CN103834048A - Preparation method for in-situ composite short fiber/hydrogel - Google Patents
Preparation method for in-situ composite short fiber/hydrogel Download PDFInfo
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- CN103834048A CN103834048A CN201310702115.0A CN201310702115A CN103834048A CN 103834048 A CN103834048 A CN 103834048A CN 201310702115 A CN201310702115 A CN 201310702115A CN 103834048 A CN103834048 A CN 103834048A
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Abstract
The invention discloses a preparation method for in-situ composite short fiber/hydrogel. The preparation method comprises the following steps of (1) mixing DMSO and deionized water into a mixed solvent, adding PVA into the mixed solvent, putting the mixture in to a water bath with a constant temperature of 90-95 DEG C, refluxing by condensation until the PVA is completely dissolved, thus obtaining a PVA solution with a mass percentage of 10-15%; (2). dissolving an inorganic salt into the deionized water to prepare a salt solution with mass percentage of 15%-40%, adding the PVA solution obtained by the step (1), stirring uniformly, putting in a vacuum drying oven with a temperature of 95 DEG C, degassing for 10-30 minutes; and (3) pouring the solution to a mold after degassing; putting the mold in a freezing chamber with a temperature ranging from -20DEG C to -40 DEG C, freezing, taking the mold out, unfreezing and melting at a room temperature to obtain the in-situ composite short fiber/hydrogel. The hydrogel prepared by the method has relatively high mechanical strength. The strength can be adjusted conveniently by controlling the short fiber content and a freezing-melting circulation number, so as to adapt different requirements in different application fields.
Description
Technical field
The present invention relates to a kind of preparation method of staple fibre composite aquogel, particularly a kind of staple fibre composite aquogel that utilizes inorganic salt recrystallization to prepare with in-situ compounding process, belongs to technical field of polymer materials.
Background technology
Hydrogel is that a class is high moisture but water insoluble, has the soft wet stock of three-dimensional net structure, is subject to extensive concern because it has good biocompatibility, environmental sensitivity and environmental sound.All demonstrate tempting application prospect in fields such as agricultural, industry, biology and materials.But most of traditional hydrogel intensity is all very poor, becomes and limits the major cause that it further develops.In recent years, because PVA hydrogel has stable chemical property, is easy to moulding, the feature such as snappiness, wear-resisting and good histocompatibility, toxicity be little is in the prospect that is medically commonly employed, if but PVA hydrogel is applied to joint cartilage equivalent material, its intensity is still lower.
Cartilage is made up of chondrocyte, matrix, collegen filament and perichondrium, and cartilage is compared with other hydrogel, conventionally contains collegen filament and makes it have higher intensity.Current also have relevant report people to utilize fiber reinforcement to improve the mechanical property of hydrogel, (the A.Agrawal such as Agrawa, N.Wanasekara, V.Chalivendra, et al. Strong fiber reinforced hydrogels for biomedical applications[C] //Bioengineering Conference (NEBEC), 2011 IEEE 37th Annual Northeast. IEEE, 2011:1-2.) using urethane as fortifying fibre and polyethyleneglycol diglycidylether (PEGDGE) prepared fibre-reinforced composite aquogel, the hydrogel mechanical property obtaining is than obviously not improving with fibre-reinforced hydrogel.But the preparation complexity of polyurethane fiber, and the preparation of fiber and the moulding of hydrogel be proceed step by step, is subject to the impact of environmental factors, wayward.
US Patent No. 5422050 reported a kind of fiber reinforcement hydrogel preparation method.This patent, by being first to configure PVA solution, then will be grown for 1mm, and diameter is that the PVA fiber of 16 μ m adds PVA solution and fully mixes, then this mixing solutions is carried out to freezing melting, obtains fibre-reinforced hydrogel.In the preparation process of PVA hydrogel, also may there is the phenomenons such as deposition and maldistribution in PVA fiber.
Summary of the invention
In view of the mechanical strength of current hydrogel generally lower, the present invention utilizes single stage method to prepare a kind of original position composite short fiber/hydrogel, a kind of preparation method who utilizes inorganic salt recrystallization to prepare staple fibre enhancing hydrogel with in-situ compounding process is provided, and the method has significantly improved the mechanical property of hydrogel.
In order to realize object of the present invention, contriver studies and persistent exploration by lot of experiments, has finally obtained following technical scheme:
A preparation method for original position composite short fiber/hydrogel, this preparation method comprises the steps:
Step 1: DMSO and deionized water are made into mixed solvent, then PVA are added to this mixed solvent, be placed in 90～95 DEG C of water bath with thermostatic control condensing refluxes 2～4 hours, dissolve completely to PVA, be made into massfraction and be 10～15% PVA solution;
Step 2: inorganic salt are dissolved in to deionized water, and to be made into massfraction be 15%～40% salts solution, and add step (1) gained PVA solution, making the mass ratio of inorganic salt and PVA in the mixing solutions of gained is 0.1～1:1, stirs and is placed in 95 DEG C of vacuum drying ovens degassed 10～30 minutes;
Step 3: degassed complete after, solution is poured in mould, insert-20～-40 DEG C of refrigeration chambers after freezing 10～24 hours, the room temperature melting 2～4 hours of thawing after taking out, obtains the original position composite short fiber/hydrogel containing staple fibre.
Preferably, the preparation method of original position composite short fiber/hydrogel as above, wherein in the mixed solvent described in step (1), the massfraction of DMSO is 60%～95%.
Preferably, the preparation method of original position composite short fiber/hydrogel as above, wherein said inorganic salt are selected from and are easy at low temperatures crystallization and the elongated inorganic salt of crystal formation from solution.
Further preferably, the preparation method of original position composite short fiber/hydrogel as above, wherein said inorganic salt are following one or more: Potassium Persulphate, Sodium phosphate dibasic, ammonium acetate.
It should be noted that, in above-mentioned preparation method, use the mixed solvent that solvent is DMSO and deionized water, this is because the solubility parameters of DMSO is close to the solubility parameters of PVA, after DMSO mixes with water, can play solvation to PVA segment, form network structure more closely.
In above-mentioned preparation method, can adjust by changing the cycle number of freezing melting the performance of composite aquogel, when the cycle number of freezing melting increases, interchain tangles to be increased, be that intermolecular hydrogen chain effect meeting is more remarkable, the point that tangles increases, and forms finer and close three-dimensional net structure, thereby affects the performance of hydrogel.
In above-mentioned preparation method, can adjust by changing the consumption of inorganic salt the performance of hydrogel, under certain condition inorganic salt surface can and PVA hydrogel between form interfacial layer, play the effect of enhancing, interfacial layer effect when inorganic salt content changes and between hydrogel also changes, and therefore the performance of hydrogel is exerted an influence.
Above-mentioned preparation method, composite aquogel be prepared as in-situ compositing, original position is compound be material under certain condition, generate one or more wild phases by chemical reaction or physical action in matrix inside, thereby reach the method for enhancement purpose, this method is simple to operate, and resulting materials bonding strength is high, and interface is pollution-free.
The present invention utilizes freezing scorification to make molecular chain be combined closely and be formed the point that tangles and prepare PVA hydrogel by the physical action of Van der Waals force and hydrogen bond etc., and inorganic salt are added wherein with the form of solution, inorganic salt are recrystallization in freezing middle process, and inorganic salt surface can form interfacial layer with hydrogel and plays the effect of enhancing and be dispersed in PVA hydrogel, finally obtain a kind of matrix material of staple fibre/PVA hydrogel, improve PVA hydrogel mechanical property, this method is simple to operate, the Inorganic Salts of required low temperature crystallization is many, range of choice is large, widen its range of application.
In a word, owing to adopting technique scheme, this law is bright relate to utilize inorganic salt recrystallization with the preparation method of the staple fibre/hydrogel of the compound preparation of original position compared with prior art, tool has the following advantages and marked improvement:
(1) this method can be easily regulates the performance of composite short fiber/hydrogel by changing the consumption of inorganic salt and kind, and Modulatory character is high;
(2) preparation process is simple, raw material be easy to get and range of choice large, easy to operate, have no side effect;
(3) composite short fiber/hydrogel tensile strength of making, modulus of compression, tearing energy etc. are all higher than pure PVA hydrogel.
(4) hydrogel that this method obtains has good mechanical property, aspect the tissue repair such as cartilage, blood vessel, skin and twice-laid stuff, is possessing potential using value.
specific implementation method
The preparation method of the original position composite short fiber/hydrogel the present invention relates to, mainly comprises following two large steps:
A) preparation of PVA solution and inorganic salt solution
DMSO and deionized water are made into mixed solvent (massfraction of DMSO is 60%～95%), then PVA is added to mixed solvent, be placed in 90～95 DEG C of water bath with thermostatic control condensing refluxes 2～4 hours, dissolve completely to PVA, be made into massfraction and be 6%～15% PVA solution;
Inorganic salt are dissolved in to deionized water, and to be made into massfraction be 15%～40% salts solution and add above-mentioned PVA solution (mass ratio of inorganic salt and PVA is 0.1～1:1), and solution stirring is evenly placed in 95 DEG C of vacuum drying ovens degassed 10～30 minutes.
B) freezing scorification is prepared staple fibre enhancing hydrogel, makes hydrogel and generated in-situ staple fibre single stage method compound
Above-mentioned solution degassed complete after, solution is poured in mould, insert-20～-40 DEG C of refrigeration chambers after freezing 10～24 hours, take out the room temperature melting 2～4 hours of thawing, obtain the original position composite short fiber/hydrogel containing staple fibre.
Below by a PVA hydrogel comparative example that there is no a composite short fiber and 3 original position composite short fiber/hydrogel specific embodiment, the invention will be further described, but the present invention is not limited to this.
Comparative example
Step 1: 33gDMSO is mixed with 11ml deionized water, then 5gPVA is added to mixed solvent, be placed in 90～95 DEG C of water bath with thermostatic control condensing refluxes 2 hours, dissolve completely to PVA, be then placed in 95 DEG C of vacuum drying ovens degassed 30 minutes;
Step 2: degassed complete after, solution is poured in mould, insert-25 DEG C of refrigeration chambers after freezing 20 hours, take out the room temperature melting 2 hours of thawing, obtain pure PVA hydrogel.
Record: tensile strength is that 0.95MPa, elongation at break are 419.6%, modulus of compression is that 1.882MPa, tearing energy are 7.522J/m
2.
Embodiment 1
Step 1: 33gDMSO and 8.5ml deionized water are made into mixed solvent, then 5gPVA are added to mixed solvent, be placed in 90～95 DEG C of water bath with thermostatic control condensing refluxes 2 hours, dissolve completely to PVA;
Step 2: by 0.5g Na
2hPO
4after mixing with 2.5ml deionized water, add above-mentioned PVA solution, solution stirring is evenly placed on 95 DEG C of vacuum drying ovens interior degassed 30 minutes;
Step 3: degassed complete after, solution is poured in mould, insert-25 DEG C of refrigeration chambers after freezing 20 hours, take out the room temperature melting 2 hours of thawing, obtain containing Na
2hPO
49% Na
2hPO
4/ PVA staple fibre composite aquogel.
Record tensile strength and be 1.37MPa, elongation at break and be 561.27%, modulus of compression is that 5.645MPa, tearing energy are 13.285J/m
2.
Embodiment 2
Step 1: 33gDMSO is mixed with 7ml deionized water, then 5gPVA is added to mixed solvent, be placed in 90～95 DEG C of water bath with thermostatic control condensing refluxes 2 hours, dissolve completely to PVA;
Step 2: by 2.5g Na
2hPO
4after mixing with 4ml deionized water, add above-mentioned PVA solution, solution stirring is evenly placed on 95 DEG C of vacuum drying ovens interior degassed 30 minutes;
Step 3: degassed complete after, solution is poured in mould, insert-25 DEG C of refrigeration chambers after freezing 20 hours, take out the room temperature melting 2 hours of thawing, obtain containing Na
2hPO
433.3% Na
2hPO
4/ PVA staple fibre composite aquogel.
Record tensile strength and be 11.6MPa, elongation at break and be 578.72%, modulus of compression is that 9.526MPa, tearing energy are 16.918J/m
2.
Embodiment 3
Step 1: then 33gDMSO is mixed 5gPVA is added to mixed solvent with 3ml deionized water, be placed in 90～95 DEG C of water bath with thermostatic control condensing refluxes 2 hours, dissolve completely to PVA;
Step 2: by 5g Na
2hPO
4after mixing with 8ml deionized water, add above-mentioned PVA solution, solution stirring is evenly placed on 95 DEG C of vacuum drying ovens interior degassed 30 minutes;
Step 3: degassed complete after, solution is poured in mould, insert-25 DEG C of refrigeration chambers after freezing 20 hours, take out the room temperature melting 2 hours of thawing, obtain containing Na
2hPO
450% Na
2hPO
4/ PVA staple fibre composite aquogel.
Record tensile strength and be 8.9MPa, elongation at break and be 622.65%, modulus of compression is that 11.507MPa, tearing energy are 29.591J/m
2.
The mechanical property of 4 kinds of hydrogels is as following table:
Can find out by the data in form:
Three kinds of different content Na
2hPO
4the tensile strength of/PVA staple fibre composite aquogel is all higher than pure PVA hydrogel.Work as Na
2hPO
4na in/PVA staple fibre composite aquogel
2hPO
4when content increases gradually by 9%, 33.3%, 50%, its tensile strength presents the rear downward trend that first rises.
Three kinds of different content Na
2hPO
4the modulus of compression of/PVA staple fibre composite aquogel is all higher than pure PVA hydrogel.Work as Na
2hPO
4na in/PVA staple fibre composite aquogel
2hPO
4when content increases gradually by 9%, 33.3%, 50%, its modulus of compression is the trend of increase.
Three kinds of different content Na
2hPO
4the tearing energy of/PVA staple fibre composite aquogel is all higher than pure PVA hydrogel.Work as Na
2hPO
4na in/PVA staple fibre composite aquogel
2hPO
4when content increases gradually by 9%, 33.3%, 50%, its tearing energy is the trend of increase.
Claims (4)
1. a preparation method for original position composite short fiber/hydrogel, this preparation method comprises the steps:
Step 1: DMSO and deionized water are made into mixed solvent, then PVA are added to this mixed solvent, be placed in 90～95 DEG C of water bath with thermostatic control condensing refluxes 2～4 hours, dissolve completely to PVA, be made into massfraction and be 10～15% PVA solution;
Step 2: inorganic salt are dissolved in to deionized water, and to be made into massfraction be 15%～40% salts solution, and add step (1) gained PVA solution, making the mass ratio of inorganic salt and PVA in the mixing solutions of gained is 0.1～1:1, stirs and is placed in 95 DEG C of vacuum drying ovens degassed 10～30 minutes;
Step 3: degassed complete after, solution is poured in mould, insert-20～-40 DEG C of refrigeration chambers after freezing 10～24 hours, the room temperature melting 2～4 hours of thawing after taking out, obtains the original position composite short fiber/hydrogel containing staple fibre.
2. the preparation method of original position composite short fiber/hydrogel according to claim 1, is characterized in that: in the mixed solvent described in step (1), the massfraction of DMSO is 60%～95%.
3. the preparation method of original position composite short fiber/hydrogel according to claim 1, is characterized in that: described inorganic salt are selected from and are easy at low temperatures crystallization and the elongated inorganic salt of crystal formation from solution.
4. the preparation method of original position composite short fiber/hydrogel according to claim 3, is characterized in that: described inorganic salt are following one or more: Potassium Persulphate, Sodium phosphate dibasic, ammonium acetate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108295319A (en) * | 2018-03-08 | 2018-07-20 | 山东省药学科学院 | A kind of hydrophilic composite material and preparation method of medical nano fiber reinforcement type and purposes |
| CN108341996A (en) * | 2017-12-29 | 2018-07-31 | 佛山市锦彤企业管理有限公司 | A kind of pressure resistant type macromolecule hydrogel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5422050A (en) * | 1992-12-14 | 1995-06-06 | Mizu Systems Inc. | Reinforced polyvinyl alcohol hydrogels containing uniformly dispersed crystalline fibrils and method for preparing same |
| CN102219915A (en) * | 2011-06-14 | 2011-10-19 | 中国科学院长春应用化学研究所 | Aquogel scalding surgical dressing and preparation method thereof |
-
2013
- 2013-12-19 CN CN201310702115.0A patent/CN103834048B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5422050A (en) * | 1992-12-14 | 1995-06-06 | Mizu Systems Inc. | Reinforced polyvinyl alcohol hydrogels containing uniformly dispersed crystalline fibrils and method for preparing same |
| CN102219915A (en) * | 2011-06-14 | 2011-10-19 | 中国科学院长春应用化学研究所 | Aquogel scalding surgical dressing and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108341996A (en) * | 2017-12-29 | 2018-07-31 | 佛山市锦彤企业管理有限公司 | A kind of pressure resistant type macromolecule hydrogel |
| CN108295319A (en) * | 2018-03-08 | 2018-07-20 | 山东省药学科学院 | A kind of hydrophilic composite material and preparation method of medical nano fiber reinforcement type and purposes |
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