A seed emulsion for covering polymers and a method for its preparation

Abstract

The application provides a seed emulsion of a hiding polymer and a preparation method thereof. In the method, the rectorite is first modified by intercalation of adamantane with high rigidity and high hydrophobicity and a sulfonic surfactant with wettability, then inserted into acrylic monomers for original polymerization, and the organically modified rectorite gives the seed emulsion of the hiding polymer a shell with high strength, high hydrophobicity and low surface tension, can improve the structural stability of the hiding polymer, reduces the collapse rate of the hiding polymer, and thus ensures excellent hiding performance of the hiding polymer.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of hiding polymers, and particularly relates to a seed emulsion of a hiding polymer and a preparation method thereof. BACKGROUND

[0002] Hiding polymer, also known as "hollow microsphere", is a kind of water-based acrylic emulsion with hollow structure, and its Tg is generally high and cannot form a film at room temperature. The shell thereof is a high glass transition temperature polymer composed of styrene / acrylate, and the average particle size thereof is 400-600 nm. Due to its unique hollow structure, the hiding polymer utilizes the high scattering force of internal air to light to provide hiding power, so as to partially replace titanium dioxide, thereby reducing the cost and improving the application performance of the coating, such as washability and stain resistance.

[0003] The conventional preparation method of the hiding polymer mainly includes three steps. First, a high-acid seed emulsion is prepared as the "core layer" of the hiding polymer. Then, 1-2 layers of hard shell layer emulsion are wrapped outside the high-acid seed emulsion to form a core-shell structure. Finally, at the softening point temperature of the hard shell layer polymer, an alkali solution is added for neutralization, the alkali solution enters the polymer and reacts with the high-acid core layer to form a hydrophilic polymer, and due to the difference in ion concentration, a large amount of water enters the polymer to swell and form a hollow microsphere.

[0004] In the preparation method of the hiding polymer, the preparation of the seed emulsion is the most critical step. If the structure design of the seed emulsion is unreasonable, it will cause the cavity of the hollow microsphere to be too large or too small, thereby causing hiding deviation, or the structure of the hollow microsphere is not firm, and a large number of hollow microspheres collapse during the drying and film-forming process of the coating, thereby causing hiding deviation. In addition, the amount of emulsifier used in the seed is an important control variable. If the amount of emulsifier is too small, the stability of the polymerization process of the seed emulsion will be poor, there will be more residue, and the storage stability will be poor; if the amount of emulsifier is too large, the excess emulsifier will form new solubilized micelles during the preparation of the hiding polymer, thereby causing the "secondary nucleation" phenomenon. The newly generated polymer latex particles have no high-acid seed core, and after neutralization and swelling, they form solid spheres, thereby reducing the effective hollow microsphere content of the hiding polymer and reducing the hiding rate.

[0005] CN112409530A discloses a seed emulsion for opaque polymers, which uses petroleum ether with a boiling range of 60-90℃ as a continuous phase to carry out emulsion polymerization, and then performs oil-to-water conversion and petroleum ether extraction to prepare a seed emulsion with stable particle size. However, this patent uses oil phase polymerization, and after polymerization, oil-to-water conversion and petroleum ether extraction are performed, which not only makes the preparation method more complex, but also increases the VOC content of the emulsion due to the residual petroleum ether solvent, which does not comply with the international environmental protection concept.

[0006] It can be seen that the prior art cannot solve the problems of poor structure stability of seed emulsion and secondary nucleation, resulting in high collapse rate of hollow microspheres and deviation of hiding performance. SUMMARY

[0007] In order to solve the above technical problems, the present application provides a seed emulsion of a hiding polymer modified by adamantane-sulfonate intercalated rectorite, which is intercalated and modified by adamantane with high rigidity and high hydrophobicity and a sulfonic surfactant with wettability, and then inserted into acrylic monomers for in-situ polymerization. The organic rectorite gives the seed emulsion of the hiding polymer a shell with high strength, high hydrophobicity and low surface tension, which can improve the structure stability of the hiding polymer and reduce the collapse rate of the hiding polymer, thereby ensuring excellent hiding performance of the hiding polymer.

[0008] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0009] A seed emulsion of a hiding polymer, comprising a shell A and a core B;

[0010] The components of the shell A are as follows, in parts by weight:

[0011] (meth)acrylic alkyl ester and / or vinyl monomer 200-400 parts, preferably 250-350 parts

[0012] (meth)acrylic acid 50-150 parts, preferably 80-120 parts

[0013] adamantane-sulfonate intercalated rectorite 10-40 parts, preferably 20-30 parts

[0014] chain transfer agent 1-10 parts, preferably 2-5 parts

[0015] initiator I 5-20 parts, preferably 8-15 parts

[0016] organic solvent 200-800 parts, preferably 400-600 parts

[0017] neutralizing agent 20-100 parts, preferably 30-80 parts

[0018] The components of the core B are as follows, in parts by weight:

[0019] methyl methacrylate 50-200 parts, preferably 100-150 parts

[0020] methyl methacrylate 50-200 parts, preferably 100-150 parts

[0021] crosslinking agent 1-5 parts, preferably 1.5-2.5 parts

[0022] Anionic emulsifier 0.2-0.4 parts, preferably 0.25-0.35 parts

[0023] Initiator II 0.5-1.5 parts, preferably 0.8-1.2 parts

[0024] The mass ratio of the shell A and the core B is 1:(2-4).

[0025] The seed emulsion of the covering polymer has a core-shell structure, and the shell layer is modified by the adamantane-sulfonate intercalated rectorite. The rectorite is first intercalated by adamantane with high rigidity and high hydrophobicity and a sulfonic acid surfactant with wetting property, and then inserted into an acrylic monomer for original flavor polymerization. The organic rectorite gives the covering polymer seed emulsion a high-strength, high-hydrophobicity, and low-surface-tension shell, which can improve the structural stability of the covering polymer, reduce the collapse rate of the covering polymer, and thus ensure excellent covering performance of the covering polymer. The resin shell A is prepared by gradient dropping process, which ensures that the hydrophobicity of the seed emulsion shell increases from inside to outside, which is beneficial to reducing the collapse rate of the hollow microspheres and improving the covering performance of the covering polymer. In addition, since no emulsifier is introduced during the solution polymerization process, the aqueous solution of the resin A is used as the emulsifier of the resin core B, which can significantly reduce the amount of anionic emulsifier, reduce the proportion of "secondary nucleation", and improve the effective hollow microsphere content of the covering polymer to improve the covering rate.

[0026] In the present application, the (meth)alkyl acrylate in the component for preparing the shell A is (meth)acrylic acid C1-C10 alkyl ester, preferably one or more of (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid isooctyl ester, and more preferably one or more of methyl methacrylate, butyl acrylate, and isooctyl acrylate.

[0027] In the present application, the vinyl monomer in the component for preparing the shell A is selected from C1-C12 vinyl monomers, preferably one or more of styrene, α-methylstyrene, and vinyl acetate, and more preferably styrene.

[0028] In the present application, the chain transfer agent in the component for preparing the shell A is a thiol molecular weight regulator or a non-odor type molecular weight regulator, preferably one or more of n-dodecanethiol, α-methylstyrene dimer, and 3-mercapto propionic acid methyl ester, and more preferably α-methylstyrene dimer.

[0029] In the present application, the initiator I in the component for preparing the shell A is one or more of peroxide and / or azo initiator, preferably one or more of di-tert-butyl peroxide (DTBP), di-tert-amyl peroxide (DTAP), benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), more preferably di-tert-butyl peroxide (DTBP).

[0030] In the present application, the organic solvent in the component for preparing the shell A is one or more of ethanol, acetone, ethylene glycol butyl ether, dimethylbenzene, preferably acetone.

[0031] In the present application, the neutralizing agent in the component for preparing the shell A is one or more of basic compounds, preferably one or more of ammonia, ethanolamine, N,N-dimethylethanolamine, triethanolamine, triethylamine, AMP-95, sodium hydroxide and potassium hydroxide, more preferably one or more of ammonia, ethanolamine, N,N-dimethylethanolamine, most preferably ammonia.

[0032] In the present application, the crosslinking agent in the component for preparing the core B is one or more of crosslinking agents containing 2-3 C=C double bonds, preferably one or more of ethylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, 1,3-butanediol dimethacrylate, more preferably ethylene glycol dimethacrylate and / or allyl methacrylate.

[0033] In the present application, the anionic emulsifier in the component for preparing the core B is selected from fatty alcohol polyoxyethylene ether sulfate, preferably one or more of fatty alcohol polyoxyethylene ether sulfate with EO number of 1-20, more preferably one or more of Solvay RHODAPEX TR / 2030-S, Clariant Emulsion EPA073, Solvay ABEX 8018R, Solvay RHODAPEX CM-30, Clariant Emulsion EPA1963, Clariant Emulsion EPA073.

[0034] In the present application, the initiator II in the component for preparing the core B is one or more of persulfate initiators, preferably one or more of ammonium persulfate, sodium persulfate, potassium persulfate.

[0035] Another object of the present application is to provide a preparation method of adamantane-sulfonate intercalated laponite.

[0036] A preparation method of adamantane-sulfonate intercalated laponite, the intercalated laponite prepared by the method is used in the seed emulsion described above, the preparation method of the adamantane-sulfonate intercalated laponite comprises the following steps:

[0037] S1: water is added into a reaction kettle I, stirring, adding laponite, continuing stirring;

[0038] S2: Ammonium adamantane is added to the reaction kettle II, solvent is added, stirring is performed, acid solution is added, and stirring is continued;

[0039] S3: The mixed solution obtained in S2 is added to the reaction kettle I in S1 to react;

[0040] S4: A sulfonate is added to the reaction kettle I, and heat preservation is performed;

[0041] S5: Filtration, washing, drying, crushing, and sieving are performed to obtain an adamantane-sulfonate intercalated rectorite.

[0042] In the present application, the rectorite in S1 is sodium-based rectorite.

[0043] In the present application, the water in S1 is 1000 parts, and the rectorite is 50-100 parts.

[0044] In the present application, the stirring time in S1 is 3-6 h.

[0045] In the present application, the ammonium adamantane in S2 is one or more of 1,3,5,7-tetra(4-aminophenyl)adamantane, 1-acetylammonium adamantane, and 1-adamantane amine.

[0046] In the present application, the ammonium adamantane in S2 is 10-50 parts.

[0047] In the present application, the solvent in S2 is 100-500 parts; preferably, the solvent is acetone.

[0048] In the present application, the acid solution in S2 is 10-50 parts; preferably, the acid solution is a 10-15 wt% hydrochloric acid solution.

[0049] In the present application, the stirring time in S2 is 15-30 min.

[0050] In the present application, the reaction temperature in S3 is 30-60℃, and the reaction time is 3-6 h.

[0051] In the present application, the sulfonate in S4 is one or more of C10-C40 alkyl sulfonate, preferably sodium dodecyl diphenyl ether disulfonate, sodium diisooctyl succinate, and sodium maleic acid diisooctyl sulfonate; more preferably, the sodium dodecyl diphenyl ether disulfonate is DOWFAX 2A1, and the sodium diisooctyl succinate is OT-75.

[0052] In the present application, the sulfonate in S4 is 10-50 parts.

[0053] In the present application, the heat preservation time in S4 is 2-6 h.

[0054] In the present application, the washing in S5 is performed with acetone and deionized water until there is no chloride ion in the solution.

[0055] In the present application, the over 200-325 mesh sieve in S5.

[0056] Another object of the present application is to provide a preparation method of the seed emulsion of the covering polymer. The seed emulsion of the present application can be prepared by the conventional method in the art or the method provided by the present application, and the method provided by the present application can obtain better effect.

[0057] A preparation method of the seed emulsion of the covering polymer, the seed emulsion is the seed emulsion described above or the adamantane-sulfonate intercalated rectorite prepared by the preparation method described above, and the method comprises the following steps:

[0058] SS1: adding an organic solvent in a reaction kettle and heating, mixing the raw materials of preparation A, i.e. (meth)alkyl acrylate and / or vinyl monomer, (meth)acrylic acid, chain transfer agent and initiator I in a dropping tank to obtain a mixture M, dropping the mixture M into the reaction kettle, adding the mixture N of the adamantane-sulfonate intercalated rectorite to the mixture M and continuing to drop, adding a neutralizing agent when the temperature is lower than the boiling point of the neutralizing agent, adding water and removing the organic solvent to obtain the aqueous solution of A of preparation A;

[0059] SS2: adding the aqueous solution of A of preparation A obtained in SS1 into a pre-emulsification kettle, adding the components of preparation B, i.e. methyl methacrylate, methacrylic acid and crosslinking agent, and mixing with water to obtain a pre-emulsion;

[0060] SS3: adding an anionic emulsifier and water into a reaction kettle and heating, synchronously dropping the pre-emulsion and an initiator solution into the reaction kettle and keeping the temperature, and filtering to obtain the seed emulsion with core-shell structure.

