CN112972762A - Degradable resin and preparation method and application thereof - Google Patents
Degradable resin and preparation method and application thereof Download PDFInfo
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- CN112972762A CN112972762A CN202110209321.2A CN202110209321A CN112972762A CN 112972762 A CN112972762 A CN 112972762A CN 202110209321 A CN202110209321 A CN 202110209321A CN 112972762 A CN112972762 A CN 112972762A
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- degradable
- bioactive
- inorganic material
- resin
- degradable resin
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- 239000011347 resin Substances 0.000 title claims abstract description 74
- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000000975 bioactive effect Effects 0.000 claims abstract description 49
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 41
- 239000011147 inorganic material Substances 0.000 claims abstract description 41
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000005416 organic matter Substances 0.000 claims abstract description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 239000000919 ceramic Substances 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 16
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 15
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 14
- 235000012241 calcium silicate Nutrition 0.000 claims description 11
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 11
- 239000000378 calcium silicate Substances 0.000 claims description 9
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 9
- 239000005313 bioactive glass Substances 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 239000004068 calcium phosphate ceramic Substances 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000005368 silicate glass Substances 0.000 claims description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002051 biphasic effect Effects 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 2
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 2
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052637 diopside Inorganic materials 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019976 tricalcium silicate Nutrition 0.000 claims description 2
- 229910021534 tricalcium silicate Inorganic materials 0.000 claims description 2
- 229910001720 Åkermanite Inorganic materials 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 1
- 229920000954 Polyglycolide Polymers 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 102
- 210000000988 bone and bone Anatomy 0.000 abstract description 13
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 description 29
- 238000010146 3D printing Methods 0.000 description 20
- 239000007857 degradation product Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 14
- 229920006237 degradable polymer Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 229920001222 biopolymer Polymers 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007943 implant Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002643 polyglutamic acid Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- A61L27/02—Inorganic materials
- A61L27/10—Ceramics or glasses
-
- 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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- 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
-
- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- 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
- A61L27/58—Materials at least partially resorbable by the body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
-
- 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
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Composite Materials (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides a degradable resin and a preparation method and application thereof, wherein the degradable resin comprises a degradable high molecular organic substance and a bioactive inorganic material; the degradable high-molecular organic matter and the bioactive inorganic material are compounded, the rigidity, the strength and the bone conductivity of the inorganic material are combined with the strength and the biodegradability of the high-molecular material, and bioactive cells can be well attached to, prolonged and proliferated on the artificial scaffold.
Description
Technical Field
The invention belongs to the field of degradable materials, and relates to a degradable resin and a preparation method and application thereof.
Background
The biological materials used for bone repair at present comprise medical metal materials, medical polymer materials, medical biological ceramic materials and medical composite materials. A great deal of research at home and abroad finds a plurality of potential materials which can be used for preparing the artificial bone, but most of the potential materials focus on a single material or only research on a certain characteristic to obtain a certain effect, but the clinical satisfactory bone defect repairing effect cannot be achieved. Generally, the dosage of these elements in medical metal implant materials is small and acceptable to human body, while the dosage is large and unacceptable to human body. When the metal is used for the internal fixation material, the metal is ideal in the aspects of strength and biocompatibility, but due to the properties of the metal, the metal still has more complications in the application process, such as corrosion of a metal implant, metal anaphylactic reaction, stress shielding effect, osteoporosis and the need of secondary operation for removing the internal fixation material, so that a great burden is brought to a patient on the spirit and the substance. In order to overcome the defect of using metal internal fixation materials during fracture, the absorbable internal fixation materials are researched from 20 th century 60s abroad, generally, the absorbable materials are artificially synthesized high molecular organic matters or natural high molecular materials, and after hydrolysis and oxidation reactions in vivo, the final metabolites are discharged out of the body through a respiratory system or a urinary system, do not accumulate in the body, have almost no toxic effect, and do not need to be taken out through a secondary operation. Common absorbable materials are Polyglycolide (PGA), Polylactide (PLA), polylactic-co-glycolic acid (PLGA), and the like. The biological ceramic material includes two main types of biological inert ceramics and biological active ceramics. The biological inert ceramics mainly comprise zinc oxide, aluminum oxide, zirconium oxide, silicon carbide and the like, and the biological inert ceramics are often used as implant surface modification materials. The bioactive ceramics mainly comprise calcium phosphate ceramics, calcium silicate ceramics, bioactive glass ceramics and the like. The pure bioactive ceramic material has high brittleness and low strength, and cannot meet the load bearing requirement of the artificial bone. The long-term clinical practice shows that the components of the material, whether the material is a metal material or an organic polymer material, are greatly different from natural bones, and the material is not satisfactory in biocompatibility, human body adaptability and mechanical compatibility among natural bones as a substitute material of the bones. If the degradable high molecular organic substance and the bioactive ceramic are compounded, the rigidity, strength and bone conductivity of the inorganic material are combined with the strength and biodegradability of the high molecular material. Meanwhile, the degradation product of the bioactive ceramic is alkaline, so that the bioactive ceramic can be used for neutralizing the acidic degradation product of polyester biopolymer, and the effects of delaying degradation speed and improving the bioactivity and biocompatibility of the material are achieved.
3D prints and is a rapid prototyping technique, is known as the core technology of "industrial revolution for the third time", compares with traditional manufacturing technology, and 3D prints and needn't make the mould in advance, needn't get rid of a large amount of materials in manufacturing process, needn't just can obtain final product through complicated forging technology yet, can realize configuration optimization, material saving and energy saving in production.
With the increasing maturity of 3D printing technology, the development of printing materials becomes more and more a key link for promoting the progress of 3D printing. In the aspect of the existing 3D printing consumables, the application of high polymer materials and metals is the most extensive, wherein the high polymer composite material has the advantages of easy processing, simple treatment, relatively light weight and the like, and is particularly prominent in the field of material application. However, with the current social environmental pollution becoming more serious, many materials that may pollute the environment are eliminated or limited in use.
CN107337903A discloses a resin-based degradable 3D printing material, which comprises the following components in percentage by weight: 40-50 parts of epoxy resin, 30-40 parts of hydroxyl acrylic resin, 12-18 parts of phenolic resin, 10-20 parts of polylactic acid ester containing bamboo fibers, 16-20 parts of microcrystalline wax, 6-8 parts of silk fibroin, 12-16 parts of filling fine materials, 6-10 parts of polyacrylamide, 0.6-1 part of photoinitiator, 2-6 parts of cross-linking agent and 0.2-0.4 part of auxiliary agent. The printing material based on epoxy resin, hydroxyl acrylic resin, phenolic resin and polylactic acid containing bamboo fiber can be naturally degraded without causing environmental pollution, but the hardness and the porosity of the material are low.
CN106893278A discloses a low-cost biodegradable 3D printing consumable and a preparation method thereof. The low-cost biodegradable 3D printing consumable provided by the invention can meet the requirements of mechanical properties and mechanical properties of consumables required by FDM-3D printing, and compared with the existing 3D printing consumable commonly found in the market, the low-cost biodegradable 3D printing consumable has lower production cost, because of the addition of the biodegradable filler, the production cost of the 3D printing consumable is reduced, in addition, the 3D printing consumable is not added with inorganic mineral talcum powder, the pollution of the consumables to soil in the degradation process is prevented, and the 3D printing consumable can be completely degraded, so that the pollution of residues to soil is effectively avoided. But the strength of the consumable is poor and the hardness is low.
The above-mentioned solutions have problems of low hardness, low porosity or poor strength, and therefore, there is a need for developing a 3D printing material having high hardness and porosity and good strength.
Disclosure of Invention
The invention aims to provide a degradable resin and a preparation method and application thereof, wherein the degradable resin comprises a degradable high-molecular organic substance and a bioactive inorganic material, the mass fraction of the degradable high-molecular organic substance is 50-95% and the mass fraction of the bioactive inorganic material is 5-50% based on 100% of the mass of the degradable resin. The invention compounds degradable high molecular organic matter and bioactive inorganic material, combines the rigidity, strength and osteoconductivity of inorganic material with the strength and biodegradability of high molecular material, and can make bioactive cell well attached, prolonged and proliferated on artificial support.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a degradable resin, which comprises a degradable macromolecular organic substance and a bioactive inorganic material; wherein the mass fraction of the degradable high molecular organic substance is 50-95% based on 100% of the mass of the degradable resin, for example: 50%, 60%, 70%, 80%, 90%, 95%, and the like, wherein the mass fraction of the bioactive inorganic material is 5-50%, for example: 5%, 10%, 20%, 30%, 40%, or 50%, etc.
The invention compounds degradable high molecular organic matter and bioactive inorganic material, and combines the rigidity, strength and bone conductivity of inorganic material with the strength and biodegradability of high molecular material. The mechanical property and the porosity of the material can be improved to a certain degree, and meanwhile, the degradation product of the bioactive inorganic material is alkaline, so that the material can be used for neutralizing the acidic degradation product of polyester biopolymer, and the effects of delaying the degradation speed and improving the bioactivity and the biocompatibility of the material are achieved; meanwhile, the bioactive inorganic material can improve the osteoconductivity of degradable high molecular organic matters, so that bioactive cells can be well attached, prolonged and proliferated on the artificial scaffold. The degradation product of the bioactive ceramic in the degradable resin is alkaline, so that the degradation product can be used for neutralizing the acidic degradation product of polyester biopolymer, and the effects of delaying degradation speed and improving the bioactivity and biocompatibility of the material are achieved.
Preferably, the degradable polymer organic substance comprises any one of Polyglycolide (PGA), Polylactide (PLA), polylactic-co-glycolic acid (PLGA), Polycaprolactone (PCL) or Polyhydroxyalkanoate (PHA), or a combination of at least two of them.
Preferably, the bioactive inorganic material comprises any one of calcium phosphate ceramic, calcium silicate ceramic or bioactive glass or a combination of at least two of them.
Preferably, the mass fraction of the degradable high molecular organic substance is 50-75%, for example: 50%, 55%, 60%, 65%, 70%, 75%, etc.
Preferably, the bioactive inorganic material is 25-50% by mass, for example: 25%, 30%, 35%, 40%, 45%, 50%, etc.
Preferably, the calcium phosphate ceramic comprises any one of Hydroxyapatite (HAP), β -tricalcium phosphate (β -TCP), or biphasic calcium phosphate (HA-TCP), or a combination of at least two thereof.
Preferably, the calcium silicate ceramic comprises any one of calcium silicate, dicalcium silicate, tricalcium silicate, diopside, akermanite or whitlaite, or a combination of at least two thereof.
Preferably, the bioactive glass comprises a silicate glass.
Preferably, the silicate glass consists of silicon oxide, sodium oxide, calcium oxide and phosphorus oxide.
Preferably, the bioactive inorganic material has a particle size of 50 to 10000nm, for example: 50nm, 100nm, 500nm, 800nm, 1000nm, 3000nm, 5000nm or 10000nm, preferably 200-800 nm.
The degradation product of the bioactive inorganic material is alkaline, so that the degradation product can be used for neutralizing the acidic degradation product of the polyester biopolymer, and the effects of delaying the degradation speed and improving the bioactivity and biocompatibility of the material are achieved.
In a second aspect, the present invention provides a method for preparing the degradable resin according to the first aspect, the method comprising the steps of:
(1) grinding the bioactive inorganic material into bioactive inorganic material nano-micron particles;
(2) drying the degradable high molecular organic matter and the nano-micron particle bioactive inorganic material obtained in the step (1), and plasticating, mixing and granulating to obtain the degradable resin.
According to the invention, bioactive ceramic particles, especially nano particles, are added into the degradable polymer, so that the mechanical property of the material can be improved to a certain degree, and H generated during degradation of the degradable polymer can be relieved in the degradation process+(ii) a Meanwhile, the bioactive ceramic can improve the bone conductivity of the degradable polymer, so that bioactive cells can be well attached, prolonged and proliferated on the artificial scaffold. Although the bioactive inorganic material particlesThe particles are easy to agglomerate in a degradable polymer matrix especially in a nanometer size, and the interface compatibility between the particles and the degradable polymer matrix is weak, so that the interface of the composite material is easy to be firstly damaged under the action of external force, and further the mechanical strength of the composite material is quickly attenuated. Meanwhile, the nano biological ceramic particles are mixed with the degradable polymer and can be used as crystallization induction nucleation points, and the crystallinity of the degradable polymer can be obviously improved by proper heat treatment, so that the mechanical property of the degradable polymer is improved.
Preferably, the plasticating and mixing device in the step (2) comprises any one or a combination of at least two of an internal mixer, an open mill or a twin-screw extruder.
Preferably, the temperature of the plastication mixing is 100-180 ℃, for example: 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C or 180 deg.C.
The plastication temperature in the step (2) of the invention affects the performance of the prepared degradable resin, if the plastication temperature is lower than 100 ℃, the plastication effect cannot be achieved, the degradable high molecular organic substance and the nano-micron particle bioactive inorganic material obtained in the step (1) cannot be completely mixed, and if the plastication temperature is higher than 180 ℃, the degradable high molecular organic substance and the nano-micron particle bioactive inorganic material obtained in the step (1) can be denatured, so that the performance of the prepared degradable resin is affected.
Preferably, the plastication mixing time is 2-6 h, for example: 2h, 3h, 4h, 5h or 6h and the like.
The plastication time in the step (2) of the invention affects the performance of the prepared degradable resin, if the plastication time is less than 2 hours, the plastication effect cannot be achieved, the degradable high-molecular organic substance and the nano-micron particle bioactive inorganic material obtained in the step (1) cannot be completely mixed, and if the plastication mixing time is more than 6 hours, the degradable high-molecular organic substance and the nano-micron particle bioactive inorganic material obtained in the step (1) may be damaged, so that the performance of the prepared degradable resin is affected.
In a third aspect, the present invention also provides a 3D printing resin, the 3D printing resin comprising the degradable resin according to the first aspect.
In the 3D printing resin, the degradation product of the bioactive inorganic material is alkaline, so that the degradation product can be used for neutralizing the acidic degradation product of polyester biopolymer, and the effects of delaying the degradation speed and improving the bioactivity and biocompatibility of the material are achieved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the degradable resin combines the rigidity, strength and osteoconductivity of inorganic materials with the strength and biodegradability of polymer materials, so that the mechanical property of the materials is improved to a certain degree, and H generated when the degradable polymers are degraded can be relieved in the degradation process+(ii) a Meanwhile, the bioactive inorganic material can improve the bone conductivity of the degradable polymer, so that bioactive cells can be well attached, prolonged and proliferated on the artificial scaffold.
(2) The degradation product of the bioactive ceramic in the degradable resin is alkaline, so that the degradation product can be used for neutralizing the acidic degradation product of polyester biopolymer, and the effects of delaying degradation speed and improving the bioactivity and biocompatibility of the material are achieved.
(3) The standard wire for 3D printing prepared from the degradable resin has the tensile strength of more than 18MPa, the compression strength of more than 25MPa, the porosity of more than 53 percent and the hardness of more than 60Shore D.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 3 hours at 120 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 2
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the HA-TCP material into HA-TCP nanoparticles with the particle size D50 of 500 nm;
(2) 100 parts of PHA and 30 parts of HA-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 4 hours at the temperature of 130 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 3
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the calcium silicate ceramic material into calcium silicate ceramic nano-particles with the particle size D50 of 800 nm;
(2) and weighing 80 parts of PLGA powder, 20 parts of PCL powder and 50 parts of calcium carbonate ceramic nanoparticles, and mixing to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 4 hours at 120 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 4
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the bioactive glass material into bioactive glass nanoparticles with a particle size D50 of 600 nm;
(2) and weighing 90 parts of PLA powder, 10 parts of PLGA powder and 50 parts of bioactive glass nano particles, and mixing to obtain the mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 5 hours at 125 ℃ by using an internal mixer, and fully drying to obtain the degradable resin.
Example 5
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 3 hours at the temperature of 100 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 6
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 3 hours at 180 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 7
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 3 hours at the temperature of 80 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 8
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 3 hours at the temperature of 200 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 9
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 2 hours at the temperature of 200 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 10
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 6 hours at the temperature of 200 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 11
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 1h at 200 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Example 12
The embodiment provides a degradable resin, which is prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 100 parts of PHA powder and 10 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 8 hours at the temperature of 200 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Comparative example 1
A PLGA single component scaffold.
Comparative example 2
PHA single component support.
Comparative example 3
This comparative example provides a degradable resin prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 45 parts of PHA powder and 55 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 3 hours at 120 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
Comparative example 4
This comparative example provides a degradable resin prepared by the following method:
(1) grinding the beta-TCP material into beta-TCP nano-particles with the particle size D50 of 300 nm;
(2) 98 parts of PHA powder and 2 parts of beta-TCP nanoparticles are weighed and mixed to obtain a mixed material. And fully drying the mixed materials by using a vacuum drying oven, plasticating and mixing the mixed materials for 3 hours at 120 ℃ by using a double-screw extruder, and fully drying to obtain the degradable resin.
And (3) performance testing:
the degradable resins obtained in examples 1 to 12 were prepared into standard wires for 3D printing having a diameter of 1.75mm by using a twin-screw extruder again. A support material with the model size of 10 multiplied by 5mm is designed by Solidworks, a printing head with the thickness of 0.4mm is selected, the printing interval in the direction of X, Y is 0.4mm, and the printing layer is thick.
The above scaffold materials and the scaffold materials of comparative examples 1-2 were tested for tensile strength, compressive strength, porosity and hardness, respectively, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the tensile strength of the standard wire for 3D printing prepared from the degradable resin of the invention can reach more than 18MPa, the compressive strength can reach more than 25MPa, the porosity can reach more than 53%, and the hardness can reach more than 60shore D, and the tensile strength of the standard wire for 3D printing prepared from the degradable resin can reach 38MPa, the compressive strength can reach 78MPa, and the hardness can reach 92shore D by adjusting the types, the proportions and the preparation conditions of the materials.
Compared with the examples 5 to 8, the temperature of the plastication mixing in the step (2) affects the performance of the prepared degradable resin, and the mechanical strength and the porosity of the prepared degradable resin can be improved by controlling the temperature of the plastication mixing to be 100 to 180 ℃.
Compared with the examples 9 to 12, the plastication mixing time in the step (2) affects the performance of the prepared degradable resin, and the mechanical strength and the porosity of the prepared degradable resin can be improved by controlling the plastication mixing time within 2 to 6 hours.
Compared with the comparative examples 1 and 2, the invention can improve the tensile strength, the compression strength, the porosity and the hardness of the material by adding the bioactive inorganic material into the degradable high molecular organic matter.
Compared with the comparative examples 3 to 4, the proportion of the high molecular organic substance and the bioactive inorganic material in the degradable resin can affect the performance of the degradable resin, and the mass proportion of the degradable high molecular organic substance is controlled to be 50-95%, and the mass proportion of the bioactive inorganic material is controlled to be 5-50%, so that the rigidity, the strength and the bone conductivity of the inorganic material and the strength and the biodegradability of the polymer material can be fully exerted, and the mechanical property of the material can be improved to a certain degree.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A degradable resin is characterized by comprising a degradable high molecular organic substance and a bioactive inorganic material;
wherein the mass fraction of the degradable high molecular organic matter is 50-95% and the mass fraction of the bioactive inorganic material is 5-50% based on 100% of the mass of the degradable resin.
2. The degradable resin of claim 1, wherein the degradable high molecular organic substance comprises one or a combination of at least two of polyglycolide, polylactide, polylactic acid-glycolic acid copolymer, polycaprolactone or polyhydroxyalkanoate;
preferably, the bioactive inorganic material comprises any one of calcium phosphate ceramic, calcium silicate ceramic or bioactive glass or a combination of at least two of the same;
preferably, the mass fraction of the degradable high-molecular organic matter is 50-75%;
preferably, the mass fraction of the bioactive inorganic material is 25-50%.
3. The degradable resin of claim 2 wherein said calcium phosphate ceramic comprises any one of hydroxyapatite, β -tricalcium phosphate, or biphasic calcium phosphate, or a combination of at least two thereof.
4. The degradable resin of claim 2 or 3, wherein the calcium silicate ceramic comprises any one of calcium silicate, dicalcium silicate, tricalcium silicate, diopside, akermanite or whitlaite or a combination of at least two thereof.
5. The degradable resin of any one of claims 2 to 4, wherein the bioactive glass comprises a silicate glass;
preferably, the silicate glass consists of silicon oxide, sodium oxide, calcium oxide and phosphorus oxide.
6. The degradable resin of any of claims 1 to 5, wherein the bioactive inorganic material has a median particle diameter D50 of 50 to 10000nm, preferably 200 to 800 nm.
7. A method for preparing the degradable resin according to any one of claims 1 to 6, wherein the method comprises the steps of:
(1) grinding the bioactive inorganic material into bioactive inorganic material nano-micron particles;
(2) drying the degradable high molecular organic matter and the nano-micron particle bioactive inorganic material obtained in the step (1), and plasticating, mixing and granulating to obtain the degradable resin.
8. The method of claim 7, wherein the plasticating mixing device in step (2) comprises any one of an internal mixer, an open mill or a twin-screw extruder or a combination of at least two of the above.
9. The method according to claim 7 or 8, wherein the temperature of the masticating and mixing in the step (2) is 100 to 180 ℃;
preferably, the plastication mixing time is 2-6 h.
10. A 3D printed resin, wherein the 3D printed resin comprises the degradable resin of any one of claims 1-6.
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| CN104194296A (en) * | 2014-09-19 | 2014-12-10 | 叶川 | High-strength degradable 3D printing material and preparation method thereof |
| CN110051881A (en) * | 2018-01-19 | 2019-07-26 | 深圳中科精诚医学科技有限公司 | A kind of 3D printing nanometer silver antimicrobial bone renovating material and preparation method thereof |
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| CN104194296A (en) * | 2014-09-19 | 2014-12-10 | 叶川 | High-strength degradable 3D printing material and preparation method thereof |
| CN110051881A (en) * | 2018-01-19 | 2019-07-26 | 深圳中科精诚医学科技有限公司 | A kind of 3D printing nanometer silver antimicrobial bone renovating material and preparation method thereof |
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