CN106880875A - Hydroxyapatite crystal whisker strengthens the preparation method of biodegradable block copolymer calcium silicates composite bone repairing material - Google Patents
Hydroxyapatite crystal whisker strengthens the preparation method of biodegradable block copolymer calcium silicates composite bone repairing material Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
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- A61L2430/00—Materials or treatment for tissue regeneration
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/38—Materials or treatment for tissue regeneration for reconstruction of the spine, vertebrae or intervertebral discs
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Abstract
The invention discloses the preparation method that hydroxyapatite crystal whisker strengthens biodegradable block copolymer calcium silicates composite bone repairing material.Described bone renovating material is constituted by hydroxyapatite crystal whisker, degradable lactic acid basic amine group acid copolymer and calcium silicates are compound, wherein hydroxyapatite crystal whisker content is 10 20%, the content of calcium silicates is 10 30%, the total content of the two is 20 45%, and lactic acid basic amine group acid copolymer is polymerized for L lactic acid with a kind of α basic amino acids.The material that the inventive method is prepared has more preferable mechanical strength, can be used for the Bone Defect Repari of the bearing positions such as bone grafting fusion, skull reparation, and it is degradable in vivo, calcium, phosphorus, silicon ion can be provided for bone tissue, and catabolite has no significant effect to surrounding environment.
Description
Technical field
The present invention relates to a kind of compound bone renovating material of degradable organic-inorganic for bone tissue defect repair
Preparation method, is especially that a kind of compound bone of hydroxyapatite crystal whisker enhancing lactic acid-basic amine group acid copolymer-calcium silicates is repaiied
The preparation method of multiple material.
Background technology
In bone tissue agglutination, degradable biological material can form tissue in the presence of body fluid reclaimed water and enzyme
Enter (growth)-material to move back the desired tissue reproduced state of (degraded absorbs) and receive significant attention.And for support type bone
Repair degradable material and must be fulfilled for two point requirements, 1) the certain degradation speed of material holding, for freshman bone tissue provides growth sky
Between；2) material has a good initial strength, meets support reparation demand, and, during degraded, it is necessary to remain enough strong
Degree, meets the mechanical requirements in bone tissue agglutination.
Biodegradable block copolymer-calcium silicates composite bone repairing material (201510034938.X) is a kind of new active inorganic
Salt/degradable macromolecule composite bone repairing material, the materials'use basic amino acid, except adjustable and change copolymer degraded
Speed, can particularly be such that produced basic amino acid after material degradation in vivo is mutually neutralized with the acidity of lactic acid, to reduce
Stimulation of the catabolite to tissue.Meanwhile, using calcium silicates as inorganic active composition, silico-calcium salt is not relative to for the material
Siliceous active salt such as tricalcium phosphate, calcium monohydrogen phosphate etc. are with bioactivity higher.
However, the animal et al. Ke of biodegradable block copolymer-calcium silicates composite bone repairing material (201510034938.X)
Found in research, although biodegradable block copolymer-calcium silicates composite bone repairing material degraded is all right, and osteogenic activity is high, but its
Initial strength is not enough, and it is too fast to decay in degradation process, it is impossible to provide the support requirement needed for tissue healing process.Therefore,
The material can not fully meet support type Bone Defect Repari demand.
Therefore, the intensity in how improving the initial strength and degradation process of material keeps being the class that must be studied
Topic.Usually, inorganic particle filled in macromolecule body, inorganic particulate has obvious humidification to macromolecule, for example
Used as construction material by the use of calcium carbonate Reinforced PVC, fibre reinforced PEEK materials make as weight bearing area bone renovating material
With.But due to the special construction of calcium silicates, it is not obvious to high molecular humidification.
Whisker is a kind of fiber grown into single crystal form under manual control condition, and its diameter is very small, so that difficult
It is contained in the defect often occurred in big crystal, in order, thus intensity is close to the theoretical value of perfect crystal for its atom high, not only
With excellent high temperature resistant, hyperpyrexia, decay resistance, also with lightweight, the mechanical advantage such as high intensity, hardness and modulus.Cause
This, whisker reinforced polymer based composites are a kind of effective means for improving intensity.
The content of the invention
For above-mentioned situation, the hydroxyapatite crystal whisker enhancing present invention firstly provides a kind of new model is degradable compound
Bone renovating material is especially a kind of using the compound Bone Defect Repari of the enhanced biodegradable block copolymer-calcium silicates of nanometer hydroxyapatite
Material.The present invention further additionally provides the preparation method of the enhancing composite bone repairing material.
Hydroxyapatite of the present invention strengthens the preparation method of biodegradable block copolymer-calcium silicates composite bone repairing material, can be with
Carry out in the following manner：
1'：By the catalyst of described Pfansteihl and basic amino acid and catalytic amount, in 120 ± 5 DEG C and 0.1Mpa pressure
Under the conditions of be dehydrated 2 hours, described catalyst is stannous chloride, and its amount controls the 0.1-0.9% in reactant gross mass, wherein
It is preferably in a proportion of 0.3-0.6%.
2'：Under 140 ± 5 DEG C and 0.01Mpa pressure after reaction 3 hours, continue to react 12~18 small under 5000Pa pressure
When, complete prepolymerization.Because the oligomer molecules amount that initial reaction stage is formed is very low, keep anti-under relatively high pressure
Should, it is possible to prevente effectively from these low molecule products may be discharged reaction system with decompression, question response for a period of time after, with oligomeric
The raising of the molecular weight of thing, further can gradually reduce the pressure of reaction system, to obtain the product of higher molecular weight；
3'：Oligomer is further reacted 10-15 hours under the conditions of 180 DEG C -200 DEG C and 70pa, complete polymerisation.
It is maintained under the conditions of higher vacuum and completes polymerisation, the small-molecule substances such as the water that discharge reaction produces can be conducive to, obtains
The sufficiently high copolymer of molecular weight；
4'：Described hydroxyapatite crystal whisker is mixed with reactant, under 180 DEG C -200 DEG C and 70pa pressure conditions after
Continuous reaction 1 hour, obtains the polymer of whisker reinforcement；Afterwards, room temperature is cooled to, the composite target product is obtained.
5'：Described calcium silicates is mixed with reactant, continues to react 2 under 180 DEG C -200 DEG C and 70pa pressure conditions
After hour, room temperature is cooled to, obtains the composite target product.
The hydroxyapatite crystal whisker compound Bone Defect Repari material of enhancing biodegradable block copolymer-calcium silicates that the inventive method is prepared
Material, it is constituted by degradable lactic acid-basic amine group acid copolymer and calcium silicates are compound, and uses whisker reinforcement, wherein silicon
Sour calcium is the 10~35% of the bone renovating material gross mass, and hydroxyapatite crystal whisker is the 10-20% of gross mass, calcium silicates and
The quality sum of hydroxyapatite crystal whisker is not less than 25% no more than the 45% of the bone renovating material.Lactic acid-basic amino acid
Copolymer is polymerized by Pfansteihl with α-basic amino acids lysine.
Research is it has been proved that for support type bone renovating material, initial strength will meet the power in bone tissue agglutination
Learn support demand.For degradable material, because in degradation process, mechanics of materials intensity has different degrees of decline, because
This, it is necessary to there is initial strength high.In order to improve the initial strength of material, inorganic particulate enhancing is conventional mode, but inorganic
The amount that particle is added is reached when to a certain degree, and the intensity of material increases but material is changed into fragile material simultaneously, is not suitable for
Bone tissue reparation.Meanwhile, used as biomaterial, enhancing must mutually have good biocompatibility and bioactivity, in human body
Safety and skeletonization works well.It is good initial strong to obtain present invention employs hydroxyapatite crystal whisker enhancing based on this
Degree.Meanwhile, hydroxyapatite has good biocompatibility and bioactivity, can meet the primary demand of Bone Defect Repari.In order to
The material for obtaining is set to be unlikely to become fragile, the present invention is controlled to the whisker of inorganic component hydroxyapatite and the total amount of calcium silicates
System, makes it be no more than 45%.The addition of whisker is also the key factor of the mechanical strength for influenceing material.The present invention is in experiment
On the basis of summarize and obtain, when the addition of whisker is less than 10%, enhancing effect is not obvious, and during higher than 20%, the mechanics of material is strong
Degree begins to decline.Therefore, the amount of hydroxyapatite crystal whisker is limited to 10-20% by the present invention, wherein, preferred amount is 20%.
In bone renovating material of the present invention, calcium silicates is the 10~35% of the bone renovating material gross mass, preferably described
When the addition of the 25~35% of bone renovating material gross mass, wherein calcium silicates is less than 10%, silicon ion amount is too low, is unfavorable for into
Bone, when addition is higher than 35%, inorganic matter total amount is more than 45% in composite, and material is changed into fragile material.
The above-mentioned hydroxyapatite crystal whisker enhancing biodegradable block copolymer-calcium silicates composite bone repairing material of the present invention in vivo may be used
To be degraded, therefore basic amino acid described in material is the lysine that can be absorbed for human body.
Basic amino acid is used in composite bone repairing material of the present invention, except adjustable and change copolymer degraded speed
Degree, can particularly be such that produced basic amino acid after material degradation in vivo is mutually neutralized with the acidity of lactic acid, to reduce
Stimulation of the solution product to tissue.Based on this, in the polymer, the mol ratio of lactic acid and basic amino acid (60~
80)：(20~40) are preferably in a proportion of 65:35, it is less than 60 in the mol ratio of the two:When 40, polymer molecular weight is relatively low, and mechanics is strong
Degree is poor, is higher than 80 in the mol ratio of the two:When 20, basic amino acid amount is too low, and catabolite slant acidity is unfavorable for skeletonization.
Research shows that good bioactivity is that quick surface apatite deposition capability can promote material and organize the formation of
One of good synostosis, can accelerate bone tissue healing, the characteristics of be preferable bone renovating material.In this patent, experiment display,
After hydroxyapatite crystal whisker adds biodegradable block copolymer-calcium silicates composite bone repairing material, the mechanics for not only increasing material is strong
Degree, and improve the bioactivity of material.The in vitro test of reinforcing material shows that material surface forms the speed of apatite layer
It is substantially fast compared with non-reinforced material.
The initial compressive strength of hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material of the present invention is big
In 70Mpa, initial flexural strength is more than 60Mpa.
To sum up, the inventive method prepares the compound Bone Defect Repari material of hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates
The good mechanical performance of material, repairing effect also preferably, can be used for the Bone Defect Repari of the bearing positions such as bone grafting fusion, skull reparation, and
It is degradable in vivo, calcium, phosphorus, silicon ion can be provided for bone tissue, and catabolite has no significant effect to surrounding environment, clinic should
With having good prospects.
Obviously, the above of the invention, according to the ordinary technical knowledge and customary means of this area, is not departing from
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification of other diversified forms can also be made, is replaced or is changed.
The specific embodiment of form, remakes further specifically to the above of the invention by the following examples
It is bright.But this scope for being interpreted as above-mentioned theme of the invention should not be only limitted to following example.It is all based on the above of the present invention
The technology realized belongs to the scope of the present invention.
Brief description of the drawings
Fig. 1 nanometer hydroxyapatite whiskers, diameter 50nm-300nm, length 1um-5um.
Fig. 2, the surface after biodegradable block copolymer-calcium silicates composite bone repairing material soaks 1 day in simulated body fluid deposits
Thing photo (a), hydroxyapatite crystal whisker strengthens biodegradable block copolymer-calcium silicates composite bone repairing material (b) in simulated body fluid
Immersion 1 fill out after surface deposits photo.
Fig. 3 artificial neural plates.
Fig. 4 cervical vertebral fusion cages.
Fig. 5 centrum products.
Specific embodiment
Hydroxyapatite crystal whisker, Sichuan Guona Technology Co., Ltd. provides.
Embodiment 1
By 0.65 molar lactic acid, 0.35 mole of lysine, catalyst stannous chloride is (in an amount of from reactant gross mass
0.4%) add in reactor, stir, keep pressure 0.1Mpa, be warming up to 120 DEG C ± 5 DEG C, be dehydrated 2 hours；It is warming up to
140 DEG C ± 5 DEG C, pressure 0.01Mpa is kept in first 3 hours of reaction, pressure 5000Pa is kept afterwards and continues reaction 15 hours；
Afterwards, 180 DEG C -200 DEG C are warming up to, pressure 70Pa reacts 12 hours, obtains lactic acid-basic amine group acid copolymer；It is subsequently adding hydroxyl
Base apatite whiskers 20g, similarity condition reacts 1 hour, adds calcium silicates 70g, and similarity condition continues to react 2 hours, cooling
Composite is obtained to room temperature.
The cubical sample that material is processed as 10mm × 15mm × 30mm is tested for compressive strength, 10mm × 4mm ×
The sample of 100mm is used for crooked test.Result shows that the compressive strength of material is 92Mpa, and bending strength is 78Mpa.Meanwhile,
Mechanics batten is used for Degrading experiment, using phosphate buffer as soak, disk is soaked, sample quality：Soak volume
It is 1g：30ml.After soaking 12 weeks, material weight-loss ratio reaches 21%, and soak pH fluctuates in the range of 7.0-7.5.Immersion 12 weeks
The residual compression intensity of batten afterwards is 66Mpa, is bent into 53Mpa, still suitable with bone tissue intensity.
Embodiment 2
By 0.65 molar lactic acid, 0.35 mole of lysine, catalyst stannous chloride is (in an amount of from reactant gross mass
0.4%) add in reactor, stir, keep pressure 0.1Mpa, be warming up to 120 DEG C ± 5 DEG C, be dehydrated 2 hours；It is warming up to
140 DEG C ± 5 DEG C, pressure 0.01Mpa is kept in first 3 hours of reaction, pressure 5000Pa is kept afterwards and continues reaction 18 hours；
Afterwards, 180 DEG C -200 DEG C are warming up to, pressure 70Pa reacts 15 hours, obtains lactic acid-basic amine group acid copolymer；It is subsequently adding hydroxyl
Base apatite whiskers 40g, similarity condition reacts 1 hour, adds calcium silicates 50g, and similarity condition continues to react 2 hours, cooling
Composite is obtained to room temperature.
The cubical sample that material is processed as 10mm × 15mm × 30mm is tested for compressive strength, 10mm × 4mm ×
The sample of 100mm is used for crooked test.Result shows that the compressive strength of material is 113Mpa, and bending strength is 86Mpa.Meanwhile,
Mechanics batten is used for Degrading experiment, using phosphate buffer as soak, disk is soaked, sample quality：Soak volume
It is 1g：30ml.After soaking 12 weeks, material weight-loss ratio reaches 12%, and soak pH fluctuates in the range of 7.1-7.3.Immersion 12 weeks
The residual compression intensity of batten afterwards is 81Mpa, is bent into 61Mpa, still suitable with bone tissue intensity.
Embodiment 3
Composite prepared by Example 1 or 2, using conventional injection, hot pressing or general mach mode
Variously-shaped product required for preparing clinic.
Injection is commonly used for preparing the product of thickness of thin, irregular shape.Said as a example by preparing Fig. 3 artificial neural plates
It is bright.Article shape processing mold is first according to, then mould is attached on injection machine, set product injection temperature, its scope is
140 DEG C -185 DEG C, injection pressure is set, its scope is 40-90Mpa.It is molded with this understanding and can obtain injection-molded item.
Hot-press method is that composite powder is put into mould, and then being plastified in certain temperature range can be made
Product.As a example by preparing the cervical vertebral fusion cage such as Fig. 4, composite powder is fitted into mould, is moulded in the range of 170 DEG C ± 5 DEG C
Change 5-10 minutes, corresponding product is can obtain after being cooled to room temperature.
Machine-tooled method is to prepare product by modes such as car, milling, plane, mill, brills using the block of the composite of synthesis.
Centrum product shown in Fig. 5 can be prepared by machining mode.
Comparative example 1
According to the condition of embodiment 1, carry out materials synthesis, obtain being not added with (PLA-LYS) that the material of whisker obtains/
Calcium silicate material, being processed into the sample described in embodiment 1 carries out mechanics and Degrading experiment.The initial compressive strength of material is
65Mpa, bending strength is 46Mpa.After soaking 12 weeks, material weight-loss ratio reaches 31%, and the residual compression intensity of material is
33Mpa, complete intensity is 25Mpa, it is impossible to meet mechanical support demand.
The repair materials of the present invention of experimental example 1 compare with the repairing effect of prior art repair materials
Materials synthesis are carried out according to embodiment 1 and comparative example, hydroxyapatite crystal whisker enhancing biodegradable block copolymer-silicon is obtained
Sour calcium composite bone repairing material, diameter 10mm is prepared into by material, and the disk of thickness 2mm is put into immersion in simulated body fluid, immersion
Taken out after 1 day, the formational situation of surface apatite is observed under ESEM, as a result as shown in Figure 2.
Fig. 2 a are non-reinforced material surface apatite deposition situations, and Fig. 2 b are after non-reinforced hydroxyapatite crystal whisker strengthens
Material surface apatite deposition situation.It can be seen that, the surface apatite deposit of hydroxyapatite crystal whisker reinforcing material is substantially more
In non-reinforced material.
To sum up, the inventive method prepares the compound Bone Defect Repari material of hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates
The good mechanical performance of material, repairing effect also preferably, can be used for the Bone Defect Repari of the bearing positions such as bone grafting fusion, skull reparation, and
It is degradable in vivo, calcium, phosphorus, silicon ion can be provided for bone tissue, and catabolite has no significant effect to surrounding environment, clinic should
With having good prospects.
Claims (8)
1. hydroxyapatite crystal whisker strengthens the preparation method of biodegradable block copolymer-calcium silicates composite bone repairing material, it is characterized in that
Carry out in the following manner：
1'：By the catalyst of described Pfansteihl and basic amino acid and catalytic amount, in 120 ± 5 DEG C and 0.1Mpa pressure conditions
Lower dehydration 2 hours, described catalyst is stannous chloride；
2'：After being reacted 3 hours under 140 ± 5 DEG C and 0.01Mpa pressure, continue to react 12-18 hours under 5000Pa pressure,
Complete prepolymerization；
3'：Reacted 10-15 hours under the conditions of 180 DEG C -200 DEG C and 70pa, complete polymerisation, obtain polymer；
4'：Described hydroxyapatite crystal whisker is mixed with the copolymer for obtaining, is continued under the conditions of 180 DEG C -200 DEG C and 70pa
Reaction 1 hour, adds calcium silicates and mixes with reactant, continues to react 2 hours under 180 DEG C -200 DEG C and 70pa pressure conditions
Afterwards, room temperature is cooled to, the composite target product is obtained；
Wherein, the hydroxyapatite crystal whisker enhancing biodegradable block copolymer-calcium silicates composite bone repairing material is by hydroxy-apatite
Stone crystal whisker, calcium silicates are composited with degradable lactic acid-basic amine group acid copolymer, and wherein hydroxyapatite crystal whisker content is
10-20%, the content of calcium silicates is 10-35%, and the total content of the two is 25-45%, and lactic acid-basic amine group acid copolymer is L-
Lactic acid is polymerized with a kind of α-basic amino acid.
2. hydroxyapatite crystal whisker as claimed in claim 1 strengthens biodegradable block copolymer-calcium silicates composite bone repairing material
Preparation method, it is characterised in that：A diameter of 50nm-150nm of described hydroxyapatite crystal whisker, length 1um-5um.
3. hydroxyapatite crystal whisker as claimed in claim 1 or 2 strengthens biodegradable block copolymer-calcium silicates composite bone repairing material
Preparation method, it is characterised in that：The content of the hydroxyapatite crystal whisker in the composite bone repairing material is 20%.
4. the hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material as described in one of claims 1 to 3
Preparation method, it is characterised in that：Calcium silicates in the composite bone repairing material is the 25 of the bone renovating material gross mass
~35%.
5. the hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material as described in one of Claims 1-4
Preparation method, it is characterised in that：In the composite bone repairing material, hydroxyapatite crystal whisker is with the total content of calcium silicates
45%.
6. the hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material as described in one of claim 1 to 5
Preparation method, it is characterised in that：In described lactic acid-basic amine group acid copolymer, the mol ratio of lactic acid and basic amino acid
(60~80)：(20~40).
7. the hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material as described in one of claim 1 to 6
Preparation method, it is characterised in that：The basic amino acid is lysine.
8. the hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material as described in one of claim 1 to 7
Preparation method, it is characterised in that：Lactic acid and the 65 of the mol ratio of basic amino acid：35.
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| CN111437440A (en) * | 2020-04-02 | 2020-07-24 | 杭州鹿扬科技有限公司 | Controllable degradable bone implantation composite material and preparation method thereof |
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| CN101700415A (en) * | 2009-11-13 | 2010-05-05 | 中国科学院上海硅酸盐研究所 | Calcium silicate/hydroxylapatite composite biological ceramic material and preparation method and application thereof |
| CN103541006A (en) * | 2013-10-29 | 2014-01-29 | 昆明理工大学 | Preparation method of hydroxyapatite whisker |
| CN103585677A (en) * | 2013-10-30 | 2014-02-19 | 四川大学 | HA (hydroxylapatite) micro-nano whisker reinforced calcium phosphate ceramic material and preparation method and application thereof |
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| CN104524630A (en) * | 2015-01-25 | 2015-04-22 | 宁波开发区中心医院 | Degradable copolymer-calcium silicate composite bone repair material and preparation method thereof |
| CN104841011A (en) * | 2015-01-25 | 2015-08-19 | 宁波开发区中心医院 | Composite degradable copolymer-calcium silicate bone repair material preparation method |
| CN104857559A (en) * | 2015-01-25 | 2015-08-26 | 宁波开发区中心医院 | Bone repair product with degradable copolymer-calcium silicate composite bone repair materials serving as raw materials |
| CN104973878A (en) * | 2015-06-01 | 2015-10-14 | 安徽省益民工贸集团有限公司 | Hydroxyapatite whisker reinforced glass ceramic dish and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437440A (en) * | 2020-04-02 | 2020-07-24 | 杭州鹿扬科技有限公司 | Controllable degradable bone implantation composite material and preparation method thereof |
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