文献类型：期刊文献

中文题名：腰果酚基苯并噁嗪改性环氧树脂及其防腐性能

英文题名：Preparation of cardanol-based benzoxazine-modified epoxy resin and its anti-corrosion performance

作者：于金尼[1,2,3] 尚倩倩[1,3] 张猛[1,3] 周永红[1,2,3]

第一作者：于金尼

机构：[1]中国林业科学研究院林产化学工业研究所,南京210042;[2]南京林业大学化学工程学院,南京210037;[3]江苏省林业资源高效加工利用协同创新中心,南京210037

年份：2025

卷号：10

期号：3

起止页码：114-121

中文期刊名：林业工程学报

外文期刊名：Journal of Forestry Engineering

收录：;北大核心:【北大核心2023】；

基金：中央级公益性科研院所基本科研业务费专项资金(CAFYBB2022XB001);江苏省生物质能源与材料重点实验室(JSBEM-S-202301)。

语种：中文

中文关键词：腰果酚;环氧树脂;苯并噁嗪;疏水性;防腐涂层

外文关键词：cardanol;epoxy resin;benzoxazine;hydrophobicity;anti-corrosion coating

分类号：TQ632.4

摘要：环氧树脂因其耐水性差、韧性低及长期使用后附着力降低等问题,在长效防腐蚀涂层领域的发展受到限制。苯并噁嗪树脂聚合开环后的羟基能够与环氧基团发生聚合反应,可以用作环氧树脂的固化剂以改善环氧树脂的化学性能。以腰果酚为原料,将其与多聚甲醛、γ-氨丙基三乙氧基硅烷通过曼尼希反应制备了腰果酚基苯并噁嗪树脂(CBOZ)。将腰果酚先与丁二酰氯进行酯化反应,再利用过氧化氢对双键进行环氧化,得到腰果酚基环氧树脂(CEP);将CBOZ和CEP按比例进行混合并固化,研究了环氧基团与噁嗪环的物质的量比对涂层的热学性能、交联密度、涂膜性能和润湿性能等性能的影响。结果表明,当环氧基团与噁嗪环的物质的量比为1∶1时涂层(CEPBOZ-3)具有最佳的综合性能,CEPBOZ-3涂层的凝胶含量为92.49%、铅笔硬度为5H、附着力为3级、柔韧性为2 mm、水接触角(WCA)为(107.4±1.3)°,涂层还具有较好的热学性能和耐溶剂性。对CEPBOZ-3涂层进行电化学阻抗谱测试可知,涂层表现出较好的防腐蚀性能,低频下的阻抗模值(|Z|_(0.01Hz))为1.1×10^(8)Ω·cm^(2),浸泡336 h后的|Z|_(0.01Hz)为1.0×10^(6)Ω·cm^(2),表明涂层具有长期防腐蚀性。
The development of epoxy resin for long-term anti-corrosion coatings is limited due to its low water resistance,poor toughness,and reduced adhesion after long-term service.The hydroxyl group of benzoxazine resin after polymerization can undergo polymerization reaction with epoxy groups,making benzoxazine resin a curing agent for epoxy resin to improve its chemical properties.Anti-corrosion coatings are mainly prepared relying on non-renewable petrochemical resources.With the depletion and increasing consumption of petrochemical resources,the development of sustainable anti-corrosion coatings by replacing or partially substituting petrochemical materials with biomass resources has become a growing trend.Cardanol,a byproduct derived from cashew shell liquid,is an ideal feed stock for preparing epoxy resin and benzoxazine due to its double bonds and phenolic hydroxyl structure.In this work,cardanol-based epoxy resin(CEP)and cardanol-based benzoxazine resin(CBOZ)were synthesized using cardanol as the raw material.CBOZ was prepared by Mannich reaction with paraformaldehyde and aminopropyltriethoxysilane.CEP was synthesized by the esterification of cardanol and butanedionyl chloride with the subsequent oxidation of double bonds by hydrogen peroxide.The anti-corrosion coatings were fabricated by mixing the CBOZ and CEP resins in proportion.The effects of the molar ratio of the epoxy groups to the oxazine ring on the properties of the coatings,such as the thermal performance,the cross-linking density,the film properties,and the wettability,were investigated.The results indicated that the thermal stability and the wettability of CEPBOZ coating increased with the increase of CBOZ content.The coating(CEPBOZ-3)had the best comprehensive performance when the molar ratio of the epoxy groups to the oxazine ring was 1∶1.The CEPBOZ-3 coating had a gel content of 92.49%,a pencil hardness of 5H,an adhesion level of 3,a flexibility of 2 mm,and a water contact angle(WCA)of(107.4±1.3)°.In addition,the coating also exhibited excellent thermal stability with the maximum thermal decomposition temperature(T p)higher than 470℃and great solvent resistance by resisting wiping with ethanol,toluene,acetone,tetrahydrofuran,and ethyl acetate at least 200 times without any surface changes.Electrochemical impedance spectroscopy tests were conducted on the CEPBOZ-3 coating to evaluate its performance.The developed coating showed good anti-corrosion performance,with an impedance modulus(|Z|_(0.01Hz))of 1.1×10^(8)Ω·cm^(2) at low frequencies and 1.0×10^(6)Ω·cm^(2) at|Z|_(0.01Hz) after 336 h of immersion,indicating that the coating has a long-term anti-corrosion property.This work provides a facile fabrication approach of bio-based composite coatings with durable anti-corrosion performance,demonstrating potential for industrial applications.