CN105727363A - 一种尼龙纳米纤维三维交联支架及其制备方法 - Google Patents

一种尼龙纳米纤维三维交联支架及其制备方法 Download PDF

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CN105727363A
CN105727363A CN201610106719.2A CN201610106719A CN105727363A CN 105727363 A CN105727363 A CN 105727363A CN 201610106719 A CN201610106719 A CN 201610106719A CN 105727363 A CN105727363 A CN 105727363A
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楼涛
汪学军
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Qingdao University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/18Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04Macromolecular materials
    • A61L31/06Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/12Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06Polyamides derived from polyamines and polycarboxylic acids

Abstract

本发明涉及一种尼龙纳米纤维三维交联支架及其制备方法,它采用在一定条件下静电纺丝纳米尼龙纤维膜,将纳米尼龙纤维膜在水中高速剪切成短纤维,分样,在?18℃下冷冻成型,冷冻干燥后的样品用聚丙烯酸溶液交联,水洗,冷冻,再经冷冻干燥得到尼龙纳米纤维三维交联支架。尼龙纤维经聚丙烯酸交联后,纤维之间有较好的结合力,支架整体有较好的弹性和整体结构稳定性,可用于组织和器官的修复。

Description

一种尼龙纳米纤维三维交联支架及其制备方法
技术领域
本发明涉及一种尼龙纳米纤维三维交联支架及其制备方法,属于生物医用材料技术领域。
背景技术
尼龙是分子主链上含有重复酰胺基团的热塑性树脂总称,它具有良好的力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性,且摩擦系数低,有一定的阻燃性,易于加工,适于用玻璃纤维和其它填料填充增强改性,在工业中有广泛的应用。尼龙目前在生物材料领域也有广泛的应用,可被制成各种形状的支架用于骨、皮肤和心脏等器官和组织的修复(Suman Das 等, Rapid Prototyping Journal, 2003,9(1):43-49)。在支架中,尼龙一般都制成实心结构,较少制成多孔网络状的纤维支架,使细胞、血管和神经等难以在支架内部生长。工业中可将尼龙纺丝成各种尺度的纤维,但由于尼龙纤维之间无结合力,将尼龙纤维制成三维多孔网络状的纤维支架是非常困难的。
发明内容
本发明的主要设想是采用静电纺丝的方法制备纳米尼龙薄膜,将尼龙薄膜在水中高速剪切成短纤维,得到尼龙纳米纤维的悬浮液,将悬浮分样后,经冷冻干燥成型,用聚丙烯酸溶液将尼龙纤维交联,水洗后再经冷冻干燥得到尼龙纳米纤维三维交联支架。
本发明中尼龙纳米纤维三维交联支架的制备方法具体如下所述。
(1)静电纺丝纳米尼龙纤维膜,配制一定浓度的尼龙溶液,溶剂为甲酸和水混合物,通以一定的纺丝电压静电纺丝形成纳米尼龙纤维膜。
(2)称取一定量的纳米尼龙纤维膜,加入到定量的水中,在水中高速剪切成短纤维。
(3)分样至称量瓶中,在-18℃下冷冻成型并冻干。
(4)冻干后的样品用10%的聚丙烯酸溶液交联2个小时。
(5)交联后的支架经水洗,-18℃下冷冻成型,冷冻干燥可获得尼龙纳米纤维三维交联支架。
本发明制得的尼龙纳米纤维三维交联支架为白色圆盘,其形状和高度可在分样中采用不同的容器和分样体积调节。尼龙纳米纤维的直径可通过改变静电纺丝的工艺条件调节,尼龙纤维经聚丙烯酸交联后,纤维之间有较好的结合力,支架整体有较好的弹性和整体结构稳定性,可用于组织和器官的修复。该制备工艺简单,相比于单纯的静电纺丝法,该法可容易地制备三维结构的支架。
具体实施方式
下面结合具体实施例,对本发明内容作进一步的说明,但本发明的实现方式并不局限于此。
实施例1:分别取9ml的甲酸和1ml的水,混合均匀,称取1.0g尼龙6,搅拌溶解,静置2小时。将尼龙6溶液加入到注射器中,通以15kV的电压纺丝,收集在接地的铝箔上,可获得尼龙纤维平均直径为80nm的薄膜。称取0.5g纳米尼龙纤维膜,在100ml水中高速剪切成短纤维,分样至称量瓶中,在-18℃下冷冻成型,在冻干机中冻干。冻干后的样品浸泡在10%的聚丙烯酸溶液中交联,时间为2小时,取出交联支架,水洗,-18℃下冷冻,在冻干机中再次冻干可获得尼龙6纳米纤维三维交联支架。
实施例2:分别取8ml的甲酸和2ml的水,混合均匀,称取2.0g尼龙66,搅拌溶解,静置2小时。将尼龙66溶液加入到注射器中,通以20kV的电压纺丝,收集在接地的铝箔上,可获得尼龙纤维平均直径为150nm的薄膜。称取2.0g纳米尼龙66纤维膜,在100ml水中高速剪切成短纤维,分样至称量瓶中,在-18℃下冷冻成型,在冻干机中冻干。冻干后的样品浸泡在10%的聚丙烯酸溶液中交联,时间为2小时,取出交联支架,水洗,-18℃下冷冻,在冻干机中再次冻干可获得尼龙66纳米纤维三维交联支架。

Claims (5)

1.一种尼龙纳米纤维三维交联支架及其制备方法,其特征在于在一定条件下静电纺丝纳米纤维尼龙膜,将纳米尼龙纤维膜在水中高速剪切成短纤维,分样,在-18℃下冷冻成型,冷冻干燥后的样品用聚丙烯酸溶液交联,水洗,冷冻,再经冷冻干燥得到尼龙纳米纤维三维交联支架。
2.根据权利要求1所述的尼龙纳米纤维三维交联支架,其特征在于所使用的尼龙为尼龙6和尼龙66。
3.根据权利要求1所述的尼龙纳米纤维三维交联支架,其特征在于静电纺丝纳米纤维膜时,尼龙浓度为10.0~20.0%之间,溶剂为甲酸和水的混合物,体积比在90:10到80:20之间,纺丝电压在15~20kV之间。
4.根据权利要求1所述的尼龙纳米纤维三维交联支架,其特征在于纳米尼龙纤维在水中高速剪切时的浓度在0.5~2%之间。
5.根据权利要求1所述的尼龙纳米纤维三维交联支架,其特征在于使用的交联剂为10%的聚丙烯酸溶液。
CN201610106719.2A 2016-02-27 2016-02-27 一种尼龙纳米纤维三维交联支架及其制备方法 Pending CN105727363A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107022794A (zh) * 2017-06-12 2017-08-08 曾林涛 一种自扭曲螺旋、成捻结构微纳米纤维的制备方法

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* Cited by examiner, † Cited by third party
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US20030100944A1 (en) * 2001-11-28 2003-05-29 Olga Laksin Vascular graft having a chemicaly bonded electrospun fibrous layer and method for making same
CN1887365A (zh) * 2006-08-01 2007-01-03 四川大学 具有多孔结构的生物材料膜及其制备方法
CN104815355A (zh) * 2015-04-16 2015-08-05 四川大学 表面具有纳米纤维多孔结构的羟基磷灰石/聚酰胺复合生物材料及其制备方法
CN105107022A (zh) * 2015-09-21 2015-12-02 东华大学 一种在湿态下具有压缩弹性的纳米纤维多孔支架的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030100944A1 (en) * 2001-11-28 2003-05-29 Olga Laksin Vascular graft having a chemicaly bonded electrospun fibrous layer and method for making same
CN1887365A (zh) * 2006-08-01 2007-01-03 四川大学 具有多孔结构的生物材料膜及其制备方法
CN104815355A (zh) * 2015-04-16 2015-08-05 四川大学 表面具有纳米纤维多孔结构的羟基磷灰石/聚酰胺复合生物材料及其制备方法
CN105107022A (zh) * 2015-09-21 2015-12-02 东华大学 一种在湿态下具有压缩弹性的纳米纤维多孔支架的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107022794A (zh) * 2017-06-12 2017-08-08 曾林涛 一种自扭曲螺旋、成捻结构微纳米纤维的制备方法
CN107022794B (zh) * 2017-06-12 2019-05-24 苏州克劳丝纳米科技有限公司 一种自扭曲螺旋、成捻结构微纳米纤维的制备方法

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Application publication date: 20160706