Epichlorohydrin–triethanolamine reaction in the preparation of quaternary cellulose anion exchangers

The reactions between cotton cellulose and a mixture of triethanolamine and epichlorohydrin in the presence of aqueous NaOH have been studied. It has been shown that cotton fabric pretreated with aqueous base and then reacted with a 3:1 mole ratio of epichlorohydrin to triethanolamine forms a strong base anion exchanger. Resultant properties differed from those of the product made by the conventional method of preparing ECTEOLA cellulose, a commercial product of the same reactants. Titration curves of the strong base cellulose exchangers were similar to that obtained with the product of the reaction between cotton and trimethylglycidylammonium chloride. Substitution of triethylamine for the triethanolamine also resulted in a quaternary base cellulose anion exchanger. A cyclic diquaternary salt, [2,5-p-dioxanylenebismethylene] bis[tris(2-hydroxyethyl)ammonium chloride], has been isolated from the triethanolamine–epichlorohydrin mixture and a mechanism of the reaction has been proposed.     

Kinetics of addition of acetic acid to epichlorohydrin in the presence of alkali metal acetates

The kinetics of the reaction between acetic acid and epichlorohydrin in the presence of lithium, sodium and potassium acetates have been studied. The composition of the reaction mixture was followed chromatographically. Beside the two isomeric products of addition of epichlorohydrin to acetic acid, the presence was found of glycidyl acetate, glycerine dichlorohydrin and other products of parallel and subsequent reactions between the substrates and chlorohydroxyesters. A mechanism of the reaction, which takes into account the formation of the identified compounds has been proposed and a set of appropriate differential and balance equations developed. The rate constants for individual reactions as well as the catalysts used have been determined.     

Kinetics of addition of acetic acid to epichlorohydrin in the presence of DMF or DMSO

The kinetics of reaction between acetic acid and epichlorohydrin carried out in the presence of DMF or DMSO was studied. In addition, the conductivity of the reaction mixture was measured. The conductivity was found to increase considerably as the reaction proceeded. This was explained in terms of the formation of new effective forms of catalysts: the ammonium salt (in case of DMF) or sulphonium salt (for DMSO). A reaction scheme has been proposed, taking into account the active catalyst forms. The set of kinetic equations describing the reaction has been developed and the appropriate rate constants evaluated.     

正辛基缩水甘油醚的合成优化研究

以正辛醇和环氧氯丙烷为原料,在四丁基溴化铵作相转移催化剂条件下,合成了正辛基缩水甘油醚。根据正交实验设计确定了最佳反应条件,通过红外光谱表征了产物的结构,并依据气相色谱流出曲线计算了产物的纯度。实验结果表明：n（辛醇）：n（环氧氯丙烷）=1：1．4、反应温度为40～50℃、反应时间为4～5h、ω（碱）约为50％时,产物的产率最高,可达91．6％,纯度可达87％以上。     

用二氯丙烷混合副产物合成环氧树脂固化剂

利用二氯丙烷混合副产物合成了环氧树脂固化剂,得出了适宜的反应条件;对所生产的固化剂的各种应用性能和应用范围进行了讨论。     

3-氯-2-羟丙基三甲基氯化铵的合成与纯化

以环氧氯丙烷 ,三甲胺 ,浓盐酸为原料 ,常温合成了 3 氯 2 羟丙基三甲基氯化铵 ,研究了反应物质量分数 ,反应溶液的 pH ,环氧氯丙烷与三甲胺盐酸盐量比对产物质量分数的影响 ,由此对反应的可能历程进行了探讨。替代传统的减压蒸馏 ,采用载气蒸馏的方法对其进行纯化 ,纯化后的产品中环氧氯丙烷的质量分数≤ 0 0 0 0 4 % ,1,3 二氯 2 丙醇的质量分数≤ 0 0 0 18% ,3 氯 2 羟丙基三甲基氯化铵质量分数为 6 9% ,收率 >94 %。用正交实验确定的最佳工艺条件为 :反应溶液的pH =8,n(环氧氯丙烷 )∶n(三甲胺盐酸盐 ) =0 95∶1 0 0 ,盐酸w(HCl) =36 %。     

3-氯-2-羟丙基脲的合成

用环氧氯丙烷和尿素制备了一种反应中间体3-氯-2-羟丙基脲。研究了反应温度、反应时间、环氧氯丙烷与尿素的用量比、氢氧化钠的用量对氯离子的生成率和产物环氧值的影响。结果表明:当温度为80~90℃,反应时间为120 m in,V〔w(尿素)=50%〕/V(环氧氯丙烷)=1.92,c(NaOH)=0.05 mol/L的水溶液14 mL时,所得产物的环氧值和氯离子生成率都比较小,产物以3-氯-2-羟丙基脲为主。     

Diglycerin und höhere Oligomere des Glycerins als Synthesebausteine

Diglycerol and Higher Oligomers of Glycerol as Components for Synthesis Part 1 of the paper gives a survey on methods for the preparation of diglycerol and higher oligomers of glycerol. The reactions from diallylic ether, from isopropylideneglycerol with epichlorohydrin, and from glycidol with glycerol are reported. For polyglycerol the alkaline catalyzed condensation of glycerol is discussed. Gaschromatograms of DGLC and PGLC from DSW's Rheinberg production site are presented. Part 2 deals with diglycerol reaction products, e. g. the mono-to tetra-fatty acid esters useful as emulsifying agents, a complex ester prepared by the reaction of a fatty acid mixture and a dicarboxylic acid useful as wool wax substitute, an etherification product from epichlorohydrin, diglycoldialdehyde as oxidation product and diglyceroldiformal after condensation with formaldehyde. The production of so-called non-caloric fat-substitutes from protected (isopropylidene derivatives) and unprotected tri- or tetraglycerols is mentioned.     

Synthesis of Epichlorohydrin from Dichloropropanols: Kinetic Aspects of the Process

The reactions involved in the industrial production of epichlorohydrin from dichloropropanols (DCP, including 1,3-dichloro-2-propanol and 2-3-dichloro-1-propanlol) have been kinetically investigated. The kinetics of dehydrochlorination of DCP has been studied in the presence of caustic soda, by potentiometric techniques. The kinetic parameters of the reactions have been determined. The epichlorohydrin hydrolysis has been studied by measuring the decrease of the reagents during the time using titration. The whole study indicate that both dehydrochlorination and hydrolysis reaction can be considered as second order kinetic reaction. It is also indicated that the kinetic constant for dehydrochlorination reaction is far bigger than that for hydrolysis reaction in the same conditions.     

影响阳离子醚化剂结晶点的工艺条件研究

介绍了采用氯甲基环氧丙烷和三甲胺盐酸盐水相合成阳离子醚化剂(CHPTA)的工艺。考察了升温反应时间、反应温度、原料配比对产品结晶点的影响。结果表明:在低温(10±1℃)滴加氯甲基环氧丙烷,25℃反应2 h,35℃反应3 h;原料配比n(三甲胺盐酸盐)∶n(氯甲基环氧丙烷)=0.95∶1.00的条件下合成的产品结晶点可达到-18℃以下。     

3-十二烷氧基-2-羟基丙基三甲基氯化铵的合成与表征

月桂醇和环氧氯丙烷(EPIC)在相转移条件下反应得到中间体长链烷基缩水甘油醚(Ⅰ),其最佳反应条件为:n(EPIC)∶n(月桂醇)=1.8∶1,反应时间4 h,反应温度50℃,碱的浓度为50%。Ⅰ和三甲胺盐酸盐反应得到氯化N-(3-烷氧基-2羟-基)丙基-N,N,N-三甲基铵,最佳反应条件为:n(十二烷氧基缩水甘油醚)∶n(三甲胺盐酸盐)=1∶1,水浴温度30℃,反应时间3.5 h,此条件下收率可达97%。产物结构通过红外光谱及元素分析结果得以证实。     

2-羟基-3-氯丙磺酸钠的合成及结构表征

以环氧氟丙烷为原料,以亚硫酸氢钠和亚硫酸钠为混合磺化剂合成2-羟基-3-氯丙磺酸钠,探讨了磺化剂种类及摩尔比、反应温度,反应时间对产率的影响.结果表明,最佳反应条件为:NaHSO_3与环氧氯丙烷的摩尔比为1:15:1,磺化剂Na_2SO_3与NaHSO_3的摩尔比为0.20:0.62,反应2 h,产率70.8%.产物的熔点为253～254℃.并通过红外光谱、核磁、质谱等方法对产物进行了结构表征.     

3-氯-2-羟丙基三甲基氯化铵的制备

通过系统的实验研究,探索出3 氯 2 羟丙基三甲基氯化铵(CHPTMAC)的最佳生产工艺条件:n(环氧氯丙烷)∶n(三甲胺盐酸盐)=0 95∶1,反应起始pH=7 5～8 0,反应温度采用分段控制(10℃,35℃),使用合适的催化剂,反应收率可达96%以上。通过连续水汽精馏对产品进行纯化,纯化后的产品中w(CHPTMAC)=69%,w(环氧氯丙烷)≤0 0005%,w(二氯丙醇)≤0 0015%,产品性能良好,已投入生产。     

