DH-DOPO阻燃剂的合成及对醇酸树脂的阻燃研究.pdf

第44卷第8期
塑料工业
2016年8月
CHINA PLASTICS INDUSTRY
DALDOPO阻燃剂的合成及对醇酸树脂的阻燃硏究
傅应オ2,李洋,付园园',康文东,王勇“,张峰
(1.青岛科技大学环境与安全工程学院,山东青岛26042
2.灭火救援技术公安部重点实验室,河北廊坊065000
3.东营联合石化有限责任公司,山东东营257200)
摘要:以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、多聚甲醛和二乙醇胺合成了反应型阻燃剂9
10-二氢-9-氧杂-10-[N,N-ニ(羟乙基)氨甲基]-10-磷杂非-10-氧化物(DH-DOPO),采用红外光谱仪和核磁
共振波谱仪对其结构进行了表征,热重分析表明其失重1%的热解温度高达220℃。将DH-DOPO作为反应型阻燃剂
制备了阻燃醇酸树脂,锥形量热仪测试结果表明,DH-D0OPO提高了醇酸树脂的阻燃性能,并且随磷含量增加,点燃
时间(YD)和残炭率(CR)不断增加,热释放速率峰值(PHRR)和总热释放(THR)不断下降。
关键词:9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物;阻燃剂;醇酸树脂
doi;10.3969/j,isn.1005-5770.2016.08.026
中图分类号:TQ314.248;TQ3224文献标识码:A文章编号:1005-5770(2016)08-011-04
Synthesis of DH-DOPO and Its Flame Retardant Effects on Alkyd Resin
FU Ying-cai*, LI Yang, FU Yuan-yuan, KANG Wen-dong, WANG Yong, ZHANG Feng
1. College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
2. Key Laboratory of Fire Prevention and Rescue Technology, Ministry of Public Security, Lan fang 065000, China
3. Dongying United Petrochemical Company Limited, Dongying 257200, China
Abstract: A reactive flame retardant(dh-dopo was synthesized from 9, 10-dihydro-9-oxa-10
hosphaphenanthrene-10-oxide ( DOPO ) polyoxymethylene and diethanolamine. The structure of DH
DOPO was identified by Fourier transform infrared spectroscopy(FTIR) and nuclear magnetic resonance
pecos (H-M) Thermo ravimetric analysis shows that the temperature for 1%mass loss of DH
DOPO is as high as 220 C: Flame retarded alkyd resins were prepared by adding DH-DOPO as a reactant in
alkyd resin. The cone calorimeter test results indicate that the flame retardancy of alkyd resin is improved by
adding DH-DOPO. As phosphorus content increases, the time to ignition and char residue increase, and the
eak heat release rate and total heat release decrease
Keywords: 9, 10-ih ro-9-oxa-10-phosphaphenanthrene-10-oxide; Flame Retardant; Alkyd Resin
醇酸树脂合成原料来源广泛,合成技术成熟,能多溴代二苯并呋喃(PBDF),大大限制了它们的应
溶于多种溶剂,可以涂装于几乎所有的木材和金属表用。因此,具有无卤特性的磷系阻燃剂、氮系阻燃
面,在传统的涂料领域中占据重要的地位。但是,绝剂、无机填充阻燃剂等环境友好型阻燃剂开始受到人
大多数的聚合物都是易燃或可燃的,醇酸树脂也不例们的关注,而其中有机磷系阻燃剂因其低毒、低烟
外。因此,对醇酸树脂进行阻燃改性始终是人们研究无卤等优点更是人们研究的重点。最早 Toranosuke
的热点。卤素阻燃剂因其阻燃效率高、适用范围
合成了DOPO阻燃剂,其分子上的两个萃环与P=0
价格低廉而得到人们的青睐,然而卤素阻燃剂在使用键共轭形成了大π键,使P原子的电子云密度增加,
过程中产生的烟、腐蚀性气体和有毒气体较多,燃烧P一H键的H极易失去,发生亲核加成反应,能够形
产物中含有致癌物多溴代二苯并二恶英(PBDD)及成种类繁多具有阻燃特性的DOPO衍生物24,其热
*国家自然科学基金(51306097),山东省自然科学基金(ZR2014EEM037),灭火救授技术公安部重点实验室基金
(KF201405)*通信联系人85453608@qq.com
作者简介:傅应才,男,硕士研究生,主要从事聚合物阻燃研究。1015236582@qq,com