CN113621304A - Self-extinction waterborne polyurethane resin and preparation method thereof - Google Patents

Self-extinction waterborne polyurethane resin and preparation method thereof Download PDF

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Publication number
CN113621304A
CN113621304A CN202110899883.4A CN202110899883A CN113621304A CN 113621304 A CN113621304 A CN 113621304A CN 202110899883 A CN202110899883 A CN 202110899883A CN 113621304 A CN113621304 A CN 113621304A
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Prior art keywords
polyurethane emulsion
mixed solution
aqueous polyurethane
chain extender
parts
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CN202110899883.4A
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CN113621304B (en
Inventor
纪尚超
石磊
徐欣欣
沈连根
王伟
李寿伟
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ZHEJIANG HEXIN TECHNOLOGY CO LTD
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ZHEJIANG HEXIN TECHNOLOGY CO LTD
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
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Abstract

The application relates to the field of polyurethane resin manufacturing technology, and particularly discloses a self-extinction aqueous polyurethane resin and a preparation method thereof. A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the waterborne polyurethane emulsion A is prepared from the following raw materials in parts by weight: 200-400 parts of high-crystallinity polyol, 65-90 parts of toluene diisocyanate, 16-105 parts of chain extender and 500-600 parts of deionized water; the aqueous polyurethane emulsion B is prepared from the following raw materials in parts by weight: 200-400 parts of polyether polyol, 5-100 parts of graft polyol, 50-300 parts of aliphatic diisocyanate, 16-130 parts of chain extender and 500-600 parts of deionized water. The polyurethane has the advantage of improving the extinction property and the wear resistance of the waterborne polyurethane under the condition of not adding extinction powder.

Description

Self-extinction waterborne polyurethane resin and preparation method thereof
Technical Field
The application relates to the technical field of polyurethane resin manufacturing, in particular to self-extinction aqueous polyurethane resin and a preparation method thereof.
Background
The water-based polyurethane is a polyurethane using water as a solvent, is commonly used in different fields of clothes, furniture, interior decoration and the like, and along with the development of the society, the requirements of people on the surface effect of clothes and decoration are more and more diversified, and in order to create a simple and elegant style, the surface of the clothes and decoration needs to be subjected to extinction treatment.
In order to endow clothes and ornaments with a simple and elegant surface effect, matting powder is generally added into polyurethane, the matting powder is used as an inorganic powder filler, the inorganic powder filler can only disperse and dissolve in the polyurethane, after the waterborne polyurethane containing the matting powder forms a film on the surfaces of the clothes and ornaments, the matting powder can form uneven particles on the surfaces of the clothes and ornaments, and light irradiates the uneven surfaces to form diffuse reflection, so that the matting effect is achieved.
When a matting agent is added to polyurethane, the matting agent corresponds to islands in water, whereas polyurethane resin corresponds to water, the islands block water, and the fluidity of polyurethane becomes poor with the increase of matting agent, and the formed coating film is more likely to be broken or shed.
Aiming at the related technologies, the inventor thinks that the flatting powder is used as a filler incompatible with polyurethane, the flatting powder is easy to fall off, and the flatting property, the wear resistance and the smoothness of the polyurethane can be reduced, which brings many limitations to the popularization and the application of the matte waterborne polyurethane.
Disclosure of Invention
In order to improve the extinction property and the wear resistance of the waterborne polyurethane without adding extinction powder, the application provides a self-extinction waterborne polyurethane resin and a preparation method thereof.
In a first aspect, the present application provides a self-extinction aqueous polyurethane resin, which adopts the following technical scheme:
a self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds;
the waterborne polyurethane emulsion A is prepared from the following raw materials in parts by weight:
Figure BDA0003199384720000011
the aqueous polyurethane emulsion B is prepared from the following raw materials in parts by weight:
Figure BDA0003199384720000021
by adopting the technical scheme, because the compatibility of the toluene diisocyanate and the aliphatic diisocyanate is poor, the polyurethane emulsion A and the aqueous polyurethane emulsion B adopt polyols with different polarities, the polyether polyol and the aqueous polyurethane emulsion A have excellent compatibility, and the graft polyol is incompatible with the aqueous polyurethane emulsion A, so that the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B have compatible sections and incompatible sections, thermodynamic incompatibility exists between the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B, the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B have different film forming speeds, films with complete intersolubility cannot be formed after the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B are compounded, but the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B respectively have independence on a microscopic level, namely the film surfaces formed after the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B are compounded have unevenness on a microscopic level, and the matte effect can be achieved without adding matting powder, in addition, the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B are both polyurethane systems, have certain similarity in structure, and have certain compatibility with each other, so that the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B can form a film with good physical properties through intermolecular interaction, and the extinction property, the wear resistance and the slip property of the aqueous polyurethane are comprehensively improved.
Preferably, the polyether polyol is at least one of polytetrahydrofuran glycol and polypropylene glycol; the graft polyol is at least one of polyester graft polyol and polyether graft polyol;
the polyester grafted polyalcohol is styrene grafted polyethylene glycol adipate glycol diethylene glycol diol;
the polyether graft polyalcohol is prepared by graft copolymerization of polyether, styrene and acrylonitrile.
By adopting the technical scheme, products prepared from different polyether polyols have different extinction properties, and the extinction property of the product prepared from polytetrahydrofuran glycol is superior to that of the product prepared from polypropylene glycol; the effects achieved by different graft polyols are different, and the wear resistance of products prepared from polyester graft polyols is better than that of products prepared from polyether graft polyols, but the delustering property of products prepared from polyether graft polyols is better than that of products prepared from polyester graft polyols.
Preferably, the high-crystallinity polyol has a molecular weight of 1000-4000 g/mol, and is at least one of polyethylene glycol adipate glycol, polyethylene-1, 4-butanediol adipate glycol, polyethylene-1, 6-hexanediol adipate glycol, polyethylene glycol sebacate glycol, polyethylene-1, 4-butanediol sebacate glycol, polyethylene-1, 6-hexanediol sebacate glycol, polycarbonate polyol and polycaprolactone diol.
By adopting the technical scheme, different high-crystallinity polyols have different weather resistance and extinction property; polycarbonate polyol and polycaprolactone diol are generally adopted for preparing high-end products, high-crystallinity polyol used for the high-end products can endow the products with excellent extinction effect but has generally higher price, poly-1, 4-butanediol adipate diol, poly-1, 6-hexanediol adipate diol and poly-ethylene glycol adipate diol can be selected for the common products, although the high-crystallinity polyol used for the common products has lower price and can endow the products with excellent extinction effect, the extinction effect of the products prepared from the high-crystallinity polyol used for the common products is poorer than that of the products prepared from the high-crystallinity polyol used for the high-end products; although the extinction effect of the polyethylene glycol sebacate diol, the polyethylene glycol sebacate-1, 4-butanediol sebacate diol and the polyethylene glycol sebacate-1, 6-hexanediol sebacate diol is lower than that of high-crystallinity polyols used for common products, the products can have excellent anti-aging effect, and the anti-aging effect of the products prepared from the three polyethylene glycol sebacate diols is better than that of the products prepared from the high-crystallinity polyols used for high-end products; different high-crystallinity polyols are compounded, so that the ageing resistance, the wear resistance and the extinction effect of the product can be comprehensively improved.
Preferably, the chain extender in the aqueous polyurethane emulsion A comprises a linear chain extender with the molecular weight of 60-300 g/mol, and the linear chain extender is at least one of diol and diamine;
the chain extender in the waterborne polyurethane emulsion B comprises a chain extender containing a branched chain, and the chain extender containing the branched chain is at least one of 1, 2-propylene glycol, 1, 3-butanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol and neopentyl glycol.
By adopting the technical scheme, the glycol and the diamine both have hydrophilic groups to achieve excellent chain extender effect, the diamine can be added to improve the heat resistance of the product, the common chain extender used for the waterborne polyurethane emulsion B is a common chain extender containing a branched chain, and the crystallinity of the waterborne polyurethane emulsion B is reduced by adding the common chain extender containing the branched chain.
