Preparation method of a vegetable oil and its derivative functional monomer and application in a water-based ink binder

Abstract

The present invention belongs to the technical field of polymer materials, and particularly relates to a preparation method of a functional monomer of vegetable oil and its derivatives and an application in an aqueous ink binder. A solvent system of vegetable oil or its derivatives and a mercapto compound is introduced into an electrolytic cell, and the solution at the outlet is collected. The collected solution is diluted, extracted, concentrated, dissolved, washed, and finally concentrated under reduced pressure; the solvent is a single-phase solvent or a mixed solvent that is helpful for dissolving vegetable oil and its derivatives. The present invention successfully applies continuous flow electrochemistry to the thiolation of vegetable oil and its derivatives, can form a novel bio-based internal emulsifier, is expected to replace commercial DMPA and DMBA, and the prepared aqueous polyurethane film exhibits extremely high water resistance and excellent mechanical properties. The method is efficient, environmentally friendly, easy to scale up, has short residence time and effective mass transfer characteristics, opens up an alternative for sustainable biomass functionalization synthesis methods, and can be used for developing high-value-added chemicals and high-performance polymers.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a method for preparing functionalized monomers of vegetable oil and its derivatives and their application in water-based ink vehicles. Background Art

[0002] Recently, with concerns about the rapid depletion of fossil resources, extreme climate conditions, and volatile oil prices, interest in oleochemistry and industrial applications of plant oil-based polymers has continued to grow. Plant oils are fatty acid triglycerides containing 12 to 24 carbon atoms and 0 to 3 carbon-carbon double bonds, which vary depending on the plant species, crop type, growing environment, and growing conditions. They have always been one of the most important renewable raw materials and have attracted widespread attention from the chemical and materials industries due to their easy availability, sustainability, and low cost. However, with the exception of some plant oils with specific groups, such as castor oil (which carries hydroxyl groups), most plant oils cannot be directly used for polymer preparation due to the low reactivity of the functional groups in their fatty acid chains. The naturally occurring double bonds and triglycerides in the long-chain fatty acid sequences provide a platform for the conversion of this renewable resource into high-value-added chemicals and functional polymer materials, suitable for applications from surfactants and lubricants to biodiesel.

[0003] In recent decades, people have devoted their efforts to the chemical functionalization of active sites (such as carbon-carbon double bonds and triglycerides) in vegetable oils and their derivatives. Among them, the structural modification of unsaturated groups in vegetable oils has received extensive attention and in-depth research, because this method can maintain its natural triglyceride structure, thereby endowing the resulting polymers with a variety of specific properties, such as water resistance and thermal stability. Among the methods for derivatizing vegetable oils, the thiol-ene reaction, that is, the thiol-hydrogen alcoholization of carbon-carbon double bonds, is the most "dazzling pearl", and has therefore been widely used in the extraction of valuable chemicals and polymers from vegetable oils. The free radical mechanism of the thiol-ene reaction is usually photochemically induced in organic solvents, which involves the reaction of thiols with photoinitiators under ultraviolet light irradiation to produce thiol radicals. In addition to conventional redox conversion and photochemical methods, electrochemistry provides an efficient and environmentally friendly alternative for double bond conversion, which can fully promote the loss or gain of electrons by organic compounds on the electrode surface under very mild conditions without the need for catalysts, exogenous oxidants and other additives.

[0004] In this context, a series of olefin modification strategies have been established through electrochemical oxidation / reduction cross-coupling under mild conditions. Recent studies have shown that double bond functionalization can be achieved by transferring single electrons to oxidize thiophenols / thiols to produce the corresponding thiol radicals at the electrochemical anode by changing the working voltage and current. However, electrochemical oxidation / reduction cross-coupling reactions have never been realized in the modification of vegetable oils.

[0005] The bio-based waterborne polyurethane prepared by the above-mentioned functionalization of vegetable oil has great application prospects. For example, take the waterborne ink prepared from this waterborne polyurethane as an example. Waterborne ink is a new type of ink prepared by combining specific waterborne polymer resins, pigments, water, co-solvents, etc. through physical and chemical processes. It has attracted people's attention due to its environmental protection and safety characteristics. As the initial synthetic monomer of the binder in waterborne ink, the current bio-based functional monomers and corresponding preparation processes are still relatively single, which limits its popularization to a certain extent.

