阅读说明：本技术 一种氟碳基阳离子表面活性剂及其制备方法和应用 (Fluorocarbon-based cationic surfactant and preparation method and application thereof ) 是由 王晨 田咪咪 杨晓武 李刚辉 于 2020-05-28 设计创作，主要内容包括：本发明公开了一种氟碳基阳离子表面活性剂及其制备方法和应用,方法包括：1)将双季戊四醇溶于第一溶剂,加入三乙胺搅拌加热至50～60℃,边搅拌边滴加全氟戊酰氟,滴加完毕,继续升温至75～85℃,搅拌反应4～6h；洗涤、萃取得淡黄色固体；2)将得到的淡黄色固体溶于第二溶剂,待全部溶化后加入粉末状氢氧化钠在25～35℃下搅拌反应0.5～1h,然后将溶有羟丙基季铵盐的溶剂溶液一次加入四口瓶中并升温到75～85℃,保温一段时间后将反应产物进行抽滤,得固体为产物；3)将得到的固体产物加入催化剂和第三溶剂,并滴加二异氰酸酯,反应温度为40～60℃,反应3～5h,干燥,得到氟碳基阳离子表面活性剂。该表面活性剂解决了当玻璃表面温度达到周围大气的露点以下时,有水雾在表面析出的问题。(The invention discloses a fluorocarbon-based cationic surfactant and a preparation method and application thereof, wherein the method comprises the following steps: 1) dissolving dipentaerythritol in a first solvent, adding triethylamine, stirring and heating to 50-60 ℃, dropwise adding perfluorovaleryl fluoride while stirring, continuously heating to 75-85 ℃ after dropwise adding, and stirring and reacting for 4-6 hours; washing and extracting to obtain a light yellow solid; 2) dissolving the obtained light yellow solid in a second solvent, adding powdery sodium hydroxide after the light yellow solid is completely dissolved, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, then adding the solvent solution dissolved with the hydroxypropyl quaternary ammonium salt into a four-mouth bottle at one time, heating to 75-85 ℃, keeping the temperature for a period of time, and then carrying out suction filtration on a reaction product to obtain a solid product; 3) adding a catalyst and a third solvent into the obtained solid product, dropwise adding diisocyanate, reacting at the temperature of 40-60 ℃ for 3-5 h, and drying to obtain the fluorocarbon-based cationic surfactant. The surfactant solves the problem that when the temperature of the glass surface reaches below the dew point of the surrounding atmosphere, water mist is precipitated on the surface.)

1. A fluorocarbon-based cationic surfactant having the structural formula:

2. a preparation method of a fluorocarbon-based cationic surfactant is characterized by comprising the following steps:

1) dissolving dipentaerythritol in a first solvent, adding triethylamine, stirring and heating to 50-60 ℃, dropwise adding perfluorovaleryl fluoride while stirring, continuously heating to 75-85 ℃ after dropwise adding, and stirring and reacting for 4-6 hours; washing and extracting to obtain a light yellow solid;

2) dissolving the obtained light yellow solid in a second solvent, adding powdery sodium hydroxide after the light yellow solid is completely dissolved, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, then adding the solvent solution dissolved with the hydroxypropyl quaternary ammonium salt into a four-mouth bottle at one time, heating to 75-85 ℃, keeping the temperature for a period of time, and then carrying out suction filtration on a reaction product to obtain a solid product;

3) adding a catalyst and a third solvent into the obtained solid product, dropwise adding diisocyanate, reacting at the temperature of 40-60 ℃ for 3-5 h, and drying to obtain the fluorocarbon-based cationic surfactant.

3. The method for preparing fluorocarbon-based cationic surfactant according to claim 2, wherein the molar ratio of dipentaerythritol to perfluorovaleryl fluoride in step 1) is 1 (3-3.2).

4. The method of claim 2, wherein in step 1), the product is washed with HCl solution and then NaHCO solution₃Washing the solution, extracting with diethyl ether after washing with water, separating to obtain an upper organic layer, and distilling under reduced pressure to remove the solvent to obtain a light yellow solid; the HCl and NaHCO₃The concentrations of (A) and (B) were all 5 wt%.

5. The method of claim 2, wherein the first solvent is dimethylformamide in step 1).

6. The preparation method of the fluorocarbon-based cationic surfactant according to claim 2, wherein in the step 2), the hydroxypropyl quaternary ammonium salt is 3-chloro-2 hydroxypropyl-trimethyl ammonium chloride, and the molar ratio of the obtained light yellow solid to the 3-chloro-2 hydroxypropyl-trimethyl ammonium chloride is 1 (2-2.2).

7. The method of claim 2, wherein the second solvent is dimethyl sulfoxide in step 2).

8. The method for preparing a fluorocarbon-based cationic surfactant according to claim 2, wherein in step 3), the catalyst is dibutyltin dilaurate, and the mass fraction of the added catalyst is 0.5 wt%.

9. The method for preparing fluorocarbon-based cationic surfactant according to claim 2, wherein in the step 3), the third solvent is N, N-dimethylformamide, and the mass of the third solvent is 70-80 wt%.

10. The use of a fluorocarbon-based cationic surfactant as an antifogging agent according to claim 1, wherein the fluorocarbon-based cationic surfactant is mixed into a resin to be molded to form an antifogging resin lens.

Technical Field

The invention relates to the technical field of cationic surfactant preparation, and particularly relates to a fluorocarbon-based cationic surfactant as well as a preparation method and application thereof

Background

Transparent resin lenses are widely applied to a plurality of fields of daily life, industrial production, scientific research, medical application and the like, the commonly used transparent materials at present comprise methacrylic ester resin, styrene resin and polycarbonate, and the products all have good optical performance, gradually replace inorganic glass and become the mainstream of the transparent materials in the market at present. However, in any transparent material, when a certain temperature difference occurs between the two sides, and the steam pressure of the surrounding environment is higher than the saturated steam pressure of the moisture on the surface of the substrate, the water vapor is gathered towards the surface of the transparent substrate and can be separated out in the form of small water drops to form water mist, the small water drops can cause diffuse reflection to light, and the light transmittance of the surface of the transparent substrate is obviously reduced. In view of the above problems, it is necessary to prepare a material having an antifogging effect.

Disclosure of Invention

In order to solve the problem that when the transparent lens is used in the prior art, the light transmittance of the transparent base material is reduced due to the diffuse reflection of light caused by temperature difference. The invention aims to provide a fluorocarbon-based cationic surfactant, and a preparation method and application thereof. The surfactant antifogging agent is prepared by selecting short-carbon-chain perfluorovaleryl fluoride and dipentaerythritol as raw materials and connecting the raw materials by diisocyanate to generate a fluorocarbon-based cationic surfactant. The invention solves the problem of low surface activity caused by short fluorocarbon chain segment, and the diisocyanate cross-linked fluorocarbon cationic surfactant is used as an antifogging agent to improve the antifogging performance of the resin lens.

The technical scheme adopted by the invention is as follows:

a fluorocarbon-based cationic surfactant of the formula:

a preparation method of a fluorocarbon-based cationic surfactant comprises the following steps:

1) dissolving dipentaerythritol in a first solvent, adding triethylamine, stirring and heating to 50-60 ℃, dropwise adding perfluorovaleryl fluoride while stirring, continuously heating to 75-85 ℃ after dropwise adding, and stirring and reacting for 4-6 hours; washing and extracting to obtain a light yellow solid.

2) Dissolving the obtained light yellow solid in a second solvent, adding powdery sodium hydroxide after the light yellow solid is completely dissolved, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, then adding the solvent solution dissolved with the hydroxypropyl quaternary ammonium salt into a four-mouth bottle at one time, heating to 75-85 ℃, keeping the temperature for a period of time, and then carrying out suction filtration on a reaction product to obtain a solid product;

3) adding a catalyst and a third solvent into the obtained solid product, dropwise adding diisocyanate, reacting at the temperature of 40-60 ℃ for 3-5 h, and drying to obtain the fluorocarbon-based cationic surfactant.

As a further improvement of the invention, in the step 1), the molar ratio of the dipentaerythritol to the perfluorovaleryl fluoride is 1 (3-3.2).

As a further development of the invention, in step 1), the product obtained is washed first with HCl solution and then with NaHCO₃Washing the solution, extracting with diethyl ether after washing with water, separating to obtain an upper organic layer, and distilling under reduced pressure to remove the solvent to obtain a light yellow solid; the HCl and NaHCO₃The concentrations of (A) and (B) were all 5 wt%.

As a further improvement of the present invention, in step 1), the first solvent is dimethylformamide.

As a further improvement of the invention, in the step 2), the hydroxypropyl quaternary ammonium salt is 3-chloro-2 hydroxypropyl-trimethyl ammonium chloride, and the molar ratio of the obtained light yellow solid to the 3-chloro-2 hydroxypropyl-trimethyl ammonium chloride is 1 (2-2.2).

As a further improvement of the present invention, in step 2), the second solvent is dimethyl sulfoxide.

As a further development of the invention, in step 3) the catalyst is dibutyltin dilaurate, the mass fraction added being 0.5 wt%.

As a further improvement of the invention, in the step 3), the third solvent is N, N-dimethylformamide, and the mass of the third solvent accounts for 70-80 wt%.

The application of fluorocarbon-based cationic surfactant as antifogging agent is characterized by that the fluorocarbon-based cationic surfactant is mixed in resin, and formed so as to obtain the invented antifogging resin lens.

Compared with the prior art, the invention has the following advantages:

since the glass surface is generally negatively charged, a cationic surfactant having a large adhesion ability is used. The invention selects perfluorovaleryl fluoride and dipentaerythritol containing short carbon chains as basic raw materials, and generates the fluorocarbon-based cationic surfactant through diisocyanate connection. The surfactant antifogging agent is a substance which is coated on the surface of glass or plastic and can prevent water mist from forming for a long time. After the antifogging agent is coated, the glass is not influenced by the external environment (weather, temperature and humidity) and is always kept clear and transparent. The surfactant is applied to the antifogging agent, and has the advantages of low cost of raw materials, simple operation, simple production process and good antifogging effect.

The application of the surfactant as an antifogging agent solves the problem that water mist is separated out on the surface when the temperature of the glass surface reaches the dew point of the surrounding atmosphere.

Description of the drawings:

FIG. 1 is a diagram showing the mechanism of synthesis of the fluorocarbon-based cationic surfactant obtained in example 3;

FIG. 2 nuclear magnetic hydrogen spectrum of fluorocarbon-based cationic surfactant obtained in example 3;

FIG. 3 is a temperature resistance chart of the fluorocarbon-based cationic surfactant obtained in example 3;

fig. 4 light transmittance of example 3 of the resulting fluorocarbon-based cationic surfactant as an antifogging agent.

Detailed Description

The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention relates to a fluorocarbon-based cationic surfactant, which has the following structural formula:

specifically, the preparation method of the fluorocarbon-based cationic surfactant comprises the following steps:

(1) dissolving dipentaerythritol in dimethylformamide to obtain a dipentaerythritol solution, adding triethylamine, stirring and heating to 50-60 ℃, and dropwise adding perfluorovaleryl fluoride while stirring. Wherein the molar ratio of the dipentaerythritol to the perfluorovaleryl fluoride is 1 (3-3.2). After the dropwise adding is finished, continuously heating to 75-85 ℃, and stirring for reacting for 4-6 hours; the product was washed 2 times with 5% HCl solution and then with 5% NaHCO₃Washing the solution for 1 time, extracting with diethyl ether after washing with water, separating to obtain an upper organic layer, and distilling under reduced pressure to remove the solvent to obtain a light yellow solid.

(2) Dissolving the light yellow solid obtained in the step 1 in dimethyl sulfoxide (DMSO), adding the dissolved light yellow solid into a four-neck flask, adding about 2g of powdery sodium hydroxide after the light yellow solid is completely dissolved, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, then adding a solution of a dimethyl sulfoxide solvent dissolved with 3-chloro-2 hydroxypropyl-trimethyl ammonium chloride into the four-neck flask at one time, heating to 75-85 ℃, wherein the molar ratio of the obtained light yellow solid to the 3-chloro-2 hydroxypropyl-trimethyl ammonium chloride is 1 (2-2.2), carrying out suction filtration on a reaction product after heat preservation is carried out for a period of time, wherein the liquid is a mixture of the dimethyl sulfoxide and alkali, and the solid is a product.

(3) Adding a mixture of the solid product in the step 2 and 0.5 wt% of dibutyltin dilaurate into a flask, adding 70 wt% of N, N-dimethylformamide solvent, and slowly dropwise adding hexamethylene diisocyanate, wherein the molar ratio of the hexamethylene diisocyanate to the product I is 1: reacting for 3-5 h at the temperature of 2, 40-60 ℃, and drying in vacuum to obtain the fluorocarbon-based cationic surfactant (antifogging agent).

And uniformly coating the obtained fluorocarbon-based cationic surfactant (antifogging agent) on the resin lens by a blade coating method or a pulling method, then putting the resin lens into an oven at the temperature of 25 ℃, slowly heating to 60-100 ℃, keeping the temperature for 6-12 hours, taking out the resin lens, cooling to room temperature, and finishing coating and curing to obtain the antifogging resin lens.

The invention is further illustrated by the following specific examples and figures: