CN113372548A

CN113372548A - Vegetable oil-based antifouling polyol and preparation method and application thereof

Info

Publication number: CN113372548A
Application number: CN202110492294.4A
Authority: CN
Inventors: 张超群; 张怡
Original assignee: South China Agricultural University
Current assignee: South China Agricultural University
Priority date: 2021-05-06
Filing date: 2021-05-06
Publication date: 2021-09-10
Anticipated expiration: 2041-05-06
Also published as: CN113372548B

Abstract

The invention discloses a vegetable oil-based antifouling polyol and a preparation method and application thereof. The preparation method comprises the following steps: epoxidized vegetable oil neutralization

Carrying out epoxy ring-opening reaction to obtain the vegetable oil-based antifouling polyol; wherein n is an integer of 1 to 30. According to the invention, the vegetable oil-based antifouling polyol is obtained by performing an epoxy ring-opening reaction on a specific raw material and coupling a PEG antifouling group on a vegetable oil fatty acid side chain, and the preparation process is simple, easy to control and convenient for realizing industrial production; the vegetable oil-based antifouling polyol has hydroxyl with a crosslinking effect and a hydrophilic structure for preventing microorganisms and protein viscosity, is liquid at normal temperature, and is used as polyol to introduce polyurethane, and antifouling groups are suspended on a polyurethane macromolecular side chain, so that the waterborne polyurethane emulsion can be endowed with good storage stability and excellent antifouling performance, and further can be widely applied to the fields of textiles, daily necessities, marine antifouling and medical sanitation.

Description

Vegetable oil-based antifouling polyol and preparation method and application thereof

Technical Field

The invention relates to the field of high polymer materials, and in particular relates to a vegetable oil-based antifouling polyol, and a preparation method and application thereof.

Background

The surfaces of living goods, furniture building materials, biomedical appliances, ship outer walls and other materials are easy to adhere with microorganisms such as bacteria, on one hand, the surfaces of the materials are easy to be polluted by the microorganisms such as the bacteria, and on the other hand, the surfaces of the materials are seriously polluted by the microorganisms such as the bacteria, and more seriously, the surfaces of the materials have risks of inducing microbial infection and the like, the daily life of people is seriously influenced, and the life health and the property safety of human beings are threatened. At present, one of the effective methods for treating microbial pollution such as bacteria is to reduce the adhesion of microorganisms on the surface of a material and block the pollution path. Polyethylene glycol (PEG) and derivatives thereof can effectively reduce biological pollution on the surface of the material caused by protein adhesion, and the PEG has no toxicity, no immunogenicity and immunogenicity, and good biocompatibility, and is one of the few polymers which are approved by the United states Food and Drug Administration (FDA) and can be used for human bodies.

Researches show that the mobility of the antifouling group in a macromolecular chain has great influence on the antifouling effect (Chenyun Dong et al, 2018), the mobility of the antifouling group suspended on a side chain is better than that of the antifouling group embedded in the main chain, and the better the flexibility of a side chain connecting group is, the better the mobility of the antifouling group is, and the more effective the antifouling effect can be exerted. Currently, many studies are made on the preparation of an antifouling surface antifouling brush based on PEG, for example, PEG is connected to various substrates to form an antifouling brush-shaped surface through physical adsorption, chemical adsorption, direct covalent bond connection, block or graft copolymerization, active radical graft polymerization and the like. However, the antifouling sterilization modification process is complex, the surface grafting amount is difficult to control, the cost is high, and various substrates are difficult to carry out antifouling sterilization modification, so that the coating with the antifouling function is designed to be coated on the surface of the substrate, the surface of the substrate can be endowed with good antifouling performance on the premise of not damaging the basic performance and the service performance of the material, the process is simple, the application range is wide, and the antifouling sterilization modification process has great development potential.

Polyurethane (PU) is a multi-block polymer, has good compatibility with most materials, is widely applied to the fields of wood coatings, leather coatings, building coatings, automobile coatings, corrosion protection coatings and biomedical materials as a coating, and can avoid introducing a large amount of organic solvents compared with the traditional solvent type PU, thereby effectively reducing environmental pollution and harm to human health. Therefore, the antifouling property is endowed with great significance. At present, PEG-based polyurethane is mostly directly introduced into a polyurethane main chain by being used as dihydric alcohol, and the mobility of PEG in the structure is limited, so that the antifouling activity of the PEG-based polyurethane is influenced. Or end capping to the end of the macromolecular chain, but end capping reactions have limited incorporation of PEG.

Therefore, the development of the polyurethane with good antifouling effect has important significance and great economic value.

Disclosure of Invention

The invention aims to overcome the defect or deficiency of poor antifouling performance of the existing PEG-based polyurethane, and provides a preparation method of vegetable oil-based antifouling polyol. According to the invention, the vegetable oil-based antifouling polyol is obtained by performing an epoxy ring-opening reaction on a specific raw material and coupling a PEG antifouling group on a vegetable oil fatty acid side chain, and the preparation process is simple, easy to control and convenient for realizing industrial production; the vegetable oil-based antifouling polyol has hydroxyl with a crosslinking effect and a hydrophilic structure for preventing microorganisms and protein viscosity, is liquid at normal temperature, and is used as polyol to introduce polyurethane, and antifouling groups are suspended on a polyurethane macromolecular side chain, so that the waterborne polyurethane emulsion can be endowed with good storage stability and excellent antifouling performance, and further can be widely applied to the fields of textiles, daily necessities, marine antifouling and medical sanitation.

Another object of the present invention is to provide a vegetable oil-based antifouling polyol.

The invention also aims to provide application of the vegetable oil-based antifouling polyol in preparation of waterborne polyurethane.

The invention also aims to provide a preparation method of the antifouling plant oil-based waterborne polyurethane.

In order to achieve the above purpose of the present invention, the present invention provides the following technical solutions:

a preparation method of vegetable oil-based antifouling polyol comprises the following steps: epoxidized vegetable oils and

carrying out epoxy ring-opening reaction to obtain the vegetable oil-based antifouling polyol;

wherein n is an integer of 1 to 30.

According to the invention, the vegetable oil-based antifouling polyol is obtained by performing an epoxy ring-opening reaction on a specific raw material and coupling a PEG antifouling group on a vegetable oil fatty acid side chain, and the preparation process is simple, easy to control and convenient for realizing industrial production; the vegetable oil-based antifouling polyol has hydroxyl with a crosslinking effect and a hydrophilic structure for preventing microorganisms and protein viscosity, is liquid at normal temperature, and is used as polyol to introduce polyurethane, and antifouling groups are suspended on a polyurethane macromolecular side chain, so that the waterborne polyurethane emulsion can be endowed with good storage stability and excellent antifouling performance, and further can be widely applied to the fields of textiles, daily necessities, marine antifouling and medical sanitation.

Preferably, n is an integer of 2-20.

Preferably, the number of epoxy groups in the epoxidized vegetable oil is not less than 3.

The modification can be made on either side after the epoxy ring-opening.

The following description is given by way of example of an epoxidized vegetable oil of the formula:

the structural formula of the epoxy vegetable oil is as follows:

after ring opening by epoxyThe epoxy groups at the 1, 2, 3, 4, 5, 6 and 7, 8 positions of the above formula are ring-opened, at which time

Modifications may be made at any of

positions

1 and 2, at any of

positions

3 and 4, at any of

positions

5 and 6 and at any of positions 7 and 8. The following formula is shown in the specification,

modifications at

positions

1, 3, 5, 8:

preferably, the epoxidized vegetable oil is one or more of epoxidized soybean oil, castor oil, tung oil, sunflower oil, linseed oil or olive oil.

Preferably, the

Polyethylene glycol monomethyl ether.

More preferably, the molecular weight of the polyethylene glycol monomethyl ether is 100-1000.

The epoxide ring opening reaction of the present invention can be regulated and controlled according to control conditions conventional in the art.

Preferably, the temperature of the epoxy ring-opening reaction is 40-70 ℃, and the time of the epoxy ring-opening reaction is 15-60 min.

More preferably, the time for the epoxy ring-opening reaction is 15 min.

Preferably, the molar ratio of the epoxy group in the raw material 1 to the hydroxyl group in the raw material 2 is 1.0: 1.2-5.

Preferably, the catalyst selected for the epoxy ring-opening reaction is one or more of tetrafluoroboric acid or boron trifluoride diethyl etherate.

More preferably, the catalyst is used in an amount of epoxidized vegetable oil and

0.1 to 5% of the total mass of (A).

Preferably, the epoxy ring-opening reaction further comprises the steps of extracting, drying, filtering, evaporating and drying.

Specifically, the treatment process after the epoxy ring-opening reaction is as follows: the reacted product was extracted with ethyl acetate, then dried over anhydrous magnesium sulfate, filtered and rotary evaporated to remove ethyl acetate, and then dried under vacuum at 45 ℃ overnight.

The application of the vegetable oil-based antifouling polyol in the preparation of waterborne polyurethane is also within the protection scope of the invention.

A preparation method of antifouling plant oil-based waterborne polyurethane comprises the following steps:

step a, mixing diisocyanate and the plant oil-based antifouling polyol at 65-85 ℃, uniformly dispersing, adding a chain extender and a catalyst, and reacting for 10-30 min;

and b, adding butanone for dilution, continuing to react for 30-150 min, cooling to room temperature after the reaction is finished, neutralizing by using a neutralizing agent, adding water for emulsification, and removing butanone through rotary evaporation to obtain the antifouling vegetable oil-based waterborne polyurethane emulsion.

Diisocyanates, catalysts, chain extenders and neutralizing agents conventional in the art may be used in the present invention, with the reaction conditions also being conventional controlled conditions.

Preferably, the diisocyanate is one or more of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI) or L-Lysine Diisocyanate (LDI).

Preferably, the catalyst is one or more of dibutyltin laurate, stannous octoate, zinc octoate or triethylene diamine.

Preferably, the solid content of the catalyst is 0.1-1% (based on the total mass of the diisocyanate and the vegetable oil-based antifouling polyol).

Preferably, the hydroxyl value molar ratio of the vegetable oil-based antifouling polyol to the diisocyanate to the chain extender is 1.0: 1.5-2.5: 0.5-1.5.

Preferably, the solid content of the antifouling vegetable oil-based waterborne polyurethane is 5-50%.

Preferably, the reaction temperature in the step 1 is 50-90 ℃, the reaction time is 20-30min, the reaction temperature in the step 2 is 70-80 ℃, and the reaction time is 60-90 min.

Preferably, the neutralizing agent is one or more of triethylamine, acetic acid, hydrochloric acid, glycolic acid or lysine.

The application of the antifouling vegetable oil-based waterborne polyurethane in preparing coatings, sealants, adhesives, foams or composite materials is also within the protection scope of the invention.

The application of the antifouling plant oil-based waterborne polyurethane in preparing a waterborne polyurethane coating film is also within the protection scope of the invention.

An antifouling plant oil-based waterborne polyurethane coating film is prepared by the following steps: and pouring the waterborne polyurethane emulsion into a mould, and drying to obtain the antifouling vegetable oil-based waterborne polyurethane coating.

Compared with the prior art, the invention has the following advantages and effects:

the plant oil-based antifouling polyol provided by the invention is derived from renewable biomass resources, has a crosslinking function, has a hydroxyl group and a hydrophilic PEG (polyethylene glycol) antifouling chain suspended on a side chain, is liquid at normal temperature, and has the advantage of obvious compatibility; when the polyether polyol is used as polyol for preparing waterborne polyurethane, the waterborne polyurethane emulsion can be endowed with good storage stability, the mechanical property of the waterborne polyurethane is improved, the PEG is quantitatively introduced into the waterborne polyurethane to form a surface brush-shaped antifouling structure, and the antifouling effect is superior to that of a PEG dihydric alcohol or PEG-terminated waterborne polyurethane coating.

Drawings

FIG. 1 is a reaction scheme for preparing a vegetable oil-based antifouling polyol according to example 1;

FIG. 2 is a FTIR spectrum of the vegetable oil-based anti-fouling polyol prepared in examples 1-14;

FIG. 3 is a Gel Permeation Chromatography (GPC) of examples 5-14;

FIG. 4 shows examples 1, 3, 6 to 9, 11 and 14¹H-NMR chart;

FIG. 5 is the anti-bacterial adhesion performance of examples 15, 20, 28;

FIG. 6 shows the contact sterilization effects of examples 23 to 28.

Detailed Description

The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the 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 vegetable oil-based antifouling polyol, the aqueous polyurethane emulsion or the aqueous polyurethane coating material provided in each example was characterized as follows.

(1) Fourier transform infrared spectroscopy (FT-IR)

The functional groups of the polyols were characterized using the Nicolet iS10 Fourier transform infrared spectroscopy of Sammerfei USA. The spectral scanning range is 400-4000cm^-1。

(2) Nuclear magnetic resonance spectroscopy (NMR)

The samples were analyzed for hydrogen spectra using an AV600 NMR spectrometer from Bruker.

(3) Gel Permeation Chromatography (GPC)

The molecular weight of the sample was measured by using the Prominence GPC system of Shimadzu corporation. The system was equipped with a RID-10A differential refractive detector and Shodex KF804L and KF802.5 chromatography columns. Tetrahydrofuran was used as the mobile phase, and the flow rate and column temperature were 0.3mL/min and 30 ℃ respectively. Polystyrene standards were used.

(4) Determination of hydroxyl number

The hydroxyl group content of the sample was measured according to the Unilever method. The specific operation is as follows: 10g of a mixture of acetic anhydride and pyridine (mass ratio 1:9) and 1.0g of polyol were added to the Erlenmeyer flask. After the mixture was reacted at 90-100 ℃ for 1 hour, 25mL of pyridine and 10mL of deionized water were added. After further reaction for 20min, the product was titrated with 0.5mol/L potassium hydroxide solution under phenolphthalein as an indicator. Blank assays were performed in a similar procedure.

(5) Stability of aqueous polyurethane emulsion

Aqueous polyurethane emulsion stability characterized by centrifuging the sample at 3000rpm for 30min using a Tomos 3-18 centrifuge from Shanghai Tomo scientific instruments.

(6) 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. the sample was diluted to about 0.01% by weight before the test.

(7) Antifouling properties

The antifouling properties were carried out according to the shake flask method in the literature, as follows: the bacteria capable of producing biofilms (S.aureus M4, S.aureus S45, E.coli DH5 alpha/p 253) stored in this laboratory were cultured to the logarithmic phase of growth (OD)₆₀₀About 0.5) post-dilution by 100 times to obtain 10⁶CFU/ml bacterial solution. Adding 5ml of each bacterial solution into each well of 6-well kangning plate, carefully placing 1cm of each bacterial solution with sterile forceps²Adding different vegetable oil-based waterborne polyurethane membrane materials and Nylon (a 0.22 micron Nylon microporous filter membrane used in a joint transfer experiment in a laboratory is used as a control sample) into corresponding bacteria liquid, and performing static culture at 37 ℃ for 24 hours. The 4 materials were washed 3 times with sterile PBS buffer solution and transferred to another sterile EP tube, 5ml sterile PBS was added, ultra-clean for 30min, bacteria adhered to each material were eluted to PBS and after 10-fold dilution, each gradient dilution was plated on MH agar medium. The plates were incubated in a 37 ℃ incubator for 15h, observed and counted.

The percent of adhesion resistance (viable cell number adhered to the nylon membrane-viable cell number adhered to the polyurethane membrane)/viable cell number adhered to the nylon membrane x 100%.

Examples 1 to 14

This example provides a series of vegetable oil-based antifouling polyols, vegetable oils by epoxidation and oil-freeMPEG of the same molecular weight (

Polyol) ring-opening reaction, and the specific process is as follows.

First, an excess of MPEG500 was added to a two-necked round bottom flask, 0.2% HBF tetrafluoroborate₄Catalyzing, and dripping the epoxy vegetable oil drop by drop under the environment of oil bath at the constant temperature of 65 ℃. And (3) dissolving a reaction product obtained after the reaction for 15-60 min in a small amount of ethyl acetate, adding a large amount of saturated saline solution for extraction and purification, drying the product through anhydrous magnesium sulfate after the purification is finished, and filtering and rotary-steaming to obtain a purified product. By means of FTIR, the measurement of,¹h NMR and Gel Permeation Chromatography (GPC) characterize the characteristic functional groups of the product, and determine the ring opening degree and the ring opening efficiency of the reaction. Exploring different reaction time and different proportions of hydroxyl excess (hydroxyl: epoxy is 1.5-5: 1), determining the optimal ring-opening reaction time and raw material proportion according to the ring-opening degree and relative molecular mass change of the product, titrating the hydroxyl value, wherein the specific conditions are shown in table 1, and the reaction route is shown in figure 1.

TABLE 1 preparation conditions of vegetable oil-based antifouling polyol

Table 2 shows the hydroxyl number and molecular weight of the obtained vegetable oil-based polyol.

TABLE 2 hydroxyl number and molecular weight of vegetable oil based polyols

By using¹H NMR, GPC and FTIR gave a comprehensive characterization of the structure of the product vegetable oil-based polyol. As shown in FIG. 2, FTIR spectra of examples 1 to 9 of vegetable oil-based polyols show that the sample density is 823cm^-1The vibration characteristic peak of the nearby epoxy group disappears, 2800-2900cm^-1With an increase in the methyl and methylene peaks at 1100cm^-1The peak of ether bond is also greatly enhanced, which proves that MPEG500 successfully opens ring epoxy and is coupled to vegetable oil fatty acid chain.

FIG. 3, GPC chart of the examples. As can be seen from the figure, the retention time of the obtained product is shifted to the left (the retention time is between 17-18.5 min) compared with the original epoxy vegetable oil, which indicates that the molecular weight is increased, and the retention time is shortest when 1173 is taken as an initiator, which indicates that the molecular weight is the largest and the reaction is the most complete. And also a small amount of oligomers was observed at 14.5-17min, which is likely a dimer of castor oil. Generally, under ultraviolet irradiation, oligomerization reactions are generated by the formation of hydroperoxides and cyclic peroxides according to an autoxidation mechanism. Wherein oligomers in the polyol can provide the hyperbranched molecular structure of the polyurethane.

As shown in figure 4 of the drawings, in which,¹in the H NMR spectrum, all samples disappeared the characteristic peak of epoxy group at 2.8-3.2ppm, and methoxy O-of MPEG-doped at 3.4ppm and 3.5ppm ₃CHCharacteristic peak sum ₂ ₂CHCHCharacteristic peaks of-O, it is likewise possible to demonstrate that the epoxy has been completely opened by MPEGm.

Examples 15 to 28

This example provides a series of aqueous polyurethane emulsions, each prepared by using the products provided in examples 1 to 14 as polyols, through the following processes.

The vegetable oil-based antifouling polyol prepared in examples 1 to 14 and diisocyanate were added to a two-necked flask equipped with a mechanical stirrer, and stirred and mixed at a temperature of 50 to 90 ℃ for 10 to 30 minutes (reaction stage 1). Then, a catalyst (1% by mass of the polyol) and a chain extender are added to continue the reaction for 10 to 30 minutes (reaction stage 2). And then, adding Methyl Ethyl Ketone (MEK) with the solid content of 20-50% to reduce the viscosity of the system and continuously reacting for 30-150 minutes. Then, when the temperature is cooled to room temperature, the system is neutralized by a neutralizing agent and stirred for about 5 to 60 minutes (neutralization time). Finally, the mixture is emulsified with distilled water at a speed of 400 to 1000rpm for 30 to 120 minutes (emulsification time), and then excess MEK is removed by rotary evaporation to obtain an aqueous Polyurethane (PU) having a solid content of 15 to 35%. Tables 3 and 4 show the specific parameter conditions of the examples.

Table 3 Experimental parameters for the aqueous polyurethane emulsions of examples 15-28

Table 4 Experimental conditions for the aqueous polyurethane emulsions of examples 15 to 18

Note: a, hydroxyl molar equivalent of the antifouling polyol; and b, hydroxyl molar equivalent of the chain extender.

And pouring the aqueous polyurethane emulsion into a silica gel mold and drying at room temperature to obtain a film for further analysis. All samples were dried at 60 ℃ for more than 12h prior to testing.

The measurement results are as follows.

TABLE 5 particle diameter and zeta potential of the aqueous polyurethane emulsions obtained in examples 15 to 28

Sample (I)	Particle size (nm)	Zeta potential (mV)	Storage stability (moon)
				Example 15	22.6±0.1	-42.7±5.2	＞24
Example 16	29.8±0.8	-41.2±2.8	＞24
				Example 17	47.6±1.3	-48.3±9.6	＞24
Example 18	46.6±2.2	-49.4±4.8	＞24
				Example 19	59.8±0.4	-51.6±3.3	＞24
Example 20	49.9±6.4	-48.3±9.6	＞24
				Example 21	45.4±1.8	-31.6±2.2	＞24
Example 22	63.4±1.2	-33.5±1.9	＞24
				Example 23	97.4±1.4	44.1±43.2	＞24
Example 24	74.6±1.4	43.5±2.9	＞24
				Example 25	69.3±0.9	39.2±1.8	＞24
Example 26	64.5±1.0	44.3±2.2	＞24
				Example 27	57.2±4.3	45.1±4.3	＞24
Example 28	40.1±1.1	50.2±5.1	＞24

Comparative example 1

The comparative example provides an aqueous polyurethane emulsion prepared directly with vegetable oil as the polyol, and the specific preparation process is as follows.

Castor oil and IPDI were added to a two-necked flask equipped with mechanical stirring and mixed with stirring at a temperature of 78 ℃ for 10 minutes. Then, DBTDL (1% mass fraction of polyol) was added to the mixture, followed by reaction for 10 to 30 minutes. After a subsequent DMPA chain extension reaction for 30min, 40 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 30 min. Finally, water was added to emulsify at 600rpm for 2 hours, and then excess MEK was removed by rotary evaporation to obtain an aqueous polyurethane emulsion having a solid content of 15%.

The particle size of the antifouling aqueous polyurethane emulsion obtained in examples 15 to 28 was 22.6 to 97.4 nm. In the structures of the waterborne polyurethanes obtained in examples 15 to 19, as the content of the antifouling polyol increases, the content of the hydrophilic chain extender decreases, and the particle size of the polyurethane emulsion gradually increases, which is caused by the decrease of the overall hydrophilicity of the polyurethane; secondly, as the degree of neutralization of the aqueous polyurethane increases, the content of the hydrophilic salt formed increases, causing the hydrophilicity of the aqueous polyurethane to increase and the particle size of the resulting emulsion to decrease (examples 23 to 28)

