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Preparation of polycarbonate diols (PCDLs) from dimethyl carbonate (DMC) and diols catalyzed by KNO3/γ-Al2O3

机译:由碳酸二甲酯(DMC)和KNO3 /γ-Al2O3催化的二醇制备聚碳酸酯二醇(PCDL)

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γ-Al _(2) O _(3) loaded with potassium nitrate (KNO _(3) /Al _(2) O _(3) ) catalysts were prepared, characterized and employed as a type of heterogenous solid base catalyst in the synthesis of polycarbonate (1,4-butane carbonate)-diol (PBC–OH) via the transesterification of dimethyl carbonate (DMC) and 1,4-butanediol (BD). The relationship between physicochemical properties and catalytic performance for KNO _(3) /Al _(2) O _(3) in this transesterification reaction was investigated using various techniques. The results demonstrated that the performance of KNO _(3) /Al _(2) O _(3) catalysts was highly influenced by basic site amount and strength. The medium and strong basic sites were beneficial for this reaction. The catalyst with a KNO _(3) loading of 35% and a calcination temperature of 700 °C exhibited the best catalytic activity due to its highest basic site amount and appropriate base strength. The highest BD conversion and PBC–OH yield of 80.2% and 68.4% were obtained under optimal reaction conditions. Also, this solid base catalyst was successfully employed in the synthesis of copolycarbonate diols from DMC and two different diols. Different scanning calorimetry results indicated that the thermal properties of the copolycarbonate diols can be adjusted by regulating the average segment lengths, M _(n) and copolymer composition structure.
机译:制备了负载硝酸钾的γ-Al_(2)O _(3)(KNO _(3)/ Al _(2)O _(3))催化剂,对其进行了表征和使用,作为一种多相固体碱催化剂通过碳酸二甲酯(DMC)和1,4-丁二醇(BD)的酯交换反应合成聚碳酸酯(1,4-丁烷碳酸酯)-二醇(PBC-OH)。使用各种技术研究了酯交换反应中KNO _(3)/ Al _(2)O _(3)的理化性质与催化性能之间的关系。结果表明,KNO _(3)/ Al _(2)O _(3)催化剂的性能受碱性部位数量和强度的影响很大。中等和强碱性位点对该反应有利。 KNO_(3)负载量为35%,煅烧温度为700°C的催化剂由于其最高的碱性位点量和适当的碱强度而表现出最佳的催化活性。在最佳反应条件下,最高的BD转化率和PBC-OH产率分别为80.2%和68.4%。而且,该固体碱催化剂已成功用于由DMC和两种不同的二醇合成共聚碳酸酯二醇。不同的扫描量热法结果表明,可以通过调节平均链段长度,M_(n)和共聚物组成结构来调节共聚碳酸酯二醇的热性能。

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