A fluorine-modified swellable microsphere, a hollow microsphere and their applications

Abstract

The present invention provides a highly acidic and alkali-swellable microsphere, the surface of which is fluorine-modified to endow it with good surface properties. Taking it as the core, through emulsion polymerization, polymers can be uniformly coated on its surface. The fluorine-modified microsphere provided by the present invention is used as the core, and after coating, swelling and drying, a stable hollow-structured microsphere is obtained; this hollow microsphere can be widely used in fields such as coatings, papermaking, and personal care.

Description

Technical Field

[0001] The present invention provides a fluorine-modified swellable microsphere, a hollow microsphere and their applications. Background Art

[0002] Due to its special hollow structure, the hollow microsphere has a light scattering effect, can play a covering role in the composition, improve the whiteness of the coating, can partially replace titanium white pigment in the paint, and can improve the dispersion performance of titanium white powder, thereby improving the performance of the remaining titanium white. The public patent CN104004124 discloses a method: in a mixed dispersion medium of deionized water and small molecule organic alcohol, a high-acid core is prepared, and an aromatic vinyl monomer is used as the main monomer to carry out copolymerization on the surface of the core to form a coated shell layer polymer, and a volatile base is added to make the pH value of the polymerization system reach above 7 to obtain hollow polymer microparticles. However, this method uses alcohol solvents which are not environmentally friendly. The public patent CN103524653 provides a hollow microsphere emulsion prepared by a three-stage polymerization reaction, which provides a porous sponge-like structure as a buffer layer in the second stage, then coats a shell layer on the basis of the buffer layer, and finally obtains hollow microspheres with appropriate sizes through alkali swelling. For the above synthesis methods of obtaining hollow microspheres by swelling high-acid cores, there are two defects: one is that the high-acid system has strong hydrophilicity and is not easy to coat, and it is difficult for the shell layer to evenly cover the core, and the thin part of the shell layer is prone to breakage during the later neutralization and swelling; the other is that the swollen high-acid core will shrink during the drying process, and when the shell layer is unevenly distributed, collapse will occur. Summary of the Invention

[0003] The object of the present invention is to provide a highly acidic, alkali-swellable microsphere with surface fluorine modification. After the surface of the high-acid core is fluorine-modified, it is more conducive to the coating of the shell layer, and hollow microspheres with a uniform shell layer can be obtained, which can reduce the defect rate of the hollow microspheres and provide better whiteness and covering performance for the coating. After the surface of the microsphere is fluorine-modified, it can be widely used in the preparation of various hollow microspheres. Using the fluorine-modified microsphere provided by the present invention as the core, after coating, swelling and drying, the prepared hollow microspheres can be widely used in fields such as waterborne coatings, waterborne leather, papermaking, printing ink, and personal care.

[0004] A fluorine-modified swellable microsphere, characterized in that the emulsion of the microsphere is prepared by free radical emulsion polymerization from the following components in mass ratio:

[0005] a) at least one mono-vinyl unsaturated carboxylic acid 20 - 45 wt%;

[0006] b) at least one mono-vinyl monomer soluble in the aqueous phase (solubility in water at 20 °C is 1 - 10 g) 43 - 75 wt%;

[0007] c) at least one fluorine-containing (meth)acrylic monomer 3 - 10 wt%;

[0008] d) At least one anionic or nonionic emulsifier and 0.5 - 2 wt% of at least one fluorinated nonionic emulsifier.

[0009] In the fluorine - modified swellable microspheres, the a) monovinyl unsaturated carboxylic acid is selected from one or more of acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloyloxypropionic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, monomethyl itaconate; preferably acrylic acid and / or methacrylic acid.

[0010] In the fluorine - modified swellable microspheres, the b) monovinyl monomer is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2 - hydroxyethyl acrylate, 2 - hydroxyethyl methacrylate, 2 - hydroxypropyl acrylate, 2 - hydroxypropyl methacrylate, vinyl acetate, vinyl propionate.

[0011] In the fluorine - modified swellable microspheres, the c) fluorinated (meth)acrylic acid monomer is a compound of formula (Ⅰ):

[0012]

[0013] Wherein, R is H or CH3;

[0014] x, z are integers greater than 0, preferably x ≤ 10, z ≥ 3; y is an integer greater than or equal to 0, and 2 * x + 1 = y + z.

[0015] In the fluorine - modified swellable microspheres, the d) anionic emulsifier is sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecyl oleate, fatty alcohol polyoxyethylene sulfate, alkylphenol polyoxyethylene sulfate; the nonionic emulsifier is fatty alcohol polyoxyethylene ether, cetyl oleyl polyoxyethylene ether, alkylphenol polyoxyethylene ether, block copolymer of ethylene oxide and propylene oxide; the fluorinated nonionic emulsifier is the above nonionic emulsifier with a fluorocarbon chain replacing the non - polar group.

[0016] A kind of hollow microspheres, the emulsion of which is prepared by emulsion polymerization. Using the above - mentioned fluorine - modified swellable microspheres as the core layer, at 75 - 95 °C, under the condition of an initiator, the transition layer and the shell layer are successively added for coating; after adding a plasticizing monomer to plasticize the shell layer, an alkali solution is added to neutralize and swell, and finally the plasticizing monomer is initiated to obtain a hollow microsphere emulsion. Wherein the mass of the transition layer is 1 - 4 times that of the core layer, the mass of the shell layer is 8 - 18 times that of the core layer, and the mass of the plasticizing monomer is 1 / 5 - 1 / 3 of the mass of the shell layer.

[0017] The above - mentioned hollow microspheres of each layer are prepared by free - radical emulsion polymerization containing the following components in the following mass ratios:

[0018] e) Transition layer: containing 30 - 60 wt% of at least one water-soluble (solubility in water at 20 °C is 1 - 10 g) monovinyl monomer, 35 - 60 wt% of at least one water-insoluble (solubility in water at 20 °C is less than 0.1 g) monovinyl monomer, 3 - 10 wt% of at least one monovinyl unsaturated carboxylic acid; 0.1 - 1 part of at least one anionic emulsifier; and / or,

[0019] f) Shell layer: containing 92 - 99 wt% of at least one water-insoluble (solubility in water at 20 °C is less than 0.1 g) monovinyl monomer, 0.01 - 2 wt% of at least one crosslinkable polyvinyl monomer, 0.1 - 6 wt% of at least one monovinyl unsaturated carboxylic acid, 0.1 - 1.5 wt% of at least one anionic emulsifier; and / or,

[0020] g) Plasticizing monomer: containing 99 - 99.9 wt% of at least one water-insoluble (solubility in water at 20 °C is less than 0.1 g) monovinyl monomer, 0.1 - 1 wt% of at least one anionic emulsifier; and / or,

[0021] h) The mass concentration of the alkali solution used in the neutralization swelling process is less than 3 wt%.

[0022] In the said hollow microspheres, the monovinyl unsaturated carboxylic acid described in e) and f) is selected from one or more of acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloyloxypropionic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, preferably acrylic acid and / or methacrylic acid.

[0023] In the said hollow microspheres, the water-soluble (solubility in water at 20 °C is 1 - 10 g) monovinyl monomer described in e) is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinyl acetate, vinyl propionate.

[0024] In the said hollow microspheres, the water-insoluble (solubility in water at 20 °C is less than 0.1 g) monovinyl monomer described in e), f) and g) is selected from one or more of styrene, methylstyrene, dimethylstyrene, tert-butylstyrene, isopropyl methacrylate, n-propyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, vinyl hexanoate, 2-ethylhexyl acrylate.

[0025] Among the hollow microspheres described, f) the crosslinkable polyvinyl monomer is selected from one or more of allyl acrylate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, propylene glycol diacrylate, triethylene glycol dimethacrylate, 1,1,1-trimethylolpropane trimethacrylate, pentaerythritol triallyl ester, pentaerythritol trimethacrylate, divinylbenzene, diallyl terephthalate, and methylenebisacrylamide.

[0026] Among the hollow microspheres described, h) the base is selected from alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia water; primary amines, secondary amines, and tertiary amines such as ethylamine, propylamine, monoisopropylamine, ethanolamine, dimethylamine, diethylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, dimethylethanolamine, diisopropanolamine, ethylenediamine, and 2-diethylaminoethylamine.

[0027] In order to ensure that the plasticizing monomer does not polymerize during the swelling of the shell layer, a promoter or inhibitor needs to be added before swelling. The promoter can be one or more reducing agents, which promote the consumption of free radicals during the polymerization of the shell layer, thereby restricting the polymerization of the plasticizing monomer; one or more inhibitors can inhibit the polymerization reaction of the plasticizing monomer during swelling; the above two methods can be used in combination. It is preferred to add one or more inhibitors, and the dosage is 50-1000 ppm of the total monomer mass. For example: N,N-diethylhydroxylamine, N-nitrosodiphenylamine, 2,4-dinitrophenylhydrazine, p-phenylenediamine, phenothiazine, allo-ocimene, triethyl phosphite, 4-nitrosophenol, 2-nitrophenol, p-aminophenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), hydroquinone, p-methoxyhydroquinone, tert-butyl-p-hydroquinone, 2,5-di-tert-butylhydroquinone, 1,4-naphthalenediol, 4-tert-butylcatechol, copper sulfate, copper nitrate, cresol, and phenol. After swelling with alkali, the plasticizing monomer can be reacted by adding an initiator to obtain a hollow microsphere emulsion.

