Physical properties of oleochemical carbonates

Carbonates are a class of compounds that have recently found increasing interest in commercial applications owing to their physical properties and relatively straightforward synthesis. In this work, physical and fuel properties of five straight-chain C_17–39 and three branched C_17–33 oleochemical carbonates were investigated. These properties included cetane number (CN), low-temperature properties, (kinematic) viscosity, lubricity, and surface tension. The carbonates studied had CN ranging from 47 to 107 depending on carbon chain length and branching. For the same number of carbons, the CN of carbonates were lower than those of FA alkyl esters owing to interruption of the CH₂ chain by the carbonate moiety. Kinematic viscosities at 40°C ranged from 4.9 to 22.6 mm²/s whereas m.p. ranged from +3 to below −50°C depending on the carbonate structure. High-frequency reciprocating rig testing showed the neat carbonates to have acceptable lubricity that improved as chain length increased. Finally, the carbonate's ability to influence cold-flow properties in biodiesel (methyl soyate) and lubricity in low-lubricity ultra-low sulfur diesel were examined. The carbonates studied did not significantly affect cold flow or lubricity properties at concentrations up to 10,000 ppm (1 wt%). The properties of the carbonates resemble those of fatty alkyl esters with similar trends resulting from compound structure.     

Guerbet十四醇的合成与表征

以正庚醇为原料 ,通过Guerbet反应合成Guerbet十四醇 (2 戊基壬醇 ,C14 GA)。用IR、NMR和元素分析测定了C14 GA的结构 ,并研究了反应温度和用料比对其产率的影响。实验结果如下 :(1)在较优化的反应条件下 (正庚醇的总加入量为 1mol,在实验过程中 ,先加入 1/ 3mol庚醇和 1/ 4mol的KOH ,在 16 0℃下反应 2h ,然后再加入剩下的 2 / 3mol庚醇和 4g 5 %Pd -C催化剂 ,在 15 5℃下反应 6h)合成产物 ,其产率可达到 5 4 2 0 % ;(2 )所合成的产物与试图要得到的Guerbet十四醇 (2 戊基壬醇 ,C14 GA)含有相同的基团 (2×—CH3、10×—CH2 —、1×CH、1×—CH2 —O—和 1×—OH) ,而且 ,所合成的产物中 ,w (C) =79 0 6 % ,w (H ) =13 6 2 % ,与从Guerbet十四醇分子式计算的理论值w(C) =78 5 0 % ,w (H) =14 0 1%基本一致。可见所合成的产物正是Guerbet十四醇 (C14 GA)     

Effects of branching upon some surfactant properties of sulfated alcohols

A study was undertaken to determine the surfactant properties of various sulfated alcohols. Most notably, the Krafft point and the ability to emulsify decane were studied. A series of sulfated Guerbet alcohol and Guerbet alcohol alkoxylate sulfates with 16 carbon atoms and an analogous series based upon cetyl alcohol, a linear C₁₆, were studied as hydrophobes.     

格尔伯特醇制备中镍铝合金与氢氧化钾的协同效应

分别以氢氧化钾为提供碱活性中心的催化剂,镍铝合金为提供金属脱氢活性中心的催化剂,催化癸醇合成二十碳格尔伯特醇反应,考察碱催化活性中心、金属催化脱氢活性中心、以及金属催化脱氢与碱催化活性中心同时存在对格尔伯特反应的影响。结果表明:只有碱催化活性中心存在,与金属催化脱氢与碱催化活性中心同时存在,格尔伯特反应机制不同;金属催化脱氢与碱催化中心之间存在协同效应,碱性活性中心存在的条件下,有利于金属催化醇脱氢生成相应的醛;而仅有金属活性中心时,在常压和液相条件下,醇脱氢生成醛的反应难以实现。     

古尔伯特十六醇硫酸钠的合成与性能研究

以合成的古尔伯特十六醇(2-己基-癸醇)为原料,通过SO3硫酸化法合成了相应的古尔伯特十六醇硫酸钠(C16GS),提纯后活性物含量可达96.8%。最后对古尔伯特十六醇硫酸钠(C16GS)与十二烷基硫酸钠(SDS)的性能进行了对比研究,发现C16GS表面活性、润湿性能、乳化性能均强于SDS,发泡性能与SDS相似但泡沫稳定性差。与AEO9的复配显示,C16GS和AEO9复配溶液在对碳黑污布的去污中产生了协同作用。     

乙醇缩合制高碳醇(C6+醇)多相催化剂研究进展

以乙醇为原料制备其他高附加值化工产品近期得到了广泛关注,特别是乙醇基于Guerbet反应缩合制备高碳醇(C₆₊)的过程更成为这一领域的研究热点。本文着重报道了近年来乙醇转化为高碳醇过程的几种典型的多相催化剂,包括羟基磷灰石(HAP)、类水滑石(LDHs)以及各种负载型金属催化剂的研究开发现状,分析比较了各类催化剂的优势与不足,结合反应机理针对催化剂对高碳醇选择性不高的原因进行了讨论,对理想催化剂的设计和改进进行了展望,指出应该通过促进Guerbet反应中的羟醛缩合过程增加高碳醇的选择性。金属负载型催化剂对该反应控制步骤的加速作用显著,而金属位点和载体表面酸碱活性位点的精细调控以及特定催化剂形貌结构的控制合成则是该领域未来的研究重点。     

The effect of branching and unsaturation upon some properties of polyoxyethylene glycol diesters

Fatty acid diesters based upon polyoxyethylene glycol (PEG diesters) find applications in many diverse segments of thechemical industry. PEG diesters contain both a water-soluble and an oil-soluble portion, resulting in a surface-active product. These surfactants exhibit emulsification properties. A study of PEG diesters was undertaken to determine the effect of the following variables in the fatty portion of the molecule: (i) number of carbon atoms present, (ii) branching or lack of branching, and (iii) presence of unsaturation. The objective was to compare titer point, solubilities and emulsification properties of various PEG-600 based diesters that were synthesized using high-purity linear saturated, Guerbet-branched, and unsaturated acids. Included in the test was a series of esters based upon meadowfoam oil, a high-molecular-weight unsaturated oil.     

稳态荧光探针研究Guerbet醇聚氧乙烯醚羧酸钠的聚集行为

以芘为荧光探针、二苯甲酮为猝灭剂,用稳态荧光探针法测定了合成的4种具有支链结构的Guerbet醇聚氧乙烯醚羧酸钠的临界胶束浓度和胶团的聚集数.结果表明,用稳态荧光探针法得到的临界胶束浓度（CMC）数值与表面张力法相差不大.结合临界胶束浓度、胶束微环境的极性和胶束聚集数的变化规律,推测了这类表面活性剂形成的胶束聚集体的结构形态.     

居贝特表面活性剂的合成和表面性质研究

以短碳链辛醇为起始原料制备了具有Guerbet结构的十六烷基失水甘油醚(Ⅰ)和具有Guerbet结构的十六烷基聚氧乙烯醚(EO)3的失水甘油醚(Ⅱ)以及它们对应的阳离子和两性离子表面活性剂(Ⅲ~Ⅵ)。Ⅲ~Ⅵ表面活性剂的结构如下:N-(3-支链十六烷氧基-2-羟丙基)-N,N,N-三甲基氯化铵(Ⅲ),N-〔3-支链十六烷基聚氧乙烯醚(EO)3-2-羟丙基〕-N,N,N-三甲基氯化铵(Ⅳ),N-(3-支链十六烷氧基-2-羟丙基)-N,N-二甲基羧酸甜菜碱(Ⅴ),N-〔3-支链十六烷基聚氧乙烯醚(EO)3-2-羟丙基〕-N,N-二甲基羧酸甜菜碱(Ⅵ)。通过硅胶柱色谱分离和重结晶,对所得6种化合物进行了纯化。用IR、1HNMR和ESI-MS鉴定了Ⅰ~Ⅵ的结构。并对Ⅲ~Ⅵ的表面张力进行了测定。结果表明,由于这些表面活性剂具有独特的Guerbet亲油基结构,使其具有较低的CMC(10-5~10-6mol/L)和γCMC(25~27 mN/m),有良好的表面活性和应用潜力。     

CuO-NiO催化剂在2-己基-1-癸醇合成中的催化性能

以正辛醇为原料,采用Cu O-Ni O催化剂(脱氢-加氢催化剂)/KOH催化剂(碱性催化剂)体系,通过Guerbet反应合成了2-己基-1-癸醇(2HD),考察了催化剂载体种类、Cu O-Ni O负载量、n(Cu O)∶n(Ni O)和添加不同第三组分对正辛醇转化率和2HD收率的影响。优选出催化效果相对最佳的Cu O-Ni O催化剂,并利用TEM,XRD,BET等手段表征了Cu O-Ni O催化剂的结构。实验结果表明,第三组分Zn O或Mg O的加入可提高正辛醇转化率,但2HD收率降低;以Ca CO3为载体,当Cu O-Ni O负载量为30%(w)、n(Cu O)∶n(Ni O)=1∶2时制得的Cu O-Ni O催化剂的性能最好;在此催化剂作用下,进行2HD合成反应,当反应温度为230℃、反应时间为1 h时,2HD收率最高(达73.0%),此时正辛醇转化率达到84.8%。表征结果显示,Cu O-Ni O催化剂中Cu O和Ni O之间产生协同作用。