CN110041488B - Preparation method of fluorine-containing imide modified waterborne polyurethane - Google Patents
Preparation method of fluorine-containing imide modified waterborne polyurethane Download PDFInfo
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Abstract
The invention discloses a preparation method of fluorine-containing imide modified waterborne polyurethane, which comprises the following steps: preparing HE6FPI monomer; reacting the vacuum dehydrated dihydric alcohol and diisocyanate at the temperature of 90-100 ℃ under the protection of nitrogen; adding HE6FPI monomer, dimethylolpropionic acid, acetone and DMF, and reacting at 90-100 ℃; adding diethylene glycol, acetone, a catalyst dibutyltin dilaurate and stannous octoate, and reacting at the temperature of 70-74 ℃ to obtain a reaction system; and adding triethylamine into the reaction system for neutralization, adding water for emulsification and dispersion, and then adding ethylenediamine for post-expansion to obtain the fluorine-containing imide modified waterborne polyurethane. According to the invention, the fluorine-containing water-based polyurethane is prepared by modifying the water-based polyurethane with the fluorine-containing imide monomer, so that the process is simple, the controllability is strong, the industrial production is facilitated, meanwhile, the water absorption rate of the adhesive film is low, the good mechanical property is maintained, the elongation at break and the tensile strength are excellent, the product hardness is high, and the fluorine-containing water-based polyurethane can be widely applied to the fields of printing, coating, adhesives, leather finishing, textile finishing and the like.
Description
Technical Field
The invention relates to the technical field of fluorine-containing waterborne polyurethane, in particular to a preparation method of fluorine-containing imide modified waterborne polyurethane.
Background
Waterborne Polyurethane (WPU) is an aqueous polyurethane dispersion that can be dispersed in water, is an environmentally friendly high polymer material with zero VOC emission, and has been widely used in the fields of printing, coating, adhesives, leather finishing, textile finishing, and the like. Hydrophilic groups are introduced into the waterborne polyurethane in the preparation process, so that the water resistance and oil repellency of the polyurethane are reduced, and the defect is usually compensated by introducing a strong hydrophobic chain segment into the polyurethane structure. The fluorine-functionalized waterborne polyurethane has the advantages of small fluorine atom radius, strong electronegativity, short C-F bond length and high bond energy, so that the fluorine-functionalized waterborne polyurethane has excellent water resistance, oil resistance and antifouling property. In recent years, many studies have been made on the synthesis of fluorine-containing aqueous polyurethane.
The invention patent CN101157750B discloses fluoropolyether graft modified waterborne polyurethane, and preparation and application thereof, the invention firstly prepares waterborne polyurethane, and then synthesizes the fluoropolyether graft modified waterborne polyurethane by macromolecule indirect grafting reaction with fluoropolyether, and the waterborne polyurethane can be used as waterproof and antifouling multifunctional coating and fabric finishing agent.
The invention patent CN101824130B 'preparation method of a satin side-chain fluorine-containing waterborne polyurethane', the invention firstly prepares fluorine-containing glycidyl ether, then synthesizes side-chain fluorine-containing polyether diol, and prepares the satin side-chain fluorine-containing waterborne polyurethane by using the side-chain fluorine-containing polyether diol as a raw material, so that the surface performance of the material is improved, and the high temperature resistance and the chemical resistance of the waterborne polyurethane are improved while the bonding of the waterborne polyurethane and a base material is not influenced.
The invention patent CN102816285B 'A water-based fluorine-containing acrylic modified polyurethane coating, a preparation method and an application thereof', the invention firstly prepares water-based polyurethane acrylate prepolymer emulsion, and then adds hexafluoropropylene butyl ester and azobisisobutyronitrile to prepare the water-based fluorine-containing acrylic modified polyurethane coating. The water resistance and the mechanical property of the modified coating film are greatly improved.
The invention patent CN103044649B 'a fluorine-containing cation waterborne polyurethane and a preparation method thereof', the invention synthesizes a hydroxyl-containing fluorine-containing acrylate block copolymer by an atom transfer radical polymerization method, and then the hydroxyl-containing fluorine-containing acrylate block copolymer reacts with isocyanate, polyol and a hydrophilic chain extender to prepare the fluorine-containing cation waterborne polyurethane with oil and water repellency, excellent chemical stability and mechanical property.
The invention patent CN104892850B 'a preparation method of waterborne polyurethane containing fluorine in a side chain', the invention obtains waterborne polyurethane emulsion containing fluorine in a side chain by carrying out free radical polymerization on a fluorine-containing acrylate monomer and a waterborne polyurethane prepolymer, and the waterborne polyurethane emulsion shows good surface performance and mechanical performance after film forming.
Fluorine-containing waterborne polyurethane is synthesized by using fluorine-containing dihydric alcohol as a modifier in the steps of Dutao and the like (functional materials, 2016, 9 and 09128), the influence of the using amount of the fluorine-containing dihydric alcohol on the performances of a polyurethane emulsion and a coating film is discussed, and the result shows that the water resistance and the heat resistance of the coating film can be effectively improved by adding the fluorine-containing dihydric alcohol.
Through analysis, the related patent publications and related papers refer to the preparation of fluorine-containing waterborne polyurethane by modifying waterborne polyurethane through fluorine-containing acrylate, fluorine-containing polyether, fluorine-containing dihydric alcohol and the like, and no report related to the preparation of fluorine-containing waterborne polyurethane by modifying waterborne polyurethane through fluorine-containing imide exists at present.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of fluorine-containing imide modified waterborne polyurethane. The fluorine-containing water-based polyurethane is prepared by taking a hydroxyl-terminated fluorine-containing imide monomer as a micromolecular chain extender, introducing the fluorine-containing imide monomer to a main chain of a water-based polyurethane molecule through a chain extension reaction to modify the water-based polyurethane. The method has the advantages of simple process, strong controllability, convenience for industrial production, low water absorption of the adhesive film, good mechanical property, excellent elongation at break and tensile strength, and high product hardness, and can be widely applied to the fields of printing, coating, adhesives, leather finishing, textile finishing and the like.
The invention provides a preparation method of fluorine-containing imide modified waterborne polyurethane, which comprises the following steps:
s1, adding 4,4 '-hexafluoroisopropylidene-phthalic anhydride (6FDA) and Ethanolamine (EA) into a reactor, preparing a mixed solution by using a solvent, reacting at room temperature, heating to 45-55 ℃ for reaction to obtain a light yellow liquid, heating to 120-140 ℃ for reaction, cooling, adding anhydrous methanol for precipitation to obtain a 4,4' -hexafluoroisopropylidene-phthalic diethoxylimide (HE6FPI) monomer;
wherein, the molecular structural formula of the HE6FPI monomer is as follows:
s2, reacting the vacuum dehydrated dihydric alcohol and diisocyanate at the temperature of 90-100 ℃ under the protection of nitrogen; cooling to 58-62 ℃, adding HE6FPI monomer, dimethylolpropionic acid, acetone and N, N-Dimethylformamide (DMF), and reacting at 90-100 ℃; cooling to 58-62 ℃, adding diethylene glycol, acetone, a catalyst dibutyltin dilaurate and stannous octoate, and reacting at 70-74 ℃ to obtain a reaction system;
s3, cooling to 50-60 ℃, adding acetone into the reaction system, adding triethylamine for neutralization, adding water for emulsification and dispersion, adding ethylenediamine, and extending chain to obtain the fluorine-containing imide modified waterborne polyurethane.
Preferably, the purification is also included after adding absolute methanol for precipitation in S1; preferably, in the purification process, firstly, suction filtration is carried out, then water washing and suction filtration are repeated until the filtrate is transparent, and drying is carried out for 24-48h at the temperature of 110-.
Preferably, in S1, 6FDA, EA are present in a molar ratio of 1: 1.5-2.5;
preferably, in S1, the mixed liquor has a solids content of 40-60%.
Preferably, in S1, the solvent is DMF.
Preferably, in S2, the dehydration temperature is 100-110 ℃ and the dehydration time is 30-40min during the vacuum dehydration of the dihydric alcohol.
Preferably, in S2, the diol is at least one of polyoxypropylene diol (N220), polytetrahydrofuran ether diol (PTMG), and poly neopentyl glycol adipate diol (PNA).
Preferably, in S2, the diisocyanate is at least one of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), hydrogenated xylene methane diisocyanate (H-MDI).
Preferably, in S2, the weight ratio of the dihydric alcohol to the diisocyanate is 40-80: 20-40 parts of;
preferably, the weight ratio of the HE6FPI monomer to the dimethylolpropionic acid is 1.9-12: 3-4;
preferably, the weight ratio of the diethylene glycol, the catalyst dibutyltin dilaurate and the stannous octoate is 3.8-6.0: 0.03-0.05: 0.03-0.05;
preferably, in S3, the weight ratio of triethylamine to ethylenediamine is 2-3: 1.5-2.
Preferably, the solid content of the fluorine-containing imide modified waterborne polyurethane is 15-25%.
The invention has the following beneficial effects:
1. according to the invention, the hydroxyl-terminated fluorine-containing imide monomer HE6FPI is prepared, and the HE6FPI monomer is taken as a micromolecule chain extender and is introduced onto the main chain structure of the waterborne polyurethane through a chain extension reaction, so that the modification of the waterborne polyurethane is realized, the process is simple, the controllability is strong, and the modification of different types of waterborne polyurethane can be realized through the regulation and control process.
2. The invention uses hydroxyl-terminated fluorine-containing imide monomer to react with-CF3Is simultaneously introduced into the main chain structure of the waterborne polyurethane molecule with imide nitrogen heterocycles, -CF3The introduction of the compound can effectively improve the water resistance of the aqueous polyurethane, and the imide nitrogen heterocycle can obviously improve the mechanical property of the aqueous polyurethane.
3. The adhesive film prepared from the fluorine-containing imide modified waterborne polyurethane dispersion has low water absorption rate, maintains good mechanical property, has excellent elongation at break and tensile strength and higher product hardness, and can be widely applied to the fields of printing, coating, adhesives, leather finishing, textile finishing and the like.
Drawings
FIG. 1 is an infrared spectrum of HE6FPI monomer according to examples 5-10 of the present invention.
FIG. 2 is a characteristic infrared spectrum of a waterborne polyurethane adhesive film of products of examples 6 and 10 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
s1, adding 6FDA and EA into a reactor, preparing a mixed solution by using a solvent, reacting at room temperature, heating to 46 ℃ to react to obtain a light yellow liquid, heating to 120 ℃ to react, cooling, adding anhydrous methanol to precipitate to obtain an HE6FPI monomer;
s2, reacting the vacuum dehydrated dihydric alcohol and diisocyanate at the temperature of 90 ℃ under the protection of nitrogen; cooling to 58 ℃, adding HE6FPI monomer, dimethylolpropionic acid, acetone and DMF, and reacting at 92 ℃; cooling to 59 ℃, adding diethylene glycol, acetone, a catalyst dibutyltin dilaurate and stannous octoate, and reacting at 70 ℃ to obtain a reaction system;
s3, cooling to 50 ℃, adding acetone into the reaction system, adding triethylamine for neutralization, adding water for emulsification and dispersion, adding ethylenediamine, and extending the chain to obtain the fluorine-containing imide modified waterborne polyurethane.
Example 2
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
s1, adding 6FDA and EA into a reactor, preparing a mixed solution by using a solvent, reacting at room temperature, heating to 55 ℃ to react to obtain a light yellow liquid, heating to 139 ℃ to react, cooling, adding anhydrous methanol to precipitate to obtain an HE6FPI monomer;
s2, reacting the vacuum dehydrated dihydric alcohol and diisocyanate at the temperature of 99 ℃ under the protection of nitrogen; cooling to 62 ℃, adding HE6FPI monomer, dimethylolpropionic acid, acetone and DMF, and reacting at 100 ℃; cooling to 61 ℃, adding diethylene glycol, acetone, a catalyst dibutyltin dilaurate and stannous octoate, and reacting at 74 ℃ to obtain a reaction system;
s3, cooling to 56 ℃, adding acetone into the reaction system, adding triethylamine for neutralization, adding water for emulsification and dispersion, adding ethylenediamine, and then adding a chain extender to obtain the fluorine-containing imide modified waterborne polyurethane.
Example 3
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
s1, mixing 6FDA and EA in a molar ratio of 1: 1.5 adding the mixture into a reactor, preparing a solution with the solid content of 41% by using DMF, reacting at room temperature for 22min, heating to 47 ℃ to react to obtain a light yellow liquid, heating to 121 ℃ to react for 8h, stopping the reaction, cooling to room temperature, adding absolute methanol to precipitate, performing suction filtration, repeatedly washing with water and performing suction filtration until the filtrate is transparent, and drying at 112 ℃ for 25h to obtain an HE6FPI monomer;
s2, under the protection of nitrogen, dehydrating 42 parts by weight of dihydric alcohol at 101 ℃ for 32min in vacuum, cooling to 50 ℃, adding 21 parts by weight of diisocyanate, and reacting for 1.5h at the reaction temperature of 91 ℃;
cooling to 58 ℃, adding 1.9 parts of HE6FPI monomer and 3.0 parts of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting at 90 ℃ for 1 h;
cooling to 59 ℃, adding 3.8 parts of diethylene glycol, adding 10ml of acetone, 0.032 part of catalyst dibutyltin dilaurate and 0.031 part of stannous octoate, and reacting at 70 ℃ for 1.6h to obtain a reaction system;
s3, cooling to 50 ℃, adding 5ml of acetone into the reaction system, adding triethylamine for neutralization, adding 2.1 parts of triethylamine into the reaction system for neutralization, adding water for emulsification and dispersion, adding 1.5 parts of ethylenediamine, and then carrying out chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 15%.
Example 4
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
s1, mixing 6FDA and EA in a molar ratio of 1: 2.5 adding the mixture into a reactor, preparing a solution with the solid content of 60% by using DMF, reacting at room temperature for 39min, heating to 52 ℃ to react to obtain a light yellow liquid, heating to 136 ℃ to react for 11h, stopping the reaction, cooling to room temperature, adding absolute methanol to precipitate, performing suction filtration, repeatedly washing with water and performing suction filtration until the filtrate is transparent, and drying at the temperature of 130 ℃ for 48h to obtain an HE6FPI monomer;
s2, under the protection of nitrogen, dehydrating 76 parts by weight of dihydric alcohol at 109 ℃ for 36min in vacuum, cooling to 58 ℃, adding 38 parts by weight of diisocyanate, and reacting for 1.8h at the reaction temperature of 99 ℃;
cooling to 61 ℃, adding 12.0 parts of HE6FPI monomer and 4.0 parts of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting at 100 ℃ for 2 h;
cooling to 62 ℃, adding 6.0 parts of diethylene glycol, adding 10ml of acetone, 0.049 part of catalyst dibutyltin dilaurate and 0.047 part of stannous octoate, and reacting at 73 ℃ for 2.4h to obtain a reaction system;
s3, cooling to 50 ℃, adding 5ml of acetone into the reaction system, adding 2.99 parts of triethylamine into the reaction system for neutralization, adding water for emulsification and dispersion, adding 1.8 parts of ethylenediamine, and then carrying out chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 25%.
Example 5
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
mixing 6FDA and EA in a molar ratio of 1: 2, adding the mixture into a reactor, preparing a solution with the solid content of 50% by using DMF, reacting for 30min at room temperature, heating to 50 ℃, reacting for 2h to obtain a light yellow liquid, then slowly heating to 130 ℃, reacting for 8h, stopping the reaction, and cooling to the room temperature. And adding anhydrous methanol into the cooling system, precipitating and filtering the product, and then repeatedly washing and filtering until the filtrate is transparent. The product was dried at 120 ℃ for 48h to finally obtain HE6FPI monomer.
Under the protection of nitrogen, adding N22060 g and IPDI 33g subjected to vacuum dehydration at 110 ℃ into a reactor, and reacting for 2 hours at 100 ℃ under mechanical stirring;
cooling to 60 ℃, adding 1.92g of HE6FPI monomer and 3.66g of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting for 1h at 90 ℃; cooling to 60 ℃, adding 5.21g of diethylene glycol, adding 10ml of acetone and 0.05g of dibutyltin dilaurate serving as a catalyst and 0.05g of stannous octoate, and reacting for 2h at 72 ℃;
cooling to 60 ℃, then carrying out high-speed shearing on 5ml of acetone, adding 2.76g of triethylamine in the high-speed shearing process for neutralization, then adding water for emulsification and dispersion, and finally adding 1.5g of ethylenediamine and then carrying out chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 20%.
Example 6
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
mixing 6FDA and EA in a molar ratio of 1: 2, adding the mixture into a reactor, preparing a solution with the solid content of 50% by using DMF, reacting for 30min at room temperature, heating to 50 ℃, reacting for 2h to obtain a light yellow liquid, then slowly heating to 130 ℃, reacting for 8h, stopping the reaction, and cooling to the room temperature. And adding anhydrous methanol into the cooling system, precipitating and filtering the product, and then repeatedly washing and filtering until the filtrate is transparent. The product was dried at 120 ℃ for 48h to finally obtain HE6FPI monomer.
Under the protection of nitrogen, adding N22060 g and IPDI 33g subjected to vacuum dehydration at 110 ℃ into a reactor, and reacting for 2 hours at 100 ℃ under mechanical stirring;
cooling to 60 ℃, adding 11.51g of HE6FPI monomer and 3.66g of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting for 1h at 90 ℃; cooling to 60 ℃, adding 4.04g of diethylene glycol, adding 10ml of acetone and 0.05g of dibutyltin dilaurate serving as a catalyst and 0.05g of stannous octoate, and reacting for 2h at 72 ℃;
and cooling to 60 ℃, adding 5ml of acetone, carrying out high-speed shearing, adding 2.76g of triethylamine for neutralization in the high-speed shearing process, adding water for emulsification and dispersion, and finally adding 1.5g of ethylenediamine for chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 20%.
Example 7
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
mixing 6FDA and EA in a molar ratio of 1: 2, adding the mixture into a reactor, preparing a solution with the solid content of 50% by using DMF, reacting for 30min at room temperature, heating to 50 ℃, reacting for 2h to obtain a light yellow liquid, then slowly heating to 130 ℃, reacting for 8h, stopping the reaction, and cooling to the room temperature. And adding anhydrous methanol into the cooling system, precipitating and filtering the product, and then repeatedly washing and filtering until the filtrate is transparent. The product was dried at 120 ℃ for 48h to finally obtain HE6FPI monomer.
Under the protection of nitrogen, 60g of PNA and 33g of IPDI dehydrated in vacuum at 110 ℃ are added into a reactor under the protection of nitrogen, and the PNA and the IPDI react for 2 hours at 100 ℃ under the mechanical stirring;
cooling to 60 ℃, adding 1.92g of HE6FPI monomer and 3.66g of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting for 1h at 90 ℃; cooling to about 60 ℃, adding 5.21g of diethylene glycol, adding 10ml of acetone and 0.05g of dibutyltin dilaurate serving as a catalyst and 0.05g of stannous octoate, and reacting for 2 hours at 72 ℃;
and cooling to 60 ℃, adding 5ml of acetone, carrying out high-speed shearing, adding 2.76g of triethylamine for neutralization in the high-speed shearing process, adding water for emulsification and dispersion, and finally adding 1.5g of ethylenediamine for chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 20%.
Example 8
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
mixing 6FDA and EA in a molar ratio of 1: 2, adding the mixture into a reactor, preparing a solution with the solid content of 50% by using DMF, reacting for 30min at room temperature, heating to 50 ℃, reacting for 2h to obtain a light yellow liquid, then slowly heating to 130 ℃, reacting for 8h, stopping the reaction, and cooling to the room temperature. And adding anhydrous methanol into the cooling system, precipitating and filtering the product, and then repeatedly washing and filtering until the filtrate is transparent. The product was dried at 120 ℃ for 48h to finally obtain HE6FPI monomer.
Under the protection of nitrogen, 60g of PNA and 33g of IPDI dehydrated in vacuum at 110 ℃ are added into a reactor under the protection of nitrogen, and the PNA and the IPDI react for 2 hours at 100 ℃ under the mechanical stirring;
cooling to 60 ℃, adding 6.86g of HE6FPI monomer and 3.66g of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting for 1h at 90 ℃; cooling to about 60 ℃, adding 4.43g of diethylene glycol, adding 10ml of acetone and 0.05g of dibutyltin dilaurate serving as a catalyst and 0.05g of stannous octoate, and reacting for 2 hours at 72 ℃;
and cooling to 60 ℃, adding 5ml of acetone, carrying out high-speed shearing, adding 2.76g of triethylamine for neutralization in the high-speed shearing process, adding water for emulsification and dispersion, and finally adding 1.5g of ethylenediamine for chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 20%.
Example 9
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
mixing 6FDA and EA in a molar ratio of 1: 2, adding the mixture into a reactor, preparing a solution with the solid content of 50% by using DMF, reacting for 30min at room temperature, heating to 50 ℃, reacting for 2h to obtain a light yellow liquid, then slowly heating to 130 ℃, reacting for 8h, stopping the reaction, and cooling to the room temperature. And adding anhydrous methanol into the cooling system, precipitating and filtering the product, and then repeatedly washing and filtering until the filtrate is transparent. The product was dried at 120 ℃ for 48h to finally obtain HE6FPI monomer.
Under the protection of nitrogen, adding N22060 g and H-MDI 38.95g which are dehydrated in vacuum at 110 ℃ into a reactor, and reacting for 2 hours at 100 ℃ under mechanical stirring;
cooling to 65 ℃, adding 3.43g of HE6FPI monomer and 3.66g of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting for 1h at 90 ℃; cooling to about 60 ℃, adding 4.82g of diethylene glycol, adding 50ml of acetone and 0.05g of dibutyltin dilaurate serving as a catalyst and 0.05g of stannous octoate, and reacting for 2 hours at 72 ℃;
and cooling to 60 ℃, adding 20ml of acetone, carrying out high-speed shearing, adding 2.76g of triethylamine for neutralization in the high-speed shearing process, adding water for emulsification and dispersion, and finally adding 1.5g of ethylenediamine for chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 20%.
Example 10
A preparation method of fluorine-containing imide modified waterborne polyurethane comprises the following steps:
mixing 6FDA and EA in a molar ratio of 1: 2, adding the mixture into a reactor, preparing a solution with the solid content of 50% by using DMF, reacting for 30min at room temperature, heating to 50 ℃, reacting for 2h to obtain a light yellow liquid, then slowly heating to 130 ℃, reacting for 8h, stopping the reaction, and cooling to the room temperature. And adding anhydrous methanol into the cooling system, precipitating and filtering the product, and then repeatedly washing and filtering until the filtrate is transparent. The product was dried at 120 ℃ for 48h to finally obtain HE6FPI monomer.
Under the protection of nitrogen, adding N22060 g and H-MDI 38.95g which are dehydrated in vacuum at 110 ℃ into a reactor, and reacting for 2 hours at 100 ℃ under mechanical stirring;
cooling to about 65 ℃, adding 6.86g of HE6FPI monomer and 3.66g of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting for 1h at 90 ℃; cooling to about 60 ℃, adding 4.43g of diethylene glycol, adding 50ml of acetone and 0.05g of dibutyltin dilaurate serving as a catalyst and 0.05g of stannous octoate, and reacting for 2 hours at 72 ℃;
and cooling to 60 ℃, adding 20ml of acetone, carrying out high-speed shearing, adding 2.76g of triethylamine for neutralization in the high-speed shearing process, adding water for emulsification and dispersion, and finally adding 1.5g of ethylenediamine for chain extension to obtain the fluorine-containing imide modified waterborne polyurethane with the solid content of 20%.
Comparative examples
A preparation method of waterborne polyurethane comprises the following steps:
under the protection of nitrogen, adding N22060 g and IPDI 33g subjected to vacuum dehydration at 110 ℃ into a reactor, and reacting for 2 hours at 100 ℃ under mechanical stirring; cooling to 60 ℃, adding 3.66g of dimethylolpropionic acid, adding 10ml of acetone and 5ml of DMF, and reacting for 1h at 90 ℃; cooling to 60 ℃, adding 5.6g of diethylene glycol, adding a proper amount of acetone and a catalyst of 0.05g of dibutyltin dilaurate and 0.05g of stannous octoate, and reacting for 2h at 72 ℃; and cooling to 60 ℃, adding 5ml of acetone, carrying out high-speed shearing, adding 2.76g of triethylamine for neutralization in the high-speed shearing process, adding water for emulsification and dispersion, and finally adding 1.5g of ethylenediamine for chain extension to obtain the aqueous polyurethane emulsion with the solid content of 20%.
Performance testing and characterization
1. And (3) performance testing:
the water absorption, water contact angle, elongation at break, and tensile strength of the fluorochemical imide-modified aqueous polyurethane adhesive films of examples 5 to 10 and the aqueous polyurethane adhesive film of comparative example are shown in table 1.
TABLE 1 film Properties
2. And (3) characterization:
2.1 Infrared characterization of HE6FPI monomers
Referring to FIG. 1, FIG. 1 is a graph of the transmission infrared spectrum of HE6FPI monomer obtained in examples 1-10 of the present invention showing a distinct characteristic absorption peak of the imide group at 1776cm-1Is positioned at 1720cm, where C is O asymmetric stretching vibration absorption peak-1The position is C ═ O symmetrical stretching vibration absorption peak, 1357cm-1Is located at 721cm of C-N telescopic vibration absorption peak-1The position is C ═ O bending vibration absorption peak; 1257cm-1And 1195cm-1is-CF3A stretching vibration absorption peak of a C-F bond in the group; 3200-one 3500cm-1The absorption peak at (a) also indicates the presence of a hydroxyl structure in the molecule; indicating the presence of an imide Structure, -CF in the HE6FPI molecule3And hydroxyl, which shows that the HE6FPI monomer is successfully synthesized.
2.2 Infrared characterization of fluorochemical imide-modified waterborne polyurethane
Referring to FIG. 2, FIG. 2 is an attenuated total reflection infrared spectrum of the fluorine-containing imide modified aqueous polyurethane adhesive film obtained in examples 6 and 10 of the present invention, wherein FIG. 2(a) showsThe characteristic peak of the waterborne polyurethane is shown, such as 3350cm-1Is an N-H stretching vibration absorption peak, 2800-3000 cm-1is-CH between3and-CH2C-H stretching vibration absorption peak of (5), 1720cm-1The peak at position (1534 cm) is the absorption peak of C ═ O stretching vibration in urethane bond-1Is positioned at 1239cm which is a C-N stretching vibration absorption peak-1The peak is an asymmetric stretching vibration absorption peak of a urethane bond and is 2230cm-1The characteristic absorption peak of isocyanate does not appear, which indicates that the waterborne polyurethane still retains the structure of the polyurethane after the modification of the HE6FPI monomer and has no residual-NCO groups. FIG. 2(b) is a magnified view from 0 to 2000 of FIG. a showing characteristic peaks of HE6FPI monomer, such as 1776cm-1The position is the asymmetric stretching vibration absorption peak of C ═ O in the imide ring, 721cm-1Is marked by C ═ O bending vibration absorption peak, 1257cm-1And 1195cm-1is-CF3The expansion vibration absorption peak of the C-F bond in the group proves that the fluorine-containing imide ring is successfully introduced into the main chain of the waterborne polyurethane.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of fluorine-containing imide modified waterborne polyurethane is characterized by comprising the following steps:
s1, adding 4,4 '-hexafluoroisopropylidene-phthalic anhydride and ethanolamine into a reactor, preparing a mixed solution by using a solvent, reacting at room temperature, heating to 45-55 ℃ for reaction to obtain a light yellow liquid, heating to 120-140 ℃ for reaction, cooling, adding anhydrous methanol for precipitation to obtain a 4,4' -hexafluoroisopropylidene-phthalic dihydroxy ethyl imide monomer;
s2, reacting the vacuum dehydrated dihydric alcohol and diisocyanate at the temperature of 90-100 ℃ under the protection of nitrogen; cooling to 58-62 ℃, adding 4,4' -hexafluoroisopropylidene-o-phenylenedihydroxyethyl imide monomer, dimethylol propionic acid, acetone and DMF, and reacting at 90-100 ℃; cooling to 58-62 ℃, adding diethylene glycol, acetone, a catalyst dibutyltin dilaurate and stannous octoate, and reacting at 70-74 ℃ to obtain a reaction system;
s3, cooling to 50-60 ℃, adding acetone into the reaction system, adding triethylamine for neutralization, adding water for emulsification and dispersion, adding ethylenediamine, and extending chain to obtain the fluorine-containing imide modified waterborne polyurethane.
2. The method for preparing the fluorochemical imide-modified aqueous polyurethane according to claim 1 wherein the step of adding anhydrous methanol to S1 for precipitation further comprises purification; in the purification process, firstly, the filtration is carried out, then the water washing and the filtration are repeated until the filtrate is transparent, and the drying is carried out for 24 to 48 hours at the temperature of 110 ℃ and 130 ℃.
3. The method for producing the fluorochemical imide-modified aqueous polyurethane according to claim 1, wherein the molar ratio of 4,4' -hexafluoroisopropylidene-phthalic anhydride to ethanolamine in S1 is 1: 1.5-2.5.
4. The method for producing the fluorochemical imide-modified aqueous polyurethane according to claim 1, wherein the solid content of the mixed solution is 40 to 60% in S1.
5. The method for producing the fluorochemical imide-modified aqueous polyurethane according to claim 1 wherein in S1, the solvent is DMF.
6. The method for producing the fluorochemical imide-modified aqueous polyurethane according to claim 1 wherein in S2, the diol is at least one of polyoxypropylene diol, polytetrahydrofuran ether diol, and neopentyl glycol adipate diol.
7. The method for producing the fluorochemical imide-modified aqueous polyurethane according to claim 1 wherein in S2, the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, and hydrogenated xylene methane diisocyanate.
8. The method for preparing the fluorochemical imide-modified aqueous polyurethane according to claim 1 wherein the weight ratio of the diol to the diisocyanate in S2 is 40 to 80: 20-40 parts of;
the weight ratio of the 4,4' -hexafluoroisopropylidene-o-dihydroxyethyl imide monomer to the dimethylolpropionic acid is 1.9-12: 3-4;
the weight ratio of diethylene glycol, a catalyst dibutyltin dilaurate and stannous octoate is 3.8-6.0: 0.03-0.05: 0.03-0.05.
9. The method for preparing the fluorochemical imide-modified aqueous polyurethane according to claim 1, wherein the weight ratio of triethylamine to ethylenediamine in S3 is 2 to 3: 1.5-2.
10. The method for producing the fluorochemical imide-modified aqueous polyurethane according to any of claims 1 to 9, wherein the solid content of the fluorochemical imide-modified aqueous polyurethane is 15 to 25%.
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