[0028] For the hollow microspheres of the present invention, the defect rate will be significantly reduced, and the covering performance will be significantly improved. In our test system, the covering rate is above 50%, preferably above 60%.

[0029] The average particle size of the fluorine-modified swellable microspheres is 80-350 nm, and the average particle size of the hollow microspheres is 200-5000 nm.

[0030] The use of the hollow microspheres in the fields of architectural coatings, textile coatings, paper, water-based inks, cosmetics, etc.

[0031] The polymerization is carried out by emulsion polymerization, and the polymerization temperature can be 40-100 °C, preferably 70-95 °C.

[0032] The polymerization initiator can be selected from thermal decomposition initiators or redox system initiators, and the dosage is 0.1-2% of the total monomer mass, preferably 0.3-1%.

[0033] The thermal decomposition initiator can directly decompose into free radicals with initiating activity when heated. This type of initiator includes persulfates, aryl azoamino compounds, aryl azo alkali metal salts, etc.

[0034] The redox initiator system is composed of two or more components. Through the redox reaction between these components, free radicals with initiating activity can be generated. The oxidant can be selected from persulfates, chlorates, peroxides, organic hydroperoxides, etc. The reductant can be selected from thiosulfates, bisulfites, sulfites, sulfinates, thiosulfates, dithionites and tetrathionates, and their adducts, such as sodium hydroxymethanesulfinate and acetone bisulfite, as well as ascorbic acid, isoascorbic acid and sodium isoascorbate.

[0035] The transition metal catalyst can also be used in combination with the initiator and / or the redox initiator system. Examples thereof are salts of iron, cobalt, nickel, copper, vanadium and manganese. The available salts include, for example, iron(II) sulfate; cobalt(II) chloride; nickel(II) sulfate; copper(I) chloride; or water-soluble chelated iron complexes, such as K[Fe(III)EDTA] or Na[Fe(III)-EDTA]. Detailed implementation mode

[0036] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited to the listed embodiments.

[0037] Measurement of particle size

[0038] The particle size mentioned in this article is measured using a Malvern nano-ZS90 high-performance particle size analyzer.

[0039] Measurement of hiding power

[0040] Hiding test composition formula

[0041]

[0042] Under stirring conditions, the materials were sequentially added to the system according to the above formula to obtain a composition for testing hiding power. A film of the above composition was calendared on a hiding power test black and white cardboard (BIUBGD BGD-1101) using a 100 μm doctor blade coater at a speed of 1 cm / s. The sample was dried for 24 hours at 25 °C and a relative humidity of 45 - 55%. Then, a C84-Ⅲ type reflectometer was used to measure the reflectance values at 10 different points in both the black area and the white area respectively. After excluding the maximum and minimum values from the reflectance values in the black area, the average value a was taken, and after excluding the maximum and minimum values from the reflectance values in the white area, the average value b was taken. The hiding power was calculated using the following formula:

[0043]

[0044] Example 1:

[0045] Swelling microsphere emulsion C1

[0046] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer, and two feed containers, an initial feed consisting of 820 g of water was heated to 85 °C in a nitrogen atmosphere. A monomer pre-emulsion (ME) was prepared by mixing 288 g of deionized water, 2.6 g of 993 (alkyl polyethylene glycol ether sulfate (30 wt%)), 8 g of methacrylic acid, and 390 g of methyl methacrylate. Thus, 66 g was left in the ME (labeled as ME1). 28.5 g of 993 (emulsifier) and 96 g of methacrylic acid were added to the remaining ME, 50 g was left, and the remainder was labeled as ME2. 20 g of water, 26 g of trifluoroethyl methacrylate, and 2 g of (fluorinated polyoxyethylene ether non-ionic surfactant (25 wt%)) were added to the remaining 50 g of ME and mixed to obtain a pre-emulsion labeled as ME3. ME1 and 55 g of a 10 wt% aqueous solution of sodium persulfate were added to the reaction kettle, held at 85 °C for 15 minutes, then ME2 and ME3 were sequentially added to the reaction kettle within 3 hours at 85 °C. After addition, it was held for 1 hour, cooled to room temperature, and filtered to obtain swelling microsphere emulsion C1

