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標題: The Properties of Mannich Bases Derived from Poly(oxyalkylene)amines and Phenols
酚與聚醚胺類衍生之Mannich Bases的性質
作者: 林曉峰
Lin, Shiau Feng
關鍵字: poly(oxyalkylene)amine;聚醚胺;Mannich reaction;surfactant;epoxy;curing;self-assembling;autocatalyst;poly(oxyethylene);Mannich反應;界面活性劑;環氧樹脂;硬化;自行排列;自生催化;聚乙醚
出版社: 化學工程學系
The Mannich reaction of poly(oxyalkylene)amine, alkyl-phenol, and formaldehyde gives a series of mixing products, namely Mannich Bases. The structures of these adducts were constituted of the poly(oxyalkylene) segments, phenols, and amines which identified by GPC, H1-NMR, amine titration etc. These products were divided into two classes according to the nature of products: one is lipophilic Mannich Bases; the other is hydrophilic Mannich Bases. The lipophilic Mannich Bases are water-insoluble. And, the hydrophilic Mannich Bases consist of poly(oxyethylene)-segments which could associate with water. This renders the Mannich Bases hydrophilic water-soluble, and surface-active.
In part one, the lipophilic Mannich Bases were applied on epoxy curing system. The reaction profiles of amine adducts with epoxides were observed in DSC. The results showed that these adducts could lower the reaction temperatures and activation energies. Besides, the cured polymers also had higher Tg, better thermal stability and improved mechanical strength.
In part two, the fundamental surfactancy of hydrophilic Mannich Bases is discussed. These novel surfactants lowered the surface tension of water and interfacial tension of water/toluene (or water/n-hexane) to 31 ~ 33 dyne/cm and 5 dyne/cm, respectively. Some adducts of this series also had cloud points as same as the nonionic surfactants. But the cloud point disappeared in acidic environment due to the increased solubility by the formation of quaternary salt. The aggregating behaviors of these surfactant molecules were also observed by light scattering technique (hydrodynamic diameter) and H1-NMR in different solvents.

聚醚胺(poly(oxyalkylene)amine)和烷基酚與甲醛進行Mannich反應,合成一系列之Mannich Bases混合物,並利用GPC、H1-NMR、胺滴定等方法分析產物的基本性質。此類型之Mannich Bases的結構中含有胺(amine)、酚(phenol)、聚醚(polyether)、烷基(alkyl)等官能基,依照起始物的性質變化,產物可分成油性及水性兩種,油性之Mannich Bases,主要應用於環氧樹脂的硬化方面;而水性之Mannich Bases藉著分子中聚乙醚鏈段(poly(oxyethylene) segment)與水形成氫鍵及其他親油基性質,使其具有界面活性,是一種高分子量的界面活性劑。
第一部份探討油性的Mannich Bases在環氧樹脂上之應用,利用分子結構中的胺與環氧基反應(或稱之為硬化),在DSC中觀察硬化反應曲線,發現此系列之Mannich Bases具有較高之環氧樹脂反應性,可降低反應的活化能,加速反應。TGA的數據顯示,含有酚類結構的Mannich Bases所硬化之高分子的耐熱性,比單獨由聚醚胺所硬化之高分子佳,而高分子的玻璃轉化溫度(Tg)與機械強度也有所提昇。
第二部份主要探討水性Mannich Bases的界面現象,可將水的表面張力降低至31 ~ 33 dyne/cm;水與甲苯或水與正己烷的界面張力皆能降低至5 dyne/cm (其原始界面張力分別為36 dyne/cm與47 dyne/cm與)。而且此型化合物兼具非離子與離子型界面劑的特點,當親油基與親水基在一定比例時會在常溫下出現濁點,而在加入酸之後又會因為四級胺鹽的生成使得溶解度提高而消失。此外以光散射技術所得之水力直徑(hydrodynamic diameter)上可以看出,其分子的聚集行為隨著濃度而變化,以及在不同極性的溶劑下所測量之H1-NMR光譜,可了解分子聚集型態(微胞)的轉變。
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