在TiO2/SiO2催化下乳酸甲酯气相转化为丙交酯

А.М. Vаrvarin, S. Levytska, А.М. Mylin, V. Brei
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引用次数: 1

摘要

聚乳酸(PLA)作为生物破坏性包装材料得到了广泛的应用。通常由乳酸产生单体丙交酯。乳酸甲酯(乙基)在TiO2/SiO2催化剂上气相冷凝,温度为2600C,载气为N2,可制备丙交酯。然而,此时必须将载气加热到反应温度。本文介绍了在无载气条件下,在100-150毫巴的低压条件下,乳酸甲酯蒸汽缩合成丙交酯的结果。用Ti(OC4H9)4浸渍二氧化硅制备了钛含量为5 wt.%的负载型TiO2/SiO2催化剂。经5000C煅烧制备的催化剂具有无定形介孔结构,比表面积为335 m2/g,孔体积为0.83 m3/g。用这种方法进行了催化实验。将乳酸甲酯液体加入蒸发器(2500C)中,并在真空泵产生的100mbar压力下进入流动反应器(2600C)。催化剂负载在25 ~ 55 mmol ML/(gcath)之间变化。冷却后的产物在Agilent 7820A色谱仪和Bruker Avance-400核磁共振光谱仪上进行分析。结果表明,在50-53%的乳酸甲酯转化率下,TiO2/SiO2催化剂对丙交酯的选择性为74%,在2600C/100 mbar条件下,丙交酯的产率为7.8 mmol L/(gcath)。催化剂稳定工作80 h以上,主要杂质为乳乳酸甲酯、1-甲氧基乙醇和1,1-二甲氧基乙烷。
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Vapour-phase conversion of methyl lactate into lactide over TiO2/SiO2 catalyst at the lowered pressure
Now polylactide (PLA) widely use as biodestructive packing material. Usually monomeric lactide produce from lactic acid. Also, methyl (ethyl) lactate could be used for lactide obtaining via its vapour-phase condensation on TiO2/SiO2 catalyst at 2600C in N2 carrier-gas flow. However, at that it is necessary to heat carrier-gas to the reaction temperature. In this communication the results on methyl lactate vapour condensation into lactide with the lowered pressure of 100-150 mbar, without carrier-gas, are presented. Supported TiO2/SiO2 catalyst with 5 wt.% titania content has been prepared by impregnation of silica with Ti(OC4H9)4. After calcination at 5000C prepared catalyst has amorphous mesoporous structure with 335 m2/g surface area and 0.83 сm3/g pore volume. The catalytic experiments were performed in such way. Liquid methyl lactate was dosed into the evaporator (2500C) and further in the flowing reactor (2600C) under pressure of 100 mbar that produced by vacuum pump. Load on a catalyst was varied from 25 to 55 mmol ML/(gcath). Cooled product was analyzed on Agilent 7820A chromatograph and NMR Bruker Avance-400 spectrometer. It was shown that TiO2/SiO2 catalyst provide 74% selectivity towards lactide at 50-53% methyl lactate conversion with lactide productivity of 7.8 mmol L/(gcath) at 2600C/100 mbar. The catalyst stable work is more 80 h. Main impurities are methyl lactoillactate, 1-methoxyethanol and 1,1-dimethoxyethane.
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