Fluorine-cation-containing WPU (waterborne polyurethane) and preparation method thereof

[0036] Example 1:

[0037] (1) Preparation of fluorine-containing block acrylate copolymer: the molecular weight is 10,000, and the block mass ratio is 9:1. Preparation of the block copolymer of hydroxy-terminated butyl methacrylate and dodecafluoroheptyl methacrylate

[0038] Add 0.498g (0.002mol) initiator α-bromoisobutyric acid (4-hydroxybutanediol ester), 18g (0.127mol) butyl methacrylate monomer, 0.183g (0.00127) in a 100mL four-necked flask mol) Catalyst CuBr, 0.439g (0.00254mol) ligand PMDETA, 7.2g solvent toluene, mix well. The system was evacuated and filled with nitrogen, and the reaction was stirred in an oil bath at 60°C. After 8 hours, add 2g (0.005mol) dodecafluoroheptyl methacrylate, 0.0072g (0.00005mol) CuBr, and 0.0173g (0.0001mol) ligand PMDETA into the flask. After pumping and filling with nitrogen again, it is heated at 80℃. Stirring and reacting under the bath for 12 hours, the reaction is over, after removing the catalyst and solvent, a light yellow solid product can be obtained, the product mass is 14.96 g, and the yield is 74.8%.

[0039] The GPC chart shows that the molecular weight distribution is narrow and controllable; Mn = 10980 in the first column of the table, which proves to be almost consistent with the preset molecular weight of 10,000. The polydispersity=1.88 in the penultimate column indicates that the molecular weight distribution of the product is narrow.

[0040] (2) Preparation of fluorinated cationic waterborne polyurethane: the mass percentage of fluorinated block copolymer is 1.15%, the mass percentage of chain extender MDEA is 8%, -NCO/-OH=1.2 (molar ratio)

[0041] In a 250mL four-necked flask with a thermometer, condenser, constant pressure dropping funnel and PTFE stirring rod, add 60g of polyethylene glycol-2000 (PEG-2000), and add 1g of (1) prepared The hydroxyl-terminated polybutyl methacrylate-dodecafluoroheptyl methacrylate block copolymer is heated to 120°C for dehydration for about 30 minutes. The temperature was lowered to 80°C, 18.46g TDI was added, the temperature was raised to 80-85°C for 3h, and the reaction was reduced to room temperature. A mixture of 6.91g N-methyldiethanolamine, 1.80g acetic acid and 30.20g acetone was added dropwise with a constant pressure dropping funnel. Adding time 0.5h, temperature control at 25~40℃, stirring for 3h after dripping; then slowly add the solution in 250mL four-necked flask into 500mL four-necked flask filled with distilled water, stirring for 3h, can obtain fluorine-containing cation water Polyurethane.

[0042] Example 2:

[0043] (1) Preparation of fluorine-containing block acrylate copolymer: the molecular weight is 10,000, and the block mass ratio is 7:3. Preparation of hydroxy-terminated butyl methacrylate and hexafluorobutyl methacrylate block copolymer

[0044] Add 0.37g (0.002mol) initiator 1-bromoethylbenzene, 14g (0.0986mol) butyl methacrylate monomer, 0.1415g (0.000986mol) catalyst CuBr, 0.2291g (0.001972mol) in a 100mL four-neck flask ) Ligand tetramethylethylenediamine, 6.02g solvent anisole, mix well. The system was evacuated and filled with nitrogen, and the reaction was stirred in an oil bath at 30°C. After 24 hours, add 6g (0.024mol) hexafluorobutyl methacrylate, 0.0238g (0.00024mol) CuCl, and 0.05578g (0.00048mol) ligand tetramethylethylenediamine into the flask. After pumping and filling with nitrogen again, Stirring and reacting in an oil bath at 50°C for 24 hours, the reaction is over, after removing the catalyst and solvent, a light yellow solid product can be obtained, the product mass is 14.94 g, and the yield is 74.7%.

[0045] (2) Preparation of fluorinated cationic waterborne polyurethane: the mass percentage of fluorinated block copolymer is 0.5%, the mass percentage of chain extender MDEA is 10%, -NCO/-OH=1.5 (molar ratio)

[0046] In a 250mL four-necked flask equipped with a thermometer, condenser, constant pressure dropping funnel and PTFE stirring rod, add 120.4g of polypropylene glycol-2000 (PPG-2000), and add the end prepared in 1g (1) Hydroxy polybutyl methacrylate-hexafluorobutyl methacrylate block copolymer, heated to 120°C for dehydration for about 30 minutes. Cool down to 80°C, add 59.56g TDI, warm up to 80~85°C and react for 5 hours, then cool to room temperature, add a mixture of 20g N-methyldiethanolamine, 5.04g acetic acid and 40g acetone with a constant pressure dropping funnel, dropping time The temperature was controlled at 25-40°C for 0.5h, and the dripping was completed and stirred for 3h; then the solution in the 250mL four-necked flask was slowly added to a 500mL four-necked flask filled with distilled water and stirred for 10h to obtain fluorine-containing cationic aqueous polyurethane.

[0047] Example 3:

[0048] (1) Preparation of fluorinated block acrylate copolymer: molecular weight 5000, block mass ratio of 9:1 preparation of hydroxy-terminated butyl methacrylate and hexafluorobutyl methacrylate block copolymer

[0049] In a 100mL four-neck flask, add 0.724g (0.004mol) of the initiator 0-ethyl bromopropionate, 18g (0.127mol) of butyl methacrylate monomer, 0.183g (0.00127mol) catalyst CuBr, 0.5852g ( 0.00254mol) ligand tris-(N,N-dimethylaminoethyl)amine (Me6 TREN), 7.2g solvent toluene, mix well. The system was evacuated and filled with nitrogen, and the reaction was stirred in an oil bath at 50°C. After 18 hours was added 2g (0.008mol) hexafluorobutyl methacrylate, 0.0115g (0.00008mol) CuBr, 0.03686g (0.00016mol) ligand tri-(N,N-dimethylaminoethyl) Amine (Me6 TREN), after pumping and filling with nitrogen again, continue to stir and react for 8 hours at 120°C in an oil bath. After the reaction is over, after removing the catalyst and solvent, a light yellow translucent viscous product can be obtained, with a product quality of 15.7g. The yield was 78.5%.

[0050] (2) Preparation of fluorinated cationic waterborne polyurethane: the mass percentage of fluorinated block copolymer is 1%, the mass percentage of chain extender N-EDEA is 10%, -NCO/-OH=1.4 (molar ratio)

[0051] In a 250mL four-necked flask equipped with a thermometer, a condenser, a constant pressure dropping funnel and a PTFE stirring rod, 37.71g of polypropylene glycol-3000 (PPG-3000) and 12.57g of polyethylene glycol-1000 ( PEG-1000), adding 1g of the hydroxyl-terminated polybutyl methacrylate-hexafluorobutyl methacrylate block copolymer prepared in (1), and heating to 150°C for about 30 minutes of dehydration. Cool down to 60°C, add 38.71g MDI, increase the temperature to 80~85°C and react for 1 hour, then drop to room temperature, add 10g N-ethyldiethanolamine (N-EDEA), 2.177g hydrochloric acid and dioxane with a constant pressure dropping funnel. A mixture of 25g of six rings, dripping time 0.5h, temperature control at 25~40℃, stir for 5h after dripping; then slowly add the solution in a 250mL four-neck flask into a 500mL four-neck flask filled with distilled water, and stir for 8h , Can get fluorine-containing cationic waterborne polyurethane.