CN110452353B - Preparation method of hyperbranched self-repairing aqueous polyurethane emulsion - Google Patents
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Abstract
The invention provides hyperbranched self-repairing waterborne polyurethane and a preparation method of emulsion thereof, wherein micromolecular polyol and dimethylolpropionic acid are dissolved in a catalyst to react for 2-3 hours to obtain hyperbranched polyol; carrying out prepolymerization reaction on the dried and dehydrated polyol, dithioglycol, diisocyanate and a catalyst at the temperature of 60-90 ℃ for 2-5 hours, adding the synthesized hyperbranched polyol and hydrophilic chain extender, and continuing to react at the temperature of 60-90 ℃ for 2-4 hours; reducing the temperature to 40-50 ℃, and adding a neutralizer; after the reaction is completed, the materials are added into a dispersing device, dispersed under high-speed stirring, and kept stand for defoaming to prepare the hyperbranched self-repairing aqueous polyurethane emulsion.
Description
Technical Field
The invention relates to the field of aqueous polyurethane emulsion, in particular to a preparation method of a self-repairing high-molecular functional material, belonging to the technical field of aqueous high-molecular material synthesis.
Background
Polyurethanes, which are all referred to as polyurethanes, are high-molecular polymers having a repeating urethane group in the main chain, have excellent mechanical properties such as high strength, good abrasion resistance, large elasticity, and the like, and have been widely used in the fields of coatings, adhesives, textile coatings and finishing agents, leather finishing agents, paper surface treating agents, fiber surface treating agents, and the like. However, in the processing and using process, the polyurethane is easily damaged by some external factors (such as external force, chemistry, thermal radiation, ultraviolet radiation and the like), so that molecular chain segments of the polyurethane are broken, a plurality of micro cracks which cannot be detected from the outside are generated inside the polyurethane, the mechanical mechanics and the service performance of the material are greatly reduced along with the expansion of the micro cracks, and the service life is also sharply shortened.
In order to solve the problem of the damage which cannot be detected by the macroscopic material and is inspired by the self-healing process when organisms are damaged, a series of self-healing functional Materials are successively developed by material scientists by simulating the self-healing damage principle (Nature,2001, 409: 794-. The self-repairing functional materials can sense destructive changes of external conditions on a molecular matrix, make appropriate response, realize self-repairing of microcracks in the materials, avoid further damage, and prolong the service life of the materials, so that the self-repairing technology has huge development potential and application value in the fields of material science and intelligent buildings.
The self-repairing mechanisms of the polyurethane materials reported at present comprise various methods such as microcapsule self-repairing, photo-reversible self-repairing, thermal-reversible self-repairing, hydrogen bond self-repairing and the like. White, S.R and the like firstly embed a microcapsule repairing agent in a high molecular matrix, when the high molecular matrix generates microcracks, the embedded repairing agent is released to crack cavities by internal stress, and crosslinking reaction is carried out under the action of a catalyst, so that the 'healing' of the polymer cracks is realized, and the self-repairing effect is achieved (Nature mater, 2007, 6: 581-585.). However, the self-repairing method has the disadvantages of limited repairing times, high manufacturing cost caused by complex structure and the like. Huaping Xu et al developed a visible light-driven self-repairing polyurethane (Advanced Materials,2015,27, 7740-. The thermal-repairing polyurethane functional material can be obtained by Diels-Alder reaction on a polyurethane main chain or a polyurethane side chain (Journal of Materials Chemistry A, 2014,2, 20642-. Chinese patent (CN104151503A) discloses a self-repairing polyurethane hydrogel and a preparation method thereof, firstly, hydrophilic polyurethane macromonomer terminated by acrylic monomer is prepared; and then free radical copolymerization with methacrylic functional monomer containing UPy unit under photoinitiation. The obtained self-repairing polyurethane hydrogel can complete self-repairing of self-damage without the requirements of any repairing agent and specific environment, has high mechanical strength and low cost, can realize repeated repairing function at the same part for many times, but has extremely complex steps in the synthesis process, and does not relate to the synthesis of hyperbranched self-repairing waterborne polyurethane.