The antifouling property of the coating films of the waterborne polyurethanes obtained in examples 15, 20 and 28 was characterized by shaking table vibration method. Bacteria capable of producing biofilm (S.aureus M4, S.aureus S45, E.coli DH5 alpha/p 253) stored in the laboratory were cultured until the logarithmic phase of growth (OD600 value: 0.5), and then diluted 100-fold to prepare 106CFU/mL bacterial solution. Respectively adding 5mL of each bacterial solution into each well of a Corning 6-well plate, carefully adding 1cm2 of different plant oil-based water-based polyurethane membrane materials and Nylon (0.22 micron Nylon microporous filter membrane used in the joint transfer experiment in the laboratory) into the corresponding bacterial solutions by using sterile forceps, and standing and culturing at 37 ℃ for 24 hours. The 4 materials were washed 3 times with sterile PBS buffer solution and transferred to another sterile EP tube, 5mL sterile PBS was added, ultra-clean for 30min, bacteria adhered to each material were eluted to PBS and after 10-fold dilution, each gradient dilution was plated on MH agar medium. The plates were incubated in a 37 ℃ incubator for 15h, observed and counted. The results of the experiment are shown in fig. 5, and the anti-adhesion effect of the coating film on gram-positive bacteria (S. aureus M4, S. aureus S45-is very easy to form a biological film) and gram-negative bacteria E.coli DH5 alpha/p 253 is obtained by plate counting. The three kinds of bacteria can be adhered to the surfaces of the control nylon membrane and the polyurethane without the antifouling polyol at higher adhesion rates, after the antifouling polyol is introduced, the number of the bacteria adhered to the surface of the polyurethane membrane is obviously reduced, the adhesion rate is over 80 percent, and particularly the adhesion rate to two kinds of S.aureus is over 95 percent (figure 5). The introduction of the antifouling polyol can effectively improve the anti-bacterial adhesion capability of the polyurethane film.

And directly coating the obtained polyurethane emulsion (50 mu l) on a glass slide to form an area of 1.5 multiplied by 1.5cm, volatilizing at room temperature for 24h, putting into a 60 ℃ oven for drying for 48h, then putting into a 60 ℃ vacuum oven for drying for 48h, and putting into a clean bench for ultraviolet sterilization for at least 4 h. Then diluting to 10⁶And (3) uniformly spraying the CFU/mL staphylococcus aureus or escherichia coli bacterial liquid on the surface of the whole glass slide, placing the glass slide in sterile air, naturally drying for 10min, placing the glass slide in a culture dish, slowly pouring 0.8% agar culture medium, and placing the glass slide in an incubator for inverted culture at 37 ℃ for 24 h. The petri dish was removed, 3mL of 5mg/mL aqueous TTC solution was added, and the results were observed after half an hour of staining. As a result, almost no colonies of Escherichia coli and Staphylococcus aureus were observed on all the surfaces of the polyurethane coating films (FIG. 6), indicating that the obtained antifouling aqueous polyurethane coating has good antibacterial activity against both Escherichia coli and Staphylococcus aureus. The good antibacterial activity of these polyurethane coating films is attributed to the bactericidal activity of the resulting quaternary ammonium salt after neutralization.

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

1. The preparation method of the vegetable oil-based antifouling polyol is characterized by comprising the following stepsThe method comprises the following steps: epoxidized vegetable oils and

wherein n is an integer of 1 to 30.

2. The method according to claim 1, wherein n is an integer of 2 to 20.

3. The method of claim 1, wherein the epoxidized vegetable oil is one or more of epoxidized soybean oil, castor oil, tung oil, sunflower oil, linseed oil or olive oil.

4. The method of claim 1, wherein the step of preparing the composition is carried out in the presence of a catalyst

Polyethylene glycol monomethyl ether.

5. The method according to claim 4, wherein the molecular weight of the polyethylene glycol monomethyl ether is 100 to 1000.

6. The preparation method according to claim 1, wherein the temperature of the epoxy ring-opening reaction is 40-70 ℃ and the time is 15-60 min.

7. The preparation method according to claim 1, wherein the catalyst selected for the epoxy ring-opening reaction is one or more of tetrafluoroboric acid and boron trifluoride diethyl etherate.

8. A vegetable oil-based antifouling polyol prepared by the preparation method of any one of claims 1 to 7.

9. Use of the vegetable oil-based antifouling polyol according to claim 8 for the preparation of aqueous polyurethane.

10. The preparation method of the antifouling plant oil-based waterborne polyurethane is characterized by comprising the following steps: mixing diisocyanate and the plant oil-based antifouling polyol of claim 8 at 65-85 ℃, uniformly dispersing, adding a chain extender and a catalyst, reacting for 10-30 min, adding butanone for dilution, continuing to react for 30-150 min, cooling to room temperature after the reaction is finished, neutralizing by a neutralizer, adding water for emulsification, and removing butanone by rotary evaporation to obtain the antifouling plant oil-based waterborne polyurethane emulsion.