CN101670250B - Alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant and preparation method and application thereof - Google Patents
Alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of efficient surfactant, in particular relates to an alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant and preparation method and application thereof. The surfactant contains nonionic hydrophilic group polyoxyethylene and negative ion hydrophilic group sulfonate, the special molecular structure determines that the surfactant has good water-solubility, lower critical micelle concentration, excellent capability of reducing surface tension/interfacial tension, efficient foaming and foam stabilizing capability and outstanding temperature endurance and salt endurance, has good application prospect in a plurality of fields of pesticides, mineral flotation, tertiary oil recovery, and the like, and can be used as an effective oil displacement agent in tertiary oil recovery. The surfactant has the structure.
Description
Technical field
The invention belongs to the efficient surfactant field, particularly alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant.
Background technology
Sulfonate is that emulsified viscous oil, three is adopted maximum anionic surfactant of using in the displacement of reservoir oil prescription.Wherein alkyl benzene sulfonate surfactant is one of tertiary oil recovery surfactant industrialization major product, also is one of maximum surfactant of tertiary oil recovery consumption.The raw material of this type surfactant is all taken from crude oil, though the source is wide, quantity is big, the less stable of product has brought difficulty for production and research work.What disclose in the patent like patent No. CN1128006C is that 320～380 vacuum distillate is the synthetic petroleum sulfonate of raw material with molecular weight; Because their synthesis material is formed complicated; The heat-resistant salt-resistant performance is general; And its performance is along with raw materials used oil composition and boiling range and change, and the control of product quality of these surfactants is a great problems, is unfavorable for large-scale production and application.
To high temperature and high salt oil deposit; Conventional anionic and nonionic surface active agent are difficult to be suitable for; And anion-nonionic type surfactant; Owing to has anion and two kinds of hydrophilic radicals of oxyethylene group (EO) simultaneously in its molecule, thereby have fine solubility and compatibility, and the temperature-resistant anti-salt ability is strong.As long as through the optimal design of hydrophobic grouping and hydrophilic radical, can guarantee that promptly its good reduction table/interfacial tension, emulsification and foaming surely steeps ability.Since its particular performances, such surfactant research and development more and more causing attention of people.Researcher has been done a large amount of research to polyoxyethylene alcohol ether carboxylate, sulfate; Obtained the more excellent anionic and nonionic surfactant of performance; But less to polyoxyethylene benzene sulfonate research, especially sulfonic group is positioned at phenyl ring and anionic and nonionic surfactant that polyoxyethylene chain (EO) is positioned between phenyl ring and alkyl chain does not appear in the newspapers as yet.
Summary of the invention
One of the object of the invention is to provide surface property excellent alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant, and sulfonic group is positioned at phenyl ring and oxyethylene group (EO) is positioned between phenyl ring and alkyl chain.
Two of the object of the invention is to provide the preparation method of the excellent alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant of surface property.
Three of the object of the invention is to provide surface property excellent alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant system, make it separately or with promoter effect under, can form low or ultralow interfacial tension with simulated oil alkane or crude oil; And its solution has excellent foaminess and foam stability, the heat-resistant salt-resistant excellent performance, can be in the oil field surfactant flooding; Binary is driven; Ternary composite driving, microemulsion drives, and is used widely in the tertiary oil recovery technologies such as foam composite flooding.
The structural formula of alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant of the present invention is:
Wherein, R
1, R
2Alkyl for carbon number 6～30; EO represents oxyethylene group (C
2H
4O); M is that oxyethylene group is rolled into a ball fixed number value or mean value really, and numerical value is 4,6,15; M is the Li in the alkali metal ion
+, Na
+Or K
+, or the Ca in the alkaline-earth metal ions
2+, Mg
2+Or Ba
2+, or the ammonium ion, or the mixture of the above ion.
The preparation method of alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant of the present invention may further comprise the steps:
(I) preparation of alkyl-blocked alkylphenol polyoxyethylene ether
Method one:
The acid binding agent catalyst that with carbon number is 6～30 the pure and mild catalytic amount of alkyl polyoxyethylene places reactor, and control temperature≤50 ℃ slowly drip thionyl chloride under the stirring condition; Wherein carbon number is 6～30 alkyl polyoxyethylene alcohol: the mol ratio of thionyl chloride is 1: 1～1.5; Drip continued reaction 0.5～1 hour, be warming up to 100～140 ℃ of reactions 2～5 hours then, cooling back impouring contains in the inorganic base aqueous solution of ice; Use organic solvent extraction; Washing organic facies about three times boils off organic solvent after the organic facies of the dry extraction of drier gained, and it is 6～30 alkyl polyoxyethylene ethyl chloride that decompression distillation gets carbon number; With carbon number is that 6～30 alkyl polyoxyethylene ethyl chloride places reactor; With organic solvent diluting to 10～50wt%, add carbon number then and be 6～30 alkyl phenol, inorganic base and entrainer; Carbon number is 6～30 alkyl polyoxyethylene ethyl chloride: carbon number is 6～30 alkyl phenol: the mol ratio of inorganic base is 1: 1～1.5: 1～1.5; The entrainer consumption is heated to backflow so that steady backflow of reaction system is as the criterion, and will react the moisture that generates through water knockout drum and go out; To react the gains cooling after reaction finishes, filter; In the reaction gains, add suitable quantity of water then, use organic solvent extraction, washing organic facies about three times; Boil off organic solvent after the organic facies of the dry extraction of drier gained, purifying through silicagel column obtains alkyl-blocked alkylphenol polyoxyethylene ether.
Method two:
With carbon number is that 6～30 the APES and the acid binding agent catalyst of catalytic amount place reactor; Control temperature≤50 ℃ slowly drip thionyl chloride under stirring condition, wherein carbon number is 6～30 APES: the mol ratio of thionyl chloride is 1: 1～1.5; Drip continued reaction 0.5～1 hour; Be warming up to 100～140 ℃ of reactions 2～5 hours then, cooling back impouring contains in the inorganic base aqueous solution of ice, uses organic solvent extraction; Washing organic facies about three times boils off organic solvent after the organic facies of the dry extraction of drier gained and gets intermediate chloro thing; In another reactor, add carbon number then and be 6～30 alkylol and alkali metal or inorganic base; Reacted 1～3 hour down in 80～120 ℃; Splash into intermediate chloro thing; Intermediate chloro thing: carbon number is 6～30 alkylol: the mol ratio of alkali metal or inorganic base is 1: 1～1.5: 1～1.5, is heated to back flow reaction about 2～5 hours, uses organic solvent extraction after reaction finishes; Washing organic facies about three times boils off organic solvent after the organic facies of the dry extraction of drier gained and gets alkyl-blocked alkylphenol polyoxyethylene ether.
Method three:
With carbon number is that 6～30 APES places reactor; Adding alkali metal or inorganic base reacted 1～3 hour down in 80～120 ℃; Splash into halogenated alkane then gradually; Carbon number is 6～30 APES: alkali metal or inorganic base: the mol ratio of halogenated alkane is 1: 1～1.5: 1～1.5, is heated to back flow reaction after dropwising about 2～5 hours, uses organic solvent extraction after reaction finishes; Washing organic facies about three times boils off organic solvent after the organic facies of the dry extraction of drier gained and gets alkyl-blocked alkylphenol polyoxyethylene ether.
Wherein:
Above-mentioned acid binding agent is dimethyl formamide or pyridine.
Above-mentioned alkali metal is sodium, potassium or their mixture.
Above-mentioned inorganic base is sodium hydride, hydrofining, NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash, saleratus or their mixture.
Above-mentioned inorganic base aqueous solution is lithium hydroxide aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, magnesium hydroxide aqueous solution, calcium hydroxide aqueous solution, baryta water, ammoniacal liquor or any mixture between them, and its concentration range is that 10wt% is to its saturated solution.
Above-mentioned organic solvent is benzinum, ether, monochloro methane, carrene, chloroform or 1,2-dichloroethanes, dimethyl formamide.
Above-mentioned entrainer is benzene,toluene,xylene or cyclohexane.
Above-mentioned halogenated alkane is the chloralkane of carbon number 6～30, the bromo alkane of carbon number 6～30 or the alkane iodide of carbon number 6～30.
Above-mentioned drier is anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, silica gel or molecular sieve.(II) preparation of alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant
The alkyl-blocked alkylphenol polyoxyethylene ether that step (I) is prepared places reactor with organic solvent diluting; Control temperature≤20 ℃; At the following sulfonating agent that adds gradually that constantly stirs; Alkyl-blocked alkylphenol polyoxyethylene ether wherein: the mol ratio of sulfonating agent is 1: 1～1.5, dropwises the back room temperature reaction 1～5 hour; Add inorganic base aqueous solution then and carry out neutralization reaction to meta-alkalescence; Revolve to steam to remove and anhydrate and organic solvent; The reactant mixture that obtains is with anhydrous alcohol solution and remove by filter the inorganic salts that reaction generates, with being dissolved in the mixed solvent of short chain alcohol and water (volume ratio of short chain alcohol and water is 7: 3) behind the filtrating evaporate to dryness; Remove unreacted alkyl-blocked alkylphenol polyoxyethylene ether in the reactant mixture with organic solvent extraction; Collect pure water, evaporate to dryness short chain alcohol and water obtain the alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate crude product, get alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant through silicagel column or recrystallization purification postlyophilization.
Wherein:
Above-mentioned organic solvent is benzinum, ether, monochloro methane, carrene, chloroform or 1, the 2-dichloroethanes.
Above-mentioned sulfonating agent is selected from oleum, carrene, chloroform or 1, and the 2-dichloroethanes is diluted to the chlorosulfonic acid of 5～30wt%, any one in three kinds of the sulfur trioxides.
Above-mentioned inorganic base aqueous solution is lithium hydroxide aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, magnesium hydroxide aqueous solution, calcium hydroxide aqueous solution, baryta water, ammoniacal liquor or any mixture between them, and its concentration range is that 10wt% is to its saturated solution.
Above-mentioned short chain alcohol is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol.
Alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant preparation method technology of the present invention is simple, and yield is up to more than 65%, and table/interface performance is excellent, and its critical micelle concentration is 10
-6～10
-3Mol/L; Surface tension under critical micelle concentration is 35～23mN/m; So such surfactant can be used as emulsifying agent or wetting agent is used for agricultural chemicals separately or with other additive compound; Be used for metal cleaning processing separately or with other additive compound as wetting agent or washing agent; Be used for ore floatation separately or with other additive compound as trapping agent or foaming agent; Be used for silk dyeing and finishing separately or with other additive compound as bleeding agent, levelling agent or antistatic additive, be used for the leather processing separately or with other additive compound, also can be used for one of formula material of corrosion inhibitor, lubricant, fuel additive, blowing agent, fiber cleaning agent, antistatic additive and rust-inhibiting additive as solubilizer or softening agent.
Alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant of the present invention has high surface, uses separately or uses and can form 10 with simulated oil alkane or crude oil with other additive compound
-2The low interfacial tension of the mN/m order of magnitude, or form 10
-3The ultralow interfacial tension of the mN/m order of magnitude has excellent foaming and foam stability ability, and the heat-resistant salt-resistant performance is good, when 5wt% sodium chloride or 5000mg/L calcium ion concentration, still has excellent properties.Alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant of the present invention is used for tertiary oil recovery as oil displacement agent separately or with other additive compound in tertiary oil recovery.Wherein said alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant uses the concentration in the system to be 100mg/L～10000mg/L in above-mentioned independent use or with other additive compound.
Described auxiliary agent is inorganic base, anion surfactant, non-ionic surface active agent, amphoteric surfactant, aliphatic acid, fatty alcohol, partially hydrolyzed polyacrylamide (PHPA) base polymer, polyacrylic polymer, polysaccharide polymer, hydrophobic associated copolymer, xanthans, chelating agent etc. or any mixture between them.
Described inorganic base is NaOH, sodium acid carbonate, sodium carbonate, potassium hydroxide, saleratus, potash, ammoniacal liquor or any mixture between them.
Described anion surfactant comprises soap, alkylbenzenesulfonate, alkylnaphthalene sulfonate, alkylsulfonate, petroleum sulfonate, lignosulfonates, alkyl sulfate, phosphate ester salt or any mixture between them.
