CN101327945A 纳米氧化铜

CN101327945A 纳米氧化铜 Cupric oxide nanoparticle having superior water dispersibility and preparation thereof 氧化铜纳米粒子 CN 101327945 A 摘要 The invention discloses copper oxide nano-particles with well water dispersibility comprising: coating hydrophilic polymer materials with a thickness of 1-10 nm outside the surface of copper oxide nano-particles, wherein the hydrophilic polymer materials are selected from one of low polyacrylic acid, low potassium polyacrylate, low calcium polyacrylate, low zinc polyacrylate, low polyethyleneglycol or low polyvinyl acetate, the diameter of the copper oxide nano-particles is 60-140 nm. The copper oxide nano-particles with well water dispersibility of the invention are prepared by forming a hydrophilic oligomer single film on the surface of the copper oxide particles through a simple free radical polymerization method. The water dispersive solution of copper oxide nano-particles with well dispersiblity is directly prepared without further purify. 权利要求(2) 翻译自中文 1, having a good water dispersibility of the copper oxide nanoparticles, characterized in that: said water-dispersible with good copper oxide nanoparticles in the surface of copper oxide nanoparticles coated with a thickness of 1 ~ 10nm hydrophilic polymeric object material; said hydrophilic polymeric material is oligomeric acrylic acid, low sodium polyacrylate, polypropylene, low potassium, low calcium polypropylene, polypropylene, low zinc, oligo ethylene glycol or oligomers of vinyl acetate; wherein CuO nanoparticles have a diameter of 60 ~ 140nm. 2, A process as claimed in claim 1 having a good water dispersibility of the copper oxide nanoparticles, characterized in that it comprises the following steps: Step 1: Configure solution of cupric ions, said cupric ions solution concentration of 1 ~ 3mo 〃 Z; said divalent copper ion solution may be copper nitrate, copper sulfate, copper chloride; Second step: the first step of preparation of divalent copper ion solution was placed in a heatable ultrasonic cleaning vessel, heated to 50 ~ 100. C after the addition of solid alkali, ultrasonic treatment 50 ~ 150min black precipitate obtained after suspension; usage: said divalent copper ions and the solid alkali hydroxide in a ratio of number of atoms 1:1.5 ~ 2.5; said solid alkali is sodium hydroxide, potassium hydroxide; third step: the step of a black precipitate obtained in the suspension into the centrifuge, the centrifuge speed of 3000 ~ 8000Wmin centrifuged Processing 10 ~ 40min, remove and discard the first supernatant to obtain a first product; Fourth step: the third step the product obtained in the first deionized water and placed in the ultrasonic cleaning device, After ultrasonic treatment for 5 ~ 10min removed, drained second supernatant to obtain a second product; consumption: 100w / deionized water was added to 20 ~ 40m / a second product; Fifth step: the fourth step to obtain The second product was added to deionized water, and placed in the ultrasonic cleaning, ultrasonic treatment for 5 ~ 10min, remove and discard the supernatant III, to obtain a third product; dosage: 100 is attached / deionized water to 20 ~ 40m / third product; Sixth step: the fifth step to obtain a third product was placed in a vacuum oven at a 0.1 atm, the drying temperature is 20 ~ 40. C for 10 ~ 30min removed after drying, to obtain the fourth product; Seventh step: In the sixth step the product obtained by adding a fourth mass percent concentration of 30% 11202 stirring, then add mass percent concentration of 98% H2S04 stir 2 ~ 5min to get the fifth product; Dosage: 500mg every fourth product by adding 10 to 20 attached / a ^ 02, 30 ~ 60m ^ 9H2SO4; eighth step: get the seventh step of the fifth product is heated to 80 ~ 120. C, holding 10 ~ 30min, remove; adding deionized water, placed in the ultrasonic cleaning, ultrasonic treatment for 5 ~ 10min, remove and discard the supernatant VI to obtain the sixth product; dosage: 100m / deionized Water was added to 20 ~ 40 w / a fifth product; Ninth step: the eighth step the product obtained in the sixth mixing speed 100 ~ 300Wmin, temperature 80 ~ 12 (TC stirred in a thermostatic bath after 10 ~ 30min; added mass percentage concentration of 1% of 1 <: 23208, stir the reaction loop after 5 ~ 10min; adding a hydrophilic oligomer monomer 100 ~ 350min stirring reaction product obtained after the seventh; dosage: 100m / sixth product was added 5 ~ 10w ^ gK2S2O8 (used as an initiator), 0.5 ~ 2mo / hydrophilic oligomer monomer; said hydrophilic oligomer monomers are acrylic acid, sodium acrylate, potassium acrylate, acrylic mother, zinc acrylate, ethylene alcohol or vinyl acetate. 