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Publication numberCN1058689 C
Publication typeGrant
Application numberCN 98110645
Publication date22 Nov 2000
Filing date5 Feb 1998
Priority date5 Feb 1998
Also published asCN1193614A
Publication number98110645.5, CN 1058689 C, CN 1058689C, CN 98110645, CN-C-1058689, CN1058689 C, CN1058689C, CN98110645, CN98110645.5
Inventors刘昌胜, 许卫军, 沈卫
Applicant华东理工大学
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Porous calcium phosphate cement containing pore-creating agent
CN 1058689 C
Abstract  translated from Chinese
本发明涉及一种用于人体硬组织修复的多孔磷酸钙骨水泥,公开了一种含有成孔剂的多孔磷酸钙骨水泥的制备方法和应用。 The present invention relates to a human hard tissue repair porous calcium phosphate bone cement, discloses the preparation and application of a pore-forming agent containing a porous calcium phosphate bone cement. 本发明采用无毒的微溶性盐、酸式盐和碱式盐或无毒的表面活性剂作为成孔剂,利用成孔剂的成孔特性制备出多孔固化体,不改变磷酸钙骨水泥自行固化的特性,不改变固化后其水化产物主要为羟基磷灰石的成分,水化反应速率基本不变,孔径在100~300μm之间,主要集中在150~250μm之间,有利于骨组织及其它有机组织的长入,加速材料的降解,促进骨的快速愈合,是一种具有广阔应用前景的人体硬组织修复材料。 Feature of the present invention employs a pore non-toxic sparingly soluble salt, acid and base salts or nontoxic surfactant as a pore-forming agent, the use of pore-forming agent to prepare a porous cured, does not change the calcium phosphate cement self- curing characteristics do not change after curing its hydration products mainly hydroxyapatite composition, hydration reaction rate is essentially the same, at 100 ~ 300μm aperture between, mainly in between 150 ~ 250μm, help bone tissue and other organic tissue ingrowth, accelerated degradation of materials, and promote rapid healing of bone, is a kind of broad application prospects of human hard tissue repair material.
Claims(5)  translated from Chinese
1.一种含有成孔剂的多孔磷酸钙骨水泥,其特征在于是由常规的磷酸钙骨水泥和成孔剂所组成,所说的成孔剂为微溶性盐、酸式盐和碱式盐或表面活性剂中的一种或一种以上,磷酸钙骨水泥∶成孔剂=10∶(0.3~8.7)重量比;其中:(1)所说的微溶盐为硫酸钙,碳酸钙,醋酸钙,柠檬酸钙,磷酸氢钙,草酸钙中的一种或一种以上;(2)所说的碱式盐为碳酸氢钠、碳酸钙中的一种;所说的酸式盐为磷酸二氢钙、磷酸二氢钾中的一种;碱式盐和酸式盐应等当量加入;(3)所说的表面活性剂为脂肪酸钾盐,脂肪酸钠盐,吐温系列,壬基酚聚氧乙烯醚系列,烷基硫酸钠中的一种或一种以上的水溶液。 A porous calcium phosphate bone cement containing a pore-forming agent, which is characterized as by conventional calcium phosphate bone cement and a pore-forming agent composed of said pore-forming agent is sparingly soluble salts, acids, salts and base salt or surfactant in one or more calcium phosphate bone cement: porogen = 10 (0.3 to 8.7) by weight ratio; wherein: (1) of said sparingly soluble salt is calcium sulfate, calcium carbonate , calcium acetate, calcium citrate, calcium hydrogen phosphate, calcium oxalate of one or more; (2) of said basic salt is sodium bicarbonate, calcium carbonate one; said acid salt calcium dihydrogenphosphate, potassium dihydrogenphosphate one; basic salts and acid salts should be added an equivalent amount; (3) of said surfactant is a fatty acid potassium salts, fatty acid sodium salt, Tween series, azelaic phenol polyoxyethylene ether series, sodium alkyl sulfate in an aqueous solution of one or more.
2.如权利要求1所述的磷酸钙骨水泥,其特征在于:(1)所说的表面活性剂水溶液的浓度为0.2%~15%重量比;(2)所说的微溶盐的粒径为200~350μm。 (2) of said sparingly soluble salt tablets; (1) the concentration of said aqueous surfactant solution is 0.2% to 15% by weight: 2. The calcium phosphate cement according to claim 1, characterized in that diameter of 200 ~ 350μm.
3.如权利要求1或2所述的磷酸钙骨水泥,其特征在于所说的微溶盐为硫酸钙。 Calcium phosphate cement according to 1 or 2 claim, characterized in that the sparingly soluble salt is calcium sulfate.
4.如权利要求1或2所述的磷酸钙骨水泥,其特征在于所说的表面活性剂为硬脂酸钾或烷基硫酸钠中的一种。 The calcium phosphate cement according to claim 1 or claim 2, wherein said surfactant is potassium stearate or sodium alkyl sulfate in a.
5.如权利要求1或2所述的磷酸钙骨水泥的应用,其特征在于可作为人体硬组织的修复材料。 5. The application of a calcium phosphate cement or claim 2, wherein the body as hard tissue repair material.
Description  translated from Chinese
含有成孔剂的多孔磷酸钙骨水泥及其应用 Containing porogen porous calcium phosphate bone cement and its applications

