CN101543641B - Calcium phosphate bone cement with hollow communicating structure - Google Patents
Calcium phosphate bone cement with hollow communicating structure Download PDFInfo
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- CN101543641B CN101543641B CN 200810157832 CN200810157832A CN101543641B CN 101543641 B CN101543641 B CN 101543641B CN 200810157832 CN200810157832 CN 200810157832 CN 200810157832 A CN200810157832 A CN 200810157832A CN 101543641 B CN101543641 B CN 101543641B
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- 239000002639 bone cement Substances 0.000 title claims abstract description 22
- 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 claims abstract description 19
- 239000001506 calcium phosphate Substances 0.000 title abstract description 9
- 229910000389 calcium phosphate Inorganic materials 0.000 title description 6
- 235000011010 calcium phosphates Nutrition 0.000 title description 6
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 abstract description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 abstract description 3
- 229940078499 tricalcium phosphate Drugs 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000021164 cell adhesion Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 230000004097 bone metabolism Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
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Abstract
本发明涉及一种含中空贯通结构的多孔骨水泥及其成型方法。本发明的主要内容是在常温条件下，以双氧水为发泡剂，将α相的磷酸三钙与HA粉混合，使用注浆成型方法成型。模具纵向位置插有钢针，在材料初凝后迅速抽出钢针，制备具有较大孔径中空管结构的多孔α-TCP骨水泥。该发明不需要复杂的反应试剂和高温煅烧条件，不但成本低，设备简单，工艺参数也易于控制。制得的骨水泥具有较大尺寸中空贯通结构，有利于骨修复的进行。The invention relates to a porous bone cement with a hollow through structure and a molding method thereof. The main content of the present invention is to mix α-phase tricalcium phosphate and HA powder with hydrogen peroxide as a foaming agent under normal temperature conditions, and use the grouting molding method to form. A steel needle is inserted in the longitudinal position of the mold, and the steel needle is quickly drawn out after the initial setting of the material to prepare a porous α-TCP bone cement with a large-diameter hollow tube structure. The invention does not require complex reaction reagents and high-temperature calcination conditions, and not only has low cost, simple equipment, but also easy control of process parameters. The prepared bone cement has a large-sized hollow through structure, which is beneficial to bone repair.
Description
技术领域 technical field
本发明涉及一种一种含中空贯通结构的多孔骨水泥及其成型方法，属于生物医用骨材料技术。The invention relates to a porous bone cement with a hollow through structure and a molding method thereof, belonging to the biomedical bone material technology.
背景技术 Background technique
本发明涉及到骨水泥中空管的制备技术。自从1976年海德其·曼玛(HidekiMonma)发现α磷酸三钙(α-TCP)具有水化硬化特性以来，各国学者对磷酸钙骨水泥进行了广泛地研究。当磷酸钙骨水泥控制水化体系的酸碱度6＜pH＜8范围内时，其水化产物为HA，而HA是人骨组织中无机盐的主要成分，植入人体后可参与骨的新陈代谢，促进骨的生长，且磷酸钙骨水泥水化过程中放热少，升温小，不会造成局部过热，因而磷酸钙骨水泥在骨缺损组织中的研究和应用得到快速的发展。但是磷酸钙骨水泥作为骨组织工程应用的支架虽然能形成微孔结构，但孔径及孔的连通程度都达不到临床要求，而且材料强度不足。中空贯通结构可以为细胞提供赖以生存的三维空间，有利于细胞黏附生长，细胞外基质沉淀，营养和氧气进入，代谢产物排出，同时还有利于血管和神经长入，有利于骨的修复。The invention relates to the preparation technology of bone cement hollow tube. Since Hideki Monma discovered that α-tricalcium phosphate (α-TCP) has hydration hardening properties in 1976, scholars from various countries have conducted extensive research on calcium phosphate bone cement. When the calcium phosphate bone cement controls the pH of the hydration system within the range of 6<pH<8, its hydration product is HA, and HA is the main component of inorganic salts in human bone tissue. After being implanted in the human body, it can participate in bone metabolism and promote The growth of bone, and the hydration process of calcium phosphate bone cement has less heat release and small temperature rise, which will not cause local overheating. Therefore, the research and application of calcium phosphate bone cement in bone defect tissue has been rapidly developed. However, although calcium phosphate bone cement can form a microporous structure as a scaffold for bone tissue engineering applications, the pore size and connectivity of the pores cannot meet the clinical requirements, and the material strength is insufficient. The hollow penetrating structure can provide cells with a three-dimensional space for survival, which is conducive to cell adhesion and growth, extracellular matrix precipitation, nutrition and oxygen entry, and metabolite discharge. It is also conducive to the growth of blood vessels and nerves, and bone repair.
发明内容 Contents of the invention
鉴于上述现有技术存在的缺陷或不足，本发明目的旨在提供一种比较简单的无煅烧方法制备中空贯通结构骨水泥材料。主要是利用硝酸钙和磷酸氢二铵为原料，采用水热法合成羟基磷灰石粉体；以CaHPO4·2H2O与纯CaCO3粉按2∶1(mol)均匀混合，煅烧至1250℃，保温1h后在空气中急冷，获得α相的磷酸三钙。在常温(37℃)条件下，向α-TCP粉末中加入6％HA粉，然后加入6％的发泡剂(双氧水)成孔并在模具纵向位置插入钢针，使用注浆成型方法，在材料终凝后迅速的抽出钢针，制备具有较大孔径(Ф为0.9mm，并可调)中空贯通管结构的多孔α-TCP骨水泥。In view of the above-mentioned defects or deficiencies in the prior art, the purpose of the present invention is to provide a relatively simple non-calcination method for preparing bone cement materials with hollow penetrating structures. Mainly using calcium nitrate and diammonium hydrogen phosphate as raw materials, hydrothermal method is used to synthesize hydroxyapatite powder; CaHPO 4 2H 2 O and pure CaCO 3 powder are uniformly mixed at 2:1 (mol), calcined to 1250 ℃, heat preservation for 1 hour, and then quench in the air to obtain α-phase tricalcium phosphate. Under normal temperature (37°C) conditions, add 6% HA powder to α-TCP powder, then add 6% foaming agent (hydrogen peroxide) to form holes and insert steel needles in the longitudinal position of the mould, using the grouting method, in After the final setting of the material, the steel needle was quickly pulled out to prepare a porous α-TCP bone cement with a large pore diameter (Ф is 0.9 mm, and adjustable) hollow through-tube structure.
用本发明制得的骨水泥材料内部具有较大尺寸的中空贯通结构，孔径约为0.9mm(并可调)，有利于骨细胞的长入，其它弥散气孔的孔径分布范围较大，利于骨细胞的黏附。本发明不需要复杂的反应试剂和高温煅烧条件，不但成本低，设备简单，工艺参数也易于控制，利于骨修复的进行。The bone cement material prepared by the present invention has a relatively large hollow penetrating structure inside, with a pore diameter of about 0.9mm (and adjustable), which is conducive to the growth of bone cells, and the pore diameter distribution range of other diffuse pores is large, which is beneficial to bone. cell adhesion. The invention does not need complex reaction reagents and high-temperature calcination conditions, not only has low cost, simple equipment, but also easy control of process parameters, which is beneficial to bone repair.
附图说明 Description of drawings
附图为整体形貌以及截面的SEM图。图1为中空贯通管外观图，图2为材料中大孔的扫描电镜图。The accompanying drawings are SEM images of the overall morphology and cross-section. Figure 1 is the appearance of the hollow through-tube, and Figure 2 is the scanning electron microscope image of the macropores in the material.
具体实施方案1Specific implementation 1
(1).急冷法制备α-TCP(1).Quick cooling method to prepare α-TCP
将分析纯的CaHPO4·2H2O与分析纯CaCO3细粉按2∶1(mol)均匀混合，然后煅烧至1250℃，保温1h后在空气中急冷，可获得α相的磷酸三钙(疏松的白色粉末状固体)，将烧制的粉末放入QM-35P2型行星式球磨机里进行研磨，设置转速为720r/min，研磨4h，过250目筛，然后将其放入已编号的样品袋中供后面的实验使用。Mix the analytically pure CaHPO 4 ·2H 2 O and the analytically pure CaCO 3 fine powder at a ratio of 2:1 (mol), then calcinate to 1250°C, keep warm for 1 hour, and then quench in air to obtain α-phase tricalcium phosphate ( loose white powdery solid), the fired powder is put into the QM-35P2 planetary ball mill for grinding, the setting speed is 720r/min, grind for 4h, pass through a 250 mesh sieve, and then put it into the numbered sample bag for future experiments.
(2).水热法合成HA(2). Synthesis of HA by hydrothermal method
将28.10g硝酸钙和9.24g磷酸氢二铵混合于140mL pH值为7.5(用氨水进行调节)的蒸馏水中；同时将等量的硝酸钙和磷酸氢二铵混合于140mL pH值为10.5的蒸馏水中，分别搅拌10min后沉淀。将pH值为7.5条件下所得沉淀物分散于pH值为10.5条件下所得的清液中，再将重新混合后的悬浮液倒入100mL高压反应釜中，于180℃条件下水热处理10h。冷却至室温，沉淀，用蒸馏水将沉淀洗涤3次后于80℃条件下干燥10h，得到的HA粉放入QM-35P2型行星式球磨机里进行研磨，设置转速为720r/min，研磨4h，过250目筛，然后将其放入已编号的样品袋中供后面的实验使用。Mix 28.10g of calcium nitrate and 9.24g of diammonium hydrogen phosphate in 140mL of distilled water with a pH value of 7.5 (adjusted with ammonia water); at the same time, mix the same amount of calcium nitrate and diammonium hydrogen phosphate in 140mL of distilled water with a pH value of 10.5 , and precipitated after stirring for 10 min respectively. The precipitate obtained under the condition of pH 7.5 was dispersed in the clear liquid obtained under the condition of pH 10.5, and then the remixed suspension was poured into a 100mL autoclave, and hydrothermally treated at 180°C for 10h. Cool to room temperature, precipitate, wash the precipitate with distilled water for 3 times, and dry at 80°C for 10 hours. Put the obtained HA powder into a QM-35P2 planetary ball mill for grinding, set the speed at 720r/min, and grind for 4 hours. 250-mesh sieve, and then put them into numbered sample bags for subsequent experiments.
(3).称取20.462克的α-TCP粉末加入6％的HA粉作为晶种，放入球磨罐中，在星形球磨机上球磨四个小时。过200目筛后装入袋中密封，贴好标签。(3). Weigh 20.462 grams of α-TCP powder and add 6% HA powder as a seed crystal, put it into a ball mill jar, and mill it on a star ball mill for four hours. After passing through a 200-mesh sieve, put it into a bag, seal it, and stick a label.
取12.121克粉末，加入6％的双氧水作为发泡剂，用移液管加入蒸馏水，每克粉料中加入约0.40ml蒸馏水，调粉末的粘稠度如牙膏一样。混合均匀后倒入模具(Ф为0.9mm钢针纵向插入模具，并使得钢针容易拔出)后震平，赶走气泡，将样品放入容器中，置于温度为37℃的水浴锅内，并用保鲜膜密封，测其初凝时间为21min，终凝时间为45min，在50min时将钢针拔出，试样在水浴锅内保温24h，然后脱模，制得含直径为0.9mm中空贯通结构的多孔骨水泥。Get 12.121 grams of powder, add 6% hydrogen peroxide as a foaming agent, add distilled water with a pipette, add about 0.40ml of distilled water per gram of powder, and adjust the viscosity of the powder to be the same as toothpaste. After mixing evenly, pour it into the mold (a 0.9mm steel needle is inserted vertically into the mold and make the steel needle easy to pull out), shake it flat, drive away the air bubbles, put the sample in a container, and place it in a water bath at a temperature of 37°C , and sealed with plastic wrap, the initial setting time was 21min, the final setting time was 45min, the steel needle was pulled out at 50min, the sample was kept warm in the water bath for 24h, and then demolded to obtain a hollow sample with a diameter of 0.9mm. Porous bone cement throughout the structure.
具体实施方案2Specific implementation 2
实施方案2的步骤与方案1中除在第(3)步中以Ф为5mm的钢针为中空管的成型模具外，其它步骤相同，获得的含中空贯通结构的多孔骨水泥的中空管直径为5mm。The steps of embodiment 2 are the same as those of the embodiment 1, except that in step (3) the steel needle with a Ф of 5mm is used as the forming mold of the hollow tube, the other steps are the same, and the obtained hollow porous bone cement containing hollow penetrating structure The tube diameter is 5mm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4612053A (en) * | 1983-10-06 | 1986-09-16 | American Dental Association Health Foundation | Combinations of sparingly soluble calcium phosphates in slurries and pastes as mineralizers and cements |
| CN1313132A (en) * | 2000-03-14 | 2001-09-19 | 瑞安大药厂股份有限公司 | Two-phase alpha-tricalcium phosphate/oxyhydrogen-base apatite bone cement and its preparing process |
| CN1488680A (en) * | 2003-07-28 | 2004-04-14 | 浙江大学 | Calcium phosphate composite powder and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4612053A (en) * | 1983-10-06 | 1986-09-16 | American Dental Association Health Foundation | Combinations of sparingly soluble calcium phosphates in slurries and pastes as mineralizers and cements |
| CN1313132A (en) * | 2000-03-14 | 2001-09-19 | 瑞安大药厂股份有限公司 | Two-phase alpha-tricalcium phosphate/oxyhydrogen-base apatite bone cement and its preparing process |
| CN1488680A (en) * | 2003-07-28 | 2004-04-14 | 浙江大学 | Calcium phosphate composite powder and preparation method thereof |
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