CN101966437A - Sulphobetaine ampholytic gemini surfactant and synthesis method thereof - Google Patents
Sulphobetaine ampholytic gemini surfactant and synthesis method thereof Download PDFInfo
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- CN101966437A CN101966437A CN201010503050.3A CN201010503050A CN101966437A CN 101966437 A CN101966437 A CN 101966437A CN 201010503050 A CN201010503050 A CN 201010503050A CN 101966437 A CN101966437 A CN 101966437A
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Abstract
The invention discloses a sulphobetaine ampholytic gemini surfactant. The surfactant is an N,N'-sulphobetaine compound. The invention discloses a preparation method for the surfactant at the same time. The preparation method comprises the following synthesis routes of: performing substitution reaction on aliphatic diamine and long-chain bromoalkane to generate an intermediate product, and performing quaternization reaction on the intermediate product and 1,3-propane sultone or 1,4-butane sultone to generate a target product. The sulphobetaine ampholytic gemini surfactant is systematically researched, the final product is synthesized, and the surfactant is specifically applied in solving the problem of little research on the surfactants; the target product has good surface performance, the critical micelle concentration of the target product is 2 to 3 magnitude orders lower than that of a corresponding single-chain surfactant, and the surface tension of the target product under the critical micelle concentration is 26.47mN/m and is far lower than that of the corresponding single-chain surfactant.
Description
Technical field
The present invention relates to a kind of Gemini surface active agent, concrete is a kind of amphoteric gemini surfactant, and the synthetic method of this amphoteric gemini surfactant.
Background technology
Shuangzi (Gemini) surfactant is to have two hydrophobic chains, the surfactant of the special construction of two hydrophilic radicals and a spacer group, it synthesizes and performance study is the research focus of surfactant research field always, but the research of this type of activating agent at present mainly concentrates on the synthetic and performance study of cation and anion Gemini surfactant, synthetic and the structure activity study of above-mentioned two class Gemini surfactants is reported more, Zhao Jianxi (the research and development direction [J] of Gemini surfactant. meticulous and specialty chemicals, 2008,16 (2): 14-19.) wait respectively the synthetic of this two class Gemini surfactant summarized with structure-activity relationship, but less about the synthetic and performance study report of both sexes Gemini surfactant.2000, (Peresypkin A V such as Menger, Menger F M.Zwitterionic Gemini Coacervate Formation from a Single Organic Compound[J] .Organic Letters, 1999,1 (346): 1347-1350.) synthesized the both sexes Gemini surfactant of phosphorous acidic group and quaternary ammonium salt, belong to the phosphonate ester betaine type, synthetic similar to common betaine type; Seredyuk (V.Seredyuk, E.Alami, M.Nyden, etal.Adsorption of zwitterionic gemini surfactants at the air-water and solid-water interfaces[J] .Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2002 (203): 245-258.) grade synthesizes the both sexes Gemini surfactant of four kinds of phosphonic acid esters and its interface performance is studied, the result shows, under the lower condition of surfactant concentration (critical micelle concentration), for symmetry structure both sexes Gemini surfactant with tight arrangement and gas-liquid interface, asymmetry structure both sexes Gemini surfactant then rarefaction is arranged, and surfactant molecule tends to monolayer and aligns when hydrophobic chain length is suitable.Kummar (A.Kumar, E.Alami, K.Holmberget al.Branched zwitterionic gemini surfactants micellization and interaction with ionicsurfactants[J] .Colloids and Surfaces A:Physicochem.Eng.Aspects 2003 (228): 197-207.) grade has been synthesized the phosphonic acid ester both sexes Gemini surfactant that has branched structure, result of study shows, have branched structure both sexes Gemini surfactant micelle turn into and the surface tension reduction aspect be better than straight chain both sexes Gemini surfactant; Bright (the Yu Junming of domestic monarch Yu, Chen Hongling, Wei Yabing. the synthetic and performance [J] of novel gemini amphoteric surfactant. Nanjing University of Technology's journal, 2005,27 (5): 62-66.), Jiang Huiliang (Jiang Huiliang, Dan Cuicui, Fang Yinjun. the study on the synthesis of new type of Gemini amphoteric surfactant [J]. chemical reagent, 2008,30 (11): 839～841.), Zheng Yancheng (Zheng Yancheng, Korea Spro's winter, Yang Puhua, etc. the oil field is with the synthetic of both sexes twin surfactant and characterize [J]. petroleum gas journal (Jianghan Petroleum College's journal), 2006,28 (3): 126-128.) wait also it is syntheticly studied with performance, and obtained certain progress.
