CN100531884C - Alkyl- fragrant benzyl- polyethenoxy ether anionic surfactant and method of preparing the same and use thereof - Google Patents
Alkyl- fragrant benzyl- polyethenoxy ether anionic surfactant and method of preparing the same and use thereof Download PDFInfo
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- CN100531884C CN100531884C CNB200610088855XA CN200610088855A CN100531884C CN 100531884 C CN100531884 C CN 100531884C CN B200610088855X A CNB200610088855X A CN B200610088855XA CN 200610088855 A CN200610088855 A CN 200610088855A CN 100531884 C CN100531884 C CN 100531884C
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Abstract
The invention belongs to high efficient surface activating agent filed, in particular relating to alkylPolyoxy divinyl ether and the anion surface activating agent preparation method and use. After a series of reaction, the alkyl aromatic hydrocarbon forms a nonionic to anion surface activating agent substance with an aryl benzyl structure. The molecular structure of the surface activating agent substance decides that the invention has low acrimony and toxicity, good degradation performance, good water solubility and hardwater resistance, high efficiency forming capability and excellent anti-salt performance; the surface activating agent has high activity, the critical tension with various different crude oil can reach super low (10 to 3Mn/m), which has good application prospect in domestic chemical, sanitation, three-time oil extracting, spinning industry, leatherworking, pesticide emulsion and other fields. The chemical structure of the surface activating agent is as the drawing.
Description
Technical field
The invention belongs to the efficient surfactant field, particularly alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of nonionic-anionic species surfactant and preparation method thereof and purposes.
Background technology
Anionic and nonionic type surfactant, for example alkyl phenol ether polyoxyethylene ether sulfate, acetate because it has two class hydrophilic radicals, have overcome the low adverse effect of its cloud point, widen its application of non-ionic surface active agent greatly, in actual production, obtained extensive use.
But APES class material all can produce the alkyl phenol that has than Johnson ﹠ Johnson's thing toxicity because there is phenol oxygen key in it in degradation process, and this has all limited its application in real life and industrial production.
US4485873 has disclosed the application of polyoxyethylated alkyl phenol acetate aspect intensified oil reduction, but it does not mention alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant.
US4545912 has disclosed a kind of polyethenoxy ether sulphonate surfactant that is used for the chemical displacement of reservoir oil, and its hydrophobic group is a double-tail structure, and one of them is phenyl, with the alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant structure very big difference is arranged.
JP61236541 has disclosed a kind of light-sensitive material that is used to take a picture, and its structure is similar to alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant, but its hydrophobic group alkyl benzyl (R-C
6H
4CH
2-) in R be H, CH
3, C
2H
5, C
3H
7, and the alkyl in the hydrophobic group alkyl benzyl of the alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant among the present invention is a backbone.
CN1296115A has disclosed the application of industrial goods polyoxyethylene nonylphenyl ether acetate aspect the raising oil recovery, and it does not mention alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant equally.
Summary of the invention
One of purpose of the present invention is to provide a kind of alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of function admirable.
Two of purpose of the present invention is to provide the preparation method of alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant.
Three of purpose of the present invention is to provide the purposes of alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant.
Four of purpose of the present invention is to provide a kind of alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant system, make it independent use, mix to use or with promoter effect under, can form low or ultralow interfacial tension with crude oil, can in the tertiary oil recovery in oil field, be applied.
The structural formula of alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of the present invention is:
Wherein, R
1Be the long alkyl chain length of carbon number 4～30, R
2Be that H or carbon number are 1～30 alkyl; Ar is aromatic rings such as benzene, biphenyl, diphenyl ether, naphthalene, tetralin, indenes, indane or contains the substituent above-mentioned aromatic ring of H, methyl or ethyl; N is (C
2H
4O) number of group, numerical value are 1～30; R
3For methylene, ethylidene, propylidene or do not exist; Y is sulfonate radical, sulfate radical or carboxylate radical; M is alkali metal ion (Li
+, Na
+Or K
+), alkaline-earth metal ions (Ca
2+, Mg
2+Or Ba
2+), ammonium ion (NH
4 +) or the mixture of the above ion.
Alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of the present invention is alkyl-fragrant benzyl-polyethenoxy ether acetate, alkyl-fragrant benzyl-polyethenoxy ether sulfuric acid, alkyl-fragrant benzyl-polyethenoxy ether ethyl sulfonate or alkyl-fragrant benzyl-polyethenoxy ether propyl sulfonic acid salt.
Alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of the present invention be the alkyl virtue benzyl chlorine (bromine) that synthesizes of the inventor and the fragrant benzylalcohol of alkyl through a series of reaction, a kind of nonionic-anion surfactant material of formation.Such surfactant has the hydrophobic grouping of alkyl-fragrant benzyl structure and the (C of different numbers
2H
4O) the common hydrophilic radical that constitutes of group and sulfonate radical, sulfate radical or carboxylate radical.
The preparation method of alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of the present invention may further comprise the steps:
(a) alkyl-fragrant benzyl-polyethenoxy ether alcohol is synthetic:
Method one:
Wherein, R
1Be the long alkyl chain length of carbon number 4～30, R
2Be that H or carbon number are 1～30 alkyl; Ar is aromatic rings such as benzene, biphenyl, diphenyl ether, naphthalene, tetralin, indenes, indane or contains the substituent above-mentioned aromatic ring of H, methyl or ethyl; N is (C
2H
4O) number of group, numerical value are 1～30;
(I) with alkylaromatic hydrocarbon, anhydrous zinc chloride and paraformaldehyde or formalin are put into reactor, alkylaromatic hydrocarbon: anhydrous zinc chloride: the mol ratio of paraformaldehyde or formaldehyde is 1:0.2～1.6:1～4, add glacial acetic acid again as solvent, in 50～150 ℃ of following stirring reactions 0.5～6 hour, promptly feed dry hydrogen chloride or bromize hydrogen gas during this period, or adding energy original position generates the material (as thionyl chloride) of hydrogen chloride or hydrogen bromide, separate behind the vigorous reaction, organic layer is washed with water to neutrality, decompression distillation after the drier drying, product are alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine.
