CN102861532B - Octadecanol glucose gemini surfactant and preparation method thereof - Google Patents
Octadecanol glucose gemini surfactant and preparation method thereof Download PDFInfo
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- CN102861532B CN102861532B CN201210356216.2A CN201210356216A CN102861532B CN 102861532 B CN102861532 B CN 102861532B CN 201210356216 A CN201210356216 A CN 201210356216A CN 102861532 B CN102861532 B CN 102861532B
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- 0 CC(OCC1(C2O[C@@](*3)(*(C4)C4OC(C(Cl)(Cl)Cl)=N)C23C1C1*)[C@]1OC(C)=O)=O Chemical compound CC(OCC1(C2O[C@@](*3)(*(C4)C4OC(C(Cl)(Cl)Cl)=N)C23C1C1*)[C@]1OC(C)=O)=O 0.000 description 1
- IAHGMKWMGRCDPZ-UHFFFAOYSA-N C[O](C(COCCOCC(CON)[O]#C)CON)=C Chemical compound C[O](C(COCCOCC(CON)[O]#C)CON)=C IAHGMKWMGRCDPZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an octadecanol glucose gemini surfactant, wherein a structure of the gemini surfactant is represented as the following formula. The invention further provides a method for preparing the octadecanol glucose gemini surfactant, which comprises the steps of: (1) adding octadecanol gemini chain, tetracetylglucose trichloroacetimidate and a catalyst into an organic solvent I for ligation reaction, and obtaining a product I after the reaction; and (2) adding the product I obtained in the step (1) into an organic solvent II, and then adding alkali to completely remove acetyl groups in the product I, and obtaining the final target product octadecanol glucose gemini surfactant through posttreatment after the reaction. The octadecanol glucose gemini surfactant provided by the invention has the characteristic of high activity of the gemini surfactant, and also has the characteristics of non-toxicity and biodegradation, so that the octadecanol glucose gemini surfactant is a novel green and environmental-friendly gemini surfactant which takes a glycosyl gemini substance as a model; and the preparation method of the surfactant is simple and the industrialization is easy to implement.
Description
Technical field
The present invention relates to surfactant preparation field, be specifically related to a kind of 18 alcohol glucose Gemini surface active agents 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 18 alcohol glucose Gemini surface active agents, this surfactant surface-active is high, and be applicable to as wetting agent and finishing, and there is nontoxic, biodegradable characteristic, be the Gemini surface active agent of a class new green environment protection.
18 alcohol glucose Gemini surface active agents, its structure is shown below:
The present invention also provides a kind of method of preparing above-mentioned 18 alcohol glucose Gemini surface active agents, comprising:
(1) 18 alcohol Shuangzi chains, 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 18 alcohol glucose Gemini surface active agents;
The structure of 18 described alcohol Shuangzi chains 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 18 alcohol Shuangzi chains, as preferably, the ratio of the amount of substance of 18 described alcohol Shuangzi chains 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 18 alcohol Shuangzi chains, 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 18 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.
18 alcohol Shuangzi chains, 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.
18 alcohol glucose Gemini surface active agents of the present invention, the high activity feature both with Gemini surface active agent, extremely be suitable for using as wetting agent and finishing, have nontoxic or low toxicity, biodegradable characteristic, be that a class be take the Gemini surface active agent of the new green environment protection that glycosyl Shuangzi thing is model simultaneously; 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 295.6mg (0.60mmol), using 5ml anhydrous methylene chloride as solvent, add 18 alcohol Shuangzi chain 143.7mg (0.20mmol), the BFEE (mole be 18 alcohol Shuangzi chain moles 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: after mode 1) is collected into round-bottomed flask after purifying, rotary evaporation obtains white solid to take column chromatography.
Get 207.9mg (0.151mmol) previous step reaction products therefrom and using 20ml absolute methanol as solvent, add 16.3mg sodium methoxide (0.30mmol), reaction finishes rotary evaporation after rear filtration, obtains white solid 140.2mg (0.135mmol), productive rate 67%.
White solid is carried out to Structural Identification, and appraising datum is as follows:
Mass spectral characteristi: ESI-MS:m/z 1037.50[M-H+]-;
Nuclear-magnetism characterizes:
1H?NMR(500MHz，CD
3OD)：δ4.50(s，2H)，4.07(m，2H)，3.86(m，2H)，3.79(m，2H)，3.72-3.56(ddd，J＝15.9，8.4，4.1Hz，12H)，3.47(m，4H)，3.40(ddd，J＝8.5，6.9，2.0Hz，2H)，3.35(s，2H)，3.26-3.22(m，2H)，3.17(ddd，J＝17.0，8.2，5.3Hz，2H)，1.57(s，4H)，1.30(d，J＝18.4Hz，60H)，0.90(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 0.67mmol/L, than corresponding list surfactant octadecyl glucopyranoside (cmc=20.62mmol/L) is active, improve 31 times, the utmost point is suitable for using as wetting agent and finishing, and wherein octadecyl glucopyranoside structural formula is:
Embodiment 2
Take four acetyl glucosamine tribromo-acetyl imines ester 295.6mg (0.60mmol), using 5ml anhydrous methylene chloride as solvent, add 18 alcohol Shuangzi chain 143.7mg (0.20mmol), the TFMS trimethyl silicone grease (mole be 18 alcohol Shuangzi chain moles 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 white solid.
Get 207.9mg (0.151mmol) previous step reaction products therefrom and using 20ml absolute methanol as solvent, add 16.3mg sodium methoxide (0.30mmol), reaction finishes rotary evaporation after rear filtration, obtains white solid 143.8mg (0.1384mmol), productive rate 69%.
The Structural Identification of the 18 alcohol alcohol glucose Gemini surface active agents 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 18 alcohol Shuangzi chain 143.7mg (0.20mmol), the TFMS trimethyl silicone grease (mole be 18 alcohol Shuangzi chain moles 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 207.9mg (0.151mmol) previous step reaction products therefrom and using 20ml absolute methanol as solvent, add 5.0mg sodium hydride (0.2mmol), reaction finishes rotary evaporation after rear filtration, obtaining colourless paste liquid is 18 alcohol glucose Gemini surface active agent 145.5mg (0.140mmol), productive rate 70%.
The Structural Identification of the 18 alcohol glucose Gemini surface active agents 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 18 alcohol Shuangzi chains 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. 18 alcohol glucose Gemini surface active agents, is characterized in that, its structure is shown below:
2. a method of preparing 18 alcohol glucose Gemini surface active agents, comprising:
(1) 18 alcohol Shuangzi chains, 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 18 alcohol glucose Gemini surface active agents;
The structure of 18 described alcohol Shuangzi chains 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:
18 described alcohol glucose Gemini surface active agent structures are shown below:
Described catalyst is one or both in BFEE, TFMS trimethyl silicone grease.
3. the method for preparation 18 alcohol glucose Gemini surface active agents according to claim 2, is characterized in that, the ratio of the amount of substance of 18 described alcohol Shuangzi chains and four acetyl glucosamine tribromo-acetyl imines esters is 1:2-10.
4. the method for preparation 18 alcohol glucose Gemini surface active agents according to claim 2, is characterized in that, described organic solvent I is carrene, chloroform or toluene.
5. the method for preparation 18 alcohol glucose Gemini surface active agents according to claim 2, is characterized in that, described organic solvent II is methyl alcohol, ethanol or isopropyl alcohol.
6. the method for preparation 18 alcohol glucose Gemini surface active agents 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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