微波辐射下己二酸、壬二酸双酯的无溶剂合成

在微波辐射下,用己二酸、壬二酸分别与异辛醇、正十二醇合成四种润滑油类双酯。研究结果表明：在微波辐射下催化剂用量为3.0% ～3.5%、微波功率为300 w～320 w的反应条件下己二酸双异辛酯和壬二酸双异辛酯分别在反应时间为8 min和12 min合成得到98%和99.4%的高产率;;己二酸双十二酯和壬二酸双十二酯分别在反应时间为6.5 min和7.5 min合成得到95%和97%的高产率。研究得到了二元羧酸双异辛酯和二元羧酸双十二酯微波合成的实验参数。产物的色泽和结晶点被测定,并用1H NMR、13C NMR和 IR对产物结构进行了表征。与传统合成方法比较,微波合成法将己二酸双十二酯、壬二酸双十二酯、己二酸双异辛酯和壬二酸双异辛酯产率分别提高了3%、6%、11.5%和29%,反应时间缩短了7.1～11.4倍,且产物色泽好。微波合成方法对润滑油类双酯是一种快速、高效、新的合成方法。     

N-甲基吡咯烷酮硫酸氢盐催化合成己二酸二异辛酯

以新型离子液体N-甲基吡咯烷酮硫酸氢盐([Hnmp]HSO4)为催化剂,己二酸和异辛醇为原料,环己烷为带水剂,对己二酸二异辛酯的酯化反应进行了研究,重点考察了醇酸摩尔比、催化剂用量、带水剂加入量、反应时间等因素对己二酸二异辛酯酯化率的影响。实验结果表明,N-甲基吡咯烷酮硫酸氢盐对合成己二酸二异辛酯有着良好的催化活性,当己二酸用量为0.1mol时,醇酸摩尔比为2.6:1,催化剂用量为己二酸物质的量的1.2%,带水剂环己烷为10mL,回流温度下反应时间120min,在此条件下,反应的酯化率可达99%以上,且催化剂重复使用6次仍保持较高活性。     

对甲苯磺酸催化合成己二酸二异辛酯的研究

以己二酸和异辛醇为原料,采用对甲苯磺酸作催化剂合成己二酸二异辛酯。考察了影响反应的因素,实验结果表明酯化反应的最佳条件:己二酸∶异辛醇∶对甲苯磺酸的摩尔比为1∶2 5∶0 18,反应时间30min,带水剂甲苯10mL,产率可达97 30%。     

微波辐射对甲苯磺酸催化合成氯乙酸异辛酯

在微波辐射下,以对甲苯磺酸为催化剂合成氯乙酸异辛酯。考察微波输出功率、反应时间、催化剂用量、酸醇的物质的量比等因素对反应的影响。通过实验得出合成氯乙酸异辛酯的最佳反应条件是:氯乙酸和异辛醇的物质的量比为1:2.0,催化剂用量为2.0g,微波输出功率为522W,反应时间为20min。在此反应条件下,氯乙酸的酯化率为97.6%。     

N-甲基毗略烷酮硫酸氢盐催化合成己二酸二异辛酯

以新型离子液体N-甲基吡咯烷酮硫酸氢盐（[Hnmp]HS04）为催化剂，己二酸和异辛醇为原料，环己烷为带水剂，对己二酸二异辛酯的酯化反应进行了研究，重点考察了醇酸摩尔比、催化剂用量、带水剂加入量、反应时间等因素对己二酸二异辛酯酯化率的影响。实验结果表明，N-甲基吡咯烷酮硫酸氢盐对合成己二酸二异辛酯有着良好的催化活性，当己二酸用量为0．1mol时，醇酸摩尔此为2．6：1，催化剂用量为己二酸物质的量的1．2％，带水剂环己烷为10mL，回流温度下反应时间120min，在此条件下，反应的酯化率可达99％以上，且催化剂重复使用6次仍保持较高活性。     

新型原油降凝剂的合成及应用

以苯乙烯、富马酸二异辛酯为原料,合成了苯乙烯-富马酸二异辛酯共聚物.研究了单体配比、催化剂、阻聚剂、反应时间、反应温度等因素对反应的影响,并确定了合成该降凝剂的适宜工艺条件:苯乙烯与富马酸二异辛酯的物质的量比为5:1,引发剂添加量0.4%,溶剂甲苯加入量50%,反应温度80 ℃,反应时间5 h.     

防晒剂对二甲氨基苯甲酸异辛酯的合成研究

提出了一种合成防晒剂对二甲氨基苯甲酸异辛酯的新工艺,即以对硝基苯甲酸和异辛醇为起始原料,经酯化、硝基加氢、N-烷基化合成对二甲氨基苯甲酸异辛酯。着重讨论了合成关键步骤:N-烷基化反应。找到了较佳的反应条件:反应温度90℃～100℃,反应压力1 5MPa～2 0MPa,反应时间15h,骨架镍用量为对氨基苯甲酸异辛酯质量的10%,对氨基苯甲酸异辛酯与甲醛摩尔比1 0∶2 2。与目前文献介绍的合成工艺相比,此工艺将产物收率提高了近50%,收率达84 7%,同时还避免了使用剧毒原料硫酸二甲酯。     

高分子负载钛酸酯催化剂的制备及其在高沸点酯合成中的应用

聚乙烯醇与四氯化钛在二甲基亚砜和无水乙醇混合溶剂中反应,制得负载钛酸酯催化剂PVAC-1,用红外光谱对其分子结构进行了表征,用比色法测定了催化剂中的Ti含量。研究了PVA–1在邻苯二甲酸二异辛酯（DOP）、己二酸二庚酯、苯甲酸异辛酯等高沸点酯合成过程中的活性。结果表明该催化剂具有与烷基钛酸酯Ti(OBu)4相当的催化活性。在催化合成上述3种高沸点酯时有机酸转化率分别达到99.8%、97.5%和99.7%。催化剂可多次重复使用。     

脱水磷酰氯法合成磷酸二异辛酯

研究了脱水磷酰氯法合成磷酸二异辛酯的新方法。先以五氧化二磷和二氯亚砜反应制备了脱水磷酰氯,脱水磷酰氯再与异辛醇反应制得目标产物磷酸二异辛酯。考察了磷酰氯与异辛醇物质的量比、异辛醇的滴加温度、反应时间、反应温度和真空度等关键因素对反应的影响。实验结果表明,n(脱水磷酰氯)∶n(异辛醇)=1.0∶2.1、15℃下滴加异辛醇、60℃下反应3 h、真空度为0.08 MPa的条件下,磷酸二异辛酯的收率达96.2%,含量达97.9%。利用FT-IR和NMR对产物磷酸二异辛酯进行表征。     

烯丙基型可聚合表面活性剂——琥珀酸辛基酯磺酸钠的合成与性能

采用马来酸酐、正辛醇、氯代烯烃、亚硫酸氢钠为主要原料,合成了一类新的可聚合表面活性剂--琥珀酸双酯磺酸钠.对各步反应分别采用正交实验或单因素实验进行优化,得到其优化工艺条件为:单酯化反应,反应物配比为n(马来酸酐):n(正辛醇)=1.00:1.00,反应温度为90℃,反应时间为2 h,催化剂Ⅳ(乙酸钠)=1.0%;双酯化反应,反应物配比为n(异丁烯基氯):n(马来酸单辛酯)=1.50:1.00,催化剂W(三乙胺)=1.0%,反应温度为70℃,反应时间为5 h;磺化反应,在不使用相转移催化剂的条件下,反应物配比为n(马来酸辛基异丁烯基酯):n(NaHSO3)=1.00:1.10,反应温度为120℃,反应时间为3 h.对每步合成产物均用IR和1HNMR进行了表征,并测得最终产物琥珀酸辛基烯丙基酯磺酸钠与琥珀酸辛基异丁烯基酯磺酸钠的平衡表面张力分别为30.2 mN·m-1和30.4 mN·m-3,临界胶束浓度分别为11.57 mmol·L-1和10.41 mmol·L-1,其余基本物化性能较为适中.     

