CN113968950A - Bactericidal glycol chain extender, preparation method thereof and application of bactericidal glycol chain extender in multifunctional synergistic antifouling waterborne polyurethane - Google Patents
Bactericidal glycol chain extender, preparation method thereof and application of bactericidal glycol chain extender in multifunctional synergistic antifouling waterborne polyurethane Download PDFInfo
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Abstract
The invention provides a bactericidal glycol chain extender with a structural formula
The glycol chain extender is prepared by the following steps: dibromooctylpentanediol and 1, 2-benzisoxazoleDissolving thiazole-3-ketone in a solvent, putting the solution into a microwave reactor, reacting for 2212 hours at 22222 ℃, and purifying to obtain a diol chain extender containing a bactericidal group; the mol ratio of the dibromooctapentanediol to the 1, 2-benzisothiazole-3-ketone is 1.2: 2.222.5. The invention also provides application of the glycol chain extender in multifunctional synergistic antifouling waterborne polyurethane. The bactericidal diol chain extender is applied to the preparation of the antifouling waterborne polyurethane, and bactericidal groups are introduced into the coating through covalent bonds, so that the environmental toxicity can be effectively reduced compared with a release antifouling coating, and the prepared antifouling waterborne polyurethane can be widely applied to the fields of textiles, plastics, medical treatment and health care and the like, particularly the field of marine antifouling; on the other hand, the method does not cause environmental pollution, can also reduce the production cost of products and save energy.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a bactericidal glycol chain extender, a preparation method thereof and application thereof in multifunctional synergistic antifouling polyurethane.
Background
Biological fouling substances such as proteins, cells, microorganisms, aquatic organisms and the like are easy to adhere and aggregate on the surfaces of daily supplies, building materials, biomedical materials, marine equipment and the like, a series of problems are brought to industries such as medical treatment and health, food, shipping and the like, and the health and property safety of human beings are seriously threatened. Wherein, marine biofouling increases the ship navigation resistance, blocks the marine engineering facilities, even causes the local perforation corrosion of the base material, and influences the service performance and the service life of the marine engineering facilities. In addition, the cleaning process of marine fouling substances can also cause biological invasion, epidemic propagation and the like to cause economic and social hazards. The antifouling paint can effectively prevent various pollutants from corroding and polluting the base material without influencing the performance of the base material, and is the most convenient and effective antifouling measure. The prior antifouling paint technology also depends heavily on the use of toxic bactericides, and poses serious threats to human beings and ecological environment. Therefore, the non-release environment-friendly polymer coating replaces the traditional release coating, is used for preventing marine organism fouling and reducing the harm to the marine ecological environment, and is the future development direction of the marine antifouling coating.
TABLE 1 Main types, structural characteristics and problems of the novel environmentally friendly antifouling paints
The existing novel antifouling paint mainly comprises fouling prevention type, fouling desorption type, sterilization type, degradation self-polishing paint and the like, and the main structural characteristics and the existing problems of the existing novel antifouling paint are shown in table 1. Among a plurality of antifouling paints, fouling desorption type paints with low surface energy such as organosilicon fluorine become a hotspot of the current antifouling paint research. The fouling is difficult to attach to the surface due to the low surface energy property of the fouling, even if the fouling is not firmly attached, the fouling is easy to fall off under the action of water flow or other external force, and the fouling has great application potential in the fields of marine antifouling, medical health, public health and the like.
But coatings relying on a single antifouling mechanism cannot achieve the desired antifouling effect. The low-surface-energy antifouling silicon-fluorine coating has an unobvious antifouling effect in a static state, is difficult to prevent growth of a slime layer consisting of algae and bacteria, can only make microorganisms attached insecurely and needs to be cleaned regularly, and once grown, the attached organisms are difficult to remove. Therefore, the low-surface-energy antifouling paint is blended with an antifouling agent 4, 5-dichloro-2-N-octyl-3-isothiazolinone (DCOIT) to realize slow release or grafting of the antifouling agent (triclosan, N- (2,4, 2-trichlorophenyl) maleimide), quaternary ammonium salt and the like to construct a sterilization-fouling desorption type paint, the sterilization-fouling desorption type paint is applied to occasions with different requirements on antifouling aging, or hydrophilic polyethylene glycol (PEG), zwitterions and the like are introduced to construct a fouling-prevention desorption type paint, and the antifouling performance of the coating is further improved. However, even if the surface is sterilized and anti-adhesion, the fouling still grows for a long time, resulting in failure of antifouling. Therefore, a new idea of 'degradation antifouling' is provided by Zhanguang topic group of southern China university, a series of polyester type biodegradable high molecular base materials are developed, the surface of the coating can be continuously self-renewed through degradation, and the self-polishing antifouling purpose is achieved, but the antifouling activity of the structure is seriously dependent on the degradation performance of the coating. Therefore, the integration of multiple mechanisms to coordinate antifouling is a necessary development trend of antifouling coatings, and the interaction among multiple antifouling structures and the influence on the antifouling structures and activities of coatings are important problems to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a diol chain extender containing a bactericidal group, which can be applied to the preparation of waterborne polyurethane, so that a waterborne polyurethane coating has a good antifouling effect, and the coordination and unification of coating sterilization and anti-adhesion are realized.
In order to achieve the above object, the present invention provides the following technical solutions:
a bactericidal glycol chain extender has the structural formula:
the invention also aims to provide a preparation method of the bactericidal glycol chain extender, which comprises the following steps:
dissolving dibromooctapentanediol and 1, 2-benzisothiazol-3-one in a solvent, putting the solution into a microwave reactor, reacting for 2212 hours at 22222 ℃, and purifying to obtain a diol chain extender containing a bactericidal group; the mol ratio of the dibromooctapentanediol to the 1, 2-benzisothiazole-3-ketone is 1.2: 2.222.5.
The specific reaction route and the process are as follows:
compared with the prior art, the invention adopts dibromooctylpentanediol and 1, 2-benzisothiazol-3-one (BIT) to carry out chemical reaction in a microwave reactor, and then the diol chain extender containing the bactericidal group is prepared by purification. The prepared antifouling waterborne polyurethane can be widely applied to textiles, plastics, medical health and the like, particularly the field of marine antifouling; on the other hand, the method does not cause environmental pollution, can also reduce the production cost of products and save energy.
Preferably, the solvent is one or more of dichloromethane, dimethyl sulfoxide and methanol.
Preferably, the post-reaction purification step is: the reacted product was extracted with any one solvent of ethyl acetate, dichloromethane or chloroform, then dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered and rotary-evaporated to remove the solvent, and then dried at 45 ℃ for 8h under vacuum.
Preferably, the reaction temperature is 45255 ℃.
The invention also aims to provide a preparation method of the multifunctional synergistic antifouling waterborne polyurethane, which comprises the following steps:
s1: mixing diisocyanate and vegetable oil-based polyol at 25285 ℃, uniformly dispersing, adding a chain extender and a catalyst, and continuing to react for 12232 min; the chain extender comprises the bactericidal glycol chain extender and a conventional ionic chain extender;
s2: adding butanone or acetone for dilution, continuing to react for 322152min, cooling to room temperature after the reaction is finished, neutralizing by a neutralizing agent, adding water for emulsification, and removing the solvent (butanone or acetone) by rotary evaporation to obtain the multifunctional synergistic antifouling waterborne polyurethane emulsion.
In the preparation of polyurethanes, diisocyanates, catalysts, ionic chain extenders and neutralizing agents conventional in the art can be used in the present invention, with the reaction conditions also being conventional controlled conditions.
Preferably, the vegetable oil based polyol, diisocyanate and chain extender have a hydroxyl group molar ratio of 1.2:1.822.2: 2.521.5. Preferably, the solid content of the antifouling aqueous polyurethane emulsion is 5252%.
Preferably, the vegetable oil-based polyol is one or a mixture of two of fluorine-containing vegetable oil-based polyol and silicone vegetable oil-based polyol;
the structural formula of the fluorine-containing vegetable oil-based polyol is shown in the specification
the structural formula of the organic silicon vegetable oil-based polyol is shown in the specification
Preferably, the solid content of the aqueous polyurethane emulsion is 5252%; the catalyst has a solids content of 2.121% based on the total mass of diisocyanate and silicone vegetable oil-based polyol.
Preferably, the temperature of the reaction in the step S1 is 52292 ℃, and the reaction time is 22232 min; in step S2, the reaction temperature is 72282 ℃ and the reaction time is 22292 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the multifunctional synergistic antifouling waterborne polyurethane quantitatively introduces bactericidal and anti-adhesion groups through covalent bonds, and reduces the release of antibacterial agents and the pollution to the surrounding environment.
