Process for the production of magnesium oxide

Abstract: A process for the production of a magnesium oxide, which comprises (A) reacting a water-soluble magnesium salt with not more than 0.95 equivalent weight, per equivalent weight of the water-soluble magnesium salt, of an alkaline substance at a temperature of not more than 40°C, (B) heating the resultant reaction product and its reaction mother liquor at 50 to 120°C to form a magnesium hydroxide, (C) forming the magnesium oxide into particles having an average secondary particle diameter of 5 to 500 µm using a spray drier, (D) firing the particles at 1,100 to 1,600°C, and (E) pulverizing the resultant fired particles under conditions which do not substantially destroy the average secondary particle diameter obtained in step (C). The magnesium oxide obtained as above has further improved hydrolysis resistance, since the surface of magnesium oxide crystals exposed on the surface of the fired and pulverized product obtained at the step (E) is coated with silica or a reaction product between silica and magnesium oxide.

Description: The present invention relates to a process for the production of a magnesium oxide having high hydrolysis resistance and high fluidity. More specifically, the present invention relates to a process for the production of a magnesium oxide useful as a thermal conductivity improver of a resin, heat resistant material, electrical insulating material, sheathed heater filler, optical material, polishing material, etc., which has not only the physical properties inherent to magnesium oxide such as a high melting point (about 2,800°C), high electrical insulation, low dielectric loss, high light permeability, high thermal conductivity, basicity, etc., but also has high hydrolysis resistance and high fluidity. Magnesium oxides are classified into light burnt magnesium oxide (about 600 to 900°C) and hard burnt magnesium oxide (about 1,100 to 1,500°C). The former utilizes the excellent chemical activity which magnesium oxide exhibits in the neutralization of acids and halogens, and one typical example of such use is as an acid acceptor for halogenated rubbers such as chloroprene and Hypalon (Trade Name). The latter is used in articles which take advantage of the excellent physical properties of magnesium oxide, i.e. high melting point (about 2,800°C), high electrical insulation at high temperature, light permeability over a wide wavelength range, high thermal conductivity, etc., such as a heat resistant container, heat resistant part, heat insulating material, IC substrate, lens, sodium lamp container, sheathed heater, filler for resins, and polishing material. However, magnesium oxide has a problem that it is gradually corroded with water or steam and converted to magnesium hydroxide (hydration) whereby its various physical properties explained above are lost, and the scope of its use is hence limited. In order to solve the above problem, Japanese Laid-Open Patent Publication No. 85474/1986 proposes a firing process carried out at a temperature of not less than 1,600°C and below a melting temperature (2,800°C). Further, Japanese Laid-Open Patent Publication No. 36119/1986 proposes a process which comprises reacting a water solution containing a water-soluble magnesium salt with ammonia in such an amount that is 1 to 3.5 equivalent weight based on 1 equivalent weight of magnesium in the presence of a seed of magnesium hydroxide, thereby to form a magnesium hydroxide of an apparently spherical aggregate having an average secondary particle diameter of 5 to 500 µm, and firing the aggregate at 1,200 to 2,000°C. Japanese Laid-Open Patent Publications Nos. 288114/1987 and 45117/1988 propose processes which comprise subjecting a fine powder of magnesium oxide to surface treatment with an organic silicate compound, and then subjecting the fine powder to heat treatment to form coatings of silica on the particle surfaces of the magnesium oxide. However, in the firing process carried out at a temperature of not less than 1,600°C and below the melting temperature of magnesium oxide, the crystal growth of magnesium oxide is poor for the firing temperature, and that, because of the firing, there are formed larger masses, which have to be pulverized with high strength. Therefore, useful single crystals of magnesium oxide which are formed at this stage are destroyed, and a variety of lattice defects are caused on the crystal surfaces. For this reason, there are problems that the magnesium oxide obtained as above does not exhibit any satisfactory hydrolysis resistance, and at the same time, that the particles thereof have nonuniform profiles and exhibit poor fluidity, whereby high-filling of them in resins is made difficult. A magnesium oxide, which is formed by reacting an aqueous solution of a water-soluble magnesium salt with a prescribed amount of ammonia in the presence of a seed of magnesium hydroxide and then firing the reaction product at 1,200 to 2,000°C, has improved fluidity and can be easily filled into resins as compared with a powder-form product. In addition, the powder-form product here stands for a powder of coarse (not spherical) particles having an average particle diameter of about 10 to not more than 20 µm and nonuniform profiles, which are obtained by mechanical pulverization. Since, however, the magnesium hydroxide before the firing has a relatively large crystal form and has a fish scale-like profile, the formability by firing is not satisfactory, although it is improved more than that of a powder of magnesium hydroxide. Further, this magnesium hydroxide has to be fired at higher temperature. And, not only particles bond to each other in an aggregate, but also aggregates bond to each other, and there is an necessity of pulverization with high strength. As a result, nearly spherical secondary aggregates are concurrently destroyed, and the defect portion on the crystal surface increases in size. There is therefore formed a magnesium oxide having insufficient resistance to hydrolysis. According to the process which comprises subjecting a fine powder of magnesium oxide to surface treatment with an organic silicate compound, and then subjecting the fine powder to heat treatment to form coatings of silica on the particle surfaces of the magnesium oxide, there is provided a surface-coated magnesium oxide of which the hydrolysis resistance per unit area is improved as compared with magnesium oxide per se, since the surface of the magnesium oxide is coated with silica. Since, however, the surface area is large, the hydrolysis resistance is insufficient, and a larger amount of an organic silane is required due to large surface areas of about 5 to 20 m²/g. Therefore, this surface-coated magnesium oxide is not economical, and there is also a problem that the excellent thermal conductivity of magnesium oxide is deteriorated. DD-A-O 090 355 discloses a method for obtaining an MgO sinter with good flowing properties by reaction of Mg salts with alkali metal hydroxides, and separation in a spray drier (with partial conversion of Mg(OH)₂ to MgO). JP-A-59-321 168 discloses a method for obtaining magnesium oxide with high purity and dispersibility, which comprises reacting 1 equivalent of magnesium chloride with not more than 0.8 equivalent of calcium hydroxide at 0-50°C, aging the resulting magnesium chloride at 10-200°C and hydrolysing it to magnesium hydroxide, and calcining the magnesium hydroxide at 1,000°C for 1 hour. JP-A-61-185 158 discloses a process for producing magnesia powder having excellent hydration resistance, which comprises separating magnesia powder dispersed in an alkoxysilane solution and heat-treating the separated magnesia powder after drying. An object of the present invention is to solve the above problems and provide a process for the production, at a firing temperature lower than that used in conventional processes, of a magnesium oxide which not only has high fluidity to permit excellent workability, but also has a secondary particle diameter and bulk density to enable filling of it into a resin in an amount required for sufficient improvement of thermal conductivity, and which further has high resistance to hydrolysis. Another object of the present invention is to provide a process for the production of a magnesium oxide which comprises treating the above magnesium oxide having high hydrolysis resistance with an organic silane, whereby the magnesium oxide is imparted with excellent hydrolysis resistance. According to the present invention, there is provided a process for the production of a magnesium oxide, which comprises (A) reacting a water-soluble magnesium salt with not more than 0.95 equivalent weight, per equivalent weight of the water-soluble magnesium salt, of an alkaline substance, at a temperature of not more than 40°C, (B) heating the resultant reaction product and its reaction mother liquor at 50 to 120°C to form a magnesium hydroxide, (C) forming the magnesium hydroxide into particles having an average secondary particle diameter of 5 to 500 µm using a spray drier, (D) firing the particles at 1,100 to 1,600°C, and (E) pulverizing the resultant fired particles under conditions which do not substantially destroy the average secondary particle diameter obtained in step (C). Further, according to the present invention, there is also provided a process for the production of a magnesium oxide, which comprises bringing the magnesium oxide product of the above process into contact with a liquid mixture of alkoxysilane, alcohol, water and acid, and then firing the treated magnesium oxide at 500 to 900°C to form a silicon oxide on the surface thereof. The magnesium oxide obtained according to this process also has high fluidity and high filling ability. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron microscope photograph (crystal structure: magnification, 1,750 diameters) of particles of a magnesium hydroxide produced in Example 1. Fig. 2 is a scanning electron microscope photograph (crystal structure: magnification, 10,000 diameters) of the same. Fig. 3 is a scanning electron microscope photograph (crystal structure: magnification, 1,000 diameters) of particles of a magnesium oxide produced in Example 1. The present invention relies on the finding that a magnesium oxide having high fluidity, high filling ability and high hydrolysis resistance can be obtained by forming, at first, a high-dispersibility crystallite magnesium hydroxide synthesized by the special methods of steps (A) and (B) into particles using a spray drier in step (C), then subjecting the particles to low temperature firing in step (D) and pulverising the fired particles under conditions which do not substantially destroy them in step (E). The synthesis of the high-dispersibility crystallite magnesium hydroxide in the above steps (A) and (B) is carried out by mixing and reacting a water-soluble magnesium salt with an alkaline substance in an amount of not more than 0.95 equivalent weight, preferably 0.5 to 0.90 equivalent weight, based on 1 equivalent weight of the water-soluble magnesium salt, at a temperature of not more than 40°C, preferably not more than 30°C, and then heating the reaction product together with its reaction mother liquor at 50 to 120°C, for example under atmospheric or elevated pressure for 0.5 to several hours. According to the above synthesis, there is obtained a magnesium hydroxide which is a high-dispersibility crystallite having an average secondary particle diameter of not more than 2 µm, a BET specific surface area of 15 to 60 m²/g, a plate-like cryatal diameter of 0.01 to 0.5 µm and a thickness of 0.01 to 0.1 µm. By selecting the above magnesium hydroxide synthesis conditions suitably, a particularly preferable magnesium hydroxide can be obtained, which has an average secondary particle diameter of not more than 1.0 µm, a BET specific surface area of 20 to 40 m²/g, a plate-like crystal diameter of 0.05 to 0.3 µm and a plate-like crystal thickness of 0.02 to 0.06 µm. Examples of the water-soluble magnesium salt used in step (A) are magnesium chloride, magnesium nitrate and magnesium acetate. Examples of the alkaline substance are sodium hydroxide, calcium hydroxide and potassium hydroxide, ammonia. When the equivalent ratio of the alkaline substance and the temperature in the above reaction exceed 0.95 equivalent weight and 40°C, respectively, the intended high-dispersibility crystallite magnesium hydroxide is not obtained, but there is obtained a magnesium hydroxide having high aggregation powder, i.e. a larger secondary particle diameter. Thus, one advantage of the present invention, formability of a magnesium oxide by low-temperature firing, is lost. Further, when the heating temperature in step (B) exceeds 120°C, magnesium hydroxide crystals grow to excess, and formability by low-temperature firing and high fluidity are deteriorated. The formation of particles using a drier in the step (C) is carried out by, first, washing the magnesium hydroxide obtained in step (B) with water to remove impurities, and then forming the magnesium hydroxide into particles in the presence or absence of a binder and drying them, whereby it is freely possible to form generally spherical particles having an average secondary particle diameter of from about 5 to 500 µm. Incorporation of the binder is preferable in view of the fact that it increases the strength of the formed particles and prevents sintering among the particles at the time of firing. The particles obtained as above are composed of a magnesium hydroxide having high fluidity and high sinterability. Examples of the binder are organic binders such as polyvinyl alcohol, carboxymethyl cellulose, polyethylene wax, polyacrylic acid, polyvinyl acetate, styrene-acryl copolymer, gum arabic, polystyrene and sodium alginate. The firing of the magnesium hydroxide in step (D) is carried out at a temperature of 1,100 to 1,600, preferably 1,200 to 1,400°C, preferably for about 0.5 to several hours under a natural atmosphere or an atmosphere of oxygen, nitrogen, etc., using a firing apparatus such as a rotary kiln, tunnel furnace or muffle furnace. If the firing temperature is lower than the above lower limit, the resultant magnesium oxide has insufficient hydrolysis resistance, and when it is higher than 1,400°C, the resultant product is too hard and must be pulverized strongly, with the result that the spherical particles are damaged, deteriorating fluidity. Further, the hydrolysis resistance of the product is hardly improved as compared with that of a product formed by firing at lower temperatures than said upper limit. The pulverization of the fired particles in step (E) is carried out using a ball mill, crusher, etc., for dozens of minutes to several hours such that the particles obtained in step (C) are not substantially destroyed. When the firing temperature is suitably selected, it is possible to obtain a fired product that is so soft that it can be pulverized to the size of the particles using only e.g. a screen classifier without using any of the above pulverizing means. Only when steps (A) to (D) are carried out, i.e. only when the magnesium oxide is formed by subjecting the high-dispersibility crystallite magnesium hydroxide produced in step (B) to particle formation and drying using a spray drier in step (C) and then firing the formed particles at a low temperature in step (D), is it possible to maintain the spherical particle shape in pulverization step (E). The magnesium oxide formed in step (D) is in a state that sintering has proceeded only within each of the spray-formed particles, and the magnesium oxide can be easily pulverized and exhibits high hydrolysis resistance. Further, the magnesium oxide pulverized in step (E) has a nearly spherical form, a secondary particle diameter of 5 to 500 µm, preferably 10 to 50 µm and a bulk density of not less than 1 g/cm³. Due to these properties, this magnesium oxide can be incorporated into a resin in such an amount that is necessary to impart the resin with sufficient thermal conductivity, and has excellent workability for forming ceramics. Individual single crystals within the fired and pulverized product have a particle diameter of 0.5 to 10 µm and a BET specific surface area of not more than 1 m²/g. The magnesium oxide obtained as above can be imparted with even higher hydrolysis resistance by treating it as follows. The magnesium oxide is brought into contact, e.g. by mixing, with a liquid mixture of an alcohol such as methyl alcohol or ethyl alcohol, an alkoxysilane such as methoxy silane or ethoxy silane, water, and an acid such as hydrochloric acid, nitric acid, phosphoric acid or surfuric acid, preferably at a temperature up to 100°C, and the magnesium oxide is then separated by means of filtration, etc., and fired at a temperature of 300 to 900°C, preferably 500 to 800°C preferably for 0.1 hour to several hours. The magnesium oxide obtained as above has further improved hydrolysis resistance, since the surface of the magnesium oxide crystals exposed on the surface of the fired and pulverized product obtained in step (E) is coated with silica or a reaction product between silica and magnesium oxide. The amount of alkoxysilane, as SiO₂, for the above coating is 0.1 to 3 % by weight, preferably 0.2 to 2.0 % by weight, based on the magnesium oxide. In the present invention, those individual single crystals within the fired and pulverized product that have surface coatings of the alkoxysilane generally have a BET specific surface area of not more than 1 m²/g. Therefore, high hydrolysis resistance can be achieved using a smaller amount of silica than in a conventional technique for coating a magnesium oxide powder with silica. As a result, the excellent physical properties inherent to magnesium oxide, such as thermal conductivity, are not deteriorated. The copresence of a small amount of water and an acid is useful to promote reaction of the alkoxysilane and the magnesium oxide surface. According to the present invention: There is provided a process for the production of a magensium oxide having high hydrolysis resistance. There is also provided a process for the production of a magnesium oxide having high fluidity. There is further provided a process for the production of a magnesium oxide which can be filled in a resin in such an amount that can impart the resin with sufficient thermal conductivity. There is furthermore provided a process for the production of a magnesium oxide having a nearly spherical form, a secondary particle diameter of about 5 to 500 µm, and a bulk density of about 1 g/cm³. The present invention will be explained further in detail by reference to Examples. In the Examples, angles of repose were measured by using an angle of repose measuring device (model FK) manufactured by Konishi Seisakusho. EXAMPLE 1 Ion bittern (20 ℓ) containing 1.5 moles/ℓ of magnesium chloride and 0.5 mole/ℓ of calcium chloride was charged into a 50-liter stainless steel cylindrical reactor with a stirrer, and the temperature thereof was adjusted to about 25°C using a jacket. 12 ℓ of sodium hydroxide (4.0 moles/ℓ, corresponding to 0.8 equivalent weight based on magnesium chloride) was added over about 5 minutes while the mixture was stirred, and the reaction mixture was further stirred for 5 minutes. Then, the temperature thereof was elevated up to 90°C with stirring, and maintained at this temperature for about 2 hours. Thereafter, the reaction mixture was dehydrated by filtration under reduced pressure and washed with water to give a magnesium hydroxide. The magnesium hydroxide had a BET specific surface area of 22 m²/g and an average secondary particle diameter, measured by microtrack method, of 0.53 µm, and contained 99.6 % by weight of Mg(OH)₂ and 0.02 % by weight of CaO. The above magnesium hydroxide was dispersed in water to form a slurry containing about 20 % by weight thereof. 1 % by weight, based on the magnesium hydroxide, of a polyethylene wax in an emulsion state was added to and uniformly mixed with the slurry. Then, the mixture was formed into particles by using an NIRO spray drier in which the hot air inlet temperature was about 350 to 370°C and the air outlet temperature was about 100 to 110°C according to an atomizer method. Scanning electron microscopic observation of the magnesium hydroxide particles showed that they had nearly truly spherical profiles having a diameter of 20 to 40 µm, a crystal length of 0.1 to 0.2 µm, and a thickness of 0.02 to 0.04 µm (magnification, 1,750 diameters in Fig. 1, 10,000 diameters in Fig. 2). This spray-dried magnesium hydroxide was separated into three portions, and these portions were fired in a kanthal furnace at 1,150°C, 1,250°C and 1,400°C for 2 hours, respectively. The fired products obtained by firing at 1,150°C and 1,250°C were so soft as to be hand-crushable. The fired products each were pulverized in a ball mill for 0.5 to 1 hour, and the average secondary particle diameter of each was measured by a microtrack method as about 22 µm. Scanning electron microscopic observation showed that the fired products each were a sintered body in which nearly truly spherical crystals of magnesium oxide were densely filled (Fig. 3, magnification, 1,000 diameters). Table 1 shows the physical properties of the products fired at 1,150°C, 1,250°C and 1,400°C. EXAMPLE 2 Part of the magnesium hydroxide obtained in Example 1 was mixed with a styrene/acryl copolymer as a binder in an amount of 2 % by weight on the basis of the magnesium hydroxide, and the mixture was formed into particles and dried using a nozzle type spray drier (manufactured by NIRO) having a nozzle diameter of 2.4 mm under adjustment of the hot air inlet temperature to 400 to 420°C and the air outlet temperature to 150 to 170°C. The optical microscopic observation of the resultant magnesium hydroxide showed that it was spherical particles having a diameter of about 100 to 300 µm. These magnesium hydroxide particles were fired at 1,250°C for 3 hours. The fired particles were so soft as to be hand-crushable. These particles were treated in a ball mill for 30 minutes to give a magnesium sintered body having a nearly truly spherical form with an average secondary diameter of about 200 µm. Table 2 shows physical properties of the sintered body. EXAMPLE 3 Part (100 g) of each of the magnesium oxides (the products fired at 1,150°C, 1,250°C and 1,400°C in Example 1) was added to a liquid mixture of 3.5 g of tetraethoxysilane, 250 mℓ of ethyl alcohol, 20 mℓ of water and 20 mℓ of hydrochloric acid, and the mixture was fully stirred at about 70°C for 5 minutes, and filtered. The remaining solid was heated at 800°C for 2 hours to give a silane-treated magnesium oxide. Table 3 shows physical properties of the silane-treated magnesium oxides. Products fired at °C Hydrolysis resistance wt.% SiO₂ content wt.% MgO content wt.% 1,150 0.87 0.74 99.0 1,250 0.79 0.72 99.1 1,400 0.36 0.71 99.2 COMPARATIVE EXAMPLE 1 A magnesium hydroxide powder having a BET specific surface area of 40 m²/g and a secondary average particle diameter of 4.8 µm was fired in a kanthal furnace at 1,400°C for 2 hours, and then pulverized in a ball mill for about 6 hours. The resultant fired product had a hydrolysis resistance value of 28 wt.% and an angle of repose of 59°. This magnesium oxide was treated with tetraethoxysilane in the same way as in Example 3, and the treated product had a hydrolysis resistance value of 15.2 wt.%.

Claims: A process for the production of a magnesium oxide, which comprises (A) reacting a water-soluble magnesium salt with not more than 0.95 equivalent weight, per equivalent weight of the water-soluble magnesium salt, of an alkaline substance at a temperature of not more than 40°C, (B) heating the resultant reaction product and its reaction mother liquor at 50 to 120°C to form a magnesium hydroxide, (C) forming the magnesium hydroxide into particles having an average secondary particle diameter of 5 to 500 µm using a spray drier, (D) firing the particles at 1,100 to 1,600°C, and (E) pulverizing the resultant fired particles under conditions which do not substantially destroy the average secondary particle diameter obtained in step (C). A process according to claim 1, wherein the magnesium hydroxide formed in step (B) has a BET specific surface area of 15 to 60 m²/g, an average secondary particle diameter of not more than 2 µm and a calcium content, as CaO, of not more than 0.1% by weight based on the magnesium hydroxide. A process according to claim 1 or 2, wherein step (C) is carried out incorporating 0.1 to 10% by weight of a binder into the magnesium hydroxide. A process according to claim 1, 2 or 3 wherein the amount of alkaline substance used in seep (A) is 0.5 to 0.95 equivalent weight per equivalent weight of the water-soluble magnesium salt. A process according to any one of the preceding claims wherein the magnesium oxide product of step (E) has a single crystal particle diameter of 0.5 to 10 µm, a secondary particle diameter of 5 to 500 µm, a single crystal BET specific surface area of not more than 1 m²/g and an apparent specific gravity of not less than 1 g/cm³. A process according to any one of the preceding claims which comprises the additional step of treating the magnesium oxide obtained in step (E) by contacting it with a liquid mixture of alkoxysilane, alcohol, water and acid, and then firing the treated magnesium oxide at 300 to 900°C to form silicon oxide on the surface of the treated magnesium oxide. A process according to claim 6, wherein the treated magnesium oxide is surface-coated with 0.1 to 3% by weight, as SiO₂ and based on the magnesium oxide, of the alkoxysilane.

Inventors: ANABUKI HITOSHI, MANABE HITOSHI, MIYATA SHIGEO, ANABUKI, HITOSHI, MANABE, HITOSHI, MIYATA, SHIGEO
Applicants: KYOWA CHEM IND CO LTD, KYOWA CHEMICAL INDUSTRY CO., LTD.
Application year: 1990
Main classification: C01F5
IPC codes: C01F5, H01B3, C09C1