CN105327653A - High water solubility cationic gemini surfactant, and preparation method thereof - Google Patents
High water solubility cationic gemini surfactant, and preparation method thereof Download PDFInfo
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- CN105327653A CN105327653A CN201510675959.XA CN201510675959A CN105327653A CN 105327653 A CN105327653 A CN 105327653A CN 201510675959 A CN201510675959 A CN 201510675959A CN 105327653 A CN105327653 A CN 105327653A
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Abstract
The invention discloses a high water solubility cationic gemini surfactant, and a preparation method thereof. The chemical formula of the high water solubility cationic gemini surfactant is N,N,N',N'-tetra-hydroxyethyl-N,N'-dialkyl-2-hydroxyl propane diamine. The high water solubility cationic gemini surfactant is capable of realizing mutual dissolution with water, possesses relatively high surface activity and relatively low critical micelle concentration (CMC), CMC is 7.4*10<-4>mol/L, gamma(CMC) is 29mN/m<-1>, the high water solubility cationic gemini surfactant is capable of reducing surface resistance of fabric effectively, and possesses excellent antistatic properties. Raw materials needed by the preparation method are cheap and easily available; reaction conditions are mild; reaction is safe; and the preparation method is suitable for industrialized production.
Description
Technical field
The present invention relates to activating agent field, be specifically related to a kind of highly-water-soluble cation Gemini surfactant and preparation method thereof.
Background technology
Gemini surface active agent, also referred to as dimeric surfactant, refers to the surfactant that the class that two conventional surfactants molecules is formed by connecting with chemical bond in the position of its hydrophilic head base or close head base by linking group is novel.Compared with traditional single linked list surface-active agent, Gemini surface active agent has the character such as extremely low CMC, higher surface-active, multiple accumulation shape, special phase behavior and rheology.CMC as cation Gemini surfactant is 1/20 of corresponding conventional surfactant,
cMCabout 10mNm lower than conventional surfactant
-1, cation Gemini surfactant also has the thickening property that conventional surfactant does not have simultaneously.The high surface of Gemini surface active agent makes surfactant consumption in the application greatly reduce, thus indirectly can reduce the use amount of petrochemical materials, the pollution simultaneously also reduced environment because of the minimizing of surfactant use amount.The performance of these excellences becomes the new direction of the exploitation of the surfactant of 21st century just, is described as " surfactant of 21st century " by scientist.
The physical and chemical performance that Gemini surface active agent is good imply that good application prospect, and therefore, the application relevant for it also has large quantifier elimination.As: cation Gemini surfactant has good bactericidal property (applied chemistry (2003) 20-12, the 1208-1210 such as Zhao Jianxi); The coordinative role (K.TsuboneJournalofColloidandInterfaceScience (2003) 524-528) good with conventional surfactant; Can be used as Gene transfer vector (C.Bombelli; JournalofMedicalChemistry. (2005) 48,5378-5382); Tertiary oil recovery rate (oil-gas geology and recovery ratio (2003) 10, the 59-61 such as Wang Haifeng) etc. is improved in oil recovery.In addition, Gemini surface active agent also shows good application prospect in fields such as emulsion polymerisation, micellar catalysis, mesoporous materials.
Although carried out large quantifier elimination to Gemini surface active agent both at home and abroad, because the manufacturing condition General Requirements of Gemini surface active agent is harsher, complex operation, this Gemini surface active agent kind making it possible to realize suitability for industrialized production is few.Although wherein m-n-m type cation Gemini surfactant obtains suitability for industrialized production at home, but due to it, dissolubility is poor at normal temperatures, good synergistic function is shown when low concentration is composite with conventional anion surfactant, but easily form precipitation when high concentration, therefore, this kind of surfactant is applied more in laboratory research, and applies less in actual industrialization is produced.
Summary of the invention
In order to improve the dissolubility of cation Gemini surfactant, strengthen itself and conventional anion surfactant complex role in higher concentrations, the present invention is on the basis of m-n-m type Gemini surface active agent, design and synthesize out the cation Gemini surfactant of hydroxyl, research shows the good antistatic property that this surfactant has good surface-active, has good compound property and itself have with conventional surfactant when high concentration.This surfactant has good effect for the usefulness of raising conventional surfactant in industrial and agricultural production.Have an important significance realizing the composite application in actual production of zwitterion simultaneously.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of highly-water-soluble cation Gemini surfactant, the chemical formula of described activating agent is: N, N, N ', N '-four ethoxy-N, N '-dialkyl group-2-hydroxyl propane-diammonium, brief note DHGS, its structural formula is as follows:
n＝11，13，15，17。DHGS is white easily moisture absorption type solid, belongs to cation Gemini surfactant, has fabulous dissolubility in water.
The preparation method of above-mentioned a kind of highly-water-soluble cation Gemini surfactant, comprises the steps:
S1, in the reactor of a drying, add alkyldiethanolamine and the chloro-2-propyl alcohol of 1,3-bis-that mol ratio is 2: 1, appropriate solvent and KI or sodium iodide, stir, react 24-48 hour, obtain reactant liquor at 120-130 DEG C;
S2, reactant liquor is dry, obtain red brown solid;
S3, by this solid anhydrous alcohol solution, then use re-crystallizing in ethyl acetate, obtain white solid, solid is dried, and obtains pure DHGS.
Wherein, described solvent is the one in dimethyl formamide or dimethyl sulfoxide (DMSO), and addition is 1/3 to 2/3 of reactant quality.
Wherein, the addition of described KI is the 0.3%-0.5% of reactant quality.
This preparation method belongs to the quaternary ammonium reaction of alkyldiethanolamine and alkyl halide, and the reaction time is fixed with alkyl carbon chain lengths, and in general, increase with carbon chain lengths, the reaction time also increases accordingly.This reaction is nucleophilic substitution, and reaction rate is accelerated with the polarity increase of solvent.So this reaction selects methyl alcohol as solvent usually, although the polarity of water is very high, remove more difficult after the reaction.When selecting dichlorohydrin as reactant, can add a small amount of KI or sodium iodide as catalyst to improve reaction rate, react completely, do not need to add other auxiliary agent, reaction condition is gentle.
The surfactant of gained of the present invention contains hydroxyl due to polar head, therefore hydration when surfactant is assembled between polar head-group is strong, and surface tension test shows the CMC/C of this kind of surfactant
20be worth very large, illustrate that DHGS easily at solution interface, absorption occurs and is not easy to be formed micella, thus can better reduce solution interface tension force, simultaneously due to the strong hydration of polar head, make DHGS can carry out composite with other conventional anion surfactants, show good synergy, daily chemical industry and other production practices can be widely used in.This surfactant effectively can improve the performance of conventional anion surfactant, reduces the consumption of surfactant in industrial and agricultural production, realizes the energy-saving and emission-reduction of surfactant in chemical industry
The present invention has following beneficial effect:
(1) needed raw material is cheap and easy to get, and reaction condition is gentle, easy to operate, and reaction is carried out completely, the easy purifying of product;
(2) gained surfactant has extremely low critical micelle concentration and reduces the ability of solution interface tension force preferably:
(3) for surfactant adds new kind, under different operating situation, selective gist creates condition.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the product of embodiment of the present invention gained.
Detailed description of the invention
In order to make objects and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
N, N, N ', the preparation of N '-four ethoxy-N, N '-bis-dodecyl-2-hydroxyl propane-diammonium
173g dodecyl diethanol amine, 42g1 is added in a drying receptacle, the chloro-2-propyl alcohol of 3-bis-and 0.6gKI, 120mlN, dinethylformamide, adds hot reflux 24 hours at 130 DEG C, cooling, pressure reducing and steaming dimethyl formamide, obtains rufous DHGS crude product, and take a morsel crude product anhydrous alcohol solution, use re-crystallizing in ethyl acetate again, obtain white easily hygroscopic solid.
Embodiment 2
The structural characterization of products surfactants
Synthetic product, with the sample preparation of KBr salt sheet, makes infrared analysis with NICOLETMX-1EFT-IR type infrared spectrometer.The infrared spectrogram of the product prepared with example 2 as indicated with 1.
Analysis spectrogram obtains following result:
3386.4cm
-1the strong absworption peak at place is O-H stretching vibration absorption band, illustrates containing water in this compound, 2921.7cm
-1strong absworption peak is that the c h bond in methyl and methylene is symmetrical with asymmetric stretching vibration absorption band, 721.3cm
-1for-the CH of methylene
2the swing vibration absorption band of-plane.
Embodiment 3
The Physickemical Properties of DHGS surfactant
Measure critical micelle concentration and the surface tension of the surfactant D HGS of preparation in embodiment 1, with the table 1 compared with conventional surfactant.
The ratio of the CMC of table 1 conventional surfactant and this DHGS surfactant comparatively
| Surfactants Name | cmc/mol·L -1 | γ CMC/mN·m -1 |
| C 8H 17NMe 3Br | 2.6×10 -1 | 41 |
| C 12H 25NMe 3Br | 1.6×10 -2 | 40 |
| C 16H 33NMe 3Br | 9.0×10 -4 | 37 |
| C 8H 17SO 4Na | 1.4×10 -1 | 39 |
| C 10H 21SO 4Na | 3.1×10 -2 | 38 |
| C 12H 25SO 4Na | 8.0×10 -3 | 38 |
| 12-2-12 | 1.1×10 -3 | 30 |
| DHGS-12 | 7.4×10 -4 | 29 |
Embodiment 4
The antistatic property of DHGS surfactant characterizes
The mensuration that some cationic surfactants and DHGS surfactant affect fabric antistatic property, method adopts GB/T16801---and 1997, instrument selection ZC-36 type high resist, operating voltage is 100V, and experiment material is polyester dacron (dacron).Measurement result is as table 2.
Table 2 surfactant is on the impact of fabric side resistance
| Surfactant | 7％C-SAA | 5％18-2-18 | 2％DHGS18 |
| Surface resistance (Ω) | 1.59×10 11 | 2.03×10 12 | 8.00×10 9 |
Wherein, 18-2-18 is Common Cations Gemini surface active agent N, N, N ', N '-tetramethyl-N, N '-bis-octadecyl ethylenediamine, DHGS18 is N, N, N ', N '-four ethoxy-N, N '-bis-octadecyl-2-hydroxyl propane-diammonium.
Adopt said method to carry out antistatic property to 1%DHGS12 and 5% Henkel K570 to compare, in test, sample is undiluted directly carries out antistatic property test, and result is 1%GHDS12 surface resistance is 2.7 × 10
7, 5% Henkel K570 surface resistance is 2.13 × 10
8antistatic effect is obviously better than conventional antistatic agents.
Can be found out by antistatic property test, DHGS surfactant has the incomparable antistatic property of conventional surfactant.
Embodiment 5
DHGS surfactant and the composite energy of conventional surfactant characterize
2%DHGS12 and 2% dodecyl sodium sulfate form clear solution, 2%DHGS12 and 10%AES forms clear solution, and these two kinds of solution all have special rheologic behavio(u)r, i.e. thickening property.Illustrate that QSY12 is a kind of cationic surfactant that can be composite with anion.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. a highly-water-soluble cation Gemini surfactant, is characterized in that, the chemical formula of described activating agent is: N, N, N ', N '-four ethoxy-N, N '-dialkyl group-2-hydroxyl propane-diammonium, structural formula is as follows:
n＝11，13，15，17。
2. the preparation method of a kind of highly-water-soluble cation Gemini surfactant as claimed in claim 1, is characterized in that, comprise the steps:
S1, in the reactor of a drying, add alkyldiethanolamine and the chloro-2-propyl alcohol of 1,3-bis-that mol ratio is 2: 1, appropriate solvent and KI or sodium iodide, stir, react 24-48 hour, obtain reactant liquor at 120-130 DEG C;
S2, reactant liquor is dry, obtain red brown solid;
S3, by this solid anhydrous alcohol solution, then use re-crystallizing in ethyl acetate, obtain white solid, solid is dried, and obtains pure DHGS.
3. the preparation method of a kind of highly-water-soluble cation Gemini surfactant according to claim 2, is characterized in that, described solvent is the one in dimethyl formamide or dimethyl sulfoxide (DMSO), and addition is 1/3 to 2/3 of reactant quality.
4. the preparation method of a kind of highly-water-soluble cation Gemini surfactant according to claim 2, is characterized in that, the addition of described KI is the 0.3%-0.5% of reactant quality.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107574025A (en) * | 2017-03-24 | 2018-01-12 | 卓聪（上海）环保科技发展有限公司 | A kind of network communication equipment conserves cleaning agent and preparation method thereof online |
| CN108745197A (en) * | 2018-05-16 | 2018-11-06 | 中国日用化学研究院有限公司 | A kind of degradable gemini quaternary ammonium salt and preparation method thereof |
| CN109535015A (en) * | 2018-11-11 | 2019-03-29 | 广州市金浪星非织造布有限公司 | A kind of four ethoxy dibromo propane-diammonium of double octadecyls and preparation method thereof |
| CN111233680A (en) * | 2019-04-29 | 2020-06-05 | 河南省科学院高新技术研究中心 | Acrylic acid biquaternary ammonium salt monomer and preparation method thereof |
| CN112535996A (en) * | 2020-12-24 | 2021-03-23 | 广州天赐高新材料股份有限公司 | Gemini quaternary ammonium salt-containing surfactant composition |
| CN112969771A (en) * | 2018-10-31 | 2021-06-15 | 沙特阿拉伯石油公司 | Additive for oil and gas drilling and production |
| CN114854390A (en) * | 2022-04-14 | 2022-08-05 | 西南石油大学 | Polyhydroxy super-large hydrophilic head-based viscoelastic surfactant and synthesis method thereof |
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| US6034271A (en) * | 1996-03-02 | 2000-03-07 | Huels Aktiengesellschaft | Betaine gemini surfactants made from amines |
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| CN102240520A (en) * | 2011-05-07 | 2011-11-16 | 桂林理工大学 | Preparation method of polyhydroxy abietyl quaternary ammonium salt gemini surfactant |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107574025A (en) * | 2017-03-24 | 2018-01-12 | 卓聪（上海）环保科技发展有限公司 | A kind of network communication equipment conserves cleaning agent and preparation method thereof online |
| CN107574025B (en) * | 2017-03-24 | 2020-07-10 | 卓聪（上海）环保科技发展有限公司 | Online maintenance cleaning agent for network communication equipment and preparation method thereof |
| CN108745197A (en) * | 2018-05-16 | 2018-11-06 | 中国日用化学研究院有限公司 | A kind of degradable gemini quaternary ammonium salt and preparation method thereof |
| CN108745197B (en) * | 2018-05-16 | 2020-09-22 | 中国日用化学研究院有限公司 | Easily degradable gemini quaternary ammonium salt and preparation method thereof |
| CN112969771A (en) * | 2018-10-31 | 2021-06-15 | 沙特阿拉伯石油公司 | Additive for oil and gas drilling and production |
| CN109535015A (en) * | 2018-11-11 | 2019-03-29 | 广州市金浪星非织造布有限公司 | A kind of four ethoxy dibromo propane-diammonium of double octadecyls and preparation method thereof |
| CN111233680A (en) * | 2019-04-29 | 2020-06-05 | 河南省科学院高新技术研究中心 | Acrylic acid biquaternary ammonium salt monomer and preparation method thereof |
| CN112535996A (en) * | 2020-12-24 | 2021-03-23 | 广州天赐高新材料股份有限公司 | Gemini quaternary ammonium salt-containing surfactant composition |
| CN114854390A (en) * | 2022-04-14 | 2022-08-05 | 西南石油大学 | Polyhydroxy super-large hydrophilic head-based viscoelastic surfactant and synthesis method thereof |
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