CN112625569A - Preparation method of waterborne polyurethane/inorganic nano composite material coating with bionic micropatterning - Google Patents
Preparation method of waterborne polyurethane/inorganic nano composite material coating with bionic micropatterning Download PDFInfo
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to the field of polymer composite materials, and discloses a preparation method of a bionic micropatterned waterborne polyurethane/inorganic nano composite material coating, which comprises the following specific steps: dispersing two-dimensional inorganic nano powder in a low-boiling-point organic solvent A, and performing ultrasonic dispersion for 20-30 min to form a dispersion liquid; dispersing the dispersion liquid into the aqueous polyurethane emulsion under high-speed stirring, adding a low-boiling-point organic solvent B with the evaporation rate less than that of the low-boiling-point organic solvent A, and stirring at normal temperature for 20-30 min to obtain an aqueous polyurethane/inorganic nano composite material emulsion; pouring the mixture into a mould, and drying in an oven to obtain the bionic micropatterned waterborne polyurethane/inorganic nano composite material coating. According to the invention, the A, B solvents have different evaporation rates, and the inorganic nano powder and the waterborne polyurethane form shrinkage through molecular self-assembly and interface self-assembly, so that the bionic bottom-up micropatterned waterborne polyurethane/inorganic nano composite material coating is prepared.
Description
Technical Field
The invention relates to the field of polymer composite materials, in particular to a preparation method for preparing a bionic micropatterned composite material coating by using waterborne polyurethane and two-dimensional inorganic nano powder.
Background
The patterned surface is widely existed in nature, such as macroscopic mountains, skins of organisms, micro-nano patterns of plants such as lotus leaves and the like, has aesthetic value, super-hydrophobicity, self-cleaning, adhesion control and special optical performance, and has important research value and potential application prospect in the fields of biology, photoelectricity, energy, environment and the like. In recent years, the construction of bionic micropatterned surfaces has become one of the hot spots in scientific research on material surfaces.
Currently, surface micropatterning techniques are mainly classified into top-down and bottom-up. The method mainly comprises the steps of laser etching, chemical etching, photoetching, lithography, imprinting and the like from top to bottom, and has the advantages of mature technology and good repeatability, but the preparation process is complex, the cost is high, and large-area preparation is difficult; the bottom-up technology mainly prepares the micropattern through bionic molecule self-assembly and interface self-assembly, the preparation process is simple, the cost is lower, and the micropattern can be prepared in a large area. Therefore, in recent years, the preparation of surface micropatterning by biomimetic molecular self-assembly and interfacial self-assembly has been the focus of research.
The self-assembly of molecules means that molecules spontaneously form a stable and ordered structure from bottom to top through weak non-covalent interaction forces such as hydrogen bonds, van der waals forces, dipole-dipole forces, hydrophilic-hydrophobic forces, and synergy among the molecules. Its advantage does: the molecular units can realize rearrangement and recombination in the size and direction of space through self-assembly, and a patterned structure with new functions and characteristics of light, electricity, catalysis and the like is prepared. For example, CN 107983601A, CN 108341984 a prepared a micropatterned surface by initiating molecular self-assembly by hydrophilic-hydrophobic forces. The interface self-organization means that under the external stimulation, the thermodynamic equilibrium of a metastable state system is broken, and meanwhile, complex stress is generated in the system. According to the lowest energy principle, in order to reach a new thermodynamic equilibrium, metastable systems must release excessive internal stress, which is usually accomplished by self-organization of the system interface into a certain pattern. Thus, interfacial self-organization behavior is usually accompanied by the generation of bottom-up surface patterns. Compared with the traditional complex micropattern processing technology, the interface self-organization technology only utilizes the special instability in the system to construct the micropatterned surface, the formation of the pattern is spontaneous formation during processing, the method has the advantages of simple and convenient operation, large-area preparation, low cost and the like, and the microstructure generation mode is completely spontaneous formation from the inside of the system from bottom to top, thereby having more bionic significance. The Injejuno subject group of Shanghai traffic university in China prepares a bionic patterned photocuring coating by combining a surface self-assembly technology, a phase separation technology, an ultraviolet curing technology and an interface self-organization technology; CN 109206828A prepared a surface self-wrinkle pattern by ultraviolet light induction.
The Waterborne Polyurethane (WPU) takes water as a dispersion medium, is safe and environment-friendly, and has excellent film forming property, strong adhesive force, good air permeability of products and soft texture, so that the Waterborne Polyurethane (WPU) has important practical significance for the research of micropatterning on the surface of a waterborne polyurethane coating. On the other hand, the inorganic nano powder has rich surface morphology, and can be induced to self-assemble on an interface to form a microstructure surface by an LB technology, a hydrogen bond, the interfacial tension of liquid, a capillary force, a magnetic field force, a shearing force, a solid interface modification and the like under the action of a stabilizer. Two-dimensional inorganic nanopowders such as hexagonal boron nitride, graphene oxide and the like also have abundant two-dimensional forms, but the study of forming micropatterning based on the interaction between the two-dimensional inorganic nanopowders and polymers is rare.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a preparation method of a bionic micropatterned waterborne polyurethane/inorganic nano composite coating, and particularly relates to a method for preparing a bottom-up bionic micropatterned waterborne polyurethane/inorganic nano composite coating by molecular self-assembly and interface self-organization of two-dimensional inorganic nano powder and waterborne polyurethane. .
The technical scheme is as follows: the invention provides a preparation method of a bionic micropatterned waterborne polyurethane/inorganic nano composite material coating, which comprises the following steps: dispersing two-dimensional inorganic nano powder in a low-boiling-point organic solvent A, and performing ultrasonic dispersion for 20-30 min to form a dispersion liquid; dispersing the dispersion liquid into the aqueous polyurethane emulsion under high-speed stirring, adding a low-boiling-point organic solvent B with the evaporation rate different from that of the low-boiling-point organic solvent A, and stirring at normal temperature for 20-30 min to obtain an aqueous polyurethane/inorganic nano composite material emulsion; pouring the mixture into a mould, and drying in an oven to obtain the bionic micropatterned waterborne polyurethane/inorganic nano composite material coating.
Preferably, the two-dimensional inorganic nano powder is hexagonal boron nitride, graphene and graphene oxide with a lamellar structure, and the diameter of the two-dimensional inorganic nano powder is 20-100 nm.
Preferably, the low-boiling organic solvent a and the low-boiling organic solvent B are alcohols, ketones, ethers or esters which are miscible with water and have boiling points below 80 ℃.
Preferably, the mass ratio of the two-dimensional inorganic nano powder to the low-boiling-point organic solvent A is 1: 5-20.
Preferably, the mass ratio of the low-boiling-point organic solvent A to the low-boiling-point organic solvent B is 1: 0.2-5.
Preferably, the aqueous polyurethane emulsion is a coating special-purpose aqueous polyurethane emulsion.
Preferably, the mass ratio of the two-dimensional inorganic nano powder to the aqueous polyurethane emulsion is 20-50: 100.
Preferably, the drying temperature in the oven is 40-80 ℃, and the drying time is 0.5-24 h.
Preferably, the low-boiling-point organic solvent A is acetone, and the low-boiling-point organic solvent B is absolute ethyl alcohol.
The working principle and the beneficial effects are as follows: the two-dimensional inorganic nano-material and the waterborne polyurethane emulsion are uniformly mixed by a mechanical stirring method, and the waterborne polyurethane/inorganic nano-composite emulsion is prepared by adding a low-boiling-point organic solvent A and a low-boiling-point organic solvent B with different evaporation rates (after the two-dimensional inorganic nano-material and the waterborne polyurethane emulsion are uniformly mixed with A, the two-dimensional inorganic nano-material and the waterborne polyurethane emulsion are better and uniformly mixed by adding B). In the process of drying and film forming, a bionic bottom-up micropatterned aqueous polyurethane/inorganic nano composite material coating is formed through interface self-organization and molecular self-assembly, and is attributed to the following reasons:
(1) a, B the evaporation rates of two low boiling point organic solvents are different (the evaporation rate of A is greater than that of B), the system is in metastable state, and in order to release stress, the interface self-organizes to form micro-patterns;
(2) due to the existence of pi bonds, the molecules spontaneously form a stable and ordered structure from bottom to top through pi-pi interaction force to obtain the bionic micropatterned coating;
(3) OH or NH on surface of two-dimensional inorganic nano powder2Hydrogen bonds are formed with carbamate (-NH-COO-) in the waterborne polyurethane molecule, and the organic-inorganic interface is self-assembled to form a micro-pattern.
According to the invention, A, B two low-boiling-point organic solvents have different evaporation rates, on one hand, the system is in a metastable state, and in order to release stress, inorganic nano-powder and aqueous polyurethane emulsion form shrinkage through interface self-organization; on the other hand, in the evaporation process, the evaporation rate of the component A with better capability of dispersing the two-dimensional inorganic nano powder is faster than that of the component B, the two-dimensional inorganic nano powder gradually accumulates and grows under the pi-pi action along with the reduction of the component A to form a stable and ordered structure, and the waterborne polyurethane polymer chain is bonded and shaped, so that the bionic bottom-up micropatterned waterborne polyurethane/inorganic nano composite material coating is prepared; the bionic micropatterning preparation process can be operated at room temperature, is simple and feasible, has easily obtained raw materials and lower cost, and is suitable for industrial production.
Drawings
Fig. 1 is a polarization microscope photograph of the surface of the micro-patterned aqueous polyurethane/nano boron nitride coating prepared in embodiment 1;
FIG. 2 is a UV spectrum of the pure polyurethane (a) and the micro-patterned aqueous polyurethane/nano boron nitride composite (b) in example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Embodiment 1:
weighing 10 g of nano hexagonal boron nitride, adding the nano hexagonal boron nitride into 30 ml of acetone, and performing ultrasonic dispersion for 30 min to obtain a dispersion liquid; adding 100 g of waterborne polyurethane emulsion with the solid content of 30% into the dispersion, adding 20 ml of absolute ethyl alcohol under high-speed stirring, and continuously stirring for 30 min to obtain waterborne polyurethane/nano boron nitride emulsion; and pouring a proper amount of the emulsion into a PP box, and drying for 24 h at 60 ℃ to obtain the bionic micropatterned waterborne polyurethane/nano boron nitride coating.
The surface polarization microscope photo of the prepared micropatterned waterborne polyurethane/nano boron nitride coating is shown in figure 1. As can be seen from fig. 1: regular feather-like bionic patterns are prepared. FIG. 2 is a solid ultraviolet spectrum diagram of (a) pure water polyurethane and (b) micro-patterned aqueous polyurethane/nano boron nitride composite material, which can be seen from the following figures: compared with pure water polyurethane, the ultraviolet spectrum of the composite material is red-shifted, which proves that the composite material has pi-pi action.
Embodiment 2:
weighing 15 g of nano hexagonal boron nitride, adding the nano hexagonal boron nitride into 30 ml of acetone, and performing ultrasonic dispersion for 30 min to obtain a dispersion liquid; adding 100 g of waterborne polyurethane emulsion with the solid content of 30% into the dispersion, adding 50 ml of absolute ethyl alcohol under high-speed stirring, and continuously stirring for 30 min to obtain waterborne polyurethane/nano boron nitride emulsion; and pouring a proper amount of the emulsion into a PP box, and drying for 24 h at 60 ℃ to obtain the bionic micropatterned waterborne polyurethane/nano boron nitride coating.
Embodiment 3:
weighing 10 g of nano graphene, adding the nano graphene into 30 ml of acetone, and performing ultrasonic dispersion for 30 min to obtain a dispersion liquid; adding 100 g of aqueous polyurethane emulsion with the solid content of 30% into the dispersion liquid, adding 20 ml of absolute ethyl alcohol under high-speed stirring, and continuously stirring for 30 min to obtain aqueous polyurethane/nano-graphene emulsion; and (3) pouring a proper amount of the emulsion on a PTFE plate, and drying at 60 ℃ for 1 h to obtain the bionic micropatterned waterborne polyurethane/nano-graphene coating.
Embodiment 4:
weighing 10 g of nano graphene oxide, adding the nano graphene oxide into 30 ml of acetone, and performing ultrasonic dispersion for 30 min to obtain a dispersion liquid; adding 100 g of aqueous polyurethane emulsion with the solid content of 30% into the dispersion liquid, adding 20 ml of absolute ethyl alcohol under high-speed stirring, and continuously stirring for 30 min to obtain aqueous polyurethane/nano graphene oxide emulsion; and (3) pouring a proper amount of the emulsion on a PTFE plate, and drying at 60 ℃ for 1 h to obtain the bionic micropatterned waterborne polyurethane/nano graphene oxide coating.
The above embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A preparation method of a bionic micropatterned waterborne polyurethane/inorganic nano composite material coating is characterized by comprising the following steps: dispersing two-dimensional inorganic nano powder in a low-boiling-point organic solvent A, and performing ultrasonic dispersion for 20-30 min to form a dispersion liquid; dispersing the dispersion liquid into the aqueous polyurethane emulsion under high-speed stirring, adding a low-boiling-point organic solvent B with the evaporation rate smaller than that of the low-boiling-point organic solvent A, and stirring at normal temperature for 20-30 min to obtain an aqueous polyurethane/inorganic nano composite material emulsion; pouring the mixture into a mould, and drying in an oven to obtain the bionic micropatterned waterborne polyurethane/inorganic nano composite material coating.
2. The preparation method of the waterborne polyurethane/inorganic nanocomposite coating with biomimetic micropatterning according to claim 1, wherein the method comprises the following steps: the two-dimensional inorganic nano powder is hexagonal boron nitride, graphene and graphene oxide in a lamellar structure, and the diameter of the two-dimensional inorganic nano powder is 20-100 nm.
3. The preparation method of the waterborne polyurethane/inorganic nanocomposite coating with biomimetic micropatterning according to claim 1, wherein the method comprises the following steps: the low-boiling-point organic solvent A and the low-boiling-point organic solvent B are alcohols, ketones, ethers or esters which can be mixed and dissolved with water, and the boiling points are lower than 80 ℃.
4. The preparation method of the waterborne polyurethane/inorganic nanocomposite coating with biomimetic micropatterning according to claim 1, wherein the method comprises the following steps: the mass ratio of the two-dimensional inorganic nano powder to the low-boiling-point organic solvent A is 1: 5-20.
5. The preparation method of the waterborne polyurethane/inorganic nanocomposite coating with biomimetic micropatterning according to claim 1, wherein the method comprises the following steps: the mass ratio of the low-boiling-point organic solvent A to the low-boiling-point organic solvent B is 1: 0.2-5.
6. The preparation method of the waterborne polyurethane/inorganic nanocomposite coating with biomimetic micropatterning according to claim 1, wherein the method comprises the following steps: the aqueous polyurethane emulsion is a special coating aqueous polyurethane emulsion.
7. The preparation method of the waterborne polyurethane/inorganic nanocomposite coating with biomimetic micropatterning according to claim 1, wherein the method comprises the following steps: the mass ratio of the two-dimensional inorganic nano powder to the aqueous polyurethane emulsion is 20-50: 100.
8. The preparation method of the bionic micro-patterning waterborne polyurethane/inorganic nanocomposite coating according to claim 1, wherein the preparation method comprises the following steps: the drying temperature in the oven is 40-80 ℃, and the drying time is 0.5-24 h.
9. The preparation method of the waterborne polyurethane/inorganic nanocomposite coating with biomimetic micropatterning according to any one of claims 1 to 8, wherein the method comprises the following steps: the low-boiling-point organic solvent A is acetone, and the low-boiling-point organic solvent B is absolute ethyl alcohol.
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Application publication date: 20210409 Assignee: Yancheng Dafeng HaoChen Electronic Technology Co.,Ltd. Assignor: HUAIYIN INSTITUTE OF TECHNOLOGY Contract record no.: X2022980025827 Denomination of invention: Preparation method of waterborne polyurethane/inorganic nanocomposite coating with biomimetic micro pattern Granted publication date: 20220517 License type: Common License Record date: 20221216 |