我国烷氧基化装置的工艺进展和评述（续完）

正2.1.5第5代反应器第5代反应器是PREESS喷雾反应器和BUSS文丘里混合反应器的组合,是组合式烷氧基化反应器(见图8)。第5代工艺中也有单循环回路和双循环回路2种工艺,根据产品品种的不同而采用不同的工艺。在联泓集团昊达化学有限公司工程中,生产低增长比的产品时采用无小循环回路的单回路循环工艺,生产高增长比的产品时采用双回路循环工艺。     

非活性芳香溴化物烷氧基化研究

使用ＣｕＣｌ－ＣＯ２为催化剂，研究了非活性性芳香溴化物烷氧基化反应条件。为制备ＴＭＢ、香兰素等精细化学品提供了温和的、选择性高的和不污染瓣绿色化学工艺。     

甲氧基香茅醛合成工艺研究

以香茅醛为原料,经二甲胺羰基保护、硫酸催化条件下甲氧基化、氢氧化钠中和合成甲氧基香茅醛。考察了反应温度、反应时间、投料比等工艺条件对产品收率的影响。实验研究得到了最优的合成工艺条件为:胺化反应二甲胺与香茅醛摩尔比为2∶1,反应温度10~15℃,反应时间3 h。甲氧基化反应硫酸浓度为100%,甲醇∶硫酸∶烯胺的摩尔比为15∶5∶1,反应温度15~18℃,反应时间2 h。产品总收率47.6%。反应工艺简单,条件温和,原料易得,便于工业化。产品经IR1、H NMR、GC/MS、元素分析确证结构。     

Separation of kinetics and mass-transfer in a batch alkoxylation reaction

The quantitative aspects of the role of interfacial mass-transfer and reaction kinetics in ethoxylation of lauryl alcohol were examined in a batch recirculation reactor. The liquid droplets falling through a gas column were obtained by utilizing a recirculation loop and a set of spray nozzles. The CO₂/NaOH reaction was employed to characterize the interfacial area. The alkoxylation reaction was studied at temperatures between 124°C and 171°C, at catalyst levels between 0.09 and 0.50 weight percent and at ethylene oxide partial pressures between 68 kPa and 204 kPa. A model was developed which permits the prediction of reactor performance at various operating conditions. The mass-transfer during free fall dominates the interfacial mass-transfer and the contributions during the drop formation and coalescence stages are small. The rate of ethylene oxide (EO) addition to lauryl alcohol was constant during the batch run, indicating similar activity for the unreacted lauryl alcohol and the lauryl alcohol ethoxylated to varying extents. The rate of ethoxylation is first-order in both catalyst and ethylene oxide concentrations. The liquid-phase reaction kinetics and interfacial mass-transfer occur in series, with kinetics dominating the overall ethoxylation rate. As expected, an increasing role of mass transfer is observed at higher temperatures, and/or higher catalyst concentrations where the kinetic rate becomes significantly high. The intrinsic activation energy for the ethoxylation of lauryl alcohol is 55.2 kJ/mole.     

Highly selective synthesis of 2‐butoxy ethanol over Mg/Al/V mixed oxides catalysts derived from hydrotalcites

The catalytic activity of a series of mixed oxides obtained by the thermal decomposition of hydrotalcite‐like precursors was assessed for the alkoxylation of n-butanol with ethylene oxide. The calcination products of a decavanadate intercalated magnesium–aluminium layered double hydroxide were shown to possess extremely high activity for the alkoxylation reaction achieving up to 100% conversion in batch reaction. In all cases, the catalysts exhibit a much higher selectivity towards the monoglycol adduct than that obtained with the industrial catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

高效烷氧基化催化剂

简述了高效烷氧基化催化剂 :碱土金属催化剂、聚碳酸单酯碱土金属盐、水滑石类含镁铝化合物、用Si4 、Ba2 改性氧化镁、用铁镍铈钇改性氧化镁、铝—镁复合氧化物、钛酸和 /或锆酸的酯等 ,并分别论述了它们的化学组成、制法及效果评价     

聚醚-酯嵌段共聚物提高聚氨酯弹性体水解稳定性的研究

采用双金属络合催化剂(DMC),以脂肪族己二酸系聚酯多元醇为起始剂,与环氧丙烷、环氧乙烷进行烷氧基化反应,制得聚醚酯多元醇用于聚氨酯弹性体(PUE)的合成,可得到综合性能优良的PUE材料。在相同硬段含量下,聚醚酯型PUE的力学性能接近纯聚酯型PUE,优于纯聚醚型PUE,并且其耐水解性能得到较大的提高,接近纯聚醚型PUE。     

聚醚-酯嵌段共聚物改性微孔聚氨酯弹性体性能的研究

采用双金属氰化物络合催化剂（DMC），以脂肪族己二酸系聚酯多元醇为起始剂，与环氧丙烷（PO）、环氧乙烷（EO）进行烷氧基化反应，制得聚醚酯多元醇用于微孔聚氨酯弹性体（MPUE）的合成，可得到综合性能优良的MPUE材料。在相同硬段含量下，聚醚酯型MPUE的力学性能接近聚酯型MPUE，优于聚醚型MPUE，并且其耐水解性能得到较大的提高，接近聚醚型MPUE。     

聚醚-酯嵌段共聚物提高聚氨酯弹性体水解稳定性的研究

采用双金属络合催化剂(DMC),以脂肪族己二酸系聚酯多元醇为起始剂,与环氧丙烷、环氧乙烷进行烷氧基化反应,制得聚醚酯多元醇用于聚氨酯弹性体(PUE)的合成,可得到综合性能优良的PUE材料.在相同硬段含量下,聚醚酯型PUE的力学性能接近纯聚酯型PUE,优于纯聚醚型PUE,并且其耐水解性能得到较大的提高,接近纯聚醚型PUE...     

4,6-二乙氧基间苯二胺的合成

以1,5-二氯-2,4-二硝基苯（DCDNB）为原料,经烷氧基化和催化加氢还原反应合成4,6-二乙氧基间苯二胺（DEDAB）,并探索了其影响因素。结果表明合成中间体1,5-二乙氧基-2,4-二硝基苯（DEDNB）的较佳条件为：n(DCDNB)∶n(NaOH)∶n(无水C2H5OH)=1∶4∶30,室温下反应7 h,收率96.43%,HPLC纯度99.74%;产品DEDAB的较优合成工艺条件为：n(DEDNB)∶n(无水C2H5OH)= 1∶44,w(10%Pd/C)/w(DEDNB)= 10%,反应时间7 h,反应温度110 ℃,氢气压力1.5 MPa,收率95.42%,HPLC纯度98.87%。产品及中间体结构经1H NMR、MS 和FTIR分析表征确认。