Wherein above-mentioned drier is anhydrous magnesium sulfate, sodium sulphate, calcium chloride, silica gel or molecular sieve.
(II) get multicondensed ethylene glycol in reactor (as there-necked flask), add solid alkali metal, alkali metal hydride, caustic alkali or aqueous alkali, alkalized 1～4 hour, dropwise splash into alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine that step (I) is synthesized again, multicondensed ethylene glycol wherein: alkali metal, alkali metal hydride, caustic alkali or alkali: the mol ratio of alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine is 2～8:1～1.2:1,80～160 ℃ of reactions 6～24 hours down; Cool off after reaction is finished, add and the isopyknic water dilution of reactant, use the organic solvent extraction organic layer, merge organic facies, be washed with water to neutrality, after the drier drying, boil off organic solvent, get crude product; Decompression distillation gets alkyl-fragrant benzyl-polyethenoxy ether alcohol.
Wherein above-mentioned alkali metal is sodium, potassium or calcium; Alkali metal hydride is sodium hydride, hydrofining or calcium hydride; Caustic alkali is lithium hydroxide, NaOH or potassium hydroxide; Described aqueous alkali is the aqueous solution of lithium hydroxide, NaOH, potassium hydroxide, lithium carbonate, sodium carbonate or potash, and its concentration range is that 5wt% is to its saturated solution; Described organic solvent is benzinum, ether, monochloro methane, carrene, chloroform or 1,2-dichloroethanes etc.; Drier is anhydrous magnesium sulfate, sodium sulphate, calcium chloride, silica gel or molecular sieve etc.
Method two:
Wherein, R
1Be the long alkyl chain length of carbon number 4～30, R
2Be that H or carbon number are 1～30 alkyl; Ar is aromatic rings such as benzene, biphenyl, diphenyl ether, naphthalene, tetralin, indenes, indane or contains the substituent above-mentioned aromatic ring of H, methyl or ethyl; N is (C
2H
4O) number of group, numerical value are 1～30;
(I) alkyl virtue benzyl chlorine that makes in the access method one or alkyl virtue benzyl bromine are packed into and are had in the reactor of agitator and reflux condensing tube, add aqueous alkali, the mol ratio of alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine and alkali is 1:1～4, stir fast, be heated to boiling, reacted cooling after reaction is finished 4～24 hours; Cool off the back and divide oil-yielding stratum, wash with water to neutrality, dry back decompression distillation gets alkyl-fragrant benzyl alcohol.
Wherein above-mentioned aqueous alkali is the aqueous solution of lithium hydroxide, NaOH, potassium hydroxide, lithium carbonate, sodium carbonate or potash, and its concentration range is that 5wt% is to its saturated solution; Drier is anhydrous magnesium sulfate, sodium sulphate, silica gel or molecular sieve etc.
(II) add alkyl-fragrant benzyl pure and mild caustic alkali or alkali metal as catalyst in reactor, alkyl-fragrant benzyl alcohol is 50～100:1 with caustic alkali or alkali-metal mol ratio, and temperature is heated to 100～180 ℃; Remove air in the reactor with inert gas, then a certain amount of ethylene oxide gas is joined in the reactor; After reaction finishes, remove unreacted oxirane in the still, obtain alkyl-fragrant benzyl-polyethenoxy ether alcohol after the cooling with inert gas;
Wherein above-mentioned caustic alkali is lithium hydroxide, NaOH or potassium hydroxide; Described alkali metal is sodium, potassium or calcium; Described inert gas is nitrogen, helium or argon gas.
(b) alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant is synthetic:
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether acetate:
Get the alkyl-fragrant benzyl-polyethenoxy ether alcohol that synthesized in the step (a) in reactor, add acetone and make solvent, under constantly stirring, add monoxone, alkyl-fragrant benzyl-polyethenoxy ether alcohol wherein: monoxone: the mol ratio of acetone is 0.3～0.8:1:0.2～4, under 30～50 ℃ of conditions, heated 3～6 hours, after reaction is finished, remove the solvent in the system, reactant mixture is dissolved in the mixed solvent of short chain alcohol and water, with petroleum ether extraction alcohol water repeatedly, collect pure water, constantly stir down, add alkali metal hydroxide with alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent, alkaline earth metal hydroxide, ammonia spirit or their any mixture neutralize, and remove then and anhydrate and salt, obtain alkyl-fragrant benzyl-polyethenoxy ether acetate class surfactant.
Wherein above-mentioned short chain alcohol is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol etc.; The alcohol in the mixed solvent of described short chain alcohol and water and the volume ratio of water are 0.4～5:1; Described alkali metal hydroxide is lithium hydroxide, NaOH or potassium hydroxide, and alkaline earth metal hydroxide is calcium hydroxide, magnesium hydroxide or barium hydroxide.
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether sulfuric acid:
Get alkyl-fragrant benzyl-polyethenoxy ether alcohol synthetic in the step (a) and place reactor, make solvent with absolute ether, under continuous condition of stirring, the diethyl ether solution that adds chlorosulfonic acid, wherein alkyl-fragrant benzyl-polyethenoxy ether alcohol is 0.8～1.0:1 with the mol ratio of chlorosulfonic acid, reacts 8～22 hours down at 0～40 ℃; After reaction is finished, remove ether solvent, mixture joins in the mixed solvent of short chain alcohol and water, constantly stir down, add carry out with alkali metal hydroxide, alkaline earth metal hydroxide, ammonia spirit or their any mixture of alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent in and sulfonated bodies, revolve then to steam to remove and anhydrate, get crude product, dissolve crude product with short chain alcohol, remove by filter insoluble matter, revolve to steam and remove the short chain alcohol of desolvating, get white solid and be the alkyl-fragrant benzyl-polyethenoxy ether sulfuric acid.