[0061] In the present application, the reaction temperature in SS1 is 100-145℃.

[0062] In the present application, the dropping time in SS1 is 3-6h.

[0063] In the present application, the mixture N containing the adamantane-sulfonate intercalated rectorite is started to be added when 50-80wt% of the total amount of the mixture M is dropped, and preferably started to be added when 60-70wt% of the total amount is dropped.

[0064] In the present application, the solid content of the aqueous solution of A in SS1 is 35-50wt%.

[0065] In the present application, the temperature of the water for priming in SS3 is 84-90℃.

[0066] In the present application, the reaction temperature in SS3 is 82-88℃.

[0067] In the present application, the dropping time in SS3 is 1.5-4h.

[0068] In the present application, the holding time of SS3 is 1-4h.

[0069] In the present application, the solid content of the seed emulsion of SS3 is 25-35%.

[0070] In the present application, the pH of the seed emulsion of SS3 is 2-3.

[0071] In the present application, the particle size of the seed emulsion of SS3 is 140-200nm.

[0072] Compared with the prior art, the present application has the following beneficial effects:

[0073] The covering polymer seed emulsion of the present application adopts a core-shell structure, the shell layer is modified by introducing adamantane-sulfonate intercalated rectorite, which gives the covering polymer seed emulsion a high-strength, high-hydrophobicity and low-surface-tension shell, can improve the structural stability of the covering polymer, reduce the collapse rate of the covering polymer, and the covering rate of the covering polymer can reach more than 60%. At the same time, the seed emulsion of the present application is a water-based acrylic copolymer emulsion, which does not contain any solvent, alkylphenol polyoxyethylene ether (APEO), formaldehyde and release, and is more green and environmentally friendly. BRIEF DESCRIPTION OF DRAWINGS

[0074] Figure 1 The transmission electron microscope morphology of the covering polymer hollow microspheres prepared from the seed emulsion in Example 1. DETAILED DESCRIPTION

[0075] The present application will be further described below through specific examples, and the examples of the present application are only used to illustrate the present application and do not limit the scope of the present application.

[0076] Unless otherwise specified, all raw materials and reagents used in the examples and comparative examples of the present application are obtained by commercial channels.

[0077] Test method:

[0078] I. Solid content of emulsion:

[0079] An aluminum foil paper is made into a weighing dish with a diameter of 5cm and a height of 3cm, and is weighed in a constant weight in a blast constant temperature oven, and is cooled to room temperature in a dryer, and the weight is recorded as m0, accurate to 0.1mg. The same accuracy is used to weigh the sample to be tested in the dish, recorded as m1, and ensure that the sample is evenly dispersed on the bottom surface of the weighing dish, and the dish with the weighed sample is placed in a blast oven preheated to 150℃, and dried for 20min. The sample is taken out and placed in a dryer to cool to room temperature, and the mass is m2, and the solid content X is calculated as follows:

[0080] X=(m2-m0) / m1×100

[0081] In the formula:

[0082] X - mass fraction of non-volatile matter in the sample, referred to as solid content (%),

[0083] m0 - the mass of the weighing dish, in g,

[0084] m1 - the mass of the sample taken, in g,

[0085] m2 - the mass of the sample and the weighing dish after heating, in g.

[0086] II. Emulsion pH:

[0087] The test method in GB / T 14513-93 is referred to.

[0088] III. Emulsion particle size:

[0089] A Malvern Nano S90 particle size instrument is used, with a test temperature of 25°C and an equilibrium time of 300s. The emulsion to be tested is diluted with deionized water at a ratio of 1:2000, 1mL of the diluted solution is added to a cuvette, and the cuvette containing the sample is placed in the sample slot. The instrument will make three measurements, and the particle size value with the smallest polydispersity index (PDI) in the three measurements is taken as the final test result.

[0090] IV. Rating of the morphology of the hollow microspheres of the covering polymer

[0091] The seed emulsion is used as the raw material to first prepare the covering polymer, and then the morphology of the hollow microspheres of the covering polymer is tested by a JEOL 2100plus transmission electron microscope (TEM). According to the collapse rate of the hollow microspheres as the standard for evaluating the morphology of the hollow microspheres, a collapse rate of ≤5% is rated as A, a collapse rate in the range of 5-10% is rated as B, and a collapse rate >10% is rated as C.

[0092] V. The proportion of secondary nucleation of the hollow microspheres of the covering polymer

[0093] The seed emulsion is used as the raw material to first prepare the covering polymer, and then the morphology of the hollow microspheres of the covering polymer is tested by a JEOL 2100plus transmission electron microscope (TEM). A field of view is selected, the total number of hollow microspheres in the field of view A is counted, and the number of secondary nucleation microspheres (solid microspheres, non-hollow microspheres) in the field of view B is counted. Then B / A is the proportion of secondary nucleation.

[0094] VI. Covering performance test

[0095] The hiding polymer prepared from seed emulsion was used as raw material to prepare the building coating varnish composition. The Shanghai Modern Environment AFA-II automatic film applicator and wet film preparation device were used to draw a 120 μm thick film on black and white paper, and after drying at room temperature, the hiding power of the paint film was determined by reflectance meter, and the contrast ratio or opacity (%) was used to represent.

[0096] Seven: main raw material information

[0097]

[0098]

[0099]

[0100] Example 1

[0101] 1) Take 1000g deionized water into reaction kettle I, slowly pour 50g of attapulgite under the condition of 350rpm stirring, and stir at room temperature for 4h, so that the attapulgite is fully dispersed and swelled in water.

[0102] 2) Take 25g 1,3,5,7-tetra(4-aminophenyl)adamantane into reaction kettle II, add 100g of acetone, stir to dissolve; then add 35g of 10wt% hydrochloric acid solution, stir at room temperature for 20min.

[0103] 3) Add the mixture of step 2) to reaction kettle I of step 1), stir at 40℃ for 5h.

[0104] 4) Add 25g of DOWFAX 2A1 dropwise into the reaction kettle, drop for 15min, and keep warm for 3h.

[0105] 5) Filter and wash with acetone and deionized water for 3 times until there is no chloride ion in the solution. Dry in an oven at 85℃ for 6h, crush with a crusher and pass through a 325 mesh sieve to obtain adamantane-sulfonate intercalated attapulgite.

[0106] Example 2

[0107] 1) Take 1000g deionized water into reaction kettle I, slowly pour 80g of attapulgite under the condition of 400rpm stirring, and stir at room temperature for 3h, so that the attapulgite is fully dispersed and swelled in water.

[0108] 2) Take 50g of 1-acetylamino adamantane into reaction kettle II, add 420g of acetone, stir to dissolve; then add 15g of 10wt% hydrochloric acid solution, stir at room temperature for 25min.

[0109] 3) Add the mixture of step 2) to reaction kettle I of step 1), stir at 45℃ for 3.5h.

[0110] 4) Add 35 g of diisooctyl maleate sodium sulfonate to the reactor, dropwise, over 25 min, and maintain for 5 h.

[0111] 5) Filter and wash with acetone and deionized water 5 times until there is no chloride ion in the solution. Dry in an oven at 85°C for 24 h, crush with a crusher and pass through a 200 mesh screen to obtain adamantane-sulfonate intercalated laponite.

[0112] Example 3

[0113] 1) Take 1000 g of deionized water and add to reactor I, slowly pour in 100 g of laponite under the condition of stirring at 200 rpm, and stir at room temperature for 3.5 h to allow the laponite to be fully dispersed and swollen in the water.

[0114] 2) Take 40 g of 1-adamantane amine and add to reactor II, add 280 g of acetone and stir to dissolve; then add 45 g of 10 wt% hydrochloric acid solution and stir at room temperature for 30 min.

[0115] 3) Add the mixture of step 2) to reactor I of step 1), and stir at 60°C for 6 h.

[0116] 4) Add 30 g of OT-75 to the reactor, dropwise, over 20 min, and maintain for 4.5 h.

[0117] 5) Filter and wash with acetone and deionized water 5 times until there is no chloride ion in the solution. Dry in an oven at 85°C for 12 h, crush with a crusher and pass through a 270 mesh screen to obtain adamantane-sulfonate intercalated laponite.

[0118] Example 4

[0119] In a reactor, add 600 g of ethanol and heat to 100°C, add 120 g of methyl methacrylate, 150 g of butyl acrylate, 100 g of methacrylic acid, 3 g of n-dodecanethiol, and 9 g of di-t-butyl peroxide to a dropping tank and mix well, then drop into the reactor, the dropping time is 4 h. When 60 wt% of the above mixture is dropped into the dropping tank, add a mixture of 20 g of adamantane-sulfonate intercalated laponite of Example 1 and 30 g of methyl methacrylate to the dropping tank, the dropping time is the same as that of the remaining mixture in the dropping tank. After the dropping is completed, add 1 g of di-t-butyl peroxide, and maintain for 2 h. Cool to 50°C, add 50 g of 26 wt% ammonia solution, then add 300 g of water, and then remove ethanol under reduced pressure of 20 KPaA, and then add water to the resin water solution to a solid content of 40 wt% to obtain resin A-1 water solution.

[0120] Example 5

[0121] In a reaction kettle, 550 g of acetone was added and warmed to 120°C, 180 g of methyl methacrylate, 120 g of butyl acrylate, 80 g of methacrylic acid, 2.5 g of α-methylstyrene dimer, 7 g of di-t-amyl peroxide were added to a dropping tank and mixed uniformly, and were dropped into the reaction kettle, the dropping time was 4.5 h. When 70 wt% of the above mixture was dropped into the dropping tank, 10 g of a mixture of the adamantane-sulfonate intercalated Loochores and 20 g of methyl methacrylate were dropped into the dropping tank, the dropping time was the same as that of the remaining mixture in the dropping tank. After the dropping was completed, 2 g of di-t-amyl peroxide was added, and was kept for 2.5 h. It was cooled to 55°C, 42 g of a 26 wt% ethanolamine solution was added, then 450 g of water was added, after the acetone was removed under a reduced pressure of 20 KPa A, water was added to the resin aqueous solution to a solid content of 42 wt% to obtain a resin A-2 aqueous solution.

[0122] [Example 6]

[0123] In a reaction kettle, 750 g of ethanol was added and warmed to 140°C, 244 g of methyl methacrylate, 100 g of butyl acrylate, 90 g of methacrylic acid, 3.2 g of 2- mercaptopropionic acid methyl ester, 10 g of benzoyl peroxide were added to a dropping tank and mixed uniformly, and were dropped into the reaction kettle, the dropping time was 5.5 h. When 65 wt% of the above mixture was dropped into the dropping tank, 15 g of a mixture of the adamantane-sulfonate intercalated Loochores and 35 g of butyl acrylate were dropped into the dropping tank, the dropping time was the same as that of the remaining mixture in the dropping tank. After the dropping was completed, 2 g of benzoyl peroxide was added, and was kept for 2 h. It was cooled to 45°C, 58 g of a 26 wt% N,N-dimethylethanolamine solution was added, then 400 g of water was added, after the ethanol was removed under a reduced pressure of 20 KPa A, water was added to the resin aqueous solution to a solid content of 38 wt% to obtain a resin A-3 aqueous solution.

[0124] [Example 7]

[0125] In a reaction kettle, 500 g of xylene was added and warmed to 142°C, 266 g of methyl methacrylate, 80 g of isooctyl acrylate, 120 g of acrylic acid, 1.2 g of n-dodecanethiol, 7 g of azobis isobutyronitrile were added to a dropping tank and mixed uniformly, and were dropped into the reaction kettle, the dropping time was 5 h. When 50 wt% of the above mixture was dropped into the dropping tank, 35 g of a mixture of the adamantane-sulfonate intercalated Loochores and 20 g of butyl acrylate were dropped into the dropping tank, the dropping time was the same as that of the remaining mixture in the dropping tank. After the dropping was completed, 1 g of azobis isobutyronitrile was added, and was kept for 1.5 h. It was cooled to 50°C, 62 g of a 26 wt% triethanolamine solution was added, then 300 g of water was added, after the xylene was removed under a reduced pressure of 20 KPa A, water was added to the resin aqueous solution to a solid content of 50 wt% to obtain a resin A-4 aqueous solution.

[0126] Example 8

[0127] In a reaction kettle, 680 g of acetone was added and heated to 132°C. 215 g of methyl methacrylate, 60 g of styrene, 64 g of acrylic acid, 2.6 g of a-methylstyrene dimer, 5 g of di-t-butyl peroxide were added to a dropping tank and mixed uniformly, and then added dropwise to the reaction kettle, with a dropwise addition time of 4 h. When 65 wt% of the above mixture was added dropwise into the dropping tank, a mixture of 40 g of adamantane-sulfonate intercalated Laponite and 15 g of methyl methacrylate was added dropwise into the dropping tank, with the same dropwise addition time as the remaining mixture in the dropping tank. After the dropwise addition was completed, 1 g of di-t-butyl peroxide was added, and the temperature was maintained for 2.5 h. The temperature was lowered to 50°C, 39 g of a 26 wt% triethylamine solution was added, followed by the addition of 400 g of water. After the acetone was removed under reduced pressure of 20 KPa A, water was added to the resin water solution to a solid content of 35 wt% to obtain resin A-5 water solution.

[0128] Example 9

[0129] In a reaction kettle, 600 g of xylene was added and heated to 138°C. 265 g of methyl methacrylate, 50 g of isooctyl acrylate, 111 g of methacrylic acid, 2.1 g of 2- mercaptopropionic acid methyl ester, 10 g of di-t-amyl peroxide were added to a dropping tank and mixed uniformly, and then added dropwise to the reaction kettle, with a dropwise addition time of 6 h. When 80 wt% of the above mixture was added dropwise into the dropping tank, a mixture of 30 g of adamantane-sulfonate intercalated Laponite and 18 g of methyl methacrylate was added dropwise into the dropping tank, with the same dropwise addition time as the remaining mixture in the dropping tank. After the dropwise addition was completed, 1 g of di-t-amyl peroxide was added, and the temperature was maintained for 1.5 h. The temperature was lowered to 55°C, 62 g of a 26 wt% AMP-95 solution was added, followed by the addition of 350 g of water. After the xylene was removed under reduced pressure of 20 KPa A, water was added to the resin water solution to a solid content of 42 wt% to obtain resin A-4 water solution.

[0130] Examples 10-15 are methods for preparing a core-shell structure seed emulsion based on the resin A water solution prepared in Examples 4-9

[0131] Example 10

[0132] 1) 250 g of 40% A-1 water solution obtained in Example 4 was added to a pre-emulsification kettle, followed by the addition of 120 g of methyl methacrylate, 78 g of methacrylic acid, and 2 g of allyl methacrylate, and stirred for 30 min to obtain a pre-emulsion.

[0133] 3) Preparation of a kettle bottom initiator: 0.6 g of ammonium persulfate and 5 g of water were added to a batching tank and stirred to dissolve, to prepare a kettle bottom initiator solution for standby;

[0134] 4) Preparation of dropping initiator: 0.4 g of ammonium persulfate and 20 g of water were added into a dosing tank to be dissolved by stirring, to prepare a dropping initiator solution for standby.

[0135] 5) Seed stage: 1.11 g of Clariant Emulsion EPA1963 (effective content 27 wt%) and 450 g of water were added into a reaction kettle to be stirred uniformly and heated to 85°C; 12 g of the pre-emulsion prepared in step 2) was added into the reaction kettle, and the kettle bottom initiator solution prepared in step 3) was quickly added within 1 min, and the temperature was maintained for 20 min.

[0136] 6) Dropping polymerization: the temperature in the reaction kettle was controlled at 85°C, and the remaining pre-emulsion and the dropping initiator solution prepared in step 4) were synchronously dropped into the reaction kettle, and the dropping time was 3 h in total.

[0137] 7) Post-elimination: after the dropping was completed, the temperature was maintained for 1.5 h; the temperature was controlled at 80-88°C during the maintenance stage. The temperature was lowered to below 45°C, and 325 mesh filtration was performed to obtain the seed emulsion with core-shell structure.

[0138]

Example 11

[0139] 1) 230 g of the 42% aqueous solution of A-2 obtained in Example 5 was added into a pre-emulsification kettle, and 115 g of methyl methacrylate, 75 g of methacrylic acid and 2.2 g of ethylene glycol dimethacrylate were sequentially added, and stirring was performed for 30 min to obtain a pre-emulsion.

[0140] 3) Preparation of kettle bottom initiator: 0.5 g of sodium persulfate and 5 g of water were added into a dosing tank to be dissolved by stirring, to prepare a kettle bottom initiator solution for standby;

[0141] 4) Preparation of dropping initiator: 1.0 g of sodium persulfate and 20 g of water were added into a dosing tank to be dissolved by stirring, to prepare a dropping initiator solution for standby.

[0142] 5) Seed stage: 1.02 g of Solvay RHODAPEX TR / 2030-S (effective content 30 wt%) and 480 g of water were added into a reaction kettle to be stirred uniformly and heated to 86°C; 15 g of the pre-emulsion prepared in step 2) was added into the reaction kettle, and the kettle bottom initiator solution prepared in step 3) was quickly added within 1 min, and the temperature was maintained for 20 min.

[0143] 6) Dropping polymerization: the temperature in the reaction kettle was controlled at 86°C, and the remaining pre-emulsion and the dropping initiator solution prepared in step 4) were synchronously dropped into the reaction kettle, and the dropping time was 1.5 h in total.

[0144] 7) Post-emulsion: After the end of the dropping, keep the temperature at 80-88°C for 1 h. Cool down to below 45°C, and filter through 325 mesh to obtain the seed emulsion with core-shell structure.

[0145] Example 12

[0146] 1) Add 180 g of 38% A-3 aqueous solution obtained in Example 6 into a pre-emulsification kettle, and then add 128 g of methyl methacrylate, 86 g of methacrylic acid and 1.5 g of trimethylolpropane trimethacrylate successively, and stir for 30 min to obtain a pre-emulsion.

[0147] 3) Prepare a kettle bottom initiator: add 0.8 g of potassium persulfate and 5 g of water into a batching tank, and stir to dissolve, to prepare a kettle bottom initiator solution for standby;

[0148] 4) Prepare a dropping initiator: add 0.3 g of potassium persulfate and 20 g of water into a batching tank, and stir to dissolve, to prepare a dropping initiator solution for standby.

[0149] 5) Seed stage: at room temperature and normal pressure, add 1.21 g of Clariant Emulsion EPA073 (effective content 27 wt%) and 472 g of water into a reaction kettle, and stir to mix, and then heat to 88°C; take 10 g of the pre-emulsion prepared in step 2) and add into the reaction kettle, and then quickly add the kettle bottom initiator solution prepared in step 3) within 1 min, and keep the temperature for 20 min.

[0150] 6) Dropping polymerization: control the temperature in the reaction kettle at 88°C, and synchronously drop the remaining pre-emulsion and the dropping initiator solution prepared in step 4) into the reaction kettle, and the dropping time is 2.5 h in total.

[0151] 7) Post-emulsion: after the end of the dropping, keep the temperature at 80-88°C for 3 h. Cool down to below 45°C, and filter through 325 mesh to obtain the seed emulsion with core-shell structure.

[0152] Example 13

[0153] 1) Add 150 g of 48% A-4 aqueous solution obtained in Example 7 into a pre-emulsification kettle, and then add 130 g of methyl methacrylate, 90 g of methacrylic acid and 0.5 g of divinylbenzene successively, and stir for 30 min to obtain a pre-emulsion.

[0154] 3) Prepare a kettle bottom initiator: add 0.3 g of ammonium persulfate and 5 g of water into a batching tank, and stir to dissolve, to prepare a kettle bottom initiator solution for standby;

[0155] 4) Prepare a dropping initiator: add 0.5 g of ammonium persulfate and 20 g of water into a batching tank, and stir to dissolve, to prepare a dropping initiator solution for standby.

[0156] 5) Seed stage: under normal temperature and pressure, 1.09 g Solvay ABEX 8018R (effective content 30 wt%) and 475 g water were added into the reactor, stirred and heated to 85.5 °C; 12.2 g of the pre-emulsion prepared in step 2) was added into the reactor, and the initiator solution prepared in step 3) was quickly added within 1 min, and kept for 20 min.

[0157] 6) Dropwise polymerization: the temperature in the reactor was controlled at 85.5 °C, and the remaining pre-emulsion and the dropwise initiator solution prepared in step 4) were synchronously added into the reactor, and the dropwise time was 3.5 h.

[0158] 7) Post-elimination: after the dropwise addition was completed, it was kept for 2 h; the temperature in the keeping stage was controlled at 80-88 °C. The temperature was lowered to below 45 °C, and 325 mesh filtration was performed to obtain the seed emulsion with core-shell structure.

[0159]

Example 14

[0160] 1) 200 g of the 35% aqueous solution of A-5 obtained in Example 8 was added into a pre-emulsification reactor, and 125 g of methyl methacrylate, 70 g of methacrylic acid and 1.2 g of dimethyl acrylate 1,3-butylene glycol were sequentially added, stirred for 30 min to obtain a pre-emulsion.

[0161] 3) Preparation of bottom initiator: 0.4 g of sodium persulfate and 5 g of water were added into a batching tank, stirred and dissolved to prepare a bottom initiator solution for standby;

[0162] 4) Preparation of dropwise initiator: 0.3 g of sodium persulfate and 20 g of water were added into a batching tank, stirred and dissolved to prepare a dropwise initiator solution for standby.

[0163] 5) Seed stage: under normal temperature and pressure, 1.15 g of Solvay RHODAPEX CM-30 (effective content 27 wt%) and 442 g of water were added into the reactor, stirred and heated to 86.5 °C; 10.5 g of the pre-emulsion prepared in step 2) was added into the reactor, and the bottom initiator solution prepared in step 3) was quickly added within 1 min, and kept for 20 min.

[0164] 6) Dropwise polymerization: the temperature in the reactor was controlled at 86.5 °C, and the remaining pre-emulsion and the dropwise initiator solution prepared in step 4) were synchronously added into the reactor, and the dropwise time was 3 h.

[0165] 7) Post-elimination: after the dropwise addition was completed, it was kept for 2.5 h; the temperature in the keeping stage was controlled at 80-88 °C. The temperature was lowered to below 45 °C, and 325 mesh filtration was performed to obtain the seed emulsion with core-shell structure.

[0166]

Example 15

[0167] 1) Add 168 g of a 42% aqueous solution of A-6 from Example 9 to a pre-emulsification kettle, and sequentially add 110 g of methyl methacrylate, 82 g of methacrylic acid, and 1.8 g of allyl methacrylate, and stir for 30 min to obtain a pre-emulsion.

[0168] 3) Prepare a kettle bottom initiator: add 0.5 g of potassium persulfate and 5 g of water to a batching tank, stir to dissolve, and prepare a kettle bottom initiator solution for use;

[0169] 4) Prepare a dropwise initiator: add 0.4 g of potassium persulfate and 20 g of water to a batching tank, stir to dissolve, and prepare a dropwise initiator solution for use.

[0170] 5) Seed stage: at room temperature and atmospheric pressure, add 1.05 g of Clariant Emulsion EPA073 (effective content 27 wt%) and 615 g of water to a reaction kettle, stir to uniform, and heat to 84°C; take 11.5 g of the pre-emulsion prepared in step 2) and add to the reaction kettle, and simultaneously add the kettle bottom initiator solution prepared in step 3) within 1 min, and maintain the temperature for 20 min.

[0171] 6) Dropwise polymerization: control the temperature in the reaction kettle to be 84°C, and simultaneously add the remaining pre-emulsion and the dropwise initiator solution prepared in step 4) to the reaction kettle, and the dropwise addition time is 4 h in total.

[0172] 7) Post-elimination: after the dropwise addition is completed, maintain the temperature for 1.5 h; the temperature during the maintenance stage is controlled to be 80-88°C. Cool to below 45°C, and filter through a 325 mesh screen to obtain the seed emulsion of core-shell structure.

[0173]

Comparative Example 1

[0174] The seed emulsion is prepared according to the same formula and process conditions as in Example 4 and Example 10, except that the adamantane-sulfonate intercalated rectorite in Example 4 is not used.

[0175] The seed emulsion prepared in each example and comparative example is respectively tested for solid content, emulsion particle size, emulsion pH, and storage stability; then the seed emulsion in each example and comparative example is respectively used to prepare a hiding polymer, in order to test the morphology of the hollow microspheres of the hiding polymer and the proportion of secondary nucleation, and to perform a collapse rate rating; and further to prepare an architectural paint varnish composition, in order to determine the hiding performance. All test results are shown in Table 2.

[0176] The preparation method of the hiding polymer is as follows:

[0177] Pre-emulsion ME1 was prepared by adding 65 g deionized water, 3.5 g Cognis Emulsion EPA073 (emulsifier), 220 g styrene, 4.5 g MAA (methyl methacrylate) into a pre-emulsion kettle under normal temperature and pressure, stirring at 350 rpm for 20 min. Pre-emulsion ME2 was prepared by adding 30 g deionized water, 0.035 g p-tert-butyl hydroquinone, 2 g Cognis Emulsion EPA073 and 57.5 g styrene into a pre-emulsion kettle under normal temperature and pressure, stirring at 350 rpm for 20 min.

[0178] The kettle was controlled at 85 °C, and then the fast-release initiator solution (0.7 g sodium persulfate and 8 g deionized water) was added into the kettle, followed by the fast addition of 84.5 g seed emulsion prepared in the application. The pre-emulsion ME1 and the initiator solution (0.7 g sodium persulfate and 35 g deionized water) were simultaneously added dropwise, the temperature was controlled at 90 ± 1 °C during the dropwise addition, and the kettle was kept at this temperature for 30 min.

[0179] The pre-emulsion ME2 was added into the kettle, and the kettle was kept at this temperature for 10 min. The kettle was controlled at 85 ± 1 °C, and the NaOH solution (4.5 g NaOH and 225 g deionized water) was added dropwise for 20 min, and the kettle was kept at this temperature for 10 min. The kettle was controlled at 84-85 °C, and the oxidant (0.7 g tert-butyl hydroperoxide and 10 g deionized water) and the reducing agent solution (0.35 g erythorbic acid and 10 g deionized water) were simultaneously added dropwise for 30 min, and the kettle was kept at this temperature for 1 h, and then filtered to obtain the hiding polymer solution.

[0180] The transmission electron microscope morphology of the hiding polymer prepared from the seed emulsion in Example 1 is shown in FIG. 1. Figure 1

[0181] The building paint varnish composition was prepared according to the formulation shown in Table 1 below.

[0182] Table 1 Formulation of building paint varnish composition

[0183]

[0184] Table 2 Performance test of seed emulsion, hiding polymer and varnish

[0185]

[0186] ​From the analysis of Table 2, it can be seen that, under the reasonable raw material dosage and stable preparation method, Examples 10-15 all achieve high hiding property, the morphology of the hollow microspheres is good, the collapse is little and the proportion of secondary nucleation is low. In Comparative Example 1, due to the positive influence of no vinyl ethyl carbonate and fluorinated alkyl methacrylate, the hiding rate decreases obviously, the collapse rate increases, and the hiding power decreases significantly. In addition, in the comparative example, the emulsion polymerization process is completely used, and the emulsifier is added in a large amount in order to ensure the stability of the emulsion. The excessive emulsifier in the seed emulsion leads to the significant increase of the secondary nucleation proportion of the hiding polymer, the decrease of the proportion of the effective hollow microspheres, and the decrease of the hiding rate.

[0187] The above only describes the preferred embodiments of the present application, and it should be noted that, for those skilled in the art, without departing from the method of the present application, a number of improvements and supplements can also be made, which should also be considered as the protection scope of the present application.

Claims

1. A seed emulsion containing a masking polymer, characterized in that, The seed emulsion comprises a shell A and a core B; The components of the outer shell A are as follows, in parts by weight: The components of kernel B are as follows, by weight: The preparation method of the adamantane-sulfonate intercalated attapulgite includes the following steps: S1: Add water to reactor I, stir, add raptorite, and continue stirring; S2: Add aminoadamantane to reactor II, add solvent, stir, add acid solution, and continue stirring; S3: Add the mixture obtained in S2 into reactor I of S1 for reaction; S4: Add sulfonate to reactor I and keep it warm; S5: Filter, wash, dry, pulverize, and sieve to obtain adamantane-sulfonate intercalated attapulgite.

2. The seed emulsion according to claim 1, characterized in that, The components of the outer shell A are as follows, by weight: The components of kernel B are as follows, by weight:

3. The seed emulsion according to claim 1, characterized in that, In the components used to prepare shell A, the alkyl methacrylate is a C1-C10 alkyl methacrylate; And / or, in the components used to prepare shell A, the vinyl monomer is selected from C1-C12 vinyl monomers; And / or, in the components used to prepare shell A, the chain transfer agent is a thiol molecular weight regulator or an odorless molecular weight regulator; And / or, in the components used to prepare shell A, the initiator I is a peroxide and / or azo initiator; And / or, in the components used to prepare shell A, the organic solvent is one or more of ethanol, acetone, ethylene glycol butyl ether, and xylene; And / or, in the components used to prepare shell A, the neutralizing agent is an alkaline compound.

4. The seed emulsion according to claim 3, characterized in that, In the components used to prepare shell A, the alkyl methacrylate is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, and isooctyl methacrylate. And / or, in the components used to prepare shell A, the vinyl monomer is selected from one or more of styrene, α-methylstyrene, and vinyl acetate; And / or, in the components used to prepare shell A, the chain transfer agent is one or more of n-dodecyl mercaptan, α-methylstyrene dimer, and methyl 3-mercaptopropionate; And / or, in the components used to prepare shell A, the initiator I is one or more of di-tert-butyl peroxide (DTBP), di-tert-pentyl peroxide (DTAP), benzoyl peroxide (BPO), and azobisisobutyronitrile (AIBN); And / or, in the components used to prepare shell A, the organic solvent is acetone; And / or, in the components for preparing shell A, the neutralizing agent is one or more of ammonia, ethanolamine, N,N-dimethylethanolamine, triethanolamine, triethylamine, AMP-95, sodium hydroxide, and potassium hydroxide.

5. The seed emulsion according to claim 4, characterized in that, In the components used to prepare shell A, the alkyl methacrylate is one or more of methyl methacrylate, butyl acrylate, and isooctyl acrylate; And / or, in the components used to prepare shell A, the vinyl monomer is styrene; And / or, in the components used to prepare shell A, the chain transfer agent is α-methylstyrene dimer; And / or, in the components used to prepare shell A, the initiator I is di-tert-butyl peroxide (DTBP); And / or, in the components used to prepare shell A, the neutralizing agent is one or more of ammonia, ethanolamine, and N,N-dimethylethanolamine.

6. The seed emulsion according to claim 5, characterized in that, In the components used to prepare shell A, the neutralizing agent is ammonia.

7. The seed emulsion according to claim 1, characterized in that, In the components used to prepare kernel B, the crosslinking agent is a crosslinking agent containing 2-3 C=C double bonds; And / or, in the components for preparing core B, the anionic emulsifier is selected from fatty alcohol polyoxyethylene ether sulfate; And / or, in the components used to prepare kernel B, the initiator II is a persulfide initiator.

8. The seed emulsion according to claim 7, characterized in that, In the components used to prepare core B, the crosslinking agent is one or more of ethylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, and 1,3-butanediol dimethacrylate. And / or, in the components for preparing core B, the anionic emulsifier is selected from fatty alcohol polyoxyethylene ether sulfates with an EO number of 1-20; And / or, in the components used to prepare kernel B, the initiator II is one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

9. The seed emulsion according to claim 8, characterized in that, In the components used to prepare core B, the crosslinking agent is ethylene glycol dimethacrylate and / or allyl methacrylate; And / or, in the components for preparing core B, the anionic emulsifier is selected from one or more of Solvay RHODAPEX TR / 2030-S, Clariant Emulsion EPA073, Solvay ABEX 8018R, Solvay RHODAPEX CM-30, Clariant Emulsion EPA1963, and Clariant Emulsion EPA073.

10. A method for preparing adamantane-sulfonate intercalated attapulgite, wherein the intercalated attapulgite prepared by the method is used in the seed emulsion according to any one of claims 1-9, characterized in that, The preparation method of the adamantane-sulfonate intercalated attapulgite includes the following steps: S1: Add water to reactor I, stir, add raptorite, and continue stirring; S2: Add aminoadamantane to reactor II, add solvent, stir, add acid solution, and continue stirring; S3: Add the mixture obtained in S2 into reactor I of S1 for reaction; S4: Add sulfonate to reactor I and keep it warm; S5: Filter, wash, dry, pulverize, and sieve to obtain adamantane-sulfonate intercalated attapulgite.

11. The preparation method according to claim 10, characterized in that, The raptosite mentioned in S1 is sodium-based raptosite; And / or, S1 contains 1000 parts water and 50-100 parts tartaric acid; And / or, the stirring time described in S1 is 3-6 hours.

12. The preparation method according to claim 10, characterized in that, The aminoadamantane described in S2 is one or more of 1,3,5,7-tetra(4-aminophenyl)adamantane, 1-acetamidoadamantane, and 1-adamantaneamine; And / or, 10-50 parts of the aminodamycin described in S2; And / or, 100-500 parts of the solvent described in S2; And / or, 10-50 parts of the acid solution described in S2; And / or, as described in S2, the stirring time is to continue for 15-30 minutes.

13. The preparation method according to claim 12, characterized in that, The solvent mentioned in S2 is acetone; The acid solution mentioned in S2 is a 10-15 wt% hydrochloric acid solution.

14. The preparation method according to claim 10, characterized in that, The reaction temperature described in S3 is 30-60℃, and the reaction time is 3-6h.

15. The preparation method according to claim 10, characterized in that, The sulfonate mentioned in S4 is a C10-C40 alkyl sulfonate; And / or, the sulfonate described in S4 is 10-50 parts; And / or, the heat preservation time described in S4 is 2-6 hours.

16. The preparation method according to claim 15, characterized in that, The sulfonate S4 is one or more of sodium dodecyl diphenyl ether disulfonate, sodium diisooctyl succinate, and sodium diisooctyl maleate sulfonate.

17. The preparation method according to claim 16, characterized in that, In S4, sodium dodecyl diphenyl ether disulfonate is DOWFAX 2A1 and sodium diisooctyl succinate is OT-75.

18. The preparation method according to claim 10, characterized in that, The washing described in S5 is performed using acetone and deionized water until no chloride ions are present in the solution; And / or, S5 passes through a 200-325 mesh sieve.

19. A method for preparing a masking polymer seed emulsion, wherein the seed emulsion is the seed emulsion according to any one of claims 1-9, characterized in that, The method includes the following steps: SS1: Add an organic solvent to a reaction vessel and heat it. Mix the raw materials for preparing A (meth)acrylate alkyl ester and / or vinyl monomer, (meth)acrylate, chain transfer agent, and initiator I in a dropping tank to obtain mixture M. Add the mixture M dropwise to the reaction vessel. Add the mixture N of adamantane-sulfonate intercalated attapulgite to mixture M and continue to add it dropwise. Cool the mixture to a temperature below the boiling point of the neutralizer and add the neutralizer. Add water and remove the organic solvent to obtain an aqueous solution of A. SS2: Add the aqueous solution of A obtained from SS1 to the pre-emulsification tank, add the components for preparing B, methyl methacrylate, methacrylic acid and crosslinking agent, and add water to mix and obtain a pre-emulsion; SS3: Add anionic emulsifier and water to the reactor and heat it. Add the pre-emulsion and initiator solution dropwise to the reactor simultaneously and keep it warm. Filter to obtain the seed emulsion with the core-shell structure.

20. The method for preparing seed emulsion according to claim 19, characterized in that, The reaction temperature described in SS1 is 100-145℃; And / or, the dripping time described in SS1 is 3-6 hours; And / or, when 50-80 wt% of the total amount of mixture M has been added dropwise to SS1, mixture N containing adamantane-sulfonate intercalated attapulgite is added. And / or, the aqueous solution of A described in SS1 contains 35-50 wt% solids.

21. The method for preparing seed emulsion according to claim 20, characterized in that, When 60-70 wt% of the total amount of mixture M has been added dropwise to SS1, mixture N containing adamantane-sulfonate intercalated attapulgite is added.

22. The method for preparing seed emulsion according to claim 19, characterized in that, The temperature of the water used for SS3 as a base is 84-90℃; And / or, the reaction temperature described in SS3 is 82-88°C; And / or, the dripping time described in SS3 is 1.5-4 hours; And / or, the heat preservation time described in SS3 is 1-4 hours.

23. The method for preparing seed emulsion according to claim 19, characterized in that, The solid content of the seed emulsion described in SS3 is 25-35%; And / or, the pH of the seed emulsion described in SS3 is 2-3; And / or, the seed emulsion of SS3 has a particle size of 140-200 nm.

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