3-氯-2-羟丙基二甲基苄基氯化铵的合成研究

以N,N-二甲基苄胺(DMBA)为原料,在稀盐酸中合成了DMBA盐酸盐;通过DMBA盐酸盐与环氧氯丙烷(表氯醇)反应合成了3-氯-2-羟丙基二甲基苄基氯化铵(CHPDMBA);用连续减压水蒸汽汽提和乙酸乙酯重结晶法对产品进行了分离纯化,元素分析、熔点测定、FT IR及1HNMR方法对产物进行了表征,电位滴定法分析了产品含量。结果表明连续减压水蒸汽汽提和乙酸乙酯重结晶可有效去除产品中残留的环氧氯丙烷和DMBA及副产物二氯丙醇,产品中CHPDMBA的含量在99%以上:CHPDMBA适宜的合成条件为:甲醇-水作反应介质且V甲醇/V水为1.0,反应温度60℃,反应时间7.5 h,DMBA/表氯醇的摩尔比为0.95,在此条件下CHPDMBA的收率可达83%以上。     

一种活性染发剂的制备与应用

以酸性黄73、环氧氯丙烷、硫氢化钠为原料,采用两步法合成活性染料,考察了反应时间、反应温度、原料摩尔比对第1步反应产物收率的影响,得到的较佳反应条件为:n(环氧氯丙烷)∶n(酸性黄73)=20∶1,80℃下反应4 h,在此条件下第1步反应产物的收率为65%。再用硫氢化钠对第1步反应产物进行改性,得到巯基改性的酸性黄73。用红外光谱和液质联用对2步反应产物进行结构表征,并将巯基改性的酸性黄73用于染发剂中考察其染发效果。结果表明,目标产物可以与头发结合,且水洗牢度良好。     

Coordinate polymerization of heterocycles: 1. Oligomerization of epichlorohydrin by TiCl4

The polymerization of epichlorohydrin proceeds via the TiCl₄. 2EPC complex provided the concentration of epichlorohydrin is twice as high as that of TiCl₄. The oligomerization process requires supposedly the existence of a complex in which the epichlorohydrin is coordinate through a ClTi bond. Diethyl ether has an inhibiting effect on the reaction. The oligomerization rate is increased in the presence of acetyl chloride, diethyl ether having no effect this time. The transformation of epichlorohydrin to polymer is always kinetically non-stationary, the number of active centres decreasing with time. Both the initiation and propagation steps proceed through a rearrangement following the coordination of monomer to the activating ligands. No polymerization active free ions have been found to be present in the system. The intermediate and final products were analysed employing spectral, chromatographic, kinetic, and conductivity measurements. The reaction mechanism of oligomerization has been suggested.     

3-[4-(2,3-环氧丙氧基)苯基]丙酸甲酯的合成

对羟基苯丙酸甲酯与环氧氯丙烷，以碳酸钾为催化剂，PEG400为助催化剂，回流反应24小时，制得标题化合物，收率45％，产物径^1HNMR，^13CN0MR，IR确认。研究表明，要获取高产率，环氧氯丙烷应大大过量。一旦回流平稳，反应即按相同的机理进行。PEC400的加入可大大增加目标化合物的含量，同时大大降低产物中羟基化合物的含量，使提纯步骤易于进行。     

On the copolymerization of epichlorohydrin and glycidol

The boron trifluoride-catalyzed cationic copolymerization of epichlorohydrin and glycidol is examined in some detail, with reference to the effect of various reaction variables such as temperature, water content, and stirring rate on the polymerization process and the copolymer product. The reaction temperature does not have a strong effect on the molecular weight of the copolymer, but the water content of the reaction mixture is inversely related to the molecular weight. The stirring rate strongly affects the exotherm associated with the initial stages of the reaction: improved stirring diminishes the exotherm. Based on the relative rates of monomer consumption and other observations, a reaction mechanism is proposed for the formation of the copolymer, in which glycidol polymerizes via what is known as the activated monomer (AM) mechanism rather than by the standard cationic ring-opening polymerization mechanism. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1897–1904, 1997     

玉米羧甲基淀粉崩解剂的合成及性能改进

采用玉米淀粉为原料,以环氧氯丙烷为交联剂、氢氧化钠和氯化铵为复合催化剂、氯乙酸为醚化剂复合变性合成用作药片崩解剂的羧甲基淀粉,探讨了各种反应条件对淀粉的取代度、膨润性能及反应效率的影响,反应效率提高,反应时间大大缩短。原料最佳配比:n(脱水葡萄糖单元)∶n(环氧氯丙烷)∶n(氯乙酸)∶n(氢氧化钠)=1∶0.4∶0.6∶1.2,反应温度60°C左右,反应时间1～2h。     

海因类化合物的研究(Ⅰ)

本文合成了1，3－双（β－环氧丙基）－5，5－二甲基海因化合物。讨论了原料的配比、反应温度、溶剂等因素对海因化合物的影响，并用红外、核磁和端基分析、元素分析等手段对产物进行了分析。当环氧氯丙烷／海因摩尔比为2：1异丙醇作溶剂，反应温度低于100℃并在氮气保护下，可以获得目标产物。