WO2011091766A1 - Method for preparing modified micronized particles - Google Patents

Method for preparing modified micronized particles Download PDF

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Publication number
WO2011091766A1
WO2011091766A1 PCT/CN2011/070751 CN2011070751W WO2011091766A1 WO 2011091766 A1 WO2011091766 A1 WO 2011091766A1 CN 2011070751 W CN2011070751 W CN 2011070751W WO 2011091766 A1 WO2011091766 A1 WO 2011091766A1
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Prior art keywords
oxide
barium
hydroxide
phosphate
lead
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PCT/CN2011/070751
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French (fr)
Chinese (zh)
Inventor
张颖
刘刚
Original Assignee
Zhang Ying
Liu Gang
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Priority claimed from CN201010103394A external-priority patent/CN101792167A/en
Priority claimed from CN201010183854XA external-priority patent/CN101862273B/en
Application filed by Zhang Ying, Liu Gang filed Critical Zhang Ying
Priority to US13/575,963 priority Critical patent/US20130015398A1/en
Publication of WO2011091766A1 publication Critical patent/WO2011091766A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties

Definitions

  • the invention relates to the technical field of chemical industry, in particular to a preparation method of modified micronized particles.
  • the water-insoluble micronized particles tend to have a strong interaction between each other during the chemical reaction of nucleation and growth, so that the micronized particles can only have a particle size of several micrometers or even several micrometers in subsequent use.
  • the size distribution in the filled substrate has extremely poor monodispersity (secondary particle size), and there is a significant difference in application performance compared with micronized particle particles distributed in submicron or even nanometer order.
  • micro-particles of various materials are not well treated, or the modification is not good, it is not only difficult to uniformly disperse into the matrix material, but also tends to reduce the overall performance of the matrix material. Under microscopic observation, at this time, there is a gap region between the micronized particles and the matrix material, which shows an obvious two-phase separation phenomenon. This kind of example is hard to come by.
  • the surface modification effect of the particles is much more important than the particle size.
  • the modified micronized particles can be well dispersed into the parent material, water. But we know that when it comes to the final application, the properties of the parent material and water to which it is added often vary greatly, for example, plastics, fibers, and so on. In order to adapt to the changing parent material, only the modification is carried out at this time.
  • the enrichment of the above-mentioned micronized particles is extremely difficult in the conventional preparation process. Since the surface of the micronized particles is modified to a high degree of hydrophilicity by a small molecule dispersing agent, and the particles are small, it is difficult to be filtered, and it is difficult to separate the micronized particles from the reaction mother liquid, and there is a problem that the micronized particles are lost during the separation process.
  • the present invention provides a method for preparing modified micronized particles, which comprises the steps of: coprecipitation reaction between a freezing point and a boiling point of an aqueous solution in an aqueous solution to form a micronized particle or a micronized particle precursor Mixed precipitation of bulk and inorganic precipitates.
  • the mixed precipitate of the precipitated and inorganic precipitate of the micronized or micronized particle precursor is 0.1%-50%, most preferably 0.5%-10% in the mother liquor after the reaction; and the micronized or micronized
  • the mass ratio of the precipitation of the particle precursor to the inorganic precipitation is from 1000:1 to 1:100,000, and less preferably from 100:1 to 1:1000, most preferably from 10:1 to 1:100.
  • the coprecipitation reaction is carried out under conventional agitation or under high speed agitation/mixing/shearing/friction conditions, further under supergravity conditions.
  • the pH of the reaction solution is controlled at 3 to 14, most preferably 7-14.
  • the micronized or micronized particle precursor is an inorganic or organic substance that is poorly soluble in water and does not chemically react with water, and a mixture therebetween.
  • the inorganic substance is selected from the elemental substance, and further selected are zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin, lead, copper, bismuth, antimony, silver, antimony, palladium, Platinum, gold, carbon, silicon, tungsten, boron, antimony, selenium, sulfur or iodine, and mixtures thereof.
  • the inorganic substance is selected from the group consisting of hydroxides, and further selected are barium hydroxide, palladium hydroxide (II, IV), barium hydroxide, platinum hydroxide, Barium hydroxide, barium hydroxide, cadmium hydroxide, barium hydroxide (III, IV), barium hydroxide, gallium hydroxide, barium hydroxide, aluminum hydroxide, magnesium hydroxide, manganese hydroxide, lead hydroxide (II , IV), barium hydroxide (III , IV), iron hydroxide, ferrous hydroxide, cuprous hydroxide, copper hydroxide, indium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, Barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide,
  • the inorganic substance is selected from the group consisting of oxides, and further selected are cerium oxide, palladium oxide (II, IV), cerium oxide, platinum oxide, cerium oxide. , cerium oxide, cadmium oxide, cerium oxide (III, IV), cerium oxide, gallium oxide, cerium oxide, aluminum oxide, magnesium oxide, manganese oxide, lead oxide (II, IV), cerium oxide (III) , IV), iron oxide, ferrous oxide, cuprous oxide, copper oxide, indium oxide, antimony oxide, antimony oxide, zinc oxide, nickel oxide, tin oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, uranium oxide, titanium oxide, zirconium oxide, vanadium oxide (II) , III, IV), cerium oxide, cerium oxide, chromium oxide, cobalt oxide, molybdenum oxide (III, IV
  • the inorganic substance is selected from the group consisting of inorganic salts, and further selected are barium arsenate, barium carbonate, barium chromate, barium ferrocyanide, barium fluorosilicate, barium fluoride, barium hydrogen phosphate, barium iodate, sulfuric acid.
  • the inorganic substance is selected from the group consisting of organic metal salts, and further selected are lanthanum, cerium, calcium, lithium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, magnesium, lanthanum, cerium, ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, gallium, iron, cadmium, indium, antimony, An optional alkyl or aryl sulfate, sulfonic acid, phosphate or carboxylate of cobalt, nickel, molybdenum, tin, lead, copper, ruthenium, osmium, mercury, silver, ruthenium, palladium, platinum or gold ions.
  • the organic substance has at least one of the following elements:
  • the decomposition temperature is higher than its melting point
  • any liquid or liquid composition other than water is further selected to dissolve at least 1 g of an organic solvent or an organic solvent combination per 100 g of water at 25 °C.
  • the present invention further comprises: adding a purifying agent to the mixed precipitate, converting the inorganic precipitate or a portion thereof to a water-soluble substance, and washing and concentrating the remaining precipitate.
  • the purifying agent is a water-soluble inorganic or organic acid, and may be selected from one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, acetic acid or phosphoric acid, or a mixture thereof.
  • the present invention further comprises: adding a purifying agent to the mixed precipitate, converting the inorganic precipitate or its after-swept body into a water-soluble substance, and washing and concentrating the remaining precipitate.
  • the invention further comprises: mixing/reacting the purified mixed precipitate with the surface modifier to obtain modified micronized particles.
  • the surface modifier refers to a compound capable of forming adsorption with the surface of the microparticles, including an anionic compound, a cationic compound, a nonionic surfactant, a water-insoluble organic liquid, a coupling agent, or a parent material to which it is added, and Their composition.
  • the average particle diameter d50 of the secondary particle diameter of the modified micronized particles is less than 10 ⁇ m, further preferably less than 1000 nm, more preferably less than 100 nm, and most preferably less than 10 nm.
  • the present invention further comprises: in the presence of an inorganic precipitate in an aqueous solution and between the freezing point and the boiling point of the reaction mother liquid, which can be converted into a water-soluble substance, and subjected to a precipitation reaction of the micronized particles or the micronized particle precursor.
  • the inorganic precipitate which can be converted into a water-soluble substance has a solubility of less than 1 gram per 100 grams of water at the reaction temperature, and is further selected to be less than 0.01 gram; and the cationic portion of the inorganic precipitate is selected from the group consisting of ruthenium, osmium, calcium, and lithium.
  • the anion portion of the inorganic precipitate is cyanide ion, halide ion, sulfuric acid (hydrogen) ion, nitrite ion, carbonic acid (hydrogen) ion, sulfuric acid (hydrogen) ion, Dichromate ion, phosphoric acid (hydrogen)
  • the surface active material is added before, during and/or after the precipitation reaction, and such addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater.
  • a method for preparing modified micro-barium sulfate comprises the following steps:
  • the step (2) and the step (3) further include: adding a purifying agent to the mixed precipitate after aging, removing the inorganic salt precipitate completely, and washing and concentrating the remaining precipitate.
  • the step (2) and the step (3) further include: adding a purifying agent to the mixed precipitate after aging, partially removing the inorganic salt precipitate, and washing and concentrating the remaining precipitate.
  • the preparation method of the modified micronized particles of the present invention restricts the adhesion of the micronized particles during formation, growth and ripening by adding an inorganic precipitate which can be separated, and obtains particles having a desired micronized particle size. Moreover, such micronized or micronized particle precursor precipitated particles are easily separated from the reaction mother liquor under conventional equipment conditions. Next, selectively and different surface modifiers can be used to obtain modified micro-particles with excellent secondary particle size suitable for different materials and high specificity, and the secondary particle size can reach nano-scale distribution.
  • the present invention effectively overcomes the contradiction between the prior modification of the micro-particles of the modified micro-particles and the surface modification, and the difficulty in separating the micro-particles from the reaction mother liquid, and can conveniently obtain the performance and the fine change of the secondary particle size.
  • the micronized particles can realize the industrial production of nano-micronized particles.
  • the degree of removal of the inorganic precipitate of the present invention is elastic, and the inorganic precipitate can be removed, partially removed or completely removed according to the specific application and the type of inorganic precipitation, the application is flexible, and the application performance of the micro-particles can be enriched, and the time is saved.
  • a method for preparing a modified micronized particle of the present invention comprises the steps of: coprecipitating a reaction between a freezing point and a boiling point of a reaction mother liquid in an aqueous solution to form a mixed precipitate of a micronized particle or a micronized particle precursor and an inorganic precipitate.
  • a purifying agent is added to the mixed precipitate, and the inorganic precipitate or a portion thereof is converted into a water-soluble substance to be removed, and the remaining precipitate is washed and concentrated.
  • a purifying agent is added to the mixed precipitate, and the inorganic precipitate or its after-swept body is completely converted into a water-soluble substance to be removed, and the remaining precipitate is washed and concentrated.
  • the method for preparing a modified micronized particle of the present invention further comprises: mixing/reacting the purified mixed precipitate with a surface modifier to obtain modified micronized particles.
  • the preparation method of a modified micronized particle of the invention is carried out in the presence of an inorganic precipitate which can be converted into a water-soluble substance in an aqueous solution and between the freezing point and the boiling point of the reaction mother liquid, and the precipitation reaction of the micronized particle or the micronized particle precursor is carried out. .
  • the precipitation reaction referred to in the present invention is carried out in an aqueous solution
  • the aqueous solution is not excluded from further containing other liquid components such as an organic solvent such as ethanol.
  • the reaction carried out in the aqueous solution can also be understood to be carried out between the state in which the reaction mother liquid is not frozen and boiled under reflux.
  • pure water is a solid below 0 ° C at the freezing point, and a gas above 100 ° C above its boiling point.
  • the fluctuations in freezing point and boiling point value exist objectively.
  • the variation of the freezing point and the boiling point value of the reaction mother liquid is more remarkable. General chemical technicians have a good understanding of this.
  • the mixed precipitation formed by the coprecipitation reaction is a time-consistent mixed reaction process, which includes both the reaction process of micronizing or micronizing the precipitation of the particle precursor, and the reaction process of synthesizing the inorganic precipitation, due to The speed of response between the two cannot be absolutely identical. Therefore, there is bound to be a problem of being unsynchronized one after the other. Accordingly, the judgment of the concept of the process time of the coprecipitation reaction should include the entire process of nucleation, growth and ripening of the micronized or micronized particle precursor. The introduction of previously removable inorganic precipitation reactions at any stage of the process is considered to be within the scope of this patent.
  • the introduction of such a removable inorganic precipitate objectively reduces the particle size of the micronized particles, and the determination of such results can be easily achieved by instruments such as a laser particle size analyzer.
  • the precipitation reaction of the micronized particles or the micronized particle precursor is carried out. Since this method also reduces the particle size of the micronized particles, this embodiment is also within the protection scope of the patent.
  • the inorganic precipitate obtained in the process of the present invention is characterized in that it can be conveniently converted into a water-soluble substance by our usual inorganic or organic acid. Separation with micronized particle precipitation is achieved by using an electrodeless precipitate in which the stability of the acid in the aqueous solution is worse than that of the micronized particle or a higher pH is required to stabilize. But this separation does not necessarily require that it be necessary or thorough.
  • aluminum hydroxide is often used in plastic articles to improve its flame retardancy. Based on this, calcium carbonate and inorganic precipitated aluminum hydroxide can be added to a plastic article without being separately dispersed or modified.
  • the aging treatment is preferred.
  • the length of the aging time can be selected within the range of 0 to 24 hours depending on the curing temperature.
  • the degree of purification of the mixed precipitate is elastic, that is, it is optional to use no treatment, partial treatment or total treatment with a purifying agent, and the degree of elasticity is selected according to the specific application requirements and the type of inorganic precipitation. If purification treatment is required, the order of purification treatment and washing concentration can also be interchanged, either by first treating with a purifying agent, then by concentration, or by concentrating and then treating with a purifying agent.
  • Gravity sedimentation, vacuum suction filtration, centrifugal filtration or centrifugal sedimentation may be adopted in the solid-liquid separation in each treatment stage, and specifically, a gravity sedimentation tank, a filtration or sedimentation three-leg centrifuge and a plate and frame filter press may be employed.
  • the micronized particle precursor or the inorganic precipitated precursor is a generalized technique for preparing the micronized particles, for example, in the preparation of copper simple substance by coprecipitation reaction of copper sulfate and magnesium chloride, which is formed in the previous stage.
  • Copper oxide is the precursor of the final prepared pure copper element.
  • the formed calcium oxide is a precursor of the previously coprecipitated calcium hydroxide after dehydration by heating. This can be fully understood under the conditions of the prior art.
  • the anion portion of the inorganic precipitate is further selected as a hydroxide ion, an oxygen ion, a sulfur (hydrogen) ion, a sulfuric acid (hydrogen) ion, a phosphoric acid (hydrogen) ion or a hydrogen (hydrogen) root.
  • the anion donor may be a salt of a direct form, for example, sodium carbonate or the like, or may be a gas method.
  • ammonia gas is dissolved in water to form hydroxide
  • carbon dioxide is dissolved in water and sodium hydroxide to form sodium carbonate, and the like.
  • anions such as basic carbonates can be understood as a mixture of carbonates and hydroxides and are considered to be within the scope of this patent.
  • the volume average particle diameter d50 of the secondary particle diameter of the modified micronized particles obtained by the method of the present invention is less than 10 ⁇ m, more preferably less than 1000 nm, more preferably less than 100 nm, and most preferably less than 10 nm.
  • the determination of the specific particle diameter can be carried out by a laser particle size analyzer, an electron scanning electron microscope (SEM) or the like.
  • the coprecipitation reaction of the present invention can be carried out under conventional stirring conditions, for example, in an enamel reactor commonly used in chemical production. More preferably, it is carried out under high-speed stirring/mixing/shearing/friction conditions, for example, a coprecipitation reaction is carried out under high-speed stirring in a GFJ type disperser (Shandong Laizhou Shenglong Chemical Machinery Factory). Most preferably, it is carried out under supergravity conditions, for example, in a supergravity reaction apparatus based on the principle of supergravity, and their specific form can be found in the book "Supergravity Technology and Applications" by the Chemical Industry Press.
  • a surface active material may also be added before, during and/or after the precipitation reaction, and such addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater.
  • Preferred surface active materials are further selected as anionic alkyl or aryl organics including alkyl or aryl sulfates, sulfonic acids, phosphates or carboxylic acids and salts thereof, and mixtures thereof. It is added in an amount of from 0.05% to 100%, more preferably from 0.05% to 40%, most preferably from 0.1% to 10%, based on the weight of the precipitate of the micronized or micronized particle precursor.
  • the physical and/or chemical adsorption produced by such addition contributes to the further miniaturization of the precipitated particle size of the micronized or micronized particle precursor, the improvement of the lipophilic properties of the inorganic particles and the particles.
  • the controllability of the morphology changes.
  • this addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater: that is, under the established formulation, the turbidity of the mother liquor cannot be increased after the mixed precipitate is separated from the mother liquor, and the wastewater contains no adsorbed particles.
  • Surfactants do not increase the difficulty of wastewater treatment, which can be easily determined at the state of the art.
  • linoleic acid oleic acid
  • stearic acid sodium stearyl ether ether
  • dioctyl sulfosuccinate dioctyl sulfosuccinate
  • butylnaphthalene sulfonate a butylnaphthalene sulfonate
  • An anionic alkyl or aryl organic compound such as a salt, a polymerized alkylnaphthalenesulfonate, a dodecylbenzene phosphate, a polycarboxylate or a heavy naphthenate.
  • the surface active material may further include inorganic anionic compounds such as sodium polyphosphate and sodium hypophosphite; they may also include ethanol, lauryl betaine, octadecyl ammonium salt, fatty alcohol polyoxyethylene ether, and the like.
  • inorganic anionic compounds such as sodium polyphosphate and sodium hypophosphite; they may also include ethanol, lauryl betaine, octadecyl ammonium salt, fatty alcohol polyoxyethylene ether, and the like.
  • Other types of surface active materials may also include organic polymer compounds such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, and the like. They can be used either singly or in combination. Their specific forms can be found in the book "The Principles of Surfactant Applications" by China Chemical Industry Press.
  • the optional surface modifier comprises a compound capable of forming an adsorption with the surface of the micronized particle, including an anionic compound, a cationic compound, a nonionic surfactant, an organic solvent, a coupling agent, and a parent to which it is added. Materials, and combinations thereof.
  • the micro-particles exist only in a weak physical adhesion (also known as soft agglomeration), and then through the mixing/reaction with the surface modifier, they can be converted into monodisperse micros which meet the requirements of modification. The particles are then conveniently added to the parent material.
  • a weak physical adhesion also known as soft agglomeration
  • the nanometer calcium carbonate prepared by the method needs other complicated treatment, and can be directly agglomerated and dispersed in an aqueous solution containing the formaldehyde phthalate sulfonate dispersant MIGHTY150, and can be directly agglomerated and dispersed in liquid paraffin containing oleic acid.
  • Direct deagglomeration is dispersed in an aqueous solution containing oleic acid and penetrant JFC, and can be directly deagglomerated and dispersed in an aqueous solution containing anionic organic dye fluorescent yellow and nonionic surfactant penetrant JFC, which can be directly deagglomerated and dispersed in 3% acrylic acid.
  • the micro-calcium carbonate prepared by the method reserves a variety of modification space for its later application.
  • modifiers are very rich for different application purposes, they include:
  • Anionic compounds which are classified into anionic inorganic substances and anionic organic substances. Generally, these anionic compounds can form an ionic bond-based chemical adsorption with the exposed metal ions on the surface of the micronized particles, and more specifically include:
  • A an anionic inorganic substance such as fluoride ion, silicate, phosphate, and the like.
  • Anionic organic matter including:
  • a surfactant/dispersant having an anionic group of a sulfonic acid group, a phosphoric acid group or a carboxyl group for example, a polycarboxylate dispersing agent, stearic acid, oleic acid, a polymeric naphthalenesulfonate dispersing agent, and the like. Their specific forms can be found in the book "The Principles of Surfactant Applications” by China Chemical Industry Press.
  • a chelating agent including sodium tripolyphosphate, sodium polyphosphate, EDTA-2Na, maleic acid, citric acid, sodium pyrithione, oxalic acid, triethanolamine, and the like.
  • Such high polymers may be water soluble or water soluble or oil soluble.
  • Cationic compounds which are classified into cationic inorganic substances and cationic organic substances:
  • A cationic inorganic substances, including strontium ions, magnesium ions, calcium ions, aluminum ions, etc.
  • the addition of the above ions can enhance the anionic dye or Adsorption stability of the pigment.
  • the addition of the above ions can improve the adsorption stability of sodium carboxymethylcellulose.
  • cationic organic matter including alkyl ammonium chloride, aryl ammonium chloride, polyethylene imine, cationic guar gum and the like. Their specific forms can be found in the book “The Principles of Surfactant Applications” by China Chemical Industry Press.
  • Nonionic surfactants including alkyl polyglycol ethers, aryl polyglycol ethers, polyethylene glycol-polypropylene glycol ethers, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene wax emulsions, and the like. Their specific forms can be found in the book “The Principles of Surfactant Applications” by China Chemical Industry Press.
  • Water-insoluble organic liquid including all organic liquids which can dissolve up to 0.1 gram per 100 gram of water at 25 ° C, which may be a single component or a mixed component.
  • Carriers suitable for this purpose include all of the micronized particles listed in this patent.
  • the coupling agent includes a silane coupling agent such as vinyltrichlorosilane (A-150), vinyltriethoxysilane (A-151), vinyltrimethoxysilane (A-171), ⁇ . —(2,3-epoxypropoxy)propyltrimethoxysilane (A-187, KH-560), etc.; titanate coupling agent, for example, isopropyl tris(dioctyl pyrophosphate) titanium Acid ester (KR-38S), isopropyl tris(isostearyl) titanate (KR-TTS), isopropyl tris(dodecylbenzenesulfonyl) titanate (KR-9S), different Propyl tris(n-ethylamino-ethylamino) titanate (KB-44), etc.; aluminate coupling agent and the like.
  • silane coupling agent such as vinyltrichlorosilane (A-150),
  • parent material include plastics, rubber, fibers, coatings, inks, metals, ceramics, and the like.
  • the calcium carbonate produced by the process can be added directly to a universal pure acrylic emulsion with 3% acrylic groups.
  • the surface modifier may be used singly or in combination of two or more.
  • treatments such as heating, calcination or drying during or after the modification are also essential. These can be applied skillfully under the existing knowledge conditions.
  • the modification or dispersion of the present invention can be accomplished under optional conventional equipment conditions, for example, an emulsifying machine, a dispersing machine, a vertical horizontal sand mill, a stirred mixing kettle, and the like.
  • an emulsifying machine for example, an emulsifying machine, a dispersing machine, a vertical horizontal sand mill, a stirred mixing kettle, and the like.
  • other finer dispersion, grinding or modification means are also available.
  • the modified micronized particles according to the present invention are inorganic substances and organic substances which are hardly soluble in water and do not chemically react with water.
  • poorly soluble in water or insoluble in water is a general quantitative chemical concept.
  • the present invention is intended to solve the problems of miniaturization and surface modification of the above substances by suitable introduction of inorganic precipitation, and is characterized in that a mixed precipitate of the above substances and inorganic precipitates is formed.
  • the process of forming such a mixed precipitate may be physical, chemical, or a mixture of the two.
  • dispersing iodine dissolved in ethanol into a calcium phosphate precipitate is a physical precipitation reaction process.
  • the process in which the molten organic matter is dispersed into the inorganic precipitation liquid to form the micronized organic particles is also a physical precipitation reaction process.
  • the synthetic micro-organisms and the modified micro-particles of oxides, hydroxides, inorganic salts, other inorganic salts, some organic metal salts and some organic substances are chemical precipitation processes, and the obvious characteristics before and after the reaction process are compared.
  • the preparation techniques of modified micronized particles of simple substances, hydroxides, oxides, inorganic salts, other inorganic substances, metal organic salts and organic substances according to the present invention are known, and their preparation methods are often various. Diverse. The variety of preparation methods is not only reflected in the selection of raw materials, for example, aluminum sulfate and sodium hydroxide can react to synthesize aluminum hydroxide, aluminum sulfate and sodium sulfide can also be synthesized into aluminum hydroxide, and also in the preparation process. Change in conditions. For example, ⁇ -alumina (also known as corundum) can be obtained by calcining aluminum hydroxide at 1200 ° C or hydrothermally synthesized under high pressure and high basicity. The use of these known synthetic methods and the use of the patented technology are not contradictory. By using the patented technology, the particles synthesized by the known synthetic methods can be improved in microfabrication and surface modification by coprecipitation reaction.
  • micronized particles of zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin and lead which can be selected by hydrogen reduction of a mixture of the corresponding oxide and calcium oxide
  • preparation of copper , micronized particles of ruthenium, osmium, silver, iridium, palladium, platinum, gold and ruthenium which can be selected by reducing the corresponding oxides in aqueous solution by using a hydrazine hydrazine reducing agent
  • preparing silver, ruthenium, palladium, platinum and Gold micronized particles can also be selected by heating a mixture of their corresponding oxides and calcium carbonate
  • micronized particles for preparing carbon simple substances can be selected.
  • micronized particles of silicon, tungsten and boron It is obtained by mixing and incompletely burning calcium stearate and calcium carbonate, and preparing micronized particles of silicon, tungsten and boron.
  • the mixed precipitation of their corresponding hydrated oxides and barium sulfate can be reduced by metal magnesium powder.
  • the method of obtaining selenium, sulfur and iodine elemental micronized particles can be selected from the organic solution by physical precipitation.
  • hydroxide micronized particles can be carried out by reacting their corresponding water-soluble metal salts with water-soluble bases.
  • water soluble bases include sodium hydroxide, potassium hydroxide, aqueous ammonia, and ammonia.
  • hydroxides capable of double hydrolysis for example, aluminum hydroxide, sodium carbonate, ammonium carbonate, sodium hydrogencarbonate, sodium sulfide are also optional.
  • hydroxides include barium hydroxide and palladium hydroxide (II, IV), barium hydroxide, platinum hydroxide, barium hydroxide, barium hydroxide, cadmium hydroxide, barium hydroxide (III, IV), barium hydroxide, gallium hydroxide, barium hydroxide , aluminum hydroxide, magnesium hydroxide, manganese hydroxide, lead hydroxide (II, IV), barium hydroxide (III , IV), iron hydroxide, ferrous hydroxide, cuprous hydroxide, copper hydroxide, indium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, Barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide
  • the metal oxide micronized particles can be prepared by hydrothermal decomposition of a mixed precipitate of the corresponding hydroxide and calcium hydroxide (inorganic precipitate), which includes cerium oxide and palladium oxide (II, IV), cerium oxide, platinum oxide, cerium oxide, cerium oxide, cadmium oxide, cerium oxide (III, IV), cerium oxide, gallium oxide, cerium oxide, aluminum oxide, magnesium oxide, manganese oxide, lead oxide (II, IV), yttrium oxide (III , IV), iron oxide, ferrous oxide, cuprous oxide, copper oxide, indium oxide, antimony oxide, antimony oxide, zinc oxide, nickel oxide, tin oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, uranium oxide, titanium oxide, zirconium oxide, vanadium oxide (II) , III, IV), cerium oxide, ce
  • the preparation conditions are also very different. For example, for gold oxide, it can be obtained directly without heating.
  • the choice of calcination method is also optional.
  • the corresponding hydroxide prepared by the prior method is washed and concentrated, and then dispersed in an alcohol solvent having a boiling point higher than water, particularly a polyhydric alcohol such as 1,2-propanediol. Then heat and evaporate.
  • the preparation of the inorganic salt micronized particles can be carried out by coprecipitation reaction by selecting a corresponding water-soluble metal salt and a corresponding mixture of water-soluble acid groups and hydroxides/carbonates. In addition, it is also an option to react with an insoluble hydroxide or carbonate of the corresponding metal ion and an acid of the corresponding acid.
  • the inorganic micronized particles for preparing tungsten carbide, silicon carbide, boron carbide, silicon nitride, and boron nitride are also obtained by reducing the mixed precipitation with carbon or nitrogen (ammonia gas) on the basis of the coprecipitation reaction.
  • the preparation of the organometallic salt micronized particles can be selected in the same manner as the preparation of the inorganic salt micronized particles, including strontium, barium, calcium, lithium, strontium, barium, strontium, barium, strontium, strontium, barium, strontium, ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, An optional alkyl or aryl sulfate of gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin, lead, copper, bismuth, antimony, mercury, silver, antimony, palladium, platinum or gold ions, Sulfonic acid, phosphate or carboxylate.
  • the optional alkyl or aryl sulfate, sulfonic acid, phosphate or carboxylic acid or a salt thereof can also be coprecipitated by dissolving in a water-miscible solvent such as ethanol.
  • a water-miscible solvent such as ethanol. The way of the water emulsion is to participate in the coprecipitation reaction.
  • the present invention also discloses a method of micronizing a solid organic substance that is poorly soluble in water.
  • Carriers suitable for this purpose include all of the micronized particles recited in this patent, with inorganic micronized particles prepared by the present patent technology being particularly preferred.
  • the poorly water-soluble solid organic substance has at least a liquid or liquid composition which has a decomposition temperature higher than its melting point or below its thermal decomposition temperature and can be dissolved in water other than water, and has a solubility of not less than 1 g/100 g.
  • a liquid or liquid composition which has a decomposition temperature higher than its melting point or below its thermal decomposition temperature and can be dissolved in water other than water, and has a solubility of not less than 1 g/100 g.
  • a reaction mode of an aqueous solution and a gas When a solid organic substance which is hardly soluble in water can be reacted by an aqueous solution and an aqueous solution, a reaction mode of an aqueous solution and a gas, a reaction mode of an aqueous solution and a water-insoluble liquid, and a reaction mode of a water-insoluble liquid and a gas can be used. Chemical precipitation reaction process.
  • the water-insoluble solid organic matter can be melted to achieve this physical precipitation reaction process.
  • the water-insoluble solid organic matter can also participate in the coprecipitation reaction in a solution manner.
  • This process generally involves two physical precipitation reactions, adsorption and precipitation.
  • the precipitation process is basically a physical adsorption process; when the solvent is miscible with water, the precipitation process is basically a precipitation process.
  • a more preferable precipitation process is a precipitation process in a precipitation mode. Therefore, when the water-insoluble solid organic substance participates in the coprecipitation reaction in a solution manner, it is preferred that any liquid or liquid composition dissolve at least 1 g of an organic solvent or an organic solvent combination per 100 g of water at 25 ° C.
  • solvent Handbook edited by Cheng Nenglin, China Chemical Industry Press.
  • the water-insoluble solid organic substance participates in the coprecipitation reaction in the form of a (aqueous) suspension or a (water) suspension emulsion.
  • the water-insoluble solid organic matter can be classified into drugs, pesticides, veterinary drugs, pigments, dyes (pigments), flavors, bactericides, fungicides, catalysts, polymer resins or organic dyes.
  • the specific names of organic substances suitable for the scope of this patent can be found in the Chinese Pharmacopoeia 2010, the Chinese Pesticide Code, and the Fine Chemicals Handbook.
  • insoluble organic matter has important application significance. For example, for drugs, more than 40% of the drugs are insoluble in water. Therefore, it is obvious that the miniaturization of these drugs is effective for improving the dissolution rate of the drug and improving the efficacy.
  • the compatibility between the inorganic substance and the organic substance is generally poor, it is generally difficult to obtain a desired result by dispersing the organic substance supported by the inorganic particle as a carrier.
  • the inorganic micronized particles involved in the patent have the advantages of flexible surface modification space, free hydrophilic-lipophilic adjustment, and the like, so that the compatibility can be maximized, thereby obtaining an ideal micro-insoluble organic matter.
  • the rich modification space reserved for the micro-particles also provides convenience for the drug coating, and provides a basis for drug sustained-release control.
  • the suspension containing the precipitation of calcium carbonate and calcium hydroxide was filtered.
  • the resulting filter cake was placed in a 50 ml beaker.
  • the magnetic stirrer was turned on, and 8 ml of a 0.1 mol/L aqueous hydrochloric acid solution was slowly added under vigorous stirring. After 30 minutes, it was filtered again, then washed with about 10 ml of water, then filtered, and washed again, three times.
  • the water-soluble calcium chloride in the filtrate and the wash water can be treated by a soda ash recovery method.
  • the washed calcium carbonate precipitation slurry was placed in a 50 ml plastic beaker, and 30 ml of DEMOL containing 2% dispersant was added.
  • the GF1110 laboratory disperser (Shandong Shenglong Machinery Factory) was opened and the solution was forcedly dispersed for 20 minutes at 1200 rpm.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the calcium carbonate precipitate has a volume average particle diameter d50 of about 30 nm.
  • Example 2 The same experiment as in Example 1 was repeated, and the obtained calcium carbonate was dispersed in 30 ml of liquid paraffin containing 0.1% oleic acid; dispersed in 30 ml of an aqueous solution containing 0.1% oleic acid and 0.1% penetrant JFC; In a 30 ml aqueous solution containing 0.1% anionic organic dye fluorescent yellow and 0.1% nonionic surfactant penetrant JFC; dispersed in a pure acrylic emulsion called AT-150 with 3% acrylic group (Zhongshan An Texa Chemical Co., Ltd.).
  • Calcium carbonate in the above liquid can be well dispersed, and the deagglomeration effect of calcium carbonate is substantially the same as in the first embodiment.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 10 ml of a 0.1 mol/L suspension of calcium oxide water was added to a 50 ml closed flask, and then the reaction was stopped by introducing carbon dioxide gas to about pH 10.5. After aging, the pH was adjusted to about 9 with hydrochloric acid. Then wash repeatedly and then disperse.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the calcium carbonate precipitate has a volume average particle diameter d50 of about 80 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Into a 50 ml closed flask, 10 ml of an aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate (a mixture of water glass and sodium carbonate) was added, followed by the addition of 10 ml of 0.2 mol/L of calcium chloride. After heating at 80 ° C for two hours and standing for 24 hours, 10 ml of 0.2 mol / L hydrochloric acid was further added. Then wash repeatedly and then disperse.
  • aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate a mixture of water glass and sodium carbonate
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter precipitated by calcium silicate (hydrated calcium oxide and silica complex) has a volume average particle diameter d50 of about 50 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1.
  • 10 ml of an aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate (a mixture of water glass and sodium carbonate) was added, followed by the addition of 10 ml of 0.2 mol/L of calcium chloride.
  • 10 ml of 0.2 mol/L of calcium chloride After heating at 80 ° C for two hours and standing for 24 hours, 0.5 g of finely ground ultrafine carbon powder (above 200 mesh) was further added. After thorough dispersion, it is washed, concentrated and dried. It is placed in a corundum boat with a content of more than 99%.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the silicon carbide precipitate has a volume average particle diameter d50 of about 900 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Into a 50 ml closed flask, 10 ml of an aqueous solution of 0.1 mol/L of ferric chloride and 0.02 mol/L of calcium chloride was added, followed by addition of 5 ml of 0.7 mol/L of sodium hydroxide for coprecipitation. Not acidified, disperse after washing.
  • the dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the precipitate of the ferric hydroxide colloid has a volume average particle diameter d50 of about 30 nm.
  • the mixture of the previously washed iron hydroxide and calcium hydroxide was sufficiently dispersed with 10 ml of 1,2-propylene glycol, dried by heating, placed in a muffle furnace, and calcined at 500 ° C to obtain a micronized iron oxide.
  • the iron oxide was reduced with carbon monoxide in a DC-R tubular high temperature furnace (tubular furnace) at 450 ° C to obtain magnetic ferroferric oxide.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 10 ml of an aqueous solution of 0.1 mol/L of aluminum chloride and 0.02 mol/L of calcium chloride was added to a 50 ml closed flask, and then 5 ml of 0.7 mol/L of sodium hydroxide was added to carry out a coprecipitation reaction. After the mixed precipitate was aged, it was acidified with 10 ml of 0.06 mol/L hydrochloric acid, and then washed and concentrated. The obtained aluminum hydroxide precipitate was sufficiently dispersed in 10 ml of a 1,2-propanediol solution, and then dried in an oven at 300 °C. The dried product was again placed in a muffle furnace and calcined at 1000 ° C for 3 hours.
  • alumina also called corundum
  • ⁇ -alumina also called corundum
  • the secondary particle diameter of alumina has a volume average particle diameter d50 of about 350 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of a mixed aqueous solution of 0.2 mol/L aluminum nitrate and 0.05 mol/L silver nitrate to a 50 ml beaker, heat to 60 ° C, and then add 5 ml of 1.4 mol/L sodium hydroxide to carry out the reaction, and then add 0.01 g. Hydrazine hydrate (80% content) solution. The mixed precipitate was aged for 24 hours, concentrated and washed, then acidified with 9.5 ml of 0.7 mol/L nitric acid, and then washed and concentrated.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of silver has a volume average particle diameter d50 of about 160 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of a mixed aqueous solution of 0.2 mol/L magnesium chloride and 0.05 mol/L copper sulfate in a 50 ml beaker, heat to 80 ° C, and then add 5 ml of 2 mol/L sodium hydroxide to carry out the reaction, and then add 0.01 g of hydrazine hydrate. (80% content) solution. The mixed precipitate was aged for 24 hours, concentrated and washed, and then acidified with 9.5 ml of 1 mol/L hydrochloric acid, followed by washing and concentration.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of copper has a volume average particle diameter d50 of about 350 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 10 ml of a mixed aqueous solution of 0.2 mol/L magnesium sulfate and 0.05 mol/L copper sulfate was added to a 50 ml beaker, and after heating to 80 ° C, 10 ml of 1 mol/L sodium hydroxide was added dropwise to carry out a reaction mixture precipitation for 24 hours, and then matured. After concentration and washing, it was acidified with 9.5 ml of 1 mol/L hydrochloric acid, and then washed and concentrated.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the copper oxide has a volume average particle diameter d50 of about 50 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of 0.1 mol/L silver nitrate aqueous solution and 0.1 mol/L aluminum nitrate aqueous solution to a 50 ml beaker, and add 10 ml of a mixed aqueous solution of 0.3 mol/L sodium hydroxide and 0.1 mol/L sodium chloride (containing 0.015). The oleic acid is reacted. After concentrated washing and aging, it was acidified with 9.5 ml of 0.3 mol/L nitric acid, and then washed and concentrated.
  • the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of silver chloride has a volume average particle diameter d50 of about 320 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. 5 ml of a 0.2 mol/L aqueous solution of calcium chloride was added to a 25 ml beaker, and 5 ml of 0.12 mol/L sodium phosphate and 0.04 mol/L sodium hydroxide were added dropwise. Then, when heated to 80 ° C, 0.01 g of stearic acid was added to carry out the reaction under vigorous stirring. After the incubation was continued for ten minutes, it was cooled to room temperature with vigorous stirring. After concentration and washing, it was acidified by adding 5 ml of a 0.1 mol/L hydrochloric acid aqueous solution and then dispersed.
  • the obtained calcium phosphate and calcium stearate were mixed and precipitated for dispersion, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the mixed precipitate has a volume average particle diameter d50 of about 350 nm.
  • cod liver oil 0.01 g was added dropwise to the above dispersion, and after vigorous stirring, an aqueous suspension emulsion of cod liver oil was obtained, and the volume average particle diameter d50 of the secondary particle diameter was also about 350 nm.
  • Example 2 The same experimental procedure was carried out with reference to Example 1. Add 10 ml of 0.2 mol/L calcium chloride aqueous solution to a 50 ml beaker, add 10 ml of a mixed aqueous solution of 0.07 mol/L sodium phosphate and 0.1 mol/L sodium carbonate, and then add 0.1 g of 10% IPBC. A solution of (iodopropynyl carbamate, an excellent industrial antifungal agent) in methanol. After aging, it was acidified with 10 ml of 0.2 mol/L hydrochloric acid, concentrated and washed, and then dispersed.
  • the obtained calcium phosphate and IPBC mixed precipitate were dispersed, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the volume average particle diameter d50 of the secondary particle diameter of the mixed precipitate is also about 300 nm.
  • the IPBC of the thirteenth embodiment was replaced with 0.1 g of a 10% content of a solution of Ganbaosu 1,2-propanediol and 0.1 g of a 10% ketoconazole methanol solution.
  • the other operations were similar, and the excellent water of the two drugs was also obtained.
  • the volume average particle diameter d50 of the dispersion and the secondary particle diameter was about 300 nm.
  • the dispersant containing DEMOL in Examples 14 and 15 The aqueous solution of N is replaced with an aqueous solution containing 1% concentration of sodium carboxymethyl cellulose (Zhangjiagang Sanhui Chemical Co., Ltd., having a carboxyl group substitution degree of about 0.7) of ICM-7 type. Other operations are as good as the above mixed precipitation. Dispersions.
  • the obtained calcium phosphate and IPBC mixed precipitate were dispersed, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the volume average particle diameter d50 of the secondary particle diameter of the mixed precipitate is about 360 nm.
  • the above aqueous solutions of A and B are at a single flow rate of not more than 200 L/H, and the flow rate molar ratio is about 1: 1.1, simultaneously pumped into the supergravity reactor for synthesis.
  • the supergravity reactor was rotated at 1000 rpm; the synthetic slurry of A and B was placed in a 100 liter polypropylene plastic bucket, and the GFJ-8 type disperser was started, and the rotation speed was adjusted to 1000 rpm.
  • C was added to the synthetic slurry of A and B over 10 minutes.
  • the obtained slurry was treated in the same manner as in Example 1.
  • the centrifugal separation equipment uses an ordinary sedimentation type three-legged centrifuge.
  • the dispersing agent was selected from the Japanese Kao Company formaldehyde phthalate sulfonate dispersing agent DEMOLN.
  • the modified micro-purinated zinc pyrithione obtained in this example was subjected to particle size analysis by scanning electron microscopy (SEM), and it was found that the particle diameter of the particles was substantially less than 300 nm.
  • Example 2 5 ml of each of an aqueous solution of calcium chloride and sodium carbonate having a concentration of 0.1 mol/L was separately disposed, and treated in the same manner as in Example 1.
  • the obtained calcium carbonate dispersion obtained by the non-patent method is a laser particle size analyzer (beckman) Coulter) was tested with a d50 of about 8.5 microns. It can be seen that inorganic precipitation of calcium hydroxide can effectively improve the secondary particle size of calcium carbonate.
  • the above aqueous solution of zinc sulphate and sodium 2-pyridyl pyridine oxide solution were separately pumped into a supergravity reactor at a single flow rate of not more than 200 L/H at a flow ratio of about 1.05:1.
  • the supergravity reactor was rotated at 1000 rpm.
  • the obtained slurry was filtered with a quantitative filter paper, and as a result, a large amount of modified micro-pyridinium oxychloride zinc particles penetrated the filter paper, and the separation of the modified micro-pyridyl pyridine oxide zinc particles from the reaction mother liquid could not be achieved by this method.
  • the obtained slurry was centrifuged at 3000 rpm for 20 minutes using a bench-top low-speed centrifuge 80-2T (Shanghai Surgical Instrument Factory). As a result, a large amount of modified micronization was still contained in the centrifuged mother liquor. The zinc pyrithione particles and the DEMOLN dispersant still do not provide good separation of the reaction product from the reaction mother liquor.

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Abstract

Provided is a method for preparing modified micronized particles, which comprises the following steps: carrying out coprecipitation reaction in an aqueous solution at a temperature between the freezing point and the boiling point of the reaction liquid to obtain a mixed precipitate of micronized particles or precursor of micronized particles and other inorganic precipitate. The method effectively solves the conflict between micronization and surface modification of the particles and resolves the problem that it is difficult to separate the micronized particles from the mother liquid of reaction.

Description

一种改性微化颗粒的制备方法  Preparation method of modified micronized particles 技术领域Technical field
本发明涉及化工技术领域，尤其涉及一种改性微化颗粒的制备方法。The invention relates to the technical field of chemical industry, in particular to a preparation method of modified micronized particles.
背景技术Background technique
不溶于水的微化颗粒在成核和成长的化学反应过程中，相互间往往会产生很强作用的粘连，使得微化颗粒在后续的使用中只能以几微米甚至几十微米的粒径尺寸分布在所填充的基材中，具有极差的单分散性（二次粒径），与亚微米甚至纳米级分布的微化颗粒粒子相比，其在应用性能上存在明显差距。The water-insoluble micronized particles tend to have a strong interaction between each other during the chemical reaction of nucleation and growth, so that the micronized particles can only have a particle size of several micrometers or even several micrometers in subsequent use. The size distribution in the filled substrate has extremely poor monodispersity (secondary particle size), and there is a significant difference in application performance compared with micronized particle particles distributed in submicron or even nanometer order.
为了得到具有良好的二次粒径的改性微化颗粒，当前工业生产中，制备这种单分散微化颗粒，一般都是在水性条件下和在合成阶段通过添加小分子的分散剂来实现的。但是这种方法往往存在以下问题：In order to obtain modified micronized particles having a good secondary particle size, in the current industrial production, the preparation of such monodisperse micronized particles is generally carried out under aqueous conditions and in the synthesis stage by adding a small molecule dispersant. of. However, this method often has the following problems:
首先，颗粒微化与表面改性之间往往存在矛盾。First, there is often a contradiction between particle micronization and surface modification.
制备任何复合材料，不同材质间的界面处理至关重要，处理结果的好坏直接关系到复合材料的最终性能。To prepare any composite material, the interface treatment between different materials is very important, and the processing result is directly related to the final performance of the composite material.
各种材质的微化颗粒如果界面处理不好，或者说改性不好，不仅难以均匀分散到母体材料中，而且往往也带来了母体材料整体性能的下降。显微下观察，此时，微化颗粒和母体材料之间存在间隙区，显现出明显的两相分离现象。这种例子举不胜举。If the micro-particles of various materials are not well treated, or the modification is not good, it is not only difficult to uniformly disperse into the matrix material, but also tends to reduce the overall performance of the matrix material. Under microscopic observation, at this time, there is a gap region between the micronized particles and the matrix material, which shows an obvious two-phase separation phenomenon. This kind of example is hard to come by.
因此，对于微化颗粒来说，大多数情况下，颗粒表面改性效果的好坏要远远比颗粒粒径的大小更为重要。Therefore, for the micronized particles, in most cases, the surface modification effect of the particles is much more important than the particle size.
如上所言，现有的合成方法中，改性微化颗粒虽然可以很好的分散到母体材料——水中。但是我们知道，进入到最终应用时，它所要被添加到的母体材料与水的性质却往往相差巨大，例如，塑料、纤维等等。为了适应变化的母体材料，这时只有进行再次改性。但是，由于这种方法制取的微化颗粒表面的活性吸附位置基本都已经被先前的小分子分散剂所占据，无法除去，这时的这种再改性将会变得极其困难，或者换句话说，这种微化颗粒再怎么处理，颗粒表面也很难达到最理想化的改性效果，在接下来的应用中必然会受到诸多制约。例如，用聚丙烯酸钠分散剂制取的碳酸钙很难直接应用到聚丙烯塑料中去，即使经过相应的偶联剂等再改性，它与聚丙烯塑料间的界面融合始终达不到最优结果，导致其与原位聚合的纳米碳酸钙在应用性能上始终存在不可避免的相当差距。As mentioned above, in the existing synthesis method, the modified micronized particles can be well dispersed into the parent material, water. But we know that when it comes to the final application, the properties of the parent material and water to which it is added often vary greatly, for example, plastics, fibers, and so on. In order to adapt to the changing parent material, only the modification is carried out at this time. However, since the active adsorption sites on the surface of the micronized particles prepared by this method are basically occupied by the previous small molecule dispersant and cannot be removed, such re-modification at this time will become extremely difficult, or change In other words, how to deal with such micronized particles, it is difficult to achieve the most ideal modification effect on the surface of the particles, and it will inevitably be subject to many constraints in the next application. For example, calcium carbonate prepared by dispersing sodium polyacrylate is difficult to apply directly to polypropylene plastics. Even after modification with corresponding coupling agents, the interface fusion with polypropylene plastics is not always the most. The superior result leads to an inevitable considerable difference in the application performance of the in-situ polymerized nano-calcium carbonate.
其次，传统制备过程中，上述微化颗粒的富集也是极其困难的。由于微化颗粒表面被小分子分散剂改性为高度的亲水性，再加上颗粒小，导致其不易过滤，微化颗粒与反应母液分离困难，分离过程中存在微化颗粒流失的问题。Secondly, the enrichment of the above-mentioned micronized particles is extremely difficult in the conventional preparation process. Since the surface of the micronized particles is modified to a high degree of hydrophilicity by a small molecule dispersing agent, and the particles are small, it is difficult to be filtered, and it is difficult to separate the micronized particles from the reaction mother liquid, and there is a problem that the micronized particles are lost during the separation process.
技术问题technical problem
本发明的目的在于提供一种改性微化颗粒的制备方法，以解决现有技术中改性微化颗粒制备方法中存在的上述技术问题。 It is an object of the present invention to provide a method for preparing modified micronized particles to solve the above-mentioned technical problems existing in the prior art method for preparing modified micronized particles.
技术解决方案Technical solution
本发明的技术方案如下：The technical solution of the present invention is as follows:
为达到上述目的，本发明提供了一种改性微化颗粒的制备方法，该方法包括以下步骤：水溶液中且反应母液冰点和沸点之间进行共沉淀反应，生成微化颗粒或微化颗粒前驱体和无机沉淀的混合沉淀。In order to achieve the above object, the present invention provides a method for preparing modified micronized particles, which comprises the steps of: coprecipitation reaction between a freezing point and a boiling point of an aqueous solution in an aqueous solution to form a micronized particle or a micronized particle precursor Mixed precipitation of bulk and inorganic precipitates.
所述的微化颗粒或微化颗粒前驱体的沉淀和无机沉淀的混合沉淀在反应后母液中的含量为0.1%—50%，最优选为0.5%—10%；并且微化颗粒或微化颗粒前驱体的沉淀与无机沉淀的质量比为1000：1至1：100000，次优选为100：1至1：1000，最优选为10：1至1：100。The mixed precipitate of the precipitated and inorganic precipitate of the micronized or micronized particle precursor is 0.1%-50%, most preferably 0.5%-10% in the mother liquor after the reaction; and the micronized or micronized The mass ratio of the precipitation of the particle precursor to the inorganic precipitation is from 1000:1 to 1:100,000, and less preferably from 100:1 to 1:1000, most preferably from 10:1 to 1:100.
所述的共沉淀反应在常规搅拌条件下进行或在高速搅拌/混合/剪切/摩擦条件下进行，进一步在超重力条件下进行。The coprecipitation reaction is carried out under conventional agitation or under high speed agitation/mixing/shearing/friction conditions, further under supergravity conditions.
所述的共沉淀反应，反应液的PH控制在3-14，最优选为7-14。 In the coprecipitation reaction, the pH of the reaction solution is controlled at 3 to 14, most preferably 7-14.
所述的微化颗粒或微化颗粒前驱体为难溶于水且不与水有化学反应的无机物或有机物，以及它们之间的混合物。The micronized or micronized particle precursor is an inorganic or organic substance that is poorly soluble in water and does not chemically react with water, and a mixture therebetween.
所述的无机物选自单质，更进一步的选择为锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡、铅、铜、锝、钋、银、铑、钯、铂、金、碳、硅、钨、硼、碲、硒、硫或碘，以及它们的混合物。The inorganic substance is selected from the elemental substance, and further selected are zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin, lead, copper, bismuth, antimony, silver, antimony, palladium, Platinum, gold, carbon, silicon, tungsten, boron, antimony, selenium, sulfur or iodine, and mixtures thereof.
所述的无机物选自氢氧化物，更进一步的选择为氢氧化锕、氢氧化钯(II、 IV)、氢氧化铋、氢氧化铂、 氢氧化铒 、氢氧化钆、 氢氧化镉、氢氧化铪(III 、IV) 、氢氧化钬、 氢氧化镓、氢氧化镥 、氢氧化铝、氢氧化镁、氢氧化锰、氢氧化铅（II、 IV）、氢氧化铈(III 、IV)、氢氧化铁、氢氧化亚铁、氢氧化亚铜、氢氧化铜、氢氧化铟、氢氧化铕、氢氧化铍、氢氧化锌、氢氧化镍、氢氧化锡、氢氧化镧、氢氧化钕、氢氧化镨、氢氧化钐、氢氧化铽、氢氧化钇、氢氧化镝、氢氧化铥、氢氧化镱、氢氧化钪、氢氧化钚、氢氧化钍、氢氧化镎、氢氧化铀、氢氧化钛、氢氧化锆、氢氧化钒（II 、III、 IV）、氢氧化铌、氢氧化钽、氢氧化铬、氢氧化钴或氢氧化钼（III、 IV、V）。The inorganic substance is selected from the group consisting of hydroxides, and further selected are barium hydroxide, palladium hydroxide (II, IV), barium hydroxide, platinum hydroxide, Barium hydroxide, barium hydroxide, cadmium hydroxide, barium hydroxide (III, IV), barium hydroxide, gallium hydroxide, barium hydroxide, aluminum hydroxide, magnesium hydroxide, manganese hydroxide, lead hydroxide (II , IV), barium hydroxide (III , IV), iron hydroxide, ferrous hydroxide, cuprous hydroxide, copper hydroxide, indium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, Barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, hydroxide Uranium, titanium hydroxide, zirconium hydroxide, vanadium hydroxide (II , III, IV), barium hydroxide, barium hydroxide, chromium hydroxide, cobalt hydroxide or molybdenum hydroxide (III, IV, V).
所述的无机物选自氧化物，更进一步的选择为氧化锕、氧化钯(II、 IV)、氧化铋、氧化铂、 氧化铒 、氧化钆、 氧化镉、氧化铪(III 、IV) 、氧化钬、 氧化镓、氧化镥 、氧化铝、氧化镁、氧化锰、氧化铅（II、 IV）、氧化铈(III 、IV)、氧化铁、氧化亚铁、氧化亚铜、氧化铜、氧化铟、氧化铕、氧化铍、氧化锌、氧化镍、氧化锡、氧化镧、氧化钕、氧化镨、氧化钐、氧化铽、氧化钇、氧化镝、氧化铥、氧化镱、氧化钪、氧化钚、氧化钍、氧化镎、氧化铀、氧化钛、氧化锆、氧化钒（II 、III、 IV）、氧化铌、氧化钽、氧化铬、氧化钴、氧化钼（III、 IV、V）、氧化银、氧化锝、氧化钋、氧化铑、氧化钯、氧化铂、氧化金、氧化硅、氧化钨、氧化硼、氧化碲或氧化硒。The inorganic substance is selected from the group consisting of oxides, and further selected are cerium oxide, palladium oxide (II, IV), cerium oxide, platinum oxide, cerium oxide. , cerium oxide, cadmium oxide, cerium oxide (III, IV), cerium oxide, gallium oxide, cerium oxide, aluminum oxide, magnesium oxide, manganese oxide, lead oxide (II, IV), cerium oxide (III) , IV), iron oxide, ferrous oxide, cuprous oxide, copper oxide, indium oxide, antimony oxide, antimony oxide, zinc oxide, nickel oxide, tin oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, uranium oxide, titanium oxide, zirconium oxide, vanadium oxide (II) , III, IV), cerium oxide, cerium oxide, chromium oxide, cobalt oxide, molybdenum oxide (III, IV, V), silver oxide, cerium oxide, cerium oxide, cerium oxide, palladium oxide, platinum oxide, gold oxide, silicon oxide, tungsten oxide, boron oxide, cerium oxide or selenium oxide.
所述的无机物选自无机盐，更进一步的选择为砷酸钡、碳酸钡、铬酸钡、亚铁氰化钡、氟硅酸钡、氟化钡、磷酸氢钡、碘酸钡、硫酸钡、钼酸钡、高锰酸钡、焦磷酸钡、硒酸钡、砷酸铋、碘化铋、磷酸铋、硫化铋、溴化铂(IV) 、氟化钚(III) 、氟化钚(IV) 、碘酸钚(IV)、 砷酸钙、氟化钙、磷酸氢钙、钼酸钙、磷酸钙、钨酸钙、砷酸镉、碳酸镉、氰化镉、亚铁氰化镉、碘酸镉、磷酸镉、硫化镉、钨酸镉、叠氮化亚汞、溴化亚汞、碳酸亚汞、氯化亚汞、铬酸亚汞、氰化亚汞、硫酸亚汞、碘酸汞、碘化汞、硫化汞、硫氰酸汞、四苯硼钾、三碘化金、碘酸镧、钼酸镧、磷酸锂、氟化镁、磷酸镁、亚硒酸镁、碳酸锰、亚铁氰化锰、碳酸镍、碘酸镍、焦磷酸镍、硫化钋(II) 、钼酸镨(III) 、叠氮化铅、碳酸铅、氯酸铅、铬酸铅、亚铁氰化铅、氟化铅、磷酸氢铅、亚磷酸氢铅、碘酸铅、碘化铅、钼酸铅、硒酸铅、硫酸铅、硫化铅、硫代硫酸铅、钨酸铅、碲化铅、磷酸铈(III) 、铬酸锶硫酸锶、溴化亚铊、碘酸亚铊、碘化亚铊、碳酸亚铁、氢氧化亚铁、砷酸铁、氟化铁、氯化亚铜、氰化亚铜、碘化亚铜、硫化亚铜、硫氰酸亚铜、碳酸铜、铬酸铜、氟化铜、亚硒酸铜、硫化铜、碘酸钍(IV) 、碳酸锌、氰化锌、碘酸锌、氟化钇、碘酸铟、硫化铟、叠氮化银、溴化银、碳酸银、氯化银、铬酸银、氰化银、钒酸银、碳酸铍、亚硫酸钡、亚硫酸锶、亚硫酸钙、亚硫酸铍、亚硫酸锰、亚硫酸锌、亚硫酸镉、亚硫酸亚铁、亚硫酸镍、亚硫酸铅、亚硫酸铜、亚硫酸汞、亚硫酸银、硫化锶、硫化锰、硫化锌、硫化亚铁、硫化镉、硫化镍、硫化锡、硫化铅、硫化铜、硫化汞、硫化银、硅酸钡、硅酸钙、硅酸镁、硅酸铝、硅酸铍、硅酸锰、硅酸锌、硅酸铬、硅酸亚铁、硅酸铁、硅酸镉、硅酸镍、硅酸铅、硅酸铜、硅酸银、磷酸锂、磷酸钡、磷酸锶、磷酸钙、磷酸镁、磷酸铝、磷酸铍、磷酸锰、磷酸锌、磷酸铬、磷酸亚铁、磷酸铁、磷酸镉、、磷酸铊、磷酸镍、磷酸锡、磷酸铅、磷酸铜、磷酸汞、磷酸银、2-巯基吡啶硫酮锌、2-巯基吡啶硫酮铜、草酸镉、草酸银、草酸亚铁、酒石酸锌、草酸锌、草酸铅、酒石酸铅、草酸钡、草酸钙、草酸汞、草酸钪、草酸锰、碳化钨、碳化硅、碳化硼、氮化硅或氮化硼。The inorganic substance is selected from the group consisting of inorganic salts, and further selected are barium arsenate, barium carbonate, barium chromate, barium ferrocyanide, barium fluorosilicate, barium fluoride, barium hydrogen phosphate, barium iodate, sulfuric acid. Bismuth, bismuth molybdate, barium permanganate, barium pyrophosphate, barium selenate, barium arsenate, barium iodide, barium phosphate, barium sulfide, platinum bromide (IV) , cerium (III) fluoride, cerium (IV) fluoride, cerium (IV) iodate, Calcium arsenate, calcium fluoride, calcium hydrogen phosphate, calcium molybdate, calcium phosphate, calcium tungstate, cadmium arsenate, cadmium carbonate, cadmium cyanide, cadmium ferrocyanide, cadmium iodate, cadmium phosphate, cadmium sulfide, Cadmium Tungstate, Mercury Azide, Mercury Bromide, Mercury Carbonate, Mercury Chloride, Mercury Chromate, Mercury Cyanide, Mercury Sulfate, Mercury Iodide, Mercury Iodide, Mercury Sulfide, Sulfur Mercury cyanate, potassium tetraphenylborate, gold triiodide, barium iodate, barium bismuth citrate, lithium phosphate, magnesium fluoride, magnesium phosphate, magnesium selenite, manganese carbonate, manganese ferrocyanide, nickel carbonate, iodine Nickel acid, nickel pyrophosphate, antimony sulfide (II) , bismuth molybdate (III) , lead azide, lead carbonate, lead chlorate, lead chromate, lead ferrocyanide, lead fluoride, lead hydrogen phosphate, lead hydrogen phosphite, lead iodate, lead iodide, lead molybdate, selenate Lead, lead sulfate, lead sulfide, lead thiosulfate, lead tungstate, lead telluride, barium phosphate (III) , barium strontium sulphate, barium bromide, hydrazine hydrazide, hydrazine iodide, ferrous carbonate, ferrous hydroxide, iron arsenate, iron fluoride, cuprous chloride, cuprous cyanide, iodine Cuprous, cuprous sulfide, cuprous thiocyanate, copper carbonate, copper chromate, copper fluoride, copper selenite, copper sulfide, barium iodate (IV) , zinc carbonate, zinc cyanide, zinc iodate, barium fluoride, indium iodate, indium sulfide, silver azide, silver bromide, silver carbonate, silver chloride, silver chromate, silver cyanide, silver vanadate , barium carbonate, barium sulfite, barium sulfite, barium sulfite, barium sulfite, manganese sulfite, zinc sulfite, cadmium sulfite, ferrous sulfite, nickel sulfite, lead sulfite, copper sulfite, Mercuric sulfate, silver sulfite, barium sulfide, manganese sulfide, zinc sulfide, ferrous sulfide, cadmium sulfide, nickel sulfide, tin sulfide, lead sulfide, copper sulfide, mercury sulfide, silver sulfide, barium silicate, calcium silicate, silicon Magnesium silicate, aluminum silicate, strontium silicate, manganese silicate, zinc silicate, chromium silicate, ferrous silicate, iron silicate, cadmium silicate, nickel silicate, lead silicate, copper silicate, silicic acid Silver, lithium phosphate, strontium phosphate, strontium phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, strontium phosphate, manganese phosphate, zinc phosphate, chromium phosphate, ferrous phosphate, iron phosphate, cadmium phosphate, strontium phosphate, nickel phosphate, phosphoric acid Tin, lead phosphate, copper phosphate, mercury phosphate, silver phosphate, zinc pyrithione, copper pyrithione, oxalic acid , silver oxalate, ferrous oxalate, zinc tartrate, zinc oxalate, lead oxalate, lead tartrate, barium oxalate, calcium oxalate, mercury oxalate, barium oxalate, manganese oxalate, tungsten carbide, silicon carbide, boron carbide, silicon nitride or nitride boron.
所述的无机物选自有机金属盐，更进一步的选择为钡、锶、钙、锂、锕、镧、铈、镨、钕、钐、铕、钆、铽、钇、镁、镅、镝、钬、铒、铥、镱、镥、钪、钚、钍、镎、铍、铀、铪、铝、钛、锆、钒、锰、铌、锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡、铅、铜、锝、钋、汞、银、铑、钯、铂或金离子的任选的烷基或芳基硫酸酯、磺酸、磷酸酯或羧酸盐。The inorganic substance is selected from the group consisting of organic metal salts, and further selected are lanthanum, cerium, calcium, lithium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, magnesium, lanthanum, cerium,钬, 铒, 铥, 镱, 镥, 钪, 钚, 钍, 镎, 铍, uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, gallium, iron, cadmium, indium, antimony, An optional alkyl or aryl sulfate, sulfonic acid, phosphate or carboxylate of cobalt, nickel, molybdenum, tin, lead, copper, ruthenium, osmium, mercury, silver, ruthenium, palladium, platinum or gold ions.
所述的有机物至少具有以下要素之一：The organic substance has at least one of the following elements:
（1）分解温度高于其熔点；(1) the decomposition temperature is higher than its melting point;
（2）在其热分解温度以下能够溶于除水以外的任一液体或液体组合物，且溶解度不低于1克/100克。(2) It is soluble in any liquid or liquid composition other than water below its thermal decomposition temperature, and has a solubility of not less than 1 g/100 g.
其中，除水以外的任一液体或液体组合物更进一步的选择为25℃下每100克水中至少可以溶解1克以上的有机溶剂或有机溶剂组合。Among them, any liquid or liquid composition other than water is further selected to dissolve at least 1 g of an organic solvent or an organic solvent combination per 100 g of water at 25 °C.
本发明还包括：向混合沉淀中加入提纯剂，将无机沉淀或其后驱体部分转化为水溶性物质去除，并对剩余的沉淀进行洗涤浓缩。The present invention further comprises: adding a purifying agent to the mixed precipitate, converting the inorganic precipitate or a portion thereof to a water-soluble substance, and washing and concentrating the remaining precipitate.
所述的提纯剂为水溶性的无机酸或有机酸，可选自盐酸、硫酸、硝酸、氢氟酸、乙酸或磷酸的其中一种，或其混合物。The purifying agent is a water-soluble inorganic or organic acid, and may be selected from one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, acetic acid or phosphoric acid, or a mixture thereof.
本发明还包括：向混合沉淀中加入提纯剂，将无机沉淀或其后驱体全部转化为水溶性物质去除，并对剩余的沉淀进行洗涤浓缩。The present invention further comprises: adding a purifying agent to the mixed precipitate, converting the inorganic precipitate or its after-swept body into a water-soluble substance, and washing and concentrating the remaining precipitate.
本发明还包括：将提纯后的混合沉淀与表面改性剂混合/反应，得到改性微化颗粒。The invention further comprises: mixing/reacting the purified mixed precipitate with the surface modifier to obtain modified micronized particles.
所述的表面改性剂是指能够和微化颗粒表面形成吸附的化合物，包括阴离子化合物、阳离子化合物、非离子表面活性剂、水不溶有机液体、偶联剂或被添加到的母体材料，以及它们的组合物。The surface modifier refers to a compound capable of forming adsorption with the surface of the microparticles, including an anionic compound, a cationic compound, a nonionic surfactant, a water-insoluble organic liquid, a coupling agent, or a parent material to which it is added, and Their composition.
所述的改性微化颗粒的二次粒径的体积粒径平均值d50小于10微米，进一步优选为小于1000纳米，更优选为小于100纳米，最优选为小于10纳米。The average particle diameter d50 of the secondary particle diameter of the modified micronized particles is less than 10 μm, further preferably less than 1000 nm, more preferably less than 100 nm, and most preferably less than 10 nm.
本发明还包括：水溶液中且反应母液冰点和沸点之间，可转化为水溶性物质的无机沉淀存在下，进行微化颗粒或微化颗粒前驱体的沉淀反应。The present invention further comprises: in the presence of an inorganic precipitate in an aqueous solution and between the freezing point and the boiling point of the reaction mother liquid, which can be converted into a water-soluble substance, and subjected to a precipitation reaction of the micronized particles or the micronized particle precursor.
所述的可转化为水溶性物质的无机沉淀在反应温度下每100克水中溶解度小于1克，更进一步的选择为小于0.01克；并且该无机沉淀的阳离子部分选自钡、锶、钙、锂、锕、镧、铈、镨、钕、钐、铕、钆、铽、钇、镁、镅、镝、钬、铒、铥、镱、镥、钪、钚、钍、镎、铍、铀、铪、铝、钛、锆、钒、锰、铌、锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡、铅、铜、锝、钋、汞、银、铑、钯、铂或金离子，以及它们的混合物；无机沉淀的阴离子部分为氰离子、卤离子、硫酸（氢）根离子、亚硝酸根离子、碳酸（氢）根离子、亚硫酸（氢）根离子、重铬酸根离子、磷酸（氢）根离子、硫（氢）离子、铬酸根离子、硅酸根离子、硼酸根离子、砷酸根离子、钛酸根离子、草酸根离子、氢氧根离子或氧离子，更进一步的选择为氢氧根离子、氧离子、硫（氢）离子、亚硫酸（氢）根离子、磷酸（氢）根离子或碳酸（氢）根离子，以及它们的混合物。The inorganic precipitate which can be converted into a water-soluble substance has a solubility of less than 1 gram per 100 grams of water at the reaction temperature, and is further selected to be less than 0.01 gram; and the cationic portion of the inorganic precipitate is selected from the group consisting of ruthenium, osmium, calcium, and lithium. , 锕, 镧, 铈, 镨, 钕, 钐, 铕, 钆, 铽, 钇, 镅, 镅, 镝, 钬, 铒, 铥, 镱, 镥, 钪, 钚, 钍, 镎, 铍, uranium, 铪, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin, lead, copper, antimony, bismuth, mercury, silver, antimony, palladium , platinum or gold ions, and mixtures thereof; the anion portion of the inorganic precipitate is cyanide ion, halide ion, sulfuric acid (hydrogen) ion, nitrite ion, carbonic acid (hydrogen) ion, sulfuric acid (hydrogen) ion, Dichromate ion, phosphoric acid (hydrogen) ion, sulfur (hydrogen) ion, chromate ion, silicate ion, borate ion, arsenate ion, titanate ion, oxalate ion, hydroxide ion or oxygen ion, Further choices are hydroxide ion, oxygen ion, sulfur (hydrogen) separation , (Hydrogen) sulphite ion, phosphate (hydrogen) ions or (bi) carbonate ions, and mixtures thereof.
在本发明中，沉淀反应前、中和/或后，加入表面活性物质，并且这种加入不影响混合沉淀与母液的分离和废水的处理。In the present invention, the surface active material is added before, during and/or after the precipitation reaction, and such addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater.
表面活性物质的具体形式可以参见中国化学工业出版社《表面活性剂应用原理》一书。The specific form of surface active substances can be found in the book "The Principles of Application of Surfactants" by China Chemical Industry Press.
一种改性微化硫酸钡的制备方法，包括以下步骤：A method for preparing modified micro-barium sulfate comprises the following steps:
（1）将至少含有水溶性钡盐的水溶液和至少含有水溶性硫酸盐的水溶液在0-99℃之间进行共沉淀反应，得到硫酸钡沉淀与其他无机沉淀的混合沉淀，该无机沉淀可以与提纯剂作用转化为水溶性物质；(1) coprecipitation reaction between an aqueous solution containing at least a water-soluble cerium salt and an aqueous solution containing at least a water-soluble sulphate at 0 to 99 ° C to obtain a mixed precipitate of barium sulfate precipitate and other inorganic precipitates, which may be combined with The action of the purifying agent is converted into a water-soluble substance;
（2）将步骤（1）得到的混合沉淀静止熟化；(2) statically ripening the mixed precipitate obtained in the step (1);
（3）将熟化后的混合沉淀与表面改性剂混合/反应，得到改性微化硫酸钡。(3) Mixing/reacting the aged mixed precipitate with the surface modifier to obtain modified micro-barium sulfate.
步骤（2）和步骤（3）之间还包括：向熟化后的混合沉淀中加入提纯剂，将无机盐沉淀全部去除，并对剩余的沉淀进行洗涤浓缩。The step (2) and the step (3) further include: adding a purifying agent to the mixed precipitate after aging, removing the inorganic salt precipitate completely, and washing and concentrating the remaining precipitate.
步骤（2）和步骤（3）之间还包括：向熟化后的混合沉淀中加入提纯剂，将无机盐沉淀部分去除，并对剩余的沉淀进行洗涤浓缩。The step (2) and the step (3) further include: adding a purifying agent to the mixed precipitate after aging, partially removing the inorganic salt precipitate, and washing and concentrating the remaining precipitate.
有益效果Beneficial effect
本发明的改性微化颗粒的制备方法通过加入可以分离的无机沉淀，制约了微化颗粒在生成、长大和熟化期间的粘连，得到了所需微化粒径的颗粒。并且，在常规设备条件下，这种微化颗粒或微化颗粒前驱体沉淀粒子很容易与反应母液分离。接下来，选择性的与不同的表面改性剂作用后就能够得到适合不同材质、具有高针对性的二次粒径优良的改性微化颗粒，其二次粒径可达到纳米级分布。因此，本发明有效克服了现有改性微化颗粒颗粒微化与表面改性之间存在矛盾、微化颗粒与反应母液分离困难的缺点，能够方便的得到性能和二次粒径优良的改性微化颗粒，可以实现工业化生产纳米微化颗粒。The preparation method of the modified micronized particles of the present invention restricts the adhesion of the micronized particles during formation, growth and ripening by adding an inorganic precipitate which can be separated, and obtains particles having a desired micronized particle size. Moreover, such micronized or micronized particle precursor precipitated particles are easily separated from the reaction mother liquor under conventional equipment conditions. Next, selectively and different surface modifiers can be used to obtain modified micro-particles with excellent secondary particle size suitable for different materials and high specificity, and the secondary particle size can reach nano-scale distribution. Therefore, the present invention effectively overcomes the contradiction between the prior modification of the micro-particles of the modified micro-particles and the surface modification, and the difficulty in separating the micro-particles from the reaction mother liquid, and can conveniently obtain the performance and the fine change of the secondary particle size. The micronized particles can realize the industrial production of nano-micronized particles.
其次，本发明无机沉淀的去除程度是弹性的，可以根据具体应用和无机沉淀的类型选择将无机沉淀不去除、部分去除或全部去除，应用灵活，并且能够丰富微化颗粒应用性能，具有省时、省力、成本低的优点。Secondly, the degree of removal of the inorganic precipitate of the present invention is elastic, and the inorganic precipitate can be removed, partially removed or completely removed according to the specific application and the type of inorganic precipitation, the application is flexible, and the application performance of the micro-particles can be enriched, and the time is saved. The advantages of labor saving and low cost.
附图说明DRAWINGS
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
本发明的实施方式Embodiments of the invention
本发明的一种改性微化颗粒的制备方法，包括以下步骤：水溶液中且反应母液冰点和沸点之间进行共沉淀反应，生成微化颗粒或微化颗粒前驱体和无机沉淀的混合沉淀。A method for preparing a modified micronized particle of the present invention comprises the steps of: coprecipitating a reaction between a freezing point and a boiling point of a reaction mother liquid in an aqueous solution to form a mixed precipitate of a micronized particle or a micronized particle precursor and an inorganic precipitate.
本发明的一种改性微化颗粒的制备方法，向混合沉淀中加入提纯剂，将无机沉淀或其后驱体部分转化为水溶性物质去除，并对剩余的沉淀进行洗涤浓缩。In the preparation method of the modified micronized particles of the present invention, a purifying agent is added to the mixed precipitate, and the inorganic precipitate or a portion thereof is converted into a water-soluble substance to be removed, and the remaining precipitate is washed and concentrated.
本发明的一种改性微化颗粒的制备方法，向混合沉淀中加入提纯剂，将无机沉淀或其后驱体全部转化为水溶性物质去除，并对剩余的沉淀进行洗涤浓缩。In the preparation method of the modified micronized particles of the present invention, a purifying agent is added to the mixed precipitate, and the inorganic precipitate or its after-swept body is completely converted into a water-soluble substance to be removed, and the remaining precipitate is washed and concentrated.
本发明的一种改性微化颗粒的制备方法，还包括：将提纯后的混合沉淀与表面改性剂混合/反应，得到改性微化颗粒。The method for preparing a modified micronized particle of the present invention further comprises: mixing/reacting the purified mixed precipitate with a surface modifier to obtain modified micronized particles.
本发明的一种改性微化颗粒的制备方法，水溶液中且反应母液冰点和沸点之间，可转化为水溶性物质的无机沉淀存在下，进行微化颗粒或微化颗粒前驱体的沉淀反应。The preparation method of a modified micronized particle of the invention is carried out in the presence of an inorganic precipitate which can be converted into a water-soluble substance in an aqueous solution and between the freezing point and the boiling point of the reaction mother liquid, and the precipitation reaction of the micronized particle or the micronized particle precursor is carried out. .
上述方法中，虽然，本发明所提及的沉淀反应是在水溶液中进行，但是并不排斥该水溶液中还含有其他液体成分，例如有机溶剂乙醇等。In the above method, although the precipitation reaction referred to in the present invention is carried out in an aqueous solution, the aqueous solution is not excluded from further containing other liquid components such as an organic solvent such as ethanol.
上述方法中，水溶液中进行的反应也可以理解为在反应母液不结冰和沸腾回流的状态之间进行的。理论上，纯水在冰点0℃以下是固体，在高于其沸点100℃以上是气体。但在无机盐等其他物质存在下，其冰点和沸点值的变动是客观存在的。特别是在增加反应压力下，反应母液冰点和沸点值的变动则更是显著的。一般化工技术人员对此都有着充分的理解。In the above method, the reaction carried out in the aqueous solution can also be understood to be carried out between the state in which the reaction mother liquid is not frozen and boiled under reflux. Theoretically, pure water is a solid below 0 ° C at the freezing point, and a gas above 100 ° C above its boiling point. However, in the presence of other substances such as inorganic salts, the fluctuations in freezing point and boiling point value exist objectively. Especially in the case of increasing the reaction pressure, the variation of the freezing point and the boiling point value of the reaction mother liquid is more remarkable. General chemical technicians have a good understanding of this.
上述方法中，通过共沉淀反应生成混合沉淀是一个具有时间概念的混合反应过程，它既包括微化颗粒或微化颗粒前驱体沉淀的反应过程，也包括合成可去除无机沉淀的反应过程，由于两者的反应速度不可能绝对完全一致，因此，势必存在一先一后不同步的问题。据此，共沉淀反应这一过程时间概念的判断应包括微化颗粒或微化颗粒前驱体沉淀成核、生长和熟化的整个过程。在这一过程的任何阶段引入先前所述可去除的无机沉淀反应都视为本专利的保护范围之内。总之，这种可去除的无机沉淀的引入客观上减小了微化颗粒粒径，这种结果的判定可以轻而易举的通过激光粒度分析仪等仪器实现。同理，无机沉淀存在下，进行微化颗粒或微化颗粒前驱体的沉淀反应，由于这种方式同样减小了微化颗粒粒径，因此这种实施方式也属于本专利的保护范围。In the above method, the mixed precipitation formed by the coprecipitation reaction is a time-consistent mixed reaction process, which includes both the reaction process of micronizing or micronizing the precipitation of the particle precursor, and the reaction process of synthesizing the inorganic precipitation, due to The speed of response between the two cannot be absolutely identical. Therefore, there is bound to be a problem of being unsynchronized one after the other. Accordingly, the judgment of the concept of the process time of the coprecipitation reaction should include the entire process of nucleation, growth and ripening of the micronized or micronized particle precursor. The introduction of previously removable inorganic precipitation reactions at any stage of the process is considered to be within the scope of this patent. In summary, the introduction of such a removable inorganic precipitate objectively reduces the particle size of the micronized particles, and the determination of such results can be easily achieved by instruments such as a laser particle size analyzer. Similarly, in the presence of inorganic precipitation, the precipitation reaction of the micronized particles or the micronized particle precursor is carried out. Since this method also reduces the particle size of the micronized particles, this embodiment is also within the protection scope of the patent.
本发明的方法中得到的无机沉淀的特点是可以方便的用我们常见的无机酸或有机酸转化为水溶性物质。利用无极沉淀在水溶液中对酸的稳定性比微化颗粒更差或者需要更高的PH值才能稳定的特点，从而实现与微化颗粒沉淀的分离。但是这种分离并不一定要求是必须的或彻底的。例如，众所周知，氢氧化铝常用于塑料制品中以提高其阻燃性能，基于此，碳酸钙和无机沉淀氢氧化铝就可以无须分离的分散或改性后共同添加到塑料制品中。The inorganic precipitate obtained in the process of the present invention is characterized in that it can be conveniently converted into a water-soluble substance by our usual inorganic or organic acid. Separation with micronized particle precipitation is achieved by using an electrodeless precipitate in which the stability of the acid in the aqueous solution is worse than that of the micronized particle or a higher pH is required to stabilize. But this separation does not necessarily require that it be necessary or thorough. For example, it is known that aluminum hydroxide is often used in plastic articles to improve its flame retardancy. Based on this, calcium carbonate and inorganic precipitated aluminum hydroxide can be added to a plastic article without being separately dispersed or modified.
上述的方法中，熟化处理是优选的。一般的，视反应条件不同，熟化时间的长短可根据熟化温度在0至24小时内选择。熟化后，对混合沉淀进行提纯处理的程度是弹性的，即用提纯剂不处理、部分处理或全部处理是可以选择的，这种弹性程度根据具体应用需求和无机沉淀的种类而选择。如果需要进行提纯处理，那么提纯处理和洗涤浓缩的先后顺序也是可以互换的，既可以先用提纯剂处理，然后再浓缩洗涤，也可以先浓缩洗涤再用提纯剂处理。各处理阶段中固液分离时可采用重力沉降，真空抽滤、离心过滤或离心沉降等方法，具体可采用重力沉降桶，过滤或沉降式三足离心机和板框压滤机等设备。Among the above methods, the aging treatment is preferred. Generally, depending on the reaction conditions, the length of the aging time can be selected within the range of 0 to 24 hours depending on the curing temperature. After the aging, the degree of purification of the mixed precipitate is elastic, that is, it is optional to use no treatment, partial treatment or total treatment with a purifying agent, and the degree of elasticity is selected according to the specific application requirements and the type of inorganic precipitation. If purification treatment is required, the order of purification treatment and washing concentration can also be interchanged, either by first treating with a purifying agent, then by concentration, or by concentrating and then treating with a purifying agent. Gravity sedimentation, vacuum suction filtration, centrifugal filtration or centrifugal sedimentation may be adopted in the solid-liquid separation in each treatment stage, and specifically, a gravity sedimentation tank, a filtration or sedimentation three-leg centrifuge and a plate and frame filter press may be employed.
上述方法中，微化颗粒前驱体或无机沉淀后驱体是制备微化颗粒中一种通用技术的称谓，例如，在以硫酸铜和氯化镁的共沉淀反应制取铜单质中，先前阶段生成的氧化铜就是最终所制备微化铜单质的前驱体。再如，在以氯化钙生成氢氧化钙为分散剂制取氧化物的共沉淀反应中，经加热脱水后，所生成的氧化钙就是先前共沉淀氢氧化钙的后驱体。这一点可以在现有技术条件下得到充分理解。In the above method, the micronized particle precursor or the inorganic precipitated precursor is a generalized technique for preparing the micronized particles, for example, in the preparation of copper simple substance by coprecipitation reaction of copper sulfate and magnesium chloride, which is formed in the previous stage. Copper oxide is the precursor of the final prepared pure copper element. For example, in a coprecipitation reaction in which an oxide is prepared by using calcium chloride to form calcium hydroxide as a dispersing agent, the formed calcium oxide is a precursor of the previously coprecipitated calcium hydroxide after dehydration by heating. This can be fully understood under the conditions of the prior art.
上述方法中，这种无机沉淀的阴离子部分更进一步的选择为氢氧根离子、氧离子、硫（氢）离子、亚硫酸（氢）根离子、磷酸（氢）根离子或碳酸（氢）根离子，以及它们的混合物。这种阴离子的提供体可以是直接形式的盐，例如，碳酸钠等，也可以是气体方式，例如，氨气溶于水形成氢氧根，二氧化碳溶于水与氢氧化钠形成碳酸钠等。此外，诸如碱式碳酸盐等阴离子可以作为碳酸根和氢氧根的混合物来理解，也被视为本专利的保护范围之内。In the above method, the anion portion of the inorganic precipitate is further selected as a hydroxide ion, an oxygen ion, a sulfur (hydrogen) ion, a sulfuric acid (hydrogen) ion, a phosphoric acid (hydrogen) ion or a hydrogen (hydrogen) root. Ions, and mixtures thereof. The anion donor may be a salt of a direct form, for example, sodium carbonate or the like, or may be a gas method. For example, ammonia gas is dissolved in water to form hydroxide, carbon dioxide is dissolved in water and sodium hydroxide to form sodium carbonate, and the like. Furthermore, anions such as basic carbonates can be understood as a mixture of carbonates and hydroxides and are considered to be within the scope of this patent.
采用本发明的方法制得的改性微化颗粒的二次粒径的体积粒径平均值d50小于10微米，再优选为小于1000纳米，更优选为小于100纳米，最优选为小于10纳米。具体粒径的判定可以通过激光粒度分析仪器和电子扫描电镜（SEM）等进行。The volume average particle diameter d50 of the secondary particle diameter of the modified micronized particles obtained by the method of the present invention is less than 10 μm, more preferably less than 1000 nm, more preferably less than 100 nm, and most preferably less than 10 nm. The determination of the specific particle diameter can be carried out by a laser particle size analyzer, an electron scanning electron microscope (SEM) or the like.
本发明的共沉淀反应可以在常规搅拌条件下进行，例如，在化工生产中常用的搪瓷反应釜中进行。更优选在高速搅拌/混合/剪切/摩擦条件下进行，例如，在GFJ型分散机（山东莱州市胜龙化工机械厂）高速搅拌下进行共沉淀反应。最优选在超重力条件下进行，例如，在基于超重力原理的超重力反应装置中进行，它们的具体形式可以参见化学工业出版社《超重力技术及应用》一书。The coprecipitation reaction of the present invention can be carried out under conventional stirring conditions, for example, in an enamel reactor commonly used in chemical production. More preferably, it is carried out under high-speed stirring/mixing/shearing/friction conditions, for example, a coprecipitation reaction is carried out under high-speed stirring in a GFJ type disperser (Shandong Laizhou Shenglong Chemical Machinery Factory). Most preferably, it is carried out under supergravity conditions, for example, in a supergravity reaction apparatus based on the principle of supergravity, and their specific form can be found in the book "Supergravity Technology and Applications" by the Chemical Industry Press.
在本发明中，沉淀反应前、中和/或后，还可以加入表面活性物质，并且这种加入不影响混合沉淀与母液的分离和废水的处理。优选的表面活性物质进一步的选择为阴离子化的烷基或芳基有机物包括烷基或芳基硫酸酯、磺酸、磷酸酯或羧酸及其盐类，以及它们的混合物。其添加量为微化颗粒或微化颗粒前驱体沉淀重量的0.05%—100%，次优选为0.05%—40%，最优选为0.1%—10%。相同其他条件下，这种加入所产生的物理的和/或化学的吸附，有助于微化颗粒或微化颗粒前驱体的沉淀粒径的进一步微化、改善无机微粒的亲油性能以及颗粒形貌的可控性改变等。但是，这种加入不能影响混合沉淀与母液的分离和废水的处理：即在既定配方下，将混合沉淀从母液分离后母液的浊度不能增加，废水中所含未被微化颗粒所吸附的表面活性物质不能够加大废水处理难度，这在现有技术水平下可以轻而易举的进行判定。它们包括，例如，亚油酸、油酸、硬脂酸、硬脂醇醚硫酸钠、琥珀酸二辛酯磺酸盐、（双）丁基萘磺酸盐、（异）硬脂酸乳酸盐、聚合的烷基萘磺酸盐、十二烷基苯磷酸酯盐、聚羧酸盐、重环烷酸盐等阴离子化的烷基或芳基有机物。当然，这种表面活性物质还可以包括多聚磷酸钠、次磷酸钠等无机阴离子化合物；它们还可以包括乙醇、十二烷基甜菜碱、十八烷基铵盐、脂肪醇聚氧乙烯醚等其他类型的表面活性物质，还可以包括聚乙烯醇、聚丙烯酰胺、聚乙烯吡咯烷酮等有机高分子化合物，等等。它们既可以单一使用也可以混合使用。它们的具体形式可以参见中国化学工业出版社《表面活性剂应用原理》一书。In the present invention, a surface active material may also be added before, during and/or after the precipitation reaction, and such addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater. Preferred surface active materials are further selected as anionic alkyl or aryl organics including alkyl or aryl sulfates, sulfonic acids, phosphates or carboxylic acids and salts thereof, and mixtures thereof. It is added in an amount of from 0.05% to 100%, more preferably from 0.05% to 40%, most preferably from 0.1% to 10%, based on the weight of the precipitate of the micronized or micronized particle precursor. Under the same other conditions, the physical and/or chemical adsorption produced by such addition contributes to the further miniaturization of the precipitated particle size of the micronized or micronized particle precursor, the improvement of the lipophilic properties of the inorganic particles and the particles. The controllability of the morphology changes. However, this addition does not affect the separation of the mixed precipitate from the mother liquor and the treatment of the wastewater: that is, under the established formulation, the turbidity of the mother liquor cannot be increased after the mixed precipitate is separated from the mother liquor, and the wastewater contains no adsorbed particles. Surfactants do not increase the difficulty of wastewater treatment, which can be easily determined at the state of the art. These include, for example, linoleic acid, oleic acid, stearic acid, sodium stearyl ether ether, dioctyl sulfosuccinate, (di)butylnaphthalene sulfonate, (iso)stearic acid lactic acid An anionic alkyl or aryl organic compound such as a salt, a polymerized alkylnaphthalenesulfonate, a dodecylbenzene phosphate, a polycarboxylate or a heavy naphthenate. Of course, the surface active material may further include inorganic anionic compounds such as sodium polyphosphate and sodium hypophosphite; they may also include ethanol, lauryl betaine, octadecyl ammonium salt, fatty alcohol polyoxyethylene ether, and the like. Other types of surface active materials may also include organic polymer compounds such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, and the like. They can be used either singly or in combination. Their specific forms can be found in the book "The Principles of Surfactant Applications" by China Chemical Industry Press.
本发明的方法中，任选的表面改性剂包括能够和微化颗粒表面形成吸附的化合物，包括阴离子化合物、阳离子化合物、非离子表面活性剂、有机溶剂、偶联剂和被添加到的母体材料，以及它们的组合物。In the method of the present invention, the optional surface modifier comprises a compound capable of forming an adsorption with the surface of the micronized particle, including an anionic compound, a cationic compound, a nonionic surfactant, an organic solvent, a coupling agent, and a parent to which it is added. Materials, and combinations thereof.
经过先前的处理后，微化颗粒间仅以微弱的物理粘连方式存在（也俗称为软团聚），再通过与表面改性剂的混合/反应,就可以转化为合乎改性要求的单分散微化颗粒，然后方便的添加到到母体材料中去。After the previous treatment, the micro-particles exist only in a weak physical adhesion (also known as soft agglomeration), and then through the mixing/reaction with the surface modifier, they can be converted into monodisperse micros which meet the requirements of modification. The particles are then conveniently added to the parent material.
在后期表面改性时，本方法具有的优点显而易见。例如，本方法制取的纳米碳酸钙毋须其他复杂处理，可以直接解团聚分散于含有甲醛缩萘磺酸盐分散剂MIGHTY150的水溶液中，可以直接解团聚分散于含有油酸的液体石蜡中，可以直接解团聚分散于含有油酸和渗透剂JFC的水溶液中，可以直接解团聚分散于含有阴离子有机染料荧光黄和非离子表面活性剂渗透剂JFC的水溶液中，可以直接解团聚分散于带有3%丙烯酸基团的通用纯丙乳液中等等。总之，本方法制备的微化碳酸钙为其后期应用预留了丰富多彩的改性空间。The advantages of this method are obvious when the surface is modified in the later stage. For example, the nanometer calcium carbonate prepared by the method needs other complicated treatment, and can be directly agglomerated and dispersed in an aqueous solution containing the formaldehyde phthalate sulfonate dispersant MIGHTY150, and can be directly agglomerated and dispersed in liquid paraffin containing oleic acid. Direct deagglomeration is dispersed in an aqueous solution containing oleic acid and penetrant JFC, and can be directly deagglomerated and dispersed in an aqueous solution containing anionic organic dye fluorescent yellow and nonionic surfactant penetrant JFC, which can be directly deagglomerated and dispersed in 3% acrylic acid. The group's general purpose acrylic emulsion and so on. In summary, the micro-calcium carbonate prepared by the method reserves a variety of modification space for its later application.
因此，针对不同的应用目的，改性剂的选择十分丰富，他们包括：Therefore, the choice of modifiers is very rich for different application purposes, they include:
1、阴离子化合物，分为阴离子无机物和阴离子有机物，一般来说，这些阴离子化合物可以和微化颗粒表面裸露的金属离子形成离子键型为主的化学吸附，更详细的包括：1. Anionic compounds, which are classified into anionic inorganic substances and anionic organic substances. Generally, these anionic compounds can form an ionic bond-based chemical adsorption with the exposed metal ions on the surface of the micronized particles, and more specifically include:
A、阴离子无机物，例如氟离子、硅酸根、磷酸根等等。A, an anionic inorganic substance such as fluoride ion, silicate, phosphate, and the like.
B、阴离子有机物，包括：B. Anionic organic matter, including:
B1、带有磺酸基、磷酸基或羧基的阴离子基团的表面活性剂/分散剂，例如聚羧酸盐分散剂、硬脂酸、油酸、聚合的萘磺酸盐分散剂等。它们的具体形式可以参见中国化学工业出版社《表面活性剂应用原理》一书。B1. A surfactant/dispersant having an anionic group of a sulfonic acid group, a phosphoric acid group or a carboxyl group, for example, a polycarboxylate dispersing agent, stearic acid, oleic acid, a polymeric naphthalenesulfonate dispersing agent, and the like. Their specific forms can be found in the book "The Principles of Surfactant Applications" by China Chemical Industry Press.
B2、螯合剂，包括三聚磷酸钠、多聚磷酸钠、EDTA-2Na、马来酸、柠檬酸、吡啶硫酮钠、草酸、三乙醇胺等。B2, a chelating agent, including sodium tripolyphosphate, sodium polyphosphate, EDTA-2Na, maleic acid, citric acid, sodium pyrithione, oxalic acid, triethanolamine, and the like.
B3、带有阴离子片段的树脂溶液或树脂乳液，这种阴离子树脂的部分链段带有羧基或磺酸基，并且其在整个高聚物中所占比例在0.1%和99.9%之间。这种高聚物可以是水溶的，也可以是水分散的或油溶的。例如羧甲基淀粉钠、聚苯乙烯磺酸钠、苯丙树脂溶液或乳液，硅丙树脂溶液或乳液、羧基硅油溶液或乳液等。B3. A resin solution or resin emulsion with an anionic fragment having a carboxyl group or a sulfonic acid group in a partial segment and having a proportion of 0.1% and 99.9% in the entire polymer. Such high polymers may be water soluble or water soluble or oil soluble. For example, sodium carboxymethyl starch, sodium polystyrene sulfonate, styrene-acrylic resin solution or emulsion, silicone-acrylic resin solution or emulsion, carboxyl silicone oil solution or emulsion, and the like.
2、阳离子化合物，分为阳离子无机物和阳离子有机物：2. Cationic compounds, which are classified into cationic inorganic substances and cationic organic substances:
A、阳离子无机物，包括钡离子，镁离子、钙离子、铝离子等，例如，在用阴离子型染料或色素改性本方法的微化碳酸钙时，上述离子的加入可以提高阴离子型染料或色素的吸附稳定性。再如，在用羧甲基纤维素钠改性本方法的微化碳酸钙时，上述离子的加入可以提高羧甲基纤维素钠的吸附稳定性。A, cationic inorganic substances, including strontium ions, magnesium ions, calcium ions, aluminum ions, etc., for example, when the micro-calcium carbonate of the method is modified with an anionic dye or a pigment, the addition of the above ions can enhance the anionic dye or Adsorption stability of the pigment. For example, when the calcium carbonate of the present method is modified with sodium carboxymethylcellulose, the addition of the above ions can improve the adsorption stability of sodium carboxymethylcellulose.
B、阳离子有机物，包括烷基氯化铵、芳基氯化铵、聚乙烯亚胺、阳离子瓜尔胶等。它们的具体形式可以参见中国化学工业出版社《表面活性剂应用原理》一书。B, cationic organic matter, including alkyl ammonium chloride, aryl ammonium chloride, polyethylene imine, cationic guar gum and the like. Their specific forms can be found in the book "The Principles of Surfactant Applications" by China Chemical Industry Press.
3、非离子表面活性剂，包括烷基聚乙二醇醚、芳基聚乙二醇醚、聚乙二醇-聚丙二醇醚、聚乙烯醇、聚乙烯吡咯烷酮、聚乙烯蜡乳液等。它们的具体形式可以参见中国化学工业出版社《表面活性剂应用原理》一书。3. Nonionic surfactants, including alkyl polyglycol ethers, aryl polyglycol ethers, polyethylene glycol-polypropylene glycol ethers, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene wax emulsions, and the like. Their specific forms can be found in the book "The Principles of Surfactant Applications" by China Chemical Industry Press.
4、水不溶有机液体，包括25℃下每100克水中最多可以溶解0.1克的所有有机液体，它们可以是单一成分也可以是混合成分。以本专利技术制备的微化颗粒为载体来承载水难溶液体药物，并将其纳米化是本专利的一种应用实例。适用这种用途的载体包括本专利所列举的所有微化颗粒。4. Water-insoluble organic liquid, including all organic liquids which can dissolve up to 0.1 gram per 100 gram of water at 25 ° C, which may be a single component or a mixed component. The use of the micronized particles prepared by the patent technology as a carrier to carry the water-difficult solution drug and to nanonize it is an application example of the patent. Carriers suitable for this purpose include all of the micronized particles listed in this patent.
5、偶联剂包括硅烷偶联剂，例如，乙烯基三氯硅烷(A—150）、乙烯基三乙氧基硅烷(A—151)、乙烯基三甲氧基硅烷（A—171)、γ—(2，3—环氧丙氧基)丙基三甲氧基硅烷(A—187，KH—560)等；钛酸酯偶联剂，例如，异丙基三(焦磷酸二辛酯)钛酸酯(KR-38S）、异丙基三(异硬脂酰基)钛酸酯(KR—TTS)、异丙基三（十二烷基苯磺酰基）钛酸酯（KR-9S）、异丙基三(正乙氨基—乙氨基)钛酸酯(KB—44)等；铝酸酯偶联剂等等。5. The coupling agent includes a silane coupling agent such as vinyltrichlorosilane (A-150), vinyltriethoxysilane (A-151), vinyltrimethoxysilane (A-171), γ. —(2,3-epoxypropoxy)propyltrimethoxysilane (A-187, KH-560), etc.; titanate coupling agent, for example, isopropyl tris(dioctyl pyrophosphate) titanium Acid ester (KR-38S), isopropyl tris(isostearyl) titanate (KR-TTS), isopropyl tris(dodecylbenzenesulfonyl) titanate (KR-9S), different Propyl tris(n-ethylamino-ethylamino) titanate (KB-44), etc.; aluminate coupling agent and the like.
6、直接添加到母体材料中去。这种母体材料包括塑料、橡胶、纤维、涂料、油墨、金属、陶瓷等等。例如，本方法制取的碳酸钙可以直接添加到带有3%丙烯酸基团的通用纯丙乳液中。6. Add directly to the parent material. Such parent materials include plastics, rubber, fibers, coatings, inks, metals, ceramics, and the like. For example, the calcium carbonate produced by the process can be added directly to a universal pure acrylic emulsion with 3% acrylic groups.
需要说明的是，上述表面改性剂可以单一使用，也可以两种或两种以上混合使用。有些情况下，改性过程中或改性后的加热、煅烧或干燥等处理手段也是必不可少的。这些都可以在已有的知识条件下得到熟练应用。In addition, the surface modifier may be used singly or in combination of two or more. In some cases, treatments such as heating, calcination or drying during or after the modification are also essential. These can be applied skillfully under the existing knowledge conditions.
一般的，本发明的改性或分散在任选的常规设备条件下就可以完成，例如，乳化机、分散机、立卧式砂磨机、搅拌混合釜等。当然，其他更精细的分散、研磨或改性手段也是可以选用的。In general, the modification or dispersion of the present invention can be accomplished under optional conventional equipment conditions, for example, an emulsifying machine, a dispersing machine, a vertical horizontal sand mill, a stirred mixing kettle, and the like. Of course, other finer dispersion, grinding or modification means are also available.
本发明所涉及的改性微化颗粒是难溶于水的且不和水发生化学反应的无机物和有机物。这里，难溶于水或者说不溶于水是一个通用量化的化学概念，我们一般把25℃下每100克水中溶解质量低于0.01克物质称为难溶于水的物质。包括单质、氢氧化物、氧化物、无机盐、其他无机物、金属有机盐和有机物。本发明旨在通过适合的引入无机沉淀来解决上述物质的微细化和表面改性方面的问题，其特点是形成了上述物质和无机沉淀的混合沉淀。形成这种混合沉淀的过程可以是物理的，也可以是化学的，亦或是两者混合的。例如，将溶于乙醇的碘分散到磷酸钙沉淀液中，就是物理的沉淀反应过程。再如，熔融有机物分散到无机沉淀液中形成微化有机物颗粒的过程也是物理的沉淀反应过程。而合成部分单质以及氧化物、氢氧化物、无机盐、其他无机盐、部分有机金属盐和部分有机物的改性微化颗粒则是化学的沉淀反应过程，对比这一反应过程前后，其明显特征是改性微化颗粒都是在沉淀反应后才形成的具有新分子结构的物质。对于既可以选择化学法也可以选择物理法进行沉淀反应的，可由实施者根据具体条件灵活选用。这些知识都是一般化工技术人员所公知的。The modified micronized particles according to the present invention are inorganic substances and organic substances which are hardly soluble in water and do not chemically react with water. Here, poorly soluble in water or insoluble in water is a general quantitative chemical concept. We generally refer to a substance that dissolves less than 0.01 gram per 100 grams of water at 25 ° C as a substance that is poorly soluble in water. It includes simple substances, hydroxides, oxides, inorganic salts, other inorganic substances, metal organic salts and organic substances. The present invention is intended to solve the problems of miniaturization and surface modification of the above substances by suitable introduction of inorganic precipitation, and is characterized in that a mixed precipitate of the above substances and inorganic precipitates is formed. The process of forming such a mixed precipitate may be physical, chemical, or a mixture of the two. For example, dispersing iodine dissolved in ethanol into a calcium phosphate precipitate is a physical precipitation reaction process. As another example, the process in which the molten organic matter is dispersed into the inorganic precipitation liquid to form the micronized organic particles is also a physical precipitation reaction process. The synthetic micro-organisms and the modified micro-particles of oxides, hydroxides, inorganic salts, other inorganic salts, some organic metal salts and some organic substances are chemical precipitation processes, and the obvious characteristics before and after the reaction process are compared. It is a substance having a new molecular structure which is formed after the precipitation reaction of the modified micronized particles. For the precipitation reaction which can be selected either by chemical method or physical method, it can be flexibly selected by the implementer according to specific conditions. This knowledge is well known to the average chemical technician.
本发明所涉及的单质、氢氧化物、氧化物、无机盐、其他无机物、金属有机盐和有机物的改性微化颗粒的制备技术都是已知的，而且它们的制备方法往往是多种多样的。这种制备方法的多种多样不仅体现在原材料的选择上，例如，硫酸铝和氢氧化钠反应可以合成氢氧化铝，硫酸铝和硫化钠反应也可以合成氢氧化铝，而且也体现在制备工艺条件的改变上。例如，α-氧化铝（也称刚玉）可以在1200℃下煅烧氢氧化铝获得，也可以在高压高碱性的条件下采用水热法合成。运用这些已知的合成方法和采用本专利技术并不矛盾，采用本专利技术，通过共沉淀反应，可以对已知合成方法所合成的颗粒起到微化和表面改性方面的改进。The preparation techniques of modified micronized particles of simple substances, hydroxides, oxides, inorganic salts, other inorganic substances, metal organic salts and organic substances according to the present invention are known, and their preparation methods are often various. Diverse. The variety of preparation methods is not only reflected in the selection of raw materials, for example, aluminum sulfate and sodium hydroxide can react to synthesize aluminum hydroxide, aluminum sulfate and sodium sulfide can also be synthesized into aluminum hydroxide, and also in the preparation process. Change in conditions. For example, α-alumina (also known as corundum) can be obtained by calcining aluminum hydroxide at 1200 ° C or hydrothermally synthesized under high pressure and high basicity. The use of these known synthetic methods and the use of the patented technology are not contradictory. By using the patented technology, the particles synthesized by the known synthetic methods can be improved in microfabrication and surface modification by coprecipitation reaction.
基于上述事实，以下进一步说明的实施方式并不是唯一的选择，因为选择最优实施技术方案需要取决于所得到微化颗粒的纯度或成本等多方面因素的综合考虑。Based on the above facts, the embodiments described further below are not the only ones, since the selection of the optimal implementation technique requires a comprehensive consideration depending on various factors such as the purity or cost of the obtained micronized particles.
制备锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡和铅单质的微化颗粒，可以选择用氢气还原其相应氧化物和氧化钙的混合物的方式得到；制备铜、锝、钋、银、铑、钯、铂、金和碲的微化颗粒，可以选择在水溶液中利用水合肼类还原剂还原其相应氧化物的方式得到；制备银、铑、钯、铂和金的微化颗粒，还可以选择加热其相应氧化物和碳酸钙的混合物的方式得到；制备碳单质的微化颗粒可以选择 通过密闭不完全燃烧硬脂酸钙和碳酸钙混合沉淀的方式得到；制备硅、钨、硼单质的微化颗粒，可以选择将它们相应水合氧化物与硫酸钡的混合沉淀用金属镁粉等还原的方式得到；制备硒、硫和碘单质微化的颗粒，可以选择它们的有机溶液以物理沉淀的反应方式得到。Preparing micronized particles of zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin and lead, which can be selected by hydrogen reduction of a mixture of the corresponding oxide and calcium oxide; preparation of copper , micronized particles of ruthenium, osmium, silver, iridium, palladium, platinum, gold and ruthenium, which can be selected by reducing the corresponding oxides in aqueous solution by using a hydrazine hydrazine reducing agent; preparing silver, ruthenium, palladium, platinum and Gold micronized particles can also be selected by heating a mixture of their corresponding oxides and calcium carbonate; micronized particles for preparing carbon simple substances can be selected. It is obtained by mixing and incompletely burning calcium stearate and calcium carbonate, and preparing micronized particles of silicon, tungsten and boron. The mixed precipitation of their corresponding hydrated oxides and barium sulfate can be reduced by metal magnesium powder. The method of obtaining selenium, sulfur and iodine elemental micronized particles can be selected from the organic solution by physical precipitation.
制备氢氧化物微化颗粒可以选择其相应的水溶性金属盐和水溶性碱反应来制取。代表性的水溶性碱包括氢氧化钠、氢氧化钾、氨水、氨气。对于能够双水解的氢氧化物来说，例如氢氧化铝，碳酸钠、碳酸铵、碳酸氢钠、硫化钠也是可以选择的。这些氢氧化物包括氢氧化锕、氢氧化钯(II、 IV)、氢氧化铋、氢氧化铂、 氢氧化铒 、氢氧化钆、 氢氧化镉、氢氧化铪(III 、IV) 、氢氧化钬、 氢氧化镓、氢氧化镥 、氢氧化铝、氢氧化镁、氢氧化锰、氢氧化铅（II、 IV）、氢氧化铈(III 、IV)、氢氧化铁、氢氧化亚铁、氢氧化亚铜、氢氧化铜、氢氧化铟、氢氧化铕、氢氧化铍、氢氧化锌、氢氧化镍、氢氧化锡、氢氧化镧、氢氧化钕、氢氧化镨、氢氧化钐、氢氧化铽、氢氧化钇、氢氧化镝、氢氧化铥、氢氧化镱、氢氧化钪、氢氧化钚、氢氧化钍、氢氧化镎、氢氧化铀、氢氧化钛、氢氧化锆、氢氧化钒（II 、III、 IV）、氢氧化铌、氢氧化钽、氢氧化铬、氢氧化钴和氢氧化钼（III、 IV、V）。符合本专利技术要求，与以上这些氢氧化物进行共沉淀反应的一种通用选择为氢氧化钙（无机沉淀）。The preparation of hydroxide micronized particles can be carried out by reacting their corresponding water-soluble metal salts with water-soluble bases. Representative water soluble bases include sodium hydroxide, potassium hydroxide, aqueous ammonia, and ammonia. For hydroxides capable of double hydrolysis, for example, aluminum hydroxide, sodium carbonate, ammonium carbonate, sodium hydrogencarbonate, sodium sulfide are also optional. These hydroxides include barium hydroxide and palladium hydroxide (II, IV), barium hydroxide, platinum hydroxide, barium hydroxide, barium hydroxide, cadmium hydroxide, barium hydroxide (III, IV), barium hydroxide, gallium hydroxide, barium hydroxide , aluminum hydroxide, magnesium hydroxide, manganese hydroxide, lead hydroxide (II, IV), barium hydroxide (III , IV), iron hydroxide, ferrous hydroxide, cuprous hydroxide, copper hydroxide, indium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, Barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, hydroxide Uranium, titanium hydroxide, zirconium hydroxide, vanadium hydroxide (II , III, IV), barium hydroxide, barium hydroxide, chromium hydroxide, cobalt hydroxide and molybdenum hydroxide (III, IV, V). A general choice for coprecipitation with these hydroxides in accordance with the teachings of this patent is calcium hydroxide (inorganic precipitation).
制备金属氧化物微化颗粒可以选择其相应的氢氧化物和氢氧化钙（无机沉淀）的混合沉淀通过水热法分解来制得，它们包括氧化锕、氧化钯(II、 IV)、氧化铋、氧化铂、 氧化铒 、氧化钆、 氧化镉、氧化铪(III 、IV) 、氧化钬、 氧化镓、氧化镥 、氧化铝、氧化镁、氧化锰、氧化铅（II、 IV）、氧化铈(III 、IV)、氧化铁、氧化亚铁、氧化亚铜、氧化铜、氧化铟、氧化铕、氧化铍、氧化锌、氧化镍、氧化锡、氧化镧、氧化钕、氧化镨、氧化钐、氧化铽、氧化钇、氧化镝、氧化铥、氧化镱、氧化钪、氧化钚、氧化钍、氧化镎、氧化铀、氧化钛、氧化锆、氧化钒（II 、III、 IV）、氧化铌、氧化钽、氧化铬、氧化钴、氧化钼（III、 IV、V）、氧化银、氧化锝、氧化钋、氧化铑、氧化钯、氧化铂、氧化金。由于上述金属活动性的强弱千差万别，因此制备条件区别也很大。例如，对于氧化金来说，毋须加热就可直接得到。此外，选用煅烧法也是可以选择的。一般是将先前方法制得的相应氢氧化物清洗浓缩后，再分散于沸点高于水的醇溶剂中，特别是多羟基醇，例如1，2-丙二醇。然后加热蒸干即可。The metal oxide micronized particles can be prepared by hydrothermal decomposition of a mixed precipitate of the corresponding hydroxide and calcium hydroxide (inorganic precipitate), which includes cerium oxide and palladium oxide (II, IV), cerium oxide, platinum oxide, cerium oxide, cerium oxide, cadmium oxide, cerium oxide (III, IV), cerium oxide, gallium oxide, cerium oxide, aluminum oxide, magnesium oxide, manganese oxide, lead oxide (II, IV), yttrium oxide (III , IV), iron oxide, ferrous oxide, cuprous oxide, copper oxide, indium oxide, antimony oxide, antimony oxide, zinc oxide, nickel oxide, tin oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, uranium oxide, titanium oxide, zirconium oxide, vanadium oxide (II) , III, IV), cerium oxide, cerium oxide, chromium oxide, cobalt oxide, molybdenum oxide (III, IV, V), silver oxide, cerium oxide, cerium oxide, cerium oxide, palladium oxide, platinum oxide, gold oxide. Since the strength of the above metal activities varies widely, the preparation conditions are also very different. For example, for gold oxide, it can be obtained directly without heating. In addition, the choice of calcination method is also optional. Typically, the corresponding hydroxide prepared by the prior method is washed and concentrated, and then dispersed in an alcohol solvent having a boiling point higher than water, particularly a polyhydric alcohol such as 1,2-propanediol. Then heat and evaporate.
制备非金属氧化物氧化硅、氧化钨、氧化硼、氧化碲、氧化硒的微化颗粒，可以选择先合成其相应的酸根钙盐（也通常表达为氧化钙、非金属氧化物和水的复合物）和碳酸钙的混合沉淀，然后再加热脱水，酸除碳酸钙等即可得到。Preparation of non-metal oxide silicon oxide, tungsten oxide, boron oxide, cerium oxide, oxidized selenium micro-particles, you can choose to synthesize its corresponding acid-calcium salt (also commonly expressed as a combination of calcium oxide, non-metal oxides and water) The mixture is precipitated with calcium carbonate, and then heated and dehydrated, and the acid is removed by removing calcium carbonate or the like.
制备无机盐微化颗粒可以选择相应的水溶性金属盐与相应的水溶性酸根和氢氧根/碳酸根的混合物通过共沉淀反应来制取。此外，以相应金属离子的不溶性氢氧化物或碳酸物和相应酸根的酸来反应制取也是一种选择。它们包括砷酸钡、碳酸钡、铬酸钡、亚铁氰化钡、氟硅酸钡、磷酸氢钡、氟化钡、/碘酸钡、硫酸钡、钼酸钡、高锰酸钡、焦磷酸钡、硒酸钡、砷酸铋、碘化铋、磷酸铋、硫化铋、溴化铂(IV) 、氟化钚(III) 、氟化钚(IV) 、碘酸钚(IV)、 砷酸钙、氟化钙、磷酸氢钙、钼酸钙、磷酸钙、钨酸钙、砷酸镉、碳酸镉、氰化镉、亚铁氰化镉、碘酸镉、磷酸镉、硫化镉、钨酸镉、叠氮化亚汞、溴化亚汞、碳酸亚汞、氯化亚汞、铬酸亚汞、氰化亚汞、硫酸亚汞、碘酸汞、碘化汞、硫化汞、硫氰酸汞、四苯硼钾、三碘化金、碘酸镧、钼酸镧、磷酸锂、氟化镁、磷酸镁、亚硒酸镁、碳酸锰、亚铁氰化锰、碳酸镍、碘酸镍、焦磷酸镍、硫化钋(II) 、钼酸镨(III) 、叠氮化铅、碳酸铅、氯酸铅、铬酸铅、亚铁氰化铅、氟化铅、磷酸氢铅、亚磷酸氢铅、碘酸铅、碘化铅、钼酸铅、硒酸铅、硫酸铅、硫化铅、硫代硫酸铅、钨酸铅、磷酸铈(III) 、铬酸锶硫酸锶、溴化亚铊、碘酸亚铊、碘化亚铊、碳酸亚铁、氢氧化亚铁、砷酸铁、氟化铁、氯化亚铜、氰化亚铜、碘化亚铜、硫化亚铜、硫氰酸亚铜、碳酸铜、铬酸铜、氟化铜、亚硒酸铜、硫化铜、碘酸钍(IV) 、碳酸锌、氰化锌、碘酸锌、氟化钇、碘酸铟、硫化铟、叠氮化银、溴化银、碳酸银、氯化银、铬酸银、氰化银、钒酸银、碳酸铍、亚硫酸钡、亚硫酸锶、亚硫酸钙、亚硫酸铍、亚硫酸锰、亚硫酸锌、亚硫酸镉、亚硫酸亚铁、亚硫酸镍、亚硫酸铅、亚硫酸铜、亚硫酸汞、亚硫酸银、硫化锶、硫化锰、硫化锌、硫化亚铁、硫化镉、硫化镍、硫化锡、硫化铅、硫化铜、硫化汞、硫化银、硅酸钡、硅酸钙、硅酸镁、硅酸铝、硅酸铍、硅酸锰、硅酸锌、硅酸铬、硅酸亚铁、硅酸铁、硅酸镉、硅酸镍、硅酸铅、硅酸铜、硅酸银、磷酸锂、磷酸钡、磷酸锶、磷酸钙、磷酸镁、磷酸铝、磷酸铍、磷酸锰、磷酸锌、磷酸铬、磷酸亚铁、磷酸铁、磷酸镉、、磷酸铊、磷酸镍、磷酸锡、磷酸铅、磷酸铜、磷酸汞、磷酸银、2-巯基吡啶硫酮铜、草酸镉、草酸银、草酸亚铁、酒石酸锌、草酸锌、草酸铅、酒石酸铅、草酸钡、草酸钙、草酸汞、草酸钪和草酸锰。The preparation of the inorganic salt micronized particles can be carried out by coprecipitation reaction by selecting a corresponding water-soluble metal salt and a corresponding mixture of water-soluble acid groups and hydroxides/carbonates. In addition, it is also an option to react with an insoluble hydroxide or carbonate of the corresponding metal ion and an acid of the corresponding acid. They include barium arsenate, barium carbonate, barium strontium strontium, barium strontium cyanide, barium fluorosilicate, barium hydrogen phosphate, barium fluoride, barium iodate, barium sulfate, barium molybdate, barium permanganate, coke Barium phosphate, barium selenate, barium arsenate, barium iodide, barium phosphate, barium sulfide, platinum bromide (IV) , cerium (III) fluoride, cerium (IV) fluoride, cerium (IV) iodate, Calcium arsenate, calcium fluoride, calcium hydrogen phosphate, calcium molybdate, calcium phosphate, calcium tungstate, cadmium arsenate, cadmium carbonate, cadmium cyanide, cadmium ferrocyanide, cadmium iodate, cadmium phosphate, cadmium sulfide, Cadmium Tungstate, Mercury Azide, Mercury Bromide, Mercury Carbonate, Mercury Chloride, Mercury Chromate, Mercury Cyanide, Mercury Sulfate, Mercury Iodide, Mercury Iodide, Mercury Sulfide, Sulfur Mercury cyanate, potassium tetraphenylborate, gold triiodide, barium iodate, barium bismuth citrate, lithium phosphate, magnesium fluoride, magnesium phosphate, magnesium selenite, manganese carbonate, manganese ferrocyanide, nickel carbonate, iodine Nickel acid, nickel pyrophosphate, antimony sulfide (II) , bismuth molybdate (III) , lead azide, lead carbonate, lead chlorate, lead chromate, lead ferrocyanide, lead fluoride, lead hydrogen phosphate, lead hydrogen phosphite, lead iodate, lead iodide, lead molybdate, selenate Lead, lead sulfate, lead sulfide, lead thiosulfate, lead tungstate, barium phosphate (III) , barium strontium sulphate, barium bromide, hydrazine hydrazide, hydrazine iodide, ferrous carbonate, ferrous hydroxide, iron arsenate, iron fluoride, cuprous chloride, cuprous cyanide, iodine Cuprous, cuprous sulfide, cuprous thiocyanate, copper carbonate, copper chromate, copper fluoride, copper selenite, copper sulfide, barium iodate (IV) , zinc carbonate, zinc cyanide, zinc iodate, barium fluoride, indium iodate, indium sulfide, silver azide, silver bromide, silver carbonate, silver chloride, silver chromate, silver cyanide, silver vanadate , barium carbonate, barium sulfite, barium sulfite, barium sulfite, barium sulfite, manganese sulfite, zinc sulfite, cadmium sulfite, ferrous sulfite, nickel sulfite, lead sulfite, copper sulfite, Mercuric sulfate, silver sulfite, barium sulfide, manganese sulfide, zinc sulfide, ferrous sulfide, cadmium sulfide, nickel sulfide, tin sulfide, lead sulfide, copper sulfide, mercury sulfide, silver sulfide, barium silicate, calcium silicate, silicon Magnesium silicate, aluminum silicate, strontium silicate, manganese silicate, zinc silicate, chromium silicate, ferrous silicate, iron silicate, cadmium silicate, nickel silicate, lead silicate, copper silicate, silicic acid Silver, lithium phosphate, strontium phosphate, strontium phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, strontium phosphate, manganese phosphate, zinc phosphate, chromium phosphate, ferrous phosphate, iron phosphate, cadmium phosphate, strontium phosphate, nickel phosphate, phosphoric acid Tin, lead phosphate, copper phosphate, mercury phosphate, silver phosphate, copper pyrithione, cadmium oxalate, silver oxalate, ferrous oxalate , zinc tartrate, zinc oxalate, lead oxalate, lead tartrate, barium oxalate, calcium oxalate, mercury oxalate, barium oxalate and manganese oxalate.
制备碳化钨、碳化硅、碳化硼、氮化硅、氮化硼的无机微化颗粒也是在共沉淀反应基础上，通过对混合沉淀用碳或氮（氨气）还原制得。The inorganic micronized particles for preparing tungsten carbide, silicon carbide, boron carbide, silicon nitride, and boron nitride are also obtained by reducing the mixed precipitation with carbon or nitrogen (ammonia gas) on the basis of the coprecipitation reaction.
制备有机金属盐微化颗粒可以选择与制取无机盐微化颗粒相同的方法制取方式，它们包括钡、锶、钙、锂、锕、镧、铈、镨、钕、钐、铕、钆、铽、钇、镁、镅、镝、钬、铒、铥、镱、镥、钪、钚、钍、镎、铍、铀、铪、铝、钛、锆、钒、锰、铌、锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡、铅、铜、锝、钋、汞、银、铑、钯、铂或金离子的任选的烷基或芳基硫酸酯、磺酸、磷酸酯或羧酸盐。例如，常用于医药辅料的硬脂酸钙、硬脂酸锌。不过需要补充的是，任选的烷基或芳基硫酸酯、磺酸、磷酸酯或羧酸或其盐还可以通过溶于乙醇等可以与水混溶的溶剂中进行共沉淀反应，亦可以水乳化体的方式来参与共沉淀反应。The preparation of the organometallic salt micronized particles can be selected in the same manner as the preparation of the inorganic salt micronized particles, including strontium, barium, calcium, lithium, strontium, barium, strontium, barium, strontium, strontium, barium, strontium,铽, 钇, 镅, 镅, 镝, 钬, 铒, 铥, 镱, 镥, 钪, 钚, 钍, 镎, 铍, uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, An optional alkyl or aryl sulfate of gallium, iron, cadmium, indium, antimony, cobalt, nickel, molybdenum, tin, lead, copper, bismuth, antimony, mercury, silver, antimony, palladium, platinum or gold ions, Sulfonic acid, phosphate or carboxylate. For example, calcium stearate and zinc stearate are commonly used in pharmaceutical excipients. However, it should be added that the optional alkyl or aryl sulfate, sulfonic acid, phosphate or carboxylic acid or a salt thereof can also be coprecipitated by dissolving in a water-miscible solvent such as ethanol. The way of the water emulsion is to participate in the coprecipitation reaction.
最后，本发明还揭示了对难溶于水的固体有机物进行微化处理的方法。适合这种用途的载体包括本专利所列举的所有微化颗粒，其中特别优选的是以本专利技术制备的无机微化颗粒。Finally, the present invention also discloses a method of micronizing a solid organic substance that is poorly soluble in water. Carriers suitable for this purpose include all of the micronized particles recited in this patent, with inorganic micronized particles prepared by the present patent technology being particularly preferred.
这种难溶于水的固体有机物至少具有分解温度高于其熔点或在其热分解温度以下能够溶于除水以外的任一液体或液体组合物，且溶解度不低于1克/100克这两项要素之一。The poorly water-soluble solid organic substance has at least a liquid or liquid composition which has a decomposition temperature higher than its melting point or below its thermal decomposition temperature and can be dissolved in water other than water, and has a solubility of not less than 1 g/100 g. One of the two elements.
当难溶于水的固体有机物可以通过水溶液和水溶液的反应方式，水溶液和气体的反应方式，水溶液和不溶于水的液体的反应方式，不溶于水的液体和气体的反应方式得到时，可以采用化学的沉淀反应过程。When a solid organic substance which is hardly soluble in water can be reacted by an aqueous solution and an aqueous solution, a reaction mode of an aqueous solution and a gas, a reaction mode of an aqueous solution and a water-insoluble liquid, and a reaction mode of a water-insoluble liquid and a gas can be used. Chemical precipitation reaction process.
水不溶性固体有机物可以熔融方式实现这种物理化的沉淀反应过程。The water-insoluble solid organic matter can be melted to achieve this physical precipitation reaction process.
水不溶性固体有机物还可以溶液方式参与共沉淀反应。该过程一般有吸附和析出两种物理沉淀反应过程发生。当其溶剂与水完全不溶时，该沉淀过程基本为物理吸附过程；当其溶剂能够与水混溶时，该沉淀过程基本为析出过程。其中，更为优选的沉淀过程是析出方式的沉淀过程。因此，当水不溶性固体有机物以溶液方式参与共沉淀反应时，任一液体或液体组合物优先选用25℃下每100克水中至少可以溶解1克以上的有机溶剂或有机溶剂组合。例如，甲醇、乙醇、丙酮、乙二醇、丙二醇、甘油、聚乙二醇200/400、环丁砜, 二氧六环, 羟基丙酸, 乙胺, 乙二胺,乙二醇单甲/乙/丙醚, 二甘醇二甲醚, 1，3-二氧杂环戊烷等等。它们的具体形式可以参见中国化学工业出版社程能林编著的《溶剂手册》。The water-insoluble solid organic matter can also participate in the coprecipitation reaction in a solution manner. This process generally involves two physical precipitation reactions, adsorption and precipitation. When the solvent is completely insoluble with water, the precipitation process is basically a physical adsorption process; when the solvent is miscible with water, the precipitation process is basically a precipitation process. Among them, a more preferable precipitation process is a precipitation process in a precipitation mode. Therefore, when the water-insoluble solid organic substance participates in the coprecipitation reaction in a solution manner, it is preferred that any liquid or liquid composition dissolve at least 1 g of an organic solvent or an organic solvent combination per 100 g of water at 25 ° C. For example, methanol, ethanol, acetone, ethylene glycol, propylene glycol, glycerin, polyethylene glycol 200/400, sulfolane, Dioxane, hydroxypropionic acid, ethylamine, ethylenediamine, ethylene glycol monomethyl/ethyl/propyl ether, diglyme, 1,3-dioxolane and the like. For their specific form, please refer to the "Solvent Handbook" edited by Cheng Nenglin, China Chemical Industry Press.
此外，水不溶性固体有机物以（水）悬浮剂或（水）悬浮乳剂的形式参与共沉淀反应也是可以选择的。Further, it is also optional that the water-insoluble solid organic substance participates in the coprecipitation reaction in the form of a (aqueous) suspension or a (water) suspension emulsion.
这种水不溶性固体有机物可以被划分为药物、农药、兽药、颜料、染料（色素）、香精、杀菌剂、防霉剂、催化剂、高分子树脂或有机染料等其他多种称谓。适合本专利保护范围的有机物质具体名称可以参见《中国药典2010》、《中国农药大典》、《精细化工产品手册》等相关书籍。The water-insoluble solid organic matter can be classified into drugs, pesticides, veterinary drugs, pigments, dyes (pigments), flavors, bactericides, fungicides, catalysts, polymer resins or organic dyes. The specific names of organic substances suitable for the scope of this patent can be found in the Chinese Pharmacopoeia 2010, the Chinese Pesticide Code, and the Fine Chemicals Handbook.
难溶有机物的微细化有着重要的应用意义。例如，对于药品来说，40%以上的药品都是难溶于水的，因此，对这部分药物进行微细化处理，对于提高药物的溶出率，提高药效的意义是显而易见的。但是，由于无机物与有机物之间的相容性普遍很差，因此，一般情况下，以无机颗粒为载体来分散负载有机物难以得到理想结果。本专利所涉及的无机微化颗粒由于具有灵活的表面改性空间，亲水亲油调节自由等优点，因此可以最大限度的改善这种相容性，从而得到理想的微化难溶有机物。同时，微化颗粒预留的丰富改性空间，也为药物包膜提供了便利，为实现药物缓释控制提供了基础。The miniaturization of insoluble organic matter has important application significance. For example, for drugs, more than 40% of the drugs are insoluble in water. Therefore, it is obvious that the miniaturization of these drugs is effective for improving the dissolution rate of the drug and improving the efficacy. However, since the compatibility between the inorganic substance and the organic substance is generally poor, it is generally difficult to obtain a desired result by dispersing the organic substance supported by the inorganic particle as a carrier. The inorganic micronized particles involved in the patent have the advantages of flexible surface modification space, free hydrophilic-lipophilic adjustment, and the like, so that the compatibility can be maximized, thereby obtaining an ideal micro-insoluble organic matter. At the same time, the rich modification space reserved for the micro-particles also provides convenience for the drug coating, and provides a basis for drug sustained-release control.
上述实施方式不是唯一的选择，并不用于限定本发明。The above embodiments are not the only options and are not intended to limit the invention.
以下列举较佳实施例具体说明本发明，以下的实施例仅是对本发明的例证性的说明，并不用于限定本发明。The following examples are intended to illustrate the invention, and the following examples are merely illustrative of the invention and are not intended to limit the invention.
实施例一Embodiment 1
室温25℃下，在50毫升烧杯中加入10毫升0.1mol/L的氯化钙水溶液，放入包覆聚四氟乙烯的磁转子，将SH05-3型恒温磁力搅拌器（上海闵行虹浦仪器厂）调整转速至最大。然后在1分钟内从磁转子形成的漩涡中心的上方处滴加5毫升0.1mol/L的碳酸钠和0.2mol/L氢氧化钠的水溶液。滴加完毕后，再搅拌1个小时左右后开始静止熟化。At room temperature 25 ° C, 10 ml of 0.1 mol / L calcium chloride aqueous solution was added to a 50 ml beaker, placed in a magnetic rotor coated with polytetrafluoroethylene, and the SH05-3 type thermostatic magnetic stirrer (Shanghai Minhang Hongpu Instrument) Factory) Adjust the speed to the maximum. Then, 5 ml of an aqueous solution of 0.1 mol/L of sodium carbonate and 0.2 mol/L of sodium hydroxide was added dropwise from above the center of the vortex formed by the magnetic rotor in 1 minute. After the completion of the dropwise addition, the mixture was stirred for another hour or so and then started to stand still.
十个小时后，将含有碳酸钙和氢氧化钙沉淀的悬浊液过滤。将所得滤饼放入50毫升烧杯中。开动磁力搅拌器，激烈搅拌下缓慢加入8毫升0.1mol/L的盐酸水溶液。30分钟后，再次过滤，然后用约10毫升的水搅拌洗，然后再过滤，再水洗，反复三次。滤液和洗水中的水溶性氯化钙可以采用纯碱回收的方法处理。After ten hours, the suspension containing the precipitation of calcium carbonate and calcium hydroxide was filtered. The resulting filter cake was placed in a 50 ml beaker. The magnetic stirrer was turned on, and 8 ml of a 0.1 mol/L aqueous hydrochloric acid solution was slowly added under vigorous stirring. After 30 minutes, it was filtered again, then washed with about 10 ml of water, then filtered, and washed again, three times. The water-soluble calcium chloride in the filtrate and the wash water can be treated by a soda ash recovery method.
将水洗后的碳酸钙沉淀浆料放入50毫升塑料烧杯中，加入30毫升含有2%分散剂DEMOL N（日本花王公司甲醛缩萘磺酸盐）的水溶液。开启GF1110型实验室分散机（山东胜龙机械厂）在1200转/分钟下，对上述溶液进行20分钟的强制分散。The washed calcium carbonate precipitation slurry was placed in a 50 ml plastic beaker, and 30 ml of DEMOL containing 2% dispersant was added. An aqueous solution of N (Japan Kao Corporation formaldehyde phthalate). The GF1110 laboratory disperser (Shandong Shenglong Machinery Factory) was opened and the solution was forcedly dispersed for 20 minutes at 1200 rpm.
分散后的浆液用激光粒度分析仪进行粒度分析（beckman coulter），可以看到碳酸钙沉淀的二次粒径的体积平均粒径d50约为30纳米。The dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the calcium carbonate precipitate has a volume average particle diameter d50 of about 30 nm.
实施例二Embodiment 2
重复进行与实施例一相同的实验，将所得的碳酸钙：分散于含有0.1%油酸的30毫升液体石蜡中；分散于含有0.1%油酸和0.1%渗透剂JFC的30毫升水溶液中；分散于含有0.1%阴离子有机染料荧光黄和0.1%非离子表面活性剂渗透剂JFC的30毫升水溶液中；分散于带有3%丙烯酸基团的一种名为AT-150的纯丙乳液（中山安德士化工有限公司）中。The same experiment as in Example 1 was repeated, and the obtained calcium carbonate was dispersed in 30 ml of liquid paraffin containing 0.1% oleic acid; dispersed in 30 ml of an aqueous solution containing 0.1% oleic acid and 0.1% penetrant JFC; In a 30 ml aqueous solution containing 0.1% anionic organic dye fluorescent yellow and 0.1% nonionic surfactant penetrant JFC; dispersed in a pure acrylic emulsion called AT-150 with 3% acrylic group (Zhongshan An Texa Chemical Co., Ltd.).
上述液体中碳酸钙都可以得到良好的分散，碳酸钙的解团聚效果与实施例一基本一样。Calcium carbonate in the above liquid can be well dispersed, and the deagglomeration effect of calcium carbonate is substantially the same as in the first embodiment.
实施例三Embodiment 3
参照实施例一进行相同的实验步骤。在50毫升密闭烧瓶中加入10毫升0.1mol/L的氧化钙水悬浊液，然后再通入二氧化碳气体至约PH10.5时停止反应。熟化后，用盐酸调PH值至约9。然后反复洗涤，再分散。The same experimental procedure was carried out with reference to Example 1. 10 ml of a 0.1 mol/L suspension of calcium oxide water was added to a 50 ml closed flask, and then the reaction was stopped by introducing carbon dioxide gas to about pH 10.5. After aging, the pH was adjusted to about 9 with hydrochloric acid. Then wash repeatedly and then disperse.
分散后的浆液用激光粒度分析仪进行粒度分析（beckman coulter），可以看到碳酸钙沉淀的二次粒径的体积平均粒径d50约为80纳米。The dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the calcium carbonate precipitate has a volume average particle diameter d50 of about 80 nm.
实施例四Embodiment 4
参照实施例一进行相同的实验步骤。在50毫升密闭烧瓶中加入10毫升0.1mol/L氧化硅和0.1mol/L碳酸钠的水溶液（水玻璃和碳酸钠的混合物），然后加入10毫升0.2mol/L氯化钙。80℃下加热两个小时，并放置24小时后，再加入10毫升0.2mol/L盐酸。然后反复洗涤，再分散。The same experimental procedure was carried out with reference to Example 1. Into a 50 ml closed flask, 10 ml of an aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate (a mixture of water glass and sodium carbonate) was added, followed by the addition of 10 ml of 0.2 mol/L of calcium chloride. After heating at 80 ° C for two hours and standing for 24 hours, 10 ml of 0.2 mol / L hydrochloric acid was further added. Then wash repeatedly and then disperse.
分散后的浆液用激光粒度分析仪进行粒度分析（beckman coulter），可以看到硅酸钙（水合氧化钙和氧化硅复合体）沉淀的二次粒径的体积平均粒径d50约为50纳米。The dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter precipitated by calcium silicate (hydrated calcium oxide and silica complex) has a volume average particle diameter d50 of about 50 nm.
实施例五Embodiment 5
参照实施例一进行相同的实验步骤。在50毫升密闭烧瓶中加入10毫升0.1mol/L氧化硅和0.1mol/L碳酸钠的水溶液（水玻璃和碳酸钠的混合物），然后加入10毫升0.2mol/L氯化钙。80℃下加热两个小时，并放置24小时后，再加入0.5克经过精细研磨的超细碳粉（200目以上）。充分分散后洗涤、浓缩和干燥。放入99%以上含量的刚玉舟中，在DC-R型管式高温炉（管式炉）中通入氩气保护下（50ml/min），缓慢加热到1500℃下反应10个小时。然后将混合沉淀在空气中在750℃下保温3个小时除碳。最后，室温下用盐酸先除去钙类化合物后，再用氢氟酸除去未反应的二氧化硅等，得到碳化硅微化颗粒。The same experimental procedure was carried out with reference to Example 1. Into a 50 ml closed flask, 10 ml of an aqueous solution of 0.1 mol/L of silica and 0.1 mol/L of sodium carbonate (a mixture of water glass and sodium carbonate) was added, followed by the addition of 10 ml of 0.2 mol/L of calcium chloride. After heating at 80 ° C for two hours and standing for 24 hours, 0.5 g of finely ground ultrafine carbon powder (above 200 mesh) was further added. After thorough dispersion, it is washed, concentrated and dried. It is placed in a corundum boat with a content of more than 99%. Under a argon gas protection (50 ml/min) in a DC-R tubular high-temperature furnace (tube furnace), it is slowly heated to 1500 ° C for 10 hours. The mixed precipitate was then degassed in air at 750 ° C for 3 hours. Finally, the calcium compound is first removed with hydrochloric acid at room temperature, and then unreacted silica or the like is removed with hydrofluoric acid to obtain silicon carbide micronized particles.
分散后的浆液用激光粒度分析仪进行粒度分析（beckman coulter），可以看到碳化硅沉淀的二次粒径的体积平均粒径d50约为900纳米。The dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the silicon carbide precipitate has a volume average particle diameter d50 of about 900 nm.
实施例六Embodiment 6
参照实施例一进行相同的实验步骤。在50毫升密闭烧瓶中加入10毫升0.1mol/L氯化铁和0.02mol/L氯化钙的水溶液，然后加入5毫升0.7mol/L氢氧化钠进行共沉淀反应。不酸解，洗涤后再分散。The same experimental procedure was carried out with reference to Example 1. Into a 50 ml closed flask, 10 ml of an aqueous solution of 0.1 mol/L of ferric chloride and 0.02 mol/L of calcium chloride was added, followed by addition of 5 ml of 0.7 mol/L of sodium hydroxide for coprecipitation. Not acidified, disperse after washing.
分散后的浆液用激光粒度分析仪进行粒度分析（beckman coulter），可以看到氢氧化铁胶体沉淀的二次粒径的体积平均粒径d50约为30纳米。The dispersed slurry was subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the precipitate of the ferric hydroxide colloid has a volume average particle diameter d50 of about 30 nm.
将先前水洗后的氢氧化铁和氢氧化钙混合沉淀用10毫升1，2——丙二醇充分分散，加热干燥后放入马弗炉，在500℃下煅烧，得到微化的氧化铁。450℃下在DC-R管式高温炉（管式炉）中用一氧化碳还原该氧化铁，得磁性四氧化三铁。The mixture of the previously washed iron hydroxide and calcium hydroxide was sufficiently dispersed with 10 ml of 1,2-propylene glycol, dried by heating, placed in a muffle furnace, and calcined at 500 ° C to obtain a micronized iron oxide. The iron oxide was reduced with carbon monoxide in a DC-R tubular high temperature furnace (tubular furnace) at 450 ° C to obtain magnetic ferroferric oxide.
上述铁氧化物，在含有2%分散剂DEMOL N（日本花王公司甲醛缩萘磺酸盐）的水溶液中用GF1110型实验室分散机进行砂磨一个小时，得到二次粒径的体积平均粒径d50约为580纳米。The above iron oxide, containing 2% dispersant DEMOL An aqueous solution of N (Nippon Kao Corporation formaldehyde-naphthalene sulfonate) was sanded with a GF1110 laboratory disperser for one hour to obtain a secondary particle diameter having a volume average particle diameter d50 of about 580 nm.
实施例七Example 7
参照实施例一进行相同的实验步骤。在50毫升密闭烧瓶中加入10毫升0.1mol/L氯化铝和0.02mol/L氯化钙的水溶液，然后加入5毫升0.7mol/L氢氧化钠进行共沉淀反应。混合沉淀熟化后，用10毫升0.06mol/L盐酸酸解，然后洗涤浓缩。将所得氢氧化铝沉淀充分分散于10毫升1，2-丙二醇溶液中后，放入烘箱中300℃下烘干。将烘干物再放入马弗炉中于1000℃下煅烧3个小时。The same experimental procedure was carried out with reference to Example 1. 10 ml of an aqueous solution of 0.1 mol/L of aluminum chloride and 0.02 mol/L of calcium chloride was added to a 50 ml closed flask, and then 5 ml of 0.7 mol/L of sodium hydroxide was added to carry out a coprecipitation reaction. After the mixed precipitate was aged, it was acidified with 10 ml of 0.06 mol/L hydrochloric acid, and then washed and concentrated. The obtained aluminum hydroxide precipitate was sufficiently dispersed in 10 ml of a 1,2-propanediol solution, and then dried in an oven at 300 °C. The dried product was again placed in a muffle furnace and calcined at 1000 ° C for 3 hours.
将所得的氧化铝（α-氧化铝，也称刚玉）进行分散，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到氧化铝的二次粒径的体积平均粒径d50约为350纳米。The obtained alumina (α-alumina, also called corundum) was dispersed and subjected to particle size analysis using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of alumina has a volume average particle diameter d50 of about 350 nm.
实施例八Example eight
参照实施例一进行相同的实验步骤。在50毫升烧杯中加入10毫升0.2mol/L硝酸铝和0.05mol/L硝酸银的混合水溶液，加热至60℃后，滴入5毫升1.4mol/L氢氧化钠进行反应，然后再加入0.01克水合肼（80%含量）溶液。混合沉淀24小时熟化后，浓缩洗涤后，用9.5毫升0.7mol/L硝酸酸解，然后再洗涤浓缩。The same experimental procedure was carried out with reference to Example 1. Add 10 ml of a mixed aqueous solution of 0.2 mol/L aluminum nitrate and 0.05 mol/L silver nitrate to a 50 ml beaker, heat to 60 ° C, and then add 5 ml of 1.4 mol/L sodium hydroxide to carry out the reaction, and then add 0.01 g. Hydrazine hydrate (80% content) solution. The mixed precipitate was aged for 24 hours, concentrated and washed, then acidified with 9.5 ml of 0.7 mol/L nitric acid, and then washed and concentrated.
将所得的单质银进行分散后，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到银的二次粒径的体积平均粒径d50约为160纳米。After the obtained elemental silver was dispersed, the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of silver has a volume average particle diameter d50 of about 160 nm.
实施例九Example nine
参照实施例一进行相同的实验步骤。在50毫升烧杯中加入10毫升0.2mol/L氯化镁和0.05mol/L硫酸铜的混合水溶液，加热至80℃后，滴入5毫升2mol/L氢氧化钠进行反应，然后再加入0.01克水合肼（80%含量）溶液。混合沉淀24小时熟化后，浓缩洗涤后，用9.5毫升1mol/L盐酸酸解，然后再洗涤浓缩。The same experimental procedure was carried out with reference to Example 1. Add 10 ml of a mixed aqueous solution of 0.2 mol/L magnesium chloride and 0.05 mol/L copper sulfate in a 50 ml beaker, heat to 80 ° C, and then add 5 ml of 2 mol/L sodium hydroxide to carry out the reaction, and then add 0.01 g of hydrazine hydrate. (80% content) solution. The mixed precipitate was aged for 24 hours, concentrated and washed, and then acidified with 9.5 ml of 1 mol/L hydrochloric acid, followed by washing and concentration.
将所得的单质铜进行分散后，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到铜的二次粒径的体积平均粒径d50约为350纳米。After the obtained elemental copper was dispersed, the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of copper has a volume average particle diameter d50 of about 350 nm.
实施例十Example ten
参照实施例一进行相同的实验步骤。在50毫升烧杯中加入10毫升0.2mol/L硫酸镁和0.05mol/L硫酸铜的混合水溶液，加热至80℃后，滴入10毫升1mol/L氢氧化钠进行反应混合沉淀24小时熟化后，浓缩洗涤后，用9.5毫升1mol/L盐酸酸解，然后再洗涤浓缩。The same experimental procedure was carried out with reference to Example 1. 10 ml of a mixed aqueous solution of 0.2 mol/L magnesium sulfate and 0.05 mol/L copper sulfate was added to a 50 ml beaker, and after heating to 80 ° C, 10 ml of 1 mol/L sodium hydroxide was added dropwise to carry out a reaction mixture precipitation for 24 hours, and then matured. After concentration and washing, it was acidified with 9.5 ml of 1 mol/L hydrochloric acid, and then washed and concentrated.
将所得的氧化铜进行分散后，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到氧化铜的二次粒径的体积平均粒径d50约为50纳米。After dispersing the obtained copper oxide, the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the copper oxide has a volume average particle diameter d50 of about 50 nm.
实施例十一Embodiment 11
参照实施例一进行相同的实验步骤。在50毫升烧杯中加入10毫升0.1mol/L硝酸银水溶液和0.1mol/L硝酸铝水溶液，滴入10毫升0.3mol/L氢氧化钠和0.1mol/L氯化钠的混合水溶液（内含0.015克油酸）进行反应。浓缩洗涤、熟化后，用9.5毫升0.3mol/L硝酸酸解，然后再洗涤浓缩。The same experimental procedure was carried out with reference to Example 1. Add 10 ml of 0.1 mol/L silver nitrate aqueous solution and 0.1 mol/L aluminum nitrate aqueous solution to a 50 ml beaker, and add 10 ml of a mixed aqueous solution of 0.3 mol/L sodium hydroxide and 0.1 mol/L sodium chloride (containing 0.015). The oleic acid is reacted. After concentrated washing and aging, it was acidified with 9.5 ml of 0.3 mol/L nitric acid, and then washed and concentrated.
将所得氯化银进行分散后，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到氯化银的二次粒径的体积平均粒径d50约为320纳米。After dispersing the obtained silver chloride, the particle size analysis was carried out using a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of silver chloride has a volume average particle diameter d50 of about 320 nm.
实施例十二Example twelve
参照实施例一进行相同的实验步骤。在25毫升烧杯中加入5毫升0.2mol/L氯化钙水溶液，滴入5毫升0.12mol/L磷酸钠和0.04mol/L氢氧化钠。然后加热到80℃时，激烈搅拌下，再加入0.01克硬脂酸进行反应。继续保温十分钟后，激烈搅拌下冷却至室温。浓缩洗涤后，加入5毫升0.1mol/L盐酸水溶液酸解后再分散。The same experimental procedure was carried out with reference to Example 1. 5 ml of a 0.2 mol/L aqueous solution of calcium chloride was added to a 25 ml beaker, and 5 ml of 0.12 mol/L sodium phosphate and 0.04 mol/L sodium hydroxide were added dropwise. Then, when heated to 80 ° C, 0.01 g of stearic acid was added to carry out the reaction under vigorous stirring. After the incubation was continued for ten minutes, it was cooled to room temperature with vigorous stirring. After concentration and washing, it was acidified by adding 5 ml of a 0.1 mol/L hydrochloric acid aqueous solution and then dispersed.
将所得磷酸钙和硬脂酸钙混合沉淀进行分散后，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到混合沉淀的二次粒径的体积平均粒径d50约为350纳米。The obtained calcium phosphate and calcium stearate were mixed and precipitated for dispersion, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the secondary particle diameter of the mixed precipitate has a volume average particle diameter d50 of about 350 nm.
在上述分散体中滴入0.01克鱼肝油，激烈搅拌后得到了鱼肝油的水悬浮乳剂，其二次粒径的体积平均粒径d50也约为350纳米。0.01 g of cod liver oil was added dropwise to the above dispersion, and after vigorous stirring, an aqueous suspension emulsion of cod liver oil was obtained, and the volume average particle diameter d50 of the secondary particle diameter was also about 350 nm.
实施例十三Example thirteen
参照实施例一进行相同的实验步骤。在50毫升烧杯中加入10毫升0.2mol/L氯化钙水溶液，滴入10毫升0.07mol/L磷酸钠和0.1mol/L碳酸钠的混合水溶液进行反应，然后再加入0.1克10%含量的IPBC（碘代丙炔基氨基甲酸酯，一种优异的工业防霉剂）的甲醇溶液。熟化，用10毫升0.2mol/L盐酸酸解，浓缩洗涤后再分散。The same experimental procedure was carried out with reference to Example 1. Add 10 ml of 0.2 mol/L calcium chloride aqueous solution to a 50 ml beaker, add 10 ml of a mixed aqueous solution of 0.07 mol/L sodium phosphate and 0.1 mol/L sodium carbonate, and then add 0.1 g of 10% IPBC. A solution of (iodopropynyl carbamate, an excellent industrial antifungal agent) in methanol. After aging, it was acidified with 10 ml of 0.2 mol/L hydrochloric acid, concentrated and washed, and then dispersed.
将所得磷酸钙和IPBC混合沉淀进行分散后，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到混合沉淀的二次粒径的体积平均粒径d50也约为300纳米。The obtained calcium phosphate and IPBC mixed precipitate were dispersed, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the volume average particle diameter d50 of the secondary particle diameter of the mixed precipitate is also about 300 nm.
实施例十四Embodiment 14
将实施例十三的IPBC分别更换为0.1克10%含量的甘宝素1，2-丙二醇溶液、0.1克10%含量的酮康唑甲醇溶液，其他操作一样，同样可以得到这两种药品的优良水分散体，二次粒径的体积平均粒径d50均约为300纳米。The IPBC of the thirteenth embodiment was replaced with 0.1 g of a 10% content of a solution of Ganbaosu 1,2-propanediol and 0.1 g of a 10% ketoconazole methanol solution. The other operations were similar, and the excellent water of the two drugs was also obtained. The volume average particle diameter d50 of the dispersion and the secondary particle diameter was about 300 nm.
实施例十五Example fifteen
将实施例十四和十五中的含有分散剂DEMOL N的水溶液更换为一种含有ICM-7型号的羧甲基纤维素钠（张家港三惠化工公司，羧基取代度约0.7）1%浓度的水溶液，其他操作一样，依然可以得到上述混合沉淀的良好分散体。The dispersant containing DEMOL in Examples 14 and 15 The aqueous solution of N is replaced with an aqueous solution containing 1% concentration of sodium carboxymethyl cellulose (Zhangjiagang Sanhui Chemical Co., Ltd., having a carboxyl group substitution degree of about 0.7) of ICM-7 type. Other operations are as good as the above mixed precipitation. Dispersions.
实施例十六Example sixteen
参照实施例一进行相同的实验步骤。在50毫升烧杯中加入5毫升0.2mol/L氯化钙水溶液，滴入5毫升0.14mol/L磷酸钠水溶液进行反应，激烈搅拌下加入1毫升0.04mol/L碘化钠水溶液和含0.006 克丙炔基氨基甲酸丁酯（不溶于水的液体）的甲醇溶液1毫升。降温至10℃后，缓慢滴加5毫升0.005mol/L次氯酸钠水溶液，合成了IPBC和磷酸钙的混合沉淀。浓缩洗涤后，不酸解直接分散。The same experimental procedure was carried out with reference to Example 1. Add 5 ml of 0.2 mol/L calcium chloride aqueous solution to a 50 ml beaker, add 5 ml of 0.14 mol/L sodium phosphate aqueous solution to the reaction, and add 1 ml of 0.04 mol/L sodium iodide aqueous solution and 0.006 with vigorous stirring. 1 ml of a solution of butyl propargyl carbamate (water-insoluble liquid) in methanol. After cooling to 10 ° C, 5 ml of a 0.005 mol/L sodium hypochlorite aqueous solution was slowly added dropwise to synthesize a mixed precipitate of IPBC and calcium phosphate. After concentration and washing, it is directly dispersed without acid hydrolysis.
将所得磷酸钙和IPBC混合沉淀进行分散后，用激光粒度分析仪进行粒度分析（beckman coulter），可以看到混合沉淀的二次粒径的体积平均粒径d50约为360纳米。The obtained calcium phosphate and IPBC mixed precipitate were dispersed, and then subjected to particle size analysis by a laser particle size analyzer (beckman) Coulter), it can be seen that the volume average particle diameter d50 of the secondary particle diameter of the mixed precipitate is about 360 nm.
实施例十七Example seventeen
室温25℃下，分别配置：At room temperature 25 ° C, respectively:
A 20公斤 0.2mol/L的2-巯基吡啶氧化物钠水溶液A 20 kg 0.2 mol/L sodium 2-mercaptopyridine oxide aqueous solution
B 20公斤 0.22mol/L的硫酸锌水溶液B 20 kg 0.22 mol/L zinc sulfate aqueous solution
C 20公斤 0.1mol/L的碳酸钠水溶液（内含0.2 mol的油酸钠）C 20 kg 0.1 mol/L sodium carbonate aqueous solution (containing 0.2 mol of sodium oleate)
将以上A和B的水溶液在单个流量不超过200L/H条件下，以流量摩尔比约1: 1.1，同时分别泵入超重力反应器进行合成。超重力反应器转速为1000转/分钟；将A和B的合成浆料置于100升的聚丙烯塑料桶中，开动GFJ-8型分散机，转速调为1000转/分钟。将C在10分钟内加入到A和B的合成浆料中。The above aqueous solutions of A and B are at a single flow rate of not more than 200 L/H, and the flow rate molar ratio is about 1: 1.1, simultaneously pumped into the supergravity reactor for synthesis. The supergravity reactor was rotated at 1000 rpm; the synthetic slurry of A and B was placed in a 100 liter polypropylene plastic bucket, and the GFJ-8 type disperser was started, and the rotation speed was adjusted to 1000 rpm. C was added to the synthetic slurry of A and B over 10 minutes.
将得到的浆料参照实施例一进行处理。其中，离心分离设备选用普通的沉降式三足离心机。分散剂选用日本花王公司甲醛缩萘磺酸盐分散剂DEMOLN。本实施例得到的改性微化2-巯基吡啶氧化物锌用扫描电镜（SEM）进行粒度分析，可以看到，其颗粒的粒径基本小于300纳米。The obtained slurry was treated in the same manner as in Example 1. Among them, the centrifugal separation equipment uses an ordinary sedimentation type three-legged centrifuge. The dispersing agent was selected from the Japanese Kao Company formaldehyde phthalate sulfonate dispersing agent DEMOLN. The modified micro-purinated zinc pyrithione obtained in this example was subjected to particle size analysis by scanning electron microscopy (SEM), and it was found that the particle diameter of the particles was substantially less than 300 nm.
比较例一Comparative example one
分别配置好浓度均为0.1mol/L的氯化钙和碳酸钠的水溶液各5毫升，参照实施例一进行处理。将所得非本专利方法制取的碳酸钙分散液用激光粒度分析仪（beckman coulter）进行检测，其d50约8.5微米。由此可见，无机沉淀氢氧化钙可以有效改善碳酸钙的二次粒径水平。5 ml of each of an aqueous solution of calcium chloride and sodium carbonate having a concentration of 0.1 mol/L was separately disposed, and treated in the same manner as in Example 1. The obtained calcium carbonate dispersion obtained by the non-patent method is a laser particle size analyzer (beckman) Coulter) was tested with a d50 of about 8.5 microns. It can be seen that inorganic precipitation of calcium hydroxide can effectively improve the secondary particle size of calcium carbonate.
比较例二Comparative example two
室温20℃下，配好浓度为6.8%(重量比，下同)的硫酸锌水溶液20公斤（用硫酸调PH至4—4.5），其中含有1%日本花王公司甲醛缩萘磺酸盐分散剂DEMOLN ；另配浓度为20%的2-巯基吡啶氧化物钠水溶液15公斤，其中也含有1%日本花王公司甲醛缩萘磺酸盐分散剂DEMOLN 。At room temperature 20 ° C, a concentration of 6.8% (weight ratio, the same below) of zinc sulphate aqueous solution 20 kg (pH adjusted to 4 - 4.5 with sulfuric acid), which contains 1% of the Japanese Kao company formaldehyde phthalate sulfonate dispersant DEMOLN An additional 15 kg of a 20% aqueous solution of sodium pyrithione was added, which also contained 1% of the Japanese Kao Company's formaldehyde phthalate sulfonate dispersant DEMOLN.
将以上硫酸锌水溶液和2-巯基吡啶氧化物钠水溶液在单个流量不超过200L/H条件下，以流量摩尔比约1.05:1，同时分别泵入超重力反应器进行合成。超重力反应器转速为1000转/分钟。The above aqueous solution of zinc sulphate and sodium 2-pyridyl pyridine oxide solution were separately pumped into a supergravity reactor at a single flow rate of not more than 200 L/H at a flow ratio of about 1.05:1. The supergravity reactor was rotated at 1000 rpm.
将得到的浆料用定量滤纸过滤，结果大量改性微化2-巯基吡啶氧化物锌颗粒穿透滤纸，该方法无法实现改性微化2-巯基吡啶氧化物锌颗粒与反应母液的分离。The obtained slurry was filtered with a quantitative filter paper, and as a result, a large amount of modified micro-pyridinium oxychloride zinc particles penetrated the filter paper, and the separation of the modified micro-pyridyl pyridine oxide zinc particles from the reaction mother liquid could not be achieved by this method.
再用台式低速离心机80-2T（上海手术器械厂）以3000转/分钟对得到的浆料进行离心分离处理20分钟，结果在离心分离出来的母液中依然含有大量的改性微化2-巯基吡啶氧化物锌颗粒和DEMOLN分散剂，依然无法获得反应产物与反应母液的良好分离。The obtained slurry was centrifuged at 3000 rpm for 20 minutes using a bench-top low-speed centrifuge 80-2T (Shanghai Surgical Instrument Factory). As a result, a large amount of modified micronization was still contained in the centrifuged mother liquor. The zinc pyrithione particles and the DEMOLN dispersant still do not provide good separation of the reaction product from the reaction mother liquor.
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The above description of the embodiments is intended to facilitate the understanding and application of the present invention by those skilled in the art. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the general principles described herein can be applied to other embodiments without the inventive work. Therefore, the present invention is not limited to the embodiments herein, and those skilled in the art should be able to make modifications and changes without departing from the scope of the invention.
工业实用性Industrial applicability
序列表自由内容Sequence table free content

Claims (1)

1、一种改性微化颗粒的制备方法，其特征在于该方法包括以下步骤：A method for preparing modified micronized particles, characterized in that the method comprises the following steps:
水溶液中且反应母液冰点和沸点之间进行共沉淀反应，生成微化颗粒或微化颗粒前驱体和无机沉淀的混合沉淀。A coprecipitation reaction is carried out between the freezing point and the boiling point of the reaction mother liquid in the aqueous solution to form a micronized particle or a mixed precipitate of the micronized particle precursor and the inorganic precipitate.
2、根据权利要求1所述的改性微化颗粒的制备方法，其特征在于：所述的微化颗粒或微化颗粒前驱体的沉淀和无机沉淀的混合沉淀在反应后母液中的含量为0.1%—50%，最优选为0.5%—10%；并且微化颗粒或微化颗粒前驱体的沉淀与无机沉淀的质量比为1000：1至1：100000，次优选为100：1至1：1000，最优选为10：1至1：100。The method for preparing modified micronized particles according to claim 1, wherein the content of the precipitated and inorganic precipitated precipitates of the micronized particles or the micronized particle precursors in the mother liquor after the reaction is 0.1% to 50%, most preferably 0.5% to 10%; and the mass ratio of the precipitation of the micronized or micronized particle precursor to the inorganic precipitation is from 1000:1 to 1:100,000, and less preferably from 100:1 to 1 : 1000, most preferably from 10:1 to 1:100.
3、根据权利要求1所述的改性微化颗粒的制备方法，其特征在于：所述的共沉淀反应在常规搅拌条件下进行或在高速搅拌/混合/剪切/摩擦条件下进行，进一步在超重力条件下进行。The method for preparing modified micronized particles according to claim 1, wherein the coprecipitation reaction is carried out under conventional stirring conditions or under high-speed stirring/mixing/shearing/friction conditions, further Performed under supergravity conditions.
4、根据权利要求1所述的改性微化颗粒的制备方法，其特征在于：所述的共沉淀反应，反应液的PH控制在3-14，优选为7-14。 The method for preparing modified micronized particles according to claim 1, characterized in that in the coprecipitation reaction, the pH of the reaction liquid is controlled at 3 to 14, preferably 7-14.
5、根据权利要求1所述的改性微化颗粒的制备方法，其特征在于：所述的微化颗粒或微化颗粒前驱体为难溶于水且不与水有化学反应的无机物或有机物，以及它们之间的混合物。The method for preparing modified micronized particles according to claim 1, wherein the micronized or micronized particle precursor is an inorganic or organic substance that is insoluble in water and does not chemically react with water. , and the mixture between them.
6、根据权利要求5所述的改性微化颗粒的制备方法，其特征在于：所述的无机物选自单质，更进一步的选择为锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡、铅、铜、锝、钋、银、铑、钯、铂、金、碳、硅、钨、硼、碲、硒、硫或碘，以及它们的混合物；所述的无机物选自氢氧化物，更进一步的选择为氢氧化锕、氢氧化钯(II、 IV)、氢氧化铋、氢氧化铂、 氢氧化铒 、氢氧化钆、 氢氧化镉、氢氧化铪(III 、IV) 、氢氧化钬、 氢氧化镓、氢氧化镥 、氢氧化铝、氢氧化镁、氢氧化锰、氢氧化铅（II、 IV）、氢氧化铈(III 、IV)、氢氧化铁、氢氧化亚铁、氢氧化亚铜、氢氧化铜、氢氧化铟、氢氧化铕、氢氧化铍、氢氧化锌、氢氧化镍、氢氧化锡、氢氧化镧、氢氧化钕、氢氧化镨、氢氧化钐、氢氧化铽、氢氧化钇、氢氧化镝、氢氧化铥、氢氧化镱、氢氧化钪、氢氧化钚、氢氧化钍、氢氧化镎、氢氧化铀、氢氧化钛、氢氧化锆、氢氧化钒（II 、III、 IV）、氢氧化铌、氢氧化钽、氢氧化铬、氢氧化钴或氢氧化钼（III、 IV、V）；所述的无机物选自氧化物，更进一步的选择为氧化锕、氧化钯(II、 IV)、氧化铋、氧化铂、 氧化铒 、氧化钆、 氧化镉、氧化铪(III 、IV) 、氧化钬、 氧化镓、氧化镥 、氧化铝、氧化镁、氧化锰、氧化铅（II、 IV）、氧化铈(III 、IV)、氧化铁、氧化亚铁、氧化亚铜、氧化铜、氧化铟、氧化铕、氧化铍、氧化锌、氧化镍、氧化锡、氧化镧、氧化钕、氧化镨、氧化钐、氧化铽、氧化钇、氧化镝、氧化铥、氧化镱、氧化钪、氧化钚、氧化钍、氧化镎、氧化铀、氧化钛、氧化锆、氧化钒（II 、III、 IV）、氧化铌、氧化钽、氧化铬、氧化钴、氧化钼（III、 IV、V）、氧化银、氧化锝、氧化钋、氧化铑、氧化钯、氧化铂、氧化金、氧化硅、氧化钨、氧化硼、氧化碲或氧化硒；所述的无机物选自无机盐，更进一步的选择为砷酸钡、碳酸钡、铬酸钡、亚铁氰化钡、氟硅酸钡、氟化钡、磷酸氢钡、碘酸钡、硫酸钡、钼酸钡、高锰酸钡、焦磷酸钡、硒酸钡、砷酸铋、碘化铋、磷酸铋、硫化铋、溴化铂(IV) 、氟化钚(III) 、氟化钚(IV) 、碘酸钚(IV)、 砷酸钙、氟化钙、磷酸氢钙、钼酸钙、磷酸钙、钨酸钙、砷酸镉、碳酸镉、氰化镉、亚铁氰化镉、碘酸镉、磷酸镉、硫化镉、钨酸镉、叠氮化亚汞、溴化亚汞、碳酸亚汞、氯化亚汞、铬酸亚汞、氰化亚汞、硫酸亚汞、碘酸汞、碘化汞、硫化汞、硫氰酸汞、四苯硼钾、三碘化金、碘酸镧、钼酸镧、磷酸锂、氟化镁、磷酸镁、亚硒酸镁、碳酸锰、亚铁氰化锰、碳酸镍、碘酸镍、焦磷酸镍、硫化钋(II) 、钼酸镨(III) 、叠氮化铅、碳酸铅、氯酸铅、铬酸铅、亚铁氰化铅、氟化铅、磷酸氢铅、亚磷酸氢铅、碘酸铅、碘化铅、钼酸铅、硒酸铅、硫酸铅、硫化铅、硫代硫酸铅、钨酸铅、碲化铅、磷酸铈(III) 、铬酸锶硫酸锶、溴化亚铊、碘酸亚铊、碘化亚铊、碳酸亚铁、氢氧化亚铁、砷酸铁、氟化铁、氯化亚铜、氰化亚铜、碘化亚铜、硫化亚铜、硫氰酸亚铜、碳酸铜、铬酸铜、氟化铜、亚硒酸铜、硫化铜、碘酸钍(IV) 、碳酸锌、氰化锌、碘酸锌、氟化钇、碘酸铟、硫化铟、叠氮化银、溴化银、碳酸银、氯化银、铬酸银、氰化银、钒酸银、碳酸铍、亚硫酸钡、亚硫酸锶、亚硫酸钙、亚硫酸铍、亚硫酸锰、亚硫酸锌、亚硫酸镉、亚硫酸亚铁、亚硫酸镍、亚硫酸铅、亚硫酸铜、亚硫酸汞、亚硫酸银、硫化锶、硫化锰、硫化锌、硫化亚铁、硫化镉、硫化镍、硫化锡、硫化铅、硫化铜、硫化汞、硫化银、硅酸钡、硅酸钙、硅酸镁、硅酸铝、硅酸铍、硅酸锰、硅酸锌、硅酸铬、硅酸亚铁、硅酸铁、硅酸镉、硅酸镍、硅酸铅、硅酸铜、硅酸银、磷酸锂、磷酸钡、磷酸锶、磷酸钙、磷酸镁、磷酸铝、磷酸铍、磷酸锰、磷酸锌、磷酸铬、磷酸亚铁、磷酸铁、磷酸镉、、磷酸铊、磷酸镍、磷酸锡、磷酸铅、磷酸铜、磷酸汞、磷酸银、2-巯基吡啶硫酮锌、2-巯基吡啶硫酮铜、草酸镉、草酸银、草酸亚铁、酒石酸锌、草酸锌、草酸铅、酒石酸铅、草酸钡、草酸钙、草酸汞、草酸钪、草酸锰、碳化钨、碳化硅、碳化硼、氮化硅或氮化硼；所述的无机物选自有机金属盐，更进一步的选择为钡、锶、钙、锂、锕、镧、铈、镨、钕、钐、铕、钆、铽、钇、镁、镅、镝、钬、铒、铥、镱、镥、钪、钚、钍、镎、铍、铀、铪、铝、钛、锆、钒、锰、铌、锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡、铅、铜、锝、钋、汞、银、铑、钯、铂或金离子的任选的烷基或芳基硫酸酯、磺酸、磷酸酯或羧酸盐；所述的有机物至少具有以下要素之一：（1）分解温度高于其熔点；（2）在其热分解温度以下能够溶于除水以外的任一液体或液体组合物，且溶解度不低于1克/100克。The method for preparing modified micronized particles according to claim 5, wherein the inorganic substance is selected from the group consisting of simple substances, and further selected are zinc, chromium, gallium, iron, cadmium, indium, antimony, Cobalt, nickel, molybdenum, tin, lead, copper, antimony, bismuth, silver, antimony, palladium, platinum, gold, carbon, silicon, tungsten, boron, antimony, selenium, sulfur or iodine, and mixtures thereof; The inorganic substance is selected from the group consisting of hydroxides, and further selected are barium hydroxide and palladium hydroxide (II, IV), barium hydroxide, platinum hydroxide, barium hydroxide, barium hydroxide, cadmium hydroxide, barium hydroxide (III, IV), barium hydroxide, gallium hydroxide, barium hydroxide , aluminum hydroxide, magnesium hydroxide, manganese hydroxide, lead hydroxide (II, IV), barium hydroxide (III , IV), iron hydroxide, ferrous hydroxide, cuprous hydroxide, copper hydroxide, indium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, nickel hydroxide, tin hydroxide, barium hydroxide, Barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, barium hydroxide, hydroxide Uranium, titanium hydroxide, zirconium hydroxide, vanadium hydroxide (II , III, IV), barium hydroxide, barium hydroxide, chromium hydroxide, cobalt hydroxide or molybdenum hydroxide (III, IV, V); the inorganic substance is selected from the group consisting of oxides, and further selected is cerium oxide. Palladium oxide (II, IV), cerium oxide, platinum oxide, cerium oxide, cerium oxide, cadmium oxide, cerium oxide (III, IV), cerium oxide, gallium oxide, cerium oxide, aluminum oxide, magnesium oxide, manganese oxide, lead oxide (II, IV), yttrium oxide (III , IV), iron oxide, ferrous oxide, cuprous oxide, copper oxide, indium oxide, antimony oxide, antimony oxide, zinc oxide, nickel oxide, tin oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide, antimony oxide , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, uranium oxide, titanium oxide, zirconium oxide, vanadium oxide (II) , III, IV), cerium oxide, cerium oxide, chromium oxide, cobalt oxide, molybdenum oxide (III, IV, V), silver oxide, cerium oxide, cerium oxide, cerium oxide, palladium oxide, platinum oxide, gold oxide, silicon oxide, tungsten oxide, boron oxide, cerium oxide or selenium oxide; the inorganic substance is selected from inorganic salts Further choices are barium arsenate, barium carbonate, barium strontium strontium, barium ferrocyanide, barium fluorosilicate, barium fluoride, barium hydrogen phosphate, barium iodate, barium sulfate, barium molybdate, barium permanganate Bismuth, antimony pyrophosphate, antimony selenate, antimony arsenate, antimony iodide, antimony phosphate, antimony sulfide, platinum bromide (IV) , cerium (III) fluoride, cerium (IV) fluoride, cerium (IV) iodate, Calcium arsenate, calcium fluoride, calcium hydrogen phosphate, calcium molybdate, calcium phosphate, calcium tungstate, cadmium arsenate, cadmium carbonate, cadmium cyanide, cadmium ferrocyanide, cadmium iodate, cadmium phosphate, cadmium sulfide, Cadmium Tungstate, Mercury Azide, Mercury Bromide, Mercury Carbonate, Mercury Chloride, Mercury Chromate, Mercury Cyanide, Mercury Sulfate, Mercury Iodide, Mercury Iodide, Mercury Sulfide, Sulfur Mercury cyanate, potassium tetraphenylborate, gold triiodide, barium iodate, barium bismuth citrate, lithium phosphate, magnesium fluoride, magnesium phosphate, magnesium selenite, manganese carbonate, manganese ferrocyanide, nickel carbonate, iodine Nickel acid, nickel pyrophosphate, antimony sulfide (II) , bismuth molybdate (III) , lead azide, lead carbonate, lead chlorate, lead chromate, lead ferrocyanide, lead fluoride, lead hydrogen phosphate, lead hydrogen phosphite, lead iodate, lead iodide, lead molybdate, selenate Lead, lead sulfate, lead sulfide, lead thiosulfate, lead tungstate, lead telluride, barium phosphate (III) , barium strontium sulphate, barium bromide, hydrazine hydrazide, hydrazine iodide, ferrous carbonate, ferrous hydroxide, iron arsenate, iron fluoride, cuprous chloride, cuprous cyanide, iodine Cuprous, cuprous sulfide, cuprous thiocyanate, copper carbonate, copper chromate, copper fluoride, copper selenite, copper sulfide, barium iodate (IV) , zinc carbonate, zinc cyanide, zinc iodate, barium fluoride, indium iodate, indium sulfide, silver azide, silver bromide, silver carbonate, silver chloride, silver chromate, silver cyanide, silver vanadate , barium carbonate, barium sulfite, barium sulfite, barium sulfite, barium sulfite, manganese sulfite, zinc sulfite, cadmium sulfite, ferrous sulfite, nickel sulfite, lead sulfite, copper sulfite, Mercuric sulfate, silver sulfite, barium sulfide, manganese sulfide, zinc sulfide, ferrous sulfide, cadmium sulfide, nickel sulfide, tin sulfide, lead sulfide, copper sulfide, mercury sulfide, silver sulfide, barium silicate, calcium silicate, silicon Magnesium silicate, aluminum silicate, strontium silicate, manganese silicate, zinc silicate, chromium silicate, ferrous silicate, iron silicate, cadmium silicate, nickel silicate, lead silicate, copper silicate, silicic acid Silver, lithium phosphate, strontium phosphate, strontium phosphate, calcium phosphate, magnesium phosphate, aluminum phosphate, strontium phosphate, manganese phosphate, zinc phosphate, chromium phosphate, ferrous phosphate, iron phosphate, cadmium phosphate, strontium phosphate, nickel phosphate, phosphoric acid Tin, lead phosphate, copper phosphate, mercury phosphate, silver phosphate, zinc pyrithione, copper pyrithione, oxalic acid , silver oxalate, ferrous oxalate, zinc tartrate, zinc oxalate, lead oxalate, lead tartrate, barium oxalate, calcium oxalate, mercury oxalate, barium oxalate, manganese oxalate, tungsten carbide, silicon carbide, boron carbide, silicon nitride or nitride Boron; the inorganic substance is selected from the group consisting of organic metal salts, and further selected are lanthanum, cerium, calcium, lithium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, magnesium, lanthanum,镝, 钬, 铒, 铥, 镱, 镥, 钪, 钚, 钍, 镎, 铍, uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, gallium, iron, cadmium, indium, An optional alkyl or aryl sulfate, sulfonic acid, phosphate or carboxylic acid of ruthenium, cobalt, nickel, molybdenum, tin, lead, copper, ruthenium, osmium, mercury, silver, iridium, palladium, platinum or gold ions a salt; the organic substance having at least one of the following elements: (1) a decomposition temperature higher than a melting point thereof; (2) being soluble in any liquid or liquid composition other than water below its thermal decomposition temperature, and the solubility is not Less than 1 g / 100 g.
7、根据权利要求1所述的改性微化颗粒的制备方法，其特征在于：该方法还包括向混合沉淀中加入提纯剂，将无机沉淀或其后驱体部分或全部转化为水溶性物质去除，并对剩余的沉淀进行洗涤浓缩。The method for preparing modified micronized particles according to claim 1, characterized in that the method further comprises adding a purifying agent to the mixed precipitate to convert part or all of the inorganic precipitate or its precursor into a water-soluble substance. It was removed and the remaining precipitate was washed and concentrated.
8、根据权利要求7所述的改性微化颗粒的制备方法，其特征在于：所述的提纯剂为水溶性的无机酸或有机酸，选自盐酸、硫酸、硝酸、氢氟酸、乙酸或磷酸的其中一种，或其混合物。The method for preparing modified micronized particles according to claim 7, wherein the purifying agent is a water-soluble inorganic or organic acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, and acetic acid. Or one of phosphoric acid, or a mixture thereof.
9、根据权利要求7所述的一种改性微化颗粒的制备方法，其特征在于：该方法还包括：将提纯后的混合沉淀与表面改性剂混合/反应，得到改性微化颗粒。The method for preparing modified micronized particles according to claim 7, wherein the method further comprises: mixing/reacting the purified mixed precipitate with the surface modifier to obtain modified micronized particles. .
10、根据权利要求9所述的改性微化颗粒的制备方法，其特征在于：所述的表面改性剂是指能够和微化颗粒表面形成吸附的化合物，包括阴离子化合物、阳离子化合物、非离子表面活性剂、水不溶有机液体、偶联剂或被添加到的母体材料，以及它们的组合物。The method for preparing modified micronized particles according to claim 9, wherein the surface modifier refers to a compound capable of forming adsorption with the surface of the micronized particles, including an anionic compound, a cationic compound, and a non- An ionic surfactant, a water insoluble organic liquid, a coupling agent or a parent material to which is added, and combinations thereof.
11、根据权利要求9所述的改性微化颗粒的制备方法，其特征在于：所述的改性微化颗粒的二次粒径的体积粒径平均值d50小于10微米，再优选为小于1000纳米，更优选为小于100纳米，最优选为小于10纳米。The method for preparing modified micronized particles according to claim 9, wherein the secondary particle diameter of the modified micronized particles has an average volume diameter d50 of less than 10 μm, more preferably less than 1000 nm, more preferably less than 100 nm, most preferably less than 10 nm.
12、根据权利要求1-11中任何一项所述的一种改性微化颗粒的制备方法，其特征在于：水溶液中且反应母液冰点和沸点之间，可转化为水溶性物质的无机沉淀存在下，进行微化颗粒或微化颗粒前驱体的沉淀反应。The method for preparing a modified micronized particle according to any one of claims 1 to 11, characterized in that the inorganic precipitate in the aqueous solution and between the freezing point and the boiling point of the reaction mother liquid can be converted into a water-soluble substance. In the presence of, the precipitation reaction of the micronized particles or the micronized particle precursors is carried out.
13、根据权利要求12所述的改性微化颗粒的制备方法，其特征在于：所述的可转化为水溶性物质的无机沉淀在反应温度下每100克水中溶解度小于1克，更进一步的选择为小于0.01克；并且该无机沉淀的阳离子部分选自钡、锶、钙、锂、锕、镧、铈、镨、钕、钐、铕、钆、铽、钇、镁、镅、镝、钬、铒、铥、镱、镥、钪、钚、钍、镎、铍、铀、铪、铝、钛、锆、钒、锰、铌、锌、铬、镓、铁、镉、铟、铊、钴、镍、钼、锡、铅、铜、锝、钋、汞、银、铑、钯、铂或金离子，以及它们的混合物；该无机沉淀的阴离子部分选自氰离子、卤离子、硫酸（氢）根离子、亚硝酸根离子、碳酸（氢）根离子、亚硫酸（氢）根离子、重铬酸根离子、磷酸（氢）根离子、硫（氢）离子、铬酸根离子、硅酸根离子、硼酸根离子、砷酸根离子、钛酸根离子、草酸根离子、氢氧根离子或氧离子，更进一步的选择为氢氧根离子、氧离子、硫（氢）离子、亚硫酸（氢）根离子、磷酸（氢）根离子或碳酸（氢）根离子，以及它们的混合物。The method for preparing modified micronized particles according to claim 12, wherein the inorganic precipitate which can be converted into a water-soluble substance has a solubility of less than 1 gram per 100 g of water at the reaction temperature, further Selected to be less than 0.01 g; and the cationic portion of the inorganic precipitate is selected from the group consisting of ruthenium, osmium, calcium, lithium, cesium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, magnesium, cerium, lanthanum, cerium , 铒, 铥, 镱, 镥, 钪, 钚, 钍, 镎, 铍, uranium, thorium, aluminum, titanium, zirconium, vanadium, manganese, antimony, zinc, chromium, gallium, iron, cadmium, indium, antimony, cobalt , nickel, molybdenum, tin, lead, copper, ruthenium, osmium, mercury, silver, ruthenium, palladium, platinum or gold ions, and mixtures thereof; the anion portion of the inorganic precipitate is selected from the group consisting of cyanide ions, halide ions, sulfuric acid (hydrogen) Root ion, nitrite ion, carbonic acid (hydrogen) ion, sulfuric acid (hydrogen) ion, dichromate ion, phosphoric acid (hydrogen) ion, sulfur (hydrogen) ion, chromate ion, silicate ion, Boric acid ion, arsenate ion, titanate ion, oxalate ion, hydrogen and oxygen Ionic or oxygen ions, further selected are hydroxide ions, oxygen ions, sulfur (hydrogen) ions, sulfuric acid (hydrogen) ions, phosphoric acid (hydrogen) ions or carbonic acid (hydrogen) ions, and mixtures thereof .
14、根据权利要求1所述的改性微化颗粒的制备方法，其特征在于：该方法进一步包括在沉淀反应前、中和/或后，加入表面活性物质，并且这种加入不影响混合沉淀与母液的分离和废水的处理。The method for preparing modified micronized particles according to claim 1, wherein the method further comprises adding a surface active material before, during and/or after the precipitation reaction, and the addition does not affect the mixed precipitation. Separation from mother liquor and treatment of wastewater.
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CN113860346A (en) * 2021-10-08 2021-12-31 江西华明纳米碳酸钙有限公司 Preparation method of modified nano calcium carbonate
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CN116515321A (en) * 2023-05-09 2023-08-01 西安电子科技大学 Solvent-free gadolinium-based fluid and preparation method thereof

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CN111704164A (en) * 2020-07-01 2020-09-25 洛阳理工学院 Preparation method of barium molybdate flower-like crystal
CN111704164B (en) * 2020-07-01 2023-01-24 洛阳理工学院 Preparation method of barium molybdate flower-like crystal
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CN113540446B (en) * 2021-07-05 2022-10-25 常德昆宇新能源科技有限公司 Lithium ion battery cathode material and preparation method thereof
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CN114480883B (en) * 2021-12-16 2023-11-21 成都先进金属材料产业技术研究院股份有限公司 Method for preparing high-purity vanadium pentoxide by removing silicon and chromium in vanadium solution through nickel ion cooperation
CN116515321A (en) * 2023-05-09 2023-08-01 西安电子科技大学 Solvent-free gadolinium-based fluid and preparation method thereof

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