CN113318264A - Degradable polyurethane biomaterial and preparation method and application thereof - Google Patents
Degradable polyurethane biomaterial and preparation method and application thereof Download PDFInfo
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- CN113318264A CN113318264A CN202110592453.8A CN202110592453A CN113318264A CN 113318264 A CN113318264 A CN 113318264A CN 202110592453 A CN202110592453 A CN 202110592453A CN 113318264 A CN113318264 A CN 113318264A
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- 239000012620 biological material Substances 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 115
- 239000002105 nanoparticle Substances 0.000 claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 55
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 38
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004472 Lysine Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229940105847 calamine Drugs 0.000 claims abstract description 27
- 229910052864 hemimorphite Inorganic materials 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 235000014692 zinc oxide Nutrition 0.000 claims abstract description 27
- 239000011787 zinc oxide Substances 0.000 claims abstract description 27
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- AQXGDGODCOTEIA-UHFFFAOYSA-N bis(4-nitrophenyl) hexanedioate Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC(=O)CCCCC(=O)OC1=CC=C([N+]([O-])=O)C=C1 AQXGDGODCOTEIA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005018 casein Substances 0.000 claims abstract description 18
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000021240 caseins Nutrition 0.000 claims abstract description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 17
- 238000010894 electron beam technology Methods 0.000 claims abstract description 17
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 101
- 238000000034 method Methods 0.000 claims description 41
- 229960003646 lysine Drugs 0.000 claims description 37
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 238000010041 electrostatic spinning Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 102000004142 Trypsin Human genes 0.000 claims description 21
- 108090000631 Trypsin Proteins 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 21
- 239000012588 trypsin Substances 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims description 14
- -1 adipoyl chloropropanone Chemical compound 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 9
- 238000000520 microinjection Methods 0.000 claims description 8
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 7
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 claims description 7
- 239000007853 buffer solution Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 229960005337 lysine hydrochloride Drugs 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000000502 dialysis Methods 0.000 description 12
- 150000002009 diols Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 206010016654 Fibrosis Diseases 0.000 description 1
- 208000005422 Foreign-Body reaction Diseases 0.000 description 1
- 208000035965 Postoperative Complications Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004761 fibrosis Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
- A61L17/10—At least partially resorbable materials containing macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
Abstract
The invention provides a degradable polyurethane biomaterial and a preparation method and application thereof. The preparation method of the first solution comprises the following steps: adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, heating and stirring for reaction, adding nano calamine powder, and continuing the reaction to obtain nano particles; adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring for reaction, adding nanoparticles, and performing electron beam irradiation to prepare modified nanoparticles; and finally, adding polyether glycol, the modified nano particles and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the nano-composite material. The second solution is obtained by adding diisocyanate into N, N-dimethylacetamide and uniformly stirring. The biological material prepared by the invention has excellent mechanical property and degradation property and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a degradable polyurethane biomaterial as well as a preparation method and application thereof.
Background
The suture is one of the necessary materials for suturing the incision after clinical operation, and has important significance for accelerating the healing of the incision and reducing postoperative complications. The suture line is generally divided into absorbable suture line and non-absorbable suture line, wherein the absorbable suture line is also called biodegradable suture line, generally refers to suture line which loses most of the tensile strength within 60 days after being implanted under the skin, and gradually becomes absorbable substance by the body through degradation within 1-6 months. The absorbable suture avoids inflammatory reaction and other adverse effects caused by long-term existence of foreign matters in vivo, avoids secondary operations, and has wider and wider application in clinic. Absorbable sutures have 4 basic requirements: the degradation absorbability is predictable; negligible toxicity, adaptability to body tissues, no inflammation due to foreign body reaction; the fabric can keep proper strength in vivo for a certain time, is easy to knot and has good flexibility; it is resistant to disinfection, easy to sterilize, cheap and easy to obtain.
The biodegradable suture line has the advantages of no toxicity, no stimulation, high compatibility, good biodegradability, capability of being degraded and absorbed by a human body, no pain of the patient in removing the suture line, attractive appearance and great clinical significance.
