CN112760023A - Mixed-charge polyurethane coating material and preparation method and application thereof - Google Patents
Mixed-charge polyurethane coating material and preparation method and application thereof Download PDFInfo
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- CN112760023A CN112760023A CN202110096061.2A CN202110096061A CN112760023A CN 112760023 A CN112760023 A CN 112760023A CN 202110096061 A CN202110096061 A CN 202110096061A CN 112760023 A CN112760023 A CN 112760023A
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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
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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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
- 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
Abstract
The invention provides a mixed charge polyurethane coating material and a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing N-methyldiethanolamine with ethyl 4-bromobutyrate, and reacting at 60 ℃ for 24 hours to obtain a dihydroxy quaternary ammonium monomer; (2) mixing the dihydroxy quaternary ammonium monomer obtained in the step (1) with 2, 3-dihydroxypropionic acid and isophorone diisocyanate according to NCO/OH of 1.2, and stirring and reacting for 4 hours at 80 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer containing an end NCO group; (3) and (3) soaking the base material in the polyurethane prepolymer solution obtained in the step (2), taking out after the coating is completed, and curing to obtain the stable mixed charge polyurethane coating material. The coating material disclosed by the invention is coated on the surface of a base material, so that the coating material not only has good bactericidal performance, but also has excellent impedance protein adsorption effect, and shows excellent antifouling potential.
Description
Technical Field
The invention belongs to the technical field of solvent polyurethane coating material preparation, and particularly relates to a mixed charge polyurethane coating material, and a preparation method and application thereof.
Background
Microbial colonization on various surfaces has been an important issue, not only causing impairment of surface function and significant economic loss, but also microbial infection and environmental consequences. In response to these problems, treatment and prevention are two major antimicrobial strategies based on application. The purpose of the prevention is to kill the microorganisms before they settle on the surface. Once precipitated, the microorganisms can produce a protective Exopolysaccharide (EPS) matrix, including polysaccharides, proteins and DNA. Microbial colonies encapsulated in EPS are also known as biofilms, in which bacteria are 100 to 1000 times more resistant to bactericides than in the planktonic state. Thus, intervention in the early uptake and precipitation (i.e., prevention) of microorganisms at the surface is also critical to the antimicrobial effect.
Among various high molecular coatings, multi-component Polyurethane (PU) coatings are an important class of surface protective materials due to their excellent mechanical properties and properties such as abrasion resistance, corrosion resistance, and chemical resistance. The PU coating can be tailored to provide suitable toughness, gloss, and specific functionality to meet the material requirements of most substrates. The molecular structure of the polyurethane can be adjusted to show antibacterial performance. Antibacterial polyurethane coatings are one of the most popular areas of research at present, aimed at conferring on surfaces the ability to withstand microbial colonization. Typical methods for polyurethane coating to combat biofilm and kill bacteria are: 1) adding an antibacterial component into the coating substrate; 2) and (4) surface modification.
The polyurethane system is constructed by adding the antibacterial component into the coating matrix, and the polyurethane system can generally have good antibacterial property when being coated on the surface of a base material, but because the surface of the coating material obtained by the method is mostly positively charged, a large amount of protein can be adsorbed in the using process, so that the antifouling property is not provided, and the potential of a biological film can be resisted, therefore, the existing polyurethane coating material is urgently needed to be improved.
How to provide a polyurethane coating material, which not only has good bactericidal performance, but also has excellent protein adsorption resistance effect, and shows excellent antifouling potential, is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problems and provides a mixed charge polyurethane coating material and a preparation method and application thereof. The method provided by the invention constructs a new polyurethane system, obtains the quaternary ammonium type mixed charge polyurethane, coats the quaternary ammonium type mixed charge polyurethane on the surface of a base material to obtain the base material with the mixed charge polyurethane on the surface, and experiments show that the quaternary ammonium type mixed charge polyurethane has good bactericidal performance, excellent impedance protein adsorption effect and excellent antifouling potential.
One of the purposes of the invention is to provide a preparation method of a mixed charge polyurethane coating material, which adopts the following technical scheme:
(1) mixing N-methyldiethanolamine with ethyl 4-bromobutyrate, and reacting at 60 ℃ for 24 hours to obtain a dihydroxy quaternary ammonium monomer;
(2) mixing the dihydroxy quaternary ammonium monomer obtained in the step (1) with 2, 3-dihydroxypropionic acid and isophorone diisocyanate according to NCO/OH of 1.2, and stirring and reacting for 4 hours at 80 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer containing an end NCO group;
(3) and (3) soaking the base material in the polyurethane prepolymer solution obtained in the step (2), taking out after the coating is completed, and curing to obtain the stable mixed charge polyurethane coating material.
Further, the molar ratio of the N-methyldiethanolamine to the ethyl 4-bromobutyrate in the step (1) is 1: 1.
Further, the structural formula of the dihydroxy quaternary ammonium monomer in the step (1) is shown as the following formula (I):
further, the molar ratio of the dihydroxy quaternary ammonium monomer to the 2, 3-dihydroxypropionic acid in step (2) is 1: 1.
Further, the diisocyanate in the step (2) includes any one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
Further, the structural formula of the polyurethane prepolymer containing the terminal NCO group in the step (2) is shown as the following formula (II):
wherein-R-is
Further, the curing in the step (3) is performed at 80 ℃ for 12 hours.
Further, the base material in step (3) comprises a biomedical material, and the biomedical material comprises a cardiovascular system material such as a prosthetic heart valve, a blood vessel and an intravascular catheter, or a urinary system material such as a ureteral stent and a catheter.
The invention also aims to provide a mixed-charge polyurethane coating material which is obtained by the preparation method.
The invention also aims to provide the application of the mixed charge polyurethane coating material, wherein the mixed charge polyurethane coating material is coated on the surface of a base material for sterilization and antifouling, and the coating thickness can reach more than 50 micrometers, and is preferably 50-100 micrometers.
Specifically, the bacterial species against which the sterilization is directed include escherichia coli, staphylococcus aureus, pseudomonas aeruginosa or other drug-resistant strains.
The invention has the following beneficial effects:
according to the invention, the antibacterial component quaternary ammonium salt is added into the coating substrate, and the carboxyl with negative charge is introduced to prepare the mixed charge polyurethane, and the mixed charge polyurethane is coated on the surface of the substrate to obtain the quaternary ammonium mixed charge polyurethane coated substrate. The invention brings new inspiration for the development and application of new antifouling coatings.
Drawings
FIG. 1 is an IR spectrum of a CBD product obtained in step (1) of example 1;
FIG. 2 is a reaction scheme for preparing MPU in step (2) of example 1;
FIG. 3 is a Zeta potential diagram for different coatings;
FIG. 4 is SEM and AFM surface morphology of different coatings;
FIG. 5 is a graph showing the result of XPS analysis of surface elements of a coating layer;
FIG. 6 is a graph showing the results of a bactericidal performance test on a coating;
FIG. 7 is a microscopic topography of bacteria on the surface of the coating;
FIG. 8 is a graph of bactericidal performance test results for coatings obtained with different monomer ratios;
FIG. 9 is a graph of the results of a test for quantifying protein adsorption on a coating;
FIG. 10 is a graph showing the results of performance tests of different coatings on resistance to protein and cell adhesion.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is described in detail below with reference to the following embodiments, and it should be noted that the following embodiments are only for explaining and illustrating the present invention and are not intended to limit the present invention. The invention is not limited to the embodiments described above, but rather, may be modified within the scope of the invention.
Example 1
A preparation method of a mixed-charge polyurethane coating material comprises the following steps:
(1) taking 1mol of N-methyldiethanolamine and 1mol of 4-ethyl bromobutyrate, reacting for 24 hours at 60 ℃ under the condition of magnetic stirring to obtain a dihydroxy quaternary ammonium monomer (CBD), wherein the obtained product is used directly without any purification; performing infrared characterization on the product CBD obtained in the step, wherein the obtained infrared spectrum is shown in figure 1;
(2) feeding the obtained dihydroxy quaternary ammonium monomer, 2, 3-dihydroxypropionic acid and isophorone diisocyanate (IPDI) according to the proportion of NCO: OH being 1.2:1, wherein the molar ratio of the dihydroxy quaternary ammonium monomer to the dihydroxy propionic acid is 1:1, and mechanically stirring to react for 4 hours under the conditions of nitrogen atmosphere and 80 ℃ to obtain an NCO-terminated mixed charge polyurethane prepolymer (MPU); the reaction formula of the mixed charge polyurethane MPU is shown in fig. 2;
(3) and soaking a base material in the prepolymer solution for 5s, taking out and curing for 12h at the temperature of 80 ℃ to obtain a base material (MPU @ PU) with the surface being mixed charge polyurethane, and characterizing and testing the base material.
Example 2
Polyurethane prepolymers (MPU 2:1, MPU 1:2) having different charge ratios were prepared by adjusting the molar ratio of the bishydroxy quaternary ammonium monomer to the 2, 3-dihydroxypropionic acid monomer in the step (2) according to the method of example 1, and were characterized and tested.
Comparative example 1
The step of adding 2, 3-dihydroxypropionic acid in the step (2) in example 1 was omitted, CBD was directly mixed with IPDI to prepare polyurethane, to obtain quaternary ammonium polyurethane (QPU), which was coated on the surface of a substrate to obtain quaternary ammonium polyurethane-coated substrate (QPU @ PU).
Test example 1
The potential effect of different monomer ratios on the material in example 2 was examined and the results are shown in figure 3. As can be seen from FIG. 3, only when the monomer ratio is 1:1, the Zeta potential of the resulting coating is close to zero, determining a molar ratio of the monomers of 1: 1.
Test example 2
SEM and AFM surface topography observations were made for the coatings of example 1 and comparative example 1 and the results are shown in FIG. 4.
As can be seen from the three SEM pictures of a, b and c in FIG. 4, the coating is relatively flat, the thickness of the coating is 60-70 microns, and the proper thickness provides guarantee for the good effect of the coating. As can be seen from the AFM image, the coated material becomes more even, and this conclusion can be further confirmed in connection with the roughness of fig. 4e, since the coating liquid, which is liquid in the initial state, fills the defects of the substrate itself, and the increase of the smoothness of the material is also advantageous for the subsequent application.
Test example 3
The surface elements of the obtained coating were analyzed (XPS) to examine the roughness of the coating and the change in contact angle, and the results are shown in fig. 5. It was found from fig. 5a that the material coated with the quaternary ammonium coating and the mixed charge coating produced a new peak-Br peak, indicating that elemental bromine has been introduced, demonstrating that the bishydroxy quaternary ammonium monomer has been immobilized on the surface of the material. Through the peak separation treatment, the material surface coated with the quaternary ammonium coating and the mixed charge coating generates a new peak compared with the original material, and the peak is C-N+Peak, C-N, due to the introduction of bishydroxypropionic acid in the mixed charge coating, reduces the bis-hydroxy quaternary ammonium occupancy+The peak intensity decreased, which indicates that both coatings prepared contained quaternary ammonium groups on the surface. The contact angle change shows that the contact angle of the mixed charge coating formed by introducing the dihydroxypropionic acid is obviously reduced, because the mixed charge has good hydration capacity and is similar to zwitterion, so that a better hydrophilic effect is generated.
Test example 4
The coatings were tested for bactericidal properties and the samples were cut to 1 x 1cm2The square of (2) was prepared by dropping 20. mu.L of a bacterial culture solution (10) onto the surface of the sample7CFU/mL), culturing for 2h in a constant-temperature incubator, taking out, washing with sterile water, removing quantitative washing liquid, culturing for 24h in a culture medium, observing the formation amount of bacterial colonies, and investigating the antibacterial property. The results are shown in FIG. 6. As is clear from FIG. 6, the sterilization rate of the quaternary ammonium coating and the mixed charge coating to escherichia coli, staphylococcus aureus, pseudomonas aeruginosa and drug-resistant bacteria is close to 100%, and the quaternary ammonium coating and the mixed charge coating have good sterilization effects. It is well known that quaternary ammonium coatings have good biocidal properties, and the mechanism of biocidal activity for mixed charge coatings is due to the microstructure of the coating surface which is still in a positively charged state, which results in biocidal activity, but the macroscopic state of the coating shows a state close to charge neutrality, which is why mixed charge coatings still have a relatively good biocidal activityCause of bactericidal activity of (1).
The microscopic morphology of the bacteria on the coating surface was observed and the results are shown in fig. 7. The survival status of bacteria on the surface of the material can be seen more clearly, and Escherichia coli and Staphylococcus aureus are taken as examples. It can be seen from figures 7b and e that the material coated with the quaternary ammonium coating adheres more bacteria, as the positively charged quaternary ammonium attracts the negatively charged bacteria, creating more adhesion. However, by careful observation of the bacterial morphology, it was found that all of the bacteria adhered to the surface of the quaternary ammonium coating were shriveled, unsaturated, indicating that they had been killed. The surface coated with the mixed charge coating layer has little bacterial adhesion, which shows that the mixed charge coating layer has good effect of resisting bacterial adhesion, because the hydration layer caused by the mixed charge has the effect of resisting bacterial adhesion. Further observation of the bacterial morphology revealed that the micro-scale adhesion of the bacteria, rupture of the cell membrane, collapse of the bacterial morphology and killing of the bacteria. This shows that the mixed charge coating not only has good bactericidal properties but also has good effect of resisting adhesion of bacteria.
Coatings obtained with different monomer ratios were tested for bactericidal performance and the results are shown in table 8.
Test example 5
The coating obtained in example 1 was subjected to a quantitative protein adsorption assay using the BCA protein concentration assay kit. Fig. 9 a, b, c are laser confocal pictures of protein adsorption of three materials, and it can be seen that the material coated with the quaternary ammonium coating has higher protein adsorption amount (the more protein is adsorbed, the brighter the picture is), and the mixed charge coating has better resistance to protein adsorption. The d graph is a real graph of the test, the darker the color represents the more protein adsorbed, the basic value of the protein adsorption of the material can be clearly seen from the e graph, and the adsorption amount of the mixed charge to the protein is 6.67 micrograms per square centimeter, which is in a better anti-protein adhesion state.
Test example 6
Examining the adhesion performance of the coating on the impedance protein and the cell, taking Bovine Serum Albumin (BSA) as a model organic pollutant, and adopting staticThe anti-adhesion performance of the sample is evaluated by the protein adsorption method. A protein solution (0.05 mg. multidot.mL) was prepared by dissolving fluorescein-bound BSA (FITC-BSA) in PBS (pH 7.4)-1). Samples were placed in cell culture plates and FITC-BSA solution (3ml) was added to each cell culture well, contacted with the sample surface for 3h in the dark with gentle shaking and then the solution was removed and the sample surface was washed twice with PBS buffer to remove unbound proteins. The sample was then removed and placed on a glass slide, and the sample was covered with a cover slip by dropping PBS buffer thereon. The sample was imaged using a nikon N-SIM camera equipped with a 488nm diode pumped solid state laser, which can reflect the anti-fouling capability of the material. The coating materials obtained at different monomer ratios were examined separately and the test results are shown in fig. 10.
In fig. 10, a, b, c, d, e are fluorescence photographs of protein adhesion resistance, it can be seen that the substrate itself has a certain adhesion to the protein, the protein adhesion of the coating coated with pure quaternary ammonium is greatly increased because most proteins have negative charges, and the positive charges attract the negative charges to generate a more serious adhesion result, when the negative charge monomer is added, the adhesion effect is improved to a certain extent, when the ratio of the positive charges to the negative charges is adjusted to 1:1, the protein adhesion amount is greatly reduced because of the super strong hydration of the uniformly mixed charges, the protein adhesion is hindered, when the negative charges are excessive, the adhesion is low because the negative charges repel each other, the adhesion resistance effect is not as good as that of the 1:1 coating hydration, and the experiment also determines that the molar ratio of the monomers is 1:1 to be optimal. f. g, h, i, j are anti-cell adhesion, since the cells are also negatively charged, the results are similar as above. From fig. 10, it can be seen that the material coated with the quaternary ammonium coating has a higher protein adsorption amount (the more protein is adsorbed, the brighter the picture), and the mixed charge coating has better resistance to protein adsorption.
Claims (10)
1. The preparation method of the mixed charge polyurethane coating material is characterized by comprising the following steps:
(1) mixing N-methyldiethanolamine with ethyl 4-bromobutyrate, and reacting at 60 ℃ for 24 hours to obtain a dihydroxy quaternary ammonium monomer;
(2) mixing the dihydroxy quaternary ammonium monomer obtained in the step (1) with 2, 3-dihydroxypropionic acid and diisocyanate according to NCO/OH of 1.2, and stirring and reacting for 4 hours at 80 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer containing an end NCO group;
(3) and (3) soaking the base material in the polyurethane prepolymer solution obtained in the step (2), taking out after the coating is completed, and curing to obtain the stable mixed charge polyurethane coating material.
2. The preparation method according to claim 1, wherein the molar ratio of N-methyldiethanolamine to ethyl 4-bromobutyrate in step (1) is 1: 1.
3. The method according to claim 1, wherein the structural formula of the bishydroxy quaternary ammonium monomer in step (1) is represented by the following formula (i):
4. the method of claim 1, wherein the molar ratio of bishydroxy quaternary ammonium monomer to 2, 3-dihydroxypropionic acid in step (2) is 1: 1.
5. The method according to claim 1, wherein the diisocyanate in step (2) comprises any one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
6. The process according to claim 1, wherein the polyurethane prepolymer having a terminal NCO group in the step (2) has the following formula (II):
wherein-R-is
7. The method according to claim 1, wherein the curing in step (3) is performed at 80 ℃ for 12 hours.
8. The method of claim 1, wherein the substrate in step (3) comprises a biomedical material, and the biomedical material comprises a material of a heart valve prosthesis, a blood vessel, a cardiovascular system including an intravascular catheter, or a material of a urinary system including a ureteral stent or a catheter.
9. A mixed charge polyurethane coating material prepared by the process of any one of claims 1 to 8.
10. Use of a mixed charge polyurethane coating material according to claim 9 for bactericidal and antifouling application to a substrate surface, preferably said application is in the range of 50-100 μm; the bactericidal strains comprise escherichia coli, staphylococcus aureus, pseudomonas aeruginosa or other drug-resistant bacteria.
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