CN102895914B - Dodecanol glucose gemini surfactant and preparation method thereof - Google Patents
Dodecanol glucose gemini surfactant and preparation method thereof Download PDFInfo
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- CN102895914B CN102895914B CN201210356186.5A CN201210356186A CN102895914B CN 102895914 B CN102895914 B CN 102895914B CN 201210356186 A CN201210356186 A CN 201210356186A CN 102895914 B CN102895914 B CN 102895914B
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- lauryl alcohol
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- OXGBFDBWKHHDFY-UHFFFAOYSA-N COC(COCCOCC(CON)O)CON Chemical compound COC(COCCOCC(CON)O)CON OXGBFDBWKHHDFY-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a dodecanol glucose gemini surfactant, the structure of which is shown as the following formula. The invention also provides a preparation method of the dodecanol glucose gemini surfactant. The method includes: (1) adding a dodecanol gemini chain, tetracetylglucose trichloroacetimidate, and a catalyst into an organic solvent I, conducting a connection reaction, and performing treatment after the reaction so as to obtain a product I; and (2) adding the product I obtained in step (1) into an organic solvent II, adding an alkali till the acetyl in the product I is totally removed, and carrying out post-treatment after the end of the reaction, thus obtaining the final target product, i.e. the dodecanol glucose gemini surfactant. With the high activity characteristic of gemini surfactants, the dodecanol glucose gemini surfactant provided in the invention also has the characteristics of no toxicity, and biodegradability, thus being a novel green and environmental protection gemini surfactant with a sugar-based gemini substance as the model. Also, the preparation method of the surfactant is simple and is easy to realize industrialization.
Description
Technical field
The present invention relates to surfactant preparation field, be specifically related to a kind of lauryl alcohol glucose Gemini surface active agent and preparation method thereof.
Background technology
Surfactant and synthetic detergent form one industrially must trace back to 1930's, with the derivative synthetic surfactant of petrochemical materials and washing agent, broken the situation that soap rules all the land, and the research direction of surfactant mainly contains alkyl phosphorus carboxylate (AEC) industrialization manufacture, Gemini surface active agent of new generation, AB type block macromolecular surfactant, Bola type surfactant, Dendrimer type surfactant, low bubble or bulb-less surface activity agent at present.Continuous lifting along with living standards of the people and environmental consciousness, traditional business type surfactant can not meet people's Surfactant safety, environmental protection and low-cost this requirement of 3, therefore gradually eliminated, it is instead novel green surfactant.Therefore such as the such green surfactant of Gemini surface active agent, be subject to countries in the world scientist's favor, and started one new research boom.
Gemini surface active agent be by chemical bond by two or more same or same surfactant monomers almost, at hydrophilic base or near near hydrophilic base, with spacer group, this amphiphilic composition is linked together to a kind of surfactant of formation.Such surfactant has anionic, nonionic, cationic, amphoteric ion type and anion-nonionic type, sun-nonionic etc.It has better performance than conventional surfactant the special structures shape of Gemini surface active agent.It has two hydrophilic groups and hydrophobic group, by spacer group, two parts are connected, spacer group has chemical bond, has reduced electrostatic repulsion forces between bipolarity and the active force between hydrated sheath thereof, makes Gemini surface active agent have low cmc (critical micelle concentration) characteristic.Gemini surface active agent molecule is because it claims the self-organizing behavior that structure produces and reduces the capillary ability of the aqueous solution simultaneously, make it at washing agent, outside widely applying in cosmetics industry, also can in industry such as oil, coal, mining and metallurgy, machinery, weaving, medicine and the production such as agriculture, there be huge potentiality.
Application number is that the patent documentation of CN 201010532886.6 discloses a kind of Gemini surface active agent and preparation method thereof, and the structure of this Gemini surface active agent is suc as formula shown in (I):
Wherein: R is selected from C
8-C
16alkyl; N is the natural number of 1-3, and shown in the formula also providing in the document (I), the preparation method of cation Gemini surfactant, comprises the steps: 1) C
8-C
16fatty alcohol and epoxychloropropane react compound shown in production (II) under the condition of alkali compounds and phase transfer catalyst existence, wherein, and the definition cotype (I) of R; 2) under the condition that compound and polyethylene glycol shown in described formula (II) exist at alkali metal, react and obtain compound shown in formula (III) through acidifying, the degree of polymerization of described polyethylene glycol is 1-3; 3) compound shown in described formula (III) reacts with chlorosulfonic acid and obtains Gemini surface active agent shown in formula (I) through alkalization.The temperature tolerance of the surfactant that above-mentioned document provides, salt-resistance, foaming characteristic, emulsibility are stronger, and other type list surface-active agent has good Synergistic ability.But prepare in above-mentioned Gemini surface active agent process, because epoxychloropropane is unstable, and volatility is stronger, and has potential carcinogenic toxicity, causes the preparation cost of above-mentioned Gemini surface active agent higher, has also limited its further suitability for industrialized production.
Summary of the invention
The invention provides a kind of lauryl alcohol glucose Gemini surface active agent, this surfactant surface-active is high, being applicable to the separation and Extraction of scale remover and membrane protein, and having nontoxic, biodegradable characteristic, is the Gemini surface active agent of a class new green environment protection.
A lauryl alcohol glucose Gemini surface active agent, its structure is shown below:
The present invention also provides a kind of method of preparing above-mentioned lauryl alcohol glucose Gemini surface active agent, comprising:
(1) lauryl alcohol Shuangzi chain, four acetyl glucosamine tribromo-acetyl imines esters, catalyst are joined in organic solvent I, carry out coupled reaction, reacted post processing and obtained product I;
(2) product I step (1) being obtained joins in organic solvent II, adds alkali, until the acetyl group in product I all removes, reaction finishes, and post processing obtains final goal product lauryl alcohol glucose Gemini surface active agent;
The structure of described lauryl alcohol Shuangzi chain is shown below:
The structure of four described acetyl glucosamine tribromo-acetyl imines esters is shown below:
The course of reaction of above-mentioned reaction is shown below:
In above-mentioned preparation method, the mole adding of four described acetyl glucosamine tribromo-acetyl imines esters need to be more than or equal to the twice of the mole adding of lauryl alcohol Shuangzi chain, as preferably, the ratio of the amount of substance of described lauryl alcohol Shuangzi chain and four acetyl glucosamine tribromo-acetyl imines esters is 1: 2-10.
In above-mentioned preparation method, described catalyst is conventional organic acid, and the amount adding is catalytic amount, and experiment shows, the good organic acid of catalytic effect is one or both in BFEE, TFMS trimethyl silicone grease.
Described organic solvent I is to lauryl alcohol Shuangzi chain, the good non-proton organic solvent of four acetyl glucosamine tribromo-acetyl imines ester dissolubilities, generally selects carrene, chloroform, toluene etc.Described organic solvent II is to the good solvent of lauryl alcohol glucose Gemini surface active agent dissolubility, and the general solvent of selecting to have certain polarity, comprises methyl alcohol, ethanol, isopropyl alcohol etc. such as conventional polar solvent.
In step (2), described alkali is for common are machine alkali or inorganic base, and for example described alkali comprises at least one in potash, sodium carbonate, sodium methoxide, caustic alcohol, NaOH, potassium hydroxide, sodium hydride.In this step, the addition of alkali is not strict with, and the acetyl group of take removes completely as object.
Lauryl alcohol Shuangzi chain, four acetyl glucosamine tribromo-acetyl imines esters that the present invention uses are existing compound, can adopt commercial product, also can adopt existing method to prepare.The present invention is not in the situation that there is no specified otherwise, and reaction is all carried out at normal temperatures.
Lauryl alcohol glucose Gemini surface active agent of the present invention, had both had the high activity feature of Gemini surface active agent, was applicable to the separation and Extraction of scale remover and membrane protein; Also having nontoxic or low toxicity, biodegradable characteristic, is that a class be take the Gemini surface active agent of the new green environment protection that glycosyl Shuangzi thing is model; And the preparation method of this surfactant is simple, be easy to realize industrialization.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Take four acetyl glucosamine tribromo-acetyl imines ester 305.5mg (0.62mmol), using 5ml anhydrous methylene chloride as solvent, add lauryl alcohol Shuangzi chain 112.9mg (0.207mmol), the BFEE (mole be lauryl alcohol Shuangzi chain mole 5%) that adds catalytic amount after cooling stirring 15min, thin-layer chromatography monitoring reaction process, reaction finishes by extraction, dry and rotary evaporation, and (eluant, eluent is benzinum: ethyl acetate=3: mode 1) is collected into after purifying to rotary evaporation after round-bottomed flask and obtains light yellow liquid to take column chromatography.
(methyl alcohol adding is excessive with 20ml absolute methanol to get 180.9mg (0.15mmol) previous step reaction products therefrom, during object in order to cushion the pH value that adds alkali process, avoid that local pH value is excessive causes occurring side reaction) as solvent, add 16.2mg sodium methoxide (0.3mmol), reaction finishes rotary evaporation after rear filtration, obtain colourless paste liquid 120.1mg (0.0996mmol), productive rate 50%.
Colourless pulpous state is carried out to Structural Identification, and appraising datum is as follows:
Mass spectral characteristi: ESI-MS:m/z869.39[M-H+]
-;
Nuclear-magnetism characterizes:
1H?NMR(500MHz，CD
3OD)δ4.51(m，2H)，4.07(m，2H)，3.85(dd，J＝14.2，8.8Hz，2H)，3.79(m，2H)，3.72-3.57(m，12H)，3.47(m，4H)，3.42(dd，J＝9.3，3.1Hz，2H)，3.35(s，2H)，3.26-3.12(m，4H)，1.61-1.52(m，4H)，1.41-1.25(m，36H)，0.89(t，J＝6.9Hz，6H).
Surface-active test:
The critical micelle concentration (cmc) that adopts adopting platinum plate method to measure target product at 20 ℃ is 0.029mmol/L, than corresponding list surfactant dodecyl glucopyranoside (cmc=0.21mmol/L) is active, improve 7 times, be suitable for the separation and Extraction of scale remover and membrane protein, wherein, the structure of dodecyl glucopyranoside is as follows:
Embodiment 2
Take four acetyl glucosamine tribromo-acetyl imines ester 305.5mg (0.62mmol), using 5ml anhydrous methylene chloride as solvent, add lauryl alcohol Shuangzi chain 112.9mg (0.207mmol), the TFMS trimethyl silicone grease (mole be lauryl alcohol Shuangzi chain mole 5%) that adds catalytic amount after cooling stirring 15min, reaction finishes by extraction, dry and rotary evaporation, is collected into rotary evaporation after round-bottomed flask obtains light yellow liquid in the mode of column chromatography after purifying.
Get 180.9mg (0.15mmol) previous step reaction products therefrom and using 20ml absolute methanol (buffering ph just adds so much) as solvent, add 16.2mg sodium methoxide (0.3mmol), reaction finishes rotary evaporation after rear filtration, obtain colourless paste liquid 161.0mg (0.1335mmol), productive rate 67%.
The Structural Identification of the lauryl alcohol alcohol glucose Gemini surface active agent that this embodiment prepares and surface-active test data are with embodiment 1.
Embodiment 3
Take four acetyl glucosamine tribromo-acetyl imines ester 591.2mg (1.2mmol), using 5ml anhydrous methylene chloride as solvent, add lauryl alcohol Shuangzi chain 143.7mg (0.20mmol), the TFMS trimethyl silicone grease (mole be lauryl alcohol Shuangzi chain mole 5%) that adds catalytic amount after cooling stirring 15min, reaction finishes by extraction, dry and rotary evaporation, after purifying in the mode of column chromatography, be collected into round-bottomed flask after rotary evaporation obtain light yellow liquid.
Get 180.9mg (0.15mmol) previous step reaction products therefrom and using 20ml absolute ethyl alcohol as solvent, add 13.6mg caustic alcohol (0.2mmol), reaction finishes rotary evaporation after rear filtration, obtaining colourless paste liquid is lauryl alcohol glucose Gemini surface active agent 122.0mg (0.140mmol), productive rate 70%.
The Structural Identification of the lauryl alcohol glucose Gemini surface active agent that this embodiment prepares and surface-active test data are with embodiment 1.
The reaction reagent using in embodiment 1-3 all can adopt commercial product, or adopt existing method to prepare, wherein, the preparation method of lauryl alcohol Shuangzi chain can be referring to existing document (Reactions of oligoethylene glycol diglycidyl ethers with hydroxy compounds, Yohji Nakatsuji, Yuichi Tsuji, Isao Ikeda, Mitsuo Okahara, J.Org.Chem.1986,51,78-81).
Claims (6)
1. a lauryl alcohol glucose Gemini surface active agent, is characterized in that, its structure is shown below:
2. a method of preparing lauryl alcohol glucose Gemini surface active agent, comprising:
(1) lauryl alcohol Shuangzi chain, four acetyl glucosamine tribromo-acetyl imines esters, catalyst are joined in organic solvent I, carry out coupled reaction, reacted post processing and obtained product I;
Described catalyst is one or both in BFEE, TFMS trimethyl silicone grease;
(2) product I step (1) being obtained joins in organic solvent II, adds alkali, until the acetyl group in product I all removes, reaction finishes, and post processing obtains final goal product lauryl alcohol glucose Gemini surface active agent;
The structure of described lauryl alcohol Shuangzi chain is shown below:
The structure of four described acetyl glucosamine tribromo-acetyl imines esters is shown below:
The structure of described product I is shown below:
The structure of described target product lauryl alcohol glucose Gemini surface active agent is shown below:
3. the method for preparing lauryl alcohol glucose Gemini surface active agent according to claim 2, is characterized in that, the ratio of the amount of substance of described lauryl alcohol Shuangzi chain and four acetyl glucosamine tribromo-acetyl imines esters is 1:2-10.
4. the method for preparing lauryl alcohol glucose Gemini surface active agent according to claim 2, is characterized in that, described organic solvent I is carrene, chloroform or toluene.
5. the method for preparing lauryl alcohol glucose Gemini surface active agent according to claim 2, is characterized in that, described organic solvent II is methyl alcohol, ethanol or isopropyl alcohol.
6. the method for preparing lauryl alcohol glucose Gemini surface active agent according to claim 2, is characterized in that, described alkali is at least one in potash, sodium carbonate, sodium methoxide, caustic alcohol, NaOH, potassium hydroxide, sodium hydride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104324656B (en) * | 2014-09-30 | 2017-01-11 | 广州蓝月亮实业有限公司 | Dodecanol glucose gemini surfactant compound and preparation method thereof |
| US10093883B2 (en) | 2014-09-30 | 2018-10-09 | Zhejiang University | Glucose gemini surfactant compound and method for preparation thereof |
| CN104307430B (en) * | 2014-09-30 | 2016-08-24 | 浙江大学 | A kind of Tetradecanol glucose gemini surfactant compound and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1128267A (en) * | 1994-09-07 | 1996-08-07 | 希尔斯股份公司 | Process for preparing alkyglycosides |
| WO1998019783A2 (en) * | 1996-11-02 | 1998-05-14 | Henkel Kommanditgesellschaft Auf Aktien | Twin surfactants |
| WO2006100091A1 (en) * | 2005-03-24 | 2006-09-28 | Beiersdorf Ag | Novel surfactants and novel emulsifiers made from disaccharides |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1128267A (en) * | 1994-09-07 | 1996-08-07 | 希尔斯股份公司 | Process for preparing alkyglycosides |
| WO1998019783A2 (en) * | 1996-11-02 | 1998-05-14 | Henkel Kommanditgesellschaft Auf Aktien | Twin surfactants |
| WO2006100091A1 (en) * | 2005-03-24 | 2006-09-28 | Beiersdorf Ag | Novel surfactants and novel emulsifiers made from disaccharides |
Non-Patent Citations (5)
| Title |
|---|
| Reactions of Oligoethylene Glycol Diglycidyl Ethers with Hydroxy Compounds;Yohji Nakatsuji等;《The Journal of Organic Chemistry》;19860131;第51卷(第1期);第81-87页 * |
| Yohji Nakatsuji等.Reactions of Oligoethylene Glycol Diglycidyl Ethers with Hydroxy Compounds.《The Journal of Organic Chemistry》.1986,第51卷(第1期),第81-87页. |
| 一些新型非离子表面活性剂的制备和应用;梁梦兰;《表面活性剂工业》;20001231(第04期);第1-7页 * |
| 张培成,程凯,吴宏宇,燕方龙.正辛基葡萄糖苷的合成及其性能.《沈阳化工学院学报》.1995,第9卷(第02期),第139-145页. * |
| 梁梦兰.一些新型非离子表面活性剂的制备和应用.《表面活性剂工业》.2000,(第04期),第1-7页. |
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