KR101637934B1 - Preparation method of porous alumino silica, and the porous alumino silica thereby - Google Patents
Preparation method of porous alumino silica, and the porous alumino silica thereby Download PDFInfo
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- KR101637934B1 KR101637934B1 KR1020150044064A KR20150044064A KR101637934B1 KR 101637934 B1 KR101637934 B1 KR 101637934B1 KR 1020150044064 A KR1020150044064 A KR 1020150044064A KR 20150044064 A KR20150044064 A KR 20150044064A KR 101637934 B1 KR101637934 B1 KR 101637934B1
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0082—Digital printing on bodies of particular shapes
- B41M5/0088—Digital printing on bodies of particular shapes by ink-jet printing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C01P2006/14—Pore volume
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention relates to a process for producing porous aluminosilica and porous aluminosilica produced thereby, and more particularly to a process for producing a porous aluminosilicate by dispersing crystalline aluminosilicate in a solution phase, followed by acid treatment by adding an acidic solution ); Adding a basic solution to the acid-treated aluminosilicate in step 1 to gelate (step 2); And hydrothermally synthesizing the gelled aluminosilicate in the step 2 to produce an alumino silica powder (step 3). The process for producing porous aluminosilica according to the present invention is a process for producing porous aluminosilica which is capable of easily controlling the particle size distribution and pore volume and the like and is a process for producing a crystalline aluminosilicate compound in which the molar ratio of aluminum and silicon is determined, A porous aluminosilica having a desired aluminum / silicon ratio can be prepared by appropriately selecting a crystalline aluminosilicate compound having an aluminum / silicon ratio suitable for its use.
Description
The present invention relates to a process for the preparation of porous aluminosilica and porous aluminosilicates produced thereby.
Alumino silica is used in a wide variety of fields such as coatings for catalysts, adsorbents, photographic films for photojournal advertising and photo paper, and tire fillers. As one of fields in which aluminosilica can be applied in this way, films and printing papers for printing are porous particles capable of capturing ink or the like well on the surface thereof in order to develop vivid colors and maintain color, that is, Alumina, silica and the like are coated and used. It is known that the alumina and silica particles for absorbing the ink to be used in this way are very important for uniformity of particles and formation of porous pores.
Meanwhile, with the expansion of the digital camera market worldwide and the increase in demand for high-quality digital output in the advertising and printing fields, large-sized manufacturing companies that manufacture photo paper and film for the United States, Japan, and Germany have developed alumina and silica, In the domestic market, alumina and silica are all imported from manufacturing countries such as Japan and Germany to manufacture photo paper and film. Accordingly, it is required to secure stable raw materials in producing photo paper and film.
In addition, expensive porous alumina is used as a high-grade coating material because it has nano-sized particles and a uniform distribution, while silica particles are used as a low-grade coating material due to their relatively large particle size. At this time, there is no particular coating material corresponding to the intermediate grade between porous alumina and silica, and it is a level where the porous alumina and silica are appropriately mixed when necessary. However, in the case of a mixed coating material in which porous alumina and silica are simply mixed, there is a problem that even if they are uniformly mixed, the result of some uneven coating can be derived, and the performance of the produced photo paper and film is deteriorated .
Korean Patent Laid-Open Publication No. 10-2007-0000665 (published on Jan. 03, 2007) discloses cation-modified polyvinyl alcohol and cation-modified polyvinylpyrrolidone, and has a primary particle size of 10 to 25 nm, (BET) of 103 to 171 m < 2 > / g, and porosity of 0.6 to 0.9 cg / g, and then drying the coated alumina sol. A method of manufacturing a printer photo paper has been disclosed.
However, as described above, the expensive porous alumina has the advantages of exhibiting nano-sized particles and a uniform distribution, but has a problem of poor price competitiveness due to its high price.
Therefore, studies have been made to prepare alumino silica having a high price competitiveness by using a mixture of alumina and silica as a coating material. In particular, alumino silica having a particle size distribution and physical properties capable of exhibiting a more uniform coating result Studies are underway to produce silica.
