KR20090011358A - Method of making hydroxyapatite powder - Google Patents
Method of making hydroxyapatite powder Download PDFInfo
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- KR20090011358A KR20090011358A KR1020070074846A KR20070074846A KR20090011358A KR 20090011358 A KR20090011358 A KR 20090011358A KR 1020070074846 A KR1020070074846 A KR 1020070074846A KR 20070074846 A KR20070074846 A KR 20070074846A KR 20090011358 A KR20090011358 A KR 20090011358A
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- apatite
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 19
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 19
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 6
- 229910052586 apatite Inorganic materials 0.000 claims description 48
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 31
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229940048084 pyrophosphate Drugs 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 241000237502 Ostreidae Species 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000020636 oyster Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- -1 apatite hydroxides Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229940043256 calcium pyrophosphate Drugs 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000012442 analytical experiment Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
Description
본 발명은 수산화아파타이트 분말의 제조 방법에 관한 것으로서, 더욱 상세하게는 증류수에 피로인산을 희석하여 수산화칼슘과 직접 반응시켜 고순도의 수산화아파타이트 분말을 대량으로 제조할 수 있는 방법에 관한 것이다.The present invention relates to a method for producing apatite hydroxide powder, and more particularly, to a method for producing a high purity apatite hydroxide powder by diluting pyrophosphate in distilled water and directly reacting with calcium hydroxide.
통상적으로, 인체의 경조직은 무기질인 수산화아파타이트(Hydroxyapatite)와 유기질인 콜라겐(Collagen) 섬유로 구성되어 있다. 이 중에서 수산화아파타이트는 뼈나 치아를 이루는 무기성분, 즉 칼슘과 인으로 이루어진 무기성분의 화합물이다. 또한 인체에 존재하는 전 칼슘의 99%와 약 85%의 인이 경조직에 존재한다고 알려져 있다. 따라서 생체 무기성분과 동일한 조성인 수산화아파타이트는 인공치근 또는 뼈 충전재 등의 생체 경조직 대체 재료로서 매우 큰 관심을 불러일으키고 있으며, 생화학적인 관점에서 그 특성에 관한 연구가 광범위하게 진행되고 있다.Typically, the hard tissue of the human body is composed of inorganic hydroxyapatite (Hydroxyapatite) and organic collagen (Collagen) fibers. Among these, the hydroxide apatite is an inorganic compound consisting of bones and teeth, ie, calcium and phosphorus. In addition, 99% of the total calcium and about 85% of the phosphorus in the human body is known to exist in hard tissues. Therefore, apatite hydroxide, which has the same composition as the biological inorganic component, has attracted great interest as a substitute material for living hard tissues such as artificial tooth roots or bone fillers, and research on its properties from a biochemical point of view has been widely conducted.
한편, 합성 수산화아파타이트는 생체조직에 높은 친화성을 갖고 있으며, 수 산화아파타이트 세라믹스를 생체에 이식한 결과 뼈와 직접 결합한다는 사실이 보고된 바 있고, 현재 임상 실험에 응용되고 있다. 또한 수산화아파타이트는 흡착특성을 이용하여 알코올의 탈수촉매, 크로마토그래피용 고정상으로 이용되어 단백질이나 핵산류의 분리 등에 이용되고 있다. 그리고 형광재료, 감습재료, 효소담체, 치아 연마제, 칼슘 강화제 등에 응용되고 있으며, 항균성을 이용하여 치약이나 화장품 등의 다양한 제품에 사용되고 있는 실정이다.On the other hand, synthetic apatite has a high affinity for living tissue, and has been reported to be directly bonded to bone as a result of transplanting apatite hydroxide ceramics in vivo, and is currently applied in clinical trials. Apatite hydroxide is used as a dehydration catalyst for alcohol and a stationary phase for chromatography using adsorption characteristics, and is used for separation of proteins and nucleic acids. In addition, it is applied to fluorescent materials, moisture-sensitive materials, enzyme carriers, tooth abrasives, calcium enhancers, etc., and is used in various products such as toothpaste or cosmetics using antibacterial properties.
이와 같은 특성 및 용도를 갖는 수산화아파타이트를 합성하는 종래의 방법으로는 습식 합성법, 건식 합성법, 수열 합성법, 침전법 등을 들 수 있으며, 합성에 따라서 제조되는 분말의 특성, 즉 입자크기와 형태 및 입도 분포도가 각각 달라진다. 이러한 방법들 중에서 건식 합성법과 수열 합성법은 사용되는 장치가 고가이고 소비에너지가 크다는 단점이 있다. 또한 침전법은 제조과정이 간단하고 치밀한 소결체를 제조하기 위한 입자크기 등의 분말 특성이 우수하여 상기 방법들 중 가장 많이 사용되고 있다. 그러나 상기 침전법은 합성할 때 결정을 갖게 하기 위해 높은 온도에서 결정화시키는 과정을 포함한다. 이 경우 침전 조성물에 따라 약 600℃ 이상의 결정화 온도에서 화학당량적 조성의 수산화아파타이트(HAp)는 바람직하지 못한 제2상들인 α-TCP, β-TCP 등으로 열분해가 일어나고, 상분리를 일으켜 균열성장을 용이하게 하거나, 체액에 대한 침식성이 강하게 되는 등의 심각한 특성 저하가 초래된다. 또한 결정화 온도가 너무 낮은 경우에는 생체 불안정상인 비정질 상이 잔류하게 되고, 결국 안정한 결정성 수산화아파타이트를 제조할 수가 없었다.Conventional methods for synthesizing apatite hydroxides having such properties and uses include wet synthesis, dry synthesis, hydrothermal synthesis, precipitation, and the like. The properties of powders produced according to the synthesis, that is, particle size, shape, and particle size Each distribution is different. Among these methods, dry synthesis and hydrothermal synthesis have disadvantages in that the apparatus used is expensive and energy consumption is high. In addition, the precipitation method is the most used among the above methods because the manufacturing process is simple and excellent powder characteristics such as particle size for producing a compact sintered body. However, the precipitation process involves crystallizing at high temperatures to give crystals in the synthesis. In this case, depending on the precipitation composition, at a crystallization temperature of about 600 ° C. or more, the chemically equivalent apatite hydroxide (HAp) is thermally decomposed into undesired second phases, α-TCP and β-TCP, resulting in phase separation and crack growth. Serious property degradation, such as facilitating or strong erosion to body fluids, is caused. In addition, when the crystallization temperature is too low, an amorphous phase, which is a biostable phase, remains, and thus a stable crystalline apatite cannot be produced.
한편, 본 발명의 선행기술로는 국내 특허공개번호 제10-2003-0087789호(공개 일: 2003. 11. 15.) 및 제10-2004-0016750호(공개일: 2004. 2. 25.)가 있으며, 상기 선행기술을 통해 굴 양식업 등에서 발생하는 폐기물인 굴패각을 이용하여 수산화아파타이트 분말을 제조하는 방법이 공개된 바가 있다.Meanwhile, prior arts of the present invention include Korean Patent Publication Nos. 10-2003-0087789 (published date: November 15, 2003) and 10-2004-0016750 (published date: February 25, 2004) In the above prior art, a method of manufacturing apatite hydroxide powder using oyster shells, which are wastes generated from oyster farming, has been disclosed.
이러한 선출원 공개발명은 굴패각 분말 또는 굴패각으로 제조된 경질 침강성 탄산칼슘을 증류수에 분산시킨 후 인산(H3PO4) 용액과 8시간 동안 반응시킨 다음 이를 열처리하여 수산화아파타이트 분말을 제조하는 방법으로서, 이와 같은 제조방법은 아래와 같은 많은 문제점을 가지고 있다.This prior application discloses a method of preparing hydroxyapatite powder or hard precipitated calcium carbonate prepared by oyster shell in distilled water, reacting with phosphoric acid (H 3 PO 4 ) solution for 8 hours, and then heat treating it to prepare apatite hydroxide powder. The same manufacturing method has many problems as follows.
위와 같은 선출원 공개발명은 굴패각을 탄산칼슘으로 만들어 사용하는 과정에서 굴패각에 붙어 있는 무기물의 제거가 어려울 뿐만 아니라 완전히 제거가 되지 않은 이물질이 함유가 되어 있어 고순도의 수산화아파타이트를 제조할 수 없는 단점이 있었다.As described above, the present invention has a disadvantage in that it is difficult to remove the minerals attached to the oyster shell in the process of making the oyster shell made of calcium carbonate, and it is not possible to manufacture high purity apatite hydroxide because it contains foreign substances that are not completely removed. .
또한, 상기 공개발명은 탄산칼슘과 인산을 반응시킬 경우 이산화탄소 가스가 반응 도중에 발생하여 반응기 내에서 많은 거품이 발생하게 되며, 이로 인해 반응용기가 커져야만 하고 설치공간에 많은 제약을 받는 단점이 있었다,In addition, the present invention is a carbon dioxide gas is generated during the reaction when the reaction of calcium carbonate and phosphoric acid generates a lot of bubbles in the reactor, this has a disadvantage that the reaction vessel must be large and the installation space is restricted a lot,
특히, 선출원 공개발명과 같이 굴패각 분말을 증류수에 분산시킨 다음 인산을 투입할 경우 이산화탄소 가스가 반응 도중에 발생하게 되고 이에 따라 반응기 내에서는 많은 거품이 발생하게 되는데, 이때 상기 거품을 제거하기 위해서는 알코올 등과 같은 휘발성 물질을 분무하여 거품을 제거하는 별도의 공정이 추가되어야 하고 또한 상기 휘발성 물질에 들어있는 이물질이 제조 과정에서 수산화아파타이트에 함유될 수 있는 문제점이 있었다.In particular, when the oyster shell powder is dispersed in distilled water and then phosphoric acid is added as in the prior art, the carbon dioxide gas is generated during the reaction, and thus a lot of bubbles are generated in the reactor. A separate process of removing bubbles by spraying a volatile material has to be added, and there is a problem that foreign matter contained in the volatile material may be contained in the apatite hydroxide during the manufacturing process.
따라서, 본 발명은 위와 같은 문제점을 해결하기 위한 것으로 종래의 복잡한 공정을 거쳐 수산화아파타이트 분말을 제조하는 방법과 달리 우리나라에서 손쉽게 구할 수 있는 수산화칼슘을 출발 원료로 하여 피로인산과 습식 반응시켜 고순도의 수산화아파타이트를 대량으로 제조할 수 있는 방법을 제공함에 있다.Accordingly, the present invention is to solve the above problems, unlike the conventional method for producing apatite hydroxide powder through a complex process, the high purity apatite by wet reaction with pyrophosphoric acid by using calcium hydroxide which is easily available in Korea as a starting material To provide a method for producing a large amount of.
바람직하게는, 피로인산을 증류수에 희석시킨 다음 수산화칼슘을 직접 반응시킨 후 이를 열처리하여 고순도의 수산화아파타이트 분말을 제조하는 방법을 기술적 특징으로 한다.Preferably, the technical feature of the method of producing a high purity apatite hydroxide powder by diluting pyrophosphoric acid in distilled water and then directly reacting with calcium hydroxide.
본 발명은 굴패각을 사용하지 않고 석회석에서 채취한 수산화칼슘과 피로인산을 사용하고 특히 피로인산을 증류수에 희석시킨 후 수산화칼슘을 직접 반응시킴으로써 생체 친화성이 양호하고 가공성이 우수할 뿐만 아니라 제조 과정 중에 휘발성 물질 등의 이물질이 유입되지 않아 고순도의 수산화아파타이트를 대량으로 생산할 수 있는 장점이 있다.The present invention uses calcium hydroxide and pyrophosphate collected from limestone without using oyster shells, and in particular, dilutes pyrophosphoric acid in distilled water and directly reacts with calcium hydroxide to provide good biocompatibility and excellent processability as well as volatile substances during the manufacturing process. There is an advantage that can be produced in a large amount of high purity apatite hydroxide does not flow such as foreign matter.
또한, 본 발명은 의료용으로 유용한 생체 재료인 수산화아파타이트를 저렴하게 생산 및 공급할 수 있으며, 현재 수입에 의존하고 있는 수산화아파타이트의 수입 대체효과를 기대할 수 있는 상승적인 효과가 있다.In addition, the present invention can produce and supply inexpensive apatite hydroxide, which is a biomaterial useful for medical use, and has a synergistic effect of expecting an import substitution effect of apatite hydroxide, which currently depends on imports.
이하 본 발명의 실시 예를 첨부된 도면을 참조하여 설명하면 다음과 같다. 후술 될 상세한 설명에서는 상술한 기술적 과제를 이루기 위해 본 발명에 있어 대표적인 실시 예를 제시할 것이다. 그리고 본 발명으로 제시될 수 있는 다른 실시 예들은 본 발명의 구성에서 설명으로 대체한다.Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings. In the following description will be presented a representative embodiment in the present invention to achieve the above technical problem. And other embodiments that can be presented with the present invention are replaced by the description in the configuration of the present invention.
본 발명에서는 종래기술에서 제시하고 있는 굴패각 분말과 인산을 사용하지 않고 수산화칼슘과 피로인산을 사용하며, 특히 피로인산을 증류수에 희석시킨 다음에 수산화칼슘을 첨가하여 직접 반응시켜 고순도의 수산화아파타이트 분말을 제조하는 방법을 구현한다.In the present invention, calcium hydroxide and pyrophosphate are used without using the oyster shell powder and phosphoric acid proposed in the prior art, and in particular, the pyrophosphoric acid is diluted with distilled water, and then calcium hydroxide is added to directly react to prepare high purity apatite hydroxide powder. Implement the method.
이와 같이 피로인산을 증류수에 희석시킨 후에 수산화칼슘을 직접 반응시키는 이유는, 수산화칼슘에 피로인산을 직접 반응시키면 빠른 반응으로 인하여 발열 현상과 고상화 반응이 일어나게 되고 이로 인해 고상화된 부분이 열처리시에 인산칼슘으로 남아있는 경우가 발생할 수 있기 때문이다.The reason for directly reacting calcium hydroxide after diluting pyrophosphoric acid in distilled water is that when pyrophosphate is directly reacted with calcium hydroxide, an exothermic phenomenon and a solidification reaction occur due to a rapid reaction. This is because it can happen if it remains with calcium.
또한 굴패각 분말을 사용하지 않고 수산화칼슘을 사용함으로써 수산화아파타이트(HAp) 분말을 제조하는 과정 중에 이물질(알코올 등과 같은 휘발성 물질)이 유입되지 않기 때문에 고순도의 수산화아파타이트 분말을 제조할 수 있다.In addition, by using calcium hydroxide instead of oyster shell powder, high purity apatite hydroxide powder may be prepared because foreign substances (volatile substances such as alcohol) do not flow in the process of preparing apatite hydroxide (HAp) powder.
그리고 본 발명에서 사용하는 피로인산은 시판되는 85%의 인산을 감압시킨 채 약 180℃로 가열ㆍ탈수하거나, 82%의 인산에 오산화이인을 녹여 결정화시킨 것으로서, 과산화물의 분해를 억제하는 작용을 하기 때문에 피로인산을 사용할 경우 보다 높은 고순도의 수산화아파타이트를 제조할 수 있다. 또한 인산으로 반응시킬 경우 6시간 정도의 반응시간을 거쳐야 하나 피로인산을 반응시킬 경우 1시간 정도의 짧은 반응시간이 소요되므로 제조시간을 단축할 수 있다.The pyrophosphoric acid used in the present invention is heated and dehydrated at about 180 ° C. under reduced pressure of commercially available 85% phosphoric acid, or crystallized by dissolving diphosphorous pentoxide in 82% phosphoric acid, thereby inhibiting decomposition of peroxide. Therefore, when using pyrophosphoric acid, it is possible to produce a higher purity apatite hydroxide. In addition, when reacting with phosphoric acid, a reaction time of about 6 hours must be passed, but when reacting pyrophosphoric acid, a short reaction time of about 1 hour is required, thereby shortening the manufacturing time.
{실시예 1}{Example 1}
본 발명에서는 97%의 수산화칼슘(판매자: 한국 대정화금주식회사)과 93%의 피로인산(판매자: 일본 준세이 케미컬)을 사용한다. In the present invention, 97% of calcium hydroxide (seller: Korea Daejung Chemical Co., Ltd.) and 93% of pyrophosphoric acid (seller: Japan Junsei Chemical) are used.
상기 93%의 피로인산을 증류수에 희석시킨 다음, 여기에 97%의 수산화칼슘을 분산시켜 1시간 이상 직접 반응시킨다. 이때 피로인산과 수산화칼슘을 직접 반응시키면 발열 현상과 고상화되는 현상이 발생함으로 피로인산을 증류수에 희석한 후에 사용한다. 여기서 피로인산 0.2~0.5몰(바람직하게는, 0.3 mole)에 대해 수산화칼슘 1몰을 반응시키는 것이 가장 이상적이며, 반응식은 아래와 같다.The 93% pyrophosphate is diluted in distilled water, and then 97% calcium hydroxide is dispersed therein and reacted directly for at least 1 hour. At this time, when pyrophosphoric acid and calcium hydroxide are directly reacted, exothermic phenomenon and solidification occur, so that pyrophosphate is diluted with distilled water before use. Here, it is most ideal to react 1 mole of calcium hydroxide with 0.2 to 0.5 mole (preferably 0.3 mole) of pyrophosphoric acid, and the reaction formula is as follows.
Ca(OH)2 + 0.3O[P(O)(OH)2]2 = Ca10(PO4)6(OH)2 Ca (OH) 2 + 0.3O [P (O) (OH) 2 ] 2 = Ca 10 (PO 4 ) 6 (OH) 2
이후, 위와 같이 반응시킨 분말을 건조기에서 건조시킨 다음, 이를 가열로를 이용하여 1250℃~1300℃에서 10분~60분 동안 열처리하여 고순도의 수산화아파타이트 분말을 제조한다. 이때 1250℃에서는 60분 동안 열처리하는 것이 바람직하고, 1300℃에서는 10분 동안 열처리하는 것이 바람직하다.Thereafter, the powder reacted as above is dried in a dryer, and then heat-treated at 1250 ° C. to 1300 ° C. for 10 minutes to 60 minutes using a heating furnace to prepare a high purity apatite hydroxide powder. At this time, the heat treatment is preferably performed at 1250 ° C. for 60 minutes, and preferably at 1300 ° C. for 10 minutes.
한편, 본 발명에서는 93%의 피로인산 대신에 인산을 사용할 수도 있으며, 이때 상기 인산은 0.4~0.7몰(구체적으로는 0.6몰)를 사용하는 것이 바람직하다.Meanwhile, in the present invention, phosphoric acid may be used instead of 93% pyrophosphoric acid, and in this case, it is preferable to use 0.4 to 0.7 mol (specifically, 0.6 mol).
상기한 바와 같은 방법으로 제조된 수산화아파타이트 분말의 결정상을 확인하기 위해 X선회질 분석기로 측정, 온도별 상변화측정, 제조된 분말의 미세구조를 확인하기 위해 주사전자현미경으로 미세 구조를 관찰하였으며, 이는 도 1 내지 도 4에 구체적으로 나타내었다.In order to confirm the crystal phase of the apatite hydroxide powder prepared by the method as described above, the microstructure was observed with a scanning electron microscope to determine the microstructure of the powder, the phase change measurement by temperature, X-ray grey analyzer, This is specifically illustrated in FIGS. 1 to 4.
이하에서는 본 발명의 제조방법에 따라 만들어진 고순도의 수산화아파타이트 분말에 대한 각종 분석 실험 결과를 도 1 내지 도 4를 참조하여 구체적으로 설명한다.Hereinafter, the results of various analytical experiments on the high purity apatite hydroxide powder made according to the manufacturing method of the present invention will be described in detail with reference to FIGS. 1 to 4.
도 1은 전술한 실시예 1의 방법에 따라 제조된 수산화아파타이트를 X선 회절분석기(XRD)로 측정한 데이터를 그래프로 나타낸 것이다.1 is a graph showing data measured by X-ray diffractometer (XRD) of the apatite hydroxide prepared according to the method of Example 1 described above.
상기 도 1의 그래프에 나타난 수산화아파타이트 분말의 XRD 측정 결과를 보면, 주요 피크는 31.8°, 32.9°, 49.5°,46.7°,25.9°,34.1°,39.8°에서 나타났고 이들은 수산화아파타이트로 확인되었으며 CaO 상은 잔존하지 않았다.In the XRD measurement results of the apatite hydroxide powder shown in the graph of FIG. 1, the main peaks were found at 31.8 °, 32.9 °, 49.5 °, 46.7 °, 25.9 °, 34.1 °, and 39.8 °, and they were identified as hydroxide apatite and CaO The statue did not remain.
또한 본 발명에서는 도 2에서 보는 바와 같이 증류수에 희석화된 피로인산 0.3몰에 대해 수산화칼슘 1몰을 분산시켜 1시간 이상 반응시킨 후 건조기를 이용하여 건조한 분말에 대하여 온도별 열처리 결과로 CaO 상이 나타나지 않는 온도를 열처리 온도로 정하는 실험을 하였다. 이 결과 1250℃~1300℃가 가장 바람직한 것으 로 나타났다.In addition, in the present invention, as shown in FIG. 2, 1 mole of calcium hydroxide is dispersed in 0.3 mole of pyrophosphoric acid diluted in distilled water and reacted for 1 hour or more. Was performed to determine the heat treatment temperature. As a result, 1250 ℃ ~ 1300 ℃ appeared to be the most preferable.
한편, 도 3은 본 발명의 제조방법에 따라 만들어진 수산화아파타이트의 적외선 분광 분석 결과를 나타낸 그래프이다. 상기 도 3에 도시한 바와 같이 증류수에 희석한 피로인산 0.3몰에 대해 수산화칼슘 1몰을 분산시켜 1시간 이상 반응시킨 후, 건조기를 이용하여 건조한 다음, 가스로를 이용하여 1250℃~1300℃에서 10분~60분 동안 열처리한 후, KBr과 1:100으로 혼합하여 펠리트(pellet)로 성형한 다음, 적외선 분광분석기를 이용하여 적외선 스펙트럼을 측정하였다. 상기 적외선 분광분석(FT-IR) 결과에 나타난 바와 같이, 피크는 570cm-1, 603cm-1, 962cm-1, 1000~1100cm-1에서 나타났으며, 3574cm-1에서는 오차범위 내에서 OH-에 관련된 수산화아파타이트의 특성 피크를 보이고 있다.On the other hand, Figure 3 is a graph showing the results of infrared spectroscopy analysis of apatite hydroxide prepared according to the production method of the present invention. As shown in FIG. 3, 1 mol of calcium hydroxide was dispersed in 0.3 mol of pyrophosphoric acid diluted in distilled water and reacted for 1 hour or more, and then dried using a dryer, followed by 10 minutes at 1250 ° C. to 1300 ° C. using a gas furnace. After heat treatment for ˜60 minutes, the mixture was mixed with KBr 1: 100, molded into pellets, and the infrared spectrum was measured using an infrared spectrometer. As shown in the infrared spectroscopy (FT-IR), the peaks were found at 570 cm-1, 603 cm-1, 962 cm-1, and 1000 to 1100 cm-1, and at 3574 cm-1 to OH- within an error range. The characteristic peaks of the related apatite hydroxides are shown.
그리고, 도 4는 본 발명의 제조방법에 따라 만들어진 수산화아파타이트 분말을 충격을 가하여 분산되는 것을 슬라이드 글라스에 떨어뜨린 후 주사전자현미경으로 관찰한 미세구조 사진이다. 상기 도 4에서 보는 바와 같이, 수산화아파타이트 분말에는 침상이 관찰되었음을 확인할 수 있다.And, Figure 4 is a photograph of the microstructure observed by scanning electron microscope after dropping the dispersion of the apatite hydroxide powder prepared according to the method of the present invention by applying a shock to the slide glass. As shown in Figure 4, it can be confirmed that the needle bed was observed in the apatite hydroxide powder.
한편, 도 1과 도 3 및 도 4에서 보는 바와 같이 본 발명의 제조방법으로 만들어진 수산화아파타이트 분말과 위에서 언급한 선행기술의 방법으로 제조된 수산화아파타이트 분말의 특성 및 결과치는 거의 유사함을 알 수 있다.On the other hand, as shown in Figures 1 and 3 and 4 it can be seen that the properties and results of the apatite hydroxide powder prepared by the method of the present invention and the apatite hydroxide powder prepared by the above-described prior art method are almost similar. .
이는 상기 선행기술에서 언급한 바와 같이, 『K. C. Blakeslee와 R. A. Condrate, Sr. 공저인 "Vibrational Spectra of Hydrothermally Prepared Hydroxyapatites", T. Am. Ceram. Soc., 54(11), p559(1970)』 및 『이진호와 박 훈, 김창은 공저인 "균일침전법을 이용한 수산화아파타이트 분말의 제조 및 가열 변화", 33(1), p10~13(1996)』에서 제시하고 있는 특성에 부합해야지 수산화아파타이트로서 효과를 구현할 수 있기 때문에 본 발명의 수산화아파타이트 분말 역시 위와 같은 특성을 가지고 있다.This is referred to in the prior art, as described in K. C. Blakeslee and R. A. Condrate, Sr. Co-authored "Vibrational Spectra of Hydrothermally Prepared Hydroxyapatites", T. Am. Ceram. Soc., 54 (11), p559 (1970) and 『Lee Jin-ho, Park Hoon, and Chang-eun Kim,” Preparation and Heating Changes of Apatite Hydroxide Powder Using Uniform Precipitation Method, 33 (1), p10 ~ 13 (1996) The apatite hydroxide powder of the present invention also has the same characteristics as the above-described properties can be implemented as the hydroxide apatite.
따라서, 본 발명에서 구현하고자 하는 모태(idea)는 수산화아파타이트 분말 그 자체에 있는 것이 아니라 전술한 실시예 1에서 제시하고 있는 수산화아파타이트 분말의 제조방법에 기술적 특징이 있다 할 것이다.Therefore, the mother (idea) to be implemented in the present invention is not in the apatite hydroxide powder itself, but the technical features of the method for preparing the apatite hydroxide powder presented in Example 1 described above.
도 1은 본 발명에 따른 수산화아파타이트에 대한 X선 회절분석 결과를 보여주고 있는 그래프.1 is a graph showing the results of X-ray diffraction analysis of the hydroxide apatite according to the present invention.
도 2는 본 발명에 따른 수산화아파타이트의 온도별 열처리 결과로 CaO 상이 나타나지 않는 온도를 보여주고 있는 그래프.Figure 2 is a graph showing the temperature at which the CaO phase does not appear as a result of heat treatment of the temperature of the apatite hydroxide according to the present invention.
도 3은 본 발명에 따른 수산화아파타이트의 적외선 분광 분석 결과를 보여주고 있는 그래프.3 is a graph showing the results of infrared spectroscopy analysis of apatite hydroxide according to the present invention.
도 4는 본 발명에 따른 수산화아파타이트 분말을 주사전자현미경으로 관찰한 상태를 보여주고 있는 미세구조 사진.Figure 4 is a microstructure photograph showing a state observed by scanning electron microscope of the apatite hydroxide powder according to the present invention.
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|---|---|---|---|---|
| KR20200091632A (en) | 2019-01-23 | 2020-07-31 | 김인 | A process for crystallizing hydroxy apatite and mouthwash composition containing crystal of the hydroxy apatite |
| CN115197052A (en) * | 2022-07-29 | 2022-10-18 | 常州大学 | Method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis |
-
2007
- 2007-07-26 KR KR1020070074846A patent/KR20090011358A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200091632A (en) | 2019-01-23 | 2020-07-31 | 김인 | A process for crystallizing hydroxy apatite and mouthwash composition containing crystal of the hydroxy apatite |
| CN115197052A (en) * | 2022-07-29 | 2022-10-18 | 常州大学 | Method for synthesizing o-hydroxy phenetole by hydroxyapatite catalysis |
| CN115197052B (en) * | 2022-07-29 | 2023-11-03 | 常州大学 | Method for synthesizing o-hydroxyphenylethyl ether by catalyzing hydroxyapatite |
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