Reaction type phosphate dispersing agent as well as preparation method and application thereof

Abstract

The invention provides a reaction type phosphate dispersing agent as well as a preparation method and application thereof, and the preparation method comprises the following steps: designing a molecular structure, adding a polyester segment, reacting with glycidyl ether to introduce a side chain double bond to form a multifunctional double bond, and phosphorylating to obtain the modified reaction type phosphate dispersing agent. The preparation method comprises the following steps: (1) reacting monohydric alcohol with glycidyl ether and / or hydroxy acid or hydroxy acid lactone capable of reacting to obtain hydroxy acid or dibasic acid with dihydric alcohol to obtain an intermediate; and (2) reacting the intermediate obtained in the step (1) with a phosphorylation reagent in a non-oxidation environment to obtain the phosphate ester compound. The dispersant shows excellent viscosity reduction effect, good compatibility and remarkable solvent wiping resistance when being used for dispersing pigments in coatings and printing ink. Meanwhile, raw materials of the dispersing agent are easy to obtain, high-pressure conditions are not needed in the reaction process, the process safety is high, and industrial large-scale production is facilitated.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of dispersants, and particularly relates to a reactive phosphate ester dispersant, a preparation method thereof and application thereof. BACKGROUND

[0002] In the field of coatings, inks and the like, the dispersion stability of solid pigment particles is the key to determining the performance of the product. In order to achieve uniform dispersion and long-term stability of pigments, it is usually necessary to add efficient dispersants. Among them, phosphate ester dispersants are widely used due to their unique structure: the phosphate ester end group in the molecule can be adsorbed on the surface of the pigment as an anchoring group, and the monohydric alcohol solubilizing segment connected can ensure the stability of the dispersion system in the medium through the steric hindrance effect.

[0003] The solubilizing segment structure in the phosphate ester dispersant is crucial to the dispersion performance. Common ones are alkyl, polyether, polyester or block copolymers thereof, which are adjusted in polarity to achieve good compatibility with the resin system. In the prior art, in order to optimize the compatibility, block copolymers are often used as solubilizing segments. For example: CN1649933A discloses a phosphate ester dispersant with an alkyl-polyester-polyether tri-block structure. However, after extending the polyether segment to polypropylene glycol or polytetrahydrofuran, the overall polarity of the dispersant may be reduced, the dissociation degree may be reduced, and the temperature may be more sensitive, thereby the effect is not good in high-polarity systems or hydrophilic pigment dispersion.

[0004] US5130463A and CN1203601A and the like describe phosphate ester dispersants with alkyl polyether polyester block copolymers as solubilizing segments. Although this structure improves the poor water resistance problem caused by a single polyether segment to some extent, it still has obvious defects: the polyester segment is prone to hydrolysis, resulting in insufficient stability of the dispersant; the hydrophilic-lipophilic balance value (HLB) is difficult to accurately control; the range of applicable solvents is narrow; and the controllability of the molecular structure and molecular weight during synthesis is low.

[0005] Further, if the dispersant molecule not only can anchor the pigment, but also can participate in the final film-forming reaction (i.e. has a reactive functional group), it will significantly improve the film performance, such as enhancing gloss, reducing viscosity, improving color strength, and improving solvent resistance, etc. CN104193782B reports a solution: glycerol monoallyl ether is used as a starting agent to react with alkylene oxide to synthesize a polyether monohydric alcohol with a double bond, and then phosphate ester is used to prepare a reactive phosphate ester dispersant that can participate in crosslinking. However, the alkoxylation reaction in the synthesis route needs to be carried out under high pressure conditions, which has safety risks, and the viscosity reduction performance, compatibility and solvent resistance performance of the reactive phosphate ester dispersant when used in the dispersion of color paste in the resin system still need to be further improved. SUMMARY

[0006] The technical problem to be solved by the present application is to overcome the deficiencies of the prior art, and to provide a new reactive phosphate dispersant which has better viscosity reduction performance, compatibility and solvent wiping resistance when used in coatings or inks.

