CN107185051B - Polyvinyl alcohol hydrogel and preparation method thereof - Google Patents
Polyvinyl alcohol hydrogel and preparation method thereof Download PDFInfo
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- CN107185051B CN107185051B CN201710389381.0A CN201710389381A CN107185051B CN 107185051 B CN107185051 B CN 107185051B CN 201710389381 A CN201710389381 A CN 201710389381A CN 107185051 B CN107185051 B CN 107185051B
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- polyvinyl alcohol
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 182
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 182
- 239000000017 hydrogel Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000936 Agarose Polymers 0.000 claims abstract description 35
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010257 thawing Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 210000001188 articular cartilage Anatomy 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 230000004087 circulation Effects 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 150000002085 enols Chemical class 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims 3
- 230000008014 freezing Effects 0.000 claims 3
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000010977 jade Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 238000010828 elution Methods 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 14
- 210000003321 cartilage cell Anatomy 0.000 description 10
- 210000000845 cartilage Anatomy 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000005138 cryopreservation Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012424 Freeze-thaw process Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 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
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- A61L27/26—Mixtures of macromolecular compounds
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- 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
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J3/075—Macromolecular gels
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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；It is in terms of 100 parts by polyvinyl alcohol hydrogel quality, wherein the mass fraction of polyvinyl alcohol is 15-20 parts, and the mass fraction of agarose is 2~6, remaining is deionized water.The preparation method comprises the following steps: after polyvinyl alcohol is completely dissolved in deionized water, agarose is added, after mixing, deaeration is carried out, after freeze-thaw-elution processes to mixed liquor, is prepared and has both the polyvinyl alcohol hydrogel of high-intensitive and porous structure to polyvinyl alcohol hydrogel.Preparation method of the present invention is simple；The water-setting gum forming being prepared is simple, stable structure, and mechanical property and pore structure can satisfy the requirement of native articular cartilage material.
Description
Technical field
The invention belongs to technical field of biological material, especially artificial articular cartilage alternative materials field, are related to having both high intensity
With the polyvinyl alcohol hydrogel of porous structure and preparation method thereof.
Background technique
Polyvinyl alcohol (PVA) hydrogel has the mechanical property of good biocompatibility, lubricity, 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 ideal alternative materials.Cartilage cell, growth factor, related gene and drug can be contained in hydrogel
And bio-matrix, it is planted to diseased region, induces cells in situ proliferation, breaks up and form cartilage.
In order to combine alternative materials preferably with cartilaginous tissue, hydrogel material need to have the hole of suitable size.
Polyvinyl alcohol hydrogel can generate porous structure using vacuum freeze-drying method, surfactants' templating and pore former method etc..
There was only several microns by the aperture of the polyvinyl alcohol hydrogel of freeze-drying preparation, and the size of cartilage cell is generally 15~20
Micron, size is smaller to be not suitable for planting cartilage cell.Using surfactant method prepare polyvinyl alcohol hydrogel can get it is larger
The aperture of size, and by the form of the adjustable hydrogel of change of template size and aperture, but surfactant is easily residual
It stays, influences the bioactivity of polyvinyl alcohol hydrogel.Pore former method is to be prepared into water-setting by the way that pore former is added in the polymer
Glue, then by hydrogel specific solvent soaking, flushing, pore former is removed, hole is left, reported pore former 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 shortcomings that kind method, is that removing pore former expends the time, and the pore former not washed away is easily remained in hydrogel.
Polyvinyl alcohol hydrogel can do pore former with water, without having to worry about residue problem, but the polyethylene of only low concentration
Polyvinyl alcohol hydrogel of the alcohol solution by the preparation of freeze-thaw method has pore structure, and aperture is small (generally there was only several microns),
Water in the polyvinyl alcohol water solution of high concentration tends to generate super cold water, manufactured polyvinyl alcohol hydrogel in refrigerating process
Middle no hole generates, it is difficult to obtain the polyvinyl alcohol hydrogel for having both high-intensitive and pore structure.
