CN113173892B - Morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant and preparation and application thereof - Google Patents
Morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant and preparation and application thereof Download PDFInfo
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- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract
The invention relates to a morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant, and preparation and application thereof, wherein the structural formula is as follows:
wherein m =3 to 8, n =5 to 11. According to the invention, the morpholine functional group and the fluorocarbon chain are combined, so that the morpholine functional group is used as a hydrophilic group, and the fluorocarbon chain is used as a hydrophobic group, and the molecules have excellent surface activity. The introduced two ester groups can increase the hydrophilicity of the whole surfactant molecule, and have degradability and environmental protection; the polymer can also be used as a coupling body of a fluorocarbon chain and a hydrophilic chain, so that molecules can have better adhesion capacity on the metal surface. The morpholine functional group, the fluorocarbon chain, the two ester groups and the quaternary ammonium salt are combined together, so that the morpholine head group quaternary ammonium salt type gemini fluorocarbon surface has the advantages of smaller CMC and smaller gamma CMC, and not only has better wettability and lower surface tension, but also has the anti-corrosion effect. Can be applied to the corrosion prevention and the wetting of the metal surface. The preparation method is simple and quick.
Description
Technical Field
The invention belongs to the field of surfactant science and application, and particularly relates to a morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant as well as preparation and application thereof.
Background
Gemini surfactants, also known as Gemini surfactants, contain 2 hydrophilic groups and 2 hydrophobic groups in the structure. Two conventional single-chain surfactants are commonly linked by a linking group near the hydrophilic head group thereof through a covalent bond to form a novel surfactant. In the prior art, most gemini cationic surfactants usually adopt alkane chains as hydrophobic groups, belong to hydrocarbon surfactants, but the traditional gemini surfactants have poor surface activity (gamma-gamma) cmc Large), high use concentration (high CMC), and residues in the product after use.
The fluorocarbon surfactant is a special surfactant. Compared with the traditional hydrocarbon surfactant, in the fluorocarbon surfactant, all or part of hydrogen atoms in a hydrocarbon chain are replaced by F atoms. Fluorocarbon surfactants have unique "three high two hydrophobic" properties, namely: high surface activity, high thermal and chemical stability and corresponding hydrophobicity and oleophobicity. Because F atom and C atom can form a strong covalent bond, and the radius of fluorine atom is larger than that of hydrogen atom, the fluorocarbon chain is arranged in a Z shape, and the carbon chain can be tightly wrapped in the fluorocarbon chain. This configuration provides the fluorocarbon surfactant with high thermal stability as well as high chemical stability. Secondly, the fluorocarbon bond is a very low polarity bond, and the fluorocarbon chain has extremely strong hydrophobic property, so that the fluorocarbon surfactant can obviously reduce the surface tension of the aqueous solution at low concentration.
Morpholine and its derivatives are commonly used as corrosion inhibitors. As an adsorption corrosion inhibitor, the planar structure of morpholine can be greatly covered on the metal surface, so that the metal surface is isolated from the external corrosive environment.
Metal corrosion protection is a new and promising field of application for surfactants. Because, through proper molecular design, surfactants as organic corrosion inhibitors can provide not only the desired metal corrosion inhibition properties, but also additional functions such as degreasing, scale control, film formation, lubrication, anti-wear, etc., which are particularly useful in various metal treatment processes. At present, fluorocarbon surfactants have very few reports of their application as organic corrosion inhibitors, despite their superior film forming ability.
Disclosure of Invention
The invention aims to provide a morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant, and preparation and application thereof, so as to solve the problems in the prior art.
Morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant has the following structural formula:
wherein m =3 to 8, n =5 to 11.
Preferably, n is 9.
Preferably, m is 3 or 4.
