CN108728931B - Composite fiber for artificial ligament and preparation method and application thereof - Google Patents
Composite fiber for artificial ligament and preparation method and application thereof Download PDFInfo
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- 210000003041 ligament Anatomy 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000000835 fiber Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004417 polycarbonate Substances 0.000 claims abstract description 56
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 56
- XNHHSKNFXPNYEB-UHFFFAOYSA-N hexyl 2-hydroxybutanoate Chemical compound CCCCCCOC(=O)C(O)CC XNHHSKNFXPNYEB-UHFFFAOYSA-N 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000001112 coagulating effect Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 15
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 15
- XCWGNVPLXFLFQY-UHFFFAOYSA-N 2-ethyl-2-hydroxyoctanoic acid Chemical compound CCCCCCC(O)(CC)C(O)=O XCWGNVPLXFLFQY-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 12
- 229960001763 zinc sulfate Drugs 0.000 claims description 12
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000701 coagulant Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000002166 wet spinning Methods 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- XAPCMTMQBXLDBB-UHFFFAOYSA-N butanoic acid hexyl ester Natural products CCCCCCOC(=O)CCC XAPCMTMQBXLDBB-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- DILOFCBIBDMHAY-UHFFFAOYSA-N methyl 2-(3,4-dimethoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(OC)C(OC)=C1 DILOFCBIBDMHAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000009958 sewing Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000523 sample Substances 0.000 description 55
- 230000000052 comparative effect Effects 0.000 description 30
- 229920003023 plastic Polymers 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 210000001264 anterior cruciate ligament Anatomy 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 9
- 230000015271 coagulation Effects 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 8
- 239000004033 plastic Substances 0.000 description 6
- 239000013068 control sample Substances 0.000 description 5
- 230000003013 cytotoxicity Effects 0.000 description 5
- 231100000135 cytotoxicity Toxicity 0.000 description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 102000008186 Collagen Human genes 0.000 description 4
- 108010035532 Collagen Proteins 0.000 description 4
- 229920001436 collagen Polymers 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- IBIKHMZPHNKTHM-RDTXWAMCSA-N merck compound 25 Chemical compound C1C[C@@H](C(O)=O)[C@H](O)CN1C(C1=C(F)C=CC=C11)=NN1C(=O)C1=C(Cl)C=CC=C1C1CC1 IBIKHMZPHNKTHM-RDTXWAMCSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/10—Materials or treatment for tissue regeneration for reconstruction of tendons or ligaments
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials For Medical Uses (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the field of new materials, and discloses a composite fiber for an artificial ligament, and a preparation method and application thereof. According to the invention, the poly (hexyl hydroxybutyrate) and the polycarbonate are organically combined, and the obtained composite fiber combines the advantages of the poly (hexyl hydroxybutyrate) and the polycarbonate, and not only has the excellent mechanical properties and other properties of the polycarbonate, but also has the good biocompatibility and other properties endowed by the poly (hexyl hydroxybutyrate). In addition, the composite fiber has superior properties to the single component based on a synergistic enhancement mechanism. When the composite fiber is used for preparing the artificial ligament, the composite ligament has the characteristics of strong wear resistance, good cell affinity and high mechanical property, and can meet the basic requirements required by the artificial ligament.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a composite fiber for an artificial ligament, and a preparation method and application thereof.
Background
Currently, partially commercialized artificial ligaments are used clinically, such as Trevira ligament, Meadox ligament, Gore-Tex ligament, ABC ligament, L eeds-Keio ligament, and Kennedy L AD ligament (Bernardino s.ac L prosthesis: any promise for the future [ J ]. kneurg.sport. tr.tr.a., 18 (6): 797. 804).
The artificial ligament is prepared from Silk fibers, and has good mechanical properties. L aureucin et al (L aureucin C T, L. organic materials J. W. L. organic materials engineering: three-dimensional artificial ligaments: obtained by three-dimensional engineering materials J. 7536. polylactic acid, 7536. A variety of natural and synthetic polymeric materials are used in the research of the artificial ligament materials.
