双辛醇琥珀酸双酯磺酸钠二聚表面活性剂的合成与性能

大庆石油学院学报第31卷第3期2007年6月J OU RNAL OF DAQ IN G PETROL EUM INSTITU TE Vol.31No.3J un.2007收稿日期:2006-11-09;审稿人:荆国林;编辑:任志平 基金项目:黑龙江省教育厅科学技术研究项目(10531173) 作者简介:何锡凤(1971-),女,实验师,主要从事有机合成方面的研究.双辛醇琥珀酸双酯磺酸钠二聚表面活性剂的合成与性能何锡凤,宋伟明,安　红(齐齐哈尔大学化学化工学院,黑龙江齐齐哈尔　161006) 摘　要:为合成二聚表面活性剂双辛醇琥珀酸双酯磺酸钠(TAOSS ),首先在n (二乙二醇)∶n (顺酐)为1∶2.10,催化剂w (乙酸钠)为0.5%,反应温度为95℃,反应时间为2.50h 条件下,得到二乙二醇双马来酸单酯;然后分离提纯的酯化产物,在n (辛醇)∶n (单酯)为2.2∶1.0,反应温度为140℃,催化剂w (对甲苯磺酸)为0.5%,反应时间为2.00h 条件下,得到产率为93%的双酯化产物;最后在n (亚硫酸氢钠)∶n (双酯)为3∶1,反应温度为130℃,反应时间为2.25h 条件下,得到磺化率为90%的TAOSS.通过红外光谱分析其产物结构,并测定产物的表面张力、临界胶束浓度、润湿性等.结果表明,所合成的TAOSS 与单基表面活性剂辛醇琥珀酸酯磺酸钠相比,具有更好的表面活性.关　键　词:双辛醇琥珀酸双酯磺酸钠;二聚表面活性剂;合成;表面活性中图分类号:TQ423.11 文献标识码:A 文章编号:1000-1891(2007)03-0074-03二聚表面活性剂是一类性能优良的新型表面活性剂[1,2],其分子结构中含有2个疏水基团和2个亲水基团,与传统表面活性剂(含有1个亲水基团和1个疏水基团)相比,具有更高、更优越的性能,因而成为当前国际研究的热点[3,4].国内对二聚表面活性剂的研究正处在基础研究阶段,探索新的可行合成路线已经成为关注的焦点[5,6].琥珀酸酯磺酸钠盐(SS )是具有优异的乳化性、润湿性和渗透性等特点的阴离子表面活性剂[7].早期所开发的磺基琥珀酸双己酯钠盐[8](D HSS )是SS 中的一种,它具有优良的表面性能,广泛用做渗透剂和分散剂,但其具有溶解性、抗硬水能力较差等缺点,从而抑制其性能的充分发挥.文中合成的二聚表面活性剂双辛醇双琥珀酸酯磺酸钠(TAOSS ),与单基表面活性剂琥珀酸二辛酯磺酸钠(AO TS )相比,具有合成路线简单,原料来源广泛,产品性能优良的特点.1　实验1.1　仪器和试剂Spect rum One 型傅里叶变换红外光谱仪(美国PE 公司);XZD -3型表面张力仪(德国Kruss Gmb H 公司);GCF -1型高压反应釜(大连自控设备厂);NDJ -1旋转黏度仪(上海亚荣生化仪器厂);琥珀酸二辛酯磺酸钠(AO TS )实验室自备,其它试剂均为市场售分析纯试剂.1.2　合成原理OCH 2CH 2O HCH 2CH 2O H +2O C O CH C O CH O CH 2CH 2O C O CH CH C O O H CH 2CH 2O C O CH CH C O O H +O CH 2CH 2O H CH 2CH 2O C O CH CH C O O H (副产物)・47・OCH 2CH 2OC OCH CH C O O H CH 2CH 2O C OCH CH C O O H +2C 8H 17O H O CH 2CH 2O C O CH CH C O OC 7H 14CH 3CH 2CH 2O C O CH CH C O OC 7H 14CH 3+O CH 2CH 2O C O CH CH C O O H CH 2CH 2O C O CH CH C O OC 7H 14CH 3(副产物)O CH 2CH 2O C OCH CH C O OC 7H 14CH 3CH 2CH 2O CO CH CH C O OC 7H 14CH 3+Na HSO 3O CH 2CH 2O C O CH 2CH NaSO 3C O OC 7H 14CH 3CH 2CH 2O C O CH 2CH NaSO 3C O OC 7H 14CH 3+O CH 2CH 2O C O CH CH C O OC 7H 14CH 3CH 2CH 2O C O CH 2CH NaSO 3C OOC 7H 14CH 31.3　合成方法(1)二乙二醇双马来酸单酯.在配有搅拌器、温度计和回流冷凝器的250mL 四口瓶中加入一定量的二乙二醇、马来酸酐及占酸酐质量分数为0.05%的无水乙酸钠,20min 内搅拌升温到预定温度并反应,定时取样测定酸值并计算酯化率.直至酸值变化小于1mg ・h -1时视为酯化反应终点.(2)双辛醇马来酸双酯.在配有搅拌器、温度计和分水器的250mL 四口瓶中,加入一定量的精制后的二乙二醇双马来酸单酯、正辛醇、对甲苯磺酸,甲苯为带水剂,将其升温到指定温度并计时,反应过程中不断析出水,定时取样测定酸值并计算酯化率.选择合适的配料比、反应温度、反应时间将双酯化应的酯化率[8-10]控制在93%.(3)磺化反应.在高压反应釜中,将酯化产物用质量分数为30%的NaO H 水溶液中和至p H 值为7,亚硫酸氢钠配制成饱和溶液,将双辛醇马来酸双酯与亚硫酸氢钠按n (亚硫酸氢钠)∶n (双酯)=3∶1的比例进行投料.在密闭的情况下,待反应体系达到磺化温度时计时,定时取样,测定磺化率[8-10],直至磺化率变化小于0.005h -1时视为反应终点.产物经提纯备用.1.4　分析与表征红外光谱分析样品采用K Br 压片的方法进行.按照国家标准G B/T 5549-90的方法,分析产品的表面张力、分散、乳化、润湿、增溶等性能.2　结果分析2.1　乙二醇酯反应条件及产物结构参照文献[7-9]的方法进行正交实验,在n (二乙二醇)∶n (马来酸酐)为1∶2.10,反应温度为95℃,反应时间为2.50h 时,酸酐转化率达到95%.测定酯化产物红外光谱图,双键的吸收峰为1670～1620cm -1;C O 出现在1718cm -1处;C —O —C 出现在1257～1162cm -1;顺酐1846cm -1,1775cm -1特征峰消失.说明合成的产物符合二乙二醇双马来酸单酯的结构特征.2.2　双辛醇马来酸双酯的合成工艺及分离提纯参照文献[7-9]的方法进行正交实验,酯化产物在n (辛醇)∶n (乙二醇酯)为2.2∶1.0,反应温度为140℃条件下,催化剂w (对甲苯磺酸)为0.5%,反应时间为2.00h 时,得到产率为93%的双酯化产物.薄层色谱分析确定产物通过φ(三氯甲烷)∶φ(乙醇)为4∶1溶剂洗脱,去除杂质,得到双酯化产物.2.3　磺化反应条件及产物结构经过正交实验得到最佳反应条件:n (亚硫酸氢钠)∶n (双酯)为3∶1,反应温度为130℃,反应时间为3.00h 时,磺化率达到90%.测定磺化后的琥珀酸盐红外光谱图,1670～1620cm -1的双健吸收峰已基本消失,表明双键断裂生成磺酸盐,产物用质量分数为50%乙醇溶液萃取,分离提纯用于性能测定.2.4　TAOSS 表面化学性能2.4.1　产物的表面张力测定TAOSS 的表面张力γ,并与单基表面活性剂AO TS 比较,所合成的双辛醇琥珀酸双酯磺酸钠具有较好的降低水溶液表面张力的作用(见图1).溶液的临界胶束浓度c (cmc )为0.001mol ・L -1.・57・第3期 何锡凤等:双辛醇琥珀酸双酯磺酸钠二聚表面活性剂的合成与性能2.4.2　产物表面物理化学性能TAOSS 和AO TS 的表面张力、临界胶束浓度c (cmc )、钙皂分散指数L SDP 、乳化力EP 、泡沫高度FP 和润湿力WP 见表1.由表1可以看出,TAOSS 具有更优良的表面活性.原因是二聚表面活性剂有2条疏水链,使得水分子有序结构的扭曲程度比只有1条疏水链的单基表面活性剂大,而溶剂结构的扭曲程度是表面活性剂具有表面活性的基础[10,11].2.4.3　增溶性能将TAOSS 配成0.01mol ・L -1的溶液,每次取苯加入量V 为25.00mL 增溶苯,测得的光密度与苯质量分数的关系见图2.由图2可以看出,TAOSS 水溶液增溶苯的极限为0.66mL ,而同样条件下,A TOS 增溶苯的极限仅为0.48mL.TAOSS 的增溶性能明显强于单基表面活性剂琥珀酸二辛酯磺酸钠.表1　产物表面物理化学性能产物γ/(mN ・m -1)c (cmc )/(mol ・L -1)L SDP/%EP/s FP/mm WP/s TAOSS29.40.001182432938A TOS 31.50.003121824872图1　溶液的表面张力与样品摩尔浓度的关系曲线图2　样品增溶苯时光密度与苯加入量的关系曲线3　结论(1)经过两步酯化和一步磺化反应,合成二聚表面活性剂双辛醇琥珀酸双酯磺酸钠(TAOSS ),工艺比较简单,产物转化率高.(2)所合成的双辛醇琥珀酸双酯磺酸钠具有较好的降低水溶液表面张力的能力,临界胶束浓度为0.001mol ・L -1,与单基琥珀酸二辛酯磺酸钠相比,具有更好的乳化、润湿、增溶等性能.参考文献:[1]　MEN GER F M ,L IT TAL U C A.Gemini surfactant :a new class of self 2assembling molecules [J ].J Am Chem Soc ,1993,115:10083-10090.[2]　ROSEN M J.Geminis :A new geneation of surfactant s[J ].Chem tech ,1993(3):30-33.[3]　姚志钢,李干佐,董凤岚,等.Gemini 表面活性剂合成进展[J ].化学进展,2004,16(3):349-364.[4]　ZANA R.Gemini (dimeric )surfactant [J ].Current Opinion in colliod and surface Science ,1996,1(15):566-571.[5]　MEN GER F M ,KEIPER J S K.Gemini surfactant s [J ].Angew Chem Int Ed ,2000,39:1906-1920.[6]　范歆,方云.双亲水基-双亲油基型表面活性剂[J ].日用化学工业,2000,30(3):21-24.[7]　华平,张跃军.琥珀酸二(2一甲基戊基)酯磺酸钠的合成与性能研究[J ].现代化工,2002,(3):31-34.[8]　张万忠,乔学亮,邱小林,等.琥珀酸二异辛酯磺酸钠的合成与新应用[J ].材料导报,2006,20(1):89-91.[9]　华平,张跃军.琥珀酸二(4一甲基一2一戊基)酯磺酸钠的合成与性能研究[J ].精细化工,2001,18(11):631-633.[10]　姚志钢,李干佐,胡艾希.双子表面活性剂一一二元醇双琥珀酸双酯磺酸钠(GMI -01)的合成与性能研究[J ].精细化工,2003,20(11):656-704.[11]　付冀峰,徐宝财,朱承根.二聚表面活性剂的性质及其应用[J ].日用化学工业,2001,31(5):41-43.大　庆　石　油　学　院　学　报 第31卷　2007年activity was as much as D TAB,but t he CMC is about27times lower t han D TAB.K ey w ords:gemini surfactant;surface tension;critical micelle concent rationE ffect of polyacrylamide residue on treatment of produced w ater from polymer flooding reservoir in en2 hanced oil recovery/2007,31(3):65-67ZHAO Xiao2fei,L IU Li2xin,WAN G Yu2chan,YUAN Dan2dan,SU Le(1.S chool of Chemist ry&Chemical Engi neeri n g,D aqi n g Pet roleum I nstit ute,D aqi ng,Hei2 long j i ang163318,Chi na;2.Oil Recovery Pl ant N o.3,D aqi ng Oil f iel d Cor p.L t d.,D aqi ng,Hei2 long j i ang163511,Chi na;3.Chemist ry De p artment of T ang g u Oil f iel d of Chi na Ocean Oil f iel d S ervice L t d.,Ti anj i n,Hebei300452,Chi na)Abstract:The effect of polyacrylamide residue on t reat ment of waste water was investigated wit h simula2 ted water of polymer flooding reservoir in enhanced oil recovery and wit h certain hardness wit h t he inor2 ganic flocculant of polymerization aluminum chloride and organic flocculant cationic polyacrylamide.The result s proved t hat t he t reat ment effect drop s remarkably wit h t he increase of polymer residue in waste water at he same temperat ure and t he same dosage of polymerization aluminum chloride and cationic or2 ganic flocculant.The t reat ment effect imp roves for polymerization aluminum chloride at increased tem2 perat ure.Result s by comparing wit h act ual waste water f rom oil field proves t hat t he simulated wasted water has reference value.K ey w ords:oilfield wastewater;polymer;flocculayion;effect;polyacrylamidePreparation and property analysis of Tb(BTC)(DMF)(DMSO)/rare earth metal organic carboxylate frame2 w orks/2007,31(3):68-70DEN G J un,ZHAN G Hong2sheng(D aqi ng I nstit ute of A p plied S cience&Technolog y,D aqi ng,Heilong j i ang163316,Chi na) Abstract:Metal2organic coordination f ramework materials have attracted much attention in recent years due to t heir inherent design flexibility and highly2porous scaffolds,which make t hem potentially usef ul in a number of applications such as gas storage,optics,magnetics,catalysis etc.Here,we selected or2 ganic ligand B TC coordinated to rare2eart h metal Tb to const ruct a novel rare2eart h metal2organic car2 boxylate f ramework Tb(B TC)(DM F)(DMSO).This compound could be potentially used for catalysis, adsorption and fluorescence according to t he characterization of relative properties.K ey w ords:rare eart h element s;ABW topology;luminescent;t hermal stabilityModif ication of Ni-F/H M catalyst for n-pentane isomerization/2007,31(3):71-73B IN G Guo2Qing1,GAO Wen2Yuan2(1.S chool of Chemist ry&Chemical Engi neeri ng,D aqi ng Pet roleum I nstit ute,D aqi n g,Hei2 long j i ang163318,Chi na;2.L ong y ang Com p any,D aqi n g T ri um p h Grou p,D aqi ng,Heilong j i ang 166405,Chi na)Abstract:In order to improve t he isomerization activity of Ni-F/HM catalyst,t he effect of loaded nick2 le,temperat ure of calcinations Ni,content of ammonium fluoro silicate on catalyst for pentane isomeriza2 tion was investigated respectively.According to altering acidity f unction of non2noble metal catalyst for pentane isomerization wit h ammonium fluoro silicate,t he isomerization temperat ure drop s by as much as 50℃.It shows t hat n-pentane isomerization adhered to t he rep resentative bif unctional catalytic reac2 tion mechanism.The well match between metal and acid f unction is t he key to t he research of light par2 affine isomerization catalyst.It shows t hat prepared Ni-F/HM catalyst achieved superior activity under t he conditio n t hat t he co ntent of nickel is4.0%,t he temperat ure of calcinations Ni is450℃and t he content of ammonium fluoro silicate is5.0%.On t he proper reaction conditions(T=250℃,p=2.0 M Pa,W HSV=1.0h-1,H2/Hydrocarbon molar ration is4∶1),n-pentane conversion rate is70.49%, isopentane yield is68.27%,isopentane selectivity is96.85%,liquid product yield is97.78%.K ey w ords:n-pentane;isomerization;nickel;mordenite;ammonium fluorosilicateSynthesis and performance of dimeric surfactants couple octanol suf isuccinate sodium/2007,31(3):74-76 H E Xi2feng,SON G Wei2ming,AN Hong(College of Chemist ry and Chemical Engi neeri n g of Qiqi har Uni versit y,Qiqi har,Heilong j i ang 161006,Chi na)Abstract:In t he paper,t he dimeric surfactant s couple octanol sufisuccinate sodium was synt hesized u2sing sodium bisulfite as sulfonating agent.The diet hylene glycol maleate was obtained as follows:n(ma2 leic anhydride)∶n(diet hylene alcohol)=2.1∶1.0,reaction temperat ure95℃and reaction time2.50h using0.5%sodium acetate as catalyst.The co uple octanol maleate was obtained as follows:n(octanol)∶n(diet hylene glycol maleate)=2.2∶1.0,140℃and reaction2.00h by0.5%para2met hyl benzene sulfonic acid catalysis.The couple octanol sufisuccinate sodium was p repared by reacting t he couple oc2 tanol maleate and sodium bisulfite.The optimum reaction conditions were as follows:n(maleate)∶n (sodium bisulfite)=1.0∶3.0,reaction temperat ure130℃and reaction time2.25h by ort hogonal ex2 periment.The yield of t he p roduct reached90%.The st ruct ure of t he p roduct was determined by IR spect ra and t he p roperties,such as surface tension,t hickening and wetting of t he p roduct were deter2 mined.The result indicated t hat t he couple octanol sufisuccinate was a dimeric surfactant.K ey w ords:couple octanol sufisuccinate sodium;dimeric surfactant s;synt hesis;surface activityProbe into the m atch of microorganisms for oil recovery to the form ation of the oil f ield north of S aertu, Daqing/2007,31(3):77-79WU Song,L I Bai2ling,DUAN Ji2guo(Chemist ry and Chemical Engi neeri ng College,D aqi ng Pet roleum I nstit ute,D aqi ng,Heilong j i ang 163318,Chi na)Abstract:In order to imp rove t he recovery of crude oil of t he nort h of Saert u,Daqing oil field,t he char2 acteristics of t he injected and back-flown waters and crude oil were analyzed.At t he same time,t he re2 lationship s of t he indigenous microorganisms and injected microorganisms and t he content s of nut rient solution were discussed.The result shows t hat crude oil of t he nort h Saert u was heavy oil wit h high co n2 tent s of waxes and colloids.The size of t he pore t hroat of t he cores are suitable for migration of microor2 ganism.But because of less nut rient for microbes in underground water,t he nut rient solution must be injected.The content s of nut rient solution was1×104～5×104mg/L,t he content s of living microbe must be more t han106/mL.K ey w ords:microorganisms for oil recovery;nut rient solution;migration;matchVibration characteristics of ball bearing with w aviness/2007,31(3):80-83WU Yun2peng1,2,ZHAN G Wen2ping1(1.College of Pow er an d N uclear Energ y Engi neeri ng,H arbi n En gi neeri ng U ni versit y,H arbi n, Heilong j i ang150001,Chi na;2.De p artment of M at hem atics an d Mechanics,Heilong j i ang I nstit ute of S cience and Technolog y,H arbi n,Heilong j i ang150027,Chi na)Abstract:By means of mechanics analysis,t he ball bearing vibration model was established,t he effect of waviness on surface rolling element s for bearing vibration system and t he vibration characteristics were analyzed when a defect on surface rolling element s of bearing was detected by t his model.The result s show t hat t he t heoretic calculation and experimental investigation agree wit h each ot her very well.The conclusions are very usef ul for reducing vibration and noise of ball bearing.K ey w ords:ball bearing;waviness;vibrationApplication of grey prediction control to the polymer concentration control/2007,31(3):84-86DUAN Yu2bo1,L I Guo2feng1,SHAO Ke2yong1,2,SON G Jin2bo1(1.College of Elect ric and I nf orm ation Engi neeri ng,D aqi ng Pet roleum I nstit ute,D aqi ng,Hei2 long j i ang163318,Chi na;2.A utom ation College,H arbi n En gi neeri ng Uni versit y,H arbi n,Hei2 long j i ang150001,Chi na)Abstract:This paper is based on t he t heory of grey prediction cont rol.First we use an uncertain linear grey model GM in t he polymer concentration cont rol system of oil fields polymer configure station.It in2 tegrated traditio nal PID feedback cont roller and grey prediction cont roller to build a novel self2adjusted grey p rediction cont rol.This cont roller,according to old concent ration data,can p redict new concent ra2 tion data and t hen auto adjust t he parameter of t he cont roller.This cont roller can also reduce t he error in t he p roduction.The p ractice result s are given to demonst rate t he effectiveness of t he proposed met h2 od.K ey w ords:grey prediction cont rol;GM;polymer concent ration cont rol;PID cont rol;auto adjusted Non2fragile H2/H∞robust controller for systems with controller gain perturbations/2007,31(3):87-91 SHAO Ke2yong1,2,SON G Yan2ru1,WAN G Ting2ting1,ZHAN G Liang1,SON G Jin2bo1・・155。