Due to the unique branched molecular structure of the hyperbranched polymer, molecules are not entangled and contain a large number of end groups, so that the hyperbranched polymer shows special properties which are not possessed by many linear polymers such as high solubility, low viscosity, high chemical reaction activity and the like, and the properties enable the hyperbranched polymer to show attractive application prospects in polymer films, high molecular liquid crystals, drug release systems and other aspects. The hyperbranched polymer is introduced into the molecular chain of the self-repairing waterborne polyurethane, so that the viscosity of the emulsion can be effectively reduced, the self-repairing efficiency of the waterborne polyurethane is improved, and the waterborne polyurethane has good chemical stability and interface adhesion. So far, no examples of synthesis of hyperbranched self-repairing aqueous polyurethane emulsion have been reported.
Disclosure of Invention
The invention aims to provide a preparation method of hyperbranched self-repairing aqueous polyurethane emulsion, and the aqueous polyurethane emulsion prepared by the method has the advantages of effectively reducing the viscosity of the emulsion, improving the self-repairing efficiency of the aqueous polyurethane, having good chemical stability and interface adhesion and having good application prospect.
The invention is realized by the following technical scheme: dissolving small molecular polyol and dimethylolpropionic acid in the presence of a catalyst, and reacting at 80-120 ℃ for 2-3 hours to obtain yellow transparent hyperbranched polyol; carrying out prepolymerization reaction on the dried and dehydrated polyol, dithioglycol, diisocyanate and a catalyst for 2-5 hours at the temperature of 60-90 ℃, adding the synthesized hyperbranched polyol and hydrophilic chain extender, and continuing to react for 2-4 hours at the temperature of 60-90 ℃; reducing the temperature to 40-50 ℃, and adding a neutralizing agent; and after the reaction is completed, adding the materials into a dispersing device, dispersing under high-speed stirring, standing for defoaming, and thus obtaining the hyperbranched self-repairing aqueous polyurethane emulsion.
The invention provides a preparation method of a hyperbranched self-repairing waterborne polyurethane material, which comprises the following steps:
synthesis of hyperbranched polyol: dissolving micromolecular polyalcohol and dimethylolpropionic acid in a solvent according to a molar ratio of 1: 3-1: 21, adding a catalyst at the same time, reacting for 2-3 hours at 80-120 ℃ to obtain a yellow transparent solution, and decompressing the obtained yellow transparent solution to 10-30 KPa by adopting vacuum pumping equipment to remove the solvent to obtain a hyperbranched polyalcohol prepolymer a;
synthesis of hyperbranched self-repairing polyurethane prepolymer: adding 2-hydroxyethyl disulfide, diisocyanate and dehydrated polyester or polyether into a reactor according to a molar ratio of 1:3: 1-1: 4:1, adding 0.05-0.1% of organic tin catalyst serving as a reactant, and carrying out prepolymerization reaction at 60-90 ℃ for 2-5 hours to obtain a prepolymer b; adding the prepolymer a and a hydrophilic chain extender into the prepolymer b, continuously reacting for 2-4 hours at the temperature of 60-90 ℃, and adding a solvent; reducing the temperature to 40-50 ℃, adding a neutralizing agent, and continuing to react for 0.5-1 hour to obtain a prepolymer c;
dispersing the prepolymer c prepared in the step II while stirring at 1500-2000rpm, adding the dispersed prepolymer c into deionized water, dispersing the dispersed prepolymer c at a high speed for 10-30 minutes, standing and defoaming the dispersed prepolymer c to obtain the hyperbranched self-repairing aqueous polyurethane emulsion with the solid content of 30-50 percent;
further, in the step I, the micromolecular polyalcohol is trimethylolpropane, pentaerythritol or a mixture of the trimethylolpropane and the pentaerythritol according to a molar ratio of 1:5-5: 1;
in the step (i), the small-molecule polyol is polyester polyol or polyether polyol or a mixture of the polyester polyol and the polyether polyol in a molar ratio of 1:10 to 10:1, and the small-molecule polyol is used as a soft segment molecular structure of the polyurethane, and the polyester polyol can be selected from one or a mixture of any several of the following components in an equal molar ratio: poly (l, 4-butylene adipate), poly (ethylene glycol adipate), poly (diethylene glycol adipate), poly (hexanediol adipate); the polyether polyol can be selected from one or a mixture of any of the following in an equimolar ratio: polyoxypropylene glycol, polytetrahydrofuran ether glycol;
further, in the step I, the catalyst is concentrated sulfuric acid or p-toluenesulfonic acid, and the dosage of the catalyst is 1-2% of the total mass of the reactants of the small molecular polyol and the dimethylolpropionic acid;
further, in the step (i), the solvent is pyridine, DMF or DMAc.
