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聚环氧化物已广泛应用于各个工业部门。本文开发一种新的三乙基铝一单烷基磷酸酯体系作为环氧化物聚合的催化剂。其最佳聚合条件为三乙基铝/单丁基磷酸酯和三乙基铝/单乙基磷酸酯分别为1:0.24和1:0.19摩尔％;催化剂/单体为2.5～3.0摩尔％;同对发现二烷基及三烷基磷酸酯具有较低的活性。 由三乙基铝/单烷基磷酸酯催化体系所得的聚合物用X-衍射、~(13)C-NMR,凝胶色谱进行表征,其结果和三乙基铝/磷酸体系及三乙基铝/乙酰丙酮/水体系相比,本文开发的新催化体系所得的聚合物具有较窄的分子量分布和较高的结晶度。 本文还对超高分子量的聚环氧丙烷用~(13)C-NMR进行了研究,发现聚环氧丙烷具有四种立体异构体,分别为全同、间同和二种异同立体异构体。其中全同构型的化学位移用结晶部分的聚环氧丙烷证实是在相对低场。
Polyepoxides have been widely used in various industrial sectors. In this paper, a new triethylaluminum mono-alkyl phosphate ester system was developed as a catalyst for epoxide polymerization. The optimal polymerization conditions are triethyl aluminum / monobutyl phosphate and triethyl aluminum / monoethyl phosphate respectively 1: 0.24 and 1: 0.19 mol%; catalyst / monomer is 2.5-3.0 mol% It was found that dialkyl and trialkyl phosphates have lower activity. The results of X-ray diffraction, ~ (13) C-NMR and gel chromatography showed that the polymer obtained from the triethylaluminum / monoalkyl phosphate catalyzed system was characterized with triethyl aluminum / phosphoric acid system and triethyl Compared with aluminum / acetylacetone / water system, the new catalyst system developed in this paper has a narrower molecular weight distribution and higher crystallinity. In this paper, ~ (13) C-NMR of ultrahigh molecular weight polypropylene oxide has also been studied. It has been found that poly (propylene oxide) has four stereoisomers, which are the same, the same and the two isomers . Wherein the chemical shift of the isotactic structure is confirmed by the polypropylene oxide in the crystalline portion at a relatively low field.