侧羟基氟碳低聚物的合成及固化性能研究  

Synthesis and curing properties of side hydroxyl fluorocarbon oligomers

作　　者：安靖怡 张天福 张孝阿[1] 王成忠[1] 江盛玲[1] 张军营[1] An Jingyi;Zhang Tianfu;Zhang Xiaoa;Wang Chengzhong;Jiang Shengling;Zhang Junying(Key Laboratory of Carbon Fiber and Functional Polymers of Ministry of Education,College of Materials Science and Engineering,Beijing University of Chemical Technology,Beijing 100029,China;Science and Technology on Aerospace Chemical Power Laboratory,Hubei Institute of Aerospace Chemotechnology,Xiangyang 441003,Hubei,China)

机构地区：[1]北京化工大学,碳纤维及功能高分子教育部重点实验室,材料科学与工程学院,北京100029 [2]航天化学动力技术国防科技重点实验室,湖北航天化学技术研究所,湖北襄阳441003

出　　处：《中国胶粘剂》2025年第2期57-63,共7页China Adhesives

基　　金：航天化学动力技术重点实验室开放基金资助项目(STACPL120201B07)。

摘　　要：以低分子量偏氟乙烯(VDF)-六氟丙烯(HFP)共聚物和氨基醇为主要原料,通过迈克尔加成反应,设计合成了三种侧羟基氟碳低聚物,并进一步与固化剂HDI三聚体、扩链剂1,4-丁二醇反应,得到固化产物。然后采用傅里叶变换红外光谱仪(FT-IR)和核磁共振波谱仪(1H-NMR),研究了氨基醇种类及用量、氧化镁用量、反应温度、反应时间对侧羟基氟碳低聚物合成的影响,进一步研究了固化物的力学性能、热性能和耐溶剂性能。研究结果表明:(1)成功合成了侧羟基氟碳低聚物,且采用4-氨基-1-丁醇作为亲核试剂时,制备的侧羟基氟碳低聚物具有较高的接枝率。当投料比为20∶10,接枝率为17.39%,反应时间在6.5~9.0 h时为相对最佳制备条件。(2)侧羟基氟碳低聚物固化产物拉伸强度在3.41~9.21 MPa之间。随着氟碳低聚物接枝率的提高,交联反应位点增多,形成了稳定的三维网状结构,使拉伸强度提升。(3)固化后形成交联结构,阻止了聚合物链段的移动,提高了热稳定性。(4)所制备的固化产物具有良好的耐强酸、强碱以及极性溶剂特性。Three types of side hydroxyl fluorocarbon oligomers were designed and synthesized via Michael addition reaction by using low-molecular-weight vinylidene fluoride(VDF)-hexafluoropropylene(HFP)copolymer and amino alcohol as the main raw materials.Subsequently,they were reacted with curing agent HDI trimer and chain extender 1,4-butanediol to obtain the cured products.Then,Fourier transform infrared spectroscopy(FT-IR)and nuclear magnetic resonance spectroscopy(1H-NMR)were used to investigate the effects of amino alcohol type and dosage,magnesium oxide dosage,reaction temperature,and reaction time on the synthesis of side hydroxyl fluorocarbon oligomers.Furthermore,the mechanical properties,thermal properties,and solvent resistance of the cured products were studied.The research results showed that,(1)The side hydroxyl fluorocarbon oligomers were successfully synthesized.When 4-amino-1-butanol was used as the nucleophilic reagent,the oligomers exhibited a higher grafting rate.When the feeding ratio was 20:10,the grafting rate was 17.39%,and the reaction time was between 6.5 and 9.0 hours,which were the optimal preparation conditions.(2)The tensile strength of the cured product of side hydroxyl fluorocarbon oligomers was between 3.41 and 9.21 MPa.As the grafting rate of fluorocarbon oligomers increased,the number of crosslinking reaction sites increased,forming a stable three-dimensional network structure that enhanced tensile strength.(3)After curing,a cross-linked structure was formed,which prevented the movement of polymer segments and improved thermal stability.(4)The prepared cured product had good resistance to strong acids,strong bases,and polar solvents.

关 键 词：侧羟基氟碳低聚物 氨基醇 迈克尔加成 活性基团 

分 类 号：TQ430.4[化学工程]