JPH0141155B2 - - Google Patents
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- Publication number
- JPH0141155B2 JPH0141155B2 JP58194670A JP19467083A JPH0141155B2 JP H0141155 B2 JPH0141155 B2 JP H0141155B2 JP 58194670 A JP58194670 A JP 58194670A JP 19467083 A JP19467083 A JP 19467083A JP H0141155 B2 JPH0141155 B2 JP H0141155B2
- Authority
- JP
- Japan
- Prior art keywords
- acid ion
- ion
- phosphate
- hpo
- present
- 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.)
- Expired
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- Dental Preparations (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials For Medical Uses (AREA)
Description
本発明は一般式
Ca8（PO4）4（HPO4）2-z（Ｒ）z・mH2O
（ただし、式中Ｒはシトラコン酸イオン、β―
ジヒドロムコン酸イオン、フタル酸イオン又はイ
ソフタル酸イオン、ｚは０より大きく１以下の
数、ｍは５〜８の数を表わす）で示される新規な
複合化合物（以下、本発明の複合化合物という）
およびその製造法に関する。
従来、燐酸カルシウムと有機質との相互作用に
ついては、主に生体内での骨歯、結石の生理を理
解するため、また、燐酸カルシウムの有機質に対
するクロマトグラフイツクな性質を調べる材料と
して研究されてきたが、燐酸八カルシウムがその
結晶構造内に有機質を取り込んだ複合化合物は知
られていない。また一般に分子またはイオンサイ
ズが大きく、かつ立体構造を持つ有機質が、いわ
ゆる層状またはかご状構造の化合物に分類されな
い燐酸八カルシウム構造内に取り込まれる可能性
は予期されていなかつた。
本発明の目的は従来の表面吸着型の燐酸カルシ
ウムと有機質との複合体とは異なる構造内収容型
の新規な燐酸八カルシウムと有機酸との複合化合
物を提供するにある。
本発明は前記目的を達成すべく研究の結果、α
―燐酸三カルシウム（α―Ca3（PO4）2）を、一般
式R2-（ただし、R2-はシトラコン酸イオン
（C3H4C2O2- 4）、β―ジヒドロムコン酸イオン
（C4H6C2O2- 4）、フタル酸イオン（C6H4C2O2- 4）
又はイソフタル酸イオン（C6H4C2O2- 4）を表わ
す）で示される有機酸イオンの共存下、PH５〜７
の下で加水分解したところ、該有機酸イオンを燐
酸八カルシウムの構造内に取り込んだ本発明の複
合化合物が得られることを知見し得た。この知見
に基いて本発明を完成した。
本発明の複合化合物が燐酸八カルシウムの構造
内に有機酸イオンを取り込んでいることは、次の
ことによつて証明し得られる。
１ 燐酸八カルシウムの構造の底面間隔が拡がつ
ていること。その測定結果は次の表１の通りで
ある。
The present invention is based on the general formula Ca 8 (PO 4 ) 4 (HPO 4 ) 2-z (R) z・mH 2 O (wherein R is a citraconic acid ion, β-
A novel complex compound (hereinafter referred to as the complex compound of the present invention) represented by a dihydromucinate ion, a phthalate ion, or an isophthalate ion, where z is a number greater than 0 and less than or equal to 1, and m is a number from 5 to 8.
and its manufacturing method. Previously, the interaction between calcium phosphate and organic matter has been studied primarily to understand the physiology of bones, teeth, and calculus in vivo, and as a material for investigating the chromatographic properties of calcium phosphate with respect to organic matter. However, there are no known complex compounds in which octacalcium phosphate incorporates organic matter into its crystal structure. Furthermore, it was not anticipated that organic substances, which generally have a large molecular or ion size and a three-dimensional structure, could be incorporated into the octacalcium phosphate structure, which is not classified as a compound with a so-called layered or cage structure. An object of the present invention is to provide a novel composite compound of octacalcium phosphate and an organic acid that is housed within the structure, which is different from the conventional surface-adsorbed composite of calcium phosphate and an organic substance. The present invention has been made as a result of research to achieve the above object.
- Tricalcium phosphate (α-Ca 3 (PO 4 ) 2 ) is expressed by the general formula R 2- (where R 2- is citraconic acid ion (C 3 H 4 C 2 O 2- 4 ), β-dihydromuconic acid ion (C 4 H 6 C 2 O 2- 4 ), phthalate ion (C 6 H 4 C 2 O 2- 4 )
or isophthalic acid ion (representing C 6 H 4 C 2 O 2- 4 )), pH 5 to 7.
It has been found that when hydrolyzed under the following conditions, a composite compound of the present invention in which the organic acid ion is incorporated into the structure of octacalcium phosphate can be obtained. The present invention was completed based on this knowledge. The fact that the composite compound of the present invention incorporates an organic acid ion into the structure of octacalcium phosphate can be demonstrated by the following. 1. The basal spacing of the structure of octacalcium phosphate is expanding. The measurement results are shown in Table 1 below.
【表】
１ 一般式
Ca8（PO4）4（HPO4）2-z（Ｒ）z・mH2Oにおける
ｚを表わす。
２ 該有機酸イオンがHPO2- 4イオンと置換して
いることは、燐酸八カルシウム（Ca8（PO4）4
（HPO4）2・5H2O）のCa／Ｐモル比が1.33より
増大していることによつて確められる。すなわ
ち、結晶構造を保つたままで、Ca／Ｐ比を増
大させるためには、燐酸イオンの溶出を考える
のが自然であり、また同時に電気的中性条件に
よつて有機酸イオンが取り入れられたものと考
える。
本発明の複合化合物の赤外線吸収スペクトルを
示すと第１図の通りである。またその底面間隔の
加熱による変化ならびに加熱による重量変化を示
すと、それぞれ、第２図と第３図ならびに第４図
と第５図の通りである。なお、加熱による重量変
化は、静止空気中で、試料20.0mgを昇温10℃／分
で加熱してその重量の減少を測定した結果であ
る。
本発明の複合化合物は、α―リン酸三カルシウ
ムを該当有機酸イオン含有水溶液中に懸濁させ、
PHを５〜７の範囲で加水分解することにより製造
される。
前記製造法において、α―燐酸三カルシウムに
代え、燐酸八カルシウム粉末を使用すると、構造
内収容型の複合化合物は得られない。
また、PHは５〜７の範囲であることが必要であ
る。PHが５より小さいと燐酸―水素カルシウム
（CaHPO4・2H2O）が生成し、７を超えると水酸
アパタイトが生成して構造内収容型の複合化合物
は得られない。
本発明の複合化合物は、燐酸八カルシウムへの
種々の有機化合物の複合化の中間原料、生体骨
歯・石灰化の生理研究の模擬試料として使用し得
られる。また、他の粉末の防結および流動調整
剤、蛋白質または核酸類のクロマトグラフイー吸
着体、プラスチツクス用フイラー、イオン交換体
触媒、触媒担当などに使用し得られる。
以上のように、本発明によると、新規な燐酸八
カルシウムの構造内に有機酸イオンを取り込んだ
複合化合物およびその製造法を提供し得た優れた
効果を奏し得られる。
実施例 １
α―燐酸三カルシウム粉末１ｇを、アンモニア
水でPH6.0に調製した0.25モル濃度のシトラコン
酸水溶液50ml中に投入し、40℃で３時間保持した
後、固相を濾過・水洗し、40℃で乾燥した。その
反応率は100％であつた。固相分のCa／Ｐモル比
は1.56で、その構造の底面間隔は22.8Aであり、
その化学組成はCa8（PO4）4（HPO4）1.14
（C3H4C2O4）0.86・5.0H2O相当であつた。
実施例 ２
実施例１においてシトラコン酸に代えβ―ジヒ
ドロムコン酸を使用した。その反応率は100％で
あつた。固相分のCa／Ｐモル比は1.52で、その構
造の底面間隔は23.7Aであり、その化学組成は
Ca8（PO4）4（HPO4）1.27（C4H6C2O4）0.73・7.0H2O
相当であつた。
実施例 ３
実施例１において、0.25モル濃度のシトラコン
酸に代え0.1モル濃度のフタル酸を使用した。そ
の反応率は100％であつた。固相分のCa／Ｐモル
比は1.44で、その構造の底面間隔は23.7Aであり、
その化学組成はCa8（PO4）4（HPO4）1.55
（C6H4C2O4）0.44・7.5H2O相当であつた。
実施例 ４
実施例１において、シトラコン酸に代えイソフ
タル酸を使用した。その反応率は100％であつた。
固相分のCa／Ｐモル比は1.49で、その構造の底面
間隔は23.0Aであり、その化学組成はCa8（PO4）4
（HPO4）1.39（C6H4C2O4）0.61・7.1H2O相当であつ
た。[Table] 1 General formula Ca 8 (PO 4 ) 4 (HPO 4 ) 2-z (R) z ·mH 2 Represents z in O. 2 The fact that the organic acid ion is substituted with HPO 2-4 ion means that octacalcium phosphate (Ca 8 (PO 4 ) 4
This is confirmed by the Ca/P molar ratio of (HPO 4 ) 2 ·5H 2 O) increasing from 1.33. In other words, in order to increase the Ca/P ratio while maintaining the crystal structure, it is natural to consider elution of phosphate ions, and at the same time, organic acid ions are introduced under electrically neutral conditions. I think so. FIG. 1 shows the infrared absorption spectrum of the composite compound of the present invention. Further, the changes in the distance between the bottom surfaces due to heating and the changes in weight due to heating are shown in FIGS. 2 and 3, and FIGS. 4 and 5, respectively. Note that the weight change due to heating is the result of heating 20.0 mg of a sample in still air at a heating rate of 10° C./min and measuring the decrease in weight. The composite compound of the present invention is prepared by suspending α-tricalcium phosphate in an aqueous solution containing the corresponding organic acid ion,
It is produced by hydrolyzing the pH within the range of 5 to 7. In the above production method, if octacalcium phosphate powder is used instead of α-tricalcium phosphate, a structurally encapsulated composite compound cannot be obtained. Further, the pH needs to be in the range of 5 to 7. If the pH is less than 5, calcium phosphate-hydrogen (CaHPO 4 .2H 2 O) is produced, and if it exceeds 7, hydroxyapatite is produced, making it impossible to obtain a structurally contained composite compound. The composite compound of the present invention can be used as an intermediate raw material for conjugating various organic compounds to octacalcium phosphate, and as a simulated sample for physiological research on living bones, teeth, and mineralization. It can also be used as an anti-caking and flow control agent for other powders, a chromatographic adsorbent for proteins or nucleic acids, a filler for plastics, an ion exchange catalyst, a catalyst agent, etc. As described above, the present invention has the excellent effect of providing a novel composite compound in which an organic acid ion is incorporated into the structure of octacalcium phosphate, and a method for producing the same. Example 1 1 g of α-tricalcium phosphate powder was added to 50 ml of a 0.25 molar citraconic acid aqueous solution adjusted to pH 6.0 with aqueous ammonia, kept at 40°C for 3 hours, and the solid phase was filtered and washed with water. , dried at 40°C. The reaction rate was 100%. The Ca/P molar ratio of the solid phase is 1.56, and the basal spacing of the structure is 22.8A.
Its chemical composition is Ca 8 (PO 4 ) 4 (HPO 4 ) 1.14
(C 3 H 4 C 2 O 4 ) It was equivalent to 0.86 ·5.0H 2 O. Example 2 In Example 1, β-dihydromuconic acid was used instead of citraconic acid. The reaction rate was 100%. The Ca/P molar ratio of the solid phase is 1.52, the basal spacing of its structure is 23.7A, and its chemical composition is
Ca 8 (PO 4 ) 4 (HPO 4 ) 1.27 (C 4 H 6 C 2 O 4 ) 0.73・7.0H 2 O
It was quite a lot. Example 3 In Example 1, 0.1 molar phthalic acid was used in place of 0.25 molar citraconic acid. The reaction rate was 100%. The Ca/P molar ratio of the solid phase is 1.44, and the basal spacing of the structure is 23.7A.
Its chemical composition is Ca 8 (PO 4 ) 4 (HPO 4 ) 1.55
(C 6 H 4 C 2 O 4 ) It was equivalent to 0.44 ·7.5H 2 O. Example 4 In Example 1, isophthalic acid was used instead of citraconic acid. The reaction rate was 100%.
The Ca/P molar ratio of the solid phase is 1.49, the basal spacing of its structure is 23.0 A, and its chemical composition is Ca 8 (PO 4 ) 4
It was equivalent to (HPO 4 ) 1.39 (C 6 H 4 C 2 O 4 ) 0.61 ·7.1H 2 O.
第１図は本発明の複合化合物の赤外線吸収スペ
クトル、第２図と第３図は底面間隔の加熱変化曲
線、第４図と第５図は加熱重量減少曲線をそれぞ
れ示す。
FIG. 1 shows the infrared absorption spectrum of the composite compound of the present invention, FIGS. 2 and 3 show the heating change curves of the base spacing, and FIGS. 4 and 5 show the heating weight loss curves, respectively.
Claims (1)
ジヒドロムコン酸イオン、フタル酸イオンまたは
イソフタル酸イオン、ｚは０より大きく１以下の
数、ｍは５〜８の数を表わす。）で示される燐酸
八カルシウムと有機酸との複合化合物。 ２ α―燐酸三カルシウムを一般式R2-（ただし、
R2-はシトラコン酸イオン、β―ジヒドロムコン
酸イオン、フタル酸イオンまたはイソフタル酸イ
オンを表わす）で示される有機酸イオンの共存
下、PH５〜７の下で加水分解することを特徴とす
る、 一般式 Ca8（PO4）4（HPO4）2-z（Ｒ）z・mH2O （ただし、式中Ｒは該有機酸イオン、ｚは０よ
り大きく１以下の数、ｍは５〜８の数を表わす）
で示される燐酸八カルシウムと有機酸との複合化
合物の製造法。[Claims] 1 General formula Ca 8 (PO 4 ) 4 (HPO 4 ) 2-z (R) z・mH 2 O (wherein R is a citraconic acid ion, β-
dihydromuconic acid ion, phthalic acid ion or isophthalic acid ion, z represents a number greater than 0 and less than or equal to 1, and m represents a number from 5 to 8. ) A complex compound of octacalcium phosphate and an organic acid. 2 α-tricalcium phosphate with the general formula R 2- (however,
R2- represents a citraconic acid ion, a β-dihydromuconic acid ion, a phthalic acid ion or an isophthalic acid ion). Formula Ca 8 (PO 4 ) 4 (HPO 4 ) 2-z (R) z・mH 2 O (However, in the formula, R is the organic acid ion, z is a number greater than 0 and less than or equal to 1, and m is 5 to 8. )
A method for producing a complex compound of octacalcium phosphate and an organic acid shown in
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58194670A JPS6087240A (en) | 1983-10-18 | 1983-10-18 | Complex compound of octacalcium phosphate and organic acid and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58194670A JPS6087240A (en) | 1983-10-18 | 1983-10-18 | Complex compound of octacalcium phosphate and organic acid and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6087240A JPS6087240A (en) | 1985-05-16 |
| JPH0141155B2 true JPH0141155B2 (en) | 1989-09-04 |
Family
ID=16328349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58194670A Granted JPS6087240A (en) | 1983-10-18 | 1983-10-18 | Complex compound of octacalcium phosphate and organic acid and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6087240A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62230708A (en) * | 1986-03-31 | 1987-10-09 | Sangi:Kk | Calcium phosphate composition |
| SE539377C2 (en) * | 2016-02-24 | 2017-08-29 | Deflamo Ab | A process for manufacturing of fire suppressing crystals |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0610931B2 (en) * | 1984-07-05 | 1994-02-09 | 株式会社村田製作所 | Non-reducing dielectric ceramic composition |
-
1983
- 1983-10-18 JP JP58194670A patent/JPS6087240A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6087240A (en) | 1985-05-16 |
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