Fluorinated polyurethane and preparation method thereof

Abstract

The invention relates to fluorinated polyurethane and a preparation method thereof and belongs to the technical field of polymer materials. A vinyl monomer is inserted in the main chain of the fluorinated polyurethane. The method adopts the following raw materials: benzophenone I, isopropanol II, polymeric diol III, diisocyanate IV, and or hexafluorobutyl acrylate V or hexafluorobutyl methacrylate VI. The method comprises: mixing the raw materials I and II and adding a first catalyst to perform a reaction under the radiation of ultraviolet light to obtain a product of 1,1,2,2-tetraphenylethylene glycol, performing recrystalization and purification by using acetic acid, mixing the III and the IV, adding the mixture of the III and the IV into a solvent, and stirring and mixing the mixture and the solvent to perform a reaction to obtain a prepolymer; and adding the 1,1,2,2-tetraphenylethylene glycol into the prepolymer to obtain reactants, adding a second catalyst into reactants and purifying to obtain a tetraphenylethylene glycol-terminated polyurethane, mixing the polyurethane with the V or the VI to perform a reaction and purifying to obtain the fluorinated polyurethane. The preparation method of the fluorinated polyurethane is simple and easy to implement. The synthesized fluorinated polyurethane has a good mechanical property and can be used in fields such as biomedical materials and paints.

Description

Technical field

[0001] The invention relates to a fluorinated polyurethane and a preparation method thereof, and belongs to the technical field of polymer materials. Background technique

[0002] After the accidental discovery of polytetrafluoroethylene in 1938, due to the demand for new materials in modern industry, especially due to the rapid development of aerospace, new weapons, semiconductors, computers, and communications, after more than half a century, fluorine-containing polymers have become a class Special engineering materials and special rubbers have made great progress and are still under development. The strong electronegativity of fluorine, high CF bond energy (540kJ / mol), the smallest van der Waals radius except hydrogen, and the shielding and protective effect on the carbon chain give fluoropolymers superior thermal stability, weather resistance and good biological properties. Compatibility, and special electrical properties, surface characteristics, etc. [0003...

Examples

preparation example Construction

[0027] The method for preparing the above-mentioned fluorinated polyurethane proposed by the present invention, the raw materials used in the method include: benzophenone I, isopropanol II, polymer diol III, diisocyanate IV, hexafluorobutyl acrylate V and methacrylic acid Hexafluorobutyl ester VI, the structural expression of each raw material is:

[0028]

[0029]

[0030] The method for preparing the above-mentioned fluorinated polyurethane includes the following steps:

[0031] (1) First, mix 0.05-10 mol of raw material benzophenone I and 0.25-50 mol of isopropanol II, and then add 0.01-0.2% of the first catalyst of the total amount of raw materials I and II. Reaction under ultraviolet light at temperature to obtain 1,1,2,2-tetraphenylethylene glycol product, and then recrystallization and purification by adding 10-200 times acetic acid of the product, the reaction expression is:

[0032]

[0033] (2) Mix 0.01~10mol polymer diol III and 0.03~20mol diisocyanate IV into the solvent...

Embodiment 1

[0039] Step 1: First mix benzophenone (0.1mol) and isopropanol (0.5mol), and then add acetic acid (0.005mol). The mixture is put into a 500mL round-bottomed flask and exposed to a temperature of 25℃. Under 365nm ultraviolet light, the product (1,1,2,2-tetraphenylethylene glycol) was precipitated, and the precipitated product was purified by recrystallization from acetic acid.

[0040] NMR of the pure product 1 H-NMR(CDCl 3 ): δ=3.05 (hydroxyl, 2H), 7.00-7.50 (phenyl, 20H) (see attached figure 2 ). Infrared spectrum IR: 3500-3550cm -1 (Hydroxy), 3010cm -1 (Phenyl) (see attached figure 1 A).

[0041] Step 2: Mix polytetrahydrofuran ether glycol (0.01mol) and 4,4'-diphenylmethane diisocyanate (0.02mol) into 50-100mL tetrahydrofuran, the mixture is charged into a 500mL three-necked round bottom flask, nitrogen Under protection, stir and mix and react for 3 hours at 60~85℃ to obtain a prepolymer; the temperature is reduced to 35℃, and 1,1,2,2-tetraphenylglycol (0.01mol) is added, and ...

Embodiment 2

[0046] Step 1: First mix benzophenone (0.1mol) and 2-propanol (0.5mol), then add glacial acetic acid (0.005mol), the mixture is charged into a 500mL round-bottomed flask, at a temperature of 30℃ After exposure to 365nm ultraviolet light, the product (1,1,2,2-tetraphenylethylene glycol) was precipitated, and the precipitated product was purified by recrystallization from acetic acid.

[0047] Step 2: Mix polycarbonate 1,4-butanediol ester diol (0.01mol) and 2,6-toluene diisocyanate (0.02mol) into 100mL methyl ethyl ketone, and the mixture is charged into a 500mL three-necked round bottom flask , Under the protection of nitrogen, the mixture was stirred and reacted at 85°C for 3h to obtain a prepolymer; the temperature was reduced to 35°C, and 1,1,2,2-tetraphenylethylene glycol (0.01mol) was added. The molar ratio of the addition was 1 , 1,2,2-tetraphenylethylene glycol: diisocyanate = 1:2, then add 0.03% of stannous octoate based on the total weight of the reactants, stir and reac...

Technical field

[0001] The invention relates to a fluorinated polyurethane and a preparation method thereof, and belongs to the technical field of polymer materials. Background technique

[0002] After the accidental discovery of polytetrafluoroethylene in 1938, due to the demand for new materials in modern industry, especially due to the rapid development of aerospace, new weapons, semiconductors, computers, and communications, after more than half a century, fluorine-containing polymers have become a class Special engineering materials and special rubbers have made great progress and are still under development. The strong electronegativity of fluorine, high CF bond energy (540kJ / mol), the smallest van der Waals radius except hydrogen, and the shielding and protective effect on the carbon chain give fluoropolymers superior thermal stability, weather resistance and good biological properties. Compatibility, and special electrical properties, surface characteristics, etc. [0003...

Examples

preparation example Construction

[0027] The method for preparing the above-mentioned fluorinated polyurethane proposed by the present invention, the raw materials used in the method include: benzophenone I, isopropanol II, polymer diol III, diisocyanate IV, hexafluorobutyl acrylate V and methacrylic acid Hexafluorobutyl ester VI, the structural expression of each raw material is:

[0028]

[0029]

[0030] The method for preparing the above-mentioned fluorinated polyurethane includes the following steps:

[0031] (1) First, mix 0.05-10 mol of raw material benzophenone I and 0.25-50 mol of isopropanol II, and then add 0.01-0.2% of the first catalyst of the total amount of raw materials I and II. Reaction under ultraviolet light at temperature to obtain 1,1,2,2-tetraphenylethylene glycol product, and then recrystallization and purification by adding 10-200 times acetic acid of the product, the reaction expression is:

[0032]

[0033] (2) Mix 0.01~10mol polymer diol III and 0.03~20mol diisocyanate IV into the solvent...

Embodiment 1

[0039] Step 1: First mix benzophenone (0.1mol) and isopropanol (0.5mol), and then add acetic acid (0.005mol). The mixture is put into a 500mL round-bottomed flask and exposed to a temperature of 25℃. Under 365nm ultraviolet light, the product (1,1,2,2-tetraphenylethylene glycol) was precipitated, and the precipitated product was purified by recrystallization from acetic acid.

[0040] NMR of the pure product 1 H-NMR(CDCl 3 ): δ=3.05 (hydroxyl, 2H), 7.00-7.50 (phenyl, 20H) (see attached figure 2 ). Infrared spectrum IR: 3500-3550cm -1 (Hydroxy), 3010cm -1 (Phenyl) (see attached figure 1 A).

[0041] Step 2: Mix polytetrahydrofuran ether glycol (0.01mol) and 4,4'-diphenylmethane diisocyanate (0.02mol) into 50-100mL tetrahydrofuran, the mixture is charged into a 500mL three-necked round bottom flask, nitrogen Under protection, stir and mix and react for 3 hours at 60~85℃ to obtain a prepolymer; the temperature is reduced to 35℃, and 1,1,2,2-tetraphenylglycol (0.01mol) is added, and ...

Embodiment 2

[0046] Step 1: First mix benzophenone (0.1mol) and 2-propanol (0.5mol), then add glacial acetic acid (0.005mol), the mixture is charged into a 500mL round-bottomed flask, at a temperature of 30℃ After exposure to 365nm ultraviolet light, the product (1,1,2,2-tetraphenylethylene glycol) was precipitated, and the precipitated product was purified by recrystallization from acetic acid.

[0047] Step 2: Mix polycarbonate 1,4-butanediol ester diol (0.01mol) and 2,6-toluene diisocyanate (0.02mol) into 100mL methyl ethyl ketone, and the mixture is charged into a 500mL three-necked round bottom flask , Under the protection of nitrogen, the mixture was stirred and reacted at 85°C for 3h to obtain a prepolymer; the temperature was reduced to 35°C, and 1,1,2,2-tetraphenylethylene glycol (0.01mol) was added. The molar ratio of the addition was 1 , 1,2,2-tetraphenylethylene glycol: diisocyanate = 1:2, then add 0.03% of stannous octoate based on the total weight of the reactants, stir and reac...

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