CN107376026A - Absorbable bio-medical composition and preparation method thereof - Google Patents
Absorbable bio-medical composition and preparation method thereof Download PDFInfo
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- CN107376026A CN107376026A CN201710578058.8A CN201710578058A CN107376026A CN 107376026 A CN107376026 A CN 107376026A CN 201710578058 A CN201710578058 A CN 201710578058A CN 107376026 A CN107376026 A CN 107376026A
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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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—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
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention provides a kind of absorbable bio-medical composition and preparation method.Wherein, the absorbable bio-medical composition includes：Base particle, it includes calcium phosphorous compound；Intermediate layer, it is coated on the surface of the base particle, and the intermediate 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 in the intermediate layer, and the polymeric matrix has the second glass transition temperature, and second glass transition temperature is more than first glass transition temperature.In accordance with the invention it is possible to providing a kind of can either improve mechanical strength and absorbable bio-medical composition that toughness is improved.
Description
Technical field
The invention belongs to bio-medical composition field, more particularly to a kind of absorbable bio-medical composition and
Its preparation method.
Background technology
Containing compositions such as water, organic matter (gelatine) and inorganic salts in skeleton, wherein, the composition of inorganic salts is with calcium-phosphorus ratio
Based on compound, it is with the formal distribution of crystalline hydroxy apatite and amorphous calcium phosphate in organic matter.Therefore, comprising calcium-phosphorus ratio
The inorganic salts of compound, especially hydroxyapatite, calcium phosphate etc., it is similar with skeleton component of inorganic salts, there is excellent life
Thing compatibility and bioactivity.Biodegradable polyesters material, such as PLA, polycaprolactone, PGA, have well
Biological degradability, biocompatibility and mechanical property, be common absorbable medical polymeric material, medical field apply compared with
To be extensive.Inorganic salts comprising calcium phosphorous compound and the combination of Bioabsorbable Polyesters material are made into composite can combine two
The advantages of kind of material, with good biocompatibility, bioactivity and mechanical property as bone fixation and during bone renovating material.
However, the inorganic salts comprising calcium phosphorous compound are hydrophilic mostly, itself and absorbable polyester material simple blend
When, the compatibility at both interfaces is poor, lacks the interface interaction power of some strength, assembles inorganic salt particle, in polyester
Disperse uneven in material matrix, therefore be easily caused stress concentration, and interface is easily drawn because of coming off between matrix and filler
Micro-flaw, have a strong impact on the mechanical property of composite.In addition, the addition of inorganic salt particle would generally damage the tough of polyester material
Property, brittle failure is easily caused, limits application of the composite in field of orthopaedics.Therefore, closed by common polyester and comprising calcium-phosphorus ratio
Orthopedic medical device made of the inorganic salts composite of thing, very big risk may be brought to patient in actual applications.
In view of the above-mentioned problems, in patent document 1, a kind of hydroxyapatite/polylactic acid composite material is proposed.Wherein, hydroxyl
Base apatite surface is modified by adsorbing low molecular weight, however, although modified hydroxyapatite is with gathering
The adhesion of lactic acid matrix material has strengthened, but still lacks strong interface interaction power, the mechanical property of final composite
Many improvement parts can be still suffered from.
In addition, patent document 2 it is also proposed a kind of hydroxyapatite/polylactic acid composite material.Wherein, this material is main
It is made up of hydroxyapatite in-situ polymerization polylactic acid, i.e., covalent bond is present between hydroxyapatite and PLA.Although this can be
Largely contribute to the scattered of hydroxyapatite and improve interface interaction power, improve the mechanical property of material, but at this
In hydroxyapatite/polylactic acid composite material, due to there is no buffering between rigid hydroapatite particles and PLA, hold
The toughness for being easily caused composite is badly damaged, and brittle failure easily occurs, and is unfavorable for its application in Orthopedic Clinical.
【Prior art literature】
【Patent document】
Patent document 1：Chinese granted patent CN102153058B
Patent document 2：Chinese granted patent CN103319696A
The content of the invention
The present invention completes in view of the situation of above-mentioned prior art, and its object is to provide one kind to improve mechanics
The absorbable bio-medical composition that intensity and toughness and can are improved.
Therefore, one aspect of the present invention provides a kind of absorbable bio-medical composition, it includes：Base particle,
It includes calcium phosphorous compound；Intermediate layer, it is coated on the surface of the base particle, and the intermediate 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 in intermediate layer is stated, the polymeric matrix has the second glass transition temperature, and second glass transition
Temperature is more than first glass transition temperature.
In in one aspect of the invention, intermediate layer between base particle and polymeric matrix be present, the glass in the intermediate layer
State conversion temperature is not higher than normal body temperature, therefore, when the composite of the present invention being applied into Orthopedic Clinical treating, in this
Interbed can remain rubbery state (elastomeric state) in human body, and the intermediate layer of the rubbery state can be discharged as caused by base particle
Stress concentration and alleviate its micro-crack, improve the toughness of composite.In addition, the base particle can also suppress to be in rubbery state
Drastic mechanical deformation of the intermediate layer under certain stress, so as to suppress the addition of the intermediate layer material of rubbery state bring it is compound
The decline of the strength of materials.
In addition, in one aspect of the invention in involved composite, alternatively, the base particle includes and is selected from hydroxyl
Base apatite, calcium polyphosphate and tricalcium phosphate one or more of are worked as.In this case, the composition due to base particle and people
The composition of body skeletal tissue is approximate, therefore can improve the bioactivity and biocompatibility of composite.
In addition, in one aspect of the invention in involved composite, alternatively, the base particle is rigid
Grain.Thereby, it is possible to improve the mechanical strength of composite.
In addition, in one aspect of the invention in involved composite, alternatively, the intermediate layer is polymeric layer,
And with Covalent bonding together between the base particle and the intermediate layer.In this case, in base particle and intermediate layer
Between can form strong interface active force, so as to effectively improve adhesion therebetween, be advantageous to the conduction of power.
In addition, in one aspect of the invention in involved composite, alternatively, the quality percentage of the base particle
Number is 1wt%~10wt%, and the mass percent in the intermediate layer is 1wt%~10wt%.In this case, can improve
The mechanical strength of composite, but other performance characteristics such as toughness on composite do not have an impact or influenceed smaller.
In addition, in one aspect of the invention in involved composite, alternatively, on the intermediate layer, with original position
The mode of polymerization forms the polymeric matrix.In this case, can be formed between intermediate layer and polymeric matrix all
Such as the strong interface active force of covalent bond, so as to effectively improve adhesion therebetween, be advantageous to the conduction of power.
In addition, in one aspect of the invention in involved composite, alternatively, the intermediate layer includes hands over selected from third
A kind of homopolymer of monomer among ester, caprolactone, Lanthanum Isopropoxide and glycolide, or selected from lactide, caprolactone, right
Random copolymer or block copolymer more than binary among dioxanone and glycolide.In this case, intermediate layer
Absorbable polymer material can be formed, beneficial to composite in field of orthopaedics, especially absorbable orthopaedics Material Field
Using.
In addition, in one aspect of the invention in involved composite, alternatively, the intermediate layer and the polymer
Matrix is with Covalent bonding together.In this case, strong interface active force can be formed between intermediate layer and polymeric matrix, from
And adhesion therebetween is effectively improved, be advantageous to the conduction of power.
Another aspect provides a kind of preparation method of absorbable bio-medical composition, its step bag
Include：Prepare the base particle being made up 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 that the intermediate layer being made up of first reaction monomers is coated on the base particle；And add the
Two reaction monomers, heating is maintained, and continue reaction 2 hours to 48 hours, so as to form polymer matrix on the intermediate layer
Body.In such a case, it is possible to form the composite comprising intermediate layer, the mechanical strength and toughness of the composite can obtain
To raising, this important in inhibiting in orthopedic medical device application.
In addition, in another aspect of this invention in the preparation method of involved composite, alternatively, described first is anti-
Monomer and second reaction monomers are answered to be respectively selected among lactide, caprolactone, Lanthanum Isopropoxide and glycolide at least
It is a kind of.In such a case, it is possible to which absorbable intermediate layer and polymeric matrix is prepared, this is advantageous to composite in bone
Section field, the application of especially absorbable orthopaedics Material Field.
In addition, in another aspect of this invention in the preparation method of involved composite, alternatively, described first is anti-
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., the glass transition temperature of intermediate layer or polymeric matrix is controlled, 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
Its preparation method.
Brief description of the drawings
Fig. 1 is the structural representation for showing the absorbable bio-medical composition involved by embodiments of the present invention
Figure.
Fig. 2 shows the partial structural diagram of the bio-medical composition involved by present embodiment.
Fig. 3 is the preparation process schematic diagram for showing absorbable bio-medical composition.
Symbol description：
10 ... composites, 11 ... base particles, 12 ... intermediate layers, 13 ... polymeric matrixs.
Embodiment
Hereinafter, refer to the attached drawing, the preferred embodiment of the present invention is explained.In the following description, for identical
Part assign identical symbol, the repetitive description thereof will be omitted.Scheme in addition, accompanying drawing is simply schematical, the mutual chi of part
Very little ratio or the shape of part etc. can be with the differences of reality.
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 content described under subhead being limited in the theme of subhead.
(composite)
Fig. 1 is the structural representation for showing the absorbable bio-medical composition involved by present embodiment.Fig. 2
Show the partial structural diagram of the bio-medical composition involved by present embodiment.
As depicted in figs. 1 and 2, the composite 10 involved by present embodiment can include base particle 11, intermediate layer
12 and polymeric matrix 13.Specifically, intermediate layer 12 is coated with the outer surface of base particle 11, polymeric matrix is formed in
The outer surface of interbed 12.In some instances, base particle 11 and intermediate layer 12 can be used as entirety to be homogeneously dispersed in polymerization
In thing matrix 13.
As described above, formed with intermediate 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 base particle 11 and polymeric matrix can be strengthened
13 interface interaction power, improve base particle 11 and disperse in polymeric matrix 13, so as to improve the power of composite 1 simultaneously
Learn intensity and toughness.
(base particle)
In the present embodiment, base particle 11 can include calcium phosphorous compound.Preferably, base particle 11 can include
One or more of work as selected from hydroxyapatite, calcium polyphosphate and tricalcium phosphate.In this case, it is favorably improved composite wood
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 involved composite 10 is implanted in vivo as orthopaedics repair materials, intermediate layer 12 and polymeric matrix 13 (are retouched later
State) it can be absorbed by the body, therefore calcium, the element such as phosphorus that base particle 11 is included can be systemically absorbed, and form new bone
Bone tissue, therefore contribute to 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 the composition of skeleton tissue similar in material, just can improve composite 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 more than 2 × 1011Pa rigid particles.In this case, the mechanics of composite 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 spherical.But present embodiment not limited to this, 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
10 mechanical strength and the consideration of 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 10
In, base particle 11 plays a part of improving the mechanical strength of composite 10, it is however generally that, the content of base particle 11 is got over
More, the mechanical strength of composite 10 is higher.When the content of base particle 11 is less, the mechanical strength of composite 10 is not
Foot, and when the content of base particle 11 is excessive, then it can make the relative reduction of content of polymeric matrix 13 in composite 10, by
This influences the mechanical strength of composite 10.Therefore, the mass percent of base particle 11 is taken as 1wt%~10wt%, can
To improve the mechanical strength of composite 10, or ensure that the mechanical strength of composite 10 is not influenceed by or by smaller.
In addition, in the present embodiment, the average grain diameter of base particle 11 is not particularly limited.For composite 10
The consideration of mechanical strength and toughness, the average grain diameter of base particle 11 is preferably 5nm~200 μm, for example, base particle 11 is flat
Equal particle diameter 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 particle diameter of usual base particle 11 is smaller, and its rigidity is stronger, therefore selects grain
During the less base particle 11 in footpath, the effect that base particle 11 strengthens the mechanical strength of composite 10 can be given full play to；With
The increase of the particle diameter of base particle 11, its surface energy reduces, and can suppress to reunite to a certain extent, but when base particle 11
Particle diameter is excessive, can influence its scattered uniformity, so as to influence the mechanical strength of lactic acid composite material 1.Therefore, by substrate
The particle diameter of particle 11 limits within the above range, can play a part of strengthening the mechanical strength of composite 10, and can keeps base
Bottom particle 11 it is scattered enough uniformly.
(intermediate layer)
In the present embodiment, intermediate layer 12 can be coated on the surface of base particle 11.That is, intermediate layer 12 is covered in
The surface of base particle 11.In addition, intermediate 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 material,
When ambient temperature is higher than the glass transition temperature of polymer, material will be resilient state or rubbery state；It is less than in ambient temperature
Or equal to polymer glass transition temperature when, material will be in glassy state.
When the composite 10 involved by present embodiment is applied into human body, due to first glass in the intermediate layer 12
State conversion temperature T1 is not higher than normal body temperature's (such as 37 DEG C), and therefore, intermediate layer 12 can remain rubbery state.This
In the case of, it can discharge (such as release in situ) stress concentration as caused by base particle 11 in the intermediate layer 12 of rubbery state and delay
Solution thus caused micro-crack, the toughness thus, it is possible to improve composite 10.In addition, the base particle 11 can also consolidate
The drastic mechanical deformation of (such as in situ firm) in the intermediate layer 12 of rubbery state under certain stress, thus, it is possible to suppress composite 10
The decline of mechanical strength.
In the present embodiment, intermediate layer 12 can be made up of polymeric material, and intermediate 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 intermediate layer 12, from
And adhesion therebetween is effectively improved, be advantageous to the conduction of power.In addition, can be between intermediate layer 12 and base particle 11
Combined with the strong interface such as ionic bond active force.
In the clinical practice of human body orthopaedics reparation, when strong in existing between the intermediate layer 12 of rubbery state and base particle 11
During active force, it can aid in the conduction of power between intermediate layer 12 and base particle 11 and promote the connected effect of the two.Specifically
For, on the one hand, the stress collection that (such as in situ discharge) is triggered by base particle 11 can be discharged in the intermediate layer 12 of rubbery state
In and alleviate micro-crack, so as to improve the toughness of composite 10；On the other hand, base particle 11 can consolidate (such as former
Position is firm) drastic mechanical deformation of the intermediate layer 12 of rubbery state under certain stress, so as to effectively suppress the intermediate layer due to rubbery state
The decline of the mechanical strength of composite 10 caused by 12 addition.Therefore, it is possible to improve simultaneously the intensity of composite 10 with
Toughness, this important in inhibiting in orthopedic medical device application for the composite 10 involved by present embodiment.
In the present embodiment, the mass percent (wt%) in intermediate layer 12 is not particularly limited.For composite 10
Mechanical strength and toughness consideration, the mass percent in intermediate layer 12 is preferably 1wt%~10wt%, such as intermediate layer 12
Mass percent can take 1wt%, 3wt%, 5wt%, 8wt% or 10wt%.Specifically, it is middle in composite 10
Layer 12 plays a part of strengthening the toughness of composite 10, it is however generally that, the content in intermediate layer 12 is more, the toughness of composite 10
Better.When the content in intermediate layer 12 is less, the toughness deficiency of composite 10, and when the content in intermediate layer 12 is excessive, then
The performance characteristics such as the mechanical strength of composite 10 can be influenceed.Therefore, by the mass percent in intermediate layer 12 be taken as 1wt%~
10wt%, can improve the toughness of composite 10, and other performance characteristics such as mechanical strength to composite 10 do not produce
Influence or influence smaller.
In the present embodiment, intermediate layer 12 can include and be selected from lactide, caprolactone, Lanthanum Isopropoxide and glycolide
A kind of homopolymer of central monomer.In addition, intermediate layer 12 can also be included selected from lactide, caprolactone, Lanthanum Isopropoxide
With random copolymer or the block copolymer more than binary among glycolide.In this case, intermediate layer 12 can be formed
Absorbable polymer material, be advantageous to composite 10 in field of orthopaedics, the application of especially absorbable orthopaedics Material Field.
As described above, in the present embodiment, first glass transition temperature T1 can not be high possessed by intermediate layer 12
In normal body temperature.In addition, first glass transition temperature T1 concrete numerical value scope is not particularly limited, it is preferable that
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
Spend T1 and meet -37 DEG C≤T1≤36 DEG C.
In addition, in the present embodiment, the glass transition temperature T1 in intermediate layer 12 size can be according to being actually needed
Regulated and controled.For homopolymer, different glass transition temperature can be obtained by the species or quality for regulating and controlling monomer
Spend T1；For copolymer, glass transition temperature can be realized by regulating and controlling in mix monomer ratio of each monomer etc.
T1 change.
In addition, in the present embodiment, the molding mode in intermediate layer 12 is not particularly limited.In some instances, can be with
By triggering in-situ polymerization to be formed in the outer surface of base particle 11.In addition, in other examples, can also be by substrate
The mode that the surface of particle 11 is modified is formed.
(polymeric matrix)
In the present embodiment, polymeric matrix 13 is formed in the outer surface in intermediate layer 12.In addition, polymeric matrix 13 can
With with the second glass transition temperature T2.In some instances, the second glass transition temperature T2 can be more than intermediate layer 12
The first glass transition temperature T1 having, i.e. T2 ＞ T1.Thus, under same temperature conditionss, polymeric matrix 13 can
Keep than 12 more preferable mechanical strength of intermediate layer, so as to strengthen the mechanical property of composite 10.
In addition, in the present embodiment, second glass transition temperature T2 can be higher than possessed by polymeric matrix 13
Normal body temperature.Thus, when the composite 10 involved by present embodiment is applied into human body, polymeric matrix 13 can
To remain glassy state, it may further ensure that the mechanical strength of composite 10 is sufficiently high.
In the present embodiment, on intermediate 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 intermediate layer 12 and polymeric matrix 13, so as to have
Effect improves adhesion therebetween, is advantageous to the conduction of power.
In the present embodiment, intermediate 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, so as to effectively improve adhesion therebetween, is advantageous to
The conduction of power.In addition, it can also be combined between intermediate layer 12 and polymeric matrix 13 with the strong interface active force such as ionic bond.
In addition, in the present embodiment, polymeric matrix 13 can be included selected from lactide, caprolactone, to dioxocyclohex
A kind of homopolymer of monomer among ketone and glycolide.In addition, polymeric matrix 13 can also be included selected from lactide, in oneself
Random copolymer or block copolymer more than binary among ester, Lanthanum Isopropoxide and glycolide.In this case, gather
Compound matrix 13 can form absorbable polymer material, be advantageous to composite 10 in field of orthopaedics, especially absorbable
The application in bone material field.
Fig. 3 is the preparation process schematic diagram for showing absorbable bio-medical composition.
Hereinafter, with reference to figure 3, the system of the absorbable bio-medical composition involved by present embodiment is described in detail
Preparation Method.
As shown in figure 3, the method for preparing absorbable bio-medical composition involved in present embodiment can be with
Comprise the following steps：Prepare the base particle 11 (step S1) being made up of calcium phosphorous compound；Base particle 11 and first is reacted
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 that the intermediate layer 12 being made up of first reaction monomers is wrapped
It is overlying on base particle 11 (step S3)；The second reaction monomers are added, maintain heating, and continue reaction 2 hours to 48 hours, so as to
Polymeric matrix 13 is formed on the intermediate layer 12, it is final to obtain composite 10 (step S4).
In the present embodiment, in step sl, the base particle 11 being made up of calcium phosphorous compound is prepared first.At 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 the composite wood involved by present embodiment
After material 10 is implanted in vivo as orthopaedics repair materials, intermediate layer 12 and polymeric matrix 13 (being described later on) can be inhaled by human body
Receive, therefore calcium, the element such as phosphorus that base particle 11 is included 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 the composition of skeleton tissue similar in material, can also improve composite 10
Repair to skeleton tissue.
In the present embodiment, in step s 2, it is the reaction monomers of base particle 11 and first in step S1 are fully mixed
Close, obtain mixed solution.In some instances, in step s 2, can be simultaneously molten by the reaction monomers of base particle 11 and first
In organic solvent, it 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 among lactide, caprolactone, Lanthanum Isopropoxide and glycolide
Kind.In addition, the first reaction monomers can also be selected from lactide, caprolactone, Lanthanum Isopropoxide and glycolide among two kinds with
On.In this case, resulting intermediate layer 12 is comprising selected from lactide, caprolactone, Lanthanum Isopropoxide and glycolide
A kind of homopolymer of central monomer, or binary among lactide, caprolactone, Lanthanum Isopropoxide and glycolide with
On random copolymer or block copolymer.Thus, intermediate layer 12 can form absorbable polymer material, be advantageous 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, can include once with
On addition.In some instances, added next time again after equal question response certain time after addition every time, it is possible thereby to shape
Into block polymer.
In the present embodiment, in step s3, catalyst is added in mixed solution resulting in step s 2,
And under conditions of inert gas, 80 DEG C~180 DEG C are heated to, react 2 hours to 48 hours, so that by the first reaction monomers structure
Into intermediate layer 12 be coated on base particle 11.In some instances, with such as covalent between base particle 11 and intermediate layer 12
The high forces of key etc combine, it is possible thereby to improve the adhesion of the two, are advantageous 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 trigger 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 ensure
The smooth generation of reaction, effectively avoids the generation of other impurities.
In the present embodiment, in step s 4, in step S3 reaction system, the second reaction monomers are added, are maintained
Heating, and continue reaction 2 hours to 48 hours, so as to form polymeric matrix 13 on intermediate layer 12, finally obtain compound
Material 10.
Wherein, the second reaction monomers can be one among lactide, caprolactone, Lanthanum Isopropoxide and glycolide
Kind.In addition, the second reaction monomers can also be two kinds among lactide, caprolactone, Lanthanum Isopropoxide and glycolide
More than.In this case, resulting polymeric matrix 13 be comprising selected from lactide, caprolactone, Lanthanum Isopropoxide and
A kind of homopolymer of monomer among glycolide, or among lactide, caprolactone, Lanthanum Isopropoxide and glycolide
More than binary random copolymer or block copolymer.Thus, polymeric matrix 13 can form absorbable polymer material,
Be advantageous to application of the composite 10 in 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 species difference, contained
Amount is different or species and content not equivalent situations.
In addition, in the present embodiment, in step s 4, add the process of the second reaction monomers, can include once with
On addition.In some instances, added next time again after equal question response certain time after addition every time, it is possible thereby to shape
Into 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, by centrifugal treating, then through the second organic solvent deposit and clean,
Preferably, second organic solvent is methanol, may finally obtain the polymer of intermediate layer 12 (intermediate layer 12), base particle 11 with
The composition (base particle 11- intermediate layers 12) in intermediate layer 12, and include base particle 11, intermediate layer 12 and polymeric matrix
13 composite 10 (base particle 11- intermediate layers 12- polymeric matrixs 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 determined.
In addition, in the present embodiment, the composite 10 that step S4 is obtained is through injection molding, then obtains it after tested
Mechanics property analysis result.
In the present embodiment, wrapped by the absorbable bio-medical composition 10 prepared by step S1 to step S4
Base particle 11 and polymeric matrix 13, and the intermediate layer 12 between base particle 11 and polymeric matrix 13 are included.
As described above, the glass transition temperature in intermediate layer 12 is not higher than normal body temperature, therefore, by involved by present embodiment
When composite 10 is applied to Orthopedic Clinical treatment, the intermediate layer 12 can remain rubbery state in human body, should be in rubbery state
Intermediate layer 12 can alleviate stress concentration and micro-crack as caused by base particle 11, improve the toughness of composite 10.Together
When, the base particle 11 can also consolidate the drastic mechanical deformation under certain stress in the intermediate layer 12 of rubbery state, therefore also can
Suppress the decline of the mechanical strength of composite 10.
It is compound to absorbable bio-medical provided by the invention with reference to embodiments in order to further illustrate the present invention
Material and preparation method thereof is described in detail, and combines the beneficial effect that comparative example is realized to the present invention and absolutely prove.
(embodiment 1)
By the hydroxyapatite that 0.1g particle diameters are 5nm, 0.06g levorotatory lactide monomer and 0.06g caprolactone
Monomer is well mixed, and is added 40ul stannous octoates, is then stirred and heated to 180 DEG C under nitrogen protection, question response mixture melts
After changing uniformly, continue stirring reaction 2 hours, form hydroxyapatite-rubber state layer.Then it is left that 10g is added into reaction system
Lactide is revolved, continues to react 2 hours at 180 DEG C.
After reaction terminates, reactant mixture is dissolved with chloroform, then precipitated in methyl alcohol, and cleaned 3 times with methanol, obtained
To hydroxyapatite-rubber state layer-lactic acid composite material.
Resulting hydroxyapatite-rubber state layer composite and hydroxyapatite-rubber state layer-PLA is compound
Material is dissolved in chloroform respectively, is then centrifuged with 15000rpm speed, 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 chromatogram (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 determined 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
The weight average molecular weight of rubber state layer-PLA, obtains with reference to the cubage of hydroxyapatite, the results are shown in Table 1.
Table 2
(embodiment 2)
By the hydroxyapatite that 1g particle diameters are 200um, 0.4g levorotatory lactide monomers, 0.4g Lanthanum Isopropoxide lists
Body and 0.4g glycolide monomers are well mixed in 100ml dry toluenes, add 160ul stannous octoates, are then protected in argon gas
Under be heated with stirring to 80 degrees Celsius, after question response thing mixed dissolution is uniform, continue stirring reaction 48 hours, form hydroxy-apatite
Stone-rubber state layer.Then 8.5g glycolides are added into reaction system, continue to react 48 hours at 80 degrees celsius.
Reaction precipitates reactant mixture after terminating in methyl alcohol, and is cleaned 3 times with methanol, obtains hydroxyapatite-rubber
Colloidal state layer-PGA composite.
Resulting hydroxyapatite-rubber state layer composite and hydroxyapatite-rubber state layer-PGA is multiple
Condensation material is dissolved in chloroform respectively, is then centrifuged with 15000rpm speed, is taken supernatant liquor to precipitate and clean in methyl alcohol,
Obtain free rubbery feel polymer and rubbery state-polyglycolide polymers carry out material characterization, differential scanning calorimetry (DSC)
1 is shown in Table with gel permeation chromatography (GPC) data result.
Hydroxyapatite-rubber state layer-PGA composite is subjected to injection molding, stretching mechanical property testing knot
Fruit is shown in Table 2.The mass content of hydroxyapatite is determined by TGA in hydroxyapatite-rubber state layer-PGA composite,
For 10%.The mass content of rubber state layer in hydroxyapatite-rubber state layer-PGA composite is by rubber in table 1
The weight average molecular weight of state layer and rubber state layer-PLA, obtains with reference to the cubage of hydroxyapatite, the results are shown in Table 1.
(embodiment 3)
Hydroxyapatite and 0.3g caprolactone monomers that 0.5g particle diameters are 200nm are mixed in 100ml dry toluenes
Close uniformly, add 100ul stannous octoates, be then heated with stirring to 120 degrees Celsius under argon gas protection, question response thing mixed dissolution
After uniformly, continue stirring reaction 12 hours, then add 0.3g Lanthanum Isopropoxide monomers, continuation is reacted at one hundred and twenty degrees centigrade
12 hours, form hydroxyapatite-rubber state layer.Then 4.6g glycolides are added into reaction system, are continued at 130 degrees Celsius
Lower reaction 24 hours, adds 4.6g levorotatory lactides, continues to react 24 hours under 130 degrees Celsius afterwards.
Reaction precipitates reactant mixture after terminating in methyl alcohol, and is cleaned 3 times with methanol, obtains hydroxyapatite-rubber
Colloidal state layer-poly (lactic acid-glycolic acid) composite.
By resulting hydroxyapatite-rubber state layer composite and hydroxyapatite-rubber state layer-PLA ethanol
Sour composite is dissolved in chloroform respectively, is then centrifuged with 15000rpm speed, is taken supernatant liquor 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
Hot method (DSC) and gel permeation chromatography (GPC) data result are shown in Table 1.
Hydroxyapatite-rubber state layer-poly (lactic acid-glycolic acid) composite 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 the mass content of hydroxyapatite by
TGA is determined, and is 5%.The mass content of rubber state layer in hydroxyapatite-rubber state layer-poly (lactic acid-glycolic acid) composite
By rubber state layer in table 1 and the weight average molecular weight of rubber state layer-PLA, obtain, tie with reference to the cubage of hydroxyapatite
Fruit is shown in Table 1.
(comparative example 1)
Hydroxyapatite and 10g levorotatory lactide monomers that 0.1g particle diameters are 5nm are well mixed, it is pungent to add 40ul
Sour stannous, 180 degrees Celsius, after question response mixture melts uniformly are then stirred and heated under nitrogen protection, it is anti-to continue stirring
Answer 2 hours, form hydroxyapatite-lactic acid composite material.
Reaction dissolves reactant mixture with chloroform after terminating, and then precipitates in methyl alcohol, and is cleaned 3 times with methanol, obtains
To hydroxyapatite-lactic acid composite material.
Resulting hydroxyapatite-lactic acid composite material is dissolved in chloroform, then with 15000rpm speed
Centrifugation, takes supernatant liquor to precipitate and clean in methyl alcohol, obtains free PLA 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 determined by TGA in base apatite-lactic acid composite material, is 1%.
(comparative example 2)
By hydroxyapatite and 9.9g the PLLAs dispersing and dissolving in chloroform that 0.1g particle diameters are 5nm, stirring
Uniformly, then precipitate in methyl alcohol, obtain hydroxyapatite/polylactic acid composite material.
The molecular weight and the test result of glass transition temperature and comparative example 1 for the PLLA that this comparative example uses 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 determined by TGA, is 1.2%.
(comparative example 3)
PLLA in comparative example 2 is subjected to injection molding, stretching mechanical property testing the results are shown in Table 2.
The Interface Design of the present invention can be improved effectively simultaneously it can be seen from the comparison of embodiment 1 and comparative example 3
The intensity (being represented by Young's modulus and tensile strength) and toughness (being represented by elongation at break) of polyester material.
The comparison of embodiment 1 and comparative example 1 can be seen that what rubber state layer was formed between hydroxyapatite and PLA
Cushioning effect improves helpful to the toughness of poly-lactic acid material.
Lack strong interface interaction power in comparative example 2 between hydroxyapatite and PLA matrix, therefore embodiment 1,
The comparison of comparative example 1 and comparative example 2 can be seen that the high forces being can absorb in the present invention at composite median surface for carrying
The mechanical property of high composite plays the role of important.
Although being illustrated above in association with drawings and embodiments to the present invention, 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
The present invention can be deformed and changed as needed, these deformations and change are within the scope of the present invention.
Claims (10)
- A kind of 1. absorbable bio-medical composition, it is characterised in that：Including：Base particle, it includes calcium phosphorous compound；Intermediate layer, it is coated on the surface of the base particle, and the intermediate layer has the first glass transition temperature, and institute State the first glass transition temperature and be not higher than normal body temperature；AndPolymeric matrix, it is formed has the second glass transition temperature in the outer surface in the intermediate layer, the polymeric matrix Degree, and second glass transition temperature is more than first glass transition temperature.
- 2. bio-medical composition as claimed in claim 1, it is characterised in that：The base particle includes at least one of works as selected from hydroxyapatite, calcium polyphosphate and tricalcium phosphate.
- 3. bio-medical composition as claimed in claim 1, it is characterised in that：The intermediate layer is polymeric layer, and with Covalent bonding together between the base particle and the intermediate layer.
- 4. bio-medical composition as claimed in claim 1, it is characterised in that：The mass percent of the base particle is 1wt%~10wt%, the mass percent in the intermediate layer for 1wt%~ 10wt%.
- 5. the bio-medical composition as described in claim 1 or 3, it is characterised in that：On the intermediate layer, the polymeric matrix is formed in a manner of in-situ polymerization.
- 6. bio-medical composition as claimed in claim 1, it is characterised in that：The intermediate layer includes a kind of homopolymerization of monomer among lactide, caprolactone, Lanthanum Isopropoxide and glycolide Thing, or random copolymer or block more than the binary among lactide, caprolactone, Lanthanum Isopropoxide and glycolide Copolymer.
- 7. the bio-medical composition as described in claim 1 or 3, it is characterised in that：The intermediate layer is with the polymeric matrix with Covalent bonding together.
- A kind of 8. preparation method of absorbable bio-medical composition, it is characterised in that：Including：Prepare the base particle being made up of calcium phosphorous compound；The base particle and the first reaction monomers are sufficiently mixed, obtain mixed 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 is small Up to 48 hours, so that the intermediate layer being made up of first reaction monomers is coated on the base particle；AndThe second reaction monomers are added, maintain heating, and continue reaction 2 hours to 48 hours, so as to the shape on the intermediate layer Into polymeric matrix.
- 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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| CN201910134926.2A CN109701081B (en) | 2017-07-15 | 2017-07-15 | Absorbable biomedical composite material and preparation method thereof |
| 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 |
| EP18835430.2A EP3656406B1 (en) | 2017-07-15 | 2018-07-15 | Absorbable biomedical composite material and preparation method therefor |
| PCT/CN2018/095731 WO2019015542A1 (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 |
| US17/656,642 US11786638B2 (en) | 2017-07-15 | 2022-03-26 | 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 |
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| CN113101421B (en) * | 2019-08-31 | 2023-01-10 | 立心(深圳)医疗器械有限公司 | Artificial bone composite material with bone repair capability |
| CN110694104B (en) * | 2019-10-21 | 2021-08-06 | 深圳市立心科学有限公司 | Composite artificial fiber element and artificial ligament |
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| CN109701081B (en) | 2019-12-06 |
| CN109876191A (en) | 2019-06-14 |
| CN109876191B (en) | 2020-04-03 |
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| CN109701081A (en) | 2019-05-03 |
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