CN108221079A - Nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre and preparation method thereof - Google Patents

Nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre and preparation method thereof Download PDF

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Publication number
CN108221079A
CN108221079A CN201711389388.9A CN201711389388A CN108221079A CN 108221079 A CN108221079 A CN 108221079A CN 201711389388 A CN201711389388 A CN 201711389388A CN 108221079 A CN108221079 A CN 108221079A
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polycaprolactone
nanometer hydroxyapatite
composite fibre
nanocrystal composite
preparation
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CN201711389388.9A
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王富军
陈培峰
王璐
郝艺
赵健安
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Donghua University
National Dong Hwa University
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Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/005—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters containing a biologically active substance, e.g. a medicament or a biocide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06—At least partially resorbable materials
    • A61L17/10—At least partially resorbable materials containing macromolecular materials
    • A61L17/12—Homopolymers or copolymers of glycolic acid or lactic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L31/00—Materials 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
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L31/00—Materials 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
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L31/00—Materials 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
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L31/00—Materials 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
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent

Abstract

The invention discloses a kind of nanometer hydroxyapatite/polycaprolactone nanocrystal composite fibres and preparation method thereof.The composite fibre includes polycaprolactone, nanometer hydroxyapatite and dispersant.Preparation method is：Polycaprolactone is dissolved in organic solvent, nanometer hydroxyapatite and dispersant is then added in, obtains mixed solution；It is dry after mixed solution is freezed, obtain dry composite sample；By composite sample shred, be put into vacuum drying oven and dry, place into melting extrusion in double screw extruder and obtain as-spun fibre, by quenching by a up- coiler winding receipt；As-spun fibre is finally subjected to two sections of drawing-offs.Nanometer hydroxyapatite prepared by the present invention/polycaprolactone nanocrystal composite fibre has higher mechanical strength, and hydroxyapatite makes fiber possess good bioactivity, can become the candidate materials in the fields such as dentistry, orthopaedics.Present invention process is simple, and environmental pollution is small, and production cost is low.

Description

Nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre and preparation method thereof
Technical field
The present invention relates to a kind of nanometer hydroxyapatite polycaprolactone nanocrystal composite fibres and preparation method thereof, belong to Bio-medical fiber field of material technology.
Background technology
Bio-medical fiber refers to one kind for its disease damage tissue, device to be diagnosed, treated, repaired or replaced to organism Official or the novel high technical fibre material for promoting its function can be divided into natural polymer subbundle and synthesis macromolecule according to source Fiber.Since natural macromolecular material is restricted on source, synthesis high molecular material can more meet vast clinical demand. There is a fiber that can slowly degrade in vivo in bio-medical fiber and absorbed by organism, avoid second operation taking-up Injury, more meet the demand of clinical operation.At present, the degradable biological medical fiber of synthesis high molecular material class is main There are poly-p-dioxanone (PPDO), polyglycolide (PGA), polylactide (PLA), poly (glycolide-lactide) (PGLA), polyethylene Alcohol (PVA), polycaprolactone (PCL) and poly (hydroxyalkanoate) class (PHB) etc..
Polycaprolactone (PCL) is the biodegradable material by FDA certifications.This artificial synthesized polyester-based polymer Material possesses good biocompatibility, applied to each neck such as slow releasing carrier of medication, tissue engineering bracket, operation suture thread Domain.For the fusing point of PCL at 60 DEG C or so, heat decomposition temperature possesses very wide hot-working section, therefore very suitable at 350 DEG C or more Close various thermal processing molding methods.Hydroxyapatite is the main inorganic composition in human skeletal and tooth, has good life Object compatibility is a kind of biomaterial for being widely used in dentistry and bone injury reparation.But pure ha ceramic material is crisp Property big, poor toughness and be difficult degradation in vivo, therefore be above restricted in application.And nanometer hydroxyapatite (nHA) is not only With good biocompatibility, and with good osteoconductive and osteoinductive, adhering to, giving birth to for osteocyte can be induced Long and migration.Numerous studies surface, nHA nanocrystals can enhance the mechanical property of polymeric matrix.
Tsinghua University (CN104027840A) is prepared for polycaprolactone and nanometer hydroxyapatite available for Bone Defect Repari Porous support.This material primarily serves the subjective role of support in Bone Defect Repari, and it is suitable still to lack in terms of binding is sutured Material.Biodegradable polyester nanocomposite and this patent prepared by Southern Yangtze University (CN103937181A) has been used similar Material has directly been prepared into available by material, this patent with it difference lies in this patent with simpler and at low cost method In the fibrous material of bio-medical field.
The present invention prepares a kind of nanometer hydroxyapatite/compound fibre of polycaprolactone nanocrystal using the method for melt spinning Dimension, tensile strength can reach 280MPa, 80MPa are higher by than pure polycaprolactone melt spun fibre.And this composite fiber surface There are exposed nanometer hydroxyapatites, possess good hydrophily and bioactivity.Nano-hydroxy-apatite prepared by the present invention Stone/polycaprolactone nanocrystal composite fibre can be advantageously applied to absorbable medical suture, noninvasive sunken cord and all kinds of spinnings Knit base implantation instrument etc. field.
Invention content
The technical problems to be solved by the invention are：A kind of nanometer hydroxyapatite/polycaprolactone nanocrystal is provided to answer The preparation method of condensating fiber, to obtain the good nanometer hydroxyapatite of tensile property/polycaprolactone nanocrystal composite fibre.
To solve the above-mentioned problems, the present invention takes following technical scheme：
A kind of nanometer hydroxyapatite/polycaprolactone nanocrystal composite fibre, which is characterized in that including polycaprolactone, Nanometer hydroxyapatite and dispersant；Wherein, the quality of nanometer hydroxyapatite is the 0.01%~30% of polycaprolactone quality, The quality of dispersant is the 0.01%~10% of polycaprolactone quality.
Preferably, the dispersant is the mixture of polyethylene glycol, lecithin or both.
Preferably, the number-average molecular weight of the polycaprolactone is more than 80,000.
Preferably, the nanometer hydroxyapatite is rhabdolith, and a diameter of 20~30nm, length is 200~250nm.
The present invention also provides a kind of preparation sides of above-mentioned nanometer hydroxyapatite/polycaprolactone nanocrystal composite fibre Method, which is characterized in that include the following steps：
Step 1)：Polycaprolactone is completely dissolved in organic solvent, obtains the polymerization of a concentration of 0.05~0.25g/mL Then object solution adds in nanometer hydroxyapatite and dispersant, first magnetic agitation, rear ultrasonic disperse obtains mixed solution；
Step 2)：The mixed solution that step 1) obtains is freezed 10~24 hours under -20 DEG C and the following conditions, Zhi Houfang Enter in freeze drier and be freeze-dried 8~24 hours, obtain dry composite sample；
Step 3)：The composite sample that step 2) obtains is shredded, be put into 0~40 DEG C of vacuum drying oven drying 24~ 48h places into melting extrusion in double screw extruder and obtains as-spun fibre, by quenching by a up- coiler winding receipt；
Step 4)：The as-spun fibre that step 3) obtains is subjected to two sections of drawing-offs, drafting multiple 3 under the conditions of 5~15 DEG C ~6 times.
Preferably, extrusion temperature is 80~200 DEG C in the step 3), and extruded velocity is 10~200m/min, and blowing is warm Spend is 0~10 DEG C.
Preferably, the double screw extruder in the step 3) uses the miniature blending instrument of bipyramid.
Compared with prior art, the beneficial effects of the present invention are：
1st, in preparation method of the invention, nano hydroxyl phosphorite crystal enhances the mechanical property of polycaprolactone matrix, So that composite fibre stretches intensity and reaches 280MPa, far above the tensile strength of pure polycaprolactone fiber, it disclosure satisfy that and be woven into Type it is upper it is confidential ask, can other fiber assemblies be prepared by molding method of weaving；
2nd, whole preparation process of the invention is simple, mild, non-environmental-pollution, and the nanometer hydroxyapatite of fiber surface is protected Stay the bioactie agent of script so that fiber possesses good biocompatibility and bioactivity.
3rd, the polycaprolactone and nanometer hydroxyapatite that the present invention uses all have longer degradation cycle, and prepared answers Condensating fiber has in degradation process and can keep good mechanical property, and by change the content of nHA can regulate and control it is compound The degradation cycle and mechanical property of fiber；
4th, the preparation method main process that the present invention uses is the melting process of a lower temperature, energy conservation and environmental protection, production It is at low cost, possess the development prospect of industrialization；
5th, the composite fibre for preparing of the present invention can be advantageously applied to absorbable medical suture, it is noninvasive sunken cord with it is all kinds of Weaving base implantation instrument.
Description of the drawings
Fig. 1 is the exterior appearance of nanometer hydroxyapatite/polycaprolactone nanocrystal composite fibre prepared by embodiment 1 Figure.
Specific embodiment
To be clearer and more comprehensible the present invention, hereby with preferred embodiment, and attached drawing is coordinated to be described in detail below.
Embodiment 1
A kind of preparation method of nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre：
(1) 10g PCL (number-average molecular weight is 80,000) are weighed, (0.2g/mL) are dissolved in 50mL acetic acid solutions, in room temperature Lower magnetic agitation 8h adds in 300mg nHA (mass percent 3%) and 100mg soybean lecithins to uniform solution to solution (mass percent 1%), first magnetic agitation 2h, rear ultrasonic disperse 20min obtain mixed solution；
(2) gained mixed solution in step (1) is poured into culture dish, freezes in -20 DEG C of refrigerators for 24 hours, be put into later Drying obtains porous membranaceous composite material for 24 hours in freeze drier；
(3) resulting materials in step (2) are shredded into particle, is dried in 40 DEG C of vacuum drying chambers for 24 hours, added in later double Melting extrusion in screw extruder is wound machine reception after quenching, and spinning temperature is 180 DEG C, and blowing temperature is 0 DEG C, Up- coiler rotating speed is 100 turns/min (corresponding speed of spinning is 50m/min)；
(4) gained spun filament in step (3) is subjected to two sections of drawing-offs at 10 DEG C at room temperature, total draft multiple is 4 times, finally Obtained nanometer hydroxyapatite/polycaprolactone nanocrystal composite fibre (as shown in Figure 1), 145 μm of average diameter are average Fracture strength is 232MPa, average elongation at break 48%.
Embodiment 2
A kind of preparation method of nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre：
(1) 10g PCL (number-average molecular weight is 80,000) are weighed, (0.15g/mL) are dissolved in 67mL acetic acid solutions, in room temperature Lower magnetic agitation 8h adds in the drops of 500mg nHA (mass percent 5%) and one about 0.2mL's to uniform solution to solution Polyethylene glycol (mass percent is about 2%), first magnetic agitation 2h, rear ultrasonic disperse 20min obtain mixed solution；
(2) gained mixed solution in step (1) is poured into culture dish, freezes in -20 DEG C of refrigerators for 24 hours, be put into later Drying obtains porous membranaceous composite material for 24 hours in freeze drier；
(3) resulting materials in step (2) are shredded into particle, is dried in 40 DEG C of vacuum drying chambers for 24 hours, added in later double Melting extrusion in screw extruder is wound machine reception after quenching, and spinning temperature is 170 DEG C, and blowing temperature is 0 DEG C, Up- coiler rotating speed is 80 turns/min (corresponding speed of spinning is 40m/min)；
(4) gained spun filament in step (3) is subjected to two sections of drawing-offs at 8 DEG C at room temperature, total draft multiple is 6 times, finally Obtained nanometer hydroxyapatite/233 μm of polycaprolactone nanocrystal composite fibre average diameter, average fracture strength are 278MPa, average elongation at break 32%.