本发明属于医用材料领域,涉及一种用于人体硬组织修复的多孔磷酸钙骨水泥及其应用。 The invention belongs to the field of medical material, relates to a human hard tissue repair porous calcium phosphate bone cement.

磷酸钙骨水泥(简称CPC)是由几种磷酸钙盐组成的混合物,可以按常规的方法进行配制。 Calcium phosphate cement (abbreviated CPC) is a blend of several calcium salts thereof, can be formulated according to conventional methods. 其水化产物为羟基磷灰石,由于羟基磷灰石与脊椎动物的骨和牙齿的矿物成分非常相近,故其与人体组织的生物相容性好,因而通过几种磷酸钙盐的水化反应而生成的羟基磷灰石或人工合成的羟基磷灰石,常作为人体硬组织修复用的材料,它的研究和应用特别引入注目,近年来发展特别迅速。 Its hydration products of hydroxyapatite, due to the mineral composition of hydroxyapatite and vertebrate bones and teeth are very similar, so its good biocompatibility with human tissue, and thus several hydrated calcium salt reaction generated hydroxyapatite or synthetic hydroxyapatite, often as a human hard tissue repair material used, its research and applications especially compelling, especially the rapid development in recent years. 目前在临床研究和应用上涉及较多的有以下几种:(1)按常规的方法进行配制磷酸钙骨水泥(CPC),用水调和后成糊状物,根据缺损部位任意填充塑型,并在人体环境和温度下自行固化,其最终成分转化为羟基磷灰石,这种水化形成的固化体的孔径<10μm。 Currently in clinical research and applications involving more of the following: (1) be formulated according to conventional methods of calcium phosphate cement (CPC), to reconcile into a paste with water, filling plastic according to any defect, and Under the environment and human body temperature self-curing, the final component into hydroxyapatite, the aperture formed in this hydration cured body <10μm. 动物实验表明:由于内部孔径小,磷酸钙骨水泥植入骨内后,早期只能与骨组织形成界面结合,它是靠组织长入植入物粗造不平的表明而形成的一种机械性锁和,强度不高,且由于骨组织无法长入,使磷酸钙骨水泥降解缓慢,而影响骨的改建。 Animal experiments show that: Due to the small internal aperture, after implantation in the calcium phosphate bone cement, early bone formation can only interface bonding, it is by tissue ingrowth into the implant roughness uneven indicate the formation of a mechanical locks and the intensity is not high, and because the bone tissue ingrowth can not make a slow degradation of calcium phosphate bone cement, and bone remodeling.

(2)文献(KESalyer.,Plastic and Reconstructive Surgery,1989,84(2):236~244)报道的一种人工合成的羟基磷灰石陶瓷,是较为成功的一种人体硬组织修复用的材料,经过各国科学家多年的共同努力,已形成了多种成熟的制备方法:(US3929971)公开了它的制备技术,其它如气体分解法、浸渍法、水热热压法、有机质填充法、微波工艺法、蜡复型法等。 (2) literature (KESalyer, Plastic and Reconstructive Surgery, 1989,84 (2):. 236 ~ 244) reported a synthetic hydroxyapatite ceramic, is more successful with a human hard tissue repair material After years of joint efforts of scientists from various countries have formed a variety of mature preparation: (US3929971) discloses its preparation techniques, other issues such as gas decomposition, impregnation, hydrothermal hot pressing method, organic filler, microwave technology France, wax replica method. 它们是将碱性条件下形成的磷灰石加热到800-1200℃制得的。 They are formed under alkaline conditions the apatite is heated to 800-1200 ℃ obtained. 这种工合成的羟基磷灰石陶瓷,具有有利于新骨向材料内部的快速生长,增加材料同宿主骨之间的界面结合强度的150~500μm的孔径,其共同特点是必须经过高温烧结步骤,高温烧结是导致颗粒间连接而产生强度、并产生多孔的必要条件。 This synthetic hydroxyapatite ceramic work, with new bone is conducive to the rapid growth of the interior materials, increased 150 ~ 500μm aperture with the host bone interface material between the bond strength, their common feature is the need to go through high temperature sintering step , high-temperature sintering among the particles is led to the connection strength is generated, and generates a necessary condition porous. 这种加热过程会引起磷灰石晶体的烧结,形成不被吸收的植入体,以致使它的应用受到了限制。 This heating process causes the sintered apatite crystal formation is not absorbed by the implant, so that its application is limited.

(3)(US4869906)公开了通过高温烧结的方式产生多孔的磷酸钙盐小球,用作丙烯酸类骨水泥的填充料的技术,多孔颗粒内的孔径成为丙烯酸自由基聚合后固化体的孔径,所述方法也因为需要高温烧结而受到了限制。 (3) (US4869906) discloses a porous calcium phosphate produced by high temperature sintering pellets way, is used as an acrylic bone cement filler technology, the pore size of the porous particles present in the radical polymerization of acrylic acid becomes cured after the aperture, The method also requires a high temperature sintering because limited. 因此,加速新骨长入和材料降解的用于骨缺损修复的材料依然是困扰外科医生的棘手问题。 Therefore, to accelerate new bone ingrowth and material degradation for bone defect repair material is still troubled by the thorny issue of the surgeon.

本发明的目的在于公开一种含有成孔剂的多孔磷酸钙骨水泥,利用成孔剂的成孔特性而制备出多孔固化体,避免因高温烧结而形成不被吸收的植人体,以解决骨缺损的修复的难题。 Object of the present invention is to disclose a pore-forming agent comprising a porous calcium phosphate bone cement, the use of pore-forming agent and pore-forming properties of the cured body prepared porous, sintered at high temperature to avoid the formation of the implant is not absorbed by the body, in order to solve the bone defect repair problems.

本发明的构思是这样的:1.利用微溶盐在水溶液中具有一定的溶解度的特性可制备多孔磷酸钙骨水泥。 The inventive concept is this: 1. use sparingly soluble salts have some solubility in aqueous solution properties of porous calcium phosphate bone cement can be prepared. 把微溶盐均匀地与磷酸钙骨水泥粉末搅合在一起,当磷酸钙骨水泥固化时,微溶盐占据固化体的部分空间,从而形成一个独立的单元,植入体内后,经过体液的不断渗透和清洗,由于体液中离子浓度积(Ksp)小于微溶盐的Ksp,微溶盐逐步被溶解,于是就形成了多孔结构。 After the salt evenly and sparingly soluble calcium phosphate bone cement powder mixing together, when the calcium phosphate bone cement curing, sparingly soluble salts occupy part of the space solidified to form a single unit, implanted in the body, through body fluids continue to penetrate and clean, because the ion concentration in body fluids product (Ksp) of less than sparingly soluble salts Ksp, sparingly soluble salt gradually dissolved, so he formed a porous structure. 其孔径的分布和大小由微溶盐的粒径控制。 Pore size distribution and size is controlled by the size of sparingly soluble salts. 这种材料在骨组织不断长入的同时才逐步形成多孔的,所以它的初始强度是很高的,克服了单纯多孔材料植到体内后初期强度较低的不良影响。 This material in bone tissue ingrowth, while it continues to gradually form a porous, so it is a very high initial strength, overcome the simple porous material implanted into the body after the initial strength of the lower adverse effects.

