CN107670103A - The bone cement and preparation method that polyethylene pyrrole network alkanone is modified - Google Patents

The bone cement and preparation method that polyethylene pyrrole network alkanone is modified Download PDF

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Publication number
CN107670103A
CN107670103A CN201710835020.4A CN201710835020A CN107670103A CN 107670103 A CN107670103 A CN 107670103A CN 201710835020 A CN201710835020 A CN 201710835020A CN 107670103 A CN107670103 A CN 107670103A
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bone cement
liquid
polyethylene pyrrole
pyrrole network
bone
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CN201710835020.4A
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Chinese (zh)
Inventor
成艳琪
李朝阳
梁砚琴
朱胜利
崔振铎
杨贤金
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Tianjin University
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Tianjin University
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Publication of CN107670103A publication Critical patent/CN107670103A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/16Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/025Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/06Flowable or injectable implant compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The bone cement and preparation method being modified the present invention relates to polyethylene pyrrole network alkanone, including pulvis and solidify liquid:Pulvis is half-H 2 O calcium sulphate, and solidify liquid is the polyethylene pyrrole network alkanone aqueous solution, and concentration is 0.1%~5%, and liquid-solid ratio is 0.4~0.6ml/g.Prepare the polyethylene pyrrole network alkanone solidify liquid that concentration is 0.1%~5%;Then the mixing of half-H 2 O calcium sulphate pulvis is added according to liquid-solid ratio, stirred, cold curing forms injectable type bone cement.Because polyethylene pyrrole network alkanone is a kind of high molecular polymer for being highly soluble in water, its is odorless, tasteless, almost non-toxic, and has good biocompatibility and stronger associativity.Bone cement in the present invention also has good biocompatibility and degradability, can be used in the filling and reparation of various Cranial defects.Applied to organizational project and field of medicaments.

Description

The bone cement and preparation method that polyethylene pyrrole network alkanone is modified
Technical field
The present invention relates to a kind of injectable type bone cement and preparation method for human body hard tissue reparation, particularly poly- second The bone cement and preparation method that alkene pyrrole network alkanone is modified;It is mainly used in the fields such as bio-medical material.
Background technology
Because contingency, wound or disease can cause bone damage or Cranial defect, traditional surgical operation not only hold high by expense It is expensive, but also pain can be brought to patient.For a long time, in order to seek preferable bone grafting material, many scientific research personnel are unremitting Effort.At present, bone grafting material is broadly divided into three major types:Autologous bone bone grafting material, allograph bone bone grafting material and people Work bone bone grafting material.Although autologous bone can cause due to its limited amount and to itself secondary wound without immunological rejection Evil the shortcomings of and it is restricted in clinical practice;Although allograph bone quantity is more compared with autologous bone, because it there may be Immunological rejection, donor may have the limitation of virus and social morality ethics problem etc., so allograph bone is nor bone grafting material Be preferably selected.In order to solve the problems, such as both the above bone grafting material, in order to obtain preferable bone grafting material, then, section The workers of grinding begin one's study artificial bone.
Bone cement is the bone alternate material of a new generation, in fixation of the filling of Cranial defect, bone collection and bone grafting material etc. Aspect has a wide range of applications.Bioactive bone cement is made up of solid phase and liquid phase two parts, and solid liquid phase is according to certain ratio Can be formed after mixing with can self-curing slurry, the slurry has any formability thereof.Calcium sulfate bone cement (CSC) is repaiied as bone Existing more than the 100 years history of multiple material, because its can self solidified in situ, there is syringeability and osteoinductive, and can drop completely The shortcomings of the advantages that solution becomes good bone renovating material, but its bioactivity is low, degradation rate is fast constrains its again Development and clinical practice.Therefore, calcium sulfate bone cement is improved so that it is more widely used is repaiied as bone One of emphasis of multiple Material Field research.
Half-H 2 O calcium sulphate has the hydraulicity, run into after the aqueous solution can self solidified in situ be high intensity calcium sulphate dihydrate, two H 2 O calcium sulphate can promote Gegenbaur's cell to adhere to, and promote skeletonization, while osteoclast can absorb calcium sulfate, achieve biology Degraded.But in clinical practice, because the degradation rate of calcium sulfate is faster than the speed of New born formation, easily cause operative failure.
Polyethylene pyrrole network alkanone (polyvinylpyrrolidone, PVP) is a kind of high molecular polymerization for being highly soluble in water Thing, its is odorless, tasteless, almost non-toxic, and has good biocompatibility and stronger associativity.Good biocompatibility PVP is set to be received much concern in medicine and technical field of biological material, stronger associativity enables PVP to be combined well with other materials, So that it has a wide range of applications.
Because the synthetic bone graft prepared by single material typically can all have intensity deficiency, degradation rate and new bone again The shortcomings of raw speed is not consistent, therefore, the bone that the material of other Safe beneficials is prepared according to certain ratio combination is moved Plant material material, it can be learnt from other's strong points to offset one's weaknesses, it is a kind of preferably artificial so as to obtain so as to improve the physics and chemistry of material and biology performance Bone renovating material.
The content of the invention
The bone cement and preparation method being modified it is an object of the invention to provide a kind of new polyethylene pyrrole network alkanone, lead to Crossing bone cement material made from this method has strong stronger anti-collapsibility, preferable syringeability and higher pressure resistance Degree, while also there is good biocompatibility and biodegradability.
The bone cement that a kind of new polyethylene pyrrole network alkanone that the present invention uses is modified, including pulvis and solidify liquid:Its Middle pulvis is half-H 2 O calcium sulphate, and solidify liquid is polyethylene pyrrole network alkanone (PVP) aqueous solution, and concentration is 0.1%~5%, liquid-solid ratio For 0.4~0.6ml/g.
The preparation method for the bone cement that the polyethylene pyrrole network alkanone of the present invention is modified, comprises the following steps:
(1) polyethylene pyrrole network alkanone (PVP) solidify liquid that concentration is 0.1%~5% is proportionally prepared;
(2) mixing of half-H 2 O calcium sulphate pulvis is added according to liquid-solid ratio, be uniformly mixed, cold curing forms injectable type Bone cement.
Described half-H 2 O calcium sulphate is the half-H 2 O calcium sulphates of α mono-.
In the present invention, half-H 2 O calcium sulphate is mixed according to certain liquid-solid ratio with the polyethylene pyrrole network alkanone aqueous solution, solidified, Prepare a kind of new injectable type bone cement.Polyethylene pyrrole network alkanone is a kind of high molecular polymer for being highly soluble in water, Its is odorless, tasteless, almost non-toxic, and has good biocompatibility and stronger associativity.Good biocompatibility makes PVP receives much concern in medicine and technical field of biological material, and stronger associativity enables PVP to be combined well with other materials, institute The mechanical property of bone cement can be improved with the addition of polyethylene pyrrole network alkanone.Meanwhile the bone cement in the present invention is also with good Good biocompatibility and degradability, can be used in the filling and reparation of various Cranial defects.Applied to organizational project and medicine Field.
