CN110372840B - Inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion and preparation method thereof - Google Patents

Inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion and preparation method thereof Download PDF

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CN110372840B
CN110372840B CN201910637169.0A CN201910637169A CN110372840B CN 110372840 B CN110372840 B CN 110372840B CN 201910637169 A CN201910637169 A CN 201910637169A CN 110372840 B CN110372840 B CN 110372840B
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aqueous polyurethane
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李新平
周雷
薛白亮
王文亮
高晨
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Shaanxi University of Science and Technology
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Abstract

The invention discloses an inorganic-organic composite modified cross-linking type waterborne polyurethane emulsion and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, mixing polyester polyol and diisocyanate, dropwise adding a catalyst dibutyltin dilaurate, and introducing nitrogen to perform reaction; step 2, adding a hydrophilic chain extender for reaction, and then adding furan resin for reaction; step 3, adding a neutralizing agent for reaction, and adding water for dispersion to obtain a waterborne polyurethane emulsion; step 4, adding nano SiO into the aqueous polyurethane emulsion2And dispersing and emulsifying in an ultrasonic reactor, and removing the solvent after the reaction is finished to obtain the crosslinking type waterborne polyurethane. According to the invention, a furan resin chain segment is introduced into a polyurethane chain segment, and Diels-Alder reaction is carried out between double bonds on a furan ring, so that the mechanical property of the crosslinking type waterborne polyurethane is improved; introduction of nano SiO2The polymer coating film has increased crosslinking density and reduced water molecule spaceIs difficult to enter and has improved water resistance.

Description

Inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion and a preparation method thereof
Background
The aqueous polyurethane emulsion has the problem of slow drying due to the fact that water is used as a medium, and the defects of poor heat resistance, poor solvent resistance, low tensile strength and the like are caused by the fact that hydrophilic groups such as carboxyl groups, sulfonic groups and the like are introduced during synthesis and a linear structure lacking chemical crosslinking is lack, so that the large-scale popularization and application of the aqueous polyurethane are severely limited. Therefore, in order to improve the water resistance and mechanical properties of the waterborne polyurethane, deeper crosslinking modification is required.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of an inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion, and the water resistance and the mechanical property of a glue film formed by the crosslinking type waterborne polyurethane are greatly improved.
The invention is realized by the following technical scheme:
a preparation method of inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion comprises the following steps:
step 1, mixing polyester polyol and diisocyanate, dropwise adding dibutyltin dilaurate, introducing nitrogen, and reacting to obtain a system 1;
step 2, adding a hydrophilic chain extender into the system 1 for reaction; then adding furan resin, and reacting to obtain a system 2;
step 3, adding a neutralizing agent into the system 2, adding water for dispersion after reaction to obtain a water-based polyurethane emulsion;
step 4, mixing the nano SiO2And (3) adding the mixture into the aqueous polyurethane emulsion obtained in the step (3), and carrying out ultrasonic reaction to obtain the inorganic-organic composite modified crosslinking aqueous polyurethane emulsion.
Preferably, in the step 1, the reaction temperature is 60-80 ℃ and the reaction time is 1-3 h.
Preferably, in step 1, the molar ratio of polyester polyol to diisocyanate is 1: (2.7-3.3), wherein the addition amount of dibutyltin dilaurate is 0.05-0.09% of the total mass of diisocyanate and polyester polyol.
Preferably, step 2 is specifically: adding a hydrophilic chain extender into the system 1, reacting for 2 to 4 hours at the temperature of between 60 and 80 ℃, then adding furan resin, and reacting for 1 to 2 hours at the temperature of between 30 and 40 ℃.
Preferably, in the step 2, the hydrophilic chain extender is 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid, and the adding amount of the hydrophilic chain extender is 4-6% of the total mass of the diisocyanate and the polyester polyol.
Preferably, in step 2, the addition amount of the furan resin is 5.5-7.5% of the total mass of the diisocyanate and the polyester polyol.
Preferably, step 3 is specifically: adding a neutralizing agent into the system 2 for reaction for 15-30 min, adjusting the pH value to 7-8, and adding water for dispersion to obtain the aqueous polyurethane emulsion.
Preferably, in step 3, the neutralizing agent is triethylamine; the mole ratio of the neutralizer to the hydrophilic chain extender is (0.8-1.5): 1.
preferably, step 4 is specifically: adding 0.5-2.5 percent of nano SiO (silicon dioxide) in terms of the solid content of the aqueous polyurethane emulsion into the aqueous polyurethane emulsion obtained in the step 32And carrying out ultrasonic reaction at 10-15 ℃ for 5-13 min to obtain the inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion.
The inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the cross-linked waterborne polyurethane comprises the steps of preparing polyurethane prepolymer containing end isocyanate groups by polyester polyol, diisocyanate and hydrophilic chain extender, carrying out nucleophilic addition reaction on furan resin containing end hydroxyl groups and the polyurethane prepolymer, emulsifying and dispersing the obtained product, and adding nano SiO2And (3) performing ultrasonic dispersion to finally obtain the inorganic-organic composite crosslinking modified waterborne polyurethane. The furan resin is grafted into the structure of the waterborne polyurethane and can generate Diels-Alder reaction to form the productThe crosslinking type waterborne polyurethane with the space network structure has the advantages that the crosslinking degree of the system is increased, the hydrogen bond action in molecules and among molecules is enhanced, and a compact network structure is formed, so that the tensile strength of the latex film is increased, the polyurethane molecules and the chain segments of the HK-6 molecules are twisted together to a certain degree, the deformation capacity of the glue film is greatly limited, and the mechanical property of the glue film is finally improved. And because of the nanometer SiO2The addition of the (B) increases the crosslinking density of the polyurethane emulsion when forming a glue film, increases the space density in the polymer, reduces the space, makes water molecules difficult to enter and improves the water resistance.
The water resistance and the mechanical property of a glue film formed by the crosslinking type waterborne polyurethane prepared by the invention are greatly improved. Along with the gradual increase of the content of HK-6, the degree of the random copolymerization reaction in the system is increased, the crosslinking degree of the system is increased, the hydrogen bond action in molecules and among molecules is enhanced, and the cohesive force of the glue film is increased, so that the tensile strength of the latex film is increased; the crosslinking degree of the system is increased, the interpenetrating crosslinking forms a body-shaped structure, the movement of a molecular chain is hindered, and as the furan ring chain segment in the HK-6 chain segment is introduced into the side chain of the prepolymer chain segment, the rigidity of the system chain segment can be enhanced due to larger volume, large internal rotation steric hindrance and poor flexibility, so that the breaking elongation of the adhesive film is reduced; on the other hand, because of SiO2The nano material belongs to a rigid substance, molecules are mostly in a net-shaped and three-dimensional chain structure, the inorganic Si-O network and the modified WPU network are mutually crossed and penetrated, the crosslinking density of the coating is enhanced, the specific surface area of the nano material is large, and pores generated in the curing and shrinking process of the coating can be filled. Water molecules are difficult to spread on the surface of the adhesive film and cannot permeate into the adhesive film, so that the water resistance of the adhesive film is greatly enhanced.
Drawings
FIG. 1 is an infrared spectrum of the crosslinking type aqueous polyurethane of the present invention.
FIG. 2 is a graph showing the effect of HK-6 content on the mechanical properties of latex films.
FIG. 3 is a graph showing the effect of HK-6 content on the water absorption of latex films.
FIG. 4 shows a view of nano SiO2Influence of the content on the water absorption of the latex film.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
A preparation method of inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion comprises the following steps:
the method comprises the following steps: carrying out reduced pressure dehydration on polyester polyol at 120 ℃ for 2h for later use; mixing the components in a molar ratio of 1: (2.7-3.3) adding polyester polyol and diisocyanate into a reaction vessel, dropwise adding a catalyst dibutyltin dilaurate (DBTDL) accounting for 0.05-0.09% of the total mass of the diisocyanate and the polyester polyol, introducing nitrogen, heating to 60-80 ℃, and keeping the temperature for 1-3 h;
step two: then adding 4-6% of 2, 2-dimethylolpropionic acid (DMPA) based on the total mass of diisocyanate and polyester polyol, and reacting for 2-4 h at 60-80 ℃; reducing the temperature to 25-35 ℃, adding furan resin (HK-6) accounting for 5.5-7.5% of the total mass of diisocyanate and polyester polyol, keeping the temperature for 1-2 h, and adding metered acetone or butanone in the reaction process to reduce the viscosity of the system;
step three: adding a measured neutralizer to react for 15-30 min to obtain a Polyurethane (PU) emulsion, adjusting the pH value to 7-8, adding distilled water to disperse at a high speed to obtain a Waterborne Polyurethane (WPU) emulsion;
step four: adding 0.5-2.5 percent of nano SiO (silicon dioxide) by the solid content of the emulsion into the aqueous polyurethane emulsion obtained in the step three2Reacting in an ultrasonic reactor for 5-13 min at 10-15 deg.C until the emulsion is stable and transparent, and distilling under reduced pressure to remove acetone or butanone as solvent to obtain the inorganic-organic composite modified cross-linked aqueous polyurethane emulsion.
In the first step, the diisocyanate is isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or Hexamethylene Diisocyanate (HDI); the polyester polyol is polycaprolactone polyol, polycarbonate diol or polyethylene glycol adipate, and has an average molecular weight of 1200.
In the second step, 2, 2-dimethylolpropionic acid (DMPA) as a hydrophilic chain extender can also be replaced by 2, 2-dimethylolbutyric acid (DHPA).
Step three, the neutralizing agent is Triethylamine (TEA), and the mol ratio of the Triethylamine (TEA) to the DMPA is (0.8-1.5): 1.
the following are specific examples.
Example one
The method comprises the following steps: carrying out reduced pressure dehydration on polyester polyol PE-3020 at 120 ℃ for 2h for later use; adding polyester polyol PE-3020 and Hexamethylene Diisocyanate (HDI) in a molar ratio of 1:2.7 into a three-necked flask, dropwise adding dibutyltin dilaurate (DBTDL) serving as a catalyst in an amount of 0.05% of the total mass of the HDI and the PE-3020, introducing nitrogen, heating to 60 ℃, and keeping the temperature for 3 hours;
step two: adding 4 percent of 2, 2-dimethylolpropionic acid DMPA (dimethyl formamide) based on the total mass of HDI and polyester polyol, and keeping the temperature at 60 ℃ for 4 hours; when the temperature is reduced to 30 ℃, adding furan resin (HK-6) accounting for 5.5 percent of the total mass of the diisocyanate and the polyester polyol, and preserving the heat for 2 hours, wherein the acetone or butanone is added in the reaction process to reduce the viscosity of the system;
step three: raising the temperature to 40 ℃, adding Triethylamine (TEA) with the mol ratio of 0.8:1 to the hydrophilic chain extender DMPA, quickly stirring for 15min, adjusting the pH value to 7, adding distilled water, and dispersing at high speed to obtain the waterborne polyurethane emulsion (marked as HK-6-WPU);
step four: adding 0.5 percent of nano SiO (based on the solid content of the emulsion) into the WPU emulsion obtained in the third step2Reacting for 5min in an ultrasonic reactor, and controlling the reaction temperature at 15 ℃; distilling under reduced pressure to remove the solvent to obtain the inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion (marked as SiO)2/HK-WPU)。
Example two
The method comprises the following steps: carrying out reduced pressure dehydration on polyester polyol PE-3020 at 120 ℃ for 2h for later use; adding polyester polyol PE-3020 and Hexamethylene Diisocyanate (HDI) in a molar ratio of 1:2.9 into a three-necked flask, dropwise adding dibutyltin dilaurate (DBTDL) serving as a catalyst in an amount of 0.06% by mass of the total of the HDI and the PE-3020, introducing nitrogen, heating to 65 ℃, and keeping the temperature for 2 hours;
step two: adding 4.5 percent of 2, 2-dimethylolpropionic acid DMPA based on the total mass of HDI and polyester polyol, and keeping the temperature at 65 ℃ for 3.5 h; when the temperature is reduced to 35 ℃, adding furan resin (HK-6) accounting for 6.5 percent of the total mass of the diisocyanate and the polyester polyol, and preserving the heat for 1.7h, wherein acetone or butanone is added in a metering manner during the reaction process to reduce the viscosity of the system;
step three: raising the temperature to 37 ℃, adding Triethylamine (TEA) with the mol ratio of 1:1 to the hydrophilic chain extender DMPA, quickly stirring for 20min, adjusting the pH value to 7, adding distilled water, and dispersing at a high speed to obtain WPU emulsion;
step four: adding 1.0 percent of nano SiO (based on the solid content of the emulsion) into the WPU emulsion obtained in the third step2Reacting for 8min in an ultrasonic reactor, and controlling the reaction temperature at 13 ℃; and distilling under reduced pressure to remove the solvent to obtain the inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion.
