环三磷腈和DOPS双基协同阻燃对环氧树脂性能的影响  

Synergistic Flame Retardant Effect of Cyclotriphosphazene and DOPS Double Functional Groups on Epoxy Resin

作　　者：侯泽明 许志彦 祁钰昭 许松江 叶小林[1] 宝冬梅[1] 张道海 蔡晓东 周国永 邹光龙[1] 文竹 Zeming Hou;Zhiyan Xu;Yuzhao Qi;Songjiang Xu;Xiaolin Ye;Dongmei Bao;Daohai Zhang;Xiaodong Cai;Guoyong Zhou;Guanglong Zou;Zhu Wen(School of Chemical Engineering,Guizhou Minzu University,Guiyang 550025,China)

机构地区：[1]贵州民族大学化学工程学院,贵州贵阳550025

出　　处：《高分子材料科学与工程》2023年第4期40-49,共10页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(51863004,52163001);贵州省省级科技计划项目(黔科合基础[2020]1Y211,ZK[2021]一般248,ZK[2022]216;黔科合平台人才-CXTD[2021]005);贵州民族大学高分子复合材料工程研究中心(GZMUGCZX[2021]-01)。

摘　　要：为了提高环氧树脂(EP)的阻燃性能,将双基阻燃剂六(4-(9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物)-羟甲基苯氧基)环三磷腈(HAP-DOPS)和六苯氧基环三磷腈(HPCTP)/9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(DOPS)分别添加到EP中,在含磷量为1.8%(质量分数)时,对比研究了磷腈、磷杂菲基团在分子内和分子间双基协同阻燃对EP性能的影响,探索了其阻燃规律,同时研究了不同添加量的HAP-DOPS对EP的热稳定性、阻燃性能和成炭性能的影响,并分析了其阻燃机理。结果表明,15%HAP-DOPS/EP的极限氧指数(LOI)值提高至31.4%,垂直燃烧测试(UL-94)达到V-0级;当HPCTP/DOPS/EP的含磷量为1.8%,PHPCTP∶PDOPS=1∶1时,复合体系的LOI值为31.2%,达到UL-94 V-0级,即阻燃剂HAP-DOPS和HPCTP/DOPS均能有效改善EP的阻燃性能,但HAP-DOPS在降低热释放方面更有优势,HAP-DOPS/EP的潜在火灾危险性低于HPCTP/DOPS/EP。残炭分析结果表明,HAP-DOPS/EP的成炭能力和炭层质量均优于HPCTP/DOPS/EP,在凝聚相的阻燃效果更优异。阻燃机理研究表明,HAP-DOPS通过在气相中的稀释作用、自由基猝灭作用和凝聚相中炭层的屏蔽作用发挥协同阻燃作用。因此,HAP-DOPS/EP体系中的磷腈、磷杂菲双官能团在气相和凝聚相发挥了协同阻燃作用,而HPCTP/DOPS/EP则以凝聚相阻燃作用为主。In order to improve the flame retardancy of epoxy resin(EP),the flame retardants with double functional groups,hexa(4-(9,10-dihydro-9-oxa-10-hosphaphenanthrene-10-sulfide)-hydroxymethylphenoxy)cyclotriphosphazene(HAP-DOPS)and hexaphenoxy cyclotriphosphazene(HPCTP)/9,10-dihydro-9-oxa-10-phosphophene-10-sulfide(DOPS)with the phosphorus mass fraction of 1.8%were respectively added to EP by melt blending.The effects of intermolecular and intramolecular synergistic flame retardancy of phosphazene and phosphoheterophene on EP were studied,and the flame retardancy,thermal degradation behavior and char residues of HAP-DOPS/EP with different mass fractions of HAP-DOPS were investigated.At last,the flame retardant mechanism was analyzed.The experimental results show that both HAP-DOPS and HPCTP/DOPS can effectively improve the flame retardancy of EP.But HAP-DOPS is better in reducing heat release,and the potential fire risk of HPCTP/DOPS/EP is higher than that of HAP-DOPS/EP.The results of char residue analysis show that HAP-DOPS/EP has better char forming ability and char layer quality than HPCTP/DOPS/EP,and exhibits excellent flame retardant effect in condensed phase.The study of flame retardant mechanism shows that when HAP-DOPS is added to EP,its diluting effect in gaseous phase,quenching effect of free radical and shielding effect of char layer in condensed phase play a synergistic flame retardant effect.Therefore,the flame retardant HAP-DOPS plays a synergistic flame retardant role both in the gas phase and condensed phase,while HPCTP/DOPS mainly in the condensed phase.

关 键 词：DOPS 磷腈 环氧树脂 协同阻燃 双基阻燃剂 

分 类 号：TQ323.5[化学工程—合成树脂塑料工业]