CN101279218A - Novel kation gemini surfactant and process for synthesizing the same - Google Patents

Novel kation gemini surfactant and process for synthesizing the same Download PDF

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CN101279218A
CN101279218A CNA2008100451693A CN200810045169A CN101279218A CN 101279218 A CN101279218 A CN 101279218A CN A2008100451693 A CNA2008100451693 A CN A2008100451693A CN 200810045169 A CN200810045169 A CN 200810045169A CN 101279218 A CN101279218 A CN 101279218A
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surfactant
gemini surfactant
toluene
tdi
reaction
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胡星琪
王东增
王梓民
黄俊莉
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Southwest Petroleum University
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Southwest Petroleum University
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Abstract

The invention relates to a novel cationic gemini surfactant used for the petroleum industry and a composition method thereof, which is provided in order to satisfy the requirements of the cationic gemini surfactant, proposed by different application conditions. The technical scheme is as follows: the cationic gemini surfactant is toluene-2, 4-diamino acid-N-dimethyl alkyl amidocyanogen ethyl ester; a drying reactor is firstly added with proper amount of acetone as a solvent, then is added with N, N-deanol and is dripped with 2, 4-TDI of a mol ratio of 2:1, all of which are stirred well and sealed for a rest at the room temperature and for a reaction for 6 hours; the solution is added with bromoalkane of the same molar weight as the 2, 4-TDI and is stirred, sealed and kept at a constant temperature of 45 DEG C for a water bath reaction for 12 hours; at last a solid product is acquired by drying at 80 DEG C. The surfactant has higher surface activity, excellent concertedness, simple composition method, mild reaction condition, high productive rate and good stability; besides, the surfactant can be used for producing household chemicals and for tertiary oil recovery.