说明 翻译自中文 Having a good water-dispersible copper oxide nanoparticles and its preparation method TECHNICAL FIELD The present invention relates to a transition metal oxide nano-materials preparation technology, in particular to a good dispersion in water having a copper oxide Nanoparticles Methods. BACKGROUND ART Nanomaterials are defined particle size 1 ~ 100 "m ultrafine particles of nano-materials, the special structure, it has a conventional material does not have the excellent properties, such as fine grain nanoparticle quantum size effect, small size effect, surface effect and macroscopic quantum tunneling effect in many areas showing potential applications, among which copper oxide as an important transition metal oxides, in catalysis as the main catalyst component with a variety of catalytic activity was widely used in ceramics, printing and dyeing, pharmaceutical, defense and other fields, but because copper oxide nanoparticles high activity and large surface area, so when it is formed in the base liquid multiphase system is highly decentralized, exists between the particles and the medium giant screen. while copper oxide nanoparticles have high surface energy, causing thermodynamic instability of the dispersion, nano-copper oxide particles attract each other to form agglomeration and precipitation, so mention Gao CuO nanoparticles in the base liquid dispersion stability, which is the nano-materials in the application process must be addressed now, the commonly used dispersion technology can be broadly divided into two categories, namely physical dispersion and chemical dispersion of chemical dispersion including dispersion and chemical modification dispersant may be used. chemically modified by a chemical reaction given dispersed nanoparticles certain organic film, an organic base to improve nanoparticle ^ stroma dispersion. object of the present invention is to provide a precipitation method in diameter of 60 ~ 140 "m copper oxide surface of the particles coated with a layer 1 ~ 10" m thick hydrophilic polymer material, the copper oxide particles have good water dispersion of the present invention has good water-dispersible copper oxide nanoparticles, copper oxide nanoparticles in the surface-coated with a thickness of 1 ~ 10mn hydrophilic polymer material; said hydrophilic polymeric material is oligomeric acrylic acid, low sodium polyacrylate, potassium polyacrylate low, oligomeric acrylic acid calcium, low zinc polypropylene, oligo ethylene glycol or oligomers of vinyl acetate; the CuO nanoparticles have a diameter of 60 ~ 140 "m. Preparation of the present invention having good water-dispersible copper oxide nanoparticles, which comprises the following steps: Step 1: Configure solution of cupric ions, said divalent copper ion concentration of the solution of l ~ 3mo 〃 ?; said divalent copper ion solution may be copper nitrate, copper sulfate, copper chloride; Second step: the first step in the preparation of a divalent copper ion solution was placed in a heatable ultrasonic cleaning vessel and heated to 50 to 10 ( TC, the addition of solid alkali, ultrasonic treatment 50 ~ 150min black precipitate obtained after suspension; usage: said divalent copper ion concentration of copper ions and the solid alkali hydroxide in the ratio of number of atoms 1:1.5 ~ 2.5; said solid alkali is sodium hydroxide, potassium hydroxide; third step: the step of a black precipitate obtained in the suspension into the centrifuge, the centrifuge speed of 3000 ~ 8000Wmin under 10 ~ 40min, after centrifugation, remove and discard the first supernatant to obtain a first product; Fourth step: the third step the product obtained in the first deionized water and placed in ultrasonic cleaning, the ultrasonic treatment for 5 ~ 10min, remove and discard the second supernatant to obtain a second product; dosage: 100 w / deionized water was added to 20 ~ 40 m / second product; Fifth Step: the fourth step of the second product obtained by adding deionized water, and placed in the ultrasonic cleaning, ultrasonic treatment 5 ~ 10min, remove and discard the supernatant III, to obtain a third product; dosage: 100m / of deionized water was added to 20 ~ 40w / third product; Sixth step: the fifth step to obtain a third product was placed in a vacuum oven at a 0.1 atm, a drying temperature of 20 ~ 4 (TC Conditions drying out after 10 ~ 30min, to obtain the fourth product; Seventh step: In the sixth step the product obtained by adding a fourth mass percent concentration of 30% ^ 02 stirring, then add mass percent concentration of 98% ^ 304 stir 2 ~ 5min to get the fifth product; Dosage: Every 500wg fourth product by adding 10 to 20 >> 7 / a 11202, 30 ~ 60w /'s H2S04; eighth step: get the seventh step of the fifth product is heated to 80 ~ 120. C, holding 10 ~ 30min, remove; adding