Wherein above-mentioned short chain alcohol is: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol etc.; The alcohol in the mixed solvent of described short chain alcohol and water and the volume ratio of water are 0.4～5:1; Described alkali metal hydroxide is lithium hydroxide, NaOH or potassium hydroxide, and alkaline earth metal hydroxide is calcium hydroxide, magnesium hydroxide or barium hydroxide.
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether ethyl sulfonate:
Get the alkyl-fragrant benzyl-polyethenoxy ether alcohol that is synthesized in the step (a) and place reactor, under continuous condition of stirring, add sodium isethionate and catalytic amount caustic catalyst, wherein alkyl-fragrant benzyl-polyethenoxy ether alcohol is 0.8～1.2:1 with the mol ratio of sodium isethionate, is heated to 170～190 ℃ of dehydrations 1～12 hour under the pressure condition of 2000～5000 handkerchiefs; Cooling after reaction is finished, cooling back mixture joins in the mixed solvent of short chain alcohol and water, constantly stir down, add carry out with alkali metal hydroxide, alkaline earth metal hydroxide, ammonia spirit or their any mixture of alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent in and sulfonated bodies, revolve then to steam to remove and anhydrate, crude product, dissolve crude product with short chain alcohol, remove by filter insoluble matter, revolve to steam and remove the short chain alcohol of desolvating, get white solid and be the alkyl-fragrant benzyl-polyethenoxy ether ethyl sulfonate.
Wherein above-mentioned short chain alcohol is: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol etc.; The alcohol in the mixed solvent of described short chain alcohol and water and the volume ratio of water are 0.4～5:1; Described caustic alkali is lithium hydroxide, NaOH or potassium hydroxide; Described alkali metal hydroxide is lithium hydroxide, NaOH or potassium hydroxide, and alkaline earth metal hydroxide is calcium hydroxide, magnesium hydroxide or barium hydroxide.
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether propyl sulfonic acid salt:
Get the alkyl-fragrant benzyl-polyethenoxy ether alcohol that is synthesized in the step (a) and place reactor, make solvent with refining oxolane, under continuous condition of stirring, add 1,3-propane sultone is made catalyst with the caustic alkali of catalytic amount, wherein alkyl-fragrant benzyl-polyethenoxy ether alcohol is with 1, the mol ratio of 3-propane sultone is 1:1～2, is heated to solvent refluxing, reacts 2～6 hours; Cooling after reaction is finished, cooling back mixture joins in the mixed solvent of short chain alcohol and water, constantly stir down, adding neutralizes to sulfonated bodies with alkali metal hydroxide, alkaline earth metal hydroxide, ammonia spirit or their any mixture of alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent, revolve then to steam to remove and anhydrate, get crude product, dissolve crude product with short chain alcohol, remove by filter insoluble matter, revolve and steam to remove the short chain alcohol of desolvating, white or light yellow solid is alkyl-fragrant benzyl-polyethenoxy ether propyl sulfonic acid salt.
Wherein said short chain alcohol is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol etc.; Described caustic alkali as catalyst is NaOH, potassium hydroxide, magnesium hydroxide, calcium hydroxide or their any mixture; Described alkali metal hydroxide is lithium hydroxide, NaOH or potassium hydroxide, and alkaline earth metal hydroxide is calcium hydroxide, magnesium hydroxide or barium hydroxide.
The hydrophilic group of alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of the present invention is oxyethylene group group and acid radical anion, it is good efficient surfactant, it has low irritant, hypotoxicity, soft and good degradation property, good water-solubility and stability in hard water, foaming and saline-alkaline tolerance efficiently, can select the variety classes anionic group at needs.Has good application prospect in various fields such as daily use chemicals health, tertiary oil recovery, industry weaving and emulsions.Can be used as one of formula material of farm chemical emulgent, oil contamination on metal scale remover, ore floatation collecting agent and foaming agent, silk dyeing and finishing levelling agent and dispersant, leather processing tanning agent, lubricating additive, fuel additive, rust-inhibiting additive, fiber cleaning agent and blowing agent.
Studied the surface tension of the alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant aqueous solution of the present invention, and the interfacial tension between the oil, find that this type of surfactant has high activity, find that by measuring surface tension its critical micelle concentration (CMC) is 10
-6～10
-3Mol/L, the surface tension under CMC is 45～23mN/m, can reach ultralow (10 with the interfacial tension of numerous different crude oils
-3MN/m), therefore, alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of the present invention can form low by (10 with crude oil
-2MN/m) or ultralow (10
-3MN/m) interfacial tension, it can use separately also and can use with additive compound in use.In a word, such surfactant has broad application prospects in three displacement of reservoir oil fields, can form low or ultralow interfacial tension with oil, can use in tertiary oil recovery as effective oil displacement agent.
Wherein above-mentioned auxiliary agent is: alkali, anion surfactant, non-ionic surface active agent, amphoteric surfactant, fatty alcohol, hydrolyzed polyacrylamide base polymer, polyacrylic polymer, polysaccharide polymer, hydrophobic associated copolymer, xanthans, chelating agent etc. or their any mixture.
Described alkali is: NaOH, Na
2CO
3, NaHCO
3, KOH, K
2CO
3, KHCO
3Or their any mixture.
Described anion surfactant is: petroleum sulfonate, lignosulfonates, sulphosuccinates, alkyl and alkene sulfonate, alkylaryl sulfonates, alkylaryl sulfonate, alkyl sulfate, alkylphosphonic, petroleum carboxylate, lignin carboxylate, amido-carboxylic acid salt, fat carboxylate or their any mixture.
Described non-ionic surface active agent is: AEO, polyoxyethylene carboxylate, APES, polyoxyethylene alkyl amine, polyxyethylated acyl hydramine, how pure surfactant, polyethet surfactant, N-alkyl pyrrolidone, sulfoxide surface-active, alkyl poly glucoside, acetylene uncle glycol or their any mixture.