Description

A kind of novel kation gemini surfactant and synthetic method thereof
Technical field
The present invention relates to a kind of novel kation gemini surfactant and synthetic method thereof that is used for the petroleum industry tertiary oil recovery and produces household chemicals such as high-duty detergent, solubilizer, emulsifying agent.
Background technology
Gemini (Shuangzi) surfactant is to be connected by chemical bond at ion head Ji Chu by two common strand single head based surfactants to form.This structure makes and more is easy to generate strong Van der Waals force between carbochain, and the distance between the ion head base has realized the tight arrangement on the gas-liquid interface of solution, thereby had higher surface-active because the syndeton of covalent bond makes it to reduce.
The U.S. Pat 2 of nineteen forty-six application, 524,218[Frederick C B, VeronaNJ.Washing Composition.US:2524218, (1950)], Frederick CBersworth etc. are for a kind of main huge legendary turtle of exploitation closed, the detergent builders of dispersion, wetting action, synthetic a series of compounds.Wherein have a kind of structural formula to be two carboxylate compounds, this compound is the Gemini surfactant of reporting the earliest.For the comparatively systematic research of Gemini surfactant then since the nineties.China is later relatively to the research of Gemini surfactant, the Zhao Jianxi of University of Fuzhou in 1999 [Zhao Jianxi, surfactant of new generation, chemical progress, 1999,11 (4)] external Gemini surface active agent has been carried out the summary of system, caused the attention of domestic correlative study unit.Cao Yafeng etc. [Cao Yafeng, two alkyl γ-bi-quaternary ammonium salts synthetic, surfactant industry, 1993,4 (3), 22-23] utilize the ring-opening reaction of tertiary amine and epoxychloropropane, and having prepared is the bi-quaternary ammonium salt compound that connects base with the hydroxypropyl.More and more to the research report of Gemini surfactant at present, because it has special performances, become the research focus of colloid and surface chemistry in recent years, receive much attention.
The main type of Gemini surface active agent has: anion, cation, nonionic and amphoteric ion type, such as: the two phenyl of single phenyl and vinyl are the phosphate type Gemini surface active agent of spacer group, with single phenyl is the quaternary ammonium salt type gemini surfactant of spacer group, is quaternary ammonium salt type gemini surfactant of spacer group etc. with the 2-propyl alcohol.Domestic research and external bigger gap in addition to Gemini surface active agent, but because high surface and other special natures of Gemini surface active agent all are a strong temptation to academia and business circles, this field has caused the common concern of domestic scholars, and correlative study has been launched in aspects such as synthetic at it, character.{ twin two connect quaternary surfactant [J], oilfield chemistry, 2001,12 (3): 278-290 for ability journey, Ge Jijiang; Luo Mingdao, Yan Xiaoci, Zhang Gaoyong, the research that concerns between the structure and properties of Gemini surface active agent [J], daily chemical industry, 2002,32 (3): 5-7; Fu Jifeng, Xu Baocai, Zhu Chenggen. the character of dimeric surfactant and application thereof [J], daily chemical industry, 2001,31 (5): 41-42; The Ikeda merit, Cui Zhenggang, the synthetic and performance (1) [J] of new type of Gemini cationic surfactant, daily chemical industry, 2001,31 (3): 27-30}.
The good water-soluble and hydrotropy, higher surface activity, the cooperative effect that Gemini surface active agent has is good, the good tackifying under the low concentration, better biocompatibility etc.But the external at present Gemini surface active agent of producing costs an arm and a leg, and the Gemini surface active agent kind of domestic-developed is limited.Current, the factor that the scale of restriction Gemini surface active agent is used is the cost of material height, and the preparation process productive rate is not high, is difficult to realize suitability for industrialized production, makes this type of surfactant promote the use of on a large scale and is restricted.
Summary of the invention
The objective of the invention is: in order to overcome the deficiency of existing surfactant, increase the kind of Gemini surface active agent, satisfy of the requirement of different application condition for Gemini surface active agent; Reach simultaneously that raw material is cheap and easy to get, the preparation method is simple, reaction condition is gentle, be easy to control, productive rate height, the spy provides a kind of novel kation gemini surfactant and synthetic method thereof.
In order to achieve the above object, the present invention is by the following technical solutions: a kind of novel kation gemini surfactant, its chemical name is a Toluene-2,4-diisocyanate, 4-diamino acid-N-dimethyl alkylamine base ethyl ester, brief note is for BG07, notes by abridging respectively as n=11,13,15 the time to be BG07-12, BG07-14, BG07-16;
Its structural formula is:
Figure A20081004516900051
Synthetic route is undertaken by following two step chemical reactions:
(1) ammonia esterification
(2) quaterisation
Figure A20081004516900062
The synthetic method of BG07 series of surfactants comprises following two steps:
(1) reactive urethane of isocyanates and hydramine
In the reactor of a drying, add an amount of acetone and make solvent, add N, N-dimethylethanolamine earlier, drip 2 again, the 4-toluene di-isocyanate(TDI), its consumption mol ratio is 2: 1, stirs, sealing back room temperature leaves standstill, reaction 6h gets intermediate product toluene 2,4-diamino acid-N-dimethylamino ethyl ester.
(2) preparation of BG07 series of surfactants
In above-mentioned solution, add and 2, the bromoalkane of 4-toluene di-isocyanate(TDI) equimolar amounts (n=11,13,15) stirs, and it is to react 12h in 45 ℃ the water bath with thermostatic control reaction that sealed reaction liquid is placed on temperature, and end product is through 80 ℃ of dry BG07 solids.
Compared with prior art, the present invention has following beneficial effect: (1) object surface-active of the present invention is good, and its critical micelle concentration is 1.0 * 10 -5MolL -1, much smaller than like product; Than low 3 orders of magnitude of common quaternary surfactant; (2) have good stable, the product room temperature is exposed to the several months in the air, but its cmc and corresponding γ CmcKeep initial value; (3) synthetic method of the present invention is simple, and synthesis program was made of ammonia esterification and two steps of quaterisation, used lower boiling acetone to make solvent, and is cheap, and the reaction condition gentleness is simple to operate; (4) Du Te synthetic order, productive rate is very high, and the gravimetric detemination value is more than 95%.High productive rate is to realize industrialized prerequisite.This surfactant can be applicable to produce household chemicals such as high-duty detergent, solubilizer, emulsifying agent, also can be used for alkali/surfactant binary combination flooding, alkali/surfactant/fields such as polymer ternary combination flooding in the tertiary oil recovery.
Description of drawings
Fig. 1 is the infrared spectrogram of surfactant B G07-14 of the present invention.
Fig. 2 is the nmr spectrum of surfactant B G07-14 of the present invention.
Fig. 3 is γ-C curve (20 ℃) of this surfactant B G07-14.
Fig. 4 is the γ-C curve (20 ℃) of this surfactant B G07 series.
Fig. 5 is that γ under this surfactant B G07-14 and the SDS optimal proportion-C schemes (20 ℃).
The specific embodiment
The present invention is described further below in conjunction with drawings and Examples.
Embodiment 1 ammonia esterification
Under the room temperature condition (25 ℃), in 250ml three neck round-bottomed flasks, add solvent acetone 17.5ml, drip N, N-dimethylethanolamine 5ml is after mixing, slowly add an amount of 2,4-toluene di-isocyanate(TDI) (TDI) 3.55ml (its mole is half of hydramine).Leave standstill after the sealing, normal-temperature reaction 6h gets final product, and product is light yellow liquid, slightly viscosity.
Embodiment 2 BG07's is synthetic
The example that synthesizes with BG07-14.Above-mentioned round bottom flask is gone in the water-bath, under the stirring condition, drip n-tetradecane base bromine 12.5ml (identical) with the mole of dimethylethanolamine.Sealing is stirred, and 45 ℃ of constant temperature reacted 12 hours, gets high viscosity yellowish-brown liquid.80 ℃ of oven dry get yellow solid and are BG07-14, and weighing is 21.4158～22.0544g (yield is 95～98%).
The surface-active of embodiment 3 BG07 series of surfactants is measured
Surface-active with BG07-14 is determined as example, Fig. 3.Critical surface tension (the γ of BG07-14 Cmc) be 21.9mNm -1, its critical micelle concentration is 1.0 * 10 -5MolL -1(as DTAB cmc is 1.6 * 10 with conventional surfactants -2MolL -1, γ CmcBe 40mNm -1) compare, its surface-active has improved greatly.
Embodiment 4 measures the cooperative effect of BG07-14 and conventional surfactants (with the dodecyl sodium sulfate is example, brief note SDS)
The total concentration of BG07-14 and SDS is 1mmolL -1The time, BG07-14 in solution surface tension and the compound system: the relation of SDS mol ratio, at BG07-14: SDS=1: minimum of a value occurs under 2 the condition.And under certain molar concentration, the surface tension of the complexed surfactant system aqueous solution is littler than the surface tension of one-component solution; And the surfactant compound system solution of above-mentioned optimal proportion is diluted one by one, measure the surface tension under each concentration, the results are shown in Figure 5, the cmc that can be got compound system by this figure is 1.33 * 10 -5MolL -1, γ CmcBe 19.8mNm -1Though its cmc slightly raises than BG07-14, γ Cmc2mN/m has descended again.This shows that BG07 and common anion surfactant have good composite character.
The structural characterization of embodiment 5 BG07 series of surfactants
