSD was used as an amine curing agent,and the transparent,strength-enhanced epoxy resins named EP-DSD were prepared via thermal curing reactions among EP,4,4-Diaminodiphenyl methane( DDM) and DSD. The chemical structure of DSD was characterized by FTIR-ATR,and NMR. When the content of DSD reached 9%,the LOI values of EP-DSD composite reached 35. 4%,and a V-0 flammability rating passed in the UL 94 vertical test. SEM photographs of char residues after UL 94 test indicate that an intumescent and tight char layer with honeycombed cavity inside was formed. The TGA results reveal that EP-DSD thermosets decomposed ahead of time,and char yield was increased to 3. 98% in air and 22. 87% in nitrogen,respectively. The measurement of tensile strength at break showed that the tensile strength of epoxy thermosets was increases to 88. 83 MPa,but the elongation at break decreased. Py-GC/MS analysis showed that phosphorus fragments released in the decomposition of EPDSD thermosets,which could inhibit the free radical reaction in the gas phase. Owing to the formation of intumescent and compact char residuesin condensed phase and nonflammable phosphorusfragments formed from decomposition of DOPO groups,EP-DSD composite displayed obvious flame-retardancy.

关 键 词：环氧树脂 热固性树脂 DOPO 阻燃剂 协同效应 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]