CN1817430A - Surface activator with double-ether bisbensulfosalt and double molecule - Google Patents
Surface activator with double-ether bisbensulfosalt and double molecule Download PDFInfo
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- CN1817430A CN1817430A CN200510022477.0A CN200510022477A CN1817430A CN 1817430 A CN1817430 A CN 1817430A CN 200510022477 A CN200510022477 A CN 200510022477A CN 1817430 A CN1817430 A CN 1817430A
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Abstract
A dual-component surfactant of biether biphenylsulfonate is 2.2-bis (4-alkoxy-3- sodium phenylsulfonate) propane. Its preparing process includes such steps as adding biphenol A and the aqueous solution of NaOH into reactor, reaction at 50-78 deg.C, sequentially adding absolute alcohol and long-chain alkyl bromine into reactor, reacting at 50-78 deg.C for 12-36 hr, evaporating alcohol, washing the resultant, recrystallizing, drying to obtain biether compound, adding it into reactor, using dichloromethane as solvent, dripping chlorosulfonic acid, reaction at 15-35 deg.C for 1-3 hr, neutralizing resultant, salting out, filtering and drying. Its advantages are high surface activity, and high foam stability.
Description
Technical field
The present invention relates to two benzene sulfonate Gemini surface active agents of a kind of novel bis ether and preparation method thereof, belong to sulfosalt surfactant of a kind of anionic and preparation method thereof.
Background technology
Shuangzi (Gemini) surfactant is to be connected by chemical bond at ion head Ji Chu by two common strand single head based surfactants to form.Compare with traditional surfactant, many advantages are arranged.Mainly be presented as: γ cmc and cmc are lower than the conventional surfactants that contains the identical polar group; Have good dissolution in low temperature performance and characteristic of solubilizing; Composite with conventional surfactants, can produce bigger cooperative effect; In solution, under the very low concentration, can make solution produce apparent viscoelastic behavior.(Zhao Jianxi. surfactant of new generation: Geminis. chemical progress, 1999,11 (4): 348-357; Zana.R, Benrraou.M, Rueff.R.Langmuir, 1991 (7): 1072-1075; Kern.F, Lequeux.F, Zana.R.Langmuir, 1994 (10): 1714-1723; Wanless.E.J, Ducker.W.A.J.Phys.Chem, 1996 (100): 3207-3214; Buhler.E, Mendes.E.Langmuir, 1997 (13): 3096-3102).The performance that Gemini surface active agent is good has determined it to have broad application prospects.It can be used for preparing new material, administer sewage, as bactericide, anticorrisive agent and chemical agent for oil recovery.
The high surface of Gemini surface active agent and other special nature all have very big temptation to academia and business circles, and this field has caused scholars' common concern, and correlative study has been launched in aspects such as synthetic at it, character.(absorption, autohemagglutination and the character of Wang Yue star .Gemini surfactant. chemistry world, 2003,4:216-219; The gathering character of Zhu Sen .Gemini aqueous solution of anionic surfactant. Acta PhySico-Chimica Sinica, 2004,20 (10): 1245-1248; Zhao Jianxi. quaternary ammonium salt Gemini surfactant bactericidal activity and related with molecular structure thereof. applied chemistry, 2003,20 (12): 1208-1210; Luo Mingdao, Yan Xiaoci, Zhang Gaoyong. the research that concerns between the structure and properties of Gemini surface active agent. daily chemical industry, 2002,32 (3): 5-7; The water tinkling of pieces of jades, Zheng Liqiang, Zhao Jianxi etc. the interfacial activity research of Gemini surface active agent system. fine chemistry industry, 2001,18 (2): 67-69).
Gemini surface active agent is divided into anionic, cationic, nonionic and amphoteric ion type.Up to now, synthesize the Gemini surface active agent of kind more than 100 altogether, wherein the bibliographical information of synthetic, the performance of cationic Gemini surfactant, application facet research is maximum, has almost accounted for 2/3rds.Synthetic at present cationic Gemini surfactant mostly is quaternary.Because the Gemini surface active agent cost height that has been synthesized costs an arm and a leg, this has just limited its sizable application.
In petroleum works, particularly in the oil producing operation, need a large amount of surfactants that use.But also there are some shortcomings in the surfactant that uses at present.For example: the performance of some surfactants can not adapt to engine request, is difficult to realize ultralow surface (and/or interface) tension force, and salt-resistance is relatively poor, easily by surface of clay absorption or the like.Therefore, the surfactant of exploitation excellent combination property is the high-tech research problem that deep development utilizes petroleum resources.
The present invention mainly is by several cheap raw materials, desk study and synthetic a kind of surface-active height, good water solubility, acid and alkali-resistance, the two benzene sulfonate Gemini surface active agents of bis ether that anti-salt temperature resistance ability is good, expectation can be promoted the use of in oil field and other industry, to reach the purpose that reduces cost.For the deficiency that overcomes existing surfactant, increase the kind of Gemini surface active agent, satisfy of the requirement of different application condition for Gemini surface active agent, have realistic meanings.
Summary of the invention
One of purpose of the present invention provides the two benzene sulfonate Gemini surface active agents of a kind of novel bis ether, and this surfactant has better water solubility and surface-active, overcomes the deficiency of conventional surfactant aspect application performance.
Another object of the present invention is to provide the preparation method of the two benzene sulfonate Gemini surface active agents of this bis ether, and this method raw material is cheap and easy to get, the reaction condition gentleness, and the preparation method is simple, overcomes the some shortcomings in the Gemini surface active agent preparation.
For reaching above technical purpose, the invention provides following technical scheme.
The two benzene sulfonate Gemini surface active agents of a kind of novel bis ether are 2,2-two (4-alkoxyl-3-benzene sulfonic acid sodium salt) propane, and its structural formula is as follows:
n＝9，11，13，15
This surfactant brief note is DEDS, notes by abridging respectively as n=9,11,13,15 the time to be DEDS-10, DEDS-12, DEDS-14, DEDS-16.
The preparation method of the two benzene sulfonate Gemini surface active agents of a kind of bis ether, with industrial common chemical product 2,2-(4,4 '-the dihydroxy diphenyl) propane (abbreviation bisphenol-A) is for primary raw material prepares, and synthetic route comprises following three step chemical reactions:
(1) etherification reaction
n＝9、11、13、15
(2) sulfonating reaction
n＝9、11、13、15
(3) neutralization reaction
n＝9，11，13，15
This reacts raw materials used bisphenol-A, and is homemade for industrial common chemical product, chemical pure, and white particle, commercially available; Bromoalkane and chlorosulfonic acid, homemade, chemical pure, commercially available.
The preparation method of the two benzene sulfonate Gemini surface active agents of this bis ether may further comprise the steps successively:
(1) add the bisphenol-A and the NaOH aqueous solution in reactor, the mole of NaOH is 2.0-2.5 a times of bisphenol-A mole, stirs down at 50-78 ℃ it is fully reacted, and generates bis-phenol sodium;
(2) add absolute ethyl alcohol, chain alkyl bromine successively in reactor, the carbon number of chain alkyl bromine is respectively 10,12,14 or 16, and the mole of chain alkyl bromine is 2.0-2.4 a times of bis-phenol sodium mole, at 50-78 ℃ of following stirring reaction 12-36h;
(3) steam ethanol, with the product washing, recrystallization, vacuum drying promptly obtains pure two etherates;
(4) two etherates being poured in the reactor, is solvent with the carrene, drips mole then for two etherate 2.0-2.1 chlorosulfonic acid doubly, at 15-35 ℃ of following stirring reaction 1-3h, in reaction, with the HCl that produces in the NaOH aqueous solution absorption reaction;
(5) with the product neutralization, saltout, filter, vacuum drying promptly obtains this surfactant.
Violent and cause other side reaction in order to prevent that chlorosulfonic acid is added drop-wise to reaction in two etherates, two etherates are dissolved in carrene after, available trash ice with its cooling 10min after, drip chlorosulfonic acid again.The etherification reaction of bisphenol-A and bromoalkane, under identical temperature, productive rate is relevant with the length of the carbochain of bromoalkane, and in general, with the growth of carbon chain lengths, productive rate reduces.Solvent has considerable influence to etherification reaction, and experiment shows that in the system of ethanol as solvent, etherificate is more complete.Intermediate product 2, the degree that the sulfonating reaction of 2-two (4-alkoxyl phenyl)-propane is carried out is relevant with the carbon chain lengths and the temperature of alkyl, and in general, with the growth of alkyl carbon chain length, productive rate also reduces accordingly, and suitable raising temperature helps increasing productive rate.
