CN105582577B - Nanometer hydroxyapatite is grafted the preparation method of polyhydroxybutyrate valeric acid copolyesters - Google Patents
Nanometer hydroxyapatite is grafted the preparation method of polyhydroxybutyrate valeric acid copolyesters Download PDFInfo
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- CN105582577B CN105582577B CN201610105462.9A CN201610105462A CN105582577B CN 105582577 B CN105582577 B CN 105582577B CN 201610105462 A CN201610105462 A CN 201610105462A CN 105582577 B CN105582577 B CN 105582577B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
The invention discloses a kind of preparation methods of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters, mainly include the following steps：（1）Using the method that ammonia plasma treatment is handled amino is introduced on PHBV molecules；（2）Amidized PHBV with glutaraldehyde is handled, makes PHBV aldehyde radicals；（3）Nanometer hydroxyapatite is handled using silane coupling agent, makes nanometer hydroxyapatite amination；（4）The PHBV of aldehyde radical with amidized nanometer hydroxyapatite is reacted and obtains PHBV engrafted nanometer hydroxyapatites.The present invention effectively solves the problems, such as that nanometer hydroxyapatite is easily reunited in PHBV matrixes, while the present invention substantially carries out at normal temperatures, and reaction condition is mild, and preparation process is simple, and preparation efficiency is higher, has a extensive future；The nanometer hydroxyapatite that the present invention is prepared is grafted polyhydroxybutyrate valeric acid copolyesters has potential application in organizational project and bone defect healing.
Description
Technical field
Preparation method and application the present invention relates to a kind of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters,
Belong to biological medical polymer material technical field.
Background technology
Hydroxyapatite（HA）, there is the Nomenclature Composition and Structure of Complexes similar with body bone tissue, and with biology well
Compatibility is generally acknowledged bone renovating material, but it does not have degradability in vivo, and toughness is poor.Poly- hydroxyl fourth
Sour valeric acid copolyesters（PHBV）It is a kind of good medical macromolecular materials, there is biodegradability, no antigen and nontoxic,
Non-carcinogenesis receives significant attention in recent years.In recent years, the PHBV/HA composite woods prepared after PHBV and HA being mixed
Material shows good mechanical property and degradability, at the same composite material also combine PHBV toughness and HA it is strong
Degree, suitable for organizational project bone defect healing field.
But by the study found that finding that the interface compatibility between PHBV and HA is poor, HA can be higher due to surface
The phenomenon that reason can reunite in PHBV matrixes defect can be formed in PHBV matrixes, HA reunites during use
Region the premature actual effect of mechanical property can occur, so as to which the application range of PHBV/HA composite materials can be influenced.PHBV/HA
The mechanical property of composite material depends primarily on the interface compatibility between PHBV and HA, therefore, between improvement PHBV and HA
Interface compatibility is the key point for solving the problems, such as that PHBV/HA composite materials properties are poor.
Invention content
The purpose of the present invention is to provide a kind of preparations of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters
Method.The modifted-nano-hydroxyapatite that the preparation method obtains improves nanometer hydroxyapatite and is total to polyhydroxybutyrate valeric acid
Compatibility between polyester matrix solves what nanometer hydroxyapatite was easily reunited in polyhydroxybutyrate valeric acid copolyesters matrix
Problem improves the mechanical property of PHBV/HA composite materials；The present invention substantially carries out at normal temperatures, and reaction condition is mild, system
Standby simple for process, preparation efficiency is higher, in addition, material shows good cell and histocompatbility, especially suitable for
Application in terms of organizational project.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters, includes the following steps：
（1）PHBV films are passed through ammonia to 40-80Pa after 7Pa is evacuated in plasma processor, in 60-80W intensity
Lower processing 120-180 second, then will treated PHBV material cleans, dry to get to amidized PHBV（PHBV-NH2）；
（2）Glutaraldehyde water solution is prepared, then PHBV-NH2 materials are added in glutaraldehyde water solution, in the item of stirring
It reacts 6-8h under part, is centrifuged, washed after the completion of reaction, dried to get to the PHBV of surface aldehydes（PHBV-CHO）；
（3）3- aminopropyl-triethoxy silicon is added in the aqueous solution of ethyl alcohol, is fully hydrolyzed to obtain mixed solution,
Then hydroxyapatite is added in mixed solution, reacts 6h, the product after reaction is centrifuged, wash, is dried, is obtained
Surface carries the hydroxyapatite of-NH2（HA-NH2）；
（4）PHBV-CHO is dissolved in dichloromethane and obtains PHBV-CHO solution, HA-NH2 is then added to PHBV-
In CHO solution, 4-6h is stirred to react under room temperature, the product after reaction is centrifuged, then dichloromethane washing is freeze-dried, obtains
To polyhydroxybutyrate valeric acid copolyesters engrafted nanometer hydroxyapatite（PHBV-g-HA）.
The step（2）In PHBV-NH2 and glutaraldehyde molar ratio be 1:1-1.5.
The step（4）In HA-NH2 and PHBV-CHO molar ratio be 1:1.5-2.5.
The step（2）The mass concentration of middle glutaraldehyde water solution is 1%.
The step（3）The volume ratio of second alcohol and water is 9 in the aqueous solution of middle ethyl alcohol:1.
The step（3）The molar ratio of middle hydroxyapatite and 3- aminopropyl-triethoxy silicon is 1:1-1:2.
The step（3）The volume of middle 3- aminopropyl triethoxysilanes and ethanol water is 1:100-1:200.
Beneficial effects of the present invention：1st, the present invention is by nanometer hydroxyapatite surface grafting PHBV, improving PHBV
Interface compatibility between HA improves the biocompatibility of PHBV/HA composite materials.2nd, the present invention is effectively solved and is received
The problem of rice hydroxyapatite is easily reunited in PHBV matrixes, while the present invention substantially carries out at normal temperatures, reaction condition temperature
With preparation process is simple, and preparation efficiency is higher, has a extensive future.3rd, method used in the present invention is relatively simple, and is all
It carries out at normal temperatures, substantially reduces the reaction time, improve preparation efficiency, be conducive to industrialized production.4th, after the present invention
Processing is simple, and will not residual organic solvent, the biocompatibility of material is good.5th, nanometer hydroxyapatite prepared by the present invention
Grafting polyhydroxybutyrate valeric acid copolyester material effectively solves the problems, such as that hydroxyapatite is easily reunited in PHBV matrixes, can
The effective mechanical property for increasing PHBV/HA composite materials.6th, the nanometer hydroxyapatite that the present invention is prepared is grafted poly- hydroxyl
Base butyric acid valeric acid copolyesters has potential application in organizational project and bone defect healing.
Specific embodiment
Embodiment 1
The preparation method of the nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters of the present embodiment is as follows：
（1）PHBV films are passed through ammonia to 40Pa after 7Pa is evacuated in plasma processor, are handled under 60W intensity
It 120 seconds, then will treated PHBV material cleans, dry to get to amidized PHBV（PHBV-NH2）；
（2）The glutaraldehyde weak solution of 100mL1% is prepared, then by PHBV-NH2 materials according to molar ratio 1：1 is added to penta
In dialdehyde aqueous solution, 6h is reacted under conditions of stirring, centrifuged, washed after the completion of reaction, dried to get to surface aldehydes
The PHBV of change（PHBV-CHO）；
（3）1ml 3- aminopropyl-triethoxy silicon is added in the mixed solution of 100ml ethanol waters, fully carries out water
4.29g hydroxyapatites, are then added in mixed solution by solution, react 6h, then centrifuge the product after reaction, wash
It washs, dry, obtain the hydroxyapatite that surface carries-NH2（HA-NH2）；
（4）PHBV-CHO is dissolved in dichloromethane, then by HA-NH2 according to molar ratio 1：1.5 are added to PHBV-CHO
In solution, 4h is stirred to react under room temperature, the product after reaction is centrifuged, then dichloromethane washing is freeze-dried to get to poly-
Hydroxybutyric acid valeric acid copolyesters engrafted nanometer hydroxyapatite（PHBV-g-HA）.
Embodiment 2
The preparation method of the nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters of the present embodiment is as follows：
（1）PHBV films are passed through ammonia to 80Pa after 7Pa is evacuated in plasma processor, are handled under 80W intensity
It 180 seconds, then will treated PHBV material cleans, dry to get to amidized PHBV（PHBV-NH2）；
（2）The glutaraldehyde weak solution of 100mL 1% is prepared, then by PHBV-NH2 materials according to molar ratio 1：1.5 it is added to
In glutaraldehyde water solution, 8h is reacted under conditions of stirring, centrifuged, washed after the completion of reaction, dried to get to surface aldehyde
The PHBV of base（PHBV-CHO）；
（3）1ml 3- aminopropyl-triethoxy silicon is added in the mixed solution of 200ml ethanol waters, fully carries out water
4.29g hydroxyapatites, are then added in mixed solution by solution, react 6h, then centrifuge the product after reaction, wash
It washs, dry, obtain the hydroxyapatite that surface carries-NH2（HA-NH2）；
（4）PHBV-CHO is dissolved in dichloromethane, then by HA-NH2 according to molar ratio 1：2.5 are added to PHBV-CHO
In solution, 6h is stirred to react under room temperature, the product after reaction is centrifuged, then dichloromethane washing is freeze-dried to get to poly-
Hydroxybutyric acid valeric acid copolyesters engrafted nanometer hydroxyapatite（PHBV-g-HA）.
Embodiment 3
The preparation method of the nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters of the present embodiment is as follows：
（1）PHBV films are passed through ammonia to 60Pa after 7Pa is evacuated in plasma processor, are handled under 80W intensity
It 180 seconds, then will treated PHBV material cleans, dry to get to amidized PHBV（PHBV-NH2）；
（2）The glutaraldehyde weak solution of 100mL1% is prepared, then by PHBV-NH2 materials according to molar ratio 1：1 is added to penta
In dialdehyde aqueous solution, 8h is reacted under conditions of stirring, centrifuged, washed after the completion of reaction, dried to get to surface aldehydes
The PHBV of change（PHBV-CHO）；
（3）1ml 3- aminopropyl-triethoxy silicon is added in the mixed solution of 100ml ethanol waters, fully carries out water
8.56g hydroxyapatites, are then added in mixed solution by solution, react 6h, then centrifuge the product after reaction, wash
It washs, dry, obtain the hydroxyapatite that surface carries-NH2（HA-NH2）；
（4）PHBV-CHO is dissolved in dichloromethane, then by HA-NH2 according to molar ratio 1：2.5 are added to PHBV-CHO
In solution, 6h is stirred to react under room temperature, the product after reaction is centrifuged, then dichloromethane washing is freeze-dried to get to poly-
Hydroxybutyric acid valeric acid copolyesters engrafted nanometer hydroxyapatite（PHBV-g-HA）.
Embodiment 4
The preparation method of the nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters of the present embodiment is as follows：
（1）PHBV films are passed through ammonia to 60Pa after 7Pa is evacuated in plasma processor, are handled under 60W intensity
It 150 seconds, then will treated PHBV material cleans, dry to get to amidized PHBV（PHBV-NH2）；
（2）The glutaraldehyde weak solution of 100mL1% is prepared, then by PHBV-NH2 materials according to molar ratio 1：1.5 it is added to
In glutaraldehyde water solution, 8h is reacted under conditions of stirring, centrifuged, washed after the completion of reaction, dried to get to surface aldehyde
The PHBV of base（PHBV-CHO）；
（3）1ml 3- aminopropyl-triethoxy silicon is added in the mixed solution of 200ml ethanol waters, fully carries out water
8.56g hydroxyapatites, are then added in mixed solution by solution, react 6h, then centrifuge the product after reaction, wash
It washs, dry, obtain the hydroxyapatite that surface carries-NH2（HA-NH2）；
（4）PHBV-CHO is dissolved in dichloromethane, then by HA-NH2 according to molar ratio 1：1.5 are added to PHBV-CHO
In solution, 4h is stirred to react under room temperature, the product after reaction is centrifuged, then dichloromethane washing is freeze-dried to get to poly-
Hydroxybutyric acid valeric acid copolyesters engrafted nanometer hydroxyapatite（PHBV-g-HA）.
Embodiment 5
The preparation method of the nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters of the present embodiment is as follows：
（4）PHBV is passed through ammonia to 40Pa after 7Pa is evacuated in plasma processor, is handled under 80W intensity
It 120 seconds, then will treated PHBV material cleans, dry to get to amidized PHBV（PHBV-NH2）；
（2）The glutaraldehyde weak solution of 100mL1% is prepared, then by PHBV-NH2 materials according to molar ratio 1：1 is added to penta
In dialdehyde aqueous solution, 6h is reacted under conditions of stirring, centrifuged, washed after the completion of reaction, dried to get to surface aldehydes
The PHBV of change（PHBV-CHO）；
（3）1ml 3- aminopropyl-triethoxy silicon is added in the mixed solution of 100ml ethanol waters, fully carries out water
4.29g hydroxyapatites, are then added in mixed solution by solution, react 6h, then centrifuge the product after reaction, wash
It washs, dry, obtain the hydroxyapatite that surface carries-NH2（HA-NH2）；
（4）PHBV-CHO is dissolved in dichloromethane, then by HA-NH2 according to molar ratio 1：1.5 are added to PHBV-CHO
In solution, 6h is stirred to react under room temperature, the product after reaction is centrifuged, then dichloromethane washing is freeze-dried to get to poly-
Hydroxybutyric acid valeric acid copolyesters engrafted nanometer hydroxyapatite（PHBV-g-HA）.
Basic principle of the invention and main feature and advantages of the present invention has been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (7)
1. a kind of preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters, it is characterised in that including as follows
Step：
（1）PHBV films are passed through ammonia to 40-80Pa after 7Pa is evacuated in plasma processor, under 60-80W intensity
Reason 120-180 second, then general's treated PHBV material cleans, drying, obtains PHBV-NH2；
（2）Glutaraldehyde water solution is prepared, then by PHBV-NH2Material is added in glutaraldehyde water solution, under conditions of stirring
6-8h is reacted, is centrifuged, washed, dried after the completion of reaction, obtaining PHBV-CHO；
（3）3- aminopropyl triethoxysilanes are added in the aqueous solution of ethyl alcohol, are fully hydrolyzed to obtain mixed solution, so
Hydroxyapatite is added in mixed solution afterwards, 6h is reacted, the product after reaction is centrifuged, wash, is dried, is obtained
HA-NH2；
（4）PHBV-CHO is dissolved in dichloromethane and obtains PHBV-CHO solution, then by HA-NH2It is added to PHBV-CHO solution
In, 4-6h is stirred to react under room temperature, the product after reaction is centrifuged, then dichloromethane washing is freeze-dried, obtains poly- hydroxyl
Butyric acid valeric acid copolyesters engrafted nanometer hydroxyapatite.
2. the preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters according to claim 1,
It is characterized in that：The step（2）In PHBV-NH2Molar ratio with glutaraldehyde is 1:1-1.5.
3. the preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters according to claim 1,
It is characterized in that：The step（4）In HA-NH2Molar ratio with PHBV-CHO is 1:1.5-2.5.
4. the preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters according to claim 1,
It is characterized in that：The step（2）The mass concentration of middle glutaraldehyde water solution is 1%.
5. the preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters according to claim 1,
It is characterized in that：The step（3）The volume ratio of second alcohol and water is 9 in the aqueous solution of middle ethyl alcohol:1.
6. the preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters according to claim 1,
It is characterized in that：The step（3）The molar ratio of middle hydroxyapatite and 3- aminopropyl triethoxysilanes is 1:1-1:2.
7. the preparation method of nanometer hydroxyapatite grafting polyhydroxybutyrate valeric acid copolyesters according to claim 1,
It is characterized in that：The step（3）The volume of middle 3- aminopropyl triethoxysilanes and ethanol water is 1:100-1:200.
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Inventor after: Yu Xiang Inventor after: Fan Lidan Inventor after: Wang Yanwei Inventor after: Yang Liu Inventor after: Xu Qian Inventor after: Ding Ning Inventor after: Wang Fei Inventor before: Yu Xiang Inventor before: Wang Yanwei Inventor before: Yang Liu Inventor before: Xu Qian Inventor before: Ding Ning |
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