含联萘结构环氧树脂的合成、固化动力学及其性能

Synthesis,Curing Kinetics and Properties of Epoxy Resin Containing Binaphthalene Unit

合成了两种含联萘结构的环氧树脂2,2'-二(9-环氧基壬酰氧基)-1,1'-联萘(R1)和2,2'-二(3-环氧基丙酰氧基)-1,1'-联萘(R2)。通过1HNMR和EA对目标产物结构进行了表征。以4,4'-二氨基二苯基甲烷(DDM)为固化剂,通过Ozawa法计算出R1/DDM和R2/DDM固化体系的反应活化能(E_a)分别为56.29和56.88 k J/mol,随着固化反应转化率(α)的增加,R1/DDM的E_a不断增大,而R2/DDM的E_a略微减小。考察了不同长度碳链对固化物的热稳定性、玻璃化转变温度(T_g)、力学性能和吸水率的影响。结果表明:短碳链的R2/DDM较长碳链的R1/DDM,固化物的初始分解温度由220.3℃下降到210.5℃,800℃下残炭率由3.45%上升至6.77%,T_g由135℃上升到141℃,断裂伸长率由6.7%下降至4.3%,吸水率由0.35%降至0.28%。

In order to understand the effect of the varying the carbon chain length of the initial resin on curing kinetics and the final properties of the cured products,two resins both containing binaphthalene unit,2,2＇-bis [9-epoxy（ 1-oxononyl） oxy]-1,1＇-naphthalene（ R1） and 2,2＇-bis（ 3-epoxy propionyloxy）-1,1＇-naphthalene（ R2）,were synthesized and characterized by means of proton nuclear magnetic resonance spectrum（1HNMR） and elemental analysis（ EA）. Subsequently,both epoxy resins were cured with 4,4＇-diaminodiphenylmethane（ DDM） and their kinetic analyses were performed by Ozawa＇s isoconversional method. The activation energy（ Ea） of R1/DDM and R2/DDM curing system was 56. 29 k J/mol and 56. 88 k J/mol,respectively. Moreover,the Eaof R1/DDM increased while that of R2/DDM decreased slightly with increasing of conversion（ α）. In addition,the influence of different chain length on thermostability,glass transition temperature（ Tg）,mechanical property and water absorption of the cured epoxy resins was investigated. The results showed that as the length of carbon chain increased from C2H5 to C8H（17）,the initial decomposition temperature decreased from 220. 3 ℃ to210. 5 ℃,the carbon residue rate at 800 ℃ increased from 3. 45% to 6. 77%,the Tgincreased from135 ℃ to 141 ℃,the elongation at break decreased from 6. 7% to 4. 3%,and the water absorption decreased from 0. 35% to 0. 28%.