含胺基功能性单体的聚合研究 Ⅴ.4-N,N-二甲胺基苯乙烯的合成及其作为氧化还原引发体系组分的研究

<正> 前文我们报告了含有芳香叔胺基的丙烯酸酯、甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA)在过氧化二月桂酰(LPO)引发下的聚合动力学。从所得的聚合速度方程式及低的聚合活化能,认为DMABMA与LPO形成氧化还原体系而使DMABMA聚合,在本文第Ⅳ报中报道了DMABMA不仅能引发甲基丙烯酸甲酯的聚合,还参与聚甲基丙烯酸甲酯的链中,因此称这种既能参与引发聚合反应,又参与聚合物链中的引发“引发剂单体(initiatomer)”。这种含有可聚合胺引发体系的优点是,用于丙烯酸酯类医用

STUDIES ON THE POLYMERIZATION OF FUNCTIONAL MONOMERS CONTAINING AMINO-GROUPS Ⅴ. THE SYNTHESIS OP 4-N,N-DIMETHYLAMINOSTYRENE AND ITS USES AS A COMPONENT OP REDOX INITIATION SYSTEM

A vinyl monomer having tertiary aromatic ammo-groups, 4-N, N-dimethylaminosty-rene (DMAS) has been synthesized from 4-N, N-dimethylaminobenzaldehyde with mal-onic acid by knoevenagel reaction and then decarboxylated.Although the DMAS hardly proceeds the radical polymerization initiated with organic peroxide such as BPO, LPO, bet it was found that DMAS under lower concentration would form redox system with BPO to initiate the polymerization of some vinyl monomers such as MMA readily. The rate equation of the polymerization of MMA initiated by DMAS-BPO system is given as Rp=Kp MMA] DMAS]0.5BPO]0.5. The rate constants of the polymerization were determined at 30, 40, 50 and 60℃, and the overall activation energy was calculated as low as 7.4 kcal/mol. The UV-analysis of the obtained polymers confirmed that DMAS not only initiated the polymerization of MMA by combining with BPO, but also entered into the polymer chains.