CN1272383A - 纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法 - Google Patents

纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法 Download PDF

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CN1272383A
CN1272383A CN00107493A CN00107493A CN1272383A CN 1272383 A CN1272383 A CN 1272383A CN 00107493 A CN00107493 A CN 00107493A CN 00107493 A CN00107493 A CN 00107493A CN 1272383 A CN1272383 A CN 1272383A
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崔福斋
蔡强
张曙明
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Tsinghua University
Qinghai University
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    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • A61F2002/2817—Bone stimulation by chemical reactions or by osteogenic or biological products for enhancing ossification, e.g. by bone morphogenetic or morphogenic proteins [BMP] or by transforming growth factors [TGF]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2002/30001—Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
    • A61F2002/30003—Material related properties of the prosthesis or of a coating on the prosthesis
    • A61F2002/3006—Properties of materials and coating materials
    • A61F2002/30062—(bio)absorbable, biodegradable, bioerodable, (bio)resorbable, resorptive
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2210/00—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
    • A61F2210/0004—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof bioabsorbable
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00179—Ceramics or ceramic-like structures
    • A61F2310/00293—Ceramics or ceramic-like structures containing a phosphorus-containing compound, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00365—Proteins; Polypeptides; Degradation products thereof

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Abstract

本发明涉及一种纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法,将H3P04逐滴加入胶原溶液中,使CaCl2·6H2O溶于去离子水,将其逐滴加入到上述溶液中,逐滴加入NaOH溶液以使pH值为6～8,在聚乳酸中加入溶剂得到均质的溶液;再加入钙磷盐粉料,最后使聚乳酸/钙磷盐/胶原复合多孔材料通过热致分相及随后溶剂的升华制得本发明的材料。本发明制备的材料具有大量连通微孔,强度和生物相容性也很好。

Description

纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法
本发明涉及一种纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法，属生物工程技术领域。
现有的人造骨替代材料有金属材料、陶瓷材料、高分子材料、复合材料等几种，各有其优缺点。从仿生的角度将如果能得到成分与人骨相近的材料是最好的。为此材料的无机成分应该是钙磷盐。但是普通的钙磷盐材料如果经过烧结会很难降解，且脆性大不易加工。未烧结则强度很差。
本发明的目的是提出一种纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法，克服已有技术中的缺点，使用胶原为分子模板，制备出一定程度上排列有序的纳米相钙磷盐。并用热致分相随后冰冻干燥的方法使它与聚乳酸(PLA)共同组成多孔框架材料以制备出有一定强度，高孔隙率且生物相容性好的骨替代材料。
本发明提出的纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法，包括下列各步骤：
(1)将H3PO4逐滴加入胶原溶液中，每0.1mol H3PO4加入1.79g胶原，滴加H3PO4时要注意滴加的速度要慢～1滴/秒，同时要用搅拌器搅拌，滴加完毕后继续搅拌此溶液20分钟；
(2)称取结晶良好的CaCl2·6H2O溶于去离子水使其完全溶解，随后将其逐滴加入到步骤1制备的溶液中，其中CaCl2和H3PO4的摩尔比为1.66，并继续搅拌1小时以保证钙离子和磷酸根的充分分散；
(3)逐滴加入NaOH溶液以使PH值为6～8，PH值用试纸测定，在PH值为5～6时开始出现沉淀pH值为7时出现白色悬浊液；
(4)静置溶液除去上清，离心分离出沉淀，用去离子水反复清洗三次后，放入冻干机内冰冻干燥，制得钙磷盐干粉备用；
(5)聚乳酸称量后置于烧瓶中，加入1，4-二氧六环溶剂以制备浓度为1％-10％重量体积比的溶液，混合物在40～50℃搅拌10～15分钟，得到均质的溶液；
(6)在上述溶液中加入钙磷盐粉料，钙磷盐与聚乳酸的质量比为0.8～1.2，制得聚乳酸/钙磷盐/胶原混合物；
(7)聚乳酸/钙磷盐/胶原复合多孔材料通过热致分相及随后溶剂的升华制得。取聚乳酸/钙磷盐/胶原/1，4-二氧六环混合物加热至40～50℃停留3～5分钟后转移到冰箱中在-15～0℃冷冻以固化溶剂并引起固液分相，固液分相是指1，4-二氧六环结晶后溶质也析出固化，固化的混合物在此温度下保温1～2小时然后浸入液氮深度冷冻10～15秒钟，随后拿到冻干机中冰冻干燥72～100小时以彻底移除溶剂，即为本发明的纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料。
本发明制备的材料具有大量连通的60～200微米微孔，且孔隙率很高约为65％～85％，孔隙率与溶液浓度有关浓度越小孔隙率越大。此材料的强度和生物相容性也很好。很有希望作为骨材料得到应用。
下面介绍本发明的实施例
实施例1：
所用材料为CELLON公司购买的液态I型胶原(浓度：0.3％溶液PH值由HCl调整所含胶原为纯化的牛皮胶原)、分析纯的CaCl2·6H2O、分析纯磷酸(含量＞＝85％密度1.689g/ml)。
(1)100ml胶原中滴加1.125ml磷酸时滴加速度1为滴/秒。滴加完毕后继续搅拌此溶液20分钟；
(2)称取结晶良好的CaCl2·6H2O 6.01g溶于20ml去离子水使其完全溶解将其滴加入上一步制得的溶液中后，继续搅拌1小时；
(3)加入0.75mol/l NaOH溶液至pH值为7；
(4)静置溶液除去上清，离心分离出沉淀用去离子水反复清洗三次后放入冻干机内进行冰冻干燥，制得干粉备用；
(5)称取0.5g聚乳酸置于烧瓶中，加入5ml 1，4-二氧六环得到10％的溶液。混合物在50℃搅拌10分钟，得到均质的溶液；
(6)加入0.5g制得的钙磷盐粉料；
(7)取上一步制的混合物加热至50℃停留3分钟后转移到冰箱中温度为-10℃，冷冻固液分相，固化的混合物在此温度下保温2小时然后浸入液氮l0秒，样品随后拿到冻干机中冰冻干燥，时间为72小时；
实施例2：
所用原料与钙磷盐/胶原干粉的制备方法与实施例一同
(1)称取0.25g聚乳酸置于烧瓶中，加入5ml 1，4-二氧六环得到5％的溶液，溶液在50℃搅拌10分钟，得到均质的溶液。加入0.25g制得的钙磷盐粉料。
(2)上一步制得的混合物加热至50℃保温3分钟后转移到冰箱中温度为0℃，冷冻固液分相，固化的混合物在此温度下保温2小时然后浸入液氮10秒，随后拿到冻干机中冰冻干燥，时间为96小时；
实施例3：
所用原料与钙磷盐/胶原干粉的制备方法与实施例一同
(1)称取0.375g聚乳酸置于烧瓶中，加入5ml 1，4-二氧六环得到7.5％的溶液在50℃搅拌10分钟，得到均质的溶液。加入0.3g制得的钙磷盐粉料，钙磷盐与聚乳酸比例为0.8；
(2)上一步制得的混合物加热至50℃停留4分钟后转移到冰箱中，温度为-10℃，冷冻固液分相，固化的混合物在此温度下保温2小时然后浸入液氮10秒。样品随后拿到冻干机中冰冻干燥，时间为72小时。

Claims (1)

1.一种纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法，包括下列各步骤：
(1)将H3PO4逐滴加入胶原溶液中，每0.1mol H3PO4加入1.79g胶原，同时要用搅拌器搅拌，滴加完毕后继续搅拌此溶液20分钟；
(2)称取结晶良好的CaCl2·6H2O溶于去离子水使其完全溶解，随后将其逐滴加入到步骤1制备的溶液中，其中CaCl2和H3PO4的摩尔比为1.66，并继续搅拌1小时以保证钙离子和磷酸根的充分分散；
(3)逐滴加入NaOH溶液以使PH值为6～8；
(4)静置溶液除去上清，离心分离出沉淀，用去离子水反复清洗三次后，放入冻干机内冰冻干燥，制得钙磷盐干粉备用；
(5)称取聚乳酸，再加入1，4-二氧六环溶剂，以制备重量体积比浓度为1％-10％的溶液，混合物在40～50℃搅拌10～15分钟，得到均质的溶液；
(6)在上述溶液中加入钙磷盐粉料，钙磷盐与聚乳酸的质量比为0.8～1.2，制得聚乳酸/钙磷盐/胶原混合物；
(7)取聚乳酸/钙磷盐/胶原/1，4-二氧六环混合物加热至40～50℃停留3～5分钟，然后在-15～0℃冷冻以固化溶剂并引起固液分相，固化的混合物在此温度下保温1～2小时，浸入液氮深度冷冻10～15秒钟，最后冰冻干燥72～100小时，即为本发明的纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料。
CN00107493A 2000-05-19 2000-05-19 纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料的制备方法 Expired - Lifetime CN1106861C (zh)

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Cited By (22)

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DE102007043859A1 (de) 2006-09-14 2008-07-10 Beijing Allgens Medical Science & Technology Co. Ltd. Mineralisierte Polypeptidsubstanz für den Knochenaufbau und deren Herstellung
CN101015712B (zh) * 2007-02-26 2010-05-26 福建师范大学 聚己内酯－壳聚糖网络/羟基磷灰石复合多孔支架材料的制备方法
CN102458374A (zh) * 2009-05-06 2012-05-16 实验室护肤股份有限公司 包含活性剂-磷酸钙颗粒复合物的皮肤递送组合物及其使用方法
CN101401969B (zh) * 2008-11-07 2012-10-24 东南大学 胶原-壳聚糖-羟基磷灰石球形多孔颗粒材料的制备方法
CN101401967B (zh) * 2008-11-07 2012-10-24 东南大学 胶原-β-磷酸三钙复合球形颗粒的制备方法
CN101401959B (zh) * 2008-11-07 2012-10-24 东南大学 明胶-壳聚糖-β-磷酸三钙球形多孔颗粒材料的制备方法
CN101401961B (zh) * 2008-11-07 2012-10-24 东南大学 明胶-壳聚糖-羟基磷灰石球形多孔颗粒材料的制备方法
CN101401968B (zh) * 2008-11-07 2012-10-24 东南大学 胶原-壳聚糖-β-磷酸三钙球形多孔颗粒材料的制备方法
CN101401956B (zh) * 2008-11-07 2012-11-28 东南大学 壳聚糖球形多孔颗粒材料及其制备方法和装置
CN101401971B (zh) * 2008-11-07 2012-11-28 东南大学 胶原球形多孔颗粒材料及其制备方法和装置
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