Although amphoteric gemini surfactant has been carried out certain research both at home and abroad, less for the research of sulfobetaines type Gemini surface active agent, make the application of such surfactant be subjected to certain restriction.
Summary of the invention
The object of the present invention is to provide a kind of sulfobetaines type amphoteric gemini surfactant, this surfactant has excellent surface property, good foam enhancing performance, foam stability energy and interface performance.
Another object of the present invention is to provide the synthetic method of this Shuangzi amphoteric surfactant.
In order to realize the foregoing invention purpose, the technical scheme that the application adopted is as follows: 1. sulfobetaines type amphoteric gemini surfactant is a kind of N, N '-sulfobetaines compound, and its structural formula is as follows:
Wherein: m is 3 or 4; N is 8～18 even number; R is-CH
3Or-CH
2CH
3
2. synthetic volume and the mass ratio according to absolute ethyl alcohol and aliphatic diamine that the preparation method of above-mentioned sulfobetaines type amphoteric gemini surfactant may further comprise the steps (1) intermediate is the ratio of 1.0L: 1.0mol, and aliphatic diamine: NaOH: the ratio of the mol ratio of long-chain bromoalkane=1: 2: 2, aliphatic diamine is dissolved in the absolute ethyl alcohol, stirs and be warming up to 50 ℃; Add NaOH after stirring, drip the long-chain bromoalkane, after dropwising, the control reaction temperature is no more than 80 ℃, continues to react after 12～24 hours, steams absolute ethyl alcohol, and decompression distillation promptly gets intermediate; Above-mentioned aliphatic diamine preferably adopts N, N '-dimethyl-ethylenediamine, and the long-chain bromoalkane preferably adopts bromotetradecane; (2) the synthetic volume and the mass ratio according to acetone and intermediate of target product is the ratio of 1.0L: 1.0mol, getting intermediate is dissolved in the acetone, add 3 times to 1 of intermediate mole, 3-propane sultone or 1,4-butane sultone, after stirring, be warming up to backflow, under reflux temperature, continue reaction after 12～48 hours, steam acetone, with methyl alcohol and acetone solvent recrystallization, get the white powder solid and be sulfobetaines type amphoteric gemini surfactant.
Above-mentioned synthetic method, use chemical equation to represent that its synthetic route is as follows: 1, substitution reaction:
2, quaterisation:
Beneficial effect of the present invention: the synthetic method of the long alkyl carbon chain sulfobetaines type Shuangzi amphoteric surfactant that (1) the present invention proposes, do not appear in the newspapers at present; (2) synthetic method of the present invention is simple, the reaction condition gentleness, and accessory substance is few, is easy to separate; (3) target product surface property of the present invention is good, low 2～3 orders of magnitude of the corresponding single linked list surface-active agent of its critical micelle concentration, and the surface tension under the critical micelle concentration is 26.47mN/m, far below corresponding single linked list surface-active agent.
Description of drawings
Fig. 1: the frothing capacity result of GS 14-4.
The specific embodiment
The present invention is described further below in conjunction with specific embodiment: the raw materials used N of the present invention, N '-dimethyl-ethylenediamine, N, N '-diethyl ethylenediamine, long-chain bromoalkane are homemade AR, 1,3-propane sultone and 1,4-butane sultone are homemade industrial goods.
Embodiment 1,1, synthesizing of two [N-methyl-N-(4-sulphur butyl)-myristyl ammonium] the ethyl betaine Shuangzi amphoteric surfactantes of 2-: one, intermediate (N, N '-(two) myristyl-N, synthesizing N '-dimethyl-ethylenediamine): reflux condensing tube is being housed, magnetic stirring apparatus, constant pressure funnel, add 0.2mol (8.00g) NaOH and 100ml absolute ethyl alcohol in the 250ml four-hole reaction bulb of thermometer, 45 ℃ fully the dissolving after, add 0.1mol (8.80g) N, in N '-dimethyl-ethylenediamine reactor, after dropping in the system, the interior bromotetradecane with 0.2mol (55.46g) of 3h is warming up to backflow 48h.After reaction finishes, system is cooled to room temperature, after the solids removed by filtration, be warming up to 100 ℃ of vacuum rotary steams, filter, add an amount of absolute ethyl alcohol, repeat aforesaid operations to do not have solid separate out end intermediate N, N '-(two) myristyl-N, N '-dimethyl-ethylenediamine, intermediate is a colourless transparent liquid, and productive rate is 79.40%; Two, target product (1, synthesizing two [N-methyl-N-(4-sulphur butyl)-myristyl ammonium] the ethyl betaines of 2-): the N that takes by weighing 27.01g, N '-(two) myristyl-N, 1 of N '-dimethyl-ethylenediamine and 29.93g, the 4-butane sultone places reflux condensing tube is housed, magnetic stirring apparatus, constant pressure funnel, in the 250ml four-hole bottle of thermometer, 100ml acetone is as reaction dissolvent, stir, be warming up to backflow, be cooled to room temperature behind the reaction 40h, vacuum rotary steam is removed solvent acetone, the adularescent solid is separated out, and filters the acetone washing leaching cake, the volume ratio that adopts mixed solvent acetone and methyl alcohol is that 3: 7 recrystallizations are purified, filter, vacuum drying promptly gets white solid 1 to constant weight, two [N-methyl-N-(4-sulphur butyl)-myristyl ammonium] the ethyl betaine Shuangzi amphoteric surfactantes (GS 14-4) of 2-, productive rate is 75.59%.
The structural characterization of embodiment 2, target product: table 1 GS14-4's
1H NMR composes parsing
The above results shows that synthetic target product structure conforms to project organization.
Embodiment 3, Ross-Miles measure GS 14-4 foaming properties and test: experimental technique is under (45 ± 0.5) ℃ condition in temperature, the 200mL sample solution is flowed down from the pore of high 900mm, internal diameter 2.9mm, pour in the sample solution that 50mL has uniform temp and same concentrations, write down foam height when having flowed 200mL solution as the foamability evaluation index of detected sample, the different foam heights constantly in back of bubbling are as the evaluation index of foam stability, and experimental result is seen Fig. 1.
Frothing capacity to the amphoteric gemini surfactant GS 14-4 among the embodiment 1 experimentizes, the result as shown in Figure 1, increase along with GS 14-4 concentration, foam height increases gradually, but after concentration is greater than 0.15%, foam height increases hardly, and the concentration that the GS 14-4 that is developed is described is all to have in 0.10%～0.20% o'clock to bubble preferably and the foam stability energy.
Embodiment 4,1, two [N-methyl-N-(4-sulphur butyl)-myristyl ammonium] the ethyl betaine Shuangzi amphoteric surfactant interface performance experiments of 2-: preparation series concentration GS 14-4 surfactant solution sample shakes up set aside for use.Extract distilled water and solution to be measured respectively with syringe, clean capillary 3～4 times.Capillary is filled with solution to be measured, inject Daqing oil field oil extraction No.1 Factory dehydration degassed crude 0.6? L.Rapidly capillary is installed on Texas 500 interfacial tensimeters that are preheating to 45 ℃, shape according to oil droplet is turned speed, width when the length 〉=4 times oil droplet of oil droplet is elongated, width when the record oil droplet elongates and rotating speed by formula calculate interfacial tension: γ=(ρ to stable reading
w-ρ
o) r Δ d
3/ T
2In the formula :-interfacial tension, mN/m;-instrument multiplication factor (0.5615);-oil droplet width, mm;-swing circle, ms/r;-water oil density poor (0.1643g/cm3).
