CN101041709A - Fluorine-containing aqueous polyurethane and preparation method and application thereof - Google Patents

Abstract

The invention discloses a water-based fluorine-containing polyurethane and its preparation method and application. The general formulas of cationic fluorine-containing water-based polyurethane and anionic fluorine-containing water-based polyurethane are respectively the above formulas, and the preparation includes (1) synthesizing brominated epoxy Butane (2) to synthesize fluorobutylene oxide (3) to synthesize fluorine-containing polyether (4) to synthesize waterborne polyurethane. The invention can be used for water-repellent, waterproof and anti-fouling treatment on the surfaces of textiles, metals, paper, glass, plastics, rubber, ceramics, etc., using water as the dispersion medium, and is a high-performance green and environmentally friendly water-repellent, waterproof and anti-fouling material , has a broad market prospect.

Description

A kind of fluorine-containing waterborne polyurethane and its preparation method and application

technical field

The invention belongs to the field of surface coatings, in particular to a fluorine-containing water-based polyurethane and its preparation method and application.

Background technique

At present, with the development of coating technology at home and abroad and the improvement of people's living standards, people pay more and more attention to multi-functional coating products with high technical content. Coating agents that can not only endow the substrate with excellent water repellency, waterproof, antifouling, weather resistance, and light fastness, but also are environmentally friendly, have increasingly attracted people's attention.

The wettability of the material surface is a very important property, which is usually controlled by the chemical composition and geometry of the surface, and has a wide range of applications in industry. This is because the hydrophobic surface reduces the contact with water, and the chemical bonds or chemical reactions formed by water are limited. As a result, various desirable phenomena appear on such surfaces, such as water-repellent finishing of textiles, self-cleaning buildings, prevention of snow from adhering to antennas and glass, self-cleaning traffic lights, reduced The friction of the hull and the prevention of the spread of disease, etc. Due to its excellent properties, polyurethane has very important applications in coatings and fabric finishing agents. However, traditional polyurethanes are mostly solvent-based polyurethanes, which volatilize a large amount of organic solvents during the construction process, causing great pollution and damage to the environment and the health of construction workers, and because organic solvents are easy to burn, it increases the cost of transportation, Hazards in storage and use.

Contents of the invention

The technical problem to be solved by the present invention is to provide a fluorine-containing water-based polyurethane and its preparation method and application. The fluorine-containing water-based polyurethane can be water-repellent, waterproof and anti-fouling, and has no pollution to the environment, and can be used in textiles, construction, plastics, paper, Surface treatment of glass, metal, rubber or ceramics.

A kind of fluorine-containing waterborne polyurethane of the present invention comprises two kinds of waterborne fluorine-containing polyurethanes:

Cationic fluorinated water-based polyurethane and anionic fluorinated water-based polyurethane. The polymer is a bluish white emulsion.

A kind of preparation method of fluorine-containing waterborne polyurethane of the present invention, comprises the following steps:

(1) Synthesis of brominated butylene oxide

Its molecular formula is Two kinds, the synthesis steps are as follows:

已经商品化，可直接购买。

It has been commercialized and can be purchased directly.

Tribromoneopentyl alcohol, base, phase transfer catalyst and solvent, react at 10-100°C for 1-20 hours, stand to separate layers, take the organic layer, extract, combine the organic layers, and dry. Distillation under reduced pressure to obtain bromobutylene oxide.

(2) Synthetic fluorobutylene oxide FOX, its general formula is:

两种，合成步骤以下式表示：

Two kinds, the synthesis steps are represented by the following formula:

Among them, R _f1 and R _f2 are the same or different, and are straight or branched fluorine-containing carbon chains, such as CF ₃ -, CF ₃ (CF ₂ ) _o -, HCF ₂ (CF ₂ ) _o -, CF ₃ (CF ₃ )CF(CF ₂ ) _o -, CF ₃ (CF ₂ ) _o (CFH) _p -, F(CF(CF ₃ )CF ₂ O) _o -, etc. m, n, o, p are all integers of 0-30.

Under the protection of nitrogen, add bromobutylene oxide and solvent into the reaction flask. Add phase transfer catalyst, fluorine-containing alcohol and compound 1 aqueous solution, and react at 10-200° C. for 1-48 hours. Distilled water was added, cooled to room temperature, the solution was separated into layers, and the organic layer was collected and dried. Solvent was removed under vacuum. Distillation under reduced pressure gave the compound fluorobutylene oxide FOX as a colorless liquid.

As a preferred technical solution: the phase transfer catalysts are ammonium salts, polyethers, sulfur-containing polymers, phosphonium salts, N-alkylphosphonamides, methine bridge phosphorus or oxygen sulfur compounds, etc., such as chlorine Tetraphenylphosphonium chloride, hexadecyltributylphosphonium chloride, tetra-n-butylammonium bromide (TBAB), etc.

The solvent is diethanol dimethyl ether, diethylene glycol, tetrahydrofuran, acetonitrile, dichloromethane, methanol, ethanol, propanol, butanol, ether, acetone, butanone, petroleum ether, ethyl acetate and the like.

The compound 1 is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, sodium methoxide, sodium ethoxide and the like.

(3) The preparation of fluorine-containing polyether PFOX, its reaction formula is as follows:

Wherein, HO～～R ₁ ～～OH are general formulas of polyhydric alcohols, and x and y are integers ranging from 0 to 500000.

Under the protection of nitrogen, react the polyhydric alcohol, BF ₃ ·Et ₂ O, FOX and anhydrous solvent at 0-100° C. for 1-24 hours. The reaction was stopped and finally the solvent was removed under vacuum. The resulting polymer was a colorless viscous wax. Described polyol is ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol, triethylene glycol, glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, 1,4-butanediol Alcohol etc.

(4) Preparation of fluorine-containing waterborne polyurethane

By introducing different hydrophilic groups, cationic fluorine-containing waterborne polyurethane and anionic fluorine-containing waterborne polyurethane are respectively prepared. The reaction formula for preparing cationic fluorine-containing waterborne polyurethane is:

Among them, HO～～R ₂ ～～OH is the general formula of polyether polyol, OCN～～R ₃ ～～NGO is the general formula of polyisocyanate, and x is an integer of 0-500000.

Under the protection of nitrogen, the water-removed fluorine-containing polyether PFOX, polyether polyol, polyisocyanate and catalyst are added into the reactor. Heat to 1-100°C to react for 1-20 hours, add solvent to dilute the prepolymer, then add chain extender and epichlorohydrin, heat to 1-100°C to react for 1-20 hours after adding. Finally an aqueous carboxylic acid solution was added and after cooling to room temperature the residual solvent was removed in vacuo. Prepare cationic fluorine-containing waterborne polyurethane;

The reaction formula for preparing anionic fluorine-containing waterborne polyurethane is:

Among them, HO～～R ₂ ～～OH is the general formula of polyether polyol, OCN～～R ₃ ～～NCO is the general formula of polyisocyanate, HO～～R ₄ (R ₅ )～～OH is the general formula of compound 2 , R ₅ ^- is -COO ^- , -SO ₄ ^- , -SO ₃ ^- and other anionic hydrophilic groups, R ₆ is the general formula of the chain extender, and x is an integer of 0-500000.

React fluorine-containing polyether PFOX, polyether polyol, compound 2, solvent, catalyst, and polyisocyanate at 5 to 100° C. for 1 to 10 hours, and add amine compounds to neutralize carboxylic acid groups. Add a chain extender, react for 0.1-10 hours, add water to disperse, and finish the reaction to prepare anionic fluorine-containing waterborne polyurethane.

As a preferred technical solution, the catalyst is a tertiary amine catalyst, an organotin catalyst and a non-tin metal organic compound catalyst, such as triethylenediamine, triethylamine, N-methylmorpholine, N-ethyl Mapline, N, N'-dimethylpiperazine, N, N'-diethylpiperazine, bis(2-dimethylamino) ethyl ether, tetramethylbutanediamine, pentamethyldipropylenetri Amine, dimethylethanolamine, dibutyltin dilaurate, stannous octoate, lead isooctanoate, lead octoate, zinc isooctanoate, zinc octoate, phenylmercuric acetate, lead oleate, potassium oleate, zinc naphthenate, cyclic Cobalt alkanoate etc. The solvent is diethanol dimethyl ether, diethylene glycol, tetrahydrofuran, acetonitrile, dichloromethane, methanol, ethanol, propanol, butanol, ether, acetone, butanone, petroleum ether, ethyl acetate and the like. The compound 2 is dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA), dihydroxyethyl octadecylamine and the like. Described polyisocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), ethylbenzene diisocyanate (EDI) ), polyphenyl polyisocyanate (PAPI), 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 4,6-xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), cyclohexyl diisocyanate (THDI), 3,3'-dimethylbiphenyl-4,4'-diisocyanate (TODI), 3,3'-dimethyl-4,4 'Diphenylmethane diisocyanate, 4,4',4"-triphenylmethane triisocyanate, tetraisocyanate, etc. The chain extenders are diamines, polyols, enamines and alcohol amine compounds, such as 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 1,4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, 1,4-cyclohexanol , neopentyl glycol, 1,6-hexanediol, hydroquinone-di(β-hydroxyethyl) ether (HQEE), trimethylolpropane (TMP), glycerol, diethylenetriamine, triethylene Tetramine, tetraethylenepentamine, ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc. The amine compounds are ethylamine, diethylamine, triethylamine, trimethylamine, n-propylamine, ortho-phenylenediamine Amine, n-pentylamine, dipropylamine, tripropylamine, etc.

The application of the fluorine-containing water-based polyurethane of the present invention can be used for surface treatment of textiles, construction, plastics, paper, glass, metal, rubber or ceramics.

For example, the product of the present invention is used for water-repellent finishing of textiles, and adopts the method described in antifouling finishing in "Principles of Dyeing and Finishing Technology" (volume two, edited by Wang Jusheng), and the present invention will not repeat them. Cationic water-based polyurethane FPU containing short fluorine chains was applied to the surface modification of cotton fabrics, and the contact angle of the finished fabrics to water reached 147°. In addition, the finished fabric also showed good durability, and even after 30 washes, the contact angle to water still reached 130°. It can be seen that it has excellent water repellency and durability effects. When the product of the present invention is used in the paint industry, the contact angle to water on the surface of the substrate can reach 110°, which can make the surfaces of buildings, metals, etc. have excellent waterproof effects and self-cleaning properties. The prepared fluorocarbon coating has excellent weather resistance and sunlight resistance, greatly improves the service life of traditional coatings, saves costs, and solves the problem of waste of resources. Since the prepared fluorine-containing water-based polyurethane uses water as the medium, it does not contain organic solvents such as formaldehyde, and has no pollution to the environment. It is a new type of environmentally friendly coating agent with excellent water repellency, friendly to the environment and harmless to the human body. .

The invention discloses a new type of fluorine-containing water-based polyurethane, which uses water as a dispersant, has no pollution to the environment, and introduces fluorine-containing groups into it. Due to the high electronegativity of fluorine, the C-F bond is very stable and can be polymerized simultaneously. The perfluorinated side chain of the compound is oriented outward, forming a "shielding protection" for the main chain and internal molecules, so that fluorine-containing polyurethane has many excellent properties, such as good chemical inertness, weather resistance, stain resistance, water and oil resistance, and Ultraviolet light, etc., can not only endow the surface of the material with excellent water-repellent, waterproof, oil-repellent, and anti-fouling effects, but also greatly extend the service life of the coating agent, greatly save construction costs, and advantageously solve the problem of waste of resources. Water-based PU slurry is the general trend. With the enhancement of people's awareness of environmental protection, water-based PU slurry will soon be popularized, and the market potential is immeasurable.

The beneficial effects of the present invention are: the present invention respectively prepares cationic fluorine-containing waterborne polyurethane and anionic fluorine-containing waterborne polyurethane, which have excellent water-repellent, waterproof and anti-fouling properties. It is a high-performance, green and environmentally friendly product with broad market prospects.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

Add tribromoneopentyl alcohol (20.0g, 61.5mmol), NaOH (20g), phase transfer catalyst TBAB (0.79g, 2.46mmol) and CH ₂ Cl ₂ (100mL ), stirred evenly by magnetic force, then raised the temperature to 35°C and reacted for 12 hours, stopped the reaction, and cooled to room temperature. The layers were allowed to stand, the organic matter in the lower layer was removed, the aqueous layer was extracted with dichloromethane, the organic layers were combined, and dried over anhydrous magnesium sulfate. The organic solvent was removed under vacuum. Distilled under reduced pressure to obtain bromobutylene oxide as a colorless liquid (10.5 g, yield 70%).

The relevant data are as follows: ¹ H NMR (300 MHz, CDCl ₃ ) δ: 3.9 (s, 4H), 4.4 (s, 4H).

Under the protection of nitrogen, the compound bromobutylene oxide (10.0 g, 40.9 mmol) was added into a 100 mL three-necked flask equipped with a reflux condenser, a dropping funnel and a thermometer. The phase transfer catalyst TBAB (12.2%wt, 3.0g), trifluoroethanol (8.2g, 82.0mmol) and aqueous KOH (45%wt, 6.0g) were added to the reaction mixture. Then heated to 80-85°C and stirred for 24 hours. Distilled water (20 mL) was added, cooled to room temperature, the solution was separated into layers, and the organic layer was collected and dried over anhydrous sodium sulfate. Solvent was removed under vacuum. Distillation under reduced pressure gave compound FOX as a colorless liquid (10.4 g, yield 90%).

The relevant data are as follows: ¹ H NMR (400MHz, CDCl ₃ ): 4.4 (s, 4H), 3.7-3.8 (m, 8H).

¹⁹ F NMR (376 MHz, CDCl ₃ ): -74.2 (s, 3F).

IR (cm ^-1 , KBr): 2950, 2882, 1479, 1461, 1443, 1417, 1311, 1279, 1205, 1163.

Under nitrogen protection, neopentyl glycol (7.37g, 70.9mmol), BF3.Et2O (4.03g, 28.4mmol) and anhydrous dichloromethane (185mL) were added to a dry 500mL three-necked flask . Stir at room temperature for 30 minutes. The monomer FOX (120 g, 0.426 mol) was slowly added dropwise to the reaction mixture. This reaction is an exothermic reaction, and a slight rise in temperature can be found at this time. After the addition was complete, the reaction was continued at room temperature for 6 hours. Stop the reaction, the obtained fluorine-containing polyether PFOX, the polymer is a colorless viscous wax (yield 95%).

Under nitrogen protection, PFOX, IPDI ([IPDI]/[PFOX]=2.1/1, mol) and DBTDL ([DBTDL]/[monomers]=0.001/1, mol) were added into a dry 500 mL three-necked flask. Heat to 40°C to react for 2.5 hours, add anhydrous acetone to dilute the prepolymer, then slowly add the prepolymer to diethylenetriamine and epichlorohydrin ([diethylenetriamine]/[epoxychlorohydrin] at room temperature ]/[prepolymer]=1:1:1, mol) in acetone solution, heated to 45°C to continue the reaction for 2 hours after the addition was completed. Finally, add acetic acid aqueous solution, and the degree of neutralization is controlled at 60%. After cooling to room temperature, residual acetone was removed in vacuo. The obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 2000 and 5000.

The cationic waterborne polyurethane obtained above is made into a solution, a crosslinking agent is added, and the padding-drying-baking process is adopted for finishing. The contact angle of the finished fabric to water reaches 147°, and the finished fabric also shows In order to ensure better durability, after 30 times of washing, the contact angle to water still reaches 130°.

Example 2

Under nitrogen protection, PFOX, IPDI ([IPDI]/[PFOX]=3.1/1, mol) and DBTDL ([DBTDL]/[monomers]=0.001/1, mol) were added to dry 500mL in a three-neck flask. Heating to 50°C for 3 hours, then adding the prepolymer to triethylenetetramine and epichlorohydrin ([triethylenetetramine]/[epichlorohydrin]/[prepolymer]=1:1.2 : 1, mol) in the acetone solution, heated to 50 ℃ after adding and continued to react for 3 hours. Finally, add acetic acid aqueous solution to control the degree of neutralization at 70%. After cooling to room temperature, residual acetone was removed in vacuo. The obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 5,000 and 10,000.

The cationic water-based polyurethane obtained above is formulated into a solution, a crosslinking agent is added, and the padding-drying-baking process is used for finishing. The contact angle of the finished fabric to water reaches 142°, and the finished fabric also shows In order to ensure better durability, after 30 times of washing, the contact angle to water still reaches 128°.

Example 3

Under nitrogen protection, add PFOX, MDI (MDII]/[PFOX]=3.1/1, mol) and DBTDL ([DBTDL]/[monomers]=0.001/1, mol) to a dry 500mL three-port in the flask. Heating to 60°C for 4 hours, then adding the prepolymer to tetraethylenepentamine and epichlorohydrin ([triethylenetetramine]/[epichlorohydrin]/[prepolymer]=1:1.2 : 1, mol) in the acetone solution, heated to 70 ℃ after adding and continued to react for 5 hours. Finally, add acetic acid aqueous solution, and the degree of neutralization is controlled at 60%. After cooling to room temperature, residual acetone was removed in vacuo. The obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 10,000 and 50,000.

The cationic water-based polyurethane obtained above is formulated into a solution, a crosslinking agent is added, and the padding-drying-baking process is used for finishing. The contact angle of the finished fabric to water reaches 145°, and the finished fabric also shows In order to ensure better durability, after 30 times of washing, the contact angle to water still reaches 132°.

Example 4

Under nitrogen protection, PFOX, IPDI ([IPDI]/[PFOX]=3.1/1, mol) and DBTDL ([DBTDL]/[monomers]=0.001/1, mol) were added to dry 500mL in a three-neck flask. Heating to 60°C for 4 hours, then adding the prepolymer to triethylenetetramine and epichlorohydrin ([triethylenetetramine]/[epichlorohydrin]/[prepolymer]=1:1.2 : 1, mol) in the acetone solution, heated to 60 ℃ after adding and continued to react for 4 hours. Finally, add acetic acid aqueous solution to control the degree of neutralization at 70%. After cooling to room temperature, residual acetone was removed in vacuo. The obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 50,000 and 200,000.

The cationic waterborne polyurethane obtained above is made into a solution, a crosslinking agent is added, and the padding-drying-baking process is adopted for finishing. The contact angle of the finished fabric to water reaches 140°, and the finished fabric also shows In order to ensure better durability, after 30 times of washing, the contact angle to water still reaches 128°.

The obtained cationic water-based polyurethane is used for the coating on the glass surface, and the contact angle to water can reach 110°, which has excellent waterproof effect. It can be used as water-repellent, waterproof and antifouling treatment on the surface of textiles, metal, paper, glass, plastic, rubber, ceramics, buildings and so on.

Example 5

Under nitrogen protection, PFOX, XDI ([XDI]/[PFOX]=4/1, mol) and zinc naphthenate (zinc naphthenate/[monomers]=0.003/1, mol) that had been removed from water were added into a dry 100mL three-neck flask. Heating to 60°C for 3 hours, then adding the prepolymer to triethylenetetramine and epichlorohydrin ([triethylenetetramine]/[epichlorohydrin]/[prepolymer]=1:1.2 : 1, mol) in the acetone solution, heated to 60 ℃ after adding and continued to react for 4 hours. Finally, add acetic acid aqueous solution, and the degree of neutralization is controlled at 80%. After cooling to room temperature, residual acetone was removed in vacuo. The obtained polymer belt is a white milky liquid, and the molecular weight distribution is between 200,000 and 500,000.

The obtained anionic water-based polyurethane is used for the coating on the glass surface, and the contact angle to water can reach 109°, which has excellent waterproof effect. It can be used as water-repellent, waterproof and antifouling treatment on the surface of textiles, metal, paper, glass, plastic, rubber, ceramics, buildings and so on.

Example 6

Under nitrogen protection, 3 g of PFOX, 2 g of polyethylene glycol 1000, 1.8 g of IPDI and 0.2 g of DMPA were added into a three-necked flask. Heat to 40° C. for 3 hours to react, add 0.3 g of diethylenetriamine, and finally add aqueous ammonia solution, and control the degree of neutralization at 60%. After cooling to room temperature, the obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 2000 and 5000.

The anionic water-based polyurethane obtained above is made into a solution, a crosslinking agent is added, and the padding-drying-baking process is used for finishing. The contact angle of the finished fabric to water reaches 146°.

The obtained anionic water-based polyurethane is used for the coating on the glass surface, and the contact angle to water can reach 106°, which has excellent waterproof effect. It can be used as water-repellent, waterproof and antifouling treatment on the surface of textiles, metal, paper, glass, plastic, rubber, ceramics, buildings and so on.

Example 7

Under nitrogen protection, 3 g of PFOX, 5 g of polyethylene glycol 400, 3 g of MDI and 0.2 g of DMPA were added into a three-necked flask. Heat to 40° C. for 3 hours to react, add 0.3 g of diethylenetriamine, and finally add aqueous ammonia solution, and control the degree of neutralization at 60%. After cooling to room temperature, the obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 5,000 and 10,000.

The anionic water-based polyurethane obtained above is made into a solution, a crosslinking agent is added, and the padding-drying-baking process is used for finishing. The contact angle of the finished fabric to water reaches 142°.

The obtained anionic water-based polyurethane is used for the coating on the glass surface, and the contact angle to water can reach 110°, which has excellent waterproof effect. It can be used as water-repellent, waterproof and antifouling treatment on the surface of textiles, metal, paper, glass, plastic, rubber, ceramics, buildings and so on.

Example 8

Under nitrogen protection, 3 grams of PFOX, 4 grams of GE220, 3 grams of MDI and 0.4 grams of DMPA were added into a three-necked flask. React at 60° C. for 6 hours, add 0.5 g of MOCA, and finally add triethylamine, and control the degree of neutralization at 80%. After cooling to room temperature, the obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 10,000 and 50,000.

The anionic water-based polyurethane obtained above is made into a solution, a crosslinking agent is added, and the padding-drying-baking process is used for finishing. The contact angle of the finished fabric to water reaches 146°.

The obtained anionic waterborne polyurethane is used for the coating on the glass surface, and the contact angle to water can reach 100°, which has excellent waterproof effect. It can be used as water-repellent, waterproof and antifouling treatment on the surface of textiles, metal, paper, glass, plastic, rubber, ceramics, buildings and so on.

Example 9

Under nitrogen protection, 5 grams of PFOX, 3 grams of GE3000, 2 grams of polyethylene glycol 1000, 1 gram of 7 grams of PPDII and 0.4 grams of DMPA were added into a three-necked flask. React at 70° C. for 8 hours, add 0.8 g of neopentyl glycol, and finally add diethylamine, and control the degree of neutralization at 60%. After cooling to room temperature, the obtained polymer is a translucent liquid with blue fluorescence, and the molecular weight distribution is between 50,000 and 200,000.

The anionic water-based polyurethane obtained above is made into a solution, a crosslinking agent is added, and the padding-drying-baking process is used for finishing. The contact angle of the finished fabric to water reaches 141°.

The obtained anionic water-based polyurethane is used for the coating on the glass surface, and the contact angle to water can reach 103°, which has excellent waterproof effect. It can be used as water-repellent, waterproof and antifouling treatment on the surface of metal, paper, glass, plastic, rubber, ceramics, buildings and so on.

Example 10

Under nitrogen protection, 5 grams of PFOX, 3 grams of GE3000, 2 grams of polyethylene glycol 1000, 1 gram of 7 grams of PPDII and 0.4 grams of DMPA were added into a three-necked flask. React at 50° C. for 6 hours, add 0.8 g of neopentyl glycol, and finally add diethylamine, and control the degree of neutralization at 65%. The polymer obtained after cooling to room temperature is a translucent emulsion with a molecular weight distribution between 200,000 and 500,000.

The anionic water-based polyurethane obtained above is made into a solution, a crosslinking agent is added, and the padding-drying-baking process is used for finishing. The contact angle of the finished fabric to water reaches 140°.

The obtained anionic water-based polyurethane is used for the coating on the glass surface, and the contact angle to water can reach 105°, which has excellent waterproof effect. It can be used as water-repellent, waterproof and antifouling treatment on the surface of metal, paper, glass, plastic, rubber, ceramics, buildings and so on.

Claims (17)

1. A fluorine-containing water-based polyurethane, by introducing different hydrophilic groups, two types of water-based fluorine-containing polyurethanes are obtained: (1) Cationic fluorine-containing waterborne polyurethane, whose general formula is as follows:

Among them, HO～～R ₂ ～～OH is the general formula of polyether polyol, OCN～～R ₃ ～～NCO is the general formula of polyisocyanate, x is an integer from 0 to 500000, and the property is a white emulsion with a slight blue light; (2) Anionic fluorine-containing water-based polyurethane, whose general formula is as follows:

Among them, HO～～R ₂ ～～OH is the general formula of polyether polyol, OCN～～R ₃ ～～NCO is the general formula of polyisocyanate, HO～～R ₄ (R ₅ )～～OH is the general formula of compound 2 , R ₅ ^- is -COO ^- , -SO ₄ ^- , -SO ₃ ^- and other anionic hydrophilic groups, R ₆ is the general formula of the chain extender, x is an integer from 0 to 500000, and the property is a slightly blue white emulsion . 2. A fluorine-containing water-based polyurethane according to claim 1, characterized in that the cationic water-based polyurethane has a molecular weight of 2,000-500,000. 3. A fluorine-containing water-based polyurethane according to claim 1, characterized in that the molecular weight of the anionic water-based polyurethane is 2,000-500,000. 4. A method for preparing fluorine-containing waterborne polyurethane, comprising the following steps: (1) Synthesis of brominated butylene oxide Tribromoneopentyl alcohol, compound 1, phase transfer catalyst and solvent, react at 10-100°C for 1-20 hours, let stand to separate layers, take the organic layer, extract, combine the organic layers, dry, and distill under reduced pressure; (2) Synthesis of fluorobutylene oxide FOX Under nitrogen protection, add bromobutylene oxide and solvent into the reaction flask, add phase transfer catalyst, fluorine-containing alcohol and compound 1 aqueous solution, react at 10-200°C for 1-48 hours, add distilled water, and cool to room temperature , the solution was separated into layers, and the organic layer was collected and dried. The solvent was removed under vacuum and distilled under reduced pressure to obtain a colorless liquid; (3) Synthesis of fluorinated polyether PFOX Under the protection of nitrogen, react the polyol, BF ₃ ·Et ₂ O, FOX and anhydrous solvent at 0-100°C for 1-24 hours, and remove the solvent under vacuum to obtain a colorless viscous wax ; (4) Synthesis of fluorine-containing waterborne polyurethane a. Cationic fluorine-containing waterborne polyurethane Under the protection of nitrogen, the water-removed fluorine-containing polyether PFOX, polyether polyol, polyisocyanate and catalyst are added into the reactor. Heat to 1-100°C to react for 1-20 hours, add solvent to dilute the prepolymer, then add chain extender and epichlorohydrin, heat to 1-100°C to react for 1-20 hours after adding. Finally, add carboxylic acid aqueous solution, after cooling to room temperature, remove the residual solvent under vacuum; b. Anionic fluorine-containing waterborne polyurethane React fluorine-containing polyether PFOX, polyether polyol, compound 2, solvent, catalyst, and polyisocyanate at 5-100°C for 1-10 hours, add amine compounds and chain extenders, react for 0.1-10 hours, add water to disperse. 5. A method for preparing fluorine-containing water-based polyurethane according to claim 4, wherein said compound 1 is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, carbonic acid Potassium hydrogen, magnesium bicarbonate, sodium methoxide or sodium ethoxide. 6. A method for preparing fluorine-containing waterborne polyurethane according to claim 4, characterized in that: said compound 2 is dimethylol propionic acid (DMPA), dimethylol butyric acid (DMBA) or two Hydroxyethyl octadecylamine. 7. A method for preparing fluorine-containing water-based polyurethane according to claim 4, characterized in that: the phase transfer catalyst is ammonium salts, polyethers, sulfur-containing polymers, phosphonium salts, N-alkane Phosphonamides, methine bridge phosphorus or oxygen sulfur compounds. 8. The preparation method of a kind of fluorine-containing waterborne polyurethane according to claim 4 or 7, characterized in that: the phase transfer catalyst is tetraphenylphosphonium chloride, hexadecyltributylphosphonium chloride or tetraphenylphosphonium chloride n-Butylammonium bromide. 9. A method for preparing fluorine-containing water-based polyurethane according to claim 4, characterized in that: said solvent is diethanol dimethyl ether, diethylene glycol, tetrahydrofuran, acetonitrile, dichloromethane, methanol, ethanol , Propanol, Butanol, Ethyl Ether, Acetone, Butanone, Petroleum Ether, Ethyl Acetate or N-Methylpyridinone. 10. A method for preparing fluorine-containing waterborne polyurethane according to claim 4, characterized in that: said polyhydric alcohol is ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol, triethylene glycol, Glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol or 1,4-butanediol. 11. A method for preparing fluorine-containing waterborne polyurethane according to claim 4, characterized in that: the catalyst is a tertiary amine catalyst, an organotin catalyst or a non-tin metal organic compound catalyst. 12. The preparation method of a kind of fluorine-containing waterborne polyurethane according to claim 4 or 11, is characterized in that: described catalyst is triethylenediamine, triethylamine, N-methylmorpholine, N-ethyl Basemaline, N,N'-dimethylpiperazine, N,N'-diethylpiperazine, bis(2-dimethylamino)ethyl ether, tetramethylbutylene diamine, pentamethyldipropylene Triamine, dimethylethanolamine, dibutyltin dilaurate, stannous octoate, lead isooctanoate, lead octoate, zinc isooctanoate, zinc octoate, phenylmercury acetate, lead oleate, potassium oleate, zinc naphthenate or Cobalt naphthenate. 13. A method for preparing fluorine-containing waterborne polyurethane according to claim 4, characterized in that: said polyisocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5- Naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), ethylbenzene diisocyanate (EDI), polyphenyl polyisocyanate (PAPI), 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) , 4,6-xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), cyclohexyl diisocyanate (THDI), 3,3'-dimethylbiphenyl- 4,4'-diisocyanate (TODI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4',4"-triphenylmethane triisocyanate or tetraisocyanate. 14. A method for preparing fluorine-containing water-based polyurethane according to claim 4, characterized in that: said amine compounds are ethylamine, diethylamine, triethylamine, trimethylamine, n-propylamine, o-phthalamine, amine, n-pentylamine, dipropylamine or tripropylamine. 15. A method for preparing anionic fluorine-containing waterborne polyurethane according to claim 4, characterized in that: said chain extender is diamine, polyol, enamine or alcohol amine compound. 16. The preparation method of an anionic fluorine-containing waterborne polyurethane according to claim 4 or 15, characterized in that: the chain extender is 3,3'-dichloro-4,4'-diaminobis Benzene methane (MOCA), 1,4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, 1,4-cyclohexanol, neopentyl glycol, 1,6-hexanediol, hydroquinone - Bis(β-hydroxyethyl) ether (HQEE), trimethylolpropane (TMP), glycerol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethanolamine, diethanolamine, triethanolamine or Triisopropanolamine. 17. Application of a fluorine-containing waterborne polyurethane for surface treatment of textiles, construction, plastics, paper, glass, metal, rubber or ceramics.