9,10-2H-9-氧杂-10-磷杂菲-10-氧化物基1,3-苯并噁嗪树脂的合成与表征  

Synthesis and characterization of 9,10-2H-9-oxa-10-phosphaphenanthrene-10-oxide-(DOPO)-based 1,3-benzoxazine resin

作　　者：郭文征[1] 钟柳[1] 王浩[1] 李姜[2] 刘治国[1] 

机构地区：[1]西华大学物理与化学学院,四川成都610039 [2]四川大学高分子材料工程国家重点实验室,四川成都610039

出　　处：《化学研究》2014年第4期359-365,共7页Chemical Research

基　　金：西华大学重点资助项目(Z0723304);西华大学研究生创新基金(Ycjj201150);高分子材料工程国家重点实验室(四川大学)开放课题

摘　　要：以水杨醛、对甲基苯胺(或对氟苯胺,对甲氧基苯胺)、9,10-2H-9-氧-10-磷杂菲-10-氧化物(DOPO)及甲醛为原料,通过三步反应合成了三个含DOPO基的1,3-苯并噁嗪化合物3a-3c.第一步,水杨醛与对位取代苯胺进行缩合反应生成亚胺(1a-1c);第二步,DOPO对亚胺进行加成反应得到仲胺(2a-2c);第三步,仲胺与甲醛在强酸性离子交换树脂催化下进行关环反应形成含DOPO的1,3-苯并噁嗪树脂.采用红外光谱、核磁共振谱和质谱等表征了化合物3a-3c,同时采用热失重分析技术测定了其热稳定性.结果表明,3a-3c由两对对映体组成,质谱条件下2a-2c和3a-3c均经裂解失去稳定的DOPO基团;3a-3c热降解反应包含两个热失重过程,分别在250和400℃下出现最大热释放速率.DOPO（9,10-2H-9-oxa-10-phosphaphenanthrene-10-oxide）-containing 1,3-benzoxazine（3a-3c）resins were synthesized by a three-step procedure with 2-hydroxybenzaldehyde,p-methyl aniline（or p-fluoro aniline and p-methoxyl aniline）,formaldehyde and DOPO as raw materials.Therst step is the condensation of salicylaldehyde with p-substituted aniline,forming an intermediate imine（1a-1c）.The second step is the addition of DOPO to the imine resulting a secondary amine（2a-2c）.The third step involves the ring closure condensation catalyzed by strong acid ion exchange resin leading to DOPO-containing benzoxazine.The structures of various products were identified by Fourier transform infrared spectrometry,nuclear magnetic resonance spectrometry and mass spectrometry;and the thermal stability of 3a-3cwas examined by thermogravimetric analysis.It has been found that the DOPO-containing1,3-benzoxazine is composed of two pairs of enantiomers.DOPO fragment of 2a-2cand 3a-3cis lost under mass spectrometric conditions.Moreover,3a-3cundergo two stages of weight loss,and the highest heat release rates emerge at 250and 400℃,respectively.

关 键 词：含磷1 3-苯并噁嗪衍生物 热固性树脂 合成 表征 

分 类 号：TQ016.1[化学工程] TQ265.1