CN1850795A - Bialkylbiphenyl sodium disulfonate, and its preparing method - Google Patents
Bialkylbiphenyl sodium disulfonate, and its preparing method Download PDFInfo
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Abstract
This invention relates to bi alkyl biphenyl tiron, it has following structure, n equals to 8,10,12,14. (1) Fatty acid and protochloride sulphones are mixed and reacted for 1 hour at 65-75 degree centigrade to get alkyl acyl chloride. (2) The alkyl acyl chloride is mixed with aluminium chloride and biphenyl, and reacted for 1 hour at 43-50 degree centigrade to get bi alkyl biphenyl ketone. (3) The bi alkyl biphenyl ketone is mixed with caustic potash and hydrazinehydrate, and then heated, back flown, and heated again to get bi alkyl biphenyl. (4) The bi alkyl biphenyl is mixed with chlorosultonic acid and reacted for 6 hours at normal temperature, and then they are back flown by methanol to get bi alkyl biphenyl disulfonic acid methyl ester. (5) The ester made is mixed with sodium hydroxide solution and heated to get bi alkyl biphenyl tiron. The surface activator has good surface activity and salt resistance, synergistic effect is good, tackifying ability is strong, and its preparation method is reliable, operation is easy, yield is high and no pollution.
Description
Technical field
The present invention relates to Bialkylbiphenyl sodium disulfonate, the invention still further relates to the preparation method of this compounds.
Background technology
Tensio-active agent has become indispensable chemical of moment in national economy and human daily life, in fields such as energy mining industry, metal processing, light textile, daily-use chemical industry, food pharmaceuticals purposes is widely arranged all.
Gemini surface active agent can reduce surface tension effectively, contains two hydrophilic groups in its molecule, has enough wetting abilities and better water-solubility, and is stronger to organic lyotropy, littler to the pungency of skin, has biological safety etc.When Gemini surface active agent and monomer tensio-active agent (especially nonionic surface active agent) mix, aspect the capillary usefulness and efficient that reduce water, produce stronger synergistic effect than monomer tensio-active agent.Adopt method in actual applications with cheap surfactant compound, can reduce production costs greatly, improve its using value, can be widely used in the industrial and agricultural production every field, such as making static inhibitor, fabric softener, sterilant, sanitas and petroleum additive etc.
In the additive of many oil fields, all use tensio-active agent.As at present in tertiary oil recovery widely used chemical combined flooding be the ternary composite driving that alkali, surfactant and polymer is formed, it is by improving the swept volume that mobility recently enlarges displacing fluid, also reduce oil water interfacial tension significantly by the synergy between the tensio-active agent, increase the dissemination of crude oil in water, change the rheological of crude oil, thereby improve recovery ratio.Ternary composite driving can make oil recovery factor improve more than 20% than water drive, but because the existence of alkali is risen polymer loading, and because the high valence ion generation precipitation in alkali and the stratum causes oil layer pollution.Gemini surface active agent has very strong reduction oil/water termination tensile ability, crude oil there is good lyotropy, forming the micellar molecular arrangement closely makes micella have higher electric density, can anti-high salinity, help ternary composite driving weak baseization or do not have alkalization, reduce polymer loading significantly, for tertiary oil production in oil field is opened up new approach.
Widely used in ternary composite driving is sulfonated petro-leum, benzene sulfonate and heavy alkylbenzene sulfonate analog anion surfactants, its interfacial activity height, and temperature tolerance is good, but salt tolerance is poor.So demand carrying out the research of synthetic solubilising, anti-steady, anti-salt, the oiliness that becomes energy excellent surfactant urgently, explore cheap raw material route and synthetic method.Two alkylbenzene sulfonates are kinds of alkylbenzene sulfonate, it adopts one to connect base, at the hydrophilic group position or nearly water base position two traditional surfactant molecule bondings are got up, make and contain two hydrophilic groups and two hydrophobic groups in each molecule, with traditional tensio-active agent very big difference is arranged on the performance, so such anionic gemini surfactant is expected to play a significant role in tertiary oil recovery.
