Thermal degradation of single methyl oleate hydroperoxides obtained by photosensitized oxidation

A peroxidation mixture containing methyl 9- and 10-hydroperoxy-trans-octadecenoates (MOHP) was obtained by singlet oxygen oxidation of methyl oleate. The two hydroperoxides were collected by solid phase extraction and purified separately by high-performance liquid chromatography. Identification and single-isomer purity evaluations were carried out by comparing the chromatographic and gas chromatography-mass spectrometry parameters of the corresponding reduced hydroxy derivatives. Each purified MOHP was thermally degraded and new reaction mechanisms were proposed from the identification of the degradation products. Thermal rearrangement of each hydroperoxide isomer involved an allylic 3-carbon intermediate before further degradation steps. The two MOHP isomers obtained from singlet oxygen oxidation produced all eight hydroperoxide isomers by thermal degradation in the condensed phase at high temperature (200°C). This result supports the assumption of singlet oxygen as a promoter of the first steps of oxidation of food lipids and also reconsiders the Khan mechanism.     

油酸甲酯连续合成工艺及其动力学研究

在固定床反应器中,以阳离子交换树脂为催化剂,油酸与甲醇液液并流反应制备油酸甲酯。考察了反应各影响因素,获得较适工艺条件为:催化剂装载量20 g,醇酸摩尔比2∶1,反应温度60℃,停留时间40 min。在此条件下,油酸转化率可达99.43%。对油酸与甲醇的反应动力学进行了研究,以拟均相模型对实验数据进行拟合,得出30℃、40℃、50℃、60℃下的正、逆反应速率常数。反应速率随温度的升高而加快,二者关系符合Arrhenius方程,该反应的活化能为60.687 kJ/mol。     

杂多酸催化油酸甲酯环氧化的研究

研究了以磷钨酸-D1821(磷钨酸双十八烷基季铵盐)作催化剂,二氯甲烷作溶剂,30%过氧化氢存在下油酸甲酯的环氧化反应,考察了反应条件对油酸甲酯环氧反应的影响,得到的优化反应条件为:m(30%过氧化氢)∶m(油酸甲酯)=1∶1,m(二氯甲烷)∶m(油酸甲酯)=1.5∶1,m(催化剂)∶m(油酸甲酯)=25‰。在最优条件下得到的环氧油酸甲酯的碘值在4.3 g I2/100 g左右,环氧值在3.95 g/100 g左右,酸值在0.2 mg KOH/g左右,均达到了一等品的要求。     

碳基固体酸催化剂的制备及催化合成油酸甲酯

以蔗糖和对甲基苯磺酸混合物为原料,采用水热法一步合成了碳基固体酸催化剂,用于催化油酸和甲醇酯化合成油酸甲酯。考察了催化剂用量、原料配比、反应时间及催化剂重复使用性等对酯化率的影响。结果表明,适宜反应条件为:催化剂用量为油酸质量的3.54%,醇酸摩尔比6∶1,反应时间7 h,酯化率可达94.96%。该催化剂尚具有一定的重复使用性。     

Thermal and photolytic degradation of plates of poly(methyl methacrylate) containing monomer

Specimens of 1.5 mm thick absorber-free poly(methyl methacrylate) (PMMA) containing ～0.6% monomer but no absorber have been photolytically degraded in air at 50°, 85° and 115°C and thermally degraded in air at 115° and 125°C. Specimens were exposed to a simulated solar spectral range. Degradation was followed by gel permeation chromatographic determinations of molecular weight as a function of depth in the specimens. The results show increased photodegradation at the plate faces (back and front) over that occurring in the centres, and a rapidly attained constant amount of degradation for thermal degradation. Degradation mechanisms are proposed. The thermal degradation is ascribed to weak links and unspent initiator. Photolytic initiation is ascribed, at least in part, to degradation of the ester group by wavelengths in the range 300 to 330 nm. The effect of oxygen is to convert alkyl radicals into peroxyl radicals, some of which form alkoxyl radicals which tne undergo β-scission to give in-chain ruptures. Where the oxygen concentration is low, monomer changes non-tertiary alkyl radical sinto tertiary radicals by addition to the monomer double bond. After their peroxidation by molecular oxygen, tertiary radicals react with one another to give alkoxyl radicals and subsequent chain scission rather than undergoing the Russell termination reaction with no chain scission characteristic of non-tertiary peroxyl radicals. The effect of temperature is mostly to decrease the importance of the cage effect and to allow the initial radicals formed to diffuse away from one another. The products of photo-oxidation absorb the shorter (300 to 330 nm) radiation significantly and progressively shield the remainder of the plate as degradation proceeds.     

