CN1106861C - 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 PDFInfo
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- 102000008186 Collagen Human genes 0.000 title claims abstract description 26
- 108010035532 Collagen Proteins 0.000 title claims abstract description 26
- 229920001436 collagen Polymers 0.000 title claims abstract description 26
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 25
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 title claims description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000005057 refrigeration Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 abstract 2
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 abstract 1
- 239000001506 calcium phosphate Substances 0.000 abstract 1
- -1 calcium phosphate salts Chemical class 0.000 abstract 1
- 235000011010 calcium phosphates Nutrition 0.000 abstract 1
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 238000000859 sublimation Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- 229920013660 Cellon Polymers 0.000 description 1
- 102000012422 Collagen Type I Human genes 0.000 description 1
- 108010022452 Collagen Type I Proteins 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- 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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- 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
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- 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
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- 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]
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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
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- 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
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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H3PO4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
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,磷酸的滴加量为每100ml胶原中滴加1.125ml磷酸,滴加H3PO4时要注意滴加的速度要慢,大约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 6.0lg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/lNaOH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10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,磷酸的滴加量为每100ml胶原中滴加1.125ml磷酸,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,即为纳米相钙磷盐/胶原/聚乳酸骨复合多孔材料。
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