二乙二醇丁醚缩甲醛的催化合成及增塑丁腈橡胶性能
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1.南京林业大学 化学工程学院;2.安徽省环氧树脂及其助剂工程研究中心

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TQ413.25

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国家重点研发计划项目(2022YFD2200802)


Preparation of diethylene glycol butyl ether formaldehyde and study on the plasticized nitrile butadiene rubber
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1.College of Chemical Engineering,Nanjing Forestry University;2.Anhui Province Engineering Research Center of Epoxy Resin and Additive

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    摘要:

    经膨润土负载SnCl4制备SnCl4-膨润土-7催化剂,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对催化剂的结构和形貌进行表征,考察反应温度、n(TOX)∶n(DEGB)、带水剂环己烷用量(以TOX和DEGB总质量为基准的质量百分数,下同)对DBF选择性和收率的影响;将DBF用于丁腈橡胶(NBR)增塑剂,采用力学测试、热老化实验,对比分析DBF和进口增塑剂TP-90B对NBR的增塑性能。结果表明,反应温度110 ℃,n(TOX)∶n(DEGB)=1∶6.6,环己烷用量30%的条件下,SnCl4-膨润土-7用量3%,该条件下DBF的选择性和产率最高,分别为98.2%和94.7%;DBF/NBR比TP-90B/NBR表现出更好的硫变特性、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表现出更高的硬度、100%定伸应力、断裂伸长率、拉伸强度和撕裂强度,热空气老化实验中,其拉伸强度和撕裂强度的变化幅度显著小于TP-90B/NBR。·

    Abstract:

    The SnCl4-bentonite-7 catalyst, loaded with SnCl4 on bentonite, was prepared for the catalytic aldol condensation reaction between 1,3,5-trioxane (TOX) and diethylene glycol butyl ether (DEGB) to synthesize diethylene glycol butyl ether formaldehyde (DBF).The catalyst"s structure and morphology were characterized by FTIR, SEM, and XRD. The effects of reaction temperature, the molar ratio of TOX to DEGB, and the percentage of cyclohexane as a hydrotrope (based on the total mass of TOX and DEGB) on the selectivity and yield of DBF were examined. DBF was used as a plasticizer for nitrile butadiene rubber (NBR), with its performance compared to the imported plasticizer TP-90B through mechanical tests and thermal aging experiments.The results show that the highest selectivity (98.2%) and yield (94.7%) of DBF were achieved at 110°C, with a TOX to DEGB molar ratio of 1:6.6, and a cyclohexane content of 30%, using 3% of the SnCl4-bentonite-7 catalyst. Compared to TP-90B, DBF/NBR demonstrated superior vulcanization characteristics, mechanical properties, and aging resistance. Specifically, the maximum torque of DBF/NBR (13.01 dN·m) was higher than that of TP-90B/NBR (12.85 dN·m), with shorter scorch time and optimum vulcanization time of 0.53 min and 1.42 min, respectively, compared to 0.55 min and 1.47 min for TP-90B/NBR. Additionally, DBF/NBR showed higher hardness, tensile stress at 100% elongation, elongation at break, tensile strength, and tear strength. During thermal aging tests, DBF/NBR exhibited significantly less variation in tensile and tear strength compared to TP-90B/NBR.

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徐仁奎,任亚平,马雩霆,顾东进,谈继淮,朱新宝.二乙二醇丁醚缩甲醛的催化合成及增塑丁腈橡胶性能[J].精细化工,2025,42(3):

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  • 收稿日期:2024-01-12
  • 最后修改日期:2024-04-09
  • 录用日期:2024-03-28
  • 在线发布日期: 2025-03-14
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