Patent CN102406961B discloses an absorbable surgical suture and a preparation method thereof, the absorbable surgical suture is a chitosan surgical suture, which is a natural fiber suture; according to the method, the toughness of the chitosan is improved by adding urea and glycerol into a chitosan solution, and the cross section roundness of the suture is improved and the operability of the suture is improved by adopting a wet spinning process. However, because the chitosan is degraded at a high speed, the mechanical strength is rapidly reduced in the actual use process, so that the strength is difficult to maintain before the wound of a patient recovers, secondary cracking of the wound is easily caused, and the recovery of the patient is affected.
Disclosure of Invention
The invention aims to provide a degradable polyurethane biomaterial, a preparation method and application thereof, wherein the biomaterial has excellent mechanical property and degradation property.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of degradable polyurethane biomaterial comprises the steps of carrying out coaxial electrostatic spinning on a first solution and a second solution to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps:
(A) adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, reacting at 65-75 ℃ for 30-40 minutes under stirring, adding nano calamine powder, continuing to react under stirring under heat preservation, and performing aftertreatment to obtain nanoparticles;
(B) adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring and reacting, adding the nanoparticles obtained in the step (A), irradiating by electron beams, and performing post-treatment to prepare modified nanoparticles;
(C) finally, adding polyether glycol, modified nanoparticles and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution;
the second solution was prepared as follows, in parts by weight: and adding 1 part of diisocyanate into 15-25 parts of N, N-dimethylacetamide, and uniformly stirring to obtain the second solution.
Preferably, the specific method of coaxial electrospinning is as follows: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
Preferably, the polyether diol is polyethylene glycol 600, and the diisocyanate is toluene diisocyanate or hexamethylene diisocyanate.
Preferably, in the step (a), the molar ratio of the lysine monomer to the p-nitrophenyl adipate monomer is 1: 1.6-1.7, and the mass ratio of the lysine to the N, N-dimethylacetamide to the nano calamine powder is 1: 8-10: 0.1 to 0.2.
Preferably, in the step (A), the reaction time of the continuous heat preservation stirring reaction is 15-25 minutes; the specific method of post-treatment is as follows: adding the reaction product into 5-7 times of trypsin solution, stirring for 3-4 days at 35-37 ℃, dialyzing, and freeze-drying to obtain nanoparticles; wherein the trypsin solution is prepared by adding 1 part of trypsin into 8-10 parts of PBS buffer solution with pH of 7.4 by weight, and uniformly stirring.
Preferably, in the step (a), the lysine monomer is prepared by the following method in parts by weight: adding 1 part of 1, 4-butanediol, 4.1-4.3 parts of lysine hydrochloride and 5-6 parts of p-toluenesulfonic acid monohydrate into 15-18 parts of toluene, stirring and reacting at 120-130 ℃ for 22-24 hours, centrifuging to obtain a precipitate, adding the precipitate into 7-9 parts of isopropanol, stirring and dispersing uniformly at 70-80 ℃, transferring to a temperature of-15-20 ℃ for standing for 10-12 hours, centrifuging to obtain the precipitate, fully washing and drying to obtain the lysine monomer.
Preferably, in the step (a), the preparation method of the p-nitrophenyladipate monomer comprises the following steps: firstly, adding 1 part of adipoyl chloride, 2-2.2 parts of p-nitrophenol and 1.1-1.2 parts of triethylamine into 8-10 parts of acetone, uniformly stirring at-78 ℃, dropwise adding an adipoyl chloropropanone solution, reacting for 5-7 hours while stirring at a constant temperature, performing suction filtration, washing with water and drying to obtain the compound; wherein, the adipic acid chloropropanone solution is prepared by mixing adipic acid chloride and acetone according to the volume ratio of 1: 5-7, and uniformly stirring to obtain the product.
Preferably, in the step (A), the particle size of the nano calamine powder is 20-30 nm.
Preferably, in the step (B), the mass ratio of casein, acrylic acid, water, potassium persulfate and nanoparticles is 1: 7-9: 20-25: 0.08-0.1: 1 to 1.5.
Preferably, in the step (B), the process conditions of the stirring reaction are as follows: stirring and reacting for 6-8 hours at 80-90 ℃.
Preferably, in the step (B), the process conditions of the electron beam irradiation are as follows: irradiating for 3-5 s under the dosage of 20-30 kGy.
Preferably, the specific method of the post-treatment in the step (B) is as follows: dialysis was performed using water with pH 3 as the dialysis medium.
Preferably, in the step (C), the mass ratio of the polyether glycol, the modified nanoparticles, the dibutyltin dilaurate and the N, N-dimethylacetamide is 1: 0.008-0.01: 0.02-0.03: 10 to 12.
