CN107185051A - Polyvinyl alcohol hydrogel and preparation method thereof - Google Patents
Polyvinyl alcohol hydrogel and preparation method thereof Download PDFInfo
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Abstract
Polyvinyl alcohol hydrogel and preparation method thereof, belongs to technical field of biological material.The polyvinyl alcohol hydrogel is using agarose AG as pore former, using polyvinyl alcohol as matrix, is prepared after chilled defrosting；Counted using polyvinyl alcohol hydrogel quality as 100 parts, wherein the mass fraction of polyvinyl alcohol is 15-20 parts, the mass fraction of agarose is 2~6, and remaining is deionized water.Preparation method is：Polyvinyl alcohol is completely dissolved in after deionized water, agarose is added, after being well mixed, deaeration is carried out to mixed liquor, after freeze-thaw elution processes, prepares and has the polyvinyl alcohol hydrogel of high intensity and loose structure concurrently to polyvinyl alcohol hydrogel.Preparation method of the present invention is simple；The water-setting gum forming for preparing is simple, Stability Analysis of Structures, and its mechanical property and pore structure disclosure satisfy that the requirement of native articular cartilage material.
Description
Technical field
The invention belongs to technical field of biological material, particularly artificial articular cartilage alternative materials field, it is related to and has high intensity concurrently
With the polyvinyl alcohol hydrogel of loose structure and preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) hydrogel has good biocompatibility, lubricity, the mechanical property of similar human body cartilage
Pore structure (plantation cartilage cell), wearability and the fatigue resistance of energy, High water cut (60% -80%), sufficient size, be
Articular cartilage tissue repairs preferable alternative materials.Cartilage cell, growth factor, related gene and medicine can be contained in hydrogel
And bio-matrix, planted to diseased region, induction cells in situ breeds, breaks up and form cartilage.
In order that alternative materials are preferably combined with cartilaginous tissue, hydrogel material need to possess the hole of suitable size.
Polyvinyl alcohol hydrogel can utilize the generation loose structure such as vacuum freeze-drying method, surfactants' templating and pore former method.
The aperture of the polyvinyl alcohol hydrogel prepared by freeze-drying only has several microns, and the size of cartilage cell is generally 15~20
Micron, size is smaller to be not suitable for planting cartilage cell.Preparing polyvinyl alcohol hydrogel using surfactant method can obtain larger
The aperture of size, and form and the aperture of hydrogel can be adjusted by the change of template size, but surfactant is easily residual
Stay, influence the bioactivity of polyvinyl alcohol hydrogel.Pore former method is to be prepared into water-setting by adding pore former in the polymer
Glue, then by hydrogel specific solvent soaking, flushing, pore former is removed, hole is left, the pore former reported includes poly-
Ethylene glycol (PEG), sodium chloride, aerosil particles and sucrose etc., pore former are dissolved in water or acid solution and do not dissolve in organic solvent.This
The shortcoming of the method for kind, which is to remove in the pore former consuming time, and hydrogel, easily remains the pore former not washed away.
Polyvinyl alcohol hydrogel can do pore former with water, without having to worry about residue problem, but the only polyethylene of low concentration
The polyvinyl alcohol hydrogel that alcohol solution is prepared by freeze-thaw method has pore structure, and aperture is small (typically there was only several microns),
Water in the polyvinyl alcohol water solution of high concentration tends to generate super cold water in refrigerating process, the polyvinyl alcohol hydrogel being made
It is middle to be generated without hole, it is difficult to obtain the polyvinyl alcohol hydrogel for having high intensity and pore structure concurrently.
Therefore, the consuming time is short and technique is simple, processing quality prepares high intensity easily-controllablely, loose structure and with good
Biocompatibility polyvinyl alcohol hydrogel as articular cartilage alternative materials turn into this area research direction.
The content of the invention
The problem of existing for prior art, the present invention provides a kind of polyvinyl alcohol hydrogel and preparation method thereof.
The technical scheme is that：
A kind of polyvinyl alcohol hydrogel, the polyvinyl alcohol hydrogel is using agarose AG as pore former, using polyvinyl alcohol as base
Matter, is prepared after chilled defrosting；Described polyvinyl alcohol hydrogel is loose structure, with high intensity；With polyvinyl alcohol
Hydrogel quality is 100 parts of meters, and the wherein mass fraction of polyvinyl alcohol is 15~20 parts, and the mass fraction of agarose is 2~6,
Remaining is deionized water.The polyvinyl alcohol hydrogel of swelling equilibrium is white, opaque, and sense of touch is similar to rubber, and elasticity is big, by force
Degree is high, many micropores, with good biocompatibility.The pore diameter range of described polyvinyl alcohol hydrogel is 25~150 μm, by force
Spend for 0.4~19.8MPa.
The preparation method of above-mentioned polyvinyl alcohol hydrogel, comprises the following steps：
The first step, polyvinyl alcohol is added in deionized water, under 90~99 DEG C of constant temperatures, is stirred complete to polyvinyl alcohol
Thawing forms polyvinyl alcohol water solution；Agarose AG is added in polyvinyl alcohol water solution again, stirred under 90~99 DEG C of constant temperatures
Mix to agarose and be completely dissolved, and uniformly mixed with polyvinyl alcohol water solution, form mixed solution.Gather in described mixed solution
Vinyl alcohol mass fraction is 15~20wt%, and agarose mass fraction is 2~6wt%, and remaining is deionized water.
Second step, mixed solution is poured into mould, is put into deaeration more than 2 hours in vacuum drying chamber, to complete deaeration
Afterwards, then to mixed solution freeze-thaw circulation is carried out, forms polyvinyl alcohol hydrogel.The freeze-thaw circulation refers to mixed solution
Take out and thaw after freeze forming, then carry out freeze forming and take out defrosting, it is described repeatedly to polyvinyl alcohol hydrogel is formed
Polyvinyl alcohol hydrogel mechanical property and pore structure disclosure satisfy that the requirement of native articular cartilage material.Described cryogenic temperature
For -18~-23 DEG C, cooling time is 8~16 hours, and thaw point is 15~20 DEG C or -1 DEG C~-5 DEG C, and thawing time is 6-
10 hours.Cycle-index is more than 1 time.
Agarose AG is as pore former for present invention selection, the only chilled step such as thaw, and just can prepare high intensity, many
The polyvinyl alcohol hydrogel of pore structure, preparation technology is simple, and processing quality is easily-controllable, removes pore former without expending the time, also not
It must worry that the pore former remained in hydrogel produces influence, its mechanical property and pore structure energy to the performance of hydrogel and application
Enough meet the requirement of native articular cartilage material.
The mechanical property for the polyvinyl alcohol hydrogel that the present invention is prepared partially overlaps with native articular cartilage, in order to increase
The crystallinity of strength polyethylene alcohol molecule, further enhances its mechanical property, the polyvinyl alcohol that can also be prepared to second step
Hydrogel carries out liquid nitrogen frozen processing, concretely comprises the following steps：The polyvinyl alcohol hydrogel that second step is obtained is thinly sliced, first through liquid
Chilled nitrogen 6~10 hours, then it is freeze-dried after, soaked in the constant temperature deionized water for being put into 45~50 DEG C more than two weeks, to molten
Swollen balance.The cooling time of described liquid nitrogen frozen is 6~10 hours.The temperature of described freeze-drying is -45~-50 DEG C,
Time determines by the thickness of laminar polyvinyl alcohol hydrogel, and every 2 mm of thickness dries more than 12 hours, by that analogy.
AG particles are remained in the polyvinyl alcohol hydrogel of above-mentioned process liquid nitrogen frozen processing, are taken up space, in order to be formed
The penetrating polyvinyl alcohol hydrogel of hole, can also carry out agarose removing processing to the hydrogel, concretely comprise the following steps：Will be through going
Polyvinyl alcohol hydrogel after being soaked in ionized water takes out, and is positioned in 45~50 DEG C of constant temperature deionized water and soaks, during immersion
Between determined according to thickness, every 2 mm of thickness is soaked more than 4 days, by that analogy, a solution is changed every 6~10 hours.
According to the present invention polyvinyl alcohol hydrogel preparation method, can overcome in the past using vacuum freeze-drying method,
When surfactants' templating prepares polyvinyl alcohol hydrogel, the off size suitable, biocompatibility in hole is bad, chemical agent residue
The shortcomings of, and can overcome in the past using pore former method prepare polyvinyl alcohol hydrogel when, remove pore former expend the time, and
Easily remained in hydrogel, the shortcomings of performance and application of the not removed pore former easily on hydrogel produce influence prepares one
Kind hole size is suitable, hole is penetrating, the polyvinyl alcohol hydrogel with biocompatibility, no chemical residues.
Beneficial effects of the present invention are：Preparation technology of the present invention is simple, and processing quality is easily-controllable, is removed into without expending the time
Hole agent, does not have to concern yet and the pore former not washed away is remained in hydrogel and performance and application on hydrogel produce influence.System
Standby obtained water-setting gum forming is simple, Stability Analysis of Structures；Agarose produces physical crosslinking with polyvinyl alcohol, does not occur polymerisation,
Toxic side effect without chemical cross-linking agent；Agarose has good biocompatibility and nontoxicity, it is to avoid chemical residual and life
Thing toxicity；Intensity meets artificial cartilage material performance requirement；And loose structure provides basis for plantation cartilage cell.
Brief description of the drawings
Fig. 1 (a) is the PVA hydrogel ESEM shape appearance figures that AG contents are 4%.
Fig. 1 (b) is the PVA hydrogel ESEM shape appearance figures that AG contents are 2%.
Fig. 1 (c) is the PVA hydrogel ESEM shape appearance figures that AG contents are 6%.
Fig. 2 is the PVA hydrogel ESEM shape appearance figures after 45 DEG C of constant temperature deionized water immersions.
Fig. 3 is the modulus of compressibility and the variation relation figure of dependent variable for removing the PVA hydrogels after AG.
Embodiment
Referring to the drawings and the present invention will be described in detail according to embodiment.It will be appreciated that this
Specification is not intended to limit the invention to implementation below.On the contrary, it is contemplated that not only cover these embodiments,
And covering can be included in the various selection shapes within the spirit and scope of the present invention being defined by the appended claims
Formula, modification, equivalents and other embodiments.
Embodiment 1
The first step, weighs 15 parts by weight PVA and is added in 81 parts by weight deionized waters, 95 DEG C of constant temperature agitating and heatings 2
Hour is until PVA melts and forms polyvinyl alcohol water solution completely.Second step, is slow added into 4 parts by weight agaroses, keeps
95 DEG C of heated at constant temperature stir 2 hours up to agarose is completely dissolved and uniformly mixed with the PVA aqueous solution, obtain PVA mass parts
Number is 15wt%, and AG mass fractions are 4wt% mixed solution.3rd step, the mixed solution being made is poured into mould, and is put
Enter vacuum drying chamber deaeration 2 hours, cryopreservation case freeze forming is put into afterwards.Cryogenic temperature is set as -20 DEG C, the time is 16
Hour, sample is taken out and thawed, thaw point is 18 DEG C, thawing time is 8 hours.Above-mentioned freeze-thaw process is repeated, is made
Freeze-thaw circulation number of times is the PVA hydrogels for the physical crosslinking that the AG mass fractions of 3 times are 4wt%.
Fig. 1 (a) is the scanning electron microscope observation figure for the PVA hydrogels that AG contents are 4wt%, be can be seen that in figure, AG contents
Many for 4wt% PVA hydrogel Hole proportions, aperture size is distributed 25~150 μm, and size is big more than 100 μm
Hole number is more and connective good, can transmit moisture and other nutriments, and cartilage cell is planted after being and does basis, and
Intensity disclosure satisfy that artificial cartilage material performance requirement.Therefore by the preparation method of this polyvinyl alcohol hydrogel, it can prepare
Go out high intensity, the polyvinyl alcohol hydrogel of loose structure, and do not have to concern the pore former remained in hydrogel to hydrogel
Performance and application produce influence.
Similarly, PVA mass fractions can be prepared for 15wt%, AG mass fractions are respectively 2wt% and 6wt% PVA
Hydrogel.
The first step, weighs 15 parts by weight PVA and is added in 83 parts by weight deionized waters, 95 DEG C of constant temperature agitating and heatings 2
Hour is until PVA melts and forms polyvinyl alcohol water solution completely.Second step, is slow added into 2 parts by weight agaroses, keeps
95 DEG C of heated at constant temperature stir 2 hours up to agarose is completely dissolved and uniformly mixed with the PVA aqueous solution, obtain PVA mass parts
Number is 15wt%, and AG mass fractions are 2wt% mixed solution.3rd step, the mixed solution being made is poured into mould, and is put
Enter vacuum drying chamber deaeration 2 hours, cryopreservation case freeze forming is put into afterwards.Cryogenic temperature is set as -20 DEG C, the time is 16
Hour, sample is taken out and thawed, thaw point is 18 DEG C, thawing time is 8 hours.Above-mentioned freeze-thaw process is repeated, is made
Freeze-thaw circulation number of times is the PVA hydrogels for the physical crosslinking that the AG mass fractions of 3 times are 2wt%.
The first step, weighs 15 parts by weight PVA and is added in 79 parts by weight deionized waters, 95 DEG C of constant temperature agitating and heatings 2
Hour is until PVA melts and forms polyvinyl alcohol water solution completely.Second step, is slow added into 6 parts by weight agaroses, keeps
95 DEG C of heated at constant temperature stir 2 hours up to agarose is completely dissolved and uniformly mixed with the PVA aqueous solution, obtain PVA mass parts
Number is 15wt%, and AG mass fractions are 6wt% mixed solution.3rd step, the mixed solution being made is poured into mould, and is put
Enter vacuum drying chamber deaeration 2 hours, cryopreservation case freeze forming is put into afterwards.Cryogenic temperature is set as -20 DEG C, the time is 16
Hour, sample is taken out and thawed, thaw point is 18 DEG C, thawing time is 8 hours.The above-mentioned freeze-thaw process of repetition, 3 times,
Obtain the PVA hydrogels for the physical crosslinking that AG mass fractions are 6wt%.
Fig. 1 (b), Fig. 1 (c) they are respectively the scanning electron microscope observation figure for the PVA hydrogels that AG contents are 2wt%, 6wt%, by
It can be seen that in figure, compared with PVA hydrogel of the AG contents for 4wt%, in the PVA hydrogels that AG contents are 2wt%, hole institute
Accounting example is less, and aperture size is distributed 20~150 μm, and AG particle residues are seldom；In the PVA hydrogels that AG contents are 6wt%,
Hole proportion is more, and aperture size is distributed 25~150 μm, and the aperture of multiple holes is at 75 μm or so, and AG particle residues are more.
In summary, AG contents meet cartilage cell's plantation for the hole quality in 2wt%, 4wt% and 6wt% PVA hydrogels
It is required that, high intensity, the polyvinyl alcohol hydrogel of loose structure can be prepared, and do not have to concern the pore former remained in hydrogel
Performance and application on hydrogel produce influence.
Therefore, by the preparation method of this polyvinyl alcohol hydrogel, it can expend that the time is short and technique simple, processing quality
High intensity, the polyvinyl alcohol hydrogel of loose structure are prepared easily-controllablely, and do not have to concern the pore former pair remained in hydrogel
The performance of hydrogel and application produce influence.
Embodiment 2
Further, can also be in above-mentioned polyvinyl alcohol water in order that the crystallinity of PVA molecules strengthens in PVA hydrogels
Increase the steps such as liquid cryogenic in the preparation method of gel.
(1) first step, weighs 15 parts by weight PVA and is added in 81 parts by weight deionized waters, and 95 DEG C of constant temperature stirrings add
Heat 2 hours is until PVA melts and forms polyvinyl alcohol water solution completely.Second step, is slow added into 4 parts by weight agaroses,
Keep 95 DEG C of heated at constant temperature to stir 2 hours up to agarose is completely dissolved and uniformly mixed with the PVA aqueous solution, obtain PVA matter
Amount number is 15wt%, and AG mass fractions are 4wt% mixed solution.3rd step, the mixed solution being made is poured into mould,
It is put into vacuum drying chamber deaeration 2 hours, cryopreservation case freeze forming is put into afterwards.Cryogenic temperature is set as -20 DEG C, the time is
16 hours, sample is taken out and thawed, thaw point is 18 DEG C, thawing time is 8 hours.Repeat above-mentioned freeze-thaw process, system
Obtain PVA hydrogel of the freeze-thaw circulation number of times for the physical crosslinking of 3 times.
(2) the 4th steps, the PVA hydrogels prepared in step (1) are first cut into being cut into 6mm × 6mm × 6mm fritter,
Through liquid nitrogen frozen 8 hours, then after freeze-dried 40 hours, it is put into 45 DEG C of constant temperature deionized waters and soaks two weeks, it is flat to being swelled
Weighing apparatus.
Contrast increases above-mentioned steps (2) PVA water-setting of the PVA hydrogels of swelling equilibrium with not carrying out above-mentioned steps (2) afterwards
One group of experimental result of glue, increase above-mentioned steps (2) afterwards the PVA hydrogels of swelling equilibrium compressive strength be 6.616MPa, than
The compressive strength 5.122MPa for not carrying out the PVA hydrogels of above-mentioned steps (2) adds 29%.
Through experimental summary, increase above-mentioned steps (2) cause the crystallinity enhancing of PVA molecules in PVA hydrogels.Increase is above-mentioned
The PVA hydrogels of step (2) swelling equilibrium afterwards, the compressive strength enhancing of the PVA hydrogels than not carrying out above-mentioned steps (2).
Therefore, by the preparation method of this polyvinyl alcohol hydrogel, above-mentioned steps are increased on the basis of embodiment one
(2) higher intensity, the polyvinyl alcohol hydrogel of loose structure, can be prepared, also there is no concern that the pore-forming remained in hydrogel
Agent and performance on hydrogel and application produce influence.
Embodiment 3
Further, in order to improve the pore space structure in PVA hydrogels, can also above-mentioned polyvinyl alcohol hydrogel system
Increase the steps such as desugar in Preparation Method.
(1) first step, weighs 15 parts by weight PVA and is added in 81 parts by weight deionized waters, and 95 DEG C of constant temperature stirrings add
Heat 2 hours is until PVA melts and forms polyvinyl alcohol water solution completely.Second step, is slow added into 4 parts by weight agaroses,
Keep 95 DEG C of heated at constant temperature to stir 2 hours up to agarose is completely dissolved and uniformly mixed with the PVA aqueous solution, obtain PVA matter
Amount number is 15wt%, and AG mass fractions are 4wt% mixed solution.3rd step, the mixed solution being made is poured into mould,
And it is put into vacuum drying chamber deaeration 2 hours, cryopreservation case freeze forming is put into afterwards.Cryogenic temperature is set as -20 DEG C, the time
For 16 hours, sample is taken out and thawed, thaw point is 18 DEG C, thawing time is 8 hours.Above-mentioned freeze-thaw process is repeated,
PVA hydrogel of the freeze-thaw circulation number of times for the physical crosslinking of 3 times is made.
(2) the 4th steps, the thin of 10mm × 17mm × 2mm sizes is first cut into by the PVA hydrogels prepared in step (1)
Piece, through liquid nitrogen frozen 8 hours, then after freeze-dried 12 hours, is put into 45 DEG C of constant temperature deionized waters and soaks two weeks, to being swelled
Balance.
(3) the 5th steps, the polyvinyl alcohol hydrogel are soaked 4 days in 45 DEG C of constant temperature deionized waters, during which every 8 hours
Change once 45 DEG C of constant temperature deionized waters.
Fig. 2 is the PVA hydrogel microscopic appearance figures after 45 DEG C of constant temperature deionized water soaking and washings, and observation can in figure
Know, observed after no AG particle residues, 1000 times of amplification are estimated in the hydrogel after 45 DEG C of constant temperature deionized water soaking and washings
Only particle (4 μm or so of the diameter) residual of very little, 20~150 μm of aperture size distribution, macropore occupies volume more and size is equal
It is even, it is connective good between Kong Yukong, and soaked with deionized water, no chemical agent residue, meet wanting for plantation cartilage cell
Ask.Observed more than, the hydrogel pore structure effect that 45 DEG C of constant temperature deionized water immersions are obtained preferably, disclosure satisfy that articular cartilage
The requirement of alternative materials.
Therefore, by the preparation method of this polyvinyl alcohol hydrogel, above-mentioned steps are increased on the basis of embodiment two
(3) the more preferable polyvinyl alcohol hydrogel of higher intensity, pore space structure, can be prepared, also there is no concern that being remained not in hydrogel
The pore former that is washed away and performance and application on hydrogel produce influence.
By specifically testing, the experiment condition in embodiment of above is not defined as concrete numerical value, as long as
It is that rational experiment condition can prepare high intensity, loose structure and the polyvinyl alcohol hydrogel with good biocompatibility
Glue.
For example, in the first step and second step, being counted using the polyvinyl alcohol hydrogel quality prepared as 100 parts, inciting somebody to action
When polyvinyl alcohol is added in deionized water, the polyvinyl alcohol of 15~20 parts by weight is added in deionized water, and in poly- second
When adding agarose in the enol aqueous solution, the agarose of 2~6 parts by weight is slowly added to, so as to obtain polyvinyl alcohol mass parts
Number is the polyvinyl alcohol hydrogel that 15~20wt%, agarose mass fraction are 2~6wt%.
For example, in the first step and second step, the stirring is carried out under 90~99 DEG C of temperature constant states.
For example, in the third step, the mixed solution being made is poured into mould, and it is put into vacuum drying chamber deaeration 2 hours
To be put into cryopreservation case freeze forming after up to complete deaeration, cryogenic temperature is set as -18~-23 DEG C, the time is set to 8~16
Hour, take out thaw afterwards, thaw point is 15~20 DEG C, thawing time is 6~10 hours.
For example, in the 4th step, the PVA hydrogels prepared in step (1) are first cut into thickness thin for 2~6 millimeters
Piece, the time through liquid nitrogen frozen is 6~10 hours, then freeze-dried, and the time of freeze-drying is determined by the thickness of PVA hydrogels
Fixed, every 2 mm of thickness need to be dried 12 hours, and 45~50 DEG C of constant temperature deionized waters are put into afterwards and are soaked more than two weeks, flat to being swelled
Weighing apparatus.For example, being dried 24 hours when PVA hydrogels are cut into the thin slice that thickness is 4 millimeters, it is cut into PVA hydrogels
Drying 36 hours when thickness is 6 millimeters of thin slice, by that analogy.
For example, in the 5th step, by the polyvinyl alcohol hydrogel after being soaked in constant temperature deionized water in 45~50 DEG C of perseverances
The time soaked in warm deionized water is that every 2 mm of thickness is soaked 4 days, during which changes once 45 DEG C of perseverances every 6~10 hours
Warm deionized water.For example, being soaked 8 days when PVA hydrogels are cut into the thin slice that thickness is 4 millimeters, in PVA hydrogel quilts
Immersion 12 days when being cut into the thin slice that thickness is 6 millimeters, by that analogy.
The parts by weight PVA of above embodiment weighing 15 is added in 81 parts by weight deionized waters, 95 DEG C of perseverances
The situation that warm agitating and heating forms polyvinyl alcohol water solution in 2 hours up to PVA melts completely is illustrated, but the stirring
Heat time is an example, however it is not limited to 2 hours, as long as PVA melts and forms polyvinyl alcohol water solution completely.
Above embodiment keeps 95 DEG C of heated at constant temperature to stir 2 hours directly to being slowly added to 4 parts by weight agaroses
It is completely dissolved and is uniformly mixed with the PVA aqueous solution to agarose, the situation for obtaining mixed solution is illustrated, but this is stirred
It is an example to mix mode of heating, however it is not limited to be slowly added to, and is also not limited to 2 hours, as long as agarose is completely dissolved simultaneously
And uniformly mixed with the PVA aqueous solution, obtain mixed solution.
Above embodiment by the mixed solution after deaeration to carrying out 3 freeze-thaw circulations, so as to form poly- second
The situation of enol hydrogel is illustrated, but the number of times of freeze-thaw circulation is not limited to 3 times or 1 time or 2 times,
It can also be more than 4 times, as long as polyvinyl alcohol hydrogel can be formed.
Cryopreservation case cooling time was illustrated above embodiment for the situation of 16 hours, but freezing
Time is not limited to 16 hours, can be 8~16 hours, as long as polyvinyl alcohol hydrogel can be formed.
Thaw point is illustrated above embodiment for 15~20 DEG C of situation, but thaw point is not limited
15~20 DEG C are made as, the PVA hydrogels of freeze forming can also be thawed by low temperature thawing mode, thaw point is set
For -5~-1 DEG C.
In summary, by the preparation method of the polyvinyl alcohol hydrogel of the application, it can expend that the time is short and technique is simple
Single, processing quality prepares high intensity, loose structure and the polyvinyl alcohol hydrogel with good biocompatibility easily-controllablely.
Further, the present invention also provides a kind of polyvinyl alcohol hydrogel, and the polyvinyl alcohol hydrogel is by above-mentioned polyethylene
What the preparation method of alcohol hydrogel was prepared from.
Fig. 3 be embodiment one in removing AG after PVA hydrogels modulus of compressibility and the variation relation figure of dependent variable.Pressure
Contracting intensity has obvious strain correlation, and when dependent variable increases to 0.7 from 0.2, modulus of compressibility increases to from 0.64MPa
19.8MPa, partially overlaps with 1.9~14.4MPa of modulus of compressibility of natural joint cartilage.The PVA hydrogels are through liquid nitrogen frozen
With immersion reaches swelling equilibrium and removes the hydrogel that AG is obtained, the hydrogel in 45 DEG C of constant temperature deionized waters after freeze-drying
Loose structure meet plantation cartilage cell size requirement, and compressive strength strengthen, reached the intensity of cartilage replacement material
It is required that.
It can be seen that, the hydrogel prepared using the preparation method has the following advantages that：Shaping is simple, Stability Analysis of Structures；Agarose
Physical crosslinking is produced with polyvinyl alcohol, does not occur polymerisation, the toxic side effect of no chemical cross-linking agent；Agarose has good
Biocompatibility and nontoxicity, it is to avoid chemical residual and bio-toxicity；Intensity meets artificial cartilage material performance requirement；And
Loose structure provides basis for plantation cartilage cell.
Above in association with preferred embodiment, the present invention is described, but those skilled in the art should recognize
Know, above-mentioned example is intended merely to explanation, and cannot function as limitation of the present invention.It therefore, it can in claims
The present invention is modified and modification in spirit, these modifications and variations will all fall in claims of the present invention
Within the scope of required.
Claims (10)
1. a kind of preparation method of polyvinyl alcohol hydrogel, it is characterised in that following steps：
The first step, polyvinyl alcohol is added in deionized water, under constant temperature, and stirring melts to form poly- second completely to polyvinyl alcohol
The enol aqueous solution；Agarose AG is added in polyvinyl alcohol water solution again, stirs to agarose and is completely dissolved under constant temperature, and
Uniformly mixed with polyvinyl alcohol water solution, form mixed solution；In described mixed solution polyvinyl alcohol mass fraction be 15~
20wt%, agarose mass fraction is 2~6wt%, and remaining is deionized water；
Second step, mixed solution is poured into mould, is put into vacuum drying chamber after complete deaeration, then mixed solution is carried out cold
Freeze thaw cycles, form polyvinyl alcohol hydrogel；The freeze-thaw circulation, which refers to take out after mixed solution freeze forming, to thaw, then
Freeze forming is carried out, repeatedly to formation polyvinyl alcohol hydrogel, obtained polyvinyl alcohol hydrogel mechanical property and hole
Structure disclosure satisfy that the requirement of native articular cartilage material.
2. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 1, it is characterised in that described freezing solution
It is -18~-23 DEG C to freeze cryogenic temperature in circulation, and cooling time is 8~16 hours；Thaw point is 15~20 DEG C or -1 DEG C~-5
DEG C, thawing time is 6-10 hours.
3. the preparation method of a kind of polyvinyl alcohol hydrogel according to claim 2, it is characterised in that described in the first step
Constant temperature be 90~99 DEG C.
4. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 1 or 2 or 3, it is characterised in that can be with
The polyvinyl alcohol hydrogel prepared to second step carries out liquid nitrogen frozen processing, concretely comprises the following steps：By gathering that second step is obtained
Polyvinyl alcohol hydrogel is thinly sliced, and first through liquid nitrogen frozen 6~10 hours, after being freeze-dried at -45~-50 DEG C, is put into
Soaked in constant temperature deionized water more than two weeks, to swelling equilibrium.
5. the preparation method of a kind of polyvinyl alcohol hydrogel according to claim 4, it is characterised in that described freezing is done
The dry time is determined that every 2 mm of thickness is dried more than 12 hours by the thickness of laminar polyvinyl alcohol hydrogel.
6. the preparation method of a kind of polyvinyl alcohol hydrogel according to claim 5, it is characterised in that can also be to passing through
The polyvinyl alcohol hydrogel of liquid nitrogen frozen processing carries out agarose removing processing, concretely comprises the following steps：Will be through being soaked in deionized water
Polyvinyl alcohol hydrogel afterwards takes out, and is positioned in constant temperature deionized water and soaks.
7. the preparation method of a kind of polyvinyl alcohol hydrogel according to claim 5, it is characterised in that can also be to passing through
The polyvinyl alcohol hydrogel of liquid nitrogen frozen processing carries out agarose removing processing, concretely comprises the following steps：Will be through being soaked in deionized water
Polyvinyl alcohol hydrogel afterwards takes out, and is positioned in constant temperature deionized water and soaks.
8. the preparation method of a kind of polyvinyl alcohol hydrogel according to claim 5 or 6 or 7, it is characterised in that described
The temperature of constant temperature deionized water is 45~50 DEG C.
9. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 6 or 7, it is characterised in that described perseverance
Soak time is determined according to the thickness of polyvinyl alcohol hydrogel in warm deionized water, and every 2 mm of thickness is soaked more than 4 days, with this
Analogize, a solution was changed every 6~10 hours.
10. the polyvinyl alcohol hydrogel prepared according to any preparation method of claim 1 to 9, it is characterised in that institute
The polyvinyl alcohol hydrogel stated is loose structure, with high intensity and good biocompatibility；Polyvinyl alcohol hydrogel is with fine jade
Lipolysaccharide AG is pore former, and using polyvinyl alcohol as matrix, chilled defrosting is prepared；Using polyvinyl alcohol hydrogel quality as 100
Part meter, the wherein mass fraction of polyvinyl alcohol are 15-20 parts, and the mass fraction of agarose is 2~6 parts, and remaining is deionized water；
The pore diameter range of described polyvinyl alcohol hydrogel is 25~150 μm；Strength range is 0.4-19.8MPa.
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