双官能团液体脂环族环氧化合物的合成与性能  

SYNTHESIS AND PROPERTIES OF DIFUNCTIONAL CYCLOALIPHATIC EPOXIDES

作　　者：谢美然[1] 王忠刚[1] 赵云峰[1] 

机构地区：[1]中国科学院化学研究所分子科学中心,北京100080

出　　处：《高分子学报》2001年第4期517-522,共6页Acta Polymerica Sinica

基　　金：中国科学院重点资助项目 (编号 990 4);中国博士后基金资助项目

摘　　要：脂环族烯烃类化合物经过环氧化反应制备了三种液体脂环族环氧化合物 ,即 3,4 环氧环己基甲基 2′ ,3′ 环氧环己醚 (Ⅰe ) ,双 (2 ,3 环氧环己基 )醚 (Ⅱe )和双 (2 ,3 环氧环己烷 ) (Ⅲe ) .反应收率大于 80 % .用红外光谱、核磁共振谱、元素分析、环氧当量测定等方法证实了它们的结构 .三种环氧化合物在固化前都具有很低的粘度 (<10 0mPa·s ,2 5℃ ) ,用酸酐类固化剂热固化后得到的交联聚合物具有高的玻璃化转变温度 (Tg=15 0～ 180℃ )、低的线性热膨胀系数 (α1 =6 .0× 10 - 5 ～ 7.6× 10 - 5 ℃ ,α2 =14.5× 10 - 5 ～ 17.0× 10 - 5 ℃ )和较高的储存模量 (E′1 =2 .1～ 3.0GPa ,E′2 =0 .0 2 0～ 0 .0 33GPa) ,它们的总体性能好于国外同类产品ERL 42 2 1.在涂料。Three novel cycloaliphatic difunctional epoxides containing symmetric or asymmetric epoxycyclohexyl moieties linked with an ether bond or with a carbon-carbon bond, 3,4-epoxycyclohexylmethyl-2 ', 3 ' -epoxycyclohexyl ether (I e), bis(2,3-epoxycyclohexyl) ether (II e) and di(2,3-epoxycyclohexane) (II e) were synthesized by epoxidation of their corresponding dicycloolefin, respectively. Their precursor compounds, 3-cyclohexene-1-methyl-2 ' -cyclohexene ether (I), bis (2-cyclohexenyl) ether (II), and di (2-cyclohexane) (III) were also prepared. The structure of the three epoxides and cycloolefins was confirmed by infrared spectroscopy (IR), elemental analysis (EA), and H-1-NM-R spectroscopy. To evaluate the thermal properties of the cycloaliphatic epoxy compounds, a commercial bicycloaliphatic epoxy, 3,4-epoxycyclohexylmethyl 3 ' ,4 ' -epoxycyclohexane carboxylate (marked name ERL-4221) was used for comparison. Three epoxides and ERL-4221 were cured with HMPA, and thermal properties of the cured polymers were examined by thermomechanical analysis, differential scanning calorimetry, and dynamic mechanical analysis. The cured polymers obtained from epoxy I e, II e and III e showed higher glass transition temperature, higher storage modulus, and lower coefficient of thermal expansion than those of ERL-4221.

关 键 词：脂环族烯烃 脂环族环氧树脂 合成 固化 性能 环氧化反应 脂环族环氧化合物 

分 类 号：O624[理学—有机化学]