橡胶防老剂RD的合成工艺及微观结构表征  

Synthesis Process and Microstructure Characterization of Rubber Antioxidant RD

作　　者：贾太轩[1] 苗进之 王春艳 李林东 肖莹霞 邢琳琳 Jia Tai-xuan;Miao Jin-zhi;Wang Chun-yan;Li Lin-dong;Xiao Ying-xia;Xing Lin-lin(College of Chemistry&Environmental Engineering,Anyang institute of technology,Anyang Henan 455000,China;Henan Kailun Chemical Co.,LTD,Anyang Henan 456463,China)

机构地区：[1]安阳工学院化学与环境工程学院,河南安阳455000 [2]河南省开仑化工有限责任公司,河南安阳456463

出　　处：《江西化工》2023年第5期71-75,共5页Jiangxi Chemical Industry

基　　金：国家自然科学基金项目(5220020929);河南省中央引导地方科技发展专项跨区域研发合作项目(Z20221343016);安阳市重大科技专项计划项目(2022A02GX008)资助课题。

摘　　要：本研究以苯胺和丙酮为原料,物料比n(苯胺):n(丙酮)=1.0:6.0;反应温度:120℃,采取一步合成法合成橡胶防老剂2,2,4-三甲基-1,2-二氢喹啉聚合物(RD),首先,在酸性环境下丙酮先缩合生成异亚丙基丙酮,然后异亚丙基丙酮和苯胺发生反应生成RD单体。单体以液体酸为催化剂,发生聚合反应生成RD聚合物。此清洁工艺技术避免了传统方法含甲苯废水的产生,从根源上消除废水的产生。利用现代仪器对样品进行检测分析,经过对红外图谱的分析确定产物含有苯环、甲基、氨基和苯环的邻位取代振动吸收峰;使用UV-vis确定紫外最大吸收峰在286 nm处,利用HPLC以甲醇和水为流动相在286 nm处对0.001 g/mL的样品溶液进行检测,结果显示有6个明显吸收峰,分析为杂质和RD单体、二、三、四聚体。通过GC-MS测定确定样品中含有RD单体和二聚体。XRD图谱分析表明出现了3个聚合物弥散峰,与HPLC和GC-MS检测结果相互呼应。通过NMR确定样品中含有15个氢原子、12个碳原子,通过归一化法确定各组分含量。总之,样品聚合物达到防老剂RD的GB/T 8826—2003技术指标和各项要求。In this study,rubber antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer(RD)could be obtained by a one-step synthesis method with aniline and acetone as raw materials.The material ratio of which was 1.0:6.0,and reaction temperature 120℃.Isopropylidene acetone was first formed by acetone through condensation reaction in an acidic environment.Then RD monomer was synthesized by the reaction between isopropylidene acetone and aniline.Using liquid acid as catalyst,the RD monomer underwent polymerization reactions for final RD polymer products.The generation of toluene containing wastewater could be avoided by the clean process technology at the originate,which was inevitable in traditional methods.The sample was detected by modern characterization instruments.The sample exhibited ortho substituted vibration absorption peaks of benzene ring,methyl group and amino group confirmed by the infrared spectrum analysis.The maximum absorption peak was determined at 286 nm using UV-vis spectroscopy.A sample solution of 0.001 g/mL was utilized for HPLC detection at 286 nm with methanol and water as mobile phases.Six obvious absorption peaks were contributed by impurities,RD monomers,dimers,triads,and tetramers,respectively.The existence of RD monomers and dimers were confirmed in the sample through GC-MS determination.Three polymer dispersion peaks were demonstrated in XRD characterization,which corresponded well with HPLC and GC-MS detection results.15 hydrogen atoms and 12 carbon atoms were contained as indicated by NMR characterization,where the content of each component was determined by normalization method.In summary,the technical specifications and requirements could be reached by the sample polymer of GB/T 8826—2003 for antioxidant RD.

关 键 词：橡胶防老剂RD FTIR UV-VIS XRD HPLC GC-MS NMR 

分 类 号：TQ330.382[化学工程—橡胶工业]