EXAMPLE III
The method comprises the following steps: carrying out reduced pressure dehydration on polyester polyol PE-3020 at 120 ℃ for 2h for later use; adding polyester polyol PE-3020 and Hexamethylene Diisocyanate (HDI) in a molar ratio of 1:3 into a three-necked flask, dropwise adding dibutyltin dilaurate (DBTDL) serving as a catalyst in an amount of 0.07 percent based on the total mass of the HDI and the PE-3020, introducing nitrogen, heating to 70 ℃, and keeping the temperature for 1.5 h;
step two: adding 5 percent of 2, 2-dimethylolpropionic acid DMPA (dimethyl formamide) based on the total mass of HDI and polyester polyol, and keeping the temperature at 70 ℃ for 3 hours; when the temperature is reduced to 38 ℃, adding 7 percent of furan resin (HK-6) by the total mass of diisocyanate and polyester polyol, and preserving the heat for 1.4h, and adding metered acetone or butanone during the reaction to reduce the viscosity of the system;
step three: adding Triethylamine (TEA) with the mol ratio of the TEA to the hydrophilic chain extender DMPA being 1.2:1, quickly stirring for 25min, adjusting the pH value to 7, adding distilled water, and dispersing at high speed to obtain WPU emulsion;
step four: adding 2.0 percent of nano SiO (based on the solid content of the emulsion) into the WPU emulsion obtained in the third step2Reacting in an ultrasonic reactor for 10min, and controlling the reaction temperature at 12 ℃; and distilling under reduced pressure to remove the solvent to obtain the inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion.
Example four
The method comprises the following steps: carrying out reduced pressure dehydration on polyester polyol PE-3020 at 120 ℃ for 2h for later use; adding polyester polyol PE-3020 and Hexamethylene Diisocyanate (HDI) in a molar ratio of 1:3.3 into a three-necked flask, dropwise adding dibutyltin dilaurate (DBTDL) serving as a catalyst of 0.08% of the total mass of the HDI and the PE-3020, introducing nitrogen, heating to 80 ℃, and keeping the temperature for 1.2 h;
step two: adding 6 percent of 2, 2-dimethylolpropionic acid DMPA (dimethyl formamide) based on the total mass of HDI and polyester polyol, and keeping the temperature at 80 ℃ for 2.5 hours; when the temperature is reduced to 40 ℃, adding 7.5 percent of furan resin (HK-6) by the total mass of diisocyanate and polyester polyol, and preserving the heat for 1h, wherein acetone or butanone is added in the reaction process to reduce the viscosity of the system;
step three: adding Triethylamine (TEA) with the mol ratio of the TEA to the hydrophilic chain extender DMPA being 1.5:1, quickly stirring for 30min, adjusting the pH value to 7, adding distilled water, and dispersing at high speed to obtain WPU emulsion;
step four: adding 2.5 percent of nano SiO into the WPU emulsion obtained in the third step based on the solid content of the emulsion2Reacting for 13min in an ultrasonic reactor, and controlling the reaction temperature at 10 ℃; and distilling under reduced pressure to remove the solvent to obtain the inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion.
EXAMPLE five
The method comprises the following steps: carrying out reduced pressure dehydration on polyester polyol PE-3020 at 120 ℃ for 2h for later use; adding polyester polyol PE-3020 and Hexamethylene Diisocyanate (HDI) in a molar ratio of 1:2.8 into a three-necked flask, dropwise adding dibutyltin dilaurate (DBTDL) serving as a catalyst in an amount of 0.09% by mass of the total of the HDI and the PE-3020, introducing nitrogen, heating to 70 ℃, and keeping the temperature for 1 h;
step two: adding 6 percent of 2, 2-dimethylolpropionic acid DMPA (dimethyl formamide) based on the total mass of HDI and polyester polyol, and keeping the temperature at 75 ℃ for 2 hours; when the temperature is reduced to 40 ℃, adding 7.2 percent of furan resin (HK-6) by the total mass of diisocyanate and polyester polyol, and preserving the heat for 1h, wherein acetone or butanone is added in the reaction process to reduce the viscosity of the system;
step three: adding Triethylamine (TEA) with the mol ratio of the TEA to the hydrophilic chain extender DMPA being 1.3:1, quickly stirring for 30min, adjusting the pH value to 8, adding distilled water, and dispersing at high speed to obtain WPU emulsion;
step four: adding 1.5 percent of nano SiO (based on the solid content of the emulsion) into the WPU emulsion obtained in the third step2Reacting for 13min in an ultrasonic reactor, and controlling the reaction temperature at 8 ℃; and distilling under reduced pressure to remove the solvent to obtain the inorganic-organic composite modified crosslinking type waterborne polyurethane emulsion.
As shown in FIG. 1, which is an infrared spectrum of the cross-linked waterborne polyurethane prepared in the first example, 3316cm-1Is located as the stretching vibration peak of N-H bond in-NHCO-, 1710cm-1C ═ O stretching vibration peak in-NHCO-, 2268cm-1No characteristic absorption peak of-NCO appears, which indicates that-NCO in the system completely participates in the reaction. 1537cm-1And 1450cm-1The absorption peak is the stretching vibration peak of carboxyl, 2942cm-1C-H stretching vibration absorption peak of saturated carbon, 776cm-1The out-of-plane bending vibration absorption peak at the C-H bond in the furan ring structure indicates that furan resin has been successfully introduced into the polyurethane segment, except that SiO21247cm in infrared spectrogram of/HK-WPU-1And 1161cm-1Is SiO2The asymmetric and symmetric stretching vibration peak of Si-O shows that the nano SiO2The molecules are dispersed in the polyurethane segment.
The obtained crosslinking type aqueous polyurethane was tested: pouring a certain amount of emulsion on a polytetrafluoroethylene plate, and naturally drying the emulsion at room temperature to form a glue film with the thickness of about 1 mm.
The physical and mechanical properties of the adhesive film were measured by a GTS-2000-S servo system tensile machine, manufactured by Taiwan high-speed rail science and technology Co., Ltd, with reference to GB/T528-2009.
The results are shown in FIG. 2, which lists the influence of different HK-6 addition amounts on the mechanical properties of WPU latex films. As can be seen from FIG. 2, the increase of HK-6 makes the tensile strength of the latex film show a trend of increasing and then decreasing, the elongation at break of the latex film is continuously reduced, along with the gradual increase of the content of HK-6, the degree of the irregular copolymerization reaction in the system is increased, the crosslinking degree of the system is increased, the hydrogen bonding effect in molecules and between molecules is enhanced, and the cohesive force of the glue film is increased, so that the tensile strength of the latex film is increased; the crosslinking degree of the system is increased, the interpenetrating crosslinking forms a body type structure, the movement of a molecular chain is hindered, and because the furan ring chain segment in the HK-6 chain segment is introduced into a side chain of a prepolymer chain segment, the rigidity of the system chain segment can be enhanced due to larger volume, large internal rotation steric hindrance and poor flexibility, so that the breaking elongation of the glue film is reduced. When the w (HK-6) is increased from 4% to 6%, the crosslinking density in the system is gradually increased, the effective entanglement among molecules is increased, and the tensile strength of the adhesive film is gradually increased; when the w (HK-6) exceeds 6 percent, the content of the introduced HK-6 in the system is too much, active sites participating in nucleophilic addition reaction are increased, so that partial molecular chains are excessively crosslinked, the stress of polymer network chains is uneven, and the strength of the modified polyurethane adhesive film is greatly reduced.
Preparing the adhesive film into square film of 3mm × 3mm, vacuum drying to constant weight, weighing the mass m on an analytical balance1Placing the film in distilled water for 24h, taking out the film to remove surface water, and weighing the film as m2The water absorption of the adhesive film is calculated according to the following formula:
water absorption (%) - (m)2-m1)/m1×100％。
As a result, as shown in FIG. 3, it was found that the water resistance was enhanced with the increase of the addition amount of HK-6. The furan resin is a chain structure formed by connecting furan rings by methine and saturated carbon-carbon bonds, has no active functional groups, and has water resistance and corrosion resistance. The furan resin chain segment and the polyurethane prepolymer chain segment penetrate through each other to form an IPN structure, so that the space density in the polymer is increased, water molecules are difficult to enter due to space reduction, and the water absorption is reduced.
The results are shown in FIG. 4, where it can be seen that with nano SiO2The water resistance is enhanced by increasing the addition amount. This is because SiO2The nano material belongs to a rigid substance, molecules are mostly in a net-shaped and three-dimensional chain structure, the inorganic Si-O network and the modified WPU network are mutually crossed and penetrated, the crosslinking density of the coating is enhanced, the specific surface area of the nano material is large, and pores generated in the curing and shrinking process of the coating can be filled. Water molecules are difficult to spread on the surface of the adhesive film and cannot permeate into the adhesive filmAnd the water resistance of the adhesive film is greatly enhanced.
The furan resin is mainly prepared by furfuryl alcohol or furfural through polycondensation under the action of strong acid, the chemical structure of the furan resin is a chain structure formed by connecting furan rings by methine and saturated carbon-carbon bonds, and the double bonds in the furan rings and the furan rings conjugated by the triple bonds on other chains have Diels-Alder reaction under the acidic condition to generate polymers which have no active functional groups, are solvent-resistant, and are chemical-resistant and heat-resistant. One of the synthetic raw materials of the furfural is derived from agricultural and sideline products such as rice hulls, corn stalks and the like, and is a raw material with energy conservation, environmental protection and low price. The introduction of the furan resin chain segment increases the crosslinking degree in the polyurethane polymer, and the mechanical property of the prepared adhesive film can be greatly improved.
Nano SiO2The material belongs to a rigid substance, the molecules are mostly in a net structure and are intersected and penetrated with a polymer network, the crosslinking density of a coating is enhanced, the specific surface area of the nano material is large, the weight is light, and the compatibility with a polyurethane polymer is poor. Introducing nano SiO into modified polyurethane emulsion2The inorganic material can greatly increase the surface hydrophobicity of the polyurethane adhesive film, thereby reducing the water absorption of the adhesive film and improving the water resistance.
The invention is not limited to the examples, and any equivalent changes that can be made by one skilled in the art through reading the technical scheme of the invention in the specification of the invention are covered by the claims of the invention.

Claims (5)

1. A preparation method of inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion is characterized by comprising the following steps:
step 1, mixing polyester polyol and diisocyanate, dropwise adding dibutyltin dilaurate, introducing nitrogen, and reacting to obtain a system 1;
step 2, adding a hydrophilic chain extender into the system 1 for reaction; then adding furan resin, and reacting to obtain a system 2;
step 3, adding a neutralizing agent into the system 2, adding water for dispersion after reaction to obtain a water-based polyurethane emulsion;
step 4, mixing the nano SiO2Adding the mixture into the aqueous polyurethane emulsion obtained in the step (3), and carrying out ultrasonic reaction to obtain inorganic-organic composite modified cross-linked aqueous polyurethane emulsion;
in step 1, the molar ratio of polyester polyol to diisocyanate is 1: (2.7-3.3), wherein the addition amount of dibutyltin dilaurate is 0.05-0.09% of the total mass of diisocyanate and polyester polyol;
in the step 2, the hydrophilic chain extender is 2, 2-dimethylolpropionic acid or 2, 2-dimethylolbutyric acid, and the addition amount of the hydrophilic chain extender is 4-6% of the total mass of the diisocyanate and the polyester polyol;
in the step 2, the addition amount of the furan resin is 5.5-7.5 percent of the total mass of the diisocyanate and the polyester polyol;
in the step 3, the neutralizing agent is triethylamine; the mole ratio of the neutralizer to the hydrophilic chain extender is (0.8-1.5): 1;
the step 4 is specifically as follows: adding 0.5-2.5 percent of nano SiO (silicon dioxide) in terms of the solid content of the aqueous polyurethane emulsion into the aqueous polyurethane emulsion obtained in the step 32And carrying out ultrasonic reaction at 10-15 ℃ for 5-13 min to obtain the inorganic-organic composite modified crosslinking type aqueous polyurethane emulsion.
2. The method for preparing the inorganic-organic composite modified crosslinking aqueous polyurethane emulsion according to claim 1, wherein in the step 1, the reaction temperature is 60 ℃ to 80 ℃ and the reaction time is 1h to 3 h.
3. The method for preparing the inorganic-organic composite modified crosslinking aqueous polyurethane emulsion according to claim 1, wherein the step 2 specifically comprises: adding a hydrophilic chain extender into the system 1, reacting for 2 to 4 hours at the temperature of between 60 and 80 ℃, then adding furan resin, and reacting for 1 to 2 hours at the temperature of between 30 and 40 ℃.
4. The method for preparing the inorganic-organic composite modified crosslinking aqueous polyurethane emulsion according to claim 1, wherein the step 3 is specifically: adding a neutralizing agent into the system 2 for reaction for 15-30 min, adjusting the pH value to 7-8, and adding water for dispersion to obtain the aqueous polyurethane emulsion.
5. The inorganic-organic composite modified crosslinking aqueous polyurethane emulsion obtained by the preparation method of any one of claims 1 to 4.
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