CN113577369B - Porous composite bone cement and preparation method thereof - Google Patents
Porous composite bone cement and preparation method thereof Download PDFInfo
- Publication number
- CN113577369B CN113577369B CN202110962977.1A CN202110962977A CN113577369B CN 113577369 B CN113577369 B CN 113577369B CN 202110962977 A CN202110962977 A CN 202110962977A CN 113577369 B CN113577369 B CN 113577369B
- Authority
- CN
- China
- Prior art keywords
- bone cement
- porous composite
- powder
- liquid
- composite bone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002639 bone cement Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000012620 biological material Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 210000002449 bone cell Anatomy 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000011049 filling Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 238000012669 compression test Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000399 orthopedic effect Effects 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001356 surgical procedure Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- 208000001164 Osteoporotic Fractures Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 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 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 238000005303 weighing Methods 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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing 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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
-
- 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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0036—Porous materials, e.g. foams or sponges
-
- 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
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained 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
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained 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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- 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
Abstract
The invention relates to the technical field of biomedical materials, in particular to porous composite bone cement and a preparation method thereof. The porous composite bone cement mainly comprises two parts of powder and liquid, wherein the powder and liquid are mixed according to a powder-liquid ratio of 2: 1g/mL, and the powder mainly comprises the following raw materials in percentage by mass: 29.5-84% of methacrylic acid polymer, 10-40% of degradable biological material, 5-30% of barium sulfate and 0.01-0.5% of benzoyl peroxide; the liquid mainly comprises the following raw materials in percentage by mass: 93-99.45% of methyl methacrylate, 0.5-5% of N, N-dimethyl-p-toluidine and 0.05-2% of hydroquinone. The invention solves the problems that the interface bonding force between the traditional bone cement and the autologous bone is low, bone cells can not grow in, and the mechanical property and the biocompatibility of the bone cement are influenced by the residual reactants of the pore-forming agent after the existing porous bone cement is cured.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to porous composite bone cement and a preparation method thereof.
Background
Bone cement is a common name of bone cements, and is a medical material used in orthopedic operations. PMMA bone cement was an injectable filling and bonding material, the first used in prosthetic replacements. At present, the method is widely applied to orthopedics clinic, in particular to the aspect of spine repair and formation.
PMMA bone cement has many advantages as a fillable material in bone surgery: the injectability is good; the adhesive has good viscosity, and can be well adhered to bones and implant devices; the mechanical strength is excellent; fast curing time, etc. Meanwhile, the defect of PMMA bone cement as an injection material for a human body is obvious. PMMA bone cement is an artificially synthesized polymer, and the material has poor compatibility with bones and cannot form good combination with the surfaces of the bones; and can not directly induce the growth of bone tissue, and the material is easy to loosen after being implanted in the body for a period of time, thereby causing the failure of implantation.
Chinese patent CN102552986B discloses a method for preparing porous bone cement by using metal pore-forming agent, which comprises weighing beta-TCP and Ca (H2PO4) according to the molar ratio of 1:12·H2Grinding the O powder to prepare composite powder, adding 0.5mol/L citric acid solution for blending, and then adding metal powder to naturally foam and solidify to obtain the porous bone cement material. In the method, the mechanical property and the biological property of the bone cement can be influenced by residual metal salts and alkaline substances after the bone cement is solidified, and meanwhile, the residual substances are possibly safe after being dissolved in body fluid or blood of a human body.
Disclosure of Invention
The invention aims to provide porous composite bone cement and a preparation method thereof, overcomes the defects of the prior art, can be used for orthopedic surgery, osteoporotic fracture fixation, bone defect filling and the like, and solves the problems that the interface bonding force between the traditional bone cement and self bone is low, bone cells cannot grow in, and the mechanical property and biocompatibility of the bone cement are influenced by residual reactants of a pore-forming agent after the existing porous bone cement is cured.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a porous composite bone cement mainly comprises powder and liquid, wherein the powder and liquid are in a powder-liquid ratio of (1.8-2.5): (0.8-1.2) g/mL, wherein:
the powder mainly comprises the following raw materials in percentage by mass: 29.5-84% of methacrylic acid polymer, 10-40% of degradable biological material, 5-30% of barium sulfate and 0.01-0.5% of benzoyl peroxide;
the liquid mainly comprises the following raw materials in percentage by mass: 93-99.45% of methyl methacrylate, 0.5-5% of N, N-dimethyl-p-toluidine and 0.05-2% of hydroquinone.
