CN106268497A - One class contains abietyl Gemini surface active agent and the performance thereof of polyoxyethylene ether coupling link - Google Patents
One class contains abietyl Gemini surface active agent and the performance thereof of polyoxyethylene ether coupling link Download PDFInfo
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- CN106268497A CN106268497A CN201610562867.5A CN201610562867A CN106268497A CN 106268497 A CN106268497 A CN 106268497A CN 201610562867 A CN201610562867 A CN 201610562867A CN 106268497 A CN106268497 A CN 106268497A
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Abstract
The present invention relates to a class and there is abietyl Gemini surface active agent R (EO) of polyoxyethylene ether (EO) coupling linkn(wherein n is 1 and 2 to E R, and E represents CH2CH2) and performance.Wherein R (EO)nThe molecular structure of E R is as follows: The present invention gives this new rosin base Gemini surface active agent molecular structure and synthetic method.This surfactant has good dissolubility, foam stability energy and viscoelasticity, forms the half-life of foam more than 800min；Its aqueous solution the most just can form viscoelastic solution.Can be used in the formula of household chemicals and detergent.The main synthesis material dehydroabietic acid of this surfactant, from product of natural product rosin, has renewable, biodegradable, abundance, structure and is prone to the advantages such as modification.The premium properties of this surfactant makes it can be applicable in the formula of oil field chemical, household chemicals, antibacterial, antistatic additive and detergent.
Description
Technical field
The present invention relates to the Gemini surface active agent that a class synthesizes with dehydroabietic acid as raw material, in the middle of a class
Coupling link is the double type surfactant of EO group, belongs to synthesis and the application of natural product surfactant.
Background technology
Along with people's growing interest to environmental problem, seek the mesh that natural and green raw materials for production are chemical industry every profession and trades
Mark, surfactant industry is also such.Present in Appropriate application nature, some biomass resource molecule can be novel
Preparation and the application of surfactant provide effective approach.Colophonium is a kind of abundant renewable forest products resource, with Colophonium is
The product of raw material or deep processed product be widely used to the industry such as rubber, ink, coating, pesticide, medicine, food, electronics and
In the every field of life.Colophonium also have renewable, biodegradable, abundance, structure are prone to the advantages such as modification, are green
One of important source material source of color surfactant.But, the resinic acid constituting Colophonium usually contains a large amount of unsaturated bond so that
Colophonium is very easy to be aoxidized by the oxygen in air, cause darken, a series of changes such as chemical composition change, affect table
The synthesis of face active agent product and purity.Disproportionated rosin is the important derivatives of Colophonium, and dehydroabietic acid is in disproportionated rosin
Main component.Owing to its skeleton having the existence of phenyl ring, thus there is stable chemical property.Therefore, it is former with dehydroabietic acid
Material carries out the design of surfactant molecule and prepares the surfactant product that can obtain high-quality.
Gemini surface active agent is easily formed the aggregated structure of novelty, is the weight of current surfactant scientific domain research
Point.The present invention is with dehydroabietic acid as raw material, through serial reaction step, synthesizes a class coupling link and contains polyoxyethylene ether (EO) base
The new rosin base Gemini surface active agent of group.The existence of EO group has the compatibility beneficially improving surfactant, favorably
In product of natural product rosin in the application of new technical field.This novel surfactant also apply be applicable to oil field chemical, dailyization
In the formula of product and detergent.
Summary of the invention
It is an object of the invention to the master having in the disproportionated rosin of the advantages such as renewable, biodegradable, abundance
Wanting composition dehydroabietic acid is raw material, through serial reaction, synthesizes a class coupling link and contains the novel of polyoxyethylene ether (EO) group
Abietyl Gemini surface active agent, and its key property is provided.
For achieving the above object, the present invention adopts the following technical scheme that
With the main component dehydroabietic acid in disproportionated rosin as raw material, synthesize the dehydrogenation fir that a class coupling link contains EO group
Acidic group surfactant R-(EO)n(wherein n is 1 and 2 to-E-R, and E represents CH2CH2), its structural formula is as follows:
The synthetic route of this surfactant is as follows:
Its concrete synthesis step is as follows:
The synthesis of 3-(N, N-dimethyl)-propyl group dehydrogenation fir amide: by SOCl2It is slowly dropped to dehydroabietic acid after purification
In, reacting and produce to bubble-free, rotary evaporation removes the thionyl chloride of excess.By a certain amount of 3-dimethylaminopropylamine with a large amount of
Triethylamine be placed in ice-water bath, be slowly added dropwise the dichloromethane solution of dehydrogenation fir acyl chlorides.After reaction terminates, pour product into burning
In Bei, washing it with alkalescent water, be then extracted twice the product after washing with dichloromethane, anhydrous magnesium sulfate is dried,
Sucking filtration removes magnesium sulfate, then will remove dichloromethane and triethylamine under filtrate decompression.
The synthesis of dibromo glycol: under the conditions of ice-water bath, by PBr3It is slowly dropped in corresponding glycol, transfers room temperature afterwards to
Reaction 1h, finally reacts 12h at 50 DEG C～60 DEG C.After reaction terminates, saturated with dchloromethane, deionized water and 50mL
Sodium bicarbonate aqueous solution extracts, and takes oil phase, and anhydrous sodium sulfate is dried, and rotary evaporation removes solvent, with the Methods For Purification of column chromatography
Product.
R-(EO)nThe synthesis of-E-R: with a small amount of anhydrous alcohol solution a certain amount of dibromo glycol and 3-(N, N-dimethyl)-
Propyl group dehydrogenation fir amide, in airtight single port bottle, reacts 72h at 80 DEG C.Reaction terminates, and rotary evaporation removes etoh solvent
After, by ethanol/re-crystallizing in ethyl acetate three times.
The viscoelasticity measurement of surfactant solution: surfactant R-(EO) of preparation variable concentrationsn-E-R's is water-soluble
Liquid, measures stable state and the Dynamic Rheological Properties of its correspondence.
The foaming properties of surfactant solution: add the water-soluble of 10mL surfactant in the tool plug graduated cylinder of 100mL
Liquid (surfactant qualities mark is 0.1%), firmly shaking 25 times, the change in time of the foam volume of recording surface activating agent
Change graph of a relation.
Beneficial effect
With the derivant dehydroabietic acid of product of natural product rosin as raw material, obtain coupling link by series synthesis step and contain EO
The Dehydroabietic acid surfactant R of group-(EO)n-E-R (n is 1 and 2).Such surfactant has good focusing energy
Power.When 25 DEG C, R-EO-E-R and R-(EO)2The dissolubility of-E-R is respectively greater than 160mmol/L and 300mmol/L；Its critical glue
Bundle concentration is respectively 0.45mmol/L and 0.60mmol/L；The half-life of two kinds of formed foams of aqueous surfactant solution is respectively
For 1485min and 825min；When reaching finite concentration, the aqueous solution of such surfactant also presents obvious viscoelastic
Property, can apply to the formula of oil field chemical, household chemicals, antibacterial, antistatic additive and detergent.
Accompanying drawing explanation
Fig. 1 surfactant R-EO-E-R's1H NMR。
Fig. 2 surfactant R-(EO)2-E-R's1H NMR。
Fig. 3 surfactant R-(EO)n-E-R surface tension γ is with concentration C change curve (25 DEG C).
Fig. 4 surfactant R-(EO)nThe foam volume of-E-R changes over graph of a relation (25 DEG C).
The steady state shearing rheogram (25 DEG C) of Fig. 5 surfactant R-EO-E-R.
Fig. 6 surfactant R-(EO)2The steady state shearing rheogram (25 DEG C) of-E-R.
The dynamic shear rheological figure (25 DEG C) of Fig. 7 surfactant R-EO-E-R.
Fig. 8 surfactant R-(EO)2The dynamic shear rheological figure (25 DEG C) of-E-R.
Detailed description of the invention
The synthesis of embodiment 1:3-(N, N-dimethyl)-propyl group dehydrogenation fir amide: take dehydroabietic acid after purification (40.0g,
0.133mol) it is placed in the there-necked flask with return stirring and tail gas absorption, adds a small amount of DMAP and make catalyst, at temperature liter
During to 60 DEG C, by SOCl2(20.6g, 0.173mol) is slowly dropped in dehydroabietic acid, after completion of dropwise addition, temperature is set to
72 DEG C, reacting and produce to bubble-free, rotary evaporation removes the thionyl chloride of excess.By 3-dimethylaminopropylamine (15.3g,
The triethylamine of 0.15mol) He three times of moles is placed in ice-water bath, is slowly added dropwise dehydrogenation fir acyl chlorides (43.4g, 0.136mol)
Dichloromethane solution, successive reaction 2h after completion of dropwise addition.After reaction terminates, product is poured in the beaker of 1000mL, use weak base
Property water to its wash 2～3 times, then with dichloromethane to washing after product be extracted twice, combining extraction liquid, use anhydrous slufuric acid
Magnesium is dried, and sucking filtration removes solid magnesium sulfate, then by removing dichloromethane and triethylamine under filtrate decompression, obtains sticky shape
Liquid.
Embodiment 2: the synthesis of dibromo diethylene glycol: under the conditions of ice-water bath, by PBr3(30.6g, 0.113mol) is slowly added dropwise
In the there-necked flask equipped with diethylene glycol (15.0g, 0.141mol), transfer room temperature reaction 1h afterwards to, finally at 50 DEG C～60 DEG C
Reaction 12h.After reaction terminates, cooling, with dchloromethane, respectively with deionized water, 50mL saturated sodium bicarbonate aqueous solution
And deionized water wash, collect oil phase, anhydrous sodium sulfate is dried, and rotary evaporation removes solvent.Column chromatography purified product (eluant
For petroleum ether).Obtain transparency liquid.
Embodiment 3: the synthesis of dibromo 2,2'-ethylenedioxybis(ethanol).: under the conditions of ice-water bath, by PBr3(43.3g, 0.160mol) is slowly added dropwise
In the there-necked flask equipped with 2,2'-ethylenedioxybis(ethanol). (30.0g, 0.200mol), transfer room temperature reaction 1h afterwards to, finally at 50 DEG C～60 DEG C
Reaction 12h.After reaction terminates, cooling, with dchloromethane, respectively with deionized water, 100mL saturated sodium bicarbonate aqueous solution
And deionized water wash, collect oil phase, anhydrous sodium sulfate is dried, and rotary evaporation removes solvent.Column chromatography purified product (eluant
For petroleum ether).Obtain transparency liquid.
The synthesis of embodiment 4:R-EO-E-R: take dibromo diethylene glycol (10.0g, 0.042mol), 3-(N, N-dimethyl)-the third
Base dehydrogenation fir amide (38.0g, 0.099mol) and 15mL ethanol are placed in airtight single port bottle, react 72h at 80 DEG C.Reaction
Terminating, rotary evaporation removes after etoh solvent, by ethanol/re-crystallizing in ethyl acetate three times.White powder is obtained after vacuum drying
Shape solid.
Embodiment 5:R-(EO)2The synthesis of-E-R: take dibromo 2,2'-ethylenedioxybis(ethanol). (12.0g, 0.045mol), 3-(N, N-diformazan
Base)-propyl group dehydrogenation fir amide (38.4g, 0.100mol) and 15mL ethanol is placed in airtight single port bottle, reacts at 80 DEG C
72h.Reaction terminates, and rotary evaporation removes after etoh solvent, by ethanol/re-crystallizing in ethyl acetate three times.Obtain after vacuum drying
White powdery solids.
Embodiment 6: capillary mensuration: prepare surfactant R-(EO) of a series of variable concentrationsn(n is 1 to-E-R
With 2) aqueous solution, at 25 DEG C, measure its surface tension by suspension ring method, each point is repeated 3 times, and takes its meansigma methods, draws sample
Surface tension with the variation relation curve of concentration.Concentration corresponding at turning point confirms as the critical glue of such surfactant
Bundle concentration.
Embodiment 7: add the aqueous solution (surfactant qualities of 10mL surfactant in the tool plug graduated cylinder of 100mL
Mark is 0.1%), stand after firmly shaking 25 times, at 25 DEG C, the foam volume of recording surface activating agent is over time
Graph of a relation.From fig. 4, it can be seen that such surfactant has good foam stability energy.
Embodiment 8: the R-(EO) of preparation variable concentrationsnThe aqueous solution of-E-R, uses stable state and dynamic rheological property at 25 DEG C
Method tests its performance.Before dynamic scan, first carry out stress scans to determine the linear viscoelastic region of test sample, all samples
Test is all carried out in linear viscoelastic region.From Fig. 5, Fig. 6, Fig. 7 and Fig. 8, such surfactant solution presents significantly
Viscoelasticity, and have certain microstructure.
Claims (4)
1. the class abietyl Gemini surface active agent containing polyoxyethylene ether coupling link, its molecular structure is as follows:
。
Abietyl Gemini surface active agent containing polyoxyethylene ether coupling link the most according to claim 1, its feature
It is, is that reaction obtains according to the following formula:
。
Abietyl Gemini surface active agent containing polyoxyethylene ether coupling link the most according to claim 1, its feature
Being, the dissolubility of such surfactant is more than 160mmol/L；The half-life of the foam formed is more than 825min.
Gemini surface active agent the most according to claim 1, it is characterised in that at 25 DEG C, surfactant R-EO-E-R
With R-(EO)2It is molten that-E-R can form viscoelastic respectively in the range of 50mmol/L-160mmol/L and 90mmol/L-450mmol/L
Liquid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106943948A (en) * | 2017-03-28 | 2017-07-14 | 江南大学 | One class abietyl sulfobetaines amphoteric surfactant and its performance |
| CN107298444A (en) * | 2017-06-26 | 2017-10-27 | 江南大学 | It is a kind of using preparation of the abietyl Gemini surface active agent as the Metaporous silicon dioxide material of template and its performance |
| CN115124438A (en) * | 2022-07-14 | 2022-09-30 | 江南大学 | Preparation and application of efficient natural product-based viscoelastic solution |
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| CN101831066A (en) * | 2010-03-31 | 2010-09-15 | 中国林业科学研究院林产化学工业研究所 | Method for preparing rosin-based surfactant |
| CN103406066A (en) * | 2013-07-26 | 2013-11-27 | 中国林业科学研究院林产化学工业研究所 | Rosinyl polyoxyethylene amine type gemini surfactant and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101831066A (en) * | 2010-03-31 | 2010-09-15 | 中国林业科学研究院林产化学工业研究所 | Method for preparing rosin-based surfactant |
| CN103406066A (en) * | 2013-07-26 | 2013-11-27 | 中国林业科学研究院林产化学工业研究所 | Rosinyl polyoxyethylene amine type gemini surfactant and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106943948A (en) * | 2017-03-28 | 2017-07-14 | 江南大学 | One class abietyl sulfobetaines amphoteric surfactant and its performance |
| CN107298444A (en) * | 2017-06-26 | 2017-10-27 | 江南大学 | It is a kind of using preparation of the abietyl Gemini surface active agent as the Metaporous silicon dioxide material of template and its performance |
| CN115124438A (en) * | 2022-07-14 | 2022-09-30 | 江南大学 | Preparation and application of efficient natural product-based viscoelastic solution |
| CN115124438B (en) * | 2022-07-14 | 2023-11-10 | 江南大学 | Preparation and application of efficient natural product-based viscoelastic solution |
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Application publication date: 20170104 |