CN102872752A - Decanol glucose dimeric surfactant and preparation method thereof - Google Patents
Decanol glucose dimeric surfactant and preparation method thereof Download PDFInfo
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- CN102872752A CN102872752A CN2012103562887A CN201210356288A CN102872752A CN 102872752 A CN102872752 A CN 102872752A CN 2012103562887 A CN2012103562887 A CN 2012103562887A CN 201210356288 A CN201210356288 A CN 201210356288A CN 102872752 A CN102872752 A CN 102872752A
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- decyl alcohol
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Abstract
The invention discloses a decanol glucose dimeric surfactant, which has a structural formula in the specifications. The invention also provides a method for preparing the decanol glucose dimeric surfactant. The method comprises the following steps of: (1) adding a decanol dimer chain, tetracetylglucose trichloroacetimidate and a catalyst into an organic solvent I for coupled reaction, and after the reaction is finished, obtaining a product I; and (2) adding the product I obtained in the step (1) into an organic solvent II, adding alkali until acetyls are totally removed from the product I, finishing the reaction, and performing posttreatment to obtain the final target product, namely the decanol glucose dimeric surfactant. The decanol glucose dimeric surfactant has the characteristic of high activity of a dimeric surfactant, also has the characteristics of no toxicity and biological degradability, and is a novel environment-friendly dimeric surfactant taking a sugar-based dimer as a template; and moreover, the preparation method for the surfactant is simple and suitable for industrialization.
Description
Technical field
The present invention relates to the surfactant field, specifically relate to a kind of decyl 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, broken the situation that soap rules all the land with synthetic surfactant and washing agent that petrochemical materials is derived, and the research direction of surfactant mainly contains alkyl phosphorus carboxylate (AEC) industrialization manufacturing, 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 commercial type surfactant has not satisfied people's Surfactant safety, environmental protection and low-cost this requirement of 3, so gradually eliminated, what replace is the novel green surfactant.Therefore be subject to countries in the world scientist's favor such as the such green surfactant of Gemini surface active agent, and started one new research boom.
Gemini surface active agent be by chemical bond with two or more same or same surfactant monomers almost, this amphiphilic composition is linked together a kind of surfactant of formation with spacer group at hydrophilic head base or near near hydrophilic head base.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 b `, has reduced electrostatic repulsion forces between bipolarity and the active force between hydrated sheath thereof, so that Gemini surface active agent has low CMC (critical micelle concentration) characteristic.The Gemini surface active agent molecule claims the self-organizing behavior that structure produces and reduces the capillary ability of the aqueous solution owing to it simultaneously, make it at washing agent, outside widely applying in the cosmetics industry, also can in industry such as oil, coal, mining and metallurgy, machinery, weaving, medicine and the production such as agriculture, huge potentiality be arranged.
The glycosyl Gemini surface active agent is a kind of novel Gemini surface active agent, has the surface-active that is better than the conventional commercial surfactant.And, carbohydrate is as a kind of compound of food-grade, numerous at occurring in nature content, not only can greatly reduce the cost of producing surfactant, effectively utilize the materials such as some trade waste, also have microbe killing properties, antistatic behaviour and the less advantages such as excitant, and can carry out compositely with other conventional surfactants, synergistic function is arranged.The report of at present relevant Gemini surface active agent is more, but the report of relevant glycosyl Gemini surface active agent is less, the patent documentation that mainly contains application number and be CN 201010538350.5 discloses a kind of sugar-based quaternary ammonium salt Gemini surface active agent, and its general structure is as follows:
In the following formula: glycosyl is glucosyl group, and R is C
8～C
18Chain alkyl, X is chlorine, bromine or iodine, m=1～2, n=1～2.The method is simple, and step is made of direct synthesis dihalo glucosides and quaterisation, and synthesis technique is simple, and equipment requirement is low, is fit to industrialization.Sugar-based quaternary ammonium salt structurally not only has the glucose hydrophilic group of nonionic, and has cationic bi-quaternary ammonium salt hydrophilic group; Product has outside bactericidal properties, antistatic behaviour and the anti-hard water of cationic surfactant, and excitant is lower; Product can be composite with anion surfactant, has simultaneously synergistic function; Having possessed again simultaneously the excellent properties of Gemini surface active agent as Gemini surface active agent, is a kind of Mobyneb surfactant, may be widely used in the industries such as weaving, papermaking, cosmetics and mining, has potential application foreground.Yet only one or more glycosyl Gemini surface active agents are difficult to the demand of satisfying the market.Existing market is badly in need of the new glycosyl Gemini surface active agent of exploitation and new synthetic method.
