曲酸双棕榈酸酯的制备和性能

研究了新型美白剂曲酸双棕榈酸酯的合成。该合成由棕榈酸的酰氯化和棕榈酰氯与曲酸的缩合两步反应完成。对棕榈酰氯制备过程中棕榈酸与PCl3的摩尔比、反应时间等工艺条件进行了考察,获得了适宜的棕榈酰氯的制备方法。采用了正交实验法对曲酸与棕榈酰氯的缩合反应(酯化反应)的工艺条件进行了优化,获得酯化反应的最佳工艺条件为:n(曲酸)/n(棕榈酰氯)为1 0/2 5,反应温度为35℃,反应时间为2h,丙酮用量为18mL/g曲酸,吡啶用量为3mL/g曲酸。在此条件下,酯化转化率可达88 9%,重结晶纯化得熔点为92℃～94℃的白色固体产品。     

酶法合成果糖棕榈酸酯

以固定化脂肪酶Novozyme435为催化剂,分子筛为除水剂,叔戊醇和丁酮为溶剂,研究了用果糖和棕榈酸生成果糖棕榈酸酯的反应。考察了叔戊醇、丁酮、叔戊醇与丁酮混合溶剂和果糖与棕榈酸摩尔比对产物浓度的影响。实验结果表明,较好的合成条件为果糖与棕榈酸的摩尔比1∶2,叔戊醇占混合溶剂体积总量的40%,0.1 g酶,4A型分子筛适量,反应温度60℃,摇床转速180 r/min。反应12 h后产物浓度达37.7 g/L,果糖转化率达到92.1%,棕榈酸转化率为72.2%。与单一溶剂相比,在混合溶剂中反应,可提高果糖溶解度,增加酶活,缩短反应时间。     

曲酸双棕榈酸酯的合成

以棕榈酸、氯化亚砜为原料,在60~65℃下卤化合成棕榈酰氯;再以吡啶为催化剂、N,N-二甲基甲酰胺为溶剂,与曲酸酰化合成标题化合物,反应温度为15~25℃,收率88.0%。该方法具有操作简单、成本低等优点,适合工业化生产。     

棕榈酸-2-羟基-3-磺酸钠丙酯的合成及性能研究

本文以棕榈酸为主要原料,经磺化、皂化、酯化合成了棕榈酸-2-羟基-3-磺酸钠丙酯,对最佳工艺条件进行了考察,确定了中间产物3-氯-2-羟基丙磺酸钠的最佳合成条件为:环氧氯丙烷与亚硫酸氢钠物质的量比为0.87∶1,反应温度85℃,反应时间3.5 h,产物的转化率为80.4%;棕榈酸钠的最佳合成条件为:棕榈酸与氢氧化钠物质的量比为1∶1,反应温度85℃,反应时间4.5 h,产物的转化率为83%;目的产物棕榈酸-2-羟基-3-磺酸钠丙酯的最佳合成条件为:3-氯-2-羟基丙磺酸钠与棕榈酸钠物质的量比为1.1∶1,反应温度65℃,反应时间6.5 h,产物的转化率为86.82%。经红外光谱分析,确定产物为目的产物,通过测定其溶液的表面张力、乳化性等,表明该产物具有优良的表面活性和较好的乳化性、起泡性等。     

酯交换工艺合成维生素A棕榈酸酯

采用酯交换工艺合成VA棕榈酸酯。K2CO3作为酯交换催化剂,采用过量VA醋酸酯,促使棕榈酸甲酯完全反应。开发了结晶精制技术,把反应产物中未反应的VA醋酸酯结晶分离,获得的VA棕榈酸酯产品含量≥170万IU/g。     

棕榈酰胺丙基甜菜碱两性表面活性剂的合成及其性能

以棕榈酸、N,N-二甲基-1,3-丙二胺为原料,通过酰胺缩合反应合成中间产物——棕榈酰胺丙基二甲基叔胺,再与氯乙酸钠反应合成了两性表面活性剂——棕榈酰胺丙基甜菜碱(PAPB),并考察了反应温度和时间、反应物物质的量比、催化剂KOH用量和4A分子筛对棕榈酸转化率的影响;通过红外光谱和核磁共振氢谱对产物结构进行了表征;测试合成产物及其复配体系的表面活性。得到的酰胺缩合反应的最佳条件为:反应温度160℃、反应时间10 h、n(N,N-二甲基-1,3-丙二胺)∶n(棕榈酸)=1.05∶1.00,KOH用量为反应物总质量的0.5%,在该条件下,棕榈酸的转化率可达92.4%;产物的临界胶束浓度CMC为1.12×10~(-4)mol/L,γ_(CMC)为31.63 m N/m,对苯的增溶能力为X=4 980 m L/mol。     

磷钨酸铈催化合成棕榈酸和硬脂酸混合酸甲酯

采用磷钨酸铈作为催化剂,在反应温度67 ℃合成棕榈酸和硬脂酸混合酸甲酯反应,研究酸醇物质的量比、催化剂用量和反应时间对酯化反应的影响,并在最佳反应条件基础上研究催化剂的循环利用工艺。结果表明,在酸醇物质的量比1∶10、催化剂用量为棕榈酸和硬脂酸混合酸质量的8%、反应时间4 h和催化剂重结晶后循环利用10次条件下,棕榈酸和硬脂酸混合酸转化率均≥96.0%,催化剂反应前后的IR和XRD表征发现,催化剂均为Keggin型结构,未发生变化,表现出良好的催化活性。     

利用棕榈油合成棕榈酸甲酯的研究

以甲醇和从棕榈油中获得的棕榈酸为原料，以甲醇钠为催化剂，在８０℃下反应２．５ｈ合成棕榈酸甲酯。其产率为９８．８％，熔点为３０℃，酸价为０．９１。     

疏水化水溶性羧甲基纤维素的制备

通过羧甲基纤维素与棕榈酸酰氯在DMF介质中反应制备疏水化水溶性羧甲基纤维素，讨论了羧甲基纤维素、棕榈酸酰氯用量，pH值，反应温度，溶剂对反应的影响，确定了适宜的反应条件：羧甲基纤维素10g，棕榈酸酰氯2．5g，pH8～10，反应温度50℃，反应时间3h。     

棕榈酰胺丙基甜菜碱两性表面活性剂的合成、表征与性能

以天然产物棕榈酸、N,N-二甲基-1,3-丙二胺为原料通过酰胺化反应合成中间产物棕榈酰胺丙基二甲基叔胺,再与氯乙酸钠反应合成了两性表面活性剂——棕榈酰胺丙基甜菜碱（PAPB）,并考察了反应温度和时间、反应物摩尔比、催化剂用量和4A分子筛等因素对合成中间产物的影响;通过红外光谱和核磁共振对产物结构进行了表征;测试合成产物及其复配体系的表面活性。得到的酰胺化反应的最佳条件为：反应温度160℃、反应时间10 h、n(N,N-二甲基-1,3-丙二胺): n(棕榈酸)=1.05:1,KOH用量为反应物总质量的0.5%,在该条件下,棕榈酸的转化率可达92.41%;产物的临界胶束浓度CMC为1.12×10-4 mol•L-1,γCMC为31.63 mN•m-1,对苯的增溶性能为X=4980mL/mol。     

维生素B_6中关键杂质A的制备与分析

以维生素B6为起始原料,在硫酸存在下合成了欧洲药典中的维生素B6杂质A,并通过1H NMR、MS、FT-IR、HPLC方法对其结构进行鉴定,为生产维生素B6质量控制提供了一种简便的杂质标准物制备方法。     

Solubility and heat stability of fat-soluble derivatives of vitamin B6

Summary The heat stability of several fatty acid esters of pyridoxine and their solubility in fats was tested. Short chain fatty acid esters of pyridoxine, such as pyridoxine triacetate, and long chain saturated fatty acid esters of the vitamin, such as pyridoxine tripalmitate were almost insoluble or had a rather limited solubility in fats. An improvement in solubility was observed when pyridoxine was partially esterified with palmitic acid, fully esterified with a long chain unsaturated fatty acid, such as linoleic acid, or when it was esterified with a fatty acid of intermediate chain length (C₆, C₈ or C₁₀). Free pyridoxine and the acetate were destroyed by heat when mixed in a fat and heated at 205–210°C. A profound improvement in heat stability in pyridoxine was noted when one palmitoyl group was introduced, and the ester became completely stable when it was fully esterified with a saturated fatty acid of C₁₀ or longer chain length. Portion of a thesis presented by T. Sakuragi as partial fulfillment of the requirement for the degree of Doctor of Philosophy in Food Technology. This work was supported by research grant No. A-257 from the National Institute of Health, U. S. Public Health Service, Department of Health, Education and Welfare. Presented at the 29th annual meeting of the American Oil Chemists’ Society, Oct. 10–12, 1955, Philadelphia, Pa.     

