CN100427153C - Composite biological material and preparing method - Google Patents

Composite biological material and preparing method Download PDF

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CN100427153C
CN100427153C CN 200610050190 CN200610050190A CN100427153C CN 100427153 C CN100427153 C CN 100427153C CN 200610050190 CN200610050190 CN 200610050190 CN 200610050190 A CN200610050190 A CN 200610050190A CN 100427153 C CN100427153 C CN 100427153C
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polylactic acid
hydroxyapatite
pla
carbon fibers
obtain
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CN 200610050190
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CN1850300A (en
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飞 乔
张稚燕
懋 彭
烈 沈
强 郑
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浙江大学
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Abstract

本发明公开的复合生物材料含有重量百分比80-90%的聚乳酸、8.8-19.2%的羟基磷灰石、0.8-1.2%的碳纤维。 Composite biomaterials of the present invention is disclosed comprising 80-90% by weight of polylactic acid, hydroxyapatite 8.8-19.2%, 0.8-1.2% carbon fibers. 制备步骤如下:按比例取聚乳酸、羟基磷灰石和碳纤维,先将聚乳酸和羟基磷灰石混合,加入溶剂氯仿,充分搅拌,得到聚乳酸/羟基磷灰石悬浮液,将碳纤维分散在聚乳酸/羟基磷灰石悬浮液中,挥发溶剂得到浸渍带,将浸渍带放入模具中,在10-12MPa压力,160-180℃温度下热压成型。 Preparation steps are as follows: take the proportion of polylactic acid, hydroxyapatite and the carbon fiber, the first polylactic acid and hydroxyapatite mixed solvent of chloroform was added, stirred sufficiently to obtain a polylactic acid / hydroxyapatite suspension, carbon fibers dispersed in the polylactic acid / hydroxyapatite suspension, is impregnated with a volatile solvent to obtain the impregnated strip into a mold, in 10-12MPa pressure, hot pressing at a temperature of 160-180 ℃. 发明的碳纤维增强羟基磷灰石/聚乳酸三元复合材料制备方法简单,与已有CF增强聚乳酸复合材料和HA/PLA复合材料相比,能克服酸性过大引起体内炎症、机械强度低、在X光片上显影差等缺点。 Carbon fiber reinforced invention hydroxyapatite / polylactic acid composite material prepared three yuan simple, with existing CF reinforced composites and polylactic acid HA / PLA composites compared to overcome the acidity caused by excessive inflammation in vivo, low mechanical strength, in the X-ray film developing poor shortcomings.

