一种新型醌亚胺化合物的合成、表征及应用

Synthesis and characteristics of a new type of quinoneimine compound

以3-甲基二苯胺为原料,通过亲核取代、水解和氧化反应,获得了3-甲基-10-羟基-5,10-二氢磷杂吖嗪-10-氧化物。在此基础之上,经过硝化、加氢还原和缩合反应,得到了一种新型的醌亚胺化合物(PPBQ)。PPBQ具有调控乙烯基单体乳液聚合反应的能力,在单体含量为4mol/L、引发剂(K_2S_2O_8)浓度为3.7×10^(–3)mol/L、PPBQ与引发剂的摩尔投料比[n(PPBQ)∶n(K_2S_2O_8)]小于0.8的条件下,能够获得平均分子量(Mw)不高于65769、分子量分散度(Mw/Mn)不高于2.49的甲基丙烯酸乙酯乳液及平均分子量小于1000的寡聚体产品,为高固体涂料、聚丙烯酸类阻垢剂、净水剂的制备提供了一条新的思路。运用红外、质谱和1H和13C核磁等检测方法,对生成的中间体和产物的结构进行了正确表征,运用红外、质谱和凝胶色谱等检测方法,对甲基丙烯酸乙酯寡聚体的结构进行了表征。

Using3-methty-diphenylamine as raw materials,a tricyclic system of benzazaphosphazinephosphinic acid,3-methyl-10-hydroxyl-5,10-dihydrophenopho-sphazine-10-oxide(1)wasobtained through one-pot reactions involving nucleophilic substitution,hydrolysis,and oxidation.Further manipulation of compound(1)via nitration,catalytic hydrogenation and condensation led to a novel diiminobenzoquinone compound(PPBQ).The novel diiminobenzoquinone compound can control the emulsion free radical polymerization of vinyl monomer efficiently.The ethyl methacrylate(EMA)latex with controllable average molecular weight(Mw≤65769)and polydispersity(Mw/Mn≤2.49)and oligomer of EMA(Mw<1000)could be provided when the molar concentration of monomer and initiator(K2S2O8)were4mol/L and3.7×10-3mol/L,respectively,the loading of the molar ratio of PPBQ to initiator(K2S2O8)was less than0.8.A new way of preparing high solid coatings(HSC),antisludging agent and water clarifying agent containing component of acrylic oligomer was propopsed.The structure of the synthesized intermediates and PPBQ were characterized by IR,MS and1H NMR analysis.The structure of EMA oligomer was characterized also by FTIR,MS and gel chromatograph(GC)analysis.