添加六次甲基四胺对芘热缩聚产物的影响

为了研究六次甲基四胺对芘热缩聚的影响,分别以芘或芘与六次甲基四胺的混合物为原料在480℃进行热缩聚反应,并利用MALDI-TOF-MS、13C-NMR、FT-IR、元素分析和热台显微镜对热缩聚产物的组分、结构进行分析表征。测试结果表明,添加六次甲基四胺后,芘单体能够完全转化为低聚体,热缩聚产物中的碳元素含量和氯仿不溶物含量升高。此外,元素分析结果显示六次甲基四胺在芘热缩聚过程中(400℃)能够与芘相结合,随着反应温度的提高(480℃),大部分六次甲基四胺从反应体系中排出。这些研究结果说明六次甲基四胺对于芘的热缩聚反应具有明显的催化作用。     

添加六次甲基四胺对芘热缩聚产物的影响北大核心

为了研究六次甲基四胺对芘热缩聚的影响,分别以芘或芘与六次甲基四胺的混合物为原料在480℃进行热缩聚反应,并利用MALDI-TOF-MS、13C-NMR、FT-IR、元素分析和热台显微镜对热缩聚产物的组分、结构进行分析表征。测试结果表明,添加六次甲基四胺后,芘单体能够完全转化为低聚体,热缩聚产物中的碳元素含量和氯仿不溶物含量升高。此外,元素分析结果显示六次甲基四胺在芘热缩聚过程中(400℃)能够与芘相结合,随着反应温度的提高(480℃),大部分六次甲基四胺从反应体系中排出。这些研究结果说明六次甲基四胺对于芘的热缩聚反应具有明显的催化作用。     

高效铝换热器酸洗缓蚀剂的研制

以钼酸钠、硫脲、吖啶、六次甲基四胺、硫酸锌、表面活性剂等合成了铝翅片换热器酸洗缓蚀剂,并用腐蚀失重法进行了评价.在8%盐酸介质中,钼酸钠:硫脲:吖啶:六次甲基四胺:硫酸锌:表面活性剂=0.6:1.0:0.2:0.8:0.5:0.05,40℃时,铝缓蚀率可达97%以上.     

尿素工艺冷凝液中甲醛的测定

工艺冷凝液中的甲醛以六次甲基四胺的形式存在，以强酸分解其中的六次甲基四胺，使其分解出甲醛和氨。甲醛与变色酸形成紫红色物质，以分光光度法测定。     

有机胺介质中硫酸钾制备工艺研究

以石膏和氯化钾为原料,探讨了有机胺介质中硫酸钾的制备工艺.选用三乙醇胺、二甲基甲酰胺、甲酰胺3种不同的有机胺做介质,同时选取乙醇作为有机介质的稀释剂,进行了反应介质筛选的单因素实验,得出三乙醇胺作为介质效果较好.通过正交实验,得出优化工艺方案为:配料比n(CaSO4)∶n(KCl)=1.1∶1,液固比6∶1,三乙醇胺质量分数65%,反应温度30 ℃,搅拌速度300 r/min,反应时间2 h,结晶温度12 ℃,结晶时间0.5 h.在此条件下,制得产品硫酸钾的K2O质量分数为38.66%,氯离子质量分数为0.96%,水分质量分数为1.86%,氯化钾的转化率为84.17%.     

甲酰胺合成工艺的改进及其质谱结构指认

以六次甲基四胺,甲酸为原料,常压下反应制得甲酰胺(FA)。主要考查了反应时间,反应温度,物料比等因素对反应产率的影响。借助IR光谱及ESI-MS对产物FA进行了官能团验证和结构表征,研究并归属了该化合物主要特征碎片离子的裂解途径。实验结果表明:其较佳反应条件为T=85℃,t=8h,n_(六次甲基四胺)∶n_(甲酸)=1∶1.4,产率为78.32%。本方法所需反应条件温和,后处理简单,产物产率相对较高,适合工业生产。     

微波辐射磷酸催化合成2-羟基-1-萘甲醛

2-羟基-1-萘甲醛简称HNA,其作为一种重要的有机化学合成中间体,在金属络合染料,织物,油墨,橡胶用甲亚胺染料及荧光增白剂等方面有着广泛的应用。其传统合成方法主要有Duff法,Gattermann法和Reimer-Tiemann法等。本文在微波加热条件下,以磷酸代替浓硫酸作催化剂催化2-萘酚与六次甲基四胺反应合成了2-羟基-1-萘甲醛,设计了四因素三水平正交实验方案探讨合成2-羟基-1-萘甲醛的最佳工艺条件,获得最佳反应条件:反应物摩尔比2-萘酚:六次甲基四胺1∶1.3,反应时间5分钟,催化剂磷酸3 mL,微波功率500W,平均产率可以达到76.21%。     

固相配位化学反应研究Ⅰ．钴（Ⅱ）－六次甲基四胺配合物的固相合成与应用

室温条件下，六水合二氯化钴与六次甲基四胺固相反应得到钴（Ⅱ） 六次甲基四胺配合物，经ＩＲ、薄层色谱扫描、元素分析、ＤＴＡ和ＴＧ分析表征了该产物。研究了该配合物的可逆示温性能，并将其研制成了可作为防伪材料的水溶性可逆示温油墨。     