Further, in the step (II), the diisocyanate is selected from one or a mixture of several of the following in an equal molar ratio: isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI);
further, in the step (II), the organic tin catalyst is dibutyl tin dilaurate or stannous octoate;
further, in the second step, the hydrophilic chain extender is selected from one or a mixture of two of the following components in any mass ratio: 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid;
further, in the second step, the solvent is selected from one of acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone and N-methylpyrrolidone;
further, the hyperbranched self-repairing aqueous polyurethane emulsion comprises the following components in percentage by mass: 0.01-0.5 part of hyperbranched polyol, 20-40 parts of micromolecular dihydric alcohol, 2-8 parts of dithioglycol, 20-30 parts of diisocyanate, 3-6 parts of hydrophilic chain extender, 2-5 parts of neutralizer, 0.02 part of organic tin catalyst and the balance of deionized water;
further, the solid content of the hyperbranched self-repairing polyurethane emulsion is 30-50%, and the preferable solid content is controlled at 36%;
compared with the prior art, the invention has the following beneficial effects:
(1) the hyperbranched polyol and the dithiodiol molecules are added into the molecular chain structure of the polyurethane, the self-repairing function of the polymer is realized at normal temperature, the whole preparation process is low in reaction temperature and stable in reaction speed, and the technical scheme provided by the invention is simple and convenient to operate, low in energy consumption and safe in preparation process.
(2) In view of the unique branched molecular structure of the branched polymer and no entanglement among molecules, the hyperbranched self-repairing aqueous polyurethane emulsion prepared by the technical scheme provided by the invention has good stability and self-repairing efficiency, the self-repairing rate is up to 90.6%, the stability is good, and the hyperbranched self-repairing aqueous polyurethane emulsion can be maintained for more than six months.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of hyperbranched self-repairing waterborne polyurethane.
FIG. 2 is a graph showing the effect of double sulfide addition on self-healing efficiency.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited to the contents.
Example 1
(1) Adding 2.23g of trimethylolpropane and 6.69g of dimethylolpropionic acid into a four-neck flask respectively, then adding 1% of p-toluenesulfonic acid (based on the total mass of reactants), adding 10ml of pyridine, stirring at 80 ℃ for reaction for 6 hours, and removing a solvent and a catalyst to obtain hyperbranched polyol; (2) putting 100g of poly-adipate-l, 4-butanediol glycol (Mn is 1000) and l00g polytetrahydrofuran glycol (Mn is 1000) into a reactor, vacuumizing and dehydrating for 2h at 120 ℃, cooling to 70 ℃, adding 151.2g of IPDI, 4.62g of 2-hydroxyethyl disulfide and 0.5g of dibutyl tin dilaurate into the reactor, and reacting for 2-3 h at 80-86 ℃; then adding 28.5g of dimethylolpropionic acid and 8.05g of hyperbranched polyol, and reacting at 80-86 ℃ until the-NCO concentration reaches a theoretical value; cooling to 60 ℃, adding 60g of acetone for dilution, adding 21.2g of ethylenediamine for neutralization, and continuing to react for 30 min; (3) adding the prepolymer into 960g of deionized water under the high-speed shearing condition of 1600r/min, stirring at a high speed for 20-30 min, and performing low-pressure vacuum pumping and acetone removal at the temperature of 50-60 ℃ to obtain the hyperbranched self-repairing aqueous polyurethane emulsion.
Example 2
(1) Adding 2.23g of trimethylolpropane and 6.69g of dimethylolpropionic acid into a four-neck flask respectively, adding 1% of p-toluenesulfonic acid (based on the total mass of reactants), adding 10ml of pyridine, stirring at 80 ℃ for reaction for 6 hours, and removing a solvent and a catalyst to obtain hyperbranched polyol; (2) putting 100g of poly-adipate-l, 4-butanediol glycol (Mn is 1000) and l00g polytetrahydrofuran glycol (Mn is 1000) into a reactor, vacuumizing and dehydrating for 2h at 120 ℃, cooling to 70 ℃, adding 151.2g of IPDI, 9.3g of 2-hydroxyethyl disulfide and 0.5g of dibutyl tin dilaurate into the reactor, and reacting for 2-3 h at 80-86 ℃; then adding 21.5g of dimethylolpropionic acid and 8.05g of hyperbranched polyol, and reacting at 80-86 ℃ until the-NCO concentration reaches a theoretical value; cooling to 60 ℃, adding 60g of acetone for dilution, adding 16.2g of ethylenediamine for neutralization, and continuing to react for 30 min; (3) adding the prepolymer into 960g of deionized water under the high-speed shearing condition of 1600r/min, stirring at a high speed for 20-30 min, and performing low-pressure vacuum pumping and acetone removal at the temperature of 50-60 ℃ to obtain the hyperbranched self-repairing aqueous polyurethane emulsion.
