WO2012077846A1 - Composite organique/inorganique d'une grande robustesse à structure minérale en pont, et son procédé de fabrication - Google Patents

Composite organique/inorganique d'une grande robustesse à structure minérale en pont, et son procédé de fabrication Download PDF

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Publication number
WO2012077846A1
WO2012077846A1 PCT/KR2010/008847 KR2010008847W WO2012077846A1 WO 2012077846 A1 WO2012077846 A1 WO 2012077846A1 KR 2010008847 W KR2010008847 W KR 2010008847W WO 2012077846 A1 WO2012077846 A1 WO 2012077846A1
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Prior art keywords
inorganic composite
polymer
high strength
strength organic
inorganic
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PCT/KR2010/008847
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English (en)
Korean (ko)
Inventor
김영희
김수룡
권우택
이윤주
이준경
임형미
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한국세라믹기술원
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Publication of WO2012077846A1 publication Critical patent/WO2012077846A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • the present invention relates to a high-strength organic-inorganic composite having a mineral bridge structure and a method of manufacturing the same, and more particularly, to manufacturing an organic-inorganic composite in which inorganic particles having a matrix structure in a polymer polymer are regularly arranged using a hydrothermal hot press method.
  • the present invention relates to an organic-inorganic composite having a high strength by forming a mineral bridge between inorganic particles filled in a high molecular polymer and a method of preparing the same.
  • nanocomposite materials As a result, researches on polymer nanocomposites centering on nanoclays having very large aspect ratios (200 to 1000) have been actively conducted as nanocomposite materials.
  • nanoclays due to the nature of nanoclays, many layers are attached, making it difficult to exfoliate them. Therefore, it is difficult to obtain nanocomposites in which constituent materials are well dispersed.
  • Biomimetic nanocomposites are 25-50% lighter than metals of the same strength, and are emerging as materials to replace metals in automobile and aircraft parts. Since natural structures have very complex structures, it is difficult to imitate them. have.
  • nanocomposites that mimic high-strength natural materials, such as nacres and bones, but they have yet to develop materials with satisfactory performance.
  • lightweight nanocomposites composed of nanoclays and polymers that mimic the microstructure of abalone shells have been reported.
  • the present technology can only manufacture thin films.
  • Hydrothermal hot pressing method is a method for producing a solid sintered body at a relatively low temperature under saturated vapor pressure conditions, and has been mainly used for the solid body of calcium carbonate, magnesium carbonate, etc. which is difficult to sinter.
  • this method has been applied to the manufacture of biomaterials, and US Patent No. 6,338,810 discloses that calcium phosphate powders such as calcium triphosphate ( ⁇ -TCP: ⁇ -tricalcium phosphate) and calcium phosphate (TeCP) It describes the method of solidifying to a compact by applying the pressure of 100-500 Mpa between 100-500 degreeC in presence.
  • the present inventors use the hydrothermal hot pressing method to increase the filling rate of the inorganic particles in the polymer polymer, when the inorganic inorganic particles having a matrix structure in the polymer polymer is regularly arranged, and the inorganic particles filled in the polymer polymer Forming a mineral bridge between them was found to exhibit a significantly higher strength than the conventional organic-inorganic composites to complete the present invention.
  • An object of the present invention is to provide an organic-inorganic composite having a light weight and high strength that can be used in high value-added industries such as aviation industry, aerospace industry, automobile industry, energy industry, environmental industry, defense industry, construction industry, There is.
  • the present invention comprises a high-strength organic-inorganic composite comprising a polymer polymer and inorganic particles having a matrix structure uniformly arranged in the polymer polymer, a mineral bridge is formed between the inorganic particles to provide.
  • the present invention comprises the steps of dispersing the plate-shaped inorganic particles in a solvent in a container, followed by freezing casting to remove the solvent to prepare a solid (step 1); It provides a method for producing a high-strength organic-inorganic composite comprising the step of impregnating the solid in the polymer polymer to prepare a mixture (step 2) and the hydrothermal hot pressing step (step 3) after adding the mineralizer to the mixture.
  • the high strength organic-inorganic composite according to the present invention is prepared by uniformly dispersing 50 to 80% by weight of inorganic particles in 20 to 50% by weight of the polymer.
  • the polymer may be polyethylene, polypropylene, phenolic resin, polyamide, polycarbonate, and the like, and the plate-shaped inorganic particles may include nanoclay, calcium carbonate, silica, alumina, ceria, magnesium hydrooxide, and zinc oxide. , Iron oxide, titanium oxide and the like can be used.
  • a basic solution or an acid solution may be used as the mineralizer, and specifically, a basic solution such as sodium hydroxide or potassium hydroxide or an acid solution such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, or the like may be used.
  • the high strength organic-inorganic composite according to the present invention is prepared by uniformly dispersing plate-shaped inorganic particles in the polymer, and the inorganic particles may exhibit high strength by forming a mineral bridge by hydrothermal hot pressing.
  • the present invention provides a high strength and light weight organic-inorganic composite by regularly dispersing the plate-shaped inorganic particles in the polymer polymer to increase the filling rate of the inorganic particles, and forming a mineral bridge between the inorganic particles, thereby providing aerospace, aerospace, It can be widely used in high value-added industries such as automobile industry, energy industry, environmental industry, defense industry, construction industry and so on.
  • FIG. 1 is a process flow diagram schematically showing a manufacturing process of a high-strength organic-inorganic composite according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of the organic-inorganic composite showing a state in which a mineral bridge is formed between the inorganic particles dispersed in the polymer by a hydrothermal hot pressing process in the manufacturing process of the high-strength organic-inorganic composite of the present invention.
  • the present invention provides a high-strength organic-inorganic composite comprising a polymer polymer and inorganic particles having a matrix structure uniformly arranged in the polymer polymer, wherein a mineral bridge is formed between the inorganic particles.
  • the high strength organic-inorganic composite may be prepared including 20 to 50% by weight of the polymer polymer and 50 to 80% by weight of the inorganic particles.
  • the polymer may be polyethylene, polypropylene, phenolic resin, polyamide, polycarbonate, or the like, but is not limited thereto.
  • an oxide-based ceramic such as nanoclay, calcium carbonate, silica, alumina, ceria, magnesium hydrooxide, zinc oxide, iron oxide, titanium oxide, etc. including bentonite and montmorillonite may be used. It may be dispersed in the polymer polymer in the form of a plate.
  • the high-strength organic-inorganic composite according to the present invention has a structure in which inorganic particles are uniformly dispersed in a high molecular polymer, and a mineral bridge is formed between inorganic particles by hydrothermal hot pressing to obtain a high mechanical strength of 150-250 Mpa and 1.5- A density of 3 g / cm 3 is shown.
  • the inorganic particles are dispersed in a solvent such as a beaker, then freeze cast to remove the solvent to prepare a solid (step 1).
  • step 1 inorganic particles are dispersed in a solvent in a container, for example, water, alcohol, acetone, dichloroethylene, and the like, and then solidified by freezing at -100 to 0 ° C from the bottom of the container.
  • the freezing casting method is performed to form a porous skeleton and a solvent is removed using a vacuum pump to prepare a solid.
  • one or two or more plate-shaped particles selected from the group consisting of oxide ceramics such as nanoclays including bentonite and montmorillonite, calcium carbonate, silica, alumina and titanium oxide may be used. .
  • step 2 the solid prepared in step 1 is impregnated into the polymer polymer to prepare a mixture (step 2).
  • the polymer may be polyethylene, polypropylene, phenolic resin, polyamide, polycarbonate, or the like, but is not limited thereto.
  • step 3 the mineralizer is added to the mixture prepared in step 2, followed by hydrothermal hot press treatment (step 3).
  • step 3 100 to 200 parts by weight of the mineralizer may be added to the mixture with respect to the total weight of the mixture prepared in step 2, and then hydrothermal hot pressing may be performed.
  • a basic solution or an acid solution may be used.
  • a basic solution such as sodium hydroxide or potassium hydroxide or an acid solution such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, or the like may be used.
  • the addition of mineralizers to the mixture can enhance the solubility of the inorganic particles at high temperatures.
  • the mixture of the mixture prepared in step 2 and the mineralizer were introduced into a cell of a hydrothermal hot press device, and then a hydrothermal hot pressing process was performed at a pressure of 50 to 150 kN at 100 to 300 ° C. Can be performed.
  • This hydrothermal hot press process can be used to prepare a solid of inorganic matter using a dissolution-precipitation mechanism using a mineralizer at a low temperature.
  • the mineral bridge 120 is formed between the inorganic particles 110 when the hydrothermal hot pressing process is performed while the plate-shaped inorganic particles 110 are dispersed in the polymer 100 in step 3. do.
  • the high strength organic-inorganic composite of the present invention can be obtained by removing and drying the mineralizer from the product obtained by performing step 3 above.
  • the inorganic particles having a matrix structure is uniformly dispersed in the polymer polymer, a high-strength organic-inorganic composite having a structure in which a mineral bridge is formed between the inorganic particles can do.
  • the organic-inorganic composite prepared by the hydrothermal hot pressurization according to the present invention has excellent mechanical strength, which is a mineral bridge between the inorganic particles in the organic-inorganic composite of the present invention by hydrothermal hot pressurization. This is due to the formed structure.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composite organique/inorganique d'une grande robustesse faisant intervenir un procédé de pressage à chaud hydro-thermique, ainsi que son procédé de fabrication. Le composite organique/inorganique de l'invention comprend : un polymère ; des particules inorganiques à structure matricielle agencées uniformément à l'intérieur du polymère, des ponts minéraux étant formés entre les particules inorganiques. Des particules inorganiques en plaque sont réparties régulièrement à l'intérieur du polymère dans le but d'accroître le taux de remplissage de ces particules pour l'obtention d'un composite organique/inorganique très résistant et léger. Cette invention peut donc être largement utilisée dans des industries de premier rang, dans des domaines tels que l'aéronautique, l'espace, l'automobile, l'énergie, l'environnement, la défense ou le bâtiment.
PCT/KR2010/008847 2010-12-06 2010-12-10 Composite organique/inorganique d'une grande robustesse à structure minérale en pont, et son procédé de fabrication WO2012077846A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100123755A KR101268883B1 (ko) 2010-12-06 2010-12-06 미네랄브릿지 구조를 갖는 고강도 유무기 복합체 및 이의 제조방법
KR10-2010-0123755 2010-12-06

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WO2012077846A1 true WO2012077846A1 (fr) 2012-06-14

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889879A (en) * 1986-07-30 1989-12-26 Pluess Staufer Ag Thermoplastic compositions with very high content of pulverized mineral materials for incorporation in polymers
US20020038582A1 (en) * 1999-07-02 2002-04-04 Richard A. Holl Composites of powdered fillers and polymer matrix
US20060127480A1 (en) * 2002-10-11 2006-06-15 Michael Tobyn Pharmaceutical excipients comprising inorganic particles in association with an organic polymeric material and forming a solid reticulated matrix, compositions, manufacturing and use thereof
WO2009074554A1 (fr) * 2007-12-13 2009-06-18 Renault S.A.S. Procédé de préparation d'un matériau polymère transparent comprenant un polycarbonate thermoplastique et des nanoparticules minérales modifiées en surface
KR20100078741A (ko) * 2008-12-30 2010-07-08 주식회사 엘지화학 유무기 복합 조성물, 그 제조 방법, 상기를 포함하는 수처리 분리막 및 수처리 모듈

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100533734B1 (ko) * 2003-04-16 2005-12-22 한국화학연구원 고분자―유기 층상화합물 나노복합체의 제조방법
JP4375092B2 (ja) 2003-06-04 2009-12-02 株式会社村田製作所 セラミック組成物の製造方法
KR100599253B1 (ko) 2004-06-24 2006-07-13 한국화학연구원 무기 아세테이트의 열분해에 의한 무기나노입자/폴리머복합체의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889879A (en) * 1986-07-30 1989-12-26 Pluess Staufer Ag Thermoplastic compositions with very high content of pulverized mineral materials for incorporation in polymers
US20020038582A1 (en) * 1999-07-02 2002-04-04 Richard A. Holl Composites of powdered fillers and polymer matrix
US20060127480A1 (en) * 2002-10-11 2006-06-15 Michael Tobyn Pharmaceutical excipients comprising inorganic particles in association with an organic polymeric material and forming a solid reticulated matrix, compositions, manufacturing and use thereof
WO2009074554A1 (fr) * 2007-12-13 2009-06-18 Renault S.A.S. Procédé de préparation d'un matériau polymère transparent comprenant un polycarbonate thermoplastique et des nanoparticules minérales modifiées en surface
KR20100078741A (ko) * 2008-12-30 2010-07-08 주식회사 엘지화학 유무기 복합 조성물, 그 제조 방법, 상기를 포함하는 수처리 분리막 및 수처리 모듈

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KR101268883B1 (ko) 2013-05-29

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KR101268884B1 (ko) 미네랄브릿지 구조를 갖는 고강도 유무기 복합체 및 이의 제조방법

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