CN108675934A - A kind of worm micella formed by abietyl Gemini surface active agent - Google Patents
A kind of worm micella formed by abietyl Gemini surface active agent Download PDFInfo
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- CN108675934A CN108675934A CN201810441594.8A CN201810441594A CN108675934A CN 108675934 A CN108675934 A CN 108675934A CN 201810441594 A CN201810441594 A CN 201810441594A CN 108675934 A CN108675934 A CN 108675934A
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- compound
- active agent
- surface active
- gemini surface
- abietyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/12—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
Abstract
The invention discloses a kind of worm micellas formed by abietyl Gemini surface active agent, belong to synthesis and the application field of natural products surfactant.The molecular structure of the abietyl Gemini surface active agent of the present invention is as follows：The present invention gives the synthetic method of this abietyl Gemini surface active agent and the preparation methods of worm micella.The relative molecular mass of the abietyl Gemini surface active agent is 1071.26, and critical micelle concentration value is 0.1009mmolL‑1, have preferable water-soluble.When its solution concentration is more than 50mmolL‑1When, itself can form vermiculate glues.As a kind of environmentally protective surfactant, the industrial process such as household chemicals formula and oil exploitation are can be applied to.
Description
Technical field
The present invention relates to a kind of worm micellas formed by abietyl Gemini surface active agent, belong to the work of natural products surface
The synthesis of property agent and application field.
Background technology
Rosin is the characteristic in China and important forest resourceies, has recyclability, biodegradable, cheap etc.
Advantage, abundance.Chemically from the point of view of ingredient, the mixture that rosin is made of various kinds of resin acid, the bone with tricyclic diterpene
Frame structure has apparent hydrophobicity.As other fragrant cluster compounds, a variety of parental materials can occur for rosin acid
Reaction introduces substituent group or active group, is readily synthesized multiple target compounds, is that the important raw material of green surfactant comes
Source.
Gemini surface active agent is by chemical bond by two or more surfactant monomers, in hydrophilic head base
Or close to a kind of neighbouring novel surfactant for being linked together and being formed with spacer group of hydrophilic head base.It lives with conventional surface
Property agent is compared, and the unique structure of Gemini surface active agent makes it show higher surface-active, lower critical micelle concentration,
Effective wetability, low-temperature water-soluble, good solubilising, unique rheological characteristic, good anti-calcium soap dispersive property etc..Cause
This, before Gemini surface active agent is applied in the fields such as oil-gas mining, chemical, nano material, biotechnology, detergents and cosmetic
Scape is wide.And abietyl Gemini surface active agent is obtained using rosin as Material synthesis, meets world today's surfactant industry
Development trend.
Invention content
The present invention, by serial reaction step, has synthesized a kind of pine using the important derivatives dehydroabietic acid of rosin as raw material
Perfume base Gemini surface active agent.This surfactant has lower critical micelle concentration, and when its solution concentration is more than
50mmol·L-1When, itself can form vermiculate glues, and solution is made to show significant viscoplasticity, be that rosin is lived in novel surface
Property agent synthesis and the application of new technical field lay the foundation.
The first purpose of the invention is to provide a kind of abietyl Gemini surface active agent compound (R-D-12-D-R),
Shown in structure formula (I)：
Second object of the present invention is to provide a kind of synthetic method of the compound.
In one embodiment, the method is closed using the main component dehydroabietic acid in disproportionated rosin as raw material
At.
In one embodiment, the route of the synthesis is as follows：
In one embodiment, the synthetic method, including：Make dehydroabietic acid and SOCl2Reaction generates compound 1；
Make compound 1 that compound 2 be obtained by the reaction with dimethylethanolamine；Structural formula is obtained by the reaction with 1,12- dibromo-dodecanes in compound 2
(I) compound R-D-12-D-R.
In one embodiment, the synthetic method specifically includes：
The synthesis of dehydrogenation fir acyl chlorides 1：The there-necked flask with device for absorbing tail gas and reflux condensing tube is added in dehydroabietic acid
In；Temperature is risen to 55 DEG C, starts that SOCl is slowly added dropwise2, there is bulk gas generation；After completion of dropwise addition, setting temperature is 60 DEG C,
React 3h；After reaction, excessive SOCl is removed under reduced pressure2, dehydrogenation fir acyl chlorides 1 is made；
The synthesis of compound 2：Under condition of ice bath, the dichloromethane solution of obtained chloride dehydroabietic 1 is slowly added dropwise
To after dimethylethanolamine, the reaction was continued 0.5h；After reaction, then by viscous solution after the lower removing solvent of decompression it is dissolved in water
In, system pH is adjusted to 12-13 with NaOH aqueous solutions, with petroleum ether extraction, organic layer is washed with water 5-6 times, then with anhydrous
Sodium sulphate is dried；After suction filtration, filtrate is removed into solvent under reduced pressure, (eluant, eluent is petroleum ether with silica gel column chromatography purified product：
Ethyl acetate=2:1) yellow, viscous liquid, is obtained；
The synthesis of abietyl Gemini surface active agent R-D-12-D-R：To the 250mL eggplants of the acetone soln equipped with compound 2
1,12- dibromo-dodecanes are added in shape bottle, are placed in back flow reaction 12h in 70 DEG C of oil baths；After acquired solution is cooled to room temperature, have white
Color solid is precipitated；After obtained solid is washed 3 times with petroleum ether, it is dried in vacuo 12h at 60 DEG C, obtains finished product abietyl Shuangzi
Surfactant R-D-12-D-R.
Third object of the present invention is to provide a kind of vermiculate glues, the compounds of the structure formula (I) containing the present invention.
In one embodiment, the vermiculate glues is formed by the compound of the structure formula (I) of the present invention.
In one embodiment, the concentration range of the compound of structure formula (I) is 50-200mmolL-1。
In one embodiment, the zero-shear viscosity of the aqueous solution of the compound of structure formula (I) is up to 3 × 103Pa·
s。
Fourth object of the present invention provides the application of the compound of the structure formula (I).
In one embodiment, the application includes being used as surfactant applications in various fields.
In one embodiment, the application includes for fields such as oil-gas mining, chemical, nano materials.
Advantageous effect
The present invention obtains abietyl Gemini surface active agent using product of natural product rosin as raw material, by a series of synthesis steps
R-D-12-D-R.The relative molecular mass of R-D-12-D-R is 1071.26, and critical micelle concentration value is 0.1009mmolL-1, there is good water solubility.When its solution concentration is more than 50mmolL-1When, itself can form vermiculate glues.As one
The environmentally protective surfactant of kind, R-D-12-D-R can be used for the industrial process such as oil exploitation.
With the compound close with structure of the invention(its
Middle n=10) it compares, overcome that its dissolubility is relatively low, can not form the defect of worm micella.
The present invention uses the compound of bromine ion-containing, and synthetic yield is higher, and performance is more stablized.
Description of the drawings
Fig. 1 is abietyl Gemini surface active agent R-D-12-D-R's1H NMR。
The surface tension γ that Fig. 2 is abietyl Gemini surface active agent R-D-12-D-R is with the change curve (25 of concentration C
℃)。
Fig. 3 is viscosity of the abietyl Gemini surface active agent R-D-12-D-R aqueous solutions under various concentration with shear rate
Variation (25 DEG C).
Fig. 4 be elasticity modulus (G ') of the abietyl Gemini surface active agent R-D-12-D-R aqueous solutions under various concentration and
Viscous modulus (G ") with angular frequency (ω) variation (25 DEG C).
Specific implementation mode
Embodiment 1：The synthesis of dehydrogenation fir acyl chlorides 1
Dehydroabietic acid (30g, 0.1mol) is added in the there-necked flask with device for absorbing tail gas and reflux condensing tube.It will be warm
Degree rises to 55 DEG C, starts that SOCl is slowly added dropwise2(14.3g, 0.12mol) has bulk gas generation.After completion of dropwise addition, setting temperature
Degree is 60 DEG C, reacts 3h.After reaction, excessive SOCl is removed under reduced pressure2, dehydrogenation fir acyl chlorides 1 is made.
Embodiment 2：The synthesis of compound 2
Under condition of ice bath, the dichloromethane solution of obtained chloride dehydroabietic (31.9g, 0.10mol) is slowly added dropwise
To after dimethylethanolamine (10.7g, 0.12mol), the reaction was continued 0.5h.It after reaction, then will be after the lower removing solvent of decompression
Viscous solution be dissolved in the water, with NaOH aqueous solution tune pH=12-13, with petroleum ether extraction, organic layer is washed with water 5-6 times,
Then it is dried with anhydrous sodium sulfate.After suction filtration, filtrate is removed into solvent under reduced pressure, with (the elution of silica gel column chromatography purified product
Agent is petroleum ether：Ethyl acetate=2:1) yellow, viscous liquid, is obtained.
Embodiment 3：The synthesis of abietyl Gemini surface active agent R-D-12-D-R
Be added into the acetone soln of compound 2 (5g, 0.0135mol) 1,12- dibromo-dodecanes (2.1g,
0.0064mol), it is placed in back flow reaction 12h in 70 DEG C of oil baths.Acquired solution is cooled to room temperature, after suction filtration, by obtained solid stone
After oily ether washes 3 times, solid is dried in vacuo 12h at 60 DEG C, and it is R-D-12-D-R to obtain white solid.Yield：80%.
Embodiment 4：The measurement of surface tension
The aqueous solution of the abietyl Gemini surface active agent R-D-12-D-R of various concentrations a series of is prepared, experimental water is
The ultra-pure water of resistivity 18.2M Ω cm.The aqueous surfactant solution configured is placed in Air-Them air baths and is balanced
For 24 hours, control equilibrium temperature is 25 ± 0.5 DEG C.The surface tension of aqueous solution is measured with hanging ring method at 25 DEG C, each point repeats 3
It is secondary, its average value is taken, draws the surface tension of sample with the variation relation curve of concentration.
The results are shown in Figure 2, as a result shows：Surfactant R-D-12-D-R has very strong ability of aggregation, critical
Micellar concentration is only 0.1mmolL-1, it is rigid dehydroabietic acid hydrophobic grouping and the coefficient result of long coupling link.
Embodiment 5：The measurement of rheological behaviour
By a series of surfactant solutions prepared, constant temperature for 24 hours, uses model in 25 DEG C of insulating box
The rheometer of Discovery DHR-3 carries out viscoelastic properties test to R-D-12-D-R aqueous solutions.Select Stress Control pattern, cone
Plate gauge lattice are standard ETC steel, and cone angle is 1 °, a diameter of 60mm of cone-plate.Before starting test, by sample pipetting volume to platform, into
After row trimming operation, the sample solution of platform edges spilling is slowly scraped off, sample is then stood into balance 2min.When being tested
Final distance between cone-plate and platform is 29 μm.Sample first carries out strain sweep before testing, to determine the linear-viscoelastic of sample
Area, it is ensured that the test of all samples carries out in its linear viscoelastic region.Temperature control is at 25 DEG C in experimentation, experimental implementation
It is the ultra-pure water of 18.2M Ω cm with water.
As a result as shown in Figure 3 and Figure 4.
Wherein, Fig. 3 is shown, when the concentration of surfactant R-D-12-D-R is in 50mmolL-1When above, with shearing
The increase of rate, aqueous solution show the behavior of shear shinning, illustrate there is worm micelle formation in solution.This shows rigidity
Dehydroabietic acid hydrophobic grouping and long coupling link common presence, increase the molecular geometry of surfactant R-D-12-D-R,
Be conducive to the formation of this asymmetric aggregated structure of worm micella.
Fig. 4 shows that in the angular frequency range of measurement, elasticity modulus is always positioned on viscous modulus, illustrates that surface is lived
Property agent R-D-12-D-R aqueous solutions have fabulous elasticity, be conducive to its application in fields such as oilfield exploitation, household chemicals.
Claims (10)
1. a kind of compound, which is characterized in that the structure of the compound is as shown in structure formula (I)：
2. the synthetic method of compound described in claim 1, which is characterized in that the method be in disproportionated rosin it is main at
Point dehydroabietic acid synthesizes for raw material.
3. synthetic method according to claim 2, which is characterized in that the route of the synthesis is as follows：
4. synthetic method according to claim 2, which is characterized in that the method includes：Make dehydroabietic acid and SOCl2Instead
Compound 1 should be generated；Make compound 1 that compound 2 be obtained by the reaction with dimethylethanolamine；Compound 2 and 1,12- dibromo-dodecanes
Compound R-the D-12-D-R of structure formula (I) is obtained by the reaction.
5. a kind of vermiculate glues, which is characterized in that the compound of the structure formula (I) containing claim 1.
6. vermiculate glues according to claim 5, which is characterized in that the vermiculate glues by claim 1 knot
The compound of structure formula (I) is formed.
7. vermiculate glues according to claim 5 or 6, which is characterized in that the concentration range of the compound of structure formula (I)
For 50-200mmolL-1。
8. the application of the compound of structure formula (I) described in claim 1.
9. application according to claim 8, which is characterized in that the application includes as surfactant in each field
Using.
10. application according to claim 8, which is characterized in that the application include for oil-gas mining, chemical,
The fields such as nano material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810441594.8A CN108675934A (en) | 2018-05-10 | 2018-05-10 | A kind of worm micella formed by abietyl Gemini surface active agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713445A (en) * | 2019-10-10 | 2020-01-21 | 江南大学 | Preparation and application of rosin-based chiral worm micelle |
| CN111111549A (en) * | 2019-12-17 | 2020-05-08 | 广东省石油与精细化工研究院 | Dehydroabietyl-based saccharide surfactant and preparation method and application thereof |
| CN112142613A (en) * | 2020-09-22 | 2020-12-29 | 江南大学 | Rosin-based small-molecule organic gel and cyclohexane gel formed by same |
| CN116262888A (en) * | 2021-12-13 | 2023-06-16 | 上海新阳半导体材料股份有限公司 | Neutralizing cleaning agent after plasma etching cleaning |
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| CN101284794A (en) * | 2008-05-27 | 2008-10-15 | 中国林业科学研究院林产化学工业研究所 | Rosinyl quaternary ammonium salt type gemini surfactant and method for preparing same |
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| CN101284794A (en) * | 2008-05-27 | 2008-10-15 | 中国林业科学研究院林产化学工业研究所 | Rosinyl quaternary ammonium salt type gemini surfactant and method for preparing same |
Non-Patent Citations (4)
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| 中国林业科学研究院学位论文: "松香基双子表面活性剂的合成及性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713445A (en) * | 2019-10-10 | 2020-01-21 | 江南大学 | Preparation and application of rosin-based chiral worm micelle |
| CN111111549A (en) * | 2019-12-17 | 2020-05-08 | 广东省石油与精细化工研究院 | Dehydroabietyl-based saccharide surfactant and preparation method and application thereof |
| CN112142613A (en) * | 2020-09-22 | 2020-12-29 | 江南大学 | Rosin-based small-molecule organic gel and cyclohexane gel formed by same |
| CN112142613B (en) * | 2020-09-22 | 2021-06-25 | 江南大学 | Rosin-based small-molecule organic gel and cyclohexane gel formed by same |
| CN116262888A (en) * | 2021-12-13 | 2023-06-16 | 上海新阳半导体材料股份有限公司 | Neutralizing cleaning agent after plasma etching cleaning |
| CN116262888B (en) * | 2021-12-13 | 2024-03-08 | 上海新阳半导体材料股份有限公司 | Neutralizing cleaning agent after plasma etching cleaning |
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