碳硼烷双酚二缩水甘油醚的合成与表征及耐高温性能研究  

Synthesis,Characterization and High Temperature Resistance of Diglycidyl Ether of Carborane Bisphenol

作　　者：齐士成[1] 汪尧双 韩果[1] 杨震[1] 张孝阿[1] 江盛玲[1] 吕亚非[1] 

机构地区：[1]北京化工大学碳纤维及功能高分子教育部重点实验室材料科学与工程学院,北京100029

出　　处：《高分子学报》2015年第8期921-926,共6页Acta Polymerica Sinica

基　　金：中央高校基本科研业务费(项目号北京化工大学ZY-1310)资助项目

摘　　要：以o-(3)和m-碳硼烷双酚(4)为原料,经两步法合成了o-(1)和m-碳硼烷双酚二缩水甘油醚(2),FTIR、1H-NMR、GPC和环氧值测试都表明得到了预期结构的碳硼烷环氧树脂.固化反应动力学研究结果显示,1/DDS和2/DDS体系的反应活化能(Ea)分别为79.0和67.1 k J·mol-1,比E-51/DDS略高,说明碳硼烷结构的存在降低了环氧树脂的反应活性.以Ea结果为依据,确定了1(2)/DDS体系的固化工艺为180℃/2h+200℃/2h.热分析结果表明,以DDS为固化剂时,1和2的Tg分别为175.8和167.6℃,高于TDE-85的154.1℃.TGA结果表明,2/DDS固化物在空气气氛下700℃的残炭率高达78.7%,说明碳硼烷结构的存在极大提高了环氧树脂高温稳定性.碳硼烷环氧树脂空气气氛中的高温残炭率比氮气中高,原因是碳硼烷结构中的B-H键与空气中的氧气反应生成B—O—B结构,因而提高了残炭率,并在一定程度上延缓了体系的失重.Two diglycidyl ethers of carborane bispheno[s （1 and 2） were synthesized v/a a two-step method from carborane bisphenols and epichlorohydrin. The obtained carborane-containing epoxy resins were characterized with spectroscopic techniques including FTIR, 1H-NMR, and GPC which give satisfactory results. When the etherification step of the synthesis of 1 and 2 was conducted at 100℃ for 2 and 3 h respectively, resins with the highest epoxy value, 0. 366 for 1 and 0. 381 for 2, were obtained. 4,4＇- Diaminodiphenylsulfone （DDS） was utilized as curing agent and the curing kinetics studies show that the activation energy （E） of 1 /DDS and 2/DDS were calculated to be 79.0 and 67. 1 kJ· mol-1 which are higher than that of E-51/DDS, indicating that the carborane structure plays a negative role in the reactivity of epoxy resins. On the basis of Ea values, the optimum curing condition is determined to be 180℃/2h ＋ 200%/ 2h. DSC results show that Ts of 1 /DDS and 2/DDS are 175.8 and 167.6℃, which are higher than that of TDE-85 （ 154.1℃）. The introduction of carborane endows epoxy resin with ultrahigh char yield. Particularly, the char yield of the obtained carborane-containing epoxy resin under air is higher than that under nitrogen. For example, 2 shows char yield of 65.4% and 78.7% at 700℃ under nitrogen and air, respectively. This could be explained by the fact that the carborane cage could react with oxygen to form B--O--B structure, which further postpones the thermal decomposition of epoxy resin and accounts for the high char yield.

关 键 词：碳硼烷 环氧树脂 热稳定性 残炭率 

分 类 号：O633.13[理学—高分子化学]