[0006] Therefore, a simple functionalization treatment of vegetable oil is needed to obtain bio-based functional monomers with excellent performance and better apply them to practical applications, such as the preparation of vegetable oil-based waterborne ink. Summary of the Invention

[0007] In order to make up for the deficiencies of the prior art, the present invention provides a preparation method of functional monomers of vegetable oil and its derivatives and their application in waterborne ink binders. The functional monomers of traditional vegetable oil and its derivatives are prepared by thiol-ene chemistry under a continuous flow electrochemical cell.

[0008] The primary object of the present invention is to provide a preparation method of functional monomers of vegetable oil and its derivatives.

[0009] To achieve the above object, the present invention provides the following technical solutions:

[0010] A preparation method of functional monomers of vegetable oil and its derivatives, the preparation method is an electrochemical reaction method. The solvent system of vegetable oil or its derivatives and thiol compounds flows into the electrolytic cell, and the solution at the outlet is collected. The collected solution is diluted, extracted, further concentrated, then dissolved, washed, and finally concentrated under reduced pressure; wherein, the solvent is a single-phase solvent or a mixed solvent that helps dissolve vegetable oil and its derivatives.

[0011] As a preferred technical solution, the constant cell potential of the flow electrolytic cell used in the electrochemical reaction is 0.5 - 10V, the inner surface area of the flow electrolytic cell is 10 cm 2 -100 cm 2 , the distance between the electrodes is 100 μm - 500 μm, and the anode and cathode equipped in the flow electrolytic cell are graphite or stainless steel.

[0012] Preferably, the electrolyte in the electrochemical reaction is one of tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, tetrabutylammonium fluoride, and the dosage of the electrolyte is 0.01 - 0.1M.

[0013] Preferably, the vegetable oil and its derivatives include vegetable oils containing carbon-carbon double bonds and vegetable oil acid derivatives.

[0014] Preferably, the vegetable oil and its derivatives include tung oil, almond oil, eucommia seed oil, peony seed oil, walnut oil, rubber seed oil, castor oil, olive oil, camellia oil, palm oil, soybean oil, linseed oil, peanut oil, cottonseed oil, sunflower oil, rapeseed oil, corn oil, Span-80, Span-85; the thiol compounds include N-acetyl-L-cysteine, 2-mercaptoethanol, 2-mercaptoacetic acid, L-cysteine ethyl ester hydrochloride, L-cysteine methyl ester hydrochloride.

[0015] Preferably, the molar ratio of the vegetable oil or its derivatives to the thiol compound is 1:2 - 1:6.

[0016] Preferably, the vegetable oil and its derivatives are castor oil, Span-80, Span-85, and the solvent is ethanol:water with a volume ratio of 1:1 - 5:1;

[0017] Preferably, the vegetable oil is soybean oil, linseed oil, palm oil, rubber seed oil or camellia oil, and the solvent is ethanol:dichloromethane with a volume ratio of 1:1 - 5:1.

[0018] Preferably, the flow rate of the solvent system flowing into the electrolytic cell is 0.1 - 2.0 mL min -1 。

[0019] Preferably, the temperature of the electrochemical reaction is 30 - 80 °C.

[0020] Another object of the present invention is to provide an application of the functionalized monomer of the vegetable oil and its derivatives prepared by the above method in the preparation of an aqueous ink binder.

[0021] Compared with the prior art, the beneficial effects of the present invention are:

[0022] (1) In the present invention, the electrochemical thiol-ene coupling reaction of vegetable oil and thiol is carried out in a continuous flow electrochemical reactor. Under mild electrochemical conditions, Span (Span-80, Span-85) can undergo a thiol-ene coupling reaction with N-acetyl-L-cysteine in an aqueous solution, and the conversion rate of the carbon-carbon double bond can reach more than 90%.

[0023] (2) The present invention applies the electrochemical thiol-ene coupling reaction to the functionalization of vegetable oil and its derivatives to form a new type of bio-based internal emulsifier (SPNAC), which is expected to replace commercial DMPA and DMBA. The aqueous ink binder WPU film prepared by using the obtained SPNAC exhibits extremely high water resistance and excellent mechanical properties.

[0024] (3) The present invention successfully applies continuous-flow electrochemistry to the thiolation of vegetable oils and their derivatives, while demonstrating its remarkable features. The method is efficient, environmentally friendly, easy to scale up, has a short residence time, and effective mass transfer characteristics, opening up practical alternatives for the development of sustainable biomass functionalization synthesis methods, and can be used to develop high-value-added chemicals and high-performance polymers. Description of the Drawings

[0025] Figure 1 It is a reaction device diagram of the present invention.

[0026] Figure 2 Samples prepared in the examples and comparative examples of the present invention 1 1H NMR hydrogen spectrum.

[0027] Figure 3 It is a schematic diagram (a), appearance (b), and particle size distribution (c) of the monomer prepared in Example 1 of the present invention applied to the preparation of an aqueous ink binder WPU dispersion. Detailed Description of the Invention

[0028] The technical solutions of the present invention will be clearly and completely described below in conjunction with the examples and comparative examples of the present invention. Obviously, the described examples are only a part of the examples of the present invention, rather than all the examples. All other examples obtained by those of ordinary skill in the art based on the examples of the present invention without creative efforts fall within the scope of protection of the present invention.

[0029] The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents, etc. used are all reagents and materials that can be obtained from commercial channels unless otherwise specified.

[0030] Example 1

[0031] An electrochemical reaction was carried out at a constant cell potential of 4.5 V using a flow electrolytic cell equipped with a graphite anode and cathode. The internal surface area of the flow electrolytic cell was 10 cm 2 , and the distance between the electrodes was 250 μm. Tetrabutylammonium tetrafluoroborate (0.02 M) was used as the electrolyte. A syringe pump was used to push Span-80 (molecular weight 428.61) (1.0 M) and N-acetyl-L-cysteine (5.0 M) (0.1 M Span-80 in dry EtOH / H2O (v / v) = 1 / 1 at 40 °C) into the electrolytic cell at a flow rate of 1.2 mL min -1 , and the solution was collected in a beaker at the outlet. The solution was diluted with H2O, extracted with ethyl acetate, and further concentrated. Then it was dissolved in ethyl acetate, the organic residue was washed with saturated brine, and finally concentrated under reduced pressure.

[0032] Example 2

[0033] An electrochemical reaction was carried out at a constant cell potential of 4.5 V using a flow electrolytic cell equipped with a graphite anode and cathode. The internal surface area of the flow electrolytic cell was 10 cm 2 , and the distance between the electrodes was 250 μm. Tetrabutylammonium tetrafluoroborate (0.02 M) was used as the electrolyte. A syringe pump was used to push Span-80 (1.0 M) and 2-mercaptoacetic acid (5.0 M) (0.1 M Span-80 in dry EtOH / H2O (v / v) = 1 / 1 at 40 °C) into the electrolytic cell at a flow rate of 1.2 mL min -1 , and the solution was collected in a beaker at the outlet. The solution was diluted with H2O, extracted with ethyl acetate, further concentrated, dissolved in ethyl acetate, washed with saturated brine for the organic residue, and finally concentrated under reduced pressure.

[0034] Example 3

[0035] An electrochemical reaction was carried out at a constant cell potential of 4.5 V using a flow electrolytic cell equipped with a stainless steel anode and cathode. The internal surface area of the flow electrolytic cell was 10 cm 2 , and the distance between the electrodes was 250 μm. Tetrabutylammonium tetrafluoroborate (0.02 M) was used as the electrolyte. A syringe pump was used to push Span-80 (1.0 M) and 2-mercaptoacetic acid (5.0 M) (0.1 M Span-80 in dry EtOH / H2O (v / v) = 1 / 1 at 40 °C) into the electrolytic cell at a flow rate of 1.2 mL min -1 , and the solution was collected in a beaker at the outlet. The solution was diluted with H2O, extracted with ethyl acetate, further concentrated, dissolved in ethyl acetate, washed with saturated brine for the organic residue, and finally concentrated under reduced pressure.

[0036] Example 4

[0037] An electrochemical reaction was carried out at a constant cell potential of 4.5 V using a flow electrolytic cell equipped with a graphite anode and cathode. The internal surface area of the flow electrolytic cell was 10 cm 2 , and the distance between the electrodes was 250 μm. Tetrabutylammonium tetrafluoroborate (0.02 M) was used as the electrolyte. A syringe pump was used to push castor oil (1.0 M) and N-acetyl-L-cysteine (5.0 M) (0.1 M castor oil in dry EtOH / H2O (v / v) = 5 / 1 at 40 °C) into the electrolytic cell at a flow rate of 1.2 mL min -1 , and the solution was collected in a beaker at the outlet. The solution was diluted with H2O, extracted with ethyl acetate, further concentrated, dissolved in ethyl acetate, washed with saturated brine for the organic residue, and finally concentrated under reduced pressure.

