双酚A型邻苯二甲腈树脂的合成及固化性能研究

Synthesis and curing properties of bisphenol A-type phthalonitrile resin

以双酚A和4-硝基邻苯二甲腈为原料,合成了双酚A型邻苯二甲腈树脂。然后利用傅里叶红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征了合成树脂的结构。以双酚A型邻苯二甲腈树脂为基体,筛选了过渡金属盐、芳香二胺、有机酚类等固化剂,通过差示扫描量热仪(DSC)研究了ZnCl2、DBTDL、m-BAPS、DDM、4,4′-联苯二酚及各类复合固化剂对树脂的固化行为。研究结果表明:(1)成功合成了目标产物双酚A型邻苯二甲腈树脂单体。(2)在复合固化剂的组合中,ZnCl2和DDM组成的无机金属盐/有机胺复合固化剂具有较高的固化反应活性,ZnCl2和4,4′-联苯二酚组成的无机金属盐/有机酚复合固化剂以及DBTDL和4,4′-联苯二酚组成的有机金属盐/有机酚复合固化剂次之,DBTDL和DDM组成的有机金属盐/有机胺复合固化剂以及DDM/4,4′-联苯二酚组成的有机胺/有机酚复合固化剂的固化活性则较弱。(3)对比各类代表性催化剂、固化剂及其复合固化剂,以无机金属盐为代表的过渡金属盐催化剂及其复合固化剂具有最高的固化反应活性,有机胺类次之,有机酚类及其复合固化剂的反应活性较低。

Bisphenol A-type phthalonitrile resin was synthesized by using bisphenol A and 4-nitrophthalic acid as raw materials.Then,the structure of the synthesized resin was characterized by Fourier transform infrared spectroscopy(FT-IR)and nuclear magnetic resonance hydrogen spectroscopy(1H-NMR).Transition metal salts,aromatic diamines,organic phenols,and other curing agents were screened by using bisphenol A-type phthalonitrile resin as the matrix.The curing behavior of ZnCl2,DBTDL,m-BAPS,DDM,4,4'-biphenol,and various composite curing agents on the resin was studied by differential scanning calorimeter(DSC).The research results showed that,(1)The target product,bisphenol A-type phthalimide resin monomer was successfully synthesized.(2)In the combination of composite curing agents,the inorganic metal salt/organic amine composite curing agent composed of ZnCl2 and DDM had higher curing reaction activity,followed by the inorganic metal salt/organic phenol composite curing agent composed of ZnCl2 and 4,4'-biphenol,and the organic metal salt/organic phenol composite curing agent composed of DBTDL and 4,4'-biphenol.The organic metal salt/organic amine composite curing agent composed of DBTDL and DDM and the organic amine/organic phenol composite curing agent composed of DDM/4,4'-biphenol had relatively weaker curing activity.(3)Comparing various representative catalysts,curing agents and their composite curing agents,transition metal salt catalysts and their composite curing agents represented by inorganic metal salts had the highest curing reaction activity,followed by organic amines,and organic phenols and their composite curing agents had relatively lower reaction activity.