CN114316195B - Breathable and moisture-permeable waterborne polyurethane resin and preparation method thereof - Google Patents
Breathable and moisture-permeable waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- CN114316195B CN114316195B CN202111530449.5A CN202111530449A CN114316195B CN 114316195 B CN114316195 B CN 114316195B CN 202111530449 A CN202111530449 A CN 202111530449A CN 114316195 B CN114316195 B CN 114316195B
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Abstract
The invention provides a breathable moisture-permeable waterborne polyurethane resin and a preparation method thereof, wherein the breathable moisture-permeable waterborne polyurethane resin comprises a first component and a second component, the first component is an alkyd resin modified waterborne polyurethane resin dispersoid, and the second component is a curing agent which reacts with carboxyl in the first component; the first component comprises the following raw materials in parts by weight: oligomer polyol 28.92-82.85 weight portions; isocyanate in 7.10-42.74 weight portions; 0-10.52 parts of glycol chain extender; 1.01-4.78 parts of a hydrophilic chain extender; 0-4.82 parts of a salt forming agent; 0.33 to 13.31 portions of amine chain extender; 2.77-18.64 parts of polyethylene glycol; 0.34 to 8.91 portions of adipic acid; 0-0.02 part of catalyst; 0.2 to 0.5 portion of defoaming agent. The waterborne polyurethane resin disclosed by the invention has good water resistance, air permeability and moisture permeability at the same time.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to breathable and moisture-permeable waterborne polyurethane resin and a preparation method thereof.
Background
China is a country with large consumption for synthetic leather production, and the solvent type polyurethane resin mainly adopted in the current synthetic leather production causes serious environmental pollution because the solvent is incompletely recovered in the production process. With the enhancement of environmental awareness and the pursuit of high-quality life quality of people, the requirements on synthetic leather products are higher and higher, particularly for furniture, home decoration and car washing interior leather, the synthetic leather is required to have zero formaldehyde and low VOC (volatile organic solvent content is less than or equal to 5mg/Kg (leather)), the traditional solvent-based synthetic leather cannot meet the requirements, and the development of the synthetic leather tends to be promoted by using the waterborne polyurethane to replace the solvent-based polyurethane.
Compared with natural leather, the synthetic leather has poor air permeability and moisture permeability, the air permeability and the moisture permeability of the leather depend on the air permeability and the moisture permeability of a coating, the air permeability and the moisture permeability of the coating are good, the use comfort of the leather can be improved, along with the development of the synthetic leather, the requirements of people on the air permeability and the moisture permeability of the synthetic leather are higher and higher, and how to improve the air permeability and the moisture permeability of the aqueous polyurethane becomes an important direction for the research of the synthetic leather.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a breathable and moisture-permeable waterborne polyurethane resin and a preparation method thereof, and aims to solve the problems of insufficient breathability, moisture permeability and the like when waterborne polyurethane on the market is used for dry synthetic leather.
In order to achieve the above purpose, the invention provides the following technical scheme:
a breathable and moisture-permeable aqueous polyurethane resin comprises a first component and a second component, wherein the first component is an alkyd resin modified aqueous polyurethane resin dispersion, and the second component is a curing agent which reacts with carboxyl in the first component;
the first component comprises the following raw materials in parts by weight: oligomer polyol 28.92-82.85 weight portions; 7.10-42.74 parts of isocyanate; 0-10.52 parts of dihydric alcohol chain extender; 1.01 to 4.78 portions of hydrophilic chain extender; 0-4.82 parts of a salt forming agent; 0.33 to 13.31 portions of amine chain extender; 2.77-18.64 parts of polyethylene glycol; 0.34 to 8.91 portions of adipic acid; 0-0.02 portion of catalyst; 0.2 to 0.5 portion of defoaming agent.
Alternatively, the reaction equivalent ratio of the second component to the carboxyl groups in the first component is 0.7 to 1.
Optionally, the polyethylene glycol has a number average molecular weight of 200 to 2000g/mol and a functionality of 2;
preferably, the oligomer polyol is at least one of polyether polyol, polyester polyol and polycarbonate polyol, the number average molecular weight of the oligomer polyol is 1000-4000 g/mol, and the functionality is 2;
the isocyanate is at least one of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and xylylene diisocyanate;
the dihydric alcohol chain extender is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and diethylene glycol;
the hydrophilic chain extender comprises a sulfonic acid hydrophilic chain extender and a carboxylic acid hydrophilic chain extender, the sulfonic acid hydrophilic chain extender is ethylene diamine ethyl sodium sulfonate, and the carboxylic acid hydrophilic chain extender is dimethylolpropionic acid and/or dimethylolbutyric acid;
the salt forming agent is triethylamine;
the catalyst is at least one of organic titanium, organic tin and organic bismuth;
the amine chain extender is at least one of hydrazine hydrate, ethylenediamine, isophoronediamine, diethylenetriamine and triethylene tetramine.
Optionally, the second component is a polyfunctional aziridine and/or polycarbodiimide-based crosslinking agent.
The invention also provides a preparation method of the breathable and moisture-permeable aqueous polyurethane resin, wherein the waterborne polyurethane resin dispersion modified by the alkyd resin as the first component in the breathable and moisture-permeable aqueous polyurethane resin is prepared by the following steps:
step one, preparing alkyd resin: mixing polyethylene glycol and adipic acid in an inert gas atmosphere, and heating to react to obtain alkyd resin;
step two, preparing a waterborne polyurethane prepolymer: mixing oligomer polyol and isocyanate, heating to react, reacting to a first theoretical isocyanate group content, cooling, adding a dihydric alcohol chain extender and a part of hydrophilic chain extender, continuing to react to a second theoretical isocyanate group content, cooling and diluting, adding the rest part of hydrophilic chain extender, reacting for a period of time, adding a salt forming agent, continuing to react for a period of time, and stirring uniformly to obtain the waterborne polyurethane prepolymer; wherein the first theoretical isocyanate group content and the second theoretical isocyanate group content are both the isocyanate group content when the hydroxyl group in the reaction system is reacted;
step three, preparing the alkyd resin modified waterborne polyurethane resin dispersion: and (3) diluting the waterborne polyurethane prepolymer obtained in the step two, adding the alkyd resin obtained in the step one, stirring, adding water, emulsifying, adding an amine chain extender after emulsifying, reacting with residual isocyanate groups in a system, adding a defoaming agent after reaction, and removing a solvent to obtain the alkyd resin modified waterborne polyurethane resin dispersoid.
Optionally, the first step is specifically that polyethylene glycol and adipic acid are added into a reaction kettle, nitrogen is introduced while stirring, the temperature is raised to 200-240 ℃, and the mixture is reacted for 25-30 hours to obtain the alkyd resin;
preferably, the molar ratio of adipic acid to polyethylene glycol is 1; the acid value of the alkyd resin is 5-15 mgKOH/g;
more preferably, in the first step, a catalyst is also added into the reaction kettle.
Optionally, the second step is specifically that oligomer polyol and isocyanate are put into a reaction kettle, after being uniformly stirred, the temperature is raised to 70-80 ℃ for reaction, the reaction is carried out until the content of a first theoretical isocyanate group is reached, the temperature is lowered to 60-70 ℃, a diol chain extender and a carboxylic acid hydrophilic chain extender are added, the temperature of a reaction system is kept at 65-75 ℃, the reaction is carried out until the content of a second theoretical isocyanate group is reached, the temperature is lowered to 40-45 ℃, acetone is added for dilution, the adding amount of the acetone is 10-25% of the total mass of the added oligomer polyol, the isocyanate, the hydrophilic chain extender and the diol chain extender, after being uniformly stirred, an aqueous solution of a sulfonic acid hydrophilic chain extender with the mass concentration of 50% is dripped, the reaction is carried out for 20-30 min after being maintained at 40-45 ℃, a salt forming agent is added after being uniformly stirred, the reaction is carried out for 20-30 min below 40 ℃, and after being uniformly stirred, the aqueous polyurethane prepolymer is obtained;
preferably, in the second step, the molar ratio of isocyanate groups to hydroxyl groups in the added raw materials is 1.25; the molar ratio of the salt forming agent to the carboxyl in the waterborne polyurethane prepolymer is 1-2;
more preferably, in the second step, a catalyst is also added to the raw materials in the reaction vessel.
Optionally, in the third step, the waterborne polyurethane prepolymer obtained in the second step is diluted by acetone, the viscosity is 300-500 cps at 25 ℃, the alkyd resin obtained in the first step is added, the mixture is stirred for 10-20 min, water is added for emulsification, an amine chain extender is added after emulsification is carried out for 5-10 min, the amine chain extender is reacted with residual isocyanate groups in the system, a defoaming agent is added after the reaction, and the alkyd resin modified waterborne polyurethane resin dispersoid is obtained after acetone is removed.
Optionally, in the third step, the addition amount of the alkyd resin is 5 to 20 percent of the weight of the aqueous polyurethane dispersion;
preferably, in the third step, the molar ratio of the number of the amino groups in the amine chain extender to the number of the remaining isocyanate groups in the aqueous polyurethane prepolymer is 0.7.
Optionally, the solid content in the first component is 40-55% by weight.
Has the beneficial effects that:
the breathable moisture-permeable waterborne polyurethane resin disclosed by the invention is a two-component resin, namely, the breathable moisture-permeable waterborne polyurethane resin comprises a first component and a second component, wherein the first component is an alkyd resin modified waterborne polyurethane resin dispersoid, and the second component is a curing agent which reacts with carboxyl in the first component. When the water-based polyurethane synthetic leather is actually used, the first component and the second component are mixed, and the curing agent in the second component reacts with the carboxyl in the first component, so that the alkyd resin can be well grafted onto a molecular chain of polyurethane to form a space network structure, the water resistance of the polyurethane resin is favorably improved, and the space network structure is formed, so that when the water-based polyurethane is used for the polyurethane synthetic leather, the rebound resilience of the synthetic leather preparation is favorably ensured. Meanwhile, as the raw material of the first component contains polyethylene glycol, the air permeability and the moisture permeability of the waterborne polyurethane resin can be effectively improved. Therefore, the aqueous polyurethane resin of the present invention has both good water resistance and good air and moisture permeability.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Aiming at the defects of air permeability, moisture permeability and the like when the waterborne polyurethane on the market is used for dry synthetic leather, the invention provides the air permeable and moisture permeable waterborne polyurethane.
In the embodiment of the invention, the breathable moisture-permeable waterborne polyurethane resin comprises a first component and a second component, wherein the first component is an alkyd resin modified waterborne polyurethane resin dispersoid, and the second component is a curing agent which reacts with carboxyl in the first component; the first component comprises the following raw materials in parts by weight: oligomer polyol, 28.92 to 82.85 parts (such as 28.92 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, or 82.85 parts); isocyanate, 7.10 to 42.74 parts (such as 7.10 parts, 10 parts, 20 parts, 30 parts, 40 parts or 42.74 parts); 0-10.52 parts of glycol chain extender (such as 0 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts or 10.52 parts); 1.01-4.78 parts (such as 1.01 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 4.78 parts) of a hydrophilic chain extender; 0-4.82 parts of salt forming agent (such as 0 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 4.82 parts); amine chain extender, 0.33 to 13.31 parts (e.g., 0.33, 1,3, 5, 7, 10, 12, or 13.31 parts); 2.77-18.64 parts of polyethylene glycol (such as 2.77 parts, 5 parts, 7.5 parts, 10 parts, 12.5 parts, 15 parts, 17.5 parts or 18.64 parts); adipic acid, 0.34 to 8.91 parts (such as 0.34 parts, 1 part, 3 parts, 5 parts, 7.5 parts, or 8.91 parts); 0 to 0.02 parts (such as 0 part, 0.01 part or 0.02 part) of catalyst; 0.2 to 0.5 part (for example, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part or 0.5 part) of a defoaming agent.
It is understood that the breathable and moisture-permeable aqueous polyurethane resin of the present invention is a two-component resin, that is, includes a first component which is an alkyd resin modified aqueous polyurethane resin dispersion and a second component which is a curing agent that reacts with carboxyl groups in the first component. During the actual use, mix first component and second component, the curing agent in the second component reacts with the carboxyl in the first component for alkyd can graft well on the molecular chain of polyurethane, form the space network structure, be favorable to improving polyurethane resin's water resistance, and owing to formed the space network structure, when being used for polyurethane synthetic leather with waterborne polyurethane, be favorable to guaranteeing the resilience of synthetic leather preparation. Meanwhile, as the raw material of the first component contains polyethylene glycol, the air permeability and the moisture permeability of the waterborne polyurethane resin can be effectively improved. Therefore, the aqueous polyurethane resin of the present invention has good water resistance, air permeability and moisture permeability at the same time.
In an alternative embodiment of the present invention, the ratio of the reaction equivalents of the carboxyl groups in the second component to the reaction equivalents in the first component is 0.7. For example, the reaction equivalent ratio of the two is 0.7.
In alternative embodiments of the invention, the polyethylene glycol has a number average molecular weight of 200 to 2000g/mol (e.g., 200g/mol, 500g/mol, 1000g/mol, 1500g/mol, or 2000 g/mol) and a functionality of 2. Preferably, the polyethylene glycol is a polyethylene glycol having a number average molecular weight of 200 to 1000g/mol and a functionality of 2.
In an alternative embodiment of the present invention, the oligomer polyol is at least one of polyether polyol, polyester polyol, and polycarbonate polyol. When in use, one or more mixtures of the above substances can be selected, and are not limited herein, and the invention is within the protection scope.
Preferably, the oligomeric polyol has a number average molecular weight of 1000 to 4000g/mol (such as 1000g/mol, 2000g/mol, 3000g/mol, or 4000 g/mol) and a functionality of 2.
In an alternative embodiment of the present invention, the isocyanate is at least one of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and xylylene diisocyanate. When in use, one or more mixtures of the above substances can be selected, and are not limited herein, and are within the protection scope of the present invention.
In an alternative embodiment of the present invention, the glycol chain extender is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 6-hexylene glycol, neopentyl glycol, and diethylene glycol. When in use, one or more mixtures of the above substances can be selected, and are not limited herein, and are within the protection scope of the present invention.
In an alternative embodiment of the present invention, the hydrophilic chain extender is at least one of dimethylolpropionic acid, dimethylolbutyric acid and ethylenediamine ethanesulfonic acid sodium salt. When in use, one or more mixtures of the above substances can be selected, and are not limited herein, and the invention is within the protection scope.
In an alternative embodiment of the invention, the salt forming agent is triethylamine.
In an optional embodiment of the invention, the catalyst is at least one of organic titanium, organic tin and organic bismuth. When in use, one or more mixtures of the above substances can be selected, and are not limited herein, and are within the protection scope of the present invention.
In an optional embodiment of the present invention, the amine chain extender is at least one of hydrazine hydrate, ethylenediamine, isophoronediamine, diethylenetriamine, and triethylenetetramine. When in use, one or more mixtures of the above substances can be selected, and are not limited herein, and the invention is within the protection scope.
In an alternative embodiment of the invention, the second component is a polyfunctional aziridine and/or polycarbodiimide-based crosslinking agent, preferably a polyfunctional aziridine.
The invention also provides a preparation method of the breathable and moisture-permeable aqueous polyurethane resin, wherein the waterborne polyurethane resin dispersion modified by the alkyd resin as the first component in the breathable and moisture-permeable aqueous polyurethane resin is prepared by the following steps:
step one, preparing alkyd resin: mixing polyethylene glycol and adipic acid in an inert gas atmosphere, and heating to react to obtain alkyd resin;
step two, preparing a waterborne polyurethane prepolymer: mixing oligomer polyol and isocyanate, heating to react, reacting to a first theoretical isocyanate group content, cooling, adding a dihydric alcohol chain extender and a part of hydrophilic chain extender, continuing to react to a second theoretical isocyanate group content, cooling and diluting, adding a part of hydrophilic chain extender, reacting for a period of time, adding a salt forming agent, continuing to react for a period of time, and stirring uniformly to obtain the waterborne polyurethane prepolymer; wherein the first theoretical isocyanate group content and the second theoretical isocyanate group content are both the isocyanate group content when the hydroxyl group in the reaction system is reacted;
step three, preparing the alkyd resin modified waterborne polyurethane resin dispersion: and (3) diluting the waterborne polyurethane prepolymer obtained in the step two, adding the alkyd resin obtained in the step one, stirring, adding water for emulsification, adding an amine chain extender after emulsification, reacting with residual isocyanate groups in a system, adding a defoaming agent after reaction, and removing a solvent to obtain an alkyd resin modified waterborne polyurethane resin dispersoid.
The raw materials used in the above examples were the raw materials of the above examples, and the defoaming agent was a commercially available conventional defoaming agent.
In the invention, the selected polyethylene glycol has strong water absorption, can absorb water from air at normal temperature, even can be dissolved in water under certain conditions, and if the polyethylene glycol is directly added into the aqueous polyurethane dispersion, the water resistance of the aqueous polyurethane dispersion is reduced, which is not beneficial to the practical application of the aqueous polyurethane. In the preparation method, the polyethylene glycol and the adipic acid react to form the carboxyl-terminated alkyd resin, and then the carboxyl-terminated alkyd resin is added into the aqueous polyurethane prepolymer for emulsification, so that the alkyd resin can be uniformly dispersed in the aqueous polyurethane dispersion, and the storage stability of the aqueous polyurethane dispersion is facilitated due to the specific hydrophilic property of the alkyd resin. During the actual use, mix first component and second component, the curing agent in the second component reacts with the carboxyl in the first component for alkyd can graft well on the molecular chain of polyurethane, form the space network structure, be favorable to improving polyurethane resin's water resistance, and owing to formed the space network structure, when being used for polyurethane synthetic leather with waterborne polyurethane, be favorable to guaranteeing the resilience of synthetic leather preparation. The water resistance of the waterborne polyurethane prepared by the preparation method of the invention cannot be reduced, and the air permeability and moisture permeability of the waterborne polyurethane resin are increased due to the addition of the polyethylene glycol.
In an optional embodiment of the present invention, the first step is specifically, adding polyethylene glycol and adipic acid into a reaction kettle, introducing nitrogen while stirring, heating to 200-240 ℃ (for example, 200 ℃, 210 ℃, 220 ℃, 230 ℃ or 240 ℃), and reacting for 25-30 h (25 h, 26h, 27h, 28h, 29h or 30 h) to obtain the alkyd resin.
Preferably, the molar ratio of adipic acid to polyethylene glycol is 1; the acid value of the alkyd resin is 5-15 mgKOH/g (5 mgKOH/g, 7mgKOH/g, 10mgKOH/g, 12mgKOH/g or 15 mgKOH/g).
Preferably, in the first step, a catalyst is also added into the reaction kettle. The addition of the catalyst can accelerate the reaction and thus increase the reaction rate. Wherein, the catalyst is one or the mixture of any more of organic titanium, organic tin and organic bismuth.
In an optional embodiment of the present invention, in the second step, the oligomer polyol and the isocyanate are put into a reaction kettle, and after being uniformly stirred, the temperature is raised to 70 to 80 ℃ (70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃) to enable the reaction to be performed, the reaction is performed until the first theoretical isocyanate group content is reached, the temperature is reduced to 60 to 70 ℃ (such as 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃ or 70 ℃), the dihydric alcohol chain extender and the carboxylic acid hydrophilic chain extender are added, the temperature of the reaction system is kept at 65 to 75 ℃ (such as 65 ℃, 67 ℃, 70 ℃, 72 ℃ or 75 ℃) to be reacted until the second theoretical isocyanate group content is reached, the temperature is reduced to 40 to 45 ℃ (such as 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃ or 45 ℃), adding acetone for dilution, wherein the adding amount of the acetone is 10% -25% (such as 10%, 12%, 15%, 17%, 20%, 22% or 25%) of the total mass of the oligomer polyol, the isocyanate, the hydrophilic chain extender and the diol chain extender, uniformly stirring, then dripping aqueous solution of sulfonic acid hydrophilic chain extender with the mass concentration of 50%, keeping 40-45 ℃ (such as 40 ℃, 42 ℃ or 45 ℃) for reaction for 20-30 min (such as 20min, 22min, 24min, 26min, 28min or 30 min), uniformly stirring, then adding a salt forming agent, reacting for 20-30 min (such as 20min, 22min, 24min, 26min, 28min or 30 min) below 40 ℃, and uniformly stirring to obtain the waterborne polyurethane prepolymer.
Preferably, in the second step, the molar ratio of isocyanate groups to hydroxyl groups in the added raw materials is 1.25. Preferably, the molar ratio of isocyanate groups to hydroxyl groups in the added raw materials is 1.25.
Optionally, the molar ratio of the salt-forming agent to the carboxyl groups in the aqueous polyurethane prepolymer is 1. Preferably, the molar ratio of the salt forming agent to the carboxyl groups in the aqueous polyurethane prepolymer is 1.
More preferably, in the second step, a catalyst is also added to the raw materials in the reaction kettle to accelerate the reaction.
In an optional embodiment of the invention, the third step is specifically that acetone is adopted to dilute the waterborne polyurethane prepolymer obtained in the second step, the viscosity is 300-500 cps (such as 300cps, 350cps, 400cps, 450cps or 500 cps) at 25 ℃, the alkyd resin obtained in the first step is added, the mixture is stirred for 10-20 min (such as 10min, 12min, 14min, 16min, 18min or 20 min), water is added for emulsification, amine chain extender is added after emulsification for 5-10 min (such as 5min, 6min, 7min, 8min, 9min or 10 min), the amine chain extender is made to react with residual isocyanate groups in the system, a defoaming agent is added after the reaction, and the alkyd resin modified waterborne polyurethane resin dispersoid is obtained after acetone is removed.
In an optional embodiment of the present invention, in step three, the alkyd resin is added in an amount of 5 to 20% (such as 5%, 10%, 15%, or 20%) of the total solid content of the aqueous polyurethane dispersion.
Preferably, in the third step, the molar ratio of the number of moles of amino groups in the amine chain extender to the number of moles of isocyanate groups remaining in the aqueous polyurethane prepolymer is 0.7.
In alternative embodiments of the invention, the first component has a solids content of 40 to 55% (e.g., 40%, 45%, 50% or 55%) by weight. Preferably, the solids content of the first component is 45 to 50%.
The air-permeable and moisture-permeable aqueous polyurethane resin and the process for producing the same of the present invention will be described in detail with reference to the following specific examples.
Example 1
The raw materials of the first component in the breathable moisture-permeable waterborne polyurethane resin of the embodiment are shown in table 1, and the curing agent of the second component is XC-113 (which is a trifunctional aziridine crosslinking agent which does not contain any solvent and has a solid content of more than 99% and has a reaction equivalent of 166 with carboxyl) of shanghai zelong chemical industry.
Table 1 raw material of first component in breathable moisture-permeable aqueous polyurethane resin of example 1
| Raw materials | Dosage of |
| Polycarbonate diol (number average molecular weight 2000 g/mol) | 400kg |
| Isophorone diisocyanate | 70.78kg |
| 1, 4-butanediol | 0.34kg |
| Dimethylolpropionic acid | 4.81kg |
| Ethylenediamineethanesulfonic acid sodium salt | 2.92kg |
| Triethylamine | 7.25kg |
| Hydrazine hydrate | 1.75kg |
| Diethylenetriamine | 0.96kg |
| Polyethylene glycol (number average molecular weight 200 g/mol) | 14.92kg |
| Adipic acid | 10.92kg |
| Defoaming agent | 2.59kg |
The preparation method of the first component in the breathable and moisture-permeable aqueous polyurethane resin comprises the following steps:
(1) Preparation of alkyd resin: adding 14.92kg of polyethylene glycol and 10.92kg of adipic acid into a reaction kettle, introducing nitrogen while stirring, heating to 200 ℃ for reaction for 25 hours, and determining the acid value of the alkyd resin to be 15mgKOH/g to obtain the alkyd resin.
(2) Preparing a waterborne polyurethane prepolymer: adding 400kg of polycarbonate diol (the number average molecular weight is 2000 g/mol) and 70.87kg of isophorone diisocyanate into a reaction kettle, stirring uniformly, heating to 70 ℃ for reaction until the weight percentage content of-NCO is 2.12%, cooling to 60 ℃, adding 0.34kg of 1, 4-butanediol and 4.81kg of dimethylolpropionic acid, keeping the temperature of a reaction system at 65 ℃, reacting until the weight percentage content of-NCO is 1.37%, cooling to 40 ℃, adding acetone for dilution, wherein the adding amount of the acetone is 25% of the total mass of the added polycarbonate diol, isophorone diisocyanate, 1, 4-butanediol and dimethylolpropionic acid, stirring uniformly, dripping a 50% aqueous solution prepared from 2.92kg of ethylenediamine ethanesulfonic acid sodium salt, keeping the temperature for reaction for 20-30 min, stirring uniformly, adding 7.25kg of triethylamine, reacting for 20-30 min below 40 ℃, and stirring uniformly to obtain the aqueous polyurethane prepolymer.
(3) Preparation of alkyd resin modified aqueous polyurethane resin dispersion: adding acetone to dilute the polymer viscosity prepared in the step (2) to 300cps at 25 ℃, adding the alkyd resin prepared in the step (1), uniformly mixing, adding 416.30kg of water for emulsification, after emulsification for 10min, sequentially dripping 40% aqueous solution prepared from 1.75kg of hydrazine hydrate and 0.96kg of diethylenetriamine to react with residual-NCO in the system, adding 2.59kg of defoaming agent, and vacuumizing to remove acetone to obtain the alkyd resin modified waterborne polyurethane dispersion with the solid content of 55%.
When in use, the second component and-COOH in the synthesized first component are mixed according to the reaction equivalent ratio of 1.
Example 2
The raw materials of the first component in the breathable moisture-permeable waterborne polyurethane resin of the embodiment are shown in table 2, and the curing agent of the second component is XC-113 (which is a trifunctional aziridine crosslinking agent which does not contain any solvent and has a solid content of more than 99% and has a reaction equivalent of 166 with carboxyl) of shanghai zelong chemical industry.
Table 2 raw material of first component in breathable moisture-permeable aqueous polyurethane resin of example 2
The preparation method of the first component in the breathable and moisture-permeable aqueous polyurethane resin comprises the following steps:
(1) Preparation of alkyd resin: adding 126.66kg of polyethylene glycol (with the number average molecular weight of 400 g/mol), 50.90kg of adipic acid and 0.050kg of organic tin catalyst into a reaction kettle, introducing nitrogen while stirring, heating to 220 ℃ for reaction, wherein the reaction time is 28h, and determining the acid value of the alkyd resin to be 5mgKOH/g to prepare the alkyd resin;
(2) Preparing a waterborne polyurethane prepolymer: putting 400.00kg of polyoxypropylene glycol (with the number average molecular weight of 4000 g/mol), 172.36kg of isophorone diisocyanate, 32.60kg of hexamethylene diisocyanate and 0.13kg of organic tin catalyst into a reaction kettle, stirring uniformly, heating to 75 ℃ to react until the weight percentage content of-NCO is 12.07%, cooling to 65 ℃, adding 16.79kg of ethylene glycol and 8.47kg of dimethylolbutyric acid, keeping the temperature of a reaction system at 70 ℃, reacting to the weight percentage content of-NCO at 7.22%, cooling to 43 ℃, adding acetone for dilution, adding 10% of the total mass of the added polyoxypropylene glycol, isophorone diisocyanate, hexamethylene diisocyanate, ethylene glycol and dimethylolbutyric acid, stirring uniformly, dropping a prepolymer with the mass concentration of 50% prepared from 10.87kg of ethylenediamine sodium ethanesulfonate, keeping the prepolymer at 43 ℃ for reaction for 25min, stirring uniformly, adding 5.78kg of triethylamine, reacting for 20-30 min below 40 ℃, and stirring uniformly to obtain the waterborne polyurethane.
(3) Preparation of alkyd resin modified aqueous polyurethane resin dispersion: adding acetone to dilute the polymer viscosity prepared in the step (2) to 400cps at 25 ℃, adding the alkyd resin prepared in the step (1), uniformly mixing, adding 1228.72kg of water for emulsification, emulsifying for 10min, sequentially dripping 40% water solution prepared from 51.90kg of isophorone diamine and 9.34kg of diethylenetriamine, reacting with residual-NCO in the system, adding 1.78kg of defoaming agent, vacuumizing, and removing acetone to obtain the alkyd resin modified waterborne polyurethane resin with 40% of solid content.
When in use, the second component and-COOH in the synthesized first component are mixed according to the reaction equivalent ratio of 0.7 to 1, 100kg of the first component and 0.38kg of the second component are taken and uniformly mixed for use.
Example 3
The raw materials of the first component in the breathable and moisture-permeable aqueous polyurethane resin of this example are shown in table 3, and the second component curing agent is XC-113 (a trifunctional aziridine crosslinking agent which does not contain any solvent and has a solid content of more than 99% and a reaction equivalent of 166 with carboxyl) in shanghai zelong chemical industry.
Table 3 raw material of first component in breathable moisture-permeable aqueous polyurethane resin of example 3
| Raw materials | Amount of the composition |
| Polyoxypropylene diol (number average molecular weight 3000 g/mol) | 200.00kg |
| Polytetrahydrofuran diol (number average molecular weight 1000 g/mol) | 200.00kg |
| Methylene (methylene)Radical-dicyclohexyl-4, 4' -diisocyanate | 88.44kg |
| Isophorone diisocyanate | 74.94kg |
| 1, 6-hexanediol | 5.97kg |
| Dimethylolbutanoic acid | 15.43kg |
| Triethylamine | 15.81kg |
| Ethylene diamine | 7.28kg |
| Triethylene tetramine | 5.92kg |
| Polyethylene glycol (number average molecular weight 2000 g/mol) | 63.63kg |
| Adipic acid | 4.88kg |
| Organic bismuth catalyst | 0.070kg |
| Defoaming agent | 2.74kg |
The preparation method of the first component in the breathable and moisture-permeable waterborne polyurethane resin comprises the following steps:
(1) Preparation of alkyd resin: 63.63kg of polyethylene glycol (with the number average molecular weight of 2000 g/mol), 4.88kg of adipic acid and 0.035kg of organic bismuth catalyst are added into a reaction kettle, nitrogen is introduced while stirring, the temperature is raised to 240 ℃ for reaction, the reaction time is 30 hours, and the acid value of the alkyd resin is measured to be 10mgKOH/g, so that the alkyd resin is prepared.
(2) Preparing a waterborne polyurethane prepolymer: 200.00kg of polyoxypropylene glycol (with the number average molecular weight of 3000 g/mol), 200.00kg of polytetrahydrofuran glycol (with the number average molecular weight of 1000 g/mol), 74.94kg of isophorone diisocyanate, 88.44kg of methylene-dicyclohexyl-4, 4 '-diisocyanate and 0.035kg of organic bismuth catalyst are put into a reaction kettle, after uniform stirring, the temperature is increased to 80 ℃ for reaction until the weight percentage content of-NCO is 6.08%, the temperature is reduced to 70 ℃, 5.97kg of 1, 6-hexanediol and 15.43kg of dimethylolbutyric acid are added, the temperature of a reaction system is kept at 75 ℃, the reaction is carried out until the weight percentage content of-NCO is 3.63%, the temperature is reduced to 45 ℃, acetone is added for dilution, the addition amount of the acetone is 10% of the total mass of the added polyoxypropylene glycol, the polytetrahydrofuran glycol, the methylene-dicyclohexyl-4, 4' -diisocyanate, 1, 6-hexanediol and the dimethylolbutyric acid, and after uniform stirring, 15.81kg of triethylamine is added, the prepolymer is obtained after uniform stirring, the prepolymer is reacted at the temperature of below 40 ℃ for 30 min.
(3) Preparation of alkyd resin modified aqueous polyurethane resin dispersion: adding acetone to dilute the viscosity of the polymer prepared in the step (2) to 500cps at 25 ℃, adding the alkyd resin prepared in the step (1), uniformly mixing, adding 665.31g of water for emulsification, after emulsification for 10min, sequentially dripping 40% aqueous solution prepared from 7.28kg of ethylenediamine and 5.92kg of triethylene tetramine respectively to react with residual-NCO in the system, adding 2.74kg of defoaming agent, and vacuumizing to remove acetone to obtain the alkyd resin modified waterborne polyurethane resin with 50% of solid content.
When in use, the second component and-COOH in the synthesized first component are mixed according to the reaction equivalent ratio of 0.8 to 1, 100kg of the first component is taken, and 1.12kg of the second component is uniformly mixed for use.
Comparative example 1
The difference between the raw materials of the first component in the aqueous polyurethane resin of this comparative example and example 1 is that no alkyd resin is added in this comparative example, the molar ratio of triethylamine to-COOH in the aqueous polyurethane prepolymer is 1, and the raw materials are shown in table 4.
Table 4 raw material of first component in aqueous urethane resin of comparative example 1
| Raw materials | Dosage of |
| Polycarbonate diol (number average molecular weight 2000 g/mol) | 400kg |
| Isophorone diisocyanate | 70.78kg |
| 1, 4-butanediol | 0.34kg |
| Dimethylolpropionic acid | 4.81kg |
| Ethylenediamineethanesulfonic acid sodium salt | 2.92kg |
| Triethylamine | 3.63kg |
| Hydrazine hydrate | 1.75kg |
| Diethylenetriamine | 0.96kg |
| Defoaming agent | 2.44kg |
The preparation method of the first component in the breathable moisture-permeable aqueous polyurethane resin of the present comparative example comprises the following steps:
(1) Preparing a waterborne polyurethane prepolymer: adding 400kg of polycarbonate diol (the number average molecular weight is 2000 g/mol) and 70.87kg of isophorone diisocyanate into a reaction kettle, stirring uniformly, heating to 70-80 ℃ to react until the weight percentage content of-NCO is 2.12%, cooling to 60 ℃, adding 0.34kg of 1, 4-butanediol and 4.81kg of dimethylolpropionic acid, keeping the temperature of a reaction system at 65 ℃, reacting until the weight percentage content of-NCO is 1.37%, cooling to 40 ℃, adding acetone for dilution, adding 25% of the total mass of the added polycarbonate diol, isophorone diisocyanate, 1, 4-butanediol and dimethylolpropionic acid, stirring uniformly, dripping a 50% aqueous solution prepared from 2.92kg of ethylenediamine ethanesulfonic acid sodium salt, keeping the temperature for reaction for 20min, stirring uniformly, adding 3.63kg of triethylamine, reacting for 20min below 40 ℃, and stirring uniformly to obtain the aqueous polyurethane prepolymer.
(2) Preparing the waterborne polyurethane: adding acetone to dilute the viscosity of the waterborne polyurethane prepolymer prepared in the step (2) to 300cps at 25 ℃, adding 401.45kg of water to emulsify for 10 minutes, sequentially dripping 40% aqueous solution prepared from 1.75kg of hydrazine hydrate and 0.96kg of diethylenetriamine to react with residual-NCO in the system, adding 2.44kg of defoamer, and vacuumizing to remove acetone to obtain waterborne polyurethane with 55% of solid content.
Comparative example 2
The difference between the raw materials of the first component in the aqueous polyurethane resin of the comparative example and example 1 is that only polyethylene glycol is added to the aqueous polyurethane prepolymer of the comparative example, the molar ratio of triethylamine to-COOH in the aqueous polyurethane prepolymer is 1, and the raw materials are shown in table 5.
TABLE 5 raw material for first component in aqueous polyurethane resin of comparative example 2
| Starting materials | Dosage of |
| Polycarbonate diol (number average molecular weight 2000 g/mol) | 400kg |
| Isophorone diisocyanate | 70.78kg |
| 1, 4-butanediol | 0.34kg |
| Dimethylolpropionic acid | 4.81kg |
| Ethylenediamineethanesulfonic acid sodium salt | 2.92kg |
| Triethylamine | 7.25kg |
| Hydrazine hydrate | 1.75kg |
| Diethylenetriamine | 0.96kg |
| Polyethylene glycol (number average molecular weight 200 g/mol) | 14.92kg |
| Defoaming agent | 2.59kg |
The preparation method of the first component in the breathable moisture-permeable aqueous polyurethane resin of the present comparative example comprises the following steps:
(1) Preparing a waterborne polyurethane prepolymer: adding 400kg of polycarbonate diol (the number average molecular weight is 2000 g/mol) and 70.87kg of isophorone diisocyanate into a reaction kettle, stirring uniformly, heating to 70 ℃ for reaction until the weight percentage content of-NCO is 2.12%, cooling to 60 ℃, adding 0.34kg of 1, 4-butanediol and 4.81kg of dimethylolpropionic acid, keeping the temperature of a reaction system at 65 ℃, reacting until the weight percentage content of-NCO is 1.37%, cooling to 40 ℃, adding acetone for dilution, adding 25% of the added polycarbonate diol, isophorone diisocyanate, 1, 4-butanediol and dimethylolpropionic acid, stirring uniformly, dripping an aqueous solution which is prepared from 2.92kg of ethylenediamine ethanesulfonic acid sodium and has the mass concentration of 50%, keeping the temperature of 40 ℃ for reaction for 20min, stirring uniformly, adding 3.63kg of triethylamine, reacting for 20min below 40 ℃, and stirring uniformly to obtain the waterborne polyurethane prepolymer.
(2) Preparing the waterborne polyurethane: adding acetone to dilute the viscosity of the waterborne polyurethane prepolymer prepared in the step (2) to 300cps at 25 ℃, adding 14.92kg of polyethylene glycol, uniformly mixing, adding 410.20kg of water for emulsification, after emulsification for 10min, sequentially dripping 40% aqueous solution prepared from 1.75kg of hydrazine hydrate and 0.96kg of diethylenetriamine to react with residual-NCO in the system, adding 2.44kg of defoaming agent, and vacuumizing to remove acetone to obtain waterborne polyurethane with 55% of solid content.
The waterborne polyurethanes of examples 1-3 and comparative example 1 were tested for air and moisture permeability by the following methods:
the air and moisture permeability of the waterborne polyurethane is characterized by the moisture permeability of the coating, the moisture permeability of the coating is determined according to the method A in GB/T12704.2-2009 standard, and the determination temperature is 25 ℃.
Preparing a sample: preparing working slurry with viscosity of 9000-10000 cps/25 and solid content of 40% at DEG C according to the formula in Table 6 in examples 1-3 and comparative examples 1-2, removing bubbles in the working slurry under vacuum, uniformly coating the working slurry on a base cloth by using a wire rod with thickness of 0.09mm, drying in an oven at 120 ℃, taking out, cooling, and scraping once, wherein the coating weight of the working slurry is 100-150 g/m 2 。
Table 6 moisture permeability test formulations of examples 1-3 and comparative example 1
| Materials for use | Example 1 | EXAMPLE 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| PU (polyurethane) | 100kg | 100kg | 100kg | 100kg | 100kg |
| H 2 O | 37.5kg | 0 | 25kg | 37.5kg | 37.5kg |
| Crosslinking agent | 0.52kg | 0.38 | 1.12kg | / | / |
| BYK-349W | 1kg | 1kg | 1kg | 1kg | 1kg |
| HLD-9808A | Proper amount of | Proper amount of | Proper amount of | Proper amount of | Proper amount of |
In Table 6, BYK-349 is an aqueous wetting and leveling agent with a brand of German Bike, HLD-9808A is an aqueous thickener with a brand of Jiangxi Honglida
And (4) calculating a result: according to the formula
And (4) calculating.
In the formula: WVT-moisture permeability, unit is g/(m) 2 24 h); Δ m-two weighings at the beginning and at the end of the measurement of the same test assemblyThe difference, in g; a-effective test area in m 2 (ii) a t is the test time in h.
The test results are shown in table 7.
TABLE 7 moisture vapor transmission rate results for aqueous polyurethanes prepared in examples 1 to 3 and comparative examples 1 to 2
| Sample name | Moisture permeability/(m) 2 ·24h) |
| Example 1 | 290 |
| Example 2 | 686 |
| Example 3 | 320 |
| Comparative example 1 | 68 |
| Comparative example 2 | 320 |
As can be seen from the results in Table 7, the moisture permeability of the aqueous polyurethanes prepared in examples 1 to 3 of the present invention was higher than that of comparative example 1. Further, as can be seen from the raw materials for the preparation of comparative examples 1 to 3, the more the alkyd resin is added, the higher the moisture permeability of the aqueous polyurethane obtained therefrom.
The water resistance of the aqueous polyurethane obtained in examples 1 to 3 and comparative examples 1 to 2 was measured. And (3) testing water resistance: working slurries having a solids content of 40% were prepared according to the formulations in Table 7 for examples 1 to 3 and comparative examples 1 to 2.
TABLE 8 Water resistance test formulas of examples 1 to 3 and comparative examples 1 to 2
| Materials for use | Example 1 | EXAMPLE 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| PU (polyurethane) | 100kg | 100kg | 100kg | 100kg | 100kg |
| H 2 O | 37.5kg | 0 | 25kg | 37.5kg | 37.5kg |
| Crosslinking agent | 0.52kg | 0.38 | 1.12kg | / | / |
Drying the formulated aqueous emulsion working slurry to form a film, and weighing the mass (m) 1 ) Soaking the dry film in distilled water at room temperature for 2h, quickly removing water on the surface of the film by using filter paper, and weighing the mass (m) again 2 ) Calculating the water absorption, i.e.
TABLE 9 Water absorption results of the aqueous polyurethanes obtained in examples 1 to 3 and comparative examples 1 to 2
| Sample name | Water absorption/%) |
| Example 1 | 4.88％ |
| Example 2 | 5.88％ |
| Example 3 | 4.66％ |
| Comparative example 1 | 5.22％ |
| Comparative example 2 | 8.67％ |
As can be seen from the results in Table 9, in comparative example 2, since polyethylene glycol was directly added to the aqueous polyurethane emulsion, the water absorption was higher than that in examples 1 to 3 of the present invention, and the water resistance was poor.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The air-permeable and moisture-permeable aqueous polyurethane resin is characterized by comprising a first component and a second component, wherein the first component is an alkyd resin modified aqueous polyurethane resin dispersion, and the second component is a curing agent which reacts with carboxyl in the first component;
the first component comprises the following raw materials in parts by weight: 28.92-82.85 parts of oligomer polyol; isocyanate in 7.10-42.74 weight portions; 0-10.52 parts of glycol chain extender; 1.01 to 4.78 portions of hydrophilic chain extender; 0-4.82 parts of a salt forming agent; 0.33 to 13.31 portions of amine chain extender; 2.77-18.64 parts of polyethylene glycol; 0.34 to 8.91 portions of adipic acid; 0-0.02 part of catalyst; 0.2-0.5 part of defoaming agent;
the hydrophilic chain extender comprises a sulfonic acid hydrophilic chain extender and a carboxylic acid hydrophilic chain extender;
the second component is a polyfunctional aziridine and/or polycarbodiimide crosslinking agent;
the waterborne polyurethane resin dispersion modified by the alkyd resin as the first component in the breathable and moisture-permeable waterborne polyurethane resin is prepared by the following steps:
step one, preparing alkyd resin: mixing polyethylene glycol and adipic acid in an inert gas atmosphere, and heating to react to obtain alkyd resin;
step two, preparing a waterborne polyurethane prepolymer: mixing oligomer polyol and isocyanate, heating to react, reacting to a first theoretical isocyanate group content, cooling, adding a dihydric alcohol chain extender and a part of hydrophilic chain extender, continuing to react to a second theoretical isocyanate group content, cooling and diluting, adding the rest part of hydrophilic chain extender, reacting for a period of time, adding a salt forming agent, continuing to react for a period of time, and stirring uniformly to obtain the waterborne polyurethane prepolymer; wherein the first theoretical isocyanate group content and the second theoretical isocyanate group content are both the isocyanate group content when the hydroxyl group in the reaction system is reacted;
step three, preparing the alkyd resin modified waterborne polyurethane resin dispersion: diluting the waterborne polyurethane prepolymer obtained in the step two, adding the alkyd resin obtained in the step one, stirring, adding water for emulsification, adding an amine chain extender after emulsification, reacting with residual isocyanate groups in a system, adding a defoaming agent after reaction, and removing a solvent to obtain an alkyd resin modified waterborne polyurethane resin dispersion;
in the first step, the molar ratio of adipic acid to polyethylene glycol is 1-1.1; the acid value of the alkyd resin is 5-15 mgKOH/g.
2. The breathable moisture-permeable aqueous polyurethane resin according to claim 1, wherein the reaction equivalent ratio of the carboxyl groups in the second component to the carboxyl groups in the first component is 0.7 to 1.
3. The breathable, moisture-permeable aqueous polyurethane resin according to claim 1, wherein the polyethylene glycol has a number average molecular weight of 200 to 2000g/mol and a functionality of 2.
4. The breathable, moisture-permeable aqueous polyurethane resin according to claim 3, wherein said oligomeric polyol is at least one of polyether polyol, polyester polyol and polycarbonate polyol, and has a number average molecular weight of 1000 to 4000g/mol and a functionality of 2;
the isocyanate is at least one of 4, 4-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and xylylene diisocyanate;
the dihydric alcohol chain extender is at least one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol and diethylene glycol;
the sulfonic acid hydrophilic chain extender is ethylenediamine ethanesulfonic acid sodium salt, and the carboxylic acid hydrophilic chain extender is dimethylolpropionic acid and/or dimethylolbutyric acid;
the salt forming agent is triethylamine;
the catalyst is at least one of organic titanium, organic tin and organic bismuth;
the amine chain extender is at least one of hydrazine hydrate, ethylenediamine, isophoronediamine, diethylenetriamine and triethylene tetramine.
5. The breathable moisture-permeable aqueous polyurethane resin according to claim 1, wherein the first step is to add polyethylene glycol and adipic acid into a reaction kettle, introduce nitrogen while stirring, raise the temperature to 200-240 ℃ and react for 25-30 h to obtain the alkyd resin.
6. The breathable moisture-permeable aqueous polyurethane resin according to claim 5, wherein in the first step, a catalyst is further added to the reaction vessel.
7. The breathable moisture-permeable aqueous polyurethane resin according to claim 1, wherein the second step is to put oligomer polyol and isocyanate into a reaction kettle, stir the mixture uniformly, heat the mixture to 70-80 ℃ for reaction, cool the mixture to 60-70 ℃ after the first theoretical isocyanate group content is reached, add glycol chain extender and carboxylic acid hydrophilic chain extender, keep the temperature of the reaction system at 65-75 ℃ for reaction to the second theoretical isocyanate group content, cool the mixture to 40-45 ℃, add acetone for dilution, add acetone in an amount of 10-25% of the total mass of the oligomer polyol, isocyanate, hydrophilic chain extender and glycol chain extender, stir the mixture uniformly, drop aqueous solution of sulfonic acid hydrophilic chain extender with a mass concentration of 50%, keep the temperature at 40-45 ℃ for reaction for 20-30 min, add salt former after the mixture is stirred uniformly, react for 20-30 min at a temperature below 40 ℃, and stir the mixture uniformly to obtain the aqueous polyurethane prepolymer.
8. The breathable and moisture-permeable aqueous polyurethane resin according to claim 7, wherein in the second step, the molar ratio of isocyanate groups to hydroxyl groups in the added raw materials is 1.25 to 1; the molar ratio of the salt forming agent to the carboxyl in the waterborne polyurethane prepolymer is 1-2.
9. The breathable moisture-permeable aqueous polyurethane resin according to claim 8, wherein in the second step, a catalyst is further added to the raw materials in the reaction vessel.
10. The breathable moisture-permeable aqueous polyurethane resin according to claim 1, wherein the third step is to dilute the aqueous polyurethane prepolymer obtained in the second step with acetone to a viscosity of 300-500 cps at 25 ℃, add the alkyd resin obtained in the first step, stir for 10-20 min, add water to emulsify, add amine chain extender after emulsifying for 5-10 min to react with residual isocyanate groups in the system, add a defoamer after reaction, and remove acetone to obtain the alkyd resin modified aqueous polyurethane resin dispersion.
11. The breathable moisture-permeable aqueous polyurethane resin according to claim 10, wherein in step three, the alkyd resin is added in an amount of 5 to 20% by weight of the aqueous polyurethane dispersion.
12. The air-permeable and moisture-permeable aqueous polyurethane resin according to claim 11, wherein in step three, the molar ratio of the number of moles of amino groups in the amine chain extender to the number of moles of the isocyanate groups remaining in the aqueous polyurethane prepolymer is 0.7 to 0.9.
13. The breathable, moisture-permeable aqueous polyurethane resin according to any one of claims 1 to 12, wherein the first component has a solid content of 40 to 55% by weight.
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