The infrared spectrum of the BG07-14 surfactant that obtains by embodiment 1,2 is seen Fig. 1, is learnt by spectrum elucidation:
1727.84cm -1Stretching vibration peak show the existence of carbonyl; 818cm -1Near be 1,2, C-H outside sweep vibration peak on the 4-trisubstituted benzene ring; 1467.35,1537.69, and 1602.43cm -1It is the aromatic ring frame characteristic peak; 1231.21; 1075.09cm -1Be respectively C-O key SP 2And SP 3Flexible peak; 1280.87cm -1Show the existence of C-N key; 1537cm -1Characteristic peak for N-H; 2800～3000cm -1It is the peak of methyl and methylene.The nuclear magnetic resoance spectrum of BG07-14 surfactant is seen Fig. 2.
The chemistry checking of BG07 quaternary ammonium salt product:
In above-mentioned quaterisation, bromoalkane and ammonia esterification products react, and make the latter's tertiary amine group generation alkylated reaction generate the band quaternary ammonium salt, and the bromine of raw material bromoalkane exists with the covalency attitude, and the bromine in the product is converted into ionic state.Therefore, utilize Br -With Ag +Whether the chemical reaction that generates the AgBr yellow mercury oxide can carry out by confirmatory reaction.Experiment light-yellow precipitate occurred after finding to drip silver nitrate in the reaction system, we can say in the phaneroplasm system and carried out alkylated reaction, has obtained quarternary ammonium salt compound.
The object structural characterization
This research adopts infra-red sepectrometry that the various functional groups in the BG07-14 molecule have been carried out initial analysis.The object thing is made infrared analysis with the Paragon 100 type infrared spectrometers that PE company produces to product with the sample preparation of KBr compressing tablet, sees shown in Figure 1.
Know by infrared spectrum Fig. 1 analysis:
1727.84cm -1Stretching vibration peak for carbonyl;
1467.35,1537.69, and 1602.43cm -1It is aromatic ring frame stretching vibration characteristic peak;
818.897 and 878.212cm -1Be 1,2, C-H outside sweep vibration peak on the 4-trisubstituted benzene ring;
1231.21 and 1075.09cm -1Be respectively SP 2And SP 3The C-O key peak that stretches;
1280.87cm -1Be C-N key stretching vibration peak;
3422.33 and 1537cm -1Be respectively the characteristic peak of the flexible and flexural vibrations of N-H;
2956.79cm -1It is methyl asymmetric stretching vibration peak;
2923.84cm -1It is methylene asymmetric stretching vibration peak;
2853.07cm -1It is methylene symmetrical stretching vibration peak.
According to the map analysis of Fig. 2 nuclear magnetic resoance spectrum
End product BG07-14 D 2The O dissolving, TMS does interior mark, records 1HNMR wave spectrum (Fig. 6), in target molecule, each hydrogen atom correspondence is as follows:
Figure A20081004516900091
In Fig. 2, be D near δ=4.7 wherein 2The proton peak of O, all the other proton displacement δ are: a (0.833), b (1.225), c (1.535), d (2.987 ~ 3.078), e (3.223 ~ 3.682), f (4.479), g (6.8 ~ 7.7), h (2.123).The data cases of handling from spectrogram is as can be known: end product is consistent with the design object product.
The surface-active of object
Surface tension is the critical nature of liquid, and the capillary ability that surfactant reduces water is to estimate its surface-active important parameter.The full-automatic surface tension instrument of BZY-1 that this research uses Shanghai Hengping Instrument ﹠ Meter Plant to produce has carried out measuring (hanging the sheet method) to the surface tension of product solution under the serial variable concentrations, obtain this series of surfactants aqueous solution surface tension to the dependence of concentration (Fig. 3, Fig. 4).Curve break obtains critical micelle concentration value (cmc) and is～0.01mmolL from figure -1, less than DTAB (16mmolL -1) the cmc value 1/1000; Surface tension (γ under critical micelle concentration Cmc) be low also than the latter.Illustrate that gained object BG07 of the present invention has very high surface-active.
The composite character of object and dodecyl sodium sulfate
Studied the composite effect of BG07 and anion surfactant dodecyl sodium sulfate (SDS).Fig. 3 is that the surfactant total concentration is 1mmolL -1The time, the relation of the surface tension of the complexed surfactant aqueous solution and BG-7 and SDS ratio.The result shows that in research range, it is that BG07 appears at composite ratio with the composite best results value of anion surfactant SDS at 1: 2 o'clock.
To solution dilution metering surface tension one by one, obtain the dependence of the surface tension of the complexed surfactant aqueous solution to total concentration under best proportioning, the result as shown in Figure 4.
Turning point data by Fig. 5 can get, and at GB07-14: SDS=1: 2 o'clock, the cmc value of complexed surfactant solution was 1.33 * 10 -5MolL -1, γ CmcBe 19.8mNm -1Wherein the concentration of this Shuangzi is 1/3cmc, promptly 4.44 * 10 -6MolL -1Show that this product has composite preferably effect.