Summary of the invention
The object of the present invention is to provide Bialkylbiphenyl sodium disulfonate and preparation method thereof, this Gemini surface active agent has surface of good activity and anti-salt property, compare with conventional surfactants, its surfactivity height, synergistic effect is good, and tackifying ability is strong, its preparation method is convenient and reliable, easy handling, yield is higher, and free from environmental pollution.
For reaching above technical purpose, the invention provides following technical scheme.
Bialkylbiphenyl sodium disulfonate has following structure:
The preparation method of Bialkylbiphenyl sodium disulfonate may further comprise the steps successively:
(1) with the cyclohexane give being solvent, is 8,10,12,14 lipid acid and sulfur oxychloride by 1: 1～2 mixed in molar ratio with carbonatoms, and temperature is controlled at 65 ℃～75 ℃, and insulated and stirred is about 1 hour, and underpressure distillation goes out alkyl acyl chloride;
(2) with the cyclohexane give be solvent, with alkyl acyl chloride and aluminum chloride mixed in molar ratio by 1: 1.1, heated and stirred, again biphenyl is joined in the mixing solutions, the mol ratio of acyl chlorides and biphenyl is 3～4: 1, maintain the temperature at 43～50 ℃ and stirred about 1 hour, the white precipitate that temperature rising reflux obtained after 3～4 hours is two alkyl biphenyl ketone;
(3) with glycol ether as solvent, with two alkyl biphenyl ketone, potassium hydroxide and hydrazine hydrate (hydrazine hydrate) respectively by 1: 3: 2 mixed in molar ratio, be heated to 140～160 ℃, about back flow reaction 8 hours, temperature is risen to 235～250 ℃, react 50～60 hours postcooling, with the sherwood oil recrystallization again by obtaining two alkyl biphenyls behind the chromatography column;
(4) with methylene dichloride as solvent, with two alkyl biphenyls and chlorsulfonic acid (chlorosulfuricacid) mixed in molar ratio by 1: 4, stirring reaction is after 6 hours under the normal temperature, reaction solution is handled with sherwood oil, use methanol eddy again 3 hours, and obtained two alkyl biphenyl disulfonic acid methyl esters behind cooling, suction filtration, the column chromatography;
(5) with two alkyl biphenyl disulfonic acid methyl esters and sodium hydroxide solution Hybrid Heating, react 1 hour postcooling, regulate PH to neutral with dilute hydrochloric acid, boil off solvent and recrystallization after, obtain Bialkylbiphenyl sodium disulfonate.
Reaction formula of the present invention is as follows:
In preparation method of the present invention, at first take by weighing a certain amount of lipid acid, join in the three-necked flask, add hexanaphthene again, after the heated and stirred fusing, in 1 hour, splash into sulfur oxychloride SOCl with the normal pressure dropping funnel
2, because sulfur oxychloride is poisonous, and very easily hydrolysis, should in stink cupboard, carry out, temperature is controlled at 65 ℃～75 ℃.About insulated and stirred 1 hour, be warming up to 85 ℃～90 ℃ again, refluxed 3～4 hours.After reaction finished, normal pressure steamed unreacted SOCl
2And hexanaphthene, underpressure distillation again, the colourless liquid that must have irritating smell is alkyl acyl chloride, and its productive rate is higher.
With the cyclohexane give is solvent, alkyl acyl chloride and aluminum chloride are joined in the three-necked flask, and heated and stirred, and then biphenyl divided join several times in the reaction flask, temperature is controlled in 43～50 ℃ approximately, insulated and stirred about 1 hour again, back temperature rising reflux 3～4 hours.After reaction finished, normal pressure steamed solvent, handled with ice-concentrated hydrochloric acid again, isolated precipitation.Use acetone successively, the ethyl acetate washing precipitation.Get white precipitate with the ethanol heat filtering again and be two alkyl biphenyl ketone.