[0038] Example 5

[0039] An electro-chemical reaction was carried out at a constant cell potential of 4.5 V using a flow electrolytic cell equipped with a graphite anode and cathode. The inner surface area of the flow electrolytic cell was 10 cm 2 , and the distance between the electrodes was 250 μm. Tetrabutylammonium tetrafluoroborate (0.02 M) was used as the electrolyte. A syringe pump was used to push palm oil (1.0 M) and N-acetyl-L-cysteine (5.0 M) (0.1 M palm oil in dry EtOH / DCM (v / v) = 1 / 1 at 40 °C) into the electrolytic cell at a flow rate of 1.2 mL min -1 , and the solution was collected in a beaker at the outlet. The solution was diluted with H2O, extracted with ethyl acetate, and further concentrated. The residue was dissolved in ethyl acetate, washed with saturated brine, and finally concentrated under reduced pressure.

[0040] Comparative Example 1

[0041] The difference between Comparative Example 1 and Example 1 was that the syringe pump pushed at a flow rate of 0.5 mL min -1 , and the other preparation methods and condition parameters were the same and will not be repeated here.

[0042] Comparative Example 2

[0043] The difference between Comparative Example 2 and Example 1 was that only H2O was used as the solvent, and the other preparation methods and condition parameters were the same and will not be repeated here.

[0044] Comparative Example 3

[0045] The difference between Comparative Example 3 and Example 1 was that the solvent was selected as HFIP:H2O with a volume ratio of 1:2, and the other preparation methods and condition parameters were the same and will not be repeated here.

[0046] Comparative Example 4

[0047] The difference between Comparative Example 4 and Example 1 was that the solvent was selected as EtOH:H2O with a volume ratio of 1:2, and the other preparation methods and condition parameters were the same and will not be repeated here.

[0048] Comparative Example 5

[0049] The difference between Comparative Example 5 and Example 1 was that the electrolyte n-Bu4NBF4 was not added, and the other preparation methods and condition parameters were the same and will not be repeated here.

[0050] Comparative Example 6

[0051] The difference between Comparative Example 6 and Example 1 was that the electro-chemical reaction temperature was 25 °C, and the other preparation methods and condition parameters were the same and will not be repeated here.

[0052] Comparative Example 7

[0053] The difference between Comparative Example 7 and Example 1 lies in that the molar ratio of Span-80 to N-acetyl-L-cysteine used is 2:1, and the other preparation methods and condition parameters are the same, which will not be repeated here.

[0054] Comparative Example 8

[0055] The difference between Comparative Example 8 and Example 1 lies in that the mercapto compound used is L-cysteine, and the other preparation methods and condition parameters are the same, which will not be repeated here.

[0056] Experimental Example Electrochemical Thiol-ene Coupling Reaction Efficiency

[0057] Method: Proton nuclear magnetic resonance (NMR). The samples prepared in the examples and comparative examples were dissolved in deuterated chloroform, and the 1H NMR spectra of the chemical substances were obtained by operating a Bruker AV 600 spectrometer at 600 MHz. 1 The conversion rate (A) of the carbon-carbon double bond was calculated using the following formula:

[0058]

[0059] where a and b correspond to the areas of the C═C signals (5.2 - 5.5 ppm) in the 1H NMR spectra of the raw material and the product, respectively. The calculation results of the conversion rate are shown in Table 1. 1 The conversion rate calculation results are shown in Table 1.

[0060] Table 1

[0061] Group Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Conversion Rate % 95 91 91 91 90 47 9 Group Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 - Conversion Rate % 32 24 26 69 41 0 -

[0062] As can be seen from the data in Table 1, the conversion rates of the electrochemically reacted carbon-carbon double bonds in the examples of the present invention are all superior to those of the comparative examples, and can reach up to 95%. In Comparative Example 1, the flow rate pushed by the syringe pump was too slow, and N-acetyl-L-cysteine would be over-oxidized, and the reaction would produce a mixture or dimer of N-acetyl-L-cysteine; in Comparative Examples 2 - 4, the selection of different solvents and mixing ratios had a great influence on the efficiency of the thiol-ene coupling reaction. In Comparative Example 2, due to the poor solubility of Span-80 in H2O, when H2O was used as the solvent, the reaction showed very low conversion efficiency; in Comparative Example 8, since L-cysteine has an amino group that is easily peroxidized, no desired product was obtained.

[0063] Application Example Preparation of Bio-based Aqueous Polyurethane Dispersion

[0064] Taking the monomer SPNAC prepared from Span-80 and N-acetyl-L-cysteine in Example 1 of the present invention as an example. First, polyols (PPG, PCDL, CO 164Castor oil derivatives) and IPDI were added to a two-necked flask and mixed at 78 °C with a mechanical stirring speed of 250 revolutions per minute for 10 minutes. Then, the catalyst DBTDL (1.0% by weight of polyol) was added dropwise to the mixture and reacted for 30 minutes. Subsequently, SPNAC prepared in Example 1 of the present invention was dissolved in MEK as an internal emulsifier and added dropwise to the mixture, and the dropping process was maintained for 30 minutes. When the viscosity of the prepolymer increased, 5.0 - 10.0 mL of MEK was added to the mixture to reduce the viscosity of the system, and the reaction was continued until the NCO content was reduced to less than 10.0% by back titration method, then cooled to room temperature, and then neutralized with TEA for about 30 minutes. Finally, distilled water was added and emulsified at 400 - 500 revolutions per minute for 2 hours. After removing the excess MEK by rotary evaporation, a bio-based WPU with a solid content of 12.0 - 15.0% was obtained.

[0065] The molar ratio of the OH groups of SPNAC, the NCO groups of IPDI, and the OH groups of polyol in all samples was 0.99:2:1. The obtained WPU was named WPU-X, where X represents the polyol used.

[0066] Under the condition that other reaction conditions and parameters remained unchanged, DMPA, DMBA, NACCO, and EG were used as internal emulsifiers for comparison.

[0067] Performance Testing

[0068] Preparation of aqueous polyurethane film samples: The bio-based WPU dispersion prepared in the application example was poured into a silicone mold and dried at room temperature for 48 hours to obtain a surface-dried polymer film, and then the film was transferred to a 60 °C vacuum environment for 48 hours to remove residual moisture for subsequent testing.

[0069] 1. Zeta potential and particle size measurement: Zeta-seizer Nano ZSE (Malvern Instruments, UK) was used to measure the Zeta potential and particle size of the samples. The samples were diluted to 0.01% before testing, and the final results were the average of four measurements.

[0070] 2. Stability testing: The storage stability of all WPU dispersions was evaluated by centrifuging at 3000 rpm for 30 minutes using a Tomos 3-18 centrifuge. In addition, the dilution stability of all WPU dispersions was tested using the same method after dilution to a concentration of 1 - 10%. The freeze-thaw stability of all WPU dispersions was measured by storing the samples at -20 °C for 24 hours and then thawing at room temperature for 2 hours, and then seven cycles of freezing and thawing were performed.

[0071] 3. Mechanical property test: Cut all the film samples into splines with a size of 30 mm × 10 mm (length × width), and conduct a tensile test on an MTS electronic universal testing machine at a tensile rate of 100.0 mm min -1 and repeat the test 4 times for each sample.

[0072] 4. Water absorption test: Cut the film into squares with a side length of 10 mm, dry it at 60 °C for 12 h, and then immerse the dried film in deionized water for 72 h. The weights of the samples before and after soaking are m0 and m1, respectively. Measure each sample more than four times and take the average value.

[0073] The above test results are shown in Figure 3 , Table 2 and Table 3

[0074] Table 2

[0075]

[0076]

[0077] Combined with Figure 3 and Table 2, it can be seen that the particle sizes of the WPU dispersions prepared from SPNAC and different polyols are all in the range of 50 - 500 nm, the appearance is light yellow to milky white, and the absolute value of the Zeta potential is higher than 40 Mv, indicating that the WPU dispersions have good stability. After all the samples were diluted to 1 wt.% and centrifuged at 3000 rpm for 30 minutes, no precipitation or stratification occurred in all the samples, indicating that they have good storage stability. In addition, all the WPU dispersions did not gel after 7 freeze-thaw cycles, indicating that they have good freeze-thaw stability.

[0078] Table 3

[0079]

[0080]

[0081] Note: The NACCO data are from the literature A bio-based internal emulsifier prepared from soybean oil by the photo-chemical thiol-ene reaction; the EG data are from the literature A bio-based internal emulsifier prepared from soybean oil by the ring opening reaction; a water absorption value after soaking for 52 h.

[0082] Compared with other single-component WPU films reported previously, the WPU film prepared from SPNAC obtained in Application Example 1 exhibits significantly better performance than other single-component WPU films reported previously, with higher tensile strength and toughness, and the water resistance is 4-5 times that of the WPU film prepared with DMBA and DMPA as internal emulsifiers.

