CN107376026B - Absorbable bio-medical composition and preparation method thereof - Google Patents
Absorbable bio-medical composition and preparation method thereof Download PDFInfo
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- CN107376026B CN107376026B CN201710578058.8A CN201710578058A CN107376026B CN 107376026 B CN107376026 B CN 107376026B CN 201710578058 A CN201710578058 A CN 201710578058A CN 107376026 B CN107376026 B CN 107376026B
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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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The present invention provides a kind of absorbable bio-medical composition and preparation methods.Wherein, which includes: base particle, and it includes calcium phosphorous compounds；Middle layer is coated on the surface of the base particle, and the middle layer has the first glass transition temperature, and first glass transition temperature is not higher than normal body temperature；And polymeric matrix, it is formed in the outer surface of the middle layer, the polymeric matrix has the second glass transition temperature, and second glass transition temperature is greater than first glass transition temperature.In accordance with the invention it is possible to provide a kind of absorbable bio-medical composition that can either improve mechanical strength and toughness is improved.
Description
Technical field
The invention belongs to bio-medical composition field, in particular to a kind of absorbable bio-medical composition and
Preparation method.
Background technique
Contain the ingredients such as water, organic matter (gelatine) and inorganic salts in skeleton, wherein the ingredient of inorganic salts is with calcium-phosphorus ratio
It closes based on object, with the formal distribution of crystalline hydroxy apatite and amorphous calcium phosphate in organic matter.It therefore, include calcium-phosphorus ratio
The inorganic salts of object, especially hydroxyapatite, calcium phosphate etc. are closed, it is similar with skeleton component of inorganic salts, there is excellent life
Object compatibility and bioactivity.Biodegradable polyesters material, such as polylactic acid, polycaprolactone, polyglycolide have good
Biological degradability, biocompatibility and mechanical property are common absorbable medical polymer materials, medical field apply compared with
It is extensive.Composite material is made in inorganic salts comprising calcium phosphorous compound and the combination of Bioabsorbable Polyesters material can be in conjunction with two
The advantages of kind material, has good biocompatibility, bioactivity and mechanical property when being used as bone fixation and bone renovating material.
However, the inorganic salts comprising calcium phosphorous compound be mostly it is hydrophilic, with absorbable polyester material simple blend
When, the compatibility at the two interface is poor, lacks the interface interaction power of some strength, assembles inorganic salt particle, in polyester
Disperse uneven in material matrix, therefore easily lead to stress concentration, and interface is easily drawn because of falling off between matrix and filler
Micro-flaw seriously affects the mechanical property of composite material.In addition, the addition of inorganic salt particle would generally damage the tough of polyester material
Property, brittle failure is easily led to, limits composite material in the application of field of orthopaedics.Therefore, it is closed by common polyester and comprising calcium-phosphorus ratio
Orthopedic medical device made of the inorganic salts composite material of object may bring very big risk to patient in practical applications.
In view of the above-mentioned problems, in patent document 1, proposing a kind of hydroxyapatite/polylactic acid composite material.Wherein, hydroxyl
Base apatite surface is modified by adsorbing low molecular weight, however, although modified hydroxyapatite and poly-
The binding force of lactic acid basis material is enhanced, but still lacks strong interface interaction power, the mechanical property of final composite material
Place can be improved there are still very much.
In addition, patent document 2 also proposed a kind of hydroxyapatite/polylactic acid composite material.Wherein, this material is main
It is made of hydroxyapatite in-situ polymerization polylactic acid, i.e., there are covalent bonds between hydroxyapatite and polylactic acid.Although this can be
Largely facilitate the dispersion of hydroxyapatite and improve interface interaction power, improves the mechanical property of material, however at this
In hydroxyapatite/polylactic acid composite material, due to there is no buffering between rigid hydroapatite particles and polylactic acid, hold
The toughness for easily leading to composite material is badly damaged, and is easy to happen brittle failure, is unfavorable for its application in Orthopedic Clinical.
[existing technical literature]
[patent document]
Patent document 1: Chinese granted patent CN102153058B
Patent document 2: Chinese granted patent CN103319696A
Summary of the invention
The present invention in view of the above-mentioned prior art situation and complete, its purpose is to provide one kind can either improve mechanics
The absorbable bio-medical composition that intensity and toughness can be improved again.
For this purpose, one aspect of the present invention provides a kind of absorbable bio-medical composition comprising: base particle,
It includes calcium phosphorous compounds；Middle layer, is coated on the surface of the base particle, and the middle layer turns with the first glassy state
Change temperature, and first glass transition temperature is not higher than normal body temperature；And polymeric matrix, it is formed in institute
The outer surface of middle layer is stated, the polymeric matrix has the second glass transition temperature, and second glass transition
Temperature is greater than first glass transition temperature.
In in one aspect of the invention, there are middle layer, the glass of the middle layer between base particle and polymeric matrix
State conversion temperature is not higher than normal body temperature, therefore, when composite material of the invention being applied to Orthopedic Clinical treating, in this
Interbed is able to maintain as rubbery state (elastomeric state) in human body, and the middle layer of the rubbery state can be discharged as caused by base particle
Stress is concentrated and alleviates its micro-crack, and the toughness of composite material is improved.In addition, the base particle can also inhibit to be in rubbery state
Drastic mechanical deformation of the middle layer under certain stress, so as to inhibit the addition bring of intermediate layer material of rubbery state compound
The decline of the strength of materials.
In addition, optionally, the base particle includes to be selected from hydroxyl in composite material involved in one aspect of the invention
Base apatite, calcium polyphosphate and tricalcium phosphate one or more of are worked as.In this case, due to the ingredient of base particle and people
The ingredient of body skeletal tissue is approximate, therefore can be improved the bioactivity and biocompatibility of composite material.
In addition, optionally, the base particle is rigid in composite material involved in one aspect of the invention
Grain.Thereby, it is possible to improve the mechanical strength of composite material.
In addition, optionally, the middle layer is polymeric layer in composite material involved in one aspect of the invention,
And with Covalent bonding together between the base particle and the middle layer.In this case, in base particle and middle layer
Between can form strong interface active force, to effectively improve binding force between the two, be conducive to the conduction of power.
In addition, in composite material involved in one aspect of the invention, optionally, the quality percentage of the base particle
Number is 1wt%~10wt%, and the mass percent of the middle layer is 1wt%~10wt%.In this case, it can improve
The mechanical strength of composite material, and other performance characteristics such as toughness of composite material are not had an impact or influenced smaller.
In addition, in composite material involved in one aspect of the invention, optionally, on the middle layer, with original position
The mode of polymerization forms the polymeric matrix.In this case, it can be formed between middle layer and polymeric matrix all
As the strong interface active force of covalent bond is conducive to the conduction of power to effectively improve binding force between the two.
In addition, optionally, the middle layer includes to hand over selected from third in composite material involved in one aspect of the invention
Ester, caprolactone, Lanthanum Isopropoxide and glycolide one of work as the homopolymer of monomer, or selected from lactide, caprolactone, right
Random copolymer or block copolymer more than binary in dioxanone and glycolide.In this case, middle layer
Absorbable polymer material can be formed, is conducive to composite material in field of orthopaedics, especially can absorb orthopaedics Material Field
Using.
In addition, in composite material involved in one aspect of the invention, optionally, the middle layer and the polymer
Matrix is with Covalent bonding together.In this case, strong interface active force can be formed between middle layer and polymeric matrix, from
And binding force between the two is effectively improved, be conducive to the conduction of power.
Another aspect provides a kind of preparation method of absorbable bio-medical composition, step packets
It includes: preparing the base particle being made of calcium phosphorous compound；The base particle and the first reaction monomers are sufficiently mixed, mixed
Close solution；Catalyst is added in the mixed solution, and under conditions of inert gas, is heated to 80 DEG C~180 DEG C, reaction
2 hours to 48 hours, so as to be coated on the base particle by the middle layer that first reaction monomers are constituted；And it is added the
Two reaction monomers maintain heating, and the reaction was continued 2 hours to 48 hours, to form polymer matrix on the middle layer
Body.In such a case, it is possible to form the composite material comprising middle layer, the mechanical strength and toughness of the composite material can be obtained
To raising, this important in inhibiting in orthopedic medical device application.
In addition, optionally, described first is anti-in the preparation method of composite material involved in another aspect of this invention
Monomer and second reaction monomers is answered to be respectively selected from lactide, caprolactone, Lanthanum Isopropoxide and glycolide at least
It is a kind of.In such a case, it is possible to which absorbable middle layer and polymeric matrix is prepared, this is conducive to composite material in bone
Section field, the application of especially absorbable orthopaedics Material Field.
In addition, optionally, described first is anti-in the preparation method of composite material involved in another aspect of this invention
Answer monomer different from second reaction monomers.In such a case, it is possible to by adjusting monomeric species, monomer mass or monomer
Ratio etc. controls the glass transition temperature of middle layer or polymeric matrix, so that it is in the application of field of orthopaedics.
In accordance with the invention it is possible to a kind of high mechanical strength is provided and the absorbable bio-medical composition of good toughness and
Preparation method.
Detailed description of the invention
Fig. 1 is to show the structural representation of absorbable bio-medical composition involved in embodiments of the present invention
Figure.
Fig. 2 shows the partial structural diagrams of bio-medical composition involved in present embodiment.
Fig. 3 is to show the preparation step schematic diagram of absorbable bio-medical composition.
Symbol description:
10 ... composite materials, 11 ... base particles, 12 ... middle layers, 13 ... polymeric matrixs.
Specific embodiment
Hereinafter, explaining the preferred embodiment of the present invention in detail with reference to attached drawing.In the following description, for identical
Component assign identical symbol, the repetitive description thereof will be omitted.Scheme in addition, attached drawing is only schematical, the mutual ruler of component
Very little shape of ratio or component etc. can be with actual difference.
In the following description, the mode of subhead has been used to be described for convenience of explanation, but these subheads
Suggesting effect is only played, is not intended to for content described under subhead being limited in the theme of subhead.
(composite material)
Fig. 1 is to show the structural schematic diagram of absorbable bio-medical composition involved in present embodiment.Fig. 2
Show the partial structural diagram of bio-medical composition involved in present embodiment.
As depicted in figs. 1 and 2, composite material 10 involved in present embodiment may include base particle 11, middle layer
12 and polymeric matrix 13.Specifically, being coated with middle layer 12 in 11 outer surface of base particle, during polymeric matrix is formed in
The outer surface of interbed 12.In some instances, base particle 11 and middle layer 12 can be used as entirety and be homogeneously dispersed in polymerization
In object matrix 13.
As described above, being formed with middle layer 12 between base particle 11 and polymeric matrix 13.In this case, exist
Buffering is introduced between base particle 11 and polymeric matrix 13, therefore can enhance base particle 11 and polymeric matrix
13 interface interaction power improves dispersion of the base particle 11 in polymeric matrix 13, to improve the power of composite material 1 simultaneously
Learn intensity and toughness.
(base particle)
In the present embodiment, base particle 11 may include calcium phosphorous compound.Preferably, base particle 11 may include
One or more of work as selected from hydroxyapatite, calcium polyphosphate and tricalcium phosphate.In this case, composite wood is helped to improve
The bioactivity of material 10, promotes its repair to skeleton tissue.
It is well known that in the inorganic constituent of skeleton tissue, based on the compound of calcium phosphorus.By present embodiment
After related composite material 10 is implanted in vivo as orthopaedics repair materials, middle layer 12 and polymeric matrix 13 (are retouched later
State) it can be absorbed by the body, therefore the elements such as calcium, phosphorus for being included of base particle 11 can be systemically absorbed, and form new bone
Bone tissue, therefore facilitate the growth and reparation of bone.
In addition, base particle 11 is also not necessarily limited to above-mentioned hydroxyapatite, calcium polyphosphate, tricalcium phosphate etc..In this implementation
In mode, if base particle 11 comprising with substance similar in the ingredient of skeleton tissue, just can be improved composite material 10
Repair to skeleton tissue.
In the present embodiment, it is preferable that base particle 11 is rigid particles.In some instances, base particle 11 can
Think that Young's modulus is greater than 2 × 1011The rigid particles of Pa.In this case, the mechanics of composite material 10 can be effectively improved
Intensity.
In addition, in the present embodiment, the shape of base particle 11 is not particularly limited.For example, in some instances,
Base particle 11 can be sphere shape.But present embodiment is without being limited thereto, and in other examples, base particle 11 can be ellipse
Spherical, irregular stereo structure etc..
In the present embodiment, the mass percent (wt%) of base particle 11 is not particularly limited.For composite material
The considerations of 10 mechanical strength and toughness, the mass percent of base particle 11 are preferably 1wt%~10wt%, such as substrate
The mass percent of grain 11 can take 1wt%, 3wt%, 5wt%, 8wt% or 10wt%.Specifically, in composite material 10
In, base particle 11 plays the role of improving the mechanical strength of composite material 10, it is however generally that, the content of base particle 11 is got over
More, the mechanical strength of composite material 10 is higher.When the content of base particle 11 is less, the mechanical strength of composite material 10 is not
Foot, and when the content of base particle 11 is excessive, then it can make the opposite reduction of the content of polymeric matrix 13 in composite material 10, by
This influences the mechanical strength of composite material 10.Therefore, the mass percent of base particle 11 is taken as 1wt%~10wt%, it can
To improve the mechanical strength of composite material 10, or guarantee that the mechanical strength of composite material 10 is not influenced by or by smaller.
In addition, in the present embodiment, the average grain diameter of base particle 11 is not particularly limited.For composite material 10
The considerations of mechanical strength and toughness, the average grain diameter of base particle 11 are preferably 5nm~200 μm, for example, base particle 11 is flat
Equal partial size can take 5nm, 10nm, 30nm, 50nm, 1 μm, 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 130
μm, 150 μm, 180 μm or 200 μm.Specifically, the partial size of usually base particle 11 is smaller, rigidity is stronger, therefore selects grain
When the lesser base particle 11 of diameter, the effect of mechanical strength enhancing of the base particle 11 to composite material 10 can be given full play to；With
The increase of 11 partial size of base particle, surface can reduce, can inhibit to reunite to a certain extent, but when base particle 11
Partial size is excessive, will affect the uniformity of its dispersion, to influence the mechanical strength of lactic acid composite material 1.Therefore, by substrate
The partial size of particle 11 limits within the above range, can play the role of enhancing 10 mechanical strength of composite material and base
The dispersion of bottom particle 11 is uniform enough.
(middle layer)
In the present embodiment, middle layer 12 can be coated on the surface of base particle 11.That is, middle layer 12 is covered on
The surface of base particle 11.In addition, middle layer 12 can have the first glass transition temperature T1.In some instances, first
Glass transition temperature T1 can be not higher than normal body temperature.For the glass transition temperature of substance,
When ambient temperature is higher than the glass transition temperature of polymer, substance will be resilient state or rubbery state；It is less than in ambient temperature
Or equal to polymer glass transition temperature when, substance will be in glassy state.
When composite material 10 involved in present embodiment is applied to human body, due to the first glass of the middle layer 12
State conversion temperature T1 is not higher than normal body temperature (such as 37 DEG C), and therefore, middle layer 12 is able to maintain as rubbery state.This
In the case of, (such as in situ discharge) stress as caused by base particle 11 can be discharged in the middle layer 12 of rubbery state to be concentrated and delay
Solution thus caused by micro-crack, thus, it is possible to improve the toughness of composite material 10.In addition, the base particle 11 can also consolidate
The drastic mechanical deformation of (such as in situ firm) in the middle layer 12 of rubbery state under certain stress, thus, it is possible to inhibit composite material 10
The decline of mechanical strength.
In the present embodiment, middle layer 12 can be made of polymer material, and middle layer 12 and base particle 11
Between can be with Covalent bonding together.In this case, strong interface active force is formed between base particle 11 and middle layer 12, from
And binding force between the two is effectively improved, be conducive to the conduction of power.In addition, can be between middle layer 12 and base particle 11
With the combination of the strong interfaces active force such as ionic bond.
It is strong when existing between the middle layer 12 and base particle 11 in rubbery state in the clinical application of human body orthopaedics reparation
When active force, the connected effect that both can aid in the conduction of power between middle layer 12 and base particle 11 and promote.Specifically
For, on the one hand, the stress collection that (such as release in situ) is caused by base particle 11 can be discharged in the middle layer 12 of rubbery state
In and alleviate micro-crack, so as to improve the toughness of composite material 10；On the other hand, base particle 11 can consolidate (such as former
Position is firm) drastic mechanical deformation of the middle layer 12 of rubbery state under certain stress, to effectively inhibit the middle layer due to rubbery state
The decline of 10 mechanical strength of composite material caused by 12 addition.Therefore, can improve simultaneously the intensity of composite material 10 with
Toughness, this important in inhibiting in orthopedic medical device application for composite material 10 involved in present embodiment.
In the present embodiment, the mass percent (wt%) of middle layer 12 is not particularly limited.For composite material 10
Mechanical strength and the considerations of toughness, the mass percent of middle layer 12 is preferably 1wt%~10wt%, such as middle layer 12
Mass percent can take 1wt%, 3wt%, 5wt%, 8wt% or 10wt%.Specifically, in composite material 10, it is intermediate
Layer 12 plays the role of enhancing 10 toughness of composite material, it is however generally that, the content of middle layer 12 is more, the toughness of composite material 10
Better.When the content of middle layer 12 is less, the toughness of composite material 10 is insufficient, and when the content of middle layer 12 is excessive, then
It will affect the performance characteristics such as the mechanical strength of composite material 10.Therefore, by the mass percent of middle layer 12 be taken as 1wt%~
10wt% can improve other performance characteristics such as the toughness of composite material 10 and the mechanical strength of composite material 10 and not generate
It influences or influences smaller.
In the present embodiment, middle layer 12 may include selected from lactide, caprolactone, Lanthanum Isopropoxide and glycolide
When one of monomer homopolymer.In addition, middle layer 12 also may include selected from lactide, caprolactone, Lanthanum Isopropoxide
With random copolymer or the block copolymer more than binary in glycolide.In this case, middle layer 12 can be formed
Absorbable polymer material is conducive to composite material 10 in field of orthopaedics, especially can absorb the application of orthopaedics Material Field.
As described above, in the present embodiment, first glass transition temperature T1 can not be high possessed by middle layer 12
In normal body temperature.In addition, the specific value range of first glass transition temperature T1 is not particularly limited, it is preferable that
The first glass transition temperature T1 meets -40 DEG C≤T1≤36 DEG C, for example, the first glass transition temperature T1 can be -40
DEG C, -37 DEG C, -30 DEG C, -20 DEG C, -10 DEG C, -5 DEG C, 0 DEG C, 10 DEG C, 20 DEG C or 36 DEG C；It is highly preferred that the first glass transition temperature
It spends T1 and meets -37 DEG C≤T1≤36 DEG C.
In addition, in the present embodiment, the size of the glass transition temperature T1 of middle layer 12 can be according to actual needs
Regulated and controled.For homopolymer, different glass transition temperature can be obtained by the type or quality for regulating and controlling monomer
Spend T1；For copolymer, glass transition temperature can be realized by ratio of each monomer in regulation mix monomer etc.
The change of T1.
In addition, in the present embodiment, the molding mode of middle layer 12 is not particularly limited.It in some instances, can be with
It is formed and causing in-situ polymerization in 11 outer surface of base particle.In addition, in other examples, it can also be by substrate
The modified mode in 11 surface of particle is formed.
(polymeric matrix)
In the present embodiment, polymeric matrix 13 is formed in the outer surface of middle layer 12.In addition, polymeric matrix 13 can
To have the second glass transition temperature T2.In some instances, the second glass transition temperature T2 can be greater than middle layer 12
The first glass transition temperature T1 having, i.e. T2 > T1.As a result, under the conditions of same temperature, polymeric matrix 13 can
It keeps than the better mechanical strength of middle layer 12, to enhance the mechanical property of composite material 10.
In addition, in the present embodiment, the second glass transition temperature T2 possessed by polymeric matrix 13 can be higher than
Normal body temperature.As a result, when composite material 10 involved in present embodiment is applied to human body, polymeric matrix 13 can
To remain glassy state, it may further ensure that the mechanical strength of composite material 10 is sufficiently high.
In the present embodiment, in middle layer 12, polymeric matrix 13 can be formed in a manner of in-situ polymerization.At this
In the case of kind, the strong interface active force of such as covalent bond can be formed between middle layer 12 and polymeric matrix 13, to have
Effect improves binding force between the two, is conducive to the conduction of power.
In the present embodiment, middle layer 12 can be with polymeric matrix 13 with Covalent bonding together.In this case, in
Strong interface active force is formed between interbed 12 and polymeric matrix 13 to be conducive to effectively improve binding force between the two
The conduction of power.In addition, middle layer 12 can also be with the strong interfaces active force such as ionic bond between polymeric matrix 13 in conjunction with.
In addition, in the present embodiment, polymeric matrix 13 may include selected from lactide, caprolactone, to dioxocyclohex
Ketone and glycolide one of work as the homopolymer of monomer.In addition, polymeric matrix 13 also may include selected from lactide, in oneself
Random copolymer or block copolymer more than binary in ester, Lanthanum Isopropoxide and glycolide.In this case, gather
Absorbable polymer material can be formed by closing object matrix 13, be conducive to composite material 10 in field of orthopaedics, especially can absorb
The application in bone material field.
Fig. 3 is to show the preparation step schematic diagram of absorbable bio-medical composition.
Hereinafter, describing the system of absorbable bio-medical composition involved in present embodiment in detail with reference to Fig. 3
Preparation Method.
As shown in figure 3, the method for preparing absorbable bio-medical composition involved in present embodiment can be with
Include the following steps: the base particle 11 (step S1) for preparing to be made of calcium phosphorous compound；Base particle 11 is reacted with first
Monomer is sufficiently mixed, and obtains mixed solution (step S2)；Catalyst is added in mixed solution, and in the condition of inert gas
Under, 80 DEG C~180 DEG C are heated to, is reacted 2 hours to 48 hours, so as to be wrapped by the middle layer 12 that first reaction monomers are constituted
It is overlying on base particle 11 (step S3)；The second reaction monomers are added, maintain heating, and the reaction was continued 2 hours to 48 hours, thus
Polymeric matrix 13 is formed on the middle layer 12, it is final to obtain composite material 10 (step S4).
In the present embodiment, in step sl, prepare the base particle 11 being made of calcium phosphorous compound first.Some
One or more of in example, base particle 11 can work as selected from hydroxyapatite, calcium polyphosphate and tricalcium phosphate.Many institute's weeks
Know, in the inorganic constituent of skeleton tissue, based on the compound of calcium phosphorus.By composite wood involved in present embodiment
After material 10 is implanted in vivo as orthopaedics repair materials, middle layer 12 and polymeric matrix 13 (being described later on) can be inhaled by human body
It receives, therefore the elements such as calcium, phosphorus for being included of base particle 11 can be systemically absorbed, and form new skeletal tissue, therefore have
Help the growth and reparation of bone.
In addition, base particle 11 is also not necessarily limited to above-mentioned hydroxyapatite, calcium polyphosphate, tricalcium phosphate etc..In this implementation
In mode, if base particle 11 comprising with substance similar in the ingredient of skeleton tissue, also can be improved composite material 10
Repair to skeleton tissue.
In the present embodiment, in step s 2, by step S1 base particle 11 and the first reaction monomers it is sufficiently mixed
It closes, obtains mixed solution.It in some instances, in step s 2, can be molten by base particle 11 and the first reaction monomers simultaneously
It in organic solvent, is sufficiently mixed, forms mixed solution.In other examples, organic solvent is preferably dry toluene.
Wherein, the first reaction monomers can be selected from one in lactide, caprolactone, Lanthanum Isopropoxide and glycolide
Kind.In addition, the first reaction monomers can also two kinds in lactide, caprolactone, Lanthanum Isopropoxide and the glycolide with
On.In this case, obtained middle layer 12 is comprising being selected from lactide, caprolactone, Lanthanum Isopropoxide and glycolide
When one of monomer homopolymer, or binary in lactide, caprolactone, Lanthanum Isopropoxide and glycolide with
On random copolymer or block copolymer.Middle layer 12 can form absorbable polymer material as a result, be conducive to compound
Application of the material 10 in the especially absorbable orthopaedics Material Field of field of orthopaedics.
In addition, in the present embodiment, in step s 2, add the process of the first reaction monomers, may include once with
On addition.In some instances, it is added next time again after a certain period of time wait react after addition every time, it is possible thereby to shape
At block polymer.
In the present embodiment, in step s3, catalyst is added in obtained mixed solution in step s 2,
And under conditions of inert gas, 80 DEG C~180 DEG C are heated to, is reacted 2 hours to 48 hours, so that by the first reaction monomers structure
At middle layer 12 be coated on base particle 11.In some instances, with such as covalently between base particle 11 and middle layer 12
The high forces of key etc combine, it is possible thereby to improve the binding force of the two, be conducive to the conduction of power and promote the connection of the two
Dynamic effect.
In addition, in the present embodiment, in step s3, catalyst is preferably stannous octoate.Thus, it is possible to cause monomer
In-situ polymerization, formed such as covalent bond strong interface active force.
In addition, in the present embodiment, in step s3, inert gas can be nitrogen or argon gas.Thus, it is possible to guarantee
The smooth generation of reaction, effectively avoids the generation of other impurities.
In the present embodiment, in step s 4, in the reaction system of step S3, the second reaction monomers are added, maintain
Heating, and the reaction was continued 2 hours to 48 hours, to form polymeric matrix 13 on middle layer 12, finally obtains compound
Material 10.
Wherein, the second reaction monomers can be one in lactide, caprolactone, Lanthanum Isopropoxide and glycolide
Kind.In addition, the second reaction monomers may be two kinds in lactide, caprolactone, Lanthanum Isopropoxide and glycolide
More than.In this case, obtained polymeric matrix 13 be comprising selected from lactide, caprolactone, Lanthanum Isopropoxide and
Glycolide one of works as the homopolymer of monomer, or in lactide, caprolactone, Lanthanum Isopropoxide and glycolide
More than binary random copolymer or block copolymer.Polymeric matrix 13 can form absorbable polymer material as a result,
Be conducive to composite material 10 in the application of the especially absorbable orthopaedics Material Field of field of orthopaedics.
In some instances, the second reaction monomers can be different from the first reaction monomers.The difference includes that type is different, contains
Amount is different or type and content not equivalent situations.
In addition, in the present embodiment, in step s 4, add the process of the second reaction monomers, may include once with
On addition.In some instances, it is added next time again after a certain period of time wait react after addition every time, it is possible thereby to shape
At block polymer.
In addition, in the present embodiment, it is organic molten that the product in two stages of step S3 and step S4 is dissolved in first respectively
Agent, it is preferable that first organic solvent is chloroform.Then, it by centrifugal treating, then through the second organic solvent deposit and cleans,
Preferably, which is methanol, may finally obtain 12 polymer of middle layer (middle layer 12), base particle 11 with
The composition (base particle 11- middle layer 12) of middle layer 12, and include base particle 11, middle layer 12 and polymeric matrix
13 composite material 10 (base particle 11- middle layer 12- polymeric matrix 13).
In addition, in the present embodiment, the glass transition temperature of differential scanning calorimetry (DSC) test material can be passed through
Degree, the weight average molecular weight (Mw) of material can also be obtained by gel permeation chromatography (GPC), can also pass through thermogravimetric analysis
(TGA) constituent content of material is measured.
In addition, in the present embodiment, the composite material 10 that step S4 is obtained is through injection molding, then obtains it after tested
Mechanics property analysis result.
In the present embodiment, it is wrapped by absorbable bio-medical composition 10 prepared by step S1 to step S4
Base particle 11 and polymeric matrix 13 are included, and the middle layer 12 between base particle 11 and polymeric matrix 13.
As described above, the glass transition temperature of middle layer 12 therefore will be involved in present embodiment not higher than normal body temperature
Composite material 10 is applied to Orthopedic Clinical when treating, which is able to maintain as rubbery state in human body, should be in rubbery state
Middle layer 12 can alleviate the stress collection as caused by base particle 11 neutralize micro-crack, improve composite material 10 toughness.Together
When, which can also consolidate the drastic mechanical deformation in the middle layer 12 of rubbery state under certain stress, therefore also can
Inhibit the decline of 10 mechanical strength of composite material.
In order to further illustrate the present invention, compound to absorbable bio-medical provided by the invention with reference to embodiments
Material and preparation method thereof is described in detail, and the beneficial effect for combining comparative example to realize the present invention absolutely proves.
(embodiment 1)
The hydroxyapatite for being 5nm by 0.1g particle diameter, the levorotatory lactide monomer of 0.06g and the caprolactone of 0.06g
Monomer is uniformly mixed, and 40ul stannous octoate is added, is then stirred and heated to 180 DEG C under nitrogen protection, melts to reaction mixture
After changing uniformly, continue to be stirred to react 2 hours, forms hydroxyapatite-rubber state layer.Then it is left that 10g is added into reaction system
Lactide is revolved, continuation is reacted 2 hours at 180 DEG C.
After reaction, reaction mixture is dissolved with chloroform, is then precipitated in methyl alcohol, and cleaned 3 times with methanol, obtained
To hydroxyapatite-rubber state layer-lactic acid composite material.
Obtained hydroxyapatite-rubber state layer composite material and hydroxyapatite-rubber state layer-polylactic acid is compound
Material is dissolved in chloroform respectively, is then centrifuged with the rate of 15000rpm, is taken supernatant liquor to precipitate and clean in methyl alcohol, obtain
Material characterization is carried out to free rubbery feel polymer and rubbery state-polylactic acid polymer, differential scanning calorimetry (DSC) and is coagulated
Glue penetration chromatography (GPC) data are shown in Table 1.
Table 1
Hydroxyapatite-rubber state layer-lactic acid composite material is subjected to injection molding, stretching mechanical property testing result
It is shown in Table 2.The mass content of hydroxyapatite is measured by TGA in hydroxyapatite-rubber state layer-lactic acid composite material, is
1%.The mass content of rubber state layer in hydroxyapatite-rubber state layer-lactic acid composite material by rubber state layer in table 1 and
Rubber state layer-polylactic acid weight average molecular weight, is calculated in conjunction with the content of hydroxyapatite, the results are shown in Table 1.
Table 2
(embodiment 2)
The hydroxyapatite for being 200um by 1g particle diameter, 0.4g levorotatory lactide monomer, 0.4g Lanthanum Isopropoxide list
Body and 0.4g glycolide monomer are uniformly mixed in 100ml dry toluene, and 160ul stannous octoate is added, and are then protected in argon gas
Under be heated with stirring to 80 degrees Celsius, after reactant mixed dissolution is uniform, continue to be stirred to react 48 hours, formed hydroxy-apatite
Stone-rubber state layer.Then 8.5g glycolide is added into reaction system, continues to react 48 hours at 80 degrees celsius.
Reaction mixture is precipitated in methyl alcohol after reaction, and is cleaned 3 times with methanol, hydroxyapatite-rubber is obtained
Colloidal state layer-polyglycolide composite material.
Obtained hydroxyapatite-rubber state layer composite material and hydroxyapatite-rubber state layer-polyglycolide is multiple
Condensation material is dissolved in chloroform respectively, is then centrifuged with the rate of 15000rpm, supernatant liquor is taken to precipitate and clean in methyl alcohol,
It obtains free rubbery feel polymer and rubbery state-polyglycolide polymers carries out material characterization, differential scanning calorimetry (DSC)
1 is shown in Table with gel permeation chromatography (GPC) data result.
Hydroxyapatite-rubber state layer-polyglycolide composite material is subjected to injection molding, stretching mechanical property testing knot
Fruit is shown in Table 2.The mass content of hydroxyapatite is measured by TGA in hydroxyapatite-rubber state layer-polyglycolide composite material,
It is 10%.The mass content of rubber state layer in hydroxyapatite-rubber state layer-polyglycolide composite material is by rubber in table 1
State layer and rubber state layer-polylactic acid weight average molecular weight, are calculated in conjunction with the content of hydroxyapatite, the results are shown in Table 1.
(embodiment 3)
Hydroxyapatite and 0.3g caprolactone monomer that 0.5g particle diameter is 200nm are mixed in 100ml dry toluene
It closes uniformly, 100ul stannous octoate is added, 120 degrees Celsius are then heated with stirring under protection of argon gas, to reactant mixed dissolution
After uniformly, continues to be stirred to react 12 hours, 0.3g Lanthanum Isopropoxide monomer is then added, continuation is reacted at one hundred and twenty degrees centigrade
12 hours, form hydroxyapatite-rubber state layer.Then 4.6g glycolide is added into reaction system, continues at 130 degrees Celsius
Lower reaction 24 hours, adds 4.6g levorotatory lactide later, and continuation is reacted 24 hours under 130 degrees Celsius.
Reaction mixture is precipitated in methyl alcohol after reaction, and is cleaned 3 times with methanol, hydroxyapatite-rubber is obtained
Colloidal state layer-poly (lactic acid-glycolic acid) composite material.
By obtained hydroxyapatite-rubber state layer composite material and hydroxyapatite-rubber state layer-polylactic acid ethyl alcohol
Sour composite material is dissolved in chloroform respectively, is then centrifuged with the rate of 15000rpm, supernatant liquor is taken to precipitate in methyl alcohol simultaneously
Cleaning, obtains free rubbery feel polymer and rubbery state-poly (lactic acid-glycolic acid) polymer carries out material characterization, differential scanning amount
Thermal method (DSC) and gel permeation chromatography (GPC) data result are shown in Table 1.
Hydroxyapatite-rubber state layer-poly (lactic acid-glycolic acid) composite material is subjected to injection molding, tensile mechanical properties are surveyed
Test result is shown in Table 2.In hydroxyapatite-rubber state layer-poly (lactic acid-glycolic acid) composite material the mass content of hydroxyapatite by
TGA measurement is 5%.The mass content of rubber state layer in hydroxyapatite-rubber state layer-poly (lactic acid-glycolic acid) composite material
It by rubber state layer in table 1 and rubber state layer-polylactic acid weight average molecular weight, is calculated, ties in conjunction with the content of hydroxyapatite
Fruit is shown in Table 1.
(comparative example 1)
Hydroxyapatite and 10g levorotatory lactide monomer that 0.1g particle diameter is 5nm are uniformly mixed, it is pungent that 40ul is added
Then sour stannous is stirred and heated to 180 degrees Celsius under nitrogen protection, after reaction mixture melts uniformly, it is anti-to continue stirring
It answers 2 hours, forms hydroxyapatite-lactic acid composite material.
Reaction mixture is dissolved with chloroform after reaction, is then precipitated in methyl alcohol, and is cleaned 3 times with methanol, is obtained
To hydroxyapatite-lactic acid composite material.
Obtained hydroxyapatite-lactic acid composite material is dissolved in chloroform, then with the rate of 15000rpm
Centrifugation, takes supernatant liquor to precipitate and clean in methyl alcohol, obtains free polylactic acid and carries out material characterization, differential scanning calorimetry
(DSC) and gel permeation chromatography (GPC) data result is shown in Table 1.
Hydroxyapatite-lactic acid composite material is subjected to injection molding, stretching mechanical property testing the results are shown in Table 2.Hydroxyl
The mass content of hydroxyapatite is measured by TGA in base apatite-lactic acid composite material, is 1%.
(comparative example 2)
Hydroxyapatite and 9.9g the l-lactic acid dispersing and dissolving in chloroform for being 5nm by 0.1g particle diameter, stirring
Uniformly, it then precipitates in methyl alcohol, obtains hydroxyapatite/polylactic acid composite material.
The molecular weight and glass transition temperature of the l-lactic acid that this comparative example uses and the test result of comparative example 1 connect
Closely, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) data result are shown in Table 1.Hydroxyapatite/polylactic acid is answered
Condensation material carries out injection molding, and stretching mechanical property testing the results are shown in Table 2.Hydroxyl in hydroxyapatite/polylactic acid composite material
The mass content of apatite is measured by TGA, is 1.2%.
(comparative example 3)
L-lactic acid in comparative example 2 is subjected to injection molding, stretching mechanical property testing the results are shown in Table 2.
Interface Design of the invention can be improved effectively simultaneously it can be seen from the comparison of embodiment 1 and comparative example 3
The intensity (being indicated by Young's modulus and tensile strength) and toughness (being indicated by elongation at break) of polyester material.
The comparison of embodiment 1 and comparative example 1 can be seen that rubber state layer was formed between hydroxyapatite and polylactic acid
Buffer function improves the toughness of poly-lactic acid material helpful.
Lack strong interface interaction power in comparative example 2 between hydroxyapatite and polylactic acid matrix, therefore embodiment 1,
The comparison of comparative example 1 and comparative example 2 can be seen that the high forces being can absorb at composite material median surface in the present invention for mentioning
The mechanical property of high composite material has important role.
Although above combine drawings and embodiments the present invention is illustrated, it will be appreciated that on state
It is bright that the invention is not limited in any way.Those skilled in the art are without departing from the true spirit and scope of the present invention
It can according to need and the present invention is deformed and is changed, these deformations and variation are within the scope of the present invention.
Claims (10)
1. a kind of absorbable bio-medical composition, it is characterised in that:
Include:
Base particle, it includes calcium phosphorous compounds；
Middle layer, is coated on the surface of the base particle, and the middle layer has the first glass transition temperature, and institute
The first glass transition temperature is stated not higher than normal body temperature；And
Polymeric matrix, is formed in the outer surface of the middle layer, and the polymeric matrix has the second glass transition temperature
Degree, and second glass transition temperature is greater than first glass transition temperature.
2. bio-medical composition as described in claim 1, it is characterised in that:
The base particle includes at least one of to work as selected from hydroxyapatite, calcium polyphosphate and tricalcium phosphate.
3. bio-medical composition as described in claim 1, it is characterised in that:
The middle layer is polymeric layer, and with Covalent bonding together between the base particle and the middle layer.
4. bio-medical composition as described in claim 1, it is characterised in that:
The mass percent of the base particle is 1wt%~10wt%, the mass percent of the middle layer be 1wt%~
10wt%.
5. bio-medical composition as claimed in claim 1 or 3, it is characterised in that:
On the middle layer, the polymeric matrix is formed in a manner of in-situ polymerization.
6. bio-medical composition as described in claim 1, it is characterised in that:
The middle layer includes one of to work as the homopolymerization of monomer selected from lactide, caprolactone, Lanthanum Isopropoxide and glycolide
Object, or random copolymer or block more than the binary in lactide, caprolactone, Lanthanum Isopropoxide and glycolide
Copolymer.
7. bio-medical composition as claimed in claim 1 or 3, it is characterised in that:
The middle layer and the polymeric matrix are with Covalent bonding together.
8. a kind of preparation method of absorbable bio-medical composition, it is characterised in that:
Include:
Prepare the base particle being made of calcium phosphorous compound；
The base particle and the first reaction monomers are sufficiently mixed, mixed solution is obtained；
Catalyst is added in the mixed solution, and under conditions of inert gas, is heated to 80 DEG C~180 DEG C, reaction 2 is small
Up to 48 hours, so as to be coated on the base particle by the middle layer that first reaction monomers are constituted；And
The second reaction monomers are added, heating are maintained, and the reaction was continued 2 hours to 48 hours, thus the shape on the middle layer
At polymeric matrix,
Wherein, the middle layer has the first glass transition temperature, and first glass transition temperature is not higher than people
Body normal body temperature,
The polymeric matrix has the second glass transition temperature, and second glass transition temperature is greater than described the
One glass transition temperature.
9. preparation method as claimed in claim 8, it is characterised in that:
First reaction monomers and second reaction monomers are respectively selected from lactide, caprolactone, Lanthanum Isopropoxide and second
Lactide at least one of is worked as.
10. preparation method as claimed in claim 8 or 9, it is characterised in that:
First reaction monomers are different from second reaction monomers.
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| CN201910134927.7A CN109876191B (en) | 2017-07-15 | 2017-07-15 | Absorbable biomedical composite material and preparation method thereof |
| CN201710578058.8A CN107376026B (en) | 2017-07-15 | 2017-07-15 | Absorbable bio-medical composition and preparation method thereof |
| PCT/CN2018/095731 WO2019015542A1 (en) | 2017-07-15 | 2018-07-15 | Absorbable biomedical composite material and preparation method therefor |
| EP18835430.2A EP3656406B1 (en) | 2017-07-15 | 2018-07-15 | Absorbable biomedical composite material and preparation method therefor |
| US16/615,133 US11311651B2 (en) | 2017-07-15 | 2018-07-15 | Absorbable biomedical composite material and preparation method therefor |
| US17/656,643 US11819589B2 (en) | 2017-07-15 | 2022-03-26 | Absorbable biomedical polylactic acid composite material and preparation method therefor |
| US17/656,642 US11786638B2 (en) | 2017-07-15 | 2022-03-26 | Biomedical composite material and preparation method therefor |
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| CN110801537B (en) * | 2019-08-31 | 2021-04-23 | 深圳市立心科学有限公司 | Plastic artificial bone composite material and preparation method thereof |
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| EP3954402A4 (en) * | 2019-08-31 | 2023-01-11 | Shenzhen Corliber Scientific Co., Ltd. | Plastic artificial bone composite material and preparation method therefor |
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| CN109701081A (en) | 2019-05-03 |
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