Antibacterial fluorine modified acrylate emulsion and preparation method thereof

Abstract

The invention relates to the technical field of coating emulsion preparation, in particular to a preparation method of an antibacterial fluorine modified acrylate emulsion, which comprises the following steps: weighing a compound emulsifier, stirring and dissolving in a three-neck flask filled with deionized water to prepare an emulsifier aqueous solution; the preparation method comprises the following steps: respectively adding styrene, a soft monomer butyl acrylate, a hard monomer methyl methacrylate and a modified monomer hexafluorobutyl methacrylate into an emulsifier solution, and stirring and pre-emulsifying for a period of time at a certain temperature to obtain a pre-emulsified liquid; at room temperature, a platinum needle anode and a graphite rod cathode are inserted into a three-neck flask filled with the pre-emulsified liquid, and then glow discharge electrolysis plasma is carried out under a certain voltage to initiate emulsion polymerization; after discharging is finished, putting the three-neck flask into a constant-temperature oil bath at a certain temperature, continuously stirring and reacting for a period of time, and then cooling to room temperature to obtain a polymerization product; and filtering the obtained polymerization product through a 200-mesh filter screen to remove gel, thereby obtaining the milky white antibacterial fluorine modified acrylate emulsion with blue light.

Description

Technical Field

[0001] This invention relates to the field of coating emulsion preparation technology, specifically to an antibacterial fluorinated modified acrylate emulsion and its preparation method. Background Technology

[0002] Acrylic emulsions have a wide range of applications in the construction, textile, coating and daily chemical industries. However, due to the presence of active groups such as -COOH and -COOR in their structure, acrylic emulsion films have shortcomings in terms of heat resistance and water resistance. At the same time, the special linear molecular chain structure leads to hot adhesion and cold brittleness of the film and poor mechanical properties, which seriously limit the application range of acrylic emulsions.

[0003] In recent years, research on improving the performance of acrylic emulsions by adding fluorine (F) groups to modify their structure has attracted much attention. From a chemical perspective, F atoms have high electronegativity and high bond energies when combined with other atoms. For example, when an F atom replaces a H atom in a CH bond, the resulting CF bond has an extremely short bond length and a bond energy as high as 460 kJ / mol. Simultaneously, compared to H atoms, F atoms have a slightly larger radius, making it easier to tightly encapsulate the CC backbone and internal molecules, forming a "shielded protection" and thus improving the stability of the acrylic emulsion. Furthermore, by introducing F-containing groups into acrylic emulsions, during film formation, the perfluorinated side chains tend to face outwards and accumulate at the polymer-air interface, resulting in F-modified acrylic resin emulsions exhibiting strong chemical inertness. Therefore, organic fluorine-modified acrylic emulsions possess good hydrophobicity, antifouling properties, durability, heat resistance, abrasion resistance, and corrosion resistance. Currently, fluorinated acrylic emulsions have been successfully applied in textile treatment, architectural coatings, optical fiber coatings, and automotive coatings, showing broad application prospects.

[0004] Common methods for synthesizing fluorinated modified acrylate emulsions include emulsion polymerization, reverse emulsion polymerization, seed emulsion polymerization, and soap-free emulsion polymerization. Regardless of the polymerization method, the addition of initiators and emulsifiers is essential. Initiators include ammonium persulfate, potassium (sodium) persulfate, hydrosulfite, sodium pyrosulfate, azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO). Commonly used emulsifiers include nonylphenol polyoxyethylene ether (NP-10), octylphenol polyoxyethylene ether (OP-10), sodium dodecyl sulfate (SDS), and the nonionic fluorinated emulsifier DF-10. Furthermore, after emulsion polymerization, NaOH needs to be added for hydrolysis and neutralization. This means that a large amount of chemicals are consumed, and many byproducts may be generated due to initiator decomposition, emulsifier recovery, and emulsion neutralization, leading to environmental pollution. Additionally, during the preparation process using initiators, the one-time addition of the initiator makes the reaction too rapid and the structure difficult to control, resulting in easy agglomeration of latex particles or a large particle distribution range. Therefore, the development of efficient, green and environmentally friendly synthesis methods has attracted much attention. Summary of the Invention

[0005] The purpose of this invention is to address the problems existing in the prior art by providing a novel method for preparing antibacterial fluorinated modified acrylate emulsions using glow discharge electrolysis (GDE) plasma technology. Simultaneously, the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) and the nonionic emulsifier lauryl glucoside (APG-1200) are used as a composite emulsifier to improve the antibacterial properties and environmental friendliness of the emulsion.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] An antibacterial fluorinated modified acrylate emulsion, characterized in that it is composed of the following raw materials in parts by weight: 12-26 parts styrene (ST), 14-31 parts soft monomer butyl acrylate (BA), 1 part hard monomer methyl methacrylate (MAA), 1-10 parts modified monomer hexafluorobutyl methacrylate (HFMA), 2-8 parts cationic emulsifier cetyltrimethylammonium bromide (CTAB), 0.5-4 parts nonionic emulsifier lauryl glucoside (APG-1200), and 42-100 parts deionized water.

[0008] A method for preparing an antibacterial fluorinated modified acrylate emulsion, characterized by comprising the following steps:

[0009] Step 1: Weigh 1 to 10 parts of the composite emulsifier and dissolve it in a three-necked flask containing 42 to 100 parts of deionized water to prepare an emulsifier aqueous solution;

[0010] Step 2: Add styrene (ST), soft monomer butyl acrylate (BA), hard monomer methyl methacrylate (MAA), and modified monomer hexafluorobutyl methacrylate (HFMA) to the emulsifier aqueous solution in Step 1, and stir and pre-emulsify for a period of time at a certain temperature to obtain a pre-emulsion.

[0011] Step 3: At room temperature, insert two electrodes into a three-necked flask containing the pre-emulsion, and then perform glow discharge electrolysis plasma-induced emulsion polymerization under a certain voltage.

[0012] Step 4: After the discharge is complete, place the three-necked flask in an oil bath at a certain temperature and continue stirring the reaction for a period of time. After the reaction is complete, cool to room temperature to obtain the polymerization product.

[0013] Step 5: Remove the gel from the polymerization product of Step 4 by passing it through a 200-mesh filter to obtain a milky white antibacterial fluorinated modified emulsion with a bluish tint.

[0014] Preferably, in step one, the composite emulsifier is composed of the cationic surfactant hexadecyltrimethylammonium bromide (CTAB) and the nonionic surfactant lauryl glucoside (APG-1200).

[0015] Preferably, the mass ratio of hexadecyltrimethylammonium bromide (CTAB) to lauryl glucoside (APG-1200) is 3:1.

[0016] Preferably, in step two, the mass ratio of styrene, soft monomer butyl acrylate, hard monomer methyl methacrylate and modified monomer hexafluorobutyl methacrylate is (12-26):(14-31):1:(1-10), and the pre-emulsification temperature is 40-60°C.

[0017] Preferably, in step three, the electrode is a platinum needle as the anode and a graphite carbon rod as the cathode.

[0018] Preferably, in step three, the discharge voltage is 500–600V and the discharge time is 10–30 minutes.

[0019] Preferably, in step four, the oil bath temperature is 70–100°C, and the stirring reaction time is 2–6 hours.

[0020] The principle of this invention: Glow discharge electrolysis (GDE) is a non-traditional electrolysis technology that generates plasma through the interaction between a needle-shaped electrode and an electrolyte. This technology uses a metal sheet or graphite rod as one electrode and a platinum needle (Pt needle) as the other. When a high DC voltage is applied, glow discharge is generated between the Pt needle and the electrolyte, forming a stable plasma and producing H·, OH·, O·, H2O2, and e-. aq - OH - Highly reactive species. The main reactions occurring at the plasma-liquid interface are:

[0021] H2O+e * →e aq - +OH·+H·+O·+H2O2+OH -

[0022] Among them, OH is generated - The reaction of ions is as follows:

[0023] e aq - +e aq - →H2+OH -

[0024] e aq - +OH·→OH -

[0025] e aq - +H·+H2O→H2+OH -

[0026] The reaction that occurs during cathode electrolysis is: 2H₂O + 2e⁻ - →H2+2OH -

[0027] Because H· has strong reducing properties (standard electrode potential is -2.87V) and OH· has strong oxidizing properties (standard electrode potential is 2.85V), they can initiate radical-initiated addition polymerization reactions of double-bonded monomers:

[0028]

[0029] The resulting polymer is then reacted with OH generated at the anode and cathode. - Neutralization occurs, and emulsion particles are formed under the action of emulsifiers. This is due to the active species and OH groups during the GDE process. - Both rely on voltage or current for gradual and slow release, greatly overcoming the problems of latex particle agglomeration and uneven particle size caused by the one-time addition of initiators in existing preparation methods. Therefore, GED technology is a new method for controlled polymerization. Compared with other emulsion preparation technologies, this patented glow discharge electrolysis avoids the use of expensive chemical initiators and large amounts of NaOH neutralizing agents. Furthermore, the use of hexadecyltrimethylammonium bromide and lauryl glucoside as composite emulsifiers in this patent makes the prepared emulsion more environmentally friendly. In addition, this patent does not require nitrogen protection during the synthesis process, demonstrating advantages such as high cost-effectiveness, simple operation, environmental friendliness, and ease of implementation.

[0030] The beneficial effects of this invention are as follows:

[0031] 1. This invention uses styrene (ST), butyl acrylate (BA), methacrylic acid (MAA), and hexafluorobutyl methacrylate (HFMA) as monomers, and hexadecyltrimethylammonium bromide (CTAB) and lauryl glucoside (APG-1200) as composite emulsifiers, and employs glow discharge plasma technology to initiate polymerization, thereby synthesizing antibacterial fluorinated modified acrylate emulsions in one step. The preparation method of this invention is highly efficient, environmentally friendly, and uses simple equipment.

[0032] 2. This invention requires no chemical initiator, no neutralizing agent such as NaOH, does not produce secondary pollution, the reaction is controllable, and it is green and environmentally friendly.

[0033] 3. This invention uses environmentally friendly cetyltrimethylammonium bromide (CTAB) and lauryl glucoside (APG-1200) as composite emulsifiers, making the product greener.

[0034] 4. The fluorinated modified emulsion prepared by this invention has good thermal stability, good film-forming properties, strong weather resistance, good antibacterial properties, and a wide range of applications.

[0035] 5. The fluorinated modified acrylate emulsion prepared by this invention has an antibacterial rate of 100% against Staphylococcus aureus. Attached Figure Description

[0036] Figure 1 Experimental apparatus for preparing antibacterial fluorinated modified acrylate emulsion;

[0037] Figure 2 The current-voltage characteristic curve of the glow discharge electrolysis of the present invention is shown in the inset (the inset is a glow discharge photograph at 560V);

[0038] Figure 3 The infrared spectrum of the antibacterial fluorinated modified acrylate emulsion in Example 1 of this invention;

[0039] Figure 4 TEM images and particle size distribution of the antibacterial fluorinated modified acrylate emulsions in Examples 1(a,a'), 2(b,b'), and 3(c,c') of this invention.

[0040] Figure 5 The figures show the Zeta potential (a) and particle size distribution (b) of the antibacterial fluorinated modified acrylate emulsion in Example 1 of this invention.

[0041] Figure 6 This is a thermogravimetric curve of the antibacterial fluorinated modified acrylate emulsion in Example 1 of the present invention;

[0042] Figure 7 This is a differential scanning calorimeter of the antibacterial fluorinated modified acrylate emulsion in Example 1 of the present invention;

[0043] Figure 8 This is a contact angle test diagram of the antibacterial fluorinated modified acrylate emulsion in Example 1 of the present invention;

[0044] Figure 9 The X-ray photoelectron spectra of the antibacterial fluorinated modified acrylate emulsion and the unfluorinated modified emulsion in Example 1 of the present invention are compared (a is the full spectrum, b is the F1s fine spectrum).

[0045] Figure 10 The diagram shows the antibacterial performance test results of the antibacterial fluorinated modified acrylate emulsion in Example 1 of this invention (a) culture medium without emulsion, b) original emulsion culture medium, c) 10% concentration emulsion culture medium, d) 3% concentration emulsion culture medium. Detailed Implementation

[0046] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0047] Example 1

[0048] Weigh 3.21g of composite emulsifier (CTAB and APG-1200 in a 3:1 ratio) and add it to a 250mL three-necked flask containing 82.5g of deionized water. Stir until the emulsifier is completely dissolved. Then, add 12g of styrene, 32g of butyl acrylate, 1g of methacrylic acid, and 4.5g of hexafluorobutyl methacrylate according to the formula. Pre-emulsify by stirring in a 45℃ water bath for 40min to obtain a milky white pre-emulsified solution. Insert the cathode graphite rod and anode platinum needle into the solution in the three-necked flask and perform glow discharge at 500V for 20min. After the discharge, continue stirring and reflux in a 90℃ oil bath for 4h. Cool to room temperature, and pass the product through a 200-mesh sieve to remove the gel, finally obtaining a milky white antibacterial fluorinated modified acrylate emulsion with a bluish tint. Its infrared spectrum is shown in [insert infrared spectrum here]. Figure 3 TEM Figure 4 a. Zeta potential and particle size testing are shown in [reference]. Figure 5 Hot Re-encounter Figure 6 Differential thermal analysis can be found in Figure 7 Contact angle analysis can be found in Figure 8 See XPS Figure 9 Antibacterial test results can be found in [link to relevant documentation]. Figure 10 .

[0049] Example 2

[0050] Weigh 3.07 g of composite emulsifier (CTAB and APG-1200 in a 3:1 ratio) and add it to a 250 mL three-necked flask containing 79 g of deionized water. Stir until the emulsifier is completely dissolved. Then, add 12 g of styrene, 32 g of butyl acrylate, 1 g of methacrylic acid, and 2.25 g of hexafluorobutyl methacrylate according to the formula. Place the flask in a 55 °C water bath and stir for 50 min to pre-emulsify, obtaining a milky white pre-emulsified solution. Insert a graphite electrode and a platinum needle electrode into the solution in the three-necked flask and perform glow discharge at 560 V for 15 min. Then, transfer the flask to a 95 °C oil bath and continue stirring and reflux for 5 h. After the reaction is complete, cool to room temperature and pass the product through a 200-mesh sieve to remove the gel, finally obtaining a milky white cationic fluorine-modified antibacterial acrylate emulsion with a bluish tint. TEM results are shown below. Figure 4 b.

[0051] Example 3

[0052] Weigh 3g of composite emulsifier (CTAB and APG-1200 in a 3:1 ratio) and add it to a 250mL three-necked flask containing 75g of deionized water. Stir until the emulsifier is completely dissolved. Then, add 12g of styrene, 32g of butyl acrylate, 1g of methacrylic acid, and 0.45g of hexafluorobutyl methacrylate according to the formula. Pre-emulsify by stirring in a 50℃ water bath for 50min to obtain a milky white pre-emulsified solution. Insert a graphite electrode and a platinum needle electrode into the solution in the three-necked flask and perform glow discharge at 600V for 10min. After the discharge, transfer it to an oil bath at 100℃ and continue stirring and reflux for 6h. After the reaction is complete, cool to room temperature and pass the product through a 200-mesh sieve to remove the gel, finally obtaining a milky white antibacterial fluorinated modified acrylate emulsion with a bluish tint. TEM results are shown below. Figure 4 c.

[0053] Example 4

[0054] The structure of the antibacterial fluoropolymer emulsion prepared in this invention is analyzed below using current-voltage curves, infrared spectroscopy, scanning electron microscopy, zeta potential and particle size distribution, thermogravimetric analysis, etc., during the emulsion preparation process.

[0055] See experimental setup Figure 1 The system consists of a high-voltage power supply and a reaction vessel. The high-voltage power supply is a LW100J1 type DC regulated power supply. The reaction vessel is a three-necked flask containing a platinum wire anode (0.3–0.8 mm in diameter), a graphite rod cathode (3–7 mm in diameter), and a reflux condenser. The immersion depth of the anode and cathode in the liquid is controlled between 0.5 and 1.5 cm, and the distance between the two electrodes is 1–2 cm. The entire three-necked flask is placed in a temperature-adjustable oil bath, and a magnetic stir bar is added inside the flask to ensure thorough mixing of the solution.

[0056] 1. Current-voltage curve

[0057] Figure 2 The figure shows the current-voltage curves during the emulsion preparation process. As can be seen from the figure, the entire process can be divided into three parts. In the AB segment (0-360V), the current increases with increasing voltage, which is consistent with Faraday's law and represents the classic electrochemical electrolysis region. In the BC segment (360-440V), as the voltage increases, a large number of bubbles appear around the platinum needle electrode, and a vapor sheath begins to form. The formation and disappearance of the vapor sheath cause current fluctuations; in addition, the non-conductive vapor sheath forms a large equivalent resistance on the anode surface, causing a sudden drop in current. This region is also known as the unstable region. 440V is the critical voltage for glow discharge, which produces intermittent weak glow. In the CD region (440-660V), the current tends to stabilize; this is the normal glow region. At this time, glow discharge electrolysis produces a large amount of H·, OH·, H2O2, and e-.aq - After exceeding point D (700V), the glow becomes extremely dazzling. The intense glow will cause the carbonization of organic monomers near the platinum needle electrode and also cause the high-temperature melting and damage of the platinum needle. Therefore, the voltage range required for synthesizing the emulsion is 500 - 600V. Figure 2 The inset is a glow photo at 560V voltage, indicating that the synthesis of the emulsion is carried out under plasma conditions.

[0058] 2. Infrared Test

[0059] The structure of the sample was characterized by an iS50 ATR-FTIR spectrometer from Thermo Fisher Scientific, USA. The infrared spectrum is as Figure 3 shown. The peaks at 2959, 2920, and 2863 cm -1 of the rubber film are the stretching vibration peaks of C-H (-CH3, -CH2). The peaks at 1713 and 1162 cm -1 correspond to the stretching vibration absorption peaks of C=O and C-O-C respectively. The peak at 1457 cm -1 is the absorption peak of the benzene ring skeleton vibration, and the peak at 760 cm -1 is the stretching vibration peak of monosubstituted benzene ring. The peak at 700 cm -1 is the bending vibration peak of C-F. In addition, there is no characteristic absorption peak of C=C between 1620 - 1700 cm -1 , indicating that the polymerization reaction proceeds completely.

[0060] 3. Transmission Electron Microscopy Test

[0061] The morphology of emulsion particles was observed using a Hitachi HT7800 transmission electron microscope (TEM) from Japan. Figure 4 a and a' are the transmission electron microscopy (TEM) and particle size analysis diagrams of the antibacterial fluorine-modified acrylate emulsion in Example 1. It can be seen that the latex particles are spherical, evenly distributed, and the particle size is about 108.5 nm. Figure 4 b and b' are the transmission electron microscopy (TEM) and particle size analysis diagrams of the antibacterial fluorine-modified acrylate emulsion in Example 2. It can be seen that the latex particles are spherical, evenly distributed, and the particle size is about 101.5 nm. Figure 4 c and c' are the transmission electron microscopy (TEM) and particle size analysis diagrams of the antibacterial fluorine-modified acrylate emulsion in Example 3. It can be seen that the latex particles are spherical, evenly distributed, and the particle size is about 81.1 nm. In summary, the latex particles prepared by glow discharge electrolysis are spherical, and the average particle size is 80 - 110 nm.

[0062] 4. Zeta Potential and Particle Size Test

[0063] The zeta potential of the emulsion and the particle size of the emulsion particles were measured using a Zetasizer NanoZS nanoparticle size analyzer from the UK. Figure 5 a is the Zeta potential diagram of the antibacterial fluorinated modified acrylate emulsion. Figure 5 b is the particle size distribution diagram of the emulsion. From Figure 5 As shown in 5b, the zeta potential is +64.4 mV. This is because CTAB is a cationic emulsifier, providing a positive charge to the emulsion, thus making the emulsion positively charged. Simultaneously, the absolute value of the zeta potential is greater than 30 mV, indicating good emulsion stability. From 5b, it can be seen that the emulsion particle size ranges from 30 to 200 nm, with an average particle size of 85 nm. This is basically consistent with the TEM analysis results. It is generally believed that the smaller the particle size, the more stable the emulsion, the larger the specific surface area of ​​the latex particles, and the better the adhesion performance.

[0064] 5. Thermogravimetric test

[0065] A DTG-6A thermogravimetric analyzer was used under a nitrogen atmosphere at a temperature of 20℃·min. -1 The heating rate was adjusted to raise the temperature from 20°C to 600°C to analyze the thermal stability of the film. Figure 6 The thermogravimetric curve of the antibacterial fluorinated modified acrylic emulsion shows that the initial decomposition temperature of the emulsion film is 380℃ and the maximum thermal decomposition temperature is 436℃, indicating that the antibacterial fluorinated modified acrylic emulsion has good thermal stability, which is crucial for improving the application performance of coatings.

[0066] 6. Differential Scanning Calorimetry Analysis

[0067] The glass transition temperature of the latex film was measured using a differential scanning calorimeter (DSC, model 214 Polyma, Netzsch Instruments, Germany). Figure 7 It can be seen that the latex film has only one glass transition temperature (T). g The theoretical temperature (T) is 23.72℃. This is calculated using the FOX equation. g The measured glass transition temperature is 8.7℃, which is about 15℃ higher than the theoretical value. This is because the introduction of fluorine atoms increases the interaction between molecular chains, thereby increasing the glass transition temperature.

[0068] 7. Contact Angle Test

[0069] The contact angle was measured at room temperature using a contact angle meter (DSA100E, KYUSS, Germany) via the seat drop method. Figure 8 As shown, the static water contact angle of the antibacterial fluorinated modified acrylate emulsion after film formation is 77.62°, indicating that the emulsion has a certain degree of hydrophilicity.

[0070] 9. X-ray photoelectron spectroscopy

[0071] To further verify the successful modification of the polymer by the fluorine monomer, surface elemental analysis was performed on polymers with and without fluorine-modified monomers (with 5% fluorine). The results are as follows: Figure 9 As shown. From Figure 9 As can be seen, the two samples have characteristic peaks of C1s (285eV), N1s (398eV) and O1s (533eV). After modification with fluorine monomer, an F1s peak appeared at 688eV, indicating that the modification was successful. Figure 9 b is the fine spectrum of F1s, and the characteristic peak at 288.6 eV represents the CF functional group. In summary, fluorine-modified monomers have been successfully introduced into the polymer.

[0072] 10. Antibacterial test of fluorinated modified acrylate emulsion

[0073] The antibacterial properties of Staphylococcus aureus against the emulsion were studied. A certain amount of bacterial solution was diluted to 10... 6 CFU / mL was evenly spread on beef peptone medium (NB) containing different concentrations of fluorinated acrylic emulsion and incubated at 37°C for 24 h. Figure 10 It can be seen that after 24 hours of incubation, tens of thousands of colonies appeared on the culture medium without emulsion (a), but no colonies appeared on the culture medium containing the original emulsion (b), 10% emulsion (c), and 3% emulsion (d). This indicates that the fluorinated acrylic emulsion has strong antibacterial properties. This is because the fluorinated acrylic emulsion contains quaternary ammonium salt groups, which can be adsorbed on the surface of Staphylococcus aureus, changing the permeability of the cell wall, thereby playing an antibacterial role.

[0074] Example 5 Stability Test

[0075] (1) Centrifugal stability test. Emulsions with mass fractions of 1%, 2%, and 3% as described in Examples 1 to 3 were prepared and centrifuged at 4000 r·min. -1 Centrifuge at high speed for 30 minutes and observe whether there is sedimentation or stratification.

[0076] (2) Dilution stability. Emulsions with mass fractions of 1%, 2%, and 3% as described in Examples 1 to 3 were prepared respectively, and allowed to stand at room temperature for 48 hours. The presence or absence of precipitation and stratification was observed.

[0077] (3)Ca 2+ Ion stability. Emulsions with mass fractions of 1%, 2%, and 3% (as in Examples 1-3) and CaCl2 solutions with mass fractions of 0.5% and 1% were prepared and mixed at a volume ratio of 4:1. The mixtures were then left at room temperature for 48 hours to observe for any stratification.

[0078] (4) Freeze-thaw stability test. Prepare emulsion samples with a mass fraction of 1%, 2%, and 3% as described in Examples 1 to 3, respectively, and place them in a -17°C freezer for 8 hours. Then, thaw them at 20°C for 6 hours and observe whether there is any stratification.

[0079] (5) Thermal stability test. The emulsion samples with solid contents of 1%, 2% and 3% from Examples 1 to 3 were injected into glass bottles, sealed, and then placed in an oven at 60°C for 48 hours. After that, the samples were taken out, cooled to room temperature, and observed for any stratification.

[0080] Experimental results

[0081] The performance indicators of Example 1 are as follows: solid content 30.4%, conversion rate 86.7%, gelation rate 0.71%, and stability (Ca). 2+ It exhibits good ionic stability, centrifugal stability, thermal stability, and freeze-thaw stability, with an average emulsion particle size of approximately 108.5 nm.

[0082] The performance indicators of Example 2 are as follows: solid content 31.2%, conversion rate 88.9%, gelation rate 1.0%, and stability (Ca). 2+ It exhibits good ionic stability, centrifugal stability, thermal stability, and freeze-thaw stability, with an average emulsion particle size of approximately 101.5 nm.

[0083] The performance indicators of Example 3 are as follows: solid content 32.8%, conversion rate 93.6%, gelation rate 1.1%, and stability (Ca). 2+ It exhibits good ionic stability, centrifugal stability, thermal stability, and freeze-thaw stability, with an average emulsion particle size of approximately 81.1 nm.

[0084] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered illustrative rather than restrictive in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

Claims

1. An antibacterial fluorinated modified acrylate emulsion, characterized in that, It is composed of the following raw materials in parts by weight: 12-26 parts styrene, 14-31 parts soft monomer butyl acrylate, 1 part hard monomer methyl methacrylate, 1-10 parts modified monomer hexafluorobutyl methacrylate, 1-5 parts emulsifier cetyltrimethylammonium bromide, 1-5 parts nonionic emulsifier lauryl glucoside, and 42-100 parts deionized water.

2. A method for preparing an antibacterial fluorinated modified acrylate emulsion, characterized in that, Includes the following steps: Step 1: Weigh 1 to 10 parts of the composite emulsifier into a three-necked flask containing 42 to 100 parts of deionized water, stir and dissolve to prepare an emulsifier aqueous solution; Step 2: Add styrene, soft monomer butyl acrylate, hard monomer methyl methacrylate, and modified monomer hexafluorobutyl methacrylate to the emulsifier aqueous solution in Step 1, and stir and pre-emulsify for a period of time at a certain temperature to obtain a pre-emulsion. Step 3: At room temperature, insert two electrodes into a three-necked flask containing the pre-emulsion, and then initiate monomer polymerization by glow discharge under a certain voltage. Step 4: After the discharge is complete, place the three-necked flask in a constant temperature oil bath at a certain temperature and continue stirring the reaction for a period of time. After the reaction is complete, cool to room temperature to obtain the polymerization product. Step 5: Pass the polymer obtained in Step 4 through a 200-mesh filter to remove the gel, and obtain a milky white antibacterial fluorinated modified acrylate emulsion with a bluish tint.

3. The method for preparing an antibacterial fluorinated modified acrylate emulsion according to claim 2, characterized in that: In step one, the composite emulsifier is composed of the cationic surfactant hexadecyltrimethylammonium bromide and the nonionic emulsifier lauryl glucoside.

4. The method for preparing an antibacterial fluorinated modified acrylate emulsion according to claim 3, characterized in that: The mass ratio of the emulsifier cetyltrimethylammonium bromide to lauryl glucoside is 3:

1.

5. The method for preparing an antibacterial fluorinated modified acrylate emulsion according to claim 2, characterized in that: In step two, the mass ratio of styrene, soft monomer butyl acrylate, hard monomer methyl methacrylate and modified monomer hexafluorobutyl methacrylate is (12-26):(14-31):1:(1-10), and the pre-emulsification temperature is 40-60℃.

6. The method for preparing an antibacterial fluorinated modified acrylate emulsion according to claim 2, characterized in that: In step three, the electrodes are: a platinum needle as the anode and a graphite carbon rod as the cathode.

7. The antibacterial fluorinated modified acrylate emulsion and its preparation method according to claim 2, characterized in that: In step three, the discharge voltage is 500–600V and the discharge time is 10–30 minutes.

8. The method for preparing an antibacterial fluorinated modified acrylate emulsion according to claim 2, characterized in that: In step four, the oil bath temperature is 70–100°C, and the polymerization reaction time is 2–6 hours.

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