Therefore, the consuming time is short and simple process, processing quality prepare high-intensitive, porous structure easily-controllablely and have good
Biocompatibility polyvinyl alcohol hydrogel as articular cartilage alternative materials become this field research direction.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of polyvinyl alcohol hydrogel and preparation method thereof.
The technical solution of the present invention is as follows:
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；The polyvinyl alcohol hydrogel is porous structure, has high intensity；With polyvinyl alcohol
Hydrogel quality is 100 parts of meters, and wherein the 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, more micropores, has good biocompatibility.The pore diameter range of the polyvinyl alcohol hydrogel is 25~150 μm, by force
Degree is 0.4~19.8MPa.
The preparation method of above-mentioned polyvinyl alcohol hydrogel, comprising the following steps:
Polyvinyl alcohol is added in deionized water the first step, under 90~99 DEG C of constant temperatures, stirs complete to polyvinyl alcohol
Thawing forms polyvinyl alcohol water solution；Agarose AG is added in polyvinyl alcohol water solution again, is stirred under 90~99 DEG C of constant temperatures
It mixes to agarose and is completely dissolved, and uniformly mixed with polyvinyl alcohol water solution, form mixed solution.Gather in the mixed solution
Vinyl alcohol mass fraction is 15~20wt%, and agarose mass fraction is 2~6wt%, remaining is deionized water.
Second step pours into mixed solution in mold, is put into vacuum oven deaeration 2 hours or more, until 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
It takes out and thaws after freeze forming, then carry out freeze forming and take out defrosting, repeatedly extremely form polyvinyl alcohol hydrogel, it is described
Polyvinyl alcohol hydrogel mechanical property and pore structure can satisfy the requirement of native articular cartilage material.The cryogenic temperature
It is -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, thawing time 6-
10 hours.Cycle-index is 1 time or more.
The present invention selects agarose AG as pore former, only chilled to thaw, and just can prepare high-intensitive, more
The polyvinyl alcohol hydrogel of pore structure, preparation process is simple, and processing quality is easily-controllable, without expending time removal pore former, also not
It must worry that remaining pore former has an impact the performance of hydrogel and application in hydrogel, mechanical property and pore structure energy
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, can also be to the polyvinyl alcohol that second step is prepared
Hydrogel carries out liquid nitrogen frozen processing, specific steps are as follows: the polyvinyl alcohol hydrogel for obtaining second step is thinly sliced, first through liquid
Chilled nitrogen 6~10 hours, then it is freeze-dried after, be put into 45~50 DEG C of constant temperature deionized water and impregnate two weeks or more, until molten
Swollen balance.The cooling time of the liquid nitrogen frozen is 6~10 hours.The temperature of the freeze-drying is -45~-50 DEG C,
Time determines by the thickness of laminar polyvinyl alcohol hydrogel, and every 2 mm of thickness is 12 hours dry or more, and so on.
Remain AG particle in the above-mentioned polyvinyl alcohol hydrogel handled by liquid nitrogen frozen, takes up space, in order to be formed
The penetrating polyvinyl alcohol hydrogel of hole can also carry out agarose removing processing, specific steps are as follows: will be through going to the hydrogel
Polyvinyl alcohol hydrogel after impregnating in ionized water takes out, and is placed in 45~50 DEG C of constant temperature deionized water and impregnates, when immersion
Between determined according to thickness, every 2 mm of thickness is impregnated 4 days or more, and so on, every the solution of replacement in 6~10 hours.
The preparation method of polyvinyl alcohol hydrogel according to the present invention, can overcome in the past using vacuum freeze-drying method,
When surfactants' templating prepares polyvinyl alcohol hydrogel, pore size is improper, biocompatibility is bad, chemical agent residue
The disadvantages of, and can overcome in the past using pore former method prepare polyvinyl alcohol hydrogel when, removal pore former expend the time, and
It is easily remained in hydrogel, the pore former not being removed easily to the performance of hydrogel and applies the disadvantages of having an impact, and prepares one
The polyvinyl alcohol hydrogel that kind pore size is suitable, hole is penetrating, with biocompatibility, no chemical residues.
The invention has the benefit that preparation process of the present invention is simple, processing quality is easily-controllable, without expend the time removal at
Hole agent, also there is no concern that the pore former not washed away is remained in hydrogel and the performance to hydrogel and application have an impact.System
Standby obtained water-setting gum forming is simple, stable structure；Agarose and polyvinyl alcohol generate physical crosslinking, and polymerization reaction does not occur,
Toxic side effect without chemical cross-linking agent；Agarose has good biocompatibility and nontoxicity, avoids chemical residual and life
Object toxicity；Intensity meets artificial cartilage material performance requirement；And porous structure provides basis for plantation cartilage cell.
Detailed description of the invention
Fig. 1 (a) is the PVA hydrogel scanning electron microscope shape appearance figure that AG content is 4%.
Fig. 1 (b) is the PVA hydrogel scanning electron microscope shape appearance figure that AG content is 2%.
Fig. 1 (c) is the PVA hydrogel scanning electron microscope shape appearance figure that AG content is 6%.
Fig. 2 is the PVA hydrogel scanning electron microscope shape appearance figure after 45 DEG C of constant temperature deionized waters are impregnated.
Fig. 3 is the compression modulus for removing the PVA hydrogel after AG and the variation relation figure of dependent variable.
Specific embodiment
The present invention will be described in detail referring to the drawings and according to specific embodiment.It will be appreciated that this
Specification is not intended to limit the invention to following implementation.On the contrary, the present invention is directed to not only cover these embodiments,
And covering can be included in 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 completely and forms polyvinyl alcohol water solution.Second step is slow added into 4 parts by weight agaroses, keeps
95 DEG C of heated at constant temperature stir 2 hours until agarose is completely dissolved and uniformly mixes with PVA aqueous solution, obtain PVA mass parts
Number is 15wt%, and AG mass fraction is the mixed solution of 4wt%.Manufactured mixed solution is poured into mold, and put by third step
Enter vacuum oven deaeration 2 hours, is put into cryopreservation case freeze forming later.Cryogenic temperature is set as -20 DEG C, the time 16
Hour, sample is taken out and is thawed, thaw point is 18 DEG C, and thawing time is 8 hours.Above-mentioned freeze-thaw process is repeated, is made
The PVA hydrogel for the physical crosslinking that the AG mass fraction that freeze-thaw circulation number is 3 times is 4wt%.
Fig. 1 (a) is the scanning electron microscope observation figure for the PVA hydrogel that AG content is 4wt%, and You Tuzhong can be seen that, AG content
More for the PVA hydrogel Hole proportion of 4wt%, aperture size is distributed 25~150 μm, and size is big at 100 μm or more
Hole number is more and connectivity is good, can transmit moisture and other nutriments, does basis for plantation cartilage cell later, and
Intensity can satisfy artificial cartilage material performance requirement.Therefore the preparation method for passing through this polyvinyl alcohol hydrogel, can prepare
High-intensitive out, porous structure polyvinyl alcohol hydrogel, and do not have to concern that remaining pore former is to hydrogel in hydrogel
Performance and application have an impact.
Similarly, can prepare PVA mass fraction is 15wt%, and AG mass fraction is respectively the PVA of 2wt% and 6wt%
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 completely and forms polyvinyl alcohol water solution.Second step is slow added into 2 parts by weight agaroses, keeps
95 DEG C of heated at constant temperature stir 2 hours until agarose is completely dissolved and uniformly mixes with PVA aqueous solution, obtain PVA mass parts
Number is 15wt%, and AG mass fraction is the mixed solution of 2wt%.Manufactured mixed solution is poured into mold, and put by third step
Enter vacuum oven deaeration 2 hours, is put into cryopreservation case freeze forming later.Cryogenic temperature is set as -20 DEG C, the time 16
Hour, sample is taken out and is thawed, thaw point is 18 DEG C, and thawing time is 8 hours.Above-mentioned freeze-thaw process is repeated, is made
The PVA hydrogel for the physical crosslinking that the AG mass fraction that freeze-thaw circulation number is 3 times is 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 completely and forms polyvinyl alcohol water solution.Second step is slow added into 6 parts by weight agaroses, keeps
95 DEG C of heated at constant temperature stir 2 hours until agarose is completely dissolved and uniformly mixes with PVA aqueous solution, obtain PVA mass parts
Number is 15wt%, and AG mass fraction is the mixed solution of 6wt%.Manufactured mixed solution is poured into mold, and put by third step
Enter vacuum oven deaeration 2 hours, is put into cryopreservation case freeze forming later.Cryogenic temperature is set as -20 DEG C, the time 16
Hour, sample is taken out and is thawed, thaw point is 18 DEG C, and thawing time is 8 hours.The above-mentioned freeze-thaw process of repetition, 3 times,
Obtain the PVA hydrogel for the physical crosslinking that AG mass fraction is 6wt%.
Fig. 1 (b), Fig. 1 (c) they are respectively the scanning electron microscope observation figure for the PVA hydrogel that AG content is 2wt%, 6wt%, by
It can be seen that in figure, compared with AG content is the PVA hydrogel of 4wt%, in the PVA hydrogel that AG content is 2wt%, hole institute
Accounting example is less, and aperture size is distributed 20~150 μm, and AG particle residue is seldom；In the PVA hydrogel that AG content is 6wt%,
Hole proportion is more, and aperture size is distributed 25~150 μm, and at 75 μm or so, AG particle residue is more in the aperture of multiple holes.
In summary, AG content is that the hole quality in the PVA hydrogel of 2wt%, 4wt% and 6wt% meets cartilage cell's plantation
It is required that high-intensitive, porous structure polyvinyl alcohol hydrogel can be prepared, and remaining pore former in hydrogel is not had to concern
Performance and application to hydrogel have an impact.
Therefore, by the preparation method of this polyvinyl alcohol hydrogel, short time and simple process, processing quality can be expended
High-intensitive, porous structure polyvinyl alcohol hydrogel is prepared easily-controllablely, and does not have to concern remaining pore former pair in hydrogel
The performance of hydrogel and application have an impact.
Embodiment 2
It further, can also be in above-mentioned polyvinyl alcohol water in order to enhance the crystallinity of PVA molecule in PVA hydrogel
Increase 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 until PVA melts completely and forms polyvinyl alcohol water solution.Second step is slow added into 4 parts by weight agaroses,
It keeps 95 DEG C of heated at constant temperature to stir 2 hours until agarose is completely dissolved and uniformly mixes with PVA aqueous solution, obtains PVA matter
Amount number is 15wt%, and AG mass fraction is the mixed solution of 4wt%.Third step pours into manufactured mixed solution in mold,
It is put into vacuum oven deaeration 2 hours, is put into cryopreservation case freeze forming later.Cryogenic temperature is set as -20 DEG C, the time is
16 hours, sample is taken out and is thawed, thaw point is 18 DEG C, and thawing time is 8 hours.Repeat above-mentioned freeze-thaw process, system
Obtain the PVA hydrogel for the physical crosslinking that freeze-thaw circulation number is 3 times.
The PVA hydrogel prepared in step (1) is first cut into and is cut into 6mm × 6mm × 6mm fritter by (2) the 4th steps,
It behind liquid nitrogen frozen 8 hours, then freeze-dried 40 hours, is put into 45 DEG C of constant temperature deionized waters and impregnates two weeks, until swelling is flat
Weighing apparatus.
Comparison increases above-mentioned steps (2) the PVA hydrogel of swelling equilibrium and PVA water-setting for not carrying out above-mentioned steps (2) afterwards
One group of experimental result of glue, increase above-mentioned steps (2) afterwards the PVA hydrogel of swelling equilibrium compressive strength be 6.616MPa, than
The compressive strength 5.122MPa for not carrying out the PVA hydrogel of above-mentioned steps (2) increases 29%.
Through experimental summary, increases above-mentioned steps (2) and the crystallinity of PVA molecule in PVA hydrogel is enhanced.Increase above-mentioned
The PVA hydrogel of step (2) swelling equilibrium afterwards, the compressive strength enhancing of the PVA hydrogel than not carrying out above-mentioned steps (2).
Therefore, by the preparation method of this polyvinyl alcohol hydrogel, increase above-mentioned steps on the basis of embodiment one
(2), the polyvinyl alcohol hydrogel of higher intensity, porous structure can be prepared, also there is no concern that remaining pore-forming in hydrogel
Agent and performance to hydrogel and application have an impact.
Embodiment 3
It further, can also be in the system of above-mentioned polyvinyl alcohol hydrogel in order to improve the hole configurations in PVA hydrogel
Increase 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 until PVA melts completely and forms polyvinyl alcohol water solution.Second step is slow added into 4 parts by weight agaroses,
It keeps 95 DEG C of heated at constant temperature to stir 2 hours until agarose is completely dissolved and uniformly mixes with PVA aqueous solution, obtains PVA matter
Amount number is 15wt%, and AG mass fraction is the mixed solution of 4wt%.Third step pours into manufactured mixed solution in mold,
And it is put into vacuum oven deaeration 2 hours, it is put into cryopreservation case freeze forming later.Cryogenic temperature is set as -20 DEG C, the time
It is 16 hours, sample is taken out and is thawed, thaw point is 18 DEG C, and thawing time is 8 hours.Above-mentioned freeze-thaw process is repeated,
The PVA hydrogel for the physical crosslinking that freeze-thaw circulation number is 3 times is made.
It is thin to be first cut into 10mm × 17mm × 2mm size by (2) the 4th steps for the PVA hydrogel prepared in step (1)
Piece is put into 45 DEG C of constant temperature deionized waters and impregnates two weeks behind liquid nitrogen frozen 8 hours, then freeze-dried 12 hours, until swelling
Balance.
(3) the 5th steps impregnate the polyvinyl alcohol hydrogel 4 days, during which every 8 hours in 45 DEG C of constant temperature deionized waters
Replace primary 45 DEG C of constant temperature deionized waters.
Fig. 2 is the PVA hydrogel microscopic appearance figure after 45 DEG C of constant temperature deionized water soaking and washings, can by observing in figure
Know, range estimation is observed after 1000 times of amplification without AG particle residue in the hydrogel after 45 DEG C of constant temperature deionized water soaking and washings
Only (4 μm of diameter or so) of the particle of very little residuals, aperture size are distributed 20~150 μm, and macropore occupies volume mostly and size is equal
Even, connectivity is good between Kong Yukong, and is impregnated with deionized water, no chemical agent residue, meets wanting for plantation cartilage cell
It asks.It is observed above, the hydrogel pore structure effect that 45 DEG C of constant temperature deionized waters are impregnated is preferable, can satisfy articular cartilage
The requirement of alternative materials.
Therefore, by the preparation method of this polyvinyl alcohol hydrogel, increase above-mentioned steps on the basis of embodiment two
(3), the better polyvinyl alcohol hydrogel of higher intensity, hole configurations can be prepared, also there is no concern that remaining not in hydrogel
The pore former that is washed away and performance and application to hydrogel have an impact.
By specifically testing, the experiment condition in embodiment of above is not defined as specific value, as long as
It is that reasonable experiment condition can prepare high-intensitive, porous structure and the polyvinyl alcohol hydrogel with good biocompatibility
Glue.
For example, being to be incited somebody to action in terms of 100 parts by the polyvinyl alcohol hydrogel quality prepared in the first step and second step
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 agarose being added in enol aqueous solution, it is slowly added to the agarose of 2~6 parts by weight, to obtain polyvinyl alcohol mass parts
The polyvinyl alcohol hydrogel that number is 15~20wt%, agarose mass fraction is 2~6wt%.
For example, the stirring carries out under 90~99 DEG C of temperature constant states in the first step and second step.
For example, in the third step, manufactured mixed solution is poured into mold, and it is put into vacuum oven deaeration 2 hours
To be put into cryopreservation case freeze forming after complete deaeration, cryogenic temperature is set as -18~-23 DEG C, the time is set as 8~16
Hour, it takes out thaw later, thaw point is 15~20 DEG C, and thawing time is 6~10 hours.
For example, in the 4th step, the PVA hydrogel prepared in step (1) is first cut into thin with a thickness of 2~6 millimeters
Piece, the time through liquid nitrogen frozen are 6~10 hours, then freeze-dried, and the time of freeze-drying is determined by the thickness of PVA hydrogel
Fixed, every 2 mm of thickness need to be dried 12 hours, be put into later 45~50 DEG C of constant temperature deionized waters immersions two weeks or more, until swelling is flat
Weighing apparatus.For example, it is 24 hours dry when PVA hydrogel is cut into the thin slice with a thickness of 4 millimeters, it is cut into PVA hydrogel
With a thickness of 36 hours dry when 6 millimeters of thin slice, and so on.
For example, in the 5th step, by the polyvinyl alcohol hydrogel after being impregnated in constant temperature deionized water in 45~50 DEG C of perseverances
The time impregnated in warm deionized water is that every 2 mm of thickness is impregnated 4 days, and primary 45 DEG C of perseverances were during which replaced every 6~10 hours
Warm deionized water.For example, being impregnated 8 days when PVA hydrogel is cut into the thin slice with a thickness of 4 millimeters, in PVA hydrogel quilt
It is impregnated 12 days when being cut into the thin slice with a thickness of 6 millimeters, and so on.
The above 15 parts by weight PVA of specific embodiment weighing is added in 81 parts by weight deionized waters, 95 DEG C of perseverances
It is illustrated the case where PVA melts completely and forms polyvinyl alcohol water solution within warm agitating and heating 2 hours, but the stirring
Heating time is an example, however it is not limited to and 2 hours, as long as PVA melts completely and forms polyvinyl alcohol water solution.
The above specific embodiment keeps 95 DEG C of heated at constant temperature to stir 2 hours directly to 4 parts by weight agaroses are slowly added to
It is completely dissolved to agarose and is illustrated the case where uniformly mixing with PVA aqueous solution, obtain mixed solution, but this is stirred
Mixing heating method is an example, however it is not limited to be slowly added to, be also not limited to 2 hours, as long as agarose is completely dissolved simultaneously
And uniformly mixed with PVA aqueous solution, obtain mixed solution.
The above specific embodiment carries out 3 freeze-thaw circulations to by the mixed solution after deaeration, to form poly- second
The case where enol hydrogel, is illustrated, but the number of freeze-thaw circulation is not limited to 3 times, is also possible to 1 time or 2 times,
It can also be 4 times or more, as long as polyvinyl alcohol hydrogel can be formed.
The case where cryopreservation case cooling time is 16 hours is illustrated in the above specific embodiment, but freezes
Time is not limited to 16 hours, can be 8~16 hours, as long as polyvinyl alcohol hydrogel can be formed.
The case where thaw point is 15~20 DEG C is illustrated in the above specific embodiment, but thaw point is unlimited
15~20 DEG C are made as, can also be thawed by PVA hydrogel of the low temperature thawing mode to freeze forming, thaw point setting
It is -5~-1 DEG C.
In conclusion 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-intensitive, porous structure and the polyvinyl alcohol hydrogel with good biocompatibility easily-controllablely.
Further, the present invention also provides a kind of polyvinyl alcohol hydrogel, which is by above-mentioned polyethylene
What the preparation method of alcohol hydrogel was prepared.
Fig. 3 is the compression modulus that the PVA hydrogel after AG is removed in embodiment one and the variation relation figure of dependent variable.Pressure
Contracting intensity has apparent strain correlation, and when dependent variable increases to 0.7 from 0.2, compression modulus increases to from 0.64MPa
19.8MPa partially overlaps with 1.9~14.4MPa of compression modulus of natural joint cartilage.The PVA hydrogel is through liquid nitrogen frozen
Reach swelling equilibrium with being impregnated in 45 DEG C of constant temperature deionized waters after freeze-drying and remove the hydrogel that AG obtains, the hydrogel
Porous structure meet plantation cartilage cell size requirement, and compressive strength enhance, reached the intensity of cartilage replacement material
It is required that.
As it can be seen that have the advantages that molding is simple using hydrogel prepared by the preparation method, stable structure；Agarose
Physical crosslinking is generated with polyvinyl alcohol, polymerization reaction, the toxic side effect of no chemical cross-linking agent does not occur；Agarose has good
Biocompatibility and nontoxicity, avoid chemical residual and bio-toxicity；Intensity meets artificial cartilage material performance requirement；And
Porous structure provides basis for plantation cartilage cell.
Combining preferred embodiment above, 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, can be in claims
It modifies in spirit to the present invention and modification, these modifications and variations will all fall in claims of the present invention
Within the scope of required.
Claims (9)
1. a kind of preparation method of polyvinyl alcohol hydrogel, it is characterised in that following steps:
Polyvinyl alcohol is added in deionized water the first step, and under constant temperature, stirring is melted completely to polyvinyl alcohol forms poly- second
Enol aqueous solution；Agarose AG is added in polyvinyl alcohol water solution again, stirring to agarose is completely dissolved under constant temperature, and
It is uniformly mixed with polyvinyl alcohol water solution, forms mixed solution；In the mixed solution polyvinyl alcohol mass fraction be 15~
20wt%, agarose mass fraction are 2~6wt%, remaining is deionized water；
Second step pours into mixed solution in mold, after being put into vacuum oven complete deaeration, then carries out to mixed solution cold
Freeze thaw cycles, forms polyvinyl alcohol hydrogel；The freeze-thaw circulation takes out defrosting after referring to mixed solution freeze forming, then
Freeze forming is carried out, repeatedly to formation polyvinyl alcohol hydrogel, obtained polyvinyl alcohol hydrogel mechanical property and hole
Structure can satisfy the requirement of native articular cartilage material.
2. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 1, which is characterized in that the freezing solution
Freezing cryogenic temperature in circulation is -18~-23 DEG C, 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. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 2, which is characterized 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, which is characterized in that can be with
Liquid nitrogen frozen processing, specific steps are carried out to the polyvinyl alcohol hydrogel that second step is prepared are as follows: obtain second step poly-
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
It is impregnated in constant temperature deionized water two weeks or more, until swelling equilibrium.
5. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 4, which is characterized in that the freezing is dry
The dry time determines by the thickness of laminar polyvinyl alcohol hydrogel, and every 2 mm of thickness is 12 hours dry or more.
6. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 5, which is characterized in that can also be to process
The polyvinyl alcohol hydrogel of liquid nitrogen frozen processing carries out agarose removing processing, specific steps are as follows: will be through impregnating in deionized water
Polyvinyl alcohol hydrogel afterwards takes out, and is placed in constant temperature deionized water and impregnates.
7. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 5 or 6, which is characterized in that the perseverance
The temperature of warm deionized water is 45~50 DEG C.
8. a kind of preparation method of polyvinyl alcohol hydrogel according to claim 6, which is characterized in that the constant temperature is gone
Soaking time is determined according to the thickness of polyvinyl alcohol hydrogel in ionized water, and every 2 mm of thickness is impregnated 4 days or more, and so on,
Every the solution of replacement in 6~10 hours.
9. according to claim 1 to the polyvinyl alcohol hydrogel that 8 any preparation methods are prepared, which is characterized in that institute
The polyvinyl alcohol hydrogel stated is porous structure, has high-intensitive 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；With polyvinyl alcohol hydrogel quality for 100
Part meter, wherein the mass fraction of polyvinyl alcohol is 15-20 parts, and the mass fraction of agarose is 2~6 parts, remaining is deionized water；
The pore diameter range of the polyvinyl alcohol hydrogel is 25~150 μm；Strength range is 0.64-19.8MPa.
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| CN110157012A (en) * | 2019-05-28 | 2019-08-23 | 陕西科技大学 | A kind of preparation method of high-intensity and high-tenacity gelatin based aquagel |
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| CN113788960A (en) * | 2021-08-27 | 2021-12-14 | 大连理工大学 | Preparation method of polyvinyl alcohol-acrylamide-agarose hydrogel with high mechanical strength |
| CN114015085A (en) * | 2021-11-26 | 2022-02-08 | 燕山大学 | Preparation method of ion-conductive bioelectrode |
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