稻壳灰负载氯磺酸催化苯并咪唑化合物的合成研究

以绿色廉价的稻壳灰为载体,接着吸附氯磺酸作为固体酸催化剂,微波辅助、无溶剂条件下,利用邻苯二胺和醛分子间的缩合反应一步法制备得到2-取代苯并咪唑类化合物,其结构经IR、1HNMR和元素分析等加以确证。实验结果表明,600℃下煅烧的稻壳灰经氯磺酸处理后制备固体酸催化剂的用量为8 mol%,800 W功率下微波辐射反应5~10 min即可得目标化合物,且收率为87%~97%,该催化剂易于回收并多次使用。     

Rapid Synthesis of Flavor Compound 4-Ethyloctanoic Acid under Microwave Irradiation

Rapid synthesis of 4-ethyloctanoic acid by means of microwave irradiation is described. Diethyl malonate reacted with 2-ethyl-1-bromohexane in the presence of sodium ethoxide to give diethyl (2-ethylhexyl)malonate (1b). 1b was saponified in the solution of ethanol and potassium hydroxide and then acidified to form (2-ethylhexyl)propanedioic acid (1c), and 1c was heated and decarboxylized to give 4-ethyloctanoic acid (1d). The influence of reaction temperature and reaction time on the yield of 1b and the effect of reaction time on the yield of 1c and 1d were investigated in order to optimize the synthetic conditions. The relative optimal conditions for the synthesis of 1b were a mole ratio of sodium to diethyl malonate to 2-ethylhexyl bromide of 0.1:0.11:0.11, a reaction temperature of 80-85 °C, and a reaction time of 2-2.5 h. The yield of 1b was about 79%. 1b was saponified for 30 min and then acidified to form 1c, and the yield of 1c was 96%. 1c was heated for 16 min at 180°C to give 1d, and the yield of 1d was about 90%. The overall yield of 1d is 70% under microwave irradiation. The reaction time was reduced greatly. In order to compare the result of microwave irradiation with that of an oil bath, the reactions were also performed in an oil bath. The structures of intermediates, product and by-product were confirmed by HRMS, (1)H NMR, (13)C-NMR and IR.     

活性炭负载硅钨酸催化合成壬二酸二辛酯

以颗粒状活性炭负载硅钨酸作催化剂,由壬二酸和异辛醇反应合成壬二酸二辛酯,通过正交试验,探讨了主要因素对酯化率的影响。实验结果表明,活性炭负载硅钨酸具有良好的催化活性,当酸醇摩尔比为1:3.5,负载催化剂用量为壬二酸质量的12.9%,反应时间为2.0h,酯化率可达96.79%。     

Brφnsted酸性离子液体中苯甲酸酯、苄酯的无溶剂微波合成

该文以1-甲基咪唑、吡啶、苄基氯、硫酸、磷酸为原料,合成了4种B r nsted酸性离子液体:1-甲基-3-苄基咪唑硫酸氢根盐(a),1-甲基-3-苄基咪唑磷酸二氢根盐(b),N-苄基吡啶硫酸氢根盐(c),N-苄基吡啶磷酸二氢根盐(d),以它们作为催化剂和反应介质,考察了苯甲酸与系列脂肪醇、苄醇与系列脂肪酸、苯甲酸在无溶剂和微波辐射反应条件下的F ischer酯化反应,结果表明,当苯甲酸或苄醇与离子液体的摩尔比为1∶0.5时,无需外加催化剂,反应即可在化学计量条件下进行,12~20 m in完成反应,苯甲酸酯与苄酯的收率分别为77%~98%和78%~98.5%,气相色谱纯度≥95%。离子液体循环使用3次,催化活性仅下降1.8%~3.4%。     

含氟Schiff碱的无溶剂法合成与结构表征

无溶剂无催化剂条件下,2-(4-氨基苯基)六氟异丙醇和苯甲醛类物质经室温研磨得到了系列含氟Schiff碱化合物。产物结构经EA、IR、1HNMR和MS确认。结果表明,采用无溶剂法,反应时间可由常规溶液法的90～240 min缩短至10～50 min,目标物收率由71%～87%提高至98%～99%。     

新型含氟Schiff碱的无溶剂法合成与结构表征

无溶剂无催化剂条件下,2-(4-氨基苯基)六氟异丙醇和苯甲醛类物质经室温研磨得到了系列新型含氟Schiff碱化合物。产物结构经EA、IR、1 H NMR和MS确认。结果表明,采用无溶剂法,反应时间可由常规溶液法的90-240min缩短至10-50min,目标物收率由71%-87%提高至98%-99%。     

Production of high purity rare earth mixture from iron-rich spent fluid catalytic cracking (FCC) catalyst using acid leaching and two-step solvent extraction process

Acid leaching and a two-step solvent extraction procedure were developed to produce high purity mixture of La and Ce from iron-rich spent FCC catalyst discharged from Dzung Quat refinery (Vietnam). Acid leaching of the spent catalyst with 2M HNO₃ and a solid-to-liquid ratio of 1/3 at 80 °C in 1 h dissolved almost 90% of La while 12% of Al and 25% of Fe were transferred to the leachate. The extraction of RE metals and main impurities such as Al and Fe by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) was investigated. Experiments showed that it was necessary to remove Fe before extracting RE and the optimum extraction conditions for a high recovery of RE while 0% of Al extraction were pH-1, contact time=10min, and D2EHPA/TBP volume ratio= 4: 1. At these conditions, the extraction yields of La(III) and Ce(III) were 72% and 89%, respectively. A two-step solvent extraction was developed to achieve a high purity of RE mixture, which included (1) the removal of impurity Fe by 25% (v/v) diisooctyl phosphinic acid (DiOPA) in n-octane for 140 min, (2) the extraction of rare earths by a mixture of di-2-ethylhexyl phosphoric acid (D2EHPA) and tributyl phosphate (TBP) in n-octane for 10 min without the need for adjusting the pH of the leaching solution.     

Synthesis of polyfunctional glycerol esters: Lipase-Catalyzed esterification of glycerol with diesters

The enzymatic esterification of glycerol with dicarboxylic acids or esters was studied to produce mono- and/or diesterified glycerol adducts. Such materials are useful synthons in the synthesis of biodegradable polymers and surfactants. In this work two strategies were studied for preparing these prepolymeric glycerol derivatives: the lipase-catalyzed esterification of free glycerol with diacids or esters and the reaction of supported or protected glycerol with diesters. For example, reaction of isopropylidene glycerol with dimethyl sebacate gave a >95% yield of isopropylidene glycerol-monomethyl sebacate ester. Reaction of glycerol supported on silica with dimethyl adipate gave a 40% yield of glycerol-monomethyl adipate ester. Best yields of glycerol-mono- and diesters (70% and 10%, respectively) were obtained by direct esterification of free glycerol with a diester in a solvent-free system containing small amounts of water (<4%). Presented in part at the 89th Annual Meeting of the American Oil Chemists’ Society, Chicago, Illinois, May 1998.     

Effect of plasticizers on the viscoelastic properties of poly(vinyl chloride)

Stress relaxation modulus data, E_r(t), have been determined between ?70 and +170°C on blends of three samples of poly(vinyl chloride) of different molecular weights with di-2-ethylhexyl adipate, di-2-ethylhexyl phthalate, epoxidized soybean oil, and a poly(propyl adipate), respectively. The relaxation modulus-time–temperature data could be combined into master curves. However, probably owing to the finite contributions of the crystalline phase to the elastic properties, time–temperature superposition is here just marginally valid, and the master curves are only crude, yet still useful approximations. Combination of the present data with the accumulated published information suggests that the viscoelastic properties of plasticized poly(vinyl chloride) are determined primarily by the glass transition temperàture of the plasticizer, the compatibility of polymer and plasticizer, and probably also by the crystallites (as crosslinks). The exact role of the crystallites will remain elusive until the advent of plasticized poly(vinyl chloride) with controlled crystallinity.     

无溶剂条件下用微波辐射及相转移催化合成香茅腈

以香茅醛为原料,在微波辐射及相转移催化剂聚乙二醇-600催化作用下由SiO2/Na2CO3-NaOH混合碱促进的无溶剂一步法直接制备香茅腈。确定的最佳反应条件是:香茅醛与盐酸羟胺摩尔比1∶1.4~1∶1.6;对应每mmol香茅醛,SiO2的用量为0.25~0.30 g;催化剂为PEG-600和Na2CO3-NaOH(7∶3,n/n),彻底研磨后用微波辐射功率为730 W,反应时间为4~5 min,制备效果最佳。在此条件下从香茅醛制备香茅腈的平均得率达85.05%。