[0083] In summary, under mild electrochemical conditions, Tween-80 can undergo a thiol-ene coupling reaction with N-acetyl-L-cysteine in aqueous solution, and the conversion rate of carbon-carbon double bonds can reach 95%, forming a new type of bio-based internal emulsifier that can replace commercial DMPA and DMBA. The WPU film prepared by using the obtained SPNAC shows extremely high water resistance (the water absorption rate after soaking for 72 hours is as low as 3.5%) and excellent mechanical properties (the tensile strength can reach 35 MPa). In addition, it can be foreseen that the successful application of continuous flow electrochemistry to the thiolation of vegetable oils and their derivatives while showing its remarkable characteristics, such as easy scale-up, short residence time, and effective mass transfer characteristics, opens up a practical alternative for the development of sustainable biomass functionalization synthesis methods. Electrochemical thiol-ene coupling reaction is an efficient and environmentally friendly alternative method for the functionalization of vegetable oils and their derivatives, which can be used to develop high-value-added chemicals and high-performance polymers.

[0084] The above embodiments of the present invention are merely examples for clearly illustrating the technical solutions of the present invention, rather than limitations on the specific implementation manners of the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the claims of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. A preparation method of a functionalized monomer of a vegetable oil and its derivatives, characterized in that, The preparation method is an electro-chemical reaction method. A solvent system of vegetable oil or its derivative and a mercapto compound is introduced into an electrolytic cell, and the solution at the outlet is collected. The collected solution is diluted, extracted, further concentrated, then dissolved, washed, and finally concentrated under reduced pressure. Among them, the solvent is a single-phase solvent or a mixed solvent that helps dissolve vegetable oil and its derivative. The vegetable oil and its derivative refer to vegetable oil containing carbon-carbon double bonds and vegetable oil acid derivatives. The mercapto compound is one of N-acetyl-L-cysteine, 2-mercaptoethanol, 2-mercaptoacetic acid, L-cysteine ethyl ester hydrochloride, and L-cysteine methyl ester hydrochloride. The vegetable oil or its derivative and the thiol compound undergo an electrochemical thiol-ene coupling reaction in a continuous flow electrochemical reactor; the constant cell potential of the flow electrolytic cell used in the electrochemical reaction is 0.5 V - 10 V, and the inner surface area of the flow electrolytic cell is 10 cm 2 - 100 cm 2 , the distance between the electrodes is 100 µm - 500 µm, and the anode and cathode equipped in the flow electrolytic cell are graphite or stainless steel.

2. The preparation method of a functional monomer of a vegetable oil and its derivatives according to claim 1, characterized in that In the electro-chemical reaction, the electrolyte is one of tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, and tetrabutylammonium fluoride, and the dosage of the electrolyte is 0.01 M - 0.1 M.

3. The preparation method of a functionalized monomer of a vegetable oil and its derivatives according to claim 1, characterized in that, The vegetable oil and its derivative include tung oil, almond oil, eucommia seed oil, peony seed oil, walnut oil, rubber seed oil, castor oil, olive oil, camellia oil, palm oil, soybean oil, linseed oil, peanut oil, cottonseed oil, sunflower seed oil, rapeseed oil, corn oil, Span-80, and Span-85.

4. The preparation method of a functionalized monomer of a vegetable oil and its derivatives according to claim 1, characterized in that, The molar ratio of the vegetable oil or its derivative to the mercapto compound is 1:2 - 1:

6.

5. The preparation method of a functionalized monomer of a vegetable oil and its derivatives according to claim 1, characterized in that, The vegetable oil and its derivative are castor oil, Span-80, and Span-85, and the solvent is ethanol:water with a volume ratio of 1:1 - 5:

1.

6. The preparation method of a functionalized monomer of a vegetable oil and its derivatives according to claim 1, characterized in that, The vegetable oil is soybean oil, linseed oil, palm oil, rubber seed oil, or camellia oil, and the solvent is ethanol:dichloromethane with a volume ratio of 1:1 - 5:

1.

7. A method for preparing a functional monomer of a vegetable oil and its derivatives according to claim 1, characterized in that, The temperature of the electro-chemical reaction is 30 °C - 80 °C.

8. Application of the functionalized monomer of the vegetable oil and its derivative prepared by the method according to any one of claims 1 - 7 in the preparation of an aqueous ink binder.

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