2.利用产气物质制备多孔磷酸钙骨水泥,将酸式盐和碱式盐加入到磷酸钙骨水泥粉末中。 2. The use of gas preparing porous calcium phosphate bone cement material, the acid and base salts are added to the calcium phosphate bone cement powder. 当混合粉末同水接触调成浆体以后,酸式盐和碱式盐发生反应而产生气体:浆体内部产生气体从而形成多孔,固化以后形成多孔磷酸钙骨水泥。 When mixing the powder with water contact tune into slurry, acid and base salts react to produce gas: gas is generated inside the slurry to form a porous form a porous calcium phosphate bone cement after curing.

3.在磷酸钙骨水泥骨水泥体系中加入无毒的表面活性剂。 3. Add nontoxic surfactant calcium phosphate bone cement cement system. 在磷酸钙骨水泥粉末同液体混合后调浆时由于表面张力较小而产生气泡。 When calcium phosphate bone cement powder mixed with liquid pulp due to the smaller surface tension bubbles. 气泡均匀分布于浆体中,固化后即形成多孔结构。 Bubbles uniformly distributed in the slurry to form a porous structure on solidification.

本发明详细的技术方案如下所述:本发明所说的含有成孔剂的多孔磷酸钙骨水泥主要由磷酸钙骨水泥(CPC)和成孔剂所组成,其比例如下: Detailed technical solutions of the present invention are as follows: The present invention comprises a pore-forming agent said porous calcium phosphate bone cement is mainly composed of calcium phosphate cement (CPC) and a pore-forming agent, whose proportions are as follows:

磷酸钙骨水泥∶成孔剂=10∶(0.3~8.7) (重量比)(1)所说的磷酸钙骨水泥(CPC)是由几种磷酸钙盐按一定的比例混合的混合物,可以按(US5525148,US5545254)公开的方法配制,可以是磷酸三钙(α型或β型)、磷酸四钙中的一种或两者的混合物;磷酸八钙、磷酸二氢钙、羟基磷灰石、氟磷灰石中的一种或它们的混合物。 Calcium phosphate bone cement: porogen = 10 (0.3 to 8.7) (weight ratio) (1) of said calcium phosphate cement (CPC) is composed of several calcium salt by a certain percentage blended mixture, you can press (US5525148, US5545254) discloses a method of preparation, may be (α-type or β-type), tetracalcium phosphate in a mixture of one or both of tricalcium phosphate; octacalcium phosphate, calcium dihydrogen phosphate, hydroxyapatite, fluorapatite one or mixtures thereof.

(2)所说的成孔剂为无毒的微溶性盐、酸式盐和碱式盐或无毒的表面活性剂中的一种或一种以上,其中:所说的微溶盐可以是在水中微溶的钙盐等,如硫酸钙,碳酸钙,醋酸钙,柠檬酸钙,磷酸氢钙,草酸钙等,以硫酸钙为佳;所说的碱式盐为能在酸性条件下产生CO2的碳酸盐,如碳酸氢钠,碳酸钙等;所说的酸式盐为在水中呈酸性的盐,如磷酸二氢钙,磷酸二氢钾等,碱式盐和酸式盐应等当量加入;所说的表面活性剂为脂肪酸钾盐,脂肪酸钠盐,吐温系列,壬基酚聚氧乙烯醚系列,烷基硫酸钠等,以硬脂酸钾及烷基硫酸钠为佳。 (2) of said pore-forming agent is a non-toxic sparingly soluble salt, acid and base salts or nontoxic surfactant in one or more, wherein: said sparingly soluble salt can be sparingly soluble in water, the calcium salt, such as calcium sulfate, calcium carbonate, calcium acetate, calcium citrate, calcium hydrogen phosphate, calcium oxalate, preferably calcium sulfate; said basic salt is capable of producing under acidic conditions CO2 carbonates, such as sodium bicarbonate, and calcium carbonate; salts of said acid in water, acidic salts, such as calcium dihydrogen phosphate, potassium dihydrogen phosphate, basic salts and acid salts should etc. equiv added; said surfactant is a fatty acid potassium, fatty acid sodium salt, Tween series, nonylphenol ethoxylates series, alkyl sulfate and the like, with potassium stearate and sodium alkyl sulfate is preferred.

本发明所说的骨水泥是按下述方法进行制备和应用的:(1)将直径小于20μm的磷酸钙骨水泥粉末和直径为200~350μm的微溶盐按磷酸钙骨水泥∶微溶盐=10∶(0.3~8.7)(重量比)的比例混合,即获得含有成孔剂为微溶盐的多孔磷酸钙骨水泥,用生理盐水或其他盐溶液作为固化液,按固液比为3∶1的比例与其混合均匀,即可植入体内;(2)将直径小于20μm的磷酸钙骨水泥与以等当量配置的酸式盐和碱式盐按磷酸钙骨水泥∶微溶盐=10∶(0.3~8 7)(重量比)的比例混合,即获得含有成孔剂为酸式盐和碱式盐的多孔磷酸钙骨水泥,用生理盐水或其他盐溶液作为固化液,按固液比为3∶1的比例与其混合均匀,即可植入体内;(3)以含有0.2%~15%的表面活性剂的水溶液为固化液与直径小于200μm的磷酸钙骨水泥,按固液比为3∶1(重量比)的比例混合均匀,即获得含有成孔剂为表面活性剂的多孔磷酸钙骨水泥,即可植入体内。 The present invention is called bone cement was prepared by the following methods and applications: (1) the diameter of less than 200 ~ 350μm sparingly soluble salt by calcium phosphate bone cement and bone cement powder diameter 20μm for: slightly soluble salts = 10 (0.3 to 8.7) (weight ratio) mixed at a ratio, i.e. the porogen is obtained containing a sparingly soluble salt of a porous calcium phosphate bone cement, with normal saline or other salt solution as a curing liquid, according to the solid-liquid ratio of 3 :1 proportion to its mix, then implanted in the body; (2) the diameter of less than 20μm with calcium phosphate bone cement in an equivalent configuration of the acid and base salts by calcium phosphate bone cement: a sparingly soluble salt = 10 : (0.3 to 87) (weight ratio) mixed at a ratio, i.e. the porogen is obtained containing the acid and base salts of a porous calcium phosphate bone cement, with normal saline or other salt solution as a curing liquid, according to the solid-liquid ratio = 3/1 mixed therewith, can be implanted in the body; aqueous solution (3) containing 0.2% to 15% of the surface active agent is a curing liquid and the calcium phosphate cement diameter of less than 200μm, according to the solid-liquid ratio 3/1 (weight ratio) mixed evenly, i.e., to obtain a pore-forming agent comprising a surfactant porous calcium phosphate bone cement, can be implanted in the body.

(4)将直径小于20μm的磷酸钙骨水泥与以等当量配置的酸式盐和碱式盐、微溶盐以及表面活性剂的水溶液(0.2%~15%)按以下比例混合均匀:磷酸钙骨水泥∶(微溶盐+酸式盐和碱式盐+0.2%~15%的表面活性剂的水溶液)=10∶(0.3~8.7) (重量比)即获得含有成孔剂为酸式盐和碱式盐、微溶盐以及表面活性剂的多孔磷酸钙骨水泥,即可植入体内。 (4) The diameter of less than 20μm calcium phosphate bone cement with an equivalent configuration of an acid salts and base salts, as well as a sparingly soluble salt aqueous solution of the surfactant (0.2% to 15%) were mixed in the following proportions uniform: calcium phosphate cement: (a sparingly soluble salt + aqueous acid and base salts + 0.2% to 15% of the surface active agent) = 10 (0.3 to 8.7) (ratio by weight) that is obtained containing the porogen is an acid salt and basic salt, sparingly soluble salts and surfactants porous calcium phosphate bone cement can be implanted in the body.

发明人对本发明所说的多孔磷酸钙骨水泥进行了模拟体内试验:将上述调制均匀的多孔磷酸钙骨水泥置于37℃和100%湿度的环境中固化2小时,然后再置于模拟体液中浸泡10小时,用体视显微镜观察,表面孔径分布均匀,孔径在100~300μm之间,断面内部有孔径为50~100μm,孔隙率为大,固化体强度好,用扫描电子显微镜观察也可得到相同的结果。 The inventors of this invention said porous calcium phosphate bone cement was simulated in vivo test: the modulation uniform porous calcium phosphate bone cement at 37 ℃ and 100% humidity curing two hours, and then placed in a simulated body fluid soak for 10 hours, even with a stereoscopic microscope, the surface pore size distribution, pore size between 100 ~ 300μm, a pore size of internal section 50 ~ 100μm, porosity, good cured strength, was observed with a scanning electron microscope can be obtained same results.

因此,本发明所说的多孔硫酸钙骨水泥具有十分显著的优点:不改变磷酸钙骨水泥自行固化的特性,不改变固化后其水化产物主要为羟基磷灰石的成份,水化反应速率基本不变,孔径在100~300μm之间,主要集中在150~250μm之间,有利于骨组织及其它有机组织的长入,加速材料的降解,促进骨的快速愈合,是一种具有广阔应用前景的人体硬组织修复材料。 Accordingly, the present invention said porous calcium sulfate cement has very significant advantages: calcium phosphate bone cement without changing the characteristics of self-curing, does not change its hydration products after curing ingredients mainly of hydroxyapatite, the hydration reaction rate basically unchanged, at 100 ~ 300μm aperture between, mainly in between 150 ~ 250μm, help bone tissue and other organic tissue ingrowth, accelerated degradation of materials, and promote rapid healing of bone, is a kind of broad application prospects of human hard tissue repair material.

下面将结合实施例进一步阐明本发明的内容,但这些实施例并不限制本发明的保护范围。 Will now be further illustrated with reference to Examples of the present invention, but these examples do not limit the scope of the present invention.

实施例1称取有磷酸氢钙、磷酸四钙和羟基磷灰石组成的粒径小于20μm的粉末3g,称取0.1g 220~350μm硫酸钙加入到粉末中,在研钵中研磨分散均匀,加入1.1g生理盐水,用牙科调制刀调和均匀成泥团,然后放入37℃ 100%湿度环境中固化2小时,然后放入模拟体液中浸泡10小时以上,用体视显微镜检测,表面孔径分布较均匀,在100~200μ之间,断面内部孔径为50~100μm,空隙率较大,固化体强度好,用扫描电子显微镜检测样品断面的孔径大小及分布与体视显微镜的结果一致。 Example 1 There were weighed dibasic calcium phosphate, particle diameter of the tetracalcium phosphate and hydroxyapatite powder composition is less than 3g 20μm, and weighed 0.1g 220 ~ 350μm calcium sulfate was added to the powder, ground in a mortar in a uniform dispersion, added 1.1g physiological saline, with a dental modulation knife reconcile evenly into mud pie, then placed in 37 ℃ 100% humidity cured for 2 hours, and then immersed into simulated body fluid for more than 10 hours, treated with stereomicroscope detection, surface pore size distribution more uniform between 100 ~ 200μ, section internal aperture of 50 ~ 100μm, large porosity, good curing strength, with a pore size and distribution of the scanning electron microscope cross-section of the test sample is consistent with the results of the stereomicroscope.

实施例2称取由磷酸氢钙、α-磷酸三钙、磷酸四钙、和羟基磷灰石组成的粉末3g,加入0.3g直径为30~60nm的超细碳酸钙,再加0.7g磷酸二氢钙(Ca(H2PO4)2),在研钵中混合均匀,然后加入2.2g生理盐水,用牙科调制刀调和均匀,然后在37℃和100%湿度的环境中固化24小时,取出,用体视显微镜检查,其孔径的分布在100~200μm,小于100μm较多,孔隙率大。 Example 2 3g prepared from the powder of said calcium hydrogenphosphate, α- tricalcium phosphate, tetracalcium phosphate and hydroxyapatite, was added 0.3g of a diameter of 30 ~ 60nm superfine calcium carbonate, dicalcium phosphate, together with 0.7g calcium hydroxide (Ca (H2PO4) 2), mixed in a mortar, and then added 2.2g physiological saline, to reconcile even with a dental modulation knife and then cured for 24 hours at 37 ℃ and 100% humidity, out, with body stereomicroscope examination, its pore size distribution in the 100 ~ 200μm, less than 100μm more porosity.

实施例3称取实施例1中的CPC粉末3g,加入0.3g柠檬酸钙,0.15g粒径为30~60nm的超细碳酸钙和0.35g磷酸二氢钾,加入1.8g 10%(质量比)的壬基酚聚氧乙烯醚的溶液,用调制刀调和均匀,然后在37℃,100%湿度环境中固化24小时,取出,用体视显微镜检查其样品表而孔径分布在100~200μm之间,断面样品分析表明孔径分布在100~200μm之间,固化体强度好,扫描电镜照片也表明孔径基本分布在100~200μm之间,并且孔很深。 3 said CPC powder 3g taken in Example 1, was added 0.3g calcium citrate, 0.15g particle size of 30 ~ 60nm superfine calcium carbonate and 0.35g of potassium dihydrogen phosphate, was added 1.8g 10% (mass ratio Example ) solution, nonylphenol ethoxylates, with the modulation knife reconcile uniform, then at 37 ℃, 100% humidity cured for 24 hours, remove and check the sample table with a stereo microscope and pore size distribution of 100 ~ 200μm room, section analysis shows the pore size distribution in the sample between 100 ~ 200μm, good cured strength, SEM photographs also show pore size distribution substantially between 100 ~ 200μm, and a deep hole.

实施例4称取实施例2中CPC与微溶盐混合的粉末4g,加入1g0.2%硬脂酸钾溶液,用调制刀调和均匀,然后在37℃,100%湿度环境下固化24小时,取出,用体视显微镜观察表面及内部的孔径,表明样品孔径主要分布在200~300μm,样品孔隙率较大。 Example 4 referred to in Example 2 CPC taken mixed with a sparingly soluble salt powder 4g, potassium stearate solution was added 1g0.2%, even harmonic modulation knife, and then at 37 ℃, cured 24 hours at 100% humidity environment, Remove with a stereoscopic surface and internal aperture microscope, indicating that the sample aperture is mainly distributed in 200 ~ 300μm, the larger the sample porosity.

实施例5称取实施例1中CPC粉末3g,加入浓度为15%(重量比)的十二烷基硫酸钠水溶液0.7g,用调制刀调和均匀,然后在37℃,100%湿度环境下固化24小时,取出,用体视显微镜检测样品断面,样品孔隙率大,基本在50~150μm之间,经测定本例的粉末与固化液调和后的凝结时间为6~8min,抗压强度为3-5MPa。 Example 5 Example 1 was weighed in CPC powder 3g cases, added at a concentration of 15% (by weight) aqueous solution of sodium lauryl sulfate 0.7g, modulation knife reconcile even, then at 37 ℃, cured at 100% humidity environment 24 hours, remove the test sample with a stereomicroscope section, sample porosity, substantially between 50 ~ 150μm, clotting time was measured with a powder of this example was to reconcile after curing for 6 ~ 8min, compressive strength 3 -5MPa.

实施例6制备方法与实施例1相同,加入0.15g草酸钙和浓度为10%的脂肪酸钠水溶液0.8g作为成孔剂,其孔径分布在100~200μm之间,断面样品分析表明孔径分布在50~150μm之间,固化体强度好。 Example 6 Preparation method as in Example 1, was added 0.15g of sodium oxalate and an aqueous solution of a concentration of 0.8g 10% fat as a pore-forming agent, a pore size distribution between 100 ~ 200μm, cross-sectional analysis showed that the pore size distribution in the sample 50 between ~ 150μm, good solidified body strength.

实施例7制备方法与实施例2相同,采用碳酸氢钠0.3g、磷酸二氢钙0.48g和浓度为1%的(吐温80)水溶液2.1g作为成孔剂,其孔径分布在50~200μm之间,断面样品分析表明孔径分布在50~150μm之间,小于100μm的较多,固化体强度好。 (Tween 80) solution prepared in Example 7 the same manner as in Example 2, the use of sodium bicarbonate 0.3g, 0.48g of calcium dihydrogen phosphate and 2.1g of 1% concentration as a pore-forming agent, its pore size distribution at 50 ~ 200μm between the cross-section analysis of samples showed that the pore size distribution between 50 ~ 150μm, more of less than 100μm, good cured strength.

实施例8制备方法与实施例1相同,加入0.15g粒径为220~350μm的醋酸钙和浓度为0.5%的(吐温20)的水溶液1g,其孔径分布在50~200μm之间,断面样品分析表明孔径分布在50~150μm之间,固化体强度好。 Example 8 prepared in Example 1, was added 0.15g of a particle size of 220 ~ 350μm and calcium acetate concentration of 0.5% (Tween 20) in water 1g, pore size distribution in which between 50 ~ 200μm, cross-sectional sample Analysis showed that the pore size distribution between 50 ~ 150μm, good cured strength.

实施例9按实施例5将多孔磷酸钙骨水泥粉末同固化液混合,用调制刀调和均匀,在术中填入雄性大鼠颅顶骨全层缺损的一侧,另一侧缺损用普通的非多孔CPC填充,术中固化30min后缝合切口。 Example 9 Example 5 porous calcium phosphate bone cement powder is mixed with a curing solution, to reconcile even with a modulation knife, fill one side of the parietal bone of full-thickness defects in male rats during surgery, the other side of the defect with ordinary non- porous CPC filling, solidification 30min after surgery incision was sutured. 共手术40只大鼠,分2组,于6周和12周取样观察。 A total of 40 rats surgery, divided into two groups, at 6 weeks and 12 weeks of sampling observation. 6周时多孔CPC与骨直接愈合,内部可见明显的降解,并伴随软骨细胞的出现,而对照组内部致密,未见成骨。 6 weeks porous CPC with direct bone healing, internally visible significant degradation, and accompanied by chondrocytes, while the internal control group dense, no osteogenesis. 12周以后,多孔组内部孔洞较6周时明显增多、增大,并可见大量的软骨细胞出现及矿化骨形成,对照组内部也出现孔洞,但数量少。 After 12 weeks, the internal pores of the porous group increased significantly when compared with six weeks, increasing and seen a lot of cartilage and mineralized bone formation occurs, the control group also appeared inside the hole, but a small number.

标本在计算机内二次成像后,测量各组的孔隙率(每组10个标本,每个标本例5个视野),结果如表:6周(μm2) % 12周(μm2) %普通CPC 2257 3 3763 4多孔CPC 6773 9 11289 15**n=10,P<0.05本实施例表明本发明所说的多孔磷酸钙骨水泥可显著增加材料的降解速率,加速新骨的形成,是一种十分优良的人体硬组织修复材料。 After the computer in the second specimen imaging, measuring porosity of each group (n = 10 samples, each sample in Example 5 visual field), results shown in Table: 6 weeks (μm2)% 12 周 (μm2)% Normal CPC 2257 337,634 porous CPC 6773 9 11289 15 ** n = 10, P <0.05 This example shows that the present invention is said porous calcium phosphate bone cement can significantly increase the rate of degradation of materials, to accelerate the formation of new bone, is a very Excellent human hard tissue repair material.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
CN101913584A *27 Aug 201015 Dec 2010江苏永冠给排水设备有限公司;中国矿业大学Method for producing filter material for removing fluorine from drinking water
CN101913584B27 Aug 20104 Apr 2012中国矿业大学Method for producing filter material for removing fluorine from drinking water
Classifications
International ClassificationC04B12/02, A61F2/28
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