二氧化锰晶型对吡哆醇氧化反应的稳定性研究

以吡哆醇（1）为起始原料,经二氧化锰选择性氧化反应制得吡哆醛（2）,通过X射线衍射脚）分析不同市售二氧化锰的晶型,研究不同晶型对催化氧化能力的影响,发现较优的晶型为γα-MnO2（混铆。     

The origin of palmitic acid in brain of the developing rat

A rat milk substitute containing lower amounts of palmitic and oleic acid in the triacylglycerols in comparison to natural rat milk was fed to artificially reared rat pups from day 7 after birth to day 14. Pups reared by their mother served as controls. Free trideuterated (D₃) palmitic acid [(C²H₃)(CH₂)₁₄COOH, 98 atom % D] and free perdeuterated (D₃₁) palmitic acid [C₁₅ ²H₃₁COOH, 99 atom % D] in equal quantity were mixed into the triacylglycerols of the milk substitute in an amount equal to 100% of the palmitic acid in the triacylglycerols. A control milk substitute contained unlabeled free palmitic acid in an amount equal to 100% of the palmitic acid in the triacylglycerols of the milk substitute. The objective was to determine if palmitic acid in the diet contributed significantly to the palmitic acid content of developing brain and other organs. The methyl esters of the fatty acids were analyzed by gas chromatography and the palmitic acid methyl ester was examined by fast atom bombardment mass spectrometry. The proportion of deuterated methyl palmitate as a percentage of total palmitate was determined; 32% of the palmitic acid in liver and 12% of the palmitic acid in lung were trideuterated and perdeuterated palmitic acid in approximately equal amounts. The brain, by contrast, did not contain the deuterated palmitic acid moiety. Quantitation of palmitic acid and total fatty acids revealed a significant accumulation in organs in the interval from 7 to 14 days of age. Under our experimental conditions, labeled palmitic acid does not enter the brain. Consequently, we conclude that the developing brain produces all required palmitic acid byde novo synthesis.     

栀子油脂制取亚油酸的研究

用气相色谱法分析了栀子果实油脂中主要脂肪酸的组成 ,软脂酸和亚油酸分别占总脂肪酸的 2 5 .5 %和71.8%。栀子油脂经皂化、酸化、丙酮溶解、冷冻结晶等工艺可制出符合医药标准的亚油酸 ,并对工艺参数进行了研究     

Palmitic acid enhances cholesterol gallstone incidence in sasco hamsters fed cholesterol enriched diets

In an established hamster model of cholesterol cholelithiasis, a semipurified lithogenic diet containing 4% butterfat and 0.3% cholesterol leads to the production of cholesterol gallstones in only 50–60% of animals after a 6-wk feeding period. The purpose of this study was to investigate whether gallstone incidence could be increased while feeding a nutritionally adequate diet of moderate cholesterol content. The semipurified lithogenic diet was modified as follows: (i) substitution of 1.2% palmitic acid for 4% butterfat, and (ii) varying the amount of dietary cholesterol from 0.0 to 0.3% with either butterfat or palmitic acid as the lipid component of the diet. Substitution of palmitic acid for butterfat produced a significantly higher incidence of cholesterol gallstones (94%vs. 53%). Palmitic acid also raised the incidence of gallstones when added to the 0.1% and 0.2% cholesterol diets as compared to butterfat: 0%vs. 44% and 50%vs. 81%, respectively. Gallstone incidence increased from 0% to nearly 100% when the cholesterol content of the palmitic acid diets was raised from 0.0% to 0.3%, indicating a dose response effect with respect to dietary cholesterol. Hamsters fed cholesterol-free diets did not form gallstones. Increased dietary cholesterol led to increased liver weight associated with a significant increase in liver cholesterol concentration. However, the palmitic acid groups had significantly lower liver cholesterol values than the corresponding butterfat groups. Serum and biliary cholesterol concentrations increased with increasing dietary cholesterol intake, but there were no differences between the butterfat and palmitic acid groups. The cholesterol saturation index increased from 0.56 to 1.32 in the butterfat groups and from 0.56 to 1.30 in the palmitic acid groups upon raising the dietary cholesterol from 0.0 to 0.3%. Biliary total bile acid concentration did not vary significantly within all groups; however, the addition of cholesterol produced an increase in the ratio of chenodeoxycholic acid to cholic acid. It is concluded that in Sasco hamsters the saturated fatty acid, palmitic acid, when substituted for butterfat in a nutritionally adequate lithogenic diet, is capable of increasing gallstone incidence to almost 100% during a 6-wk feeding period.     

Synthesis of the structured lipid 1,3-dioleoyl-2-palmitoylglycerol from palm oil

Human milk fat contains 20–25% palmitic acid (16∶0) and 30–35% oleic acid (18∶1). More than 60% of the plamitic acid occurs at the sn-2 position of the glycerol backbone. Palm oil is a rich source of both palmitic and oleic acids. The structured lipid 1,3-dioleyl-2-palmitoylglycerol (OPO) is an important ingredient in infant formula. OPO was synthesized from palm oil by a three-step method. In the first step, low-temperature fractionation was applied to palm oil FA, yielding a palmitic acid-rich fraction (87.8%) and an oleic acid-rich fraction (96%). The palmitic acid content was further increased to 98.3% by transforming palmitic acid into ethyl palmitate. In the second step, esterification of ethyl palmitate and glycerol catalyzed by lipase Novozym 435 under vacuum (40 mm Hg) was employed for the synthesis of tripalmitin. Finally, OPO was obtained by the reaction of tripalmitin. Finally, OPO was obtained by the reaction of tripalmitin with oleic acid catalyzed by Lipase IM 60. In this final step, the TAG content in the product acylglycerol mixture was 97%, and 66.1% oleic acid was incorporated into TAG. Analysis of the FA composition at the sn-2 position of TAG showed 90.7 mol% of palmitic acid and 9.3 mol% of oleic acid. OPO content in the product TAG was ca. 74 mol%. Thus, an efficient method was developed for the synthesis of OPO from palm oil.     

由棕榈油无溶剂法合成蔗糖棕榈酸酯

在酸催化下,由乙醇与棕榈油反应制出了棕榈酸乙酯。在催化剂和乳化剂存在下,以棕榈酸乙酯、蔗糖为原料酯交换法合成出了蔗糖棕榈酸酯(SE),用红外光谱、激光电离质谱对SE进行了分析表征,详细考察了蔗糖粒度,乳化剂、催化剂用量,反应温度、压力及时间,原料配比等因素对SE产率的影响。通过制成易挥发衍生物方法,建立了分析SE组成的气相色谱方法。用正交实验法优化出了较佳合成条件,即n(棕榈酸乙酯)∶n(蔗糖)=3∶1,m(催化剂)∶m(蔗糖)=0 08∶1,m(乳化剂)∶m(反应物料)=0 12∶1,温度～125℃,压力～2 67kPa,时间～4h。该条件下,SE产率(以蔗糖计)在73 6%以上。     

Improved adhesion of TiO2‐based multilayer coating on HDPE and characterization of photocatalysis

Multilayered photocatalytic TiO₂‐based coating was prepared by spin coating on a high‐density polyethylene (HDPE) substrate. The multilayered coating consisted of a polyurethane (PU) barrier layer and two layers of TiO₂ nanoparticles bound with PU. The adhesion between the HDPE substrate and protective PU coating was enhanced by oxygen plasma treatment of the substrate. The improved adhesion contributed to the photocatalytic degradation of palmitic acid. Long‐term activity of the photocatalytic coating in degradation of palmitic acid under UV illumination was followed by FTIR‐ATR. The catalytic activity of the coating was maintained in three identical cycles where palmitic acid was added and UV‐irradiated for 6 h. According to FTIR measurements, the palmitic acid was almost completely decomposed after 6 h, but gas chromatography (GC) analysis showed total decomposition to require 12 h UV illumination (∼ 97% of palmitic acid decomposed in 12 h). Study of the degradation of palmitic acid by GC as a function of time indicated that the degradation kinetics was pseudofirst order, and the rate constant obtained was 0.31 h⁻¹. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

固体酸Zr(SO4)2/TiO2催化合成棕榈酸甲酯

以固体酸Zr(SO4)2/TiO2为催化剂,工业棕榈酸与甲醇为原料合成棕榈酸甲酯生物柴油。考察了Zr(SO4)2负载量、催化剂焙烧温度、焙烧时间、m(棕榈酸)∶m(甲醇)、催化剂用量和反应时间对酯化率的影响,并采用GC-MS、红外光谱仪、热重差热综合热分析仪对催化剂和产物进行表征分析。结果表明,与Zr(SO4)2催化剂相比,固体酸催化剂Zr(SO4)2/TiO2在工业棕榈酸和甲醇的酯化反应中具有较高的催化活性。适宜的反应条件为:以400℃焙烧制得的Zr(SO4)2负载量为65%的固体酸Zr(SO4)2/TiO2为催化剂,醇酸质量比为12∶25,催化剂用量为棕榈酸质量的8.0%,反应时间5 h。在该条件下,酯化率可达98.9%。经GC-MS分析,酯产物主要为直链十六烷酸甲酯和10-十八碳烯酸甲酯。