Claims (7)

1. a kind of nanometer hydroxyapatite/polycaprolactone nanocrystal composite fibre, which is characterized in that including polycaprolactone, receive Rice hydroxyapatite and dispersant；Wherein, the quality of nanometer hydroxyapatite is the 0.01%~30% of polycaprolactone quality, point The quality of powder is the 0.01%~10% of polycaprolactone quality.
2. nanometer hydroxyapatite as described in claim 1/polycaprolactone nanocrystal composite fibre, which is characterized in that institute State mixture of the dispersant for polyethylene glycol, lecithin or both.
3. nanometer hydroxyapatite as described in claim 1/polycaprolactone nanocrystal composite fibre, which is characterized in that institute The number-average molecular weight of polycaprolactone is stated more than 80,000.
4. nanometer hydroxyapatite as described in claim 1/polycaprolactone nanocrystal composite fibre, which is characterized in that institute Nanometer hydroxyapatite is stated as rhabdolith, a diameter of 20~30nm, length is 200~250nm.
5. a kind of nanometer hydroxyapatite/polycaprolactone nanocrystal composite fibre described in claim 1-4 any one Preparation method, which is characterized in that include the following steps：
Step 1)：Polycaprolactone is completely dissolved in organic solvent, the polymer for obtaining a concentration of 0.05~0.25g/mL is molten Then liquid adds in nanometer hydroxyapatite and dispersant, first magnetic agitation, rear ultrasonic disperse obtains mixed solution；
Step 2)：The mixed solution that step 1) obtains under -20 DEG C and the following conditions is freezed 10~24 hours, is put into later cold It is freeze-dried 8~24 hours in lyophilizer, obtains dry composite sample；
Step 3)：The composite sample that step 2) obtains is shredded, is put into 24~48h of drying in 0~40 DEG C of vacuum drying oven, then It is put into melting extrusion in double screw extruder and obtains as-spun fibre, by quenching by a up- coiler winding receipt；
Step 4)：The as-spun fibre that step 3) obtains is subjected to two sections of drawing-offs under the conditions of 5~15 DEG C, drafting multiple is 3~6 Times.
6. the preparation method of nanometer hydroxyapatite as claimed in claim 5/polycaprolactone nanocrystal composite fibre, special Sign is that extrusion temperature is 80~200 DEG C in the step 3), and extruded velocity is 10~200m/min, and blowing temperature is 0~10 ℃。
7. the preparation method of nanometer hydroxyapatite as claimed in claim 5/polycaprolactone nanocrystal composite fibre, special Sign is that the double screw extruder in the step 3) uses the miniature blending instrument of bipyramid.
CN201711389388.9A 2017-12-20 2017-12-20 Nanometer hydroxyapatite polycaprolactone nanocrystal composite fibre and preparation method thereof Pending CN108221079A (en)

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CN111849135A (en) * 2020-06-23 2020-10-30 南宁学院 Polycaprolactone composite material and preparation method thereof
CN112206354A (en) * 2020-10-10 2021-01-12 中国人民解放军联勤保障部队第九〇九医院 Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110205798A (en) * 2019-07-08 2019-09-06 江苏江南高纤股份有限公司 A kind of super hydrophilic fiber and preparation method thereof based on biomimetic mineralization process
CN110205798B (en) * 2019-07-08 2023-12-12 江苏江南高纤股份有限公司 Super-hydrophilic fiber based on biomimetic mineralization process and preparation method thereof
CN111849135A (en) * 2020-06-23 2020-10-30 南宁学院 Polycaprolactone composite material and preparation method thereof
CN112206354A (en) * 2020-10-10 2021-01-12 中国人民解放军联勤保障部队第九〇九医院 Polycaprolactone/nano-hydroxyapatite-citric acid composite material and patch absorbable memory elastic ring

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