Meanwhile, in the conventional method for producing alumino silica, alumina raw material and silica raw material are prepared as starting materials in order to produce alumino silica, and they are mixed so as to exhibit a desired molar ratio, The gelled raw materials were subjected to a crystallization reaction under high temperature and high pressure to produce alumino silica. However, the aluminosilica produced by the conventional production method is not a structure in which aluminum and silicon elements are bonded to each other but merely a mixture in which each element is converted into alumina and silica, There is a problem that the porous pore characteristics can not be exhibited.
The inventors of the present invention have been studying a method of producing a relatively inexpensive aluminosilica as a porous material by using a crystalline aluminosilicate having a molar ratio of aluminosilicate to be prepared as a raw material, Gelation process and hydrothermal synthesis after weakening the bond of the silicate compound, and then the alumino silica showing the porous amorphous structure and the mixing ratio of the desired alumina and silica was developed and the present invention was completed.
It is an object of the present invention to provide a process for producing porous aluminosilica and porous alumino silica produced thereby.
In order to achieve the above object,
A step of dispersing the crystalline aluminosilicate in a solution phase, followed by an acid treatment by adding an acidic solution (step 1);
Adding a basic solution to the acid-treated aluminosilicate in
And hydrothermally synthesizing the gelled aluminosilicate in the step 2 to produce an alumino silica powder (step 3).
In addition,
The porous aluminosilica is produced by the above-described method and has a uniform particle size distribution and pore size, and is amorphous.
Further,
Wherein the porous alumino silica is coated on the surface thereof,
Also, there is provided a photographic paper on which the porous alumino silica is coated on the surface.
The process for producing porous aluminosilica according to the present invention is a process for producing porous aluminosilica which is capable of easily controlling the particle size distribution and pore volume and the like and is a process for producing a crystalline aluminosilicate compound in which the molar ratio of aluminum and silicon is determined, A porous aluminosilica having a desired aluminum / silicon ratio can be prepared by appropriately selecting a crystalline aluminosilicate compound having an aluminum / silicon ratio suitable for its use.
In addition, the porous alumino silica produced according to the present invention has uniform particle size distribution and pore size, and can be applied to an inkjet print film, a photo paper, etc. as the pore volume increases, and can be used as a tire filler, a catalyst, have.
1 is a flow chart sequentially showing an example of a method for producing porous alumino silica according to the present invention;
2 is a graph showing the particle size distribution of the porous alumino silica prepared in Example 1 according to the present invention;
3 is a graph showing the particle size distribution of the mixed powder disclosed in Comparative Example 1;
4 is a photograph of the porous aluminosilica prepared in Example 1 according to the present invention and the mixed powder disclosed in Comparative Example 1 by scanning electron microscopy.
The present invention
A step of dispersing the crystalline aluminosilicate in a solution phase, followed by an acid treatment by adding an acidic solution (step 1);
Adding a basic solution to the acid-treated aluminosilicate in
And hydrothermally synthesizing the gelled aluminosilicate in the step 2 to produce an alumino silica powder (step 3).
1 is a flow chart sequentially showing an example of a method for producing porous alumino silica according to the present invention,
Hereinafter, the method for producing the porous alumino silica according to the present invention will be described in detail for each step.
In the method for producing porous alumino silica according to the present invention,
As described above, the process for producing porous aluminosilica according to the present invention is intended to produce amorphous porous aluminosilica by using crystalline aluminosilicate as a raw material. In
The crystalline aluminosilicate in
As described above, the use of the crystalline zeolite as the raw material in the
It is also preferred that the acid treatment of
In
On the other hand, when the acid treatment is carried out at a pH of less than 3, an excess of acidic solution may be required, and when the acid treatment is carried out at a pH above 4, the crystal structure of the aluminosilicate compound is weakened and destroyed There is a problem that consumes a long time. That is, when the acid treatment is carried out at a pH exceeding 4, the crystal structure of the aluminosilicate compound is weakened and the crystal structure of the aluminosilicate compound is not destroyed, which may interfere with the production of new crystals of alumino silica.
Further, in order to more smoothly carry out the acid treatment in the
In the method for producing porous alumino silica according to the present invention, step 2 is a step of gelation by adding a basic solution to the acid-treated aluminosilicate in
Through the gelation in the step 2, the aluminosilicate with weak bonding of aluminum and silicon elements can be reacted with the acid treatment in the
At this time, in order to perform the gelation of the step 2, an appropriate amount of an aqueous sodium hydroxide solution may be added as a basic solution, and the gelation may be performed at a pH of 10 to 12.
The pH at which the gelation is performed can be controlled depending on the pH conditions, so that the physical properties of the porous alumino silica to be prepared in step 3 can be determined later. When the gelation of step 2 is carried out at a pH lower than 10, there is a problem in that it can not be an economical process such as long reaction time is required in hydrothermal synthesis. When the pH is more than 12, Since the solution may be required, it is also uneconomical, and the crystallization reaction proceeds rapidly due to the high alkali concentration during the hydrothermal synthesis, which results in nonuniform particle size as well as phase transition to other crystals.
In the method for producing porous alumino silica according to the present invention, step 3 is a step of hydrothermally synthesizing gelled aluminosilicate in step 2 to produce alumino silica powder.
The gelled aluminosilicate may be prepared from amorphous porous alumino silica through the hydrothermal synthesis of step 3, and the hydrothermal synthesis of step 3 is preferably performed at a temperature of 60 to 120 ° C for 3 to 48 hours. If the hydrothermal synthesis is carried out at a low temperature outside the above range, the reaction required time becomes too long, which results in an uneconomical process. In addition, if proper agitation speed is not maintained, it is difficult to obtain uniform crystal grains, The pore volume is formed. On the other hand, when the reaction is carried out at an excessively high temperature, there is a problem that the phase transition reaction to the crystal other than the desired alumino silica crystal proceeds due to the progress of the rapid crystallization reaction.
The hydrothermal synthesis of step 3 above may also be carried out with agitation of gelled aluminosilicate at a rate of 300-350 rpm.
When the gelled aluminosilicate is maintained at a constant stirring speed during the hydrothermal synthesis process in step 3, the uniform temperature and gel state in the reactor can be maintained, so that porous alumino silica having reproducibility and uniform physical properties can be obtained .
The aluminosilica prepared through the hydrothermal synthesis in the step 3 may be dried after being washed several times and finally be made into porous alumino silica. In the present invention, the conditions under which the washing and drying are performed are not particularly limited, and may be carried out by appropriately selecting known washing and drying methods.
The porous aluminosilicate according to the present invention can be produced by using a crystalline aluminosilicate compound as a raw material and appropriately selecting a crystalline aluminosilicate compound having a ratio aluminum / silicon of a desired composition to obtain a desired aluminum / The porous aluminosilica can be easily prepared and the particle size distribution and the pore volume of the prepared porous alumino silica can be easily controlled. Therefore, it can be used for the coating of catalysts, adsorbents, films for ink jet printing and photo paper, And the like.
In addition,
The present invention provides porous aluminosilica prepared by the above-described method and characterized in that the particle size distribution and pore size are uniform and amorphous.
The porous aluminosilicate according to the present invention is prepared by using the crystalline aluminosilicate as a raw material through the above production method. More specifically, crystalline zeolite is selected as a raw material and an alkali solution in the aluminosilicate compound The components are extracted by dropping the structure below the pH at which the structure is collapsed to weaken the binding of the aluminosilicate compound, gelation using a basic solution, and hydrothermally synthesizing the compound.
At this time, in the conventional alumino silica, the alumino silica was prepared by preparing the alumina raw material and the silica raw material as starting materials, but the alumino silica thus prepared was not a structure in which aluminum and silicon elements were bonded to each other Of the raw materials are converted into alumina and silica, which are merely a mixture of them, and there is a problem in that the conversion into the crystalline compound is not carried out and thus the porous pore characteristics can not be exhibited.
On the other hand, the porous alumino silica according to the present invention is a homogeneous alumina silica in which silica and alumina are present in the form of a compound, and can exhibit fine and uniform particle size distribution. As the porous alumino silica is produced in an amorphous form, Can exhibit porosity that exhibits a pore volume of 0.9 to 1.5 cm < 3 > / g.
Accordingly, the porous alumino silica according to the present invention can be used as a coating material for a catalyst, an adsorbent, a film for inkjet printing and a photo paper, a tire filler, and the like.
Further,
Wherein the porous alumino silica is coated on the surface thereof,
Also, there is provided a photographic paper on which the porous alumino silica is coated on the surface.
As described above, aluminosilica can be used as a catalyst, an adsorbent, a coating for inkjet print film and photo paper, a tire filler, and the like. Recently, the digital camera market has expanded and the demand for high quality digital output And the use thereof as a printing film and a photo paper is increasing. At this time, the aluminosilica used as a printing film and a photo paper is coated on the surface of a printing film and a photo paper for the purpose of vivid color development and color retention of the resultant product. In order to contain ink well, Whether or not it is known to be very important.
On the other hand, the alumino silica according to the present invention can exhibit a porous property showing a pore volume of porous, preferably 0.9 to 1.5 cm 3 / g, and can exhibit a uniform particle size distribution and pore volume, A film for ink jet printing in which the porous alumino silica is coated on the surface, and a photo paper coated with the porous alumino silica on the surface.
Since the porous film of alumino silica is coated on the surface of the inkjet print film and the printing paper according to the present invention, the ink used for printing can be effectively contained in the pores of the alumino silica, .
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.
≪ Example 1 > Preparation of
Step 1: Zeolite 4A in the crystalline zeolite compound was used as a raw material, 950 g of H 2 O was added to 50 g of zeolite 4A as a raw material, and the zeolite was dispersed at a concentration of 5% by weight. 120 g of nitric acid aqueous solution was added to adjust the pH to 3.5 to destroy the crystals of zeolite 4A. Thereafter, the dispersion solution phase was sufficiently stirred at room temperature for 30 minutes at a speed of 350 rpm to completely break the crystal.
Step 2: 60 g of a 20% by weight aqueous solution of sodium hydroxide was added to the zeolite 4A slurry solution in which the crystal structure was destroyed in
Step 3: The slurry of zeolite 4A gelled in step 2 was transferred to a hydrothermal synthesis reactor and hydrothermally synthesized at a temperature of 70 or 110 ° C for 6 to 48 hours to prepare alumino silica. At this time, the hydrothermal synthesis reactor was equipped with a stirrer and hydrothermal synthesis was carried out by continuously stirring at a stirring speed of 350 rpm during hydrothermal synthesis.
After the hydrothermal synthesis reaction was completed, the reaction product was cooled to room temperature, filtered / washed several times with water, and dried at 110 ° C to prepare porous alumino silica powder.
The process conditions of Example 1 and the physical properties of the porous alumino silica prepared in Example 1 were measured and are shown in Table 1 below.
pH
(° C)
(h)
S BET (m 2 / g)
V p (cm 3 / g)
D (A)
≪ Example 2 > Preparation of porous aluminosilica 2
Step 1: Zeolite 13X in the crystalline zeolite compound was used as a raw material and 950 g of H 2 O was added to 50 g of the raw material zeolite 13X to disperse the zeolite at a concentration of 5% by weight. Then, 20% 100 g of nitric acid aqueous solution was added to adjust pH to 3.5 to destroy crystals of zeolite 13X. Thereafter, the dispersion solution phase was sufficiently stirred at room temperature for 30 minutes at a speed of 350 rpm to completely break the crystal.
Step 2: 60 g of a 20% by weight sodium hydroxide aqueous solution was added to the zeolite 13X slurry solution in which the crystal structure was destroyed in
Step 3: The zeolite 13X slurry solution gelled in step 2 was transferred to a hydrothermal synthesis reactor and hydrothermally synthesized at 70 or 110 ° C for 3 to 48 hours to prepare alumino silica. During the hydrothermal synthesis, hydrothermal synthesis was continued by stirring at a stirring speed of 350 rpm.
After the hydrothermal synthesis reaction was completed, the reaction product was cooled to room temperature, filtered / washed several times with water, and dried at 110 ° C to prepare porous alumino silica powder.
The process conditions of Example 2 and the physical properties of the porous alumino silica prepared in Example 2 were measured and are shown in Table 2 below.
pH
(° C)
(h)
S BET (m 2 / g)
V p (cm 3 / g)
D (A)
≪ Example 3 > Preparation of porous aluminosilica 3
Step 1: Zeolite Y in the crystalline zeolite compound was used as a raw material and 950 g of H 2 O was added to 50 g of zeolite Y as a raw material to disperse the zeolite at a concentration of 5 wt% 80 g of nitric acid aqueous solution was added to adjust the pH to 3.5, thereby destroying the crystals of zeolite Y. [ Thereafter, the dispersion solution phase was sufficiently stirred at a stirring speed of 350 rpm at room temperature for 30 minutes to completely break the crystal.
Step 2: 60 g of 20% by weight aqueous sodium hydroxide solution was added to the zeolite Y slurry solution having the crystal structure destroyed in the
Step 3: The zeolite Y slurry solution gelled in step 2 was transferred to a hydrothermal synthesis reactor and hydrothermally synthesized at 70 or 110 ° C for 3 to 48 hours to prepare alumino silica. During the hydrothermal synthesis, hydrothermal synthesis was continued by stirring at a stirring speed of 350 rpm.
After the hydrothermal synthesis reaction was completed, the reaction product was cooled to room temperature, filtered / washed several times with water, and dried at 110 ° C to prepare porous alumino silica powder.
The process conditions of Example 3 and the physical properties of the porous alumino silica prepared in Example 3 were measured and are shown in Table 3 below.
pH
(° C)
(h)
S BET (m 2 / g)
V p (cm 3 / g)
D (A)
≪ Example 4 > Preparation of porous aluminosilica 4
Step 1: Zeolite ZSM-5 in the crystalline zeolite compound was used as a raw material and 950 g of H 2 O was added to 50 g of zeolite ZSM-5 as a raw material to disperse the zeolite at a concentration of 5% by weight. 70 g of a nitric acid aqueous solution having a concentration of% by weight was added to adjust the pH to 3.5 to destroy crystals of zeolite ZSM-5. Thereafter, the dispersion solution phase was sufficiently stirred at room temperature for 30 minutes at 350 rpm to completely break the crystal.
Step 2: 30 g of a 20 wt% aqueous solution of sodium hydroxide was added to the zeolite ZSM-5 slurry solution having the crystal structure destroyed in the
Step 3: The zeolite ZSM-5 slurry solution gelled in step 2 was transferred to a hydrothermal synthesis reactor and hydrothermally synthesized at 70 or 110 ° C for 3 to 48 hours to prepare alumino silica. During the hydrothermal synthesis, hydrothermal synthesis was continued by stirring at a stirring speed of 350 rpm.
After the hydrothermal synthesis reaction was completed, the reaction product was cooled to room temperature, filtered / washed several times with water, and dried at 110 ° C to prepare porous alumino silica powder.
The process conditions of Example 4 and the physical properties of the porous alumino silica prepared in Example 4 were measured and are shown in Table 4 below.
pH
(° C)
(h)
S BET (m 2 / g)
V p (cm 3 / g)
D (A)
As shown in Tables 1 to 4, the specific surface area, pore volume, and pore size of the porous alumino silica prepared in Examples 1 to 4 according to the present invention can be controlled according to pH and hydrothermal synthesis process conditions And it can be confirmed that the produced alumino silica exhibits porosity.
≪ Comparative Example 1 &
Silica and alumina were simply mixed to have the same Si / Al ratio as the porous alumino silica prepared in Example 1 according to the present invention.
<Experimental Example 1> Analysis of particle size distribution
The particle size distribution of the porous aluminosilica prepared in Example 1 and the silica alumina mixed powder of Comparative Example 1 was analyzed using a particle analyzer. The results of the analysis are shown in FIG. 2 and FIG.
As shown in FIG. 2, it can be seen that the porous alumino silica powder prepared in Example 1 according to the present invention exhibits a distribution having a single particle size. On the other hand, as shown in FIG. 3, As a result, the particle size distribution of alumina and silica is different from that of alumina and silica. As a result, the mixed powder of Comparative Example 1 has a uniform particle size distribution Able to know.
Thus, it can be seen that the porous alumina silica prepared according to the present invention is an alumina silica compound which can exhibit a uniform particle size distribution.
<Experimental Example 2> Scanning electron microscopic observation
The porous aluminosilica prepared in Example 1 and the silica alumina mixed powder of Comparative Example 1 were observed using a scanning electron microscope and the results are shown in FIG.
As shown in FIG. 4, it can be seen that the porous alumino silica prepared in Example 1 exhibits an amorphous uniform shape instead of individual particles. On the other hand, in the case of the mixed powder of Comparative Example 1, It can be seen that the silica particles are a simple mixture that exists separately. Thus, it was confirmed that the porous alumina silica prepared according to the present invention is not a simple mixture but an amorphous alumina silica compound.
Claims (10)
Adding a basic solution to the acid-treated aluminosilicate in the step 1 and gelating the same into a network structure (step 2); And
(3) hydrothermally synthesizing the gelled aluminosilicate in the step (2) to produce an aluminosilica powder, the method comprising the steps of:
Wherein the alumino silica powder is amorphous and has a pore volume of 0.9 to 1.5 cm < 3 > / g, and is for surface coating of a film or a printing paper for ink jet printing.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2019059594A1 (en) * | 2017-09-22 | 2019-03-28 | 주식회사 엘지화학 | Method for manufacturing aluminosilicate nanoparticles having excellent dispersibility, rubber reinforcing member comprising aluminosilicate nanoparticles, and rubber composition comprising same for tire |
KR20190034087A (en) * | 2017-09-22 | 2019-04-01 | 주식회사 엘지화학 | Method for preparing aluminosilicate nanoparticles having excellent dispersion, a reinforcing materials for rubber comprising the aluminosilicate nanoparticles, and rubber composition for tires comprising the reinforcing materials |
KR20190034088A (en) * | 2017-09-22 | 2019-04-01 | 주식회사 엘지화학 | Method for preparing aluminosilicate nanoparticles having excellent dispersion, a reinforcing materials for rubber comprising the aluminosilicate nanoparticles, and rubber composition for tires comprising the reinforcing materials |
KR20200103957A (en) * | 2019-02-26 | 2020-09-03 | 한국화학연구원 | Manufacturing method of porous silica |
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WO2019059594A1 (en) * | 2017-09-22 | 2019-03-28 | 주식회사 엘지화학 | Method for manufacturing aluminosilicate nanoparticles having excellent dispersibility, rubber reinforcing member comprising aluminosilicate nanoparticles, and rubber composition comprising same for tire |
KR20190034087A (en) * | 2017-09-22 | 2019-04-01 | 주식회사 엘지화학 | Method for preparing aluminosilicate nanoparticles having excellent dispersion, a reinforcing materials for rubber comprising the aluminosilicate nanoparticles, and rubber composition for tires comprising the reinforcing materials |
KR20190034088A (en) * | 2017-09-22 | 2019-04-01 | 주식회사 엘지화학 | Method for preparing aluminosilicate nanoparticles having excellent dispersion, a reinforcing materials for rubber comprising the aluminosilicate nanoparticles, and rubber composition for tires comprising the reinforcing materials |
KR102150646B1 (en) | 2017-09-22 | 2020-09-01 | 주식회사 엘지화학 | Method for preparing aluminosilicate nanoparticles having excellent dispersion, a reinforcing materials for rubber comprising the aluminosilicate nanoparticles, and rubber composition for tires comprising the reinforcing materials |
KR102150645B1 (en) | 2017-09-22 | 2020-09-01 | 주식회사 엘지화학 | Method for preparing aluminosilicate nanoparticles having excellent dispersion, a reinforcing materials for rubber comprising the aluminosilicate nanoparticles, and rubber composition for tires comprising the reinforcing materials |
KR20200103957A (en) * | 2019-02-26 | 2020-09-03 | 한국화학연구원 | Manufacturing method of porous silica |
KR102229815B1 (en) | 2019-02-26 | 2021-03-22 | 한국화학연구원 | Manufacturing method of porous silica |
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