Preferably, the degradable biomaterial is a copolymer with three branched structures, which is mainly obtained by polymerizing polyethylene glycol and citric acid through an esterification reaction.
Preferably, the preparation method of the degradable biological material comprises the following steps: dehydrating agent, catalyst, citric acid and polyethylene glycol according to a molar ratio (1.7-2.3): (0.3-0.6): (0.8-1.3): (2.8-3.4), dissolving in n-butanol solvent, reacting at 20-40 ℃ for 4-8h, separating after the reaction is finished, and drying in vacuum to obtain the degradable biological material; the chemical reaction formula is as follows:
preferably, in the preparation method of the degradable biological material, a dehydrating agent, a catalyst, citric acid and polyethylene glycol are mixed according to a molar ratio of 2:0.5:1:3, mixing.
Preferably, the dehydrating agent is N, N-dicyclohexylcarbodiimide or 1-ethyl-3 (3-dimethylpropylamine) carbodiimide.
Preferably, the catalyst is any one of 4-dimethylaminopyridine, tetrabutyl titanate and tetraisopropyl titanate.
Preferably, the polyethylene glycol has a molecular weight of 200-600.
A preparation method of porous composite bone cement comprises the following steps:
(1) uniformly mixing a specified amount of degradable biological material, polymethyl methacrylate, benzoyl peroxide and barium sulfate in a mixer according to a proportion to obtain bone cement powder;
(2) uniformly mixing methyl methacrylate, N-dimethyl-p-toluidine and hydroquinone in a specified amount according to a ratio to obtain bone cement liquid;
(3) and (3) uniformly mixing the bone cement powder uniformly mixed in the step (1) and the bone cement liquid uniformly mixed in the step (2) according to a ratio to obtain the porous composite bone cement.
Preferably, the environmental conditions of step (3) are: the temperature is 23 +/-1 ℃ and the relative humidity is not lower than 40 percent.
The beneficial effects of the invention are: compared with the prior art, the porous composite bone cement and the preparation method thereof have the following advantages: the degradable biomaterial is prepared by polymerizing polyethylene glycol and citric acid through esterification reaction, the polyethylene glycol is a nonionic hydrophilic polymer, can be dissolved in water and most organic solvents to remove ether and alkane, and has the advantages of no toxicity, no antigenicity, no immunogenicity and good biocompatibility, the citric acid is tribasic acid, is one of a plurality of natural organic acids, has the chemical reaction activity of common organic acids, is non-toxic, and is a metabolite of tricarboxylic acid circulation in vivo, so the residue of the degradable biomaterial after the porous composite bone cement and the bone cement are cured has good biocompatibility and biodegradability, the water absorption and the solubility of PMMA bone cement can be improved, and the porous structure formed by metabolism is also beneficial to the growth of new bones, and the mechanical property of the bone cement is not influenced.
Detailed Description
Example 1
The porous composite bone cement mainly comprises two parts of 20g of powder and 10mL of liquid, wherein the powder mainly comprises the following raw materials: PMMA11.98g, degradable biological material 2g, barium sulfate 6g and benzoyl peroxide 0.02g, and the raw materials are uniformly mixed to obtain bone cement powder; the liquid mainly comprises the following raw materials: 9.45mL of methyl methacrylate, 0.5mL of N, N-dimethyl-p-toluidine and 0.05mL of hydroquinone are mixed to obtain the bone cement liquid.
The degradable biological material is a copolymer with three branched chain structures, which is mainly obtained by polymerizing polyethylene glycol and citric acid through esterification reaction, and the specific preparation method comprises the following steps: mixing EDCI, DMAP, citric acid and polyethylene glycol (molecular weight is 200) according to a molar ratio of 2:0.5:1:3, dissolving in n-butanol solvent, reacting for 6h at 40 ℃, separating after the reaction is finished, and drying in vacuum to obtain the product.
The preparation method of the porous composite bone cement in the embodiment comprises the following steps: blending the bone cement powder and the bone cement liquid in proportion under the conditions of 23 +/-1 ℃ and relative humidity not lower than 40%, stirring for 1-2min to obtain porous composite bone cement, filling the porous composite bone cement into an injector, injecting into a fixed mould, and carrying out physical property test after curing, wherein the size of a compression test sample is a cylinder with the height of 12mm and the diameter of 6 mm; the bending test specimen dimensions are strips approximately 75mm long, 10mm wide and 3.3mm thick.