固相配位化学反应研究：I.钴（II）—六次甲基四胺配合物的固相合成与应用

室温条件下，六水合二氯化钴与六次甲基四胺固相反应得到钴（Ⅱ）－六次甲基四胺配合物，经ＩＲ、薄层色谱扫描、元素分析、ＤＴＡ和ＴＧ分析表征了该产物。研究了该配合物的可逆示温性能，并将其研制成可作为防伪材料的水溶性可逆示温油墨。     

相转移催化合成氨基乙酸

以氨水、氯乙酸为原料,以六亚甲基四胺为相转移催化剂,在常温、常压下合成了氨基乙酸。考察了催化剂六亚甲基四胺和温度对合成氨基乙酸反应的影响。在温度５８℃、催化剂用量为氯乙酸的３％、反应原料质量配比为氨水∶氯乙酸＝１∶５的条件下,产品收率为６８８％,纯度达９９６％。     

有机胺萃取法制备碳酸钾

有机胺萃取法生产碳酸钾是20世纪70年代发展起来的新工艺路线.与现有生产工艺相比,具有钾利用率高、工艺流程简单、能耗少及成本低等优点.采用低毒的高沸点胺代替低沸点胺,研究了有机胺种类、相比及温度等试验条件对萃取转化率的影响.试验结果表明,以三丁胺为萃取剂,正丁醇为稀释剂,相比在3.0～3.6的条件下,氯化钾的一次转化率较高.萃取了盐酸的有机胺用浓氨水再生,再生后的有机胺可以循环使用.     

Intensification of enzymatic hydrolysis of penicillin G: Part 2. model for enzymatic reaction with reactive extraction

During the enzymatic hydrolysis of the potassium salt of Penicillin-G (PenGK) into Phenylacetic acid (PAA) and potassium salt of 6-Aminopenicillanic acid (6-APA), the pH of the reaction mixture falls on account of accumulation of PAA. This lowers the stability and activity of the enzyme used, viz., Penicillin-G acylase (PGA). A new approach of extracting the PAA by a long-chain tertiary amine, which is in the dispersed phase, as a liquid ion exchanger (LIX), is presented. A mathematical model has been developed for this slurry phase reactor with PenGK in the continuous aqueous phase, the amine alongwith a diluent in the dispersed organic phase and the immobilized PGA enzyme as the solid catalyst. Effects of various parameters affecting the conversion of PenG have been discussed. The model has been solved for batch and semi-batch modes. It has been shown that the semi-batch mode yields a higher productivity. This approach can also be advantageously used for other intermediates like 7-ADCA for cephalosporins.     

有机胺萃取分离钾钠制备硫酸钾

以霓辉正长岩烧结物料的水浸滤液(经CO2酸化处理后)为研究对象,该溶液为简单的NaHCO3-KHCO3-H2O三元体系。在60℃等温蒸发结晶至溶液中质量比m(Na2CO3)/m(K2CO3)≈2时,按照V(有机相)/V(无机相)=3.5:1加入有机胺萃取体系,萃取体系是由V(三正丁胺)/V(正丁醇)=1:2.5均匀混合而成,利用钾、钠的碳酸氢盐在有机相-H2O混合液体系中的溶解度差异显著进行钾钠分离。在温度25℃、搅拌条件下以流速0.15 m3.h.1通入CO2 1.5 h,可分离出碳酸钠约99%,加入适量硫酸,即得硫酸钾。分析结果表明所得产品达到了国家农用硫酸钾的优等品标准。     

萃取法由硫酸氢钾转化制取硫酸钾的工艺研究

本文提出用叔胺Ｎ２３５作为萃取剂由硫酸氢钾直接转化制取硫酸钾的方法，并系统研究了适宜的工艺条件：有机相中叔胺浓度为１．０５ｍｏｌ／Ｌ，相比为１：１，硫酸氢钾起始浓度２０％。操作温度为１０－２５℃，硫酸胺盐采用化学法再生。     

KINETIC STUDY OF S-ALKYLATION OF 2-MERCAPTOBENZIMIDAZOLE CATALYZED BY TETRABUTYLAMMONIUM BROMIDE

The S-alkylation of 2-mercaptobenzimidazole (MBI) by α-bromo-m-xylene (RBr) under phase transfer catalytic reaction condition was successfully carried out in an aqueous solution of KOH/organic solvent two-phase medium. No product was obtained from N-alkylation during or after the reaction period by using a limited quantity of α-bromo-m-xylene. The reaction is greatly enhanced by adding a small amount of tetrabutylammonium bromide (TBAB) and/or potassium hydroxide. Based on the experimental evidence, a rational reaction mechanism is proposed. A kinetic model is derived, from which a pseudo steady-state hypothesis (PSSH) is applied to the reaction system. The kinetic behaviors and the characteristics of the reaction are sufficiently described by the pseudo first-order rate law. The effects of the reaction conditions, including agitation speed, amount of TBAB catalyst, amount of KOH, quaternary ammonium salts, volume of water, volume of dichloromethane, amount of 2-mercaptobenzimidazole, amount of α-bromo-m-xylene, inorganic salts, organic solvents, and temperature on the conversion of the reactant and the apparent rate constants (k_app) were investigated in detailed. Rational explanations are provided for the observed phenomena from experimental results.     

