Macromolecular dispersing agent for digital printing glass ink as well as preparation method and application of macromolecular dispersing agent

Abstract

The invention belongs to the field of advanced functional assistants, and discloses a macromolecular dispersant for digital printing glass ink and a preparation method and application thereof.The preparation method includes the following steps that unsaturated polyether monomers (including alkynediol polyether), unsaturated ester monomers, unsaturated acid monomers, water and a phosphorus-containing reducing agent are mixed, heated and stirred till solids are completely dissolved, and a mixture is obtained; dropwise adding a persulfate aqueous solution, and carrying out reflux reaction at 60-100 DEG C for 2-2.5 hours; and continuously carrying out heat preservation reaction at 90-100 DEG C, stopping heating, adding a chain terminator solution, terminating the reaction, cooling, adding alkali liquor, and carrying out neutralization reaction to obtain a polymer solution with the concentration of 42-48wt%, namely the macromolecular dispersing agent for the digital printing glass ink. The macromolecular dispersant can significantly improve the fluidity and stability of glass ink, has excellent thermal stability, mechanical properties and weather resistance, and also has good solubility, wettability and low-foam property in ink dispersion.

Description

Technical Field

[0001] The invention discloses a macromolecular dispersant for digital printing glass ink with both grinding aid and dispersing performance, a preparation method and application thereof, and belongs to the field of advanced functional additives. Background Art

[0002] In the field of modern industrial design and manufacturing, glass is an important material, and its surface treatment technology is constantly being innovated to meet the growing demand for personalization and high performance. As one of the best, glass digital printing technology has shown great potential in many fields such as architectural decoration, art creation, and electronic product housings with its high precision and high efficiency. Digital printing glass ink is an ink that can be printed on glass and can be firmly attached. After the ink is sintered and tempered at a high temperature of 680-850℃, the pigment in the ink is firmly fused with the glass to achieve color adhesion and durability. The glass products after coloring and strengthening are rich in color, the glass structure is strong and strong, and has a certain resistance to common corrosive substances in the atmosphere, and has good hiding power. This glass ink is widely used in the exterior decoration of building curtain walls, automotive glass, home appliance glass, ceramic products, sports equipment, etc. In the field of glass deep processing, especially in digital printing technology under high temperature environment, the dispersion problem of digital ink has always been a key factor restricting the widespread application of this technology. The design and development of digital ink dispersants are the most core elements to promote the functionalization of digital printing, the personalization of design creativity, and the efficient production and storage durability of ink products. Therefore, the research and application of dispersants in the preparation of glass high-temperature digital inks is particularly important. Dispersants are also the component with the highest technical content in digital inks. Summary of the invention

[0003] The main purpose of the present invention is to provide a macromolecular dispersant for digital printing glass ink, so as to significantly improve the fluidity and stability of the glass ink and endow the glass ink with excellent thermal stability, weather resistance, wettability and mechanical properties.

[0004] Another object of the present invention is to provide a preparation method and application of the macromolecular dispersant.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A method for preparing a macromolecular dispersant for digital printing glass ink comprises the following steps:

[0007] (1) mixing an unsaturated polyether monomer, an unsaturated ester monomer, an unsaturated acid monomer, water and a phosphorus-containing reducing agent, heating (to 60-75° C.) and stirring until the solid is completely dissolved, then dripping a persulfate aqueous solution at a rate of 15-25 drops / min, and keeping the mixture at 60-100° C. while dripping and refluxing for 2-2.5 hours; the unsaturated polyether monomer comprises an acetylene glycol polyether;

[0008] (2) After the reaction in step (1) is completed, continue the reaction at 90-100° C. for 1-1.5 hours, stop heating, add a chain terminator solution, and terminate the reaction;

[0009] (3) After cooling (naturally cooling to below 40° C. under stirring), an alkali solution is added for neutralization reaction to obtain a polymer solution with a concentration of 42-48 wt %, which is a macromolecular dispersant for digital printing glass ink.

[0010] Preferably, the molecular weight of the unsaturated polyether monomer is 500-3000, and the amount used is 5-25wt% of the total monomer amount; the amount of the unsaturated ester monomer is 5-15wt% of the total monomer amount; the amount of the unsaturated acid monomer is 60-90wt% of the total monomer amount.

[0011] Preferably, the unsaturated polyether monomer is at least two of allyl polyoxyethylene ether (APEG, molecular formula is CH2=CHCH2O(CH2CH2O)nH), methyl butyl polyoxyethylene ether, isobutylene alcohol polyoxyethylene ether, isopentanol polyoxyethylene ether (TPEG), and acetylene glycol polyether; the unsaturated ester monomer is one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl acrylate, heptyl acrylate, and isooctyl acrylate; the unsaturated acid monomer is acrylic acid and / or methacrylic acid.

[0012] Preferably, the acetylene glycol polyether in step (1) is acetylene glycol polyoxyethylene ether, and the acetylene glycol polyether accounts for 20±10% of the total mass of the unsaturated polyether monomer.

[0013] Preferably, the acetylene glycol polyether is one or more of C10 acetylene glycol polyoxyethylene ether, tetramethyl-6-dodecyne-5,8-diol polyoxyethylene ether, tetramethyl-5-decyne-4,7-diol polyoxyethylene ether and dodecyne glycol polyoxyethylene ether.

[0014] Preferably, in step (1), the amount of phosphorus-containing reducing agent used is 0.1-1.2 wt% of the total monomer amount; the amount of persulfate used is 0.2-2.0 wt% of the total monomer amount; and the amount of chain terminator used is 0.1-1.0 wt% of the total monomer amount.

[0015] Preferably, the phosphorus-containing reducing agent in step (1) is one or more of ammonium hypophosphite, potassium hypophosphite, and sodium hypophosphite; the persulfate is one or more of ammonium persulfate, potassium persulfate, and sodium persulfate, and the concentration of the persulfate aqueous solution is 2.0-8.0wt%; the chain terminator in step (2) is one or more of potassium phosphite, sodium phosphite, ammonium phosphite, sodium hypophosphite, potassium hypophosphite, and ammonium hypophosphite, and the concentration of the chain terminator solution is 5.0-15wt%.

[0016] Preferably, the alkali solution in step (3) is a 30-48 wt% potassium hydroxide or sodium hydroxide aqueous solution, and the pH value of the reaction solution is adjusted to 7-9.

[0017] The macromolecular dispersant for digital printing glass ink prepared by the above method is used in digital printing glass ink. Adding the dispersant before grinding the ink can improve the grinding efficiency of the ink colorant, and has a significant effect on improving the ink drop positioning, aggregation and black edge phenomenon in digital printing of glass ink.

[0018] The initiator persulfate and the phosphorus-containing reducing agent hypophosphite together constitute an oxidation-reduction free radical initiation system (such as formula 1). Under the induced excitation of the peroxide bond, primary phosphorus-containing free radicals are generated. The primary free radicals first initiate highly active acid unsaturated monomers, and the free radical units are introduced into the polymer main chain, which then initiates the ester and polyether monomers to undergo free radical polymerization to form a multi-polymer. Before the end of the reaction, a chain terminator (phosphite) is added to react with the excess free radicals in the solution that have not participated in the reaction to undergo a chain transfer termination reaction, thereby terminating the free radical polymerization reaction. Alkali solution is added to carry out a neutralization reaction, and the pH value of the reaction solution is adjusted to 7-9, then an ion pair COO is formed in the polymer solution. - M + (M = Na, K), indicating that the prepared product is an anionic surfactant.

[0019]

[0020] The macromolecular dispersant for digital printing glass ink prepared by the present invention can significantly improve the fluidity and stability of glass ink, and endow the ink with excellent thermal stability, weather resistance, solubility, wettability and mechanical properties. In addition, due to the introduction of the acetylene glycol polyether chain segment, the dynamic surface tension of the macromolecular dispersant is effectively controlled, so that the dispersant has a foam-free or low-foaming property. The addition of the dispersant can improve the dispersion uniformity of the ink at high temperature, ensure that the printed pattern is clear and the color is full, and provide a guarantee for the ink to have good durability and corrosion resistance.

[0021] Compared with the prior art, the present invention has the following significant features:

[0022] (1) The macromolecular dispersant of the present invention can significantly improve the fluidity and stability of glass ink. Due to the presence of the functional segment acetylene glycol polyether, it is endowed with excellent thermal stability, mechanical properties and weather resistance, provides stable fluidity and slurryability in the preparation of glass ink, and has good wettability and grinding aid effect on pigment particles.

[0023] (2) The macromolecular dispersant of the present invention also has good solubility, wettability and low foaming properties in the dispersion of glass ink, so that the printed pattern of the glass ink is clear and the color is rich.

[0024] (3) The macromolecular dispersant of the present invention imparts good weather resistance and thermal stability to the glass ink, and is also beneficial for enhancing the mechanical properties and anti-corrosion properties of the printed pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Schematic diagram of the main reactants and reaction process. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto. The allyl polyoxyethylene ether and isopentanol polyoxyethylene ether in the examples were purchased from Hai'an Petrochemical Plant, Jiangsu Province, and the C10 acetylene glycol polyoxyethylene ether and dodecylene glycol polyoxyethylene ether were purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0027] Example 1

[0028] (1) Add 20 g of deionized water to a 500 ml four-necked flask equipped with electric stirring, reflux condenser, temperature monitoring and dropping device, and add 10 g of a mixture of allyl polyoxyethylene ether and C10 acetylene glycol polyoxyethylene ether (mixture weight ratio is 4:1), 10 g of methyl methacrylate, 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% sodium hypophosphite aqueous solution under stirring. Raise the temperature to 70°C, stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% sodium persulfate initiator aqueous solution at a rate of 20 drops / min, and keep the mixture at 80°C for reflux reaction for 2 hours.

[0029] (2) Continue to keep the reaction at 95° C. for 1.0 hour, stop heating, add 10 g of 5 wt % chain terminator sodium phosphite solution, and cool naturally to below 40° C. while stirring.

[0030] (3) 125 g of a 33 wt % aqueous sodium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 315 g of a 45 wt % polymer solution, which is the macromolecular dispersant T-1 for digital printing glass ink.

[0031] Example 2

[0032] (1) Add 50 g of deionized water to a 500 ml four-necked flask equipped with an electric stirrer, a reflux condenser, a temperature monitor and a drop-adding device, and add 10 g of a mixture of allyl polyoxyethylene ether, isopentanol polyoxyethylene ether and C10 acetylene glycol polyoxyethylene ether (mixture weight ratio is 2:2:1), 10 g of a mixture of methyl methacrylate and butyl methacrylate (mixture weight ratio is 1:1), 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% potassium hypophosphite aqueous solution under stirring. Raise the temperature to 70°C, stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% potassium persulfate initiator aqueous solution at a rate of 20 drops / min, and keep the mixture at 80°C for reflux reaction for 2 hours.

[0033] (2) Continue to heat the reaction at 95° C. for 1 hour, stop heating, add 10 g of 5 wt % chain terminator potassium phosphite solution, and cool naturally to below 40° C. while stirring.

[0034] (3) 125 g of a 46 wt % aqueous potassium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 345 g of a 46 wt % polymer solution, which is the macromolecular dispersant T-2 for digital printing glass ink.

[0035] Example 3

[0036] (1) Add 30 g of deionized water to a 500 ml four-necked flask equipped with an electric stirrer, a reflux condenser, a temperature monitor and a drop-adding device, and add 10 g of a mixture of allyl polyoxyethylene ether, isopentanol polyoxyethylene ether and dodecyne glycol polyoxyethylene ether (mixture weight ratio is 2:2:1), 10 g of a mixture of methyl methacrylate and butyl methacrylate (mixture weight ratio is 1:1), 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% aqueous solution of ammonium hypophosphite. Raise the temperature to 70°C, stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% aqueous solution of ammonium persulfate initiator at a rate of 20 drops / min, and keep the mixture at 80°C for reflux reaction for 2 hours.

[0037] (2) Continue to heat the reaction at 95° C. for 1 hour, stop heating, add 10 g of 5 wt % chain terminator ammonium phosphite solution, and cool naturally to below 40° C. while stirring.

[0038] (3) 125 g of a 33 wt % aqueous sodium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 325 g of a 44 wt % polymer solution, which is the macromolecular dispersant T-3 for digital printing glass ink.

[0039] Example 4

[0040] (1) Add 40 g of deionized water to a 500 ml four-necked flask equipped with an electric stirrer, a reflux condenser, a temperature monitor and a drop-adding device, and add 10 g of a mixture of allyl polyoxyethylene ether, isopentanol polyoxyethylene ether and C10 acetylene glycol polyoxyethylene ether (mixture weight ratio is 2:2:1), 10 g of a mixture of methyl methacrylate, butyl methacrylate and isooctyl acrylate (mixture weight ratio is 2:2:1), 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% sodium hypophosphite aqueous solution. Raise the temperature to 70° C., stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% sodium persulfate initiator aqueous solution dropwise at a rate of 20 drops / min, and keep the mixture at 80° C. for reflux reaction for 2 hours.

[0041] (2) Continue to heat the reaction at 95° C. for 1 hour, stop heating, add 10 g of 5 wt % chain terminator sodium phosphite solution, and cool naturally to below 40° C. while stirring.

[0042] (3) 125 g of a 33 wt % aqueous sodium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 335 g of a 43 wt % polymer solution, which is the macromolecular dispersant T-4 for digital printing glass ink.

[0043] Example 5

[0044] (1) Add 50 g of deionized water to a 500 ml four-necked flask equipped with an electric stirrer, a reflux condenser, a temperature monitor and a drop-adding device, and add 10 g of a mixture of allyl polyoxyethylene ether, isopentanol polyoxyethylene ether and dodecyne glycol polyoxyethylene ether (mixture weight ratio is 2:2:1), 10 g of a mixture of methyl methacrylate, butyl methacrylate and isooctyl acrylate (mixture weight ratio is 2:2:1), 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% potassium hypophosphite aqueous solution. Raise the temperature to 70°C, stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% potassium persulfate initiator aqueous solution at a rate of 20 drops / min, and keep the mixture at 80°C for reflux reaction for 2 hours.

[0045] (2) Continue to heat the reaction at 95° C. for 1 hour, stop heating, add 10 g of 5 wt % chain terminator potassium phosphite solution, and cool naturally to below 40° C. while stirring.

[0046] (3) 125 g of a 46 wt % aqueous potassium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 345 g of a 46 wt % polymer solution, which is the macromolecular dispersant T-5 for digital printing glass ink.

[0047] Example 6

[0048] (1) Add 50 g of deionized water to a 500 ml four-necked flask equipped with an electric stirrer, a reflux condenser, a temperature monitor and a drop-adding device, and add 10 g of a mixture of allyl polyoxyethylene ether, isopentanol polyoxyethylene ether, C10 chain acetylene glycol polyoxyethylene ether and dodecylene glycol polyoxyethylene ether (mixture weight ratio is 4:4:1:1), 10 g of a mixture of methyl methacrylate and butyl methacrylate (mixture weight ratio is 1:1), 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% potassium hypophosphite aqueous solution. Raise the temperature to 70° C., stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% potassium persulfate initiator aqueous solution at a rate of 20 drops / min, and keep the mixture at 80° C. for reflux reaction for 2 hours.

[0049] (2) Continue to heat the reaction at 95° C. for 1 hour, stop heating, add 10 g of 5 wt% potassium phosphite solution as a chain terminator, and cool naturally to below 40° C. while stirring.

[0050] (3) 125 g of a 46 wt % aqueous potassium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 345 g of a 46 wt % polymer solution, which is the macromolecular dispersant T-6 for digital printing glass ink.

[0051] Example 7

[0052] (1) Add 50 g of deionized water to a 500 ml four-necked flask equipped with an electric stirrer, a reflux condenser, a temperature monitor and a drop-adding device, and add 10 g of a mixture of allyl polyoxyethylene ether, isopentanol polyoxyethylene ether, C10 chain acetylene glycol polyoxyethylene ether and dodecylene glycol polyoxyethylene ether (mixture weight ratio is 4:4:1:1), 10 g of a mixture of methyl methacrylate, butyl methacrylate and isooctyl acrylate (mixture weight ratio is 2:2:1), 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% potassium hypophosphite aqueous solution. Raise the temperature to 70°C, stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% potassium persulfate initiator aqueous solution at a rate of 20 drops / min, and keep the mixture at 80°C for reflux reaction for 2 hours.

[0053] (2) Continue to heat the reaction at 95° C. for 1 hour, stop heating, add 10 g of 5 wt% potassium phosphite solution as a chain terminator, and cool naturally to below 40° C. while stirring.

[0054] (3) 125 g of a 46 wt % aqueous potassium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 345 g of a 46 wt % polymer solution, which is the macromolecular dispersant T-7 for digital printing glass ink.

[0055] Example 8

[0056] (1) Add 50 g of deionized water to a 500 ml four-necked flask equipped with an electric stirrer, a reflux condenser, a temperature monitor and a drop-adding device, and add 10 g of a mixture of allyl polyoxyethylene ether and isopentanol polyoxyethylene ether (mixture weight ratio is 1:1), 10 g of a mixture of methyl methacrylate, butyl methacrylate and isooctyl acrylate (mixture weight ratio is 2:2:1), 80 g of a mixture of acrylic acid and methacrylic acid (mixture weight ratio is 1:1), and 30 g of a 0.5 wt% potassium hypophosphite aqueous solution. Raise the temperature to 70°C, stir until the solid is completely dissolved, then add 30 g of a 2.5 wt% potassium persulfate initiator aqueous solution at a rate of 20 drops / min, and keep the mixture at 80°C for reflux reaction for 2 hours.

[0057] (2) Continue to heat the reaction at 95° C. for 1 hour, stop heating, add 10 g of 5 wt% potassium phosphite solution as a chain terminator, and cool naturally to below 40° C. while stirring.

[0058] (3) 125 g of a 46 wt % aqueous potassium hydroxide solution was added, and the pH value of the reaction solution was adjusted to 7-9 to obtain 345 g of a 46 wt % polymer solution, which is the macromolecular dispersant T-8 for digital printing glass ink.

[0059] Example 9

[0060] Application performance test of synthetic macromolecular dispersants in digital printing glass ink

[0061] 1. Synthetic macromolecular dispersant performance test equipment and conditions

[0062] In order to eliminate the interference of other components and objectively evaluate the dispersibility and grinding aid performance of the synthetic macromolecular dispersant, the two main components of the glass ink, the pigment powder (the most representative black pigment 2808 is selected in this patent) and the glass powder are selected for grinding and dispersion performance testing. The grinding equipment uses the German IKA dispersion grinder (model: MK 2000), 200 grams of 0.4-0.5mm zirconium beads, and continuous grinding for 60 minutes. The amount of synthetic macromolecular dispersant added is 5.5wt% of the total amount of the grind, and the solvent uses commercially available 195 and 198 (mixed solvent weight ratio is 58:32), and the solid content of the ink obtained by grinding is 45%. The dispersibility of the ink is evaluated by testing the viscosity data, and the grinding aid performance of the macromolecular dispersant is evaluated by testing the D10, D50, and D90 of its grinding product by a laser particle size analyzer.

[0063] 2. Application performance test of synthetic macromolecular dispersants

[0064] Table 1

[0065]

[0066]

[0067] Notes:

[0068] (1) T-0 is a blank sample without dispersant. From the test results, it can be seen that when no dispersant is added, the grinding aid performance and fluidity of black pigment 2808 and glass powder are relatively poor, which cannot meet the actual production needs.

[0069] (2) T-8 is a control sample without adding the two functional monomers C10 acetylene glycol polyoxyethylene ether and dodecylene glycol polyoxyethylene ether. From the test results, it can be seen that the synthetic control sample T-8 has little effect on the fluidity of black pigment 2808 and glass powder, but has a greater impact on the grinding aid performance of the two powders.

[0070] (3) T-9 is the most widely used imported product on the market (model: 91F, purchased from BYK Additives (Shanghai) Co., Ltd.). Test results show that its effects on the grinding aid and fluidity of black pigment 2808 and glass powder are relatively balanced, but compared with the best product T-7 of the present invention, both properties are inferior.

[0071] 2. Stability test of the slurry obtained by grinding

[0072] The stability test of the polishing slurry was selected after being placed at room temperature for four weeks. The slurries of the test samples of T-0, T-7, and T-9 were used as the test objects. The test indicators were D50, D90 and viscosity data. The test results are shown in Table 2 below.

[0073] Table 2

[0074]

[0075] From the test data in Table 2 above, it can be seen that after the blank sample without dispersant (T-0) was placed at room temperature for four weeks, the D90 was close to 5μm (the average particle size of the powder before grinding), indicating that the grinding slurry had completely agglomerated and returned to the particle size level before grinding. After the grinding slurry with synthetic sample T-7 and commercially available comparison sample T-9 was placed at room temperature for four weeks, the fluidity of the slurry slightly deteriorated, but it was still able to flow, which is also in line with the thixotropic properties of this inorganic slurry; the particle size of the slurry has increased, indicating that a small amount of agglomeration has occurred in the slurry, but under the action of the dispersant, the agglomeration phenomenon is not obvious. In summary, the stability of the slurry prepared after the addition of the dispersant has been significantly improved. A comprehensive comparison of the performance of the synthetic sample T-7 and the commercially available comparison sample T-9 in slurry stability shows that the synthetic sample T-7 is better than the commercially available comparison sample T-9.

[0076] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a macromolecular dispersant for digital printing glass ink, characterized in that: The steps include: (1) mixing an unsaturated polyether monomer, an unsaturated ester monomer, an unsaturated acid monomer, water and a phosphorus-containing reducing agent, heating and stirring until the solid is completely dissolved, then dripping a persulfate aqueous solution at a rate of 15-25 drops / min, and keeping the mixture at 60-100° C. and reflux for 2-2.5 hours; the unsaturated polyether monomer comprises an acetylene glycol polyether; (2) After the reaction in step (1) is completed, continue to heat the reaction at 90-100° C. for 1-1.5 hours, stop heating, add a chain terminator solution, and terminate the reaction; (3) After cooling, an alkali solution is added to carry out a neutralization reaction to obtain a polymer solution with a concentration of 42-48 wt %, which is a macromolecular dispersant for digital printing glass ink.

2. The preparation method according to claim 1, characterized in that: The molecular weight of the unsaturated polyether monomer is 500-3000, and the amount used is 5-25wt% of the total monomer amount; the amount used of the unsaturated ester monomer is 5-15wt% of the total monomer amount; the amount used of the unsaturated acid monomer is 60-90wt% of the total monomer amount.

3. The preparation method according to claim 2, characterized in that: The unsaturated polyether monomers are at least two of allyl polyoxyethylene ether, methyl butyl polyoxyethylene ether, isobutylene alcohol polyoxyethylene ether, isopentanol polyoxyethylene ether, and acetylene glycol polyether; the unsaturated ester monomers are one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl acrylate, heptyl acrylate, and isooctyl acrylate; and the unsaturated acid monomers are acrylic acid and / or methacrylic acid.

4. The preparation method according to claim 1, 2 or 3, characterized in that: The acetylene glycol polyether in step (1) is acetylene glycol polyoxyethylene ether, and the acetylene glycol polyether accounts for 20±10% of the total mass of the unsaturated polyether monomer.

5. The preparation method according to claim 4, characterized in that: The acetylene glycol polyether is one or more of C10 acetylene glycol polyoxyethylene ether, tetramethyl-6-dodecyne-5,8-diol polyoxyethylene ether, tetramethyl-5-dodecyne-4,7-diol polyoxyethylene ether and dodecyne glycol polyoxyethylene ether.

6. The preparation method according to claim 1, 2 or 3, characterized in that: In step (1), the amount of phosphorus-containing reducing agent used is 0.1-1.2 wt% of the total monomer amount; the amount of persulfate used is 0.2-2.0 wt% of the total monomer amount; and the amount of chain terminator used is 0.1-1.0 wt% of the total monomer amount.

7. The preparation method according to claim 4, characterized in that: The phosphorus-containing reducing agent in step (1) is one or more of ammonium hypophosphite, potassium hypophosphite, and sodium hypophosphite; the persulfate is one or more of ammonium persulfate, potassium persulfate, and sodium persulfate, and the concentration of the persulfate aqueous solution is 2.0-8.0wt%; the chain terminator in step (2) is one or more of potassium phosphite, sodium phosphite, ammonium phosphite, sodium hypophosphite, potassium hypophosphite, and ammonium hypophosphite, and the concentration of the chain terminator solution is 5.0-15wt%.

8. The preparation method according to claim 7, characterized in that: The alkali solution in step (3) is a 30-48 wt% potassium hydroxide or sodium hydroxide aqueous solution, and the pH value of the reaction solution is adjusted to 7-9.

9. A macromolecular dispersant for digital printing glass ink prepared by the method according to any one of claims 1 to 8.

10. Use of the macromolecular dispersant according to claim 9 in digital printing glass ink.

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