[0007] To solve the above technical problems, the present application adopts the following technical solutions: The present application provides a reactive phosphate dispersant, which is a mixture of one or more of the phosphate compounds shown in structural formula (II), (II) In formula (II), a is 1, 2 or 3, EO is -CH2-CH2-O-, PO is -CH(CH3)-CH2-O-, R 1 , R 2 are end groups, R 1 , R 2 are independently CH2=CR 4 -CH2-, CH2=CR 5 -CO- or alkyl, and at least one is CH2=CR 4 -CH2-, CH2=CR 5 -CO-, wherein R 4 is selected from H, alkyl, aryl, cycloalkyl, aryl-substituted alkyl, alkyl-substituted aryl, alkyl-substituted cycloalkyl, R 5 is selected from H, alkyl, R 3 is alkylene or alkenylene, and m -CO-R 3 -O- units are the same or different, 3 x and y are independently integers between 0 and 100, for example 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or any integer between any two of the above values, z is an integer between 0 and 100, for example 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or any integer between any two of the above values, and when R 1 is alkyl, z is not 0, ​m is an integer between 0 and 100, such as 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, or any integer between any two of the above values.

[0008] Preferably, the R 4 It is H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms. More preferably, it is H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl or decyl.

[0009] Preferably, the R 3 It is a straight-chain or branched alkylene group having 2 to 20 carbon atoms, or a straight-chain or branched alkenyl group having 3 to 20 carbon atoms. More preferably, it is a straight-chain or branched alkylene group having 4 to 10 carbon atoms, or a straight-chain or branched alkenyl group having 4 to 10 carbon atoms, more preferably, it is a straight-chain or branched alkylene group having 4 to 10 carbon atoms, and particularly preferably, it is a straight-chain or branched alkylene group having 5 to 7 carbon atoms.

[0010] Preferably, the R 5 It is H or methyl.

[0011] Preferably, x and y are not both 0, and z is not 0.

[0012] A second aspect of this invention provides a method for preparing a reactive phosphate ester dispersant, comprising the following steps: (1) An intermediate is obtained by reacting a monohydric alcohol with glycidyl ether and / or a hydroxy acid or a hydroxy acid lactone or a dihydric acid and a dihydric alcohol. (2) The intermediate from step (1) is reacted with a phosphorylating agent under an oxidizing environment to obtain the phosphate ester compound. In step (1), the intermediate is a monohydric alcohol as shown in structural formula (I). (I) In formula (I), EO is -CH2-CH2-O-, and PO is -CH(CH3)-CH2-O-. R 1 R 2 All are end bases, R 1 R 2 CH2=CR independently 4 -CH2-, CH2=CR 5 -CO- or alkyl, and at least one of them is CH2=CR 4 -CH2- or CH2=CR 5 -CO-, where R 4Selected from H, alkyl, aromatic, cycloalkyl, aromatic-substituted alkyl, alkyl-substituted aromatic, alkyl-substituted cycloalkyl, R 5 Selected from H, alkyl, R 3 It is an alkylene or alkenylene group, m-CO-R 3 R in the -O- unit 3 Same or different, x and y are independent integers between 0 and 100, for example, any integer between any two of the following values: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, or more. z is an integer between 0 and 100. For example, any integer between any two values ​​of 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, or more, and when R 1 When it is an alkyl group, z is not 0. m is an integer between 0 and 100, such as 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, or any integer between any two of the above values.

[0013] Preferably, the R 4 It is H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms. More preferably, it is H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl or decyl.

[0014] Preferably, the R 3 It is a straight-chain or branched alkylene group having 2 to 20 carbon atoms, or a straight-chain or branched alkenyl group having 3 to 20 carbon atoms. More preferably, it is a straight-chain or branched alkylene group having 4 to 10 carbon atoms, or a straight-chain or branched alkenyl group having 4 to 10 carbon atoms. More preferably, it is a straight-chain or branched alkylene group having 4 to 10 carbon atoms, and particularly preferably, it is a straight-chain or branched alkylene group having 5 to 7 carbon atoms.

[0015] Preferably, the R 5 It is H or methyl.

[0016] Preferably, x and y are not both 0, and z is not 0.

[0017] In some embodiments, in step (1), the monohydric alcohol is R. 1 -OH,R 1 CH2=CR 4 -CH2-, R 4 Selected from H and alkyl groups.

[0018] In other embodiments, the monohydric alcohol is R. 1 -O-(EO) x -(PO) y -OH, R 1 Selected from H and alkyl groups, x and y are each independent integers between 0 and 100, for example, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or any two integers above, and x and y are not both 0.

[0019] In some embodiments, in step (1), the structural formula of the glycidyl ether is: R 2 CH2=CR 4 -CH2-, CH2=CR 5 -CO- or alkyl, R 4 Selected from H, alkyl, aromatic, cycloalkyl, aromatic-substituted alkyl, alkyl-substituted aromatic, alkyl-substituted cycloalkyl, R 5 Selected from H and alkyl groups.

[0020] In some embodiments, in step (1), the hydroxy acid is fed in the form of a hydroxy acid lactone capable of reacting to obtain the hydroxy acid, wherein the hydroxy acid lactone has 4 to 20 carbon atoms.

[0021] In some embodiments, in step (1), the hydroxy acid is selected from glycolic acid, hydroxybutyric acid, hydroxyvalerate, hydroxyhexanoic acid, hydroxydodecanic acid, hydroxystearic acid, and the lactone structure residue of the corresponding hydroxy acid, or is a 1:1 polycondensation residue of diacids such as ethylene glycol, neopentyl glycol, and hexanediol with oxalic acid (oxalic acid), succinic acid (containing succinic anhydride), maleic acid (containing maleic anhydride), phthalic anhydride, adipic acid, sebacic acid, etc.

[0022] In some embodiments, the reaction of the monohydric alcohol with the glycidyl ether is carried out at 50-80°C in the presence of a Lewis acid catalyst.

[0023] Furthermore, the Lewis acid catalyst is boron trifluoride.

[0024] In some embodiments, the reaction of the monohydric alcohol with the hydroxy acid or a hydroxy acid lactone capable of reacting to yield the hydroxy acid, or the reaction of a dihydric acid with a dihydric alcohol, is carried out at 140–180 °C in the presence of an organotin catalyst.

[0025] Furthermore, the organotin catalyst is dibutyltin dilaurate or stannous octoate.

[0026] In some embodiments, the reaction of the monohydric alcohol with the glycidyl ether is carried out at 50-80°C in the presence of a Lewis acid catalyst until no epoxy peak is detected by infrared spectroscopy. The reaction of the resulting reactant with the hydroxy acid or a hydroxy acid lactone or dicarboxylic acid and dihydric alcohol that can react to obtain the hydroxy acid is carried out at 140-180°C in the presence of an organotin catalyst. The solid content (at 120°C) is >98%.

[0027] In some embodiments, the reaction in step (1) is carried out under the protection of an inert gas. The inert gas is preferably nitrogen or argon.

[0028] In some specific and preferred embodiments, the monohydric alcohol is selected from allyl polyoxyethylene ether, methoxy polyethylene glycol (MPEG) hydroxyethyl acrylate, and isooctanol; the glycidyl ether is selected from allyl alcohol glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate; and the hydroxy acid lactone is selected from oxylactone and valproic acid lactone.

[0029] In some embodiments, the phosphorylating agent is fed in the form of phosphoric acid, or in the form of other substances capable of generating phosphoric acid in the reaction system. The phosphorylating agent is further preferably derived from any one or more of polyphosphoric acid, phosphoric anhydride, phosphorus pentoxide, and phosphoric acid.

[0030] In some embodiments, the reaction temperature in step (2) is 50~110°C. More preferably, it is 70~80°C.

[0031] In some implementations, the reaction time for step (2) is 5 to 8 hours.

[0032] In some embodiments, the reaction in step (2) is carried out under the protection of an inert gas. The inert gas is preferably nitrogen or argon.

[0033] A third aspect of the present invention provides the application of the above-described reactive phosphate ester dispersant or the reactive phosphate ester dispersant prepared by the above preparation method in coatings and / or inks.

[0034] More preferably, the coating is a photoinitiated curing coating.

[0035] In some embodiments, the components of the coating and the ink respectively include resin, pigment and additives, wherein the resin includes polyurethane and / or epoxy resin, and the additives include the above-described reactive phosphate dispersant or reactive phosphate dispersant prepared by the above preparation method, and may selectively include one or more of talc, reactive diluent, and defoamer.

[0036] Furthermore, the pigment is an organic or inorganic pigment.

[0037] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art: This invention utilizes molecular structure design to incorporate polyester segments and introduce side-chain double bonds through reaction with glycidyl ether, forming multifunctional double bonds. Subsequent phosphorylation yields a modified reactive phosphate dispersant. This dispersant exhibits excellent viscosity-reducing effects, good compatibility, and significant solvent-resistant wiping properties when used for pigment dispersion in coatings and inks. Furthermore, the raw materials used in this invention are readily available, the reaction process does not require high-pressure conditions, the process is highly safe, and it is suitable for industrial-scale production. Attached Figure Description

[0038] Figure 1 Comparison of the scraping effect of polyurethane coatings with pigment 996 using different dispersants on polyester sheets; Figure 2 Comparison of the scraping effect of polyurethane coatings with pigment R706 using different dispersants on polyester sheets; Figure 3 Comparison of the scraping effect of epoxy coatings with pigment 996 using different dispersants on polyester sheets; Figure 4 Comparison of the scraping effect of epoxy coatings with pigment R706 using different dispersants on polyester sheets; Figure 5 Comparison of the solvent resistance (methyl ethyl ketone, xylene) wipe effects of polyurethane coatings with pigment 996 using different dispersants; Figure 6 Comparison of solvent resistance (methyl ethyl ketone, xylene) wipe effects of polyurethane coatings with pigment R706 using different dispersants; Figure 7 Comparison of the solvent resistance (methyl ethyl ketone, xylene) wipe effects of epoxy coatings with pigment 996 using different dispersants; Figure 8 Comparison of solvent resistance (methyl ethyl ketone, xylene) wiping effects of epoxy coatings with pigment R706 using different dispersants. Detailed Implementation

[0039] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific applications, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0040] Unless otherwise specified, the raw materials used in the following examples and comparative examples were purchased from commercial channels and can also be prepared by conventional methods in the art.

[0041] Unless otherwise specified, "%" in the following text refers to mass percentage.

[0042] Example 1: This example provides a reactive phosphate ester dispersant, the preparation method of which is as follows: Add 600 g (1 mol) of allyl polyoxyethylene ether 600 (13 EOs), 456 g (4 mol) of ε-caprolactone, and 0.53 g (0.05%) of dibutyltin dilaurate to a 2000 mL flask. First, purge the air from the flask with a small amount of nitrogen gas for 30 min, then heat to 160 °C and maintain the reaction at 160 °C for 4 h. Samples were taken and the solid content (S at 120 °C) was >98%. The reaction product is a monohydric alcohol intermediate with double bonds, denoted as intermediate MG-M1. No further processing is required; it can be used directly in the next reaction step.

[0043] Add 528 g (0.5 mol) of the above intermediate MG-M1 to a 1000 mL flask, slowly purge with nitrogen for 30 min to remove air from the flask, heat to 60 °C, slowly add 30 g of polyphosphoric acid, and then heat to 80 °C. Maintain the reaction at 80 °C for 6 h. The reaction product is the reactive phosphate ester dispersant, with the following structural formula: The reaction products require no additional processing and can be used directly for subsequent application testing.

[0044] Example 2: This example provides another reactive phosphate ester dispersant, the preparation method of which is as follows: Add 600 g (1 mol) of methoxy polyethylene glycol 600 (MPEG600) (13 EO atoms), 114 g (1 mol) of allyl glycol glycidyl ether, and 3.5 g (0.5%) of boron trifluoride to a 2000 mL flask. First, purge the flask with a small amount of nitrogen gas for 30 min to remove air. Then, heat to 60 °C and maintain the reaction at 60 °C for 4 h. Sampling and infrared absorption spectroscopy (IR) analysis showed the disappearance of the epoxy peak. The reaction product is a monohydric alcohol intermediate with double bonds, denoted as intermediate MG-M2. No further processing is required; it can be used directly in the next reaction step.

[0045] Add 357 g (0.5 mol) of the above intermediate MG-M2 to a 1000 mL flask, slowly purge with nitrogen for 30 min, then purge the air from the flask, heat to 60 °C, and slowly add 30 g of polyphosphoric acid. After the addition is complete, raise the temperature to 80 °C and maintain the reaction at 80 °C for 6 h. The reaction product is the reactive phosphate ester dispersant, with the following structural formula: The reaction products require no additional processing and can be used directly for subsequent application testing.

[0046] Example 3: This example provides a reactive phosphate ester dispersant, the preparation method of which is as follows: Add 600g (1mol) of methoxy polyethylene glycol 600 (MPEG600) (13 EOs), 114g (1mol) of allyl alcohol glycidyl ether, and 3.5g (0.5%) of boron trifluoride to a 2000mL flask. First, purge the flask with a small amount of nitrogen for 30 minutes to remove air. Then, heat to 60℃ and maintain the reaction temperature at 60℃ for 4 hours. The infrared absorption spectrum (IR) of the sample showed the disappearance of the epoxy peak. Next, add 456g (4mol) of ε-caprolactone and 0.58g (0.05%) of dibutyltin dilaurate to the flask. Purge the flask with a small amount of nitrogen for 30 minutes to remove air. Then, heat to 160℃ and maintain the reaction temperature at 160℃ for 8 hours. The solid content (S at 120℃) was >98%. The reaction product is a monohydric alcohol intermediate with double bonds, denoted as intermediate MG-M3. It requires no further processing and can be used directly in the next reaction.

[0047] Add 586 g (0.5 mol) of the above intermediate MG-M3 to a 1000 mL flask, slowly purge with nitrogen for 30 min to purge air from the flask, heat to 60 °C, slowly add 30 g of polyphosphoric acid, and after the addition is complete, raise the temperature to 80 °C and maintain the reaction at 80 °C for 6 h. The reaction product is the reactive phosphate ester dispersant, with the following structural formula: The reaction products require no additional processing and can be used directly for subsequent application testing.

[0048] Example 4: This example provides a reactive phosphate ester dispersant, the preparation method of which is as follows: 116 g (1 mol) of hydroxyethyl acrylate, 150 g (1 mol) of phenyl glycidyl ether, and 1.33 g (0.5%) of boron trifluoride were added to a 1000 mL flask. The flask was first purged with a small amount of nitrogen for 30 min to remove air. The temperature was then raised to 60 °C and maintained at 60 °C for 4 h. IR spectroscopy showed the disappearance of the epoxy peak. Next, 228 g (2 mol) of ε-caprolactone, 200 g (2 mol) of valproic acid lactone, and 0.35 g (0.05%) of stannous octoate were added. The flask was first purged with a small amount of nitrogen for 30 min to remove air. The temperature was then raised to 180 °C and maintained at 180 °C for 8 h. Solid content (S at 120 °C) was >98%. The reaction product was a monohydric alcohol intermediate with a double bond, denoted as intermediate MG-M4. No further processing was required; it was used directly in the next reaction.

[0049] Add 347 g (0.5 mol) of the above intermediate MG-M4 to a 1000 mL flask, slowly purge with nitrogen for 30 min to purge air from the flask, heat to 60 °C, slowly add 30 g of polyphosphoric acid, and after the addition is complete, raise the temperature to 80 °C and maintain the reaction at 80 °C for 6 h. The reaction product is the reactive phosphate ester dispersant, with the following structural formula: The reaction products require no additional processing and can be used directly for subsequent application testing.

[0050] Example 5: This example provides a reactive phosphate ester dispersant, the preparation method of which is as follows: Add 130 g (1 mol) isooctyl alcohol, 142 g (1 mol) glycidyl methacrylate, and 1.36 g (0.5%) boron trifluoride to a 1000 mL flask. First, purge the flask with a small amount of nitrogen for 30 min to remove air. Then, heat to 60 °C and maintain the reaction temperature at 60 °C for 4 h. IR spectroscopy showed the disappearance of the epoxide peak. Next, add 228 g (2 mol) caprolactone, 200 g (2 mol) valproic acid lactone, and 0.35 g (0.05%) stannous octoate. Purge the flask with a small amount of nitrogen for 30 min to remove air. Then, heat to 180 °C and maintain the reaction temperature at 180 °C for 8 h. The solid content (S at 120 °C) was >98%. The reaction product is a monohydric alcohol intermediate with a double bond, denoted as intermediate MG-M5. It requires no further processing and can be used directly in the next reaction.

[0051] Add 350g (0.5mol) of the above intermediate MG-M5 to a 1000mL flask, slowly purge with nitrogen for 30min, then purge the air from the flask, raise the temperature to 60℃, and slowly add 35g of phosphorus pentoxide. After the addition is complete, raise the temperature to 80℃ and maintain the reaction at 80℃ for 6h. The reaction product is the reactive phosphate ester dispersant, with the following structural formula: No additional processing is required; it can be used directly for subsequent application testing.

[0052] Comparative Example 1: This example provides a phosphate ester dispersant, the preparation method of which is as follows: Add 600 g (1 mol) of methoxy polyethylene glycol 600 (MPEG600), 228 g (2 mol) of caprolactone, 200 g (2 mol) of valerol, and 0.58 g (0.05%) of dibutyltin dilaurate to a 2000 mL flask. Purge the flask with a small amount of nitrogen gas for 30 min to remove air. Heat the flask to 180 °C and maintain the temperature at 180 °C for 6 h. Samples were taken and the solid content (S at 120 °C) was >98%. The reaction product is an intermediate monohydric alcohol without carbon-carbon double bonds, denoted as intermediate DB-M1. No further processing is required; it can be used directly in the next reaction.

[0053] Add 514 g (0.5 mol) of the above intermediate DB-M1 to a 1000 mL flask, slowly purge with nitrogen for 30 min to remove air from the flask, raise the temperature to 60 °C, slowly add 30 g of polyphosphoric acid, raise the temperature to 80 °C after the addition is complete, and maintain the reaction at 80 °C for 6 h. The reaction product is the phosphate ester dispersant, with the following structural formula: No additional processing is required; it can be used directly for subsequent application testing.

[0054] Comparative Example 2: This example provides a phosphate ester dispersant, the preparation method of which is as follows: Add 500g (1mol) AEO-7 (fatty alcohol polyoxyethylene ether-7), 236g (2mol) hexanediol, 292g (2mol) adipic acid, 0.52g (0.05%) dibutyltin dilaurate, and 100g xylene to a 2000mL flask for reflux dehydration. Purge the flask with a small amount of nitrogen for 30 minutes to remove air. Heat to 180℃ and reflux until Av < 1 mgKOH / g. The reaction product is a monohydric alcohol intermediate without carbon-carbon double bonds, denoted as intermediate DB-M2. After removing xylene by rotary evaporation under reduced pressure, it is used in the next reaction step.

[0055] Add 478 g (0.5 mol) of the above intermediate DB-M2 to a 1000 mL flask, slowly purge with nitrogen for 30 min to remove air from the flask, raise the temperature to 60 °C, slowly add 30 g of polyphosphoric acid, raise the temperature to 80 °C after the addition is complete, and maintain the reaction at 80 °C for 6 h. The reaction product is the phosphate ester dispersant, with the following structural formula: No additional processing is required; it can be used directly for subsequent application testing.

[0056] Application Experiment 1: Application in pigment dispersion Process: Polyurethane color paste formulation: 27.8 parts polyurethane 611B (Changxing polyurethane acrylate 611B-85), 2 parts dispersant (phosphate ester dispersant in the above examples and comparative examples), 22 parts reactive diluent TPGDA (dipropylene glycol diacrylate), 40 parts pigment (996 or R706), 8 parts 3000# talc powder, and 0.2 parts defoamer BYK-405.

[0057] Preparation method of polyurethane color paste: First, mix the liquid phase (polyurethane 611B-85, TPGDA, additives, BYK-405) evenly, then add the powder (pigment and talc) and shake evenly. Then add glass beads (particle size of 2-3mm), shake for 2 hours, and test the viscosity.

[0058] Paint mixing ratio: Polyurethane acrylate 611B-85 : the above polyurethane colorant = 5 : 2 (mass ratio), and add 5% of 1173D photoinitiator by weight of the total mass of the mixed paint.

[0059] Plate preparation test: A 60μm wire rod was used to scrape and coat the polyester sheet for comparison, and at the same time, a 60μm wire rod was used to scrape and coat the sheet on a 70mm×150mm iron plate, four sheets for each.

[0060] Epoxy pigment formulation: The raw materials are 27.8 parts of epoxy 621A-80 (Changxing epoxy acrylate 621A-80), 2 parts of dispersant (phosphate ester dispersant in the above examples and comparative examples), 22 parts of reactive diluent TPGDA (dipropylene glycol diacrylate), 40 parts of pigment (996 or R706), 8 parts of 3000# talc powder, and 0.2 parts of defoamer BYK405.

[0061] Preparation method of epoxy color paste: First, mix the liquid phase (epoxy 621A-80, TPGDA, additives, BYK-405) evenly, then add the powder (pigment and talc) and shake evenly, then add glass beads (particle size of 2-3mm), shake for 2 hours, and test the viscosity.

[0062] Paint mixing ratio: Epoxy acrylate 621A-80 : the above epoxy pigment = 5 : 2 (mass ratio), and add 5% of 1173D photoinitiator by weight of the total mass of the mixed paint.

[0063] Plate preparation test: A 60μm wire rod was used to scrape and coat the polyester sheet for comparison, and at the same time, a 60μm wire rod was used to scrape and coat the sheet on a 70mm×150mm iron plate, four sheets for each.

[0064] The viscosity test results of the color paste and the comparison of its coating effect on polyester sheets are shown in Tables 1-4. A comparison of the appearance of partial coatings on polyester sheets is also shown in... Figures 1-4 .

[0065] Table 1 Table 2 Table 3 Table 4 Tables 1-4 show the viscosity tests conducted using an NDJ-79 rotary viscometer at 25℃±1℃. The viscosity was measured by: pouring the color paste into the test container; vertically immersing the rotor in the middle of the sample, ensuring the liquid level covered the rotor; selecting the appropriate rotation speed; turning on the viscometer motor; and recording the pointer reading when the reading stabilized. The test was repeated twice, and the average value was multiplied by the rotor coefficient to obtain the viscosity value. Rotation speed and range are negatively correlated; the lower the rotation speed, the larger the range. The maximum range at 1 rpm is 4854, at 2 rpm it is 2427, at 5 rpm it is 970.9, at 10 rpm it is 485.4, and at 20 rpm it is 242.7. EEEE indicates a very high viscosity, exceeding the range corresponding to the test rotation speed.