Example 2
The porous composite bone cement mainly comprises 20g of powder and 10mL of liquid, wherein the powder mainly comprises the following raw materials: PMMA10.98g, degradable biological material 3g, barium sulfate 6g and benzoyl peroxide 0.02g, and the raw materials are uniformly mixed to obtain bone cement powder; the liquid mainly comprises the following raw materials: 9.3mL of methyl methacrylate, 0.5mL of N, N-dimethyl-p-toluidine and 0.2mL of hydroquinone, and the raw materials are mixed to obtain the bone cement liquid.
The degradable biological material is a copolymer with three branched chain structures, which is mainly obtained by polymerizing polyethylene glycol and citric acid through esterification reaction, and the specific preparation method comprises the following steps: mixing N, N-dicyclohexylcarbodiimide, tetrabutyl titanate, citric acid and polyethylene glycol (molecular weight of 400) according to a molar ratio of 2:0.5:1:3, dissolving in N-butanol solvent, reacting for 5h at 40 ℃, separating after the reaction is finished, and drying in vacuum to obtain the product.
The preparation method of the porous composite bone cement in the embodiment comprises the following steps: blending the bone cement powder and the bone cement liquid in proportion under the conditions of 23 +/-1 ℃ and relative humidity not lower than 40%, stirring for 1-2min to obtain porous composite bone cement, filling the porous composite bone cement into an injector, injecting into a fixed mould, and carrying out physical property test after curing, wherein the size of a compression test sample is a cylinder with the height of 12mm and the diameter of 6 mm; the bending test specimen dimensions were a strip approximately 75mm long, 10mm wide and 3.3mm thick.
Example 3
The porous composite bone cement mainly comprises two parts of 20g of powder and 10mL of liquid, wherein the powder mainly comprises the following raw materials: PMMA9.98g, degradable biological material 4g, barium sulfate 6g and benzoyl peroxide 0.02g, and the raw materials are uniformly mixed to obtain bone cement powder; the liquid mainly comprises the following raw materials: 9.945mL of methyl methacrylate, 0.05mL of N, N-dimethyl-p-toluidine and 0.005mL of hydroquinone, and the raw materials are mixed to obtain the bone cement liquid.
The degradable biological material is a copolymer with three branched chain structures, which is mainly obtained by polymerizing polyethylene glycol and citric acid through esterification reaction, and the specific preparation method comprises the following steps: mixing EDCI, tetraisopropyl titanate, citric acid and polyethylene glycol (molecular weight is 600) according to a molar ratio of 2:0.5:1:3, dissolving in n-butanol solvent, reacting at 40 ℃ for 8h, separating after the reaction is finished, and drying in vacuum to obtain the product.
The preparation method of the porous composite bone cement in the embodiment comprises the following steps: blending the bone cement powder and the bone cement liquid in proportion under the conditions of 23 +/-1 ℃ and relative humidity not lower than 40%, stirring for 1-2min to obtain porous composite bone cement, filling the porous composite bone cement into an injector, injecting into a fixed mould, and carrying out physical property test after curing, wherein the size of a compression test sample is a cylinder with the height of 12mm and the diameter of 6 mm; the bending test specimen dimensions are strips approximately 75mm long, 10mm wide and 3.3mm thick.
Example 4
The porous composite bone cement mainly comprises two parts of 20g of powder and 10mL of liquid, wherein the powder mainly comprises the following raw materials: PMMA13.98g, barium sulfate 6g and benzoyl peroxide 0.02g, and the raw materials are uniformly mixed to obtain bone cement powder; the liquid mainly comprises the following raw materials: 9.45mL of methyl methacrylate, 0.5mL of N, N-dimethyl-p-toluidine and 0.05mL of hydroquinone, and the raw materials are mixed to obtain the bone cement liquid.
The preparation method of the bone cement in the embodiment comprises the following steps: mixing the bone cement powder and the bone cement liquid in proportion under the conditions of 23 +/-1 ℃ and relative humidity not lower than 40%, stirring for 1-2min to obtain bone cement, filling the porous composite bone cement into an injector, injecting into a fixed mould, and carrying out physical property test after solidification, wherein the size of a compression test sample is a cylinder with the height of 12mm and the diameter of 6 mm; the bending test specimen dimensions are strips approximately 75mm long, 10mm wide and 3.3mm thick.
Example 4 differs from example 1 in that: in example 4, the amount of degradable biomaterial was increased to the amount of PMMA in example 1 without adding the degradable biomaterial.
Test example 1
The bone cements prepared in examples 1 to 4 were subjected to physical property tests, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the introduction of the degradable biomaterial in the bone cement preparation process in examples 1-3 of the present invention not only enables the porous composite bone cement to be obtained, but also enables the mechanical properties of the cured porous composite bone cement to meet the requirements of YY 0459-2003 standard.
The above embodiments are only specific examples of the present invention, and the protection scope of the present invention includes but is not limited to the product forms and styles of the above embodiments, and any suitable changes or modifications made by those skilled in the art according to the claims of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. A porous composite bone cement is characterized in that: the powder and liquid ratio is (1.8-2.5): (0.8-1.2) g/mL, wherein:
the powder mainly comprises the following raw materials in percentage by mass: 29.5-84% of methacrylic acid polymer, 10-40% of degradable biological material, 5-30% of barium sulfate and 0.01-0.5% of benzoyl peroxide;
the liquid mainly comprises the following raw materials in percentage by mass: 93-99.45% of methyl methacrylate, 0.5-5% of N, N-dimethyl-p-toluidine and 0.05-2% of hydroquinone;
the degradable biological material is a copolymer with three branched chain structures, which is mainly obtained by polymerizing polyethylene glycol and citric acid through esterification reaction; the molecular weight of polyethylene glycol is 200-600.
2. The porous composite bone cement of claim 1, wherein: the preparation method of the degradable biological material comprises the following steps: dehydrating agent, catalyst, citric acid and polyethylene glycol according to a molar ratio (1.7-2.3): (0.3-0.6): (0.8-1.3): (2.8-3.4), dissolving in n-butanol solvent, reacting at 20-40 ℃ for 4-8h, separating after the reaction is finished, and vacuum drying to obtain the degradable biological material; the chemical reaction formula is as follows:
3. the porous composite bone cement of claim 2, wherein: in the preparation method of the degradable biological material, a dehydrating agent, a catalyst, citric acid and polyethylene glycol are mixed according to a molar ratio of 2:0.5:1:3, mixing.
4. The porous composite bone cement according to claim 2, wherein: the dehydrating agent is N, N-dicyclohexylcarbodiimide or 1-ethyl-3 (3-dimethylpropylamine) carbodiimide.
5. The porous composite bone cement of claim 2, wherein: the catalyst is any one of 4-dimethylamino pyridine, tetrabutyl titanate and tetraisopropyl titanate.
6. The method for preparing a porous composite bone cement according to any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) uniformly mixing a specified amount of degradable biological material, polymethyl methacrylate, benzoyl peroxide and barium sulfate in a mixer according to a proportion to obtain bone cement powder;
(2) uniformly mixing methyl methacrylate, N-dimethyl-p-toluidine and hydroquinone in a specified amount according to a ratio to obtain bone cement liquid;
(3) and (3) uniformly mixing the bone cement powder uniformly mixed in the step (1) and the bone cement liquid uniformly mixed in the step (2) according to a ratio to obtain the porous composite bone cement.
7. The method for preparing a porous composite bone cement according to claim 6, wherein: the environmental conditions of the step (3) are as follows: the temperature is 23 +/-1 ℃, and the relative humidity is not lower than 40%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110962977.1A CN113577369B (en) | 2021-08-20 | 2021-08-20 | Porous composite bone cement and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110962977.1A CN113577369B (en) | 2021-08-20 | 2021-08-20 | Porous composite bone cement and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113577369A CN113577369A (en) | 2021-11-02 |
CN113577369B true CN113577369B (en) | 2022-07-22 |
Family
ID=78238700
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110962977.1A Active CN113577369B (en) | 2021-08-20 | 2021-08-20 | Porous composite bone cement and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113577369B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105131161B (en) * | 2015-09-09 | 2017-06-27 | 山东明德生物医学工程有限公司 | The preparation method of autography polymethacrylates and autography bone cement for bone cement |
CN110694099A (en) * | 2019-10-16 | 2020-01-17 | 中国人民解放军第四军医大学 | Mytilus edulis bionic adhesive based on polymalic acid and preparation method and application thereof |
CN112608457A (en) * | 2020-03-23 | 2021-04-06 | 杭州鹿扬科技有限公司 | Preparation method of poly citrate porous scaffold |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE423578T1 (en) * | 2004-05-27 | 2009-03-15 | Medtronic Inc | MEDICAL DEVICE WITH A BIOLOGICAL ACTIVE SUBSTANCE |
CN100536935C (en) * | 2006-09-29 | 2009-09-09 | 清华大学 | Composite porous calcium phosphate bone cement and method for making same |
EP2529764A1 (en) * | 2011-05-31 | 2012-12-05 | Curasan AG | Biodegradable composite material |
CN102989042A (en) * | 2012-12-21 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Injectable porous bone cement and preparation method thereof |
CN106581747A (en) * | 2016-12-08 | 2017-04-26 | 山东明德生物医学工程有限公司 | Strontium-containing bone cement and preparation method |
-
2021
- 2021-08-20 CN CN202110962977.1A patent/CN113577369B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105131161B (en) * | 2015-09-09 | 2017-06-27 | 山东明德生物医学工程有限公司 | The preparation method of autography polymethacrylates and autography bone cement for bone cement |
CN110694099A (en) * | 2019-10-16 | 2020-01-17 | 中国人民解放军第四军医大学 | Mytilus edulis bionic adhesive based on polymalic acid and preparation method and application thereof |
CN112608457A (en) * | 2020-03-23 | 2021-04-06 | 杭州鹿扬科技有限公司 | Preparation method of poly citrate porous scaffold |
Also Published As
Publication number | Publication date |
---|---|
CN113577369A (en) | 2021-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5646849B2 (en) | Apatite-type calcium phosphate cement with macroporosity and high absorbency | |
Li et al. | Collagen-based implants reinforced by chitin fibres in a goat shank bone defect model | |
CN102488925A (en) | Injectable articular cartilage tissue repair material and its preparation method | |
CN110237301B (en) | Sodium alginate-based inducible bone repair gel and preparation method and application thereof | |
CN104591679A (en) | Modified magnesium oxychloride bone cement as well as preparation method and application thereof | |
Ding et al. | Calcium phosphate bone cement with enhanced physicochemical properties via in situ formation of an interpenetrating network | |
CN101530635B (en) | Bioactive bone-repairing cement material | |
EP3488876B1 (en) | Novel formula for synthesizing bone replacement material, and manufacturing method and application method thereof | |
CN114470320A (en) | Bone adhesive, preparation method and application thereof | |
CN113577369B (en) | Porous composite bone cement and preparation method thereof | |
CN102552985A (en) | Silk fibroin/calcium phosphate bone cement-based porous composite material and preparation method thereof | |
CN112190762B (en) | Injection type magnesium-based composite fiber reinforced calcium phosphate biological bone adhesive and preparation method and application thereof | |
Guo et al. | Bioprinting of light-crosslinkable neutral-dissolved collagen to build implantable connective tissue with programmable cellular orientation | |
WO2022048126A1 (en) | Orthopedic non-invasive implantation high-viscosity adhesive material, preparation method therefor, and application | |
KR101176793B1 (en) | Bone cement composition containing silk fibroin hydrolysates and polymethylmetacrylate | |
CN114601973B (en) | Sodium polyacrylate-containing anti-collapse calcium phosphate bone cement and preparation method thereof | |
CN113350573B (en) | Porous microsphere adhesive with osteoinductive capacity and preparation method thereof | |
CN113082296B (en) | Calcium phosphate bone cement with good injectability and preparation method thereof | |
CN105461941B (en) | A kind of preparation method of self-curing high intensity macromolecular glue | |
CN110665056B (en) | Injectable bone cement with tissue self-bonding performance and preparation method and application thereof | |
CN113880474A (en) | High-strength injectable magnesium phosphate bone cement and preparation method thereof | |
CN107412874B (en) | Injectable calcium sulfate hemihydrate/octacalcium phosphate/sodium hyaluronate sulfate composite artificial bone material and preparation method thereof | |
CN110935062B (en) | Preparation method of vertebral body filling material | |
CN113527528A (en) | Sulfated gellan gum, anti-collapsibility calcium sulfate hemihydrate bone cement with anti-inflammatory and bone-promoting effects, and preparation method and application thereof | |
TWI445761B (en) | Biodegradable-bioresorbable composite and preparing method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |