CN106620871A - Bone repairing product taking degradable copolymer-calcium silicate composite bone repairing material enhanced by hydroxyapatite whisker as raw material - Google Patents
Bone repairing product taking degradable copolymer-calcium silicate composite bone repairing material enhanced by hydroxyapatite whisker as raw material Download PDFInfo
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- CN106620871A CN106620871A CN201710014907.7A CN201710014907A CN106620871A CN 106620871 A CN106620871 A CN 106620871A CN 201710014907 A CN201710014907 A CN 201710014907A CN 106620871 A CN106620871 A CN 106620871A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
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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 invention discloses a bone repairing product taking a degradable copolymer-calcium silicate composite bone repairing material enhanced by hydroxyapatite whisker as a raw material. The bone repairing product is characterized by being compound from 10 to 20 percent of hydroxyapatite whisker, 10 to 35 percent of calcium silicate and a degradable lactate-alkaline amino acid copolymer, wherein the total content of the hydroxyapatite whisker and the calcium silicate is 25 to 45 percent; the lactate-alkaline amino acid copolymer is prepared by copolymerizing L-lactate and alpha-alkaline amino acid. The bone repairing product has higher mechanical strength, can be applied to bone repairing of force-carrying positions such as bone graft fusion and cranioplasty, is degradable in vivo, and can provide calcium, phosphorus and silicon ions for one tissues; degradation products have no remarkable influence on the surrounding environment.
Description
Technical field
The present invention relates to a kind of Bone Defect Repari product for bone tissue defect repair, is especially with hydroxyapatite whisker
Bone Defect Repari product of the biodegradable block copolymer-calcium silicates composite bone repairing material for raw material must be strengthened.
Background technology
In bone tissue agglutination, degradable biological material in the presence of water and enzyme, can form tissue in body fluid
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) material keeps certain degradation speed, provide growth for freshman bone tissue empty
Between；2) material has a good initial strength, meets the reparation demand that supports, 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 degraded that is adjustable and changing copolymer
Speed, can particularly make the acidity mutually neutralization of basic amino acid produced after material degradation in vivo and 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 higher biologically active.
However, the animal et al. Ke of biodegradable block copolymer-calcium silicates composite bone repairing material (201510034938.X)
Find 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.
For this purpose, it is the class that must be studied that the intensity in how improving the initial strength and degradation process of material keeps
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 little, so that difficult
It is contained in big crystal the defect for often occurring, 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 of raising intensity.
The content of the invention
For above-mentioned situation, present invention firstly provides a kind of hydroxyapatite crystal whisker of new model strengthens 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 Bone Defect Repari with biodegradable block copolymer-calcium silicates composite bone repairing material as raw material and uses
Product.
It is described in Bone Defect Repari product of the present invention with biodegradable block copolymer-calcium silicates composite bone repairing material as raw material
Hydroxyapatite crystal whisker strengthens biodegradable block copolymer-calcium silicates composite bone repairing material, it is characterized in that by degradable newborn Acid-Base
Acidic amino acid copolymer and the compound composition of calcium silicates, and whisker reinforcement is adopted, wherein calcium silicates is the total matter of the bone renovating material
The 10～35% of amount, hydroxyapatite crystal whisker is the quality sum of the 10-20% of gross mass, calcium silicates and hydroxyapatite crystal whisker
Less than the 45% of the bone renovating material, 25% is not less than.Lactic acid-basic amine group acid copolymer is by Pfansteihl and α-alkaline ammonia
Base acid lysine is polymerized.
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 high initial strength.In order to improve the initial strength of material, it is conventional mode that inorganic particulate strengthens, but inorganic
The amount that particle is added is when reaching to a certain degree, and the intensity of material increases but while material is changed into fragile material, is not suitable for
Bone tissue reparation.Meanwhile, used as biomaterial, strengthening mutually must have good biocompatibility and biologically active, in human body
Safety and skeletonization works well.Based on this, hydroxyapatite crystal whisker enhancing is present invention employs, it is good initial strong to obtaining
Degree.Meanwhile, hydroxyapatite has good biocompatibility and biologically active, 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 so as to less than 45%.The addition of whisker is also the key factor of the mechanical strength for affecting material.The present invention is in test
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 of the present invention strengthens biodegradable block copolymer-calcium silicates composite bone repairing material and in vivo may be used
To be degraded, therefore the basic amino acid described in material is the lysine that can be absorbed for human body.
