CN112645823B - Environment-friendly fluorine-containing surfactant and preparation method thereof - Google Patents
Environment-friendly fluorine-containing surfactant and preparation method thereof Download PDFInfo
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- CN112645823B CN112645823B CN202011562009.3A CN202011562009A CN112645823B CN 112645823 B CN112645823 B CN 112645823B CN 202011562009 A CN202011562009 A CN 202011562009A CN 112645823 B CN112645823 B CN 112645823B
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
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- C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/90—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with quaternised amino groups bound to the carbon skeleton
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- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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Abstract
The invention provides an environment-friendly fluorine-containing surfactant and a preparation method thereof, wherein the preparation method comprises the steps of taking 1H,1H,2H, 2H-perfluorohexyl bromide as a reaction raw material, dropwise adding the reaction raw material into a solution of N, N-dimethyl-1, 3-propane diamine for nucleophilic substitution to prepare an intermediate, reacting the intermediate with biphenyl bromide by utilizing quaternary ammonium salinization reaction, and refluxing at high temperature to obtain the fluorine-containing surfactant. The fluorine-containing surfactant prepared by the invention has good thermal stability and lower surface tension, and simultaneously, the raw material of quaternary ammonium salinization reaction is biphenyl bromide, so that the steric hindrance between the biphenyl bromide and adjacent groups is larger and the biphenyl bromide is relatively unstable, so that the biphenyl bromide is easier to decompose in natural environment, is not easy to cause pollution, and is more environment-friendly.
Description
Technical Field
The invention relates to the technical field of preparation of fluorine-containing materials, in particular to an environment-friendly fluorine-containing surfactant and a preparation method thereof.
Background
The fluorine surfactant contains a fluorocarbon chain in a molecule, is a surfactant with hydrogen atoms in a hydrocarbon chain replaced by fluorine atoms, is more stable in carbon-fluorine bonds due to stronger electronegativity and small radius of the fluorine atoms, has higher thermal stability compared with other surfactants, has the characteristics of no other surfactants, has a good effect of reducing the surface tension of an aqueous solution, and has good compatibility with both an organic solvent and water, so that the fluorine surfactant has wide application in industry.
At present, common fluorine surfactants such as perfluorooctyl sulfonic acid, perfluorooctanoic acid and the like have certain biological toxicity, are relatively stable and are not easy to decompose, so that the use is not environment-friendly and is harmful to human health.
Disclosure of Invention
In view of the above, the invention provides a low-toxicity environment-friendly fluorine-containing surfactant and a preparation method thereof.
The technical scheme of the invention is realized as follows: the invention provides a preparation method of an environment-friendly fluorine-containing surfactant, which comprises the following steps:
mixing and stirring N, N-dimethyl-1, 3-propane diamine, a first solvent and a catalyst, and cooling to-5-5 ℃ to obtain a substrate system;
step two, dropwise adding 1H,1H,2H, 2H-perfluorohexyl bromide into a substrate system, controlling the temperature of the reaction system to be-5-5 ℃ under the stirring condition, heating to 15-25 ℃ after dropwise adding, preserving heat and reacting for 3-5 hours to obtain intermediate suspension, and filtering to obtain a filter cake to obtain an intermediate;
and step three, mixing and stirring the intermediate and a second solvent, keeping the temperature at 10-15 ℃, adding a biphenyl bromo-compound inwards, refluxing for 12-20 hours after the adding is finished and the temperature is not raised to 80-100 ℃, and evaporating the second solvent to obtain the environment-friendly fluorine-containing surfactant.
On the basis of the above technical solution, preferably, the first solvent is one of dichloromethane, trichloromethane and tetrachloromethane.
On the basis of the technical scheme, preferably, the catalyst is one of benzyltriethylammonium chloride, tetrabutylammonium bromide and tributylamine.
On the basis of the technical scheme, preferably, the biphenyl bromo-compound is one of 2-bromobiphenyl, 3-bromobiphenyl, 4-hydroxy-4 '-bromobiphenyl and 4-acetyl-4' -bromobiphenyl.
Still more preferably, the second solvent is one of methanol, tetrahydrofuran, acetonitrile, DMF and thionyl chloride.
On the basis of the above technical scheme, preferably, the N, N-dimethyl-1, 3-propanediamine: 1H, 2H-perfluorohexyl bromide: the dosage ratio of the first solvent is 1: (2.5-3.3): (1-1.5) (m: m: v).
On the basis of the above technical scheme, preferably, the intermediate: the molar use ratio of the biphenyl brominated compound is 1: (1-2), the intermediate: the dosage ratio of the second solvent is 1: (10-20) (m: v).
Based on the above technical scheme, preferably, the dosage of the catalyst is 50-80 (wt)% of the dosage of the N, N-dimethyl-1, 3-propane diamine.
The invention also provides the environment-friendly fluorine-containing surfactant prepared by the method.
In the above technical scheme, the reaction formula of the second step is as follows:
in the above technical scheme, the reaction formulas of step three are as follows:
compared with the prior art, the environment-friendly fluorine-containing surfactant has the following beneficial effects:
(1) the method adopts 1H,1H,2H, 2H-perfluorohexyl bromide as a raw material, introduces different groups through nucleophilic reaction and quaternary ammonium salinization respectively, adjusts the hydrophilicity and the lipophilicity, and simultaneously introduces the groups with biphenyl as a main body, so that the steric hindrance between the corresponding group and the adjacent group is relatively large and the groups are easy to decompose;
(2) the fluorine-containing surfactant prepared by the invention keeps the characteristic of high thermal stability of the fluorine-containing surfactant, and various groups are introduced into quaternary ammonium salt, so that the hydrophilicity and the lipophilicity are improved, meanwhile, the structural stability is poor, so that the fluorine-containing surfactant is easier to decompose, relatively speaking, the fluorine-containing surfactant has less pollution to the environment after being used, and is more environment-friendly.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
Example 1
Respectively weighing 100g N, N-dimethyl-1, 3-propane diamine, 100ml dichloromethane and 50g benzyltriethylammonium chloride, stirring and dissolving in a three-necked bottle, placing in a cold tank, keeping the temperature of a substrate system in the reaction bottle at-5 ℃, then weighing 250g 1H,1H,2H, 2H-perfluorohexylbromide, slowly dropwise adding into a substrate system, keeping the temperature of a reaction solution in the dropwise adding process at-5 ℃, after the dropwise adding is finished, placing the three-necked bottle in a water bath, keeping the temperature of the water bath at 15 ℃, keeping the temperature and stirring for reaction for 3 hours to obtain a suspension, filtering the suspension, taking a filter cake, obtaining an intermediate, and drying and retaining the intermediate;
respectively weighing 100g of intermediate and 1000ml of methanol, mixing and stirring in a three-necked bottle, placing in a water bath, weighing 100g of 2-bromobiphenyl, keeping the water bath temperature at 10 ℃, adding the 2-bromobiphenyl into the intermediate solution, heating the water bath to 80 ℃ after the addition is finished, carrying out reflux reaction for 12h, and evaporating the methanol after the reflux is finished to obtain the environment-friendly fluorine-containing surfactant.
Example 2
Respectively weighing 100g N, N-dimethyl-1, 3-propane diamine, 110ml of trichloromethane and 60g of tetrabutylammonium bromide, stirring and dissolving in a three-neck flask, placing in a cold tank, keeping the temperature of a substrate system in a reaction flask at-2 ℃, then weighing 280g of 1H,1H,2H, 2H-perfluorohexyl bromide, slowly dropwise adding into a substrate system, keeping the temperature of a reaction solution in the dropwise adding process at-2 ℃, after dropwise adding, placing the three-neck flask in a water bath, keeping the temperature of the water bath at 18 ℃, keeping the temperature and stirring for reaction for 3.5 hours to obtain a suspension, filtering the suspension, taking a filter cake to obtain an intermediate, and drying and retaining the intermediate;
respectively weighing 100g of intermediate and 1200ml of tetrahydrofuran, mixing and stirring in a three-necked bottle, placing in a water bath, weighing 120g of 3-bromobiphenyl, keeping the temperature of the water bath at 12 ℃, adding the 3-bromobiphenyl into the intermediate solution, heating the water bath to 85 ℃ after the addition is finished, carrying out reflux reaction for 16h, and evaporating out the tetrahydrofuran after the reflux is finished to obtain the environment-friendly fluorine-containing surfactant.
Example 3
Respectively weighing 100g N, N-dimethyl-1, 3-propane diamine, 120ml of tetrachloromethane and 70g of tributylamine, stirring and dissolving in a three-necked bottle, placing in a cold tank, keeping the temperature of a substrate system in a reaction bottle at 0 ℃, then weighing 300g of 1H,1H,2H, 2H-perfluorohexyl bromide, slowly dropwise adding into a substrate system, keeping the temperature of a reaction solution in the dropwise adding process at 0 ℃, after dropwise adding, placing the three-necked bottle in a water bath, keeping the temperature of the water bath at 20 ℃, keeping the temperature and stirring for reaction for 4 hours to obtain a suspension, filtering the suspension, taking a filter cake, obtaining an intermediate, and drying and retaining the intermediate;
respectively weighing 100g of intermediate and 1500ml of acetonitrile, mixing and stirring in a three-necked bottle, placing in a water bath, weighing 140g of 4-bromobiphenyl, keeping the water bath temperature at 13 ℃, adding the 4-bromobiphenyl into the intermediate solution, heating the water bath to 90 ℃ after the addition is finished, carrying out reflux reaction for 18h, and evaporating the acetonitrile after the reflux is finished to obtain the environment-friendly fluorine-containing surfactant.
Example 4
Respectively weighing 100g N, N-dimethyl-1, 3-propane diamine, 140ml dichloromethane and 80g tributylamine, stirring and dissolving in a three-mouth bottle, placing in a cold tank, keeping the temperature of a substrate system in a reaction bottle at 3 ℃, then weighing 320g 1H,1H,2H, 2H-perfluorohexyl bromide, slowly dropwise adding into a substrate system, keeping the temperature of a reaction solution in the dropwise adding process at 3 ℃, after finishing dropwise adding, placing the three-mouth bottle in a water bath, keeping the temperature of the water bath at 22 ℃, keeping the temperature and stirring for reaction for 5 hours to obtain a suspension, filtering the suspension, taking a filter cake, obtaining an intermediate, and drying and retaining the intermediate;
respectively weighing 100g of intermediate and 1700ml of DMF, mixing and stirring in a three-necked bottle, placing in a water bath, weighing 170g of 4-hydroxy-4 '-bromobiphenyl, keeping the water bath temperature at 14 ℃, adding the 4-hydroxy-4' -bromobiphenyl into the intermediate solution, heating the water bath to 95 ℃ after the addition is finished, carrying out reflux reaction for 20h, and distilling out the DMF after the reflux is finished to obtain the environment-friendly fluorine-containing surfactant.
Example 5
Respectively weighing 100g N, N-dimethyl-1, 3-propane diamine, 150ml of trichloromethane and 100g of tetrabutylammonium bromide, stirring and dissolving in a three-neck flask, placing in a cold tank, keeping the temperature of a substrate system in a reaction flask at 5 ℃, then weighing 330g of 1H,1H,2H, 2H-perfluorohexyl bromide, slowly dropwise adding into a substrate system, keeping the temperature of a reaction solution in the dropwise adding process at 5 ℃, after finishing dropwise adding, placing the three-neck flask in a water bath, keeping the temperature of the water bath at 25 ℃, keeping the temperature and stirring for reaction for 5 hours to obtain a suspension, filtering the suspension, taking a filter cake, obtaining an intermediate, and drying and retaining the intermediate;
respectively weighing 100g of intermediate and 2000ml of thionyl chloride, mixing and stirring the intermediate and 2000ml of thionyl chloride in a three-neck flask, placing the intermediate and the thionyl chloride in a water bath, then weighing 200g of 4-acetyl-4 '-bromobiphenyl, keeping the temperature of the water bath at 15 ℃, adding the 4-acetyl-4' -bromobiphenyl into the intermediate solution, transferring the three-neck flask into an oil bath, keeping the temperature of the oil bath at 100 ℃, performing reflux reaction for 20 hours, and evaporating the thionyl chloride after the reflux reaction is completed to obtain the environment-friendly fluorine-containing surfactant.
The surfactants prepared in examples 1 to 5 were subjected to performance test evaluation, surface tension and thermal stability, and exposed to natural environment for natural degradation test, and initial state purity and purity after exposure for 90 days were measured, respectively, to obtain the following results:
compared with the fluorine-containing surfactant prepared by the invention, the fluorine-containing surfactant has good thermal stability and surface tension, and the raw materials used are relatively low in toxicity, easy to degrade and more environment-friendly.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a fluorine-containing surfactant is characterized in that the structure of the fluorine-containing surfactant is selected from one of the following formulas:
the preparation method comprises the following steps:
mixing and stirring N, N-dimethyl-1, 3-propane diamine, a first solvent and a catalyst, and cooling to-5-5 ℃ to obtain a substrate system;
step two, dropwise adding 1H,1H,2H, 2H-perfluorohexyl bromide into a substrate system, controlling the temperature of the reaction system to be-5-5 ℃ under the stirring condition, heating to 15-25 ℃ after dropwise adding, preserving heat and reacting for 3-5 hours to obtain intermediate suspension, and filtering to obtain a filter cake to obtain an intermediate;
step three, mixing and stirring the intermediate and a second solvent, keeping the temperature at 10-15 ℃, adding a biphenyl bromo-compound inwards, heating to 80-100 ℃ after adding, performing reflux reaction for 12-20 hours, and evaporating the second solvent after the reflux is finished to obtain a fluorine-containing surfactant;
the catalyst is one of benzyltriethylammonium chloride, tetrabutylammonium bromide and tributylamine.
2. The method of claim 1, wherein the first solvent is one of dichloromethane, trichloromethane and tetrachloromethane.
3. The method of claim 1, wherein the biphenyl bromo compound is one of 2-bromobiphenyl, 3-bromobiphenyl, 4-hydroxy-4 '-bromobiphenyl and 4-acetyl-4' -bromobiphenyl.
4. The method of claim 1, wherein the second solvent is one of methanol, tetrahydrofuran, acetonitrile, DMF, and thionyl chloride.
5. The method of preparing a fluorosurfactant according to claim 1 wherein the ratio of N, N-dimethyl-1, 3-propanediamine: 1H, 2H-perfluorohexyl bromide: the dosage ratio of the first solvent is 1: (2.5-3.3): (1-1.5), m: m: v.
6. The process for producing a fluorosurfactant according to claim 1 wherein the intermediate: the molar use ratio of the biphenyl brominated compound is 1: (1-2), the intermediate: the dosage ratio of the second solvent is 1: (10-20), m: v.
7. The process for producing a fluorine-containing surfactant according to claim 1, wherein the amount of the catalyst is 50 to 80 wt% based on the amount of N, N-dimethyl-1, 3-propanediamine.
8. The fluorosurfactant produced by the method of any one of claims 1-7.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1379618A (en) * | 1971-09-13 | 1975-01-02 | Pechiney Ugine Kuhlmann | Quaternary polyfluoro ammonium salts |
| US20170313928A1 (en) * | 2014-10-22 | 2017-11-02 | China Petroleum & Chemical Corporation | Anionic-cationic-nonionic surfactant,production and use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1379618A (en) * | 1971-09-13 | 1975-01-02 | Pechiney Ugine Kuhlmann | Quaternary polyfluoro ammonium salts |
| US20170313928A1 (en) * | 2014-10-22 | 2017-11-02 | China Petroleum & Chemical Corporation | Anionic-cationic-nonionic surfactant,production and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| Tomokazu Yoshimura et al.."Synthesis and Solution Properties of Adamantane-Containing Quaternary Ammonium Salt-type Cationic Surfactants: Hydrocarbon-based, Fluorocarbon-based and Bola-type".《Journal of Oleo Science》.2016,第65卷第843-852页. * |
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Inventor after: Qiu Fengtao Inventor after: Zou Lanian Inventor after: Zhang Peiyu Inventor before: Qiu Fengtao Inventor before: Zou Lanian Inventor before: Zhang Peiyu Inventor before: Zhang Chengpan |
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