苯氧基改性聚氨基环三磷腈对环氧树脂固化物的阻燃作用  

Flame Retardancy of Polyamidocyclotriphosphazene Modified with Phenoxy in Epoxy Resin

作　　者：杨晶巍[1] 朱凤丽[1] 隋晓彤 毕伟[1] 唐林生[1] 

机构地区：[1]青岛科技大学化工学院,山东青岛266042

出　　处：《高分子材料科学与工程》2017年第7期53-58,64,共7页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(21276131)

摘　　要：通过极限氧指数(LOI)测定、垂直燃烧试验和锥形量热分析研究了苯氧基改性聚氨基环三磷腈(PPHACTPA)对酚醛胺固化环氧树脂(E-44/NX-2003)的阻燃作用,并与聚氨基环三磷腈(PHACTPA)进行了比较。结果表明,PPHACTPA对E-44/NX-2003的阻燃作用与PPHACTPA中苯氧基的数量有关。当每个磷腈环约含有1个苯氧基时(PPHACTPA-1),其阻燃作用略优于PHACTPA,而每个磷腈环所含苯氧基数增至2(PPHACTPA-2)时,其阻燃作用明显降低,差于PHACTPA。PHACTPA和PPHACTPA主要是通过凝聚相机理对E-44/NX-2003产生阻燃作用。阻燃剂在高温下生成具有强脱水作用的磷酸类化合物而促进环氧树脂固化物炭化,同时环氧体系分解生成的惰性气体使炭层发泡形成膨胀性炭层。这种致密的膨胀性炭层通过隔热隔氧及抑制环氧体系进一步地分解而产生阻燃作用。PPHACTPA-1更易转变成磷酸类化合物,因而促进成炭的能力更强,阻燃作用更好。PPHACTPA-2含磷量低,因而促进成炭的能力较差,阻燃作用较弱。The flame retardancy of polyamidocyclotriphosphazene modified with phenoxy （PPHACTPA） in epoxy resin cured with phenolic amine（E-44/NX-2003） was studied by limiting oxygen index （LOI） measurement, vertical burning test and cone calorimeter test（CCT）, and compared with polyaminocyclotriphosphazene （PHACTPA）. The results reveal that the flame retardancy of PPHACTPA in E-44/NX-2003 is related with the number of phenoxy groups. As a cyclotriphosphazene unit in PPHACTPA contains about a phenoxy（PPHACTPA-1）, its flame retardancy is slightly better than PHACTPA, but the number of phenoxy in the unit increases to about two（（PPHACTPA-2）, its flame retardancy becomes obviously poorer than that of PHACTPA. The analysis of the residues obtained in CCT reveals that PHACTPA and PPHACTPA play flame retardant effect mainly by condensed phase mechanism, where PHACTPA and PPHACTPA are decomposed into non-volatile phosphoric acid compounds in the process of combustion, which promotes the charring of E-44/NX-2003, and the char is changed into the intumescent layer by foaming of inert gases released from decomposition of the composite, which results in good condensed phase flame retardancy by the barrier effect on heat, air and decomposition products. PPHACTPA -1 is more easily decomposed into phosphoric acid compounds, then its promoting char-forming ability is stronger, so its flame retardancy is better. But the P content of PPHACTPA -2 is lower, so its promoting char-forming ability and flame retardancy are poorer.

关 键 词：聚氨基环三磷腈 苯氧基 改性 环氧树脂 阻燃作用 

分 类 号：TQ323.8[化学工程—合成树脂塑料工业]