Acylation reaction is used Louis's acid as catalyst always; because carbonylic oxygen atom contains not sharing electron; therefore the initial product of acidylate is to have formed 1: 2 complex compound by the ketone and the aluminum chloride that generate; and the katalysis that further needs acid of acylation process; but will lose katalysis in conjunction with the aluminum chloride behind the carbonylic oxygen atom, so the required aluminum chloride of reaction should be excessive.If the consumption of aluminum chloride is less, then might except that the aluminum chloride that combines, just there be enough catalyzer to carry out catalyzed reaction, cause reaction not exclusively.If aluminum chloride is excessive, it is more then to generate mono-substituted biphenyl ketone, i.e. side reaction accounts for leading, is unfavorable for the carrying out of main reaction, thereby has influenced the productive rate of two alkyl biphenyl ketone.When the mol ratio of acyl chlorides and aluminum chloride was about 1: 1.1 left and right sides, the productive rate of product was higher.
Find that in experiment along with the growth of carbochain, the fusing point of two alkyl biphenyl ketone is descending gradually, and decline scope is lower.This may be that the arrangement between the molecule is not very tight because the growth of carbochain makes the sterically hindered increase of molecule, and carbochain long array more is loose more, causes the lattice energy of molecule to reduce, and fusing point descends.Again because the just growth of four methylene radical between each molecule is not very big to whole molecules influence, so the fusing point difference is also smaller.
Carbonyl reduction is that the methylene radical reaction is the main method of synthesis of alkyl biphenyl, reflux condensing tube is being housed, add in the three neck round-bottomed flasks of thermometer necessarily than the two alkyl biphenyl ketone that are listed as, potassium hydroxide and 80% hydrazine hydrate (hydrazine hydrate), with glycol ether (glycol ether) is solvent, mix back solution and be blue, be heated to 140～160 ℃, material dissolution, present safran, after the back flow reaction 8 hours, change reflux condensing tube into division box, steam low-boiling point materials such as hydrazine hydrate, and make the temperature of reaction system rise to 235～250 ℃, react after 50～60 hours, stopped reaction, cooling washes out mixture in the reaction flask with sherwood oil, does the white products that obtains by chromatography column again behind the recrystallization with sherwood oil and is two alkyl biphenyls.
Carbonyl reduction is the reaction of methylene radical, if general huang-Minlon reaction, the decomposition temperature of hydrazone class is 190-200 ℃.And the middle hydrazone compounds decomposition temperature of the present invention's preparation is higher, general 235-250 ℃.When temperature was hanged down, hydrazone compounds was not easy to decompose, and temperature is too high, and by product increases, and productive rate reduces.Along with the growth in reaction times, productive rate raises gradually.Time is too short, and reaction is incomplete, and by product monoalkyl biphenyl is more.Increase in time, reaction is tending towards complete gradually.
Adopt chlorsulfonic acid as sulphonating agent in the present invention, after introducing sulfonic group on the aromatic ring, can make water-soluble increase greatly.In the there-necked flask that has drying tube, reflux condensing tube and constant pressure funnel, add two alkyl biphenyls, methylene dichloride, after this device put into ice-water bath cooling 10mim, from dropping funnel, slowly drip chlorsulfonic acid, maintain the temperature between 0～5 ℃, after dripping off, stirring reaction at normal temperatures, treated raw material reaction about fully 6 hours with the thin-layer chromatography following response, reaction solution is handled the generation white precipitate with sherwood oil, use methanol eddy again, white solid is separated out in cooling, and suction filtration obtains white two alkyl biphenyl disulfonic acid methyl esters by column chromatography.
Two alkyl biphenyl disulfonic acid methyl esters and 40%NaOH solution Hybrid Heating that the last step was obtained, the reaction postcooling, regulate PH to neutral with dilute hydrochloric acid, boil off solvent and obtain slightly yellowy product, use methanol=1: 1 recrystallization again, obtain white solid and be Bialkylbiphenyl sodium disulfonate, its fusing point is higher than 300 ℃.Along with the growth of alkyl chain, reaction yield descends, and mainly is because of sterically hindered cause, and the fusing point of methylmesylate also raises with the growth of alkyl chain simultaneously, and this is due to Intermolecular Forces strengthens.
The present invention has done change to the solvent of reaction.In bibliographical information in the past, react as solvent with excessive sulfur oxychloride during the acyl chlorides of preparation low carbon number, substantially without other solvent, but sulfur oxychloride highly volatile hydrolysis, finally cause the reaction soln temperature to raise, productive rate descends, and in aftertreatment, have a large amount of hydrogenchloride and sulfurous gas toxic gas to produce, environmental pollution is serious.When the acyl chlorides of the high carbon number of preparation is to make solvent with benzene, and benzene belongs to toxicity than higher solvent.Given this, the present invention uses the cyclohexane give solvent instead, and its toxicity is little, and boiling point and benzene are approaching, and temperature is also easy to control.
Compared with prior art, the present invention has following beneficial effect:
(1) Bialkylbiphenyl sodium disulfonate has the surface of good activity, and the present invention has increased the new variety of anionic dimeric surfactant;
(2) preparation method's principle of Bialkylbiphenyl sodium disulfonate is reliable, method is simple, easy handling, yield height;
(3) replace benzene or thionyl chloride to make solvent with hexanaphthene among the preparation method, reduced the toxicity of reaction and the pollution of environment;
(4) Bialkylbiphenyl sodium disulfonate has anti-salt property and lathering property preferably, with conventional surfactants and polymkeric substance composite after, show good synergistic effect and tackify effect, be expected in tertiary oil recovery, play a significant role.
Description of drawings
Fig. 1 is the infrared spectrogram of two dodecyl biphenyl disulfonic acid dimethyl esters
Fig. 2 is the hydrogen spectrogram of two dodecyl biphenyl disulfonic acid dimethyl esters
Fig. 3 is the carbon spectrogram of two dodecyl biphenyl disulfonic acid dimethyl esters
Fig. 4 is the change curve of the surface tension of two dodecyl biphenyl sodium disulfonates (GB12) with concentration
Fig. 5 is GB12 and the composite rear surface of cetyl trimethylammonium bromide (TAC-16) the tension force change curve with concentration
Fig. 6 is GB12 and the composite rear surface of Sodium dodecylbenzene sulfonate (SDBS) the tension force change curve with concentration
Fig. 7 is the influence of surfactant concentration to 5000mg/L polyacrylamide (PAM) soltion viscosity
Embodiment
Below in conjunction with accompanying drawing, further specify the present invention.
In an embodiment of the present invention, raw materials used be commercially available.
The preparation of 1 pair of dodecyl biphenyl of embodiment sodium disulfonate (GB12)
The preparation of (1) ten two carbonyl chloride takes by weighing lauric acid 0.1mol, adds in the 50ml three-necked flask, adds hexanaphthene 10ml again, splashes into sulfur oxychloride 0.15mol with constant pressure funnel in 1h, and temperature is controlled at 70～75 ℃.After dripping off, about insulated and stirred 1h, be warming up to 85 ℃～90 ℃ again, refluxed 3～4 hours, underpressure distillation goes out 12 carbonyl chlorides then.
(2) preparation of two 12 carbonic acyl radical biphenyl takes by weighing aluminum chloride (mol ratio of alkyl acyl chloride and aluminum chloride is 1: 1.1); add in the 50ml three-necked flask; add the about 10ml of hexanaphthene again, heated and stirred, 12 carbonyl chlorides that impouring has made; stir; take by weighing a certain amount of biphenyl (mol ratio of acyl chlorides and biphenyl is 4: 1) then and be dissolved in the hexanaphthene, divide to join several times in the reaction flask, temperature is controlled in 43 ℃～50 ℃ approximately; again about insulated and stirred 1h, back temperature rising reflux 3～4h.After reaction finishes, cooling.Steam solvent,, isolate precipitation with the acid treatment of ice-salt.Use acetone successively, ethyl acetate, hot ethanol washing precipitation.At last, with chloroform repeatedly recrystallization get the promptly two 12 carbonic acyl radical biphenyl of white solid, yield 38%.
(3) reflux condensing tube is being equipped with in the preparation of two dodecyl biphenyl; add a certain proportion of two 12 carbonic acyl radical biphenyl and potassium hydroxide (mol ratio of two 12 carbonic acyl radical biphenyl and potassium hydroxide is 1: 3) in the 50ml three neck round-bottomed flasks of thermometer; 80% hydrazine hydrate (mol ratio of two 12 carbonic acyl radical biphenyl and hydrazine hydrate is 1: 2); add solvent glycol ether 10ml again; mix; be heated to 140-160 ℃; behind the back flow reaction 8h; change reflux condensing tube into division box; steam low-boiling point materials such as hydrazine hydrate; and the temperature that makes reaction system rises to 235-250 ℃, behind the reaction 50h, and stopped reaction; cooling; wash out mixture in the reaction flask with sherwood oil, get the promptly two dodecyl biphenyl of white solid, yield 72% by chromatography column again after doing recrystallization with sherwood oil.
(4) preparation of two dodecyl biphenyl disulfonic acid methyl esters is having drying tube, add two alkyl biphenyl 0.003mol in the 50ml there-necked flask of reflux condensing tube and constant pressure funnel, methylene dichloride 10ml, after this device put into ice-water bath cooling 10mim, from dropping funnel, slowly drip the chlorsulfonic acid of 0.012mol, maintain the temperature between 0-5 ℃, after dripping off, stirring reaction at normal temperatures, treat the about fully 6h of raw material reaction with the thin-layer chromatography following response, reaction solution is handled the generation white precipitate with sherwood oil, use methanol eddy 3h again, white solid, suction filtration are separated out in cooling, get white products by column chromatography, yield 38%, white plates crystal, fusing point 90-91 ℃.
(5) preparation of two dodecyl biphenyl sodium disulfonates will be gone up two dodecyl biphenyl disulfonic acid methyl esters and the 40%NaOH solution Hybrid Heating that the step obtains, reaction 1h postcooling is regulated PH to neutral with dilute hydrochloric acid, boil off solvent and obtain slightly yellowy product, use methanol=1: 1 recrystallization again, obtain white solid, be two dodecyl biphenyl sodium disulfonates (GB12).
The structural characterization of embodiment 2 pairs of dodecyl biphenyl disulfonate and sodium salt thereof
Because two dodecyl biphenyl sodium disulfonates are almost insoluble in organic solvent, therefore can only characterize the structure of its sodium salt with infrared spectrogram (Fig. 1), hydrogen spectrogram (Fig. 2), the carbon spectrogram (Fig. 3) of two dodecyl biphenyl disulfonic acid dimethyl esters.
Referring to Fig. 1, at 3435.68cm
-1The place is the absorption peak of hydroxyl, 2916.43cm
-1, 2851.86cm
-1And 1472.12cm
-1The place is the charateristic avsorption band of methyl and methylene radical; At 1150.08cm
-1And 1296.61cm
-1There are two strong peaks at the place and have near this two peak than the broad peak appearance, and this may be the stretching vibration peak of S=O in the sulfonic acid; At 839.00cm
-1There is a peak at the place, and there is a small peak adjacent this front, peak, and this is the absorption peak (all there is replacement the adjacency pair position) of the wherein a kind of pattern in three replacements of phenyl ring.