Described amphoteric surfactant is: imidazolidine derivatives, betanin derivative, alanine derivatives, Taurine derivative or their any mixture.
The concentration of described alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant in above-mentioned system is 100mg/L～10000mg/L.
Description of drawings
Fig. 1. the embodiment of the invention 1 intermediate octyl group benzyl chlorine
1HNMR (solution:CDCl
3) spectrogram.
Fig. 2. the embodiment of the invention 1 intermediate octyl group benzyl three oxygen vinethenes
1H NMR (solution:CDCl
3) spectrogram.
Fig. 3. IR spectrum (KBr compressing tablet) spectrogram of the embodiment of the invention 1 octyl group benzyl three oxygen vinethene sodium acetates.
Fig. 4. the embodiment of the invention 2 lauryl benzyls four oxygen vinethene sulfuric ester ammoniums
1H NMR (solution:D
2O) spectrogram.
Fig. 5. the embodiment of the invention 3 octyl group benzyls three oxygen vinethene propane sulfonic acid sodium
1H NMR (solution:D
2O) spectrogram.
Fig. 6. the embodiment of the invention 3 octyl group benzyls three oxygen vinethene propane sulfonic acid sodium ESI-MS spectrograms.
Fig. 7. the embodiment of the invention 4 dibutyl naphthalene benzyls five oxygen vinethene ethylsulfonic acid sodium
1HNMR (solution:D
2O) spectrogram.
Fig. 8. IR spectrum (KBr compressing tablet) spectrogram of the embodiment of the invention 5 octyl group benzyls, three oxygen vinethene sodium acetates and octyl group benzyl three oxygen vinethene calcium acetates.
Fig. 9. the sample in the embodiment of the invention 6 is the aqueous solution of 600mg/L at sample concentration, is 8wt%, Na at NaCl content
2CO
3When content is 0.1wt%, with the dynamic interface tension curve figure (65 ℃ of test temperatures) of triumph CBE11-3# crude oil.
Figure 10. the sample in the embodiment of the invention 7 is the aqueous solution of 600mg/L in sample quality concentration, is 8wt%, Na at calcium ion concentration 1000mg/L, NaCl content
2CO
3When content is 0.1wt%, with the dynamic interface tension curve figure (65 ℃ of test temperatures) of triumph CBE11-3# crude oil.
Figure 11. the surface tension figure in pure water of sample octyl group benzyl three oxygen vinethene sodium acetates in the embodiment of the invention 1.
The specific embodiment
Embodiment 1: the preparation of octyl group benzyl three oxygen vinethene sodium acetates
(a) preparation of octyl group benzyl chlorine
With 0.5mol octyl group benzene in reactor, add the Powdered anhydrous zinc chloride of 1mol paraformaldehyde and 0.35mol again, add the 110mL glacial acetic acid and make solvent, vigorous stirring also promptly feeds dry hydrogen chloride gas, in 70～80 ℃ down reaction till the absorbing hydrogen chloride no longer, about 2 hours, be cooled to room temperature, tell upper organic phase, lower floor's acetate is used petroleum ether extraction 2～3 times mutually, use sodium carbonate and the water washing of 10wt% extremely neutral after the merging organic facies successively, use anhydrous sodium sulfate drying, add a little sodium acid carbonate decompression distillation, collect 165～167 ℃/3.5mmHg cut, productive rate is 75%, and normal temperature is colourless liquid down.Its
1H NMR spectrogram is seen Fig. 1.
(b) preparation of octyl group benzyl three oxygen ethene ether alcohols
Method one:
Get the 2.2mol triethylene-glycol in there-necked flask, add 0.4mol NaOH at leisure, under nitrogen protection, stir and be warming up to 80 ℃, after treating that solid sodium hydroxide all dissolves, dropwise splash into the 0.37mol octyl group benzyl chlorine that makes in the step (a), 90～100 ℃ of reactions of maintenance system temperature 24 hours; Cooling adds isopyknic water dilution, uses extracted with diethyl ether again three times, merges diethyl ether solution, uses the careful washing of 1.8wt% hydrochloric acid solution and water to neutral successively, behind the anhydrous magnesium sulfate drying, boils off ether and gets crude product; Fraction is collected in decompression distillation, get final product octyl group benzyl three oxygen ethene ether alcohols, productive rate is 64%.Its
1The HNMR spectrogram is seen Fig. 2.
Method two:
Get the 0.37mol octyl group benzyl chlorine that makes in the step (a) and pack into and have in the reactor of magnetic stirring apparatus and reflux condensing tube, add the 0.75mol aqueous sodium carbonate, stir fast, be heated to boiling, reacted 6 hours.Oil-yielding stratum is divided in the cooling back, washes with water to neutrality, and decompression distillation behind the anhydrous magnesium sulfate drying gets the octyl group benzyl alcohol, and productive rate is 82%.
In the 500mL reactor, add 0.30mol octyl group benzyl alcohol and 0.5g potassium hydroxide, temperature is heated to 160～180 ℃; Remove air in the reactor with nitrogen gas, then the 0.9mol ethylene oxide gas is joined in the reactor; After reaction finishes, remove unreacted oxirane in the still, obtain octyl group benzyl three oxygen ethene ether alcohols after the cooling with nitrogen.Its
1The HNMR spectrogram is seen Fig. 2.
(c) preparation of octyl group benzyl three oxygen vinethene sodium acetates
In the three-neck flask that reflux condensing tube, thermometer, agitator are housed, add 0.30mol octyl group benzyl three oxygen ethene ether alcohols.Start stirring, add the NaOH of 1.2mol grind into fine powder, treat that NaOH dissolves after, add the acetone of 1.5mol, slowly drip the 0.60mol chloroacetic acid that is dissolved in the small amount of acetone again, adjust bath temperature to 50 ℃, reacted 4 hours.After reaction is finished, remove the crude product of the acetone in the system, add V (C again
2H
5OH): V (H
2O)=mixed solvent of 1:1 makes it dissolving, transfers pH=7～7.5 with dilute hydrochloric acid solution, with petroleum ether extraction alcohol water three times, steams pure water and gets blocks of solid, pulverizes postlyophilization Ex-all small amount of moisture; The anhydrous alcohol solution of reusable heat, heat filtering is removed inorganic salts, revolves to obtain the thickness paste after ethanol is removed in steaming, is product, and yield is 85%.Its IR spectrogram is seen Fig. 3.The surface tension of octyl group benzyl three oxygen vinethene sodium acetates in pure water seen Figure 11.
