CN108837770A - The four poly- surfactant worm-like micelle systems containing azobenzene group - Google Patents

Abstract

The invention discloses the four poly- surfactant worm-like micelle systems containing azobenzene group, belong to surfactant science and applied technical field.The synthesis of surfactant of the invention includes using enuatrol, trimethylamine, para-nitrotoluene as starting material, synthesize N1, N1'- ((diazene -1,2- diyl bis- (4,1- phenylene)) two (methylene)) two (N1, N1, N3, N3, N3- pentamethyl -1,3- diamines), finally with four polyquaternium and sodium oleae mixture, obtain the vermiculate glues of high viscoelasticity.Raw material sources are wide, biorenewable, environmentally protective, and biological degradability is high, enrich the type for the oligo surfactant that renewable resource is raw material, can be widely used in the research of surfactant self-organizing system.

Description

Tetrameric Surfactant Worm-Like Micellar System Containing Azophenyl Groups

technical field

The present invention relates to a tetrameric surfactant worm-like micelle system containing an azophenyl group, in particular to a worm-like micelle constructed by an electrostatically constructed tetrameric surfactant with an azophenyl group, which belongs to the surface Active agent science and application technology field.

Background technique

Surfactants are a class of substances that can significantly reduce the surface tension of a solution and form ordered molecular aggregates in the bulk phase when added in a very small amount, consisting of hydrophobic groups and hydrophilic groups. Due to its amphiphilic properties, surfactants can not only adsorb on the interface, but also form ordered aggregates in a solution of a certain concentration, so they have the properties of wetting, emulsifying, solubilizing, washing, and dispersing. In solution, it can self-organize to form various ordered molecular aggregates, such as spherical micelles, rod micelles, worm micelles, vesicles and liquid crystals, etc. The morphology, formation conditions and related mechanisms of surfactant aggregates have always been the focus of attention and research in the field of surfactant science. Among them, worm micelles play an important role in recent research. When the worm micelles are entangled with each other as the concentration increases, it forms a dynamic network structure, and its aqueous solution has viscoelastic properties. It is precisely because of its unique properties that it has been widely used in the fields of controlled drug release, bioengineering, microfluidics, cosmetics, and coatings.

"Pseudo" oligomeric surfactants are a class of amphiphilic compounds that are simple to prepare and have excellent performance. The construction of "pseudo" oligomeric surfactants through non-covalent interactions is the most efficient way to form oligomeric surfactants. Complicated synthetic reactions, and have lower critical micelle concentration (cmc), higher viscosity, richer self-assembly behavior and unique rheological behavior. The molecular structure of the amphiphile is conducive to the formation of worm micelles, and it is expected to self-assemble into viscoelastic fluids at a relatively low dosage. Therefore, the research on the self-assembly behavior of "pseudo" oligomeric surfactants constructed through non-covalent bonds has both theoretical research and practical value.

The worm-like micelles constructed by tetrameric surfactants with azophenyl groups refer to the surfactant molecular structure of the formed worm-like micelles containing groups with azophenyl groups (such as azobenzene) The corresponding mechanism is that the surfactant solution is irradiated with ultraviolet light of a certain wavelength, and the azobenzene molecule is converted from a cis structure to a trans structure, thereby causing a change in the hydrophilic-lipophilic balance value of the surfactant molecule or The structural changes of the counterions participating in the micellar self-assembly lead to the destruction or reconstruction of the worm-like micellar structure, thereby realizing the controllable change of the macroscopic viscoelasticity of the system, and the cycle can be repeated.

Contents of the invention

In order to obtain worm-like micelles with azophenyl groups, the present invention enhances the aggregation ability of oligomeric ionic surfactants, introduces azophenyl groups in oligomeric salts, and passes four quaternary ammonium head groups through Azophenyl group linkage.

First object of the present invention is to provide a kind of tetrameric surfactant of electrostatic construction, and its structure is as follows:

The second object of the invention is to provide a preparation method of worm-like micelles containing azophenyl group, said method is to use p-nitrotoluene, dimethylamine, magnesium strips, sodium oleate as starting materials , to synthesize a tetrameric quaternary ammonium salt containing azobenzene, and finally compound the tetrameric quaternary ammonium salt with sodium oleate at a molar ratio of 1:4 to obtain the final highly viscoelastic worm-like micelles.

In one embodiment of the present invention, the preparation method specifically includes: using p-nitrotoluene and magnesium bars as starting materials, azobenzene is synthesized through a substitution reaction, and azobenzene and N-bromosuccinyl Amines are mixed and reacted to form 1,2-bis(4-(bromomethyl)phenyl)diazene, and 1,2-bis(4-(bromomethyl)phenyl)diazene and dimethylamine solution Mix and react to generate 1,1'-(diazene-1,2-diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine), and 1,1'- (Diazene-1,2-diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine) and 3-bromo-N,N,N-trimethylpropane- 1-ammonium reacts to form N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3 , N3-pentamethyl-1,3-diaminium), the synthetic product N1, N1'-((diazene-1,2-diylbis(4,1-phenylene)) bis( Methyl)) bis(N1, N1, N3, N3, N3-pentamethyl-1,3-diaminium) and sodium oleate are mixed uniformly to obtain the final electrostatically constructed light containing azophenyl group Polysurfactant.

In one embodiment of the present invention, the 1,1'-(diazene-1,2-diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine ) to 3-bromo-N, N, N-trimethylpropan-1-ammonium in a molar ratio of 1:2 to 1:3.

In one embodiment of the present invention, the 1,1'-(diazene-1,2-diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine ) and 3-bromo-N,N,N-trimethylpropan-1-ammonium under the conditions of 60°C-85°C for 8-12 hours.

In one embodiment of the present invention, said N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1 , N1, N3, N3, N3-pentamethyl-1,3-diaminium) and sodium oleate were uniformly mixed in a molar ratio of 1:4 to obtain the final electrostatically constructed tetrameric surfactant.

In one embodiment of the present invention, the preparation method specifically includes: using p-nitrotoluene (27g, 0.2mol) and magnesium strips (9.6g, 0.4mol) as starting materials, mixing them in a molar ratio of 1:2, Warming up to 60°C for a substitution reaction to synthesize azobenzene (21g, 0.1mol), azobenzene (21.0g, 0.1mol) and N-bromosuccinimide (35.6g, 0.2mol) in a molar ratio of 1: 2 mixed, heated to 80°C, the reaction produced 1,2-bis(4-(bromomethyl)phenyl)diazene (29g, 0.08mol), 1,2-bis(4-(bromomethyl) Phenyl)diazene (29g, 0.08mol) and dimethylamine solution (18g, 0.4mol) were mixed in a molar ratio of 1:5, heated to 50°C, and reacted to form 1,1'-(diazene-1, 2-diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine) (20.74g, 0.07mol), 1,1'-(diazene-1,2- Diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine) (20.74g, 0.07mol) and 3-bromo-N,N,N-trimethylpropane-1- Ammonium (36.4 g, 0.14 mol) was reacted to form N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1, N1, N3, N3, N3-pentamethyl-1,3-diaminium) (49.0g, 0.06mol), the synthetic product N1, N1'-((diazene-1,2-diylbis( 4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3-pentamethyl-1,3-diaminium) (49.0g, 0.06mol) with oleic acid Sodium (73.0 g, 0.24 mol) was mixed evenly at a molar ratio of 1:4 to obtain the final electrostatically constructed tetrameric surfactant containing azophenyl groups.

In one embodiment of the present invention, the synthetic route of the tetrameric quaternary ammonium salt containing azophenyl group:

The third object of the present invention is to provide the change of solution viscoelasticity with light through rheological verification of the electrostatically structured tetrameric surfactant with azophenyl groups.

In one embodiment of the present invention, the range of regulation by ultraviolet light is 300nm-500nm.

In one embodiment of the present invention, as the ultraviolet light irradiates the surfactant solution, the solution changes from a high-viscosity gel-like liquid to a low-viscosity solution.

The fourth object of the present invention is to expand the scope of application of oleic acid. my country is a large agricultural country, and the output of oleic acid ranks in the forefront of the world. The invention provides a wide application potential for renewable resources and green environmental protection oleic acid.

In one embodiment of the present invention, the application is in the field of environment, textile, chemistry, medicine preparation, industrial cleaning, and daily chemicals.

In one embodiment of the present invention, the application includes: application to environmental protection, oil field exploitation, textile printing and dyeing, industrial cleaning, and daily chemicals.

Beneficial effects of the present invention:

(1) The electrostatically constructed tetrameric surfactant of the present invention uses 18 carbons of oleic acid as the hydrophobic chain, has a wide source of oleic acid, is bio-renewable, green and environmentally friendly, has high biodegradability, and enriches renewable resources as raw materials The types of bio-based surfactants can be widely used in the research of surfactant self-organized systems. Oleic acid with eighteen chain lengths was utilized as starting material. If the short carbon chain saturated fatty acid is selected as the starting material, the self-assembly ability and aggregation morphology of the surfactant are not as superior as the viscoelastic properties of the surfactant formed from ultra-long chain oleic acid as the raw material.

(2) The present invention uses sodium oleate, N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1 , N3, N3, N3-pentamethyl-1,3-diamine) as the starting material to synthesize the electrostatically constructed tetrameric surfactant, which is the most efficient method and avoids the complicated process compared with the traditional synthesis process In the synthetic reaction of the present invention, the last step only needs to be added to the sample bottle according to the charge ratio to construct the tetrameric surfactant, which greatly improves the yield (100%); while the traditional chemical synthesis route requires multiple recrystallizations Only then can a purer product be obtained, and the yield is low (about 20%). It can be seen that the purification process of the present invention is relatively simple and the yield is high.

(3) The present invention combines sodium oleate with N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1 , N3, N3, N3-pentamethyl-1,3-diamine) compounded to obtain a tetrameric surfactant constructed electrostatically, the molecular structure of the amphiphile is conducive to the formation of worm micelles, and at a lower It can self-assemble into a viscoelastic fluid at a low dosage. Therefore, the research on the self-assembly behavior of "pseudo" oligomeric surfactants constructed through non-covalent bonds has both theoretical research and practical value.

(4) The stability of the viscoelasticity of the electrostatically constructed tetrameric surfactant with azophenyl groups constructed by the present invention is verified by rheology, and the results show that when irradiated with ultraviolet light for 2h, the solution viscoelasticity remains stable constant. The azophenyl groups of the present invention are electrostatically combined with protonated tertiary amines to form a tetrameric structure, and the hydrophobic volume is further increased, so that the packing parameter P is more likely to fall within the range of 1/2-1/3, and it is easier to form a long and soft Worm-like micelles, worm-like micelles are intertwined to form a three-dimensional network structure, so that the solution exhibits viscoelasticity similar to that of polymers.

(5) The tetrameric surfactant containing azobenzene of the present invention can be widely used in many fields such as cosmetics, mineral flotation agents, textile fiber softeners and antistatic agents, and pigment dispersants.

(6) The existing literature has never reported that the azophenyl group is introduced into the tetrameric surfactant. The present invention introduces the azophenyl group into the tetrameric surfactant for the first time, and through NMR, ultraviolet spectrum, flow The effects of ultraviolet light on the molecular structure of tetrameric salts containing azophenyl groups and the viscoelasticity of quasi-tetrameric surfactants were studied. For the first time, we have discovered tetrameric surfactants containing azophenyl groups that are not affected by UV light.

Description of drawings

Figure 1 is N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3- Pentamethyl-1,3-diaminium) nuclear magnetic resonance 1HNMR spectrogram;

Figure 2 is N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3- Pentamethyl-1,3-diaminium) nuclear magnetic resonance 1HNMR spectrogram after ultraviolet irradiation for 1h;

Fig. 3 is the ultraviolet spectrogram of the tetrameric surfactant solution of electrostatic construction at 25 DEG C before and after ultraviolet light irradiation of tetrameric quaternary ammonium salt;

Figure 4 is a comparison chart of static rheological curves before and after ultraviolet light irradiation at 25° C. for tetrameric surfactant solution constructed electrostatically at a concentration of 250 mmol/L.

Detailed ways

Embodiment 1: tetramer quaternary ammonium salt surfactant synthetic route

Electrostatically constructed tetrameric surfactant, the structural formula is as follows:

The synthetic route of tetrameric quaternary ammonium salt is as follows:

The preparation method of the tetrameric surfactant of electrostatic construction is N1, N1'-((diazene-1,2-diyl bis(4,1-phenylene)) two (methylene)) two ( N1, N1, N3, N3, N3-pentamethyl-1,3-diaminium) mixed with sodium oleate in a molar ratio of 1:4 to generate the final tetrameric surfactant with azophenyl groups.

Example 2: Synthesis of 1,1'-(diazene-1,2-diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine)

In a 250mL round bottom flask, add 6.86g (0.050mol) of p-nitrotoluene, 110mL of methanol, 1.5g (0.063mol) of magnesium chips and a small grain of iodine. Keep reflux. When the magnesium scrap basically reacts, cool down, add 1.5g (0.063mol) magnesium scrap, and then reflux on a hot water bath at 70-80°C until the magnesium scrap basically disappears. Cool, pour the mixture into a beaker filled with 200mL of water, slowly add glacial acetic acid to weak acidity under stirring, and precipitate a light yellow solid, filter under reduced pressure, wash the filter cake with water, recrystallize from absolute ethanol three times, and obtain crystals in the first two times. The type did not meet the requirements, and a golden yellow solid was obtained after three times. In a 250mL beaker, add 2.8g (0.013mol) 4,4'-dimethylazobenzene, 5.2g (0.029mol) NBS, benzoyl peroxide and a sufficient amount of acetonitrile, first dissolve with acetonitrile, then add half NBS and a sufficient amount of catalyst benzoyl peroxide are completely dissolved, and then the other half of NBS is added, stirred and heated to reflux for 4 hours, cooled and filtered. Take the filter residue, dissolve it with ethanol, add 1.33g (0.029mol) dimethylamine solution, stir and heat to reflux for 5h, and remove the ethanol by rotary evaporation. The remaining solid was dissolved in ethanol, and then ethyl acetate was added until a small amount of product precipitated. After cooling and precipitation, recrystallization was carried out, and the solid was obtained by suction filtration. The above steps were repeated three times to obtain a khaki solid product. Yield 60.5% (yield = p-nitrotoluene molar weight/1,1'-(diazene-1,2-diylbis(4,1-phenylene))bis(N,N-dimethyl methylamine) molar weight).

Example 3: N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3 -Synthesis of pentamethyl-1,3-diaminium)

Mix 6 g (0.02 mol) of 1,1'-(diazene-1,2-diylbis(4,1-phenylene))bis(N,N-dimethylmethylamine) with 3-bromo- N, N, N-trimethylpropan-1-ammonium 7.3g (0.04mol) was mixed in a molar ratio of 1:2, and ethanol was used as a solvent at a temperature of 80°C for 24 hours to generate N1, N1'-(( Diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3-pentamethyl-1,3-diamine Onium) 11.2 g (0.014 mol). Yield 70% (yield = moles of product/moles of starting materials).

Embodiment 4: Construction of tetrameric surfactant

N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3-pentamethyl Base-1,3-diaminium) (0.327g, 4×10 ^-4 mol), sodium oleate (0.486g, 1.6×10 ^-3 mol), ultrapure water (1.187g, 0.066mol) were added to 10mL in a glass bottle. It was then stirred well to obtain a clear solution (200 mmol/L) of the tetrameric surfactant.

Example 5: N1, N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3 -NMR ¹ HNMR spectrum and properties of -pentamethyl-1,3-diaminium)

The nuclear magnetic resonance 1HNMR spectrum of the final product obtained in Example 3 is shown in Figure 1.

According to the analysis of the nuclear magnetic resonance spectrum in Figure 1, the final product N1, N1 '-((diazene-1,2-diyl bis(4,1-phenylene)) two (methylene)) two (N1, N1, N3, N3, N3-pentamethyl-1,3-diaminium) was dissolved in D ₂ O, and the ¹ H-NMR spectrum was measured. In Fig. 1, δ=4.80 is the solvent peak of DMSO. The remaining proton displacements δ are: 8.05(d,2H), 7.80(d,2H), 3.50(t,8H), 3.23(t,30H), 2.50(t,4H). Analyzing the spectrogram data, it can be known that the final product is consistent with the designed target product. Figure 2 is the nuclear magnetic spectrum after 2 hours of irradiation. It can be seen from the figure that the tetrameric salt containing azobenzene changes from trans structure to cis structure after ultraviolet irradiation, and new peaks appear at 7.14, 6.96, and 2.97.

Electrostatically constructed tetrameric surfactants are a new class of surfactants that are electrostatically connected to multiple surfactant molecules. The rheological behavior of surfactant aqueous solution is closely related to the type of micelles in the aqueous solution. Traditional surfactants with one head and one tail tend to form spherical micelles in dilute solutions, and these micelles do not contribute much to the viscosity of aqueous solutions. The electrostatically constructed tetrameric surfactant has two hydrophobic carbon chains, and the tetrameric surfactant exhibits various types of aggregate structures when the chain length of the linking group and the length of the hydrophobic carbon chain are changed.

In Example 4, the tetrameric surfactant formed by the electrostatic attraction of the tetrameric quaternary ammonium salt with the azophenyl group and sodium oleate at a molar ratio of 1:4, the hydrophobic part of the surfactant of this structure is approximately considered It is made up of four long chains of oleic acid side by side. As shown in Figure 3, the steady-state shear rheological behavior of the tetrameric surfactant with a concentration of 200mmol/L before and after ultraviolet irradiation changed a little. After ultraviolet irradiation, the peak at 323nm decreased after irradiation, and the peak at 445nm decreased raised. When the concentration reaches 250mmol/L, the zero-shear viscosity of the tetrameric surfactant is as high as 57.5Pa.s. When the concentration remains unchanged, the zero-shear viscosity is 55.5Pa.s after 2 hours of ultraviolet light (wavelength is 365nm). Tetrameric surfactants with azobenzene groups exhibit good UV stability, which is very rare in azobenzene derivatives.

The data indicate that N1,N1'-((diazene-1,2-diylbis(4,1-phenylene))bis(methylene))bis(N1,N1,N3,N3,N3 -Pentamethyl-1,3-diamine) and sodium oleate attract each other with positive and negative charges in aqueous solution, forming a "pseudo" tetrameric surfactant, which is similar to traditional surfactants, The molecule is easy to form a cylindrical structure, which is conducive to the self-assembly of surfactants in aqueous solution to form worm-like micelles.

Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore The scope of protection of the present invention should be defined by the claims.

Claims (10)

1. the four poly- surfactants that a kind of electrostatic is constructed, which is characterized in that compound to obtain with oleate by four polyquaterniums, institute Stating four polyquaterniums is four polyquaterniums containing azobenzene for coupling four quaternary ammonium head bases by azobenzene group.

2. the four poly- surfactants that a kind of electrostatic according to claim 1 is constructed, which is characterized in that structure such as following formula institute Show：

3. the preparation method for the four poly- surfactants that a kind of electrostatic of any of claims 1 or 2 is constructed, which is characterized in that with Para-nitrotoluene, dimethylamine, magnesium rod, enuatrol are starting material, four polyquaterniums containing azobenzene are synthesized, by the four poly- season Ammonium salt and sodium oleae mixture obtain the vermiculate glues of the high viscoelasticity with azobenzene group.

4. preparation method according to claim 3, which is characterized in that using para-nitrotoluene, magnesium rod as starting material, through taking Generation reaction synthesis azobenzene, azobenzene is mixed with N-bromosuccinimide, reaction generates bis- (4- (bromomethyl) benzene of 1,2- Base) diazene, bis- (4- (bromomethyl) phenyl) diazene of 1,2- are mixed with dimethylamine solution, reaction generates 1,1'- (phenodiazine Alkene -1,2- diyl is bis- (4,1- phenylene)) two (N, N- dimethyl methylamines), by 1,1'-, (diazene -1,2- diyl is bis-, and (4,1- is sub- Phenyl)) two (N, N- dimethyl methylamines) and the bromo- N of 3-, N, N- trimethyl propyl- 1- ammonium, which reacts, generates N1, N1'- ((phenodiazine Alkene -1,2- diyl is bis- (4,1- phenylene)) two (methylene)) two (N1, N1, N3, N3, N3- pentamethyl -1,3- diamines), it will Synthetic product N1, N1'- ((diazene -1,2- diyl is bis- (4,1- phenylene)) two (methylene)) two (N1, N1, N3, N3, N3- Pentamethyl -1,3- diamines) it is uniformly mixed with enuatrol, it obtains the light that final electrostatic is constructed and contains the four poly- of azobenzene group Surfactant.

5. the preparation method according to claim 4, which is characterized in that 1,1'- (diazene -1,2- diyl bis- (4,1- Phenylene)) two (N, N- dimethyl methylamines) and the bromo- N of 3-, N, the molar ratio of N- trimethyl propyl- 1- ammonium is 1:2~1:3.

6. preparation method according to claim 4 or 5, which is characterized in that (diazene -1,2- diyl is double by 1, the 1'- (4,1- phenylene)) two (N, N- dimethyl methylamines) and the bromo- N of 3-, N, N- trimethyl propyl- 1- ammonium reaction condition is 60 DEG C~85 DEG C Reaction 8-12 hours.

7. according to preparation method described in claim 4 or 5 or 6, which is characterized in that the N1, N1'- ((diazene -1,2- bis- Base is bis- (4,1- phenylene)) two (methylene)) two (N1, N1, N3, N3, N3- pentamethyl -1,3- diamines) and enuatrol according to Molar ratio 1:4 are uniformly mixed, and obtain final electrostatic is constructed four poly- surfactants.

8. regulating and controlling a kind of method of the viscosity for the four poly- surfactants that electrostatic is constructed of any of claims 1 or 2, feature exists In with the ultraviolet light irradiation four poly- surfactant.

9. a kind of four polyquaterniums containing azobenzene group, which is characterized in that structural formula is shown below：

10. a kind of application four poly- surfactants that electrostatic is constructed of any of claims 1 or 2 as claimed in claim 9 contain Coating, pharmaceutical carrier, detergent, cosmetics, the mineral flotation agent, weaving for thering are four polyquaterniums of azobenzene group to be prepared Softening agent for fibres, antistatic agent or pigment dispersing agent.