Referring to Fig. 2, two dodecyl biphenyl disulfonic acid dimethyl esters
1HNMR such as following table:
| Absorption peak | δ(ppm) | Little peak number | Peak area | Number of |
| 1 2 3 4 5 6 | 7.77 7.55 2.84 1.79 1.44 1.03 | t d t m t t | 2.015 1.000 1.978 2.045 19.087 3.357 | 2 1 2 2 19 3 |
As can be seen from the above table, 1 group, 2 groups is the benzene ring hydrogen, and the number ratio is 2: 1, and 3 groups hydrogen is that 4 groups of hydrogen are the methylene radical hydrogen that links to each other with methyl near a methylene radical hydrogen on the phenyl ring alkyl chain, 5 groups of hydrogen then are the peaks of middle long-chain methylene radical hydrogen, these methylene radical hydrogen environment of living in is basic identical, and some covering each other of the peak of formation shows as irregular multiplet.6 groups of hydrogen are methyl hydrogen of chain alkyl.Sulfonic hydroxyl hydrogen is very weak, can't see on collection of illustrative plates.Can be inferred by hydrogen number on the phenyl ring: the symmetrical configuration of molecule, the hydrogen atom number conforms to the hydrogen number of target product than enlarging twice.
Referring to Fig. 3, two dodecyl biphenyl disulfonic acid dimethyl esters
13CNMR sees the following form:
| | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| δ(cm -1) Absorption peak δ(cm -1) | 145.7 9 31.04 | 137.8 10 29.65 | 133.9 11 29.50 | 129.4 12 29.39 | 121.7 13 29.33 | 121.0 14 29.16 | 35.81 15 22.67 | 31.90 16 14.11 |
Carbon atom kind number on the spectrogram has only 16 kinds as can be seen from the above table, and this has proved absolutely the symmetry of molecular structure.Have a look the ownership of displacement: 145.7cm again
-1The place is the carbon peak of sulfonic group substituted benzene ring position, because sulfonic group electrophilic influence is subjected to lower screening of nucleus, and shifts to low.121.0-137.8 carbon all be other carbon on the phenyl ring.35.81cm
-1The place is the mesomethylene carbon peak near phenyl ring.31.90cm
-1Be second the mesomethylene carbon peak that leans on phenyl ring on the chain alkyl, 14.11cm
-1Be methyl carbon peak, 22.67cm
-1Be the mesomethylene carbon peak near methyl, 29.16-31.04cm
-1Between six peaks be intermediary mesomethylene carbon peak, these methylene radical hydrogen environment of living in is basic identical, each other some covering of the peak of formation, therefore carbonatoms is less than actual number from collection of illustrative plates.
The surfactivity that 3 pairs of dodecyl biphenyl of embodiment disulfonic acid is received characterizes
1), the mensuration of the equilibrium surface tension of the GB12 aqueous solution and cmc
Under 20 ℃, measure its surfactivity, obtain its concentration and solution surface tension relation as shown in Figure 4.As can be seen from Figure 4 to have very high surfactivity: C20 be 0.002mmol/L to this Gemini surface active agent, and cmc is 0.17mmol/L, and γ cmc is 31.2mN/m, and conventional surfactants sodium alkyl benzene sulfonate cmc 1.57mmol/L; γ cmc 37mN/m, C20 are 0.2mmol/L.
2), the GB12 anti-salt property is measured
In solution, add inorganic salt the surfactivity of tensio-active agent is strengthened, study four kinds of inorganic salt,, also studied the influence of salt pair Sodium dodecylbenzene sulfonate SDBS, the results are shown in Table 1 for the ease of contrast to the capillary influence of GB12.
Table 1 salt pair GB12 and the influence of SDBS surfactivity
| Con.(salt) (mol/L) | Cmc(mmol/L)(GB12) | γ cmc(mN/m)(GB12) | ||||||
| NaCl | NH 4Cl | KCl | CaCl 2 | NaCl | NH 4Cl | KCl | CaCl 2 | |
| 0.01 0.02 0.04 0.06 0.08 | 0.043 0.0216 0.0144 0.0144 0.0216 | 0.0216 0.0144 0.0144 0.0144 0.0216 | 0.086 0.043 0.0216 0.0216 0.043 | 0.086 0.043 0.043 0.086 0.043 | 28.2 28.0 27.9 28.1 28.8 | 27.9 27.7 27.7 27.5 28.0 | 29.6 30.1 31.6 30.7 31.2 | 34.3 35.7 35.8 37.1 38.4 |
| Con.(salt) (mol/L) | Cmc(mmol/L)(SDBS) | γ cmc(mN/m)(SDBS) | ||||||
| NaCl | NH 4Cl | KCl | CaCl 2 | NaCl | NH 4Cl | KCl | CaCl 2 | |
| 0.01 0.02 0.04 0.06 0.08 | 0.575 0.287 0.287 0.287 0.287 | 0.0216 0.0144 0.0144 0.0144 0.0216 | 0.086 0.043 0.0216 0.0216 0.043 | 32.6 32.6 32.3 32.4 31.8 | 28.7 30.4 28.9 28.4 28.4 | 29 29 28.9 29 31.2 | 28.1 32.8 28.8 32.1 | |
1 as seen, four kinds of inorganic salt all can reduce the cmc and the γ cmc of the GB12 and the SDBS aqueous solution, wherein NaCl, NH from table
4Cl is apparent in view to the capillary change of compound.
3), the GB12 lathering property is measured
The 10ml solution of in 50ml tool plug graduated cylinder, packing into, by the velocity fluctuation of 2 times/s 10 times, the foam height when just stopping is as elemental height, foam height when measuring 5min and initial foam height liken measuring to for its stability.Foam height is that half time of original height is as the foamy transformation period.Every kind of solution repeats 3 times, averages.(measuring temperature is 25 ℃.) experimental result sees Table 2.
The whipability experimental result of table 2 GB12
| Sample | Elemental height (mm) | Height (mm) after 5 minutes | Froth stability (%) | Transformation period (s) |
| GB12 SDBS | 460 80 | 440 56.8 | 95.6％ 71％ | 72’3” 56’17” |
Find out that from table 2 column data what institute of the present invention synthetic Gemini surface active agent will be good than the whipability of corresponding conventional surfactants-Sodium dodecylbenzene sulfonate is many.
Embodiment 4 GB12 and conventional surfactants composite
As can be seen from Fig. 5, add GB12 and can make its surface tension reduce 9.8mN/m in TAC-16 solution, cmc reduces 0.79mmol/L.
Mixed system is along with the increase of GB12 molar fraction, and surface tension descends, and cmc is near GB12, and the lowest surface tension that the while combination solution can reach is all lower than one-component, and the minimum 27.9mN/m that reaches shows good synergistic.
As can be seen from Fig. 6, GB12 and common anion and cation tensio-active agent have good synergy, and this characteristic will remedy that Gemini surface active agent is synthetic to be separated difficultly, and expensive deficiency is widened its Application Areas.
Embodiment 5 GB12 and polyacrylamide composite
As can be seen from Fig. 7, adding GB12 and SDBS in aqueous solutions of polymers can tackify to solution, but amplification difference, wherein Gemini surface active agent is the peak point of 1/3 (about 50ppm) of its micelle-forming concentration to the polymer solution viscosity influence in concentration, make the viscosity of PAM improve more than 3 times, when concentration continuation increase, thereby the surfactant molecule autohemagglutination becomes micelle to be unfavorable for that the stretching, extension viscosity of PAM macromolecular chain presents downtrending.And SDBS soltion viscosity near its micelle-forming concentration (150mg/L) time reaches maximum.
Claims (2)
1 Bialkylbiphenyl sodium disulfonate has following structure:
n＝8，10，12，14。
The preparation method of 2 Bialkylbiphenyl sodium disulfonates as claimed in claim 1 may further comprise the steps successively:
(1) with the cyclohexane give being solvent, is 8,10,12,14 lipid acid and sulfur oxychloride by 1: 1～2 mixed in molar ratio with carbonatoms, and temperature is controlled at 65 ℃～75 ℃ and stirred about 1 hour, and underpressure distillation goes out alkyl acyl chloride;
(2) with the cyclohexane give be solvent, with alkyl acyl chloride and aluminum chloride mixed in molar ratio by 1: 1.1, heated and stirred, again biphenyl is joined in the mixing solutions, the mol ratio of acyl chlorides and biphenyl is 3～4: 1, maintain the temperature at 43～50 ℃ and stirred about 1 hour, temperature rising reflux obtains two alkyl biphenyl ketone after 3～4 hours;
(3) with glycol ether as solvent, two alkyl biphenyl ketone, potassium hydroxide and hydrazine hydrate respectively by 1: 3: 2 mixed in molar ratio, are heated to 140～160 ℃, and back flow reaction is about 8 hours, be warming up to 235～250 ℃, react and obtain two alkyl biphenyls after 50～60 hours;
(4) with methylene dichloride as solvent, with two alkyl biphenyls and the chlorsulfonic acid mixed in molar ratio by 1: 4, normal temperature reaction 6 hours down obtains pair alkyl biphenyl disulfonic acid methyl esters with methanol eddy after 3 hours;
(5), react and obtain Bialkylbiphenyl sodium disulfonate after 1 hour with two alkyl biphenyl disulfonic acid methyl esters and sodium hydroxide solution Hybrid Heating.
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| CN116731695A (en) * | 2023-06-14 | 2023-09-12 | 大庆再创科技有限公司 | Composite ionic surfactant and preparation process thereof |
| CN117187004A (en) * | 2023-09-11 | 2023-12-08 | 深圳市合明科技有限公司 | Water-based cleaning agent for semiconductor packaging industry and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4943656A (en) * | 1984-07-19 | 1990-07-24 | King Industries, Inc. | Process for the production of polyalkylaromatic polysulfonic acids and recovery by heavy phase separation |
| US5929408A (en) * | 1996-09-26 | 1999-07-27 | Cytec Technology Corp. | Compositions and methods for ore beneficiation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101104794B (en) * | 2007-07-06 | 2010-05-19 | 中国石化股份胜利油田分公司地质科学研究院 | Method for preparing highly effective anion surfactant for third oil extraction |
| CN102964189A (en) * | 2012-02-03 | 2013-03-13 | 天津法莫西医药科技有限公司 | Improved Huang Minlon reaction |
| CN102964189B (en) * | 2012-02-03 | 2013-08-14 | 天津法莫西医药科技有限公司 | Improved Huang Minlon reaction |
| CN102875424A (en) * | 2012-09-18 | 2013-01-16 | 太仓市运通化工厂 | Synthetic method of double-straight chain tetradecyl diphenylmethane bisulfonate |
| CN106715642A (en) * | 2014-09-24 | 2017-05-24 | 陶氏环球技术有限责任公司 | Method for subterranean petroleum recovery using a surfactant blend |
| CN106715642B (en) * | 2014-09-24 | 2020-06-23 | 陶氏环球技术有限责任公司 | Process for recovering subterranean petroleum using surfactant blends |
| WO2020131287A1 (en) * | 2018-12-19 | 2020-06-25 | Exxonmobil Chemical Patents Inc. | Bicyclic surfactants |
| US11168053B2 (en) * | 2019-09-10 | 2021-11-09 | Exxonmobil Chemical Patents Inc. | Amphiphilic biphenyl compounds derived from alpha olefins or vinylidene alpha olefin dimers |
| CN116731695A (en) * | 2023-06-14 | 2023-09-12 | 大庆再创科技有限公司 | Composite ionic surfactant and preparation process thereof |
| CN117187004A (en) * | 2023-09-11 | 2023-12-08 | 深圳市合明科技有限公司 | Water-based cleaning agent for semiconductor packaging industry and preparation method thereof |
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| CN100354258C (en) | 2007-12-12 |
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