CN106730023A - A kind of polyphosphoric acids calcium is modified IPDI PCLLA PEG PCLLA porous supports and preparation and application - Google Patents
A kind of polyphosphoric acids calcium is modified IPDI PCLLA PEG PCLLA porous supports and preparation and application Download PDFInfo
- Publication number
- CN106730023A CN106730023A CN201611183896.7A CN201611183896A CN106730023A CN 106730023 A CN106730023 A CN 106730023A CN 201611183896 A CN201611183896 A CN 201611183896A CN 106730023 A CN106730023 A CN 106730023A
- Authority
- CN
- China
- Prior art keywords
- pclla
- peg
- preparation
- cpp
- ipdi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
-
- 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
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- A61L2430/40—Preparation and treatment of biological tissue for implantation, e.g. decellularisation, cross-linking
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Dermatology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a kind of polyphosphoric acids calcium modified IPDI PCLLA PEG PCLLA porous supports and preparation and application, including calcium polyphosphate（CPP）Preparation, the preparation of crosslinking timbering material and the preparation of CPP/ crosslinked polymer row supports, PCLLA PEG PCLLA are reacted in inert environment with IPDI, material after gained is crosslinked is with ultra-pure water with mass ratio 1:1 is mixed, and after adding CPP particles, magnetic stirrer over night after standing overnight, will be put into freezing in 20 degrees Celsius of refrigerators, and freeze-drying obtains support.Micron order calcium polyphosphate particle as filling inorganic material, it is compound after Medical rack play rush bone uptake, effect from inducing cell to osteoblast differentiation.
Description
Technical field
The present invention relates to a kind of polyphosphoric acids calcium modified IPDI-PCLLA-PEG-PCLLA porous supports and preparation and application,
Specifically solid portion is with polycaprolactone PLA-PEG-PLA（PCLLA-PEG-PCLLA）It is soft segment structure, it is different
Isophorone diisocyanate（IPDI）It is hard segment structure, as the main component of biological support after build crosslinking.The poly- phosphorus of micron order
Sour calcium particle plays rush bone uptake as filling inorganic material, the Medical rack after being combined, and inducing cell is to osteoblast differentiation
Effect.
Technical background
The defect repair of tissue and organ is always the significant problem for influenceing human health.For a long time, scientist is always
Various methods, means and material in the tissue defect that seeks treatment.Regenerative medicine is a new branch of science, is regeneration and repaiies
Extremely promising treatment concept is provided again, and its basic ideas is that a number of normal cell is extracted in human body, is carried out external
Propagation amplification；Then its adhesion, propagation, differentiation will on cell seeding to biomaterial, be made；The compound of cell and material is planted
Enter internal defect location, as material is gradually degraded and absorbed, extracellular matrix is constantly secreted and organizes constantly formation, rebuilds work(
Energy and form, reach the purpose that tissue or organ defect are repaired.
Macromolecule for manufacturing medical reparation can be divided into degradable and non-degradable type, and degradable material can be by people
The degradable absorption of body, it is not necessary to which second operation takes out, and is received significant attention in development process, and its use can be tissue defect
Basic mechanics and physiological function support is provided, material can be excluded in vitro by degrading, and defect can be repaired completely.Hydrogel
Material is made up of crosslinking comprising the macromolecule that substantial amounts of water is but not dissolved in water, is the preferable tissue renovation material of a class, is used for
Filling tissue defect and minimally invasive Plugging.By hydrophilic polyethylene glycol（PEG）With hydrophobic degradable polyester（PCLLA）Composition
Triblock copolymer（PCLA-PEG-PCLA）Have in terms of in prevention intestinal adhesion and as injectivity tissue engineering material extensive
Purposes.By the gel formed after Amphipathilic block polymer micelle self assembly, a large amount of hydrophilic PEG fragments of surface enrichment can have
The adhesion of effect resistance albumen and cell.But the organization bracket mechanical property after hydrogel is freeze-dried is poor, therefore add friendship
The crosslinking agent of-NCO- functional groups the material of connection property, increases the mechanical strength of triblock polymer.
