Reactive phosphate functional emulsifier and preparation method thereof

Abstract

The application discloses a reactive phosphate functional emulsifier and a preparation method thereof, relates to the technical field of emulsifiers, and comprises the following steps: mixing vinyl salicylaldehyde, ethyl acetate and triethylamine, stirring under an inert atmosphere, adding phenyl phosphorodichloridate in an ice bath, centrifuging, washing and drying after warming reaction to obtain a preform; ultrasonically mixing the preform with anhydrous ethanol, adding hyperbranched polyether amine, continuously ultrasonically mixing, then adding 2-amino-4-fluorothiophenol for constant-temperature reaction, washing and drying after removing the solvent to obtain a mixture; stirring the mixture with anhydrous ethanol and an initiator, high-speed dispersing cyclic siloxane, adding glycidyl methacrylate for heating reaction, washing and drying after gradient cooling and solidification to obtain the emulsifier; by introducing cyclic siloxane and hyperbranched polyether amine, a hydrophobic film and a hydrogen bond network hierarchical protection system are constructed, the hydrolysis resistance and the flame resistance of the emulsifier are improved, and the stability of water-based paint is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of emulsifiers, and particularly relates to a reactive phosphate functional emulsifier and a preparation method thereof. BACKGROUND

[0002] An emulsifier is a kind of substance capable of forming a stable emulsion of two or more mutually insoluble components. The principle of action is that, in the emulsification process, the dispersed phase is dispersed in the form of droplets in the continuous phase, the emulsifier reduces the interfacial tension of each component in the mixed system, and forms a relatively strong film on the surface of the droplets or a double electric layer on the surface of the droplets due to the charges given by the emulsifier, thereby preventing the droplets from gathering with each other and maintaining a uniform emulsion. From the perspective of phases, the emulsion is still a heterogeneous system.

[0003] As a key component of water-based paint, the stability of the emulsifier directly affects the durability of the coating. However, in the prior art, the hydrolysis failure of the imine bond in the alkaline environment, the insufficient flame retardant performance, and the short service life of the material limit the application of the emulsifier. The traditional phosphorus-based flame retardant can only achieve flame retardation by generating a phosphate protective layer, but it is easy to volatilize at high temperatures, resulting in a low carbon residue rate. The emulsifier without introducing a chemical passivation mechanism has an insufficient imine bond retention rate under the condition of pH>10, and the service life of the coating is insufficient. Therefore, developing an emulsifier with hydrolysis resistance, high-efficiency flame retardation, and long-term stability has become a technical problem to be solved in the industry. SUMMARY

[0004] The present application provides a reactive phosphate functional emulsifier and a preparation method thereof, which solves the problem of hydrolysis failure of the imine bond in the emulsifier in the prior art under an alkaline environment. By introducing a cyclic siloxane and a hyperbranched polyether amine, a hydrophobic film and a hydrogen bond network hierarchical protection system are constructed. The siloxane forms a superhydrophobic film to block water erosion, and the polyether amine passivates the active sites of the imine bond through the hydrogen bond network. The synergistic effect of the three components of the polyether amine realizes functional division at the molecular scale. Combined with the ceramic reaction of the cyclic siloxane, the emulsifier is endowed with self-repairing, high-efficiency flame retardation, and long-term stability.

[0005] The present application provides a preparation method of a reactive phosphate functional emulsifier, which comprises the following steps:

[0006] (1) mixing vinyl salicylaldehyde, ethyl acetate, and triethylamine, stirring under an inert atmosphere, adding phenylphosphoryl dichloride in an ice bath, centrifuging, washing, and drying after warming reaction to obtain a preform;

[0007] (2) ultrasonically mixing the preform with anhydrous ethanol, adding a hyperbranched polyether amine, continuing ultrasonic treatment, adding 2-amino-4-fluorothiophenol for constant temperature reaction, washing and drying after removing the solvent to obtain a mixture;

[0008] (3) stirring the mixture with anhydrous ethanol, initiator, adding cyclic siloxane high-speed dispersion, adding glycidyl methacrylate and heating reaction, gradient cooling and curing, then washing and drying to obtain the emulsifier.

[0009] Further, the mass ratio of vinyl salicylaldehyde: ethyl acetate: triethylamine: phenyl phosphorodichloridate in step (1) is 13:130:8.6:8.5.

[0010] Further, the mass ratio of the preform: anhydrous ethanol: hyperbranched polyether amine: 2-amino-4-fluorothiophenol in step (2) is 10:45:(0.5-1.0):2.5.

[0011] Further, the mass ratio of the cyclic siloxane to the hyperbranched polyether amine is (3.5-4.5):(0.5-1.0).

[0012] Further, the mass ratio of the cyclic siloxane to the hyperbranched polyether amine is 3:1.

[0013] Further, the hyperbranched polyether amine in step (2) comprises low molecular weight 2 kDa, medium molecular weight 8 kDa and high molecular weight 20 kDa polyether amines, and the mass ratio of the three is 1:1:1.

[0014] Further, the gradient cooling process in step (3) is specifically as follows: cooling at 3℃ / min from 85℃ to 65℃, cooling at 1℃ / min from 65℃ to 50±1℃, and constant temperature at 50±1℃ for 30 min.

[0015] A reactive phosphate functional emulsifier is prepared by the above method.

[0016] The one or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:

[0017] Firstly, by introducing cyclic siloxane and hyperbranched polyether amine, a hydrophobic film and a hydrogen bond network hierarchical protection system are constructed, the siloxane forms a superhydrophobic film to block water erosion, and the polyether amine passivates the imine bond active sites through the hydrogen bond network, solving the problem of easy hydrolysis and failure of the imine bond in an alkaline environment, improving the hydrolysis resistance of the emulsifier, enhancing the flame retardation performance, prolonging the service life of the material through self-repairing and mechanical interlocking structure, and improving the stability and safety of the water-based paint.

[0018] The spatiotemporal coordination of water defense, the cyclic siloxane first forms a rigid hydrophobic barrier on the surface of the emulsifier, and the superhydrophobic effect is generated by the directional arrangement of the methyl group, which directly bounces off most of the environmental water, and the trace amount of water that penetrates is captured by the flexible hydrogen bond network of the hyperbranched polyether amine. The ether bond oxygen atoms in the polyether amine molecular chain form strong hydrogen bonds with water molecules, locking them into stable hydration clusters and depriving them of chemical reactivity. Through the combination of internal and external defense structures, a comprehensive blockade of water molecules is achieved. The element-level synergy of the flame-retardant function, in the high-temperature combustion scene, the cyclic siloxane and the polyether amine activate different flame-retardant paths: the cyclic siloxane decomposes to generate silicon dioxide, which fills the pores of the carbon layer in a molten state, making the residual carbon structure denser, reducing the pore size, and improving the barrier efficiency; the gaseous ammonia released by the hyperbranched polyether amine reacts with the phosphorus-containing radicals (PO·) to form phosphorus-nitrogen compounds, enhancing the gas-phase radical capture ability, and the two form a dual-extinguishing mechanism of solid and gas phases, significantly improving the flame-retardant efficiency;

[0019] Secondly, by introducing a complex system of low molecular weight, medium molecular weight, and high molecular weight hyperbranched polyether amine, a functional division and cooperation at the molecular scale is achieved. The different molecular weights of polyether amine have different advantages in spatial scale, bonding ability, and thermal response characteristics, and a multi-level defense network is constructed.

[0020] The three molecular weights of polyether amine form a hierarchical defense, the low molecular weight polyether amine penetrates into the siloxane network pores and anchors the silanol group through hydrogen bonding, the high molecular weight polyether amine intertwines with the siloxane long chain to form a rigid-flexible composite interface, and the medium molecular weight fills the gaps and bridges the interface to eliminate the risk of phase separation and improve the interface bonding.

[0021] Different molecular weights of polyether amine achieve hierarchical flame-retardant response during combustion, low temperature stage (200-300℃): low molecular weight rapidly decomposes to release NH3, diluting oxygen concentration; medium temperature stage: medium molecular weight catalyzing carbonization, siloxane decomposing to generate SiO2 filling micropores; high temperature stage: high molecular weight maintaining the integrity of the carbon layer skeleton, combined with the SiO2 generated by siloxane to form a dense ceramic layer, improving the heat insulation efficiency;

[0022] When microcracks occur, the low molecular weight polyether amine instantaneously reorganizes hydrogen bonds to repair molecular-level damage, the siloxane exposed silanol group automatically condenses to repair the hydrophobic membrane, the medium molecular weight bridges the two sides of the crack through chain segment motion to prevent expansion, and the high molecular weight forms an elastic cover layer on the surface to block external erosion. DETAILED DESCRIPTION

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application; the use herein of the terms "and / or" includes a set of one or more associated listed items.

[0024] Embodiment one: a preparation method of a reactive phosphate functional emulsifier, specifically comprising the following steps,

[0025] Step 1, preparation of a preform

[0026] 1.1 Add vinyl salicylaldehyde (13 parts by weight), ethyl acetate (130 parts by weight), and triethylamine (8.6 parts by weight) into a reaction kettle, and stir at 300-400 r / min under nitrogen protection for 30-45 min;

[0027] 1.2 Slowly add phenylphosphonic dichloride (8.5 parts by weight) in an ice bath, and stir at 65-70°C for 12-15 h;

[0028] 1.3 Centrifuge, wash with saturated sodium chloride solution, and freeze-dry to obtain a preform;

[0029] Step 2: preparation of a mixture

[0030] 2.1 Add the preform (10 parts by weight) and anhydrous ethanol (45 parts by weight) into an ultrasonic reactor, and ultrasonicate at 120-150 W for 7-10 min;

[0031] 2.2 Add hyperbranched polyether amine (HBPO-12) (0.5-1.0 parts by weight), and continue ultrasonication for 5 min;

[0032] 2.3 Add 2-amino-4-fluorothiophenol (2.5 parts by weight), and maintain the temperature at 60-65°C for 5-6 h;

[0033] 2.4 Remove the solvent by rotary evaporation, wash with alcohol, and freeze-dry to obtain a mixture;

[0034] Step 3: synthesis of an emulsifier

[0035] 3.1 Stir the mixture (13 parts by weight), anhydrous ethanol (45 parts by weight), and azobisisobutyronitrile (0.35 parts by weight) for 30-45 min;

[0036] 3.2 Add cyclic siloxane (D4H) (3.5-4.5 parts by weight), and disperse at 800-1000 r / min for 10 min;

[0037] 3.3 Glycidyl methacrylate (2.5 parts by weight) is added, heated at 80-85°C for 5-6h, and stirring is maintained at 300-400 r / min;

[0038] 3.4 Gradient cooling to 50±1°C for curing, centrifugation, and alcohol washing;

[0039] The gradient cooling is specifically cooling from 85°C to 65°C at a rate of 3°C / min, cooling from 65°C to 50±1°C at a rate of 1°C / min, and maintaining at 50±1°C for 30 min;

[0040] 3.5 Drying at 80°C to constant weight, and the product is obtained.

[0041] Experiments are conducted for the technical solution, and the components added in each experiment are shown in Table 1:

[0042] Table 1

[0043]

[0044] Each group of experiments prepares 500g of emulsifier samples, and the emulsifier samples are made into paints. Specifically, the emulsifier (3 parts), n-butanol (3 parts), epoxy resin E-44 (12 parts), calcium carbonate (4 parts), methyl methacrylate (15 parts), butyl acrylate (40 parts), acrylic acid (8 parts), benzoyl peroxide (2.5 parts), deionized water (50 parts), and ammonium polyphosphate (1 part) are used. The paints made from the emulsifiers of experiments one to seven are cured into films.

[0045] Performance detection:

[0046] Limiting oxygen index (LOI): A JF-3 type oxygen index tester is used to test the limiting oxygen index according to GB / T2406.2-2009;

[0047] Residual carbon rate: 1g of paint is burned in a muffle furnace at 800°C for 30 min, and the residual carbon mass ratio is calculated after cooling and weighing. Residual carbon rate = residual carbon mass / sample initial mass x 100%.

[0048] Imine bond retention rate (alkali resistance): 0.5g of emulsifier sample is soaked in 50mL of NaOH solution (60°C) with pH=12 for 72h; filtration, drying, and FT-IR detection of 1665cm -1 The change in the area of the imine bond characteristic peak after soaking: retention rate (%) = (peak area after soaking / peak area before soaking) x 100%;

[0049] Alkali resistance grade: 5 = perfect; 4 = slight blistering; 3 = blistering; 2 = obvious blistering; 1 = peeling

[0050] The detection results of experiments one to seven are shown in Table 2:

[0051] Table 2

[0052]

[0053] The technical solutions in the embodiments of the present application have at least the following technical effects or advantages:

[0054] By introducing cyclic siloxane and hyperbranched polyether amine, through multi-level synergistic effect, the technical problem of easy hydrolysis and failure of imine bond in alkaline water-based coating environment is solved, and the flame retardation performance and long-term stability are significantly improved.

[0055] The Si-H bond in the cyclic siloxane molecule undergoes hydrolysis reaction in the presence of water, and the generated silanol group further dehydrates and condenses to form a continuous and dense Si-O-Si three-dimensional network film. The hydrophobic film is arranged by methyl groups, and an ultrahydrophobic barrier is constructed on the surface of the emulsifier;

[0056] The introduction of cyclic siloxane produces the following effects:

[0057] Physical isolation of moisture: moisture permeability is reduced by 90%, blocking the erosion path of alkaline solution to the imine bond;

[0058] Thermal stability enhancement: at high temperature, silicon element is oxidized to form SiO2, enhancing the carbon layer density and heat insulation, and the residual carbon rate is increased from 32% to 40.5%;

[0059] Long-term protection: in a metal anticorrosive coating with pH=12, the service life of the coating is significantly prolonged.

[0060] The ether bond of the hyperbranched polyether amine and the imine hydrogen (=N-H) of the imine bond form a high-strength hydrogen bond network (-CH=N-···H-O-), which improves the chemical stability through steric hindrance effect and electron cloud shielding effect, and the stereoscopic barrier structure effectively hinders OH - ions from approaching the active site of the imine bond; at the same time, the electron cloud around the ether bond inhibits the attack of nucleophiles through electrostatic repulsion, thereby greatly enhancing the hydrolysis resistance of the material.

[0061] The introduction of hyperbranched polyether amine produces the following effects:

[0062] Chemical passivation protection: the imine bond retention rate is significantly improved after 72 hours of immersion in pH=12 solution at 60°C;

[0063] Self-repairing function: the dynamic hydrogen bond network can repair molecular micro-damage autonomously, maintaining the structural integrity;

[0064] Flame retardation synergism: nitrogen element decomposes and releases NH3 to dilute combustible gas, and the limiting oxygen index (LOI) is increased from 32.1% to 33.8%.

[0065] Cyclic siloxane and hyperbranched polyether amine achieve functional complementation through hierarchical protection of physical insulation and chemical passivation, producing synergistic effects;

[0066] The spatiotemporal synergy of water defense, cyclic siloxane first forms a rigid hydrophobic barrier on the surface of the emulsifier, and through the directional arrangement of methyl groups, it produces a superhydrophobic effect, directly bouncing off most of the environmental moisture. The small amount of water that penetrates is then captured by the flexible hydrogen bond network of the hyperbranched polyether amine. The ether bond oxygen atoms in the polyether amine molecular chain form strong hydrogen bonds with water molecules, locking them into stable hydration clusters and depriving them of their chemical reactivity. Through the combination of internal and external defense structures, a comprehensive blockade of water molecules is achieved.

[0067] Elemental-level synergy of flame-retardant function, in high-temperature combustion scenarios, cyclic siloxane and polyether amine activate different flame-retardant paths: cyclic siloxane decomposes to generate silicon dioxide, which, in its molten state, fills the pores of the carbon layer, densifying the carbon structure and reducing the pore size, thereby enhancing the barrier efficiency; the gaseous ammonia released by the hyperbranched polyether amine reacts with phosphorus-containing radicals (PO·) to form phosphorus-nitrogen compounds, enhancing the gas-phase radical capture ability, and the two form a dual-extinguishing mechanism of solid and gas phases, significantly improving the flame-retardant efficiency.

[0068] Molecular synergy of dynamic self-repair, when the coating is mechanically damaged: the silanol groups (≡Si-OH) of cyclic siloxane are exposed to air, automatically condensing to repair the hydrophobic film; the hydrogen bond network of polyether amine reorganizes through molecular chain segment motion, instantaneously filling the imine bond microcracks, and the combined response linkage of the two damage makes the protection system have self-healing properties.

[0069] The critical surface tension of the siloxane film matches the solubility parameter of the polyether amine, allowing the two-phase interface to form a molecular-level interpenetrating structure. The polyether amine branches embed into the siloxane network pores, forming a mechanically interlocked interface with a much higher binding energy than physical mixing, thereby improving the mechanical properties of the composite material.

[0070] The hydrogen bond network (-CH=N-···H-O-) in the polyether amine molecule changes the hydrolysis reaction path of the imine bond (-CH=N-) through steric hindrance and electronic effects. The hydrogen bond network combines with the imine bond in advance to form a stable intermediate (-CH=N-···H-O-). At this time, OH - must first break the hydrogen bond to approach the imine bond, resulting in a significant increase in the reaction energy barrier. Therefore, the hydrolysis rate of the imine bond in the composite material is greatly reduced, significantly improving the hydrolysis resistance and chemical stability of the material.

[0071] By introducing cyclic siloxane and hyperbranched polyether amine, the stability of imine bond in emulsifier is obviously improved, avoiding hydrolysis failure in alkaline environment, and the flame retardant performance is improved, the LOI is improved to 33.8%, the carbon residue rate breaks through 40.5%, the synergistic effect of quaternary flame retardant elements (P / F / N / S) and silicon / nitrogen is improved, and the flame retardant efficiency is improved by 30%.

[0072] In the above embodiment one, by introducing cyclic siloxane and hyperbranched polyether amine, a hydrophobic film and a hydrogen bond network hierarchical protection system is constructed, siloxane forms a superhydrophobic film to block water erosion, and polyether amine passivates the imine bond active site through hydrogen bond network, solves the problem that imine bond is easy to hydrolyze and fail in alkaline environment, improves the hydrolysis resistance of emulsifier, enhances the flame retardant performance, and prolongs the service life of material through self-repairing and mechanical interlocking structure, improves the stability and safety of water-based paint, and further improves the stability of emulsifier on the basis of embodiment one.

[0073] The hyperbranched polyether amine includes low molecular weight 2kDa, medium molecular weight 8kDa and high molecular weight 20kDa; the mass ratio of low molecular weight, medium molecular weight and high molecular weight is 1:1:1.

[0074] The experiment of the present embodiment is carried out on the basis of experiment eight of embodiment one, which is experiment nine. The difference between experiment nine and experiment eight is that experiment nine includes hyperbranched polyether amine with different molecular weights, and the detection results of experiment nine are shown in Table 3.

[0075] Table 3

[0076]

[0077] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages:

[0078] By introducing a complex system of low molecular weight (2kDa), medium molecular weight (8kDa) and high molecular weight (20kDa) hyperbranched polyether amine, the functional division and cooperation of molecular scale are realized, and a multi-level defense network is constructed by taking advantage of the differences in spatial scale, bonding ability and thermal response characteristics of polyether amine with different molecular weights.

[0079] The low molecular weight polyether amine (2kDa) has a short molecular chain, high permeability and high reactivity. Strong hydrogen bonds are formed between the ether bonds and the imine bonds, which quickly embed the nanoscale gaps around the imine bonds and construct a dense hydrogen bond layer at the molecular scale. The structure significantly improves the hydrolysis activation energy of the imine bond through the electronic cloud shielding effect, effectively passivating the chemical activity of the imine bond. The reversible rupture / recombination characteristics of hydrogen bonds enable the material to form hydrogen bonds again through chain segment movement when microcracks occur under stress, improving the repair efficiency.

[0080] The molecular chain length of the medium molecular weight polyether amine (8kDa) is moderate, and has penetration and steric hindrance effect. On the one hand, it penetrates into the imine bond micro area which is not covered by the low molecular weight polyether amine, and fills the protection gap; on the other hand, it bridges the high and low molecular weight polyether amines through flexible molecular chains to form a continuous hydrogen bond network, eliminating the stress concentration at the interface, so that the coating still maintains structural integrity when mechanically deformed, and significantly enhances the anti-cracking property of the carbon layer;

[0081] The long molecular chain of the high molecular weight polyether amine (20kDa) forms a three-dimensional network skeleton, providing a macro-level physical barrier, and through molecular-level interpenetration with the hydrophobic film of cyclic siloxane, a rigid-flexible combined composite structure is constructed. The rigid silicon-carbon skeleton of siloxane provides mechanical strength, and the flexible chain of polyether amine absorbs impact energy, so that the peeling strength is improved, and at high temperature, nitrogen gas is released to dilute combustible gas, enhancing the gas phase flame retardant efficiency;

[0082] The low molecular weight penetrates into the active site of the imine bond and preoccupies the reaction site through hydrogen bonding, blocking the hydrolysis path; the medium molecular weight connects the high and low molecular weight regions, eliminating the protection blind area, and forming a high protection hydrogen bond network; the high molecular weight covers the surface and cooperates with siloxane to prevent external moisture and OH - The ions constitute a physical barrier, and in a basic environment with pH=12, the retention rate of the imine bond is improved, and the service life of the coating is prolonged.

[0083] The three molecular weight polyether amines form a hierarchical defense, the low molecular weight polyether amine penetrates into the siloxane network pores and anchors the silanol group through hydrogen bonding, the high molecular weight polyether amine intertwines with the long chain of siloxane to form a rigid-flexible composite interface, and the medium molecular weight fills the gap and bridges the interface to eliminate the risk of phase separation and improve the interface bonding;

[0084] Different molecular weight polyether amines achieve hierarchical flame retardant response during combustion, low temperature stage (200-300℃): low molecular weight decomposes rapidly to release NH3, diluting oxygen concentration; medium temperature stage: medium molecular weight catalyzes carbonization, and siloxane decomposes to generate SiO2 to fill micropores; high temperature stage: high molecular weight maintains the integrity of the carbon layer skeleton, combined with the SiO2 generated by siloxane to form a dense ceramic layer, improving the heat insulation efficiency;

[0085] When microcracks occur, the low molecular weight polyether amine instantaneously reorganizes hydrogen bonds to repair molecular-level damage, the silanol group exposed by siloxane automatically condenses to repair the hydrophobic film, the medium molecular weight bridges the two sides of the crack through chain segment motion to prevent expansion, and the high molecular weight forms an elastic covering layer on the surface to block external erosion;

[0086] By introducing a synergistic system of low molecular weight, medium molecular weight and high molecular weight hyperbranched polyether amine and cyclic siloxane, the emulsifier long-term stability and flame retardant performance are breakthroughly improved.

[0087] The above merely describes the preferred embodiments of the present application and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a reactive phosphate ester functional emulsifier, characterized in that, Includes the following steps: (1) Mix vinyl salicylaldehyde, ethyl acetate and triethylamine, stir under an inert atmosphere, add phenylphosphodichloro in an ice bath, heat and react, then centrifuge, wash and dry to obtain the preform; (2) The preform is ultrasonically mixed with anhydrous ethanol, hyperbranched polyetheramine is added, and after ultrasonication is continued, 2-amino-4-fluorothiophenol is added and reacted at a constant temperature. After removing the solvent, the mixture is washed and dried to obtain the mixture. (3) The mixture is stirred with anhydrous ethanol and an initiator, cyclic siloxane is added and dispersed at high speed, then glycidyl methacrylate is added and heated to react. After gradient cooling and curing, it is washed and dried to obtain an emulsifier. In step (1), the mass ratio of vinyl salicylaldehyde: ethyl acetate: triethylamine: phenylphosphine dichloride is 13:130:8.6:8.5; In step (2), the mass ratio of preform: anhydrous ethanol: hyperbranched polyetheramine: 2-amino-4-fluorothiophenol is 10:45:(0.5-1.0):2.5; The mass ratio of the cyclic siloxane to the hyperbranched polyetheramine is (3.5–4.5):(0.5–1.0).

2. The preparation method of the reactive phosphate ester functional emulsifier as described in claim 1, characterized in that, The mass ratio of the cyclic siloxane to the hyperbranched polyetheramine is 3:

1.

3. The preparation method of the reactive phosphate ester functional emulsifier as described in claim 1, characterized in that, The hyperbranched polyetheramine mentioned in step (2) comprises low molecular weight 2 kDa, medium molecular weight 8 kDa and high molecular weight 20 kDa polyetheramine, with a mass ratio of 1:1:

1.

4. The preparation method of the reactive phosphate ester functional emulsifier as described in claim 1, characterized in that, The gradient cooling process in step (3) is as follows: the temperature is reduced from 85℃ to 65℃ at 3℃ / min, the temperature is reduced from 65℃ to 50±1℃ at 1℃ / min, and the temperature is kept constant at 50±1℃ for 30 min.

5. A reactive phosphate ester functional emulsifier, characterized in that, It is prepared by any one of the methods of claims 1-4.

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