[0066] Based on Tables 1, 2, 3, and 4, it can be seen that the phosphate ester dispersants in the above examples and comparative examples have the following effects on viscosity reduction, color development, and hiding power of the color pastes, from best to worst: The viscosity reduction results, from best to worst, are: Example 3 > Example 1 > Example 4 > Example 5 > Example 2 > Comparative Example 1 > Comparative Example 2.

[0067] Color development and coverage, from best to worst: Example 3 > Example 1 > Example 4 > Example 5 > Example 2 > Comparative Example 1 > Comparative Example 2.

[0068] Application Experiment 2: Application in solvent-resistant wiping Process: After applying the coating in Experiment 1, the iron plate was dried and cured, and then conditioned for 1 hour at a temperature of (23±2)℃ and a relative humidity of (50±5)%. A 120mm long wiping area was then selected on the sample surface. The coating surface was cleaned with tap water to remove loose material, and then dried. A 120mm × 25mm test area was marked on the clean, undamaged coating surface using a pencil or other suitable solvent-resistant marker. A cotton ball was soaked in the specified solvent until it was moistened (no liquid should drip off when squeezed by hand). The coating surface was wiped 25 times within the marked test area. Finally, it was observed whether the coating was damaged and the substrate was exposed.

[0069] The results of the solvent resistance wiping test are shown in Tables 5-8. A comparison of the appearance of some solvent resistance wiping test results is shown below. Figures 5-8 .

[0070] Table 5 Table 6 Table 7 Table 8 Based on Tables 5, 6, 7, and 8, it can be seen that the solvent resistance of the coatings after using the phosphate ester dispersants of the above examples and comparative examples, from best to worst, is as follows: Example 1 > Example 2 (omitted) > Example 4 > Example 5 > Example 1 > Comparative Example 1 > Comparative Example 2.

[0071] The results above show that the reactive phosphate dispersants in each embodiment exhibit superior performance in reducing pigment viscosity and improving solvent wiping resistance. Furthermore, the embodiments involve non-high-pressure reactions, ensuring production safety.

[0072] The present invention has been described in detail above, with the aim of enabling those skilled in the art to understand and implement the invention. However, this description should not be construed as limiting the scope of protection of the invention. All equivalent changes or modifications made in accordance with the spirit and essence of the invention should be included within the scope of protection of the invention.

Claims

1. A reactive phosphate ester dispersant, characterized in that: The reactive phosphate ester dispersant is one or more of the phosphate ester compounds represented by structural formula (II) and their mixtures. ； In formula (II), a is 1, 2, or 3, EO is -CH2-CH2-O-, and PO is -CH(CH3)-CH2-O-. R 1 R 2 All are end bases, R 1 R 2 CH2=CR independently 4 -CH2-, CH2=CR 5 -CO- or alkyl, and at least one of them is CH2=CR 4 -CH2- or CH2=CR 5 -CO-, where R 4 Selected from H, alkyl, aromatic, cycloalkyl, aromatic-substituted alkyl, alkyl-substituted aromatic, alkyl-substituted cycloalkyl, R 5 Selected from H, alkyl, R 3 It is an alkylene or alkenylene group, m-CO-R 3 R in the -O- unit 3 Same or different, x and y are independent integers between 0 and 100. z is an integer between 0 and 100, and when R 1 When it is an alkyl group, z is not 0. m is an integer between 0 and 100.

2. The reactive phosphate ester dispersant according to claim 1, characterized in that: The R 4 It is H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms; And / or, the R 3 It is a straight-chain or branched alkylene group having 2 to 20 carbon atoms or a straight-chain or branched alkenyl group having 3 to 20 carbon atoms; And / or, the R 5 It is H or methyl; And / or, x and y are not both 0, and z is not 0.

3. A method for preparing a reactive phosphate ester dispersant, characterized in that: It includes the following steps: (1) An intermediate is obtained by reacting a monohydric alcohol with glycidyl ether and / or a hydroxy acid or a hydroxy acid lactone or a dihydric acid and a dihydric alcohol. (2) The intermediate from step (1) is reacted with a phosphorylating agent under an oxidizing environment to obtain the phosphate ester compound. In step (1), the intermediate is a monohydric alcohol as shown in structural formula (I). ； In formula (I), EO is -CH2-CH2-O-, and PO is -CH(CH3)-CH2-O-. R 1 R 2 All are end bases, R 1 R 2 CH2=CR independently 4 -CH2-, CH2=CR 5 -CO- or alkyl, and at least one of them is CH2=CR 4 -CH2- or CH2=CR 5 -CO-, where R 4 Selected from H, alkyl, aromatic, cycloalkyl, aromatic-substituted alkyl, alkyl-substituted aromatic, alkyl-substituted cycloalkyl, R 5 Selected from H, alkyl, R 3 It is an alkylene or alkenylene group, m-CO-R 3 R in the -O- unit 3 Same or different, x and y are independent integers between 0 and 100. z is an integer between 0 and 100, and when R 1 When it is an alkyl group, z is not 0. m is an integer between 0 and 100.

4. The method for preparing the reactive phosphate ester dispersant according to claim 3, characterized in that: The R 4 It is H or a straight-chain or branched alkyl group having 1 to 10 carbon atoms; And / or, the R 3 It is a straight-chain or branched alkylene group having 2 to 20 carbon atoms or a straight-chain or branched alkenyl group having 3 to 20 carbon atoms; And / or, the R 5 It is H or methyl; And / or, x and y are not both 0, and z is not 0.

5. The method for preparing the reactive phosphate dispersant according to claim 3, characterized in that: In step (1), the monohydric alcohol is R. 1 -OH,R 1 CH2=CR 4 -CH2-, R 4 Selected from H, alkyl; Alternatively, the monohydric alcohol is R. 1 -O-(EO) x -(PO) y -OH,R 1 Selected from H and alkyl groups, x and y are independent integers between 0 and 100, and x and y are not both 0. And / or, in step (1), the structural formula of glycidyl ether is: R 2 CH2=CR 4 -CH2-, CH2=CR 5 -CO- or alkyl, R 4 Selected from H, alkyl, aromatic, cycloalkyl, aromatic-substituted alkyl, alkyl-substituted aromatic, alkyl-substituted cycloalkyl, R 5 Selected from H, alkyl, And / or, in step (1), the hydroxy acid is fed in the form of a hydroxy acid lactone capable of reacting to obtain the hydroxy acid, wherein the hydroxy acid lactone has 4 to 20 carbon atoms.

6. The method for preparing the reactive phosphate ester dispersant according to claim 3, characterized in that: The reaction of the monohydric alcohol with the glycidyl ether is carried out at 50-80°C in the presence of a Lewis acid catalyst. And / or, the reaction of the monohydric alcohol with the hydroxy acid or a hydroxy acid lactone capable of reacting to give the hydroxy acid or the reaction of the dihydric acid and the dihydric alcohol is carried out at 140-180°C in the presence of an organotin catalyst. And / or, the reaction of the monohydric alcohol with the glycidyl ether is carried out at 50-80°C in the presence of a Lewis acid catalyst, and the reaction of the resulting reactant with the hydroxy acid or a hydroxy acid lactone or a dicarboxylic acid and a dihydric alcohol is carried out at 140-180°C in the presence of an organotin catalyst. And / or, the reaction in step (1) is carried out under the protection of an inert gas.

7. The method for preparing the reactive phosphate dispersant according to claim 3, characterized in that: In step (2), the phosphorylation reagent is fed in the form of phosphoric acid or in the form of other substances that can generate phosphoric acid in the reaction system; And / or, the reaction temperature in step (2) is 50~110℃; And / or, the reaction in step (2) is carried out under the protection of an inert gas.

8. The method for preparing the reactive phosphate dispersant according to claim 3, characterized in that: In step (2), the phosphorylation reagent is any one or more of polyphosphoric acid, phosphoric anhydride, phosphorus pentoxide, and phosphoric acid; And / or, the reaction temperature in step (2) is 70~80℃; And / or, the reaction time for step (2) is 5~8h.

9. The application of the reactive phosphate dispersant as described in claim 1 or 2, or the reactive phosphate dispersant prepared by any one of claims 3 to 8, in coatings and / or inks.

10. The application according to claim 9, characterized in that: The components of the coating and the ink respectively include resin, pigment and additives. The resin includes polyurethane and / or epoxy resin. The additives include the reactive phosphate dispersant as described in claim 1 or 2 or the reactive phosphate dispersant prepared by the preparation method as described in any one of claims 3 to 8, and may selectively include one or more of talc, reactive diluent and defoamer.

Images