Calcium polyphosphate（CPP）It is a kind of degradable inorganic polymer, this main polymer chain is not by simple covalent
Key link is formed, but the phosphate anion of tetrahedral structure is linked, it is possible to use polymer property, is polymerized by changing material
The parameters such as degree improve to its performance.In recent years, CPP had made intensive studies as bone holder material, it is found that its mechanics is strong
Degree is high, and degradable, bio-compatible model promotes Bone Defect Repari after implantation
The present invention combines PCLLA-PEG-PCLLA materials and CPP materials, adds isocyanates crosslinking agent, will after support solidification
CPP particulate materials are fixed on internal stent, and the supporting structure containing compound CPP micron particles of formation, its mechanical strength ensures
Structural behaviour of the support in implantation process, while its composition is as the progressively degraded of shell is slowly discharged and is dropped
Solution, and then be safely metabolized out external.
The content of the invention
To overcome the deficiencies in the prior art, the present invention to provide a kind of polyphosphoric acids calcium modified IPDI-PCLLA-PEG-PCLLA
Porous support and preparation and application.Solid phase method prepares calcium polyphosphate micron particles, and particle diameter is controlled by ball milling, method for sieving.
By PCLLA-PEG-PCLLA and isophorone diisocyanate（IPDI）Crosslinking, enhances the mechanical strength of raw water gel stent,
Filling in the support of CPP, increases and promotees bone uptake effect, promotes cell differentiation.
The purpose of the present invention is achieved through the following technical solutions：
The preparation method of the modified IPDI-PCLLA-PEG-PCLLA porous supports of a kind of polyphosphoric acids calcium, it is characterised in that include
Following steps：
（1）Calcium polyphosphate（CPP）Preparation：
Taken out from Muffle furnace after calcining under 500 degrees Celsius of calcium dihydrogen phosphate, it is quenched after obtain the amorphous imitation frosted glass of CPP, treat
CPP powders powder after drying, takes 300 ~ 400 mesh products；
（2）It is crosslinked the preparation of timbering material：
By polycaprolactone PLA-PEG-PLA polycaprolactone（PCLLA-PEG-PCLLA）In inert environment with
Isocyanates（IPDI）Reaction, the material after gained is crosslinked is with ultra-pure water with mass ratio 1:1 is mixed, ultrasound 25 minutes,
Magnetic stirrer over night, after standing overnight, will be put into freezing in -20 degrees Celsius of refrigerators, and freeze-drying obtains powder support；
（3）The preparation of CPP/ crosslinked polymer row supports：
PCLLA-PEG-PCLLA is reacted in inert environment with IPDI, the material after gained is crosslinked is with ultra-pure water with matter
Amount compares 1:1 is mixed, and after adding CPP particles, magnetic stirrer over night after standing overnight, will be put into cold in -20 degrees Celsius of refrigerators
Freeze, freeze-drying obtains support.
Step（2）The mass ratio of IPDI and PCLLA-PEG-PCLLA is 1:500~1:5000；Manner of formulation is room-temperature dissolution
Or less than 60 DEG C heated hydrotropy, mechanical agitation or magnetic agitation can also be aided with.
Step（3）The granular size of described CPP is 2 ~ 5um, and mass fraction is 0% ~ 50%.
The modified IPDI-PCLLA-PEG-PCLLA porous supports of a kind of polyphosphoric acids calcium, it is characterised in that according to above-mentioned
One methods described is prepared.
A kind of application of the modified IPDI-PCLLA-PEG-PCLLA porous supports of polyphosphoric acids calcium.
