CN111607318A - Preparation method of anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating - Google Patents

Preparation method of anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating Download PDF

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CN111607318A
CN111607318A CN202010552448.XA CN202010552448A CN111607318A CN 111607318 A CN111607318 A CN 111607318A CN 202010552448 A CN202010552448 A CN 202010552448A CN 111607318 A CN111607318 A CN 111607318A
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repairing
modified graphene
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杜卫宁
林蒋
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Abstract

The invention discloses a preparation method of an anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating, wherein the composite coating is prepared by carrying out solution polymerization on modified graphene loaded by nano titanium dioxide and a self-repairing waterborne polyurethane prepolymer containing disulfide bonds, the modified graphene is obtained by covalently modifying graphene oxide, nano titanium dioxide and diisocyanate, and the composite coating can synergistically exert the graphene and the nano titanium dioxide loaded on the surface of the graphene, so that the waterborne polyurethane material has good anti-ultraviolet and anti-static properties. Meanwhile, the main chain of the waterborne polyurethane contains dynamic disulfide bonds, and damages such as polyurethane broken sections, scratches and the like can be repaired under room-temperature visible light; the preparation method provided by the invention has the advantages of low cost and simple operation, and the prepared composite coating has good ultraviolet resistance, antistatic property and photoinduced self-repairing property, and can be applied to the fields of leather, textile, wood and other intelligent coatings.

Description

Preparation method of anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating
Technical Field
The invention relates to the field of intelligent coatings such as leather, textile, wood and the like, in particular to a preparation method of an anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating.
Background
The waterborne polyurethane coating material is widely applied to the fields of buildings, light industry, aerospace and the like (Angewandte Chemie, 2013, 52: 9422-9435) due to the advantages of light weight, simple processing, stable property, strong adhesion and the like. However, the waterborne polyurethane coating material is prone to damage such as microcrack and aging during use or placement, which greatly limits the safety and practicability of the material and further affects the application performance of the material (Chemical Engineering Journal, 2019, 368: 1033-. Based on self-repairing capability and dynamic chemical theory of organisms, dynamic covalent bonds are introduced into a water-based polyurethane structure, and the material generates covalent or non-covalent actions under external stimuli such as light, heat, electricity, magnetism and the like to realize self-repairing (advanced functional Materials, 2018, 28: 1706050). Aromatic disulfide bonds can be dynamically exchanged at room temperature, and a micromolecular monomer containing disulfide bonds and isocyanate-terminated waterborne polyurethane prepolymer are polymerized to obtain a polyurethane-polyurea elastomer with a self-repairing function, and the molecular chains of disulfide bonds can be promoted to be dynamically exchanged at room temperature so as to realize self-healing (Macromolecular Rapid Communications, 2015, 36: 1255-1260).
Most polyurethane coating materials are easy to age under ultraviolet light and do not have an antistatic function, so that the appearance and the application performance of the coating materials are seriously influenced, and the application range of the coating materials is limited. The traditional aging resistant agent or conductive agent can be commonly used for preparing the anti-ultraviolet or anti-static polyurethane coating material, but has the bottleneck problems of large dosage and difficult dispersion, and has certain limitations because a dispersant is often required to be added when the traditional aging resistant agent or conductive agent is compounded with a polyurethane matrix (Composites Part B: Engineering, 2019, 172: 555-.
With organic/inorganic nanocompositesIn the deep research of the composite material, the combination of the inorganic nano material with the functions of absorbing ultraviolet light and conducting electricity to the polymer matrix is expected to improve the ultraviolet resistance and the antistatic performance of the polymer coating in a synergistic manner (Progress in materials Science, 2018, 97: 230-). sup.282). The graphene is represented by sp2The two-dimensional layered material with the hexagonal lattice honeycomb lattice structure formed by bonding the hybridized Carbon atoms has the characteristics of high specific surface, high conductivity, high light absorption and the like, and is widely applied to the field of polymer composite materials (Carbon, 2015, 93: 555-. However, graphene sheets have strong van der waals force therebetween, are easily agglomerated in a polyurethane matrix, and have a very limited amount of graphene supported in the polyurethane matrix and an improved ultraviolet light absorption (reflection) rate and conductivity of polyurethane. Therefore, how to prepare the functionalized graphene which is high in dispersion efficiency and can greatly improve the ultraviolet resistance and the electrostatic resistance of the waterborne polyurethane coating is an urgent problem to be solved. Graphene oxide is one of important derivatives of graphene, and has the advantages of simple preparation and low cost, and a large number of oxygen-containing active groups (such as hydroxyl, carboxyl, epoxy and the like) exist on the surface of graphene oxide, so that selective chemical grafting modification is easy to perform. In addition, as a spherical nano material, the nano titanium dioxide has better properties of shielding ultraviolet rays, conducting electricity and the like (Polymer Testing, 2011, 30: 381-389). Based on the method, the graphene oxide and the nano titanium dioxide are chemically bonded through organic micromolecules containing isocyanate groups to prepare the modified graphene loaded with the nano titanium dioxide, and the modified graphene is further polymerized with the disulfide bond-containing self-repairing polyurethane prepolymer, so that the problem of the dispersibility of the graphene in the aqueous polyurethane matrix can be solved, and the ultraviolet resistance and the antistatic performance of the self-repairing aqueous polyurethane coating material can be obviously improved.
Chinese patent (CN110511344A) discloses a self-repairing polyurethane elastomer based on multiple dynamic reversible functions and a preparation method thereof, wherein the self-repairing polyurethane elastomer is obtained by solution polymerization of diisocyanate, polyester diol and a disulfide chain extender, and has a self-repairing function, but the self-repairing function needs to be realized by external heating (60 ℃), and the self-repairing polyurethane elastomer does not have ultraviolet resistance and antistatic functions, and the application range is limited. Chinese patent (CN103145943A) discloses waterborne polyurethane with high antistatic performance and a preparation method thereof, wherein the waterborne polyurethane is prepared by polymerizing isophorone diisocyanate, polycaprolactone polyol, sebacic acid polyester polyol, trimethylolpropane, ethylenediamine, bis (hydroxymethyl) propionic acid, polymethylsiloxane, acetone and deionized water, and the polyurethane coating has excellent antistatic and anti-aging performance, but does not have a self-repairing function and has potential safety hazard. At present, researches on self-repairing, ultraviolet-resistant and antistatic functions of the photoinduced self-repairing aqueous polyurethane/modified graphene composite coating at home and abroad are not reported. Therefore, the nano titanium dioxide loaded modified graphene and the disulfide bond-containing self-repairing polyurethane prepolymer are polymerized, and the antistatic and aging-resistant performances of the composite coating can be remarkably improved based on the characteristics of nano titanium dioxide, electric conduction and the like of the graphene and the nano titanium dioxide. Meanwhile, the main chain of the polyurethane contains dynamic disulfide bonds, and damages such as polyurethane broken sections and scratches can be repaired under room temperature visible light. The preparation method provided by the invention has the advantages of low cost and simple and convenient operation, and the prepared composite coating has good ultraviolet resistance, antistatic performance and photoinduced self-repairing performance.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems, the invention provides a preparation method of the anti-ultraviolet and anti-static self-repairing aqueous polyurethane/modified graphene composite coating, which is low in cost and simple and convenient to operate, and the prepared composite coating has good anti-ultraviolet, anti-static and photoinduced self-repairing performances.
(II) technical scheme
The preparation method of the anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating is synthesized according to the following specific process:
preparing modified graphene: mixing and dispersing 1-10 parts of graphene oxide and 1-10 parts of nano titanium dioxide in 100-1000 parts of organic solvent, adding 0.1-1.0 part by mass of diisocyanate, reacting for 24-48 h at 60-80 ℃ under the protection of nitrogen, centrifuging, and drying to obtain nano titanium dioxide loaded modified graphene for later use; (2) preparing self-repairing waterborne polyurethane: placing 1-10 parts of high-molecular diol, 3-30 parts of diisocyanate, 2-20 parts of a functional chain extender, 0.001-0.01 part of an organic bismuth catalyst, 1-10 parts of tributylamine and 12-120 parts of an organic solvent with a solid content in a three-neck flask with a stirring device, reacting for 4-8 hours at 60-80 ℃ under the protection of nitrogen to obtain a disulfide bond-containing self-repairing polyurethane precursor, adding 10-100 parts of deionized water and 0.1-1 part of propylene diamine, and dispersing at a high speed of 1000-3000 r/min for 1-3 hours to obtain disulfide bond-containing self-repairing waterborne polyurethane for later use; (3) preparing a self-repairing waterborne polyurethane/modified graphene composite coating: carrying out solution polymerization on 1-10% by mass of modified graphene loaded with nano titanium dioxide and a waterborne polyurethane precursor, carrying out nitrogen protection, and reacting at 60-80 ℃ for 4-8 h to obtain the self-repairing waterborne polyurethane/modified graphene composite coating.
Wherein the particle size of the nano titanium dioxide is one of 20nm, 30nm and 50 nm; the diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate; the high molecular dihydric alcohol is one of polycarbonate diol and acrylate dihydric alcohol; the functional chain extender is one or two of dimethylolpropionic acid, ethylene diamine ethyl sodium sulfonate and bis (4-hydroxyphenyl) disulfide; the organic solvent is one of ethyl acetate, butanone and tetrahydrofuran.
(III) advantageous effects
Compared with the prior art, the invention has the following beneficial effects: the self-repairing aqueous polyurethane/modified graphene composite coating is prepared by carrying out solution polymerization on modified graphene loaded with nano titanium dioxide and a self-repairing aqueous polyurethane prepolymer containing disulfide bonds, and the characteristics of nano titanium dioxide, electric conduction and the like of the composite coating graphene and the nano titanium dioxide can obviously improve the antistatic and anti-aging properties of the composite coating. In addition, the main chain of the waterborne polyurethane of the composite coating contains dynamic disulfide bonds, and damages such as broken sections and scratches of the waterborne polyurethane can be repaired under room-temperature visible light. The preparation method provided by the invention has the advantages of low cost and simple operation, and the prepared composite coating has good ultraviolet resistance, antistatic property and photoinduced self-repairing property, and can be applied to the fields of leather, textile, wood and other intelligent coatings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an infrared spectrum of a self-repairing aqueous polyurethane modified graphene composite coating material prepared in the first embodiment.
Fig. 2 is a self-repairing effect diagram of the self-repairing aqueous polyurethane modified graphene composite coating material prepared in the second embodiment.
Fig. 3 is a mechanical property diagram of the self-repairing aqueous polyurethane modified graphene composite coating material prepared in the third embodiment before and after aging.
Fig. 4 is a conductivity diagram of the self-repairing aqueous polyurethane modified graphene composite coating material prepared in the fourth embodiment.
Detailed Description
The first embodiment is as follows: mixing and dispersing 10g of graphene oxide and 10g of nano titanium dioxide in 1000 mL of butanone, adding 10g of isophorone diisocyanate, reacting for 24 hours at 70 ℃ under the protection of nitrogen, centrifuging, and drying to obtain modified graphene loaded with nano titanium dioxide for later use; (2) preparation of disulfide bond-containing self-repairing aqueous polyurethane precursor: 50g of polycarbonate diol (M)n1000), 44.4g of isophorone diisocyanate, 30.5g of bis (4-hydroxyphenyl) disulfide, 3.1g of dimethylolpropionic acid, 200mL of butanone and 0.14g of organic bismuth catalyst are placed in a three-neck flask with a stirring device, nitrogen is used for protection, the reaction is carried out at 70 ℃ for 6h to obtain a disulfide bond-containing self-repairing aqueous polyurethane precursor, 50g of deionized water and 1.3g of propylene diamine are added, and the mixture is dispersed at a high speed of 2000r/min for 2h to obtain the disulfide bond-containing self-repairing aqueous polyurethane precursorThe self-repairing waterborne polyurethane is used for standby; (3) preparing a self-repairing waterborne polyurethane/modified graphene composite coating: compounding 1g of nano titanium dioxide loaded modified graphene with 100g of disulfide bond-containing self-repairing aqueous polyurethane precursor, continuously stirring for 4h at 70 ℃, cooling to room temperature, pouring a film, and drying for 48h at 60 ℃ to obtain the self-repairing aqueous polyurethane/modified graphene composite coating material. As can be seen from FIG. 1, 1705, 1632, 1543 and 1223cm-1 are absorption peaks of carbonyl or/and carbamate segments, 1623cm-1 is absorption peak of carbon-carbon bond, 682cm-1 is absorption peak of disulfide bond, and the above results confirm the structure of the prepared target coating material.