This surfactant is the two benzene sulfonate surfactants of bis ether, in the molecule except containing hydrophilic radical sulfonate, also has the hydrophilic radical ether group, under the situation that does not influence the antiacid alkali ability of surfactant, increase the hydrophily of surfactant simultaneously, sulfonic group itself has very strong anti-salt property, and the introducing of phenyl ring has increased the rigidity of molecule.This surfactant has higher surface activity, foam stability and good synergistic, can be widely used in the production practices.
Compared with prior art, the present invention has following beneficial effect:
(1) method raw material provided by the invention is cheap and easy to get, does not need to add other auxiliary agent, and the reaction condition gentleness is easy and simple to handle, and reaction is carried out more complete, the product purity height;
(2) the two benzene sulfonate surfactants of bis ether provided by the invention are that existing surfactant has increased new varieties, for it selects to use the condition of having created in different working conditions;
(3) object surface-active of the present invention is good, and its ratio of the CMC conventional surfactants is hanged down 1～3 order of magnitude; Surface tension under the critical micelle concentration of DEDS-10 is 34.5mN/m, much smaller than conventional surfactants.
Description of drawings
Fig. 1 is DEDS-10 surfactant γ-C curve of the present invention (25 ℃)
Fig. 2 is a DEDS-10/DTAB aqueous solution surface tension curve of the present invention (25 ℃)
Fig. 3 is the infrared spectrum of DEDS-12 of the present invention
The specific embodiment
Further specify the present invention below by example
In being housed, the 250ml three-neck flask of agitator, thermometer adds bisphenol-A 4.5658g (0.02mol), 10%NaOH17.6g (containing NaOH0.044mol), fully react 30min down at 50-70 ℃, add the 60ml absolute ethyl alcohol then, add ten alkyl bromide 10.1798g (0.046mol), in 70 ℃ of waters bath with thermostatic control, react 24h.Reaction steams absolute ethyl alcohol after finishing, and washing product twice leaves standstill separatory then, gets the upper strata solid and is recrystallized with ethyl acetate and acetone mixed solvent, obtains white crystal, is 2,2-two (4-ten alkoxyl phenyls)-propane.Subnatant body and function AgNO
3Carry out titration, 2,2-two (4-ten alkoxyl phenyls)-propane yield is 98.5%, crystalline melt point is 35.7～36.1 ℃.
Get 2,2-two (4-ten alkoxyl phenyls)-propane 5.1029g (0.01mol) puts into there-necked flask, with the 25ml carrene it is dissolved, cool off 10min with trash ice then, chlorosulfonic acid 1.31ml (0.02mol) is dissolved in the 10ml carrene, dropwise slowly join in the there-necked flask, be no more than stirring reaction 2h under 25 ℃ the situation in temperature, in reaction, the HCl that will produce during the NaOH aqueous solution with 5% will react fully absorbs, after sulfonation finished, air-dry solvent under the normal pressure was to neutralize under 40 ℃ of conditions in temperature then, again product is saltoutd, filter, vacuum drying obtains final products.
Embodiment 2 DEDS-12's is synthetic
In being housed, the 250ml three-neck flask of agitator, thermometer adds bisphenol-A 4.5658g (0.02mol), 10%NaOH17.6g (containing NaOH0.044mol), fully react 30min down at 50-70 ℃, add the 60ml absolute ethyl alcohol then, add dodecyl bromide 11.4678g (0.046mol), in 60 ℃ of waters bath with thermostatic control, react 24h.Reaction steams absolute ethyl alcohol after finishing, and washing product twice leaves standstill separatory then, gets the upper strata solid and is recrystallized with ethyl acetate and acetone mixed solvent, obtains white crystal, is 2,2-two (4-dodecyloxy phenyl)-propane.Subnatant body and function AgNO
3Carry out titration, record 2,2-two (4-dodecyloxy phenyl)-propane yield is 89.3%, and crystalline melt point is 45.7～46.4 ℃.