However, whether natural polymer or synthetic polymer materials, the artificial ligament obtained from the individual components has certain defects in mechanical strength, degradability, biocompatibility and the like, and is difficult to satisfy clinical requirements, so that a novel composite material is formed by organically combining several single materials, combining the advantages and the disadvantages of different materials, and making good use and good effect, and the like, so that the artificial ligament obtained from the composite material has wide application prospect in practical application and good effect, the composite material has good compatibility with collagen fibers such as collagen fibers, collagen fibers, collagen.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a composite fiber for an artificial ligament.
The invention also aims to provide a preparation method of the composite fiber for the artificial ligament.
The invention further aims to provide application of the composite fiber which can be used for the artificial ligament in preparing the artificial ligament.
The purpose of the invention is realized by the following scheme:
a preparation method of composite fiber for artificial ligament mainly comprises the following steps:
(1) taking and drying the poly hexyl hydroxybutyrate and the polycarbonate respectively for later use;
(2) adding the poly (hexyl hydroxybutyrate) and the polycarbonate dried in the step (1) into a solvent, heating and refluxing under the stirring condition to fully dissolve, filtering out insoluble impurities, and defoaming to obtain a mixed solution for later use;
(3) adding sulfuric acid, acetic acid and zinc sulfate into a saturated sodium sulfate solution serving as a coagulant, and stirring at room temperature to obtain a coagulating bath solution;
(4) and (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the coagulating bath solution in the step (3), carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing and drying to obtain the polyhydroxybutyrate-polycarbonate composite fiber.
Preferably, the poly (hexylhydroxybutyrate) of step (1) has a numerical molecular weight of 1.9 × 105～2.6×105The molecular weight of the polycarbonate is 1.4 × 104～2.9×104。
Preferably, the drying in the step (1) refers to vacuum drying at 60-70 ℃ for 12-24 h.
Preferably, the mass ratio of the polyhydroxy hexyl butyrate and the polycarbonate dried in the step (1) in the step (2) is 1: 1-8;
preferably, the solvent in step (2) is one of absolute ethyl alcohol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexafluoroisopropanol, trifluoroethanol, dichloromethane, chloroform, diethyl ether and petroleum ether.
Preferably, the heating reflux under the stirring condition in the step (2) is that the mixture is heated to 90-120 ℃ and refluxed for 2-5 hours at the stirring speed of 750-1200 r/min;
preferably, the filtration mode in the step (2) is vacuum filtration;
preferably, the defoaming manner in the step (2) is defoaming in a vacuum state, the temperature is 75-90 ℃, and the time is 60-120 min.
Preferably, the total solute concentration of the mixed solution in the step (2) is 3-9 wt.%.
Preferably, the concentration of the sulfuric acid added in the step (3) is 0.1-0.5 g/L, the concentration of the acetic acid is 0.2-0.6 g/L, and the concentration of the zinc sulfate is 0.5-1.5 g/L;
preferably, the volume ratio of the saturated sodium sulfate, the sulfuric acid, the acetic acid and the zinc sulfate in the step (3) is 100: 2-7: 4-8: 5-9;
preferably, the stirring at room temperature in the step (3) is stirring at a speed of 200 to 450r/min for 30 to 60 min.
Preferably, the mixed solution stream extruded from the capillary holes of the spinneret in the step (2) in the step (4) enters the coagulating bath solution in the step (3) for a residence time of 20-40 s;
preferably, the washing in the step (4) is washing with absolute ethyl alcohol and deionized water sequentially, and the washing times are 2-3 times;
preferably, the drying in the step (4) is natural air drying at normal temperature and normal pressure.
A composite fiber for artificial ligament prepared by the above method.
The application of the composite fiber which can be used for the artificial ligament in the preparation of the artificial ligament.