Experimental result sees the following form 2: table 2GS 14-4 Surfactants at Interface performance study result
By to GS 14-4 Surfactants at Interface performance study as can be known, GS 14-4 surfactant solution that is synthesized and Daqing oil field oil extraction No.1 Factory crude oil can reach ultralow interfacial tension scope (10
-3MN.m
-1), illustrate that the GS 14-4 surfactant that is synthesized has excellent interface performance, can be applicable to the tertiary oil production in oil field field.
Gemini surface active agent has low cmc and high surface in theory, makes it can reach ultralow interfacial tension under littler concentration, can increase substantially oil displacement efficiency; Again because Gemini surface active agent contains two hydrophilic head bases, so Gemini surface active agent has better water-solublely, compares with conventional surfactants and to have better salt tolerance; The required Gemini surface active agent concentration ratio conventional surfactant of solubilising same amount crude oil is much lower, and this has potential meaning for the microemulsion flooding technology; Under finite concentration, the solution of Gemini surface active agent has shear thinning behavior, and viscosity is low under the high shear, easy infusion, and network structure forms again under the low flow velocity in depths, stratum, and viscoelasticity recovers, and is conducive to enlarge displacement of reservoir oil swept volume; Better with other oil displacement assistant compatibilities, therefore can reduce Gemini surface active agent practical application cost.
Claims (4)
1. a sulfobetaines type amphoteric gemini surfactant is a kind of N, N '-sulfobetaines compound, and its structural formula is as follows:
Wherein: m is 3 or 4; N is 8～18 even number; R is-CH
3Or-CH
2CH
3
2. according to the described sulfobetaines type of claim 1 amphoteric gemini surfactant, it is characterized in that: n=14 in the described surfactant structure formula.
3. prepare the method for the described sulfobetaines type of claim 1 amphoteric gemini surfactant, may further comprise the steps:
(1) intermediate is synthetic
Volume and mass ratio according to absolute ethyl alcohol and aliphatic diamine are the ratio of 1.0L: 1.0mol, and aliphatic diamine: NaOH: the ratio of the mol ratio of long-chain bromoalkane=1: 2: 2, aliphatic diamine is dissolved in the absolute ethyl alcohol, and stir and be warming up to 50 ℃; Add NaOH after stirring, drip the long-chain bromoalkane, after dropwising, the control reaction temperature is no more than 80 ℃ and continues to react after 12～24 hours, steams absolute ethyl alcohol, promptly gets intermediate after the decompression distillation;
(2) target product is synthetic
Volume and mass ratio according to acetone and intermediate are the ratio of 1.0L: 1.0mol, getting intermediate is dissolved in the acetone, add 3 times to 1 of intermediate mole, 3-propane sultone or 1,4-butane sultone, after stirring, be warming up to backflow, under reflux temperature, continue reaction after 12～48 hours, steam acetone, with methyl alcohol and acetone solvent recrystallization, get the white powder solid and be sulfobetaines type amphoteric gemini surfactant.
4. according to the synthetic method of the described sulfobetaines type of claim 3 amphoteric gemini surfactant, it is characterized in that: aliphatic diamine is N, N '-dimethyl-ethylenediamine.
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Cited By (10)
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| CN102351749A (en) * | 2011-08-05 | 2012-02-15 | 蚌埠丰原医药科技发展有限公司 | Benzenesulphonate anionic gemini surfactant and preparation method thereof |
| CN103173198A (en) * | 2013-04-07 | 2013-06-26 | 陕西省石油化工研究设计院 | Amphoteric gemini surfactant capable of being used as oil displacement agent |
| CN104263341A (en) * | 2014-08-08 | 2015-01-07 | 中国石油天然气股份有限公司 | Anionic and cationic surfactant compound mixture and preparation method thereof |
| CN105218410A (en) * | 2015-09-11 | 2016-01-06 | 江苏振宇环保科技有限公司 | A kind of preparation method of novel sulfobetaine type Gemini surface active agent |
| CN105884661A (en) * | 2016-06-14 | 2016-08-24 | 陕西省石油化工研究设计院 | Method for preparing ternary mixed solvent and method for preparing amphoteric gemini surfactant from ternary mixed solvent |
| CN106835719A (en) * | 2017-02-10 | 2017-06-13 | 深圳天鼎新材料有限公司 | A kind of betaine type amphoteric silicone softening agent and preparation method thereof |
| CN110683991A (en) * | 2019-10-11 | 2020-01-14 | 东北石油大学 | Gemini ionic liquid surfactant, synthetic method thereof and oil displacement system |
| CN112521316A (en) * | 2020-11-05 | 2021-03-19 | 中国石油集团渤海钻探工程有限公司 | Gemini surfactant type clay stabilizer and preparation method thereof |
| CN114921008A (en) * | 2022-07-09 | 2022-08-19 | 山东奥格新材料创新中心有限公司 | Production method of reinforced carboxylic acrylonitrile butadiene latex |
| CN116376087A (en) * | 2023-05-04 | 2023-07-04 | 江苏海洋大学 | Hydrophilic antibacterial antifouling modification method for polyurethane material surface |
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| CN101607183A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院成都有机化学有限公司 | Carboxylic acid betaine type gemini surfactant and preparation method |
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| CN102351749B (en) * | 2011-08-05 | 2013-06-12 | 蚌埠丰原医药科技发展有限公司 | Benzenesulphonate anionic gemini surfactant and preparation method thereof |
| CN102351749A (en) * | 2011-08-05 | 2012-02-15 | 蚌埠丰原医药科技发展有限公司 | Benzenesulphonate anionic gemini surfactant and preparation method thereof |
| CN103173198A (en) * | 2013-04-07 | 2013-06-26 | 陕西省石油化工研究设计院 | Amphoteric gemini surfactant capable of being used as oil displacement agent |
| CN104263341B (en) * | 2014-08-08 | 2017-07-07 | 中国石油天然气股份有限公司 | Cationic-anionic surfactants compounding mixture and preparation method thereof |
| CN104263341A (en) * | 2014-08-08 | 2015-01-07 | 中国石油天然气股份有限公司 | Anionic and cationic surfactant compound mixture and preparation method thereof |
| CN105218410A (en) * | 2015-09-11 | 2016-01-06 | 江苏振宇环保科技有限公司 | A kind of preparation method of novel sulfobetaine type Gemini surface active agent |
| CN105884661A (en) * | 2016-06-14 | 2016-08-24 | 陕西省石油化工研究设计院 | Method for preparing ternary mixed solvent and method for preparing amphoteric gemini surfactant from ternary mixed solvent |
| CN106835719A (en) * | 2017-02-10 | 2017-06-13 | 深圳天鼎新材料有限公司 | A kind of betaine type amphoteric silicone softening agent and preparation method thereof |
| CN110683991A (en) * | 2019-10-11 | 2020-01-14 | 东北石油大学 | Gemini ionic liquid surfactant, synthetic method thereof and oil displacement system |
| CN110683991B (en) * | 2019-10-11 | 2023-05-09 | 东北石油大学 | Gemini ionic liquid surfactant, synthesis method thereof and oil displacement system |
| CN112521316A (en) * | 2020-11-05 | 2021-03-19 | 中国石油集团渤海钻探工程有限公司 | Gemini surfactant type clay stabilizer and preparation method thereof |
| CN114921008A (en) * | 2022-07-09 | 2022-08-19 | 山东奥格新材料创新中心有限公司 | Production method of reinforced carboxylic acrylonitrile butadiene latex |
| CN114921008B (en) * | 2022-07-09 | 2022-11-22 | 山东奥格新材料创新中心有限公司 | Production method of reinforced carboxylic acrylonitrile butadiene latex |
| CN116376087A (en) * | 2023-05-04 | 2023-07-04 | 江苏海洋大学 | Hydrophilic antibacterial antifouling modification method for polyurethane material surface |
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Application publication date: 20110209 |