Embodiment 2: the preparation of lauryl benzyl four oxygen vinethene sulfuric ester ammoniums
(a) preparation of lauryl benzyl chlorine
With 0.5mol lauryl benzene in reactor, add the Powdered anhydrous zinc chloride of 0.9mol paraformaldehyde and 0.32mol again, add the 120mL glacial acetic acid and make solvent, vigorous stirring also promptly feeds dry hydrogen chloride gas, in 85～90 ℃ down reaction till the absorbing hydrogen chloride no longer, about 1.5 hours, be cooled to room temperature, tell upper organic phase, lower floor's acetate is used petroleum ether extraction 2～3 times mutually, use sodium carbonate and the water washing of 10wt% extremely neutral after the merging organic facies successively, use anhydrous sodium sulfate drying, add a little sodium acid carbonate decompression distillation, collect 190～193 ℃/3.5mmHg cut, productive rate is 72%, and normal temperature is white solid down.
(b) preparation of lauryl benzyl four oxygen ethene ether alcohols
Get the 0.35mol lauryl benzyl chlorine that makes in the step (a) and pack into and have in the reactor of magnetic stirring apparatus and reflux condensing tube, add the caustic soda aqueous solution of the 40wt% that contains 0.70mol NaOH, stir fast, be heated to boiling, reacted 4 hours.Oil-yielding stratum is divided in the cooling back, washes with water to neutrality, and decompression distillation behind the anhydrous magnesium sulfate drying gets the octyl group benzyl alcohol, and productive rate is 93%.
In the 500mL reactor, add 0.33mol dodecyl benzyl alcohol and 1g NaOH, temperature is heated to 170～180 ℃; Remove air in the reactor with nitrogen gas, then the 1.32mol ethylene oxide gas is joined in the reactor; After reaction finishes, remove unreacted oxirane in the still, obtain lauryl benzyl four oxygen ethene ether alcohols after the cooling with nitrogen.
(c) preparation of lauryl benzyl four oxygen vinethene sulfuric ester ammoniums
The anhydrous ether solution 330mL that gets 1mol/L octyl group benzyl three oxygen vinethenes under continuous stirring condition, dropwise adds 1.5mol/L chlorosulfonic acid anhydrous ether solution 265mL in three-neck flask, ice bath (0 ℃) reacted 18 hours down.Rise to room temperature then, continue reaction 4 hours.After reaction was finished, rotary evaporation was removed absolute ether, and reactant mixture joins V[(CH
3)
2CHOH]: V (H
2O)=mixed solvent of 1:1 in, constantly stir down, add the ammoniacal liquor saturated solution and be neutralized to pH=8.Extract unreacted lauryl benzyl four oxygen ethene ether alcohols three times completely with benzinum, pure water rotary evaporation is to doing, and vacuumizes dry 48h in vacuum drying oven, and temperature is not more than 50 ℃.The back anhydrous alcohol solution filters, and removes sodium sulphate.Filtrate rotates to dried, and product is thick product.Thick product is recrystallized three times with ethanol, obtains white waxy solid, is lauryl benzyl four oxygen vinethene sulfuric ester ammoniums, and productive rate is 85%.Its
1H NMR spectrogram is seen Fig. 4.
Embodiment 3: the preparation of octyl group benzyl three oxygen vinethene propyl sulfonic acid sodium
(a) preparation of octyl group benzyl chlorine
With 0.5mol octyl group benzene in reactor, add the Powdered anhydrous zinc chloride of 1mol paraformaldehyde and 0.35mol again, add the 110mL glacial acetic acid and make solvent, vigorous stirring also promptly feeds dry hydrogen chloride gas, in 70～80 ℃ down reaction till the absorbing hydrogen chloride no longer, about 2 hours, be cooled to room temperature, tell upper organic phase, lower floor's acetate is used petroleum ether extraction 2～3 times mutually, use sodium carbonate and the water washing of 10wt% extremely neutral after the merging organic facies successively, use anhydrous sodium sulfate drying, add a little sodium acid carbonate decompression distillation, collect 165～167 ℃/3.5mmHg cut, productive rate is 75%, and normal temperature is colourless liquid down.
(b) preparation of octyl group benzyl three oxygen ethene ether alcohols
Get the 2.2mol triethylene-glycol in there-necked flask, add 0.4mol NaOH at leisure, under nitrogen protection, stir and be warming up to 80 ℃, after treating that solid sodium hydroxide all dissolves, dropwise splash into the 0.37mol octyl group benzyl chlorine that makes in the step (a), 90～100 ℃ of reactions of maintenance system temperature 24 hours; Cooling adds isopyknic water dilution, uses extracted with diethyl ether again three times, merges diethyl ether solution, uses the careful washing of 1.8wt% hydrochloric acid solution and water to neutral successively, behind the anhydrous magnesium sulfate drying, boils off ether and gets crude product; Fraction is collected in decompression distillation, get final product octyl group benzyl three oxygen ethene ether alcohols, productive rate is 64%.