Claims (2)

1, a kind of novel kation gemini surfactant, it is characterized in that: its chemical name is a Toluene-2,4-diisocyanate, 4-diamino acid-N-dimethyl alkylamine base ethyl ester is noted by abridging and is BG07, notes by abridging respectively as n=11,13,15 the time to be BG07-12, BG07-14, BG07-16; Its structural formula is:
Figure A20081004516900021
Synthetic route comprises following two response procedures, and equation is as follows:
(1) ammonia esterification
(2) quaterisation
Figure A20081004516900023
2, cation Gemini surfactant according to claim 1, it is characterized in that: the synthetic method of this cation Gemini surfactant, comprise following two steps, the reactive urethane of first step isocyanates and hydramine, in the reactor of a drying, add an amount of acetone and make solvent, add N earlier, the N-dimethylethanolamine drips 2 again, the 4-toluene di-isocyanate(TDI), its consumption mol ratio is 2: 1, stir, sealing back room temperature leaves standstill, reaction 6h, get intermediate product toluene 2,4-diamino acid-N-dimethylamino ethyl ester; The preparation of the second step BG07 series of surfactants, in above-mentioned solution, add and 2, the bromoalkane of 4-toluene di-isocyanate(TDI) equimolar amounts, its n=11,13,15, stir, it is to react 12h in 45 ℃ of waters bath with thermostatic control that sealed reaction liquid is placed on temperature, and end product is through 80 ℃ of dry BG07 solids that get.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101766972B (en) * 2009-01-07 2012-11-14 湖北大学 Preparation method of asymmetric cationic surfactant
CN103406065A (en) * 2013-08-20 2013-11-27 齐齐哈尔大学 Novel amido-linkage imidazolium salt gemini surfactant and preparation method thereof
CN105797643A (en) * 2016-03-30 2016-07-27 四川大学 Method for preparing non-ionic polyurethane Gemini surfactant
CN110950785A (en) * 2019-11-26 2020-04-03 陕西科技大学 Twin-tail hook type viscoelastic surfactant gel, preparation method thereof and gel removing method
CN111117787A (en) * 2019-12-23 2020-05-08 万华化学集团股份有限公司 Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent
CN116165196A (en) * 2023-04-13 2023-05-26 河南心连心化肥检测有限公司 Method for detecting cyanuric acid in high-purity urea

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101766972B (en) * 2009-01-07 2012-11-14 湖北大学 Preparation method of asymmetric cationic surfactant
CN103406065A (en) * 2013-08-20 2013-11-27 齐齐哈尔大学 Novel amido-linkage imidazolium salt gemini surfactant and preparation method thereof
CN103406065B (en) * 2013-08-20 2015-04-15 齐齐哈尔大学 Novel amido-linkage imidazolium salt gemini surfactant and preparation method thereof
CN105797643A (en) * 2016-03-30 2016-07-27 四川大学 Method for preparing non-ionic polyurethane Gemini surfactant
CN110950785A (en) * 2019-11-26 2020-04-03 陕西科技大学 Twin-tail hook type viscoelastic surfactant gel, preparation method thereof and gel removing method
CN110950785B (en) * 2019-11-26 2021-10-01 陕西科技大学 Twin-tail hook type viscoelastic surfactant gel, preparation method thereof and gel removing method
CN111117787A (en) * 2019-12-23 2020-05-08 万华化学集团股份有限公司 Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent
CN111117787B (en) * 2019-12-23 2021-05-14 万华化学集团股份有限公司 Bactericidal acaricidal surfactant, preparation method thereof and laundry detergent
CN116165196A (en) * 2023-04-13 2023-05-26 河南心连心化肥检测有限公司 Method for detecting cyanuric acid in high-purity urea
CN116165196B (en) * 2023-04-13 2023-08-29 河南心连心化肥检测有限公司 Method for detecting cyanuric acid in high-purity urea

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