（1）The preparation of CPP：
Weigh 200g calcium dihydrogen phosphates to be put into 200ml crucibles, 4 hours are incubated under 500 degrees Celsius, from Muffle furnace after calcining
Middle taking-up, it is directly poured on trash ice and is quickly cooled down, it is quenched after obtain the amorphous imitation frosted glass of CPP, dried with ethanol, in vacuum
Standby in drying box, rear CPP powders powder to be dried takes 300 ~ 400 mesh products, ball milling, institute's score after being disperseed with absolute ethyl alcohol
Dispersion liquid is closed to preserve stand-by.Pattern is as shown in Figure 1.
（2）It is crosslinked the preparation of timbering material
After PCLLA-PEG-PCLLA raw materials are heated, reacted with IPDI in inert environment, magnetic agitation, and keep reaction
Temperature is 50 degrees Celsius, overnight static.Material after gained is crosslinked is with ultra-pure water with mass ratio 1:1 is mixed, ultrasound 25
Minute, magnetic stirrer over night.After standing overnight, freezing in -20 degrees Celsius of refrigerators will be put into, be subsequently placed in general in freeze drier
Moisture is detached, and freeze-drying obtains powder support, and pattern is as shown in Figure 2.
（3）The preparation of CPP/ crosslinked polymer row supports.
After PCLLA-PEG-PCLLA raw materials are heated, reacted with IPDI in inert environment, magnetic agitation, and keep
Reaction temperature is 50 degrees Celsius, overnight static.Material after gained is crosslinked is with ultra-pure water with mass ratio 1:1 is mixed, and is surpassed
Sound 25 minutes, after adding CPP particles, magnetic stirrer over night.After standing overnight, freezing in -20 degrees Celsius of refrigerators will be put into, then
It is placed in freeze drier and detaches moisture, freeze-drying obtains support, pattern is as shown in Figure 3.
The present invention is comprised the following steps：
1. the polymer of PCLLA-PEG-PCLLA is prepared, and specific composition is PCLLA55/45 1700-PEG2000-PCLLA55/
45。
2. the ratio being added to according to IPDI in PCLLA-PEG-PCLLA is 1000:1 500:1 200:1, preparation turns into
Crosslinking polymer gel.
3. it is 0%, 10%, 30%, 50% according to the mass ratio of CPP and above-mentioned polymer gel.
If 4. support is long-term without closed its is stored in into 4 DEG C of environment.
The advantage of the invention is that：
1. preparation method is simple, raw materials used simple, is suitable to a large amount of productions.
2. the load medicine developed newly is formulated improves the mechanical property of PCLLA-PEG-PCLLA materials, by adding IPDI
Deng the polymer being crosslinked with build containing-NCO- group crosslinking agents, generation, wherein include hard section and soft section composition, effectively
Improve mechanical property.Inserting for CPP particles has enhancing after hydrogel.
Brief description of the drawings
Fig. 1 is the SEM photograph of CPP materials in embodiment 1,2,3,4.
Fig. 2 is the SEM photograph of the porous support materials of preparation in embodiment 1.
Fig. 3 is the SEM photograph of the porous C PP/ timbering materials of preparation in embodiment 1.
Fig. 4 is the strain stress curve of the support mechanics of the solidification of embodiment 1,2,3,4.
Fig. 5 is cells survival rate curve in embodiment 1,2,3,4.
Specific embodiment
Following examples are implemented premised on inventive technique scheme, give detailed implementation method and specific behaviour
Make process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1：
Weigh 200g calcium dihydrogen phosphates to be put into 200ml crucibles, 4 hours are incubated under 500 degrees Celsius, from Muffle furnace after calcining
Middle taking-up, it is directly poured on trash ice and is quickly cooled down, it is quenched after obtain the amorphous imitation frosted glass of CPP, dried with ethanol, in vacuum
Standby in drying box, rear CPP powders powder to be dried takes 300 ~ 400 mesh products, ball milling, institute's score after being disperseed with absolute ethyl alcohol
Dispersion liquid is closed to preserve stand-by.
