CN114907760A - Preparation method of multifunctional coating based on polyurethane - Google Patents
Preparation method of multifunctional coating based on polyurethane Download PDFInfo
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- CN114907760A CN114907760A CN202210662884.1A CN202210662884A CN114907760A CN 114907760 A CN114907760 A CN 114907760A CN 202210662884 A CN202210662884 A CN 202210662884A CN 114907760 A CN114907760 A CN 114907760A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a multifunctional coating based on polyurethane, wherein the multifunctional coating is a PPU waterproof coating, and the preparation method comprises the following steps: weighing corresponding amount of polyglycolic acid and hydrochloric acid tyrosine hydrochloride, adding the polyglycolic acid and the hydrochloric acid tyrosine hydrochloride into deionized water, magnetically stirring the mixture until the hydrochloric acid tyrosine hydrochloride is dissolved, adding the hydrochloric acid tyrosine hydrochloride into the solution for standby dissolution in the first step, continuously magnetically stirring the mixture until the hydrochloric acid tyrosine hydrochloride is dissolved to obtain a polyglutamic acid prepolymer solution, weighing a polyurethane prepolymer, placing the polyurethane prepolymer in a beaker, stirring the polyurethane prepolymer in a water bath, heating the mixture, adding the polyglutamic acid prepolymer prepared in the second step, stirring the mixture until the mixture is fully mixed to obtain the polyurethane prepolymer, proportionally mixing the polyurethane prepolymer prepared in the third step, I P6@ Z IF-8(Zn) and BTA @ CNT together (v/v), adding one drop of the mixed solution into an electromagnetic stirrer, stirring the mixture until the polyurethane prepolymer, uniformly dissolving and mixing the mixture, curing the mixture to obtain a coating, and obtaining the coating named PPU through curing.
Description
Technical Field
The invention relates to the technical field of nano coating protection, in particular to a preparation method of a multifunctional coating based on polyurethane.
Background
Aiming at the track traffic construction developed in the western world, not only the corrosion and further failure of the aluminum alloy caused by acid rain in the southwest area are considered, but also the Qinghai-Tibet railway laid on the northwest of the west is considered, the land has high altitude and low air temperature, and simultaneously the ultraviolet rays in the whole year in the plateau are stronger, so that the service life of structural members such as a vehicle body and a rail in the track traffic is influenced, and then multifunctional coatings such as self-repairing, ultraviolet resistance and the like are developed on the basis of an anti-corrosion function, so that the problem that the aluminum alloy member fails due to the influence of the environment in the use in the western world development is particularly important;
at present, in the face of point corrosion of small local corrosion of aluminum alloy, failure of an aluminum alloy member can be caused, and particularly, an anticorrosive coating which can quickly and efficiently self-repair without additional conditions and has excellent mechanical properties is needed under the conditions of high ultraviolet light intensity, low temperature, high speed and the like of a high-speed train developed in western China.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a multifunctional coating based on polyurethane, and the multifunctional coating which integrates the functions of corrosion resistance, self-repair, bacteriostasis, ultraviolet resistance and the like is prepared and attached to the surface of an aluminum alloy in a spraying and high polymer coating mode, so that the problems that a vehicle body on a plateau is easy to damage and corrode are solved.
The technical scheme of the invention is as follows: a preparation method of a multifunctional coating based on polyurethane, wherein the multifunctional coating is a PPU waterproof coating, comprises the following steps:
the method comprises the following steps: weighing corresponding amount of 0.6-0.8g of polyglycolic acid and 0.3-0.5g of hydrochloric acid tyrosine hydrochloride, adding into 8-12mL of deionized water, and magnetically stirring for dissolving for later use;
step two: weighing 0.3-0.5g of tyrosine hydrochloride, adding the tyrosine hydrochloride into the solution for standby dissolution in the step one, and continuing to stir by magnetic force until the tyrosine hydrochloride is dissolved to obtain a polyglutamic acid prepolymer solution for standby;
step three: measuring 30-50m of polyurethane prepolymer, placing the polyurethane prepolymer in a beaker, stirring in water bath, heating to 65-75 ℃, adding 8-12mL of the polyglutamic acid prepolymer prepared in the second step, and stirring until the components are fully mixed to obtain the polyurethane prepolymer for later use;
step four: mixing the polyurethane prepolymer prepared in the third step, IP6@ ZIF-8(Zn) and BTA @ CNT in a ratio of 8:1:1 (v/v), adding a drop of the mixed solution into an electromagnetic stirrer, stirring for 1-3h to dissolve and mix the mixed solution uniformly for later use, curing to obtain a coating, and naming the cured coating as PPU.
Preferred for the present invention are: the mass percentage of polyurethane in the polyurethane prepolymer is 10-20%.
Preferred for the present invention are: the polyurethane prepolymer contains 10-20% of IP6@ ZIF-8(Zn) and BTA @ CNT serving as doping items by mass percent.
Preferred for the present invention are: the BTA @ CNT in the whole doping item accounts for 60-70% by mass.
The beneficial effects of the invention are as follows:
1. the environment-friendly waterborne polyurethane is selected as a substrate of the organic coating, and the waterborne polyurethane is modified by polyglutamic acid to have self-repairing performance;
2. the BTA @ CNTs and the prepared self-repairing material are blended through a mechanical blending method to obtain a multifunctional aluminum alloy surface coating material which integrates the functions of corrosion resistance, self-repairing, bacteriostasis, ultraviolet resistance and the like;
3. the plateau vehicle body is attached to the surface of the aluminum alloy in a spraying and high polymer coating mode, so that the problems that the plateau vehicle body is easy to damage and corrode are solved, and the service life of the plateau vehicle body is prolonged.
Description of the drawings:
FIG. 1 is a diagram showing the mechanism of synthesis of PGA/WPU according to an embodiment of the present invention;
FIG. 2 is a schematic self-healing illustration of a coating prepared in an embodiment of the present invention;
FIG. 3 is a graph showing the tensile strain curve (a) and cyclic tensile curve (b) at different times of self-healing for coatings prepared in examples of the present invention;
FIG. 4 is a schematic view showing bacteriostatic rings (a: Escherichia coli; b: Staphylococcus aureus) after culturing ZIF-8(Zn)/PPU bacteria in the examples of the present invention;
FIG. 5 is a graph of corrosion-resistant electrochemistry (a) and polarization (b) for different coatings treated in an acid rain simulation solution according to an embodiment of the invention;
FIG. 6 shows the corrosion-resistant electrochemical curve (a) and polarization curve (b) of the acid rain simulation solution of the present invention in different immersion times.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Research shows that tyrosine hydrochloride can perform reversible oxidation coupling reaction under the catalysis of enzyme, the enzyme can oxidize phenolic hydroxyl in a substrate into phenolic oxygen free radical under the existence of oxygen, then C-O-C or C-C coupling is performed between the free radicals to form dimer, active ester is formed under the action of NHS, and tyramine hydrochloride loses electrons to generate the phenolic oxygen free radical, so that O (tyrosine hydrochloride) catalysis can be presumed to generate the phenolic oxygen free radical 2 Can induce the oxidative coupling reaction between the tyrosine hydrochlorides under the condition of room temperature;
in addition, because the structure of the O-substituted phenol is similar to that of dopamine, the introduction of the O-substituted phenol can generate strong hydrogen bond interaction between the O-substituted phenols on the polymer chain, and has high binding affinity with various nucleophiles (such as amine, thiol and imidazole), so that the coating is endowed with high strength and high stability adhesion characteristics, and therefore, the embodiment of the invention provides a preparation method of the multifunctional coating based on polyurethane.
Example 1:
a preparation method of a multifunctional coating based on polyurethane, wherein the multifunctional coating is a PPU waterproof coating, comprises the following steps:
the method comprises the following steps: weighing corresponding amount of 0.6g of polyglycolic acid and 0.3g of hydrochloric acid tyrosine hydrochloride, adding into 8mL of deionized water, and magnetically stirring until the polyglycolic acid and the hydrochloric acid tyrosine hydrochloride are dissolved for later use;
step two: weighing 0.3g of tyrosine hydrochloride, adding the tyrosine hydrochloride into the solution for standby dissolution in the step one, and continuously performing magnetic stirring until the tyrosine hydrochloride is dissolved to obtain a polyglutamic acid prepolymer solution for standby;
step three: measuring 30m of polyurethane prepolymer, placing the polyurethane prepolymer in a beaker, stirring in water bath, heating to 65 ℃, adding 8mL of the polyglutamic acid prepolymer prepared in the second step, and stirring to fully mix to obtain the polyurethane prepolymer for later use;
step four: mixing the polyurethane prepolymer prepared in the third step, IP6@ ZIF-8(Zn) and BTA @ CNT in a ratio of 8:1:1 (v/v), adding a drop of the mixed solution into an electromagnetic stirrer, stirring for 1h to dissolve and mix the mixed solution uniformly for later use, curing to obtain a coating, and finally obtaining the coating named PPU.
In the above examples, the mass percentage of polyurethane in the polyurethane prepolymer was 10%.
In the above examples, the total mass percentage of IP6@ ZIF-8(Zn) and BTA @ CNT as doping components in the polyurethane prepolymer was 10%.
In the above example, the mass percentage of BTA @ CNT in the whole doping term is 60%.
Example 2:
a preparation method of a multifunctional coating based on polyurethane, wherein the multifunctional coating is a PPU waterproof coating, comprises the following steps:
the method comprises the following steps: weighing corresponding amount of 0.7g of polyglycolic acid and 0.4g of hydrochloric acid tyrosine hydrochloride, adding into 10mL of deionized water, and magnetically stirring until the polyglycolic acid and the hydrochloric acid tyrosine hydrochloride are dissolved for later use;
step two: weighing 0.4g of tyrosine hydrochloride, adding the tyrosine hydrochloride into the solution for standby dissolution in the step one, and continuing to magnetically stir until the tyrosine hydrochloride is dissolved to obtain a polyglutamic acid prepolymer solution for standby;
step three: measuring 40m of polyurethane prepolymer, placing the polyurethane prepolymer in a beaker, stirring in water bath, heating to 70 ℃, adding 10mL of the polyglutamic acid prepolymer prepared in the second step, and stirring until the mixture is fully mixed to obtain polyurethane prepolymer for later use;
step four: mixing the polyurethane prepolymer prepared in the third step, IP6@ ZIF-8(Zn) and BTA @ CNT in a ratio of 8:1:1 (v/v), adding a drop of the mixed solution into an electromagnetic stirrer, stirring for 2 hours to dissolve and mix the mixed solution uniformly for later use, curing to obtain a coating, and finally obtaining the coating named PPU.
In the above examples, the mass percentage of polyurethane in the polyurethane prepolymer was 15%.
In the above examples, the total mass percentage of IP6@ ZIF-8(Zn) and BTA @ CNT as doping items in the polyurethane prepolymer was 15%.
In the above example, the mass percentage of BTA @ CNT in the entire doping term was 65%.
Example 3:
a preparation method of a multifunctional coating based on polyurethane, wherein the multifunctional coating is a PPU waterproof coating, comprises the following steps:
the method comprises the following steps: weighing corresponding amount of 0.8g of polyglycolic acid and 0.5g of hydrochloric acid tyrosine hydrochloride, adding into 12mL of deionized water, and magnetically stirring until the polyglycolic acid and the hydrochloric acid tyrosine hydrochloride are dissolved for later use;
step two: weighing 0.5g of tyrosine hydrochloride, adding the tyrosine hydrochloride into the solution for standby dissolution in the step one, and continuously performing magnetic stirring until the tyrosine hydrochloride is dissolved to obtain a polyglutamic acid prepolymer solution for standby;
step three: measuring 50m of polyurethane prepolymer, placing the polyurethane prepolymer in a beaker, stirring in water bath, heating to 75 ℃, adding 12mL of the polyglutamic acid prepolymer prepared in the second step, and stirring to fully mix to obtain the polyurethane prepolymer for later use;
step four: mixing the polyurethane prepolymer prepared in the third step, IP6@ ZIF-8(Zn) and BTA @ CNT in a ratio of 8:1:1 (v/v), adding a drop of the mixed solution into an electromagnetic stirrer, stirring for 3 hours to dissolve and mix the mixed solution uniformly for later use, curing to obtain a coating, and finally obtaining the coating named PPU.
In the above examples, the mass percentage of polyurethane in the polyurethane prepolymer was 20%.
In the above examples, the total mass percentage of IP6@ ZIF-8(Zn) and BTA @ CNT as doping items in the polyurethane prepolymer was 20%.
In the above example, the mass percentage of BTA @ CNT in the entire doping term was 70%.
The above-described embodiments are further described in detail below.
As shown in figure 1, a polyethylene glycol long chain is selected as a soft segment of the waterborne polyurethane to play a role in increasing toughness, when the molar ratio IPDI to PEG200 is equal to 2:1, a prepolymer with NCO at two ends is generated in a dibutyltin dilaurate catalyst, so that isocyanate at two ends of a WPU long chain and hydroxyl in polyglutamic acid react, the synthesized long chain and the polyglutamic acid are uniformly mixed at a ratio of 1:2 to generate a new polyurethane long chain.
The specific polyurethane product is shown in fig. 1, a large number of polar groups exist on the surface of the composite, a large number of carboxyl groups and phenolic hydroxyl groups exist on the modified PGA, the carboxyl groups and WPU exist on the PGA and are combined to form isocyanate, and a substituted phenol similar to dopamine exists on the long chain of the PGA, so that strong hydrogen bond interaction can be generated between polymer chains, and the polyurethane has the characteristic of self-healing through hydrogen bonds. The PGA long chain is highly crosslinked with the WPU, so that the stability and strength of the WPU can be improved;
as shown in fig. 2, the modified PPU has good elasticity, and its tensile strain can reach 300%. After the samples are cut off and spliced together again for 4 hours, the coating fracture interface can be observed to be well fused, which shows that the CNTs modified PPU can realize high-efficiency self-repairing at room temperature;
as shown in fig. 3, the tensile strain performance of the coating at different self-repairing times and the cyclic tensile performance of the coating after self-repairing are tested by using a universal mechanical testing machine, and as a result, as shown in the tensile strain performance (a) in fig. 3, it can be known that the recovery degree of the mechanical performance of the coating is better as the repairing time increases, after 4 hours of self-repairing, the tensile strength and the elongation at break of the coating can reach more than 99% of those of the original sample, the self-repairing of the coating is successfully realized on the surface of the coating under the natural condition of room temperature for 4 hours, and as shown in the cyclic tensile curve (b) in fig. 3, the tensile strength is slightly reduced as the self-repairing times increase, but 98% of the original performance can still be maintained after 7 times of cycle;
as shown in figure 4, the coating is cut into 1 x 2mm strips in the experiment, whether the bacteria generate inhibition rings is observed after the coating and gram bacteria are co-cultured for 24 hours, the most typical cocci and bacilli represent the adopted bacteria, staphylococcus aureus and escherichia coli are experimental objects, the result is shown in figure 4, the inhibition rings of the coating on escherichia coli and staphylococcus aureus obviously appear, the diameters of the inhibition rings are 3.13mm and 4.49mm respectively, the inhibition effects of the coating on escherichia coli and staphylococcus aureus are low sensitivity and medium sensitivity by referring to the inhibition ring evaluation standard, the inhibition effect of CNTs or PPU film on staphylococcus aureus is better because gram-positive gram-bacteria is more sensitive to MOFs nano materials, and meanwhile, the bacterial film on gram-negative bacteria is thicker and more stable, which shows that ZIF-8(Zn) in the coating still has horseradish enzyme activity and can reduce oxygen in the environment into ROS, the genetic material of the bacteria is oxidized, and the cell membrane of the bacteria is decomposed, so that the efficient bacteriostasis effect is realized;
as shown in FIG. 5, the coating is taken as a research object, a steady-state polarization curve and alternating-current impedance of the coating are tested by a three-electrode electrochemical workstation, in an electrochemical test, a potentiodynamic polarization curve is a function relation between an impulse point position of a corrosion galvanic cell reaction and a reaction rate current, an EIS test is usually carried out by adopting an equivalent circuit method, the EIS curve is generally divided into two parts, the first part is a semicircle (ohmic impedance of a solution medium) positioned in a high-frequency region, the later part is impedance of a capacitor, the diameter of the curve represents charge transfer resistance of a material, the larger the diameter of the curve is, the larger the contact resistance of the material is, from FIG. 5, in PU compounded on the surface of the aluminum alloy, a blank group of pure PU can also obviously improve the corrosion resistance of the surface of the aluminum alloy, and when CNTs are simultaneously intervened on the surface, PPU is better than PU in self-repairing in the aspect of the corrosion resistance, which is probably because the PPU can be damaged on the surface, therefore, the enhancement of corrosion current is prevented, an impedance spectrum and a polarization curve in the upper graph are fitted through software, the specific fitting numerical value is shown in table 1, the table shows that the BTA @ CNTs and polyurethane composite coating and a pure PU coating are used, the self-corrosion current density is reduced, the impedance radius is increased, the corrosion rate is reduced, the BTA @ CNTs doping can obviously improve the corrosion resistance of the coating, and the results are obtained by combining the above results that the corrosion inhibitor BTA doping can generate compact corrosion prevention deposition when corrosion media invade, and is combined with polyurethane to generate a more compact corrosion prevention coating, meanwhile, the CNTs can enhance the mechanical property of the polyurethane, and a more stable coating is formed through a mutually-penetrated network crosslinking form;
TABLE 1 summary of simulated values of simulated acid rain solutions after different corrosion times
Meanwhile, as can be seen from the above table, the corrosion current density, the impedance radius and the like of the coating are improved, because at the position where the corrosion medium is damaged, the PPU can reconstruct a three-dimensional network structure which is cross-linked with each other through a self-reversible covalent bond, so as to realize the function of self-active repair, the process of the active repair effectively hinders the free diffusion of oxygen and the corrosion medium on the surface of the aluminum alloy, so that the corrosion power is obviously restrained, the cathode and anode branches are shown to move towards the direction of low current density in a chemical curve, and finally the self-corrosion current density of the CNTs or the PPU is 4.7 x 10 < -4 > a/cm2, and the impedance radius is 49.832k omega;
as shown in fig. 6, as the treatment time in the acid rain simulation solution increases, the impedance radius of the multifunctional coating is continuously increased, then the impedance reaches an extreme value after 240 hours, and then the impedance starts to gradually decrease, and the measured data is characterized by the simulation software, and the obtained simulation values are as shown in table 2;
Table 4.5Simulated values after different corrosion of acid rain solution
TABLE 2 simulation values for acid rain solution corrosion at different times
As can be seen from Table 2, after the IP6@ MOFs or PPU coating is combined on the CNTs layer of the aluminum alloy, the resistance radius Rp of the BTA @ CNTs or PPU coating material is increased after being treated for different time, which shows that the BTA in the CNTs and the IP6 in the functional coating have synergistic effect on metal corrosion protection, and the corrosion inhibitor is continuously and actively released along with the continuous invasion of a corrosion medium, so that a compact protective coating is formed on the surface, after the coating is treated in a simulation solution for 240 hours, the resistance radius of the coating reaches an extreme value 259.837k omega, the self-corrosion current is 1.21 x 10 < -9 > A/cm2, and compared with the IP6@ MOFs or PPU coating, the protection time of the coating on the corrosion of the aluminum alloy is greatly prolonged, and the self-corrosion current of a metal substrate can be reduced, so that the protection effect on the aluminum alloy is improved. However, when the film fails after 240h due to the corrosion inhibitor being gradually reacted out and damaged by the corrosive medium, the self-corrosion current thereof is continuously increased and the radius of resistance is continuously decreased, which indicates that the corrosion rate of the aluminum alloy surface is increasing after that.
At present, the mainstream metal protective coating is prepared by modifying organic silicon resin, enhancing the crosslinking degree of the organic silicon resin, replacing more excellent anti-corrosion performance by losing certain elasticity, adopting graphene modified organic silicon resin and preparing the coating on the surface of the aluminum alloy by a spraying method, wherein the minimum self-corrosion current density of a sample is 1.66 multiplied by 10 < -6 > A/cm 2 The maximum polarization resistance is 1.45X 105. omega. cm 2 。
The sample prepared in the experiment is only equivalent to the anticorrosion performance of common organic silicon resin in the initial stage, but after the corrosion inhibitor is combined, the corrosion inhibitor and the corrosion medium form stable precipitates along with the continuous invasion of the corrosion medium so as to enhance the anticorrosion performance of the coating, and as can be seen from table 2, after the coating is treated in a simulated solution for 240 hours, the impedance radius of the coating is increased to 259.837k omega, and the self-corrosion current is reduced to 1.0110-8A/cm 2 In this case, the protective effect of the coating on metal is 2 times that of the resin coating reinforced by the general reinforcing phase and 20 times that of the polyurethane coating. Moreover, after the coating is subjected to 720h of simulation treatment, the self-corrosion current reaches 6.143 multiplied by 10 < -7 > A/cm2, the impedance radius is 121.681k omega, the self-corrosion current is still larger than that of an anti-corrosion coating directly using aqueous polyurethane, the self-corrosion coating still exceeds three orders of magnitude compared with an unprotected aluminum alloy, and still maintains the unsophisticated anti-corrosion performance, which is probably not only the active prevention of the corrosion inhibitorThe protective effect and the self-repairing property of the PPU can be realized at room temperature, so that the coating prepared by the experiment has improved metal corrosion resistance in an organic coating, improves the durability of the organic coating, and prolongs the failure time of a simulated solution to be more than 30 days.
The preparation method of the multifunctional coating based on polyurethane, which is provided by the embodiment of the invention, obtains a high molecular material with self-repairing performance through polyglutamic acid modified polyurethane, uses a metal organic framework and a reinforcing phase of a carbon nano tube polyurethane coating to prepare an antibacterial and ultraviolet-resistant nano material, inspects the antibacterial activity of the nano material by adopting an antibacterial ring method, shows that the coating has certain antibacterial performance, gram-positive bacteria shows medium sensitivity, inspects the ultraviolet-resistant performance by adopting ultraviolet absorbance, shows that IP6@ ZIF-8 can obviously enhance the ultraviolet absorption strength and range, inspects the self-repairing performance by a cyclic stretching experiment, shows that the coating has certain self-repairing performance, the self-repairing rate can reach 99.8% after 4 hours under natural conditions, and can recover to more than 98% of the original sample after 7 times of circulation, the corrosion protection performance of the coating is tested by adopting an alternating current impedance method and a steady-state polarization curve, and under the synergistic action of the corrosion inhibitor and the self-repairing material, the coating shows a protection effect 20 times higher than that of pure PU after being treated in a simulated acid rain solution for 240 hours, so that the failure time is prolonged to be more than 30 days; the surface of the nano coating can achieve super-hydrophobicity after being grafted with low surface energy substances;
the coating applied to metal corrosion prevention at present mainly comprises polyacrylate and polyurethane materials, the polyurethane coating is widely used due to the characteristics of high elasticity and changeability, and the coating prepared by the method has the capability of active protection by using a corrosion inhibitor aiming at the problem that the surface of an aluminum alloy member is easy to lose efficacy due to corrosion, but the common coating is lack of active protection, and meanwhile, the service life of the coating is greatly prolonged by combining with a self-repairing material due to the limited cycle times of the corrosion inhibitor.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (4)
1. A preparation method of a multifunctional coating based on polyurethane is provided, wherein the multifunctional coating is a PPU waterproof coating, and is characterized by comprising the following steps:
the method comprises the following steps: weighing corresponding amount of 0.6-0.8g of polyglycolic acid and 0.3-0.5g of hydrochloric acid tyrosine hydrochloride, adding into 8-12mL of deionized water, and magnetically stirring for dissolving for later use;
step two: weighing 0.3-0.5g of tyrosine hydrochloride, adding the tyrosine hydrochloride into the solution for standby dissolution in the step one, and continuing to stir by magnetic force until the tyrosine hydrochloride is dissolved to obtain a polyglutamic acid prepolymer solution for standby;
step three: measuring 30-50m of polyurethane prepolymer, placing the polyurethane prepolymer in a beaker, stirring in water bath, heating to 65-75 ℃, adding 8-12mL of the polyglutamic acid prepolymer prepared in the second step, and stirring until the components are fully mixed to obtain the polyurethane prepolymer for later use;
step four: mixing the polyurethane prepolymer prepared in the third step, IP6@ ZIF-8(Zn) and BTA @ CNT in a ratio of 8:1:1, adding a drop of the mixed solution into an electromagnetic stirrer, stirring for 1-3h to dissolve and mix the mixed solution uniformly for later use, curing to obtain a coating, and obtaining the coating named PPU after curing.
2. The preparation method of the multifunctional coating based on polyurethane as claimed in claim 1, wherein the mass percentage of polyurethane in the polyurethane prepolymer is 10% -20%.
3. The preparation method of the multifunctional polyurethane-based coating as claimed in claim 1, wherein the polyurethane prepolymer contains 10-20% by mass of IP6@ ZIF-8(Zn) and BTA @ CNT as doping items.
4. The method according to claim 3, wherein the BTA @ CNT in the blend is 60-70 wt%.
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| CN114410209A (en) * | 2021-12-24 | 2022-04-29 | 江南大学 | Preparation method of double self-repairing waterborne polyurethane anticorrosive coating |
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| JPH03281581A (en) * | 1990-03-29 | 1991-12-12 | Nippon Oil & Fats Co Ltd | Coating composition |
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