TW200835649A - Method of manufacturing composite hybrid particles by coating aluminum trihydrate on calcium carbonate microparticle - Google Patents

Abstract

The present invention provides a method of manufacturing composite hybrid particles by coating aluminum trihydrate (ATH) onto precipitated calcium carbonate (PCC) microparticles. By using the carbonation chemical method, the porous PCC microparticles are treated as the core and the aluminum trihydrate is coated on the calcium carbonate microparticles by the van der Waals' force to produce the nano-grade aluminum trihydrate which is purified by a water-thermal treatment. The grains of crystallization of original composite blending particles (PCC+ATH) are added in the sodium aluminate solution to carry out a crystal growth reaction. The ATH crystals grow to coated on calcium carbonate microparticles to generate the composite blending particles (PCC + ATH) having a core-shell crystal structure.

Description

200835649 IX. Description of the Invention: [Technical Field of the Invention] The present invention is a method for preparing composite mixed particles in which aluminum hydroxide (ATH) is coated on a precipitated (PCC) particle shell, and further, The invention relates to a preparation method related to carbonization and crystallization, and an invention of the composite mixed particle of the nucleus-shell structure (PCC+ATH). BACKGROUND OF THE INVENTION It has been known in the art that the surface of carbonated dance particles has more water and hydroxyl groups, and has hydrophilic and oleophobic properties, and easily forms aggregates in solution, and the dispersion property is ^ ί = fruit: surface treatment of carbonic acid touch, To be applied; when it is too large, it is necessary to increase the organic effect of the plastic or rubber formed by at least one selected from the group consisting of saturated fatty acids and non-t: groups, which may be impaired. The effect of the hourly 'fine microparticles' ^ ^ j rubber material may be reduced. Thin and recorded her raw money, she is more careful, and enhance the flame retardant effect. Reduce the general flame retardant material can also be corrected (4) / wind oxidation Ming 0H base can be bonded with Shi Xizhuo coupling agent,

'Performed with KOH = machine = Qiaoxin surface modification f method, which will make it more widely used, the shoal I carbonic acid f-storage tank h) is covered in the sinking system, that is, the particle formation wins the shell structure (PCC) Side composite hybrid granules 5 200835649 Main invention of gas invention _ In the new method for the preparation of composite mixed particles (PCC+ATH) of the cedar-structure having the prior art method, providing improved carbonic acid composite composite particles , in particular, using its synergistic effect, applied to halogen-free flame-retardant wire and cable; further hope to provide improved (four) carbon-particles on other systems, such as flame-retardant fillers in PE, PP plastic materials; It is desirable to be able to provide two methods for the same chemical compounding, and to provide improved carbonic acid per composite mixed particles in these applications. [Summary of the Invention] The present invention provides a chemical synthesis of oxidized water (ATH) coated on stone. A method for producing composite mixed particles of calcium acid sulphate (PCC) microparticles, comprising a second solution, a calcium carbonate slurry solution having good dispersibility (using a dioxide = rolling body to make an aqueous solution of cerium oxide dance) Acidification to produce carbonic acid crystals and high temperature ripening reaction); Second ········································································· Third, the crystal growth reaction is used to grow aluminum hydroxide crystals to produce a core-shell crystal (PCC+ATH) composite mixed particle. As is generally known, the surface treatment of calcium carbonate can be through physical adsorption or chemistry. The reaction method coats the surface treatment agent on the surface of the calcium carbonate to form a surface-modified layer, which is surface-activated. At present, the surface modification of carbonic acid is mostly, the surface modification, the surface modification of the coupling agent, and the high Molecular (polymer) surface specificity, in order to improve the dispersibility and reinforcement of cerium carbonate in organic polymers, but the research on inorganic surface modification is rare. The surface of carbonic acid I bow is coated with inorganic ATH layer. It can have the advantages of two materials at the same time, such as · · surface gloss, whiteness, dispersibility, flame retardant, etc. have been significantly improved, and can use the composite mixed particle shell ΑΊΉ 0H base and decane coupling agent official The energy base is used as a bonding surface treatment to produce a new composite hybrid material and application. The above-mentioned core-shell structure (PCC+ΑΤΗ) composite mixed particle is composed of carbonic acid 6 200835649 M1~G·5 and nanometer-sized hydroxide. Ming crystals ^ 'Γ U-grade hydrogen oxygen is coated with van der Waals force to block acid and grow through the crystal 'forming the shell of the core-shell structure (PCC+ATH), and then obtain the inorganic modification The quality of the carbonic acid is about tmt' also (four) material characteristics of the read-shell structure of the CPCC + ATH) composite hybrid material. Hereinafter, the present invention will be described in more detail.

In the present invention, the type of carbonate which is a raw material is obtained by chemically synthesizing (precipitating) calcium carbonate. The (precipitated) calcium carbonate can be obtained by a known method such as a lime milk-carbon dioxide reaction method, a calcium chloride-alkali ash reaction method, or a lime milk-alkali ash reaction method. Taking the lime milk-carbon dioxide reaction method as an example, the limestone rough stone and the anthracite coal are calcined to form quicklime, and the quicklime is synthesized into lime milk (calcium hydroxide aqueous solution) by water, and the concentration is 1 to 25% by weight. The dioxin released when the lime is calcined (the ruthenium carbon is passed through the bottom of the reactor to react it) and the reaction initiation temperature is about 8 to 50 ° C, thereby generating a carbonation dance. Under the condition, the desired sub-micron-sized carbonic acid i-core microparticles can be obtained. The carbonic acid-like carbonated carbonic acid solution is subjected to a ripening reaction and condition control at a temperature of about 60 to 90 ° C to form a completely dispersed carbonic acid. The slurry BET specific surface area is not particularly limited, and is usually 5 to 120 m 2 /g, preferably 1 to 110 m 2 /g, more preferably 20 to 100 m 2 /g. Here, the BET specific surface area can be calculated by detecting the volume of nitrogen molecules adsorbed by the carbonic acid particles by the gas adsorption method. 200835649 The particle size of the raw acid-breaking mother can be appropriately selected to obtain the desired However, in general, it is better to use 0. 02~0·3/zm for the primary particle diameter of the acid-storing fresh particles in the scanning electron microscope. Alumina coating] In the present invention, the hydrogenation coating refers to a hydroxide coating obtained by subjecting an aqueous solution of sodium sulphate to carbonization and crystallization. 1. Aluminosilicate aqueous solution dissolves aluminum hydroxide in a sheet. In an alkali solution (at a high temperature, the temperature is about 80 to 110 ° C) to produce a supersaturated aqueous solution of sodium nitrate, wherein the molar ratio of Na1〇 to Al1〇2 in the preparation condition is preferably L 2~2. As shown below: A1 (OH)a+NaOH->NaAl〇2+2H2〇1 Aluminium hydroxide-carbonization method under appropriate reaction conditions (concentration, temperature), via carbonization reaction, and root 2 'The nano-hydroxide is coated with van der Waals on the carbonated microparticles: 2NaAl〇2+C〇2+3H2〇^Na2C〇3+2A1 (OH)3 where the hydroxide on the carbonate #5 microparticles The crystallization process of aluminum is carried out by the aqueous sodium aluminate solution of the item 1. The temperature is about 15~3 (rCT, the reverse of carbon dioxide gas It is a heterogeneous reaction involving gas, liquid and solid phases, including the absorption of carbon dioxide by sodium metasilicate aqueous solution, and the chemical reaction between the two and the crystallization of aluminum hydroxide. The process of precipitation and the like is obtained by the above carbonization reaction, which is a "sodium aluminosilicate" (molecular formula: 2C〇1 · η & Ο), which must be purified by hydrothermal treatment to produce aluminum hydroxide. The hydrothermal treatment is The dawsonite gel is redispersed into deionized water at a temperature of about 8 〇~ and fixed at a fixed time to convert the .200835649 and =ίί stone into hydroxide crystals, and then transition and repeat The hydrothermal treatment method is three times, and (4) busy drying. Since the "silk sodium ls stone transfer" has an ultrafine structure, it is obtained by hydrothermal treatment, and the nano-aluminum hydroxide is coated on the carbonic acid particles. 3·Aluminum Hydroxide-Crystalization Method, the (10) yeah composite mixed particle seed crystal J^ suitable ratio obtained by the carbonation reaction is added to the aqueous solution of 1. item-Ming sodium, the temperature is about 60~90 C. The stirring time is about 12 to 5 hours, and the nano-sized aluminum hydroxide crystal coated on the carbonic acid particle Φ continues to grow. The crystallization reaction is shown by the following chemical reaction formula:

NaAl〇2+2H2〇->Al (OH)3+NaOH * According to the above concept, wherein the carbonated toluene solution can be used in a solid concentration of 1 to 30% by weight, preferably 2 to 15% by weight. . According to the above concept, the sodium aluminate aqueous solution can be used in a concentration of 1 to 50% by weight. According to the above concept, the amount of aluminum hydroxide coated on the calcium carbonate particles is usually 1 to 80 parts by weight relative to 100 parts by weight of the raw material calcium carbonate. Further, it is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight. The amount of aluminum hydroxide coated can be appropriately adjusted depending on the BET specific surface area of carbonic acid. According to the above concept, the aluminum hydroxide coated with the calcium carbonate fine particles has a BET specific surface area of 4 to 110 mVg. The present invention provides a process for preparing (PCC + ATH) composite mixed particles. The method comprises the steps of: preparing a first aqueous solution comprising a fully dispersed calcium sulphate slurry solution, and a second aqueous solution comprising a sodium aluminate aqueous solution, the first aqueous solution And the second aqueous solution is mixed in proportion to form a mixed liquid' control reaction temperature of the mixed liquid, and carbonization and crystallization reaction are used to form a 200835649 (PCC+ΑΤΗ) composite mixed particle having a core-shell structure. According to the above concept, the fully highly dispersible hydrophobic body described herein, the stabilized carbonic acid particles suitably have a particle size of about 〇", preferably about 〇2~〇3//m. The particle size is large. ·5. With the calcium carbonate particles with better particle size as the core, the ATH / rate will increase significantly.

According to the above concept, calcium carbonate particles are monodisperse in nature, that is, they have a rather narrow particle size distribution. Suitably, the calcium-retaining particles have a relative standard deviation of particle size distribution of less than about 2%, preferably less than about 12%, and most preferably less than about 8%. The relative standard deviation of the particle size distribution is the ratio between the mean of the number = small and the standard deviation of the particle size distribution. According to the above concept, the vanadium 8~ muscle of the aluminum hydroxide carbonization reaction is preferably 12~ peach, and optimally = 5 degrees $f. According to the above concept, the crystallization reaction is optimally 70. ~9〇°C. The reaction mixture is suitably stirred to provide a homogeneous solution. According to the above concept, the composite mixed particles coated with carbonic acid dance (PCC) by KOH must undergo a separation step in order to wash away any possible excess = electrolyte, which can be separated by, for example, filtration or centrifugation. To be done. The present invention is further directed to obtaining composite hybrid particles coated with aluminum hydroxide (pCC) particles via aluminum hydroxide by the methods described herein. The composite admixture of the calcium carbonate (ATH) coated with calcium carbonate (PCC) particles utilizes the synergistic effect of the two to provide advantageous physical and chemical properties, particularly for use in flame retardant materials, and the use of composite mixed particles. The 0H group of the outer shell ATH is bonded to a decane coupling agent. The composite mixed particles coated with aluminum hydroxide (ATH) on carbonic acid #5 (PCC) particles can be provided in any size because the size of the calcium carbonate microparticles can be controlled via the reaction conditions, and the hydrogen peroxide can be prepared in combination with the size of the 200835649 TT particle. Ming (ATH) is coated with calcium carbonate (PCC) compound mixed material training _ light application. According to the above concept, the hydroquinone is directly coated on the porous dance particles with van der Waals force, without any intercalation between carbonic acid and aluminum hydroxide, such as organic surface modification and coupling. The surface modification of the agent, or the high score = (polymer) surface enthalpy; the crystallization reaction of the growth of the crystal of the recorded crystal, the formation of the nucleus of the nuclear phase (PGG + ATH) complex mixed silk is described here.

[Embodiment] Hereinafter, the present invention will be described by way of specific examples, but the present invention and the examples. Unless otherwise mentioned, all parts and percentages are considered to be 1 part by weight and percentage by weight. Strict volume % C〇2 The gas mixture in the air is led to a =3 liters of 3 liters of agitated glass reactor, L has 56 g / liter of quicklime ((10) concentration; temperature It is 2 〇 ° C and the temperature is 12 liters / minute, so that the slurry is charcoalized to sink the temple carbon dance. After 36 minutes of acidification reaction, the pH value is about 8 or less, and ι〇〇% = oxidation_exchange to carbonic acid _ The slurry was passed through a US Standard No. = micron sieve to remove coarse residue. The bottle of carbonated liquid is heated to a temperature of about 8 〇

Hi continued the lion 2 to do high temperature ripening should be mixed into a good state. The SEM (Scanning Electron Microscope) display (Fig. 2) showed that the particle size of the test product was 60 nm. 5 parts by weight of a 40% aqueous solution of sodium sulphate was added at room temperature with respect to 100 parts by weight of the precipitated fresh carbonate in the above slurry, and the temperature was controlled to be about 15 liters per minute. , c〇2 carbonation to the value of 邱-〇~11, and purified by hydrothermal treatment to produce aluminum hydroxide by 11 200835649 coating (method · filtration, deionized water washing, and heating deionization temperature about 80~l〇〇°C, with appropriate agitation and fixing time of about 2 hours, the above steps are repeated three times). Filter and place the oven at a temperature of about 11 Torr when it is dry. The core-shell structure (PCC+ATH) composite mixed particle seed crystal ^天, =0: Ming = ΓΛ, crystallization reaction, so that the nano-sized bismuth hydroxide: body growth sub-covering slaves | ^_ On the particles, the crystallization temperature is other seven, 24 hours. It is then washed by filtration, deionized water, repeated three times to lick other electrolytes, and then filtered and placed in an oven temperature of about 11 (rc dry 2 / s

According to the SEM (Scanning Electron Microscope) (Fig. 3), the average size of the material was 120 nm and it was well dispersed. Figure 10 is a device for the present invention. Figure 2 shows the size of the carbonated particles after carbonation and the average particle size is 6 〇. ^(四),反反3· Figure 3 is a scanning electron microscope showing that the present invention is coated with carbon oxide and crystallization reaction coated with carbonic acid (PCC) particles, and the average particle size is 12 nanometers. And have good grades'/

[Main component symbol description] 1 : C〇2 cylinder 2 : N2 cylinder 3 : C〇 2 flow meter 4 : team flow meter 5 : constant temperature circulating water tank 6 : speed controller 7 : mixer 8 z pH electrode 9 : temperature sensing 1: pH indicator 11: temperature indicator 12: reactor 13 · C〇2 gas diffuser 12

Claims (1)

200835649 X. Patent Application Range: 1 · A method for preparing (PCC+ΑΤΗ) composite mixed particles coated with aluminum hydroxide particles by aluminum hydroxide, comprising the steps of: providing a calcium hydroxide slurry solution, carbonating the hydrogen The calcium oxide slurry solution is converted into a carbonated slurry solution, the high temperature matured into the carbonated slurry solution, and the sodium aluminate aqueous solution is added as a dispersion mixed solution 'by carbonization, crystallization reaction, and hydrothermal treatment to form a calcium carbonate (PCC + ΑΤΗ) composite mixed particles having an argon-aluminum-coated core-shell structure on the microparticles. 2. The method of claim 1, wherein the concentration of the hydroxide slurry is from 1 to 25% by weight. 3. The method of claim 1, wherein the carbonated slurry solution has a starting temperature of between 8 and 50 ° C before the carbonation reaction. 4. The method according to claim 1, wherein the high temperature ripening reaction temperature of the carbonated slurry solution is between 6 Torr and 9 Torr. 5. The method of claim 1, wherein the carbonic acid has a BET specific surface area of from 5 to 120 m2/g. 6. The method of claim 1, wherein the sodium aluminate water is dissolved in an amount of from 1 to 50% by weight. 7. The method according to the first aspect of the patent application, wherein the dispersion mixed solution is subjected to carbonization and crystallization, wherein the aluminum layer is coated in an amount of from 1 to 80 parts by weight based on 1 part by weight of the carbonate. & 8. The method according to claim 7, wherein the carbonization reaction temperature of the dispersion mixed solution is between 15 and 30 °C. 9. According to the method of the special fiber product, item 7, the crystallization reaction temperature of the towel dispersion solution is between 70 and 90 °C. The core-shell structure (PCC+ΑΤΗ) composite mixed particle having a BET having a specific surface area ranging from 4 to 110 m/g, and a method according to any one of the claims of claim 9 Can be applied to flame retardant materials. 13