Preferably, the chain extender in the aqueous polyurethane emulsion a further comprises a linear diamine chain extender, wherein the linear diamine chain extender is one of ethylenediamine, hydrazine hydrate, 1, 4-butanediamine and 1, 6-hexanediamine;
the chain extender in the aqueous polyurethane emulsion B also comprises a diamine chain extender containing a branched chain, wherein the diamine chain extender containing the branched chain is at least one of isophorone diamine, 2, 6-toluene diamine, diethyl toluene diamine, 4' -methylene bis (2, 6-diethylaniline) and 4, 4-methylene bis (2-ethylaniline).
By adopting the technical scheme, as the diamine chain extender and the diamine chain extender are adopted for post chain extension, strong-polarity urea bond structures can be introduced into the obtained aqueous polyurethane emulsion A and aqueous polyurethane emulsion B, so that the aging resistance and the mechanical property of the product prepared by the method are improved; the aqueous polyurethane emulsion A adopts a linear diamine chain extender, and the aqueous polyurethane emulsion B adopts a diamine chain extender containing a branched chain, so that the crystallinity difference between the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B is further increased, and in addition, after the aqueous polyurethane emulsion B is compounded with the diamine chain extender containing the branched chain, the crystallinity of the aqueous polyurethane emulsion B can be further reduced, so that the crystallinity difference between the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B is further increased, and the extinction effect of the application is comprehensively enhanced.
Preferably, the chain extender in the aqueous polyurethane emulsion A and the chain extender in the aqueous polyurethane emulsion B both contain hydrophilic chain extenders, and the hydrophilic chain extenders are at least one of Ymer N120, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, ethylenediamine ethanesulfonic acid sodium salt, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt, 2, 4-diaminobenzene sulfonic acid sodium salt and diaminobutanesulfonic acid.
By adopting the technical scheme, the hydrophilic chain extender can endow the hydrophilic groups to the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B, so that the compatibility between the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B and water is enhanced; the polarity of the 2, 2-dimethylolpropionic acid, the 2, 2-dimethylolbutyric acid and the diaminobutanesulfonic acid is higher than that of other hydrophilic chain extenders, so that the 2, 2-dimethylolpropionic acid, the 2, 2-dimethylolbutyric acid and the diaminobutanesulfonic acid are used in an aqueous polyurethane emulsion A system, and other hydrophilic chain extenders are used in an aqueous polyurethane emulsion B system, so that the polarity difference between the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B can be further increased, and a better light extinction effect is achieved; when the waterborne polyurethane emulsion A system and the waterborne polyurethane emulsion B system both use the hydrophilic chain extenders with lower polarity, such as Ymer N120, N-bis (2-hydroxyethyl) -2-aminoethyl sulfonate and 2, 4-diaminobenzene sodium sulfonate, the compatibility between the waterborne polyurethane emulsion A and the waterborne polyurethane emulsion B can be improved, so that the wear resistance of the product prepared by the method is improved; therefore, the hydrophilic chain extenders with different polarities are compounded and used for the aqueous polyurethane emulsion A system and the aqueous polyurethane emulsion B system, and the compatible section and the incompatible section of the polyurethane emulsion A and the aqueous polyurethane emulsion B can be increased, so that the wear resistance and the extinction effect of the polyurethane emulsion are comprehensively improved.
Preferably, the aqueous polyurethane emulsion B further comprises 0.5-3 parts of a cross-linking agent, wherein the cross-linking agent is at least one of trimethylolpropane, triethanolamine, glycerol, castor oil and HPAE.
By adopting the technical scheme, the crystallinity of the aqueous polyurethane emulsion B can be further reduced by adding the cross-linking agent into the aqueous polyurethane emulsion B, so that the crystallinity difference between the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B is further increased, in addition, the HPAE is a hydroxyl-terminated branched poly (amine-ester), and the HPAE has a large number of active end groups, so that the HPAE has good compatibility with other components in the aqueous polyurethane emulsion B, and in addition, due to the unique three-dimensional shape-obtaining structure of the HPAE, the fluidity and the mechanical property of the aqueous polyurethane emulsion B can be improved while the cross-linking degree of the aqueous polyurethane emulsion B is increased, the compatibility between the aqueous polyurethane emulsion B and the aqueous polyurethane emulsion A is increased, so that the extinction effect and the mechanical property of the product prepared by the method are comprehensively enhanced.
In a second aspect, the present application provides a method for preparing a self-extinction aqueous polyurethane resin, which adopts the following technical scheme: a preparation method of self-extinction waterborne polyurethane resin comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively, and adding other auxiliaries when preparing the waterborne polyurethane emulsion A and the waterborne polyurethane emulsion B, wherein the other auxiliaries comprise one or more of a surfactant, an antioxidant, an ultraviolet absorbent, a weather-resistant stabilizer and a water-proofing agent;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1-9: 1-9, and mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
By adopting the technical scheme, different compounding ratios of the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B can also influence the extinction effect and the mechanical property of the product; in addition, other adjuvants are typically added or compounded selectively according to the needs of the customer.
Preferably, in step S1, the aqueous polyurethane emulsion a is prepared by the following steps:
s31, dehydrating the high-crystallinity polyol for 1-2 hours under reduced pressure at the temperature of 110-120 ℃;
s32, adjusting the temperature to 65-75 ℃, adding a linear chain extender and toluene diisocyanate into the high-crystallinity polyol subjected to decompression and dehydration, and uniformly mixing and stirring to obtain a mixed solution A1;
s33, adding a catalyst into the mixed solution A1 or adding a mixed solution of the catalyst and other auxiliaries into the mixed solution A1, adjusting the temperature to 70-90 ℃, and reacting for 2-4 hours to obtain a mixed solution A2, wherein the catalyst is one of stannous octoate and bismuth carboxylate; s34, adding a hydrophilic chain extender into the reacted mixed solution A2, controlling the temperature to be 70-80 ℃, and reacting for 2-4 hours to obtain a mixed solution A3;
s35, adding acetone into the mixed solution A3 for dilution, adjusting the temperature to be below 50 ℃, adding triethylamine, and reacting for 5-15 min to obtain a mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 with deionized water uniformly, adding a linear diamine chain extender, mixing and stirring for 1-2 h to obtain a mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain the aqueous polyurethane emulsion A.
By adopting the technical scheme, the high-crystallinity polyol is purified by performing reduced pressure dehydration at 110-120 ℃; the mixed solution A1 has good reaction activity, so that the chain extension reaction can be carried out at 70-80 ℃; the compatibility between the mixed solution A3 and the system can be enhanced by diluting with acetone, so that the subsequent reaction is facilitated to obtain the mixed solution A4; the catalytic effect of stannous octoate is better than that of bismuth carboxylate, but bismuth carboxylate is more environment-friendly, and stannous octoate is not environment-friendly and has certain harm to human bodies, and is generally selected according to the requirements of customers; in addition, because the mixed solution A3 reacts with water at high temperature, by reducing the temperature, byproducts can be reduced, the product purity can be improved, and the compatibility between the mixed solution A3 diluted by acetone and water can be promoted by adding triethylamine; thereby further improving the matting property, weather resistance and abrasion resistance of the product.
Preferably, the aqueous polyurethane emulsion B in step S1 is prepared by the steps comprising:
s41, dehydrating polyether glycol and graft polyol under reduced pressure at 110-120 ℃ for 1-2 h to obtain an alcohol mixed solution;
s42, adjusting the temperature to 65-75 ℃, adding a chain extender containing a branched chain and aliphatic diisocyanate into the alcohol mixed solution after decompression and dehydration, and uniformly mixing and stirring to obtain a mixed solution B1, wherein the aliphatic diisocyanate is at least one of 4, 4-dicyclohexylmethane diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate;
s43, adding a catalyst into the mixed liquid B1 or adding a mixed liquid of the catalyst and other auxiliaries into the mixed liquid B1, adjusting the temperature to be 80-95 ℃, and reacting for 2-4 hours to obtain a mixed liquid B2, wherein the catalyst comprises stannous octoate or bismuth carboxylate; s44, adding a cross-linking agent and a hydrophilic chain extender into the reacted mixed solution B2, controlling the temperature to be 70-80 ℃, and reacting for 2-4 hours to obtain a mixed solution B3;
s45, adding acetone into the mixed solution B3 for dilution, adjusting the temperature to be below 50 ℃, adding triethylamine, and reacting for 5-15 min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly by using deionized water, adding a diamine chain extender containing branched chains, mixing and stirring for 1-2 h to obtain a mixed solution B5;
s47, removing acetone in the mixed solution B5 under reduced pressure to obtain the aqueous polyurethane emulsion B.
By adopting the technical scheme, 4-dicyclohexyl methane diisocyanate has excellent crystallization property, so that the product prepared by adopting 4, 4-dicyclohexyl methane diisocyanate has better transparency, isophorone diisocyanate is noncrystalline aliphatic diisocyanate, and the reaction speed is high, so that isophorone diisocyanate is adopted for processing, the processing efficiency is higher, but the transparency of the product is lower, the product prepared by adopting 1, 6-hexamethylene diisocyanate has better light stability, and generally can be selected or compounded according to different requirements of customers on the product, and in addition, the reaction activity of the mixed solution B1 is lower than that of the mixed solution A, so that the temperature needs to be controlled to be 80-95 ℃ for reacting for 2-4 hours.
In summary, the present application has the following beneficial effects:
1. the polyurethane emulsion is prepared from a water-based polyurethane emulsion A and a water-based polyurethane emulsion B, and the polyurethane emulsion A and the water-based polyurethane emulsion B are polyurethane systems and have certain similarity in structure, so that the polyurethane emulsion A and the water-based polyurethane emulsion B have certain compatibility with each other; and the polyurethane emulsion A and the waterborne polyurethane emulsion B adopt polyols with different polarities, and the compatibility of the adopted isocyanate is poor, so that the polyurethane emulsion A and the waterborne polyurethane emulsion B have different film forming speeds, and the film surface formed by compounding the polyurethane emulsion A and the waterborne polyurethane emulsion B has microscopically unevenness, thereby improving the extinction property, the wear resistance and the smoothness of the waterborne polyurethane under the condition of not adding extinction powder.
2. According to the method, different common chain extenders and diamine chain extenders are adopted to prepare the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B, so that the crystallinity difference between the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B is increased, and the extinction effect of the method is further enhanced.
3. According to the method, the high-purity and good-stability aqueous polyurethane emulsion A and aqueous polyurethane emulsion B are prepared by adjusting the reaction temperature and limiting the adding sequence of different chain extenders and solvents, and then the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B with different film forming speeds are compounded according to different proportions, so that the extinction effect and the mechanical property of the polyurethane paint are comprehensively improved.
Detailed Description
The present application is described in further detail below.
Raw materials
Table 1 source table of raw materials used in the present application
Figure BDA0003199384720000071
Figure BDA0003199384720000081
Figure BDA0003199384720000091
Examples
Example 1
A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the amount of the raw materials used in the aqueous polyurethane emulsion a in this example is specifically shown in table 2; the amounts of the raw materials used in the aqueous polyurethane emulsion B of this example are specified in Table 3.
TABLE 2 dosage of raw materials for the aqueous polyurethane emulsion A in example 1
Figure BDA0003199384720000092
Figure BDA0003199384720000101
TABLE 3 dosage of raw materials for the aqueous polyurethane emulsion B in example 1
Figure BDA0003199384720000102
A preparation method of self-extinction waterborne polyurethane resin specifically comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively;
the waterborne polyurethane emulsion A is prepared by the following steps:
s31, dehydrating 300g of poly adipic acid-1, 4-butanediol ester diol under reduced pressure for 2h at the temperature of 110 ℃;
s32, adjusting the temperature to 70 ℃, adding 9g of 1, 4-butanediol into the decompressed and dehydrated poly adipic acid-1, 4-butanediol diol, mixing and stirring uniformly at the rotating speed of 45rpm, adding 48.7g of toluene diisocyanate, mixing and stirring uniformly to obtain a mixed solution A1;
s33, adding 0.03g of stannous octoate and 0.03g of antioxidant 1010 into the mixed solution A1, adjusting the temperature to 80 ℃, and reacting for 2 hours to obtain mixed solution A2;
s34, adding 12g of 2, 4-diaminobenzene sodium sulfonate into the reacted mixed solution A2, controlling the temperature at 70 ℃, and reacting for 2 hours to obtain a mixed solution A3;
s35, adding 35g of acetone into the mixed solution A3 for dilution, adjusting the temperature to 50 ℃, adding 6g of triethylamine for reaction for 10min to obtain mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 by 600g of deionized water in a high-speed shearing machine at the rotating speed of 2000rpm uniformly, adding 3g of ethylenediamine, mixing and stirring for 1h to obtain mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain aqueous polyurethane emulsion A with the solid content of 40.8%;
the waterborne polyurethane emulsion B is prepared by the following steps:
s41, dehydrating 200g of polypropylene glycol and 100g of polyester graft polyol for 2 hours at 110 ℃ under reduced pressure to obtain an alcohol mixed solution;
s42, adjusting the temperature to 70 ℃, adding 10.4g of neopentyl glycol into the alcohol mixed solution after decompression and dehydration, mixing and stirring uniformly at the rotating speed of 45rpm, adding 68.5g of isophorone diisocyanate, mixing and stirring uniformly to obtain a mixed solution B1;
s43, adding 0.02g of stannous octoate and 0.03g of antioxidant 1010 into the mixed solution B1, adjusting the temperature to 95 ℃, and reacting for 4 hours to obtain mixed solution B2;
s44, adding 3.7g of 2, 2-dimethylolbutyric acid, 20g of ethylenediamine ethanesulfonic acid sodium salt and 0.5g of trimethylolpropane into the reacted mixed solution B2, controlling the temperature at 80 ℃, and reacting for 3 hours to obtain a mixed solution B3;
s45, adding 35g of acetone into the mixed solution B3 for dilution, adjusting the temperature to 50 ℃, adding 6.6g of triethylamine, and reacting for 10min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly in a high-speed shearing machine by 550g of deionized water at the rotating speed of 2000rpm, adding 17g of isophorone diamine, mixing and stirring for 1h to obtain a mixed solution B5;
s47, removing acetone in the mixed solution B5 under reduced pressure to obtain aqueous polyurethane emulsion B with solid content of 44%;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1:1, mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
Example 2
A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the amount of the raw materials used in the aqueous polyurethane emulsion A in this example is specifically shown in Table 4; the amounts of the raw materials used in the aqueous polyurethane emulsion B in this example are specified in Table 5.
TABLE 4 dosage of raw materials for the aqueous polyurethane emulsion A of example 2
Figure BDA0003199384720000111
Figure BDA0003199384720000121
TABLE 5 dosage of raw materials for the aqueous polyurethane emulsion B of example 2
Figure BDA0003199384720000122
A preparation method of self-extinction waterborne polyurethane resin specifically comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively;
the waterborne polyurethane emulsion A is prepared by the following steps:
s31, dehydrating 200g of poly adipic acid-1, 6-hexanediol glycol under reduced pressure for 2h at 110 ℃;
s32, adjusting the temperature to 70 ℃, adding 9g of 1, 6-hexanediol into the decompressed and dehydrated poly adipic acid-1, 6-hexanediol glycol, uniformly mixing and stirring at the rotating speed of 45rpm, adding 69.6g of toluene diisocyanate, and uniformly mixing and stirring to obtain a mixed solution A1;
s33, adding 0.02g of bismuth carboxylate and 0.03g of antioxidant 1076 into the mixed solution A1, adjusting the temperature to 80 ℃, and reacting for 3 hours to obtain mixed solution A2;
s34, adding 15g of YmerN120 and 3g of 2, 2-dimethylolpropionic acid into the reacted mixed solution A2, controlling the temperature at 70 ℃, and reacting for 2 hours to obtain mixed solution A3;
s35, adding 40g of acetone into the mixed solution A3 for dilution, adjusting the temperature to 50 ℃, adding 2.2g of triethylamine for reaction for 10min to obtain mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 uniformly by 600g of deionized water in a high-speed shearing machine at the rotating speed of 2000rpm, adding 5g of hydrazine hydrate, mixing and stirring for 1h to obtain mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain aqueous polyurethane emulsion A with the solid content of 35.7%;
the waterborne polyurethane emulsion B is prepared by the following steps:
s41, dehydrating 400g of polypropylene glycol and 60g of polyether graft polyol for 2 hours at 110 ℃ under reduced pressure to obtain an alcohol mixed solution; s42, adjusting the temperature to 70 ℃, adding 31.5g of 1, 3-butanediol into the alcohol mixed solution after decompression and dehydration, mixing and stirring uniformly at the rotating speed of 45rpm, adding 205.8g of 4,4' -dicyclohexylmethane diisocyanate, mixing and stirring uniformly to obtain a mixed solution B1;
s43, adding 0.02g of stannous octoate and 0.03g of triphenyl phosphite into the mixed solution B1, adjusting the temperature to 93 ℃, and reacting for 3 hours to obtain mixed solution B2;
s44, adding 3.7g of 2, 2-dimethylolbutyric acid, 20g of ethylenediamine ethanesulfonic acid sodium salt and 0.5g of glycerol into the reacted mixed solution B2, controlling the temperature at 80 ℃, and reacting for 2.5 hours to obtain a mixed solution B3;
s45, adding 50g of acetone into the mixed solution B3 for dilution, adjusting the temperature to 50 ℃, adding 9.6g of triethylamine, and reacting for 10min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly in a high-speed shearing machine by 900g of deionized water at the rotating speed of 2000rpm, adding 12.2g of 2, 6-toluenediamine, mixing and stirring for 1h to obtain a mixed solution B5;
s47, removing acetone in the mixed solution B5 under reduced pressure to obtain aqueous polyurethane emulsion B with the solid content of 43.6%;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1:1, mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
Example 3
A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the amount of the raw materials used in the aqueous polyurethane emulsion A in this example is specifically shown in Table 6; the amounts of the raw materials used in the aqueous polyurethane emulsion B in this example are specified in Table 7.
