CN112239622A - Preparation method of waterborne polyurethane composite coating for glass substrate - Google Patents

Preparation method of waterborne polyurethane composite coating for glass substrate Download PDF

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CN112239622A
CN112239622A CN202011176422.6A CN202011176422A CN112239622A CN 112239622 A CN112239622 A CN 112239622A CN 202011176422 A CN202011176422 A CN 202011176422A CN 112239622 A CN112239622 A CN 112239622A
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polyurethane
preparation
water
polycarbonate
chain extender
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高光辉
任秀艳
徐资凯
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Changchun University of Technology
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Changchun University of Technology
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
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    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract

The invention provides a preparation method of a waterborne polyurethane composite coating for a glass substrate, belonging to the technical field of high-molecular waterborne coatings. The water-based polyurethane composite coating for the glass substrate prepared by the step-by-step method has the performance superior to that of the traditional single-component and double-component water-based coating, and the water-based coating prepared by the step-by-step method consists of a first component of polycarbonate polyurethane resin and a second component containing ethylenically unsaturated polyurethane resin, wherein the second component is an ethylenically unsaturated polyurethane prepolymer formed by polymerizing diisocyanate monomers, polyether (ester) polyol, a water-based chain extender and hydroxy acrylate, so that the water-based coating is cured and crosslinked by free radicals at a dry/high temperature to form a firm coating. The tensile strength of the prepared polyurethane composite coating reaches up to 30 MPa. Solves the key technical problem of protecting the substrate by the aqueous polyurethane coating, improves the mechanical property of the aqueous polyurethane coating and anticipates the widening of the application field of the aqueous polyurethane.

Description

Preparation method of waterborne polyurethane composite coating for glass substrate
Technical Field
The invention belongs to a synthesis technology of a water-based paint, and relates to a preparation method of a water-based polyurethane composite paint for a glass substrate.
Background
The water-based paint is one of the most rapidly developed green environment-friendly paints, wherein the water-based paint with a larger specific weight is a water-based polyurethane paint. The waterborne polyurethane coating has the characteristics of strong adhesive force, high hardness, good heat resistance and the like, also has the characteristic of low Volatile Organic Compound (VOC) content, and gradually replaces solvent type polyurethane coatings. The waterborne polyurethane coating has extremely wide application in the aspect of wood lacquer, and can also be applied to furniture coatings, automobile coatings, building coatings, plastic coatings, anticorrosive coatings and the like in daily life. Meanwhile, some coatings in special fields such as aerospace, war industry, energy and the like are water-based coatings. But the wear resistance and the breakage resistance of the protective base material of the water-based polyurethane coating film are poor. The aqueous polyurethane coating has no shatter resistance to brittle substrates, such as glass substrates. Therefore, the comprehensive performance of the waterborne polyurethane coating is improved, the defects in practical application are overcome, the domestic market share of the waterborne polyurethane coating is improved, the development pace of the waterborne polyurethane coating industry in China is accelerated, and the waterborne polyurethane coating has milestone significance.
The traditional waterborne polyurethane coating is researched and improved in the aspects of environmental protection and hydrophobicity, and the environment-friendly waterborne two-component polyurethane coating invented by Wanaiarmy (application patent number: CN 201910220226.5) is widely applied to the surface coating of various automobile surfaces, passenger car carriages, locomotive heads, electric equipment, automobile parts, instruments and meters and the like. The Liuwei brocade (application patent number: CN 201710763936.3) is used for preparing a fluorosilane modified polyurethane hydrophobic film, and can be applied to the fields of self-cleaning and waterproof materials due to excellent hydrophobicity and simple preparation method.
However, coatings that require protection for brittle substrates or substrates in extreme environments are still under development, and therefore increasing the strength of aqueous polyurethane coatings is a first problem that must be solved for the preparation of aqueous polyurethane coatings. The free radical cured waterborne polyurethane composite coating adopted by the invention overcomes the problem of low strength of the traditional waterborne polyurethane. The application of the waterborne polyurethane in the aspect of fragile base materials is widened.
Disclosure of Invention
In order to improve the protective capability of the aqueous polyurethane coating on the substrate, the application of the aqueous polyurethane coating on a fragile matrix is widened. The invention provides a preparation method of a waterborne polyurethane composite coating for a glass substrate.
The invention provides a main component free radical curing and composite reinforcing component.
The invention provides a preparation method of a waterborne polyurethane composite coating for a glass substrate, which comprises the following steps and conditions:
(1) preparation of first component aqueous emulsion of polycarbonate polyurethane
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 60-70: 6-8: 0.1-0.3: 0.5-1, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2-4 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer; the diisocyanate I is isophorone diisocyanate, the polycarbonate polyol is polycarbonate diol, the aqueous chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, and the micromolecular chain extender is 1, 4-butanediol;
b. preparation of aqueous emulsion of polycarbonate polyurethane
Cooling the polycarbonate polyurethane polymer prepared in the step (1) a to 50 ℃, adding triethylamine with the same molar ratio with a water-based chain extender for neutralization, and adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the polycarbonate polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain a polycarbonate polyurethane aqueous emulsion;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 898449DEST_PATH_IMAGE001
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 40-50: 5-7: 0.1-0.3, uniformly mixing, putting into a four-opening reactor, putting the four-opening reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, keeping the temperature for 2-4 hours, and finishing the polymerization reaction to obtain a polyurethane prepolymer; cooling the obtained polyurethane prepolymer to 55 ℃, and adding the polyurethane prepolymer and diisocyanate
Figure 813316DEST_PATH_IMAGE001
The mass ratio of (A) to (B) is 100: 10 hydroxy acrylic acid esters, reacting for 1 hour to obtain an ethylenically unsaturated polyurethane polymer; the diisocyanates
Figure 599875DEST_PATH_IMAGE001
Toluene diisocyanate, polyether glycol, 2-bis (hydroxymethyl) propionic acid as a water-based chain extender, dibutyltin dilaurate as a catalyst and hydroxyethyl methacrylate as a hydroxyacrylate;
b. preparation of aqueous emulsions containing ethylenically unsaturated polyurethanes
Cooling the ethylenically unsaturated polyurethane polymer prepared in the step (2) a to 50 ℃, adding triethylamine in the same molar ratio with the water-based chain extender for neutralization, and adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the ethylenically unsaturated polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain an ethylenically unsaturated polyurethane aqueous emulsion;
(3) preparation of waterborne polyurethane composite coating
Mixing a first component of polycarbonate polyurethane aqueous emulsion and a second component of aqueous emulsion containing ethylenically unsaturated polyurethane in a volume ratio of 1-2: 1, putting the mixture into a stirrer, adding an initiator, wherein the adding amount of the initiator is 1 percent of the total mass of the water-based emulsion containing the ethylenic unsaturated polyurethane resin in the second component, and magnetically stirring the mixture for 30 to 50 minutes to obtain the water-based polyurethane composite coating; the initiator is benzophenone;
has the advantages that: the waterborne polyurethane composite coating for the glass matrix is obviously characterized in that a main component is cured by free radicals and a composite reinforcing component is added. The strong network structure formed by free radical curing and the physical curing network structure formed by adding the composite reinforcing component are interpenetrated, so that the tensile strength of the prepared waterborne polyurethane composite film for the glass matrix is up to 30 MPa. The invention solves the problem of low strength of the traditional waterborne polyurethane coating. The application of the waterborne polyurethane in the aspect of fragile base materials is widened.
Detailed Description
Example 1
(1) Preparation of first component aqueous emulsion of polycarbonate polyurethane
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 60: 6: 0.1: 0.5, uniformly mixing, putting into a four-opening reactor, putting the four-opening reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer; the diisocyanate I is isophorone diisocyanate, the polycarbonate polyol is polycarbonate diol, the aqueous chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, and the micromolecular chain extender is 1, 4-butanediol;
b. preparation of aqueous emulsion of polycarbonate polyurethane
Cooling the polycarbonate polyurethane polymer prepared in the step (1) a to 50 ℃, adding triethylamine with the same molar ratio with a water-based chain extender for neutralization, and adding deionized water after 0.5 hour, wherein the mass ratio of the added deionized water to the polycarbonate polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain a polycarbonate polyurethane aqueous emulsion;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 863366DEST_PATH_IMAGE001
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 40: 5: 0.1, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain a polyurethane prepolymer; cooling the obtained polyurethane prepolymer to 55 ℃, and adding the polyurethane prepolymer and diisocyanate
Figure 384477DEST_PATH_IMAGE001
The mass ratio of (A) to (B) is 100: 10 hydroxy acrylic acid esters, reacting for 1 hour to obtain an ethylenically unsaturated polyurethane polymer; the diisocyanates
Figure 761756DEST_PATH_IMAGE001
Toluene diisocyanate, polyether glycol, 2-bis (hydroxymethyl) propionic acid as a water-based chain extender, dibutyltin dilaurate as a catalyst and hydroxyethyl methacrylate as a hydroxyacrylate;
b. preparation of aqueous emulsions containing ethylenically unsaturated polyurethanes
Cooling the ethylenically unsaturated polyurethane polymer prepared in the step (2) a to 50 ℃, adding triethylamine in the same molar ratio with the water-based chain extender for neutralization, and adding deionized water after 1 hour, wherein the mass ratio of the added amount of the deionized water to the ethylenically unsaturated polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain an ethylenically unsaturated polyurethane aqueous emulsion;
(3) preparation of waterborne polyurethane composite coating
Mixing a first component of polycarbonate polyurethane aqueous emulsion and a second component of aqueous emulsion containing ethylenically unsaturated polyurethane in a volume ratio of 1: 1, putting the mixture into a stirrer, adding an initiator, wherein the adding amount of the initiator is 1 percent of the total mass of the second component of the water-based emulsion containing the ethylenic unsaturated polyurethane resin, and magnetically stirring the mixture for 40 minutes to obtain the water-based polyurethane composite coating; the initiator is benzophenone;
the method for measuring the mechanical property of the prepared waterborne polyurethane composite coating film for the glass substrate comprises the following steps: cutting a polyurethane film with the thickness of 0.5cm into a dumbbell shape with the width of 4cm and the length of 6cm, preparing 3 samples from the polyurethane film prepared under the conditions of each embodiment, performing a mechanical tensile test on a universal material testing machine, wherein the gauge length is 15mm, the tensile rate is 20mm/min, and measuring the mechanical property of the polyurethane film;
the tensile strength is calculated as follows:
Figure 871664DEST_PATH_IMAGE002
in the formula: p is the maximum load in N; b is the sample width in mm; d is the specimen thickness in mm.
The average values of the tensile strengths of the waterborne polyurethane composite coating films for glass substrates prepared in example 1 were 30.9 MPa respectively.
Example 2
(1) Preparation of first component aqueous emulsion of polycarbonate polyurethane
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 65: 7: 0.2: 0.6, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer; obtaining a polycarbonate polyurethane polymer; the diisocyanate I is isophorone diisocyanate, the polycarbonate polyol is polycarbonate diol, the aqueous chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, and the micromolecular chain extender is 1, 4-butanediol;
b. preparation of aqueous emulsion of polycarbonate polyurethane
Cooling the polycarbonate polyurethane polymer prepared in the step (1) a to 50 ℃, adding triethylamine with the same molar ratio with a water-based chain extender for neutralization, and adding deionized water after 1 hour, wherein the mass ratio of the added amount of the deionized water to the polycarbonate polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain a polycarbonate polyurethane aqueous emulsion;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 306056DEST_PATH_IMAGE003
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 45: 6: 0.2, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain a polyurethane prepolymer; cooling the obtained polyurethane prepolymer to 55 ℃, and adding the polyurethane prepolymer and diisocyanate
Figure 563731DEST_PATH_IMAGE003
The mass ratio of (A) to (B) is 100: 10 hydroxy acrylic acid esters, reacting for 1 hour to obtain an ethylenically unsaturated polyurethane polymer; the diisocyanates
Figure 554821DEST_PATH_IMAGE003
Toluene diisocyanate, polyether glycol, 2-bis (hydroxymethyl) propionic acid as a water-based chain extender, dibutyltin dilaurate as a catalyst and hydroxyethyl methacrylate as a hydroxyacrylate;
b. preparation of aqueous emulsions containing ethylenically unsaturated polyurethanes
Cooling the ethylenically unsaturated polyurethane polymer prepared in the step (2) a to 50 ℃, adding triethylamine in the same molar ratio with the water-based chain extender for neutralization, and adding deionized water after 1 hour, wherein the mass ratio of the added amount of the deionized water to the ethylenically unsaturated polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain an ethylenically unsaturated polyurethane aqueous emulsion;
(3) preparation of waterborne polyurethane composite coating
Mixing the first component of the aqueous emulsion of polycarbonate polyurethane and the second component of the aqueous emulsion containing the ethylenically unsaturated polyurethane in a volume ratio of 2: 1, putting the mixture into a stirrer, adding an initiator, wherein the adding amount of the initiator is 1 percent of the total mass of the second component of the water-based emulsion containing the ethylenic unsaturated polyurethane resin, and magnetically stirring the mixture for 50 minutes to obtain the water-based polyurethane composite coating; the initiator is benzophenone;
the average values of the tensile strengths of the aqueous polyurethane composite coating films for glass substrates prepared in example 2 were 32.5 MPa, respectively, by the measuring method of example 1.
Example 3
(1) Preparation of first component aqueous emulsion of polycarbonate polyurethane
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 70: 8: 0.3: 1, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 4 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer; the diisocyanate I is isophorone diisocyanate, the polycarbonate polyol is polycarbonate diol, the aqueous chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, and the micromolecular chain extender is 1, 4-butanediol;
b. preparation of aqueous emulsion of polycarbonate polyurethane
Cooling the polycarbonate polyurethane polymer prepared in the step (1) a to 50 ℃, adding triethylamine with the same molar ratio with a water-based chain extender for neutralization, and adding deionized water after 0.5 hour, wherein the mass ratio of the added deionized water to the polycarbonate polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain a polycarbonate polyurethane aqueous emulsion;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 602059DEST_PATH_IMAGE003
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 50: 7: 0.3, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, keeping the temperature for 24 hours, and finishing the polymerization reaction to obtain a polyurethane prepolymer; cooling the obtained polyurethane prepolymer to 55 ℃, and adding the polyurethane prepolymer and diisocyanate
Figure 20402DEST_PATH_IMAGE003
The mass ratio of (A) to (B) is 100: 10 hydroxy acrylic acid esters, reacting for 1 hour to obtain an ethylenically unsaturated polyurethane polymer; the diisocyanates
Figure 499794DEST_PATH_IMAGE003
Toluene diisocyanate, polyether glycol, 2-bis (hydroxymethyl) propionic acid as a water-based chain extender, dibutyltin dilaurate as a catalyst and hydroxyethyl methacrylate as a hydroxyacrylate;
b. preparation of aqueous emulsions containing ethylenically unsaturated polyurethanes
Cooling the ethylenically unsaturated polyurethane polymer prepared in the step (2) a to 50 ℃, adding triethylamine in the same molar ratio with the water-based chain extender for neutralization, and adding deionized water after 1 hour, wherein the mass ratio of the added amount of the deionized water to the ethylenically unsaturated polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain an ethylenically unsaturated polyurethane aqueous emulsion;
(3) preparation of waterborne polyurethane composite coating
Mixing the first component of the aqueous emulsion of polycarbonate polyurethane and the second component of the aqueous emulsion containing the ethylenically unsaturated polyurethane in a volume ratio of 2: 1, putting the mixture into a stirrer, adding an initiator, wherein the adding amount of the initiator is 1 percent of the total mass of the second component of the water-based emulsion containing the ethylenic unsaturated polyurethane resin, and magnetically stirring the mixture for 50 minutes to obtain the water-based polyurethane composite coating; the initiator is benzophenone;
the average values of the tensile strengths of the aqueous polyurethane composite coating films for glass substrates prepared in example 3 were 31.6 MPa, respectively, by the measuring method of example 1.

Claims (4)

1. A preparation method of a waterborne polyurethane composite coating for a glass substrate is characterized by comprising the following steps and conditions:
(1) preparation of first component aqueous emulsion of polycarbonate polyurethane
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 60-70: 6-8: 0.1-0.3: 0.5-1, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2-4 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer; the diisocyanate I is isophorone diisocyanate, the polycarbonate polyol is polycarbonate diol, the aqueous chain extender is 2, 2-bis (hydroxymethyl) propionic acid, the catalyst is dibutyltin dilaurate, and the micromolecular chain extender is 1, 4-butanediol;
b. preparation of aqueous emulsion of polycarbonate polyurethane
Cooling the polycarbonate polyurethane polymer prepared in the step (1) a to 50 ℃, adding triethylamine with the same molar ratio with a water-based chain extender for neutralization, and adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the polycarbonate polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain a polycarbonate polyurethane aqueous emulsion;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 912751DEST_PATH_IMAGE001
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 40-50: 5-7: 0.1-0.3, uniformly mixing, putting into a four-opening reactor, putting the four-opening reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, keeping the temperature for 2-4 hours, and finishing the polymerization reaction to obtain a polyurethane prepolymer; cooling the obtained polyurethane prepolymer to 55 ℃, and adding the polyurethane prepolymer and diisocyanate
Figure 436136DEST_PATH_IMAGE001
The mass ratio of (A) to (B) is 100: 10 hydroxy acrylic acid esters, reacting for 1 hour to obtain an ethylenically unsaturated polyurethane polymer; the diisocyanates
Figure 803664DEST_PATH_IMAGE001
Toluene diisocyanate, polyether glycol, 2-bis (hydroxymethyl) propionic acid as a water-based chain extender, dibutyltin dilaurate as a catalyst and hydroxyethyl methacrylate as a hydroxyacrylate;
b. preparation of aqueous emulsions containing ethylenically unsaturated polyurethanes
Cooling the ethylenically unsaturated polyurethane polymer prepared in the step (2) a to 50 ℃, adding triethylamine in the same molar ratio with the water-based chain extender for neutralization, and adding deionized water after 0.5-1 hour, wherein the mass ratio of the added amount of the deionized water to the ethylenically unsaturated polyurethane polymer is 6: 4, stirring and emulsifying at a high speed to obtain an ethylenically unsaturated polyurethane aqueous emulsion;
(3) preparation of waterborne polyurethane composite coating
Mixing a first component of polycarbonate polyurethane aqueous emulsion and a second component of aqueous emulsion containing ethylenically unsaturated polyurethane in a volume ratio of 1-2: 1, putting the mixture into a stirrer, adding an initiator, wherein the adding amount of the initiator is 1 percent of the total mass of the water-based emulsion containing the ethylenic unsaturated polyurethane resin in the second component, and magnetically stirring the mixture for 30 to 50 minutes to obtain the water-based polyurethane composite coating; the initiator is benzophenone.
2. The method for preparing the aqueous polyurethane composite coating for the glass substrate according to claim 1, wherein the steps and conditions are as follows:
the first component of the aqueous emulsion of polycarbonate polyurethane is prepared
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 60: 6: 0.1: 0.5, uniformly mixing, putting into a four-opening reactor, putting the four-opening reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 45289DEST_PATH_IMAGE001
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 40: 5: 0.1, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain the polyurethane prepolymer.
3. The method for preparing the aqueous polyurethane composite coating for the glass substrate according to claim 1, wherein the steps and conditions are as follows:
the first component of the aqueous emulsion of polycarbonate polyurethane is prepared
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 65: 7: 0.2: 0.6, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 320413DEST_PATH_IMAGE001
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 45: 6: 0.2, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 2 hours, and finishing the polymerization reaction to obtain the polyurethane prepolymer.
4. The method for preparing the aqueous polyurethane composite coating for the glass substrate according to claim 1, wherein the steps and conditions are as follows:
(1) preparation of first component aqueous emulsion of polycarbonate polyurethane
a. Preparation of polycarbonate polyurethane polymers
Diisocyanate I, polycarbonate polyol, a water-based chain extender, a catalyst and a micromolecule chain extender are mixed according to the mass ratio of 100: 70: 8: 0.3: 1, uniformly mixing, putting into a four-port reactor, putting the four-port reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, preserving the heat for 4 hours, and finishing the polymerization reaction to obtain a polycarbonate polyurethane polymer;
(2) preparation of a second component aqueous emulsion containing an ethylenically unsaturated polyurethane
a. Preparation of polymers containing ethylenically unsaturated polyurethane
Reacting diisocyanates
Figure 901567DEST_PATH_IMAGE001
The polyether polyol, the water-based chain extender and the catalyst are mixed according to the mass ratio of 100: 50: 7: 0.3, uniformly mixing, putting into a four-opening reactor, putting the four-opening reactor into a constant-temperature water tank, stirring, introducing nitrogen into the system, keeping the temperature at 70 ℃, keeping the temperature for 24 hours, and finishing the polymerization reaction to obtain the polyurethane prepolymer.
CN202011176422.6A 2020-10-29 2020-10-29 Preparation method of waterborne polyurethane composite coating for glass substrate Pending CN112239622A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482530A (en) * 2009-08-18 2012-05-30 拜尔材料科学有限公司 Coating compositions for glass substrates
CN105419625A (en) * 2015-12-30 2016-03-23 中物功能材料研究院有限公司 Self-cleaning aqueous UV cured paint and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482530A (en) * 2009-08-18 2012-05-30 拜尔材料科学有限公司 Coating compositions for glass substrates
CN105419625A (en) * 2015-12-30 2016-03-23 中物功能材料研究院有限公司 Self-cleaning aqueous UV cured paint and preparation method thereof

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