The invention also claims a degradable polyurethane biomaterial obtained by the preparation method and application of the degradable polyurethane biomaterial as a surgical suture.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention prepares the polyurethane biomaterial by coaxially and electrostatically spinning the first solution and the second solution, and the polyurethane biomaterial has excellent mechanical property and degradation property. The preparation method of the first solution comprises the following steps: firstly, adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, heating and stirring for reaction, adding nano calamine powder, continuing to keep the temperature and stir for reaction, and performing aftertreatment to obtain nano particles; adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the condition of nitrogen protection, stirring and reacting, adding nanoparticles, irradiating by electron beams, and performing post-treatment to prepare modified nanoparticles; and finally, adding polyether glycol, the modified nano particles and dibutyltin dilaurate into N, N-dimethylacetamide, and carrying out ultrasonic oscillation uniformly to obtain the nano-composite material. The second solution is obtained by adding diisocyanate into N, N-dimethylacetamide and uniformly stirring;
the invention realizes polyurethane polymerization and fibrosis treatment simultaneously in the coaxial electrostatic spinning process, has simple process, and adjusts the composition of polyurethane biomaterials to ensure that the biomaterials have good mechanical properties and degradation properties.
(2) The technical key point of the invention is the addition of modified nanoparticles, which take nano calamine powder as a main raw material, have a reinforcing effect and can be absorbed by a human body, but the modified nanoparticles are inorganic mixtures, and the dispersibility of the modified nanoparticles in a system cannot be ensured. According to the invention, the nano calamine powder is introduced into the polymerization reaction of the lysine monomer and the p-nitrophenyl adipate monomer to generate gel, and the nano calamine powder is wrapped and uniformly dispersed in the gel to obtain the nano particles.
(3) The invention introduces the nano particles into the polymerization reaction of casein and acrylic acid, and the amino group and the like contained in the nano particles can form hydrogen bond action with the hydroxyl group, the amino group and the like in the casein and the acrylic acid, thereby further improving the mechanical property and the degradation property of the product. Proper electron beam irradiation can adjust the composition of the three-dimensional structure of the surface of the nanoparticle, and the mechanical property and the degradation property of the product are ensured.
(4) The present invention introduces modified nanoparticles into a first solution, but not a second solution. In the first solution, polyether glycol and the like can form a hydrogen bond effect with the modified nanoparticles, which is beneficial to the uniform dispersion of the modified nanoparticles, and the modified nanoparticles are uniformly dispersed in the polyurethane formed by the polymerization of the polyether glycol and diisocyanate, so that the corresponding effect is exerted, and the mechanical property and the degradation property of the product are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of degradable polyurethane biomaterial comprises the steps of carrying out coaxial electrostatic spinning on a first solution and a second solution to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps:
(A) firstly, adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, reacting for 40 minutes at 65 ℃ with stirring, adding nano calamine powder, continuing to perform heat preservation and stirring reaction, and performing post-treatment to obtain nanoparticles;
(B) adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring and reacting, adding the nanoparticles obtained in the step (A), irradiating by electron beams, and performing post-treatment to prepare modified nanoparticles;
(C) finally, adding polyether glycol, modified nanoparticles and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution;
the second solution was prepared as follows: adding 10g of diisocyanate into 150g of N, N-dimethylacetamide, and uniformly stirring to obtain the second solution.
The specific method of coaxial electrostatic spinning comprises the following steps: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
The polyether diol is polyethylene glycol 600, and the diisocyanate is toluene diisocyanate.
In the step (A), the molar ratio of the lysine monomer to the p-nitrophenyl adipate monomer is 1:1.7, and the mass ratio of the lysine to the N, N-dimethylacetamide to the nano calamine powder is 1: 8: 0.2.
in the step (A), the reaction time of the continuous heat preservation stirring reaction is 15 minutes; the specific method of post-treatment is as follows: adding the reaction product into 7 times of trypsin solution, stirring at 35 deg.C for 4 days, dialyzing, and freeze-drying to obtain nanoparticles; wherein, the trypsin solution is prepared by adding 10g of trypsin into 80g of PBS buffer solution with pH value of 7.4, and uniformly stirring.