Example 3
(1) Adding 2.23g of trimethylolpropane and 6.69g of dimethylolpropionic acid into a four-neck flask respectively, adding 1% of p-toluenesulfonic acid (based on the total mass of reactants), adding 10ml of pyridine, stirring at 80 ℃ for reaction for 6 hours, and removing a solvent and a catalyst to obtain hyperbranched polyol; (2) putting 100g of poly-adipate-l, 4-butanediol glycol (Mn is 1000) and l00g polytetrahydrofuran glycol (Mn is 1000) into a reactor, vacuumizing and dehydrating for 2h at 120 ℃, cooling to 70 ℃, adding 151.2g of IPDI, 13.8g of 2-hydroxyethyl disulfide and 0.5g of dibutyl tin dilaurate into the reactor, and reacting for 2-3 h at 80-86 ℃; then adding 18.8g of dimethylolpropionic acid and 8.05g of hyperbranched polyol, and reacting at 80-86 ℃ until the-NCO concentration reaches a theoretical value; cooling to 60 ℃, adding 60g of acetone for dilution, adding 14.2g of ethylenediamine for neutralization, and continuing to react for 30 min; (3) adding the prepolymer into 960g of deionized water under the high-speed shearing condition of 1600r/min, stirring at a high speed for 20-30 min, and performing low-pressure vacuum pumping and acetone removal at the temperature of 50-60 ℃ to obtain the hyperbranched self-repairing aqueous polyurethane emulsion.
Example 4
(1) Adding 2.23g of trimethylolpropane and 6.69g of dimethylolpropionic acid into a four-neck flask respectively, adding 1% of p-toluenesulfonic acid (based on the total mass of reactants), adding 10ml of pyridine, stirring at 80 ℃ for reaction for 6 hours, and removing a solvent and a catalyst to obtain hyperbranched polyol; (2) putting 100g of poly-adipate-l, 4-butanediol glycol (Mn is 1000) and l00g polytetrahydrofuran glycol (Mn is 1000) into a reactor, vacuumizing and dehydrating for 2h at 120 ℃, cooling to 70 ℃, adding 151.2g of IPDI, 18.5g of 2-hydroxyethyl disulfide and 0.5g of dibutyl tin dilaurate into the reactor, and reacting for 2-3 h at 80-86 ℃; then 16.2g of dimethylolpropionic acid and 8.05g of hyperbranched polyol are added, and the mixture reacts at the temperature of 80-86 ℃ until the-NCO concentration reaches a theoretical value; cooling to 60 ℃, adding 60g of acetone for dilution, adding 12.2g of ethylenediamine for neutralization, and continuing to react for 30 min; (3) adding the prepolymer into 960g of deionized water under the high-speed shearing condition of 1600r/min, stirring at a high speed for 20-30 min, and performing low-pressure vacuum pumping and acetone removal at the temperature of 50-60 ℃ to obtain the hyperbranched self-repairing aqueous polyurethane emulsion.
Example 5
(1) Adding 2.23g of trimethylolpropane and 6.69g of dimethylolpropionic acid into a four-neck flask respectively, adding 1% of p-toluenesulfonic acid (based on the total mass of reactants), adding 10ml of pyridine, stirring at 80 ℃ for reaction for 6 hours, and removing a solvent and a catalyst to obtain hyperbranched polyol; (2) 100g of poly (adipic acid-l, 4-butanediol ester diol) (Mn 1000) and l00g polytetrahydrofuran diol (Mn 1000) are put into a reactor, vacuum dehydration is carried out at 120 ℃ for 2h, the temperature is reduced to 70 ℃, then 151.2g of IPDI, 23.1g of 2-hydroxyethyl disulfide and 0.5g of dibutyl tin dilaurate are added into the reactor, and the reaction is carried out at 80-86 ℃ for 2-3 h; then adding 13.5g of dimethylolpropionic acid and 8.05g of hyperbranched polyol, and reacting at 80-86 ℃ until the-NCO concentration reaches a theoretical value; cooling to 60 ℃, adding 60g of acetone for dilution, adding 10.2g of ethylenediamine for neutralization, and continuing to react for 30 min; (3) adding 960g of deionized water into the prepolymer under the high-speed shearing condition of 1600r/min, stirring at a high speed for 20-30 min, and vacuumizing at a low temperature of 50-60 ℃ to remove acetone to obtain the hyperbranched self-repairing aqueous polyurethane emulsion.
Example 6
(1) Adding 2.23g of trimethylolpropane and 6.69g of dimethylolpropionic acid into a four-neck flask respectively, adding 1% of p-toluenesulfonic acid (based on the total mass of reactants), adding 10ml of pyridine, stirring at 80 ℃ for reaction for 6 hours, and removing a solvent and a catalyst to obtain hyperbranched polyol; (2) putting 100g of poly-adipate-l, 4-butanediol glycol (Mn is 1000) and l00g polytetrahydrofuran glycol (Mn is 1000) into a reactor, vacuumizing and dehydrating for 2h at 120 ℃, cooling to 70 ℃, adding 151.2g of IPDI, 27.3g of 2-hydroxyethyl disulfide and 0.5g of dibutyl tin dilaurate into the reactor, and reacting for 2-3 h at 80-86 ℃; then 10.8g of dimethylolpropionic acid and 8.05g of hyperbranched polyol are added, and the mixture reacts at the temperature of 80-86 ℃ until the-NCO concentration reaches a theoretical value; cooling to 60 ℃, adding 60g of acetone for dilution, adding 8.2g of ethylenediamine for neutralization, and continuing to react for 30 min; (3) adding the prepolymer into 960g of deionized water under the high-speed shearing condition of 1600r/min, stirring at a high speed for 20-30 min, and vacuumizing at a low temperature of 50-60 ℃ to remove acetone to obtain the hyperbranched self-repairing aqueous polyurethane emulsion.
The invention also performs an experiment of a linear self-repairing aqueous polyurethane emulsion comparative example, and in order to ensure the accuracy of the experimental result of the comparative example, the self-repairing rate experimental result obtained by the comparative example is an average value obtained by three identical experimental results:
comparative example 1 synthesis of a linear self-repairing aqueous polyurethane emulsion:
100g of poly (adipic acid-l, 4-butanediol ester diol) (Mn 1000) and l00g polytetrahydrofuran diol (Mn 1000) are put into a reactor, vacuum dehydration is carried out at 120 ℃ for 2 hours, the temperature is reduced to 70 ℃, 140.2g of IPDI, 27.3g of 2-hydroxyethyl disulfide and 0.5g of dibutyl tin dilaurate are added into the reactor, and the reaction is carried out at 80-86 ℃ for 2-3 hours; (2) then 10.8g of dimethylolpropionic acid is added, and the reaction is carried out at 80-86 ℃ until the-NCO concentration reaches a theoretical value; cooling to 60 ℃, adding 60g of acetone for dilution, adding 8.2g of ethylenediamine for neutralization, and continuing to react for 30 min; (3) adding 960g of deionized water into the prepolymer under the high-speed shearing condition of 1600r/min, stirring at a high speed for 20-30 min, and vacuumizing at a low temperature of 50-60 ℃ to remove acetone to obtain the hyperbranched self-repairing aqueous polyurethane emulsion.
The self-repairing and stability tests were performed on the hyperbranched aqueous polyurethane obtained in examples 1 to 6 and the linear self-repairing aqueous polyurethane emulsion obtained in comparative example 1, and the results are shown in table 1:
TABLE 1 self repair Rate and stability test results
According to the results, the hyperbranched waterborne polyurethane prepared by the technical scheme provided by the invention has good self-repairing efficiency and emulsion stability; with the increase of disulfide compounds in a system, the self-repair efficiency of the hyperbranched waterborne polyurethane emulsion is gradually enhanced (even up to 90.6%), the linear self-repair waterborne polyurethane prepared by adding the same mass of disulfide into the embodiment 6 and the comparative example 1 of the invention, but the self-repair rate of the comparative example 1 can only reach 43% of that of the embodiment 6, and the hyperbranched structure has higher self-repair rate; meanwhile, after the aqueous polyurethane adhesive emulsion provided by the invention is placed at normal temperature for 6 months, no sedimentation phenomenon occurs, and the performance is stable and excellent.