(c) octyl group benzyl three oxygen vinethene propyl sulfonic acid sodium is synthetic
Getting the 0.24mol octyl group benzyl three oxygen ethene ether alcohols that synthesized in the step (b) is dissolved in the oxolane of 30mL, under constantly stirring, add powdery 0.50mol NaOH, alkalized 1 hour, being heated to oxolane refluxes, dropwise splash into the 0.25mol 1, the 3-propane sultone that are dissolved in the 20mL oxolane, add 4～6 hours afterreactions of hot reflux then and finish.After boiling off solvent, with V (C
2H
5OH): V (H
2O)=mixed solvent of 1:1 dissolving crude product, with benzinum (bp:60～90 ℃) extraction three times, tell pure water, boil off behind the solvent the thick product of faint yellow waxy solid, solid product obtains cellular white solid 3 times with ethyl alcohol recrystallization, is octyl group benzyl three oxygen vinethene propyl sulfonic acid sodium; Its
1The HNMR spectrogram is seen Fig. 5, and its ESI-MS spectrogram is seen Fig. 6.
Embodiment 4: the preparation of dibutyl naphthalene benzyl five oxygen vinethene ethylsulfonic acid sodium
(a) preparation of dibutyl naphthalene benzyl chlorine
With the 0.5mol dibutyl naphthalene in reactor, add 1.1mol paraformaldehyde and Powdered 0.30mol anhydrous zinc chloride again, add the 100mL glacial acetic acid and make solvent, vigorous stirring also promptly feeds dry hydrogen chloride gas, in 70～75 ℃ down reaction till the absorbing hydrogen chloride no longer, about 1.5 hours, be cooled to room temperature, tell organic facies, acetate is used petroleum ether extraction 3 times mutually, use sodium carbonate and the water washing of 10wt% extremely neutral after the merging organic facies successively, use anhydrous sodium sulfate drying, add a little sodium acid carbonate decompression distillation, high boiling fraction, productive rate is 62%, and normal temperature is white solid down.
(b) preparation of dibutyl naphthalene benzyl five oxygen ethene ether alcohols
Get the 0.31mol dibutyl naphthalene benzyl chlorine that makes in the step (a) and pack into and have in the reactor of magnetic stirring apparatus and reflux condensing tube, add the caustic potash aqueous solution of the 30wt% that contains 0.60mol NaOH, stir fast, be heated to boiling, reacted 2 hours.Oil-yielding stratum is divided in the cooling back, washes with water to neutrality, and decompression distillation behind the anhydrous magnesium sulfate drying gets the dibutyl naphthalene benzyl alcohol, and productive rate is 91%.
In the 500mL reactor, add 0.28mol dibutyl naphthalene benzyl alcohol and 0.8g NaOH, temperature is heated to 165～175 ℃; Remove air in the reactor with nitrogen gas, then the 1.41mol ethylene oxide gas is joined in the reactor; After reaction finishes, remove unreacted oxirane in the still, obtain dibutyl naphthalene benzyl five oxygen ethene ether alcohols after the cooling with nitrogen.
(c) preparation of dibutyl naphthalene benzyl five oxygen vinethene ethylsulfonic acid sodium
Getting step (b) synthesizes in the 0.28mol dibutyl naphthalene benzyl five oxygen ethene ether alcohols adding reactor, add 0.28mol sodium isethionate and 0.0375mol powdered potassium hydroxide again, 185 ℃ of dehydrations of heating are 2 hours under the condition of 2666～3999 handkerchief pressure, after the cooling, remove unreacted oil phase with the benzinum flushing, dissolve crude product, remove by filter insoluble matter with ethanol, revolve to steam and remove ether, get faint yellow solid and be dibutyl naphthalene benzyl five oxygen vinethene ethylsulfonic acid sodium.Its IR spectrogram is seen Fig. 7.
Embodiment 5: the preparation of octyl group benzyl three oxygen vinethene sodium acetates and octyl group benzyl three oxygen vinethene calcium acetates
(a). the preparation of octyl group benzyl chlorine
With 0.5mol octyl group benzene in reactor, add 1mol 40% formalin and 110mL concentrated hydrochloric acid again, be heated to 70～80 ℃, feed dry hydrogen chloride gas simultaneously, kept 5 hours, tell upper organic phase after being cooled to room temperature, lower floor's concentrated acid is used petroleum ether extraction 2～3 times mutually, use sodium carbonate and the water washing of 10wt% extremely neutral after the merging organic facies successively, use anhydrous sodium sulfate drying, add a little sodium acid carbonate decompression distillation, collect 165～167 ℃/3.5mmHg cut, productive rate is 75%, and normal temperature is colourless liquid down.Its
1H NMR spectrogram is seen Fig. 1.
(b). the preparation of octyl group benzyl three oxygen ethene ether alcohols
Get the 2.2mol triethylene-glycol in there-necked flask, add 0.4mol NaOH at leisure, under nitrogen protection, stir and be warming up to 80 ℃, after treating that solid sodium hydroxide all dissolves, dropwise splash into the 0.37mol octyl group benzyl chlorine that makes in the step (a), 90～100 ℃ of reactions of maintenance system temperature 24 hours; Cooling adds isopyknic water dilution, uses extracted with diethyl ether again three times, merges diethyl ether solution, uses the careful washing of 1.8wt% hydrochloric acid solution and water to neutral successively, behind the anhydrous magnesium sulfate drying, boils off ether and gets crude product; Fraction is collected in decompression distillation, get final product octyl group benzyl three oxygen ethene ether alcohols, productive rate is 64%.Its
1H NMR spectrogram is seen Fig. 2.
(c). the preparation of octyl group benzyl three oxygen vinethene sodium acetates and octyl group benzyl three oxygen vinethene calcium acetates
In the three-neck flask that reflux condensing tube, thermometer, agitator are housed, add 0.30mol octyl group benzyl three oxygen ethene ether alcohols.Start stirring, add the NaOH (0.6mol) and the calcium hydroxide (0.6mol) of grind into fine powder, treat that alkali dissolves after, the acetone that adds 1.5mol, slowly drip the 0.60mol chloroacetic acid be dissolved in the small amount of acetone again, adjust bath temperature to 50 ℃, reacted 4 hours.After reaction is finished, remove the crude product of the acetone in the system, add V (C again
2H
5OH): V (H
2O)=mixed solvent of 1:1 makes it dissolving, transfers pH=7～7.5 with dilute hydrochloric acid solution, with petroleum ether extraction alcohol water three times, steams pure water and gets blocks of solid, pulverizes postlyophilization Ex-all small amount of moisture; The anhydrous alcohol solution of reusable heat, heat filtering is removed inorganic salts, revolves to obtain the thickness paste after ethanol is removed in steaming, is product, and yield is 81%.Its IR spectrogram is seen Fig. 8.
A kind of aqueous surfactant solution system, this system comprises following several composition: the lauryl benzyl four oxygen vinethene propyl sulfonic acid acid sodium among the 600mg/L embodiment 3, the sodium chloride of 8wt%, the sodium carbonate of 0.1wt%, this system can form ultralow interfacial tension with Shengli Oil Field CBE11-3# crude oil in the time of 65 ℃, and its dynamic surface tension curve is seen Fig. 9.
A kind of aqueous surfactant solution system, this system comprises the lauryl benzyl four oxygen vinethene sulfuric ester ammoniums of following several composition: 600mg/L embodiment 2, the sodium chloride of 8wt%, the sodium carbonate of 0.1wt%, when calcium ion concentration 1000mg/L, this system can form ultralow interfacial tension with Shengli Oil Field CBE11-3# crude oil, and its dynamic surface tension curve is seen Figure 10 (65 ℃ of experimental temperatures).
Claims (9)
1. an alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant is characterized in that, the structural formula of this alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant is:
Wherein, R
1Be the long alkyl chain length of carbon number 4～30, R
2Be that H or carbon number are 1～30 alkyl; Ar is benzene, biphenyl, diphenyl ether, naphthalene, tetralin, indenes, indane aromatic ring or contains methyl or the substituent above-mentioned aromatic ring of ethyl; N is (C
2H
4O) number of group, numerical value are 1～30; R
3For methylene, ethylidene, propylidene or do not exist; Y is sulfonate radical, sulfate radical or carboxylate radical; M is the Li in the alkali metal ion
+, Na
+Or K
+, the Mg in the alkaline-earth metal ions
2+, Ca
2+Or Ba
2+, ammonium ion or the above ion mixture.
2. alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant according to claim 1 is characterized in that: described alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant is alkyl-fragrant benzyl-polyethenoxy ether acetate, alkyl-fragrant benzyl-polyethenoxy ether sulfuric acid, alkyl-fragrant benzyl-polyethenoxy ether ethyl sulfonate or alkyl-fragrant benzyl-polyethenoxy ether propyl sulfonic acid salt.
3. alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant according to claim 1 and 2 is characterized in that: the critical micelle concentration of described alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant is 10
-6～10
-3Mol/L, the surface tension under critical micell is 45～23mN/m.
4. alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant according to claim 3 is characterized in that: described alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant can form 10 with oil
-2The interfacial tension of mN/m, or form 10
-3The interfacial tension of mN/m.
5. the preparation method according to each described alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of claim 1～4 is characterized in that, this method may further comprise the steps:
(a) alkyl-fragrant benzyl-polyethenoxy ether alcohol is synthetic:
Method one:
Wherein, R
1Be the long alkyl chain length of carbon number 4～30, R
2Be that H or carbon number are 1～30 alkyl; Ar is benzene, biphenyl, diphenyl ether, naphthalene, tetralin, indenes, indane aromatic ring or contains methyl or the substituent above-mentioned aromatic ring of ethyl; N is (C
2H
4O) number of group, numerical value are 1～30;
(I) alkylaromatic hydrocarbon, anhydrous zinc chloride and paraformaldehyde or formalin are put into reactor, alkylaromatic hydrocarbon: anhydrous zinc chloride: the mol ratio of paraformaldehyde or formaldehyde is 1:0.2～1.6:1～4, add glacial acetic acid again as solvent, in 50～150 ℃ of following stirring reactions, promptly feed dry hydrogen chloride or bromize hydrogen gas during this period, or adding energy original position generates the material of hydrogen chloride or hydrogen bromide, separate the reaction back, organic layer is washed with water to neutrality, decompression distillation after the drier drying, product are alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine;
(II) get multicondensed ethylene glycol in reactor, add a kind of in solid alkali metal, alkali metal hydride, caustic alkali or the aqueous alkali, alkalized 1～4 hour, splash into alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine that step (I) is synthesized again, multicondensed ethylene glycol wherein: alkali metal, alkali metal hydride, caustic alkali or alkali: the mol ratio of alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine is 2～8:1～1.2:1,80～160 ℃ of reactions down; Cool off after reaction is finished, add and the isopyknic water dilution of reactant, use the organic solvent extraction organic layer, merge organic facies, be washed with water to neutrality, after the drier drying, boil off organic solvent, get crude product; Decompression distillation gets alkyl-fragrant benzyl-polyethenoxy ether alcohol; Or
Method two:
Wherein, R
1Be the long alkyl chain length of carbon number 4～30, R
2Be that H or carbon number are 1～30 alkyl; Ar is benzene, biphenyl, diphenyl ether, naphthalene, tetralin, indenes, indane aromatic ring or contains methyl or the substituent above-mentioned aromatic ring of ethyl; N is (C
2H
4O) number of group, numerical value are 1～30;
(I) alkyl virtue benzyl chlorine that makes in the access method one or alkyl virtue benzyl bromine are packed into and are had in the reactor of agitator and reflux condensing tube, add aqueous alkali, the mol ratio of alkyl virtue benzyl chlorine or alkyl virtue benzyl bromine and alkali is 1:1～4, stirs fast, be heated to boiling, cooling after reaction is finished; Cool off the back and divide oil-yielding stratum, wash with water to neutrality, dry back decompression distillation gets alkyl-fragrant benzyl alcohol;
(II) add alkyl-fragrant benzyl pure and mild caustic alkali or alkali metal as catalyst in reactor, alkyl-fragrant benzyl alcohol is 50～100:1 with caustic alkali or alkali-metal mol ratio, and temperature is heated to 100～180 ℃; Remove air in the reactor with inert gas, then ethylene oxide gas is joined in the reactor; After reaction finishes, remove unreacted oxirane in the still, obtain alkyl-fragrant benzyl-polyethenoxy ether alcohol after the cooling with inert gas;
Wherein said alkali metal is sodium, potassium or calcium; Alkali metal hydride is sodium hydride, hydrofining or calcium hydride; Caustic alkali is lithium hydroxide, NaOH or potassium hydroxide; Aqueous alkali is the aqueous solution of lithium hydroxide, NaOH, potassium hydroxide, lithium carbonate, sodium carbonate or potash;
(b) alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant is synthetic:
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether acetate:
Get the alkyl-fragrant benzyl-polyethenoxy ether alcohol that synthesized in the step (a) in reactor, add acetone and make solvent, under constantly stirring, add monoxone, alkyl-fragrant benzyl-polyethenoxy ether alcohol wherein: monoxone: the mol ratio of acetone is 0.3～0.8:1:0.2～4, under 30～50 ℃ of conditions, add thermal response, after reaction is finished, remove the solvent in the system, reactant mixture is dissolved in the mixed solvent of short chain alcohol and water, with petroleum ether extraction alcohol water repeatedly, collect pure water, constantly stir down, add alkali metal hydroxide with alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent, alkaline earth metal hydroxide, ammonia spirit or their any mixture neutralize, and remove then and anhydrate and salt, obtain alkyl-fragrant benzyl-polyethenoxy ether acetate class surfactant;
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether sulfuric acid:
Get alkyl-fragrant benzyl-polyethenoxy ether alcohol synthetic in the step (a) and place reactor, make solvent with absolute ether, under continuous condition of stirring, the diethyl ether solution that adds chlorosulfonic acid, wherein alkyl-fragrant benzyl-polyethenoxy ether alcohol is 0.8～1.0:1 with the mol ratio of chlorosulfonic acid, 0～40 ℃ of reaction down; After reaction is finished, remove ether solvent, mixture joins in the mixed solvent of short chain alcohol and water, constantly stir down, add carry out with alkali metal hydroxide, alkaline earth metal hydroxide, ammonia spirit or their any mixture of alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent in and sulfonated bodies, revolve then to steam to remove and anhydrate, get crude product, dissolve crude product with short chain alcohol, remove by filter insoluble matter, revolve to steam and remove the short chain alcohol of desolvating, get white solid and be the alkyl-fragrant benzyl-polyethenoxy ether sulfuric acid;
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether ethyl sulfonate:
Get the alkyl-fragrant benzyl-polyethenoxy ether alcohol that is synthesized in the step (a) and place reactor, under constantly stirring, the caustic catalyst that adds sodium isethionate and catalytic amount, wherein alkyl-fragrant benzyl-polyethenoxy ether alcohol is 0.8～1.2:1 with the mol ratio of sodium isethionate, is heated to 170～190 ℃ of dehydrations under the pressure condition of 2000～5000 handkerchiefs; Cooling after reaction is finished, after the cooling, mixture joins in the mixed solvent of short chain alcohol and water, constantly stir down, add carry out with alkali metal hydroxide, alkaline earth metal hydroxide, ammonia spirit or their any mixture of alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent in and sulfonated bodies, revolve then to steam to remove and anhydrate, get crude product, dissolve crude product with short chain alcohol, remove by filter insoluble matter, revolve to steam and remove the short chain alcohol of desolvating, get white solid and be the alkyl-fragrant benzyl-polyethenoxy ether ethyl sulfonate;
Synthesizing of alkyl-fragrant benzyl-polyethenoxy ether propyl sulfonic acid salt:
Get the alkyl-fragrant benzyl-polyethenoxy ether alcohol that is synthesized in the step (a) and place reactor, make solvent with oxolane, under continuous condition of stirring, add 1,3-propane sultone is made catalyst with the caustic alkali of catalytic amount, and wherein alkyl-fragrant benzyl-polyethenoxy ether alcohol is with 1, the mol ratio of 3-propane sultone is 1:1～2, is heated to solvent refluxing; Cooling after reaction is finished, cooling back mixture joins in the mixed solvent of short chain alcohol and water, constantly stir down, adding neutralizes to sulfonated bodies with alkali metal hydroxide, alkaline earth metal hydroxide, ammonia spirit or their any mixture of alkyl-fragrant benzyl-polyethenoxy ether alcohol equivalent, revolve then to steam to remove and anhydrate, get crude product, dissolve crude product with short chain alcohol, remove by filter insoluble matter, revolve and steam to remove the short chain alcohol of desolvating, white or light yellow solid is alkyl-fragrant benzyl-polyethenoxy ether propyl sulfonic acid salt;
Wherein said short chain alcohol is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol; Described caustic alkali as catalyst is NaOH, potassium hydroxide, magnesium hydroxide, calcium hydroxide or their any mixture; Described alkali metal hydroxide is lithium hydroxide, NaOH or potassium hydroxide, and alkaline earth metal hydroxide is calcium hydroxide, magnesium hydroxide or barium hydroxide.
6. method according to claim 5 is characterized in that: described drier is: anhydrous magnesium sulfate, sodium sulphate, calcium chloride, silica gel or molecular sieve; Described organic solvent is: benzinum, ether, monochloro methane, carrene, chloroform or 1,2-dichloroethanes.
7. method according to claim 5 is characterized in that: described aqueous alkali concentration range is that 5wt% is to its saturated solution.
8. method according to claim 5 is characterized in that: in the mixed solvent of described short chain alcohol and water, alcohol is 0.4～5:1 with the volume ratio of water.
9. purposes according to each described alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant of claim 1～4, it is characterized in that: this alkyl-fragrant benzyl-polyethenoxy ether anionic surfactant can be used in tertiary oil recovery as effective oil displacement agent.
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