Diphenyltridecafluorooctyl phosphite as well as preparation method and application thereof

Abstract

The invention discloses diphenyltridecafluorooctyl phosphite ester as well as a preparation method and application of the diphenyltridecafluorooctyl phosphite ester. The preparation method of the diphenyltridecafluorooctyl phosphite ester comprises the following steps: carrying out substitution reaction on phosphorus oxychloride and phenol in a first organic solvent in the presence of an acid-binding agent, filtering after the reaction is finished to obtain a reaction solution, washing, drying and carrying out rotary evaporation on the reaction solution, then carrying out reduced pressure distillation, and collecting fractions at 160-180 DEG C to obtain diphenylphosphoryl chloride; and dissolving diphenyl phosphoryl chloride in a second organic solvent, adding perfluorohexyl ethyl alcohol and an alkali reagent under an ice bath condition to carry out substitution reaction, and separating and purifying after the reaction is finished. The diphenyltridecafluorooctyl phosphite prepared by the method has excellent oil resistance (contact angle gt and 140 degrees) and water resistance (contact angle gt and 150 degrees), the preparation process is simple and easy to implement, and the product yield is high.

Description

Technical Field

[0001] The invention belongs to the field of water- and oil-resistant finishing agents for textiles, and in particular relates to diphenyl tridecafluorooctyl phosphite, a preparation method and application thereof. Background Art

[0002] Per- and polyfluoroalkyl substances (PFASs) are a class of synthetic organic compounds with an alkyl chain backbone and hydrogen atoms fully or partially replaced by fluorine atoms. These compounds have been widely used in industrial applications since the 1950s as waterproof, oil-repellent, and anti-fouling fabric finishes due to their excellent thermal and chemical stability, as well as their hydrophobic and oleophobic properties.

[0003] The unique properties of PFASs stem from the characteristics of the fluorine atom: as the ninth element in the periodic table, fluorine has an extremely high electronegativity, which means that when forming compounds with other elements, fluorine can strongly attract electrons. This characteristic gives fluorine compounds extremely high stability because the chemical bonds formed by fluorine atoms with other elements are very difficult to break. In addition, because the fluorine atom has a small atomic radius, it can easily embed itself into the molecular structure of a variety of compounds, thereby significantly changing the physical and chemical properties of these substances. Therefore, this type of compound is often used to produce waterproof, oil-proof, and anti-fouling fabric finishing agents.

[0004] However, many existing PFASs are highly toxic, and the resulting products still have room for improvement in terms of water and oil repellency. Perfluorooctyl and perfluorinated compounds containing more than eight carbon atoms are highly toxic and difficult to degrade in nature. Fluorinated compounds with less than eight carbon atoms are relatively less toxic and easily degraded. Organophosphine compounds have important applications in flame retardancy and surface treatment. With these considerations in mind, we designed and developed a new phosphorus- and fluorine-containing surfactant, optimized its preparation method, and evaluated the product's performance and application, which will facilitate its future application and promotion. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a diphenyl tridecafluorooctyl phosphite and its preparation method and application, aiming to solve the problem of high toxicity in the existing preparation method and improve the waterproof and oil-proof effects of the product.

[0006] The purpose of the present invention is achieved through the following technical solutions: A diphenyl tridecafluorooctyl phosphite, whose chemical structural formula is as follows: .

[0007] The preparation method of the above-mentioned diphenyl tridecafluorooctyl phosphite comprises the following steps: S1, phosphorus oxychloride and phenol are subjected to a substitution reaction in a first organic solvent in the presence of an acid-binding agent. After completion of the reaction, a reaction solution is obtained by filtration. The reaction solution is washed, dried, rotary evaporated and then distilled under reduced pressure. A fraction at 160-180° C. is collected to obtain diphenylphosphoryl chloride; S2. Dissolve diphenylphosphoryl chloride in a second organic solvent, add perfluorohexylethyl alcohol and an alkaline reagent under ice bath conditions to carry out a substitution reaction, and after the reaction is completed, separate and purify to obtain diphenyl tridecafluorooctyl phosphite.

[0008] Preferably, in step S1, the molar ratio of phosphorus oxychloride to phenol is 1:2.1-2.2.

[0009] Preferably, in step S1, the molar ratio of the acid binding agent to phosphorus oxychloride is 2.2:1.

[0010] Preferably, in step S1, the first organic solvent is at least one of dichloromethane, chloroform and anhydrous toluene.

[0011] Preferably, in step S1, the acid binding agent is at least one of pyridine, triethylamine and diisopropylethylamine.

[0012] Preferably, in step S1, the specific operating steps of carrying out the substitution reaction of phosphorus oxychloride and phenol in the presence of an acid binding agent in a first organic solvent are as follows: first, phosphorus oxychloride and the acid binding agent are added to the first organic solvent, and then phenol is added under ice bath conditions. After the addition is completed, the temperature is raised to room temperature under a protective atmosphere and stirred for 1 hour, and then heated to 70° C. and refluxed for 5 hours.

[0013] Preferably, the protective atmosphere is at least one of nitrogen and an inert gas; and the temperature of the ice bath is 0-10°C.

[0014] Preferably, in step S1, the specific washing operation is: the product is washed with dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, and saturated saline in sequence, with each reagent washing 2 to 3 times. More preferably, the concentration of the dilute hydrochloric acid is 5%.

[0015] Preferably, in step S1, anhydrous sodium sulfate is used for drying.

[0016] Preferably, in step S2, the second organic solvent is at least one of dichloromethane, anhydrous tetrahydrofuran and anhydrous methanol.

[0017] Preferably, in step S2, the alkaline reagent is at least one of triethylamine and diisopropylethylamine.

[0018] Preferably, in step S2, the molar ratio of perfluorohexylethyl alcohol to phosphorus oxychloride in S1 is 1:2.67.

[0019] Preferably, in step S2, the temperature of the substitution reaction is 45° C., and the reaction time is 4 h.

[0020] Preferably, in step S2, the temperature of the ice bath is 0-10°C.

[0021] Preferably, in step S2, the specific operation of separation and purification is: the reaction solution is subjected to rotary evaporation to remove the second organic solvent, the residue is dissolved with a third organic solvent, insoluble matter is removed by suction filtration, and the filtrate is collected and the solvent is again removed by rotary evaporation to obtain a purified product.

[0022] Preferably, the third organic solvent is at least one of tetrahydrofuran, dichloromethane and toluene.

[0023] The above-mentioned diphenyl tridecafluorooctyl phosphite is used as a waterproof and oil-proof conditioning agent for fabrics.

[0024] Compared with the prior art, the present invention has the following beneficial effects: This invention synthesizes a long-fluorocarbon-chain phosphate compound through a substitution reaction between phosphorus oxychloride and perfluorohexylethyl alcohol. This compound exhibits excellent oil repellency (contact angle >140°) and water repellency (contact angle >150°) and is less toxic and bioaccumulative than perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The following is a synthetic route for diphenyl tridecafluorooctyl phosphite described in an embodiment of the present invention.

[0026] Figure 2 This is the infrared spectrum of diphenyl tridecafluorooctyl phosphite prepared in Example 1.

[0027] Figure 3 This is the infrared spectrum of diphenyl tridecafluorooctyl phosphite prepared in Example 2.

[0028] Figure 4 This is the infrared spectrum of diphenyl tridecafluorooctyl phosphite prepared in Example 3.

[0029] Figure 5 This is the infrared spectrum of diphenyl tridecafluorooctyl phosphite prepared in Example 4.

[0030] Figure 6 This is the infrared spectrum of diphenyl tridecafluorooctyl phosphite prepared in Example 5.

[0031] Figure 7 This is the infrared spectrum of diphenyl tridecafluorooctyl phosphite prepared in Example 6. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0033] Example 1 A method for preparing diphenyl tridecafluorooctyl phosphite, comprising the following steps: S1. Add 5.62 g of dry phosphorus oxychloride, 6.42 g of pyridine and 20 mL of anhydrous dichloromethane to a 250 mL dry three-necked flask, add 7.66 g of phenol dropwise in an ice bath at 0°C, and pass nitrogen protection after the addition is complete. Then gradually warm to room temperature and stir for 1 h, then heat to 70°C and reflux for 5 h. After the reaction is complete, filter the reaction solution with a sand-core funnel, wash the filtrate with 5% dilute hydrochloric acid (50 ml×2), saturated sodium bicarbonate (50 ml×2) and saturated brine (50 ml×2) in sequence, dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation at 40°C, and distill the obtained crude product under reduced pressure. Collect the 165°C fraction to obtain 7.88 g of product, i.e., diphenylphosphoryl chloride, with a yield of 78%.

[0034] S2. Add 2.744 g of diphenylphosphoryl chloride and 20 mL of anhydrous dichloromethane to a 100 mL round-bottom flask, dissolve with ultrasound, add 1.414 g of triethylamine to the reaction flask under 0°C ice bath conditions, add 5 g of perfluorohexylethyl alcohol dropwise, raise the temperature to 45°C after the addition is complete, and reflux for 4 h. After the reaction is complete, remove dichloromethane by rotary evaporation at 40°C, add 25 mL of THF to the residue, and stir at room temperature for 15 min. Filter to obtain the filtrate, and remove THF by rotary evaporation at 66°C to obtain the diphenyl tridecafluorooctyl phosphite liquid.

[0035] Example 2 A method for preparing diphenyl tridecafluorooctyl phosphite, comprising the following steps: S1. Add 5.62 g of dry phosphorus oxychloride, 6.13 g of pyridine and 20 mL of anhydrous dichloromethane to a 250 mL dry three-necked flask, add 7.31 g of phenol dropwise in an ice bath at 0°C, and pass nitrogen protection after the addition is complete. Then gradually warm to room temperature and stir for 1 h, then heat to 70°C and reflux for 5 h. After the reaction is complete, filter the reaction solution with a sand-core funnel, wash the filtrate with 5% dilute hydrochloric acid (50 ml×2), saturated sodium bicarbonate (50 ml×2) and saturated brine (50 ml×2) in sequence, dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation at 40°C, and distill the obtained crude product under reduced pressure. Collect the fraction at 165°C to obtain diphenylphosphoryl chloride.

[0036] S2. Add 2.744 g of diphenylphosphoryl chloride and 20 mL of anhydrous dichloromethane to a 100 mL round-bottom flask, dissolve with ultrasound, add 1.414 g of triethylamine to the reaction flask under 0°C ice bath conditions, add 5 g of perfluorohexylethyl alcohol dropwise, raise the temperature to 45°C after the addition is complete, and reflux for 4 h. After the reaction is complete, remove dichloromethane by rotary evaporation at 40°C, add 25 mL of THF to the residue, and stir at room temperature for 15 min. Filter to obtain the filtrate, and remove THF by rotary evaporation at 66°C to obtain the diphenyl tridecafluorooctyl phosphite liquid.

[0037] Example 3 A method for preparing diphenyl tridecafluorooctyl phosphite, comprising the following steps: S1. Add 5.62 g of dry phosphorus oxychloride, 6.42 g of pyridine and 20 mL of anhydrous dichloromethane to a 250 mL dry three-necked flask, add 7.66 g of phenol dropwise in an ice bath at 0°C, and pass nitrogen protection after the addition is complete. Then gradually warm to room temperature and stir for 1 h, then heat to 70°C and reflux for 5 h. After the reaction is complete, filter the reaction solution with a sand-core funnel, wash the filtrate with 5% dilute hydrochloric acid (50 ml×2), saturated sodium bicarbonate (50 ml×2) and saturated brine (50 ml×2) in sequence, dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation at 40°C, distill the obtained crude product under reduced pressure, and collect the fraction at 175°C to obtain diphenylphosphoryl chloride.

[0038] S2. Add 2.744 g of diphenylphosphoryl chloride and 20 mL of anhydrous dichloromethane to a 100 mL round-bottom flask, dissolve with ultrasound, add 1.414 g of triethylamine to the reaction flask under 0°C ice bath conditions, add 5 g of perfluorohexylethyl alcohol dropwise, raise the temperature to 45°C after the addition is complete, and reflux for 4 h. After the reaction is complete, remove dichloromethane by rotary evaporation at 40°C, add 25 mL of THF to the residue, and stir at room temperature for 15 min. Filter to obtain the filtrate, and remove THF by rotary evaporation at 66°C to obtain the diphenyl tridecafluorooctyl phosphite liquid.

[0039] Example 4 A method for preparing diphenyl tridecafluorooctyl phosphite, comprising the following steps: S1. Add 5.62 g of dry phosphorus oxychloride, 6.42 g of pyridine and 20 mL of anhydrous dichloromethane to a 250 mL dry three-necked flask, add 7.66 g of phenol dropwise in an ice bath at 0°C, and pass nitrogen protection after the addition is complete. Then gradually warm to room temperature and stir for 1 h, then heat to 70°C and reflux for 5 h. After the reaction is complete, filter the reaction solution with a sand-core funnel, wash the filtrate with 5% dilute hydrochloric acid (50 ml×2), saturated sodium bicarbonate (50 ml×2) and saturated brine (50 ml×2) in sequence, dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation at 40°C, and distill the obtained crude product under reduced pressure. Collect the 165°C fraction to obtain 7.88 g of product, i.e., diphenylphosphoryl chloride, with a yield of 78%.

[0040] S2. Add 2.744 g of diphenylphosphoryl chloride and 20 mL of anhydrous dichloromethane to a 100 mL round-bottom flask, dissolve them by ultrasonication, add 1.806 g of diisopropylethylamine to the reaction flask under 0°C ice bath conditions, add 5 g of perfluorohexylethyl alcohol dropwise, raise the temperature to 45°C after the addition is complete, and reflux for 4 h. After the reaction is complete, remove dichloromethane by rotary evaporation at 40°C, add 25 mL of THF to the residue, and stir at room temperature for 15 min. Filter to obtain the filtrate, and remove THF by rotary evaporation at 66°C to obtain the diphenyl tridecafluorooctyl phosphite liquid.

[0041] Example 5 A method for preparing diphenyl tridecafluorooctyl phosphite, comprising the following steps: S1. Add 5.62 g of dry phosphorus oxychloride, 6.42 g of pyridine and 20 mL of anhydrous dichloromethane to a 250 mL dry three-necked flask, add 7.66 g of phenol dropwise in an ice bath at 5°C, and pass nitrogen protection after the addition is complete. Then gradually warm to room temperature and stir for 1 h, then heat to 70°C and reflux for 5 h. After the reaction is complete, filter the reaction solution with a sand-core funnel, wash the filtrate with 5% dilute hydrochloric acid (50 ml×2), saturated sodium bicarbonate (50 ml×2) and saturated brine (50 ml×2) in sequence, dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation at 40°C, and distill the obtained crude product under reduced pressure. Collect the fraction at 165°C to obtain diphenylphosphoryl chloride.

[0042] S2. Add 2.744 g of diphenylphosphoryl chloride and 20 mL of anhydrous dichloromethane to a 100 mL round-bottom flask, dissolve with ultrasound, add 1.414 g of triethylamine to the reaction flask under 5 ° C ice bath conditions, add 5 g of perfluorohexylethyl alcohol dropwise, raise the temperature to 45 ° C after the addition is complete, and reflux for 4 h. After the reaction is complete, remove dichloromethane by rotary evaporation at 40 ° C, add 25 mL of THF to the residue, and stir at room temperature for 15 min. Filter to obtain the filtrate, and remove THF by rotary evaporation at 66 ° C to obtain the diphenyl tridecafluorooctyl phosphite liquid.

[0043] Example 6 A method for preparing diphenyl tridecafluorooctyl phosphite, comprising the following steps: S1. Add 5.62 g of dry phosphorus oxychloride, 6.42 g of pyridine and 20 mL of anhydrous dichloromethane to a 250 mL dry three-necked flask, add 7.66 g of phenol dropwise in an ice bath at 0°C, and pass nitrogen protection after the addition is complete. Then gradually warm to room temperature and stir for 1 h, then heat to 70°C and reflux for 5 h. After the reaction is complete, filter the reaction solution with a sand-core funnel, wash the filtrate with 5% dilute hydrochloric acid (50 ml×2), saturated sodium bicarbonate (50 ml×2) and saturated brine (50 ml×2) in sequence, dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation at 40°C, and distill the obtained crude product under reduced pressure. Collect the 165°C fraction to obtain 7.88 g of product, i.e., diphenylphosphoryl chloride, with a yield of 78%.

[0044] S2. Add 2.744 g of diphenylphosphoryl chloride and 20 mL of anhydrous dichloromethane to a 100 mL round-bottom flask, dissolve them by ultrasonication, add 1.414 g of triethylamine to the reaction flask under 0°C ice bath conditions, add 5 g of perfluorohexylethyl alcohol dropwise, raise the temperature to 45°C after the addition is complete, and reflux for 4 h. After the reaction is complete, remove dichloromethane by rotary evaporation at 40°C, add 25 mL of THF to the residue, and stir at room temperature for 15 min. Filter to obtain the filtrate, and remove THF by rotary evaporation at 70°C to obtain the diphenyl tridecafluorooctyl phosphite liquid.

[0045] Application Examples A textile (made of pure cotton, measuring 10 cm × 10 cm) was first immersed in a mixture of ethanol, acetone, and deionized water (volume ratio of 1:1:1) for 24 hours. The textile was then rinsed with deionized water multiple times and dried at 60°C to remove surface contaminants. The textile was then immersed in a 300 g / L sodium hydroxide solution at 80°C for 60 minutes. This process roughened the fiber surface through alkaline etching and introduced reactive functional groups such as hydroxyl and hydrocarbon groups, thereby enhancing surface reactivity. After the alkaline treatment, the textile was rinsed with copious amounts of deionized water to a neutral pH of 7 and dried again at 60°C to stabilize the surface. Finally, 1.0 g of each of the diphenyl tridecafluorooctyl phosphite prepared in Examples 1–6 was added to the textile and immersed for 30 minutes. The textile was then dried at 60°C for 2 hours to obtain modified textiles with waterproof, oil-repellent, and antifouling properties.

[0046] The static contact angles of water and salad oil on the surface of the modified textiles were measured using a DSA100 contact angle measuring device (whose measurement system measures the contact angle of an object surface based on the shape analysis method). The measurement results are shown in Table 1.

[0047] Table 1 Water contact angle and oil contact angle test results

[0048] Referring to Table 1, we can see that the water contact angles of the pure cotton fabrics treated with the fabric finishing agents prepared in Examples 1 to 6 are all greater than 150°, and the oil contact angles are all greater than 140°, indicating that the finishing agents have excellent water and oil repellency.

[0049] Figures 2 to 7 The infrared spectrum of diphenyl tridecafluorooctyl phosphite prepared in Examples 1 to 6 shows that at 953 cm -1 The absorption peak at 768 cm is the asymmetric stretching vibration of PO-Ar. -1 The absorption peak is PO stretching vibration, at 1000-1250cm -1 The strong and broad absorption band at 1487cm is the stretching vibration of the C-F bond. -1 、1589cm -1 The absorption peak at 3067cm is the skeleton vibration of the benzene ring. -1 The absorption peak at is the stretching vibration of the aromatic ring CH. The characteristic signal of the above absorption peak is highly consistent with the theoretical structure of diphenyl tridecafluorooctyl phosphite, proving that the target product has been successfully synthesized by the present invention.

[0050] The specific embodiments of the present invention described above do not limit the scope of protection of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. A diphenyl tridecafluorooctyl phosphite, characterized in that, It has the following chemical structure: 。 2. The method for preparing diphenyl tridecafluorooctyl phosphite according to claim 1, wherein The steps include: S1, phosphorus oxychloride and phenol are subjected to a substitution reaction in a first organic solvent in the presence of an acid-binding agent. After completion of the reaction, a reaction solution is obtained by filtration. The reaction solution is washed, dried, rotary evaporated and then distilled under reduced pressure. A fraction at 160-180° C. is collected to obtain diphenylphosphoryl chloride; S2. Dissolving diphenylphosphoryl chloride in a second organic solvent, adding perfluorohexylethyl alcohol and an alkaline reagent in an ice bath to carry out a substitution reaction, and separating and purifying after the reaction to obtain the diphenyl tridecafluorooctyl phosphite.

3. The preparation method of diphenyl tridecafluorooctyl phosphite according to claim 2, wherein In step S1, the molar ratio of phosphorus oxychloride to phenol is 1:2.1-2.2; The molar ratio of the acid binding agent to phosphorus oxychloride in step S1 is 2.2:

1.

4. The preparation method of diphenyl tridecafluorooctyl phosphite according to claim 2, wherein Step S1: the first organic solvent is at least one of dichloromethane, chloroform and anhydrous toluene; The acid binding agent in step S1 is at least one of pyridine, triethylamine and diisopropylethylamine.

5. The method for preparing diphenyl tridecafluorooctyl phosphite according to claim 3, wherein The specific operation steps of the substitution reaction of phosphorus oxychloride and phenol in the presence of an acid binder in a first organic solvent in step S1 are as follows: first, the phosphorus oxychloride and the acid binder are added to the first organic solvent, and then phenol is added under ice bath conditions. After the addition is completed, the temperature is raised to room temperature under a protective atmosphere and stirred for 1 hour, and then heated to 70°C and refluxed for 5 hours.

6. The method for preparing diphenyl tridecafluorooctyl phosphite according to claim 2, wherein The specific operation of the washing in step S1 is: the product is washed with dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution and saturated brine in sequence, and each reagent is used for washing 2 to 3 times; The drying method in step S1 is anhydrous sodium sulfate; Step S2: the second organic solvent is at least one of dichloromethane, anhydrous tetrahydrofuran and anhydrous methanol; The alkaline reagent in step S2 is at least one of triethylamine and diisopropylethylamine.

7. The method for preparing diphenyl tridecafluorooctyl phosphite according to claim 2, wherein: The molar ratio of the perfluorohexylethyl alcohol in step S2 to the phosphorus oxychloride in step S1 is 1:2.67; the temperature of the substitution reaction in step S2 is 45° C., and the reaction time is 4 hours.

8. The method for preparing diphenyl tridecafluorooctyl phosphite according to claim 2, wherein The specific operation of the separation and purification in step S2 is: the reaction solution is subjected to rotary evaporation to remove the second organic solvent, the residue is dissolved with a third organic solvent, the insoluble matter is removed by suction filtration, and the filtrate is collected and the solvent is again removed by rotary evaporation to obtain a purified product.

9. The method for preparing diphenyl tridecafluorooctyl phosphite according to claim 8, wherein The third organic solvent is at least one of tetrahydrofuran, dichloromethane and toluene.

10. Use of the diphenyl tridecafluorooctyl phosphite according to claim 1 as a waterproof and oil-proof conditioning agent for fabrics.

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