CN113968959A - Polyurethane for gravure printing ink - Google Patents
Polyurethane for gravure printing ink Download PDFInfo
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- CN113968959A CN113968959A CN202111459445.2A CN202111459445A CN113968959A CN 113968959 A CN113968959 A CN 113968959A CN 202111459445 A CN202111459445 A CN 202111459445A CN 113968959 A CN113968959 A CN 113968959A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Discloses a polyurethane for gravure printing ink, which is prepared by the following method: reacting dicyclohexylmethane-4, 4' -diisocyanate with polytetrahydrofuran ether glycol and other diols to obtain a waterborne polyurethane prepolymer; then the nano SiO is put into2Mixing with hydrogen peroxide deionized water solution to obtain nano dispersion liquid, continuously dropwise adding the nano dispersion liquid into a reaction system, and heating; discharging after the reaction is finished to obtain milkWhite aqueous polyurethane emulsion. Compared with the prior art, the polyurethane emulsion particles for the gravure printing ink have smaller average particle size and better storage stability.
Description
Technical Field
The invention belongs to the technical field of gravure printing ink; relates to a resin for gravure printing ink, in particular to polyurethane for gravure printing ink.
Background
The water-based ink is printing ink which is prepared by compounding water serving as a main solvent, water-based polymer resin (a binder), pigment and an auxiliary agent. The water-based ink is mainly applied to packaging printing at present, and the printing mode is mainly gravure printing. Among them, the performance of the aqueous ink vehicle resin mainly determines the performance of the gravure ink, so the key for improving the performance of the aqueous ink is to improve the performance of the aqueous ink vehicle resin.
Polyurethane is short for polyurethane, and the molecular structure of the polyurethane comprises a soft segment consisting of oligomer polyol and a hard segment consisting of isocyanate and a small molecule chain extender. Polyurethane has excellent flexibility, wear resistance, adhesion, chemical resistance and the like due to its special structure. At present, gravure printing ink for food packaging plastic films is mainly solvent type polyurethane ink, and excellent performances of polyurethane endow gravure printing products with excellent wear resistance, steaming resistance and the like. With the continuous improvement of environmental protection and safety requirements, the water-based polyurethane ink is required to be developed to replace solvent-based polyurethane ink, and the key for developing the water-based polyurethane ink is to prepare the water-based polyurethane ink binder resin with excellent performance.
The water-based polyurethane is a binary colloidal resin formed by introducing hydrophilic groups on a polyurethane molecular chain to endow the polyurethane molecular chain with hydrophilicity and dispersing the polyurethane molecular chain in water. Due to the introduction of hydrophilic groups, the viscosity of the waterborne polyurethane is higher, and the solid content is lower; meanwhile, the average particle size of emulsion particles of the waterborne polyurethane is large, and the storage stability after long-time storage is poor.
Chinese patent application publication CN102898597A discloses a composite ink vehicle for gravure printing. Firstly, preparing polyurethane prepolymer with double bonds at one end, and then carrying out free radical polymerization on acrylate, methacrylate, vinyl acetate and the polyurethane prepolymer with double bonds at one end. Because only one end of the polyurethane prepolymer with double bonds at one end participates in the free radical polymerization reaction, the proportion of each raw material can be changed at will in the preparation of the ink vehicle, and the occurrence of gel phenomenon caused by the generation of a network structure by the reaction is avoided. The polyurethane branched chain is introduced into the polyacrylate molecular main chain, so that the polarity of the molecules of the composite ink binder for gravure printing is effectively adjusted, the ink binder has good adhesive force to various plastic film substrates, and can be matched with alcohol-soluble type and ester-soluble type laminating adhesives for use, and the preparation requirement of the composite ink for gravure printing can be met.
Chinese patent application publication CN110041752A discloses a PVC edge banding gravure printing water-based ink with good stability, which comprises the following components in parts by mass: 30-40 parts of a connecting material, 30-40 parts of water, 10-20 parts of a pigment and 5-10 parts of an auxiliary agent; the connecting material is modified polyurethane acrylic emulsion, and hexafluoropropylene dimer, hexafluoropropylene trimer and dialkyl maleate are introduced into a branched chain of an acrylic acid molecular chain of the modified polyurethane acrylic emulsion for modification. The PVC edge banding gravure printing water-based ink with good stability has the characteristics of high stability, strong adhesive force and simple process.
However, the above prior art still has the technical defects that the average particle size of emulsion particles is large and the storage stability after long-term storage is poor.
Therefore, in view of the various drawbacks of the prior art, there is a need to find a polyurethane for gravure ink having a smaller average particle size of emulsion particles and better storage stability.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a polyurethane for gravure ink. Compared with the prior art, the polyurethane emulsion particles for the gravure printing ink have smaller average particle size and better storage stability.
In order to achieve the purpose, the invention adopts the following technical scheme: polyurethane for intaglio printing inks, characterized in that it is prepared according to the following process:
(1) heating dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol to 70-90 ℃, stirring for 0.5-2h, adding a proper amount of catalyst dibutyltin dilaurate, and continuously stirring for 15-50min for reaction;
(2) reducing the temperature of the reaction solution to 50-60 ℃, adding dimethylolpropionic acid fully dispersed in N-methylpyrrolidone into the reaction solution, heating to 65-75 ℃, reacting for 5-20min, heating the water bath to 70-90 ℃, and reacting for 2-4h to obtain a waterborne polyurethane prepolymer;
(3) then cooling the temperature of the waterborne polyurethane prepolymer to room temperature, slowly adding 1, 4-butanediol into the waterborne polyurethane prepolymer, stirring and shearing at a high speed of 1000rpm for 0.5-2h at 600-;
(4) mixing nano SiO2Mixing with hydrogen peroxide deionized water solution at the rotating speed of 100-;
(5) continuously dropwise adding the nano dispersion liquid into a reaction system under the high-speed stirring of 600-1000rpm, raising the temperature of a constant-temperature water bath to 35-45 ℃ and accelerating the decomposition of hydrogen peroxide to generate water;
(6) adding potassium hydroxide, adjusting the pH value of the system to 8.0-9.0, reducing the rotation speed to 100-300rpm, and continuing to react for 0.5-2 h; discharging after the reaction is finished to obtain the milky waterborne polyurethane emulsion.
The polyurethane provided by the invention is characterized in that the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to polytetrahydrofuran ether glycol is (1.6-2.0): 1.
Advantageously, the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to polytetrahydrofuran ether glycol is (1.7-1.9): 1.
The polyurethane has the number average molecular weight Mn of 1600 dalton and PDI of 1.55-1.75.
Advantageously, the polytetrahydrofuran ether glycol has a number average molecular weight Mn of 1800-2200 dalton and a PDI of 1.6 to 1.7.
The polyurethane of the invention is characterized in that the addition amount of the catalyst dibutyl tin dilaurate is less than 0.01% relative to the sum of the weight of dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol.
Advantageously, the amount of catalyst dibutyltin dilaurate added is less than 0.005%, relative to the sum of the weight of dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol.
The polyurethane provided by the invention is characterized in that the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to dimethylolpropionic acid is 18 (4-6).
Advantageously, the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to dimethylolpropionic acid is 18 (4.5-5.5).
The polyurethane provided by the invention has a mole ratio of dicyclohexylmethane-4, 4' -diisocyanate to 1, 4-butanediol of 18 (2-4).
Advantageously, the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to 1, 4-butanediol is 18 (2.5-3.5).
The polyurethane of the invention, wherein the nano SiO2The average particle diameter of (2) is 10-30 nm; BET specific surface area of 170-200m2/g。
Advantageously, the nano SiO2The average particle diameter of (2) is 15-25 nm; BET specific surface area of 180-2/g。
The polyurethane provided by the invention is characterized in that the concentration of the hydrogen peroxide deionized water solution is 50-70 wt%.
Advantageously, the concentration of the deionized water solution of hydrogen peroxide is between 55 and 65% by weight.
The polyurethane of the invention, wherein the nano SiO2The weight ratio of the hydrogen peroxide to the deionized water solution is 1 (17-21).
Advantageously, the nano SiO2The weight ratio of the hydrogen peroxide to the deionized water solution is 1 (18-20).
The polyurethane of the invention, wherein the nano SiO is relative to the sum of the weight of dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol2The addition amount of (B) is 0.5-1.5 wt%.
Advantageously, the nano SiO is present in a proportion by weight relative to the sum of the weights of dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol2The addition amount of (B) is 0.8-1.2 wt%.
Compared with the prior art, the polyurethane emulsion for the gravure printing ink has smaller average particle size and better storage stability.
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods described and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for.
Unless otherwise indicated, parts are parts by weight, temperatures are in degrees Celsius or at ambient temperature, and pressures are at or near atmospheric. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Example 1
(1) Heating 18mmol of dicyclohexylmethane-4, 4' -diisocyanate and 10mmol of polytetrahydrofuran ether glycol (Mn is 2000 daltons, PDI is 1.64) to 80 ℃, stirring for 1h, adding 1mg of catalyst dibutyltin dilaurate, and continuously stirring for 30min for reaction;
(2) reducing the temperature of the reaction solution to 55 ℃, adding 5mmol of dimethylolpropionic acid fully dispersed in N-methyl pyrrolidone into the reaction solution, heating to 70 ℃, reacting for 10min, heating the water bath to 80 ℃, and reacting for 3h to obtain an aqueous polyurethane prepolymer;
(3) then cooling the temperature of the waterborne polyurethane prepolymer to room temperature, slowly adding 3mmol of 1, 4-butanediol into the waterborne polyurethane prepolymer, and stirring and shearing at a high speed of 800rpm for 1 h;
(4) mixing 250mg of nano SiO2(average particle diameter 20 nm; BET specific surface area 185 m)2/g) was mixed with 9.75g of 60 wt% hydrogen peroxide in deionized water at 200rpm for 5min to obtain a nanodispersion；
(5) Continuously dropwise adding the nano dispersion liquid into a reaction system under the high-speed stirring of 800rpm, raising the temperature of a constant-temperature water bath to 40 ℃, and accelerating the decomposition of hydrogen peroxide to generate water;
(6) adding potassium hydroxide, adjusting the pH value of the system to 8.5, reducing the rotating speed to 200rpm, and continuing to react for 1 h; discharging after the reaction is finished to obtain the milky waterborne polyurethane emulsion.
Comparative example 1
(1) Heating 18mmol of dicyclohexylmethane-4, 4' -diisocyanate and 10mmol of polytetrahydrofuran ether glycol (Mn is 2000 daltons, PDI is 1.64) to 80 ℃, stirring for 1h, adding 1mg of catalyst dibutyltin dilaurate, and continuously stirring for 30min for reaction;
(2) reducing the temperature of the reaction solution to 55 ℃, adding 5mmol of dimethylolpropionic acid fully dispersed in N-methyl pyrrolidone into the reaction solution, heating to 70 ℃, reacting for 10min, heating the water bath to 80 ℃, and reacting for 3h to obtain an aqueous polyurethane prepolymer;
(3) then cooling the temperature of the waterborne polyurethane prepolymer to room temperature, slowly adding 3mmol of 1, 4-butanediol into the waterborne polyurethane prepolymer, and stirring and shearing at a high speed of 800rpm for 1 h; mixing 250mg of nano SiO2(average particle diameter 20 nm; BET specific surface area 185 m)2/g) adding the mixture into the waterborne polyurethane prepolymer, and uniformly mixing the mixture under high-speed stirring at 800 rpm;
(4) continuously dropwise adding 9.75g of 60 wt% hydrogen peroxide deionized water solution into a reaction system under high-speed stirring at 800rpm, and raising the temperature of a constant-temperature water bath to 40 ℃ to accelerate the decomposition of hydrogen peroxide to generate water;
(5) adding potassium hydroxide, adjusting the pH value of the system to 8.5, reducing the rotating speed to 200rpm, and continuing to react for 1 h; discharging after the reaction is finished to obtain the milky waterborne polyurethane emulsion.
Comparative example 2
(1) Heating 18mmol of dicyclohexylmethane-4, 4' -diisocyanate and 10mmol of polytetrahydrofuran ether glycol (Mn is 2000 daltons, PDI is 1.64) to 80 ℃, stirring for 1h, adding 1mg of catalyst dibutyltin dilaurate, and continuously stirring for 30min for reaction;
(2) reducing the temperature of the reaction solution to 55 ℃, adding 5mmol of dimethylolpropionic acid fully dispersed in N-methyl pyrrolidone into the reaction solution, heating to 70 ℃, reacting for 10min, heating the water bath to 80 ℃, and reacting for 3h to obtain an aqueous polyurethane prepolymer;
(3) then cooling the temperature of the waterborne polyurethane prepolymer to room temperature, slowly adding 3mmol of 1, 4-butanediol into the waterborne polyurethane prepolymer, and stirring and shearing at a high speed of 800rpm for 1 h;
(4) continuously dropwise adding 10g of 60 wt% hydrogen peroxide deionized water solution into a reaction system under high-speed stirring at 800rpm, raising the temperature of a constant-temperature water bath to 40 ℃, and accelerating the decomposition of hydrogen peroxide to generate water;
(5) adding potassium hydroxide, adjusting the pH value of the system to 8.5, reducing the rotating speed to 200rpm, and continuing to react for 1 h; discharging after the reaction is finished to obtain the milky waterborne polyurethane emulsion.
Performance testing
The average particle diameter (nm) of the aqueous polyurethane emulsion for gravure ink of the present invention was measured by a dynamic light scattering instrument.
The storage stability of the waterborne polyurethane emulsion for the gravure printing ink is characterized in that a plurality of samples are stored at room temperature, one sample is taken out every day for a fixed time, the samples are centrifuged for 15min at the rotating speed of 6000rpm, whether demulsification is layered or not is observed, and the number of days (d) before demulsification is layered is recorded and is used as an index for evaluating the storage stability.
See table 1 for results.
TABLE 1
| Sample (I) | Average particle diameter (nm) | Storage stability (d) |
| Example 1 | 73.8 | >35 |
| Comparative example 1 | 89.2 | 23 |
| Comparative example 2 | 125.3 | 6 |
As can be seen from Table 1, the polyurethane emulsion particles for gravure ink according to example 1 of the present invention have a smaller average particle diameter and better storage stability.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (10)
1. Polyurethane for intaglio printing inks, characterized in that it is prepared according to the following process:
(1) heating dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol to 70-90 ℃, stirring for 0.5-2h, adding a proper amount of catalyst dibutyltin dilaurate, and continuously stirring for 15-50min for reaction;
(2) reducing the temperature of the reaction solution to 50-60 ℃, adding dimethylolpropionic acid fully dispersed in N-methylpyrrolidone into the reaction solution, heating to 65-75 ℃, reacting for 5-20min, heating the water bath to 70-90 ℃, and reacting for 2-4h to obtain a waterborne polyurethane prepolymer;
(3) then cooling the temperature of the waterborne polyurethane prepolymer to room temperature, slowly adding 1, 4-butanediol into the waterborne polyurethane prepolymer, stirring and shearing at a high speed of 1000rpm for 0.5-2h at 600-;
(4) mixing nano SiO2Mixing with hydrogen peroxide deionized water solution at the rotating speed of 100-;
(5) continuously dropwise adding the nano dispersion liquid into a reaction system under the high-speed stirring of 600-1000rpm, raising the temperature of a constant-temperature water bath to 35-45 ℃ and accelerating the decomposition of hydrogen peroxide to generate water;
(6) adding potassium hydroxide, adjusting the pH value of the system to 8.0-9.0, reducing the rotation speed to 100-300rpm, and continuing to react for 0.5-2 h; discharging after the reaction is finished to obtain the milky waterborne polyurethane emulsion.
2. The polyurethane of claim 1, wherein the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to polytetrahydrofuran ether glycol is (1.6-2.0): 1.
3. The polyurethane as claimed in claim 1 or 2, wherein the polytetrahydrofuran ether glycol has a number average molecular weight Mn of 1600-2400 dalton and a PDI of 1.55-1.75.
4. A polyurethane according to any one of claims 1 to 3 wherein the catalyst dibutyltin dilaurate is added in an amount of less than 0.01% relative to the sum of the weight of dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol.
5. A polyurethane according to any one of claims 1 to 4 wherein the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to dimethylolpropionic acid is 18 (4-6).
6. A polyurethane according to any one of claims 1 to 5 wherein the molar ratio of dicyclohexylmethane-4, 4' -diisocyanate to 1, 4-butanediol is 18 (2-4).
7. The polyurethane of any one of claims 1-6, wherein the nano-SiO2The average particle diameter of (2) is 10-30 nm; BET specific surface area of 170-200m2/g。
8. A polyurethane according to any one of claims 1 to 7 wherein the concentration of the hydrogen peroxide in deionized water is from 50 to 70 wt%.
9. The polyurethane of any one of claims 1-8, wherein the nano-SiO is2The weight ratio of the hydrogen peroxide to the deionized water solution is 1 (17-21).
10. The polyurethane of any one of claims 1-9, wherein the nano SiO is relative to the sum of the weight of dicyclohexylmethane-4, 4' -diisocyanate and polytetrahydrofuran ether glycol2The addition amount of (B) is 0.5-1.5 wt%.
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2021
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