CN108675934A - A kind of worm micella formed by abietyl Gemini surface active agent - Google Patents

Abstract

The invention discloses a worm micelle formed from a rosin-based gemini surfactant, and belongs to the field of synthesis and application of natural product surfactants. The molecular structure of rosin base gemini surfactant of the present invention is as follows: The invention provides the synthesis method of the rosin-based gemini surfactant and the preparation method of the worm micelles. The relative molecular mass of the rosin-based gemini surfactant is 1071.26, and its critical micelle concentration is 0.1009mmol·L ^‑1 , which has good water solubility. When its solution concentration is greater than 50mmol·L ^-1 , it can form worm-like micelles by itself. As a green and environment-friendly surfactant, it can be used in daily chemical formulations and industrial processes such as oil exploitation.

Description

A worm micelle formed from a rosin-based gemini surfactant

technical field

The invention relates to a worm micelle formed from a rosin-based gemini surfactant, and belongs to the field of synthesis and application of natural product surfactants.

Background technique

Rosin is a characteristic and important forestry resource in my country. It has the advantages of renewability, biodegradability, and low price, and its output is abundant. From the perspective of chemical composition, rosin is a mixture of various resin acids, which has a tricyclic diterpene skeleton structure and has obvious hydrophobicity. Like other aromatic cluster compounds, rosin resin acid can undergo a variety of electrophilic substitution reactions, introduce substituents or active groups, and easily synthesize a variety of target compounds. It is an important source of raw materials for green surfactants.

Gemini surfactants are a new type of surfactants formed by linking two or more surfactant monomers together with linking groups at or near the hydrophilic head group through chemical bonds. Compared with traditional surfactants, the unique structure of gemini surfactants makes them exhibit higher surface activity, lower critical micelle concentration, effective wettability, low temperature water solubility, good solubilization, unique Rheology, good anti-calcium soap dispersion performance, etc. Therefore, gemini surfactants have broad application prospects in the fields of oil and gas exploration, chemical engineering, nanomaterials, biotechnology, and daily chemistry. The rosin-based gemini surfactant is synthesized from rosin, which is in line with the development trend of the surfactant industry in the world today.

Contents of the invention

The invention uses dehydroabietic acid, an important derivative of rosin, as a raw material, and through a series of reaction steps, synthesizes a rosin-based gemini surfactant. This surfactant has a low critical micelle concentration, and when its solution concentration is greater than 50mmol·L ^-1 , it can form worm-like micelles by itself, so that the solution exhibits significant viscoelasticity, which is a new type of surface active agent for rosin. It lays the foundation for the synthesis of pharmaceuticals and the application of new technologies.

First object of the present invention is to provide a kind of rosin-based gemini surfactant compound (R-D-12-D-R), shown in its structural formula (I):

The second object of the present invention is to provide a synthetic method of said compound.

In one embodiment, the method is synthesized by using dehydroabietic acid, the main component of disproportionated rosin, as a raw material.

In one embodiment, the synthetic route is as follows:

In one embodiment, the synthesis method includes: reacting dehydroabietic acid with SOCl ₂ to generate compound 1; reacting compound 1 with dimethylethanolamine to obtain compound 2; reacting compound 2 with 1,12-dibromodeca The dioxane reacts to obtain the compound RD-12-DR of the structural formula (I).

In one embodiment, the synthesis method specifically includes:

Synthesis of dehydroabietic acid chloride 1: Add dehydroabietic acid into a three-neck flask with tail gas absorption device and reflux condenser; raise the temperature to 55°C, start to slowly add SOCl ₂ dropwise, and a large amount of gas is generated; dropwise end Finally, set the temperature at 60°C and react for 3 hours; after the reaction, excess SOCl ₂ was removed under reduced pressure to obtain dehydroabietoyl chloride 1;

Synthesis of Compound 2: Under ice-bath conditions, slowly drop the obtained dichloromethane solution of dehydroabietic acid chloride 1 into dimethylethanolamine, and continue the reaction for 0.5h; after the reaction, remove the solvent under reduced pressure Finally, the viscous solution was dissolved in water, the pH value of the system was adjusted to 12-13 with NaOH aqueous solution, extracted with petroleum ether, the organic layer was washed 5-6 times with water, and then dried with anhydrous sodium sulfate; after suction filtration, the filtrate was The solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 2:1) to obtain a yellow viscous liquid;

Synthesis of rosin-based gemini surfactant R-D-12-D-R: Add 1,12-dibromododecane to a 250mL eggplant-shaped bottle containing compound 2 in acetone solution, and place it in an oil bath at 70°C for reflux reaction for 12 hours; After the obtained solution was cooled to room temperature, a white solid precipitated out; the obtained solid was washed 3 times with petroleum ether, and then vacuum-dried at 60°C for 12 hours to obtain the final product of rosin-based gemini surfactant R-D-12-D-R.

The third object of the present invention is to provide a worm-like micelle containing the compound of formula (I) of the present invention.

In one embodiment, the worm-like micelles are formed from compounds of formula (I) of the present invention.

In one embodiment, the concentration of the compound of formula (I) is in the range of 50-200 mmol·L ^-1 .

In one embodiment, the zero-shear viscosity of the aqueous solution of the compound of structural formula (I) can reach 3×10 ³ Pa·s.

The fourth object of the present invention is to provide the use of the compound of formula (I).

In one embodiment, the application includes application as a surfactant in various fields.

In one embodiment, the application includes fields such as oil and gas extraction, chemical engineering, and nanomaterials.

Beneficial effect

The invention uses the natural product rosin as a raw material to obtain the rosin-based gemini surfactant RD-12-DR through a series of synthesis steps. The relative molecular mass of RD-12-DR is 1071.26, its critical micelle concentration is 0.1009mmol·L ^-1 , and it has good water solubility. When its solution concentration is greater than 50mmol·L ^-1 , it can form worm-like micelles by itself. As a green surfactant, RD-12-DR can be used in industrial processes such as oil extraction.

Compounds close to the structure of the present invention (where n=10), it overcomes the defects of low solubility and inability to form worm micelles.

The invention adopts the compound containing bromide ions, the synthesis yield is higher, and the performance is more stable.

Description of drawings

Figure 1 is the ¹ H NMR of rosin-based gemini surfactant RD-12-DR.

Fig. 2 is a graph showing the surface tension γ of the rosin-based gemini surfactant R-D-12-D-R changing with the concentration C (25° C.).

Fig. 3 is the change of the viscosity of the rosin-based gemini surfactant R-D-12-D-R aqueous solution at different concentrations with the shear rate (25° C.).

Figure 4 is the change of elastic modulus (G') and viscous modulus (G") with angular frequency (ω) at different concentrations of rosin-based gemini surfactant R-D-12-D-R aqueous solution (25°C).

Detailed ways

Embodiment 1: the synthesis of dehydroabietoyl chloride 1

Add dehydroabietic acid (30g, 0.1mol) into a three-neck flask equipped with an exhaust gas absorption device and a reflux condenser. The temperature was raised to 55°C, and SOCl ₂ (14.3 g, 0.12 mol) was slowly added dropwise, and a large amount of gas was generated. After the dropwise addition, set the temperature to 60°C and react for 3 hours. After the reaction, excess SOCl ₂ was removed under reduced pressure to obtain dehydroabietoyl chloride 1.

Embodiment 2: the synthesis of compound 2

Under the condition of ice bath, the obtained dichloromethane solution of dehydroabietic acid chloride (31.9 g, 0.10 mol) was slowly added dropwise to dimethylethanolamine (10.7 g, 0.12 mol), and the reaction was continued for 0.5 h. After the reaction is over, dissolve the viscous solution after removing the solvent under reduced pressure in water, adjust the pH to 12-13 with NaOH aqueous solution, extract with petroleum ether, wash the organic layer with water for 5-6 times, and then wash it with anhydrous sodium sulfate dry. After suction filtration, the solvent was removed from the filtrate under reduced pressure, and the product was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 2:1) to obtain a yellow viscous liquid.

Embodiment 3: the synthesis of rosin-based gemini surfactant R-D-12-D-R

Add 1,12-dibromododecane (2.1 g, 0.0064 mol) to the acetone solution of compound 2 (5 g, 0.0135 mol), and place it in an oil bath at 70° C. for reflux reaction for 12 h. The obtained solution was cooled to room temperature, and after suction filtration, the obtained solid was washed 3 times with petroleum ether, and the solid was vacuum-dried at 60°C for 12 hours to obtain a white solid which is R-D-12-D-R. Yield: 80%.

Embodiment 4: the mensuration of surface tension

A series of aqueous solutions of rosin-based gemini surfactant R-D-12-D-R with different concentrations were prepared, and the experimental water was ultrapure water with a resistivity of 18.2MΩ·cm. Place the prepared aqueous surfactant solution in an Air-Them air bath to balance for 24 hours, and control the balance temperature to 25±0.5°C. Measure the surface tension of the aqueous solution at 25°C by the suspension ring method, repeat 3 times for each point, take the average value, and draw the relationship curve of the surface tension of the sample with the concentration.

The results are shown in Figure 2. The results show that the surfactant RD-12-DR has a strong aggregation ability, and its critical micelle concentration is only 0.1mmol·L ^-1 . It is a rigid hydrophobic group of dehydroabietic acid and The result of the joint action of long chains.

Example 5: Determination of Rheological Behavior

A series of prepared surfactant solutions were kept in an incubator at 25°C for 24 hours, and the viscoelastic properties of the R-D-12-D-R aqueous solution were tested with a Discovery DHR-3 rheometer. The stress control mode is selected, the cone plate specification is standard ETC steel, the cone angle is 1°, and the cone plate diameter is 60mm. Before starting the test, add the sample to the platform, and after cutting the edge, slowly scrape off the sample solution overflowing from the edge of the platform, and then let the sample stand for 2 minutes to balance. The final distance between the cone-plate and the platform at the time of the test was 29 μm. The sample is subjected to strain scanning before testing to determine the linear viscoelastic region of the sample, ensuring that all samples are tested within its linear viscoelastic region. During the experiment, the temperature was controlled at 25°C, and the water used in the experiment was 18.2 MΩ·cm ultrapure water.

The results are shown in Figure 3 and Figure 4.

Among them, Figure 3 shows that when the concentration of the surfactant RD-12-DR is above 50mmol·L ^-1 , as the shear rate increases, its aqueous solution exhibits a behavior of shear thinning, indicating that there are worms in the solution Micelle formation. This indicated that the co-existence of rigid dehydroabietic acid hydrophobic groups and long linkage chains increased the molecular geometry of the surfactant RD-12-DR, which was beneficial to the formation of the asymmetric aggregation structure of worm micelles.

Figure 4 shows that in the measured angular frequency range, the elastic modulus is always above the viscous modulus, indicating that the aqueous solution of the surfactant R-D-12-D-R has excellent elasticity, which is beneficial to its application in oil field production, daily chemicals applications in other fields.

Claims (10)

1. a compound, is characterized in that, the structure of described compound is as shown in structural formula (I): 2. the compound method of the described compound of claim 1 is characterized in that, described method is to be that raw material is synthesized with the main component dehydroabietic acid in the disproportionated rosin. 3. synthetic method according to claim 2, is characterized in that, the route of described synthesis is as follows: 4. synthetic method according to claim 2, is characterized in that, described method comprises: make dehydroabietic acid and SOCl Reaction generates compound ₁ ; Make compound 1 react with dimethylethanolamine to obtain compound 2; Compound 2 and The compound RD-12-DR of structural formula (I) is obtained by reacting 1,12-dibromododecane. 5. A worm-like micelle, characterized in that it contains the compound of structural formula (I) according to claim 1. 6. The worm-like micelle according to claim 5, characterized in that, the worm-like micelle is formed by the compound of the structural formula (I) of claim 1. 7. The worm-like micelles according to claim 5 or 6, characterized in that the concentration of the compound of structural formula (I) is in the range of 50-200 mmol·L ^-1 . 8. The application of the compound of structural formula (I) described in claim 1. 9. The application according to claim 8, characterized in that the application comprises applications in various fields as a surfactant. 10. The application according to claim 8, characterized in that the application includes fields such as oil and gas exploration, chemical engineering, and nanomaterials.