MOF一步法催化制备多胺基烯类单体  

One-step catalytic synthesis of polyamine-based olefin monomers by MOF

作　　者：韩午丽 魏天星 方元浡 王素云 HAN Wuli;WEI Tianxing;FANG Yuanbo;WANG Suyun(College of Chemistry&Environmental Engineering,Yangtze University,Jingzhou 434023,Hubei;Exploration Division,Tarim Oilfield Company,PetroChina,Korla 841001,Xinjiang)

机构地区：[1]长江大学化学与环境工程学院,湖北荆州434023 [2]中石油塔里木油田分公司勘探事业部,新疆库尔勒841001

出　　处：《长江大学学报（自然科学版）》2023年第6期118-124,共7页Journal of Yangtze University(Natural Science Edition)

基　　金：国家科技重大专项“低渗油气藏钻井液完井液及储层保护技术”(2016ZX 05040-005)。

摘　　要：聚合物类处理剂如能通过胺基官能团所赋予的分子间氢键作用形成超分子缔合体,则有助于其在高温高盐钙环境中维持高聚物特性。以六水合氯化铁和均苯三甲酸为原料,制得MIL-100(Fe)型金属有机框架材料(MOF),以MOF为催化剂,使丙烯酰胺(AM)中与羰基相连的N原子可直接进攻氮丙啶(AZ),通过开环加成反应,用一步法制得胺值与胺基密度均较大的多胺基烯类单体N,N-双(2-氨基乙基)丙烯酰胺(N,N-BAM)。由SEM、BET与XRD的分析结果,可知MIL-100(Fe)的形貌为高度规整,平均粒径为200~300 nm的纳米级多棱晶体,其内部孔洞主要为微孔和介孔,且介孔占比较大,同时其结晶度极高,有利于MIL-100(Fe)发挥催化活性。由FITR与元素分析的结果,可知N,N-BAM的实测分子结构与理论预期一致。由DSC曲线分析与钻井液性能评价结果,可知AM/N,N-BAM二元共聚物的玻璃化转变温度T g2随N,N-BAM占比增大而升高,证明N,N-BAM确实可在共聚物中形成氢键作用,进而增强其抗温耐盐性能。The polymer-based treatment agents can maintain their high polymer properties in a high-temperature and high-salt calcium environment with the help of intermolecular hydrogen bonds endowed by amine functional groups to form supramolecular linkages.MIL-100(Fe)type metal organic framework material(MOF)was prepared with ferric chloride hexahydrate and trimarboxylic acid as raw materials.Using MOF as catalyst,the carbonyl-linked N atom in acrylamide(AM)can directly attack azipropyl(AZ).Through the ring-opening addition reaction,the polyamine-based alkene monomer called N,N-bis(2-Aminoethyl)acrylamide(N,N-BAM)with high amine value and amine group density was prepared by one-step method.The analysis results of SEM,BET and XRD show that the morphology of MIL-100(Fe)is a highly regular nano-polygonal crystal with an average particle size of 200~300 nm.The internal voids of MIL-100(Fe)are mainly micropores and mesoporous,and mesoporous accounts for a large proportion,and its crystallinity is very high,which are beneficial to the catalytic activity of MIL-100(Fe).The results of FITR and elemental analysis show that the measured molecular structure of N,N-BAM is consistent with the theoretical expectation.The DSC curve analysis and drilling fluid performance evaluation results show that the glass transition temperature T g2 of AM/N,N-BAM binary copolymer increases with the increase of N,N-BAM ratio,which shows that N,N-BAM can indeed form hydrogen bonding in the polymer,thereby,enhancing the heat and salt resistance of polymers.

关 键 词：多胺基烯类单体 金属有机框架材料 催化活性 开环加成 钻井液 

分 类 号：TE254[石油与天然气工程—油气井工程]