When m =3, the structural formula is:
when m =4, the structural formula is:
the preparation method of the morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant comprises the following steps:
(a) And (3) synthesis of an intermediate: adding N- (3-hydroxypropyl) morpholine and diiodo according to the molar ratio of 2.4; after the reaction is finished, standing and cooling to room temperature, then distilling the mixture under reduced pressure, removing the solvent, and washing with the solvent to obtain an intermediate;
(b) Synthesis of final product: toluene and 1,4-dioxane 1:1 are used as solvents, perfluoroalkyl acid is added according to the molar ratio of the intermediate to the perfluoroalkyl acid being 1.5, the reaction temperature is raised to 85-100 ℃, the reaction is carried out for 24-48h, and nitrogen is introduced for the reaction; and after the reaction is finished, standing and cooling to room temperature, then carrying out reduced pressure distillation on the mixture, removing the solvent, and recrystallizing to obtain the corresponding morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant.
Preferably, in step (a), isopropanol is used as the solvent. Because the quaternization reaction is a bimolecular nucleophilic substitution reaction, the selection of a polar solvent can facilitate the reaction. Because the morpholine functional group has larger steric hindrance and the quaternization process is slower, the isopropanol with higher boiling point is used as the solvent to accelerate the reaction. The reaction is slower if the solvent is ethanol.
Preferably, in step (b), 2 mol of water is generated while the reaction product is generated, and as can be seen from the principle of le chatelier, the reaction is facilitated to proceed in the forward direction by reducing the water content in the system, and the reaction yield is increased. Toluene is used as a reaction solvent and water scavenger in the reaction. Because the catalyst can be azeotroped with water, the water content in a reaction system can be reduced, so that the reaction rate is accelerated, and the reaction yield is increased. The nitrogen introduced in the reaction can protect the reaction group from being oxidized by air and carry a small amount of moisture generated in the reaction, so that the reaction is smoothly carried out.
Preferably, the reaction temperature in step (a) is 85 ℃ and the reaction temperature in step (b) is 90 ℃. The selection of the reaction temperature mainly depends on the boiling point of the solvent and the raw materials, wherein the boiling point of the solvent is particularly important, the reaction temperature of the step (a) is 85 ℃, because the boiling point of the isopropanol is 82 ℃ at normal temperature and normal pressure, and the selection of the reaction temperature of 85 ℃ is favorable for full reflux of the reaction. The reaction temperature of the step (b) is 90 ℃, the boiling point of the toluene is about 111 ℃ under normal temperature and normal pressure, the azeotropic temperature of the toluene and water is 85 ℃ because water is generated in the reaction process, and the reaction temperature is slightly higher than the boiling point, so that the full reflux of the reaction is facilitated. While both feedstocks have boiling points higher than toluene. Therefore, it is most preferable to use 90 ℃ as the reaction temperature.
The perfluoroalkyl acid is added in step (b) in a molar ratio of 1.5, below which the reaction is insufficient.
Further, the solvent used in the washing process in the step (a) is ethanol, and the solvent used in the recrystallization process in the step (b) is a mixed solvent of ethanol and water 5:1. The intermediate in the step (a) does not need recrystallization, and only ethanol is used for washing the product to obtain a solid. Since the reaction impurities are only the reaction starting materials in the case of a sufficient reaction. The reaction raw materials are easy to dissolve in ethanol, the solubility of the intermediate in the ethanol is extremely low, and the separation can be realized by ethanol washing. The intermediate is a biquaternary ammonium salt structure, the polarity is very high, and the polarity of ethanol is weaker than that of ethanol. Ethanol is difficult to dissolve intermediates according to similar compatibility principles. The mixed solvent used in the recrystallization of step (b) is ethanol and water. Under the condition of sufficient reaction, the reaction impurity is perfluoro alkyl acid with certain polarity. Therefore, the substance is easily dissolved in a mixed solvent of ethanol and water, and the recrystallization method can be used for separating the product from the raw material.