Summary of the invention
The invention provides a kind of decyl alcohol glucose Gemini surface active agent, this surfactant has higher surface-active, solubilizing effect is better during as solubilizer, and this Gemini surface active agent has nontoxic, biodegradable characteristic, is the Gemini surface active agent of a class new green environment protection.
The present invention also provides a kind of preparation method who prepares above-mentioned decyl alcohol glucose Gemini surface active agent, and the method step is simple, and is easy to operate, and overall process avoids adopting toxic solvent, can conveniently realize suitability for industrialized production.
A kind of decyl alcohol glucose Gemini surface active agent, its structure is shown below:
The present invention also provides a kind of method for preparing above-mentioned decyl alcohol glucose Gemini surface active agent, comprising:
(1) decyl alcohol Shuangzi chain, tetrem acyl glucose tribromo-acetyl imines ester, catalyst are joined in the organic solvent I, carry out coupled reaction, reaction is finished post processing and is obtained product I;
(2) the product I that step (1) is obtained joins in the organic solvent II, adds alkali, until the acetyl group among the product I all removes, reaction finishes, and post processing obtains final goal product decyl alcohol glucose Gemini surface active agent;
The structure of described decyl alcohol Shuangzi chain is shown below:
The structure of described tetrem acyl glucose tribromo-acetyl imines ester is shown below:
The course of reaction of above-mentioned reaction is shown below:
Among the above-mentioned preparation method, the mole of the adding of described tetrem acyl glucose tribromo-acetyl imines ester need to be more than or equal to the twice of the mole of the adding of decyl alcohol Shuangzi chain, as preferably, the ratio of the amount of substance of described decyl alcohol Shuangzi chain and tetrem acyl glucose tribromo-acetyl imines ester is 1: 2-10.
Among the above-mentioned preparation method, described catalyst is organic acid commonly used, and the amount of adding is catalytic amount, and experiment shows that the preferably organic acid of catalytic effect is one or both in BFEE, the TFMS trimethyl silicone grease.
Described organic solvent I is to decyl alcohol Shuangzi chain, tetrem acyl glucose tribromo-acetyl imines ester dissolubility non-proton organic solvent preferably, generally selects carrene, chloroform, toluene etc.Described organic solvent II is to decyl alcohol glucose Gemini surface active agent dissolubility solvent preferably, and the general solvent with certain polarity selected comprises methyl alcohol, ethanol, isopropyl alcohol etc. such as polar solvent commonly used.
In the step (2), described alkali is for common are machine alkali or inorganic base, and for example described alkali comprises at least a in potash, sodium carbonate, sodium methoxide, caustic alcohol, NaOH, potassium hydroxide, the sodium hydride.In this step, the addition of alkali is not strict with, and removes fully as purpose take acetyl group.
Decyl alcohol Shuangzi chain, tetrem acyl glucose tribromo-acetyl imines ester that the present invention uses are existing compound, can adopt commercial product, also can adopt existing method to prepare.The present invention is not having in the situation of specified otherwise, and reaction is all carried out at normal temperatures.
Decyl alcohol glucose Gemini surface active agent of the present invention, the high activity characteristics that both had Gemini surface active agent, being suitable for using as solubilizer, having simultaneously nontoxic, biodegradable characteristic, is the Gemini surface active agent of a class take glycosyl Shuangzi thing as the new green environment protection of model; And the preparation method of this surfactant is simple, is easy to realize industrialization.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
Take by weighing tetrem acyl glucose tribromo-acetyl imines ester 295.6mg (0.6mmol), with the 5ml anhydrous methylene chloride as solvent, add decyl alcohol Shuangzi chain 98.08mg (0.2mmol), the BFEE that adds catalytic amount behind the 15min (mole be decyl alcohol Shuangzi chain mole 5%) is stirred in cooling, thin-layer chromatography monitoring reaction process, reaction finishes by extraction, drying and rotary evaporation, and (eluant, eluent is as benzinum: rotary evaporation obtains light yellow liquid after being collected into round-bottomed flask after mode ethyl acetate=3: 1) is purified take column chromatography.
