CN108250423A - A kind of functionalized polyester and its three-dimensional porous rack and preparation method - Google Patents
A kind of functionalized polyester and its three-dimensional porous rack and preparation method Download PDFInfo
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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
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
The present invention relates to a kind of functionalized polyester and its three-dimensional porous rack and preparation method, the functionalized polyester is poly- fumaric acid terephthalic acid (TPA) butane diepoxide maleate PTFB M.The three-dimensional porous rack is made using functionalized polyester PTFB M as raw material by salting out method and heat cross-linking.The present invention prepares new function polyester material using acid induction epoxy addition polymerization and carboxylic acid reaction, three-dimensional porous rack material is further prepared by salting out method and heat cross-linking, with good thermal stability, mechanical property and bioactivity, repair field in field of tissue engineering technology, histoorgan and have broad application prospects.
Description
Technical field
The invention belongs to tissue engineering material technical field, more particularly to a kind of functionalized polyester and its three-dimensional porous rack
And preparation method.
Background technology
At present, there are many degradable high polymer material such as polylactic acid, polyglycolic acid, polycaprolactone and its copolymerization
Object, polyanhydride etc. are used for biologic medical field, their easy to process, good biocompatibilities.But these high molecular materials are usual
For bio-inert material, while lack chemical active sites, be not easy to be modified, therefore their chemistry, physics and biology performance
Modulatory character it is relatively poor, further applied so as to limit these materials.Thus the bioactive materials of functionalization have become
Hot spot for current biomaterial research field.
Organizational project combines engineering science and life science basic principle, the form and work(of gentrify injury tissue
Can, it is quite promising disease treatment new way.And three-dimensional timbering material is the important component of organizational project.It is good
Tissue engineering bracket should usually have good mechanical property and bioactivity;Higher porosity, and pore space structure intercommunication.Mesh
Before, it is ground extensively with the tissue engineering bracket of the material preparations such as polylactic acid, polyglycolic acid, polycaprolactone and its copolymer
Study carefully, but there is currently tissue engineering bracket still have some drawbacks such as lack bioactive sites, be not easy it is modified, limit
It has been made further to apply.
Invention content
The technical problems to be solved by the invention are to provide a kind of functionalized polyester and its three-dimensional porous rack and preparation
Method, functionalized polyester PTFB-M have good thermal stability, are hydrophilic material at room temperature in rigid glassy state,
Strand has exposed hydroxyl and carboxyl, conducive to further modification, can form the bioactive materials with different function;Profit
Heat cross-linking is carried out with PTFB-M and can obtain corresponding three-dimensional porous rack, and there is good thermal stability and certain compression resistance force
Performance is learned, growth factor-loaded specific bioactivity can be obtained, lay the first stone for its application in field of tissue engineering technology.This hair
Bright preparation method process is simple, and reaction efficiency is high, convenient, fast.
A kind of functionalized polyester of the present invention, for poly- fumaric acid terephthalic acid (TPA) butane diepoxide maleate PTFB-M,
Chemical structural formula is:
Wherein 1≤x≤3,1≤y≤3.
A kind of functionalized polyester three-dimensional porous rack of the present invention, using functionalized polyester PTFB-M as raw material, by saltouing
Method and heat cross-linking are made.
A kind of preparation method of functionalized polyester of the present invention, including:
(1) fumaric acid of recrystallization, terephthalic acid (TPA), butane diepoxide, catalyst are dissolved in N '-N ' dimethylformamides
In DMF, acid induction epoxide polymerization reaction is carried out under nitrogen protection, and purifying obtains the poly- fumaric acid terephthalic acid (TPA) two of prepolymer
Epoxy butane ester PTFB;The fumaric acid that wherein recrystallizes, terephthalic acid (TPA), butane diepoxide, catalyst molar ratio be 1:3:
4:0.02~0.03;
(2) PTFB for obtaining step (1) is dissolved in DMF with maleic anhydride, carries out carboxylic acid reaction under nitrogen protection, pure
Change, obtain functionalized polyester PTFB-M;The mass ratio of wherein PTFB and maleic anhydride is 1:0.7~0.9.
The process conditions of recrystallization fumaric acid are in the step (1):Fumaric acid is added in three neck round bottom flask, by it
It is placed in 100 DEG C of oil bath pans, and connects condensation reflux unit;Distilled water is gradually added dropwise in flask, is completely dissolved fumaric acid;
The fumaric acid aqueous solution of dissolving is placed in beaker later, cooling and standings at room temperature, fumaric acid crystal is precipitated;Again containing richness
The solution of horse acid crystal is filtered to obtain fumaric acid crystal, is continuously repeated three times, products therefrom is placed in 100 DEG C, 1Torr is true
Drying for 24 hours, obtains pure fumaric acid crystal in empty baking oven.
Catalyst in the step (1) is tetrabutylammonium bromide.
The process conditions of acid induction epoxide polymerization reaction are in the step (1):With 900 under the conditions of 85~95 DEG C of oil baths
The rotating speed of~1100r/min stirs 24~28h.
The process conditions of carboxylic acid reaction are in the step (2):With 900~1100r/ under the conditions of 80~90 DEG C of oil baths
The rotating speed of min stirs 4~5h.
Purifying uses the anhydrous ether precipitation method in the step (2), and concrete technology condition is:By PTFB-M polymer solutions
It is added dropwise in anhydrous ether dropwise, the polymer of precipitation is dissolved in tetrahydrofuran THF/H2O, wherein THF:H2O=9:1, then in second
It is precipitated in ether, continuously repeats three times, remove the solvent in polymer solution and unreacted monomer;Gained sediment is taken out again true
After the more low-boiling solvent such as sky, removal ether to obtain the final product.
A kind of preparation method of functionalized polyester three-dimensional porous rack of the present invention, including:
PTFB-M is dissolved in DMF, the solution that mass fraction is 3~4wt% is obtained, adds in into salt mould and volatilize, heat cross-linking,
Room temperature is down to, is washed, vacuum freeze drying obtains functionalized polyester PTFB-M three-dimensional porous racks.
The salt mould is applied by the way that the sodium chloride salt particle that grain size is 75~150 μm to be placed in the Teflon of permanent magnet connection
Between layer stainless steel disk and steel disc model, kept for 37 DEG C, after 88% relative humidity 1.5h, in 120 DEG C, 100mTorr suctions 2h
It is made.
The process conditions of the volatilization are:It is placed in 20~40min of volatilization in draught cupboard.The purpose of volatilization is to remove THF.
The process conditions of the heat cross-linking are:Heat cross-linking 22 at 145~155 DEG C is placed in 1001mTorr heating in vacuum casees
~26h.
The process conditions of the washing are:22~26h is embathed using distilled water.The purpose of washing is to remove sodium chloride.
The process conditions of the vacuum freeze drying are:Vacuum freeze drying temperature is -25~-15 DEG C, and vacuum refrigeration is done
The dry time is 22~26h.
The present invention is prepared using fumaric acid, terephthalic acid (TPA), butane diepoxide as raw material using acid induction epoxide polymerization reaction
A kind of polyester material containing three components, and it is Carboxylation to prepolymer progress, obtain functional poly ester material.The material molecule
There is abundant active group, such as exposed carboxyl and hydroxyl.On the one hand these groups can be used as reaction site, adjust the reason of material
Change performance, on the other hand can be conducive to cell attachment as the recognition site of cell, grow and organize the formation of.The polymer exists
This rigid molecule of introducing terephthalic acid (TPA) in monomer is conducive to improve the mechanical property of material, better conforms to the demand of application.
The polymer backbone is built by ester bond, therefore with good degradability, and can be by controlling the introducing of terephthalic acid (TPA)
It measures to regulate and control its degradation rate.And fumaric acid and maleic acid unit can further be modified material rich in double bond.
The present invention is further using functionalized polyester PTFB-M as stent raw material, and by carrying out salting out method and heat to it
Crosslinking be prepared for it is a kind of have the characteristics that can functionalization, the PTFB-M three-dimensional porous racks to interconnect.
Advantageous effect
(1) raw material of the present invention is easy to get, and building-up process is simple, and reaction efficiency is high, convenient, fast.
(2) functionalized polyester PTFB-M is made using acid induction epoxide polymerization reaction and carboxylic acid reaction in the present invention, has
Good thermal stability is hydrophilic material at room temperature in rigid glassy state.
(3) strand of PTFB-M materials of the invention has exposed hydroxyl and carboxyl, is potentially conducive to cell and exists
It grows on material, on the other hand material can further be modified as the active site of cell, be conducive to cell attachment, growth
With organize the formation of, ultimately form the bioactive materials with different function.
(4) PTFB-M further is made by salting out method and heat cross-linking using functionalized polyester PTFB-M as raw material in the present invention
Three-dimensional porous rack has the macroporous structure that is evenly distributed and formation three-dimensional network communicating together, be conducive to the growth of cell with
Proliferation.In addition, with good thermal stability and certain incompressible mechanical property.
(5) PTFB-M porous supports of the invention can be modified easily, obtain specific bioactivity, in tissue work
Journey field, histoorgan repair field and have broad application prospects.
Description of the drawings
Fig. 1 is the reaction schematic diagram that PTFB-M is prepared in embodiment 1, wherein 1≤x≤3,1≤y≤3.
Fig. 2 is the PTFB-M prepared in embodiment 11H NMR analysis results, wherein x=1, y=3.
Fig. 3 is the IR analysis results of PTFB-M prepared in embodiment 1.
Fig. 4 is the thermogravimetric curve (left side) of PTFB-M and DSC curve (right side) prepared in embodiment 1.
Fig. 5 is the contact angle picture of PTFB-M prepared in embodiment 1.
Fig. 6 is the scanning electron microscope (SEM) photograph of PTFB-M three-dimensional porous racks prepared in embodiment 2.
Fig. 7 is the TGA curve (left side) of PTFB-M three-dimensional porous racks and DSC curve (right side) prepared in embodiment 2.
Fig. 8 is the compressive stress strain curve of PTFB-M three-dimensional porous racks prepared in embodiment 2.
Fig. 9 is that the PTFB-M three-dimensional porous racks prepared in embodiment 2 meet different growth factor AVEGF (left side), BMP2
The elution profiles on (right side).
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) 85g fumaric acid is weighed in 500mL three neck round bottom flask, is placed it in 100 DEG C of oil bath pans, and connect cold
Solidifying reflux;Distilled water is gradually added dropwise in flask, is completely dissolved fumaric acid;The fumaric acid aqueous solution of dissolving is put later
In beaker, cooling and standings at room temperature, fumaric acid crystal is precipitated;Again the solution containing fumaric acid crystal is filtered to obtain
Fumaric acid crystal;Above step continuously repeats three times, and products therefrom is placed in 100 DEG C, dries for 24 hours, obtains in 1Torr vacuum drying ovens
To pure recrystallization fumaric acid.Charging process carries out (water content≤0.01ppm, oxygen content≤0.01ppm) in glove box,
The fumaric acid that 0.469g (10mmol) is recrystallized, 2.000g (30mmol) terephthalic acid (TPA), 1.383g (40mmol) diepoxy
Butane, 31mg (0.24mmol) tetrabutylammonium bromide are dissolved in 5.5mL DMF, are placed in 25mL eggplant type reaction bulbs, sealing reaction
Bottle takes out glove box;Secondly nitrogen ball is inserted in reaction bulb, and places it in stirring (1000r/min) in 90 DEG C of oil bath pans, instead
It should be carried out in nitrogen atmosphere, react 26h, it is purified, obtain prepolymer PTFB.
(2) charging process carries out (water content≤0.01ppm, oxygen content≤0.01ppm) in glove box, by 1g prepolymers
PTFB, 0.819g maleic anhydride are dissolved in 2.5mL DMF, are placed in 10mL eggplant type reaction bulbs, and sealing reaction bulb takes out glove box;
Secondly nitrogen ball is inserted in reaction bulb, and places it in stirring (1000r/min) in 85 DEG C of oil bath pans, is reacted in nitrogen atmosphere
It carries out, reacts 4.5h, polymer solution is added dropwise in anhydrous ether dropwise, it is 9 that the polymer of precipitation, which is dissolved in volume ratio,:1
THF/ water mixed solvents in, then precipitated in ether, above step continuously repeats three times, removes the solvent in polymer solution
And unreacted monomer;Gained sediment is vacuumized again, the more low-boiling solvent such as removal ether, the functionalization purified
Polyester PTFB-M.
The reaction schematic diagram that the present embodiment prepares PTFB-M is as shown in Figure 1.
Embodiment 2
By grain size be 75~150 μm of sodium chloride salt particle be placed in the Teflon coating stainless steel disk of permanent magnet connection with
Between steel disc model, kept for 37 DEG C, after 88% relative humidity 1.5h, in 120 DEG C, salt mould is made in 100mTorr suctions 2h.It will be real
PTFB-M made from applying example 1 is dissolved in THF and obtains the PTFB-M solution of a concentration of 3.3wt%, adds in above-mentioned salt mould, is placed in draught cupboard
Middle 30min volatilizations remove major part THF.Then entire model is placed in 1001mTorr heating in vacuum casees heat cross-linking at 150 DEG C
For 24 hours, room temperature is then down to, distilled water embathes for 24 hours, removes sodium chloride, be placed in -20 DEG C of vacuum freezedryings for 24 hours, obtain functionalization
Polyester PTFB-M three-dimensional porous racks.
Embodiment 3
Using the structure of PTFB-M made from nuclear-magnetism characterization embodiment 1, the results are shown in Figure 2, wherein when-OH is free shape
CH during state, CH2Proton go out peak position be about be 4.5-3.7ppm;And under the influence of carboxyl, because of its absorption to electronics
Power, CH, CH2Proton go out peak position and be moved to about 5.5-6ppm;In addition, proton is in 6.8ppm in the middle alkylene of fumaric acid
With 6.4ppm appearances;The proton of alkylene both sides is respectively in 6.4 and 6.2ppm in maleic anhydride, this is because the electrophilic of carboxyl
Ability is better than maleate group;~8.2ppm corresponds to the proton in phenyl ring;The grafting rate of maleic anhydride is 69%.Test result
Show effectively to have obtained design polymer.
Using the structure of PTFB-M made from IR Characterization embodiment 1, the results are shown in Figure 3, wherein 3530cm-1The width at place
Peak corresponds to O-H vibrations;3080cm-1The stretching vibrations of correspondence=C-H, 3050cm-1The stretching vibrations of C-H in corresponding aromatic hydrocarbon;
1720cm-1The stretching vibrations of corresponding C=O;1640cm-1Include the stretching vibrations of C-C in C=C and aromatic hydrocarbon;1110cm-1It is right
The vibrations that C-H is weaker in aromatic hydrocarbon are answered, again demonstrate the successful synthesis of polymer P TFB-M.
Thermal property test is carried out to PTFB-M made from embodiment 1, the results are shown in Figure 4, and the heat of wherein PTFB-M is lost
Weight curve (left side) understands that PTFB-M first segments heat decomposition temperature is 180.9 DEG C (during mass losses 5%), shows it in body temperature
Nearby there is good thermal stability.In addition, the glass transition temperature that the DSC curve (right side) of PTFB-M can obtain PTFB-M is
68.27 DEG C, that is, show that at room temperature, PTFB-M is vitreous material.
Hydrophilicity test is carried out to PTFB-M made from embodiment 1, the results are shown in Figure 5, wherein the water phase of PTFB-M
Contact angle is 45.3 ± 3o, also indicates that the material as good hydrophilic material, this and exposed hydroxyls a large amount of in molecule and carboxyl
It is related.
Embodiment 4
The microstructure of PTFB-M three-dimensional porous racks made from embodiment 2 is characterized using scanning electron microscope, as a result
As shown in Figure 6, it is known that according to the grain size of screened salt grain, be successfully prepared the porous branch containing macroporous structure (75-150 μm)
Frame, and these macropores are more evenly distributed in stent formation 3 D stereo network communicating together simultaneously.It is this molten in salt grain
The structure of the intercommunication formed during solution is advantageously possible for the growth of cell, proliferation, is that PTFB-M porous supports are organizing work
The potential application in journey field lays the first stone.It is distributed on cradle wall in addition with the micropore that a part of aperture is several μm, this can
It can be formed since Exchange Ester Process small molecular by-product volatilizees.
Thermal property test is carried out to PTFB-M three-dimensional porous racks made from embodiment 2, the results are shown in Figure 7, wherein
The heat decomposition temperature that PTFB-M three-dimensional porous racks can be obtained in TGA curves (left side) is 231 DEG C, illustrates PTFB-M porous supports
With preferable thermal stability, use scope is wider.PTFB-M porous supports can be obtained from DSC heating curves (right side) to measure
In the range of in non crystallized unformed state, Tg is 161.5 DEG C.Prove that PTFB-M three-dimensional porous racks have good thermostabilization
Property.
Mechanics Performance Testing is carried out to PTFB-M three-dimensional porous racks made from embodiment 2, compressive stress strain curve is such as
Shown in Fig. 8, it is known that PTFB-M porous supports have certain compressive mechanical property in moist environment, are 40% in compression strain
Its compression stress is 8.91 ± 0.64kPa under state, it was demonstrated that PTFB-M three-dimensional porous racks have certain incompressible mechanical property
Energy.
Embodiment 5
Functionalization to probe into PTFB-M three-dimensional porous racks made from the embodiment of the present invention 2 acts on, it is given birth to
Long factor slow release test, studies its function and effect with growth factor VEGF, BMP2.
Utilize the side of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimides EDC and n-hydroxysuccinimide NHS
Method promotes the condensation reaction of carboxyl and amino in growth factor in PTFB-M stents, so as to which growth factor be made more steadily to be inoculated with
On timbering material.PTFB-M porous supports are immersed in NHS/EDC solution 30 minutes, NHS/EDC concentration is respectively
0.06mol/L and 0.6mol/L, solvent for use are that the pH of 0.05mol/L is 5.5 MES buffer solutions.Delayed after immersion with phosphate
Fliud flushing PBS is washed three times, and drying of drying in super-clean bench.Growth factor VEGF, BMP2 solution are added dropwise porous in PTFB-M
On stent, and 37 DEG C are positioned over, 5%CO2In the incubator of atmosphere, wherein a concentration of 100mg/40 μ L of growth factor solution are molten
Agent is the PBS solution containing 1% bovine serum albumin BSA.First three day culture solution (1%PBS-BSA buffer solutions) every changing one for 24 hours
It is secondary, it was hereafter changed every 3 days primary.
Growth factor slow-release than quantitative calculating, measured by enzyme-linked immunosorbent assay ELISA.First, it will be vaccinated with
The PTFB-M porous supports of growth factor are positioned over cultivated in incubator after, with 1%PBS-BSA wash buffers, in flushing liquor
VEGF contents be not seeded in growth factor amount on stent as, the content and growth factor of the initial inoculation on stent are total
The difference of amount is growth factor fixed amount corresponding on PTFB-M porous supports;The 1%PBS- replaced successively after this
The content of growth factor is corresponding sustained release amount in BSA buffer solutions.Concrete outcome is as shown in figure 9, for VEGF (left side) and BMP2
Sustained release situation of (right side) the two kinds of growth factors on PTFB-M stents, it is known that the slow release speed of two kinds of growth factors is all relatively more equal
Even, VEGF has preferable stability on material, and after 15 days, sustained release amount is about the 18% of inoculum concentration, and BMP2 sustained release speed
Degree is very fast, and after 15 days, sustained release amount is about the 95% of inoculum concentration, it was demonstrated that the stent can be modified easily, obtain specific
Bioactivity lays the first stone for its application in field of tissue engineering technology.
Claims (10)
1. a kind of functionalized polyester, it is characterised in that:For poly- fumaric acid terephthalic acid (TPA) butane diepoxide maleate PTFB-M,
Chemical structural formula is:
Wherein 1≤x≤3,1≤y≤3.
2. a kind of functionalized polyester three-dimensional porous rack, it is characterised in that:With functionalized polyester as described in claim 1
PTFB-M is raw material, is made by salting out method and heat cross-linking.
3. a kind of preparation method of functionalized polyester as described in claim 1, including:
(1) fumaric acid of recrystallization, terephthalic acid (TPA), butane diepoxide, catalyst are dissolved in N '-N ' dimethylformamides DMF
In, acid induction epoxide polymerization reaction is carried out under nitrogen protection, and purifying obtains the poly- fumaric acid terephthalic acid (TPA) diepoxy of prepolymer
Butane ester PTFB;The fumaric acid that wherein recrystallizes, terephthalic acid (TPA), butane diepoxide, catalyst molar ratio be 1:3:4:
0.02~0.03;
(2) PTFB for obtaining step (1) is dissolved in DMF with maleic anhydride, carries out carboxylic acid reaction under nitrogen protection, purifies,
Obtain functionalized polyester PTFB-M;The mass ratio of wherein PTFB and maleic anhydride is 1:0.7~0.9.
4. a kind of preparation method of functionalized polyester according to claim 3, it is characterised in that:In the step (1)
Catalyst is tetrabutylammonium bromide.
5. a kind of preparation method of functionalized polyester according to claim 3, it is characterised in that:It is sour in the step (1)
Induction epoxide polymerization reaction process conditions be:Under the conditions of 85~95 DEG C of oil baths 24 are stirred with the rotating speed of 900~1100r/min
~28h.
6. a kind of preparation method of functionalized polyester according to claim 3, it is characterised in that:Carboxylic in the step (2)
The process conditions of acidification reaction are:4~5h is stirred with the rotating speed of 900~1100r/min under the conditions of 80~90 DEG C of oil baths.
7. a kind of preparation method of functionalized polyester three-dimensional porous rack as claimed in claim 2, including:
PTFB-M is dissolved in DMF, the solution that mass fraction is 3~4wt% is obtained, adds in into salt mould and volatilize, heat cross-linking is down to
Room temperature, washing, vacuum freeze drying obtain functionalized polyester PTFB-M three-dimensional porous racks.
8. a kind of preparation method of functionalized polyester three-dimensional porous rack according to claim 7, it is characterised in that:It is described
Salt mould is the Teflon coating stainless steel disk by the way that the sodium chloride salt particle that grain size is 75~150 μm to be placed in permanent magnet connection
Between steel disc model, kept for 37 DEG C, after 88% relative humidity 1.5h, in 120 DEG C, 100mTorr suctions 2h is made.
9. a kind of preparation method of functionalized polyester three-dimensional porous rack according to claim 7, it is characterised in that:It is described
The process conditions of heat cross-linking are:22~26h of heat cross-linking at 145~155 DEG C is placed in 1001mTorr heating in vacuum casees.
10. a kind of preparation method of functionalized polyester three-dimensional porous rack according to claim 7, it is characterised in that:Institute
The process conditions for stating vacuum freeze drying are:Vacuum freeze drying temperature is -25~-15 DEG C, and the vacuum freeze drying time is 22
~26h.
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