The application of the composite fiber for the artificial ligament in preparing the artificial ligament is realized by the following steps:
the method comprises the steps of twisting 1 bundle of composite fibers with a certain quantity into 1 strand, twisting 3 strands into a string, doubling the string, twisting into a rope-shaped object with the diameter of 4-6 mm, cutting the rope to the length of 20-30 cm, fastening two ends with steel wires, fixing two ends with silk threads again in a sewing and binding mode, sequentially ultrasonically washing with absolute ethyl alcohol and deionized water with the ultrasonic power of 200-400W, the washing time of 10-30 min and the washing times of 2-3 times, and naturally drying at normal temperature and normal pressure to obtain the polyhydroxy hexyl butyrate/polycarbonate composite ligament.
The mechanism of the invention is as follows:
the obtained composite fiber combines the advantages of the poly (hexyl hydroxybutyrate) and the polycarbonate, and has the excellent mechanical properties and other properties of the polycarbonate and the good biocompatibility and other properties endowed by the poly (hexyl hydroxybutyrate).
In addition, the composite fiber has superior properties to the single component based on a synergistic enhancement mechanism. When the composite fiber is used for preparing the artificial ligament, the composite ligament has the characteristics of strong wear resistance, good cell affinity and high mechanical property, and can meet the basic requirements required by the artificial ligament.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the poly (hexyl hydroxybutyrate)/polycarbonate composite fiber obtained by the invention is used as a novel fiber material, and the preparation method is simple. Based on a synergistic enhancement mechanism, the composite fiber organically combines the advantages of all components, has the advantages of excellent mechanical property, high abrasion resistance, strong cell affinity and the like, basically meets the requirements of artificial ligaments, and can be applied to related fields.
(2) Through researches such as the preparation method, the performance analysis and the like of the composite fiber, theoretical and experimental basis and reference can be provided for further exploration and application of artificial ligament materials in the future.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) Polyhexylhydroxybutyrate (available from Plastic plastics Co., Ltd., Dongguan having a number average molecular weight of 1.9 × 10) was weighed out5) And polycarbonate (available from Dongguan plastics Co., Ltd., number average molecular weight 1.4 × 104) Vacuum drying at 60 deg.C for 12 hr.
(2) Adding the poly (hexylhydroxybutyrate) dried in the step (1) and polycarbonate into dimethylformamide according to the mass ratio of 1: 1, heating to 90 ℃ at the stirring speed of 750r/min, refluxing for 2h to fully dissolve, then filtering under reduced pressure, and defoaming at 75 ℃ for 60min under a vacuum state to obtain a mixed solution with the total solute concentration of 3 wt.% for later use.
(3) A coagulating bath solution was obtained by adding 2L g/L sulfuric acid, 4L g/L acetic acid and 5L g/L zinc sulfate to 100L saturated sodium sulfate solution as a coagulant and stirring at 200r/min for 30 min.
(4) And (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the solution of the coagulation bath in the step (3), enabling the trickle to stay in the coagulation bath for 20s, carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing the precursor filaments for 2 times by using absolute ethyl alcohol and deionized water in sequence, and naturally drying the precursor filaments under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polycarbonate composite fiber.
Example 2
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd, Dongguan, having a number average molecular weight of 2.1 × 10) was weighed out5) And polycarbonate (available from Dongguan plastics Co., Ltd., number average molecular weight 1.6 × 104) Vacuum drying at 60 deg.C for 18 h.
(2) Adding the poly (hexylhydroxybutyrate) dried in the step (1) and polycarbonate into dimethylacetamide according to the mass ratio of 1: 2, heating to 90 ℃ at the stirring speed of 800r/min, refluxing for 4h to fully dissolve, then filtering under reduced pressure, and defoaming at 75 ℃ for 70min under a vacuum state to obtain a mixed solution with the total solute concentration of 4 wt.% for later use.