(methyl alcohol of adding is excessive with the 20ml absolute methanol to get 115.1mg (0.1mmol) previous step reaction products therefrom, during purpose in order to cushion the pH value that adds the alkali process, avoid that the local pH value is excessive to cause occuring side reaction) as solvent, add 10.8mg sodium methoxide (0.2mmol), after reaction finishes, filter rotary evaporation, obtaining colourless paste liquid is decyl alcohol glucose Gemini surface active agent 70.5mg (0.0864mmol), productive rate 43%.
Colourless paste liquid is carried out Structural Identification, and appraising datum is as follows:
Mass spectral characteristi: ESI-MS:m/z 813.36[M-H+]-;
Nuclear-magnetism characterizes:
1H?NMR(500MHz，CD
3OD)δ?4.52(m，2H)，4.07(m，2H)，3.86(m，2H)，3.79(m，2H)，3.74-3.60(ddd，J＝14.9，10.3，4.9Hz，12H)，3.47(m，4H)，3.41(dd，J＝9.3，3.1Hz，2H)，3.35(s，2H)，3.26-3.12(dd，J＝14.5，7.2Hz，4H)，1.60-1.53(m，4H)，1.40?to?1.25(m，28H)，0.89(t，J＝6.9Hz，6H).
The surface-active test:
20 ℃ of lower critical micelle concentrations (cmc) that adopt the adopting platinum plate method to measure target product are 0.11mmol/L, improve 19 times than corresponding list surfactant decyl glucopyranoside (cmc=2.04mmol/L) is active, activity is higher, be suitable for using as the solubilizer of biological field, wherein, the structure of decyl glucopyranoside is as follows:
Embodiment 2
Take by weighing tetrem acyl glucose tribromo-acetyl imines ester 295.6mg (0.6mmol), with the 5ml anhydrous methylene chloride as solvent, add decyl alcohol Shuangzi chain 98.08mg (0.2mmol), the TFMS trimethyl silicone grease that adds catalytic amount behind the 15min (mole be decyl alcohol Shuangzi chain mole 5%) is stirred in cooling, reaction finishes by extraction, drying and rotary evaporation, and rotary evaporation obtains light yellow liquid as decyl alcohol glucose Gemini surface active agent after to be collected into round-bottomed flask after the mode of column chromatography is purified.
Get 115.1 (0.1mmol) previous step reaction products therefrom with the 20ml absolute methanol as solvent, add 10.8mg sodium methoxide (0.2mmol), rotary evaporation after filtering after reaction finishes obtains colourless paste liquid 78.9mg (0.0967mmol), productive rate 48%.
The Structural Identification of the decyl alcohol glucose Gemini surface active agent that this embodiment prepares and surface-active test data are with embodiment 1.
Embodiment 3
Take by weighing tetrem acyl glucose tribromo-acetyl imines ester 589.2mg (1.2mmol), with the 5ml anhydrous methylene chloride as solvent, add decyl alcohol Shuangzi chain 98.08mg (0.2mmol), the TFMS trimethyl silicone grease that adds catalytic amount behind the 15min (mole be decyl alcohol Shuangzi chain mole 5%) is stirred in cooling, reaction finishes by extraction, drying and rotary evaporation, be collected into round-bottomed flask after purifying in the mode of column chromatography after rotary evaporation obtain light yellow liquid.
Get 117.0mg (0.1mmol) previous step reaction products therefrom with the 20ml absolute methanol as solvent, add 5.0mg sodium hydride (0.2mmol), rotary evaporation after filtering after reaction finishes, obtaining colourless paste liquid is decyl alcohol glucose Gemini surface active agent 75.3mg (0.0923mmol), productive rate 46%.
The Structural Identification of the decyl alcohol glucose Gemini surface active agent that this embodiment prepares and surface-active test data are with embodiment 1.
Employed reaction reagent all can adopt commercial product among the embodiment 1-3, perhaps adopt existing method to prepare, wherein, the preparation method of decyl alcohol Shuangzi chain can be referring to existing document (Reactions ofoligoethylene glycol diglycidyl ethers with hydroxy compounds, YohjiNakatsuji, Yuichi Tsuji, Isao Ikeda, Mitsuo Okahara, J.Org.Chem.1986,51,78-81).
Claims (8)
1. decyl alcohol glucose Gemini surface active agent is characterized in that its structure is shown below:
2. method for preparing the described decyl alcohol glucose of claim 1 Gemini surface active agent comprises:
(1) decyl alcohol Shuangzi chain, tetrem acyl glucose tribromo-acetyl imines ester, catalyst are joined in the organic solvent I, carry out coupled reaction, reaction is finished post processing and is obtained product I;
(2) the product I that step (1) is obtained joins in the organic solvent II, adds alkali, until the acetyl group among the product I all removes, reaction finishes, and post processing obtains final goal product decyl alcohol glucose Gemini surface active agent;
The structure of described decyl alcohol Shuangzi chain is shown below:
The structure of described tetrem acyl glucose tribromo-acetyl imines ester is shown below:
3. the method for preparing decyl alcohol glucose Gemini surface active agent according to claim 2 is characterized in that, the ratio of the amount of substance of described decyl alcohol Shuangzi chain and tetrem acyl glucose tribromo-acetyl imines ester is 1: 2-10.
4. the method for preparing decyl alcohol glucose Gemini surface active agent according to claim 2 is characterized in that, described catalyst is organic acid, and the amount of its adding is catalytic amount.
5. the method for preparing decyl alcohol glucose Gemini surface active agent according to claim 4 is characterized in that, described organic acid is one or both in BFEE, the TFMS trimethyl silicone grease.
6. the method for preparing decyl alcohol glucose Gemini surface active agent according to claim 2 is characterized in that, described organic solvent I is carrene, chloroform or toluene.
7. the method for preparing decyl 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.
8. the method for preparing decyl alcohol glucose Gemini surface active agent according to claim 2 is characterized in that, described alkali is at least a in potash, sodium carbonate, sodium methoxide, caustic alcohol, NaOH, potassium hydroxide, the sodium hydride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307430A (en) * | 2014-09-30 | 2015-01-28 | 浙江大学 | Tetradecanol glucose dimeric surfactant compound and preparation method thereof |
| CN111992134A (en) * | 2020-09-22 | 2020-11-27 | 陕西科技大学 | Polycarboxyl amphoteric Bola type surfactant 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 |
| DE19645189A1 (en) * | 1996-11-02 | 1998-05-07 | Henkel Kgaa | Gemini surfactants |
| WO2006100091A1 (en) * | 2005-03-24 | 2006-09-28 | Beiersdorf Ag | Novel surfactants and novel emulsifiers made from disaccharides |
-
2012
- 2012-09-21 CN CN201210356288.7A patent/CN102872752B/en not_active Expired - Fee Related
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 |
| DE19645189A1 (en) * | 1996-11-02 | 1998-05-07 | Henkel Kgaa | Gemini surfactants |
| WO2006100091A1 (en) * | 2005-03-24 | 2006-09-28 | Beiersdorf Ag | Novel surfactants and novel emulsifiers made from disaccharides |
Non-Patent Citations (3)
| Title |
|---|
| YOHJI NAKATSUJI等: "Reactions of Oligoethylene Glycol Diglycidyl Ethers with Hydroxy Compounds", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| 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》 * |
| 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》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307430A (en) * | 2014-09-30 | 2015-01-28 | 浙江大学 | Tetradecanol glucose dimeric surfactant compound and preparation method thereof |
| CN111992134A (en) * | 2020-09-22 | 2020-11-27 | 陕西科技大学 | Polycarboxyl amphoteric Bola type surfactant and preparation method thereof |
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| CN102872752B (en) | 2014-04-16 |
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