Description

种复合生物材料及其制备方法技术领域本发明涉及一种复合生物材料及其制备方法,尤其是碳纤维增强羟基磷灰石/聚乳酸复合生物材料及其制备方法聚乳酸(PLA)是可吸收聚合物,它具有无毒、无刺激和生物相容性好等特性,在人体内可降解成乳酸,而且自然代谢,无残留,因此广泛用作骨折修复材料、手术缝合线、控释药物等。 Species composite biomaterial TECHNICAL FIELD The present invention relates to a composite biomaterial and its preparation method, in particular carbon fiber reinforced hydroxyapatite / polylactic acid composite biomaterials and preparation method of the polylactic acid (PLA) is a polymerizable absorbent thereof, having a non-toxic, and non-irritating properties and good biocompatibility, degradable in the human body into lactic acid, and natural metabolism, no residue, it is widely used as a bone fracture repair materials, surgical sutures, controlled release of drugs. 尽管PLA具有很多优良的性能,但由于单纯的PLA骨折内固定装置机械强度较低,还不能满足很多功能骨骼的固定要求, 因此须采用与其它材料复合达到增强的目的。 Although the PLA has many excellent properties, because of the low mechanical strength of the fixing means pure PLA fractures, can not meet the requirements of fixing bone many functions, and therefore must be employed to achieve the object and other reinforced composite materials. 而碳纤维(CF)则以其高强度和优良的生物相容性成为首选的PLA增强材料。 And carbon fibers (CF) is its high strength and excellent biocompatibility PLA as the preferred reinforcing material. 但是,CF增强PLA由于降解产物呈酸性,易引起体内炎症反应,应用受到了限制。 However, CF enhanced due to the degradation products of PLA acidic, easily cause inflammatory response in vivo, the application is limited. 羟基磷灰石(HA)具有良好的生物活性和骨传导性,能够与骨直接形成键性结合,大量地应用于骨替换植入材料。 Hydroxyapatite (HA) has good bioactivity and bone conductivity, capable of forming a bond binding directly to bone, a large amount of material applied to a bone replacement implant. 但其机械性能不佳,易脆,对负荷承载性差,不能完全适宜于骨组织工程的要求。 But its poor mechanical properties, brittle, poor load bearing, not completely suitable for bone tissue engineering requirements. 将HA与PLA复合,可以提高材料韧性,满足骨替换植入材料的机械强度要求;可以解决PLA对X光片只有穿透能力,不利于显影观察的问题;而且PLA的酸性降解产物可被HA缓冲,同时HA的骨诱导性可提供良好的骨细胞粘附生长环境,复合物的多孔结构则为细胞生长、组织再生及血管化提供条件,符合骨组织工程的生物学要求,国内外已有这方面的报道。 The HA and PLA composite can improve the toughness of the material, meet the mechanical strength requirements of the bone replacement implant material; PLA can solve the problem only on the X-ray penetration, is not conducive to the development was observed; and acidic degradation products of PLA may be HA buffer, while osteoinductive HA provides good adhesion of osteoblast growth environment, the porous structure of the complex compared to cell growth, regeneration and tissue vascularization providing condition, compliance with the requirements biological bone tissue engineering, home and abroad have reports in this regard. 但是HA/PLA复合材料的机械强度也不理想,尤其不能满足大块骨段固定强度的要求。 However, the mechanical strength of HA / PLA composite material is not satisfactory, in particular, the fixing strength can not meet the requirements of large bone segments. 本发明的目的是提供一种高强度且具有很好的生物降解性能的复合生物材料及其制备方法。 Object of the present invention is to provide a high strength and a composite biomaterial and preparation method good biodegradability. 本发明的复合生物材料,其组分及其重量百分比含量如下:上述组分之和为100%。 Composite biomaterial according to the present invention, which components and their percentage by weight as follows: The above components is 100%. 发明的复合生物材料的制备方法,其步骤如下:按比例取聚乳酸、羟基磷灰石和碳纤维,先将聚乳酸和羟基磷灰石混合,背景技术发明内容聚乳酸(PLA)羟基磷灰石(HA)碳纤维(CF)加入溶剂氯仿,充分搅拌,得到聚乳酸/羟基磷灰石悬浮液,搅拌下将碳纤维分散在聚乳酸/羟基磷灰石悬浮液中,常温下挥发溶剂得到浸渍带,将浸渍带放入模具中,在10-12MPa压力,160 - 180'C温度下热压成型。 The method of preparation of composite biomaterials of the present invention, comprises the following steps: taking proportion of polylactic acid, hydroxyapatite and the carbon fiber, first mixing the polylactic acid and hydroxyapatite, polylactic SUMMARY BACKGROUND OF THE INVENTION acid (PLA) hydroxyapatite (HA) carbon fibers (CF) the solvent of chloroform was added, stirred sufficiently to obtain a polylactic acid / hydroxyapatite suspension was stirred under carbon fibers are dispersed in a polylactic acid / hydroxyapatite suspension, volatile solvent at room temperature to obtain impregnated tape, the impregnated tape into a mold, the pressure of 10-12MPa, 160-- hot pressing at a temperature of 180'C. 本发明的有益效果在于:发明的碳纤维增强羟基磷灰石/聚乳酸三元复合材料(CF/HA/PLA),其中CF提供力学性能,HA提供生物学性能,而PLA既起到了三元复合材料中的粘结性能,该材料制备方法简单,且与已有CF增强聚乳酸复合材料和HA/PLA复合材料相比,能克服酸性过大引起体内炎症、机械强度低、在X光片上显影差等缺点,可成为既具有生物活性,又具有可吸收性和降解性的高强度骨折内固定材料。 Advantageous effects of the present invention is that: the carbon fiber reinforced invention hydroxyapatite / polylactic acid ternary composites (CF / the HA / PLA), which provide CF mechanical properties, biological properties of the HA provided, and both play a ternary complex PLA bonding properties of material, the material preparation method is simple, and with the existing CF reinforced composites and polylactic acid HA / PLA composites compared to overcome the acidity caused by excessive inflammation in vivo, low mechanical strength, developed on X-ray film poor shortcomings, both may be biologically active, but also has the degradability and absorbability of a high strength bone fixation material. 具体实施方式实施例1复合生物材料的组分及其重量百分比含量:聚乳酸(PLA)90。 Component Example 1 and its percentage by weight of the composite biomaterial embodiment DETAILED DESCRIPTION: polylactic acid (PLA) 90. /。 /. 、羟基磷灰石(HA)9.0%、碳纤维(CF) 1.0%。 , Hydroxyapatite (HA) 9.0%, the carbon fibers (CF) 1.0%. 制备方法:按比例取PLA、 HA禾卩CF,先将PLA和HA混合,加入溶剂氯仿,充分搅拌,得到HA/PLA悬浮液,然后搅拌下将CF均匀分散在HA/PLA悬浮液中, 常温下挥发溶剂得到浸渍带,将浸渍带放入模具中,将装有预浸带的模具放入热压机,在160'C和10MPa下热压20分钟成型,开模取出试样。 Preparation: PLA proportion taken, the HA CF Jie He, first mixing the HA and PLA, solvent chloroform was added, stirred sufficiently to obtain HA / PLA suspension and then stirring uniformly dispersed in the CF HA / PLA suspension, at room temperature the solvent was volatilized with impregnation, the impregnated strip into a mold, the mold with prepreg tape into the hot press molding 10MPa 20 minutes at 160'C and pressing, mold sample was taken. 测试复合材料的力学性能和生物降解性能:将制得的材料置于模拟体液(pH7.4的PBS液,配方- NaCl 137mmol/L, KC1 2.7mmol/L, Na2HP04 4.3mmol/L, KH2P04 1.4mmol/L)中,浸泡3个月, 取出洗涤干燥,测定浸泡材料溶液的pH值变化和复合材料降解过程中的力学强度变化(见表l)。 Test composite mechanical properties and biodegradability properties: The prepared material was placed in a simulated body fluid (PBS at pH7.4, formula - NaCl 137mmol / L, KC1 2.7mmol / L, Na2HP04 4.3mmol / L, KH2P04 1.4mmol / L) and soak for 3 months, taken out and washed and dried, the mechanical strength was measured change in pH change material and a composite material was soaked in the degradation process (see Table l). 表1<table>table see original document page 4</column></row> <table>在模拟体液(pH7.4的PBS液)中浸泡6个月后,发现测试材料已经支离破碎,聚乳酸基本降解,可以被体液吸收,迸而排出体外。 After TABLE 1 <table> table see original document page 4 </ column> </ row> <table> 6 months soaking in simulated body fluid (PBS at pH7.4), the fragmented material has been found in tests, substantial degradation of polylactic acid , body fluids can be absorbed, and excreted Beng. 测试浸泡材料溶液的pH值为7.0,不会引起体内炎症反应。 Test solution pH was 7.0 infusible material, it does not cause an inflammatory response in vivo. 实施例2复合生物材料的组分及其重量百分比含量:聚乳酸(PLA)85。 Components and their percentage by weight second composite biomaterial Example: polylactic acid (PLA) 85. /。 /. 、羟基磷灰石(HA) 13.8%、碳纤维(CF) 1.2°/。 , Hydroxyapatite (HA) 13.8%, a carbon fiber (CF) 1.2 ° /. . 制备方法:按比例取PLA、 HA和CF,先将PLA和HA混合,加入溶剂氯仿,充分搅拌,得到HA/PLA悬浮液,然后搅拌下将CF均匀分散在HA/PLA悬浮液中, 常温下挥发溶剂得到浸渍带,将浸渍带放入模具中,将装有预浸带的模具放入热压机,在170'C和12MPa下热压25分钟成型,开模取出试样。 Preparation: Take proportion PLA, CF and the HA, the HA first PLA and mixed, the solvent chloroform was added, stirred sufficiently to obtain HA / PLA suspension and then stirring uniformly dispersed in the CF HA / PLA suspension, at room temperature volatile solvent was impregnated with the impregnating tape into a mold, the mold with prepreg tape into the hot press, hot press forming 25 minutes, samples were taken at 170'C mold and 12MPa. 测试复合材料的力学性能和生物降解性能: 将制得的材料置于模拟体液(pH7.4的PBS液,配方同实施1)中,浸泡3个月, 取出洗涤干燥,测定浸泡材料溶液的pH值变化和复合材料降解过程中的力学强度变化(见表2)。 Test composite mechanical properties and biodegradability properties: The prepared material was placed in a simulated body fluid (pH7.4 in PBS solution with Formulation Example 1) was soaked for 3 months, taken out and washed and dried, measuring the pH of the material solution soaking variation value change and mechanical strength composite material degradation (see Table 2). 表2<formula>formula see original document page 5</formula>在模拟体液(pH7.4的PBS液)中浸泡6个月后,发现测试材料已经支离破碎,聚乳酸基本降解,可以被体液吸收,进而排出体外。 After Table 2 <formula> formula see original document page 5 </ formula> 6 months soaking in simulated body fluid (PBS at pH7.4), the fragmented material has been found in tests, substantial degradation of polylactic acid, the body fluid can be absorbed, and further excreted. 测试浸泡材料溶液的pH值为7.3,不会引起体内炎症反应。 Test solution pH was 7.3 infusible material, it does not cause an inflammatory response in vivo.

Claims (1)

1.一种复合生物材料的制备方法,其特征是步骤如下: 按重量百分比:聚乳酸80~90%,羟基磷灰石8.8~19.2%,碳纤维0.8~1.2%,取聚乳酸、羟基磷灰石和碳纤维,先将聚乳酸和羟基磷灰石混合,加入溶剂氯仿,充分搅拌,得到聚乳酸/羟基磷灰石悬浮液,搅拌下将碳纤维分散在聚乳酸/羟基磷灰石悬浮液中,常温下挥发溶剂得到浸渍带,将浸渍带放入模具中,在10-12MPa压力,160-180℃温度下热压成型。 A method for producing a composite biomaterial, characterized by the steps of: by weight percent: 80 to 90% of polylactic acid, hydroxyapatite, 8.8 to 19.2%, 0.8 to 1.2% carbon fibers, taken polylactic acid, hydroxyapatite stone and carbon fibers, polylactic acid and hydroxyapatite first mixed solvent of chloroform was added, stirred sufficiently to obtain a polylactic acid / hydroxyapatite suspension, under stirring carbon fibers are dispersed in a polylactic acid / hydroxyapatite suspension, room temperature to obtain impregnated with a volatile solvent, the impregnated strip into a mold, in 10-12MPa pressure, hot pressing at a temperature of 160-180 ℃.
CN 200610050190 2006-04-04 2006-04-04 Composite biological material and preparing method CN100427153C (en)

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WO2004091435A2 (en) 2003-04-11 2004-10-28 Etex Corporation Osteoinductive bone material
CN1613512A (en) 2003-11-04 2005-05-11 中南大学 Internal fixer composite material with living things absorption and preparation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004091435A2 (en) 2003-04-11 2004-10-28 Etex Corporation Osteoinductive bone material
CN1613512A (en) 2003-11-04 2005-05-11 中南大学 Internal fixer composite material with living things absorption and preparation

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