Example two: mixing and dispersing 10g of graphene oxide and 10g of nano titanium dioxide in 1000 mL of butanone, adding 10g of isophorone diisocyanate, reacting for 24 hours at 70 ℃ under the protection of nitrogen, centrifuging, and drying to obtain modified graphene loaded with nano titanium dioxide for later use; (2) preparation of disulfide bond-containing self-repairing aqueous polyurethane precursor: 50g of acrylate diol (M)n1000), 44.4g of isophorone diisocyanate, 30.5g of bis (4-hydroxyphenyl) disulfide, 2.3g of ethylenediamine ethanesulfonic acid sodium salt, 200mL of butanone and 0.14g of organic bismuth catalyst are placed in a three-neck flask with a stirring device, nitrogen is used for protection, the reaction is carried out at 70 ℃ for 6h to obtain a self-repairing waterborne polyurethane precursor containing disulfide bonds, 50g of deionized water and 1.3g of propylene diamine are added, and the mixture is dispersed at a high speed of 1000r/min for 2h to obtain self-repairing waterborne polyurethane containing disulfide bonds for later use; (3) preparing a self-repairing waterborne polyurethane/modified graphene composite coating: compounding 1g of nano titanium dioxide loaded modified graphene with 100g of disulfide bond-containing self-repairing aqueous polyurethane precursor, continuously stirring for 4h at 70 ℃, cooling to room temperature, pouring a film, and drying for 48h at 60 ℃ to obtain the self-repairing aqueous polyurethane/modified graphene composite coating material. As can be seen from FIG. 2, the dents on the surface of the repaired coating are almost completely disappeared, which indicates that the prepared coating has better self-repairing performance.
Example three: mixing and dispersing 10g of graphene oxide and 10g of nano titanium dioxide in 1000 mL of butanone, adding 10g of hexamethylene diisocyanate, carrying out nitrogen protection, and reacting at 70 ℃ for 2Centrifuging and drying for 4h to obtain the modified graphene loaded with the nano titanium dioxide for later use; (2) preparation of disulfide bond-containing self-repairing aqueous polyurethane precursor: 50g of acrylate diol (M)n1000), 44.4g of hexamethylene diisocyanate, 30.5g of bis (4-hydroxyphenyl) disulfide, 2.3g of ethylenediamine ethanesulfonic acid sodium salt, 200mL of butanone and 0.14g of organic bismuth catalyst are placed in a three-neck flask with a stirring device, nitrogen is used for protection, the reaction is carried out at 70 ℃ for 6h to obtain a disulfide bond-containing self-repairing waterborne polyurethane precursor, then 80g of deionized water and 1.3g of propylene diamine are added, and the mixture is dispersed at a high speed of 2000r/min for 2h to obtain disulfide bond-containing self-repairing waterborne polyurethane for later use; (3) preparing a self-repairing waterborne polyurethane/modified graphene composite coating: compounding 1g of nano titanium dioxide loaded modified graphene with 100g of disulfide bond-containing self-repairing polyurethane precursor, continuously stirring for 4h at 70 ℃, cooling to room temperature, pouring a film, and drying for 48h at 60 ℃ to obtain the self-repairing waterborne polyurethane/modified graphene composite coating material. As can be seen from FIG. 3, the mechanical properties of the coating material before and after aging do not change much, which indicates that the prepared coating has better anti-ultraviolet aging performance.
Example four: mixing and dispersing 10g of graphene oxide and 10g of nano titanium dioxide in 1000 mL of butanone, adding 10g of isophorone diisocyanate, reacting for 24 hours at 70 ℃ under the protection of nitrogen, centrifuging, and drying to obtain modified graphene loaded with nano titanium dioxide for later use; (2) preparation of disulfide bond-containing self-repairing aqueous polyurethane precursor: 50g of polycarbonate diol (M)n3000 percent), 44.4g of isophorone diisocyanate, 12.5g of bis (4-hydroxyphenyl) disulfide, 1.8g of dimethylolpropionic acid, 150mL of butanone and 0.14g of organic bismuth catalyst are placed in a three-neck flask with a stirring device, nitrogen is used for protection, the reaction is carried out at 70 ℃ for 6h to obtain a self-repairing waterborne polyurethane precursor containing disulfide bonds, then 50g of deionized water and 1.3g of propylene diamine are added, and the mixture is dispersed at a high speed of 2000r/min for 2h to obtain self-repairing waterborne polyurethane containing disulfide bonds for later use; (3) preparing a self-repairing waterborne polyurethane/modified graphene composite coating: compounding 3g of nano titanium dioxide loaded modified graphene and 100g of disulfide bond-containing self-repairing aqueous polyurethane precursor, continuously stirring for 4h at 70 ℃, cooling to room temperature, pouringAnd drying the film at 60 ℃ for 48 hours to obtain the self-repairing aqueous polyurethane/modified graphene composite coating material. As can be seen from FIG. 4, the conductivity of the prepared coating can reach 0.25S/m, and can still reach 0.20S/m after UV irradiation for 15 days, which indicates that the prepared coating has a better antistatic function.
Example five: mixing and dispersing 10g of graphene oxide and 10g of nano titanium dioxide in 1000 mL of butanone, adding 10g of isophorone diisocyanate, reacting for 24 hours at 70 ℃ under the protection of nitrogen, centrifuging, and drying to obtain modified graphene loaded with nano titanium dioxide for later use; (2) preparation of disulfide bond-containing self-repairing aqueous polyurethane precursor: 50g of polycarbonate diol (M)n3000 percent), 44.4g of isophorone diisocyanate, 12.5g of bis (4-hydroxyphenyl) disulfide, 1.8g of dimethylolpropionic acid, 150mL of butanone and 0.14g of organic bismuth catalyst are placed in a three-neck flask with a stirring device, nitrogen is used for protection, the reaction is carried out at 70 ℃ for 6h to obtain a self-repairing waterborne polyurethane precursor containing disulfide bonds, then 50g of deionized water and 1.3g of propylene diamine are added, and the mixture is dispersed at a high speed of 2000r/min for 2h to obtain self-repairing waterborne polyurethane containing disulfide bonds for later use; (3) preparing a self-repairing waterborne polyurethane/modified graphene composite coating: compounding 5g of nano titanium dioxide loaded modified graphene with 100g of disulfide bond-containing self-repairing aqueous polyurethane precursor, continuously stirring for 4h at 70 ℃, cooling to room temperature, pouring a film, and drying for 48h at 60 ℃ to obtain the self-repairing aqueous polyurethane/modified graphene composite coating material. The self-healing of the fracture surface can be realized by repairing the waterborne polyurethane/modified graphene composite coating for 6 hours at room temperature, the repair rates of the tensile strength and the elongation at break are 82.5% and 90.2%, in addition, the conductivity of the coating can reach 0.25S/m, and the coating can still be maintained at 0.20S/m after being irradiated by UV for 15 days, which indicates that the prepared coating has better ultraviolet resistance and antistatic function.
The preparation method provided by the invention has the advantages of low cost and simple operation, and the prepared composite coating has good ultraviolet resistance, antistatic property and photoinduced self-repairing property, and can be applied to the fields of leather, textile, wood and other intelligent coatings.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention and do not limit the spirit and scope of the present invention. Various modifications and improvements of the technical solutions of the present invention may be made by those skilled in the art without departing from the design concept of the present invention, and the technical contents of the present invention are all described in the claims.

Claims (2)

1. A preparation method of an anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating is characterized by comprising the following specific steps: preparing modified graphene: mixing and dispersing 1-10 parts of graphene oxide and 1-10 parts of nano titanium dioxide in 100-1000 parts of organic solvent, adding 0.1-1.0 part by mass of diisocyanate, reacting for 24-48 h at 60-80 ℃ under the protection of nitrogen, centrifuging, and drying to obtain nano titanium dioxide loaded modified graphene for later use; (2) preparing self-repairing waterborne polyurethane: placing 1-10 parts of high-molecular diol, 3-30 parts of diisocyanate, 2-20 parts of a functional chain extender, 0.001-0.01 part of an organic bismuth catalyst, 1-10 parts of tributylamine and 12-120 parts of an organic solvent with a solid content in a three-neck flask with a stirring device, reacting for 4-8 hours at 60-80 ℃ under the protection of nitrogen to obtain a disulfide bond-containing self-repairing polyurethane precursor, adding 10-100 parts of deionized water and 0.1-1 part of propylene diamine, and dispersing at a high speed of 1000-3000 r/min for 1-3 hours to obtain disulfide bond-containing self-repairing waterborne polyurethane for later use; (3) preparing a self-repairing waterborne polyurethane/modified graphene composite coating: carrying out solution polymerization on 1-10% by mass of modified graphene loaded with nano titanium dioxide and a waterborne polyurethane precursor, carrying out nitrogen protection, and reacting at 60-80 ℃ for 4-8 h to obtain the self-repairing waterborne polyurethane/modified graphene composite coating.
2. The preparation method of the self-repairing aqueous polyurethane/modified graphene composite coating according to claim 1, wherein the particle size of the used nano titanium dioxide is one of 20nm, 30nm and 50 nm; the diisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate; the high molecular dihydric alcohol is one of polycarbonate diol and acrylate dihydric alcohol; the functional chain extender is one or two of dimethylolpropionic acid, ethylene diamine ethyl sodium sulfonate and bis (4-hydroxyphenyl) disulfide; the organic solvent is one of ethyl acetate, butanone and tetrahydrofuran.
CN202010552448.XA 2020-06-17 2020-06-17 Preparation method of anti-ultraviolet and anti-static self-repairing waterborne polyurethane modified graphene composite coating Withdrawn CN111607318A (en)

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