CN102319550B - Low-concentration viscoelastic surfactant solution and preparation method thereof - Google Patents
Low-concentration viscoelastic surfactant solution and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域 technical field
本发明涉及一种粘弹表面活性剂溶液,特别涉及一种以天然产物油酸为原料的低浓度粘弹性表面活性剂溶液及其制备方法。The invention relates to a viscoelastic surfactant solution, in particular to a low-concentration viscoelastic surfactant solution using natural product oleic acid as a raw material and a preparation method thereof.
背景技术 Background technique
表面活性剂粘弹溶液在日常生活和工业生产中有着广泛的应用,如油田采油用的压裂液,拖曳减阻剂和日常清洁剂配方等。通常的表面活性剂粘弹溶液可通过向单头单尾的表面活性剂溶液中加入大量无机盐或有机盐来获得。这种体系通常需要表面活性剂达到较高的浓度,一方面增加了成本,另一方面也会对体系造成不必要的污染,增加了后处理的难度。Surfactant viscoelastic solutions are widely used in daily life and industrial production, such as fracturing fluid for oil recovery in oil fields, drag reducer and daily cleaning agent formulations, etc. A common surfactant viscoelastic solution can be obtained by adding a large amount of inorganic or organic salts to a single-headed, single-tailed surfactant solution. This kind of system usually requires a high concentration of surfactant, which increases the cost on the one hand, and causes unnecessary pollution to the system on the other hand, increasing the difficulty of post-processing.
表面活性剂溶液的粘弹性与表面活性剂的分子结构,反离子的种类,浓度等等有关。Gemini表面活性剂可以在较低浓度下表现出很强的粘弹性,引起了人们的广泛兴趣(Zana,R.Adv.Colloid Interface Sci.2002,97,205-253)。利用Gemini的分子骨架,再通过调节疏水链的种类,长度和反离子的种类与比例,即有望获得粘弹性更佳的分子物种。The viscoelasticity of the surfactant solution is related to the molecular structure of the surfactant, the type and concentration of the counter ion, and so on. Gemini surfactants can exhibit strong viscoelasticity at lower concentrations, which has aroused widespread interest (Zana, R. Adv. Colloid Interface Sci. 2002, 97, 205-253). Using the molecular skeleton of Gemini, and by adjusting the type and length of the hydrophobic chain and the type and ratio of counter ions, it is expected to obtain molecular species with better viscoelasticity.
油酸以甘油酯的形式广泛存在于自然界中,容易获得。将油酸从天然产物中分离、纯化后,经酯交换或酯化、还原可以得到油醇。油醇经卤代后,就可以广泛应用于表面活性剂的制备过程中。Oleic acid exists widely in nature in the form of glyceride and is easy to obtain. After separating and purifying oleic acid from natural products, oleyl alcohol can be obtained through transesterification, esterification and reduction. After oleyl alcohol is halogenated, it can be widely used in the preparation process of surfactants.
发明内容 Contents of the invention
为了解决现有技术存在的溶液中需要加入大量的盐,且表面活性剂的浓度要比较高,后处理难的问题,本发明提供了一种低浓度粘弹性表面活性剂溶液的制备方法。用油醇制备的Gemini表面活性剂为基础,复配后获得的表面活性剂溶液在很低浓度下即具有高的粘弹性。In order to solve the problem that a large amount of salt needs to be added to the solution in the prior art, the concentration of the surfactant is relatively high, and the post-treatment is difficult, the invention provides a method for preparing a low-concentration viscoelastic surfactant solution. Based on the Gemini surfactant prepared with oleyl alcohol, the surfactant solution obtained after compounding has high viscoelasticity at a very low concentration.
本发明的技术方案为:一种低浓度粘弹性的表面活性剂溶液,是由表面活性剂有效成分与无机盐复配得到,其中表面活性剂的有效成分为油酸基Gemini季铵盐表面活性剂18∶1-2-18∶1·2NO3,结构式如下:The technical scheme of the present invention is: a low-concentration viscoelastic surfactant solution, which is obtained by compounding active ingredients of surfactants and inorganic salts, wherein the active ingredients of surfactants are oleic acid-based Gemini quaternary ammonium salt surface active Agent 18:1-2-18:1·2NO 3 , the structural formula is as follows:
所述的无机盐为硝酸钠,表面活性剂有效成分与硝酸钠的摩尔比为1∶1~5。 The inorganic salt is sodium nitrate, and the molar ratio of the active ingredient of the surfactant to the sodium nitrate is 1:1-5.
一种所述的粘弹表面活性剂溶液的制备方法,先制备得到Gemini表面活性剂,然后再用强碱性离子交换树脂处理得到相应的季铵碱,再经过酸碱中和得到表面活性剂有效成分,最后与无机盐复配得到所述的粘弹表面活性剂;其中,所述的无机盐为硝酸钠,所述的Gemini表面活性剂是油酸基Gemini表面活性剂18∶1-2-18∶1,是按下式反应得到:A kind of preparation method of described viscoelastic surfactant solution, firstly prepare Gemini surfactant, then process with strong basic ion exchange resin to obtain corresponding quaternary ammonium base, then obtain surfactant through acid-base neutralization The active ingredient is finally compounded with an inorganic salt to obtain the viscoelastic surfactant; wherein, the inorganic salt is sodium nitrate, and the Gemini surfactant is an oleic acid-based Gemini surfactant 18:1-2 -18:1 is obtained by the following reaction:
所述的溶剂是乙醇、异丙醇、乙腈、丙酮等的任意一种或者是任意几种任意比例的混合溶剂。The solvent is any one of ethanol, isopropanol, acetonitrile, acetone, etc. or any number of mixed solvents in any proportion.
酸碱中和时所用的酸为硝酸。The acid used in acid-base neutralization is nitric acid.
油醇与对甲苯磺酰氯的摩尔比为1∶1~3,反应温度为-20℃~-5℃。The molar ratio of oleyl alcohol to p-toluenesulfonyl chloride is 1:1 to 3, and the reaction temperature is -20°C to -5°C.
所述的对甲苯磺酰氯先溶于二氯甲烷后再与油醇反应。The p-toluenesulfonyl chloride is first dissolved in methylene chloride and then reacted with oleyl alcohol.
油醇的对甲苯磺酸酯与溴化锂的摩尔比为1∶1~5,反应温度为室温。The molar ratio of p-toluenesulfonate of oleyl alcohol to lithium bromide is 1:1-5, and the reaction temperature is room temperature.
在加入溴化锂的同时加入无水丙酮作为反应溶剂。While adding lithium bromide, anhydrous acetone was added as a reaction solvent.
有益效果:Beneficial effect:
所获得的表面活性剂粘弹溶液在表面活性剂有效成分浓度较低时,在1.7wt%即具有较好的粘弹性,可明显降低使用成本。The obtained surfactant viscoelastic solution has better viscoelasticity at 1.7wt% when the active ingredient concentration of the surfactant is lower, which can significantly reduce the use cost.
附图说明 Description of drawings
图1表面活性剂粘弹溶液的动态剪切图(0.023mol/L,G’(●),G”(○))。Figure 1 Dynamic shear diagram of surfactant viscoelastic solution (0.023mol/L, G’(●), G”(○)).
图2表面活性剂粘弹溶液的稳态剪切图(0.023mol/L,1.7wt%)。Fig. 2 Steady-state shear diagram of surfactant viscoelastic solution (0.023mol/L, 1.7wt%).
具体实施方式 Detailed ways
一种低浓度粘弹性表面活性剂溶液,是由表面活性剂有效成分与无机盐复配得到,其有效成分的结构式如下:A low-concentration viscoelastic surfactant solution is obtained by compounding active ingredients of surfactants and inorganic salts, and the structural formula of the active ingredients is as follows:
为油酸基Gemini季铵盐表面活性剂18∶1-2-18∶1·2NO3,所述的无机盐为硝酸钠,表面活性剂有效成分与硝酸钠的摩尔比为1∶1~5。 It is an oleic acid-based Gemini quaternary ammonium salt surfactant 18:1-2-18:1·2NO 3 , the inorganic salt is sodium nitrate, and the molar ratio of the active ingredient of the surfactant to sodium nitrate is 1:1-5 .
一种低浓度粘弹表面活性剂溶液的制备方法,,先制备得到Gemini表面活性剂,然后再用强碱性离子交换树脂处理得到相应的季铵碱,再经过酸碱中和得到表面活性剂有效成分,最后与无机盐复配得到所述的粘弹表面活性剂;其中,所述的无机盐为硝酸钠,所述的Gemini表面活性剂是油酸基Gemini表面活性剂18∶1-2-18∶1,是按下式反应得到:A method for preparing a low-concentration viscoelastic surfactant solution, first preparing a Gemini surfactant, then treating it with a strong basic ion exchange resin to obtain the corresponding quaternary ammonium base, and then obtaining the surfactant through acid-base neutralization The active ingredient is finally compounded with an inorganic salt to obtain the viscoelastic surfactant; wherein, the inorganic salt is sodium nitrate, and the Gemini surfactant is an oleic acid-based Gemini surfactant 18:1-2 -18:1 is obtained by the following reaction:
其中油醇可以直接买市售的,也可以以天然产物油酸为原料,经过酯化、还原制备得到,制备反应式如下:Among them, oleyl alcohol can be directly purchased from the market, or can be prepared from natural product oleic acid through esterification and reduction. The preparation reaction formula is as follows:
在醇的溴化步骤中,是将油醇先与对甲苯磺酰氯反应,再和无水溴化锂反应制得。油醇与对甲苯磺酰氯的摩尔比为1∶1~3,与无水溴化锂的摩尔比为1∶1~5。In the alcohol bromination step, oleyl alcohol is first reacted with p-toluenesulfonyl chloride, and then reacted with anhydrous lithium bromide. The molar ratio of oleyl alcohol to p-toluenesulfonyl chloride is 1:1-3, and the molar ratio of anhydrous lithium bromide is 1:1-5.
在季铵化步骤中,N,N,N’,N’-四甲基乙二胺与1-溴-顺式-9-十八烯的摩尔比为1∶2~5。溶剂为乙醇,异丙醇,乙腈,丙酮,正丁醇,N,N-二甲基甲酰胺中的任意一种或者是若干种任意比例的混合溶剂,在80~100℃下反应24至120小时。In the quaternization step, the molar ratio of N,N,N',N'-tetramethylethylenediamine to 1-bromo-cis-9-octadecene is 1:2-5. The solvent is any one of ethanol, isopropanol, acetonitrile, acetone, n-butanol, N,N-dimethylformamide or several mixed solvents in any proportion, and the reaction time is 24 to 120 at 80-100°C Hour.
以油酸为起始原料,制备所述的低浓度粘弹表面活性剂溶液,具体可以按下式反应:Taking oleic acid as a starting material to prepare the low-concentration viscoelastic surfactant solution, the specific reaction can be as follows:
油酸的酯化:Esterification of oleic acid:
将油酸和10倍摩尔数的甲醇混合,在浓硫酸的催化下,在80~90℃回流5~8小时。经除甲醇、水洗、干燥后,减压蒸馏得到油酸甲酯。Mix oleic acid and 10 times the mole number of methanol, and reflux at 80-90°C for 5-8 hours under the catalysis of concentrated sulfuric acid. After removing methanol, washing with water and drying, distilled under reduced pressure to obtain methyl oleate.
油酸甲酯还原为油醇:Reduction of methyl oleate to oleyl alcohol:
将油酸甲酯与等摩尔量的氢化锂铝在-15~0℃在无水四氢呋喃中反应3~10小时。经后处理,干燥得到油醇。所述的氢化锂铝还可以是红铝等不还原双键,只还原酯基的还原剂Methyl oleate was reacted with an equimolar amount of lithium aluminum hydride in anhydrous tetrahydrofuran at -15 to 0°C for 3 to 10 hours. After post-processing and drying, oleyl alcohol is obtained. The described lithium aluminum hydride can also be a reductant that does not reduce the double bond, such as red aluminum, but only reduces the ester group.
油醇的溴化:Bromination of oleyl alcohol:
油醇与对甲苯磺酰氯的摩尔比为1∶1~3,在2~10倍摩尔量的三乙胺存在下,-20~-5℃反应2~15小时。经水洗、干燥得到油醇的对甲苯磺酸酯。对甲苯磺酸酯与无水溴化锂的摩尔比为1∶1~5,在室温下反应2~50小时。经过滤、除溶剂、柱层析得到1-溴-顺式-9-十八烯。The molar ratio of oleyl alcohol to p-toluenesulfonyl chloride is 1:1-3, in the presence of 2-10 times the molar amount of triethylamine, react at -20-5°C for 2-15 hours. After washing with water and drying, the p-toluenesulfonate of oleyl alcohol is obtained. The molar ratio of p-toluenesulfonate to anhydrous lithium bromide is 1:1-5, and the reaction is carried out at room temperature for 2-50 hours. After filtration, solvent removal and column chromatography, 1-bromo-cis-9-octadecene was obtained.
季铵化:Quaternization:
N,N,N’,N’-四甲基乙二胺与1-溴-顺式-9-十八烯的摩尔比为1∶2~5,用乙醇做溶剂,在90℃回流96小时。冷却后蒸除溶剂,用乙醇-乙酸乙酯重结晶三次,真空干燥得产品油酸基Gemini表面活性剂18∶1-2-18∶1。所述的溶剂是乙醇、异丙醇、乙腈、丙酮等的任意一种或者是任意几种任意比例的混合溶剂。The molar ratio of N,N,N',N'-tetramethylethylenediamine to 1-bromo-cis-9-octadecene is 1:2~5, use ethanol as solvent, and reflux at 90°C for 96 hours . After cooling, the solvent was evaporated, recrystallized three times with ethanol-ethyl acetate, and vacuum-dried to obtain the product oleic acid-based Gemini surfactant 18:1-2-18:1. The solvent is any one of ethanol, isopropanol, acetonitrile, acetone, etc. or any number of mixed solvents in any proportion.
离子交换:Ion exchange:
将强碱性离子交换树脂经酸浸泡-水洗-氢氧化钠溶液洗-水洗-酸洗-水洗-氢氧化钠溶液洗-水洗处理。3g油酸基Gemini表面活性剂18∶1-2-18∶1溶于20mL蒸馏水中,加入离子交换柱,用蒸馏水以5mL/min的流速洗脱。用酚酞试液检验,当流出液使酚酞变红时开始收集,得到油酸基Gemini表面活性剂18∶1-2-18∶1的季铵碱溶液。The strongly basic ion exchange resin is processed by acid immersion-water washing-sodium hydroxide solution washing-water washing-acid washing-water washing-sodium hydroxide solution washing-water washing. 3 g of oleic acid-based Gemini surfactant 18:1-2-18:1 was dissolved in 20 mL of distilled water, added to an ion exchange column, and eluted with distilled water at a flow rate of 5 mL/min. Tested with phenolphthalein test solution, began to collect when the effluent turned phenolphthalein red, and obtained quaternary ammonium alkali solution of oleic acid-based Gemini surfactant 18:1-2-18:1.
酸碱中和与复配:Acid-base neutralization and compounding:
配制一定浓度硝酸溶液,用电位滴定确定季铵碱与硝酸溶液的准确浓度。将酸、碱按照摩尔比1∶1进行中和,再与一定比例的硝酸钠复配即得到所述的表面活性剂粘弹溶液。Prepare a certain concentration of nitric acid solution, and use potentiometric titration to determine the exact concentration of quaternary ammonium base and nitric acid solution. The acid and alkali are neutralized according to the molar ratio of 1:1, and then compounded with a certain proportion of sodium nitrate to obtain the surfactant viscoelastic solution.
实施例1Example 1
(1)油酸甲酯的合成(1) Synthesis of methyl oleate
将油酸(120g),无水甲醇(120g)和浓硫酸(1g)加入500mL单颈瓶中,在82℃搅拌回流6小时。冷却后,去除低沸点物质,用稀碳酸氢钠溶液洗涤有机层至中性。加入无水硫酸镁干燥过夜。过滤后,将粗品减压蒸馏得油酸甲酯。176~178℃/6mmHg(uncorrected)产率:90.0%Add oleic acid (120 g), anhydrous methanol (120 g) and concentrated sulfuric acid (1 g) into a 500 mL single-necked bottle, and stir and reflux at 82° C. for 6 hours. After cooling, the low boiling point substances were removed, and the organic layer was washed with dilute sodium bicarbonate solution until neutral. Add anhydrous magnesium sulfate and dry overnight. After filtration, the crude product was distilled under reduced pressure to obtain methyl oleate. 176~178℃/6mmHg(uncorrected) Yield: 90.0%
1H NMR(300MHz,CDCl3,Me4Si)δ(ppm):5.35(m,2H,CH=CH),3.66(s,3H,OCH3),2.30(t,2H,CH2COOCH3),2.02(t,4H,CH2CH=CHCH2),1.62(t,2H,CH2CH2COOCH3),1.30~1.27(m,20H,CH3(CH2)6CH2CH=CHCH2(CH2)4),0.88(t,3H,CH3) 1 H NMR (300 MHz, CDCl 3 , Me 4 Si) δ (ppm): 5.35 (m, 2H, CH=CH), 3.66 (s, 3H, OCH 3 ), 2.30 (t, 2H, CH 2 COOCH 3 ) , 2.02(t, 4H, CH 2 CH=CHCH 2 ), 1.62(t, 2H, CH 2 CH 2 COOCH 3 ), 1.30~1.27(m, 20H, CH 3 (CH 2 ) 6 CH 2 CH=CHCH 2 (CH 2 ) 4 ), 0.88(t, 3H, CH 3 )
(2)油醇的合成(2) Synthesis of oleyl alcohol
将油酸甲酯(52g),经钠-二苯甲酮回流除水后的四氢呋喃(207g)加入500mL单颈瓶中。将单颈瓶放入低温反应器,温度控制在-10℃以下。将氢化锂铝(8g)缓慢加入,开始有较多气体产生。加完后搅拌半小时,再转移到室温继续反应4小时。将混合物冷却到-15℃,先和,先向其中缓慢加入8mL水,再加入8mL 10%wt氢氧化钠溶液。加完后室温搅拌半小时,抽滤得澄清滤液。将滤液用无水硫酸镁干燥,过滤后减压除掉溶剂即得产品油醇。产率:86.3%Add methyl oleate (52 g) and tetrahydrofuran (207 g) after sodium-benzophenone reflux to remove water into a 500 mL single-necked bottle. Put the single-necked bottle into a low-temperature reactor, and control the temperature below -10°C. Lithium aluminum hydride (8 g) was added slowly and more gas evolution began. Stir for half an hour after the addition, and then transfer to room temperature to continue the reaction for 4 hours. The mixture was cooled to -15°C, firstly mixed, and 8mL of water was slowly added thereto, and then 8mL of 10%wt sodium hydroxide solution was added. After the addition, stir at room temperature for half an hour, and filter with suction to obtain a clear filtrate. Dry the filtrate with anhydrous magnesium sulfate, filter and remove the solvent under reduced pressure to obtain the product oleyl alcohol. Yield: 86.3%
1H NMR(400MHz,CDCl3,Me4Si)δ(ppm):5.34(t,2H,CH=CH),3.63(t,2H,CH2OH),2.00(d,4H,CH2CH=CHCH2),1.85(s,1H,OH),1.58~1.21(m,24H,CH3(CH2)6CH2CH=CHCH2(CH2)6),0.88(t,3H,CH3) 1 H NMR (400 MHz, CDCl 3 , Me 4 Si) δ (ppm): 5.34 (t, 2H, CH=CH), 3.63 (t, 2H, CH 2 OH), 2.00 (d, 4H, CH 2 CH= CHCH 2 ), 1.85 (s, 1H, OH), 1.58~1.21 (m, 24H, CH 3 (CH 2 ) 6 CH 2 CH=CHCH 2 (CH 2 ) 6 ), 0.88 (t, 3H, CH 3 )
(3)1-溴-顺式-9-十八烯的合成:(3) Synthesis of 1-bromo-cis-9-octadecene:
向500mL三颈瓶中加入油醇(70.4g,0.26mol),三乙胺(53g,0.52mol)和100mL二氯甲烷,冷却至-10℃。搅拌下缓慢滴加对甲基苯磺酰氯的二氯甲烷溶液(65g,0.34mol),滴加过程有白色浑浊产生。加完后室温搅拌5小时。将反应液先用稀盐酸溶液洗,再用蒸馏水洗涤至中性。用无水硫酸镁干燥,抽滤得浅黄色滤液;将溶剂去除得深黄色液体。将液体转移到500mL单颈瓶中,同时加入300mL无水丙酮和无水溴化锂(35g,0.4mol),室温搅拌32小时。将丙酮蒸干,加入200mL石油醚,在-5℃静置4小时。将沉淀过滤得澄清滤液,蒸除溶剂得初产品。将初品用硅胶柱层析纯化,洗脱剂为石油醚。终产品为无色透明液体。产率:51.2%。Add oleyl alcohol (70.4 g, 0.26 mol), triethylamine (53 g, 0.52 mol) and 100 mL of dichloromethane into a 500 mL three-necked flask, and cool to -10°C. While stirring, a dichloromethane solution of p-toluenesulfonyl chloride (65 g, 0.34 mol) was slowly added dropwise, during which white turbidity occurred. After the addition was complete, it was stirred at room temperature for 5 hours. The reaction solution was first washed with dilute hydrochloric acid solution, and then washed with distilled water until neutral. Dry with anhydrous magnesium sulfate, and filter with suction to obtain a light yellow filtrate; remove the solvent to obtain a dark yellow liquid. The liquid was transferred to a 500 mL single-necked bottle, and 300 mL of anhydrous acetone and anhydrous lithium bromide (35 g, 0.4 mol) were added at the same time, and stirred at room temperature for 32 hours. Evaporate acetone to dryness, add 200 mL of petroleum ether, and let stand at -5°C for 4 hours. The precipitate was filtered to obtain a clear filtrate, and the solvent was evaporated to obtain the initial product. The primary product was purified by silica gel column chromatography, and the eluent was petroleum ether. The final product is a colorless transparent liquid. Yield: 51.2%.
1H NMR(300MHz,CDCl3)δ5.35(d,2H,CH=CH),3.39(t,2H,CH2Br),2.01(d,4H,CH2CH=CHCH2),1.90~1.77(m,2H,CH2CH2Br),1.35(m,22H,CH3(CH2)6CH2CH=CHCH2(CH2)6),0.88(t,3H,CH3). 1 H NMR (300 MHz, CDCl 3 ) δ5.35 (d, 2H, CH=CH), 3.39 (t, 2H, CH 2 Br), 2.01 (d, 4H, CH 2 CH=CHCH 2 ), 1.90~1.77 (m, 2H, CH 2 CH 2 Br), 1.35 (m, 22H, CH 3 (CH 2 ) 6 CH 2 CH=CHCH 2 (CH 2 ) 6 ), 0.88 (t, 3H, CH 3 ).
(4)油酸基Gemini表面活性剂18∶1-2-18∶1的合成(4) Synthesis of oleic acid-based Gemini surfactant 18:1-2-18:1
将1-溴-顺式-9-十八烯(44g,0.13mol),四甲基乙二胺(7g,0.06mol)和200mL乙醇加入500mL单颈瓶中回流96小时。冷却后蒸除溶剂,用乙醇-乙酸乙酯重结晶三次,真空干燥得产品,为白色蜡状固体。产率:25.1%。Add 1-bromo-cis-9-octadecene (44 g, 0.13 mol), tetramethylethylenediamine (7 g, 0.06 mol) and 200 mL of ethanol into a 500 mL single-necked bottle and reflux for 96 hours. After cooling, the solvent was distilled off, recrystallized three times with ethanol-ethyl acetate, and dried in vacuo to obtain the product as a white waxy solid. Yield: 25.1%.
1H NMR(300MHz,CDCl3)δ5.34(s,4H),4.76(s,4H),3.71(s,4H),3.52(s,12H),2.01(m,8H),1.82(m,4H),1.37~1.27(m,44H),0.88(t,6H). 1 H NMR (300MHz, CDCl 3 ) δ5.34(s, 4H), 4.76(s, 4H), 3.71(s, 4H), 3.52(s, 12H), 2.01(m, 8H), 1.82(m, 4H), 1.37~1.27(m, 44H), 0.88(t, 6H).
(5)季铵碱的制备(5) Preparation of quaternary ammonium base
强碱性离子交换树脂的处理:将717型阴离子交换树脂(氯型)400g用稀盐酸溶液浸泡两天,装入柱中,用蒸馏水洗至中性。用1mol/L的氢氧化钠溶液进行首次交换,流速10mL/min,直至硝酸酸化的硝酸银溶液检验无沉淀为止。用蒸馏水洗至中性后,再用1mol/L的盐酸溶液以20mL/min的流速交换,再用蒸馏水洗至中性。最后用1.5mol/L的氢氧化钠溶液以10mL/min的流速进行交换,直至硝酸酸化的硝酸银溶液检验无沉淀为止。用蒸馏水洗至中性,处理完毕。Treatment of strong basic ion exchange resin: Soak 400g of 717-type anion-exchange resin (chlorine type) in dilute hydrochloric acid solution for two days, put it into the column, and wash it with distilled water until neutral. Use 1mol/L sodium hydroxide solution for the first exchange, with a flow rate of 10mL/min, until the silver nitrate solution acidified with nitric acid is tested for no precipitation. After washing with distilled water until neutral, exchange it with 1mol/L hydrochloric acid solution at a flow rate of 20mL/min, and then wash with distilled water until neutral. Finally, exchange with 1.5mol/L sodium hydroxide solution at a flow rate of 10mL/min until the silver nitrate solution acidified with nitric acid has no precipitation. Wash with distilled water until neutral, and the treatment is complete.
将3g油酸基Gemini表面活性剂18∶1-2-18∶1溶于100mL蒸馏水中,加入离子交换柱,用蒸馏水以5mL/min的流速洗脱。用酚酞试液检验,当流出液使酚酞变红时开始收集,得到18∶1-2-18∶1的季铵碱溶液。3 g of oleic acid-based Gemini surfactant 18:1-2-18:1 was dissolved in 100 mL of distilled water, added to an ion exchange column, and eluted with distilled water at a flow rate of 5 mL/min. Test with phenolphthalein test solution, collect when the effluent turns phenolphthalein red, and obtain a quaternary ammonium alkali solution of 18:1-2-18:1.
(6)酸碱中和与复配(6) Acid-base neutralization and compounding
配制一定浓度的硝酸溶液,用碳酸钠标准溶液标定出准确浓度。用邻苯二甲酸氢钾标准溶液标定出季铵碱溶液的准确浓度。分别取一定体积的硝酸溶液和季铵碱溶液用蒸馏水稀释,按照酸碱中和1∶1的比例混合,最后获得的粘弹表面活性剂有效成分的浓度为0.023mol/L(1.7wt%)。称取3倍物质的量的固体硝酸钠(0.6wt%)加入该溶液中溶解后,即得到所述的低浓度粘弹表面活性剂溶液。Prepare a certain concentration of nitric acid solution, and use sodium carbonate standard solution to calibrate the exact concentration. The exact concentration of the quaternary ammonium alkali solution is calibrated with a standard solution of potassium hydrogen phthalate. Take a certain volume of nitric acid solution and quaternary ammonium alkali solution and dilute with distilled water respectively, mix according to the ratio of acid-base neutralization 1:1, the concentration of the active ingredient of the viscoelastic surfactant obtained at last is 0.023mol/L (1.7wt%) . After weighing 3 times the amount of solid sodium nitrate (0.6wt%) into the solution and dissolving, the low-concentration viscoelastic surfactant solution is obtained.
(7)将所得溶液在室温下进行动态与稳态流变测量,得到相关数据,具体数据见图1和图2,由图1可以看出,该溶液表现出明显的粘弹性能,呈现出Maxwell流体的特征。由图2可以看出,该溶液的零剪切粘度可达到7.4Pa·s,远高于相似浓度下普通表面活性剂溶液的粘度。(7) The resulting solution is subjected to dynamic and steady-state rheological measurements at room temperature to obtain relevant data. The specific data are shown in Fig. 1 and Fig. 2. As can be seen from Fig. 1, the solution shows obvious viscoelastic properties, showing Characteristics of Maxwell fluids. It can be seen from Figure 2 that the zero-shear viscosity of the solution can reach 7.4 Pa·s, which is much higher than the viscosity of common surfactant solutions at similar concentrations.
表1实施例与常见的CTAB-无机盐体系的对比The contrast of table 1 embodiment and common CTAB-inorganic salt system
对照体系r:Candau,S.J.,Hirsch,E.,Zana,R.,Delsanti,M.Langmuir 1989,5,1225.Control system r: Candau, S.J., Hirsch, E., Zana, R., Delsanti, M.Langmuir 1989, 5, 1225.
由上表可以清楚的看出本发明的体系在很低的浓度就可以有很好的零剪切粘度,无机盐的用量也很低。It can be clearly seen from the above table that the system of the present invention can have very good zero-shear viscosity at a very low concentration, and the amount of inorganic salt is also very low.
实施例2Example 2
1-溴-顺式-9-十八烯的合成:Synthesis of 1-bromo-cis-9-octadecene:
采用市售油醇,取50g油醇和36g对甲苯磺酰氯,两者的摩尔比为1∶1,在10倍摩尔量的三乙胺存在下,-20℃反应15小时。经水洗、干燥得到油醇的对甲苯磺酸酯。加入5倍摩尔量的无水溴化锂80g,同时加入丙酮,在室温下反应2小时。将丙酮蒸干,加入石油醚,在-5℃静置后,经过滤、除溶剂、柱层析得到1-溴-顺式-9-十八烯,产率21.5%。Using commercially available oleyl alcohol, take 50g oleyl alcohol and 36g p-toluenesulfonyl chloride, the molar ratio of the two is 1:1, and react at -20°C for 15 hours in the presence of 10 times the molar amount of triethylamine. After washing with water and drying, the p-toluenesulfonate of oleyl alcohol is obtained. 80 g of anhydrous lithium bromide was added in a 5-fold molar amount, and acetone was added at the same time, and the reaction was carried out at room temperature for 2 hours. Acetone was evaporated to dryness, petroleum ether was added, and after standing at -5°C, 1-bromo-cis-9-octadecene was obtained by filtration, solvent removal, and column chromatography with a yield of 21.5%.
季铵化:Quaternization:
将1-溴-顺式-9-十八烯(40g,0.12mol),N,N,N’,N’-四甲基乙二胺(5g,0.04mol),两者摩尔比为3∶1,150mL无水乙腈加入500mL单颈瓶中回流100小时。冷却后蒸除溶剂,用乙醇-乙酸乙酯重结晶三次,真空干燥得产品,为白色蜡状固体。产率:38.5%。1-Bromo-cis-9-octadecene (40g, 0.12mol), N,N,N',N'-tetramethylethylenediamine (5g, 0.04mol), the molar ratio of the two is 3: 1. Add 150mL of anhydrous acetonitrile into a 500mL single-necked bottle and reflux for 100 hours. After cooling, the solvent was distilled off, recrystallized three times with ethanol-ethyl acetate, and dried in vacuo to obtain the product as a white waxy solid. Yield: 38.5%.
实施例3Example 3
1-溴-顺式-9-十八烯的合成:Synthesis of 1-bromo-cis-9-octadecene:
向500mL三颈瓶中加入油醇(50g,0.186mol)、三乙胺(56g,0.56mol)和二氯甲烷220mL,冷却至-10℃。搅拌下缓慢滴加对甲基苯磺酰氯(71g,0.37mol)的二氯甲烷溶液,油醇与对甲苯磺酰氯的摩尔比为1∶2,滴加过程有白色浑浊产生。加完后室温搅拌15小时。将反应液先用稀盐酸溶液洗,再用蒸馏水洗涤至中性。用无水硫酸镁干燥,抽滤得浅黄色滤液;将溶剂去除得深黄色液体。将液体转移到500mL单颈瓶中,同时加入300mL无水丙酮和无水溴化锂,对甲苯磺酸酯与无水溴化锂的摩尔比为1∶3,室温搅拌50小时。将丙酮蒸干,加入200mL石油醚,在-5℃静置4小时。将沉淀过滤得澄清滤液,蒸除溶剂得初产品。将初品用硅胶柱层析纯化,洗脱剂为石油醚。终产品为无色透明液体,产率64.8%。Add oleyl alcohol (50 g, 0.186 mol), triethylamine (56 g, 0.56 mol) and 220 mL of dichloromethane into a 500 mL three-necked flask, and cool to -10°C. Under stirring, a dichloromethane solution of p-toluenesulfonyl chloride (71 g, 0.37 mol) was slowly added dropwise. The molar ratio of oleyl alcohol to p-toluenesulfonyl chloride was 1:2, and white turbidity occurred during the dropping process. Stir at room temperature for 15 hours after addition. The reaction solution was first washed with dilute hydrochloric acid solution, and then washed with distilled water until neutral. Dry with anhydrous magnesium sulfate, and filter with suction to obtain a light yellow filtrate; remove the solvent to obtain a dark yellow liquid. Transfer the liquid to a 500 mL single-necked bottle, add 300 mL of anhydrous acetone and anhydrous lithium bromide at the same time, the molar ratio of p-toluenesulfonate to anhydrous lithium bromide is 1:3, and stir at room temperature for 50 hours. Evaporate acetone to dryness, add 200 mL of petroleum ether, and let stand at -5°C for 4 hours. The precipitate was filtered to obtain a clear filtrate, and the solvent was evaporated to obtain the initial product. The primary product was purified by silica gel column chromatography, and the eluent was petroleum ether. The final product is a colorless transparent liquid with a yield of 64.8%.
季铵化:Quaternization:
将1-溴-顺式-9-十八烯(66.3g,0.2mol),N,N,N’,N’-四甲基乙二胺(5g,0.04mol),两者摩尔比为5∶1,150mL异丙醇加入500mL单颈瓶中回流100小时。冷却后蒸除溶剂,用乙醇-乙酸乙酯重结晶三次,真空干燥得产品,为白色蜡状固体。产率:25.3%。1-Bromo-cis-9-octadecene (66.3g, 0.2mol), N,N,N',N'-tetramethylethylenediamine (5g, 0.04mol), the molar ratio of the two was 5 : 1, 150mL of isopropanol was added into a 500mL single-necked bottle and refluxed for 100 hours. After cooling, the solvent was distilled off, recrystallized three times with ethanol-ethyl acetate, and dried in vacuo to obtain the product as a white waxy solid. Yield: 25.3%.
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