JPH01203206A - Production of octacalcium phosphate - Google Patents
Production of octacalcium phosphateInfo
- Publication number
- JPH01203206A JPH01203206A JP2667788A JP2667788A JPH01203206A JP H01203206 A JPH01203206 A JP H01203206A JP 2667788 A JP2667788 A JP 2667788A JP 2667788 A JP2667788 A JP 2667788A JP H01203206 A JPH01203206 A JP H01203206A
- Authority
- JP
- Japan
- Prior art keywords
- water
- ocp
- phosphoric acid
- soln
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000392 octacalcium phosphate Inorganic materials 0.000 title claims abstract description 8
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000002441 X-ray diffraction Methods 0.000 abstract description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000001110 calcium chloride Substances 0.000 abstract description 2
- 235000011148 calcium chloride Nutrition 0.000 abstract description 2
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- 150000005323 carbonate salts Chemical class 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- 238000012790 confirmation Methods 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 4
- 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 description 4
- 239000003610 charcoal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、オクタカルシウムホスフェートの〈以下ｒＯ
ｃＰＪ ）の新規な製造法に関する。Detailed Description of the Invention <Industrial Application Field> The present invention provides octacalcium phosphate (rO
cPJ).
〈従来の技術〉
従来より知られているＯＣＰの製造法は以下の通りであ
る。<Prior Art> Conventionally known methods for producing OCP are as follows.
■極稀薄なＨ３ＰＯ４−ＮａＯＨ溶液（燐酸濃度５１Ｉ
ｌｏｆ、 ｐＨ＝ ７．５）にＣａＣｌ２を加えて約４
０℃で２４時間反応熟成させて青る方法■極稀薄なＣａ
ｂ−Ｐ２０５−Ｈ２ｏ余水溶液。■Extremely dilute H3PO4-NaOH solution (phosphoric acid concentration 51I)
lof, pH = 7.5) with CaCl2 to approx.
How to turn blue by reacting and aging at 0℃ for 24 hours■Ultra dilute Ca
b-P205-H2o residual water solution.
（Ｃａ１度０．４〜４ｍ ｍｏｆ、Ｐ濃度０．８〜１０
１１Ｉ１０１）にアルカリを滴下して得られたものを回
収する方法。(Ca1 degree 0.4~4m mof, P concentration 0.8~10
A method of dropping an alkali onto 11I101) and collecting the resulting product.
■０．０４８− Ｃａ （Ｎｏ ＞ と００．３＋
４−Ｎ ８２ ＨＰＯ４をｐｌ−１６，５〜 ６．６の
０．２８−ＣＨ３Ｃ０ＯＮａ中に同時に添加し、５０
〜６０℃で数時間熟成して得る方法。■0.048- Ca (No > and 00.3+
4-N 82 HPO4 was added simultaneously into 0.28-CH3COONa at pl-16,5~6.6, and 50
A method of aging at ~60°C for several hours.
■ＣａＨＰＯ・２１−１ ０を０．５８−ＣＨ３ｃ。■CaHPO・21-1 0 to 0.58-CH3c.
ＯＮａ中でｐＨ＜６．１の条件で加水分解して得る方法
。A method of obtaining by hydrolysis in ONa under conditions of pH < 6.1.
■Ｃａ （ＰＯ４）２をＤ Ｈｅ付近で加水分解して
得る方法。■A method of obtaining Ca (PO4)2 by hydrolyzing it near D He.
〈発明が解決しようとする問題点〉
しかしながら、上記■、■の方法は、大量の水処理、大
量生産からみた問題があり、■、■の方法は排水処理の
問題や原料コストの問題及び■の方法は、容易にＯＣＰ
への転換が難しく単一相として製造するのは問題があり
、上記の方法はいずれも、−度に多量のＯＣＰを製造す
ることはできず、工業的な製造法としては欠点がありて
、今日まで確立した工業的製法は皆無であった。<Problems to be solved by the invention> However, the above methods (1) and (2) have problems from the perspective of large amounts of water treatment and mass production; The method of OCP
It is difficult to convert to OCP and producing it as a single phase is problematic, and all of the above methods cannot produce a large amount of OCP at once, and have drawbacks as an industrial production method. Until now, no industrial manufacturing method has been established.
そこで、本発明者は、Ｎａ等の炭酸塩、虫炭Ｍ塩を用い
て反応系のｐＨを５前後に保つと反応が容易に進み、−
度に多量のＯＣＲを製造すφことができることを知見し
本発明を得た。Therefore, the present inventor found that if the pH of the reaction system was maintained at around 5 using carbonate such as Na or insect charcoal M salt, the reaction would proceed easily and -
The present invention was achieved by discovering that it is possible to manufacture a large amount of OCR at a time.
く問題点を解決するための手段〉
即ち本発明は、リン酸、水溶性カルシウム塩及びＮａ、
に、ＮＨ４の炭酸塩、重炭酸塩（以下ｒＮａ等の炭酸塩
等」）から選ばれた１種以上を、ｐＩ−１４〜７で混合
して反応させることを特徴とするＯＣＰの製造法である
。Means for Solving the Problems〉 That is, the present invention solves the following problems: phosphoric acid, water-soluble calcium salt and Na,
A method for producing OCP, which is characterized in that one or more selected from carbonates and bicarbonates of NH4 (hereinafter referred to as "carbonates of rNa etc.") are mixed and reacted at a pI of -14 to 7. be.
ここで、ＯＣＲとはＣａ Ｈ（ＰＯ４）６−５．８２
０の組成を有し、Ｃａ／Ｐ＝１．３３のちのである。Here, OCR is CaH(PO4)6-5.82
It has a composition of 0 and Ca/P=1.33.
本発明に係る水溶性カルシウム塩としては、ＣａＣｌ
、Ｃａ （ＮＯ３）２、
（ＣＨ３ＣＯＯ）２Ｃａ等が挙げられる。The water-soluble calcium salt according to the present invention includes CaCl
, Ca (NO3)2, (CH3COO)2Ca, and the like.
又、本発明に係るＮａ等の炭ｉ！［！塩等としては、Ｎ
ａ２ ＣＯ３、ＮａＨＣＯ３、Ｋ２ ＣＯ３、ＫＨＣＯ
、（ＮＨ） Ｃｏ 、（ＮＨ４）ＨＣＯ３が挙げら
れる。Moreover, charcoal i! such as Na according to the present invention! [! As salt etc., N
a2 CO3, NaHCO3, K2 CO3, KHCO
, (NH) Co , and (NH4)HCO3.
本発明は、リン酸、水溶性カルシウム及びＮａ等の炭Ｍ
馬等を混合して反応させるのであるが、上記の原料の混
合の順序は特に制限はない。しかしながら、多くの場合
リン酸及び水溶性カルシウム塩を水に溶して水溶液とし
たものをＡ液とし、Ｎａ等の炭酸塩等の水溶液をＢ液と
なし、脱塩水あるいは予め用意しておいたＮａＣｊを含
んだ生成母液にＡ液とＢ液を同時に添加するのが好適で
ある。The present invention utilizes phosphoric acid, water-soluble calcium, and carbon M such as Na.
The reaction is carried out by mixing the raw materials, but there is no particular restriction on the order in which the above raw materials are mixed. However, in many cases, phosphoric acid and water-soluble calcium salts are dissolved in water to make an aqueous solution, which is called solution A, and an aqueous solution of carbonates such as Na is used as solution B, and desalinated water or prepared in advance is used. It is preferable to add liquid A and liquid B simultaneously to the produced mother liquor containing NaCj.
なお、Ａ液におけるリン酸と水溶性カルシウム塩の所用
量は、最終製品であるＯＣＰの理論量のＣａ／Ｐ＝ １
．３３又は、その前後の割合であり、Ａ液はかかる組成
の混合溶液として調製されたものである。In addition, the amount of phosphoric acid and water-soluble calcium salt required in liquid A is calculated based on the theoretical amount of OCP, which is the final product, Ca/P = 1
．． 33 or around it, and Solution A was prepared as a mixed solution with such a composition.
その理由は、リン酸と水溶性カルシウム塩を混合するこ
とによって、まず、ＣａとＰが完全に均一に混合され、
これをＮａ等の炭Ｍ塩等によって中和すると部分的にｐ
Ｈが極端に高くなる事を防げるので、ＯＣＰが生成しや
すくなると考えられる。The reason is that by mixing phosphoric acid and water-soluble calcium salt, Ca and P are mixed completely and uniformly.
When this is neutralized with charcoal M salts such as Na, some p
It is thought that since H can be prevented from becoming extremely high, OCP is more likely to be generated.
この時、混合液のｐＨを４〜７に保つことが重要である
。At this time, it is important to maintain the pH of the mixture at 4 to 7.
その理由は、ｐＨ７以上ではヒドロキシアパタイトが生
成されてしまうためであり、又、１）Ｈ４以下ではＣａ
ＨＰＯ−２１−１２０等が生成するからである。The reason for this is that hydroxyapatite is produced at pH 7 or higher, and 1) at pH 7 or lower, Ca
This is because HPO-21-120 and the like are generated.
本発明において、Ａ液及びＢ液の添加時間は特に限定は
ないが、反応温度は２０〜１００℃が好ましい。In the present invention, the addition time of liquid A and liquid B is not particularly limited, but the reaction temperature is preferably 20 to 100°C.
その理由は、２０℃より低いときには冷Ｗが必要となる
ばかりか、生成物がゲル状となり取り扱いが困難となり
１００℃を越えるとハイドロキシアパタイトが生成し易
くなる為である。The reason for this is that when the temperature is lower than 20°C, not only cold W is required, but also the product becomes gel-like and difficult to handle, and when the temperature exceeds 100°C, hydroxyapatite is likely to be formed.
また、反応時間は、添加量、添加時間等に関連してくる
が、一般に０．５〜４時間位が好ましい。The reaction time is related to the amount added, the addition time, etc., but is generally preferably about 0.5 to 4 hours.
次いで、反応終了後は、生成物を熟成した後、常法によ
り分離、水洗等を行ない濾過乾燥してＯＣＲを青る。After the reaction is completed, the product is aged, separated, washed with water, filtered and dried in a conventional manner to make the OCR blue.
ＯＣＲの確認はＸ線回折図により行なうことができる。OCR can be confirmed by X-ray diffraction diagram.
〈実施例〉
実施例１
８５％リン！７２ｇとＣａＣＩ ・２Ｈ２０１２２，
４ｇを水に溶して０．６．Ｉ！としてものをＡ液とする
。<Example> Example 1 85% phosphorus! 72g and CaCI ・2H20122,
Dissolve 4g in water and make 0.6. I! Let this be liquid A.
ＮａＨＣＯ３１４０ｇを水に溶して１．２Ｊｌとしたも
のをＢ液とする。Solution B was prepared by dissolving 140 g of NaHCO3 in water to make 1.2 Jl.
２Ｊビーカーに脱塩水 １Ｊを入れ、ＮａＣ，９５４ｇ
を溶解して温度を６５℃にする。Put 1J of demineralized water in a 2J beaker and add 954g of NaC.
Dissolve and bring the temperature to 65°C.
このＮａＣ＋溶液中にＡ液を５時間かけて滴下し、同時
にＢ液で１）Ｈ＝５．０を維持する。Ａ液の滴下終了時
のＢ液の残分は２９ｄであった。Solution A is dropped into this NaC+ solution over 5 hours, and at the same time, 1) H=5.0 is maintained with solution B. The remaining amount of B solution at the end of dropping A solution was 29 d.
滴下終了後１５分間熟成したのち生成物を濾過乾燥した
。After the addition was completed, the product was aged for 15 minutes and then filtered and dried.
生成物のＸ＠回折図はＯＣＰの単一相を示し、又、Ｃａ
／Ｐ（−Ｅル比） ハ１．３３ テアツｌ’：。The X@ diffractogram of the product shows a single phase of OCP and also Ca
/P (-E ratio) H1.33 T':.
実施例２
８５％リン酸７２ｇとＣａＣ１−２Ｈ２０１２２，４ｇ
を水に溶して０．６．ｇとしてものをＡ液とする。Example 2 72g of 85% phosphoric acid and 4g of CaCl-2H20122.
Dissolve 0.6 in water. Let g be the liquid A.
Ｎａ２ＣＯ３８８ｇを水に溶して１．２１としたものを
Ｂ液とする。Solution B was prepared by dissolving 388 g of Na2CO in water to a concentration of 1.21.
２．１！ビーカーに脱塩水ＩＪを入れ温度６５℃にする
。2.1! Pour demineralized water IJ into a beaker and bring the temperature to 65°C.
この液中にＡ液を５時間かけて滴下し、同時にＢ液でｐ
Ｈ＝５を維持する。Add liquid A dropwise into this liquid over 5 hours, and at the same time add liquid B to p.
Maintain H=5.
滴下終了後１５分間熟成したのち生成物を濾過乾燥した
。After the addition was completed, the product was aged for 15 minutes and then filtered and dried.
生成物のＸ線回折図はＯＣＰの単一相を示し、又、Ｃａ
／Ｐ （モル比） Ｇｅｔ １．３３ テ’ｌｙッだ。The X-ray diffraction pattern of the product shows a single phase of OCP and also Ca
/P (molar ratio) Get 1.33 Te'ly.
〈発明の効果〉
本発明の方法によれば、ＯＣＲを簡単な工程で一度に多
量に製造することができるので、工業的な製造法として
有利である。<Effects of the Invention> According to the method of the present invention, OCR can be produced in large quantities at once in a simple process, so it is advantageous as an industrial production method.
又、本発明により製造されたＯＣＰはヒドロキシアパタ
イトの合成の出発物質として特に、従来は困難とされて
いた各種の隣又は陰イオンヲ含有するヒドロキシアパタ
イトの合成の出発物質とすることができる利点がある。Furthermore, the OCP produced according to the present invention has the advantage that it can be used as a starting material for the synthesis of hydroxyapatite, particularly for the synthesis of hydroxyapatite containing various neighbors or anions, which has been considered difficult in the past. .
Claims (1)
炭酸塩、重炭酸塩から選ばれた１種以上を、ｐＨ４〜７
で混合して反応させることを特徴とするオクタカルシウ
ムホスフェートの製造法。One or more selected from phosphoric acid, water-soluble calcium salts, and carbonates and bicarbonates of Na, K, and NH_4 at pH 4 to 7.
A method for producing octacalcium phosphate, which comprises mixing and reacting the octacalcium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63026677A JP2584267B2 (en) | 1988-02-09 | 1988-02-09 | Production method of octacalcium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63026677A JP2584267B2 (en) | 1988-02-09 | 1988-02-09 | Production method of octacalcium phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01203206A true JPH01203206A (en) | 1989-08-16 |
| JP2584267B2 JP2584267B2 (en) | 1997-02-26 |
Family
ID=12200025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63026677A Expired - Fee Related JP2584267B2 (en) | 1988-02-09 | 1988-02-09 | Production method of octacalcium phosphate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2584267B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0383568A2 (en) * | 1989-02-17 | 1990-08-22 | Norian Corporation | Calcium phosphate fibers |
| JP2008222506A (en) * | 2007-03-14 | 2008-09-25 | Tokyo Institute Of Technology | Octacalcium phosphate crystal containing biologically active substance, method of producing the same and medical composition comprising same |
| CN106745628A (en) * | 2016-12-19 | 2017-05-31 | 中国矿业大学 | A kind of production method of carbon doping hydroxyapatite defluoridation filter material |
-
1988
- 1988-02-09 JP JP63026677A patent/JP2584267B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0383568A2 (en) * | 1989-02-17 | 1990-08-22 | Norian Corporation | Calcium phosphate fibers |
| EP0383568A3 (en) * | 1989-02-17 | 1991-09-04 | Norian Corporation | Calcium phosphate fibers |
| JP2008222506A (en) * | 2007-03-14 | 2008-09-25 | Tokyo Institute Of Technology | Octacalcium phosphate crystal containing biologically active substance, method of producing the same and medical composition comprising same |
| CN106745628A (en) * | 2016-12-19 | 2017-05-31 | 中国矿业大学 | A kind of production method of carbon doping hydroxyapatite defluoridation filter material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2584267B2 (en) | 1997-02-26 |
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| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |