CN108728931A - A kind of composite fibre and its preparation method and application can be used for artificial ligament - Google Patents
A kind of composite fibre and its preparation method and application can be used for artificial ligament Download PDFInfo
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- CN108728931A CN108728931A CN201810505568.7A CN201810505568A CN108728931A CN 108728931 A CN108728931 A CN 108728931A CN 201810505568 A CN201810505568 A CN 201810505568A CN 108728931 A CN108728931 A CN 108728931A
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- Prior art keywords
- composite fibre
- ester
- artificial ligament
- ligament
- polyhydroxybutyrate
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- 210000003041 ligament Anatomy 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000000835 fiber Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 57
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims abstract description 52
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims abstract description 52
- 239000004425 Makrolon Substances 0.000 claims abstract description 49
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- 230000001112 coagulating effect Effects 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical class [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 238000010992 reflux Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000002166 wet spinning Methods 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009941 weaving Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 230000001413 cellular effect Effects 0.000 abstract description 14
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 53
- 210000001264 anterior cruciate ligament Anatomy 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 230000003292 diminished effect Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 210000001519 tissue Anatomy 0.000 description 5
- 239000012620 biological material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001436 collagen Polymers 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ODYCAZSSUVCHNU-XLAORIBOSA-N Laurencin Natural products CC[C@H]1C[C@H](CC=CC[C@@H]1Br)[C@@H](CC=CC#C)OC(=O)C ODYCAZSSUVCHNU-XLAORIBOSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 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 description 1
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- ZFYWONYUPVGTQJ-GDHVPRBFSA-N [(e,1r)-1-[(2r,3s,5z,8r)-3-bromo-2-ethyl-3,4,7,8-tetrahydro-2h-oxocin-8-yl]hex-3-en-5-ynyl] acetate Chemical compound CC[C@H]1O[C@@H]([C@@H](C\C=C\C#C)OC(C)=O)C\C=C/C[C@@H]1Br ZFYWONYUPVGTQJ-GDHVPRBFSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XAPCMTMQBXLDBB-UHFFFAOYSA-N hexyl butyrate Chemical compound CCCCCCOC(=O)CCC XAPCMTMQBXLDBB-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 210000000629 knee joint Anatomy 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- -1 poly- hydroxyl N-hexyl butyrate Chemical compound 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 208000016261 weight loss Diseases 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 field of new materials, disclose a kind of composite fibre and its preparation method and application can be used for artificial ligament.The advantages of own ester of polyhydroxybutyrate and makrolon are carried out organic assembling by the present invention, and the composite fibre obtained combines the two, the performances such as excellent mechanical property of existing makrolon, and the performances such as good biocompatibility for having the own ester imparting of polyhydroxybutyrate.In addition, based on collaboration enhancing mechanism, composite fibre has performance more superior than one-component.When composite fibre is used to prepare artificial ligament, the characteristics of compound ligament shows strong wear resistance, good cellular affinity, strong mechanical performance, the basic demand needed for artificial ligament can reach.
Description
Technical field
The invention belongs to field of new materials, more particularly to a kind of composite fibre and preparation method thereof can be used for artificial ligament
And application.
Background technology
Cross ligament damage is clinically one of most common ligamentous injury of knee joint, and therapeutic modality mainly passes through
Graft operating substitution rebuilding anterior cruciate ligament, including autograft object, allograft object and artificial ligament.
In these three grafts, artificial ligament with no district complication, without transmission and immunological rejection, do not damage autologous tissue
The advantages that, therefore it is clinically widely used.Currently, the artificial ligament for having part commercialization is used for clinic
In, such as Trevira ligaments, Meadox ligaments, Gore-Tex ligaments, ABC ligaments, Leeds-Keio ligaments and Kennedy LAD
(the Bernardino S.ACL prosthesis such as ligament：any promise for the future？[J].Knee
Surg.Sport.Tr.A., 2010,18 (6)：797-804.).
For artificial ligament, key core composition is artificial ligament material, it determines the performance of artificial ligament.When
Before, have numerous natural and synthesis high molecular material and is used in the research of artificial ligament material.Altman et al. (Altman G
H, Horan R L, Lu H H, Moreau J, Martin I, Richmond J C, Kaplan D L.Silk matrix for
Tissue engineered anterior cruciate ligaments [J] .Biomaterials, 2002,23 (20)：
Artificial ligament 4131-4141.) is prepared by raw material of silk fiber, gained artificial ligament has good mechanical performance.
Laurencin et al. (Laurencin C T, Freeman J W.Ligament tissue engineering：An
Evolutionary materials science approach [J] .Biomaterials, 2005,26 (36)：7530-
7536) a kind of degradable, 3 D weaving polylactic acid artificial ligament has been synthesized.
However, either natural polymer still synthesizes high molecular material, the artificial ligament that independent component is obtained is in machine
There are certain defects for tool intensity, degradability or biocompatibility etc., it is difficult to preferably meet clinical requirement.In this regard,
By the way that several homogenous materials are carried out organic assembling, the advantage and disadvantage of comprehensive different materials make up for each other's deficiencies and learn from each other, form NEW TYPE OF COMPOSITE
Material, this has broad application prospects in practical applications, and has obtained good effect.Cooper et al. (Cooper
JA, Lu H H, Ko F K, Laurencin C T.Fiber-based tissue engineered scaffold for
ligament replacement：design considerations and in vitro evaluation[J]
.Biomaterials, 2005,26 (13)：Polylactic acid and polyglycolic acid 1523-1532.) are subjected to copolymerization spinning, compiled through three-dimensional
A kind of artificial ligament is obtained after knitting, and better result is obtained in terms of biocompatibility and mechanical property.Chen et al. (Chen G
P, Ushida T, Tateishi T.Hybrid biomaterials for tissue engineering：a
preparative method for PLA or PLGA-collagen hybrid sponges[J].Advanced
Materials, 2000,12 (6)：It is 455-457.) that collagen and Poly(D,L-lactide-co-glycolide progress is compound, obtain mechanics
Artificial ligament material of good performance.Long attendant of the bride or bridegroom at a wedding of Cai et al. (the long attendant of the bride or bridegroom at a wedding of Cai, Wang Fuyou, Feng Dehong, Chen Jiarong, Xiong Juan, willow .I type glue
Study on biocompatibility [J] the Third Military Medical Universitys journal of original/polyvinyl alcohol copolymer spinning, 2011,33 (20)：2107-
2111.) the compounding machine copolymer for reporting collagen and polyvinyl alcohol has good comprehensive performance, is a kind of very promising people
Work ligament material.Nevertheless, there is still a need for more researchs and deep exploration, mechanical mechanics for artificial ligament composite material
Energy, biocompatibility, wear resistance etc. need further to be improved.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing one kind can be used for people
The composite fibre of work ligament.
Another object of the present invention is to provide the preparation method of the above-mentioned composite fibre that can be used for artificial ligament.
Still a further object of the present invention is to provide the above-mentioned composite fibre that can be used for artificial ligament in preparing artificial ligament
Using.
The purpose of the present invention is realized by following proposal：
A kind of preparation method for the composite fibre can be used for artificial ligament, mainly includes the following steps that：
(1) the own ester of polyhydroxybutyrate and makrolon are taken, is separately dried, it is spare；
(2) the own ester of polyhydroxybutyrate and makrolon after will be dry in step (1) be added in solvent, in stirring condition
Under be heated to reflux and make fully to dissolve, then filter out indissoluble impurity, then deaeration, obtain mixed solution, for use；
(3) to be saturated metabisulfite solution as coagulator, sulfuric acid, acetic acid and zinc sulfate is added toward it, is stirred at room temperature, is coagulated
Admittedly bathing solution；
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixing is molten the step of extrusion from spinneret capillary
Liquid thread enters step in (3) coagulating bath solution, and the precursor of precipitation is come out by draw-off godet and winding device by auxiliary traction,
Washing, it is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
Preferably, the numeral molecular weight of the own ester of polyhydroxybutyrate described in step (1) is 1.9 × 105~2.6 × 105；
The molecular weight of the makrolon is 1.4 × 104~2.9 × 104。
Preferably, the drying described in step (1) refers both at 60~70 DEG C vacuum drying 12~for 24 hours.
Preferably, described in step (2) quality of polyhydroxybutyrate own ester and makrolon in the step of (1) after drying
Than being 1: 1~8；
Preferably, the solvent described in step (2) is absolute ethyl alcohol, dimethylformamide, dimethylacetylamide, dimethyl
One kind in sulfoxide, hexafluoroisopropanol, trifluoroethanol, dichloromethane, chloroform, ether, petroleum ether.
Preferably, be heated to reflux under the stirring condition described in step (2) refer to 750~1200r/min stirring speed
Under degree, it is heated to 90~120 DEG C of 2~5h of reflux；
Preferably, the filter type described in step (2) is that decompression filters；
Preferably, the deaeration mode described in step (2) is deaeration under vacuum state, and temperature is 75~90 DEG C, and the time is
60~120min.
Preferably, the total concentration of solutes of the mixed solution described in step (2) is 3~9wt.%.
Preferably, the sulfuric acid concentration being added in step (3) is 0.1~0.5g/L, and acetate concentration is 0.2~0.6g/L,
A concentration of 0.5~1.5g/L of zinc sulfate；
Preferably, the volume ratio of the saturation sodium sulphate described in step (3), sulfuric acid, acetic acid and zinc sulfate is 100: 2~7:
4~8: 5~9；
Preferably, being stirred at room temperature described in step (3) refer under the speed of 200~450r/min stirring 30~
60min。
Preferably, the step of being squeezed out in the slave spinneret capillary described in step (4) (2) mixed solution thread enters step
Suddenly the residence time is 20~40s in (3) coagulating bath solution；
Preferably, the washing described in step (4) is to be washed successively with absolute ethyl alcohol and deionized water, washing times 2
~3 times；
Preferably, the drying described in step (4) is natural air drying under normal temperature and pressure.
A kind of composite fibre that can be used for artificial ligament being prepared by the above method.
Application of the above-mentioned composite fibre that can be used for artificial ligament in preparing artificial ligament.
Application of the composite fibre that can be used for artificial ligament in preparing artificial ligament is specifically by following steps reality
It is existing：
It is 1 beam by a certain number of composite fibres using twisting weaving method, 3 beams are twisted 1 strand, and 3 strands are twisted cord, carefully
It is twisted the ropy of a diameter of 4~6mm after rope doubling, it is 20~30cm to be truncated to length, and both ends are tightened with steel wire, using tying
Mode fixes both ends again with silk thread, and it is 200~400W to use absolute ethyl alcohol and deionized water supersound washing, ultrasonic power successively,
Wash time is 10~30min, and washing times are 2~3 times, natural air drying under normal temperature and pressure, obtains the own ester of polyhydroxybutyrate/poly-
The compound ligament of carbonic ester.
The present invention mechanism be：
The own ester of polyhydroxybutyrate and makrolon are subjected to organic assembling, the composite fibre obtained combines the excellent of the two
Point, the performances such as excellent mechanical property of existing makrolon, and the good biocompatibility etc. for thering is the own ester of polyhydroxybutyrate to assign
Performance.
In addition, based on collaboration enhancing mechanism, composite fibre has performance more superior than one-component.When composite fibre is used
It, the characteristics of compound ligament shows strong wear resistance, good cellular affinity, strong mechanical performance, can when preparing artificial ligament
Reach the basic demand needed for artificial ligament.
The present invention compared with the existing technology, has the following advantages and advantageous effect：
(1) the obtained own ester of the polyhydroxybutyrate/makrolon composite fibre of the present invention is as a kind of new fiber materials,
Preparation method is simple.Enhance mechanism based on collaboration, the advantages of composite fibre has organically combined each component has mechanical property excellent
Different, the advantages that wear resistance is high, cellular affinity is strong, the requirement of artificial ligament is basically reached, can be used in related field.
(2) researchs such as the preparation method of composite fibre through the invention and performance evaluation can be artificial ligament material from now on
Further explore of material provides the theoretical foundation with experiment and reference with application.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Embodiment 1
(1) weigh polyhydroxybutyrate own ester (be purchased from Dongguan City Su Zhan plastic cement Co., Ltd, number-average molecular weight is 1.9 ×
105) and makrolon (be purchased from Dongguan Lian Ke plastics Co., Ltd, number-average molecular weight is 1.4 × 104), it is dried in vacuo at 60 DEG C
12h, it is spare.
(2) the own ester of polyhydroxybutyrate after being dried in step (1) and makrolon are added to diformazan for 1: 1 in mass ratio
In base formamide, under the mixing speed of 750r/min, 90 DEG C of reflux 2h is heated to, makes fully to dissolve, then be filtered under diminished pressure, very
The lower 75 DEG C of deaeration 60min of dummy status obtain the mixed solution that total concentration of solutes is 3wt.%, for use.
(3) to be saturated metabisulfite solution as coagulator, the 0.1g/L sulphur of 2L is added into the saturation metabisulfite solution of 100L
The 0.5g/L zinc sulfate of acid, the 0.2g/L acetic acid of 4L, 5L, stirs 30min under the speed of 200r/min, it is molten to obtain coagulating bath
Liquid.
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixing is molten the step of extrusion from spinneret capillary
Liquid thread enters step in (3) coagulating bath solution, and thread residence time in coagulating bath is 20s, and the precursor of precipitation passes through seal wire
Disk and winding device and come out by auxiliary traction, washed 2 times with absolute ethyl alcohol and deionized water successively, natural wind under normal temperature and pressure
It is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
Embodiment 2
(1) weigh polyhydroxybutyrate own ester (be purchased from Dongguan City Su Zhan plastic cement Co., Ltd, number-average molecular weight is 2.1 ×
105) and makrolon (be purchased from Dongguan Lian Ke plastics Co., Ltd, number-average molecular weight is 1.6 × 104), it is dried in vacuo at 60 DEG C
18h, it is spare.
(2) the own ester of polyhydroxybutyrate after being dried in step (1) and makrolon are added to diformazan for 1: 2 in mass ratio
In yl acetamide, under the mixing speed of 800r/min, 90 DEG C of reflux 4h is heated to, makes fully to dissolve, then be filtered under diminished pressure, very
The lower 75 DEG C of deaeration 70min of dummy status obtain the mixed solution that total concentration of solutes is 4wt.%, for use.
(3) to be saturated metabisulfite solution as coagulator, the 0.2g/L sulphur of 3L is added into the saturation metabisulfite solution of 100L
The 0.6g/L zinc sulfate of acid, the 0.3g/L acetic acid of 5L, 5L, stirs 40min under the speed of 250r/min, it is molten to obtain coagulating bath
Liquid.
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixing is molten the step of extrusion from spinneret capillary
Liquid thread enters step in (3) coagulating bath solution, and thread residence time in coagulating bath is 25s, and the precursor of precipitation passes through seal wire
Disk and winding device and come out by auxiliary traction, washed 2 times with absolute ethyl alcohol and deionized water successively, natural wind under normal temperature and pressure
It is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
Embodiment 3
(1) weigh polyhydroxybutyrate own ester (be purchased from Dongguan City Su Zhan plastic cement Co., Ltd, number-average molecular weight is 2.3 ×
105) and makrolon (be purchased from Dongguan Lian Ke plastics Co., Ltd, number-average molecular weight is 1.9 × 104), it is dried in vacuo at 60 DEG C
For 24 hours, spare.
(2) the own ester of polyhydroxybutyrate after being dried in step (1) and makrolon are added to diformazan for 1: 3 in mass ratio
In base sulfoxide, under the mixing speed of 900r/min, 100 DEG C of reflux 4h is heated to, makes fully to dissolve, then be filtered under diminished pressure, very
The lower 80 DEG C of deaeration 80min of dummy status obtain the mixed solution that total concentration of solutes is 5wt.%, for use.
(3) to be saturated metabisulfite solution as coagulator, the 0.3g/L sulphur of 5L is added into the saturation metabisulfite solution of 100L
The 0.8g/L zinc sulfate of acid, the 0.5g/L acetic acid of 5L, 7L, stirs 45min under the speed of 250r/min, it is molten to obtain coagulating bath
Liquid.
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixing is molten the step of extrusion from spinneret capillary
Liquid thread enters step in (3) coagulating bath solution, and thread residence time in coagulating bath is 30s, and the precursor of precipitation passes through seal wire
Disk and winding device and come out by auxiliary traction, washed 2 times with absolute ethyl alcohol and deionized water successively, natural wind under normal temperature and pressure
It is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
Embodiment 4
(1) weigh polyhydroxybutyrate own ester (be purchased from Dongguan City Su Zhan plastic cement Co., Ltd, number-average molecular weight is 2.4 ×
105) and makrolon (be purchased from Dongguan Lian Ke plastics Co., Ltd, number-average molecular weight is 2.4 × 104), it is dried in vacuo at 70 DEG C
12h, it is spare.
(2) the own ester of polyhydroxybutyrate after being dried in step (1) and makrolon are added to dichloro for 1: 4 in mass ratio
In methane, under the mixing speed of 1000r/min, 110 DEG C of reflux 4h is heated to, makes fully to dissolve, then be filtered under diminished pressure, vacuum
The lower 80 DEG C of deaeration 90min of state obtain the mixed solution that total concentration of solutes is 6wt.%, for use.
(3) to be saturated metabisulfite solution as coagulator, the 0.3g/L sulphur of 6L is added into the saturation metabisulfite solution of 100L
The 1.2g/L zinc sulfate of acid, the 0.6g/L acetic acid of 7L, 8L, stirs 50min under the speed of 350r/min, it is molten to obtain coagulating bath
Liquid.
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixing is molten the step of extrusion from spinneret capillary
Liquid thread enters step in (3) coagulating bath solution, and thread residence time in coagulating bath is 30s, and the precursor of precipitation passes through seal wire
Disk and winding device and come out by auxiliary traction, washed 3 times with absolute ethyl alcohol and deionized water successively, natural wind under normal temperature and pressure
It is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
Embodiment 5
(1) weigh polyhydroxybutyrate own ester (be purchased from Dongguan City Su Zhan plastic cement Co., Ltd, number-average molecular weight is 2.5 ×
105) and makrolon (be purchased from Dongguan Lian Ke plastics Co., Ltd, number-average molecular weight is 2.7 × 104), it is dried in vacuo at 70 DEG C
18h, it is spare.
(2) the own ester of polyhydroxybutyrate after being dried in step (1) and makrolon are added to trichlorine for 1: 5 in mass ratio
In methane, under the mixing speed of 1100r/min, 120 DEG C of reflux 4h is heated to, makes fully to dissolve, then be filtered under diminished pressure, vacuum
The lower 85 DEG C of deaeration 110min of state obtain the mixed solution that total concentration of solutes is 8wt.%, for use.
(3) to be saturated metabisulfite solution as coagulator, the 0.4g/L sulphur of 6L is added into the saturation metabisulfite solution of 100L
The 1.3g/L zinc sulfate of acid, the 0.6g/L acetic acid of 8L, 8L, stirs 50min under the speed of 400r/min, it is molten to obtain coagulating bath
Liquid.
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixing is molten the step of extrusion from spinneret capillary
Liquid thread enters step in (3) coagulating bath solution, and thread residence time in coagulating bath is 35s, and the precursor of precipitation passes through seal wire
Disk and winding device and come out by auxiliary traction, washed 3 times with absolute ethyl alcohol and deionized water successively, natural wind under normal temperature and pressure
It is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
Embodiment 6
(1) weigh polyhydroxybutyrate own ester (be purchased from Dongguan City Su Zhan plastic cement Co., Ltd, number-average molecular weight is 2.6 ×
105) and makrolon (be purchased from Dongguan Lian Ke plastics Co., Ltd, number-average molecular weight is 2.9 × 104), it is dried in vacuo at 70 DEG C
For 24 hours, spare.
(2) the own ester of polyhydroxybutyrate after being dried in step (1) and makrolon are added to oil for 1: 8 in mass ratio
In ether, under the mixing speed of 1200r/min, 120 DEG C of reflux 5h is heated to, makes fully to dissolve, then be filtered under diminished pressure, vacuum shape
The lower 90 DEG C of deaeration 120min of state obtain the mixed solution that total concentration of solutes is 9wt.%, for use.
(3) to be saturated metabisulfite solution as coagulator, the 0.5g/L sulphur of 7L is added into the saturation metabisulfite solution of 100L
The 1.5g/L zinc sulfate of acid, the 0.6g/L acetic acid of 8L, 9L, stirs 60min under the speed of 450r/min, it is molten to obtain coagulating bath
Liquid.
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixing is molten the step of extrusion from spinneret capillary
Liquid thread enters step in (3) coagulating bath solution, and thread residence time in coagulating bath is 40s, and the precursor of precipitation passes through seal wire
Disk and winding device and come out by auxiliary traction, washed 3 times with absolute ethyl alcohol and deionized water successively, natural wind under normal temperature and pressure
It is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
Embodiment 7
Artificial ligament is applied to the own ester of polyhydroxybutyrate/makrolon composite fibre that Examples 1 to 6 is prepared
In, detailed process and steps are as follows：
It is 1 beam by 60 composite fibres using twisting weaving method, 3 beams are twisted 1 strand, and 3 strands are twisted cord, cord pair
The ropy of a diameter of 6mm is twisted after folding, it is 28cm to be truncated to length, tightens both ends with steel wire, silk thread is used in the way of tying
Again fix both ends, successively use absolute ethyl alcohol and deionized water supersound washing, ultrasonic power 400W, wash time 20min,
Washing times are 3 times, and natural air drying under normal temperature and pressure obtains the own compound ligament of ester/makrolon of polyhydroxybutyrate.
The comparative example of Examples 1 to 6 is set simultaneously, the own ester of polyhydroxybutyrate in (1) the step of embodiment 1 is all replaced
It is changed to makrolon, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as comparative sample 1A；By (1) the step of embodiment 1
In makrolon all replace with the own ester of polyhydroxybutyrate, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as pair
Than sample 1B；The own ester of polyhydroxybutyrate in (1) the step of embodiment 2 is all replaced with into makrolon, remaining is constant, obtains
To artificial anterior cruciate ligament be denoted as comparative sample 2A；Makrolon in (1) the step of embodiment 2 is all replaced with into poly- hydroxyl
N-hexyl butyrate, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as comparative sample 2B；It will be in (1) the step of embodiment 3
The own ester of polyhydroxybutyrate all replaces with makrolon, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as comparative sample
3A；Makrolon in (1) the step of embodiment 3 is all replaced with into the own ester of polyhydroxybutyrate, remaining is constant, obtains
Artificial anterior cruciate ligament is denoted as comparative sample 3B；The own ester of polyhydroxybutyrate in (1) the step of embodiment 4 is all replaced with into poly- carbon
Acid esters, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as comparative sample 4A；By the poly- carbon in (1) the step of embodiment 4
Acid esters all replaces with the own ester of polyhydroxybutyrate, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as comparative sample 4B；It will
The own ester of polyhydroxybutyrate in the step of embodiment 5 (1) all replaces with makrolon, remaining is constant, and what is obtained is artificial
Anterior cruciate ligament is denoted as comparative sample 5A；By the makrolon in (1) the step of embodiment 5 all replace with polyhydroxybutyrate oneself
Ester, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as comparative sample 5B；By the poly- hydroxyl in (1) the step of embodiment 6
N-hexyl butyrate all replaces with makrolon, remaining is constant, and obtained artificial anterior cruciate ligament is denoted as comparative sample 6A；It will be real
Makrolon in the step of applying example 6 (1) all replaces with the own ester of polyhydroxybutyrate, remaining is constant, obtain it is artificial before
Ligamentaum cruciatum is denoted as comparative sample 6B.
The mechanical property of the compound ligament of the own ester/makrolon of polyhydroxybutyrate and its corresponding comparative sample obtained by investigating,
Wear resistance, cellular affinity, specific test process and steps are as follows：
(1) mechanical property
Mechanics Performance Testing is carried out using omnipotent test machine (LLOYD LR100K, China).After both ends fixture is fixed, with
The speed of 15mm/min is stretched.Experiment repeat 5 times, result is expressed as (average value ± standard deviation), as table 1~
Shown in 6.
The compound ligament of gained and its mechanical experimental results of comparative sample in 1 embodiment 1 of table
| Sample | Maximum load (N) | Tensile strength (MPa) | Elasticity modulus (GPa) |
| Embodiment 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 |
The compound ligament of gained and its mechanical experimental results of comparative sample in 2 embodiment 2 of table
| Sample | Maximum load (N) | Tensile strength (MPa) | Elasticity modulus (GPa) |
| Embodiment 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 |
The compound ligament of gained and its mechanical experimental results of comparative sample in 3 embodiment 3 of table
| Sample | Maximum load (N) | Tensile strength (MPa) | Elasticity modulus (GPa) |
| Embodiment 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 |
The compound ligament of gained and its mechanical experimental results of comparative sample in 4 embodiment 4 of table
| Sample | Maximum load (N) | Tensile strength (MPa) | Elasticity modulus (GPa) |
| Embodiment 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 |
The compound ligament of gained and its mechanical experimental results of comparative sample in 5 embodiment 5 of table
| Sample | Maximum load (N) | Tensile strength (MPa) | Elasticity modulus (GPa) |
| Embodiment 5 | 887.14±10.72 | 54.99±2.91 | 0.71±0.03 |
| Comparative sample 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 |
The compound ligament of gained and its mechanical experimental results of comparative sample in 6 embodiment 6 of table
As can be seen that the mechanical property of the obtained own compound ligament of ester/makrolon of polyhydroxybutyrate from table 1~6
Than one-component than get well, and the mechanical property of the two has been organically combined, with high mechanical strength.
(2) wear resistance
Abrasion test carries out on the omnipotent frictional testing machine of MMW-1A types.Sample is mounted in fixture and is fixed on rotation
Below axis, make circumferential slippage centered on GCr15 is on mill by main shaft.Wherein, moving radius 12mm, gliding cable structure are
100r/min, sliding time 5min, sliding distance 150m, counterweight weight are 10N, lever moment 0.35MPa.
The quality of sample is weighed before experiment with electronic analytical balance；Sample is first washed 3 times simultaneously with deionized water after experiment
Drying, then the quality with electronic analytical balance weighing sample.The wear rate of sample is calculated with weight-loss method, and sample is weighed with this
Wear resistance.Experiment repeats 3 times, and result takes the average value of experimental data, as shown in table 7~12.
The abrasion resistance properties test result of the compound ligament of gained and its comparative sample in 7 embodiment 1 of table
| Sample | Wear rate (mm3/m) |
| Embodiment 1 | 0.61×10-3 |
| Comparative sample 1A | 0.73×10-3 |
| Comparative sample 1B | 0.97×10-3 |
The abrasion resistance properties test result of the compound ligament of gained and its comparative sample in 8 embodiment 2 of table
| Sample | Wear rate (mm3/m) |
| Embodiment 2 | 0.57×10-3 |
| Comparative sample 2A | 0.71×10-3 |
| Comparative sample 2B | 1.02×10-3 |
The abrasion resistance properties test result of the compound ligament of gained and its comparative sample in 9 embodiment 3 of table
| Sample | Wear rate (mm3/m) |
| Embodiment 3 | 0.64×10-3 |
| Comparative sample 3A | 0.74×10-3 |
| Comparative sample 3B | 1.12×10-3 |
The abrasion resistance properties test result of the compound ligament of gained and its comparative sample in 10 embodiment 4 of table
| Sample | Wear rate (mm3/m) |
| Embodiment 4 | 0.56×10-3 |
| Comparative sample 4A | 0.68×10-3 |
| Comparative sample 4B | 0.99×10-3 |
The abrasion resistance properties test result of the compound ligament of gained and its comparative sample in 11 embodiment 5 of table
| Sample | Wear rate (mm3/m) |
| Embodiment 5 | 0.49×10-3 |
| Comparative sample 5A | 0.63×10-3 |
| Comparative sample 5B | 1.03×10-3 |
The abrasion resistance properties test result of the compound ligament of gained and its comparative sample in 12 embodiment 6 of table
| Sample | Wear rate (mm3/m) |
| Embodiment 6 | 0.51×10-3 |
| Comparative sample 6A | 0.66×10-3 |
| Comparative sample 6B | 1.15×10-3 |
It is found that the own compound ligament of ester/makrolon of obtained polyhydroxybutyrate has organically combined two from table 7~12
The performance of component, wear resistance is good, can meet the needs of artificial ligament.
(3) cellular affinity
According to ISO 10993-5：The requirement and suggestion of 1999 and GB/T 16886.5-2003, using polyhydroxybutyrate oneself
The method of the compound ligament leaching liquor MTT colorimetric methods of ester/makrolon, the cellular affinity of test compound ligament.Wherein, cell toxicant
Property classification rating scale it is as shown in table 13, classification numerical value it is smaller, indicate that the cytotoxicity of material is lower, then the cell of material is affine
Property is better.Cellular affinity result is as shown in table 14~19.
13 cytotoxicity of table is classified rating scale
The cellular affinity result of the compound ligament of gained and its comparative sample in 14 embodiment 1 of table
The cellular affinity result of the compound ligament of gained and its comparative sample in 15 embodiment 2 of table
The cellular affinity result of the compound ligament of gained and its comparative sample in 16 embodiment 3 of table
The cellular affinity result of the compound ligament of gained and its comparative sample in 17 embodiment 4 of table
The cellular affinity result of the compound ligament of gained and its comparative sample in 18 embodiment 5 of table
The cellular affinity result of the compound ligament of gained and its comparative sample in 19 embodiment 6 of table
From table 14~19 it is found that the own compound ligament of ester/makrolon of obtained polyhydroxybutyrate has organically combined two
The biological property of component, cytotoxicity are 0 grade, i.e. its no cytotoxicity, cellular affinity is good.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method for the composite fibre can be used for artificial ligament, it is characterised in that mainly include the following steps that：
(1) the own ester of polyhydroxybutyrate and makrolon are taken, is separately dried, it is spare；
(2) the own ester of polyhydroxybutyrate after being dried in step (1) and makrolon are added in solvent, are added under agitation
Heat reflux makes fully to dissolve, and then filters out indissoluble impurity, then deaeration, obtains mixed solution, for use；
(3) to be saturated metabisulfite solution as coagulator, sulfuric acid, acetic acid and zinc sulfate is added toward it, is stirred at room temperature, obtains coagulating bath
Solution；
(4) wet spinning technology is used, high pressure nitrogen spinneret, (2) mixed solution is thin the step of extrusion from spinneret capillary
Stream enters step in (3) coagulating bath solution, and the precursor of precipitation is come out by draw-off godet and winding device by auxiliary traction, washes
It washs, it is dry, obtain the own ester of polyhydroxybutyrate/makrolon composite fibre.
2. the preparation method of the composite fibre according to claim 1 that can be used for artificial ligament, it is characterised in that：
The numeral molecular weight of the own ester of polyhydroxybutyrate described in step (1) is 1.9 × 105~2.6 × 105；The poly- carbonic acid
The molecular weight of ester is 1.4 × 104~2.9 × 104；
Drying described in step (1) refers both at 60~70 DEG C vacuum drying 12~for 24 hours.
3. the preparation method of the composite fibre according to claim 1 that can be used for artificial ligament, it is characterised in that：
The mass ratio of the own ester of polyhydroxybutyrate and makrolon in the step of described in step (2) (1) after drying is 1: 1~8；
The total concentration of solutes of mixed solution described in step (2) is 3~9wt.%.
4. the preparation method of the composite fibre according to claim 1 that can be used for artificial ligament, it is characterised in that：
Solvent described in step (2) is that absolute ethyl alcohol, dimethylformamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), hexafluoro are different
One kind in propyl alcohol, trifluoroethanol, dichloromethane, chloroform, ether, petroleum ether.
5. the preparation method of the composite fibre according to claim 1 that can be used for artificial ligament, it is characterised in that：
Be heated to reflux under stirring condition described in step (2) refers to being heated under the mixing speed of 750~1200r/min
90~120 DEG C of 2~5h of reflux；
Filter type described in step (2) is that decompression filters；
Deaeration mode described in step (2) is deaeration under vacuum state, and temperature is 75~90 DEG C, and the time is 60~120min.
6. the preparation method of the composite fibre according to claim 1 that can be used for artificial ligament, it is characterised in that：
The sulfuric acid concentration being added in step (3) is 0.1~0.5g/L, and acetate concentration is 0.2~0.6g/L, and zinc sulfate is a concentration of
0.5~1.5g/L；
The volume ratio of saturation sodium sulphate, sulfuric acid, acetic acid and zinc sulfate described in step (3) is 100: 2~7: 4~8: 5~9；
Being stirred at room temperature described in step (3) refers to 30~60min of stirring under the speed of 200~450r/min.
7. the preparation method of the composite fibre according to claim 1 that can be used for artificial ligament, it is characterised in that：
The step of being squeezed out in slave spinneret capillary described in step (4) (2) mixed solution thread enters step (3) coagulating bath
The residence time is 20~40s in solution；
Washing described in step (4) is to be washed successively with absolute ethyl alcohol and deionized water, and washing times are 2~3 times；
Drying described in step (4) is natural air drying under normal temperature and pressure.
8. a kind of composite fibre that can be used for artificial ligament being prepared according to claim 1~7 any one of them method.
9. application of the composite fibre according to claim 8 that can be used for artificial ligament in preparing artificial ligament.
10. application of the composite fibre according to claim 9 that can be used for artificial ligament in preparing artificial ligament, special
Sign is to be realized by following steps：
It is 1 beam by a certain number of composite fibres using twisting weaving method, 3 beams are twisted 1 strand, and 3 strands are twisted cord, cord pair
The ropy of a diameter of 4~6mm is twisted after folding, it is 20~30cm to be truncated to length, both ends is tightened with steel wire, in the way of tying
Both ends are fixed again with silk thread, and it is 200~400W, washing to use absolute ethyl alcohol and deionized water supersound washing, ultrasonic power successively
Time is 10~30min, and washing times are 2~3 times, and natural air drying under normal temperature and pressure obtains the own ester of polyhydroxybutyrate/poly- carbonic acid
The compound ligament of ester.
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