CN106362217A - Preparation method of vegetable oil/glyceride-based polyurethane/nano-hydroxyapatite composite scaffold - Google Patents
Preparation method of vegetable oil/glyceride-based polyurethane/nano-hydroxyapatite composite scaffold Download PDFInfo
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- CN106362217A CN106362217A CN201610730688.8A CN201610730688A CN106362217A CN 106362217 A CN106362217 A CN 106362217A CN 201610730688 A CN201610730688 A CN 201610730688A CN 106362217 A CN106362217 A CN 106362217A
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- vegetable oil
- oil ester
- based polyurethane
- ester
- reaction
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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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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 preparation method of a vegetable oil/glyceride-based polyurethane/nano-hydroxyapatite composite scaffold, applied to bone tissue repair. The preparation method of the vegetable oil/glyceride-based polyurethane/nano-hydroxyapatite composite scaffold is characterized in that the vegetable oil/glyceride-based polyurethane/nano-hydroxyapatite composite scaffold is prepared by carrying out in situ compositing on vegetable oil/glyceride-based polyurethane and nano-hydroxyapatite, and carrying out water foaming. The preparation method has the advantages that the synthetic raw materials are natural and non-toxic, a preparation technology is simple, and the cost is low.
Description
Technical field
The present invention is applied to bone tissue restoration and in particular to a kind of vegetable oil ester-based polyurethane/nano-hydroxy-apatite
The preparation method of stone compound rest.
Background technology
The main purpose of bone tissue engineer is the treatment for clinical Cranial defect or gangrene.The key of Bone Defect Repari is to build to plant
Daughter cell and the complex of three-dimensional porous rack.In recent years, numerous studies show polyurethane have good biocompatibility and
Blood compatibility.The block polymer that polyurethane is made up of soft, hard section, therefore strand design freedom is larger.According to not
Select different soft and hard segment components with demand or adjust the polyurethane that soft and hard segments ratio can be prepared by different physicochemical properties.Using gas
The polyurethane foam of foaming or other foaming method gained becomes preferable tissue engineered porous scaffold material.Bio-mimetic syntheses bone
Tissue engineering bracket need to consider raw material and building-up process two aspect simultaneously, proposes to adopt crude vegetal conduct based on this present invention
The vegetable oil ester that the soft section raw material of polyurethane synthesis, crude vegetal and glycerol generation ester exchange reaction obtain is as poly- ammonia
Ester soft section, aliphatic isocyanates, as segmented polyurethane, can ensure do not have toxicity by the polyurethane that they synthesize.Polyurethane polyureas
Close and foaming process is all using nontoxic catalyst and foaming agent.Although polyurethane cellular support has good pore structure,
Its mechanical property is unsatisfactory, and therefore the present invention proposes vegetable oil ester-based polyurethane and natural bone tissue host inorganic phase
Composition hydroxyapatite carries out compound obtaining biocompatibility and the good porous support materials of mechanical property tool.According to the present invention
Vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound porous bone tissue engineering scaffold preparation process is simple, low cost
Honest and clean, it is expected to be applied to bone tissue restoration.
Content of the invention
The present invention provides has raw material Nantural non-toxic, preparation process is simple, a kind of vegetable oil ester group with low cost
The preparation method of polyurethane/nano hydroxyapatite compound rest.
A kind of preparation method of vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest: adopt rich in three
The vegetable oil of glyceride and glycerol occur ester exchange reaction to generate the soft section composition that vegetable oil ester synthesizes as polyurethane, should
Soft section carries out additive reaction with hard section constituents fats race isocyanates (isoflurane chalcone diisocyanate) under stannous octoate catalysis,
Again polyurethane is obtained by 1,4- chain expansion of succinic acid.This vegetable oil ester-based polyurethane and nanometer hydroxyapatite In-situ reaction,
Porous support materials are obtained as foaming agent foam by water.
Vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest has three-D space structure, aperture 100nm
~ 700nm, porosity 60% ~ 70%, comprcssive strength 600kpa ~ 5000kpa.
Vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest, as bone renovating material application.
The present invention compared with prior art has a following major advantage:
First, it is all nontoxic to human body to prepare, using this method, the raw material that osseous tissue engineering stephanoporate support used.
Second, this preparation method is simple, pollution-free, low in raw material price, it is easy to get.
Third, reaction active groups be increased to the ester exchange modification that vegetable oil is carried out, greatly improve reaction efficiency.
Fourth, vegetable oil ester-based polyurethane and nanometer hydroxyapatite meet as osseous tissue engineering stephanoporate support material
Material had both had good biocompatibility, has and has good mechanical property.
In a word, preparation process is simple of the present invention, with low cost, has a extensive future.
Specific embodiment
The present invention provides vegetable oil ester-based polyurethane/compound porous bone tissue engineering scaffold of nanometer hydroxyapatite.
Above-mentioned vegetable oil ester-based polyurethane/compound porous bone tissue engineer of nanometer hydroxyapatite that the present invention provides
Support, its preparation method is: occurs ester exchange reaction to generate vegetable oil using the vegetable oil rich in triglyceride and glycerol
The soft section composition that ester synthesizes as polyurethane, this soft section and hard section constituents fats race isocyanates (isoflurane chalcone diisocyanate)
Carry out additive reaction under stannous octoate catalysis, then polyurethane is obtained by BDO chain extension.This vegetable oil ester group gathers
Urethane and nanometer hydroxyapatite In-situ reaction, obtain porous support materials by water as foaming agent foam.
Above-mentioned vegetable oil ester-based polyurethane/compound porous bone tissue engineer of nanometer hydroxyapatite that the present invention provides
Support, it is applied as bone renovating material.
With reference to instantiation, the preparation method of the present invention is described further；
Embodiment 1
Glycerol and vegetable oil is adopted to carry out ester exchange reaction with 0.5:1 ~ 2.5:1 mol ratio, catalyst is calcium oxide, calcium oxide is
Glycerol and the 0.02% ~ 0.08% of the gross mass of vegetable oil, reaction temperature is 200 ~ 250 DEG C, and the response time is 1 ~ 3 hour, obtains
Vegetable oil ester.
Gained vegetable oil ester and isoflurane chalcone diisocyanate are reacted in 70 ~ 80 DEG C under nitrogen protection, plant
Thing oil glyceride institute hydroxyl and isoflurane chalcone diisocyanate institute cyano-containing mol ratio are 1:1.1 ~ 1:2, and catalyst is octanoic acid
Stannous, stannous octoate consumption is the 0.1% ~ 0.2% of vegetable oil ester and isoflurane chalcone diisocyanate gross mass, and reaction continues
After carrying out 2 ~ 4 hours；
Add BDO chain extending reaction 1 ~ 3 hour, the addition of BDO is the 2% ~ 5% of reaction system gross mass
BDO chain extending reaction 1 ~ 3 hour, obtains polyurethane cellular support, the use of water with 90 ~ 110 DEG C of Water blown after 1 ~ 4 hour
Amount is the 0.1 ~ 0.2% of reaction system gross mass.
Embodiment 2
Glycerol and vegetable oil is adopted to carry out ester exchange reaction with 0.5:1 ~ 2.5:1 mol ratio, catalyst is calcium oxide, calcium oxide is
The 0.02% ~ 0.08% of the gross mass of glycerol and vegetable oil, reaction temperature is 200 ~ 250 DEG C, and the response time is 1 ~ 3 hour, obtains
Vegetable oil ester.
Vegetable oil ester and isoflurane chalcone diisocyanate are reacted in 70 ~ 80 DEG C under nitrogen protection, vegetable oil
Glyceride institute hydroxyl and isoflurane chalcone diisocyanate institute cyano-containing mol ratio are 1:1.1 ~ 1:2, and stannous octoate consumption is to plant
Thing oil glyceride and the 0.1% ~ 0.2% of isoflurane chalcone diisocyanate gross mass, adds and adds 20wt% to receive while stannous octoate
Rice hydroxyapatite, the addition of nanometer hydroxyapatite is vegetable oil ester and isoflurane chalcone diisocyanate gross mass
20%；Reaction is persistently carried out 2 ~ 4 hours；Add 2% ~ 5% BDO chain extending reaction 1 ~ 3 hour, the addition of BDO
Amount is the 2% ~ 5% of reaction system gross mass；20wt% nanometer hydroxyl is obtained for foaming agent foam after 1 ~ 4 hour with 90 ~ 110 DEG C of water
Base apatite/vegetable oil ester-based polyurethane porous support.I.e. the quality of nanometer hydroxyapatite is (nanometer hydroxyapatite
+ vegetable oil ester-based polyurethane) gross mass 20%, the vegetable oil ester of such as 20 grams of nanometer hydroxyapatites and 80 grams
Based polyurethanes reaction obtains product.
The consumption of water is the 0.1 ~ 0.2% of reaction system gross mass.
Embodiment 3
Glycerol and vegetable oil is adopted to carry out ester exchange reaction with 0.5:1 ~ 2.5:1 mol ratio, catalyst is calcium oxide, calcium oxide is
The 0.02% ~ 0.08% of the gross mass of glycerol and vegetable oil, reaction temperature is 200 ~ 250 DEG C, and the response time is 1 ~ 3 hour, obtains
Vegetable oil ester.
Vegetable oil ester and isoflurane chalcone diisocyanate are reacted in 70 ~ 80 DEG C under nitrogen protection, vegetable oil
Glyceride institute hydroxyl and isoflurane chalcone diisocyanate institute cyano-containing mol ratio are 1:1.1 ~ 1:2, and catalyst is stannous octoate,
Stannous octoate consumption is the 0.1% ~ 0.2% of vegetable oil ester and isoflurane chalcone diisocyanate gross mass；
Add and while catalyst, add 40wt% nanometer hydroxyapatite, nanometer hydroxyapatite consumption is vegetable oil ester
With the 40% of isoflurane chalcone diisocyanate gross mass, reaction is persistently carried out 2 ~ 4 hours；
Add BDO chain extending reaction 1 ~ 3 hour, the addition of BDO is vegetable oil ester and isophorone
The 2% ~ 5% of diisocyanate+catalyst+nanometer hydroxyapatite gross mass；Obtained after 1 ~ 4 hour with 90 ~ 110 DEG C of Water blown
40wt% nanometer hydroxyapatite/vegetable oil ester-based polyurethane porous support.I.e. the quality of nanometer hydroxyapatite is (to receive
Rice hydroxyapatite+vegetable oil ester-based polyurethane) gross mass 40%, such as 40 grams of nanometer hydroxyapatites and 60 grams
The reaction of vegetable oil ester-based polyurethane obtains product.
The consumption of water is the 0.1 ~ 0.2% of reaction system gross mass.
Nanometer hydroxyapatite used by the present invention is to be obtained with calcium nitrate and tertiary sodium phosphate for raw material wet method.
The preparation method of nanometer hydroxyapatite: weigh ca (no for 1.67 according to calcium phosphorus mol ratio3)24h2O and
na3po412h2O, deionized water wiring solution-forming respectively.By na3po4Solution is slowly dropped into ca (no3)2In solution, keep ph 8
Quickly stir at～10,70 DEG C.Treat na3po4Solution completion of dropping, after continuing stirring 1 h, room temperature precipitation, it is washed with deionized
To ph ≈ 7, hydroxyapatite powder is obtained using being spray-dried.By powder mull sieve (～75 μm) standby afterwards.
The preparation method of nanometer hydroxyapatite using periodical can also be " Chinese Tissue Engineering Study " 2013 17
(author is Pang Guihua, Cheng Zhi to the preparation method introduced in the article of volume disclosed " preparation of nanometer hydroxyapatite and modification "
By force, Li Junfeng).
Claims (8)
1. vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest preparation method it is characterised in that: it is by planting
Thing oil glyceride based polyurethanes and nanometer hydroxyapatite In-situ reaction, are formed by Water blown.
2. the preparation method of vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest according to claim 1,
It is characterized in that: described vegetable oil ester-based polyurethane is in stannous octoate by vegetable oil ester with aliphatic isocyanates
Carry out additive reaction under catalysis, then obtained by BDO chain extension.
3. the preparation method of vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest according to claim 1,
It is characterized in that: described vegetable oil ester-based polyurethane is in octanoic acid by vegetable oil ester with isoflurane chalcone diisocyanate
Carry out additive reaction under stannous catalysis, then obtained by BDO chain extension.
4. according to Claims 2 or 3 vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest preparation side
Method it is characterised in that: described vegetable oil ester is to adopt glycerol and vegetable oil to carry out ester exchange with 0.5:1 ~ 2.5:1 mol ratio
Reaction, the catalyst of course of reaction is calcium oxide, and the consumption of calcium oxide is the 0.02% ~ 0.08% of glycerol and vegetable oil gross mass,
Reaction temperature is 200 ~ 250 DEG C, and the response time is 1 ~ 3 hour, obtains vegetable oil ester.
5. the preparation method of vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest according to claim 3,
It is characterized in that: described vegetable oil includes olive oil, soybean oil, Semen Maydis oil.
6. the preparation method of vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest according to claim 3,
It is characterized in that: vegetable oil ester and isoflurane chalcone diisocyanate are reacted in 70 ~ 80 DEG C under nitrogen protection, its
In, vegetable oil ester institute hydroxyl and isoflurane chalcone diisocyanate institute cyano-containing mol ratio are 1:1.1 ~ 1:2, and catalyst is adopted
With stannous octoate, stannous octoate consumption is the 0.1 ~ 0.2% of reaction system gross mass, after reaction persistently carries out 2 ~ 4 hours, adds
BDO chain extending reaction 1 ~ 3 hour, the consumption of BDO is the 2 ~ 5% of reaction system gross mass, with 90 ~ 110 DEG C
Water carries out foaming 1 ~ 4 hour, after obtain vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest, the consumption of water
It is the 0.1 ~ 0.2% of reaction system gross mass.
7. vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest according to any one of claim 1 ~ 6
Preparation method it is characterised in that: described vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest has three-dimensional space
Between structure, its aperture is 100nm ~ 700nm, and porosity is 60% ~ 70%, and comprcssive strength is 600kpa ~ 5000kpa.
8. the preparation method of vegetable oil ester-based polyurethane/nanometer hydroxyapatite compound rest according to claim 1,
It is characterized in that: adopt glycerol and vegetable oil to carry out ester exchange reaction with 0.5:1 ~ 2.5:1 mol ratio, catalyst is calcium oxide,
Calcium oxide is the 0.02% ~ 0.08% of the gross mass of glycerol and vegetable oil, and reaction temperature is 200 ~ 250 DEG C, and the response time is little for 1 ~ 3
When, obtain vegetable oil ester；
Vegetable oil ester and isoflurane chalcone diisocyanate are reacted in 70 ~ 80 DEG C under nitrogen protection, vegetable oil
Ester institute hydroxyl and isoflurane chalcone diisocyanate institute cyano-containing mol ratio are 1:1.1 ~ 1:2, and stannous octoate consumption is vegetable oil
Glyceride and the 0.1% ~ 0.2% of isoflurane chalcone diisocyanate gross mass, adds and adds nano hydroxyapatite while stannous octoate
Lime stone, the addition of nanometer hydroxyapatite is the 20% of vegetable oil ester and isoflurane chalcone diisocyanate gross mass；Reaction
Persistently carry out 2 ~ 4 hours；Add BDO chain extending reaction 1 ~ 3 hour, the addition of BDO is reaction system
The 2% ~ 5% of gross mass；Carry out foaming 1 ~ 4 hour with 90 ~ 110 DEG C of water, obtain nanometer hydroxyapatite/vegetable oil ester group
Polyurethane cellular support.
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| CN201610730688.8A CN106362217A (en) | 2016-08-26 | 2016-08-26 | Preparation method of vegetable oil/glyceride-based polyurethane/nano-hydroxyapatite composite scaffold |
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| CN201610730688.8A CN106362217A (en) | 2016-08-26 | 2016-08-26 | Preparation method of vegetable oil/glyceride-based polyurethane/nano-hydroxyapatite composite scaffold |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107982578A (en) * | 2017-12-15 | 2018-05-04 | 太原理工大学 | The preparation method of nanometer hydroxyapatite/compound porous bone tissue engineering stent material of Beta-cyclodextrin-based polyurethane |
| CN108421086A (en) * | 2018-04-19 | 2018-08-21 | 济南羽时信息科技有限公司 | A kind of nanometer hydroxyapatite modified polyurethane urea bone renovating material and preparation method thereof |
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| CN104356345A (en) * | 2014-12-01 | 2015-02-18 | 四川大学 | Fluorescent graft degradable block polyurethane, bone repair material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107982578A (en) * | 2017-12-15 | 2018-05-04 | 太原理工大学 | The preparation method of nanometer hydroxyapatite/compound porous bone tissue engineering stent material of Beta-cyclodextrin-based polyurethane |
| CN108421086A (en) * | 2018-04-19 | 2018-08-21 | 济南羽时信息科技有限公司 | A kind of nanometer hydroxyapatite modified polyurethane urea bone renovating material and preparation method thereof |
| CN108421086B (en) * | 2018-04-19 | 2020-11-03 | 济南羽时信息科技有限公司 | Nano-hydroxyapatite modified polyurethane urea bone repair material and preparation method thereof |
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