二乙二醇丁醚缩甲醛的催化合成及增塑丁腈橡胶性能  

Catalytic preparation of diethylene glycol butyl ether formaldehyde and its plasticizing effect on nitrile butadiene rubber

作　　者：徐仁奎 任亚平 马雩霆 顾东进 谈继淮 朱新宝[1,2] XU Renkui;REN Yaping;MA Yuting;GU Dongjin;TAN Jihuai;ZHU Xinbao(College of Chemical Engineering,Nanjing Forestry University,Nanjing 210037,Jiangsu,China;Anhui Province Engineering Research Center of Epoxy Resin and Additive,Huangshan 245900,Anhui,China)

机构地区：[1]南京林业大学化学工程学院,江苏南京210037 [2]安徽省环氧树脂及其助剂工程研究中心,安徽黄山245900

出　　处：《精细化工》2025年第3期647-653,677,共8页Fine Chemicals

基　　金：国家重点研发计划项目(2022YFD2200802)。

摘　　要：采用离子交换法制备了SnCl_(4)/膨润土催化剂,将其用于催化1,3,5-三氧六环(TOX)与二乙二醇丁醚(DEGB)缩醛交换反应合成二乙二醇丁醚缩甲醛(DBF)。采用FTIR、SEM、XRD对催化剂进行了表征,考察了反应温度、n(TOX)∶n(DEGB)、带水剂环己烷用量(以TOX和DEGB总质量计,下同)对DBF选择性和收率的影响。将DBF用于增塑丁腈橡胶(NBR),通过力学测试和热老化实验,对比了DBF和进口增塑剂TP-90B增塑硫化NBR(DBF/NBR和TP-90B/NBR)的增塑性能。结果表明,在反应温度110℃、n(TOX)∶n(DEGB)=1∶6.6、环己烷用量25%、SnCl_(4)-膨润土-7(7代表膨润土悬浮液的pH)用量3%的条件下,DBF的选择性和产率最高,分别为98.2%和94.7%。DBF/NBR比TP-90B/NBR具有更好的硫变特性、力学性能和增塑耐老化性能,DBF/NBR的最大转矩(13.01 dN·m)高于TP-90B/NBR(12.85 dN·m),其焦烧时间和正硫化时间分别为0.53、1.42 min,小于TP-90B/NBR的0.55、1.47 min。DBF/NBR比TP-90B/NBR具有更高的硬度、100%定伸应力、断裂伸长率、拉伸强度和撕裂强度,热老化实验中,其拉伸强度和撕裂强度的变化幅度显著小于TP-90B/NBR。Diethylene glycol butyl ether formaldehyde(DBF)was prepared the acetal reaction of 1,3,5-trioxane(TOX)with diethylene glycol butyl ether(DEGB)catalyzed by SnCl_(4)/bentonite,which were prepared by ion exchange method and characterized by FTIR,SEM and XRD.The effects of reaction temperature,n(TOX)∶n(DEGB),and water carrying agent cyclohexane dosage(based on the total mass of TOX and DEGB,the same below)on the selectivity and yield of DBF were investigated.The plasticizing performance of DBF and imported plasticizer TP-90B on vulcanized nitrile butadiene rubber(NBR)were then compared through mechanical test and thermal aging test.The results showed that DBF obtained under the conditions of 110℃,n(TOX)∶n(DEGB)=1∶6.6,cyclohexane dosage 25%,and SnCl_(4)-bentonite-7(7 represents the pH of the bentonite suspension)dosage 3%exhibited the highest selectivity(98.2%)and yield(94.7%).Compared with TP-90B/NBR,DBF/NBR demonstrated superior vulcanization characteristics,mechanical properties,and aging resistance.Specifically,DBF/NBR displayed improved maximum torque of 13.01 dN·m,higher than that of TP-90B/NBR(12.85 dN·m),and shorter scorch time as well as optimum vulcanization time of 0.53 and 1.42 min,respectively,compared with 0.55 and 1.47 min for TP-90B/NBR.Additionally,DBF/NBR also showed higher hardness,tensile stress at 100%elongation,elongation at break,tensile strength,and tear strength.During the thermal aging test,DBF/NBR exhibited significantly less variation in tensile and tear strength compared to TP-90B/NBR.

关 键 词：工艺合成 橡胶增塑 催化剂 缩醛反应 膨润土 绿色化学 

分 类 号：TQ333.7[化学工程—橡胶工业] TQ330.384TQ203.2