Described ionic surfactant pack is drawn together AEO, polyoxyethylene carboxylate, APES, polyoxyethylene alkyl amine, polyxyethylated acyl hydramine, alkyl poly glucoside or any mixture between them.
Described amphoteric surfactant comprises imidazolidine derivatives, betanin derivative, alanine derivatives, taurine derivatives or any mixture between them.
Surfactant of the present invention contains non-ionic hydrophilic reunion oxygen ethene and anionic hydrophilic group sulfonate; Its distinctive molecular structure has determined it to have good water-solubility, lower critical micelle concentration; Excellent reduction table/interfacial tension ability; The steady bubble ability that foams efficiently and outstanding heat-resistant salt-resistant performance have good application prospects in various fields such as agricultural chemicals, mineral floating, tertiary oil recoveries, can in tertiary oil recovery, use as effective oil displacement agent.
Description of drawings
Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt in Fig. 1 embodiment of the invention 1
1H NMR (solution:CDCl
3) spectrogram.
Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt FTIR (KBr compressing tablet) spectrogram in Fig. 2 embodiment of the invention 1.
Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt ESI-MS spectrogram in Fig. 3 embodiment of the invention 1.
Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt surface tension curve map in different temperatures pure water solution and 0.5wt% sodium chloride solution in Fig. 4 embodiment of the invention 1.
Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt concentration is 500mg/L in Fig. 5 embodiment of the invention 1, when sodium chloride is 0.5wt%, with the dynamic interface tension curve figure (30 ℃ of experimental temperatures) of simulated oil n-decane
Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt concentration is 500mg/L in Fig. 6 embodiment of the invention 1, and sodium chloride is 0.5wt%, when sodium carbonate is 0.1wt%, with the dynamic interface tension curve figure (70 ℃ of experimental temperatures) of Shengli Oil Field crude oil.
Dodecane end-blocking octyl phenol polyoxy ethene (6) ether benzene sulfonic acid sodium salt in Fig. 7 embodiment of the invention 2
1HNMR (solution:CDCl
3) spectrogram.
The surface tension curve map (30 ℃ of experimental temperatures) of dodecane end-blocking octyl phenol polyoxy ethene (6) ether benzene sulfonic acid sodium salt pure water solution in Fig. 8 embodiment of the invention 2.
Dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt in Fig. 9 embodiment of the invention 3
1HNMR (solution:CDCl
3) spectrogram.
The surface tension curve map (30 ℃ of experimental temperatures) of dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt pure water solution in Figure 10 embodiment of the invention 3.
Dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt surfactant samples is the 2000mg/L aqueous solution in concentration in Figure 11 embodiment of the invention 3, foam volume under the different sodium chloride concentrations and half-life figure.
Dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt surfactant samples is the 2000mg/L aqueous solution in concentration in Figure 12 embodiment of the invention 3, foam volume under the different calcium chloride concentrations and half foam life period figure.
The specific embodiment
Through embodiment the present invention is further described below, its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention.
The preparation of embodiment 1 octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt
(1) in the 100mL flask of electromagnetic agitation, thermometer, reflux condensing tube, drying tube, constant pressure funnel is housed, add the pure 15.35g of octyl group polyoxyethylene (4) (0.05mol), dimethyl formamide 1mL at room temperature slowly adds 7.14g (0.06mol) thionyl chloride through constant pressure funnel; Dropwise continued reaction 0.5 hour; Be warming up to 120 ℃ of reactions 2 hours then, in the frozen water solution of impouring saturated sodium carbonate, divide three extractions after cooling with the 300mL benzinum; Washing organic facies three times; With the benzinum phase of anhydrous sodium sulfate drying extraction gained, revolve to steam and remove benzinum, decompression distillation more then; Collect 184～186 ℃/532Pa component and get octyl group polyoxyethylene (3) ethyl chloride 12.98g, its productive rate is 80.5%., the 250mL three-neck flask of electromagnetic agitation, thermometer, water knockout drum, reflux condenser and drying tube adds 9.74g (0.03mol) octyl group polyoxyethylene (3) ethyl chloride then in being housed; Dilute with the 25mL dimethyl formamide; Add the dry toluene of 5.15g (0.025mol) octyl phenol and 100mL then; Under electromagnetic agitation, add 3.45g (0.025mol) Anhydrous potassium carbonate, be warming up to backflow, have moisture to go out to show that reaction begins; To react the moisture that generates through water knockout drum and go out, confirm reaction end with the some plate technique.Question response liquid cooled and filtered, filtrating are revolved earlier to steam and are removed most of dimethyl formamide and toluene, add the extraction of 100mL benzinum and 60mL water then; Water is colourless with petroleum ether extraction to petroleum ether layer, merges organic facies, washing organic facies three times; Steam after the anhydrous magnesium sulfate drying organic facies and desolventize; Cross post with acetone and benzinum [V:V=1:10] and get colourless transparent liquid 8.68g, be octyl group end-blocking octyl phenol polyoxy ethene (4) ether, its productive rate 70.3%.
(2) preparation of octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt
In the 100mL three-neck flask of electromagnetic agitation, thermometer, drying tube, constant pressure funnel is housed, add 20mL through drying refining 1; 2-dichloroethanes and 8.68g (0.0176mol) octyl group end-blocking octyl phenol polyoxy ethene (4) ether; Ice-water bath is brought down below 5 ℃, slowly drips 10mL under the electromagnetic agitation and contains 1 of 2.44g (0.021mol) chlorosulfonic acid (distillation again), 2-dichloroethane solution; Whole process guarantee system temperature is less than 5 ℃; Drip off the back and stirred 1.5 hours, remove ice-water bath, at room temperature continue stirring and obtained pale brown look liquid in 3.5 hours.Slowly adding sodium hydroxide solution (10wt%) is neutralized to about pH=8; Rotary evaporation removes and anhydrates and 1, and the 2-dichloroethanes is dissolved in absolute ethyl alcohol with the light yellow solid that obtains; Filter desalination; Add entry and ethanol, get the ethanol-water solution [V:V=7:3] of octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonate, remove unreacted octyl group end-blocking octyl phenol polyoxy ethene (4) ether with petroleum ether extraction; Isolated alcohol-water is revolved the dried grey paste that obtains mutually, cross post with acetone and benzinum [V:V=5:1] and get white paste, freeze drying gets white octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt solid 6.87g, its productive rate 65.5% to constant weight.
Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt
1H NMR, FTIR, ESI-MS spectrogram are respectively like Fig. 1, Fig. 2, shown in Figure 3; Octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt surface tension curve in the different temperatures pure water and in 30 ℃ of 0.5wt% sodium chloride is as shown in Figure 4; 500mg/L octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt; The sodium chloride of 0.5wt%, in the time of 30 ℃ and decane dynamic interface tension curve as shown in Figure 5,500mg/L octyl group end-blocking octyl phenol polyoxy ethene (4) ether benzene sulfonic acid sodium salt; The sodium chloride of 0.5wt% is in the time of 70 ℃ and crude oil dynamic interface tension curve (used crude oil be the Shengli Oil Field field of razor clam east crude oil) as shown in Figure 6.
The preparation of embodiment 2 dodecane end-blocking octyl phenol polyoxy ethene (6) ether benzene sulfonic acid sodium salts
, the 100mL flask of electromagnetic agitation, thermometer, reflux condensing tube, drying tube, constant pressure funnel adds octyl phenol polyoxy ethene (6) ether (OP-6) 4.70g (0.01mol) in being housed; Pyridine 1mL at room temperature slowly adds 1.79g (0.015mol) thionyl chloride through constant pressure funnel, dropwises continued reaction 0.5 hour; Be warming up to 100 ℃ of reactions 2 hours then; In the frozen water solution of impouring saturated sodium bicarbonate, divide three extractions after cooling, washing ethyl acetate three times mutually with 300mL ethyl acetate; Extract the ethyl acetate phase of gained then with anhydrous magnesium sulfate drying; Revolve then to steam and remove ethyl acetate, get octyl group polyoxyethylene (5) ethyl chloride 4.25g, its productive rate is 87.0%.In another reactor, add lauryl alcohol 1.86g (0.01mol) and potassium hydroxide 0.56g (0.01mol) then, be heated to potassium hydroxide dissolving back, slowly splash into octyl group polyoxyethylene (5) ethyl chloride in 100 ℃ of reactions 1 hour; Be heated to back flow reaction 2～5 hours; Reaction finishes, and the back adds the 100mL benzinum and 60mL water extracts, and water is colourless with petroleum ether extraction to petroleum ether layer, merges organic facies; Washing organic facies three times; Steaming desolventizes after the anhydrous magnesium sulfate drying organic facies, promptly gets dodecane end-blocking octyl phenol polyoxy ethene (6) ether 4.62g, its productive rate 83.3%.
In the 100mL three-neck flask of electromagnetic agitation, thermometer, drying tube, constant pressure funnel is housed, add 20mL through drying refining 1; 2-dichloroethanes and 4.62g (0.0069mol) dodecane end-blocking octyl phenol polyoxy ethene (6) ether; Ice-water bath is brought down below 5 ℃, under the electromagnetic agitation slowly Dropwise 5 mL contain 1 of 0.96g (0.0083mol) chlorosulfonic acid (distillation) again, 2-dichloroethane solution; Whole process guarantee system temperature is less than 5 ℃; Drip off the back and stirred 1.5 hours, remove ice-water bath, at room temperature continue stirring and obtained pale brown look liquid in 3.5 hours.Slowly adding potassium hydroxide solution (10wt%) is neutralized to about pH=8; Rotary evaporation removes and anhydrates and 1, and the 2-dichloroethanes is dissolved in absolute ethyl alcohol with the light yellow solid that obtains; Filter desalination; Add entry and ethanol, get the ethanol-aqueous solution [V:V=7:3] of dodecane end-blocking octyl phenol polyoxy ethene (6) ether benzene sulfonic acid potassium, remove unreacted dodecane end-blocking octyl phenol polyoxy ethene (6) ether with petroleum ether extraction; Isolated alcohol-water is revolved the dried grey paste that obtains mutually; Cross post with acetone and benzinum [V:V=7:1] and get light yellow paste; Freeze drying gets light yellow dodecane end-blocking octyl phenol polyoxy ethene (6) ether benzene sulfonic acid potassium solid 4.05g, its productive rate 78.2% to constant weight.
Dodecane end-blocking octyl phenol polyoxy ethene (6) ether benzene sulfonic acid potassium
1H NMR spectrogram is as shown in Figure 7, and pure water solution surface tension curve is as shown in Figure 8.
The preparation of embodiment 3 dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salts
, the 100mL flask of electromagnetic agitation, thermometer, reflux condensing tube, drying tube, constant pressure funnel adds octyl phenol polyoxy ethene (15) ether (OP-15) 8.66g (0.01mol) in being housed; NaOH 0.60g (0.015mol), 100 ℃ the reaction 1 hour, then gradually dripping bromine for n-dodecane 2.49g (0.01mol); Be heated to back flow reaction after dropwising 2～5 hours; Reaction finishes, and the back adds the 100mL benzinum and 60mL water extracts, and water is colourless with petroleum ether extraction to petroleum ether layer, merges organic facies; Washing organic facies three times; Steaming desolventizes after the anhydrous magnesium sulfate drying organic facies, promptly gets dodecane end-blocking octyl phenol polyoxy ethene (15) ether 7.94g, its productive rate 76.8%.
In the 100mL three-neck flask of electromagnetic agitation, thermometer, drying tube, constant pressure funnel is housed, add 20mL through drying refining 1; 2-dichloroethanes and 7.94g (0.0077mol) dodecane end-blocking octyl phenol polyoxy ethene (15) ether; Be cooled to 20 ℃, under the electromagnetic agitation slowly Dropwise 5 mL contain 1 of 1.07g (0.0083mol) chlorosulfonic acid (distillation) again, 2-dichloroethane solution; Whole process guarantee system temperature is 20 ℃; Drip off the back and stirred 1.5 hours, remove ice-water bath, at room temperature continue stirring and obtained yellow liquid in 3.5 hours.Slowly adding sodium hydroxide solution (10wt%) is neutralized to about pH=8; Rotary evaporation removes and anhydrates and 1, and the 2-dichloroethanes is dissolved in absolute ethyl alcohol with the yellow solid that obtains; Filter desalination; Add entry and ethanol, get the ethanol-water solution [V:V=7:3] of dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt, remove unreacted dodecane end-blocking octyl phenol polyoxy ethene (15) ether with petroleum ether extraction; Isolated alcohol-water is revolved the dried yellow paste that obtains mutually; Cross post with acetone and benzinum [V:V=10:1] and get yellow paste; Freeze drying gets yellow dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt solid 6.06g, its productive rate 69.2% to constant weight.
Dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt
1H NMR spectrogram is as shown in Figure 9; The surface tension curve is shown in figure 10, and foam performance that 2000mg/L dodecane end-blocking octyl phenol polyoxy ethene (15) ether benzene sulfonic acid sodium salt is measured with improvement Beckman method under different sodium chloride and calcium chloride concentration and foam stability are respectively like Figure 11, shown in Figure 12.
Claims (10)
1. an alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant is characterized in that, the structural formula of this alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant is:
Wherein, R
1, R
2Alkyl for carbon number 6～30; EO represents oxyethylene group; M is that oxyethylene group is rolled into a ball fixed number value or mean value really, and numerical value is 4,6,15; M is the Li in the alkali metal ion
+, Na
+Or K
+, or the Ca in the alkaline-earth metal ions
2+, Mg
2+Or Ba
2+, or the ammonium ion, or the mixture of the above ion.
2. the preparation method of an alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant according to claim 1 is characterized in that, this method may further comprise the steps:
(I) preparation of alkyl-blocked alkylphenol polyoxyethylene ether
The acid binding agent catalyst that with carbon number is 6～30 the pure and mild catalytic amount of alkyl polyoxyethylene places reactor, and control temperature≤50 ℃ slowly drip thionyl chloride under the stirring condition; Wherein carbon number is 6～30 alkyl polyoxyethylene alcohol: the mol ratio of thionyl chloride is 1: 1～1.5; Drip continued reaction 0.5～1 hour, be warming up to 100～140 ℃ of reactions 2～5 hours then, cooling back impouring contains in the inorganic base aqueous solution of ice; Use organic solvent extraction; The washing organic facies boils off organic solvent after the organic facies of the dry extraction of drier gained, and it is 6～30 alkyl polyoxyethylene ethyl chloride that decompression distillation gets carbon number; With carbon number is that 6～30 alkyl polyoxyethylene ethyl chloride places reactor; Use organic solvent diluting, add carbon number then and be 6～30 alkyl phenol, inorganic base and entrainer; Carbon number is 6～30 alkyl polyoxyethylene ethyl chloride: carbon number is 6～30 alkyl phenol: the mol ratio of inorganic base is 1: 1～1.5: 1～1.5; The entrainer consumption is heated to backflow so that steady backflow of reaction system is as the criterion, and will react the moisture that generates through water knockout drum and go out; To react the gains cooling after reaction finishes, filter; In the reaction gains, add entry then, use organic solvent extraction, the washing organic facies; Boil off organic solvent after the organic facies of the dry extraction of drier gained, purifying through silicagel column obtains alkyl-blocked alkylphenol polyoxyethylene ether; Or
With carbon number is that 6～30 the APES and the acid binding agent catalyst of catalytic amount place reactor; Control temperature≤50 ℃ slowly drip thionyl chloride under stirring condition, wherein carbon number is 6～30 APES: the mol ratio of thionyl chloride is 1: 1～1.5; Drip continued reaction 0.5～1 hour; Be warming up to 100～140 ℃ of reactions 2～5 hours then, cooling back impouring contains in the inorganic base aqueous solution of ice, uses organic solvent extraction; The washing organic facies boils off organic solvent after the organic facies of the dry extraction of drier gained and gets intermediate chloro thing; In another reactor, add carbon number then and be 6～30 alkylol and alkali metal or inorganic base; Reacted 1～3 hour down in 80～120 ℃, splash into intermediate chloro thing, intermediate chloro thing: carbon number is 6～30 alkylol: the mol ratio of alkali metal or inorganic base is 1:1～1.5:1～1.5; Be heated to back flow reaction; Use organic solvent extraction after reaction finishes, the washing organic facies boils off organic solvent after the organic facies of the dry extraction of drier gained and gets alkyl-blocked alkylphenol polyoxyethylene ether; Or
With carbon number is that 6～30 APES places reactor; Adding alkali metal or inorganic base reacted 1～3 hour down in 80～120 ℃; Splash into halogenated alkane then gradually; Carbon number is 6～30 APES: alkali metal or inorganic base: the mol ratio of halogenated alkane is 1:1～1.5:1～1.5, is heated to back flow reaction after dropwising, and uses organic solvent extraction after reaction finishes; The washing organic facies boils off organic solvent after the organic facies of the dry extraction of drier gained and gets alkyl-blocked alkylphenol polyoxyethylene ether;
Described entrainer is benzene,toluene,xylene or cyclohexane;
(II) preparation of alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant
The alkyl-blocked alkylphenol polyoxyethylene ether that step (I) is prepared places reactor with organic solvent diluting; Control temperature≤20 ℃; At the following sulfonating agent that adds gradually that constantly stirs; Alkyl-blocked alkylphenol polyoxyethylene ether wherein: the mol ratio of sulfonating agent is 1:1～1.5, dropwises the back room temperature reaction 1～5 hour; Add inorganic base aqueous solution then and carry out neutralization reaction; Revolve to steam to remove and anhydrate and organic solvent; The reactant mixture that obtains is with anhydrous alcohol solution and remove by filter the inorganic salts that reaction generates; With being dissolved in the mixed solvent of short chain alcohol and water behind the filtrating evaporate to dryness, remove unreacted alkyl-blocked alkylphenol polyoxyethylene ether in the reactant mixture with organic solvent extraction, collect pure water; Evaporate to dryness short chain alcohol and water obtain the alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate crude product, get alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant through silicagel column or recrystallization purification postlyophilization.
3. method according to claim 2 is characterized in that: described acid binding agent is dimethyl formamide or pyridine.
4. method according to claim 2 is characterized in that: described alkali metal is sodium, potassium or their mixture;
Described inorganic base is sodium hydride, hydrofining, NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash, saleratus or their mixture;
The concentration range of described inorganic base aqueous solution is that 10wt% is to its saturated solution; Inorganic base aqueous solution is lithium hydroxide aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, magnesium hydroxide aqueous solution, calcium hydroxide aqueous solution, baryta water, ammoniacal liquor or any mixture between them.
5. method according to claim 2 is characterized in that: described organic solvent is benzinum, ether, monochloro methane, carrene, chloroform or 1, the 2-dichloroethanes.
6. method according to claim 2 is characterized in that: described halogenated alkane is the chloralkane of carbon number 6～30, the bromo alkane of carbon number 6～30 or the alkane iodide of carbon number 6～30.
7. method according to claim 2 is characterized in that: described sulfonating agent is selected from oleum, carrene, chloroform or 1, and the 2-dichloroethanes is diluted to the chlorosulfonic acid of 5～30wt%, any one in three kinds of the sulfur trioxides.
8. method according to claim 2 is characterized in that: described short chain alcohol is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or n-butanol.
9. the purposes of an alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant according to claim 1 is characterized in that: described alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant is used for tertiary oil recovery as oil displacement agent separately or with additive compound in tertiary oil recovery; Concentration in the system that wherein said alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant uses in above-mentioned independent use or with additive compound is 100mg/L～10000mg/L.
10. the purposes of an alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant according to claim 1 is characterized in that: alkyl-blocked alkylphenol polyoxyethylene ether benzene sulfonate surfactant separately or use, be used for bleeding agent, levelling agent or antistatic additive that trapping agent or foaming agent that wetting agent or washing agent that metal cleans processing used, be used for ore floatation used, be used for silk dyeing and finishing with emulsifying agent or wetting agent that additive compound is used for agricultural chemicals and use, be used for solubilizer that leather handles or softening agent and use or be used for one of formula material of corrosion inhibitor, lubricant, fuel additive, blowing agent, fiber cleaning agent or rust-inhibiting additive.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279937A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Alkyl phenol sulfonic polyoxyethylene ether sulfonate and preparation thereof |
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