Methoxylation of methyl oleate in the presence of dealuminated Y faujasites in their protonic form

Methoxylation of methyl oleate into methyl methoxy stearate was carried out in a batch reactor at temperatures ranging from 150 to 190°C in the presence of dealuminated H-Y faujasites as catalysts. In the presence of an excess of methanol, the H-Y faujasite with a Si/Al ratio of 15 was shown to achieve the title reaction with a yield of methyl methoxy stearate that does not exceed 40% because of the parallel formation, at comparable rates, of methyl oleate isomers identified as methyl elaidate, methyl trans-vaccenate, and methyl cis-vaccenate. Isomerization reactions were confirmed to occur rapidly in an independent manner. FFA are also present in small amounts owing to the in situ dehydration of methanol and subsequent hydrolysis of the esters. Finally, starting from pure oleic acid leads to results similar to those obtained with methyl oleate as the starting material.     

用热分析方法研究药物降解过程及动力学

用热重法（TG），微分热重法（DTG）。和差热分析法（DTA）研究药物甲磺酸多沙唑嗪（C24H29N5O8S）在空气流中的热氧降解过程和热氧降解动力学，发现该药物的热氧降解过程由四个紧连步骤组成。用Coats-Redrern方程进行动力学处理，确定该药物热氧降解的表观反应级数分别为1.1 1.5 1.5 1.2和反应活性能为353.7KJ/mol 239.5KJ/mol 229.9KJ/mol 167.2KJ/mol。     

Structures of ozonolysis products of methyl oleate obtained in a carboxylic acid medium

High-performance liquid chromatography-mass spectrometry (LC-MS) and nuclear magnetic resonance spectrometry (NMR) were applied to the analysis of organic peroxide mixtures, which were labile and tended to decompose during analysis. The ozonolysis reaction of methyl oleate gives a peroxide mixture, and, finally, mono- and dibasic acids are obtained by subsequent oxidation. In this study, methyl oleate was ozonized in a nonanoic acid medium, one of the final reaction products. The reaction products were directly analyzed by LC-MS equipped with a frit-fast atom bombardment interface. The molecular ion peak of each peroxide was clearly observed, and its molecular weight was readily determined. On the other hand, each peroxide was fractionated by high-performance liquid chromatography and submitted to structural analysis by NMR. Both results indicated that the reaction products include four peroxidic species: 1,2,4-trioxolaneI, peroxide oligomerII, 1-acyloxyalkyl-1-hydroperoxideIII, and 1-acyloxyalkyl-1′-hydroxyalkyl peroxideIV, as well as an aldehydeV. Ozonolysis of methyl oleate in the absence of solvent produces mainlyI, while that in the presence of a carboxylic acid solvent characteristically produces mainlyIII andIV derived from the solvent.Bis(1-acyloxyalkyl-1-alkyl) peroxide, which was reported previously as a ozonolysis product of methyl oleate, was concluded to beIV in this study. This work was presented at the 31th Annual Meeting of the Japan Oil Chemists’ Society, 1992, Tokyo, Japan.     

Gas chromatographic study on high-temperature thermal degradation products of methyl linoleate hydroperoxides

Chromatographic techniques were used to separate secondary products generated by thermal degradation of methyl linoleate hydroperoxides (MLHP). The MLHP were obtained by oxidation, selected, and concentrated by solid-phase extraction (SPE) and thin-layer chromatography (TLC). The purified MLHP were then thermo-degraded in the gas-chromatographic glass liner and analyzed on-line by gas chromatography-mass spectrometry (GC-MS). The MLHP were also thermodegraded and collected in a short silicic acid-packed column, eluted, separated by TLC, and then analyzed by GC. By considering the elution in TLC, the GC retention times and the GC-MS analyses, it was possible to characterize the mono- and the dioxygenated secondary products, particularly those having a boiling point higher than methyl linoleate. The peaks that corresponded to the mono-oxygenated products (epoxy, hydroxy, and keto) were identified, and, on the basis of their MS spectra, molecular structures were proposed. A specific elution order was suggested for keto derivatives: 9-keto,Δ^10,12- and 13-keto,Δ^9,11-octadecadienoate. The hydroxy derivatives, which show the typical fragmentations of 9-hydroxy,Δ^10,12- and 13-hydroxy,Δ^9,11-octadecadienoate, were also identified. On the other hand, identification of the di-oxygenated compounds was more difficult, and, therefore, it was not possible to indicate each positional isomer; however, their elution order could be epoxy-hydroxy and epoxy-keto derivatives.     

油酸甲酯乙氧基化物磺酸盐的合成与性能研究

以油酸甲酯乙氧基化物(OMEE)为原料,通过与亚硫酸氢钠一步法加成磺化得到油酸甲酯乙氧基化物磺酸盐(OMEES),并通过皂化值、碘值、阴离子含量的测定以及红外光谱确定合成的产物结构。对OMEES和OMEE进行平衡表面张力、动态表面张力、动态接触角以及主要应用性能的测试。结果表明:对于OMEES,γ_(cmc)=36.3 mN/m,吸附速率较慢,吸附量较少,并且随着表面活性剂浓度的增大铺展润湿性能逐渐增强。磺酸基的引入增加了原料的亲水性,使其起泡能力有所增强。     

纳米TiO2光催化氧化愈创木酚的降解机理

以木质素的模型物愈创木酚(G-M)为研究对象,采用自制的纳米TiO2作光催化剂,在一定的降解条件下对G-M光催化降解的动力学和机理进行了研究.实验表明G-M的光催化降解过程包括吸附和降解两部分,通过对G-M在TiO2表面吸附性能的测定,得到其吸附平衡常数,在此基础上运用L-H方程对G-M光催化降解的动力学方程进行讨论,得到降解反应动力学方程1/r=1.744/C 0.103 4.采用有机物特征功能团的显色法,对G-M光催化降解反应过程的中间产物进行了分析,推断在G-M降解反应过程中出现了开环、脱羧,最终完全分解矿化生成二氧化碳和水.     

油酸甲酯催化加氢制备生物烷烃的热力学分析

采用Benson基团贡献法对油酸甲酯加氢脱氧、加氢脱羰和加氢脱羧制备生物烷烃的热力学进行了分析,计算了613~653 K温度区间内油酸甲酯加氢体系的反应热、反应熵变、反应Gibbs自由能变和标准平衡常数,在此基础上采用PRO/Ⅱ软件中的平衡反应器模型分析了温度对油酸甲酯加氢产物分布的影响并和实验数据进行了对比验证。结果表明,油酸甲酯加氢脱氧、加氢脱羧和加氢脱羰制备生物烷烃的反应均为放热反应,放热量依次递减,各反应在613~653 K范围内均能够自发进行且反应完全。升高温度能够提高平衡产物中油酸甲酯加氢脱羰/羧产物的选择性,降低温度则有利于加氢脱氧产物的选择性,加氢脱氧与脱羰/羧产物选择性的比例随温度从613 K升高到653 K相应从1.92降低到0.56,与实验测得的反应数据变化趋势吻合。     

Thermal decomposition of methyl oleate hydroperoxides and identification of volatile components by gas chromatography-mass spectrometry

The role of methyl oleate hydroperoxides as precursors of volatile compounds was investigated by thermal decomposition in the injector port of a gas chromatograph attached to a computerized mass spectrometer. The major volatile compounds identified correspond to those formed from triolein heated in air at 192 C.     

离子液体［Hnhm］H2PO4 催化合成油酸甲酯

合成并表征了离子液体［Hnhm］H₂PO₄ ,同时考察了该离子液体的溶解性及吸水性。以油酸甲酯的合成为探针反应,考察合成的离子液体对反应的催化活性。结果表明,在［Hnhm］H₂PO₄ 加入量为油酸质量的8%、n(甲醇)∶n(油酸)=3.5∶l、反应温度90 ℃和反应时间9 h条件下,油酸酯化率达63%以上,且［Hnhm］H₂PO₄离子液体与原料及产物的分离容易实现。     

聚碳酸酯的热降解

综述了聚碳酸酯的热稳定性及其影响因素,并详细论述了一些添加剂如偶联剂甲基三甲氧基硅烷、钛酸四丁酯、阻燃剂二苯砜磺酸钾(KSS)、聚氨丙基苯基倍半硅氧烷(PAPSQ)等对聚碳酸酯热稳定性的影响,阐述了Kissinger法和Ozawa法等聚合物热降解动力学的分析方法。重点介绍了近期国内外有关聚碳酸酯热降解产物和热降解机理方面的研究成果。     

Selective synthesis of oleyl alcohol via catalytic and non-catalytic liquid-phase methyl oleate reduction

The upgrading of oleyl alcohol synthesis via methyl oleate reduction using NaBH₄ without H₂ supply was investigated. It was possible to synthesize selectively oleyl alcohol with high yields. Non-catalytic and catalytic experiments were developed trying to improve the low final oleyl alcohol yield previously obtained. The effect of reaction temperature, methyl oleate/NaBH₄ molar ratio and properties of different catalysts on final oleyl alcohol yield were analyzed. Thus, alumina-supported metal (M) catalysts (M = Fe, Ce, Mo) were synthesized by incipient wetness impregnation. The M/Al₂O₃ catalysts were characterized in their chemical, textural, structural and acid–base properties using ICP, N₂ physisorption, XRD and temperature-programmed desorption (TPD) of NH₃ and CO₂. During non-catalytic methyl oleate reduction, final methyl oleate conversion and oleyl alcohol yield of 94% were obtained using a methyl oleate/NaBH₄ molar ratio of 0.11 at 333 K. Catalytic activity of M/Al₂O₃ solids increases as acid site number and ionic potential of M cations increase. In addition, the reaction mechanism for fatty acid methyl ester reduction was investigated from a theoretical approach using Density Functional Theory method at B3LYP/6-31++G(d,p) computational level. Results obtained during theoretical calculations confirmed that the formation of reducing alcoxyborohydride species is energetically favored and allowed to understand the events at microscopic level involved in the reaction mechanism.     

基于间苯三酚的磺化碳基固体酸催化剂的制备及其催化油酸甲酯的合成

采用间苯三酚与对苯二甲醛缩聚得到的树脂为碳前驱体,分别以1,4-二氧六环与去离子水为溶剂,以溶剂热和水热法、氯磺酸为磺化试剂制备两种磺化碳基固体酸催化剂。SEM、XPS和TGA等分析表明,以1,4-二氧六环为溶剂合成的TP-A-S催化剂为形貌规整、高酸密度、良好稳定性的球形,并表现出良好的催化性能。将其用于油酸与甲醇的酯化反应,最适宜的条件为:醇油物质的量比10∶1,催化剂用量占原料总质量的2.0%,反应温度70℃,反应时间4h,油酸最高转化率达98.3%。且催化剂循环使用5次后,油酸转化率仍达84.4%。将制备的TP-A-S催化剂用于长链游离脂肪酸与甲醇的酯化反应,转化率高于90%,表现出良好的催化效果。     

不锈钢基PbO2电极电催化氧化降解甲基橙性能的研究

本研究以自制的不锈钢基PbO2电极对25mg·L^-1的甲基橙溶液进行电催化氧化降解。考察了电流密度、支持电解质浓度、溶液pH值、温度等因素对甲基橙脱色率的影响,确定了电催化氧化甲基橙的最佳反应条件,即电流密度为50mA/cm^2,支持电解质Na2SO4的浓度为0．04mol·L^-1,降解20min后,甲基橙脱色率可达到90％以上。本研究还对几种不同印染废水进行了电催化氧化降解,结果表明,不锈钢基PbO2电极对不同的印染废水均有较好的脱色效果。