Although the above-described embodiments and the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above-described embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. A preparation method of hyperbranched self-repairing aqueous polyurethane emulsion is characterized by comprising the following steps: the preparation method comprises the following steps:
synthesis of hyperbranched polyol: dissolving micromolecular polyalcohol and dimethylolpropionic acid in a solvent according to a molar ratio of 1: 3-1: 21, adding a catalyst at the same time, reacting for 2-3 hours at 80-120 ℃ to obtain a yellow transparent solution, and decompressing the obtained yellow transparent solution to 10-30 KPa by adopting vacuum pumping equipment to remove the solvent to obtain a hyperbranched polyalcohol prepolymer a;
synthesis of a hyperbranched self-repairing polyurethane prepolymer: adding 2-hydroxyethyl disulfide, diisocyanate, and a dehydrated polyester and polyether mixture into a reactor according to a molar ratio of 1:3: 1-1: 4:1, adding an organic tin catalyst accounting for 0.05-0.1% of reactants, and carrying out prepolymerization reaction at 60-90 ℃ for 2-5 hours to obtain a prepolymer b; adding the prepolymer a and a hydrophilic chain extender into the prepolymer b, continuously reacting for 2-4 hours at the temperature of 60-90 ℃, and adding a solvent; reducing the temperature to 40-50 ℃, adding a neutralizing agent, and continuing to react for 0.5-1 hour to obtain a prepolymer c;
will be described in detailAdding the prepared prepolymer c into deionized water while dispersing under the stirring of 1500-2000rpm, dispersing at a high speed for 10-30 minutes, standing for defoaming, and obtaining the prepolymer with the solid content of 30-50%Hyperbranched self-repairing aqueous polyurethane emulsion;
wherein, in the step I, the micromolecular polyalcohol is trimethylolpropane, pentaerythritol or a mixture of the trimethylolpropane and the pentaerythritol according to a molar ratio of 1:5-5: 1; and the polyester and polyether mixture subjected to dehydration treatment in the step II is composed of the polyester and the polyether according to a molar ratio of 1:10-10: 1.
2. The method for preparing the hyperbranched self-repairing aqueous polyurethane emulsion according to claim 1, wherein the hyperbranched self-repairing aqueous polyurethane emulsion comprises: in the second step, the mixture of the polyester and the polyether after the dehydration treatment is used as a soft segment molecular structure of polyurethane, and the polyester is selected from one or a mixture of any several of the following components according to an equal molar ratio: 1, 4-butanediol adipate, glycol adipate, diethylene glycol adipate, and hexanediol adipate; the polyether is selected from one or a mixture of any of the following components in an equal molar ratio: polyoxypropylene glycol, polytetrahydrofuran ether glycol.
3. The method for preparing the hyperbranched self-repairing aqueous polyurethane emulsion according to claim 1, wherein the hyperbranched self-repairing aqueous polyurethane emulsion comprises: in the step I, the catalyst is concentrated sulfuric acid or p-toluenesulfonic acid, and the dosage of the catalyst is 1-2% of the total mass of reactants of micromolecular polyol and dimethylolpropionic acid.
4. The method for preparing the hyperbranched self-repairing aqueous polyurethane emulsion according to claim 1, wherein the hyperbranched self-repairing aqueous polyurethane emulsion comprises: in the step I, the solvent is pyridine, DMF or DMAc.
5. The method for preparing the hyperbranched self-repairing aqueous polyurethane emulsion according to claim 1, wherein the hyperbranched self-repairing aqueous polyurethane emulsion comprises: in the step II, the diisocyanate is selected from one or a mixture of several of the following components in an equal molar ratio: isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI).
6. The method for preparing the hyperbranched self-repairing aqueous polyurethane emulsion according to claim 1, wherein the hyperbranched self-repairing aqueous polyurethane emulsion comprises: in the step (II), the organic tin catalyst is dibutyl tin dilaurate or stannous octoate.
7. The method for preparing the hyperbranched self-repairing aqueous polyurethane emulsion according to claim 1, wherein the hyperbranched self-repairing aqueous polyurethane emulsion comprises: in the second step, the hydrophilic chain extender is selected from one or a mixture of two of the following components in any mass ratio: 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid.
8. The method for preparing the hyperbranched self-repairing aqueous polyurethane emulsion according to claim 1, wherein the hyperbranched self-repairing aqueous polyurethane emulsion comprises: in the second step, the solvent is selected from one of acetone, butanone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone and N-methylpyrrolidone.
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