deionized water, placed in the ultrasonic cleaning, ultrasonic treatment for 5 ~ 10min, remove and discard the supernatant VI to obtain the sixth product; dosage: 100 attached / deionized water to 20 to 40 with / of the fifth product; Ninth step: the eighth step the product obtained in the sixth mixing speed 100 ~ 300Wmin, temperature 80 ~ 120. C in a constant temperature bath for 10 ~ after 30min; adding mass percentage concentration of 1 ? / ^ ^ | K2S208, stirring reaction after 5 ~ 10min; adding hydrophilic oligomer monomer, stirring reaction 100 ~ 350min product obtained after the seventh; consumption: 100w / sixth product was added 5 ~ 10m ^ 9K2S2O8 (used as an initiator), 0.5 ~ 2wo / hydrophilic oligomer monomer; said hydrophilic monomers are acrylic acid oligomers, sodium acrylate, potassium acrylate, calcium acrylate, acrylic acid zinc acetate, ethylene glycol or ethylene precipitation method of the present invention has good water dispersibility of the copper oxide nanoparticles advantages: (1) by a simple radical polymerization method to form a copper oxide particle surface hydrophilic oligomer monolayers prepared directly with good dispersion of copper oxide nanoparticles aqueous dispersion, and the dispersion does not require further purification (2) of the modified method for most of the dispersibility in water containing a certain pro- water-group-containing monomer, the polymerization method is simple, and can be extended to other modified nanoparticles (3) CuO nanoparticles by the aqueous dispersion and rheological properties of the test storage stability, pH, stability, and freeze-thaw stability evaluation, the invention has been confirmed that the copper oxide nanoparticles prepared with good water dispersibility and stability. (4) rheological properties tests found CuO nanoparticles even when the temperature of the aqueous dispersion of heat to 300 ? C, as long as the water is not completely evaporated, the viscosity does not occur mutation CuO nanoparticles almost no agglomeration (see Figure 2). (5) of copper oxide particles in the aqueous dispersion of the pH stability test , found in the pH range of 1 to 13, the dispersion stability of the copper oxide nanoparticles do not agglomerate. (6) of the dispersion stability of the freeze-thaw test of three or four times (i.e. freezing or thawing three times 4 agglomeration does not occur). (7) The copper oxide nanoparticles aqueous dispersion (the product obtained in the seventh) has a good storage stability, storage for 20 days, before and after storage Zetasizer CuO nanoparticles, stored before and after the copper oxide nanoparticles almost no change in particle size distribution of the accompanying drawings Figure 1 is obtained by the present invention has good water dispersibility of the oxide of copper TEM images of nanoparticles. Figure 2 is obtained by the present invention, the oxidation Copper nanoparticles rheological properties of the aqueous dispersion curve 3A is obtained by the present invention, copper oxide particles in an aqueous dispersion of nano-particle size distribution. 3B are obtained by the present invention, the copper oxide nanoparticles aqueous dispersion at 25 ? C, 1 atm for 20 days in a closed particle size distribution diagram embodiment in conjunction with the accompanying drawings and the following embodiments of the present invention is described in further detail the present invention having a good water-dispersible copper oxide nanoparticles, copper oxide nanoparticles in the surface-coated with 1 ~ 10 "m thick hydrophilic polymer material; said copper oxide nanoparticle diameter of 60 ~ 140" w. said hydrophilic polymer material is refers to the oligomeric acrylic acid, low sodium polyacrylate, potassium polyacrylate low, low calcium polypropylene, polypropylene, low zinc, oligo ethylene glycol or oligomers of vinyl acetate. said hydrophilic polymer material is an initiator (K2S208) adding a hydrophilic oligomer monomer (acrylic acid, sodium acrylate, potassium acrylate, acrylic turn, zinc acrylate, vinyl alcohol, ethylene glycol, or vinyl acetate) obtained by the reaction in the present invention, the hydrophilic polymer material of the " oligomer "refers to the degree of polymerization of the polymer is less than iooo the present invention is prepared by the precipitation method has a good water dispersibility of the copper oxide nanoparticles steps: Step 1: Configure solution of cupric ions, said cupric ions solution concentration of 1 ~ 3wo 〃 Shang; said divalent copper ion solution may be copper nitrate, copper sulfate, copper chloride; Second step: the first step of preparation of divalent copper ion solution was placed in a heatable ultrasonic washing vessel and heated to 50 ~ 10 (TC, the addition of solid alkali, ultrasonic treatment 50 ~ 150min black precipitate obtained after suspension; usage: said divalent copper ion concentration of copper ions in the solid alkali number of atoms of the hydroxyl ratio of 1:1.5 ~ 2.5; said solid alkali is sodium hydroxide, potassium hydroxide; as cupric ions with a strong base at room temperature (20 ~ 3 (TC), often pressure (1 atm) can easily generate Cu (OH) 2, but in the present invention, preclude the use of ultrasound during the heating method cupric ions react with a strong base of CuO, CuO, the aqueous solution containing black precipitate suspensions of the present invention obtained in this step, the copper oxide nanoparticles. third step: the step of a black precipitate obtained in the suspension into the centrifuge, the centrifuge speed centrifugal treatment under 3000 ~ 8000Wmin 10 ~ 40min, remove and discard the first supernatant to obtain a first product; Fourth step: the third step the product obtained in the first deionized water and placed in the ultrasonic cleaning, ultrasonic Processing removed after 5 ~ 10min, the supernatant was drained second, to obtain a second product; dosage: 100m / deionized water was added to 20 ~ 40m / a second product; Fifth step: the fourth step the obtained The second product was added to deionized water, and placed in the ultrasonic cleaning, ultrasonic treatment 5 ~ 10min, remove and discard the supernatant III, to obtain a third product; dosage: 100m / deionized water was added to 20 ~ 40 with / third product; in the present invention, the fourth step and the fifth step is the washing treatment is to remove the sodium ions (Na +), potassium ion (K +) or trace amounts of cupric hydroxide (Cu (0H) 2 ) The sixth step: in the fifth step to obtain a third product was placed in a vacuum oven, a Ol atm drying temperature is 20 ~ 4 (TC dried for 10 ~ 30min after the removal, the fourth product obtained ; this step, vacuum dried product in favor of removing the third doped deionized water. Seventh step: In the sixth step the product obtained by adding a fourth mass percent concentration of 30% 11202 stirring, then add mass percentage H2S04 concentration of 98% was stirred for 2 ~ 5min in fifth product; Dosage: Every fourth 500wg added to the product with 10 to 20 / a 11202, 30 ~ 60w / of H2SO4; eighth step: the seventh step the obtained Fifth product was heated to 80 ~ 12 (TC, insulation 10 ~ 30min, remove; adding deionized water, placed in the ultrasonic cleaning, ultrasonic treatment, remove the 5 ~ 10min, the supernatant drained sixth, sixth obtained product; dosage: 100 of deionized water was added to 20 ~ 40 m / a fifth product; Ninth step: the eighth step the product obtained in the sixth mixing speed 100 ~ 300Wmin, temperature 80 ~ 12 (TC thermostatic bath After stirring for 10 ~ 30min; adding mass percentage concentration of 1 ? / ^ ^ K2S208, stirring after 5 ~ 10min loop response; adding hydrophilic oligomer monomer, stirring reaction 100 ~ 350min product obtained after the seventh; seventh product that is of the present invention has good water-dispersible copper oxide nano-li child. Dosage: 100m / adding a sixth product 5 ~ 10m ^ 9K2S2O8 (used as an initiator), 0.5 ~ 2mo / hydrophilic oligomer monomer ; said hydrophilic monomers are acrylic acid oligomers, sodium acrylate, potassium acrylate, calcium acrylate, zinc acrylate, vinyl acetate or ethylene glycol. to preclude the use of the product obtained by the method seventh the pH stability test, In 10w / added to the product of the seventh 15w / mass percent concentration of 35% hydrochloric acid, the product found in the seventh CuO nanoparticles sedimentation does not occur, indicating that the product having an acid VII stability obtained by the above method for the Seventh products the pH stability test, the 10m / added to the product of the seventh 15m / mass percent concentration of 80 /. sodium hydroxide solution, the product found in the seventh CuO nanoparticles sedimentation does not occur, indicating that Seventh product having an alkali stability for the product through the seventh acid, alkali stability testing, the product was found to contain the seventh test solution in the pH range of 1 to 13, the test solution can exist stably, The test solution in the copper oxide nanoparticle agglomeration does not occur. 8 copper oxide nanoparticle coated 5 "m thick acrylic oligomer prepared by the precipitation method has a good water dispersibility of the copper oxide nanoparticles steps of: Step 1: Configure solution of copper nitrate, copper nitrate solution of the concentration of lwo 〃 Shang; Second step: the first step in the preparation of copper nitrate solution was placed in a heatable ultrasonic cleaning vessel, heated to 6CTC, adding sodium hydroxide, obtained after sonication 70min black precipitate suspension; Dosage: The copper nitrate concentration of copper ions and sodium hydroxide in the root of the number of atoms in the ratio of 1:2; third step : The second step of a black precipitate obtained in the suspension into the centrifuge, the centrifuge speed of 5000Wmin centrifuged for 20min, remove and discard the first supernatant to obtain a first product; IV step: the third step the product obtained in the first deionized water and placed in the ultrasonic cleaning, ultrasonic treatment removed after 5min, drained second supernatant to obtain a second product; dosage: 100 is attached / deionized water was added to 25m / a second product; Fifth step: the fourth step of the second product obtained by adding deionized water, and placed in the ultrasonic cleaning, ultrasonic treatment removed after 5min, drained of three supernatant to obtain a third product; dosage: 100m / deionized water was added to 25m / third product; Sixth step: the fifth step to obtain a third product was placed in a vacuum oven, a Ol atm, a drying temperature of 25 "under the conditions of drying out after 15min, to obtain the fourth product; Seventh step: In the sixth step the product obtained by adding a fourth mass percent concentration of 30% 11202 stirring, then add mass percentage concentration of 98% obtained after 5min stirring 12304} fifth product; dosage: 500mg per adding the fourth product 10 is attached / a 11202, 30m ^ "H2SO4; Eighth step: the seventh step the obtained product is heated fifth to 9 (TC, heat removed after 25min; adding deionized water, and placed in the ultrasonic cleaning, ultrasonic treatment removed after 5min, the supernatant drained sixth, sixth product obtained; dosage: 100m / deionized water Join 25w / fifth product; Step 9: The eighth step to get the sixth product in stirring speed lOOWmin, constant temperature water bath temperature 8CTC After stirring for 15min; adding mass percentage concentration of 1 ? / "^ K2S208, stirring reaction After 5min; adding acrylic acid, stirring the reaction product VII obtained after 200min; the rheological properties of the products were tested seventh found CuO nanoparticles even when the temperature of the aqueous dispersion is heated to 30 (TC, as long as the water is not completely evaporated, the viscosity not mutated, CuO nanoparticles agglomeration hardly occurs, as shown in Figure 2, dosage: 100 with / added to the product of the sixth 5m / a K2S20s, lmo / acrylic. the product obtained above is set to the seventh in a vacuum oven, a Ol atm, the drying temperature is under 25 ? 0 15min removed after drying, having good water dispersibility of the copper oxide nanoparticles. to have good water dispersibility of the copper oxide nanoparticles TEM observation, the average copper oxide nanoparticle size range of 80, left, shown in Figure 1 the same as used in Example 1 Preparation of the hydrophilic monomer is selected sodium acrylate oligomer. preclude the use and implementation of Example 1 Preparation of the hydrophilic monomer is selected potassium acrylate oligomer. the same as used in Example 1 Preparation of the hydrophilic monomer is selected acrylate oligomer calcium same as used in Example 1 Preparation of the pro- Water zinc acrylate oligomer monomer selected Example 2: In the oxide coated copper particles 8 "w thick preclude the use of an oligomeric glycol precipitation method has good water dispersibility of the copper oxide nanoparticles steps : Step 1: Configure solution of copper chloride, copper chloride solution, the concentration of 1.5mo 〃 Shang; Second step: the first step of preparation of the copper chloride solution was placed in a heatable ultrasonic cleaning, the heating to 75 ? C after adding potassium hydroxide, obtained after ultrasonic treatment 100min black precipitate suspension; usage: said copper chloride, copper ions and said potassium hydroxide in a ratio of number of atoms 1:1.5; Third step: The second step in the black precipitate obtained suspension was placed in a centrifuge, the centrifuge speed centrifugation treatment 25miti 6000Wmin, remove and discard the first supernatant system The first product was obtained; Fourth step: the third step the product obtained in the first deionized water and placed in the ultrasonic cleaning, ultrasonic treatment after the removal 7min, drained second supernatant to obtain a first two products; consumption: 100w / deionized water was added with 30 / a second product; Fifth step: the fourth step of the second product obtained by adding deionized water, and placed in the ultrasonic cleaning, ultrasonic treatment 7min, remove and discard the supernatant III, to obtain a third product; consumption: 100w / deionized water was added to 30m / third product;, system low-oxide copper particles coated sodium polyacrylate material, made of copper oxide particles coated low potassium polyacrylate material, copper oxide particles coated system oligomeric acrylic f beggar materials, manufacturing copper oxide particles coated zinc low polypropylene material, the sixth step: the fifth step to obtain a third product was placed in a vacuum oven, a Ol atm, the drying temperature is 3 (TC removed after drying under 30min, to obtain the fourth product; Seventh step: In the sixth step the obtained The fourth product is added to a concentration of 30% weight percentage of 11202 stirring, then add mass percent concentration of 98c /. of H ^ 04 fifth product obtained after stirring for 2min; dosage: every 500 ?^ adding the fourth product 20 is attached / a 11202, 60 / w ^ 々 H2SO4; Eighth step: the seventh step the obtained product is heated to a fifth 100 ? C, for 15min after the removal; adding deionized water and placed in the ultrasonic cleaning, ultrasonic treatment 7min , remove and discard the supernatant sixth, sixth product; dosage: 100m / deionized water was added to 30m / a fifth product; Ninth step: the eighth step the product obtained in the sixth mixing speed 150Wmin, temperature IO (TC thermostatic bath after 20min stirring; adding mass percent concentration of 1 ? / ^ ^ K2S208, After stirring the reaction 8min; ethylene glycol, seventh stirring the reaction product obtained after 250min; dosage: 100 is attached / sixth 6 is added with the product / the! ^ 8208, 1.5mo / glycol Example 3: In the oxide coated copper particles lO "m thick preclude the use of an oligomeric vinyl acetate precipitation method has good water dispersibility copper oxide nanoparticles steps: Step 1: Configure solution of copper chloride, copper chloride solution, the concentration of 3mo 〃 i:; Second step: the first step of preparation of the copper chloride solution was placed to heated ultrasonic cleaner, heated to 80 ? C after adding sodium hydroxide, obtained after ultrasonic treatment 120min black precipitate suspension; usage: said copper chloride, copper ions in the sodium hydroxide root of the ratio of the number of atoms 1:2.5; Third step: The second step in the black precipitate obtained suspension was placed in a centrifuge, the centrifuge speed 8000Wmin centrifuged for 10min, remove and pour First off the supernatant to obtain a first product; Fourth step: the third step the product obtained in the first deionized water and placed in the ultrasonic cleaning, ultrasonic treatment removed after 10min, drained of two supernatant to obtain a second product; consumption: 100w / deionized water was added to 40m / a second product; Fifth step: the fourth step of the second product obtained by adding deionized water, and placed ultrasonic cleaner, the ultrasonic treatment removed after 10min, the supernatant was drained third, to obtain a third product; dosage: 100m / deionized water was added to 40w / third product; Sixth Step: Step system The third product was placed in a vacuum oven, a Ol atm, the drying temperature is 35 "C lOmin removed after drying under conditions to give the fourth product; Seventh step: In the sixth step the product obtained in the fourth Add mass% concentration of 30% 11202 stirring, then add mass percent concentration of 98% in fifth product stir 112804; dosage: 500mg per product by adding a fourth with 13 / a 11202, 40 / ?W ^ H2SO4 ; Eighth step: the seventh step the obtained product is heated to a fifth 120 ? C, for 20min after the removal; adding deionized water, and placed in the ultrasonic cleaning, ultrasonic treatment 7min remove, discard the supernatant VI liquid, to obtain the sixth product; dosage: 100w / deionized water was added to 35w / a fifth product; Ninth step: the eighth step the product obtained in the sixth mixing speed 300Wmin, temperature 12 (TC stirred in a constant temperature bath after 15min; adding mass percent concentration of 1% 1 ^ 8208, after 10min stirring the reaction; adding vinyl acetate, stirring the reaction product VII obtained after 300min; consumption: 100w / added to the product of the sixth 10m ^ 9K2S2O8, 2mo / a vinyl acetate. the product obtained above in the seventh 25 ? C, 1 atm measured using a laser particle size analyzer particle size distribution curve shown in Figure 3A. the product obtained above in the seventh 25 ? C, 1 sealed under atmospheric pressure for 20 days, as measured using a laser particle size analyzer particle size distribution curve shown in Figure 3B. Fig 3A, 3B for comparison and found seventh product has good storage stability.