Basic amino acid used in composite bone repairing material of the present invention, except degraded speed that is adjustable and changing copolymer
Degree, can particularly make the acidity mutually neutralization of basic amino acid produced after material degradation in vivo and 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 biologically active 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, test shows,
Hydroxyapatite crystal whisker is added after biodegradable block copolymer-calcium silicates composite bone repairing material, and the mechanics for not only increasing material is strong
Degree, and improve the biologically active 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-reinforcing material.
Bone Defect Repari product of the present invention is the symbol that described biodegradable block copolymer-calcium silicates composite bone repairing material is processed into
Close Clinical practice need including the Bone Defect Repari product including bar, block, bar form.
The above-mentioned hydroxyapatite of the present invention strengthens the preparation 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 little 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, can be prevented 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, can further be gradually lowered the pressure of reaction system, to obtain the product of higher molecular weight；
3'：Make oligomer that 10-15 hours are further reacted 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, can be conducive to discharging the small-molecule substances such as the water that reaction is produced, 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, obtains the composite target product.
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 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, hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material of the present invention is raw material preparation
Biological products, its good mechanical performance, repairing effect also preferably, can be used for bone grafting fusion, skull and the load portion such as repairs
The Bone Defect Repari of position, it is and degradable in vivo, calcium, phosphorus, silicon ion can be provided for bone tissue, and catabolite to surrounding environment without bright
Development rings, and potential applicability in clinical practice is good.
Obviously, the above of the invention, according to the ordinary technical knowledge and customary means of this area, without departing from
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification of other various ways can also be made, is replaced or is changed.
By the following examples the specific embodiment of form, remakes further specifically to the above of the present invention
It is bright.But this scope for being interpreted as above-mentioned theme of the invention should not be only limitted to Examples below.It is all based on the above of the present invention
The technology realized belongs to the scope of the present invention.
Description of the drawings
Fig. 1 nanometer hydroxyapatite whiskers, diameter 50nm-300nm, length 1um-5um.
Fig. 2 biodegradable block copolymers-calcium silicates composite bone repairing material soak 1 day in simulated body fluid after surface deposits
Photo (a), hydroxyapatite crystal whisker strengthens biodegradable block copolymer-calcium silicates composite bone repairing material (b) and soaks in simulated body fluid
Bubble 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.
Cubical sample of the materials processing for 10mm × 15mm × 30mm is tested for compressive strength, 10mm × 4mm ×
The sample of 100mm is used for crooked test.As a result show, the compressive strength of material is 92Mpa, and bending strength is 78Mpa.Meanwhile,
Mechanics batten is used for into Degrading experiment, using phosphate buffer as soak, disk is soaked, sample quality：Soak volume
For 1g：30ml.After soaking 12 weeks, material weight-loss ratio reaches 21%, and soak pH fluctuates in the range of 7.0-7.5.Soak 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.
Cubical sample of the materials processing for 10mm × 15mm × 30mm is tested for compressive strength, 10mm × 4mm ×
The sample of 100mm is used for crooked test.As a result show, the compressive strength of material is 113Mpa, and bending strength is 86Mpa.Meanwhile,
Mechanics batten is used for into Degrading experiment, using phosphate buffer as soak, disk is soaked, sample quality：Soak volume
For 1g：30ml.After soaking 12 weeks, material weight-loss ratio reaches 12%, and soak pH fluctuates in the range of 7.1-7.3.Soak 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
Prepare the variously-shaped product required for clinic.
Injection is commonly used for preparing thickness of thin, erose product.Said as a example by prepare 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 injection-molded item is obtained.
Hot-press method is that composite powder is put in mould, and then plastifying in certain temperature range can be made
Product.As a example by prepare the cervical vertebral fusion cage such as Fig. 4, composite powder is fitted in mould, is moulded in the range of 170 DEG C ± 5 DEG C
Change 5-10 minutes, be cooled to after room temperature and corresponding product is obtained.
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, obtaining hydroxyapatite crystal whisker strengthens biodegradable block copolymer-silicon
Sour calcium composite bone repairing material, by material diameter 10mm is prepared into, and the disk of thickness 2mm is put in simulated body fluid and soaks, immersion
Take 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 not enhanced material surface apatite deposition situations, and Fig. 2 b are not strengthened after hydroxyapatite crystal whisker enhancing
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-reinforcing material.
To sum up, the present invention is with hydroxyapatite crystal whisker biodegradable block copolymer-calcium silicates composite bone repairing material as raw material
Bone Defect Repari product, its good mechanical performance, repairing effect also preferably, can be used for the bearing positions such as bone grafting fusion, skull reparation
Bone Defect Repari, it is and degradable in vivo, calcium, phosphorus, silicon ion can be provided for bone tissue, and catabolite to surrounding environment without obvious
Affect, potential applicability in clinical practice is good.
Claims (9)
1. the Bone Defect Repari product with biodegradable block copolymer-calcium silicates composite bone repairing material as raw material, it is characterised in that：It is described
Repair materials are composited by hydroxyapatite crystal whisker, calcium silicates and degradable lactic acid-basic amine group acid copolymer, wherein
Hydroxyapatite crystal whisker content is 10-20%, and the content of calcium silicates is 10-35%, and the total content of the two is 25-45%, lactic acid-
Basic amine group acid copolymer is polymerized for Pfansteihl with a kind of α-basic amino acid.
2. Bone Defect Repari product as claimed in claim 1, it is characterised in that：In the repair materials, hydroxyapatite crystal whisker
A diameter of 50nm-150nm, length 1um-5um.
3. Bone Defect Repari product as claimed in claim 2, it is characterised in that：In the repair materials, hydroxyapatite crystal whisker
Content be 20%.
4. the Bone Defect Repari product as described in one of claims 1 to 3, it is characterised in that：In the repair materials, calcium silicates is
The 25～35% of the bone renovating material gross mass.
5. the Bone Defect Repari product as described in one of Claims 1-4, it is characterised in that：In the repair materials, hydroxy-apatite
Stone crystal whisker is 45% with the total content of calcium silicates.
6. the Bone Defect Repari product as described in one of claim 1 to 5, it is characterised in that：The lactic acid-basic amino acid copolymerization
In thing, (60～80) of the mol ratio of lactic acid and basic amino acid：(20～40).
7. the Bone Defect Repari product as described in one of claim 1 to 6, it is characterised in that：In the repair materials, basic amine group
Acid is lysine.
8. the Bone Defect Repari product as described in one of claim 1 to 7, it is characterised in that：In the repair materials, lactic acid and alkali
The 65 of the mol ratio of acidic amino acid：35.
9. the Bone Defect Repari product as described in one of claim 1 to 8, it is characterised in that：The Bone Defect Repari product is described
Biodegradable block copolymer-calcium silicates composite bone repairing material be processed into meet Clinical practice needs including bar, block, bar form
In interior Bone Defect Repari product.
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| CN201710014907.7A CN106620871A (en) | 2017-01-09 | 2017-01-09 | Bone repairing product taking degradable copolymer-calcium silicate composite bone repairing material enhanced by hydroxyapatite whisker as raw material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529124A (en) * | 2018-11-19 | 2019-03-29 | 昆明理工大学 | A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material |
| 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 |
| CN115591027A (en) * | 2022-11-14 | 2023-01-13 | 中鼎凯瑞科技成都有限公司（Cn） | Interpolymer materials and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120288446A1 (en) * | 2011-05-13 | 2012-11-15 | Garigapati Venkat R | Organophosphorous & multivalent metal compound compositions & methods |
| CN103541006A (en) * | 2013-10-29 | 2014-01-29 | 昆明理工大学 | Preparation method of hydroxyapatite whisker |
| 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 |
-
2017
- 2017-01-09 CN CN201710014907.7A patent/CN106620871A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120288446A1 (en) * | 2011-05-13 | 2012-11-15 | Garigapati Venkat R | Organophosphorous & multivalent metal compound compositions & methods |
| CN103541006A (en) * | 2013-10-29 | 2014-01-29 | 昆明理工大学 | Preparation method of hydroxyapatite whisker |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529124A (en) * | 2018-11-19 | 2019-03-29 | 昆明理工大学 | A kind of preparation method of graphite alkenes material/hydroxyapatite crystal whisker composite material |
| 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 |
| CN115591027A (en) * | 2022-11-14 | 2023-01-13 | 中鼎凯瑞科技成都有限公司（Cn） | Interpolymer materials and uses thereof |
| CN115591027B (en) * | 2022-11-14 | 2023-07-28 | 中鼎凯瑞科技成都有限公司 | Interpolymer material and application thereof |
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Application publication date: 20170510 |