After PCLLA-PEG-PCLLA raw materials are heated, reacted with IPDI in inert environment, ratio is 500:1, magnetic
Power is stirred, and keeps reaction temperature for 50 degrees Celsius, overnight static.Material after gained is crosslinked is with ultra-pure water with mass ratio 1:
1 is mixed, ultrasound 25 minutes, magnetic stirrer over night.After standing overnight, freezing in -20 degrees Celsius of refrigerators will be put into, then put
Moisture is detached in freeze drier, freeze-drying obtains powder support.
Embodiment 2：
Weigh 200g calcium dihydrogen phosphates to be put into 200ml crucibles, 4 hours are incubated under 500 degrees Celsius, from Muffle furnace after calcining
Middle taking-up, it is directly poured on trash ice and is quickly cooled down, it is quenched after obtain the amorphous imitation frosted glass of CPP, dried with ethanol, in vacuum
Standby in drying box, rear CPP powders powder to be dried takes 300 ~ 400 mesh products, ball milling, institute's score after being disperseed with absolute ethyl alcohol
Dispersion liquid is closed to preserve stand-by.
After PCLLA-PEG-PCLLA raw materials are heated, reacted with IPDI in inert environment, ratio is 500:1, magnetic
Power is stirred, and keeps reaction temperature for 50 degrees Celsius, after adding CPP particles（Mass fraction is 10%）, it is stirred overnight.By gained
Material after crosslinking is with ultra-pure water with mass ratio 1:1 is mixed, ultrasound 25 minutes, magnetic stirrer over night.After standing overnight, will
It is put into -20 degrees Celsius of refrigerators and freezes, be subsequently placed in freeze drier and detach moisture, freeze-drying obtains powder support.
Embodiment 3：
Weigh 200g calcium dihydrogen phosphates to be put into 200ml crucibles, 4 hours are incubated under 500 degrees Celsius, from Muffle furnace after calcining
Middle taking-up, it is directly poured on trash ice and is quickly cooled down, it is quenched after obtain the amorphous imitation frosted glass of CPP, dried with ethanol, in vacuum
Standby in drying box, rear CPP powders powder to be dried takes 300 ~ 400 mesh products, ball milling, institute's score after being disperseed with absolute ethyl alcohol
Dispersion liquid is closed to preserve stand-by.
After PCLLA-PEG-PCLLA raw materials are heated, reacted with IPDI in inert environment, ratio is 500:1, magnetic
Power is stirred, and keeps reaction temperature for 50 degrees Celsius, after adding CPP particles（Mass fraction is 30%）, it is stirred overnight.By gained
Material after crosslinking is with ultra-pure water with mass ratio 1:1 is mixed, ultrasound 25 minutes, magnetic stirrer over night.After standing overnight, will
It is put into -20 degrees Celsius of refrigerators and freezes, be subsequently placed in freeze drier and detach moisture, freeze-drying obtains powder support.
Embodiment 4：
Weigh 200g calcium dihydrogen phosphates to be put into 200ml crucibles, 4 hours are incubated under 500 degrees Celsius, from Muffle furnace after calcining
Middle taking-up, it is directly poured on trash ice and is quickly cooled down, it is quenched after obtain the amorphous imitation frosted glass of CPP, dried with ethanol, in vacuum
Standby in drying box, rear CPP powders powder to be dried takes 300 ~ 400 mesh products, ball milling, institute's score after being disperseed with absolute ethyl alcohol
Dispersion liquid is closed to preserve stand-by.
After PCLLA-PEG-PCLLA raw materials are heated, reacted with IPDI in inert environment, ratio is 500:1, magnetic
Power is stirred, and keeps reaction temperature for 50 degrees Celsius, after adding CPP particles（Mass fraction is 50%）, it is stirred overnight.By gained
Material after crosslinking is with ultra-pure water with mass ratio 1:1 is mixed, ultrasound 25 minutes, magnetic stirrer over night.After standing overnight, will
It is put into subzero 20 degrees Celsius of refrigerators and freezes, be subsequently placed in freeze drier and detach moisture, freeze-drying obtains powder branch
Frame.
It is preparation-obtained solidification after-poppet to pattern such as Fig. 2, shown in 3, support solidify after, due to freeze-drying effect
The bore hole size of generation is interleaved with each other in 200-400um, polymer architecture, with certain mechanical strength；CPP is composite filled
After entering PCLLA-PEG-PCLLA, from pattern, PCLLA-PEG-PCLLA attachment of polymers on CPP particles, CPP particles
Stacking, the size of its mesopore is 200um.
Timbering material in embodiment 1-4 is made the bulk material of 1cm x 1cm x 1cm, omnipotent power is respectively placed in
The measurement of modulus is compressed in testing machine, modulus curve is drawn, as shown in Figure 4.In embodiment 1, PCLLA-PEG-PCLLA
After IPDI crosslinkings, modulus of compressibility is 47.6Kpa；After embodiment 2 is filled with 10% CPP, modulus of compressibility is 78.7Kpa；Implement
In example 3, after being filled with 30% CPP, modulus of compressibility is 85.9Kpa；In embodiment 4, after being filled with 30% CPP, modulus of compressibility
It is 95.4Kpa.
Bone cement skeleton after solidification in embodiment 4 is put into the culture dish containing MC3T3 cells, culture 24,48
With 72 hours after contrast the contrast of cells survival rate, as a result as shown in Figure 4.Cells survival rate maintains more than 100% in timbering material
Absolutely prove that timbering material has good biocompatibility.
Claims (5)
1. a kind of preparation method of the modified IPDI-PCLLA-PEG-PCLLA porous supports of polyphosphoric acids calcium, it is characterised in that bag
Containing following steps：
（1）Calcium polyphosphate（CPP）Preparation：
Taken out from Muffle furnace after calcining under 500 degrees Celsius of calcium dihydrogen phosphate, it is quenched after obtain the amorphous imitation frosted glass of CPP, treat
CPP powders powder after drying, takes 300 ~ 400 mesh products；
（2）It is crosslinked the preparation of timbering material：
By polycaprolactone PLA-PEG-PLA polycaprolactone（PCLLA-PEG-PCLLA）In inert environment with
Isocyanates（IPDI）Reaction, the material after gained is crosslinked is with ultra-pure water with mass ratio 1:1 is mixed, ultrasound 25 minutes,
Magnetic stirrer over night, after standing overnight, will be put into freezing in -20 degrees Celsius of refrigerators, and freeze-drying obtains powder support；
（3）The preparation of CPP/ crosslinked polymer row supports：
PCLLA-PEG-PCLLA is reacted in inert environment with IPDI, the material after gained is crosslinked is with ultra-pure water with matter
Amount compares 1:1 is mixed, and after adding CPP particles, magnetic stirrer over night after standing overnight, will be put into cold in -20 degrees Celsius of refrigerators
Freeze, freeze-drying obtains support.
2. the preparation of the modified IPDI-PCLLA-PEG-PCLLA porous supports of a kind of polyphosphoric acids calcium according to claim 1
Method, it is characterised in that step（2）The mass ratio of IPDI and PCLLA-PEG-PCLLA is 1:500~1:5000；Manner of formulation is
Room-temperature dissolution or less than 60 DEG C heat hydrotropy, can also be aided with mechanical agitation or magnetic agitation.
3. the preparation of the modified IPDI-PCLLA-PEG-PCLLA porous supports of a kind of polyphosphoric acids calcium according to claim 1
Method, it is characterised in that step（3）The granular size of described CPP is 2 ~ 5um, and mass fraction is 0% ~ 50%.
4. modified IPDI-PCLLA-PEG-PCLLA porous supports of a kind of polyphosphoric acids calcium, it is characterised in that according to claim
Any methods describeds of 1-3 are prepared.
5. the application of the modified IPDI-PCLLA-PEG-PCLLA porous supports of polyphosphoric acids calcium according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611183896.7A CN106730023A (en) | 2016-12-20 | 2016-12-20 | A kind of polyphosphoric acids calcium is modified IPDI PCLLA PEG PCLLA porous supports and preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611183896.7A CN106730023A (en) | 2016-12-20 | 2016-12-20 | A kind of polyphosphoric acids calcium is modified IPDI PCLLA PEG PCLLA porous supports and preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106730023A true CN106730023A (en) | 2017-05-31 |
Family
ID=58895990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611183896.7A Pending CN106730023A (en) | 2016-12-20 | 2016-12-20 | A kind of polyphosphoric acids calcium is modified IPDI PCLLA PEG PCLLA porous supports and preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106730023A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107982575A (en) * | 2017-11-28 | 2018-05-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of LDI-PCLLA-PEG-PCLLA/ hydroxyapatite electrospun fiber membranes and products thereof and application |
| CN109529126A (en) * | 2018-10-22 | 2019-03-29 | 深圳齐康医疗器械有限公司 | A kind of artificial dermis and preparation method thereof |
| CN109568667A (en) * | 2018-12-26 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation of the degradable bone-repairing composite material of high-intensitive and no inflammation reaction and product and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1596994A (en) * | 2004-09-06 | 2005-03-23 | 四川大学 | Bone tissue repairing filler and its preparation material |
| CN1910217A (en) * | 2004-01-15 | 2007-02-07 | 伊诺科雷技术有限公司 | Biogradable multi-block co-polymers |
| CN1995099A (en) * | 2006-12-28 | 2007-07-11 | 复旦大学 | Degradable chemically-crosslinked aquagel and its preparation method |
| CN101244275A (en) * | 2008-03-05 | 2008-08-20 | 四川大学 | Long-acting sustained-release medicaments for treating and renovating bone disease and preparation thereof |
| CN101301491A (en) * | 2008-07-07 | 2008-11-12 | 四川大学 | Composite bracket made of multialdehyde sodium alginate crosslinked calcium polyphosphate/chitosan and preparation and use thereof |
| CN102068719A (en) * | 2011-01-18 | 2011-05-25 | 复旦大学 | Adhesion prevention material formed by physical crosslinking hydrogel composition and preparation method and application thereof |
| CN102875772A (en) * | 2012-10-19 | 2013-01-16 | 中国科学院长春应用化学研究所 | Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel |
| CN103157134A (en) * | 2011-12-14 | 2013-06-19 | 西安瑞捷生物科技有限公司 | Cartilage tissue engineering scaffold material |
-
2016
- 2016-12-20 CN CN201611183896.7A patent/CN106730023A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1910217A (en) * | 2004-01-15 | 2007-02-07 | 伊诺科雷技术有限公司 | Biogradable multi-block co-polymers |
| CN1596994A (en) * | 2004-09-06 | 2005-03-23 | 四川大学 | Bone tissue repairing filler and its preparation material |
| CN1995099A (en) * | 2006-12-28 | 2007-07-11 | 复旦大学 | Degradable chemically-crosslinked aquagel and its preparation method |
| CN101244275A (en) * | 2008-03-05 | 2008-08-20 | 四川大学 | Long-acting sustained-release medicaments for treating and renovating bone disease and preparation thereof |
| CN101301491A (en) * | 2008-07-07 | 2008-11-12 | 四川大学 | Composite bracket made of multialdehyde sodium alginate crosslinked calcium polyphosphate/chitosan and preparation and use thereof |
| CN102068719A (en) * | 2011-01-18 | 2011-05-25 | 复旦大学 | Adhesion prevention material formed by physical crosslinking hydrogel composition and preparation method and application thereof |
| CN103157134A (en) * | 2011-12-14 | 2013-06-19 | 西安瑞捷生物科技有限公司 | Cartilage tissue engineering scaffold material |
| CN102875772A (en) * | 2012-10-19 | 2013-01-16 | 中国科学院长春应用化学研究所 | Polyurethane block copolymer, preparation method thereof and preparation method of polyurethane block copolymer nano hydrogel |
Non-Patent Citations (1)
| Title |
|---|
| 李洁华等: "含PLA-PEG-PLA三嵌段共聚物的可降解聚氨酯的合成及表征", 《四川大学学报(工程科学版)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107982575A (en) * | 2017-11-28 | 2018-05-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of LDI-PCLLA-PEG-PCLLA/ hydroxyapatite electrospun fiber membranes and products thereof and application |
| CN109529126A (en) * | 2018-10-22 | 2019-03-29 | 深圳齐康医疗器械有限公司 | A kind of artificial dermis and preparation method thereof |
| CN109568667A (en) * | 2018-12-26 | 2019-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation of the degradable bone-repairing composite material of high-intensitive and no inflammation reaction and product and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Meng et al. | Effects of adding resorbable chitosan microspheres to calcium phosphate cements for bone regeneration | |
| Sun et al. | 3D printed calcium phosphate scaffolds with controlled release of osteogenic drugs for bone regeneration | |
| Moghadam et al. | Formation of porous HPCL/LPCL/HA scaffolds with supercritical CO2 gas foaming method | |
| Sundaram et al. | Porous scaffold of gelatin–starch with nanohydroxyapatite composite processed via novel microwave vacuum drying | |
| JP5881669B2 (en) | Collagen / hydroxyapatite composite skeleton and method for producing the same | |
| Valente et al. | Alginate based scaffolds for bone tissue engineering | |
| Saber-Samandari et al. | A novel magnetic bifunctional nanocomposite scaffold for photothermal therapy and tissue engineering | |
| Puértolas et al. | Compression behaviour of biphasic calcium phosphate and biphasic calcium phosphate–agarose scaffolds for bone regeneration | |
| Zhu et al. | Manufacture of layered collagen/chitosan-polycaprolactone scaffolds with biomimetic microarchitecture | |
| JP2009240605A (en) | Cell engineering support and its manufacturing method | |
| CN102824657A (en) | Bone restoration material and its preparation method | |
| EP1649876B1 (en) | Block-shaped scaffold for tissue engineering and production method thereof | |
| CN101219241A (en) | Biological activity bone renovation material with bone-inducing factor control-release function and production method thereof | |
| CN106730023A (en) | A kind of polyphosphoric acids calcium is modified IPDI PCLLA PEG PCLLA porous supports and preparation and application | |
| Nitti et al. | Enhancing bioactivity of hydroxyapatite scaffolds using fibrous type I collagen | |
| Guo et al. | Enhanced osseointegration of double network hydrogels via calcium polyphosphate incorporation for bone regeneration | |
| CN103463678A (en) | Multifunctional medical biological bone cement | |
| Salimi et al. | An artificial soft tissue made of nano-alginate polymer using bioxfab 3D bioprinter for treatment of injuries | |
| CN102552985B (en) | Silk fibroin/calcium phosphate bone cement-based porous composite material and preparation method thereof | |
| CN104740688B (en) | Preparation method of microsphere close-packed shape memory porous scaffold | |
| Song et al. | Constructing a biomimetic nanocomposite with the in situ deposition of spherical hydroxyapatite nanoparticles to induce bone regeneration | |
| CN107982575A (en) | Preparation method of LDI-PCLLA-PEG-PCLLA/ hydroxyapatite electrospun fiber membranes and products thereof and application | |
| Wang et al. | Cryoprinting of nanoparticle-enhanced injectable hydrogel with shape-memory properties | |
| Li et al. | Self-healing hydrogels for bone defect repair | |
| Wang et al. | Degradable smart composite foams for bone regeneration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |