CN116355249A - Self-repairing aqueous polyurethane film and preparation method thereof - Google Patents
Self-repairing aqueous polyurethane film and preparation method thereof Download PDFInfo
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- CN116355249A CN116355249A CN202310345728.7A CN202310345728A CN116355249A CN 116355249 A CN116355249 A CN 116355249A CN 202310345728 A CN202310345728 A CN 202310345728A CN 116355249 A CN116355249 A CN 116355249A
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- self
- aqueous polyurethane
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- chain extender
- repairing
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- 229920006264 polyurethane film Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 27
- 239000004814 polyurethane Substances 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical group NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 230000008439 repair process Effects 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229940065514 poly(lactide) Drugs 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2375/04—Polyurethanes
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Abstract
The invention discloses a preparation method of a self-repairing aqueous polyurethane film and the self-repairing aqueous polyurethane film prepared by the preparation method. According to the invention, by introducing the hydrazide small molecular chain extender, a higher-density hydrogen bond is formed between molecular chains, the interaction of multiple hydrogen bonds endows the material with high mechanical strength and toughness, and because the activation energy required by the hydrogen bond to realize dissociation-recombination is relatively low, the waterborne polyurethane material has a repair efficiency of about 50% at room temperature, and the self-repair efficiency at 50 ℃ is as high as 96.3%. Therefore, the self-repairing aqueous polyurethane film material has stronger mechanical property and excellent self-repairing property under mild conditions.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a self-repairing aqueous polyurethane film and a preparation method thereof.
Background
With the importance of the country to the environment and the perfection of related laws and regulations, green environment-friendly materials are widely regarded. Polyurethane materials are widely used because of their excellent mechanical properties, abrasion resistance, oil resistance, etc., and they are classified into solvent type and aqueous type according to the dispersion solvents. Because the traditional solvent polyurethane can generate a large amount of volatile organic solvents in the production and use processes, the polyurethane not only endangers the physical health of people, but also causes environmental pollution. Therefore, green and environment-friendly aqueous polyurethane has been developed and paid attention to because of its non-toxicity and wide application.
The aqueous polyurethane is developed on the basis of solvent polyurethane, and good water dispersibility is realized by introducing hydrophilic components into the molecular chain of the polyurethane or an external emulsifier. As an environment-friendly material with water instead of an organic solvent as a dispersion medium, the aqueous polyurethane not only better maintains the advantages of solvent polyurethane, such as good glossiness, flexibility, wear resistance and the like, but also is safer to prepare and use, and is an important direction for the development of polyurethane in the future. However, the service life of the waterborne polyurethane material can be greatly shortened due to cracks, fatigue and even external damage in the use process, so that resource waste is caused, and the self-repairing waterborne polyurethane material becomes a new development direction for solving the difficult problem, but the existing self-repairing waterborne polyurethane material has the problems of poor mechanical property, self-repairing of the material at high temperature and the like.
Therefore, how to design a self-repairing aqueous polyurethane material with excellent mechanical properties and excellent self-repairing properties under mild conditions is still a problem to be solved.
Disclosure of Invention
The invention aims to solve the problems that the self-repairing aqueous polyurethane material in the prior art is poor in mechanical property and needs to be subjected to self-repairing at high temperature, and provides a self-repairing aqueous polyurethane film and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the self-repairing aqueous polyurethane film comprises the following steps:
s1, mixing an isocyanate group-containing compound with macromolecular dihydric alcohol, adding a catalyst, and reacting at 80 ℃ for 2 hours;
s2, adding a hydrophilic chain extender to continue the reaction for 3 hours; adding a dihydric alcohol micromolecular chain extender, reacting for 1 hour, cooling to 50 ℃, adding triethylamine for neutralization, and obtaining polyurethane prepolymer;
s3, dissolving a dihydrazide small molecular chain extender in deionized water, dispersing the polyurethane prepolymer in the S2 in water under high-speed stirring of an emulsifier, and stirring for reaction to obtain self-repairing aqueous polyurethane emulsion;
s4, pouring the self-repairing aqueous polyurethane emulsion in the S3 into a polytetrafluoroethylene mold, drying in a baking oven at 25 ℃ for 2 days, drying at 60 ℃ for 2 days, and finally drying in a vacuum baking oven at 60 ℃ for 1 day to obtain the self-repairing aqueous polyurethane film.
Preferably, the compound containing isocyanate groups is one or a mixture of a plurality of toluene diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate.
Preferably, the macromolecular dihydric alcohol is one or a mixture of more than one of polytetrahydrofuran, polyethylene glycol, polycaprolactone dihydric alcohol, poly (1, 4-butylene glycol) adipate dihydric alcohol, polycarbonate dihydric alcohol or poly (lactide) dihydric alcohol.
Preferably, the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
Preferably, the dihydric alcohol small molecule chain extender is one or a mixture of a plurality of 1, 4-butanediol, 1, 4-cyclohexanedimethanol and terephthalyl alcohol.
Preferably, the dihydrazide small molecule chain extender is adipic acid dihydrazide.
Preferably, the R value of the aqueous polyurethane, i.e., the ratio of n (-NCO): n (-OH), is 1.5.
The invention also provides the self-repairing aqueous polyurethane film prepared by the preparation method.
The invention has the beneficial effects that:
the molar ratio of the total isocyanate groups to the total hydroxyl groups in the raw materials is controlled to be 1.5, and a hydrazide small molecular chain extender is introduced to enable the molecular chains to form higher-density hydrogen bonds, the interaction of multiple hydrogen bonds endows the material with high mechanical strength and toughness, and the activation energy required by dissociation-recombination of the hydrogen bonds is relatively low, so that the waterborne polyurethane material has a repair efficiency of about 50% at room temperature, and the self-repair efficiency at 50 ℃ is as high as 96.3%. Therefore, the self-repairing aqueous polyurethane film material has stronger mechanical property and excellent self-repairing property under mild conditions.
And secondly, the particle size of the aqueous polyurethane emulsion is regulated and controlled by changing the proportion of the chain extender, so that the stability of the aqueous polyurethane emulsion is obviously improved, and the aqueous polyurethane emulsion is convenient to transport and store for a long time.
The method has the advantages of simple synthesis process, low raw material cost, effective reduction of production cost and improvement of production efficiency.
Drawings
FIG. 1 is a stress-strain curve of the self-repairing aqueous polyurethane film of the present example 1;
fig. 2 is a stress-strain curve of the aqueous polyurethane film of example 1 after self-repairing.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
Example 1
First, dried and dehydrated polytetrahydrofuran-2000 (15 g,7.5 mmol) and isophorone diisocyanate (5.112 g,23 mmol) were charged into a three-necked flask equipped with a condenser, a mechanical stirrer and a thermometer, and after they were uniformly mixed, catalyst DBTDL was added and reacted in an oil bath at 80℃for 2 hours. Then, a further hydrophilic chain extender DMPA (1.006g, 7.5 mmol) was added and the reaction was continued for a further 2h. Then, a glycol chain extender BDO (0.034 g,0.375 mmol) was added thereto and reacted for 1 hour. Acetone was added during the reaction to adjust the viscosity of the system. The reaction system was then cooled to 50℃and TEA (0.759 g,7.5 mmol) was added to neutralize the carboxyl groups in the reaction product and reacted for 0.5 hours to give a prepolymer. The prepolymer was then poured into an aqueous solution of ADH (1.241 g,7.125 mmol), emulsified with high speed stirring at 40℃for 3h, and finally acetone was removed by rotary evaporation to give a WPU emulsion. And finally, pouring the obtained emulsion into a mold, drying the emulsion in an oven at 25 ℃ for two days, and drying the emulsion at 60 ℃ for two days to obtain the aqueous polyurethane film.
The stress-strain curve of the aqueous polyurethane film prepared in the embodiment is shown in figure 1;
the stress-strain curve of the self-repaired aqueous polyurethane film prepared by the embodiment is shown in figure 2, the repair efficiency of the aqueous polyurethane material can reach 96.3% after the aqueous polyurethane film is repaired for 5 hours at 50 ℃.
Example 2
First, dried and dehydrated polytetrahydrofuran-2000 (15 g,7.5 mmol) and isophorone diisocyanate (5.835 g,26.25 mmol) were charged into a three-necked flask equipped with a condenser, a mechanical stirrer and a thermometer, and after they were uniformly mixed, a catalyst DBTDL was added and reacted in an oil bath at 80℃for 2 hours. Then, a further hydrophilic chain extender DMPA (1.006g, 7.5 mmol) was added and the reaction was continued for a further 2h. Then adding a dihydric alcohol chain extender BDO (0.225 g,2.5 mmol) to react for 1h. Acetone was added during the reaction to adjust the viscosity of the system. The reaction system was then cooled to 50℃and TEA (0.759 g,7.5 mmol) was added to neutralize the carboxyl groups in the reaction product and reacted for 0.5 hours to give a prepolymer. The prepolymer was then poured into an aqueous solution of ADH (0.871 g,5 mmol), emulsified with stirring at high speed at 40℃for 3h, and finally acetone was removed by rotary evaporation to give a WPU emulsion. And finally, pouring the obtained emulsion into a mold, drying the emulsion in an oven at 25 ℃ for two days, and drying the emulsion at 60 ℃ for two days to obtain the aqueous polyurethane film.
Example 3
First, dried and dehydrated polycaprolactone diol-1000 (7.5 g,7.5 mmol) and toluene diisocyanate (4.578 g,26.25 mmol) were added to a three-necked flask equipped with a condenser, a mechanical stirrer and a thermometer, and after they were uniformly mixed, a catalyst DBTDL was added thereto, and reacted in an oil bath at 80℃for 2 hours. Then, a further hydrophilic chain extender DMBA (1.111 g,7.5 mmol) was added and the reaction was continued for a further 2h. Then, a diol chain extender 1, 4-cyclohexanedimethanol (0.36 g,2.5 mmol) was added thereto and the mixture was reacted for 1 hour. Acetone was added during the reaction to adjust the viscosity of the system. The reaction system was then cooled to 50℃and TEA (0.759 g,7.5 mmol) was added to neutralize the carboxyl groups in the reaction product and reacted for 0.5 hours to give a prepolymer. The prepolymer was then poured into an aqueous solution of ADH (0.871 g,5 mmol), emulsified with stirring at high speed at 40℃for 3h, and finally acetone was removed by rotary evaporation to give a WPU emulsion. And finally, pouring the obtained emulsion into a mold, drying the emulsion in an oven at 25 ℃ for two days, and drying the emulsion at 60 ℃ for two days to obtain the aqueous polyurethane film.
Example 4
First, a certain amount of polyethylene glycol-1000 (7.5 g,7.5 mmol) and 4,4' -dicyclohexylmethane diisocyanate (6.886 g,26.25 mmol) after drying and water removal were added to a three-necked flask equipped with a condenser, a mechanical stirrer and a thermometer, and after they were uniformly mixed, a catalyst DBTDL was added and reacted in an oil bath at 80℃for 2 hours. Then, a further hydrophilic chain extender DMBA (1.111 g,7.5 mmol) was added and the reaction was continued for a further 2h. Then, the diol chain extender terephthalyl alcohol (0.345 g,2.5 mmol) was added to react for 1h. Acetone was added during the reaction to adjust the viscosity of the system. The reaction system was then cooled to 50℃and TEA (0.759 g,7.5 mmol) was added to neutralize the carboxyl groups in the reaction product and reacted for 0.5 hours to give a prepolymer. The prepolymer was then poured into an aqueous solution of ADH (0.871 g,5 mmol), emulsified with stirring at high speed at 40℃for 3h, and finally acetone was removed by rotary evaporation to give a WPU emulsion. And finally, pouring the obtained emulsion into a mold, drying the emulsion in an oven at 25 ℃ for two days, and drying the emulsion at 60 ℃ for two days to obtain the aqueous polyurethane film.
The specification and figures are to be regarded in an illustrative rather than a restrictive sense, and one skilled in the art, in light of the teachings of this invention, may make various substitutions and alterations to some of its features without the need for inventive faculty, all being within the scope of this invention.
Claims (8)
1. The preparation method of the self-repairing aqueous polyurethane film is characterized by comprising the following steps of:
s1, mixing an isocyanate group-containing compound with macromolecular dihydric alcohol, adding a catalyst, and reacting at 80 ℃ for 2 hours;
s2, adding a hydrophilic chain extender to continue the reaction for 3 hours; adding a dihydric alcohol micromolecular chain extender, reacting for 1 hour, cooling to 50 ℃, adding triethylamine for neutralization, and obtaining polyurethane prepolymer;
s3, dissolving a dihydrazide small molecular chain extender in deionized water, dispersing the polyurethane prepolymer in the S2 in water under high-speed stirring of an emulsifier, and stirring for reaction to obtain self-repairing aqueous polyurethane emulsion;
s4, pouring the self-repairing aqueous polyurethane emulsion in the S3 into a polytetrafluoroethylene mold, drying in a baking oven at 25 ℃ for 2 days, drying at 60 ℃ for 2 days, and finally drying in a vacuum baking oven at 60 ℃ for 1 day to obtain the self-repairing aqueous polyurethane film.
2. The preparation method according to claim 1, wherein the compound containing isocyanate group is one or a mixture of several of toluene diisocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate.
3. The preparation method according to claim 1, wherein the macromolecular diol is one or a mixture of more of polytetrahydrofuran, polyethylene glycol, polycaprolactone diol, poly (1, 4-butylene glycol) adipate diol, polycarbonate diol and polylactide diol.
4. The method of claim 1, wherein the hydrophilic chain extender is dimethylolpropionic acid or dimethylolbutyric acid.
5. The preparation method according to claim 1, wherein the glycol small molecule chain extender is one or a mixture of a plurality of 1, 4-butanediol, 1, 4-cyclohexanedimethanol and terephthalyl alcohol.
6. The method of claim 1, wherein the dihydrazide small molecule chain extender is adipic acid dihydrazide.
7. The process according to claim 1, wherein the aqueous polyurethane has an R value, i.e., n (-NCO): n (-OH) ratio of 1.5.
8. A self-healing aqueous polyurethane film prepared by the preparation method of any one of claims 1 to 7.
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| CN106867388A (en) * | 2017-01-18 | 2017-06-20 | 华南理工大学 | A kind of selfreparing anti-dazzle aqueous polyurethane coating and preparation method thereof |
| CN115558074A (en) * | 2022-08-03 | 2023-01-03 | 重庆交通大学 | Polyurethane elastomer and preparation method thereof |
| CN115785383A (en) * | 2022-11-30 | 2023-03-14 | 浙江工业大学 | Preparation method of self-repairing polyurethane containing DA bond and acylhydrazone bond double cross-linking |
| CN115838463A (en) * | 2021-09-18 | 2023-03-24 | 四川大学 | Preparation method of water-based room temperature self-repairing polyurethane containing triple dynamic bonds |
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| CN106867388A (en) * | 2017-01-18 | 2017-06-20 | 华南理工大学 | A kind of selfreparing anti-dazzle aqueous polyurethane coating and preparation method thereof |
| CN115838463A (en) * | 2021-09-18 | 2023-03-24 | 四川大学 | Preparation method of water-based room temperature self-repairing polyurethane containing triple dynamic bonds |
| CN115558074A (en) * | 2022-08-03 | 2023-01-03 | 重庆交通大学 | Polyurethane elastomer and preparation method thereof |
| CN115785383A (en) * | 2022-11-30 | 2023-03-14 | 浙江工业大学 | Preparation method of self-repairing polyurethane containing DA bond and acylhydrazone bond double cross-linking |
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