In the step (A), the lysine monomer is prepared as follows: adding 1, 4-butanediol, 43g lysine hydrochloride and 50g p-toluenesulfonic acid monohydrate into 180g toluene, stirring at 120 ℃ for reaction for 24 hours, centrifuging to obtain a precipitate, then adding the precipitate into 70g isopropanol, stirring and dispersing uniformly at 80 ℃, transferring to-15 ℃ for standing for 12 hours, centrifuging to obtain the precipitate, fully washing and drying to obtain the lysine monomer.
In the step (A), the preparation method of the p-nitrophenyl adipate monomer comprises the following steps: firstly, adding 10g of adipoyl chloride, 20g of p-nitrophenol and 12g of triethylamine into 80g of acetone, uniformly stirring at the temperature of minus 78 ℃, dropwise adding an adipoyl chloropropanone solution, keeping the temperature, stirring, reacting for 7 hours, performing suction filtration, washing with water, and drying to obtain the compound; wherein, the adipic acid chloropropanone solution is prepared by mixing adipic acid chloride and acetone according to the volume ratio of 1: 5 stirring and mixing evenly.
In the step (A), the particle size of the nano calamine powder is 30 nm.
In the step (B), the mass ratio of casein, acrylic acid, water, potassium persulfate and nano particles is 1: 7: 25: 0.08: 1.5.
in the step (B), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 80 ℃ for 8 hours.
In the step (B), the process conditions of electron beam irradiation are as follows: irradiation was carried out for 5s at a dose of 20 kGy.
The specific method for post-treatment in the step (B) comprises the following steps: dialysis was performed using water with pH 3 as the dialysis medium.
In the step (C), the mass ratio of the polyether glycol to the modified nanoparticles to the dibutyltin dilaurate to the N, N-dimethylacetamide is 1: 0.008: 0.03: 10.
example 2
A preparation method of degradable polyurethane biomaterial comprises the steps of carrying out coaxial electrostatic spinning on a first solution and a second solution to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps:
(A) firstly, adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, reacting for 30 minutes at 75 ℃, adding nano calamine powder, continuously keeping the temperature, stirring, reacting, and performing post-treatment to obtain nano particles;
(B) adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring and reacting, adding the nanoparticles obtained in the step (A), irradiating by electron beams, and performing post-treatment to prepare modified nanoparticles;
(C) finally, adding polyether glycol, modified nanoparticles and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution;
the second solution was prepared as follows: and adding 10g of diisocyanate into 250g N N-dimethylacetamide, and uniformly stirring to obtain the second solution.
The specific method of coaxial electrostatic spinning comprises the following steps: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
The polyether diol is polyethylene glycol 600, and the diisocyanate is hexamethylene diisocyanate.
In the step (A), the molar ratio of the lysine monomer to the p-nitrophenyl adipate monomer is 1:1.6, and the mass ratio of the lysine to the N, N-dimethylacetamide to the nano calamine powder is 1: 10: 0.1.
in the step (A), the reaction time of the continuous heat preservation stirring reaction is 25 minutes; the specific method of post-treatment is as follows: adding the reaction product into 5 times of trypsin solution, stirring at 37 ℃ for 3 days, dialyzing, and freeze-drying to obtain nanoparticles; wherein, the trypsin solution is prepared by adding 10g of trypsin into 100g of PBS buffer solution with pH value of 7.4, and uniformly stirring.
In the step (A), the lysine monomer is prepared as follows: firstly adding 1, 4-butanediol, 41g lysine hydrochloride and 60g p-toluenesulfonic acid monohydrate into 150g toluene, stirring and reacting for 22 hours at 130 ℃, centrifuging to obtain precipitate, then adding the precipitate into 90g isopropanol, stirring and dispersing uniformly at 70 ℃, transferring to the condition of-20 ℃, standing for 10 hours, centrifuging to obtain precipitate, fully washing and drying to obtain the lysine monomer.
In the step (A), the preparation method of the p-nitrophenyl adipate monomer comprises the following steps: firstly, adding 10g of adipoyl chloride, 22g of p-nitrophenol and 11g of triethylamine into 100g of acetone, uniformly stirring at the temperature of minus 78 ℃, dropwise adding an adipoyl chloropropanone solution, keeping the temperature, stirring, reacting for 5 hours, performing suction filtration, washing with water, and drying to obtain the compound; wherein, the adipic acid chloropropanone solution is prepared by mixing adipic acid chloride and acetone according to the volume ratio of 1: 7 stirring and mixing evenly.
In the step (A), the particle size of the nano calamine powder is 20 nm.
In the step (B), the mass ratio of casein, acrylic acid, water, potassium persulfate and nano particles is 1: 9: 20: 0.1: 1.
in the step (B), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 90 ℃ for 6 hours.
In the step (B), the process conditions of electron beam irradiation are as follows: irradiation was carried out for 3s at a dose of 30 kGy.
The specific method for post-treatment in the step (B) comprises the following steps: dialysis was performed using water with pH 3 as the dialysis medium.
In the step (C), the mass ratio of the polyether glycol to the modified nanoparticles to the dibutyltin dilaurate to the N, N-dimethylacetamide is 1: 0.01: 0.02: 12.
example 3
A preparation method of degradable polyurethane biomaterial comprises the steps of carrying out coaxial electrostatic spinning on a first solution and a second solution to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps:
(A) firstly, adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, reacting for 35 minutes at 70 ℃ with stirring, adding nano calamine powder, continuously keeping the temperature, stirring, reacting, and performing post-treatment to obtain nano particles;
(B) adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring and reacting, adding the nanoparticles obtained in the step (A), irradiating by electron beams, and performing post-treatment to prepare modified nanoparticles;
(C) finally, adding polyether glycol, modified nanoparticles and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution;
the second solution was prepared as follows: and adding 10g of diisocyanate into 200g of N, N-dimethylacetamide, and uniformly stirring to obtain the second solution.
The specific method of coaxial electrostatic spinning comprises the following steps: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
The polyether diol is polyethylene glycol 600, and the diisocyanate is toluene diisocyanate.
In the step (A), the molar ratio of the lysine monomer to the p-nitrophenyl adipate monomer is 1:1.65, and the mass ratio of the lysine to the N, N-dimethylacetamide to the nano calamine powder is 1: 9: 0.15.
in the step (A), the reaction time of the continuous heat preservation stirring reaction is 20 minutes; the specific method of post-treatment is as follows: adding the reaction product into 6 times of trypsin solution, stirring at 36 deg.C for 3 days, dialyzing, and freeze-drying to obtain nanoparticles; wherein, the trypsin solution is prepared by adding 10g of trypsin into 90g of PBS buffer solution with pH value of 7.4, and uniformly stirring.
In the step (A), the lysine monomer is prepared as follows: adding 10g of 1, 4-butanediol, 42g of lysine hydrochloride and 55g of p-toluenesulfonic acid monohydrate into 160g of toluene, stirring and reacting at 125 ℃ for 23 hours, centrifuging to obtain a precipitate, then adding the precipitate into 80g of isopropanol, stirring and dispersing uniformly at 75 ℃, transferring to-18 ℃ for standing for 11 hours, centrifuging to obtain the precipitate, fully washing and drying to obtain the lysine monomer.
In the step (A), the preparation method of the p-nitrophenyl adipate monomer comprises the following steps: firstly, adding 10g of adipoyl chloride, 21g of p-nitrophenol and 11.5g of triethylamine into 90g of acetone, uniformly stirring at the temperature of minus 78 ℃, dropwise adding an adipoyl chloropropanone solution, keeping the temperature, stirring, reacting for 6 hours, filtering, washing with water, and drying to obtain the compound; wherein, the adipic acid chloropropanone solution is prepared by mixing adipic acid chloride and acetone according to the volume ratio of 1: 6 stirring and mixing evenly.
In the step (A), the particle size of the nano calamine powder is 30 nm.
In the step (B), the mass ratio of casein, acrylic acid, water, potassium persulfate and nano particles is 1: 8: 22: 0.09: 1.2.
in the step (B), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 85 ℃ for 7 hours.
In the step (B), the process conditions of electron beam irradiation are as follows: irradiation was carried out for 4s at a dose of 30 kGy.
The specific method for post-treatment in the step (B) comprises the following steps: dialysis was performed using water with pH 3 as the dialysis medium.
In the step (C), the mass ratio of the polyether glycol to the modified nanoparticles to the dibutyltin dilaurate to the N, N-dimethylacetamide is 1: 0.009: 0.025: 11.
comparative example 1
A preparation method of degradable polyurethane biomaterial comprises the steps of carrying out coaxial electrostatic spinning on a first solution and a second solution to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps: adding polyether glycol and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution; the mass ratio of polyether glycol, dibutyltin dilaurate and N, N-dimethylacetamide is 1: 0.03: 10;
the second solution was prepared as follows, in parts by weight:
(a) firstly, adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, reacting for 40 minutes at 65 ℃ with stirring, adding nano calamine powder, continuing to perform heat preservation and stirring reaction, and performing post-treatment to obtain nanoparticles;
(b) adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring and reacting, adding the nanoparticles obtained in the step (A), irradiating by electron beams, and performing post-treatment to prepare modified nanoparticles;
(c) and finally, adding 10g of diisocyanate and 0.80g of modified nanoparticles into 150g of N, N-dimethylacetamide, and uniformly stirring to obtain the second solution.
The specific method of coaxial electrostatic spinning comprises the following steps: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
The polyether diol is polyethylene glycol 600, and the diisocyanate is toluene diisocyanate.
In the step (a), the molar ratio of the lysine monomer to the p-nitrophenyl adipate monomer is 1:1.7, and the mass ratio of the lysine to the N, N-dimethylacetamide to the nano calamine powder is 1: 8: 0.2.
in the step (a), the reaction time of the continuous heat preservation stirring reaction is 15 minutes; the specific method of post-treatment is as follows: adding the reaction product into 7 times of trypsin solution, stirring at 35 deg.C for 4 days, dialyzing, and freeze-drying to obtain nanoparticles; wherein, the trypsin solution is prepared by adding 10g of trypsin into 80g of PBS buffer solution with pH value of 7.4, and uniformly stirring.
In step (a), the lysine monomer is prepared as follows: adding 1, 4-butanediol, 43g lysine hydrochloride and 50g p-toluenesulfonic acid monohydrate into 180g toluene, stirring at 120 ℃ for reaction for 24 hours, centrifuging to obtain a precipitate, then adding the precipitate into 70g isopropanol, stirring and dispersing uniformly at 80 ℃, transferring to-15 ℃ for standing for 12 hours, centrifuging to obtain the precipitate, fully washing and drying to obtain the lysine monomer.
In the step (a), the preparation method of the p-nitrophenyl adipate monomer comprises the following steps: firstly, adding 10g of adipoyl chloride, 20g of p-nitrophenol and 12g of triethylamine into 80g of acetone, uniformly stirring at the temperature of minus 78 ℃, dropwise adding an adipoyl chloropropanone solution, keeping the temperature, stirring, reacting for 7 hours, performing suction filtration, washing with water, and drying to obtain the compound; wherein, the adipic acid chloropropanone solution is prepared by mixing adipic acid chloride and acetone according to the volume ratio of 1: 5 stirring and mixing evenly.
In the step (a), the particle size of the nano calamine powder is 30 nm.
In the step (b), the mass ratio of casein, acrylic acid, water, potassium persulfate and nano particles is 1: 7: 25: 0.08: 1.5.
in the step (b), the process conditions of the stirring reaction are as follows: the reaction was stirred at 80 ℃ for 8 hours.
In the step (b), the process conditions of electron beam irradiation are as follows: irradiation was carried out for 5s at a dose of 20 kGy.
The post-treatment method in the step (b) comprises the following specific steps: dialysis was performed using water with pH 3 as the dialysis medium.
Comparative example 2
A preparation method of degradable polyurethane biomaterial comprises the steps of carrying out coaxial electrostatic spinning on a first solution and a second solution to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps:
(A) firstly, adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, reacting for 40 minutes at 65 ℃ with stirring, adding nano calamine powder, continuing to perform heat preservation and stirring reaction, and performing post-treatment to obtain nanoparticles;
(B) then adding polyether glycol, nano particles and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution;
the second solution was prepared as follows: adding 10g of diisocyanate into 150g of N, N-dimethylacetamide, and uniformly stirring to obtain the second solution.
The specific method of coaxial electrostatic spinning comprises the following steps: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
The polyether diol is polyethylene glycol 600, and the diisocyanate is toluene diisocyanate.
In the step (A), the molar ratio of the lysine monomer to the p-nitrophenyl adipate monomer is 1:1.7, and the mass ratio of the lysine to the N, N-dimethylacetamide to the nano calamine powder is 1: 8: 0.2.
in the step (A), the reaction time of the continuous heat preservation stirring reaction is 15 minutes; the specific method of post-treatment is as follows: adding the reaction product into 7 times of trypsin solution, stirring at 35 deg.C for 4 days, dialyzing, and freeze-drying to obtain nanoparticles; wherein, the trypsin solution is prepared by adding 10g of trypsin into 80g of PBS buffer solution with pH value of 7.4, and uniformly stirring.
In the step (A), the lysine monomer is prepared as follows: adding 1, 4-butanediol, 43g lysine hydrochloride and 50g p-toluenesulfonic acid monohydrate into 180g toluene, stirring at 120 ℃ for reaction for 24 hours, centrifuging to obtain a precipitate, then adding the precipitate into 70g isopropanol, stirring and dispersing uniformly at 80 ℃, transferring to-15 ℃ for standing for 12 hours, centrifuging to obtain the precipitate, fully washing and drying to obtain the lysine monomer.
In the step (A), the preparation method of the p-nitrophenyl adipate monomer comprises the following steps: firstly, adding 10g of adipoyl chloride, 20g of p-nitrophenol and 12g of triethylamine into 80g of acetone, uniformly stirring at the temperature of minus 78 ℃, dropwise adding an adipoyl chloropropanone solution, keeping the temperature, stirring, reacting for 7 hours, performing suction filtration, washing with water, and drying to obtain the compound; wherein, the adipic acid chloropropanone solution is prepared by mixing adipic acid chloride and acetone according to the volume ratio of 1: 5 stirring and mixing evenly.
In the step (A), the particle size of the nano calamine powder is 30 nm.
In the step (B), the mass ratio of the polyether glycol, the nano particles, the dibutyltin dilaurate and the N, N-dimethylacetamide is 1: 0.008: 0.03: 10.
comparative example 3
A preparation method of degradable polyurethane biomaterial comprises the steps of carrying out coaxial electrostatic spinning on a first solution and a second solution to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps:
(A) adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring for reaction, adding nano calamine powder, irradiating by electron beams, and performing post-treatment to prepare modified nano particles;
(B) finally, adding polyether glycol, modified nanoparticles and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution;
the second solution was prepared as follows: adding 10g of diisocyanate into 150g of N, N-dimethylacetamide, and uniformly stirring to obtain the second solution.
The specific method of coaxial electrostatic spinning comprises the following steps: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
The polyether diol is polyethylene glycol 600, and the diisocyanate is toluene diisocyanate.
In the step (A), the particle size of the nano calamine powder is 30 nm.
In the step (A), the mass ratio of casein, acrylic acid, water, potassium persulfate and nano particles is 1: 7: 25: 0.08: 1.5.
in the step (A), the technological conditions of the stirring reaction are as follows: the reaction was stirred at 80 ℃ for 8 hours.
In the step (A), the process conditions of electron beam irradiation are as follows: irradiation was carried out for 5s at a dose of 20 kGy.
The specific method for post-treatment in the step (A) comprises the following steps: dialysis was performed using water with pH 3 as the dialysis medium.
In the step (B), the mass ratio of the polyether glycol to the modified nanoparticles to the dibutyltin dilaurate to the N, N-dimethylacetamide is 1: 0.008: 0.03: 10.
the polyurethane biomaterials obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to strand-knitting (8 strands) by using a knitting machine to obtain a suture. The suture was tested for mechanical properties and degradation and the results are shown in table 1.
The specific method comprises the following steps: the suture was immersed in simulated human body fluid (purchased from Beijing Rayleigh Biotech Co., Ltd.) for in vitro degradation experiments. The mechanical properties were measured directly on a YG 021A-I single-yarn electron tensile machine at 25 deg.C, 50% humidity, 200mm/min tensile rate and 0.5kg/cm elongation at load strength.
TABLE 1 Performance test results
As can be seen from Table 1, the suture prepared from the polyurethane biomaterial obtained in the embodiments 1-3 can be completely degraded within 26 days, and relatively good mechanical properties are maintained in the degradation process, so that the suture has good mechanical properties and degradation properties.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a degradable polyurethane biomaterial is characterized in that a first solution and a second solution are subjected to coaxial electrostatic spinning to obtain the polyurethane biomaterial; the preparation method of the first solution comprises the following steps:
(A) adding a lysine monomer and a p-nitrophenyl adipate monomer into N, N-dimethylacetamide, uniformly stirring, reacting at 65-75 ℃ for 30-40 minutes while stirring, adding nano calamine powder, continuing to perform heat preservation and stirring reaction, and performing post-treatment after the reaction is finished to obtain nanoparticles;
(B) adding casein and acrylic acid into water, stirring and mixing uniformly, adding potassium persulfate under the protection of nitrogen, stirring and reacting, then adding the nanoparticles obtained in the step (A), and performing electron beam irradiation and post-treatment to prepare modified nanoparticles;
(C) adding polyether glycol, the modified nano particles prepared in the step (B) and dibutyltin dilaurate into N, N-dimethylacetamide, and uniformly oscillating by ultrasonic waves to obtain the first solution;
the second solution was prepared as follows: and adding 1 part of diisocyanate into 15-25 parts of N, N-dimethylacetamide, and uniformly stirring to obtain the second solution.
2. The preparation method according to claim 1, wherein the coaxial electrospinning is carried out by the following specific method: injecting a first solution into a first injector, injecting a second solution into a second injector, respectively installing the first injector and the second injector on two micro-injection pumps, connecting tetrafluoro sleeves at outlets of the first injector and the second injector, adjusting the distance between needle heads of the two injectors and a roller receiver to be 14cm, the voltage of a high-voltage power supply to be 19kV, the temperature of a receiving device to be 52 ℃, adjusting the flow rate of the first injector to be 1.3mL/h and the flow rate of the second injector to be 1.5mL/h, switching on the power supply, performing electrostatic spinning, and receiving fibers on the roller receiver to obtain the polyurethane biomaterial.
3. The preparation method according to claim 1, wherein in the step (A), the molar ratio of the lysine monomer to the p-nitrophenyl adipate monomer is 1: 1.6-1.7, and the mass ratio of the lysine to the N, N-dimethylacetamide to the nano calamine powder is 1: 8-10: 0.1 to 0.2.
4. The preparation method according to claim 1, wherein in the step (A), the reaction time for the continuous stirring reaction under heat preservation is 15-25 minutes; the specific method of post-treatment is as follows: adding the reaction product into 5-7 times of trypsin solution, stirring for 3-4 days at 35-37 ℃, dialyzing, and freeze-drying to obtain nanoparticles; wherein the trypsin solution is prepared by adding 1 part of trypsin into 8-10 parts of PBS buffer solution with pH of 7.4 by weight, and uniformly stirring.
5. The method according to claim 1, wherein in the step (a), the lysine monomer is prepared as follows in parts by weight: adding 1 part of 1, 4-butanediol, 4.1-4.3 parts of lysine hydrochloride and 5-6 parts of p-toluenesulfonic acid monohydrate into 15-18 parts of toluene, stirring and reacting at 120-130 ℃ for 22-24 hours, centrifuging to obtain a precipitate, adding the precipitate into 7-9 parts of isopropanol, stirring and dispersing uniformly at 70-80 ℃, transferring to a temperature of-15-20 ℃ for standing for 10-12 hours, centrifuging to obtain the precipitate, fully washing and drying to obtain the lysine monomer.
6. The method according to claim 1, wherein in the step (A), the p-nitrophenyl adipate monomer is prepared as follows: firstly, adding 1 part of adipoyl chloride, 2-2.2 parts of p-nitrophenol and 1.1-1.2 parts of triethylamine into 8-10 parts of acetone, uniformly stirring at-78 ℃, dropwise adding an adipoyl chloropropanone solution, reacting for 5-7 hours while stirring at a constant temperature, performing suction filtration, washing with water and drying to obtain the compound; wherein, the adipic acid chloropropanone solution is prepared by mixing adipic acid chloride and acetone according to the volume ratio of 1: 5-7, and uniformly stirring to obtain the product.
7. The method according to claim 1, wherein in the step (B), the mass ratio of casein, acrylic acid, water, potassium persulfate and nanoparticles is 1: 7-9: 20-25: 0.08-0.1: 1 to 1.5.
8. The method according to claim 1, wherein the process conditions of the electron beam irradiation are: irradiating for 3-5 s under the dosage of 20-30 kGy.
9. A degradable polyurethane biomaterial prepared by the preparation method of claims 1-8.
10. Use of the degradable polyurethane biomaterial of claim 9 as a surgical suture.
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