CN1193614A - Porous calcium phosphate cement containing pore-creating agent - Google Patents
Porous calcium phosphate cement containing pore-creating agent Download PDFInfo
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- CN1193614A CN1193614A CN98110645A CN98110645A CN1193614A CN 1193614 A CN1193614 A CN 1193614A CN 98110645 A CN98110645 A CN 98110645A CN 98110645 A CN98110645 A CN 98110645A CN 1193614 A CN1193614 A CN 1193614A
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Abstract
A porous calcium phosphate bone cement used for repairing human hard tissue contains pore-forming agent which may be non-toxic slightly-soluble salt, acidic salt and alkaline salt, or non-toxic surfactant. The pore-forming agent is used to make porous solidifed body without changing the characteristics of calcium phosphate bone cement such as self-solidification, its hydrated productr being hydroxyphosphorite, speed of hydrating reaction, and 100-300 microns of aperture, so benefiting the growth of bone tissue into it, accelerating degradation of material and promoting bone healing.
Description
The invention belongs to the field of medical materials, and relates to porous calcium phosphate bone cement for repairing human hard tissues and application thereof.
Calcium Phosphate Cement (CPC) is a mixture of several calcium phosphates and can be prepared by conventional method. The hydration product is hydroxyapatite which has good biocompatibility with human tissues because the hydroxyapatite isvery similar to mineral components of bones and teeth of vertebrates, so that the hydroxyapatite generated by hydration reaction of several calcium phosphate salts or the artificially synthesized hydroxyapatite is often used as a material for repairing hard tissues of human bodies, the research and the application of the hydroxyapatite are particularly remarkable, and the development of the hydroxyapatite is particularly rapid in recent years. Currently, the following are more involved in clinical research and application:
(1) calcium Phosphate Cement (CPC) is prepared according to a conventional method, is blended into paste by water, is arbitrarily filled and molded according to the defect part, and is automatically cured under the environment and the temperature of a human body, the final component is converted into hydroxyapatite, and the aperture of a cured body formed by hydration is less than 10 mu m. Animal experiments show that: because the internal pore diameter is small, after the calcium phosphate cement is implanted into the bone, the calcium phosphate cement can only form interface combination with bone tissue in the early stage, the calcium phosphate cement is a mechanical lock formed by the rough and uneven surface of the implant for tissue growth, the strength is not high, and the calcium phosphate cement is slowly degraded because the bone tissue cannot grow into the calcium phosphate cement, so that the reconstruction of the bone is influenced.
(2) An artificially synthesized hydroxyapatite ceramic reported in the literature (K.E. Salyer, plastics and Reconstructive Surgery, 1989, 84 (2): 236-244) is a more successful material for repairing human hard tissues, and through many years of concerted efforts of scientists in various countries, a plurality of mature preparation methods are formed: (US3929971) discloses a preparation technique thereof, and others such as a gas decomposition method, an impregnationmethod, a hydrothermal hot pressing method, an organic matter filling method, a microwave process method, a wax replica method, and the like. They are prepared by heating apatite formed under alkaline conditions to 800-1200 ℃. The synthetic hydroxyapatite ceramic has the common characteristic that a high-temperature sintering step is required, and the high-temperature sintering is a necessary condition for causing connection among particles to generate strength and generate porosity. This heating process causes sintering of apatite crystals to form an unabsorbed implant, so that its use is limited.
(3) (US4869906) discloses a technique for producing porous calcium phosphate salt pellets by means of high-temperature sintering for use as a filler for acrylic cement, the pore diameter within the porous particles being that of a cured body after radical polymerization of acrylic acid, which method is also limited because of the need for high-temperature sintering. Thus, materials for bone defect repair that accelerate new bone ingrowth and material degradation remain problematic for surgeons.
The invention aims to disclose porous calcium phosphate bone cement containing a pore-forming agent, which utilizes the pore-forming characteristic of the pore-forming agent to prepare a porous solidified body, avoids forming an unabsorbed implant body due to high-temperature sintering and solves the problem of repairing bone defects.
The idea of the invention is that:
1. the porous calcium phosphate cement can be prepared by utilizing the characteristic that the slightly soluble salt has certain solubility in the aqueous solution. The slightly soluble salt is uniformly mixed with the calcium phosphate cement powder, when the calcium phosphate cement is solidified, the slightly soluble salt occupies partial space of the solidified body, so that an independent unit is formed, and after the calcium phosphate cement is implanted into a body, the slightly soluble salt is gradually dissolved because the ion concentration product (Ksp) in the body fluid is less than the Ksp of the slightly soluble salt through continuous permeation and cleaning of the body fluid, so that a porous structure is formed. The distribution and size of the pore diameter are controlled by the particle size of the slightly soluble salt. The material gradually forms porous while bone tissue grows continuously, so that the initial strength of the material is very high, and the adverse effect of low initial strength of the pure porous material after being implanted into a body is overcome.
2. The gas generating substance is utilized to prepare porous calcium phosphate cement, and acid salt and basic salt are added into calcium phosphate cement powder. When the mixed powder is contacted with water to be prepared into slurry, the acid salt and the basic salt react to generate gas:
3. Adding non-toxic surfactant into calcium phosphate cement system. When the calcium phosphate cement powder is mixed with a liquid and then slurried, bubbles are generated due to the small surface tension. The air bubbles are uniformly distributed in the slurry, and a porous structure is formed after solidification.
The detailed technical scheme of the invention is as follows:
the porous calcium phosphate cement containing the pore-forming agent mainly comprises Calcium Phosphate Cement (CPC) and the pore-forming agent, and the proportion is as follows:
calcium phosphate cement pore-forming agent is 10: (0.3-8.7) (mass ratio)
(1) The Calcium Phosphate Cement (CPC) is a mixture of several calcium phosphate salts mixed according to a certain proportion, can be prepared according to the method disclosed by (US5525148, US5545254), can be one or a mixture of tricalcium phosphate (α type or β type) and tetracalcium phosphate, and can be one or a mixture of octacalcium phosphate, monocalcium phosphate, hydroxyapatite and fluorapatite.
(2) The pore-forming agent is one or more of non-toxic slightly soluble salt, acid salt and alkali salt or non-toxic surfactant, wherein:
the slightly soluble salt can be calcium salt slightly soluble in water, such as calcium sulfate, calcium carbonate, calcium acetate, calcium citrate, calcium hydrogen phosphate, calcium oxalate, etc., preferably calcium sulfate;
the basic salt can generate CO under acidic condition2Carbonates such as sodium hydrogen carbonate, calcium carbonate, etc.; the acid salt is acidic salt in water, such as monocalcium phosphate, monopotassium phosphate and the like, and the basic salt and the acid salt are added in equivalent;
the surfactant is potassium fatty acid salt, sodium fatty acid salt, Tween series, nonylphenol polyoxyethylene ether series, sodium alkyl sulfate, etc., and potassium stearate and sodium alkyl sulfate are preferred.
The bone cement of the invention is prepared and applied according to the following method:
(1) mixing calcium phosphate cement powder with the diameter of less than 20 microns and slightly soluble salt with the diameter of 200-350 microns according to the mass ratio of 10: 0.3-8.7 of the calcium phosphate cement to the slightly soluble salt to obtain porous calcium phosphate cement containing pore-forming agent as slightly soluble salt, using normal saline orother salt solutions as curing liquid, and uniformly mixing the curing liquid and the porous calcium phosphate cement according to the solid-liquid ratio of 3: 1 to implant the porous calcium phosphate cement into a body;
(2) mixing calcium phosphate bone cement with the diameter of less than 20 mu m with acid salt and alkali salt which are configured in an equivalent manner according to the weight ratio of 10: 0.3-8.7 of the calcium phosphate bone cement to the slightly soluble salt to obtain porous calcium phosphate bone cement containing pore-forming agent acid salt and alkali salt, using normal saline or other salt solutions as curing liquid, and uniformly mixing the curing liquid and the porous calcium phosphate bone cement according to the solid-liquid ratio of 3: 1 to implant the porous calcium phosphate bone cement into a body;
(3) the water solution containing 0.2-15% of surfactant is used as solidifying liquid and the calcium phosphate cement with the diameter less than 200 mu m is uniformly mixed according to the mass ratio of 3: 1, thus obtaining the porous calcium phosphate cement containing pore-forming agent as surfactant, which can be implanted into the body.
(4) Mixing calcium phosphate cement with diameter less than 20 μm with water solution (0.2-15%) of acid salt and alkali salt, slightly soluble salt and surfactant in equal amount:
calcium phosphate cement (slightly soluble salt, acid salt and alkali salt) and 0.2-15% of surfactant in water
And (2) obtaining the porous calcium phosphate cement which contains pore-forming agent which is acid salt and alkali salt, slightly soluble salt and surfactant, wherein the mass ratio of the solution to the solution is 10 to (0.3-8.7), and the porous calcium phosphate cement can be implanted into a body.
The inventor carries out simulation in vivo test on the porous calcium phosphate cement of the invention: the uniformly prepared porous calcium phosphate cement is placed in an environment with 37 ℃ and 100% humidity for curing for 2 hours, then is placed in simulated body fluid for soaking for 10 hours, and is observed by a stereomicroscope, the surface pore diameter is uniformly distributed, the pore diameter is between 100 and 300 mu m, the pore diameter in the cross section is 50 to 100 mu m, the porosity is large, the strength of the cured body is good, and the same result can be obtained by observation of a scanning electron microscope.
Therefore, the porous calcium sulfate bone cement has the following remarkable advantages:
the self-curing characteristic of calcium phosphate cement is not changed, the hydration product of the calcium phosphate cement is mainly the hydroxyapatite component after curing, the hydration reaction rate is basically unchanged, the aperture is between 100 and 300 mu m and is mainly concentrated between 150 and 250 mu m, the growth of bone tissues and other organic tissues is facilitated, the degradation of the material is accelerated, the rapid healing of bones is promoted, and the calcium phosphate cement is a human hard tissue repair material with wide application prospect.
The present invention will be further illustrated with reference to the following examples, which are not intended to limit the scope of the present invention.
Example 1
Weighing 3g of powder consisting of calcium hydrophosphate, tetracalcium phosphate and hydroxyapatite and having the particle size of less than 20 microns, weighing 0.1g of calcium sulfate of 220-350 microns, adding the calcium sulfate into the powder, grinding and dispersing the powder uniformly in a mortar, adding 1.1g of physiological saline, blendingthe powder uniformly by using a dental modulation knife to form a mud mass, then placing the mud mass into a 100% humidity environment at 37 ℃ for curing for 2 hours, then placing the mud mass into simulated body fluid for soaking for more than 10 hours, detecting the mud mass by using a stereoscopic microscope, wherein the surface pore size distribution is uniform and ranges from 100 to 200 microns, the internal pore size of a section is 50-100 microns, the void ratio is large, the strength of the cured body is good, and detecting the pore size and the distribution of the section of a sample by using a scanning electron microscope are consistent with.
Example 2
Weighing 3g of powder consisting of calcium hydrophosphate, α -tricalcium phosphate, tetracalcium phosphate and hydroxyapatite,adding 0.3g of superfine calcium carbonate with the diameter of 30-60 nm, and then adding 0.7g of calcium dihydrogen phosphate (Ca (H)2PO4)2) The preparation method comprises the steps of uniformly mixing the raw materials in a mortar, adding 2.2g of physiological saline, uniformly blending the raw materials by using a dental modulation knife, curing the raw materials for 24 hours in an environment with 37 ℃ and 100% of humidity, taking out the cured raw materials, and inspecting the cured raw materials by using a stereoscopic microscope, wherein the pore diameter distribution of the cured raw materials is 100-200 mu m, more pores are smaller than 100 mu m, and the porosity is high.
Example 3
Weighing 3g of CPC powder in example 1, adding 0.3g of calcium citrate, 0.15g of ultrafine calcium carbonate with the particle size of 30-60 nm and 0.35g of monopotassium phosphate, adding 1.8g of a solution of 10% (mass ratio) nonylphenol polyoxyethylene ether, uniformly blending by using a modulation knife, curing for 24 hours at 37 ℃ in a 100% humidity environment, taking out, inspecting the surface pore size distribution of a sample by using a stereomicroscope, and analyzing a section sample to show that the pore size distribution is 100-200 mu m, the strength of a cured body is good, and a scanning electron microscope photo also shows that the pore size is basically distributed between 100-200 mu m and the pores are deep.
Example 4
Weighing 4g of the powder mixed by the CPC and the slightly soluble salt in the embodiment 2, adding 1g of 0.2% potassium stearate solution, uniformly blending by using a modulation knife, curing for 24 hours at 37 ℃ in a 100% humidity environment, taking out, and observing the pore diameters on the surface and inside by using a stereomicroscope, wherein the pore diameters of the sample are mainly distributed in 200-300 mu m, and the porosity of the sample is larger.
Example 5
Weighing 3g of CPC powder in example 1, adding 0.7g of lauryl sodium sulfate aqueous solution with the concentration of 15% (mass ratio), uniformly blending by using a modulation knife, curing for 24 hours at 37 ℃ under the environment of 100% humidity, taking out, detecting the section of a sample by using a stereomicroscope, wherein the porosity of the sample is large and basically between 50 and 150 mu m, and the coagulation time of the powder blended with the curing solution is 6 to 8min and the compressive strength is 3 to 5MPa after determination.
Example 6
The preparation method is the same as that of the embodiment 1, 0.15g of calcium oxalate and 0.8g of 10% sodium aliphatate aqueous solution are added as pore-forming agents, the pore diameter is distributed between 100 and 200 mu m, and section sample analysis shows that the pore diameter is distributed between 50 and 150 mu m, and the strength of a solidified body is good.
Example 7
The preparation method is the same as that of the embodiment 2, 0.3g of sodium bicarbonate, 0.48g of monocalcium phosphate and 2.1g of 1% Tween 80 aqueous solution are used as pore-forming agents, the pore size distribution is between 50 and 200 mu m, and section sample analysis shows that the pore size distribution is between 50 and 150 mu m, more pores are smaller than 100 mu m, and the strength of a solidified body is good.
Example 8
The preparation method is the same as that of the embodiment 1, 0.15g of calcium acetate with the particle size of 220-350 mu m and 1g of (Tween 20) aqueous solution with the concentration of 0.5% are added, the pore size distribution is 50-200 mu m, and the analysis of a section sample shows that the pore size distribution is 50-150 mu m, and the strength of a solidified body is good.
Example 9
The porous calcium phosphate cement powder was mixed with the setting fluid as in example 5, and the mixture was mixed uniformly with a spatula, and one side of the full-thickness skull defect of the male rat was filled with the bone while the other side of the full-thickness skull defect was filled with ordinary non-porous CPC, and the incision was closed after 30min of intraoperative setting. A total of 40 rats were operated, divided into 2 groups, and sampled for observation at 6 weeks and 12 weeks. At 6 weeks porous CPC healed directly to bone with significant degradation seen internally with the appearance of chondrocytes, whereas control was dense internally with no osteogenesis. After 12 weeks, the number of pores in the porous group was significantly increased and enlarged as compared with 6 weeks, and a large amount of chondrocytes and mineralized bone formation were observed, while the number of pores was small in the control group.
After secondary imaging of the specimens in the computer, the porosity was measured for each group (10 specimens per group, 5 fields per standard example) and the results are given in the table:
6 weeks (mum)2) % 12 weeks (μm)2) % ordinary CPC 2257337634 porous CPC 677391128915*
*n＝10，P＜0.05
This example shows that the porous calcium phosphate cement of the present invention can significantly increase the degradation rate of the material, accelerate the formation of new bone, and is a very good material for repairing human hard tissue.
Claims (5)
1. A porous calcium phosphate cement containing pore-forming agent, characterized in that it is composed of conventional calcium phosphate cement and pore-forming agent, the pore-forming agent is one or more of slightly soluble salt, acid salt and alkali salt or surfactant, wherein:
(1) the slightly soluble salt is calcium sulfate, calcium carbonate, calcium acetate, calcium citrate and calcium hydrophosphate,
one or more than one of calcium oxalate;
(2) the basic salt is one of sodium bicarbonate and calcium carbonate; the acid salt is phosphoric acid
One of monocalcium and monopotassium phosphate; the basic salt and the acid salt are added in an equivalent amount;
(3) the surfactant is fatty acid potassium salt, fatty acid sodium salt, Tween series, nonyl phenol
Polyoxyethylene ether series, and one or more aqueous solutions of alkyl sodium sulfate.
2. The calcium phosphate cement of claim 1, wherein:
(1) calcium phosphate cement and pore-forming agent in a mass ratio of 10 to (0.3-8.7);
(2) the concentration of the surfactant aqueous solution is 0.2-15% (mass ratio);
(3) the particle size of the slightly soluble salt is 200-350 mu m.
3. Calcium phosphate cement according to claims 1 and 2, characterized in that said sparingly soluble salt is calcium sulfate.
4. The calcium phosphate cement according to claims 1 and 2, wherein the surfactant is one of potassium stearate or sodium alkyl sulfate.
5. The porous calcium phosphate cement containing pore forming agent is used as the repairing material for hard tissue of human body.
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| ES2246726A1 (en) * | 2004-08-12 | 2006-02-16 | Universitat Politecnica De Catalunya | Injectable, self-setting calcium phosphate foam |
| CN1475279B (en) * | 2002-08-13 | 2010-04-14 | 中国科学院福建物质结构研究所 | Preparation method of gydroxy apatite bone cement artificial bone |
| CN101843920A (en) * | 2010-06-17 | 2010-09-29 | 天津大学 | Method for preparing self pore-forming calcium phosphate cement bracket |
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| US5152791A (en) * | 1989-12-07 | 1992-10-06 | Olympus Optical Co., Ltd. | Prosthetic artificial bone having ceramic layers of different porosity |
| DE4121043A1 (en) * | 1991-06-26 | 1993-01-07 | Merck Patent Gmbh | BONE REPLACEMENT MATERIAL WITH FGF |
| DE4435680A1 (en) * | 1994-10-06 | 1996-04-11 | Merck Patent Gmbh | Porous bone substitute materials |
| FR2725625A1 (en) * | 1994-10-17 | 1996-04-19 | Euros Sa | COMPOSITE BONE CEMENT |
| US5676976A (en) * | 1995-05-19 | 1997-10-14 | Etex Corporation | Synthesis of reactive amorphous calcium phosphates |
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| CN106110299A (en) * | 2007-06-04 | 2016-11-16 | 生物模拟治疗公司 | For treating compositions and the method for spinal column |
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| CN105130226A (en) * | 2014-06-05 | 2015-12-09 | 镇江市船山第二水泥厂 | Portland cement mixing admixture |
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