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。     

Synthesis of long chain alkyl glyceryl ethers from triglycerides using boron trifluoride etherate and lithium aluminum hydride

A procedure for direct conversion of long chain triglycerides to their corresponding ether derivatives has been accomplished using a combination of lithium aluminum hydride and boron trifluoride etherate. Reaction products obtained from reduction of tristearin or trimyristin were isolated by thin layer and column chromatography and identified using infrared spectroscopy. Glyceryl triethers, glyceryl monoethers, and aliphatic alcohols were the major reaction products, making up 2–3%, 9–19%, and 43–75%, respectively, of the theoretical molar yields. Yields of both ether derivatives were increased when a lithium aluminum hydride solution was added to a mixture of triglyceride and boron trifluoride etherate rather than adding a mixture of triglyceride and boron trifluoride etherate to lithium aluminum hydride. Increasing the quantities of lithium aluminum hydride increased glyceryl triether yield, but decreased glyceryl monoether yield.     

丙烯酸甲酯和丙烯酸全氟烷基乙酯嵌段共聚物的合成和表面性能

用原子转移自由基聚合法合成了丙烯酸甲酯和丙烯酸全氟烷基乙酯的两嵌段共聚物,研究了嵌段共聚物的表面性能。结果表明,嵌段共聚物具有低表面能特性。且X射线光电子光谱法证明氟烷基链有强烈的趋于表面的特性。     

Effect of aromatic ring in the alkyl chain on surface properties of arylalkyl surfactant solutions

Surface properties of two series of anionic arylalkyl surfactants, containing different aromatic rings in the straight aliphatic chain, sodium N-aryloleyl-N-methyl-2-aminoethanesulfonates and sodium N-aryloleyl p-methoxyanili-nesulfonates, were investigated. An increase of the aromatic ring size in the alkyl chain increases the critical micelle concentration (CMC) and surface tension at CMC. However, this also decreases the efficiency and effectiveness in reducing water surface tension. The dominant factor of the decrease of efficiency and effectiveness is attributed to the function of the hydrophilic segment and hydrophobic segment for arylalkyl surfactants, respectively. The same results are found in the standard free energy of adsorption (ΔG ^o _ads) and the standard free energy of micellization (ΔG ^o _mic) values. Moreover, with the increase of the aromatic ring size, the adsorption and micellization of arylalkyl surfactants begin to weaken. The data indicate that some parts of surface properties for arylalkyl surfactants are affected by the bulkiness of the arylalkyl chain. The results provide opportunities for further detailed examination of surface properties of arylalkyl surfactants with other branched alkyl chains.     

Hybrid copolymerization of alkyl vinyl ethers with glycidyl ethers

Homopolymerization and copolymerization experiments of isobutyl and dodecyl vinyl ether with propylene oxide, and some glycidyl ethers have been carried out by using both conventional cationic initiators (BF₃, BF₃·OEt₂) and 4-chlorophenyldiazonium tetrafluoborate as cationic photoinitiator. Conventional polymerization experiments performed under vacuum at low and room temperature gave rise to a mixture of the two homopolymers, indicating that the epoxide and vinyl ethers are incompatible with respect to chemical reactivity and that apparently no hybrid copolymerization occurs. Analogous results were obtained in parallel photoinitiated polymerization experiments.     

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。     

长链烷基共晶相变材料的制备及性能

基于长链烷基良好相容性特点,以二十烷（IS）、十八烷（OC）、月桂酸（LC）和十六醇（HD）为原料,通过熔融共混法制备了IS-LC、OC-LC和OC-LC-HD三种共晶相变材料。通过施罗德公式预测理论共晶点的组成及相变温度,结合步冷曲线与差示扫描量热分析（DSC）结果共同确定共晶点最佳质量比分别为m(IS):m(LC) = 0.61:0.39、m(OC):m(LC) = 0.74:0.26和m(OC):m(LC):m(HD) = 0.61:0.21:0.18,共晶温度分别为30.2、25.4、22.6 ℃,与理论计算结果吻合。采用傅里叶变换红外光谱仪（FTIR）、X射线衍射仪（XRD）、热重分析仪（TGA）及DSC对共晶相变材料的化学结构、结晶行为、热稳定性和储热能力进行了表征。结果表明,三种共晶相变材料通过物理作用进行复合,无化学反应发生。其相变温度均在18~32 ℃之间且低于其任意单一组分,相变焓值均大于180 J/g,具有良好的热稳定性和循环稳定性。     

O-三苯基锡不饱和烃基膦酸的合成与性质

通过三苯基锡不饱和烃基膦酸反应,合成了8种新的O－三苯基锡不饱和烃基膦酸Ph3SnOP(O)(OH)R.。利用元素分析、IR、^1HNMR和MS确定了这些化合物的结构。     

二苯磺酸钠双阴离子表面活性剂的合成及性能

以氯苄和对二苯酚为原料,合成4-苄氧基苯酚,再分别与溴代十二烷、溴代十四烷、溴代十六烷反应,最后经氯磺酸磺化,制备三种烷氧二苯磺酸型表面活性剂(命名为C-12、C-14、C-16)。采用IR、1H NMR表征了结构,并测定其临界胶束浓度(CMC)分别为3.35×10-3,9.10×10-4,7.40×10-4mo L/L;表面张力(γCMC)分别为55.45,52.10,49.28 m N/m;Krafft点均<0℃,研究了其乳化性、泡沫性质。     

具有不饱和长链的对—叔烷基苯酚的合成

合成了２种带有不饱和长链的对－叔烷基苯酚：对－（１′,１′－二甲基－十一碳烯－１０基）苯酚和２－（对－羟苯基）－２－（对－十一碳烯－１０氧基苯基）丙烷,其结构通过＾ＨＮＭＲ,元素分析,ＩＲ进行了表征。     

长链烷基季铵碱的制备工艺及性能研究

以烷基叔胺和碳酸二甲酯为原料制备烷基碳酸甲酯铵,烷基碳酸甲酯铵水解得到烷基碳酸氢铵,再通过离子膜连续电解法合成长链烷基季铵碱。以十四烷基三甲基氢氧化铵为例,考察了电解反应温度、电流密度、阳极液浓度、阴极出料液浓度对电流效率的影响,得出其最优工艺条件为：反应温度65 ℃、电流密度450 A/m2、阳极液浓度1.40 mol/L、阴极液出料浓度为0.15 mol/L,在此条件下电解反应的电流效率可达67%以上;通过1H-NMR、IR对产品结构进行了鉴定,结果表明合成的产品为长链烷基季铵碱;对得到的长链烷基季铵碱的表面活性、pH值、润湿性、泡沫稳定性等性能进行了研究。     

二苯磺酸钠双阴离子表面活性剂的合成及性能

以氯苄和对二苯酚为原料,合成4-苄氧基苯酚,再分别与溴代十二烷、溴代十四烷、溴代十六烷反应,最后经氯磺酸磺化,制备三种烷氧二苯磺酸型表面活性剂(命名为C-12、C-14、C-16)。采用IR、1H NMR表征了结构,并测定其临界胶束浓度(CMC)分别为3.35×10-3,9.10×10-4,7.40×10-4mo L/L;表面张力(γCMC)分别为55.45,52.10,49.28 m N/m;Krafft点均0℃,研究了其乳化性、泡沫性质。     

煤制烯烃基长链烷基二甲苯合成研究

采用无水三氯化铝与多卤代烷组成的络合物催化体系，研究了以煤制烯烃某一馏分段和混合二甲苯为原料合成煤制烯烃基长链烷基二甲苯。采用条件实验法得出的较佳工艺参数是：起始反应温度为室温，混合二甲苯/煤制烯烃的质量比为2∶3，相当于物质的量之比2.2～2.5∶1，催化剂用量为反应液总量的1/110(质量分数)，反应时间为60 min，得到的长链烷基二甲苯的含量在80%以上；计算得到其平均分子量约为302.5，相当于十四烷基二甲苯的平均分子量，具有一定的分子量分布，是更好的生产烷基芳基磺酸盐的原料，并在30 L反应器中进行了放大实验。     

Synthesis and properties of novel alkyl sulfate gemini surfactants

Four anionic gemini surfactants of the sulfate type C₁₂C_nC₁₂, where n is the spacer chain length (n = 3, 4, 6, and 10) were synthesized. The structures of these surfactants were confirmed by FT‐IR, ¹H NMR, ESI mass spectra (ESI‐MS), and elemental analysis. The surface‐active properties of these compounds were investigated by means of surface tension, electrical conductivity, and fluorescence measurements. Premicellar aggregations were found for the four gemini surfactants, as revealed by the conductivity measurement. The formation of premicellar aggregates may account for the discrepancy between the critical micelle concentration (cmc) obtained by the surface tension and conductivity measurement. The cmc values of these gemini surfactants were much lower than that of sodium dodecylsulfate (SDS) and decreased monotonously with the increase of spacer chain length from 3 to 10. The effect of spacer chain length on the performance properties like foaming, emulsion stability, and lime soap dispersing ability were also studied and discussed. Practical applications : Alkyl sulfate surfactants are one of the most widely used surfactants. The new alkyl sulfate gemini surfactants synthesized in our study are more surface‐active than sodium dodecylsulfate. These gemini surfactants possess low critical micelle concentrations, high emulsion stability, and excellent lime soap dispersing ability. They have potential applications in the fields of cosmetics, detergents, etc.     

Aminoalkylation of cyclic and acyclic alkyl vinyl ethers

The aminoalkylation of cyclic and acyclic alkyl vinyl ethers from inexpensive starting materials yields Mannich bases 4 and 10 . Preformed and in situ generated iminium salts are used under mild reaction conditions. In some cases it is possible to isolate the α-halogenated 1,3-amino ethers 3 which have so far only ever been assumed to exist. Furthermore, the preparation of the already known 1-benzotriazolyl-3-aminoalkyl ethers 6 and 9 using this methodology is also successful.     

长链烷基改性有机硅聚醚共聚物的合成和应用性能研究

采用侧链含氢硅油、1-癸烯和烯丙基聚醚为主要原料通过硅氢加成反应,制备了一种长链烷基改性有机硅聚醚共聚物(PMGC)。利用IR和~1H NMR对产物的结构进行表征,并研究了含氢硅油的含氢量、黏度及1-癸烯与烯丙基聚醚的摩尔比对产品乳化能力、油脂兼容性及配方肤感的影响。研究表明,当含氢硅油的含氢量为0.4%,黏度为100 mPa·s,n(1-癸烯)∶n(烯丙基聚醚)=3∶1时,其乳化能力和油脂兼容性较佳,将其应用于BB霜配方中,滑感和滋润感较优。     

Preparations and reactions of alkyl ethers of some aldohexoses

Aldohexose, such asd-glucose,d-galactose ord-mannose, reacted with acetone to give the following O-isopropylidene derivatives: 1,2;5,6-di-O-isopropylidene-d-glucofuranose (IA), 1,2;3,4-di-O-isopropylidene-d-galactopyranose (IB) or 2,3;5,6-di-O-isopropylidene-D-mannofuranose (IC). The O-isopropylidene derivative (IA～IC) reacted with alkyl/alkenyl halogenide to yield aldohexose ether compounds containing di-O-isopropylidene group, 3-O-alkyl-1,2;5,6-di-O-isopropylidene-d-glucofuranose (II), 6-O-alkyl-1,2;3,4-di-O-isopropylidene-d-galactopyranose (III) or 1-O-alkyl-2,3;5,6-di-O-isopropylidene-d-mannofuranoside (IV), in good yields. The Williamson ether synthesis was carried out using phase-transfer catalysis (PTC). The derived aldohexose alkyl ether containing di-O-isopropylidene group was hydrolyzed to give 3-O-alkyl-1,2-O-isopropylidene-d-glucofuranose (V) as a partial hydrolysis product; the complete hydrolysis of I～IV gave, as expected, 3-O-alkyl-glucopyranose (VI), 6-O-alkyl-galactopyranose (VII) or 1-O-alkyl-mannofuranoside (VIII). Further alkylation of (V) with Mel under PTC and subsequent acid hydrolysis gave 3-O-alkyl-5,6-di-O-methyl-d-glucofuranose (X). Methanolysis of III with catalytic amounts of H₂SO₄ gave 1-O-methyl-6-O-alkyl-d-galactofuranoside (XI). The elucidation of the galactofuranoside skeleton of (XI) was determined by means of its¹³C nuclear magnetic resonance spectra. The O-alkyl aldohexoses, e.g., X and XI, were evaluated and found to be emulsifiers.     

以对氨基苯甲酸乙酯为端基的酰胺型开链冠醚的合成与表征

以对氨基苯甲酸乙酯为端基合成了3种酰胺型开链冠醚,并通过IR、^1HNMR、MS和元素分析确证了它们的结构.     

Metabolism of alkyl glyceryl ethers in the rat

The metabolism of¹⁴C- and³H-labeled alkyl glyceryl ethers after intraperitoneal injections was examined in the liver and intestine of the rat. Additionally, in vitro experiments were conducted with intestinal homogenates and intetinal contents. From these investigations it was concluded that the liver and the intestine metabolize the alkyl glyceryl ethers very differently. Intestinal contents can alter α-batyl alcohol, as indicated by preliminary experiments, and intestinal cells contain enzyme systems which convert the alkyl glyceryl ethers to the mono- and di-acyl derivatives. Very little esterified glyceryl ethers were found in the liver lipids. The intestine contains an enzyme system which, although it has a greater specificity for chain length and for isomeric position of the ether than that of the liver system, does cleave the glyceryl ethers. From in vivo studies, of intestinal tissue it was concluded that all of the injected glyceryl ethers were converted intact the ethanolamine, serine, and choline alkyl glyceryl ether phospholipids; with the use of α-batyl alcohol, the phosphatidyl ethanolamine fraction, contained most of the labeled glyceryl ether phospholipid with β-batyl alcohol, α-chimyl, and β-chimyl alcohols, the phosphatidyl, choline fraction contained most of the labeled alkyl glyceryl ether phospholipid. No significant amount (<1%) of labeled alkyl glyceryl ether phospholipids was found in any of the rat-liver lipids. Predoctoral trainee supported by Public Health Service Training Grant 5TI-GM-404-04 from the National Institute of General Medical Sciences, National Institutes of Health. Work done in partial fulfillment of the Ph.D. in the Department of Biochemistry at the University of North Carolina.     

Effect of alkyl chain length on the thermophysical properties of pyridinium carboxylates

In the present study,new series of pyridinium carboxylate protic ionic liquids (PILs) were synthesized by pairing pyridinium cation with carboxylate anion from C1-C3 forming pyridinium formate ([CsH6N+][HCOO-]),pyridinium acetate ([CsH6N+][CH3COO-]) and pyridinium propionate ([C5H6N+][CH3CH2COO-]) respectively.The physical properties namely,density,viscosity,surface tension (298.15-343.15) K,and refractive index (293.15-323.15) K were measured.Thermal properties namely,glass transition temperature,molar heat capacity,and thermal decomposition temperatures were also determined.The thermal expansivity was calculated using the experimental density data.The effect of increasing the alkyl chain length on the thermophysical properties of the pyridinium carboxylate PILs has been evaluated.As expected the physical properties i.e.density,viscosity,surface tension and refractive index of the investigated pyridinium carboxylates decreased with increasing temperature.In general pyridinium carboxylate PILs possessed low viscosity,high thermal stability and excellent hydrogen bonding capability,and these properties lead them to outperform conventional solvents employed for lignin dissolution.