CN110201238A - A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material and its application - Google Patents
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material and its application Download PDFInfo
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- CN110201238A CN110201238A CN201910530087.6A CN201910530087A CN110201238A CN 110201238 A CN110201238 A CN 110201238A CN 201910530087 A CN201910530087 A CN 201910530087A CN 110201238 A CN110201238 A CN 110201238A
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- polylactic acid
- calcium citrate
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- 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
- A61L2430/38—Materials or treatment for tissue regeneration for reconstruction of the spine, vertebrae or intervertebral discs
Abstract
The invention belongs to bone injuries to repair field of medical materials, and in particular to a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material and its application.Since calcium citrate and macromolecule have good compatibility, evenly dispersed composite material can be formed, and there is good mechanical property, the two recombination energy embodies good biocompatibility simultaneously, biodegradable, and in degradation process, provide a stabilization suitable calcium ion environment, local high calcium environment is created, to promote the growth of freshman bone tissue.A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material has good processability simultaneously, easy to process at size, shape needed for clinical application, can be used for being processed into and fixes required bone plate, bone screws, Invasive lumbar fusion device etc. in orthopaedics.A kind of calcium citrate/polylactic acid and caprolactone bone renovating material prepared by the present invention, can regulate and control the degradation speed of composite material by adjusting the ratio of polylactic acid and caprolactone, repair needs to meet the bone injury of different healing times.
Description
Technical field
The present invention relates to a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material and its applications, belong to bone injury and repair
Multiple biomedical materials field.
Background technique
With the development of science and technology medical level is being continuously improved, medical material is more and more widely paid attention to, wherein
The research emphasis repaired using artificial bone substitute materials, substitute bone defect as Medical orthopaedic field, and treatment is due to tight
Inflict heavy losses on the effective means of the orthopaedic diseases such as wound, birth defect, bone tumour, osteomyelitis.Ideal bone renovating material should have well
Matrix adaptability, that is, biocompatibility, there is suitable mechanical property, while there is good self-bone grafting, conductive performance, energy
Promote the growth of freshman bone tissue, the formation of induced osteogenesis cell will also have good processability, easy to process at required
Size, shape.
Polylactic acid (PLA) and polycaprolactone (PCL) be U.S. Food and Drug Administration (FDA) approval can be used for facing
The polyester-based polymer polymer of bed.Since polylactic acid and polycaprolactone all have good biodegrade and biocompatibility,
It has been widely used in Bone Defect Repari field.Wherein, polycaprolactone has special carbon-chain structure and good rheological property, has good
Good toughness and processability, degradation cycle reach 1 year or more, and degradation speed is somewhat slower than the new bone growth period.And polylactic acid
Degradation cycle be about 6 ~ 8 weeks, compared with can match with skeleton growth cycle, but the disadvantages of the brittleness and low tenacity of polylactic acid
But it limits its application.Based on the complementarity in polylactic acid and polycaprolactone mechanical property and the otherness on degradation cycle,
Research, which finds for the two to be blended, is capable of providing the optimal mechanical performance of material, and can adjust blending macromolecule to a certain extent
The degradation speed of composite material makes it match with partes corporis humani position bone repair growth cycle, to expand its application range.Poplar
(Yang Jingze, Hu Shan, Gao Huliang the polylactic acid/gather oneself in the performance study of polylactic acid and caprolactone intermingling material such as Jing Ze
Performance study [J] engineering plastics application of interior ester blend material, 2013,41 (5): 26-28.), using melt blending
Method is prepared for polylactic acid (PLA)/polycaprolactone (PCL) intermingling material, has studied the dynamic force of PLA/PCL intermingling material
Performance, mechanical property, hot property and microscopic appearance are learned, PLA/PCL intermingling material can overcome homogenous material mechanics as the result is shown
Defect in performance.But the intermingling material lacks calcium salt component, and cellular affinity is bad, and without osteoacusis and induction ostosis
The effects of.Illustrate that macromolecule polymer material, there is also cellular affinity is poor, bone-inducting active and osteoacusis is used alone
The defects of property is poor, cannot be advantageously applied in practical Bone Defect Repari field.
Therefore also usually the high molecular polymer bone renovating material compound with inorganic calcium salt is used to control in practical applications
Treat bone injury.One side polymer material can provide good mechanical property support bone growth as host material, together
When can regulate and control whole degradation rate by adjusting polymer, another aspect calcium salt component is as knitting initial stage calcium ion
Source is provided, there is good self-bone grafting and bone conduction effect, can induce the growth and regeneration of new bone tissue.
Nowadays there are hydroxyapatite, tricalcium phosphate etc. for the calcium salt component compound with polymer using more.So
And hydroxylapatite biology degradability is poor, and brittleness is big, part offer calcium ion concentration is inadequate, cannot guide new bone raw well
At the problems such as limit it in the application of biomedical materials field.In addition, hydroxyapatite, tricalcium phosphate etc. belong to inorganic calcium
Salt component, surface hydrophilic and hate oil, this characteristic with polymer substrate is on the contrary, this species diversity easily causes particle and polymer
Interface compatibility it is poor, lead to that combination interface is unstable, particle dispersing uniformity difference and easy to reunite.Such problem and not
Foot just needs to study new direction, provides new idea and method to further realize clinical treatment application.
Calcium citrate is a kind of organic calcium salt, and the calcium ion concentration of saturated solution is 5.14mmol/L, with can conducive at
The calcium ion concentration of bone cell proliferation differentiation is adapted, and is a kind of material that preferably can be used for Bone Defect Repari.Calcium citrate can be
Degrade and be absorbed in vivo, and the change human body fluid pH value that is not obvious in absorption process of degrading, degradation process discharge calcium from
Son is also very steady efficient, is conducive to effective absorb.Logical control synthesizing citric acid calcium (Chinese patent before this seminar
201410061265.2；201410612150.8；201410612039.9；201410612989.1), make the form of calcium citrate
Feature and degradation characteristic are regulated, and convenient for compound to be applied in Bone Defect Repari field, and have been applied in inorganic system
It embodies.For example, Li et al. is in Preparation and properties of calcium citrate nanosheets for
bone graft substitute (Li J, Liu Y, Gao Y, et al. Preparation and properties
of calcium citrate nanosheets for bone graft substitute [J]. Bioengineered,
2016,7 (5): 376-381.) in propose a kind of method synthesis nano sheet calcium citrate easily and effectively, and study
Application of the calcium citrate as bone renovating material.Subsequent cell and animal experiments show that, calcium citrate can promote newly
The formation of bone.Chinese invention 201511008235.6 provides a kind of bone cement and preparation method thereof containing calcium citrate, the hair
The bone cement containing calcium citrate of bright offer has good bone guided and bone-inducting active, but there are still certain defect, than
If mechanical property is poor, forming ability is limited etc..
By being studied above it was found that working as calcium citrate separately as bone renovating material application, degradation speed is too fast, long
Phase curative effect is not significant etc., and the problem of can not avoiding, is not well solved yet at present.In addition, calcium citrate and inorganic system are multiple
Close that there is also poor mechanical properties, and the problems such as can not match with internal degradation speed.
The present invention carries out melt blending using polylactic acid and polycaprolactone and calcium citrate, prepares a kind of calcium citrate/poly-
Caprolactone/polylactic acid bone renovating material.On the one hand, based on the complementarity in polylactic acid and polycaprolactone mechanical property, and drop
The otherness on the period is solved, the present invention obtains that the optimal mechanical performance of polymer composite is blended using melt blending,
And high molecular ratio can be blended to a certain extent to regulate and control the degradation speed of composite material, make itself and human body
Different parts bone repair growth cycle matches, to expand its application range.On the other hand, since calcium citrate is organic calcium
Salt has a good compatibility with high molecular material, is different from tricalcium phosphate or hydroxyapatite and macromolecule compatibility not
The situations such as good, can evenly dispersed be blended prepares composite material without modification with macromolecule, embody good
Interface affinity has excellent mechanical performances and moulding processability, while based on the coordination degradation that macromolecule matrix is blended, can
It can not be reached an agreement with the new bone formation time with solving the problem of that common citric acid calcium powder degradation is too fast.
The present invention provides a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material as a result,.Due to calcium citrate and
Macromolecule has good compatibility, can form evenly dispersed composite material, and have good mechanical property, while the two
Recombination energy embodies good biocompatibility, biodegradable, and in degradation process, provides what a stabilization was suitable for
Calcium ion environment creates local high calcium environment, to promote the growth of freshman bone tissue.The lemon prepared simultaneously by melt-blending process
Lemon acid calcium/polylactic acid and caprolactone bone renovating material has good processability, easy to process at needed for clinical application
Size, shape can be used for being processed into and fix required bone plate, bone screws, Invasive lumbar fusion device etc. in orthopaedics.Lemon prepared by the present invention
Lemon acid calcium/polycaprolactone/polylactic acid bone renovating material can also be regulated and controled multiple by adjusting polycaprolactone/polylactic acid ratio
The degradation speed of condensation material repairs needs to meet the bone injury of different healing times.
Summary of the invention
The present invention is directed to the deficiency of existing bone defect healing field composite material, provide a kind of calcium citrate/polycaprolactone/
Polylactic acid bone renovating material.The composite material is made of calcium citrate, polylactic acid and polycaprolactone, and calcium citrate is four hydration lemons
Lemon acid calcium, polylactic acid molecule amount are 10 ~ 200,000, and polycaprolactone molecular weight is 3 ~ 80,000.Calcium citrate/polycaprolactone/polylactic acid bone
By percentage to the quality, calcium citrate content is 1 ~ 30% to repair materials, and polycaprolactone accounts for 1 ~ 36%, and polylactic acid accounts for 49 ~ 89%.It draws
Stretching intensity is 11 ~ 18Mpa, and elasticity modulus is 302 ~ 605MPa, and contact angle is 56 ~ 75 °.
A kind of preparation method of calcium citrate/polycaprolactone/polylactic acid bone renovating material of the present invention, specific steps
It is as follows:
(1) polylactic acid, polycaprolactone and the calcium citrate of corresponding proportion are weighed with electronic balance；
(2) load weighted polylactic acid, polycaprolactone and calcium citrate are subjected to melt blending, melt blending at 150 ~ 180 DEG C
Including by polylactic acid, polycaprolactone and the common melt blending of calcium citrate, or polylactic acid, polycaprolactone are first melt into fluidised form again
Calcium citrate is added to be blended；
(3) by stirring to get finely dispersed mixture；Speed of agitator is 100 ~ 300r/min；
(4) it injects the mixture into mold, obtains a kind of calcium citrate/polycaprolactone/polylactic acid bone after naturally cool to room temperature
Repair materials.
The invention has the benefit that
The present invention provides a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material, which can solve inorganic
Calcium salt and the problem that macromolecule compatibility is not good enough and degradation is slower, it is too fast or single also to can solve the degradation of calcium citrate powder
The degradation of pure polylactic acid is too fast, simple poly-caprolactone degradation is excessively slow and the problem of can not reach an agreement with the new bone formation time, provide
The microenvironment of bone tissue reparation preferably.Since there is good compatibility the two to be made not have to be modified i.e. for calcium citrate and macromolecule
It can be well mixed to form evenly dispersed composite material, and there is good mechanical property and moulding processability, while the two
Recombination energy embodies good biocompatibility, and provides a stabilization with material degradation within the long period of Bone Defect Repari and fit
Suitable calcium ion environment creates local high calcium environment, shows self-bone grafting and osteoconductive energy.
Therefore, the present invention provides a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material.Due to calcium citrate and
Macromolecule has good compatibility, can form evenly dispersed composite material, and have good mechanical property, while the two
Recombination energy embodies good biocompatibility, biodegradable, and in degradation process, provides what a stabilization was suitable for
Calcium ion environment creates local high calcium environment to promote the growth of freshman bone tissue and shows good osteoacusis and self-bone grafting
Performance.There is good molding by calcium citrate/polylactic acid and caprolactone bone renovating material prepared by melt-blending process simultaneously
Performance, it is easy to process at size, shape needed for clinical application, it can be used for being processed into and fix required bone plate, bone in orthopaedics
Screw, Invasive lumbar fusion device etc..Calcium citrate prepared by the present invention/polylactic acid and caprolactone bone renovating material, can pass through adjusting
Polycaprolactone/polylactic acid ratio regulates and controls the degradation speed of composite material, is repaired with meeting the bone injury of different healing times
It is multiple to need.
Detailed description of the invention:
Fig. 1 is 1 calcium citrate of the embodiment of the present invention/polycaprolactone/polylactic acid bone renovating material XRD diagram；
Fig. 2 is 1 calcium citrate of the embodiment of the present invention/polycaprolactone/polylactic acid bone renovating material SEM figure；
Fig. 3 is 1 calcium citrate of the embodiment of the present invention/polycaprolactone/polylactic acid bone renovating material after biomineralization is tested 7 days
SEM figure；
Fig. 4 is that calcium citrate/polycaprolactone/polylactic acid bone renovating material of the embodiment of the present invention 1 ~ 3 is immersed in the PBS of pH=7.4
Degradation situation map in phosphate buffer solution；
Fig. 5 is the embodiment of the present invention 1, calcium citrate/polycaprolactone/polylactic acid bone renovating material of example 4, example 5, example 6 is immersed in
Degradation situation map in the PBS phosphate buffer solution of pH=7.4.
Fig. 6 is calcium citrate/polycaprolactone/polylactic acid bone renovating material contact angle photo of the embodiment of the present invention 6.
Specific embodiment:
Below in conjunction with specific embodiment, invention is further described in detail, but protection scope of the present invention is not limited to
The content.
Embodiment 1:
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material provided in this embodiment by calcium citrate, polycaprolactone and
Polylactic acid composition, by percentage to the quality, the content of calcium citrate are 10%, polycaprolactone content 27%, and polylactic acid content is
63%.Calcium citrate contained by material is four citric acid monohydrate calcium, and the molecular weight of polylactic acid is 200,000, and polycaprolactone molecular weight is 8
Ten thousand.Specific steps are as follows:
(1) calcium citrate of 2.7 grams of polycaprolactones and 6.3 grams of polylactic acid with 1 gram is weighed with electronic balance.
(2) load weighted polycaprolactone, polylactic acid and calcium citrate are subjected at 180 DEG C melt blending, pass through stirring
Obtain finely dispersed mixture；Speed of agitator is 200r/min.
(3) it injects the mixture into mold, after room temperature, obtains calcium citrate/polycaprolactone/polylactic acid
Bone renovating material.
Fig. 1 is calcium citrate/polycaprolactone/polylactic acid bone renovating material XRD spectra in this example.
Fig. 2 is calcium citrate/polycaprolactone/polylactic acid bone renovating material SEM figure in embodiment.
Use omnipotent test machine for mechanism measure calcium citrate/polycaprolactone/polylactic acid bone renovating material tensile strength for
14.6897MPa elasticity modulus 513.3575MPa
A kind of water of calcium citrate/polycaprolactone/polylactic acid bone renovating material in this example is measured by contact angle measurement to connect
Feeler is 63.853 °.
A kind of calcium citrate/polycaprolactone/37 DEG C of polylactic acid bone renovating material constant temperature prepared by this example is soaked in
Biological mineralization experiments are carried out in SBF simulated body fluid, are sampled after 7 days and are observed again by scanning electron microscope.Fig. 3 is
For a kind of scanning electron microscopy of calcium citrate/polycaprolactone/polylactic acid bone renovating material after immersion SBF simulated body fluid 7 days
Mirror picture.
By a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material prepared in this example by be immersed in pH=
In 7.4 PBS phosphate buffer solution, the dry weight of a sample is measured every three days, observes a kind of calcium citrate in this example/poly-
Caprolactone/polylactic acid bone renovating material 28 days degradation situations in PBS phosphate buffer solution.
Embodiment 2:
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material provided in this embodiment by calcium citrate, polycaprolactone and
Polylactic acid composition, by percentage to the quality, the content of calcium citrate are 1%, polycaprolactone content 29.7%, and polylactic acid content is
69.3%.Calcium citrate contained by material is four citric acid monohydrate calcium, and the molecular weight of polylactic acid is 200,000, and polycaprolactone molecular weight is 8
Ten thousand.Concrete operations are as follows:
(1) calcium citrate of 2.97 grams of polycaprolactones and 6.93 grams of polylactic acid with 0.1 gram is weighed with electronic balance.
(2) load weighted polycaprolactone, polylactic acid and calcium citrate are subjected at 180 DEG C melt blending, pass through stirring
Obtain finely dispersed mixture；Speed of agitator is 200r/min.
(3) it injects the mixture into mold, after room temperature, obtains calcium citrate/polycaprolactone/poly- cream
Sour bone renovating material.
Use omnipotent test machine for mechanism measure calcium citrate/polycaprolactone/polylactic acid bone renovating material tensile strength for
11.3672MPa elasticity modulus 302.5528MPa.
A kind of calcium citrate/polycaprolactone/polylactic acid the Bone Defect Repari prepared in this example is measured by contact angle measurement
The water contact angle of material is 72.396 °.
This example is identical as the blending macromolecule ratio of example 1, and difference is that the content of the calcium citrate of this example is 1%.
Embodiment 3:
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material provided in this embodiment by calcium citrate, polycaprolactone and
Polylactic acid composition, by percentage to the quality, the content of calcium citrate are 30%, polycaprolactone content 21%, and polylactic acid content is
49%.Calcium citrate contained by material is four citric acid monohydrate calcium, and the molecular weight of polylactic acid is 200,000, and polycaprolactone molecular weight is 8
Ten thousand.Specific steps are as follows:
(1) calcium citrate of 2.1 grams of polycaprolactones and 4.9 grams of polylactic acid with 3 grams is weighed with electronic balance.
(2) load weighted polycaprolactone, polylactic acid and calcium citrate are subjected at 180 DEG C melt blending, pass through stirring
Obtain finely dispersed mixture；Speed of agitator is 300r/min.
(3) inject the mixture into mold, after room temperature, obtain a kind of calcium citrate/polycaprolactone/
Polylactic acid bone renovating material.
A kind of calcium citrate/polycaprolactone/polylactic acid bone that this example is prepared is measured using omnipotent test machine for mechanism to repair
The tensile strength of multiple material is 12.78MPa, elasticity modulus 663.942MPa.
A kind of calcium citrate/polycaprolactone/polylactic acid the Bone Defect Repari prepared in this example is measured by contact angle measurement
The water contact angle of material is 57.052 °.
This example is identical as the blending macromolecule ratio of example 1, and difference is that the content of the calcium citrate of this example is
30%。
Embodiment 4:
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material provided in this embodiment is by calcium citrate, polylactic acid and gathers
Caprolactone composition, by percentage to the quality, the content 10% of calcium citrate, polycaprolactone content 1%, polylactic acid content is 89%.
Calcium citrate contained by material is four citric acid monohydrate calcium, and the molecular weight of polylactic acid is 200,000, and polycaprolactone molecular weight is 80,000.
(1) 8.9 grams of polylactic acid, 0.1 gram of polycaprolactone and 1 gram of calcium citrate are weighed with electronic balance.
(2) load weighted polylactic acid and calcium citrate are subjected to melt blending at 180 DEG C, it is equal by stirring to get dispersion
Even mixture；Speed of agitator is 100r/min.
(3) mixture is placed in template, after being cooled to room temperature, prepares a kind of calcium citrate/polycaprolactone/polylactic acid
Bone renovating material.
A kind of calcium citrate/polycaprolactone/polylactic acid bone that this example is prepared is measured using omnipotent test machine for mechanism to repair
The tensile strength of multiple material is 17.625MPa, elasticity modulus 461.386MPa.
A kind of calcium citrate/polycaprolactone/polylactic acid the Bone Defect Repari prepared in this example is measured by contact angle measurement
The water contact angle of material is 70.661 °.
This example is identical as the calcium citrate content ratio of example 1, and difference is, the blending macromolecule ratio of example 1 is
Polycaprolactone/polylactic acid is 3:7, and it is 0:1 that the blending macromolecule ratio of this example, which is polycaprolactone/polylactic acid,.
Embodiment 5:
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material provided in this embodiment by calcium citrate, polycaprolactone and
Polylactic acid composition, by percentage to the quality, the content of calcium citrate are 10%, polycaprolactone content 18%, and polylactic acid content is
72%.Calcium citrate contained by material is four citric acid monohydrate calcium, and the molecular weight of polylactic acid is 200,000, and polycaprolactone molecular weight is 8
Ten thousand.
(1) calcium citrate of 1.8 grams of polycaprolactone and 7.2 grams of polylactic acid with 1 gram is weighed with electronic balance.
(2) load weighted polycaprolactone, polylactic acid and calcium citrate are subjected at 180 DEG C melt blending, pass through stirring
Obtain finely dispersed mixture；Speed of agitator is 200r/min.
(3) mixture is placed in template, after being cooled to room temperature, prepares a kind of calcium citrate/polycaprolactone/polylactic acid
Bone renovating material.
A kind of calcium citrate/polycaprolactone/polylactic acid bone that this example is prepared is measured using omnipotent test machine for mechanism to repair
The tensile strength of multiple material is 14.0692MPa, elasticity modulus 460.5806MPa.
A kind of calcium citrate/polycaprolactone/polylactic acid the Bone Defect Repari prepared in this example is measured by contact angle measurement
The water contact angle of material is 69.360 °.
This example is identical as the calcium citrate content ratio of example 1, and difference is, the blending macromolecule ratio of example 1 is
Polycaprolactone/polylactic acid is 3:7, and it is 2:8 that the blending macromolecule ratio of this example, which is polycaprolactone/polylactic acid,.
Embodiment 6:
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material provided in this embodiment by calcium citrate, polycaprolactone and
Polylactic acid composition, by percentage to the quality, the content of calcium citrate are 10%, polycaprolactone content 36%, polylactic acid content
54%.Calcium citrate contained by material is four citric acid monohydrate calcium, and the molecular weight of polylactic acid is 200,000, and polycaprolactone molecular weight is 8
Ten thousand.
(1) calcium citrate of 3.6 grams of polycaprolactones and 5.4 grams of polylactic acid with 1 gram is weighed with electronic balance.
(2) load weighted polycaprolactone, polylactic acid and calcium citrate are subjected at 180 DEG C melt blending, pass through stirring
Obtain finely dispersed mixture；Speed of agitator is 200r/min.
(3) mixture is placed in template, after being cooled to room temperature, prepares a kind of calcium citrate/polycaprolactone/polylactic acid
Bone renovating material.
A kind of calcium citrate/polycaprolactone/polylactic acid bone that this example is prepared is measured using omnipotent test machine for mechanism to repair
The tensile strength of multiple material is 11.418MPa, elasticity modulus 418.3128MPa.
A kind of calcium citrate/polycaprolactone/polylactic acid the Bone Defect Repari prepared in this example is measured by contact angle measurement
The water contact angle of material is 56.757 °.Fig. 6 is calcium citrate/polycaprolactone/polylactic acid Bone Defect Repari material of the embodiment of the present invention
The contact angle photo of material.
This example is identical as the calcium citrate content ratio of example 1, and difference is, the blending macromolecule ratio of example 1 is
Polycaprolactone/polylactic acid is 3:7, and it is 4:6 that the blending macromolecule ratio of this example, which is polycaprolactone/polylactic acid,.
Embodiment 7:
A kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material provided in this embodiment by calcium citrate, polycaprolactone and
Polylactic acid composition, by percentage to the quality, the content of calcium citrate are 10%, polycaprolactone content 27%, and polylactic acid content is
63%.Calcium citrate contained by material is four citric acid monohydrate calcium, and the molecular weight of polylactic acid is 100,000, and polycaprolactone molecular weight is 3
Ten thousand.
(1) calcium citrate of 2.7 grams of polycaprolactones and 6.3 grams of polylactic acid with 1 gram is weighed with electronic balance.
(2) load weighted polylactic acid and calcium citrate are subjected to melt blending at 150 DEG C, it is equal by stirring to get dispersion
Even mixture；Speed of agitator is 200r/min.
(3) mixture is placed in template, after being cooled to room temperature, prepares calcium citrate/polycaprolactone/polylactic acid bone and repair
Multiple material.
Calcium citrate/polycaprolactone/polylactic acid bone renovating material the tensile strength measured using omnipotent test machine for mechanism
For 13.857MPa, elasticity modulus 502.194Mpa.Calcium citrate in this example/gather in oneself is measured by contact angle measurement
Ester/polylactic acid bone renovating material water contact angle is 63.310 °.
By a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material prepared in this example by be immersed in pH=
In 7.4 PBS phosphate buffer solution, the dry weight of a sample is measured every three days, observes a kind of calcium citrate in this example/poly-
The degradation situation of caprolactone/polylactic acid bone renovating material 28d in PBS phosphate buffer solution.
The difference of this example and example 1 is that 1 polylactic acid molecule amount of example is 200,000, and polycaprolactone molecular weight is 80,000,
This example polylactic acid molecule amount is 100,000, and polycaprolactone molecular weight is 30,000.A kind of calcium citrate prepared by this example/gather in oneself
Ester/polylactic acid bone renovating material about reaches 26.854% in 28 days weight-loss ratios.It can see polylactic acid by situation of degrading and gather oneself
The difference of lactone molecule amount will lead to composite degradation speed difference.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (10)
1. a kind of calcium citrate/polycaprolactone/polylactic acid bone renovating material, it is characterised in that: the material is by melt blending legal system
It is standby to obtain, it is made of calcium citrate, polylactic acid and polycaprolactone, by percentage to the quality, calcium citrate content is 1 ~ 30%, is gathered
Caprolactone accounts for 1 ~ 36%, and polylactic acid accounts for 49 ~ 89%.
2. calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, it is characterised in that: contained lemon
Lemon acid calcium is four water citric acid calcium.
3. calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, it is characterised in that: contained
Polylactic acid molecule amount is 10 ~ 200,000.
4. calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, it is characterised in that: contained
Polycaprolactone molecular weight is 3 ~ 80,000.
5. calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, it is characterised in that: it is stretched
Intensity is 11 ~ 18Mpa.
6. calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, it is characterised in that: its elasticity
Modulus is 302 ~ 663MPa.
7. calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, it is characterised in that: it is contacted
Angle is 56 ~ 73 °.
8. the preparation method of calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, feature
It is: the following steps are included:
(1) polylactic acid, polycaprolactone and the calcium citrate of corresponding proportion are weighed with electronic balance；
(2) load weighted polylactic acid, polycaprolactone and calcium citrate are subjected to melt blending, melt blending at 150 ~ 180 DEG C
Including by polylactic acid, polycaprolactone and the common melt blending of calcium citrate, or polylactic acid, polycaprolactone are first melt into fluidised form again
Calcium citrate is added to be blended；
(3) by stirring to get finely dispersed mixture；Speed of agitator is 100 ~ 300r/min；
(4) inject the mixture into mold, after naturally cool to room temperature obtain melt-blending process preparation a kind of calcium citrate/
Polycaprolactone/polylactic acid bone renovating material.
9. the preparation method of calcium citrate/polycaprolactone/polylactic acid bone renovating material according to claim 1, feature
Be: melt blending includes that macromolecule and the common melt blending of calcium citrate will be blended, or macromolecule will first be blended and be melt into stream
State adds calcium citrate and is blended.
10. calcium citrate/polycaprolactone/polylactic acid the bone renovating material according to claim 1 ~ 7, as what is fixed in orthopaedics
Using can be applied to be processed into and fix the purposes such as required bone plate, bone screws, Invasive lumbar fusion device in orthopaedics.
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