Brief description of the drawings
Fig. 1:Injectable time diagram after injectable type bone cement material solidification.
Fig. 2:The result figure of compression strength is tested after injectable type bone cement material solidification.
Fig. 3:XRD spectrum after injectable type bone cement material solidification.
Fig. 4:The SEM figures of injectable type bone cement material.
Embodiment
Present disclosure is described in further detail with reference to embodiment:
Embodiment 1:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the polyethylene pyrrole network alkanone that the concentration for measuring 2.5mL is 0.1% is water-soluble Liquid, it is according to the ratio mixing 0.5min that liquid-solid ratio is 0.5mL/g, injectable time by the liquid phase aqueous solution and solid phase powder 4.1min or so, as shown in Figure 1.Intensity test is carried out to bone cement sample after solidification, intensity test sample is Cylindric (Φ 6mm × 12mm), compression strength average value are 15.15Mpa, as shown in Figure 2, and human body cancellous bone compression strength Generally 5~10Mpa, so meeting the requirement of practical application.
Embodiment 2:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the polyethylene pyrrole network alkanone that the concentration for measuring 2.5mL is 0.5% is water-soluble Liquid, it is according to the ratio mixing 0.5min that liquid-solid ratio is 0.5mL/g, injectable time by the liquid phase aqueous solution and solid phase powder 4.5min or so, as shown in Figure 1.Bone cement sample carries out intensity test, pressure resistance after solidifying according to embodiment 1 to it Degree average value is 15.64Mpa, and as shown in Figure 2, and human body cancellous bone compression strength is generally 5~10Mpa, so meeting reality The requirement of border application.By the bone cement grind into powder after solidification, material phase analysis is then carried out to it by XRD, such as the institute of accompanying drawing 3 Show, the bone cement main component after solidification is calcium sulphate dihydrate, illustrates that half-H 2 O calcium sulphate quickly becomes two water sulphur in solidification process Sour calcium.Research shows that calcium sulphate dihydrate can promote Gegenbaur's cell to adhere to, and promotes skeletonization, while osteoclast can absorb sulphur Sour calcium, achieves biodegradation.
Embodiment 3:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 2.5mL is the 1% polyethylene pyrrole network alkanone aqueous solution, It is according to the ratio mixing 0.5min that liquid-solid ratio is 0.5mL/g, injectable time by the liquid phase aqueous solution and solid phase powder 4.0min or so, as shown in Figure 1.Bone cement sample carries out intensity test, pressure resistance after solidifying according to embodiment 1 to it Degree average value is 16.43Mpa, and as shown in Figure 2, and human body cancellous bone compression strength is generally 5~10Mpa, so meeting reality The requirement of border application.By the bone cement grind into powder after solidification, material phase analysis is then carried out to it by XRD, such as the institute of accompanying drawing 3 Show, the bone cement main component after solidification is calcium sulphate dihydrate, illustrates that half-H 2 O calcium sulphate quickly becomes two water sulphur in solidification process Sour calcium.Then SEM signs are carried out to the powder, as shown in Figure 4, the bone cement after solidification is in the form of a column distribution.
Embodiment 4:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 2.5mL is the 3% polyethylene pyrrole network alkanone aqueous solution, It is according to the ratio mixing 0.5min that liquid-solid ratio is 0.5mL/g, injectable time by the liquid phase aqueous solution and solid phase powder 4.03min or so, as shown in Figure 1.Bone cement sample carries out intensity test, resistance to compression after solidifying according to embodiment 1 to it Average strength is 18.34Mpa, and as shown in Figure 2, and human body cancellous bone compression strength is generally 5~10Mpa, so meeting The requirement of practical application.Characterized by XRD and SEM and carry out composition and morphology analysis, its main component is calcium sulphate dihydrate, in post Shape is distributed.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.When bone cement is used to be locally filled with, need straight The fluid flow blood at Cranial defect position is contacted, good anti-collapsibility makes it be not easy to be broken up, several so as to improve the success of operation Rate.
Embodiment 5:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 2.5mL is the 5% polyethylene pyrrole network alkanone aqueous solution, It is according to the ratio mixing 0.5min that liquid-solid ratio is 0.5mL/g, injectable time by the liquid phase aqueous solution and solid phase powder 3.56min or so, as shown in Figure 1.Bone cement sample carries out intensity test, resistance to compression after solidifying according to embodiment 1 to it Average strength is 19.01Mpa, and as shown in Figure 2, and human body cancellous bone compression strength is generally 5~10Mpa, so meeting The requirement of practical application.Characterized by XRD and SEM and carry out composition and morphology analysis, its main component is calcium sulphate dihydrate, in post Shape is distributed.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.
Embodiment 6:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, measure 2.5mL deionized water, by liquid phase water and solid phase powder according to The ratio that liquid-solid ratio is 0.5mL/g mixes 0.5min, and the injectable time is 3.81min or so.Bone cement after solidifying to it Sample carries out intensity test, and compression strength average value is 12.57Mpa, and human body cancellous bone compression strength be generally 5~ 10Mpa, so meeting the requirement of practical application.Characterizing progress composition and morphology analysis, its main component by XRD and SEM is Calcium sulphate dihydrate, it is in the form of a column distribution.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.
Embodiment 7:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 2mL is the 0.1% polyethylene pyrrole network alkanone aqueous solution, It is according to the ratio mixing 0.5min that liquid-solid ratio is 0.4mL/g, injectable time by the liquid phase aqueous solution and solid phase powder 4.2min left and right.Bone cement sample carries out intensity test after solidifying to it, and its compression strength is higher than human body cancellous bone resistance to compression The requirement of intensity (5~10Mpa).It is sulfate dihydrate to be characterized by XRD and SEM and carry out composition and morphology analysis, its main component Calcium, it is in the form of a column distribution.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.
Embodiment 8:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 2mL is the 3% polyethylene pyrrole network alkanone aqueous solution, will The liquid phase aqueous solution and solid phase powder are according to the ratio mixing 0.5min that liquid-solid ratio is 0.4mL/g, injectable time 3.9min left and right.Bone cement sample carries out intensity test after solidifying to it, and its compression strength is higher than human body cancellous bone resistance to compression The requirement of intensity (5~10Mpa).It is sulfate dihydrate to be characterized by XRD and SEM and carry out composition and morphology analysis, its main component Calcium, it is in the form of a column distribution.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.
Embodiment 9:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 2mL is the 5% polyethylene pyrrole network alkanone aqueous solution, will The liquid phase aqueous solution and solid phase powder are according to the ratio mixing 0.5min that liquid-solid ratio is 0.4mL/g, injectable time 3.8min left and right.Bone cement sample carries out intensity test after solidifying to it, and its compression strength is higher than human body cancellous bone resistance to compression The requirement of intensity (5~10Mpa).It is sulfate dihydrate to be characterized by XRD and SEM and carry out composition and morphology analysis, its main component Calcium, it is in the form of a column distribution.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.
Embodiment 10:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 3mL is the 0.1% polyethylene pyrrole network alkanone aqueous solution, It is according to the ratio mixing 0.5min that liquid-solid ratio is 0.6mL/g, injectable time by the liquid phase aqueous solution and solid phase powder 5.24min left and right.Bone cement sample carries out intensity test after solidifying to it, and its compression strength is higher than human body cancellous bone resistance to compression The requirement of intensity (5~10Mpa).It is sulfate dihydrate to be characterized by XRD and SEM and carry out composition and morphology analysis, its main component Calcium, it is in the form of a column distribution.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.
Embodiment 11:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 3mL is the 3% polyethylene pyrrole network alkanone aqueous solution, will The liquid phase aqueous solution and solid phase powder are according to the ratio mixing 0.5min that liquid-solid ratio is 0.6mL/g, injectable time 4.42min left and right.Bone cement sample carries out intensity test after solidifying to it, and its compression strength is higher than human body cancellous bone resistance to compression The requirement of intensity (5~10Mpa).It is sulfate dihydrate to be characterized by XRD and SEM and carry out composition and morphology analysis, its main component Calcium, it is in the form of a column distribution.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.
Embodiment 12:
At room temperature, 5g half-H 2 O calcium sulphates are weighed, the concentration for measuring 3mL is the 5% polyethylene pyrrole network alkanone aqueous solution, will The liquid phase aqueous solution and solid phase powder are according to the ratio mixing 0.5min that liquid-solid ratio is 0.6mL/g, injectable time 4.13min left and right.Bone cement sample carries out intensity test after solidifying to it, and its compression strength is higher than human body cancellous bone resistance to compression The requirement of intensity (5~10Mpa).It is sulfate dihydrate to be characterized by XRD and SEM and carry out composition and morphology analysis, its main component Calcium, it is in the form of a column distribution.Bone cement is put into SBF solution after solidification and soaked, anti-collapsibility is good.

Claims (3)

1. a kind of injectable type bone cement and preparation method, including pulvis and solidify liquid:Wherein pulvis is half-H 2 O calcium sulphate, solidification Liquid is the polyethylene pyrrole network alkanone aqueous solution, and concentration is 0.1%~5%, and liquid-solid ratio is 0.4~0.6ml/g.
2. material as claimed in claim 1, it is characterized in that the polyethylene pyrrole network that it is 0.1%~5% that the solidify liquid, which is concentration, The alkanone aqueous solution.
3. the preparation method of injectable type bone cement material according to claim 1 or 2, comprises the following steps:
(1) the polyethylene pyrrole network alkanone solidify liquid that concentration is 0.1%~5% is proportionally prepared;
(2) mixing of half-H 2 O calcium sulphate pulvis is added according to liquid-solid ratio, be uniformly mixed, cold curing forms injectable type bone water Mud.
CN201710835020.4A 2017-09-15 2017-09-15 The bone cement and preparation method that polyethylene pyrrole network alkanone is modified Pending CN107670103A (en)

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Application publication date: 20180209