酸催化甘油醚化合成甘油烷基醚反应的研究

以甘油和异丁烯为原料合成甘油烷基醚,考察阳离子交换树脂Amberlyst-15(dry)、Amberlyst-35(dry)、DFHS-6、分子筛H-Y(6)、ZSM-5(25)、H-Beta(15)及PTSA(对甲苯磺酸)等7种酸性催化剂以及催化剂用量、反应温度、搅拌转速、甘油/异丁烯摩尔比、反应时间、反应压力对反应的影响。结果表明,最佳催化剂为Amberlyst-35(dry),最佳工艺条件为:反应时间5 h,反应温度90℃,甘油/异丁烯摩尔比1∶4,反应压力3 MPa,搅拌转速500 r/min,催化剂用量为甘油质量的7%。在此条件下,甘油转化率可达96.4%,醚类化合物收率达77.4%。     

失水甘油烯丙醚的合成

采用相转移催化一步法合成了失水甘油烯丙醚,摸索了反应最佳条件,测定了沸点,折射率,并进行了红外谱图分析,反应的净产率达到７６％。     

丙二醇单烷基醚的合成

介绍了低温、常压下用环氧丙烷与低级脂肪醇在一种BF3改进催化剂作用下合成丙二醇单烷基醚的方法。通过实验考察了影响转化率的因素 ,并对两种不同产物的合成进行比较 ,给出了适宜的反应条件和经济的生产过程     

相转移催化合成芳基烷基醚

报道了以四丁基溴化铵为相转移催化剂，简便地合成了１０个芳基烷基醚，反应几乎是定量地快速进行。     

失水甘油烯丙醚的合成

采用相转移催化一步法合成了失水甘油烯丙醚,摸索了反应最佳条件,测定了沸点、折射率,并进行了红外谱图分析,反应的净产率达到７６％。     

烷基醚磷酸酯钾盐的合成及抗静电性探讨

本文研究了C_(11~13)醇醚磷酸酯钾盐的合成,确定出较佳的合成工艺条件,并测试了其抗静电性能,结果表明该产品作为涤纶纺丝的抗静电剂,具有较好的抗静电性能。     

利用Mitsunobu反应合成芳基吡啶烷基醚

在室温下,以取代苯酚1a-b和吡啶烷基醇2a-d为原料通过Mitsunobu反应合成了相应的芳基吡啶烷基醚,反应收率为45%￣70%,反应物2和1之比为1.11∶(摩尔比)。结果表明当酚的6-位取代基为甲氧基时,产物的收率比6-位上没有取代基时的收率高;溶剂对反应收率的影响不大。并用1H NMR、13C NMR和MS等对产物的结构进行了测定。     

寡甘醇单烷基醚的合成和性能

以寡甘醇和卤代烷为原料,利用相转移催化Ｗｉｌｌｉａｍｓｏｎ法合成了１２种寡甘醇单烷基醚,均获得较高产率。讨论了寡甘醇单醚合成的反应历程,并对其物理常数、水溶液的表面张力、起泡性能、临界胶束浓度进行了测试和分析。     

Cu(I)卤化物催化合成烷基芳基醚的研究

本文简要地介绍了未被活化芳烃的烷氧基化反应,对其反应机理、应用范围、影响因素等作以综述。     

烷基甘油醚硫酸酯盐的合成

以甘油为原料制备了二辛基甘油醚硫酸盐阴离子表面活性剂,分别以IR和MS对中间产物二辛基甘油醚进行了结构表征。考察了物料摩尔比、反应温度、反应时间等因素对中间产物二辛基甘油醚收率的影响,得出了制备二辛基甘油醚的适宜工艺条件：辛醇钠与二氯丙醇摩尔比为2.2∶1,反应温度为70 ℃,反应时间为8 h。经GC内标法分析,上述条件下二辛基甘油醚的收率大于92%。以氯磺酸为硫酸化试剂,制得了二辛基甘油醚硫酸钠,并对其表面活性进行了测定,结果显示,该新型表面活性剂具有较好的降低表面张力的能力和较低的临界胶束浓度。     

烷基甘油醚羧酸盐的合成

以甘油、氯化氢和辛醇为原料,制备二辛基甘油醚,然后与氯乙酸反应,制得二辛基甘油醚羧酸盐阴离子表面活性剂。考察了反应温度、物料摩尔比、反应时间等因素对反应的影响。结果表明,反应的最佳条件为:投料摩尔比为(二辛基甘油醚)∶(NaOH)∶(ClCH2COOH)=1∶2.5∶1.2,第一步碱化反应温度为120℃,反应时间为3 h,然后冷却至70℃进行5 h的羧甲基化反应,活性物含量为80.8%。该新型表面活性剂具有较低的表面张力(γcmc=25.38 mN/m)和较低的临界胶束浓度(cmc=1.12×10-3mol/L)。     

Thermodynamic equilibrium analysis on the dehydration of glycerol with monohydric alcohols to alkyl glyceryl ethers

Under the conditions of the feed of 400 moles of alcohol + 100 moles of glycerol, 313–573 K and 0.1 MPa, based on Gibbs free energy global minimization, an improved genetic algorithm was used for the thermodynamic equilibrium analysis on the synthesis processes of alkyl glyceryl ethers, respectively, from methanol + glycerol, ethanol + glycerol, isobutanol + glycerol, and tert-butanol + glycerol. The columnar stacking charts and three-dimensional contour graphs were used to compare the effects of temperature, pressure, and the feed ratio to the equilibrium conversion, product selectivity, and equilibrium composition. The basic laws of the synthesis processes of alkyl glycerol ethers in homogeneous and heterogeneous states were investigated in a wide temperature range. Through comparison, it was found that the isopropanol + glycerol system is easier to convert into alkyl glycerol ethers, followed by the ethanol + glycerol system. The methanol + glycerol system and tert-butanol + glycerol system are greatly affected by pressure and temperature, and their conversions and selectivities are relatively low.     

Selective oxidation of glycerol to formic acid catalyzed by iron salts

Glycerol is oxidized by hydrogen peroxide to formic acid with excellent selectivity in the presence of iron salts. The oxidation takes place at room temperature in water; at the end of the reaction the catalytic system is still active and available to restart the oxidation.     

Glyceryl ethers in insects: identification of alkyl and alk-1-enyl glyceryl ether phospholipids

Alkyl and alk-1-enyl glyceryl ethers have been identified in the phospholipids of three insect species, the American cockroach (Periplaneta americana), the tobacco budworm (Heliothis virescens), and the boll weevil (Anthonomus grandis). Glyceryl ethers were not detected in the neutral lipids. The ethers were found in the phospholipid fraction of whole insects and in isolated fat body tissue. The ether content varied among the three insect species, and fluctuated during various developmental stages. Gas liquid chromatographic analysis of the alkyl glyceryl ethers and aldehydes derived from the alk-1-enyl glyceryl ethers of the cockroach and budworm whowed striking differences in chain length. However, the hydrocarbon side-chain of the two ether fractions were similar in length for each species. Preliminary evidence indicates that 1-¹⁴C-acetate can be incorporated into alkyl ethers but not into alk-1-enyl ethers ofHeliothis pupae. Presented at the AOCS-AACC joint meeting, Washington, D.C., 1968. Under contract with the U.S. Atomic Energy Commission.     

氧化铝负载杂多酸催化甲醇脱水制备二甲醚

制备并用N2 吸附和吡啶吸附红外进行表征 ,结果表明氧化铝负载杂多酸催化剂具有中孔结构 ,表面上具有布朗斯台特酸和路易斯酸。研究了反应压力、温度和质量空速对甲醇脱水生成二甲醚转化率和选择性的影响 ,及催化剂使用寿命。使用该催化剂制备二甲醚的最佳工艺条件为 :反应压力 0 .75～ 0 .85MPa ,反应温度 2 80～ 32 0℃ ,质量空速 1 .5～ 2 .5h- 1 。     

PtAu/ZrO_2催化甘油选择性制备乳酸

采用溶胶-沉积法制备了Pt Au/ZrO_2系列催化剂,在惰性气体气氛下用于催化甘油选择性制备乳酸。研究不同反应温度下,不同单金属负载和不同比例Pt Au双金属负载催化剂的催化活性以及不同气氛下催化剂重复使用性能,对催化剂进行BET、AAS和TEM等表征。结果表明,在浓度1.1 mol·L-1甘油水溶液10 m L、(1∶1)Pt Au/ZrO_2催化剂用量0.132 g、反应温度160℃、氮气压力1.4 MPa和反应时间6 h条件下,甘油转化率90%,乳酸选择性93.7%。催化剂重复使用性能实验验证了氧气气氛下催化剂活性保持良好。     

丙烯海松酸甘油酯聚氧乙烯醚的合成及性能

合成了新的非离子表面活性剂丙烯海松酸甘油酯聚氧乙烯醚,研究丙烯海松酸与甘油的部分酯化及甘油酯与环氧乙烷的加成反应。适宜的反应条件为:丙烯海松酸与甘油反应温度260-270℃,用料摩尔比为1:3,反应时间5 h,催化剂ZnO用量为酸质量的0.08％;甘油酯与环氧乙烷的加成反应催化剂为KOH,用量为酯质量的0.7％-0.8％,温度150℃。测定了产物的表面物理化学性能,研究了环氧乙烷聚合度对产物表面物理化学性能的影响。     

Glyceryl ethers in insects: Biosynthesis of ethanolamine phosphoglycerides containing alkyl and alk-1-enyl glyceryl ether linkages

When¹⁴C-labeled acetate, fatty acids or fatty alcohols were injected into or fed to the tobacco budworm, acyl, alkyl and alk-1-enyl moieties of the phospholipids incorporated radioactivity. Fatty acids were the principal precursor in acyl bond formation and fatty alcohols in the synthesis of alkyl and alk-1-enyl glyceryl ethers. Detailed analysis of the etherlinked phosphoglycerides revealed that most of the radioactivity was in the ethanolamine phosphoglycerides, and very little¹⁴C was found in the choline phosphoglycerides. In experiments of a short duration, the alkyl glyceryl ethers incorporated more radioactivity than the alk-1-enyl glyceryl ethers. The reverse was found with long term experiments, when the alk-1-enyl ethers had higher radioactivity. In addition to demonstrating the synthesis of ether-linked ethanolamine phosphoglycerides, the data suggested that fatty alcohols and acids were interconverted by insects and that the alk-1-enyl ethers were derived from the alkyl ethers. Presented at the AOCS Meeting, Houston, May 1971. The following abbreviations and terminology will be used: PE, PC, PI and PS for the generic terms ethanolamine, choline, inositol and serine phosphoglycerides, respectfully. Alkyl glyceryl ether for 1-alkyl-2-acyl-sn-glycerol-3-phosphoryl-, and alk-1-enyl glyceryl ether for 1-alk-1′-enyl-2-acyl-sn-glycerol-3-phosphoryl-(commonly called plasmalogen). These are adapted from the tentative rules published inJ. Lipid Res. 8:522–528 (1967).     

吡啶硫酸氢盐离子液体催化甘油与乙酸酯化反应动力学

以吡啶硫酸氢盐离子液体为催化剂,系统研究其催化甘油和乙酸酯化反应生成三乙酸甘油酯的动力学行为。采用单因素实验考察反应温度、酸醇摩尔比、催化剂用量等因素对甘油转化率及产物三乙酸甘油酯收率的影响。根据拟均相一级反应机理建立微分方程组模型,通过动力学数据拟合获得指前因子和反应活化能。结果表明:甘油转化率随反应温度、酸醇摩尔比升高而增加;随着催化剂用量的增加,甘油的反应速率逐渐增大,但平衡转化率基本不变。当反应温度为110℃,乙酸/甘油摩尔比为6∶1,催化剂用量为甘油的3%(质量分数)时,甘油转化率最高为98.5%,三乙酸甘油酯收率最高为40.4%。甘油与乙酸反应逐步生成单乙酸甘油酯、二乙酸甘油酯、三乙酸甘油酯的指前因子k10、k20、k30分别为7.17、14.19、13.78 min-1,其相应的反应活化能E1、E2、E3分别为19.10、21.58、23.25 kJ·mol-1,该动力学模型计算值与实验值吻合较好。该催化剂相较于已报道的Amberlyst-15、杂多酸催化剂反应条件更温和、选择性更高、反应活化能更小,具有更好的催化效果。