(3) A coagulating bath solution was obtained by adding 3L g/L sulfuric acid, 5L g/L acetic acid and 5L g/L zinc sulfate to 100L saturated sodium sulfate solution as a coagulant and stirring at 250r/min for 40 min.
(4) And (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the solution of the coagulation bath in the step (3), enabling the trickle to stay in the coagulation bath for 25s, carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing the precursor filaments for 2 times by using absolute ethyl alcohol and deionized water in sequence, and naturally drying the precursor filaments under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polycarbonate composite fiber.
Example 3
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd, Dongguan, having a number average molecular weight of 2.3 × 10) was weighed out5) And polycarbonate (available from Dongguan plastics Co., Ltd., number average molecular weight 1.9 × 104) Vacuum drying at 60 deg.C for 24 hr.
(2) Adding the poly (hexylhydroxybutyrate) dried in the step (1) and polycarbonate into dimethyl sulfoxide according to the mass ratio of 1: 3, heating to 100 ℃ at the stirring speed of 900r/min, refluxing for 4h to fully dissolve, then filtering under reduced pressure, and defoaming at 80 ℃ for 80min under a vacuum state to obtain a mixed solution with the total solute concentration of 5 wt.% for later use.
(3) A coagulating bath solution was obtained by adding 5L g/L sulfuric acid, 5L g/L acetic acid and 7L g/L zinc sulfate to 100L saturated sodium sulfate solution as a coagulant and stirring at 250r/min for 45 min.
(4) And (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the solution of the coagulation bath in the step (3), enabling the trickle to stay in the coagulation bath for 30s, carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing the precursor filaments for 2 times by using absolute ethyl alcohol and deionized water in sequence, and naturally drying the precursor filaments under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polycarbonate composite fiber.
Example 4
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd, Dongguan, having a number average molecular weight of 2.4 × 10) was weighed out5) And polycarbonate (available from Dongguan plastics Co., Ltd., number average molecular weight 2.4 × 104) Vacuum drying at 70 deg.C for 12 hr.
(2) Adding the poly (hexylhydroxybutyrate) dried in the step (1) and polycarbonate into dichloromethane according to the mass ratio of 1: 4, heating to 110 ℃ at the stirring speed of 1000r/min, refluxing for 4h to fully dissolve, then filtering under reduced pressure, and defoaming at 80 ℃ for 90min under a vacuum state to obtain a mixed solution with the total solute concentration of 6 wt.% for later use.
(3) A coagulating bath solution was obtained by adding 6L g/L sulfuric acid, 7L g/L acetic acid and 8L g/L zinc sulfate to 100L saturated sodium sulfate solution as a coagulant and stirring at 350r/min for 50 min.
(4) And (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the solution of the coagulation bath in the step (3), enabling the trickle to stay in the coagulation bath for 30s, carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing the precursor filaments for 3 times by using absolute ethyl alcohol and deionized water in sequence, and naturally drying the precursor filaments under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polycarbonate composite fiber.
Example 5
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd, Dongguan, having a number average molecular weight of 2.5 × 10) was weighed out5) And polycarbonate (available from Dongguan plastics Co., Ltd., number average molecular weight 2.7 × 104) Vacuum drying at 70 deg.C for 18 h.
(2) Adding the poly (hexyl hydroxybutyrate) dried in the step (1) and polycarbonate into trichloromethane according to the mass ratio of 1: 5, heating to 120 ℃ at the stirring speed of 1100r/min, refluxing for 4h to fully dissolve, then filtering under reduced pressure, and defoaming at 85 ℃ for 110min under a vacuum state to obtain a mixed solution with the total solute concentration of 8 wt.% for later use.
(3) A coagulating bath solution was obtained by adding 6L g/L sulfuric acid, 8L g/L acetic acid and 8L g/L zinc sulfate to 100L saturated sodium sulfate solution as a coagulant and stirring at 400r/min for 50 min.
(4) And (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the solution of the coagulating bath in the step (3), enabling the trickle to stay in the coagulating bath for 35s, carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing the precursor filaments for 3 times by using absolute ethyl alcohol and deionized water in sequence, and naturally drying the precursor filaments under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polycarbonate composite fiber.
Example 6
(1) Polyhexylhydroxybutyrate (obtained from Plastic plastics Co., Ltd, Dongguan, having a number average molecular weight of 2.6 × 10) was weighed out5) And polycarbonate (available from Dongguan plastics Co., Ltd., number average molecular weight 2.9 × 104) Vacuum drying at 70 deg.C for 24 hr.
(2) Adding the poly (hexylhydroxybutyrate) dried in the step (1) and polycarbonate into petroleum ether according to the mass ratio of 1: 8, heating to 120 ℃ at the stirring speed of 1200r/min, refluxing for 5h to fully dissolve, then carrying out reduced pressure filtration, and defoaming at 90 ℃ for 120min under a vacuum state to obtain a mixed solution with the total solute concentration of 9 wt.% for later use.
(3) A coagulating bath solution was obtained by adding 7L g/L sulfuric acid, 8L g/L acetic acid and 9L g/L zinc sulfate to 100L saturated sodium sulfate solution as a coagulant and stirring at 450r/min for 60 min.
(4) And (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the solution of the coagulating bath in the step (3), enabling the trickle to stay in the coagulating bath for 40s, carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing the precursor filaments for 3 times by using absolute ethyl alcohol and deionized water in sequence, and naturally drying the precursor filaments under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polycarbonate composite fiber.
Example 7
The method for applying the poly (hexyl hydroxybutyrate)/polycarbonate composite fiber prepared in the embodiment 1-6 to the artificial ligament comprises the following specific steps:
the method comprises the steps of twisting 1 bundle of 60 composite fibers, twisting 3 bundles of the composite fibers into 1 strand, twisting 3 strands of the composite fibers into a string, folding the string into two halves, twisting the string into a rope-shaped object with the diameter of 6mm, cutting the rope to the length of 28cm, fastening two ends by using steel wires, fixing the two ends by using silk threads in a sewing and binding mode, sequentially performing ultrasonic washing by using absolute ethyl alcohol and deionized water, wherein the ultrasonic power is 400W, the washing time is 20min, the washing times are 3 times, and naturally drying the object under normal temperature and normal pressure to obtain the polyhydroxybutyrate/polycarbonate composite ligament.
Meanwhile, the comparative examples of examples 1 to 6 are set, all of the polyhydroxybutyrate in the step (1) of example 1 is replaced by polycarbonate, and the rest is unchanged, so that the obtained artificial anterior cruciate ligament is marked as a comparative example 1A; replacing all the polycarbonate in the step (1) of the example 1 with the poly (hexylhydroxybutyrate) and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 1B; the method comprises the following steps of (1) replacing all the hexyl polyhydroxybutyrate in the step (1) of the embodiment 2 with polycarbonate, and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 2A; replacing all the polycarbonate in the step (1) of the example 2 with the poly (hexylhydroxybutyrate) and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 2B; the method comprises the following steps of (1) replacing all the hexyl polyhydroxybutyrate in the step (1) of the embodiment 3 with polycarbonate, and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 3A; replacing all the polycarbonate in the step (1) of the example 3 with the poly (hexylhydroxybutyrate) and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 3B; the hexyl polyhydroxybutyrate in the step (1) of the embodiment 4 is completely replaced by polycarbonate, the rest is unchanged, and the obtained artificial anterior cruciate ligament is marked as a comparison sample 4A; replacing all the polycarbonate in the step (1) of the example 4 with the poly (hexylhydroxybutyrate) and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 4B; the hexyl polyhydroxybutyrate in the step (1) of the example 5 is completely replaced by polycarbonate, the rest is unchanged, and the obtained artificial anterior cruciate ligament is marked as a comparison sample 5A; replacing all the polycarbonate in the step (1) of the example 5 with the poly (hexylhydroxybutyrate) and keeping the rest unchanged, and marking the obtained artificial anterior cruciate ligament as a comparison sample 5B; the hexyl polyhydroxybutyrate in the step (1) of the example 6 is completely replaced by polycarbonate, the rest is unchanged, and the obtained artificial anterior cruciate ligament is marked as a comparison sample 6A; the polycarbonate in step (1) of example 6 was replaced with all of the polyhydroxybutyrate, and the remainder was unchanged, and the obtained artificial anterior cruciate ligament was designated as comparative example 6B.
And (3) investigating the mechanical property, wear resistance and cell affinity of the obtained poly (hexyl hydroxybutyrate)/polycarbonate composite ligament and a corresponding comparison sample thereof, wherein the specific test process and steps are as follows:
(1) mechanical properties
The mechanical properties were measured using a universal testing machine (LL OYD L R100K, China), the two ends were clamped and then stretched at a speed of 15mm/min, and the experiment was repeated 5 times, and the results are shown in tables 1 to 6 (mean. + -. standard deviation).
TABLE 1 test results of mechanical properties of the composite ligament obtained in example 1 and its comparative sample
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 1 | 789.12±10.03 | 42.63±3.01 | 0.55±0.03 |
| Comparative sample 1A | 690.98±11.01 | 35.09±1.91 | 0.34±0.02 |
| Comparative sample 1B | 330.15±10.91 | 28.94±2.23 | 0.19±0.02 |
Table 2 results of mechanical property test of composite ligament obtained in example 2 and comparative sample thereof
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 2 | 820.81±11.22 | 48.03±1.35 | 0.61±0.02 |
| Comparative sample 2A | 735.31±9.69 | 37.33±2.04 | 0.39±0.04 |
| Comparative sample 2B | 545.91±13.71 | 34.66±1.81 | 0.21±0.03 |
Table 3 results of mechanical property test of composite ligament obtained in example 3 and comparative sample thereof
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 3 | 811.98±9.67 | 44.93±1.51 | 0.59±0.04 |
| Comparative sample 3A | 708.67±11.19 | 37.53±1.97 | 0.39±0.01 |
| Comparative sample 3B | 536.33±10.53 | 33.63±1.25 | 0.22±0.02 |
Table 4 results of mechanical property test of composite ligament obtained in example 4 and comparative sample thereof
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 4 | 822.85±13.12 | 49.62±1.27 | 0.61±0.01 |
| Comparative sample 4A | 745.48±11.38 | 40.15±2.03 | 0.42±0.01 |
| Comparative sample 4B | 557.21±8.09 | 33.86±1.32 | 0.25±0.02 |
TABLE 5 results of mechanical Properties test of the composite ligament obtained in example 5 and its control
| Sample (I) | Maximum load (N) | Tensile strength (MPa) | Modulus of elasticity (GPa) |
| Example 5 | 887.14±10.72 | 54.99±2.91 | 0.71±0.03 |
| Control A | 776.15±11.25 | 43.66±1.93 | 0.49±0.03 |
| Comparative sample B | 604.24±8.99 | 36.52±2.12 | 0.29±0.04 |
Table 6 results of mechanical property test of composite ligament obtained in example 6 and comparative sample thereof
As can be seen from tables 1-6, the obtained polyhydroxybutyrate-polycarbonate composite ligament has better mechanical properties than a single component, organically combines the mechanical properties of the polyhydroxybutyrate-polycarbonate composite ligament and the single component, and has high mechanical strength.
(2) Abrasion resistance
The abrasion resistance test was carried out on a universal friction tester model MMW-1A. The sample was held in a holder and fixed below the rotating shaft and slid circumferentially on a GCr15 counter plate centered on the spindle. Wherein the movement radius is 12mm, the sliding speed is 100r/min, the sliding time is 5min, the sliding distance is 150m, the weight of the weight is 10N, and the lever moment is 0.35 MPa.
Before the experiment, the mass of the sample is weighed by an electronic analytical balance; after the experiment, the sample was washed 3 times with deionized water and dried, and then the mass of the sample was weighed with an electronic analytical balance. And calculating the wear rate of the test sample by a weight loss method, and measuring the wear resistance of the test sample. The experiment was repeated 3 times, and the results were averaged with the experimental data, as shown in tables 7-12.
TABLE 7 abrasion resistance test results of the composite ligament obtained in example 1 and its comparative sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 1 | 0.61×10-3 |
| Comparative sample 1A | 0.73×10-3 |
| Comparative sample 1B | 0.97×10-3 |
TABLE 8 abrasion resistance test results of the composite ligament obtained in example 2 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 2 | 0.57×10-3 |
| Comparative sample 2A | 0.71×10-3 |
| Comparative sample 2B | 1.02×10-3 |
TABLE 9 abrasion resistance test results of the composite ligament obtained in example 3 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 3 | 0.64×10-3 |
| Comparative sample 3A | 0.74×10-3 |
| Comparative sample 3B | 1.12×10-3 |
TABLE 10 abrasion resistance test results of the composite ligament obtained in example 4 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 4 | 0.56×10-3 |
| Comparative sample 4A | 0.68×10-3 |
| Comparative sample 4B | 0.99×10-3 |
TABLE 11 abrasion resistance test results of the composite ligament obtained in example 5 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 5 | 0.49×10-3 |
| Comparative sample 5A | 0.63×10-3 |
| Comparative sample 5B | 1.03×10-3 |
TABLE 12 abrasion resistance test results of the composite ligament obtained in example 6 and its control sample
| Sample (I) | Wear rate (mm)3/m) |
| Example 6 | 0.51×10-3 |
| Comparative sample 6A | 0.66×10-3 |
| Comparative sample 6B | 1.15×10-3 |
As can be seen from tables 7-12, the obtained polyhydroxybutyrate-polycarbonate composite ligament organically combines the performances of two components, has good wear resistance, and can meet the requirement of artificial ligaments.
(3) Affinity of cell
According to ISO 10993-5: 1999 and GB/T16886.5-2003, which utilizes MTT colorimetry of poly (hexylhydroxybutyrate)/polycarbonate complex ligament leaching liquor to test the cell affinity of complex ligaments. The cytotoxicity ranking criteria are shown in table 13, and the smaller the ranking value, the lower the cytotoxicity of the material, the better the cell affinity of the material. The results of cell affinity are shown in tables 14 to 19.
TABLE 13 cytotoxicity grading Scale rating standards
TABLE 14 cell affinity results for the composite ligament obtained in example 1 and its control
TABLE 15 cell affinity results for the composite ligament obtained in example 2 and its control
TABLE 16 cell affinity results for the composite ligament obtained in example 3 and its control
TABLE 17 cell affinity results for the composite ligament obtained in example 4 and its control
TABLE 18 cell affinity results for the composite ligament obtained in example 5 and its control
TABLE 19 cell affinity results for the composite ligament obtained in example 6 and its control
From tables 14 to 19, the obtained polyhydroxybutyrate-polycarbonate composite ligament organically combines the biological performances of the two components, and the cytotoxicity is 0 grade, namely the cytotoxicity is not generated and the cell affinity is good.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of composite fiber for artificial ligament is characterized by mainly comprising the following steps:
(1) taking and drying the poly hexyl hydroxybutyrate and the polycarbonate respectively for later use;
(2) adding the poly (hexyl hydroxybutyrate) and the polycarbonate dried in the step (1) into a solvent, heating and refluxing under the stirring condition to fully dissolve, filtering out insoluble impurities, and defoaming to obtain a mixed solution for later use;
(3) adding sulfuric acid, acetic acid and zinc sulfate into a saturated sodium sulfate solution serving as a coagulant, and stirring at room temperature to obtain a coagulating bath solution;
(4) and (3) adopting a wet spinning technology, carrying out high-pressure nitrogen spinning, feeding the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) into the coagulating bath solution in the step (3), carrying out auxiliary traction on the separated precursor filaments through a godet and a winding device, washing and drying to obtain the polyhydroxybutyrate-polycarbonate composite fiber.
2. The method for preparing a composite fiber for an artificial ligament according to claim 1, wherein:
the number average molecular weight of the polyhydroxybutyrate in the step (1) is 1.9 × 105~2.6×105The molecular weight of the polycarbonate is 1.4 × 104~2.9×104；
The drying in the step (1) refers to vacuum drying for 12-24 hours at the temperature of 60-70 ℃.
3. The method for preparing a composite fiber for an artificial ligament according to claim 1, wherein:
the mass ratio of the poly (hexylhydroxybutyrate) dried in the step (1) to the polycarbonate in the step (2) is 1: 1-8;
the total solute concentration of the mixed solution in the step (2) is 3-9 wt.%.
4. The method for preparing a composite fiber for an artificial ligament according to claim 1, wherein:
the solvent in the step (2) is one of absolute ethyl alcohol, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, hexafluoroisopropanol, trifluoroethanol, dichloromethane, trichloromethane, diethyl ether and petroleum ether.
5. The method for preparing a composite fiber for an artificial ligament according to claim 1, wherein:
the heating reflux under the stirring condition in the step (2) is that the mixture is heated to 90-120 ℃ and refluxed for 2-5 hours at the stirring speed of 750-1200 r/min;
the filtration mode in the step (2) is reduced pressure suction filtration;
and (3) defoaming in the step (2) in a vacuum state at 75-90 ℃ for 60-120 min.
6. The method for preparing a composite fiber for an artificial ligament according to claim 1, wherein:
the concentration of the sulfuric acid added in the step (3) is 0.1-0.5 g/L, the concentration of the acetic acid is 0.2-0.6 g/L, and the concentration of the zinc sulfate is 0.5-1.5 g/L;
the volume ratio of the saturated sodium sulfate, the sulfuric acid, the acetic acid and the zinc sulfate in the step (3) is 100: 2-7: 4-8: 5-9;
the room-temperature stirring in the step (3) is stirring at a speed of 200-450 r/min for 30-60 min.
7. The method for preparing a composite fiber for an artificial ligament according to claim 1, wherein:
allowing the mixed solution trickle extruded from the capillary holes of the spinning nozzle in the step (2) in the step (4) to enter the coagulating bath solution in the step (3) for 20-40 s;
washing in the step (4) is washing with absolute ethyl alcohol and deionized water sequentially, wherein the washing times are 2-3 times;
the drying in the step (4) is natural air drying at normal temperature and normal pressure.
8. A composite fiber for an artificial ligament prepared by the method according to any one of claims 1 to 7.
9. Use of the composite fiber for artificial ligament according to claim 8 for preparing artificial ligament.
10. Use of a composite fibre for an artificial ligament according to claim 9, in the preparation of an artificial ligament, characterised in that it is obtained by the following steps:
the method comprises the steps of twisting 1 bundle of composite fibers with a certain quantity into 1 strand, twisting 3 strands into a string, doubling the string, twisting into a rope-shaped object with the diameter of 4-6 mm, cutting the rope to the length of 20-30 cm, fastening two ends with steel wires, fixing two ends with silk threads again in a sewing and binding mode, sequentially ultrasonically washing with absolute ethyl alcohol and deionized water with the ultrasonic power of 200-400W, the washing time of 10-30 min and the washing times of 2-3 times, and naturally drying at normal temperature and normal pressure to obtain the polyhydroxy hexyl butyrate/polycarbonate composite ligament.
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