TABLE 6 dosage of raw materials for the aqueous polyurethane emulsion A in example 3
Figure BDA0003199384720000141
TABLE 7 dosage of raw materials for aqueous polyurethane emulsion B in example 3
Figure BDA0003199384720000142
Figure BDA0003199384720000151
A preparation method of self-extinction waterborne polyurethane resin specifically comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively;
the waterborne polyurethane emulsion A is prepared by the following steps:
s31, dehydrating 200g of poly adipic acid-1, 6-hexanediol glycol under reduced pressure for 2h at 110 ℃;
s32, adjusting the temperature to 70 ℃, adding 9.3g of ethylene glycol into the decompressed and dehydrated poly adipic acid-1, 6-hexanediol glycol, uniformly mixing and stirring at the rotating speed of 45rpm, adding 87g of toluene diisocyanate, and uniformly mixing and stirring to obtain a mixed solution A1;
s33, adding 0.02g of bismuth carboxylate and 0.03g of antioxidant 1076 into the mixed solution A1, adjusting the temperature to 80 ℃, and reacting for 3 hours to obtain mixed solution A2;
s34, adding 23.5g of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 3g of 2, 2-dimethylolpropionic acid into the reacted mixed solution A2, controlling the temperature at 70 ℃, and reacting for 3 hours to obtain a mixed solution A3;
s35, adding 40g of acetone into the mixed solution A3 for dilution, adjusting the temperature to 50 ℃, adding 4.2g of triethylamine, and reacting for 10min to obtain a mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 by 600g of deionized water in a high-speed shearing machine at the rotating speed of 2000rpm uniformly, adding 8.8g of 1, 4-butanediamine, mixing and stirring for 1h to obtain mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain aqueous polyurethane emulsion A with the solid content of 34.3%;
the waterborne polyurethane emulsion B is prepared by the following steps:
s41, dehydrating 200g of polypropylene glycol, 100g of polytetrahydrofuran diol and 60g of polyether graft polyol for 2 hours at 110 ℃ under reduced pressure to obtain an alcohol mixed solution;
s42, adjusting the temperature to 70 ℃, adding 13.5g of 2-methyl-1, 3-propylene glycol into the alcohol mixed solution after decompression and dehydration, mixing and stirring uniformly at the rotating speed of 45rpm, adding 68.4g of 4,4' -dicyclohexylmethane diisocyanate and 65.8g of 1, 6-hexamethylene diisocyanate, mixing and stirring uniformly to obtain mixed solution B1;
s43, adding 0.02g of stannous octoate and 0.03g of triphenyl phosphite into the mixed solution B1, adjusting the temperature to 95 ℃, and reacting for 4 hours to obtain mixed solution B2;
s44, adding 30g of 2, 2-dimethylolbutyric acid, 20g of sodium ethylenediamine ethanesulfonate and 0.8g of triethanolamine into the reacted mixed solution B2, controlling the temperature to be 80 ℃, and reacting for 3 hours to obtain a mixed solution B3;
s45, adding 50g of acetone into the mixed solution B3 for dilution, adjusting the temperature to 50 ℃, adding 6.2g of triethylamine, and reacting for 10min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly in a high-speed shearing machine by using 700g of deionized water at the rotating speed of 2000rpm, adding 17.8g of diethyl toluenediamine, mixing and stirring for 1h to obtain a mixed solution B5;
s47, removing acetone in the system from the mixed solution B5 under reduced pressure to obtain aqueous polyurethane emulsion B;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1:1, mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
Example 4
A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the amount of the raw materials used in the aqueous polyurethane emulsion A in this example is specifically shown in Table 8; the amounts of the raw materials used in the aqueous polyurethane emulsion B in this example are specified in Table 9.
TABLE 8 dosage of raw materials for the aqueous polyurethane emulsion A in example 4
Figure BDA0003199384720000161
TABLE 9 dosage of raw materials for the aqueous polyurethane emulsion B in example 4
Figure BDA0003199384720000162
Figure BDA0003199384720000171
A preparation method of self-extinction waterborne polyurethane resin specifically comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively;
the waterborne polyurethane emulsion A is prepared by the following steps:
s31, dehydrating 200g of poly-sebacic acid 1, 4-butanediol ester diol under reduced pressure for 2h at the temperature of 110 ℃;
s32, adjusting the temperature to 70 ℃, adding 6.1g of monoethanolamine into the decompressed and dehydrated 1, 4-butanediol polysebacate diol, uniformly mixing and stirring at the rotating speed of 45rpm, adding 75g of toluene diisocyanate, and uniformly mixing and stirring to obtain a mixed solution A1;
s33, adding 0.02g of bismuth carboxylate, 0.03g of antioxidant 1076 and 0.02g of triphenyl phosphite into the mixed solution A1, adjusting the temperature to 80 ℃, and reacting for 2 hours to obtain mixed solution A2;
s34, adding 9g of 2, 2-dimethylolpropionic acid into the reacted mixed solution A2, controlling the temperature at 70 ℃, and reacting for 2 hours to obtain a mixed solution A3;
s35, adding 70g of acetone into the mixed solution A3 for dilution, adjusting the temperature to 50 ℃, adding 6.1g of triethylamine, and reacting for 10min to obtain a mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 by 500g of deionized water in a high-speed shearing machine at the rotating speed of 2000rpm uniformly, adding 8g of ethylenediamine, mixing and stirring for 1h to obtain mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain an aqueous polyurethane emulsion A;
the waterborne polyurethane emulsion B is prepared by the following steps:
s41, dehydrating 200g of polypropylene glycol, 100g of polytetrahydrofuran diol and 80g of polyester graft polyol for 2 hours at 110 ℃ under reduced pressure to obtain an alcohol mixed solution;
s42, adjusting the temperature to 70 ℃, adding 24g of neopentyl glycol into the alcohol mixed solution after decompression and dehydration, uniformly mixing and stirring at the rotating speed of 45rpm, adding 112g of isophorone diisocyanate and 117g of 4,4' -dicyclohexylmethane diisocyanate, uniformly mixing and stirring to obtain a mixed solution B1;
s43, adding 0.02g of stannous octoate and 0.03g of triphenyl phosphite into the mixed solution B1, adjusting the temperature to 95 ℃, and reacting for 4 hours to obtain mixed solution B2;
s44, adding 30g of 2, 2-dimethylolpropionic acid and 0.9g of trimethylolpropane into the reacted mixed solution B2, controlling the temperature to be 80 ℃, and reacting for 3 hours to obtain a mixed solution B3;
s45, adding 50g of acetone into the mixed solution B3 for dilution, adjusting the temperature to 50 ℃, adding 6.2g of triethylamine, and reacting for 10min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly in a high-speed shearing machine by using 800g of deionized water at the rotating speed of 2000rpm, adding 30g of 1, 6g of hexamethylene diamine, mixing and stirring for 1h to obtain a mixed solution B5;
s47, removing acetone in the system from the mixed solution B5 under reduced pressure to obtain aqueous polyurethane emulsion B;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1:1, mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
Example 5
A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the amount of the raw materials used in the aqueous polyurethane emulsion A in this example is specifically shown in Table 11; the amounts of the raw materials used in the aqueous polyurethane emulsion B in this example are specified in Table 12.
TABLE 10 dosage of raw materials for the aqueous polyurethane emulsion A of example 5
Figure BDA0003199384720000181
TABLE 11 dosage of raw materials for the aqueous polyurethane emulsion B in example 5
Figure BDA0003199384720000182
Figure BDA0003199384720000191
A preparation method of self-extinction waterborne polyurethane resin specifically comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively;
the waterborne polyurethane emulsion A is prepared by the following steps:
s31, dehydrating 200g of polycarbonate diol under reduced pressure at 110 ℃ for 2 h;
s32, adjusting the temperature to 70 ℃, adding 23.6g of 1, 6-hexanediol into the polycarbonate diol after decompression and dehydration, uniformly mixing and stirring at the rotating speed of 45rpm, adding 105g of toluene diisocyanate, and uniformly mixing and stirring to obtain a mixed solution A1;
s33, adding 0.02g of bismuth carboxylate, 0.03g of antioxidant 1010 and 0.02g of triphenyl phosphite into the mixed solution A1, adjusting the temperature to 80 ℃, and reacting for 2 hours to obtain mixed solution A2;
s34, adding 15g of 2, 2-dimethylolpropionic acid into the reacted mixed solution A2, controlling the temperature at 70 ℃, and reacting for 2 hours to obtain a mixed solution A3;
s35, adding 70g of acetone into the mixed solution A3 for dilution, adjusting the temperature to 50 ℃, adding 6.1g of triethylamine, and reacting for 10min to obtain a mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 by 500g of deionized water in a high-speed shearing machine at the rotating speed of 2000rpm uniformly, adding 8g of hydrazine hydrate, mixing and stirring for 1h to obtain mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain an aqueous polyurethane emulsion A;
the waterborne polyurethane emulsion B is prepared by the following steps:
s41, dehydrating 200g of polypropylene glycol, 200g of polytetrahydrofuran diol and 100g of polyether graft polyol at 110 ℃ under reduced pressure for 2 hours to obtain an alcohol mixed solution;
s42, adjusting the temperature to 70 ℃, adding 12.8g of 1, 2-propylene glycol into the alcohol mixed solution after decompression and dehydration, mixing and stirring uniformly at the rotating speed of 45rpm, adding 102g of isophorone diisocyanate and 81g of 1, 6-hexamethylene diisocyanate, mixing and stirring uniformly to obtain a mixed solution B1;
s43, adding 0.02g of stannous octoate and 0.03g of triphenyl phosphite into the mixed solution B1, adjusting the temperature to 95 ℃, and reacting for 4 hours to obtain mixed solution B2;
s44, adding 27g of 2, 2-dimethylolpropionic acid and 2.5g of triethanolamine into the reacted mixed solution B2, controlling the temperature to be 80 ℃, and reacting for 3 hours to obtain a mixed solution B3;
s45, adding 50g of acetone into the mixed solution B3 for dilution, adjusting the temperature to 50 ℃, adding 6.2g of triethylamine, and reacting for 10min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly in a high-speed shearing machine by using 800g of deionized water at the rotating speed of 2000rpm, adding 19g of isophorone diamine and 20g of 2,6 toluene diamine, mixing and stirring for 1h to obtain a mixed solution B5;
s47, removing acetone in the system from the mixed solution B5 under reduced pressure to obtain aqueous polyurethane emulsion B;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1:1, mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
Example 6
A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the amount of the raw materials used in the aqueous polyurethane emulsion a in this example is specifically shown in table 12; the amounts of the raw materials used in the aqueous polyurethane emulsion B in this example are specified in Table 13.
TABLE 12 dosage of raw materials for the aqueous polyurethane emulsion A of example 6
Figure BDA0003199384720000201
Figure BDA0003199384720000211
TABLE 13 dosage of raw materials for aqueous polyurethane emulsion B in example 6
Figure BDA0003199384720000212
A preparation method of self-extinction waterborne polyurethane resin specifically comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively;
the waterborne polyurethane emulsion A is prepared by the following steps:
s31, dehydrating 200g of polycaprolactone diol under reduced pressure for 2 hours at 110 ℃;
s32, adjusting the temperature to 70 ℃, adding 18g of 1, 4-butanediol into the polycaprolactone diol after decompression and dehydration, mixing and stirring uniformly at the rotating speed of 45rpm, adding 105g of toluene diisocyanate, mixing and stirring uniformly to obtain a mixed solution A1;
s33, adding 0.02g of bismuth carboxylate, 0.02g of triphenyl phosphite and 0.03g of antioxidant 1076 into the mixed solution A1, adjusting the temperature to 80 ℃, and reacting for 2 hours to obtain mixed solution A2;
s34, adding 5g of 2, 2-dimethylolpropionic acid and 13g of ethylenediamine ethanesulfonic acid sodium salt into the reacted mixed solution A2, controlling the temperature at 70 ℃, and reacting for 2 hours to obtain mixed solution A3;
s35, adding 70g of acetone into the mixed solution A3 for dilution, adjusting the temperature to 50 ℃, adding 4.1g of triethylamine, and reacting for 10min to obtain a mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 by 500g of deionized water in a high-speed shearing machine at the rotating speed of 2000rpm uniformly, adding 10g of ethylenediamine, mixing and stirring for 1h to obtain mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain an aqueous polyurethane emulsion A;
the waterborne polyurethane emulsion B is prepared by the following steps:
s41, dehydrating 200g of polypropylene glycol, 100g of polytetrahydrofuran diol and 50g of polyether graft polyol for 2 hours at 110 ℃ under reduced pressure to obtain an alcohol mixed solution;
s42, adjusting the temperature to 70 ℃, adding 20g of 3 methyl 1,5 pentanediol into the alcohol mixed solution after decompression and dehydration, mixing and stirring uniformly at the rotating speed of 45rpm, adding 91g of isophorone diisocyanate and 70g of 1, 6-hexamethylene diisocyanate, mixing and stirring uniformly to obtain a mixed solution B1;
s43, adding 0.02g of stannous octoate and 0.03g of triphenyl phosphite into the mixed solution B1, adjusting the temperature to 95 ℃, and reacting for 4 hours to obtain mixed solution B2;
s44, adding 21g of 2, 2-dimethylolbutyric acid and 1.5g of trimethylolpropane into the reacted mixed solution B2, controlling the temperature to be 80 ℃, and reacting for 3 hours to obtain a mixed solution B3;
s45, adding 50g of acetone into the mixed solution B3 for dilution, adjusting the temperature to 50 ℃, adding 9.2g of triethylamine, and reacting for 10min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly in a high-speed shearing machine by using 800g of deionized water at the rotating speed of 2000rpm, adding 20g of isophorone diamine and 10g of 2,6 toluene diamine, mixing and stirring for 1h to obtain a mixed solution B5;
s47, removing acetone in the system from the mixed solution B5 under reduced pressure to obtain aqueous polyurethane emulsion B;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1:1, mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
Example 7
A self-extinction waterborne polyurethane resin is prepared from a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B which have different film-forming speeds; the amount of the raw materials used in the aqueous polyurethane emulsion A in this example is specifically shown in Table 14; the amounts of the raw materials used in the aqueous polyurethane emulsion B of this example are specified in Table 15.
TABLE 14 dosage of raw materials for the aqueous polyurethane emulsion A of example 7
Figure BDA0003199384720000231
TABLE 15 dosage of raw materials for the aqueous polyurethane emulsion B of example 7
Figure BDA0003199384720000232
Figure BDA0003199384720000241
A preparation method of self-extinction waterborne polyurethane resin specifically comprises the following steps:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively;
the waterborne polyurethane emulsion A is prepared by the following steps:
s31, dehydrating 200g of polyethylene glycol adipate glycol and 100g of polycaprolactone diol under reduced pressure for 2h at 110 ℃;
s32, adjusting the temperature to 70 ℃, adding 18g of 1, 6-hexanediol into the mixed solution of the polyethylene glycol adipate glycol and the polycaprolactone glycol after decompression and dehydration, mixing and stirring uniformly at a rotating speed of 45rpm, adding 105g of toluene diisocyanate, and mixing and stirring uniformly to obtain a mixed solution A1;
s33, adding 0.02g of bismuth carboxylate, 0.03g of antioxidant 1076 and 0.02g of triphenyl phosphite into the mixed solution A1, adjusting the temperature to 80 ℃, and reacting for 2 hours to obtain mixed solution A2;
s34, adding 7g of 2, 2-dimethylolbutyric acid and 15g of YmerN120 into the reacted mixed solution A2, controlling the temperature at 70 ℃, and reacting for 2 hours to obtain mixed solution A3;
s35, adding 70g of acetone into the mixed solution A3 for dilution, adjusting the temperature to 50 ℃, adding 4.6g of triethylamine, and reacting for 10min to obtain a mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 by 500g of deionized water in a high-speed shearing machine at the rotating speed of 2000rpm uniformly, adding 6g of ethylenediamine, mixing and stirring for 1h to obtain mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain an aqueous polyurethane emulsion A;
the waterborne polyurethane emulsion B is prepared by the following steps:
s41, dehydrating 200g of polypropylene glycol, 100g of polytetrahydrofuran diol and 50g of polyester graft polyol for 2 hours at 110 ℃ under reduced pressure to obtain an alcohol mixed solution;
s42, adjusting the temperature to 70 ℃, adding 12g of 1, 3-butanediol into the alcohol mixed solution after decompression and dehydration, mixing and stirring uniformly at the rotating speed of 45rpm, adding 131g of isophorone diisocyanate and 60g of 1, 6-hexamethylene diisocyanate, mixing and stirring uniformly to obtain a mixed solution B1;
s43, adding 0.02g of stannous octoate and 0.03g of triphenyl phosphite into the mixed solution B1, adjusting the temperature to 95 ℃, and reacting for 4 hours to obtain mixed solution B2;
s44, adding 21g of 2, 2-dimethylolpropionic acid and 2g of glycerol into the reacted mixed solution B2, controlling the temperature to be 80 ℃, and reacting for 3 hours to obtain a mixed solution B3;
s45, adding 50g of acetone into the mixed solution B3 for dilution, adjusting the temperature to 50 ℃, adding 8.7g of triethylamine, and reacting for 10min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly in a high-speed shearing machine by using 800g of deionized water at the rotating speed of 2000rpm, adding 10g of isophorone diamine and 10g of 2,6 toluene diamine, mixing and stirring for 1h to obtain a mixed solution B5;
s47, removing acetone in the system from the mixed solution B5 under reduced pressure to obtain aqueous polyurethane emulsion B;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1:1, mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
Example 8
This example differs from example 7 in that the sum of the amounts of the materials of both polyethylene adipate diol and polycaprolactone diol of example 7 was replaced with equimolar amounts of 1,4 butanediol sebacate diol having a molecular weight of 2000.
Example 9
This example differs from example 8 in that the 1,4 butanediol polysebacate diol of example 8 is replaced by an equimolar amount of polycaprolactone diol having a molecular weight of 2000.
Example 10
This example differs from example 8 in that the poly 1, 4-butanediol sebacate diol of example 8 is replaced by an equimolar amount of polyethylene glycol adipate diol having a molecular weight of 2000.
Example 11
This example differs from example 8 in that an equimolar polycarbonate polyol having a molecular weight of 2000 was used in this example instead of the 1, 4-butanediol polysebacate diol of example 8.
Example 12
This example differs from example 2 in that the polyether graft polyol (CHP-H30) of example 2 is replaced by an equimolar amount of polyester graft polyol (PM 445-S).
Example 13
This example differs from example 2 in that the polypropylene glycol of example 2 is replaced by an equimolar amount of polytetrahydrofuran diol having a molecular weight of 2000.
Example 14
This example differs from example 2 in that it replaces the glycerol of example 2 with equimolar amounts of water.
Example 15
This example differs from example 7 in that it replaces 1, 3-butanediol of example 7 with equimolar amounts of 1, 6-hexanediol.
Example 16
The difference between the embodiment and the embodiment 5 is that the embodiment uses equimolar composite chain extender to replace 1, 3-butanediol in the embodiment 7, the composite chain extender used for replacing 1, 3-butanediol in the embodiment 7 is compounded by 1, 2-propanediol and 1, 3-butanediol, and the mass ratio of 1, 2-propanediol to 1, 3-butanediol in the embodiment is 1: 1.
Example 17
This example differs from example 2 in that it replaces 2, 6-toluenediamine of example 2 with an equimolar amount of hydrazine hydrate.
Example 18
The difference between the embodiment and the embodiment 5 is that the embodiment uses equimolar composite diamine chain extender to replace 2, 6-toluene diamine in the embodiment 2, the composite diamine chain extender used for replacing 2, 6-toluene diamine in the embodiment 2 is compounded by isophorone diamine and 2, 6-toluene diamine, and the mass ratio of isophorone diamine and 2, 6-toluene diamine in the embodiment is 1: 1.
Example 19
This example differs from example 2 in that this example replaces the ymren 120 of example 2 with an equimolar amount of 2, 2-dimethylolpropionic acid; and this example replaces 2, 2-dimethylolpropionic acid in example 2 with equimolar amounts of sodium 2, 4-diaminobenzenesulphonate.
Example 20
This example differs from example 2 in that it replaces 2, 2-dimethylolpropionic acid in example 2 with equimolar of YmerN 120; and this example replaces 2, 2-dimethylolpropionic acid in example 2 with equimolar amounts of sodium 2, 4-diaminobenzenesulphonate.
Example 21
This example differs from example 2 in that it replaces 2, 2-dimethylolpropionic acid in example 2 with equimolar amounts of sodium 2, 4-diaminobenzenesulphonate.
Example 22
The difference between the present example and example 5 is that the mass ratio of the aqueous polyurethane emulsion a to the aqueous polyurethane emulsion B in the present example is 7: 4 in proportion.
Example 23
The difference between the present example and example 5 is that the mass ratio of the aqueous polyurethane emulsion a to the aqueous polyurethane emulsion B in the present example is 4: 7.
Example 24
This example differs from example 16 in that it replaces the glycerol of example 16 with an equal mass of HPAE.
Comparative example
Comparative example 1
This comparative example differs from example 8 in that the 1, 4-butanediol polysebacate diol of example 8 is replaced by an equimolar amount of a polypropylene oxide diol having a molecular weight of 2000.
Comparative example 2
This comparative example differs from example 8 in that it replaces 4,4' -dicyclohexylmethane diisocyanate with an equimolar amount of toluene diisocyanate.
Comparative example 3
This comparative example differs from example 2 in that it replaces the polypropylene glycol of example 2 with an equimolar amount of poly (1, 6-hexanediol adipate) glycol having a molecular weight of 2000.
Comparative example 4
This comparative example differs from example 2 in that it replaces the polyether graft polyol (CHP-H30) of example 2 with an equimolar amount of water.
Comparative example 5
This comparative example differs from example 2 in that it replaces the polypropylene glycol of example 2 with equimolar amounts of water.
Comparative example 6
This comparative example differs from comparative example 3 in that it replaces the polyether graft polyol (CHP-H30) of comparative example 3 with an equimolar amount of a 2000 molecular weight poly (1, 6-hexanediol) diol.
Comparative example 7
This comparative example differs from example 20 in that it replaces the YmerN120 of example 20 with an equimolar amount of water.
Comparative example 8
This comparative example differs from example 22 in that it replaces the sodium 2, 4-diaminobenzenesulfonate in example 20 with equimolar amounts of water.
Detection method/test method
1. And (3) gloss detection: the glossiness of the products prepared in examples 1-24 and comparative examples 1-8 was measured by a glossiness tester, wherein the glossiness tester was a WGG-60 digital display glossiness meter manufactured by Shanghai No. 02290034;
2. and (3) wear resistance test: according to the requirements of ISO-5470-1-2016 (determination of abrasion resistance of rubber or plastic coated fabric), a Taber abrasion tester detects test pieces coated with products prepared in examples 1-24 and comparative examples 1-8, and records the number of revolutions of abrasion on the surfaces of different test pieces, wherein the model of a grinding wheel is H-18 rotor, and the pressure of two arms is 1 kg;
3. jungle testing: according to the requirement of QB/T4671-2014 'determination of hydrolysis resistance of artificial leather test method', a constant temperature and humidity hydrolysis resistance method is adopted for jungle testing, products prepared in examples 1-24 and comparative examples 1-8 are coated on sample leather which has the size of (220 +/-2) mmx (150 +/-2) mm and meets the specification of QB/T2706-.
TABLE 16 tables of test results of examples 1 to 24 and comparative examples 1 to 8
Detecting an object Gloss measurement Abrasion resistance test (turn) Jungle testing
Example 1 0.2 600 No obvious change in three weeks
Example 2 0.3 650 No obvious change in three weeks
Example 3 0.2 680 No obvious change in three weeks
Example 4 0.2 700 No obvious change in three weeks
Example 5 0.2 760 No obvious change in three weeks
Example 6 0.3 710 No obvious change in three weeks
Example 7 0.3 810 No obvious change in three weeks
Example 8 0.4 720 No obvious change in the periphery
Example 9 0.3 768 No obvious change in two weeks
Example 10 0.4 766 No obvious change in three weeks
Example 11 0.2 780 No obvious change in three weeks
Example 12 0.4 690 No obvious change in three weeks
Example 13 0.2 660 No obvious change in three weeks
Example 14 0.5 630 No obvious change in three weeks
Example 15 0.4 780 No obvious change in three weeks
Example 16 0.2 820 No obvious change in three weeks
Example 17 0.4 630 No obvious change in three weeks
Example 18 0.2 670 No obvious change in three weeks
Example 19 0.4 590 No obvious change in three weeks
Example 20 0.5 610 No obvious change in three weeks
Example 21 0.4 630 No obvious change in three weeks
Example 22 0.4 730 No obvious change in three weeks
Example 23 0.4 740 No obvious change in three weeks
Example 24 0.2 829 No obvious change in the periphery
Comparative example 1 0.6 570 No obvious change in two weeks
Comparative example 2 0.6 580 No obvious change in two weeks
Comparative example 3 0.6 570 No obvious change in two weeks
Comparative example 4 0.5 550 No obvious change in two weeks
Comparative example 5 0.5 560 No obvious change in two weeks
Comparative example 6 0.8 520 No obvious change in two weeks
Comparative example 7 0.7 550 No obvious change in two weeks
Comparative example 8 0.9 510 No obvious change in two weeks
As can be seen by combining examples 7 to 11 and comparative example 1 with Table 16, the combination of matting properties, abrasion resistance and aging resistance of the products prepared using the highly crystalline polyol is superior to that of the products using polypropylene oxide; in combination with examples 7-11, it can be seen that the products prepared using different types of high crystalline polyols all have different matting properties, abrasion resistance and aging resistance, wherein the products prepared using polycarbonate polyols achieve the best matting effect and the gloss measurement can reach 0.2; the wear resistance of the product prepared by adopting the poly-sebacic acid 1, 4-butanediol ester diol is optimal, and the jungle test result can reach no obvious change around; it can be seen from the combination of example 7 and examples 9-10 that the combination properties of the product prepared by compounding polycaprolactone diol and polyethylene glycol adipate diol are superior to those of the product prepared by singly using polycaprolactone diol or polyethylene glycol adipate diol, and the product prepared by compounding polycaprolactone diol and polyethylene glycol adipate diol has the glossiness detection of 0.3, the jungle test result can reach no obvious change for three weeks, and the wear resistance of the product can reach 810 revolutions.
As can be seen by combining example 2 and comparative example 2 and table 16, the matting property and abrasion resistance of the product prepared in example 2 are better than those of example 2, so it can be demonstrated that the incompatible segments of the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B can be enhanced by using 4,4' -dicyclohexylmethane diisocyanate to the aqueous polyurethane emulsion B, thereby improving the matting effect of the product.
It can be seen by combining examples 2, 12-13 and 3-6 with Table X that the effect of the product prepared by polytetrahydrofuran diol is better than that of the product prepared by polypropylene glycol, and in addition, the abrasion resistance of the product prepared by example 12 is better than that of the product prepared by example 2, but the delustering property of the product prepared by example 2 is better than that of the product prepared by example 12, so that different graft polyols have different abrasion resistances and different delustering effects, and furthermore, by comparing the results of comparative examples 3-5 and example 2, the delustering effect and the abrasion resistance of the product prepared by compounding polyether diol and graft polyol in example 2 are better than those of the products prepared by comparative examples 3-5, the glossiness of the product prepared by example 2 can reach 0.3, and the jungle test result can reach three weeks without significant change, and the wear resistance can reach 650 turns.
It can be seen from the combination of example 2 and example 14 and table 16 that the matting effect and abrasion resistance of the product prepared in example 2 are superior to those of the product prepared in example 14, and therefore, it is inferred that the addition of the crosslinking agent enhances the difference in crystallinity between the aqueous polyurethane emulsion a and the aqueous polyurethane emulsion B, which in turn affects the matting property and abrasion resistance of the product.
It can be seen by combining example 7 and examples 15 to 16 with table X that the extinction effect of the product prepared in example 7 is superior to that of the product prepared in example 15, and thus it can be seen that the difference in crystallinity between the polyurethane emulsion a and the aqueous polyurethane emulsion B can be enhanced by preparing the aqueous polyurethane emulsion B with the normal chain extender containing a branched chain and preparing the aqueous polyurethane emulsion a with the linear chain extender, thereby improving the extinction effect of the product, and in addition, the better extinction effect can be achieved by compounding the normal chain extender containing a branched chain used for preparing the aqueous polyurethane emulsion B.
It can be seen from the combination of example 7 and examples 15 to 16 and table 16 that the extinction effect of the product prepared in example 7 is superior to that of the product prepared in example 15, and thus it can be seen that the difference in crystallinity between the polyurethane emulsion a and the aqueous polyurethane emulsion B can be enhanced by preparing the aqueous polyurethane emulsion B with the normal chain extender containing a branched chain and preparing the aqueous polyurethane emulsion a with the linear chain extender, thereby improving the extinction effect of the product, and in addition, the better extinction effect can be achieved by compounding the normal chain extender containing a branched chain used for preparing the aqueous polyurethane emulsion B.
It can be seen from the combination of example 2 and examples 17 to 18 and the combination of table 16 that the extinction effect of the product prepared in example 2 is better than that of the product prepared in example 17, and thus it can be seen that the crystallinity difference between the polyurethane emulsion a and the aqueous polyurethane emulsion B can be enhanced by using the diamine chain extender containing a branched chain to prepare the aqueous polyurethane emulsion B and by using the linear diamine chain extender to prepare the aqueous polyurethane emulsion a, so that the extinction effect of the product is improved, and the better extinction effect can be achieved by compounding the diamine chain extender containing a branched chain used for preparing the aqueous polyurethane emulsion B.
It can be seen from examples 19 to 21 and comparative examples 8 to 9 in combination with table 16 that the matting effect, the wear resistance and the anti-aging property of the present application can be improved comprehensively by adding the hydrophilic chain extender, the matting effect and the wear resistance of the product prepared in example 2 are superior to those of the products prepared in examples 17 to 21 and comparative examples 7 to 8, the glossiness of the product prepared in example 2 can reach 0.3, the jungle test result can reach no significant change for three weeks, and the wear resistance can reach 650 turns, so that it can be concluded that the wear resistance and the matting effect of the present application can be improved comprehensively by compounding hydrophilic chain extenders with different polarities and then applying the compounded hydrophilic chain extenders to the aqueous polyurethane emulsion a system and the aqueous polyurethane emulsion B system.
By combining the example 5 and the examples 22-24 with the table 16, it can be seen that different extinction effects can be achieved after the aqueous polyurethane emulsion a and the aqueous polyurethane emulsion B are compounded according to different mass ratios, when the mass ratio of the aqueous polyurethane emulsion a to the aqueous polyurethane emulsion B is 1:1, the extinction effect of the prepared product is optimal, different cross-linking agents can affect the wear resistance and the anti-aging effect of the product, when the product prepared by adopting the HPAE as the cross-linking agent has the glossiness of 0.2, the jungle test result can achieve no obvious change around, and the wear resistance can achieve 829 turns.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. The self-extinction aqueous polyurethane resin is characterized by being prepared from an aqueous polyurethane emulsion A and an aqueous polyurethane emulsion B, wherein the film forming speeds of the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B are different;
the waterborne polyurethane emulsion A is prepared from the following raw materials in parts by weight:
200-400 parts of high-crystallinity polyol,
65-90 parts of toluene diisocyanate,
16-105 parts of chain extender,
500-600 parts of deionized water;
the aqueous polyurethane emulsion B is prepared from the following raw materials in parts by weight:
200-400 parts of polyether polyol,
5-100 parts of graft polyol,
50-300 parts of aliphatic diisocyanate,
16-130 parts of chain extender,
500-600 parts of deionized water.
2. The self-matting aqueous polyurethane resin according to claim 1, wherein: the polyether polyol is at least one of polytetrahydrofuran glycol and polypropylene glycol; the graft polyol is at least one of polyester graft polyol and polyether graft polyol;
the polyester grafted polyalcohol is styrene grafted polyethylene glycol adipate glycol diethylene glycol diol;
the polyether graft polyalcohol is prepared by graft copolymerization of polyether, styrene and acrylonitrile.
3. The self-matting aqueous polyurethane resin according to claim 2, wherein: the high-crystallinity polyol has a molecular weight of 1000-4000 g/mol, and is at least one of polyethylene glycol adipate glycol, polyethylene-1, 4-butanediol adipate glycol, polyethylene-1, 6-hexanediol adipate glycol, polyethylene glycol sebacate glycol, polyethylene-1, 4-butanediol sebacate glycol, polyethylene-1, 6-hexanediol sebacate glycol, polycarbonate polyol and polycaprolactone diol.
4. The self-matting aqueous polyurethane resin according to claim 1, wherein: the chain extender in the aqueous polyurethane emulsion A comprises a linear chain extender with the molecular weight of 60-300 g/mol, and the linear chain extender is at least one of diol and diamine;
the chain extender in the waterborne polyurethane emulsion B comprises a chain extender containing a branched chain, and the chain extender containing the branched chain is at least one of 1, 2-propylene glycol, 1, 3-butanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol and neopentyl glycol.
5. The self-matting aqueous polyurethane resin according to claim 4, wherein: the chain extender in the aqueous polyurethane emulsion A also comprises a linear chain diamine chain extender, wherein the linear chain diamine chain extender is one of ethylenediamine, hydrazine hydrate, 1, 4-butanediamine and 1, 6-hexanediamine;
the chain extender in the aqueous polyurethane emulsion B also comprises a diamine chain extender containing a branched chain, wherein the diamine chain extender containing the branched chain is at least one of isophorone diamine, 2, 6-toluene diamine, diethyl toluene diamine, 4' -methylene bis (2, 6-diethylaniline) and 4, 4-methylene bis (2-ethylaniline).
6. The self-matting aqueous polyurethane resin according to claim 5, wherein: the chain extender in the aqueous polyurethane emulsion A and the chain extender in the aqueous polyurethane emulsion B both contain hydrophilic chain extenders, and the hydrophilic chain extenders are at least one of Ymer N120, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, ethylene diamine ethyl sodium sulfonate, N-bis (2-hydroxyethyl) -2-aminoethyl sodium sulfonate, 2, 4-diaminobenzene sodium sulfonate and diaminobutane sulfonic acid.
7. The self-matting aqueous polyurethane resin according to claim 6, wherein: the waterborne polyurethane emulsion B also comprises 0.5-3 parts of a cross-linking agent, wherein the cross-linking agent is at least one of trimethylolpropane, triethanolamine, glycerol, castor oil and HPAE.
8. The method for preparing a self-extinction aqueous polyurethane resin according to claim 7, characterized by comprising the steps of:
s1, preparing a waterborne polyurethane emulsion A and a waterborne polyurethane emulsion B respectively, and adding other auxiliaries when preparing the waterborne polyurethane emulsion A and the waterborne polyurethane emulsion B, wherein the other auxiliaries comprise one or more of a surfactant, an antioxidant, an ultraviolet absorbent, a weather-resistant stabilizer and a water-proofing agent;
s2, mixing the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B according to the mass ratio of 1-9: 1-9, and mixing and stirring the aqueous polyurethane emulsion A and the aqueous polyurethane emulsion B uniformly to obtain the product.
9. The method for preparing a self-extinction aqueous polyurethane resin according to claim 8, wherein in step S1, the aqueous polyurethane emulsion a is prepared by the steps of:
s31, dehydrating the high-crystallinity polyol for 1-2 hours under reduced pressure at the temperature of 110-120 ℃;
s32, adjusting the temperature to 65-75 ℃, adding a linear chain extender and toluene diisocyanate into the high-crystallinity polyol subjected to decompression and dehydration, and uniformly mixing and stirring to obtain a mixed solution A1;
s33, adding a catalyst into the mixed solution A1 or adding a mixed solution of the catalyst and other auxiliaries into the mixed solution A1, adjusting the temperature to 70-90 ℃, and reacting for 2-4 hours to obtain a mixed solution A2, wherein the catalyst is one of stannous octoate and bismuth carboxylate;
s34, adding a hydrophilic chain extender into the reacted mixed solution A2, controlling the temperature to be 70-80 ℃, and reacting for 2-4 hours to obtain a mixed solution A3;
s35, adding acetone into the mixed solution A3 for dilution, adjusting the temperature to be below 50 ℃, adding triethylamine, and reacting for 5-15 min to obtain a mixed solution A4;
s36, emulsifying and dispersing the mixed solution A4 with deionized water uniformly, adding a linear diamine chain extender, mixing and stirring for 1-2 h to obtain a mixed solution A5;
s37, removing acetone in the mixed solution A5 under reduced pressure to obtain the aqueous polyurethane emulsion A.
10. The method for preparing a self-extinction aqueous polyurethane resin according to claim 9, wherein the aqueous polyurethane emulsion B in step S1 is prepared by the steps of:
s41, dehydrating polyether glycol and graft polyol under reduced pressure at 110-120 ℃ for 1-2 h to obtain an alcohol mixed solution;
s42, adjusting the temperature to 65-75 ℃, adding a chain extender containing a branched chain and aliphatic diisocyanate into the alcohol mixed solution after decompression and dehydration, and uniformly mixing and stirring to obtain a mixed solution B1, wherein the aliphatic diisocyanate is at least one of 4, 4-dicyclohexylmethane diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate;
s43, adding a catalyst into the mixed liquid B1 or adding a mixed liquid of the catalyst and other auxiliaries into the mixed liquid B1, adjusting the temperature to be 80-95 ℃, and reacting for 2-4 hours to obtain a mixed liquid B2, wherein the catalyst comprises stannous octoate or bismuth carboxylate;
s44, adding a cross-linking agent and a hydrophilic chain extender into the reacted mixed solution B2, controlling the temperature to be 70-80 ℃, and reacting for 2-4 hours to obtain a mixed solution B3;
s45, adding acetone into the mixed solution B3 for dilution, adjusting the temperature to be below 50 ℃, adding triethylamine, and reacting for 5-15 min to obtain a mixed solution B4;
s46, emulsifying and dispersing the mixed solution B4 uniformly by using deionized water, adding a diamine chain extender containing branched chains, mixing and stirring for 1-2 h to obtain a mixed solution B5;
s47, removing acetone in the mixed solution B5 under reduced pressure to obtain the aqueous polyurethane emulsion B.
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