Get 2,2-two (4-dodecyloxy phenyl)-propane 5.6629g (0.01mol) puts into there-necked flask, with the 30ml carrene it is dissolved, cool off 10min with trash ice then, dropwise slowly add the solution that the 1.31ml chlorosulfonic acid is dissolved in the 10ml carrene, stirring reaction 2h under temperature 20-35 ℃ situation, in reaction, the HCl that will produce during the NaOH aqueous solution with 5% will react fully absorbs, after sulfonation finished, air-dry solvent under the normal pressure was to neutralize under 40 ℃ of conditions in temperature then, saltout, filtration, vacuum drying, promptly obtain final products.
The surface-active of embodiment 3 DEDS series of surfactants is measured
The DEDS-10 aqueous solution of compound concentration 1.6mmol/L, measure surface tension with the JZhy1-180 interfacial tensimeter, dilute this solution then one by one, surface tension is for several times once measured in every dilution, obtains the (see figure 1) that concerns of DEDS-10 aqueous solution surface tension and concentration.The surface tension (γ cmc) that can be obtained by Fig. 1 under the critical micelle concentration of DEDS-10 is 34.5mN/m, and its critical micelle concentration is 0.47mmol/L.Compare with conventional surfactants, its surface-active has improved greatly.
The cooperative effect of embodiment 4 DEDS series of surfactants and conventional surfactants (is example with DTAB DTAB) is measured.
DEDS-10 and DTAB (DTAB) are seen Fig. 2 by the composite aqueous solution surface tension of different proportion and the relation of surfactant concentration.The preparation method of this figure is: DEDS-10 and DTAB are respectively by 1: 9,2: 8,3: 7 (mol ratio) prepares three groups of complexed surfactants, prepares the aqueous solution of 1mmol/L then separately, obtains the relation of each complexed surfactant solution surface tension and concentration by the method for embodiment 3.As seen from Figure 2, the critical surface tension after composite is all littler than two one pack systems with DTAB for DEDS-10, illustrates that the two has good cooperative effect, especially at DEDS-10: DTAB=3: 7 o'clock, best results.
The structural characterization of embodiment 5 DEDS series of surfactants
DEDS-12 is with the sample preparation of KBr compressing tablet, and the Paragon1000 infrared spectrometer of producing with PE company carries out infrared detection.DEDS-12 surfactant infrared spectrum is seen Fig. 3, is learnt by spectrum elucidation:
The ownership of each bands of a spectrum is as follows in the spectrogram: 2923.39cm
-1And 2852.96cm
-1Be respectively-CH
2Flexible and the flexible peak of symmetry of-antisymmetry; 1603.35cm
-1And 1490.27cm
-1Be phenyl ring skeletal vibration frequency; 1187.41cm
-1And 1094.05cm
-1Flexible and the flexible peak of symmetry for the antisymmetry of sulfonic acid; 1247.33cm
-1And 1034.81cm
-1For
The flexible and flexible absworption peak of symmetry of antisymmetry of C-O-C; 814.29cm
-1Be 1,2,4 to replace
The key band of hydrocarbon out-of-plane bending.
Claims (3)
1 one kinds of two benzene sulfonate Gemini surface active agents of novel bis ether are 2,2-two (4-alkoxyl-3-benzene sulfonic acid sodium salt) propane, and its structural formula is as follows:
n＝9，11，13，15。
2 surfactants as claimed in claim 1 is characterized in that, in the described surfactant structure formula, n is 9 or 11.
The preparation method of 3 surfactants as claimed in claim 1 may further comprise the steps successively:
(1) add the bisphenol-A and the NaOH aqueous solution in reactor, the mole of NaOH is 2.0-2.5 a times of bisphenol-A mole, stirs down at 50-78 ℃ it is fully reacted, and generates bis-phenol sodium;
(2) add absolute ethyl alcohol, chain alkyl bromine successively in reactor, the carbon number of chain alkyl bromine is respectively 10,12,14 or 16, and the mole of chain alkyl bromine is 2.0-2.4 a times of bis-phenol sodium mole, at 50-78 ℃ of following stirring reaction 12-36h;
(3) steam ethanol, with the product washing, recrystallization, vacuum drying promptly obtains pure two etherates;
(4) two etherates being poured in the reactor, is solvent with the carrene, and dripping mole is two etherate 2.0-2.1 chlorosulfonic acids doubly, at 15-35 ℃ of following stirring reaction 1-3h;
(5) with the product neutralization, saltout, filter, vacuum drying promptly obtains this surfactant.
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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 |
| CN101856600A (en) * | 2010-06-25 | 2010-10-13 | 西北大学 | Amphoteric ionic Gemini surfactant and synthetic method thereof |
| CN101480590B (en) * | 2008-11-27 | 2011-05-18 | 齐齐哈尔大学 | Sulphonate Gemini surfactant and preparation method thereof |
| CN102441338A (en) * | 2012-01-04 | 2012-05-09 | 西南石油大学 | Sulfonate aralkyl anionic-nonionic surfactant and synthesis method thereof |
| CN105435706A (en) * | 2015-11-16 | 2016-03-30 | 武汉工程大学 | Sulfonate-type anion dimeric surfactant and preparation method thereof |
| CN107384357A (en) * | 2017-06-14 | 2017-11-24 | 中国石油天然气股份有限公司 | Sub- surfactant of polyoxyethylene benzene sulfonic acid salt form Composite Double and preparation method thereof |
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| CN110218166A (en) * | 2019-06-12 | 2019-09-10 | 西南石油大学 | A kind of synthetic method of the bissulfosalt double surface active agent of bisamide base connection |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5585516A (en) * | 1995-03-10 | 1996-12-17 | Exxon Research And Engineering Company | Two tail-two head and two tail-one head surfactants |
| DE10205702A1 (en) * | 2001-02-13 | 2002-08-29 | Basf Ag | Hydroformylation of compounds containing ethylenically unsaturated double bond(s) comprises reacting with carbon monoxide and hydrogen in the presence of hydroformylation catalyst |
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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 |
| CN101480590B (en) * | 2008-11-27 | 2011-05-18 | 齐齐哈尔大学 | Sulphonate Gemini surfactant and preparation method thereof |
| CN101856600A (en) * | 2010-06-25 | 2010-10-13 | 西北大学 | Amphoteric ionic Gemini surfactant and synthetic method thereof |
| CN102441338A (en) * | 2012-01-04 | 2012-05-09 | 西南石油大学 | Sulfonate aralkyl anionic-nonionic surfactant and synthesis method thereof |
| CN105435706A (en) * | 2015-11-16 | 2016-03-30 | 武汉工程大学 | Sulfonate-type anion dimeric surfactant and preparation method thereof |
| CN107384357B (en) * | 2017-06-14 | 2019-10-11 | 中国石油天然气股份有限公司 | Polyoxyethylene-sub- surfactant of benzene sulfonic acid salt form Composite Double and preparation method thereof |
| CN107384357A (en) * | 2017-06-14 | 2017-11-24 | 中国石油天然气股份有限公司 | Sub- surfactant of polyoxyethylene benzene sulfonic acid salt form Composite Double and preparation method thereof |
| CN107674667A (en) * | 2017-11-05 | 2018-02-09 | 青岛大学 | A kind of surfactant compound system of the anti-high calcium magnesium salts of heatproof |
| CN107814755A (en) * | 2017-11-05 | 2018-03-20 | 青岛大学 | A kind of anionic gemini surfactant and preparation method thereof |
| CN107674667B (en) * | 2017-11-05 | 2020-04-03 | 青岛大学 | Temperature-resistant high-calcium magnesium salt-resistant surfactant compound system |
| CN107814755B (en) * | 2017-11-05 | 2021-10-29 | 青岛大学 | Anionic gemini surfactant and preparation method thereof |
| CN108383758A (en) * | 2018-03-19 | 2018-08-10 | 青岛大学 | A kind of preparation method of sulfonic group anionic gemini surfactant |
| CN108383758B (en) * | 2018-03-19 | 2021-10-29 | 青岛大学 | Preparation method of sulfonic anionic gemini surfactant |
| CN110218166A (en) * | 2019-06-12 | 2019-09-10 | 西南石油大学 | A kind of synthetic method of the bissulfosalt double surface active agent of bisamide base connection |
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