(2) The organosilicon, fluorocarbon chain and bactericidal group in the multifunctional synergistic antifouling waterborne polyurethane have the migration property to the surface in the film forming process and the polyurethane side chain alkoxy is hydrolyzed and condensed to generate chemically bonded nano SiO in situ2Constructing a super-hydrophobic nano topological structure with surface sterilization-fouling desorption synergistic antifouling; meanwhile, an antifouling structure with different concentration gradients of Si, F and the bactericide from the surface layer to the bottom layer is obtained, and the coordination and unification of the sterilization and the adhesion resistance of the coating are realized.
(3) The main raw material of the waterborne polyurethane is renewable vegetable oil resource which is natural in source, a molecular chain is provided with a plurality of hydroxyl groups,the hydrolysis condensation reaction of the alkoxy group of the side chain of the polyurethane is combined to generate the chemically bonded nano SiO2And a nano composite network cross-linked structure is formed, so that the mechanical property and the water resistance of the antifouling waterborne polyurethane can be effectively improved.
(4) Because the multifunctional synergistic antifouling waterborne polyurethane emulsion provided by the invention takes water as a dispersion medium, and bactericidal groups are introduced into the coating through covalent bonds, compared with a release antifouling coating, the multifunctional synergistic antifouling waterborne polyurethane emulsion can effectively reduce the environmental toxicity, and can be widely applied to the fields of textiles, plastics, medical treatment, health care and the like, particularly marine antifouling; on the other hand, the method does not cause environmental pollution, can also reduce the production cost of products and save energy.
(5) The main raw materials of the multifunctional synergistic antifouling waterborne polyurethane emulsion provided by the invention are green renewable vegetable oil resources instead of petrochemical products, so that the degradability and safety are improved, secondary pollution is not generated, and the problems of global fossil resource excessive consumption, energy and environment are favorably alleviated.
On the other hand, the invention also provides multifunctional synergistic antifouling waterborne polyurethane which is prepared by the preparation method.
In addition, the application of the multifunctional synergistic antifouling waterborne polyurethane in preparing waterborne polyurethane coating films, coatings, sealants, adhesives, foams or composite materials is also within the protection scope of the invention.
Drawings
FIG. 1 is a reaction scheme of the multifunctional synergistic antifouling waterborne polyurethane in example 2212
FIG. 2 is a particle size distribution diagram of the multifunctional synergistic antifouling waterborne polyurethane obtained in example 2212 and comparative example 122;
FIG. 3 is a bar graph showing the water absorption of the multifunctional synergistic antifouling aqueous polyurethane coating films obtained in example 2212 and comparative example 122;
FIG. 4 is a histogram showing the number of viable bacteria adhered to the surface of the multifunctional synergistic antifouling aqueous polyurethane coating film obtained in example 2212 and comparative example 122;
FIG. 5 is a schematic view showing the contact sterilization effect of the multifunctional synergistic antifouling waterborne polyurethane obtained in examples 2-2 and comparative example 122.
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative of the present invention only, and are not intended to limit the scope of the present invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The bactericidal diol chain extender, the multifunctional synergistic antifouling aqueous polyurethane emulsion or the aqueous polyurethane coating material provided by each embodiment are characterized as follows.
1) Hydrogen nuclear magnetic resonance spectroscopy the hydrogen nuclear magnetic resonance spectroscopy results of the diol chain extender containing the dual bactericidal groups obtained in example 1 are as follows: (422MHz, DMSO, delta ppm):3.13(s,4H),3.34(s,4H),4.43(m,2H),7.21-7.53(m,2H), wherein, the H of 7.21-7.53ppm is the characteristic peak of hydrogen on the benzene ring.
2) In order to examine the bulk properties and antifouling properties of the multifunctional synergistic antifouling waterborne polyurethane emulsion prepared in example 1 (examples 2 to 12) and the coating, the following tests were carried out:
(1) stability of aqueous polyurethane emulsion
Aqueous polyurethane emulsion stability characterized by centrifuging the sample at 3222rpm for 32min using a Tomos 3-18 centrifuge from Shanghai Tomo scientific instruments.
(2) Particle size distribution and Zeta potential
The particle size distribution and Zeta potential of the aqueous polyurethane emulsion were measured with a Zeta-sizer Nano ZSE from malvern instruments ltd, u.k., and the sample was diluted to about 2.21 wt% before the test.
(3) Mechanical Properties
The measurement was carried out by using Shimadzu AGS-X Universal tensile tester, Shimadzu corporation, Shimadzu, Japan. The test speed is 122mmmin-1. The sample specification was 25mm × 12mm (length × width). Each sample tested 2Parallel samples were averaged.
(4) Contact angle
Using the water droplet shape analysis system DSA 122 (Kruss, Hamburg, Germany), 3. mu.L of distilled water was used at room temperature. The test results are the average of three replicates after 12s exposure to water.
(5) Pencil hardness and adhesion: testing the polyurethane coating for pencil hardness and adhesion according to ASTM D3359 and ASTM D3323 standards; the adhesion of the coating to the substrate was tested according to ASTM D4541-29.
(2) And (3) water resistance of the coating: the coating was cut into 12mm by 12mm squares and accurately weighed as W2Soaking the membrane in deionized water at room temperature for 1-72 hr, taking out, drying with filter paper, and weighing (Wt). The water absorption of the polyurethane film is calculated according to the following formula: water absorption (%) - (Wt-W)2)/W2。
(7) Test of antibacterial and antifouling Properties
The Minimum Inhibitory Concentration (MIC) test specifically includes that the bactericidal chain extender prepared in example 1, the antifouling aqueous polyurethane emulsions prepared in examples 2 to 12, and the antifouling aqueous polyurethane emulsions prepared in comparative examples 1 and 2 are subjected to a Minimum Inhibitory Concentration (MIC) test under the NCCLS standard method, and the results are shown in table 2.
Antibacterial adhesion test the aqueous non-toxic polyurethane emulsions obtained in comparative examples 1 and 2 and the aqueous non-toxic antibacterial polyurethane emulsions obtained in examples 2 to 12 were formed into films, which were then cut into 2.5X 2.5cm pieces and placed in 2ml of 12 ml of a film7CFU/ml of the bacterial broth containing Escherichia coli and Staphylococcus aureus (nutrient broth NB) was cultured at 37 ℃ and 112rpm for 2 days, and the membrane-free bacterial broth was used as a blank. After two days, the membrane was taken out and washed with sterile water 3 times, then the bacteria adhered to the membrane were shaken off by ultrasonic waves, and the plate count was performed after gradient dilution, and the results are shown in fig. 4.
Contact sterilization performance: the polyurethane emulsion (52. mu.l) obtained in example 2-2 was directly coated on a glass slide to form a region of 1.5X 1.5cm in size, evaporated at room temperature for 24 hours, placed in a 22 ℃ oven for baking for 48 hours, then placed in a 22 ℃ vacuum oven for baking for 48 hours, and placed in a clean bench for UV sterilization for at least 4 hours.Then diluting to 122And (3) uniformly spraying the CFU/mL staphylococcus aureus liquid on the surface of the whole glass slide, placing the glass slide in sterile air for naturally drying for 12min, then placing the glass slide in a culture dish, slowly pouring 2.8% agar medium, and placing the glass slide in an incubator for inverted culture at 37 ℃ for 24 h. The petri dish was removed, 3mL of an aqueous solution of 5mg/mL TTC was added, and the results were observed after half an hour of staining, as shown in FIG. 5.
In the following examples, example 1 is a diol chain extender containing a bactericidal group and a preparation method thereof, and examples 2 to 12 are multifunctional synergistic antifouling waterborne polyurethane prepared by using example 1, diisocyanate, polyol (polyol I or polyol II or a mixture of polyol I and polyol II) and a conventional chain extender and a preparation method thereof; the polyol I is fluorine-containing plant oil-based antifouling polyol with a general structural formula
The polyol II is organic silicon vegetable oil-based antifouling polyol, and the structural general formula is as follows:
wherein R is methyl or ethyl, R1Is one of alkyl, substituted alkyl, heteroalkyl and alkyl heterocyclic group, and R' is one of-O-, ester, -N-or-NH-.
Example 1:
this example provides a bactericidal diol chain extender, which is prepared by performing a chemical reaction on dibromooctylpentanediol and 1, 2-benzisothiazol-3-one (BIT) in a microwave reactor, and the specific process is as follows.
Dibromooctylpentanediol and 1, 2-benzisothiazol-3-one (BIT) in a molar ratio of 1.2: 2.4 adding the mixture into a reaction bottle, adding methanol for dissolving, placing the mixture into a microwave reactor, heating the mixture to 52 ℃ for constant-temperature reaction for 12 hours, extracting the obtained product with ethyl acetate, drying the product with anhydrous magnesium sulfate, filtering the product, performing rotary evaporation to remove the ethyl acetate, and drying the product at 45 ℃ overnight under vacuum to obtain the bactericidal glycol chain extender which is a nonionic antibacterial glycol chain extender.
Examples 2 to 6:
examples 2-2 provide a series of cationic multifunctional synergistic antifouling waterborne polyurethanes prepared using the glycol chain extender prepared in example 1.
Specifically, the aqueous polyurethane emulsion is prepared by the following steps: the polyols I and II and the diisocyanate were each introduced into a two-necked flask with mechanical stirring and mixed with stirring at a temperature of 75 ℃ for 15 minutes (reaction stage 1). Then, the catalyst (2.5 mass% of the reactants) and the chain extender obtained in example 1 and MDEA were added and the reaction was continued for 22 minutes (reaction stage 2). Methyl Ethyl Ketone (MEK) was then added at 32% solids to reduce the viscosity of the system and the reaction was continued for 22 minutes. Then, when the temperature was cooled to room temperature, the system was neutralized with acetic acid for about 15 minutes. Finally, the mixture was emulsified with distilled water at 222rpm for 22 minutes (emulsification time), and then excess MEK was removed by rotary evaporation to obtain an aqueous Polyurethane (PU). Table 2 shows the specific reaction conditions of the examples, and Table 3 shows the experimental ratios of the examples. The structures of the polyol I and the polyol II adopted in the examples 2-2 are as follows:
the structural formula of the polyol I and the fluorine-containing vegetable oil-based polyol is as follows:
polyol II, organic silicon vegetable oil base polyol structural formula:
TABLE 2 examples 2-12 Experimental parameters for aqueous polyurethane emulsions
TABLE 3 examples 2-12 formulations of aqueous polyurethane emulsions
Note: a, hydroxyl molar equivalent of the antifouling polyol; and b, hydroxyl molar equivalent of the chain extender.
Examples 7 to 8:
examples 7-8 provide a series of anionic multifunctional synergistic antifouling waterborne polyurethanes prepared using example 1
Specifically, the aqueous polyurethane emulsion is prepared by the following steps: the polyols I and II and TDI were each introduced into a two-necked flask with mechanical stirring and mixed with stirring at 22 ℃ for 32 minutes (reaction stage 1). Then, the catalyst (2.5 mass% of reactants) and the chain extender obtained in example 1 and DMPA were added and the reaction was continued for 15 to 32 minutes (reaction stage 2). Methyl Ethyl Ketone (MEK) was then added at 32% solids to reduce the viscosity of the system and the reaction was continued for 22 minutes. Then, when the temperature was cooled to room temperature, the system was neutralized with triethylamine for about 22 minutes. Finally, the mixture was emulsified with distilled water at 422rpm for 122 minutes (emulsification time), and then excess MEK was removed by rotary evaporation to obtain an aqueous Polyurethane (PU). Table 2 shows the specific reaction conditions of the examples, and Table 3 shows the experimental ratios of the examples. The structures of polyol I and polyol II used in examples 7 and 8 are as follows:
polyol I: fluorine-containing vegetable oil-based polyol:
polyol II, organic silicon vegetable oil base polyol structural formula:
examples 9 to 10:
examples 9-12 provide a series of anionic multifunctional synergistic antifouling waterborne polyurethanes prepared using example 1
Specifically, the aqueous polyurethane emulsion is prepared by the following steps: polyols i and ii and LDI were each charged to a two-necked flask equipped with mechanical stirring and mixed with stirring at a temperature of 92 ℃ for 12 minutes (reaction stage 1). Then, the catalyst (2.5% mass fraction of the reactants) and the chain extender obtained in example 1 were added and reacted with DMBA for 12 minutes (reaction stage 2). Methyl Ethyl Ketone (MEK) was then added at 32% solids to reduce the viscosity of the system and the reaction was continued for 32 minutes. Then, when the temperature was cooled to room temperature, the system was neutralized with triethylamine for about 32 minutes. Finally, the mixture was emulsified with distilled water at 822rpm for 32 minutes (emulsification time), and then excess MEK was removed by rotary evaporation to obtain an aqueous Polyurethane (PU). Table 2 shows the specific reaction conditions of the examples, and Table 3 shows the experimental ratios of the examples. The structures of the polyols I and II used in examples 9-12 are as follows:
polyol I: fluorine-containing vegetable oil-based polyol:
polyol II, organic silicon vegetable oil base polyol structural formula:
comparative example 1
The cationic waterborne polyurethane emulsion is prepared by taking common vegetable oil without organic silicon and fluorocarbon chains as polyol and not containing the bactericidal glycol chain extender prepared in example 1, and the specific preparation process is as follows.
The castor oil polyol and IPDI were added to a two-necked flask equipped with mechanical stirring and mixed with stirring at a temperature of 78 ℃ for 12 minutes. Then, DBTDL (1% mass fraction of polyol) was added to the mixture, followed by reaction for 12 to 32 minutes. After a subsequent addition of MDEA chain extension reaction for 32min, 42 wt.% butanone was added to reduce the viscosity of the system. The reaction was then continued for 2h and the system was neutralized with TEA and stirred for about 32 minutes. Wherein the molar ratio of OH (polyol) to NCO: OH (chain extender) is 1: 2: 2.9, finally adding water to emulsify for 2 hours at a speed of 222rpm, and then removing excess MEK by rotary evaporation to obtain an aqueous polyurethane emulsion with a solid content of 15%.
Comparative example 2
This comparative example provides a cationic antifouling aqueous polyurethane that does not contain the germicidal diol chain extender of example 1, but contains a silicone vegetable oil-based polyol and a fluorine-containing vegetable oil-based polyol.
Specifically, the aqueous polyurethane emulsion is prepared by the following steps: the polyols I and II and IPDI were each introduced into a two-necked flask with mechanical stirring and mixed with stirring at a temperature of 75 ℃ for 15 minutes (reaction stage 1). Then, the catalyst (2.5% mass fraction of reactants) and MDEA were added and the reaction was continued for 22 minutes (reaction stage 2). Methyl Ethyl Ketone (MEK) was then added at 32% solids to reduce the viscosity of the system and the reaction was continued for 22 minutes. Then, when the temperature was cooled to room temperature, the system was neutralized with acetic acid for about 15 minutes. Finally, the mixture was emulsified with distilled water at 222rpm for 22 minutes (emulsification time), and then excess MEK was removed by rotary evaporation to obtain an aqueous Polyurethane (PU). Wherein OH (polyol I) OH (polyol II): NCO (IPDI) OH (chain extender) molar ratio 2.5: 2.5: 2: 2.9, comparative example 2 with polyol I and polyol ii the structures are as follows:
the structural formula of the polyol I and the fluorine-containing vegetable oil-based polyol is as follows:
polyol II, organic silicon vegetable oil base polyol structural formula:
and (4) testing and analyzing results:
the aqueous polyurethane emulsions obtained in examples 2 to 12 and comparative examples 1 to 2 were poured into a silica gel mold and dried at room temperature to obtain films for further analysis. All samples were dried at 22 ℃ for more than 12h prior to testing.
TABLE 4 particle diameter, zeta potential and storage stability of the aqueous polyurethane emulsions obtained in examples 2 to 12 and comparative example
| Sample (I) | Particle size (nm) | Zeta potential (mV) | Storage stability (moon) |
| Example 2 | 1228.9±1.7 | 32.7±3.1 | ＞24 |
| Example 3 | 927.1±4.8 | 33.1±2.4 | ＞24 |
| Example 4 | 843.8±3.2 | 38.5±2.2 | ＞24 |
| Example 5 | 742.9±5.7 | 39.3±4.1 | ＞24 |
| Example 2 | 489.2±4.1 | 45.8±2.7 | ＞24 |
| Example 7 | 849.2±8.4 | -38.5±5.3 | ＞24 |
| Example 8 | 295.4±1.8 | -42.2±3.1 | ＞24 |
| Example 9 | 523.4±4.2 | -47.2±2.3 | ＞24 |
| Example 12 | 297.4±2.4 | -47.9±4.9 | ＞24 |
| Comparative example 1 | 22.3±1.9 | 37.4±1.5 | ＞24 |
| Comparative example 2 | 229.23±2.2 | 35.1±1.1 | ＞24 |
As can be seen from Table 4, the particle diameters of the antifouling aqueous polyurethane emulsion obtained in example 2-2 are between 489.2-1228.9nm, and are all higher than those of comparative example 1(22.3nm), which shows that the hydrophilicity of the aqueous polyurethane is reduced by introducing the silicone vegetable oil-based polyol and the fluorine-containing vegetable oil-based polyol. Meanwhile, as the content of the nonionic antibacterial glycol chain extender prepared in the embodiment 1 in the components is reduced and the content of the hydrophilic chain extender MDEA is increased, the particle size of the aqueous polyurethane emulsion obtained in the embodiments 2 to 2 is gradually reduced, because as the content of the hydrophilic chain extender is increased, the proportion of the hydrophilic component in the neutralized polyurethane structure is gradually increased, the overall hydrophilicity of the polyurethane is increased, and the particle size of the emulsion is gradually reduced.
Pouring the polyurethane emulsion obtained in the embodiment into a polytetrafluoroethylene or silicified glass mold, standing at room temperature for water volatilization, and drying in a common oven at 22 ℃ for 2 days after the surface of the film is dry and not sticky to hands to obtain the antifouling vegetable oil-based waterborne polyurethane coating film for testing the contact angle and the antifouling performance. The contact angle results are shown in table 5. We can see that the water contact angle (121.2-142.2 ℃) of the water-based polyurethane coating film prepared by the organic silicon polyol is far higher than that (22.3 ℃) of a comparative example without silicon, and the introduction of organic silicon and fluorocarbon chains greatly improves the hydrophobicity of the coating film, so that the antifouling property of the coating film is facilitated. The reason is that in the film forming process, the organosilicon with low surface energy and the fluorocarbon chains migrate to a gas-liquid interface (namely the surface of the coating film), so that a large number of hydrophobic organosilicon structures are accumulated on the surface of the coating film, the hydrophobicity of the coating film is improved, and the attachment of fouling substances such as microorganisms on the coating film is favorably prevented. And the introduction of the nonionic antibacterial glycol chain extender obtained in the embodiment 1 has little influence on the hydrophilic and hydrophobic properties of the surface of the antifouling coating, and does not influence the anti-adhesion property of the coating.
The tensile strength, elongation at break, pencil hardness, adhesion and the like of the antifouling aqueous coating films obtained in examples 2 to 12 were shown in table 5. The result shows that the tensile strength of the coating is enhanced and the hardness of the coating is higher by introducing the nonionic antibacterial glycol chain extender obtained in example 1, which is probably because the nonionic antibacterial glycol chain extender obtained in example 1 contains two rigid benzene ring structures, and the mechanical property of the coating is improved after the nonionic antibacterial glycol chain extender is introduced into the coating.
Next, we characterized the water resistance of the antifouling aqueous coating films obtained in examples 2 to 12, and the results are shown in FIG. 3. The water absorption of the aqueous polyurethane emulsion coatings obtained in examples 2 to 2 is gradually increased along with the decrease of the content of the nonionic antibacterial glycol chain extender obtained in example 1 and the increase of the content of the hydrophilic chain extender MDEA, because the proportion of the hydrophilic component of the polyurethane structure after neutralization is gradually increased along with the increase of the content of the hydrophilic chain extender, the overall hydrophilicity of the polyurethane is increased, and the water absorption is increased. The contact angle and the water absorption rate test result show that the multifunctional synergistic antifouling waterborne polyurethane obtained in the examples 2-12 has good water resistance.
TABLE 5 mechanical properties, adhesion and contact angle of antifouling aqueous polyurethane coatings obtained in examples 2 to 12 and comparative example
Pencil hardness (2B-HB-2H,2H is hardest) and adhesion (5B is best)
TABLE 2 minimum inhibitory concentration test (MIC)
As can be seen from the data in Table 2, when the content of the nonionic antibacterial glycol chain extender obtained in example 1 in the aqueous polyurethane emulsion is increased, the MIC thereof is gradually reduced, and the antifouling aqueous polyurethane emulsion of the present invention is endowed with good antibacterial effect. The antifouling performance of the coating films of the waterborne polyurethanes obtained in the examples 2 to 12 is represented by a table shaking method, and the comparative examples 1 and 2 are used as controls. As shown in FIG. 4, the antifouling effect of the coating film against Staphylococcus aureus and Escherichia coli was obtained by plate counting. Both bacteria can adhere to the surface of the polyurethane coating obtained in comparative example 1 without bactericidal and anti-adhesion components at a high adhesion rate, the number of bacteria adhered to the surface of the polyurethane film is obviously reduced after the organosilicon polyol and the fluorocarbon chain are introduced, and the anti-adhesion rate exceeds 92% (comparative example 2), while the number of viable bacteria on the surface of the coating is gradually reduced with the increase of the content of the chain extender of the nonionic antibacterial glycol obtained in example 1 until viable bacteria are hardly observed, and the anti-bacterial adhesion performance can reach 99.99% (figure 4). The introduction of the low surface energy organosilicon antifouling polyol and the fluorocarbon chain polyol can effectively improve the anti-bacterial adhesion capability of the polyurethane film, and the introduction of the nonionic antibacterial glycol chain extender obtained in the example 1 can kill bacteria attached to the coating, achieve a higher antibacterial effect, and realize the synergistic antifouling effect of the waterborne polyurethane coating.
In order to characterize the influence of the introduction of the nonionic antibacterial glycol chain extender obtained in example 1 on the antibacterial and antifouling performance of the coating, the invention directly coats the antifouling aqueous polyurethane emulsion obtained in example 222 on a glass slide to form a film (1.5 × 1.5cm) and tests the contact sterilization performance of the film, and the result is shown in fig. 5, wherein comparative example 1 does not contain the nonionic antibacterial glycol chain extender obtained in example 1, and a large number of bacterial colonies are uniformly distributed on the surface of the coating and around the coating and do not have the sterilization performance at all; comparative example 2 although the introduction of organosilicon fluorocarbon chains provided a coating with excellent antimicrobial adhesion ability (fig. 4), it did not have contact sterilization performance because the introduction of the nonionic antimicrobial glycol chain extender obtained in example 1 was omitted; on the other hand, if no bacterial colonies were observed on the surface of the aqueous polyurethane coating obtained by introducing the nonionic antibacterial diol chain extender obtained in example 1, the bactericidal effect was 99.99% or more. The method shows that the organosilicon, the fluorocarbon chain and the nonionic antibacterial glycol chain extender are simultaneously introduced, so that the waterborne polyurethane can be endowed with good antibacterial and anti-adhesion capabilities, and the coordination and unification of antibacterial and anti-adhesion are realized.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The bactericidal glycol chain extender is characterized by having a structural formula as follows:
2. a method for preparing the bactericidal glycol chain extender of claim 1, comprising the steps of: dissolving dibromooctapentanediol and 1, 2-benzisothiazol-3-one in a solvent, putting the solution into a microwave reactor, reacting for 2212 hours at 22222 ℃, and purifying to obtain the bactericidal glycol chain extender containing bactericidal groups; the mol ratio of the dibromooctapentanediol to the 1, 2-benzisothiazole-3-ketone is 1.2: 2.222.5.
3. The method according to claim 2, wherein the solvent is one or more of dichloromethane, dimethyl sulfoxide, and methanol.
4. The method of claim 2, wherein the post-reaction purification step is: the reacted product was extracted with any one solvent of ethyl acetate, dichloromethane or chloroform, then dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, filtered and rotary-evaporated to remove the solvent, and then dried at 45 ℃ for 8h under vacuum.
5. The preparation method of the multifunctional synergistic antifouling waterborne polyurethane is characterized by comprising the following steps:
s1: mixing diisocyanate and vegetable oil-based polyol at 25285 ℃, uniformly dispersing, adding a chain extender and a catalyst, and continuing to react for 12232 min; the chain extender comprises the bactericidal glycol chain extender of claim 1 and a conventional ionic chain extender;
s2: adding butanone or acetone for dilution, continuing to react for 322152min, cooling to room temperature after the reaction is finished, neutralizing by a neutralizing agent, adding water for emulsification, and removing the solvent by rotary evaporation to obtain the multifunctional synergistic antifouling waterborne polyurethane emulsion.
6. The method of claim 5, wherein the vegetable oil based polyol, diisocyanate and chain extender have a hydroxyl group molar ratio of 1.2:1.822.2: 2.521.5.
7. The preparation method according to claim 5, wherein the vegetable oil-based polyol is one or a mixture of two of a fluorine-containing vegetable oil-based polyol and a silicone vegetable oil-based polyol;
the structural formula of the fluorine-containing vegetable oil-based polyol is shown in the specification
the structural formula of the organic silicon vegetable oil-based polyol is shown in the specification
8. The preparation method according to claim 5, wherein the solid content of the aqueous polyurethane emulsion is 5252%; the catalyst has a solids content of 2.121% based on the total mass of diisocyanate and silicone vegetable oil-based polyol.
9. The method according to claim 5, wherein the temperature of the reaction in step S1 is 52292 ℃, and the reaction time is 22232 min; in step S2, the reaction temperature is 72282 ℃ and the reaction time is 22292 min.
10. A multifunctional synergistic antifouling waterborne polyurethane is characterized in that: prepared by the method of any of claim 529.
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