有机相中酶催化1-苯基乙胺的不对称酰胺化反应

在有机相中,对酶催化条件下的1-苯基乙胺酰胺化反应进行了研究。通过对酰基供体、酶、溶剂的筛选和酯量、底物胺浓度、酶量、摇床转速、反应温度等影响因素的考察,发现乙酸异丙烯酯为较佳的酰基供体,脂肪酶Novozym 435对该反应的催化活性和对映体选择性较高,甲苯为最适的介质,最适酯量为底物胺量的0.6倍,最佳底物胺浓度、酶量、摇床转速、温度分别为200 mmol·L^-1、4 mg·ml^-1、200 r·min^-1、30℃。在此优化条件下反应的对映体选择率（E）达到89。反应4 h转化率为39％,产物的对映体过剩值（ee_p）为96％;反应10 h转化率达到52.4％,底物的对映体过剩值（ee_s）为98％。     

SYNTHESIS OF DIALKOXYMETHANE AT HIGH ALKALINE CONCENTRATION VIA PHASE TRANSFER CATALYSIS

The phase-transfer catalytic reaction (PTC) of 2,4,6-tribromophenol and dibromomethane by quaternary ammonium salt was carried out in a high alkali content of KOH/dibromomethane two-phase medium. A large conversion of 2,4,6-tribromophenol is obtained at a region of high KOH content. Dibromomethane acts both as the organic-phase reactant and the organic solvent; thus, no extra organic solvent is required. Two main products, i.e., α -bromomethyl 2,4,6-tribromophenyl ether (mono-substituted product) and bis-(2,4,6-tribromophenoxide)methane (bis-substituted product), were detected in the solution during the phase-transfer catalytic reaction. The active catalyst (tetrabutylammonium 2,4,6-tribromophenoxide, ArOQ), which was produced from the reaction of 2,4,6-tribromophenol, potassium hydroxide, and tetrabutylammonium bromide (TBAB or QBr), is purified as the crystalline product from the reaction solution. A kinetic model is developed to describe the behaviors of the two organic-phase reactions on the basis of the experimental observation. The two intrinsic rate constants of the two organic-phase reactions, which are the rate-determining steps of the whole reaction system, are determined. Effects of the reaction conditions, such as agitation speed, amount of water, amount of TBAB catalyst, temperature, and amount of dibromomethane, quaternary ammonium salts, and inorganic salt KBr, on the conversion of 2,4,6-tribromophenol and the reaction rate are investigated in detail.     

中国硫酸铝除铁技术的研究进展

研究比较了以普通工业级硫酸铝制备无铁级或低铁级硫酸铝的主要方法。对各种除铁方法如高锰酸钾氧化沉淀法、亚铁氰化钾和铁氰化钾沉淀法、有机伯胺萃取法和有机络合沉淀法在硫酸铝产品中除铁的应用进行了详细的介绍。从反应原理、工艺流程和除铁效果几个方面对各种方法进行了对比，发现有机络合沉淀法简单、方便、效果显著，工业硫酸铝经除铁后，铁离子质量分数低于0．005％。     

Aminolysis Reaction of Glycerol Carbonate in Organic and Hydroorganic Medium

Aminolysis reaction of glycerol carbonate with primary amine in organic and hydroorganic media leads to the formation of two hydroxyurethane isomers and a partial decomposition of glycerol carbonate into glycerol. Aminolysis with a secondary amine promotes the condensation reaction and limits the formation of glycerol. The ratio of α versus β was determined by zgig ¹³C NMR. This technique permits computing the yield of α and β products in the medium. The quantity of glycerol was determined by GC analysis. The ratio of the isomers and the amount of glycerol depend on the amine and the solvent. Kinetic investigations reveal that, in hydroorganic medium, the more the alkyl chain of the amine increased, the less glycerol was formed. On the contrary, in organic medium, the alkyl chain of the amine does not play a major role in the formation of glycerol.     

真菌悬浮培养滤液对煤的溶解及产物分析

本文考察了真菌液体悬浮培养滤液的溶煤能力与菌丝体生长代谢过程的关系。发现当菌丝体进入生长衰老期时，其滤液具有较好的溶煤作用。硝酸氧化煤的溶解转化率可达６０％以上。对煤生物溶解产物及其酸沉淀物的溶解试验表明，两者在性质上存在着差异。元素分析和红外光谱分析表明，煤生物溶解物的含氧、含氮等的极性基团增多，并含有羧酸盐、胺盐以及有机酸的铵盐等。这些结果将为寻找煤生物溶解产物的利用途径提供依据。