4-二甲氨基吡啶-三氟化硼络合型固化促进剂的制备及催化环氧固化影响的研究  

Preparation of 4-dimethylaminopyridine-boron trifluoride complex type curing accelerator and its catalytic effect on epoxy curing

作　　者：戴晟伟 王晓蕾[1] 张有生 杨昶旭 韩淑军 齐悦新 刘金刚[1] Dai Shengwei;Wang Xiaolei;Zhang Yousheng;Yang Changxu;Han Shujun;Qi Yuexin;Liu Jingang(China University of Geosciences Beijing,Engineering Research Center of Ministry of Education for Geological Carbon Storage and Low Carbon Utilization of Resources,Beijing 100083,China;Zhejiang Jameen New Material Co.,Ltd.,Jiaxing 314011,Zhejiang,China)

机构地区：[1]中国地质大学(北京),地质碳储与资源低碳利用教育部工程研究中心,北京100083 [2]浙江嘉民新材料有限公司,浙江嘉兴314011

出　　处：《中国胶粘剂》2024年第6期61-68,共8页China Adhesives

摘　　要：采用4-二甲氨基吡啶(DMAP)与三氟化硼-乙醚溶液[BF3-O(C2H5)2]为起始原料,制备了络合型固化促进剂(DMAP-BF),并表征了该促进剂的化学结构。系统探究了该促进剂对联苯芳烷基型环氧树脂(NC3000)-含萘四官能团环氧树脂(HP4700)-含氮酚醛树脂(PF8705)三元复合体系(BF-1~BF-6)固化反应的催化影响。研究结果表明:(1)通过对固化促进剂和环氧-酚醛-固化促进剂预混物进行红外、核磁、XRD以及微观形貌分析等,证明成功制备了预期产物。(2)固化性能测试结果显示,DMAP-BF可催化环氧-酚醛体系的固化反应,并表现出良好的热潜伏特性。DMAP-BF对上述环氧-酚醛复合体系的固化具有良好的催化效果,不含DMAP-BF促进剂的BF-ref样品的固化反应活化能(Ea)较BF-6体系[m(NC3000)∶m(HP4700)=50∶50]高出109.4 kJ/mol。(3)BF样品体系在100~140℃温度区间的熔体黏度可低达0.1 Pa·s,但在温度达到固化工艺温度(175℃)时,DMAP-BF可催化环氧-酚醛树脂体系快速固化。这一特性对于DMAP-BF的实际应用是至关重要的,可赋予环氧塑封料(EMC)更优异的储存稳定性和工艺性能。(4)BF系列固化物的起始热分解温度均为400℃左右,500℃后失重幅度减少,表明BF复合材料固化物具有良好的耐热稳定性,可以满足后续EMC的应用需求。A complex type of curing accelerator(DMAP-BF)was prepared by using 4-dimethylaminopyridine(DMAP)and boron trifluoride-ether solution[BF3-O(C2H5)2]as the raw materials,and its chemical structure was characterized.The catalytic effects of this curing accelerator on the curing reaction of the ternary composite system(BF-1~BF-6)composed of biphenyl aromatic alkyl epoxy resin(NC3000),naphthalene-containing tetrafunctional epoxy resin(HP4700)and nitrogen-containing phenolic resin(PF8705)were systematically investigated.The research results showed that,(1)The expected product was successfully prepared by conducting infrared,nuclear magnetic,XRD,and microscopic morphology analysis on the curing accelerator and epoxy-phenolic aldehyde-curing accelerator premix.(2)The curing performance test results indicated that DMAP-BF could catalyze the curing reaction of epoxy-phenolic system and exhibited good thermal latency characteristics.DMAP-BF had a good catalytic effect on the curing of the epoxy-phenolic composite system mentioned above.The activation energy(Ea)of curing reaction of the BF-ref sample without DMAP-BF promoter was 109.4 kJ/mol higher than that of the BF-6 system[m(NC3000)∶m(HP4700)=50∶50].(3)The melt viscosity of the BF sample system in the temperature range of 100−140℃could be as low as 0.1 Pa∙s,but when the temperature reached the curing process temperature(175℃),DMAP-BF could catalyze the rapid curing of the epoxy-phenolic resin system.This characteristic was crucial for the practical application of DMAP-BF,as it could endow epoxy molding compound(EMC)with better storage stability and process performance.(4)The initial thermal decomposition temperature of BF series cured products was around 400℃,and the weight loss decreased after 500℃,indicating that BF composite cured products had good heat resistance stability and could meet the subsequent application requirements of EMC.

关 键 词：环氧塑封料 固化促进剂 热潜伏性 4-二甲氨基吡啶 三氟化硼 

分 类 号：TQ433[化学工程]