Preferably, the diiodo is 1,3-diiodopropane or 1,4-diiodobutane. The quaternization reaction is bimolecular nucleophilic substitution reaction, and iodine atoms in the iodine compounds are good leaving groups, so that the reaction is favorably carried out. Because the generated dimorpholine has larger steric hindrance, a stronger leaving group is needed to promote the reaction. Neither bromide nor chloride was tried to generate the dimorpholine structure.
The morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant is applied to metal corrosion prevention and wetting.
Compared with the prior art, the method combines the morpholine functional group and the fluorocarbon chain, so that the morpholine functional group can be used as a hydrophilic group, and the fluorocarbon chain can be used as a hydrophobic group, so that the molecules have excellent surface activity; on the basis that the morpholine functional group has the anti-corrosion performance, the hydrophobic chain is introduced to enable the morpholine functional group to have the self-assembly tendency, so that the morpholine functional group can be better adsorbed on the metal surface, and the consumption of morpholine is reduced. The invention also introduces two ester groups into the molecule, and the ester group is a hydrophilic group, so that the hydrophilicity of the whole surfactant molecule can be increased, and the invention also has degradability, safety and environmental protection. In addition, ester group is a flexible connecting group, so that the ester group can be used as a connector of a fluorocarbon chain and a hydrophilic chain, and the molecules can have better adhesion capability on the metal surface. The two quaternary ammonium salt structures are beneficial to the adsorption of molecules on the metal surface. The morpholine head group quaternary ammonium salt type gemini fluorocarbon disclosed by the invention has the advantages that the morpholine functional group, the fluorocarbon chain, the two ester groups and the quaternary ammonium salt are combined, so that the morpholine head group quaternary ammonium salt type gemini fluorocarbon has the advantages of smaller CMC (carboxyl coefficient), smaller gamma CMC, better corrosion resistance and the like, has better wettability and lower surface tension, and also has an anti-corrosion effect, the consumption is less, the residue in a product is greatly reduced, and the purity of the product is improved. Can be applied to the corrosion prevention and the wetting of the metal surface. The preparation method is simple and quick.
Drawings
FIG. 1 is a scheme for preparing the compound (B) F of example 1 19 -3mor-F 19 Reaction chemistry of (1)An equation;
FIG. 2 is preparation of Compound (D) F of example 2 19 -4mor-F 19 The reaction chemical equation of (1);
FIG. 3 shows Compound (B) F of example 1 19 -3mor-F 19 A plot of aqueous solution concentration versus surface tension;
FIG. 4 shows Compound (D) F of example 2 19 -4mor-F 19 A plot of aqueous solution concentration versus surface tension;
FIG. 5 shows Compound (B) F of example 1 19 -3mor-F 19 A plot of aqueous solution concentration versus contact angle;
FIG. 6 shows Compound (D) F of example 2 19 -4mor-F 19 A plot of aqueous solution concentration versus contact angle;
FIG. 7 is a nuclear magnetic hydrogen spectrum of intermediate compound (A) of example 1;
FIG. 8 shows Compound (B) F of example 1 19 -3mor-F 19 Nuclear magnetic hydrogen spectrum of (a);
FIG. 9 is a nuclear magnetic hydrogen spectrum of intermediate compound (C) of example 2;
FIG. 10 shows Compound (D) F of example 2 19 -4mor-F 19 Nuclear magnetic hydrogen spectrum diagram.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Compound (B) F 19 -3mor-F 19 Preparation of
The chemical equation of the reaction is shown in fig. 1, and mainly comprises the following steps:
(a) And (3) synthesis of an intermediate: adding N- (3-hydroxypropyl) morpholine and 1,3-diiodopropane into a round-bottom flask by using isopropanol as a solvent according to a molar ratio of 2.4; after the reaction is finished, standing and cooling to room temperature, then distilling the mixture under reduced pressure, removing the solvent, and washing for 3 times by using ethanol to obtain an intermediate compound (A), wherein the intermediate is a white solid;
(b) Synthesis of final product: adding perfluoroalkyl acid into a three-neck flask by taking toluene and 1,4-dioxane 1:1 as solvents according to the molar ratio of the intermediate compound (A) to the perfluoroalkyl acid being 1.5, raising the reaction temperature to 90 ℃, reacting for 48h, and introducing nitrogen; after the reaction is finished, standing and cooling to room temperature, then distilling the mixture under reduced pressure, removing the solvent, and recrystallizing for 2 times by using a mixed solvent of ethanol and water 5:1 to obtain the final product compound (B) and the Gemini type fluorocarbon surfactant.
The nuclear magnetic hydrogen spectrum of the intermediate compound (A) is shown in figure 7, the chemical name is 4,4' - (propane-1,3-diyl) bis (4- (3-hydroxypropyl)) morpholine iodide salt, and the structural formula is as follows:
the nuclear magnetic hydrogen spectrum of the intermediate compound (B) is shown in figure 8, the chemical name is 4,4' - (propane-1,3-diyl) bis (4- (3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonafluorodecanoate) hydroxypropyl)) morpholine iodide salt, and the structural formula is as follows:
example 2
Compound (D) F 19 -4mor-F 19 Preparation of (2)
The chemical equation of the reaction is shown in fig. 2, and mainly comprises the following steps:
(a) And (3) synthesis of an intermediate: adding N- (3-hydroxypropyl) morpholine and 1,4-diiodobutane into a round-bottom flask by using isopropanol as a solvent according to a molar ratio of 2.4; after the reaction is finished, standing and cooling to room temperature, then distilling under reduced pressure, removing the solvent, and washing for 3 times by using ethanol to obtain an intermediate compound (C), wherein the intermediate is a white solid;
(b) Synthesis of final product: in a three-neck flask, taking toluene and 1,4-dioxane 1:1 as solvents, adding perfluoroalkyl acid according to the molar ratio of 1.5 of the intermediate compound (C) to the perfluoroalkyl acid, raising the reaction temperature to 90 ℃, reacting for 48h, and introducing nitrogen gas for reaction; after the reaction is finished, standing and cooling to room temperature, then distilling the mixture under reduced pressure, removing the solvent, and recrystallizing for 2 times by using a mixed solvent of ethanol and water 5:1 to obtain the final product compound (D) and the Gemini type fluorocarbon surfactant.
The nuclear magnetic hydrogen spectrum of the intermediate compound (C) is shown in FIG. 9, and the chemical name is 4,4' - (butane-1,4-diyl) bis (4- (3-hydroxypropyl)) morpholine iodide salt, and the structural formula is as follows:
the nuclear magnetic hydrogen spectrum of the intermediate compound (D) is shown in FIG. 10, and the chemical name is 4,4' - (butane-1,4-diyl) bis (4- (3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonafluorodecanoate) hydroxypropyl)) morpholine iodide salt, the structural formula is:
example 3
Surface property test: the compound (B) represents a Gemini type fluorocarbon surfactant F with a hydrophilic group containing biquaternary ammonium salt morpholine functional group 19 -3mor-F 19 (B) The compound (D) represents a gemini fluorocarbon surfactant F with a hydrophilic group containing biquaternary ammonium salt morpholine functional group 19 -4mor-F 19 (D) In that respect The morpholine headquarternary ammonium salt type gemini fluorocarbon surfactants obtained in examples 1 and 2 were formulated into a series of aqueous solutions of different concentrations. The surface tension of the sample was measured by the flying ring method on a surface tension meter at 25 ℃ and the curves of the surface tension with the concentration are shown in fig. 3 and 4, and the above data are combined to obtain table 1:
TABLE 1 surface Properties of surfactants
As can be seen from FIGS. 3 and 4, the surface tension curve of the solution shows an inflection point as a function of concentration, and the concentration corresponding to the inflection point is the cmc of the surfactant. As can be seen from Table 1, F 19 -3mor-F 19 And F 19 -4mor-F 19 The gemini morpholine fluorine surfactant can reduce the surface tension of secondary distilled water to 18.13mN/m and 21.53mN/m respectively, and the cmc value is extremely low. On one hand, the hydrophilic group of the surfactant molecule is a biquaternary ammonium salt structure, so that the surfactant molecule has extremely strong hydrophilicity, and the hydrophobic group is a perfluorocarbon chain and has strong hydrophobicity. The strong adsorption tendency exists at the interface, so that the surface tension of water can be effectively reduced. On the other hand, as a gemini surfactant, such a configuration allows the molecules to form micelles at an extremely low concentration in an aqueous solution, and thus has an extremely small cmc value. Considering that electrostatic repulsive force exists between the surfactant ion head groups, the occupied cross-sectional area of each surfactant molecule on the surface is made larger, and the surface adsorption amount (Γ max) is smaller. However, because of this, the molecules with such structure can be saturated and adsorbed on the interface of steam and water at low concentration, and the usage amount can be further reduced. F 19 -3mor-F 19 And F 19 -4mor-F 19 C of the surfactant of (1) 20 The value (concentration required to reduce surface tension by 20 mN/m) was only 0.005mM, indicating that such surfactants can significantly reduce water surface tension at very trace concentrations. The surfactant can greatly reduce the residue in the product and improve the purity of the product in practical application.
Example 4
And (3) testing the corrosion resistance: the morpholine head-based quaternary ammonium salt type gemini fluorocarbon surfactant prepared in examples 1 and 2 was prepared into a series of aqueous solutions of different concentrations, and hydrochloric acid was added to make the hydrochloric acid concentration 1.0M. The surface area is 1cm 2 The Q235 carbon steel sheet of (2) was immersed in the etching solution for 24 hours. The measurement is carried out on an electrochemical workstation, and a traditional three-electrode cell is adopted, a carbon steel substrate is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and a platinum plate is used as a counter electrode. Etching solution with 1.0M hydrochloric acid containing surfactant solution of different concentrationsThe liquid acts as an electrolyte. And obtaining the corrosion current and the corrosion voltage through electrochemical tests. The corrosion inhibition rate is calculated according to the following formula:
wherein the content of the first and second substances,
and j corr The current densities when no surfactant is added and the surfactant solution is added are respectively obtained; IE% is corrosion inhibition efficiency. The relevant electrochemical parameters are summarized in tables 2,3 by the above formula:
TABLE 2F 19 -3mor-F 19 Corrosion resistance parameters of
TABLE 3F 19 -4mor-F 19 Corrosion resistance parameters of
| F 19 -4mor-F 19 | J corr /10 -3 mA/cm 2 | IE％ |
| 0 | 0.573 | - |
| 5μM | 0.419 | 26.84 |
| 7.5μM | 0.370 | 35.38 |
| 10μM | 0.365 | 36.34 |
| 50μM | 0.144 | 74.94 |
| 150μM | 0.139 | 75.68 |
In tables 2 and 3, it can be seen that as the surfactant concentration of examples 1 and 2 is increased, the sustained-release efficiency is also increased. When the surfactant concentration in example 1 was 150. Mu.M, the corrosion current was reduced by 96.67%. We can conclude that the structure has good corrosion protection properties. When the surfactant solution is applied to the industry, the surface activity of the aqueous solution can be effectively reduced, the metal can be protected from corrosion when the aqueous solution of the surfactant solution is in contact with the metal, and theoretically, the service life of the metal can be prolonged by 30 times by the aqueous solution of the surfactant solution in the embodiment 1.
Example 5
And (3) testing the wetting property: the gemini surfactants obtained in example 1 and example 2 were prepared into a series of aqueous solutions with different concentrations, and the contact angle of the sample on the polytetrafluoroethylene surface was measured on a contact angle meter, and the curves of the contact angle as a function of the concentration are shown in fig. 5 and fig. 6. Experiments prove thatThe contact angle of the aqueous solution without the surfactant (i.e., blank) on the teflon plate was 110 °. As can be seen from FIGS. 5 and 6, F is present in the tested concentration range 19 -3mor-F 19 And F 19 -4mor-F 19 The contact angle of the aqueous solution on the polytetrafluoroethylene plate can be reduced to 0 ℃ at the lowest, and good wetting performance is shown.
Comparative example 1
The following morpholine head group-containing quaternary ammonium salt type single-chain fluorocarbon surface activities are respectively synthesized, and the corrosion resistance, the surface activity and the wettability are tested and compared.
TABLE 4F 19 -N 2 -mor、F 19 -N 3 -mor and F 19- Corrosion performance parameters of es-mor
From table 4, it can be seen that the morpholine head group-containing quaternary ammonium salt type single-chain fluorocarbon surface activity not only has no corrosion resistance, but also aggravates corrosion of metal surface.
Surface property test: to F 19 -N 2 -mor、F 19 -N 3 -mor and F 19 Es-mor surface Performance test and surface tension F 19 -N 3 -mor is superior to F 19 -N 2 -mor is superior to F 19 -es-mor。
And (3) testing the wetting property: to F 19 -N 2 -mor、F 19 -N 3 -mor and F 19 Es-mor was subjected to a wetting property test to find a wetting property F 19 -N 3 -mor is superior to F 19 -N 2 -mor is superior to F 19 -es-mor。
Comparative example 2
1,3-diiodopropane from example 1 is exchanged for bromides and chlorides such as 1,3-dibromopropane, 1,3-dichloropropane. Namely, adding N- (3-hydroxypropyl) morpholine, 1,3-dibromopropane and 1,3-dichloropropane into a round-bottom flask by using isopropanol as a solvent according to the mol ratio of 2.4; after the reaction is finished, standing and cooling to room temperature, then distilling the mixture under reduced pressure, removing the solvent, and washing the solvent with ethanol, so that a solid product cannot be obtained.
Claims (8)
1. A morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant is characterized in that the structural formula is as follows:
wherein m =3 to 8, n =5 to 11.
2. The morpholino quaternary ammonium salt type gemini fluorocarbon surfactant according to claim 1, wherein n is 9.
3. The gemini fluorocarbon surfactant of morpholino head group quat type according to claim 2, wherein m is 3 or 4.
4. The method for preparing morpholine head radical quaternary ammonium salt type gemini fluorocarbon surfactant according to claim 1, characterized by comprising the following steps:
(a) And (3) synthesis of an intermediate: adding N- (3-hydroxypropyl) morpholine and diiodo according to the molar ratio of 2-3:1 by taking isopropanol as a solvent, raising the reaction temperature to 80-100 ℃ and reacting for 24-48h; after the reaction is finished, standing and cooling to room temperature, then distilling the mixture under reduced pressure, removing the solvent, and washing with the solvent to obtain an intermediate;
(b) Synthesis of final product: toluene and 1,4-dioxane 1:1 are used as solvents, perfluoroalkyl acid is added according to the molar ratio of 1.5 of an intermediate to the perfluoroalkyl acid, the temperature is raised to 85-100 ℃, the reaction is carried out for 24-48h, and nitrogen is introduced for the reaction; and after the reaction is finished, standing and cooling to room temperature, then carrying out reduced pressure distillation on the mixture, removing the solvent, and recrystallizing to obtain the corresponding morpholine head group quaternary ammonium salt type gemini fluorocarbon surfactant.
5. The method according to claim 4, wherein the reaction temperature in the step (a) is 85 ℃ and the reaction temperature in the step (b) is 90 ℃.
6. The method according to claim 4, wherein the solvent used in the washing step (a) is ethanol, and the solvent used in the recrystallization step (b) is a mixed solvent of ethanol and water 5:1.
7. The method of claim 4, wherein the diiodo in step (a) is 1,3-diiodopropane or 1,4-diiodobutane.
8. The use of the gemini fluorocarbon surfactant of morpholino head group quat type according to claim 1 for corrosion protection and wetting of metals.
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