[0047] Solid content: 30.9%

[0048] PH: 3.3

[0049] Particle size: 132 nm

[0050] Hollow microsphere emulsion H1

[0051] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, 400 g of water was heated to a temperature of 85 °C under a nitrogen atmosphere. 50 g of a 4.5 wt% sodium persulfate solution and 98 g of emulsion C1 were added, and then a pre-emulsion ME1 prepared by mixing 60 g of deionized water, 3.8 g of RHODACAL DS-4AP (sodium dodecylbenzenesulfonate (22 - 23 wt%)), 36 g of methyl methacrylate, 10.8 g of n-butyl methacrylate, 61 g of styrene and 12 g of methacrylic acid was added within 1 hour. The temperature was maintained at 80 °C during the dropping process. After the dropping of ME1 was completed, the temperature was raised to 90 °C, and 120 g of a 0.3 wt% sodium persulfate solution and a pre-emulsion ME2 prepared by mixing 200 g of deionized water, 16 g of RHODACAL DS-4AP, 14.4 g of methacrylic acid, 17.2 g of n-butyl methacrylate, 5.88 g of 2-ethylhexyl acrylate, 4.8 g of allyl methacrylate and 198 g of styrene were added simultaneously within 2 hours. After continuing to stir for 20 minutes, a pre-emulsion ME3 prepared by mixing 30 g of deionized water, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), 0.22 g of RHODACAL DS-4AP and 48 g of styrene was added within 10 min. After stirring for 10 minutes, 64 g of a 10 wt% aqueous ammonia solution was added within 20 minutes and stirred for 10 minutes. Then 5 g of a 10 wt% aqueous solution of tert-butyl hydroperoxide was added, and 12.5 g of a 2 wt% aqueous solution of IAA was added dropwise within 40 min. It was kept warm for 30 minutes, cooled to room temperature, and filtered to obtain a hollow microsphere emulsion H1.

[0052] Solid content: 30.5%

[0053] PH: 8.7

[0054] Particle size: 430 nm

[0055] Hiding power: 70.45%

[0056] Comparative Example 1:

[0057] Swelling microsphere emulsion CV1

[0058] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, the initial feed consisting of 820 g of water was heated to 85 °C in a nitrogen atmosphere. A monomer pre-emulsion (ME) was prepared by mixing 308 g of deionized water, 2.6 g of It was prepared from 993 (alkyl polyethylene glycol ether sulfate (30% by weight)) and 8 g of methacrylic acid and 416 g of methyl methacrylate. Thus, 66 g remained in the ME (labeled as ME1). To the remaining ME was added 28.5 g of 993 and 96 g of methacrylic acid were mixed to obtain a pre-emulsion ME2. ME1 and 55 g of a 10% by weight aqueous sodium persulfate solution were added to the reaction kettle, kept at 85 °C for 15 minutes, then ME2 was added to the reaction kettle within 3 hours at 85 °C, and after addition, it was kept at the temperature for 1 hour, cooled to room temperature, and filtered to obtain a swellable microsphere emulsion CV1

[0059] Solid content: 30.8%

[0060] PH: 3.3

[0061] Particle size: 136 nm

[0062] Hollow microsphere emulsion HV1

[0063] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, under a nitrogen atmosphere, 400 g of water was heated to a temperature of 85 °C. 50 g of a 4.5% by weight sodium persulfate solution and 98 g of the emulsion CV1 were added, and then a pre-emulsion ME1 composed of 60 g of deionized water, 3.8 g of RHODACAL DS-4AP (sodium dodecylbenzenesulfonate (22 - 23% by weight)), 36 g of methyl methacrylate, 10.8 g of n-butyl methacrylate, 61 g of styrene and 12 g of methacrylic acid was added within 1 hour, and the temperature was maintained at 80 °C during the dropping process. After the dropping of ME1 was completed, the temperature was raised to 90 °C, and within 2 hours, 120 g of a 0.3% by weight sodium persulfate solution and a pre-emulsion ME2 composed of 200 g of deionized water, 16 g of RHODACAL DS-4AP, 14.4 g of methacrylic acid, 17.2 g of n-butyl methacrylate, 5.88 g of 2-ethylhexyl acrylate, 4.8 g of allyl methacrylate and 198 g of styrene were added simultaneously. After continuous stirring for 20 minutes, then a pre-emulsion ME3 composed of 30 g of deionized water, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), 0.22 g of RHODACAL DS-4AP and 48 g of styrene was added within 10 min, and after stirring for 10 minutes, 64 g of a 10% by weight aqueous ammonia solution was added within 20 minutes and stirred for 10 minutes. Then 5 g of a 10% by weight aqueous solution of tert-butyl hydroperoxide was added, and 12.5 g of a 2% by weight aqueous IAA solution was added dropwise within 40 min, kept at the temperature for 30 minutes, cooled to room temperature, and filtered to obtain a hollow microsphere emulsion HV1.

[0064] Solid content: 30.9%

[0065] pH: 8.6

[0066] Particle size: 428 nm

[0067] Coverage rate: 10.8%

[0068] Example 2:

[0069] Swelling microsphere emulsion C2

[0070] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, an initial feed consisting of 750 g of water was heated to 85 °C in a nitrogen atmosphere. A monomer pre-emulsion (ME) was prepared by mixing 310 g of deionized water, 1.6 g of 993 (alkyl polyethylene glycol ether sulfate (30 wt%)), 4 g of methacrylic acid, 10.6 g of ethyl acrylate and 230 g of methyl methacrylate. Thus, 66 g remained in the ME (labeled ME1). 27.5 g of 993 and 236 g of methacrylic acid were added to the remaining ME, 64 g remained, and the remainder was labeled ME2. 20 g of water, 53 g of hexafluorobutyl methacrylate (HFMA) and 3.1 g of (fluorinated polyoxyethylene ether nonionic surfactant (25 wt%)) were added to the remaining 64 g of ME and mixed to obtain a pre-emulsion labeled ME3. ME1 and 55 g of a 10 wt% aqueous sodium persulfate solution were added to the reaction kettle, kept at 85 °C for 15 minutes, then ME2 and ME3 were added to the reaction kettle successively within 3 hours at 85 °C, and after addition, kept at the temperature for 1 hour, cooled to room temperature, and filtered to obtain swelling microsphere emulsion C2

[0071] Solid content: 32.2%

[0072] pH: 3.4

[0073] Particle size: 182 nm

[0074] Hollow microsphere emulsion H2

[0075] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, 560 g of water was heated to a temperature of 85 °C under a nitrogen atmosphere. 50 g of a 4.5 wt% sodium persulfate solution and 102 g of emulsion C2 were added, followed by the addition of pre-emulsion ME1, which was prepared by mixing 30 g of deionized water, 1.9 g of RHODACAL DS-4AP (sodium dodecylbenzenesulfonate (22 - 23 wt%)), 36 g of methyl methacrylate, 22.5 g of styrene and 5.6 g of methacrylic acid, within 1 hour. The temperature was maintained at 80 °C during the dropping process. After the addition of ME1 was completed, the temperature was raised to 90 °C, and 220 g of a 0.3 wt% sodium persulfate solution and pre-emulsion ME2, which was prepared by mixing 320 g of deionized water, 13.6 g of RHODACAL DS-4AP, 4.08 g of methacrylic acid, 15.2 g of α-methylstyrene, 12.12 g of n-butyl methacrylate, 1.2 g of divinylbenzene (80 wt% effective content) and 280.4 g of styrene, were added simultaneously within 2 hours. After stirring for another 20 minutes, pre-emulsion ME3, which was prepared by mixing 50 g of deionized water, 0.1 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), 2.4 g of RHODACAL DS-4AP and 78 g of styrene, was added within 10 min. After stirring for 10 minutes, 50 g of a 10 wt% aqueous ammonia solution was added within 20 minutes and stirred for 10 minutes. Then 8 g of a 10 wt% aqueous solution of tert-butyl hydroperoxide was added, and 20 g of a 2 wt% aqueous solution of IAA was added dropwise within 40 min. The mixture was kept warm for 30 minutes, cooled to room temperature, and filtered to obtain hollow microsphere emulsion H2.

[0076] Solid content: 26.6%

[0077] PH: 8.9

[0078] Particle size: 642 nm

[0079] Hiding power: 68.5%

[0080] Comparative Example 2:

[0081] Swelling microsphere emulsion CV2

[0082] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, the initial feed consisting of 750 g of water was heated to 85 °C in a nitrogen atmosphere. A monomer pre-emulsion (ME) was prepared by mixing 330 g of deionized water, 1.6 g of It was prepared from 993 (alkyl polyethylene glycol ether sulfate (30% by weight)) and 4 g of methacrylic acid, 10.6 g of ethyl acrylate, and 283 g of methyl methacrylate. Thus, 66 g (labeled as ME1) remained in the ME. To the remaining ME was added 27.5 g of 993 and 236 g of methacrylic acid were mixed to form a pre-emulsion ME2. ME1 and 55 g of a 10% by weight aqueous sodium persulfate solution were added to the reaction kettle, and it was kept warm at 85 °C for 15 minutes. Then, ME2 was added to the reaction kettle within 3 hours at 85 °C. After addition, it was kept warm for 1 hour, cooled to room temperature, and filtered to obtain a swellable microsphere emulsion CV2

[0083] Solid content: 32.3%

[0084] PH: 3.4

[0085] Particle size: 185 nm

[0086] Hollow microsphere emulsion HV2

[0087] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer, and two feed containers, under a nitrogen atmosphere, 560 g of water was heated to a temperature of 85 °C. 50 g of a 4.5% by weight sodium persulfate solution and 102 g of the emulsion CV2 were added. Subsequently, within 1 hour, a pre-emulsion ME1 composed of 30 g of deionized water, 1.9 g of RHODACAL DS-4AP (sodium dodecylbenzenesulfonate (22 - 23% by weight)), 36 g of MMA, 22.5 g of styrene, and 8.74 g of methacrylic acid was added dropwise. The temperature was maintained at 80 °C during the dropping process. After the dropping of ME1 was completed, the temperature was raised to 90 °C, and within 2 hours, 220 g of a 0.3% by weight sodium persulfate solution and a pre-emulsion ME2 composed of 320 g of deionized water, 13.6 g of RHODACAL DS-4AP, 4.08 g of methacrylic acid, 15.2 g of α-methylstyrene, 12.12 g of n-butyl methacrylate, 1.2 g of divinylbenzene (80% effective content), and 280.4 g of styrene were added simultaneously. After continuous stirring for 20 minutes, then within 10 min, a pre-emulsion ME3 composed of 50 g of deionized water, 0.1 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), 2.4 g of RHODACAL DS-4AP, and 78 g of styrene was added. After stirring for 10 minutes, 50 g of a 10% by weight aqueous ammonia solution was added within 20 minutes and stirred for 10 minutes. Then, 8 g of a 10% by weight aqueous tert-butyl hydroperoxide solution was added, and 20 g of a 2% by weight aqueous IAA solution was added dropwise within 40 min. It was kept warm for 30 minutes, cooled to room temperature, and filtered to obtain a hollow microsphere emulsion HV2.

[0088] Solid content: 26.7%

[0089] PH: 8.8

[0090] Particle size: 630 nm

[0091] Coverage rate: 21.5%

[0092] Example 3:

[0093] Swelling microsphere emulsion C3

[0094] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, an initial feed consisting of 450 g of water was heated to 85 °C in a nitrogen atmosphere. A monomer pre-emulsion (ME) was prepared by mixing 310 g of deionized water, 0.8 g of 993 (alkyl polyethylene glycol ether sulfate (30 wt%)), 6 g of methacrylic acid, 24 g of ethyl acrylate and 298 g of methyl methacrylate. Thus, 36 g remained in the ME (labeled ME1). 28.5 g of 993 and 188 g of methacrylic acid were added to the remaining ME, 64 g remained, and the remainder was labeled ME2. 20 g of water, 16 g of hexafluorobutyl methacrylate (HFMA) and 3.1 g of (fluorinated polyoxyethylene ether nonionic surfactant (25 wt%)) were added to the remaining 64 g of ME and mixed to obtain a pre-emulsion labeled ME3. ME1 and 55 g of a 10 wt% aqueous sodium persulfate solution were added to the reaction kettle, kept at 85 °C for 15 minutes, then ME2 and ME3 were added to the reaction kettle successively within 3 hours at 85 °C, and after addition, kept at the temperature for 1 hour, cooled to room temperature, and filtered to obtain swelling microsphere emulsion C3

[0095] Solid content: 39.1%

[0096] PH: 3.1

[0097] Particle size: 320 nm

[0098] Hollow microsphere emulsion H3

[0099] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer, and two feed vessels, 1400 g of water was heated to a temperature of 85 °C under a nitrogen atmosphere. 50 g of a 4.5 wt% sodium persulfate solution and 80.6 g of emulsion C3 were added. Subsequently, a pre-emulsion ME1 prepared by mixing 15 g of deionized water, 0.95 g of RHODACAL DS-4AP (sodium dodecylbenzenesulfonate (22 - 23 wt%)), 19 g of methyl methacrylate, 1.1 g of n-butyl methacrylate, 10.6 g of styrene, and 0.95 g of methacrylic acid was added within 1 hour, and the temperature was maintained at 80 °C during the dropping process. After the addition of ME1 was completed, the temperature was raised to 90 °C, and 400 g of a 0.3 wt% sodium persulfate solution and a pre-emulsion ME2 prepared by mixing 580 g of deionized water, 7.8 g of RHODACAL DS-4AP, 5.7 g of methacrylic acid, 27 g of α-methylstyrene, 21 g of n-butyl methacrylate, 0.075 g of divinylbenzene (80 wt% effective content), and 516 g of styrene were added simultaneously within 2 hours. After continuous stirring for 20 minutes, a pre-emulsion ME3 prepared by mixing 120 g of deionized water, 0.5 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), 8.4 g of RHODACAL DS-4AP, 180 g of styrene, and 9.6 g of α-methylstyrene was added within 10 min. After stirring for 10 minutes, 36 g of a 10 wt% aqueous ammonia solution was added within 20 minutes and stirred for 10 minutes. Then 18 g of a 10 wt% aqueous solution of tert-butyl hydroperoxide was added, and 45 g of a 2 wt% aqueous solution of IAA was added dropwise within 40 min. The mixture was kept warm for 30 minutes, cooled to room temperature, and filtered to obtain a hollow microsphere emulsion H3.

[0100] Solid content: 23.4%

[0101] PH: 8.4

[0102] Particle size: 1060 nm

[0103] Coverage rate: 69.5%

[0104] Comparative Example 3:

[0105] Swelling microsphere emulsion CV3

[0106] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer, and two feed vessels, an initial feed consisting of 450 g of water was heated to 85 °C in a nitrogen atmosphere. A monomer pre-emulsion (ME) was prepared by mixing 330 g of deionized water, 0.8 g of It was prepared from 993 (alkyl polyethylene glycol ether sulfate (30% by weight)) and 6 g of methacrylic acid, 24 g of ethyl acrylate and 314 g of methyl methacrylate. Thus, 36 g remained in the ME (labeled as ME1). 28.5 g of 993 and 188 g of methacrylic acid were mixed to form a pre-emulsion ME2. ME1 and 55 g of a 10% by weight aqueous sodium persulfate solution were added to the reaction kettle, kept warm at 85 °C for 15 minutes, ME2 was added to the reaction kettle within 3 hours at 85 °C, and after addition, it was kept warm for 1 hour, cooled to room temperature, and filtered to obtain a swellable microsphere emulsion CV3

[0107] Solid content: 39.2%

[0108] PH: 3.1

[0109] Particle size: 323 nm

[0110] Hollow microsphere emulsion HV3

[0111] In a polymerization vessel equipped with a paddle stirrer, a reflux condenser, a thermometer and two feed containers, under a nitrogen atmosphere, 1400 g of water was heated to a temperature of 85 °C. 50 g of a 4.5% by weight sodium persulfate solution and 80.6 g of the emulsion CV3 were added, and then within 1 hour, a pre-emulsion ME1 composed of 15 g of deionized water, 0.95 g of RHODACAL DS-4AP (sodium dodecylbenzenesulfonate (22 - 23% by weight)), 19 g of methyl methacrylate, 1.1 g of n-butyl methacrylate, 10.6 g of styrene and 0.95 g of methacrylic acid was added dropwise, and the temperature was maintained at 80 °C during the dropping process. After the dropping of ME1 was completed, the temperature was raised to 90 °C, and within 2 hours, 400 g of a 0.3% by weight sodium persulfate solution and a pre-emulsion ME2 composed of 580 g of deionized water, 7.8 g of RHODACAL DS-4AP, 5.7 g of methacrylic acid, 27 g of α-methylstyrene, 21 g of n-butyl methacrylate, 0.075 g of divinylbenzene (80% by weight effective content) and 516 g of styrene were added simultaneously. After continuing to stir for 20 minutes, then within 10 min, a pre-emulsion ME3 composed of 120 g of deionized water, 0.5 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), 8.4 g of RHODACAL DS-4AP and 180 g of styrene and 9.6 g of α-methylstyrene was added, stirred for 10 minutes, and then 36 g of a 10% by weight aqueous ammonia solution was added within 20 minutes and stirred for 10 minutes. Then 18 g of a 10% by weight aqueous solution of tert-butyl hydroperoxide was added, and 45 g of a 2% by weight aqueous IAA solution was added dropwise within 40 min, kept warm for 30 minutes, cooled to room temperature, and filtered to obtain the hollow microsphere emulsion HV3.

[0112] Solid content: 23.5%

[0113] pH: 8.6

[0114] Particle size: 10 - 20 nm

[0115] Coverage rate: 12.5%

Claims

1. A fluorine-modified swellable microsphere, characterized in that, The emulsion of the microspheres is prepared by free radical emulsion polymerization of components with the following mass ratios: a) At least one mono-vinyl unsaturated carboxylic acid: 20 - 45 wt%; b) At least one mono-vinyl monomer soluble in the aqueous phase: 43 - 75 wt%, and the solubility of the mono-vinyl monomer soluble in the aqueous phase in water at 20°C is 1 - 10 g; c) At least one fluorinated (meth)acrylic acid monomer: 3 - 10 wt%; d) At least one anionic or non-ionic emulsifier and at least one fluorinated non-ionic emulsifier: 0.5 - 2 wt%; The fluorinated (meth)acrylic acid monomer in c) is a compound represented by formula (Ⅰ): Wherein, R is H or CH3; x, z are integers greater than 0; y is an integer greater than or equal to 0, and 2*x + 1 = y + z.

2. The fluorine-modified swellable microspheres according to claim 1, characterized in that, The average particle size of the fluorine-modified swellable microspheres is 80 - 350 nm.

3. The fluorine-modified swellable microspheres according to claim 1, characterized in that, The mono-vinyl unsaturated carboxylic acid in a) is selected from one or more of acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloyloxypropionic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate.

4. The fluorine-modified swellable microspheres according to claim 3, characterized in that, The mono-vinyl unsaturated carboxylic acid in a) is selected from acrylic acid and / or methacrylic acid.

5. The fluorine-modified swellable microspheres according to claim 1 or 2, characterized in that, The mono-vinyl monomer in b) is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, acrylonitrile, methacrylonitrile, hydroxypropyl methacrylate, and vinyl propionate.

6. The fluorine-modified swellable microspheres according to claim 1, characterized in that, In the compound represented by formula (Ⅰ), x ≤ 10 and z ≥ 3.

7. The fluorine-modified swellable microspheres according to claim 1 or 2, characterized in that, The anionic emulsifier in d) is sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecyl oleate, sodium fatty alcohol polyoxyethylene ether sulfate, or sodium alkylphenol polyoxyethylene ether sulfate; the non-ionic emulsifier is fatty alcohol polyoxyethylene ether, hexadecyl oleyl polyoxyethylene ether, alkylphenol polyoxyethylene ether, or block copolymer of ethylene oxide and propylene oxide; the fluorinated non-ionic emulsifier is obtained by replacing the non-polar group of the above non-ionic emulsifier with a fluorocarbon chain.

8. A hollow microsphere, characterized in that, The emulsion of the microspheres is prepared by taking the fluorine-modified swellable microspheres described in any one of claims 1 - 7 as the core layer, successively coating a transition layer and a shell layer, followed by plasticization, neutralization swelling, and initiating the plasticizing monomer, wherein the mass of the transition layer is 1 - 4 times the mass of the core layer, the mass of the shell layer is 8 - 18 times the mass of the core layer, and the mass of the plasticizing monomer is 1 / 5 - 1 / 3 of the mass of the shell layer; The hollow microspheres are prepared by free radical emulsion polymerization of components with the following mass ratios in each layer: e) Transition layer: containing 30 - 60 wt% of at least one mono-vinyl monomer soluble in the aqueous phase, 35 - 60 wt% of at least one mono-vinyl monomer less soluble in the aqueous phase, and 3 - 10 wt% of at least one mono-vinyl unsaturated carboxylic acid; 0.1 - 1 wt% of at least one anionic emulsifier; f) Shell layer: containing 92 - 99 wt% of at least one mono-vinyl monomer less soluble in the aqueous phase, 0.01 - 2 wt% of at least one crosslinkable multi-vinyl monomer, 0.1 - 6 wt% of at least one mono-vinyl unsaturated carboxylic acid, and 0.1 - 1.5 wt% of at least one anionic emulsifier; g) Plasticizing monomer: containing 99 - 99.9 wt% of at least one mono-vinyl monomer that is poorly soluble in water, and 0.1 - 1 wt% of at least one anionic emulsifier; h) The mass concentration of the alkali solution used in the neutralization and swelling process is less than 3 wt%; Among them, the solubility of the water-soluble mono-vinyl monomer in water at 20 °C is 1 - 10 g; the solubility of the poorly water-soluble mono-vinyl monomer in water at 20 °C is less than 0.1 g.

9. The hollow microspheres according to claim 8, wherein, The average particle size of the hollow microspheres is 200 - 5000 nm.

10. The hollow microspheres according to claim 8, wherein, The mono-vinyl unsaturated carboxylic acid described in e) and f) is selected from one or more of acrylic acid, methacrylic acid, acryloyloxypropionic acid, methacryloyloxypropionic acid, itaconic acid, aconitic acid, maleic acid, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, monomethyl itaconate.

11. The hollow microsphere according to claim 10, characterized in that, The mono-vinyl unsaturated carboxylic acid described in e) and f) is selected from acrylic acid and / or methacrylic acid.

12. The hollow microsphere according to claim 8, wherein, The water-soluble mono-vinyl monomer described in e) is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, acrylonitrile, methacrylonitrile, hydroxypropyl methacrylate, vinyl propionate.

13. The hollow microspheres according to claim 8, characterized in that, The poorly water-soluble mono-vinyl monomer described in e), f), and g) is selected from one or more of styrene, methylstyrene, dimethylstyrene, tert-butylstyrene, isopropyl methacrylate, n-propyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, vinyl hexanoate, 2-ethylhexyl acrylate.

14. The hollow microsphere according to claim 8, wherein, The crosslinkable multi-vinyl monomer described in f) is selected from one or more of allyl acrylate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, propylene glycol diacrylate, triethylene glycol dimethacrylate, 1,1,1-trimethylolpropane trimethacrylate, pentaerythritol triallyl ester, pentaerythritol trimethacrylate, divinylbenzene, diallyl terephthalate, methylene bisacrylamide.

15. The hollow microspheres according to claim 8, wherein, The alkali described in h) is selected from one or more of alkali metal hydroxides, ammonia water, primary amines, secondary amines, and tertiary amines.

16. The hollow microsphere according to claim 15, characterized in that, The alkali described in h) is selected from one or more of sodium hydroxide, potassium hydroxide, ethylamine, propylamine, monoisopropylamine, ethanolamine, dimethylamine, diethylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, dimethylethanolamine, diisopropanolamine, ethylenediamine, 2-diethylaminoethylamine.

17. Use of the hollow microspheres according to any one of claims 8 - 16 in the fields of architectural coatings, textile coatings, paper, water-based inks, and cosmetics.

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