CN121136009A - A waterborne polyurethane resin, its preparation method and application - Google Patents
A waterborne polyurethane resin, its preparation method and applicationInfo
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- CN121136009A CN121136009A CN202511686330.5A CN202511686330A CN121136009A CN 121136009 A CN121136009 A CN 121136009A CN 202511686330 A CN202511686330 A CN 202511686330A CN 121136009 A CN121136009 A CN 121136009A
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Abstract
本发明提供一种水性聚氨酯树脂及其制备方法和应用，所述水性聚氨酯树脂原料包括以下质量分数的组分：多元醇20%～30%，异氰酸酯8%～15%，小分子二元醇0.2%～1%，羧酸型亲水扩链剂0.8%～1.5%，催化剂0.005%～0.015%，中和剂0.5%～1.5%，后扩链剂0.3%～1%，水60%～65%。本发明通过引入兼具碳酸酯结构单元与环氧乙烷片段的特殊二元醇AK‑011，显著降低了乳液的粘度。粘度的有效控制，使得体系可引入更多亲水链段，使得胶膜具备优异的透湿性与高静水压值，实现了透湿与防水性能的高度平衡。This invention provides a waterborne polyurethane resin, its preparation method, and its applications. The waterborne polyurethane resin raw material comprises the following components by mass fraction: 20%–30% polyol, 8%–15% isocyanate, 0.2%–1% small molecule diol, 0.8%–1.5% carboxylic acid-type hydrophilic chain extender, 0.005%–0.015% catalyst, 0.5%–1.5% neutralizing agent, 0.3%–1% post-chain extender, and 60%–65% water. This invention significantly reduces the viscosity of the emulsion by introducing a special diol AK-011, which combines carbonate structural units and ethylene oxide segments. Effective viscosity control allows for the introduction of more hydrophilic segments into the system, resulting in a film with excellent moisture permeability and high hydrostatic pressure, achieving a high balance between moisture permeability and waterproofing performance.
Description
Technical Field
The invention belongs to the technical field of polyurethane resin, and relates to aqueous polyurethane resin, and a preparation method and application thereof.
Background
The aqueous polyurethane (WPU) has wide application in the fields of textile coating, leather finishing, adhesive and the like due to the advantages of environmental protection, safety and the like. Particularly in the field of functional fabrics, waterproof moisture-permeable waterborne polyurethane is favored.
The production of most waterproof and moisture permeable products on the market still depends on solvent polyurethane resin, which is often accompanied by environmental protection problems and health hazard caused by organic solvent residues. Several types of water-proof moisture-permeable products made of aqueous polyurethane resins are described in the literature. It is generally necessary to introduce a large amount of hydrophilic segments (such as polyethylene glycol PEG) to maintain high moisture permeability thereof, but the hydrophilic segments easily form crystalline domains, thereby causing problems of poor emulsion stability, high viscosity, and even gelation, affecting the overall properties of the resin product. To solve this problem, it is necessary to reduce the solid content or introduce expensive modifiers, which further increases the cost.
At present, CN 109134804A discloses an aqueous polyurethane dispersion, and by introducing a multi-functionality polyether polyol with a star structure, the system viscosity is effectively controlled while the content of hydrophilic groups is ensured, and the crosslinking density and strength of a coating are improved. The hydrostatic pressure of the obtained coating can reach 7000 mm water column, and the water vapor permeability exceeds 10,000 g/m2/24h. However, this method relies on star polyether polyols having a functionality of not less than 3, and is limited in raw material sources and high in cost.
CN113061227B provides a waterproof moisture permeable aqueous polyurethane resin, achieving higher solids content by incorporating poly (ethoxy-alkoxy) diol, but still having a higher emulsion viscosity (20,000~50,000 mPa s), which can present stability problems during storage and construction.
Therefore, in the art, development of an aqueous polyurethane resin having high waterproof and moisture permeability is still an important point of research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the water-based polyurethane resin with high waterproof and moisture permeability, and the preparation method and the application thereof.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the invention provides an aqueous polyurethane resin, wherein the preparation raw materials of the aqueous polyurethane resin comprise the following components in percentage by mass:
20% -30% of polyalcohol,
8% -15% Of isocyanate,
0.2 To 1 percent of small molecular dihydric alcohol,
0.8 To 1.5 percent of carboxylic acid type hydrophilic chain extender,
0.005-0.015 Percent of catalyst,
0.5 To 1.5 percent of neutralizer,
0.3 To 1 percent of rear chain extender,
60% -65% Of water;
the polyols include polyether diols and other polyether diols having carbonate structural units and ethylene oxide segments.
In the present invention, the amount of the polyhydric alcohol used in the aqueous polyurethane resin may be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc.
In the present invention, the amount of isocyanate used in the aqueous polyurethane resin may be 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.
In the invention, the amount of the small molecular dihydric alcohol in the aqueous polyurethane resin can be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% and the like.
In the present invention, the amount of the carboxylic acid type hydrophilic chain extender used in the aqueous polyurethane resin may be 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% or the like.
In the present invention, the amount of the catalyst used in the aqueous polyurethane resin may be 0.005%, 0.007%, 0.009%, 0.01%, 0.011%, 0.012%, 0.013%, 0.014%, 0.015%, etc.
In the present invention, the amount of the neutralizing agent used in the aqueous polyurethane resin may be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc.
In the present invention, the amount of the rear chain extender used in the aqueous polyurethane resin may be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.
In the present invention, the amount of water used in the aqueous polyurethane resin may be 60%, 60.5%, 61%, 62%, 62.5%, 63%, 63.5%, 64%, 65%, etc.
In the present invention, the content of the polyether glycol having a carbonate structural unit and an ethylene oxide segment is 20 to 35% (e.g., 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, etc.), and the content of the other polyether glycol is 65 to 80% (e.g., 65%, 66%, 67%, 68%, 69%, 70%, 73%, 75%, 78%, 80%, etc.), based on 100% of the total weight of the polyol.
In the present invention, the polyether diol having carbonate structural units and ethylene oxide segments and other polyether diols are exemplified by DuranolTMAK-011, duranolTMPCDX-176, duranolTMAK021E, etc. Further preferably DuranolTMAK-011 (a random copolymer of a carbonate structural unit and ethylene oxide, a hydroxyl value of 100 to 120 mgKOH/g, a number average molecular weight of 1000, a functionality of 2, asahi chemical Co., ltd.).
Preferably, the other polyether glycol comprises one or a combination of at least two of polyethylene glycol, polytetrahydrofuran glycol, polycaprolactone glycol, polycarbonate glycol and polypropylene glycol, and more preferably one or a combination of two of polyethylene glycol and polytetrahydrofuran glycol.
Preferably, the number average molecular weight of the other polyether glycol is 1000 to 3000 (e.g., 1000, 1200, 1500, 1800, 2200, 2500, 2700, 3000, etc.), more preferably 1800 to 2200 (e.g., 1800, 1850, 1900, 1950, 2000, 2050, 2100, 2150, 2200, etc.).
Preferably, the isocyanate is selected from one or a combination of at least two of 1, 4-benzene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1, 4-cyclohexyl diisocyanate, preferably one or a combination of at least two of isophorone diisocyanate, dicyclohexylmethane diisocyanate or 1, 4-cyclohexyl diisocyanate, most preferably dicyclohexylmethane diisocyanate.
Preferably, the small molecular dihydric alcohol is any one or a combination of at least two of propylene glycol, ethylene glycol, diethylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol or 1, 6-hexanediol, and further preferably ethylene glycol or diethylene glycol.
Preferably, the carboxylic acid type hydrophilic chain extender is 2,2' -dimethylolpropionic acid (DMPA) and/or 2,2' -dimethylolbutyric acid, preferably 2,2' -dimethylolpropionic acid.
Preferably, the catalyst is an organobismuth based catalyst.
Preferably, the neutralizing agent is any one or a combination of at least two of ammonia water, diethylamine or triethylamine, preferably triethylamine.
Preferably, the rear chain extender is one or a combination of at least two of ethylenediamine, hexamethylenediamine or isophorone diamine, preferably ethylenediamine.
In a second aspect, the present invention provides a method for preparing the aqueous polyurethane resin as described above, comprising the steps of:
A. Mixing polyol and isocyanate for reaction;
B. then adding a catalyst, a carboxylic acid type hydrophilic chain extender, small molecular dihydric alcohol and a solvent into the reaction system of the step A, and reacting to obtain an NCO-terminated prepolymer;
C. adding solvent into the prepolymer obtained in the step B, stirring uniformly, adding neutralizing agent, stirring and reacting to form salt;
D. and C, adding a post-chain extender into the non-chain-extended emulsion obtained in the step C, reacting, and removing the solvent to obtain the waterborne polyurethane resin.
In the preparation method of the aqueous polyurethane resin, the reaction temperature in the step A is 75-85 ℃ (such as 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃ and the like) and the reaction time is 0.5-1.5 hours (such as 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, 1.2 hour, 1.3 hour, 1.4 hour, 1.5 hour and the like).
Preferably, the temperature of the reaction in step B is 80-90 ℃ (e.g. 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, etc.), and the reaction is carried out until the NCO value is 1.5% -2.5% (e.g. 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, etc.), preferably 1.8% -2.1% of the total mass of the prepolymer.
Preferably, the solvent in step C is acetone.
Preferably, the temperature of the system is controlled to be 30-40 ℃ before the neutralizing agent is added in the step C (such as 30 ℃, 31 ℃, 32 ℃, 33 ℃,34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃ and the like).
Preferably, the temperature in the step C is reduced to 20-25 ℃ (e.g. 20 ℃, 20.5 ℃,21 ℃, 21.5 ℃,22 ℃, 22.5 ℃,23 ℃, 23.5 ℃,24 ℃, 24.5 ℃,25 ℃, etc.).
Preferably, the water added in the step C is 3-15 ℃ water (such as 3 ℃,4 ℃,5 ℃,6 ℃, 7 ℃,8 ℃, 9 ℃,10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃,15 ℃ and the like).
Preferably, the temperature of the reaction in the step D is 20-30 ℃ (e.g. 20 ℃, 22 ℃, 25 ℃, 28 ℃, or 30 ℃) and the reaction time is 20-60 min (e.g. 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc.).
Preferably, the solvent removed in step D is removed under vacuum at a temperature of 40 to 50 ℃ (e.g. 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃,50 ℃, etc.).
Preferably, the solid content of the obtained aqueous polyurethane resin is 30-40% (such as 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%).
In another aspect, the invention provides the use of the aqueous polyurethane resin as described above in a facing.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, by introducing the special dihydric alcohol AK-011 with both the carbonate structural unit and the ethylene oxide segment, the viscosity of the emulsion is obviously reduced, so that more hydrophilic chain segments can be introduced into the system, and the adhesive film has excellent moisture permeability (50,000-60,000 g/m2.24h) and high hydrostatic pressure value (more than or equal to 9000mm water column) at the same time, and the high balance of moisture permeability and waterproof performance is realized.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The sources of the raw materials in the following examples are as follows:
PTMG2000: phosphor chemical (Jiaxing) Co., ltd;
PEG2000, PPG2000, jiangsu province sea-An petrochemical plant;
AK-011, PCDX176,176, AK-021E, asahi Kasei Chemicals Co., ltd;
HMDI, vancomic chemistry;
DMPA, cortex Cupressi Setariae.
Example 1
Stirring and mixing 110 g PTMG2000, 96 g PEG2000, 66 g AK-011 and 135 g HMDI (4, 4 '-dicyclohexylmethane diisocyanate) uniformly, heating to 78-82 ℃ for reaction for 1h, cooling to 45 ℃, adding 13 g DMPA (2, 2' -dimethylolpropionic acid), 6.9 g ethylene glycol, 0.3 g organic bismuth catalyst (organic bismuth MB 20) and 146 g acetone into the prepolymer, reacting for 4h at 80-85 ℃, sampling from a sampling port, titrating the content of residual isocyanate by adopting a di-n-butylamine method, obtaining prepolymer after reaching the standard of theoretical NCO value test (1.97 percent of total mass fraction), adding 376 g acetone into the prepolymer, stirring for 10min to obtain a homogeneous prepolymer solution, controlling the temperature to be 33-37 ℃, adding 11 g neutralizing agent triethylamine, stirring for 5min, cooling to 20-22 ℃, adding 5-10 g water for emulsification within 2-3 min, adding water for emulsifying within 1-800 ℃ for 5-2 min, adding water for amplifying the aqueous chain emulsion under the conditions of 2-37 ℃ until the water is not heated to 5-09 Mpa, stirring to obtain the aqueous polyurethane resin, and removing the aqueous polyurethane resin after the aqueous solution is subjected to vacuum amplification.
Example 2
Uniformly stirring and mixing 110 g of PTMG2000, 96 g of PEG2000, 86 g of AK-011 and 135 g of HMDI, heating to 78-82 ℃ for reaction for 1h, cooling to 50 ℃, adding 13 g of DMPA, 5.6 g of ethylene glycol, 0.3 g of organic bismuth catalyst (organic bismuth MB 20) and 90 g of acetone into the prepolymer, reacting for 4h at 80-85 ℃, sampling from a sampling port, titrating the content of residual isocyanate by adopting a di-n-butylamine method until the theoretical NCO value is tested to be qualified (1.95% of the total mass fraction), obtaining a prepolymer, adding 410 g of acetone into the prepolymer, stirring for 10min to obtain a homogeneous prepolymer solution, controlling the temperature to be 33-37 ℃, adding 11 g of neutralizing agent triethylamine, stirring for 5min, cooling to 20-22 ℃, adding 800 g of water at 5-10 ℃ for emulsification, adding 5g of aqueous solution of ethylenediamine into the unexpanded chain emulsion in 1-2 min, stirring for reaction, heating to 30 Mpa until the aqueous solution is removed under the condition that the temperature is 45-37 ℃ and the aqueous polyurethane resin is removed.
Example 3
Uniformly stirring and mixing 110 g of PTMG2000, 96 g of PEG2000, 46 g of AK-011 and 135 g of HMDI, heating to 78-82 ℃ for reaction for 1h, cooling to 30 ℃, adding 13 g of DMPA, 8.1 g of ethylene glycol, 0.3 g of organic bismuth catalyst (organic bismuth MB 20) and 90 g of acetone into the prepolymer, reacting for 4h at 80-85 ℃, sampling from a sampling port, titrating the content of residual isocyanate by adopting a di-n-butylamine method until the theoretical NCO value is tested to be qualified (1.95% of the total mass fraction), obtaining a prepolymer, adding 410 g of acetone into the prepolymer, stirring for 10min to obtain a homogeneous prepolymer solution, controlling the temperature to be 33-37 ℃, adding 11 g of neutralizing agent triethylamine, stirring for 5min, cooling to 20-22 ℃, adding 800 g of water at 5-10 ℃ for emulsification, adding 5g of aqueous solution of ethylenediamine into the unexpanded chain emulsion in 1-2 min, stirring for reaction, heating to 45-0.09 MPa, and removing the aqueous polyurethane resin.
Example 4
110 G of PTMG2000, 96 g of PEG2000, 66 g of PCDX-176 and 135 g of HMDI (4, 4 '-dicyclohexylmethane diisocyanate) are stirred and mixed uniformly and heated to 78-82 ℃ for reaction for 1h, the temperature is reduced to 45 ℃,13 g of DMPA (2, 2' -dimethylolpropionic acid), 6.9 g of ethylene glycol, 0.3 g of organic bismuth catalyst (organic bismuth MB 20) and 146 g of acetone are added into a prepolymer, after reaction for 4h at the temperature of 80-85 ℃, sampling is carried out through a sampling port, the content of residual isocyanate is titrated by adopting a di-n-butylamine method, the content of residual isocyanate is tested to be qualified (1.97 percent of the total mass fraction), the prepolymer is obtained, the acetone is added into the prepolymer, stirring is carried out for 10min, the homogeneous prepolymer solution is obtained, the temperature is kept at 33-37 ℃, the neutralizing agent triethylamine is added into the prepolymer, stirring is carried out for 5min, the temperature is reduced to 20-22 ℃, 5-10 g of water is added into the prepolymer, emulsifying solution is carried out in 2-3 min, the aqueous emulsion is added into the aqueous emulsion at the temperature of 5-10 ℃ for emulsification, the aqueous emulsion is heated to 1-30 Mpa, the aqueous emulsion is not heated until the aqueous emulsion is heated to 30 Mpa is obtained, and the aqueous emulsion is dehydrated, and the aqueous emulsion is dehydrated under the conditions of the conditions is heated to 30min conditions, and the conditions of the aqueous solution is heated to be dehydrated, and the aqueous solution is heated.
Example 5
Stirring and mixing 110 g PTMG2000, 96 g PEG2000, 66 g AK-021E and 135 g HMDI (4, 4 '-dicyclohexylmethane diisocyanate) uniformly, heating to 78-82 ℃, reacting for 1h, cooling to 45 ℃, adding 13 g DMPA (2, 2' -dimethylolpropionic acid), 8.2 g ethylene glycol, 0.3 g organic bismuth catalyst (organic bismuth MB 20) and 147 g acetone into the prepolymer, reacting for 4h at 80-85 ℃, sampling from a sampling port, titrating the residual isocyanate content by adopting a di-n-butylamine method, obtaining a prepolymer with a theoretical NCO value qualified test (accounting for 1.97% of the total mass fraction), adding 378 g acetone into the prepolymer, stirring for 10min, controlling the temperature to be 33-37 ℃, adding 11 g neutralizer triethylamine, stirring for 5min, cooling to 20-22 ℃, adding 800-5 g water for 2-3 min, emulsifying the aqueous diamine at 1-10 ℃ for 1 Mpa-30 min, heating to obtain an emulsion, stirring to remove the aqueous emulsion, and removing the aqueous emulsion, namely, heating to 30 Mpa, and stirring to obtain the aqueous polyurethane emulsion.
Example 6
Stirring and mixing 110 g PTMG2000, 96 g PEG2000, 66 g AK-011 and 114 g IPDI (isophorone diisocyanate) uniformly, heating to 78-82 ℃ for reaction for 1h, cooling to 45 ℃, adding 13 g DMPA (2, 2' -dimethylolpropionic acid), 6.9 g ethylene glycol, 0.3 g organic bismuth catalyst (organic bismuth MB 20) and 139 g acetone into the prepolymer, reacting for 4h at 80-85 ℃, sampling from a sampling port, titrating the content of residual isocyanate by a di-n-butylamine method until the content reaches the theoretical NCO value, namely 2.07 percent of the total mass fraction, obtaining the prepolymer, adding 358 g acetone into the prepolymer, stirring for 10min to obtain a homogeneous prepolymer solution, controlling the temperature to be 33-37 ℃, adding 11g neutralizing agent triethylamine, stirring for 5min, adding 800 g water at 5-10 ℃ within 2-3 min, emulsifying, adding the water at 5-10 g in 2-2 min, stirring for 5-2 m, adding the ethylene diamine which is not subjected to the amplification reaction until the aqueous solution is subjected to vacuum amplification for 30min, and removing the aqueous polyurethane resin solution after the temperature is raised to 5-22 min.
Example 7
110 G of PPG2000, 96 g of PEG2000, 66 g of AK-011 and 135 g of HMDI (4, 4 '-dicyclohexylmethane diisocyanate) are stirred and mixed uniformly and heated to 78-82 ℃ for reaction for 1h, the temperature is reduced to 45 ℃, 13 g of DMPA (2, 2' -dimethylolpropionic acid), 6.9 g of ethylene glycol, 0.3 g of organic bismuth catalyst (organic bismuth MB 20) and 146 g of acetone are added into a prepolymer, after reaction for 4h at the temperature of 80-85 ℃, sampling is carried out through a sampling port, the residual isocyanate content is titrated by adopting a di-n-butylamine method, the content of the residual isocyanate is tested to be qualified (1.97 percent of the total mass fraction) by adopting the theoretical NCO value, a homogeneous prepolymer solution is obtained, 376 g of acetone is added into the prepolymer, stirring is carried out for 10min, the temperature is controlled to be kept at 33-37 ℃, 11 g of neutralizing agent triethylamine is added, stirring is carried out for 5min, cooling is carried out to 20-22 ℃, 5-10 g of water is added into 2-3 min for emulsification, 1-800 g of water is added into the aqueous emulsion, the aqueous polyurethane resin is not subjected to expansion for 5-800 min, the aqueous polyurethane resin is removed after the aqueous polyurethane resin is heated to 30min, and the aqueous polyurethane resin is removed.
Example 8
Stirring and mixing 110 g PTMG2000, 96 g PEG2000, 66 g AK-011 and 135 g HMDI (4, 4 '-dicyclohexylmethane diisocyanate) uniformly, heating to 78-82 ℃ for reaction for 1h, cooling to 45 ℃, adding 13 g DMPA (2, 2' -dimethylolpropionic acid), 13 g 1, 6-hexanediol, 0.3 g organic bismuth catalyst (organic bismuth MB 20) and 148 g acetone into the prepolymer, reacting for 4h at 80-85 ℃, sampling from a sampling port, titrating the residual isocyanate content by adopting a di-n-butylamine method until the theoretical NCO value is tested to be qualified (1.95 percent of the total mass fraction), obtaining a prepolymer solution, adding acetone into the prepolymer, stirring for 10min, controlling the temperature to be 33-37 ℃, adding triethylamine serving as a neutralizer, stirring for 5min, cooling to 20-22 ℃, adding water of 800-10 g for emulsification in 2-3 min, carrying out emulsification in the water of 1-10 ℃ for 5-2 min, adding ethylene diamine into the water of 2-3 ℃ for emulsion, heating to the water-30 min, and removing the aqueous emulsion, namely, stirring to obtain the aqueous polyurethane resin emulsion, wherein the aqueous polyurethane emulsion is obtained after the water-expansion is heated to 30 min.
Comparative example 1
243 G of PTMG2000, 96 g of PEG2000 and 135 g of HMDI are stirred and mixed uniformly and heated to 78-82 ℃ for reaction for 1h, cooled to 30-50 ℃, 13 g of DMPA, 6.9 g of ethylene glycol, 0.3 g of organic bismuth catalyst (organic bismuth MB 20) and 90 g of acetone are added into the prepolymer for reaction for 4h at 80-85 ℃, sampling is carried out through a sampling port, titration is carried out by adopting a di-n-butylamine method to test the content of residual isocyanate until the theoretical NCO value is tested to be qualified (1.95% of the total mass fraction), a prepolymer is obtained, 410 g of acetone is added into the prepolymer, stirring is carried out for 10min to obtain a homogeneous prepolymer solution, the temperature is kept at 33-37 ℃, 11 g of neutralizing agent triethylamine is added, stirring is carried out for 5min, cooling is carried out to 20-22 ℃, 950 g of water at 5-10 ℃ is added into the prepolymer for emulsification within 2-3 min, 5g of aqueous solution of ethylenediamine is added into the unexpanded chain emulsion for reaction for 30min, stirring is carried out, and then the prepolymer is subjected to vacuum removal of acetone at 45-0.09 ℃ under the conditions of 45 MPa.
Comparative example 2
Mixing 110 g PTMG2000, 96 g PEG2000, 66 g polyhexamethylene carbonate glycol (PHCD-1000) and 135 g HMDI, stirring and mixing uniformly, heating to 78-82 ℃, reacting for 1h, cooling to 45 ℃, adding 13 g DMPA, 6.9 g ethylene glycol, 0.3 g organobismuth catalyst (organobismuth MB 20) and 90g acetone into the prepolymer, reacting for 4h at 80-85 ℃, sampling from a sampling port, titrating the content of residual isocyanate by a di-n-butylamine method until the theoretical NCO value is qualified (accounting for 1.95% of the total mass fraction), obtaining a prepolymer, adding 410 g acetone into the prepolymer, stirring for 10min to obtain a homogeneous prepolymer solution, controlling the temperature to be 33-37 ℃, adding 11 g neutralizing agent triethylamine, stirring for 5min, cooling to 20-22 ℃, adding 800 g water at 5-10 ℃ in 2-2 min for emulsification, adding 5g ethylene diamine into the unexpanded chain, heating to 45-30.09 ℃ for reacting under vacuum, and removing the aqueous solution after the temperature is raised to 1-2 min.
Performance test in the water-proof moisture-permeable aqueous polyurethane resin, a thickening agent and 0.2% of a leveling agent are added, and the viscosity (25 ℃) is regulated to be about 2000-2500 cp under mechanical stirring. And (3) doctor-coating the prepared resin on release paper with a doctor blade to form a film, and placing the film in an 80 ℃ oven for drying for 5-10 min, and then continuously drying for 2-5 min at 120 ℃. Then, a resin film with waterproof and moisture permeability is obtained, and the thickness is 0.025-0.03 mm.
After the aqueous polyurethane resin of examples 1 to 3 was formed into a film in the above manner, the mechanical properties thereof were tested with reference to GB/T19250-2013, and the test results are shown in Table 1.
After the aqueous polyurethane resins of examples 1 to 8 were formed into films, the moisture permeability and the hydrostatic pressure were measured with reference to JIS L1099 B1 and GB/T4744-2013, respectively, and the measurement results are shown in Table 1.
Table 1 results of Performance test of aqueous polyurethane resins of examples 1 to 8 and comparative examples 1 to 2
According to the data of Table 1, examples 1-3 successfully prepared high performance waterborne polyurethane resins by introducing polyether glycol AK-011 containing a carbonate structural unit and ethylene oxide in random/block copolymerization. Compared with the comparative example, the process remarkably reduces the viscosity of the emulsion, wherein the viscosity can be controlled to be 2000-5000 mPas (Brookfield viscometer, 25 ℃) in the range of 30% -40% of solid content, and the viscosity is far superior to that of a comparative example sample with gelation.
Polyether diols PCDX-176 and AK-021E having similar structures are used in examples 4-5, respectively, and the system also shows suitable viscosity and has good moisture permeability and hydrostatic pressure.
In addition, in examples 6 to 8, the isocyanate was replaced with IPDI, the polyol was replaced with PPG2000, and the small molecule chain extender was replaced with 1, 6-hexanediol, respectively, the prepared emulsion still maintained a proper viscosity, and the film moisture permeability and hydrostatic pressure were at good levels.
The effective control of the viscosity enables the system to introduce more hydrophilic groups, the final adhesive film shows excellent comprehensive performance, the moisture permeability reaches 50000-60000 g/(m2.24h), and the hydrostatic pressure is not lower than 9000 mm water column.
Comparative example 1 used only polyethylene glycol and polytetrahydrofuran ether glycol, with no AK-011 added. Because of the excessive content of polyethylene glycol and the increase of crystal micro-areas, the phase transition is incomplete in the emulsification process, the emulsion is in a microgel state, and forms jelly after acetone removal, so that a usable product cannot be obtained.
Comparative example 2 uses polyhexamethylene carbonate diol of the same molecular weight instead of AK-011, and also fails to complete the phase transition, and finally forms a jelly shape also in the desolvation stage, failing to prepare.
The applicant states that the present invention is described by way of the above examples as an aqueous polyurethane resin having high water and moisture permeability, and a method for preparing the same and application thereof, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The preparation method of the aqueous polyurethane resin is characterized by comprising the following components in percentage by mass:
20% -30% of polyalcohol,
8% -15% Of isocyanate,
0.2 To 1 percent of small molecular dihydric alcohol,
0.8 To 1.5 percent of carboxylic acid type hydrophilic chain extender,
0.005-0.015 Percent of catalyst,
0.5 To 1.5 percent of neutralizer,
0.3 To 1 percent of rear chain extender,
60% -65% Of water;
the polyols include polyether diols and other polyether diols having carbonate structural units and ethylene oxide segments.
2. The aqueous polyurethane resin according to claim 1, wherein the polyether glycol having a carbonate structural unit and an ethylene oxide segment is contained in an amount of 20 to 35% and the other polyether glycol is contained in an amount of 65 to 75% based on 100% by weight of the total polyol.
3. The aqueous polyurethane resin according to claim 1, wherein the other polyether glycol comprises one or a combination of at least two of polyethylene glycol, polytetrahydrofuran glycol, polycaprolactone glycol, polycarbonate glycol, polypropylene glycol;
The number average molecular weight of the other polyether glycol is 1000-3000.
4. The aqueous polyurethane resin according to claim 1, wherein the isocyanate is selected from one or a combination of at least two of 1, 4-phenylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and 1, 4-cyclohexyl diisocyanate.
5. The aqueous polyurethane resin according to claim 1, wherein the small molecule diol is any one or a combination of at least two of propylene glycol, ethylene glycol, diethylene glycol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, or 1, 6-hexanediol.
6. The aqueous polyurethane resin according to claim 1, wherein the carboxylic acid type hydrophilic chain extender is 2,2 '-dimethylolpropionic acid and/or 2,2' -dimethylolbutyric acid.
7. The aqueous polyurethane resin according to claim 1, wherein the catalyst is an organobismuth-based catalyst;
the neutralizer is any one or the combination of at least two of ammonia water, diethylamine or triethylamine;
The rear chain extender is one or a combination of at least two of ethylenediamine, hexamethylenediamine or isophorone diamine.
8. The method for producing an aqueous polyurethane resin according to any one of claims 1 to 7, characterized in that the method comprises the steps of:
A. Mixing polyol and isocyanate for reaction;
B. then adding a catalyst, a carboxylic acid type hydrophilic chain extender, small molecular dihydric alcohol and a solvent into the reaction system of the step A, and reacting to obtain an NCO-terminated prepolymer;
C. adding solvent into the prepolymer obtained in the step B, stirring uniformly, adding neutralizing agent, stirring and reacting to form salt;
D. and C, adding a post-chain extender into the non-chain-extended emulsion obtained in the step C, reacting, and removing the solvent to obtain the waterborne polyurethane resin.
9. The method according to claim 8, wherein the reaction temperature in the step a is 75-85 ℃ and the reaction time is 0.5-1.5 hours;
the temperature of the reaction in the step B is 80-90 ℃, and the NCO value is 1.5-2.5% of the total mass of the prepolymer;
the solvent in the step C is acetone;
Controlling the temperature of the system to be 30-40 ℃ before adding the neutralizer;
the temperature is reduced to 20-25 ℃ in the step C;
the added water in the step C is water with the temperature of 3-15 ℃;
the temperature of the reaction in the step D is 20-30 ℃ and the reaction time is 20-60 min;
Step D, removing the solvent at the temperature of 40-50 ℃ in a vacuumizing way;
The solid content of the prepared aqueous polyurethane resin is 30-40%.
10. Use of the aqueous polyurethane resin according to any one of claims 1 to 7 in a facing.
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| CN202511686330.5A CN121136009A (en) | 2025-11-18 | 2025-11-18 | A waterborne polyurethane resin, its preparation method and application |
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| CN202511686330.5A CN121136009A (en) | 2025-11-18 | 2025-11-18 | A waterborne polyurethane resin, its preparation method and application |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629402A (en) * | 1991-08-01 | 1997-05-13 | Bayer Aktiengesellschaft | Coating compositions and their use for the preparation of coatings permeable to water vapor |
| CN103910864A (en) * | 2013-01-09 | 2014-07-09 | 万华化学集团股份有限公司 | Preparation method for block oligomeric dihydric alcohol with controllable structure |
| CN115279810A (en) * | 2020-04-07 | 2022-11-01 | 科思创德国股份有限公司 | Cold-stable NCO prepolymers, method for the production thereof and use thereof |
| US20250115710A1 (en) * | 2022-06-24 | 2025-04-10 | Asahi Kasei Kabushiki Kaisha | Oxyethylene structure-containing polycarbonate polyol and use thereof |
-
2025
- 2025-11-18 CN CN202511686330.5A patent/CN121136009A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629402A (en) * | 1991-08-01 | 1997-05-13 | Bayer Aktiengesellschaft | Coating compositions and their use for the preparation of coatings permeable to water vapor |
| CN103910864A (en) * | 2013-01-09 | 2014-07-09 | 万华化学集团股份有限公司 | Preparation method for block oligomeric dihydric alcohol with controllable structure |
| CN115279810A (en) * | 2020-04-07 | 2022-11-01 | 科思创德国股份有限公司 | Cold-stable NCO prepolymers, method for the production thereof and use thereof |
| US20250115710A1 (en) * | 2022-06-24 | 2025-04-10 | Asahi Kasei Kabushiki Kaisha | Oxyethylene structure-containing polycarbonate polyol and use thereof |
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