CN103834048B - A kind of preparation method of In-situ reaction staple fibre/hydrogel - Google Patents
A kind of preparation method of In-situ reaction staple fibre/hydrogel Download PDFInfo
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- CN103834048B CN103834048B CN201310702115.0A CN201310702115A CN103834048B CN 103834048 B CN103834048 B CN 103834048B CN 201310702115 A CN201310702115 A CN 201310702115A CN 103834048 B CN103834048 B CN 103834048B
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Abstract
The invention discloses the preparation method of a kind of In-situ reaction staple fibre/hydrogel, comprise the steps: that DMSO and deionized water are made into mixed solvent by (1), then PVA is added this mixed solvent, be placed in 90 ~ 95 DEG C of water bath with thermostatic control condensing refluxes, dissolve completely to PVA, be made into the PVA solution that massfraction is 10 ~ 15%; (2) inorganic salt are dissolved in deionized water and are made into the salts solution that massfraction is 15% ~ 40%, and add step (1) gained PVA solution, stir and to be placed in 95 DEG C of vacuum drying ovens degassed 10 ~ 30 minutes; (3) degassed complete after, poured into by solution in mould, it is freezing to insert-20 ~-40 DEG C of refrigeration chambers, and thaw at RT melting after taking out, obtains In-situ reaction staple fibre/hydrogel.Hydrogel prepared by the inventive method has higher physical strength, and intensity can adjust conveniently by the cycle number controlling short fibre content and freezing melting, to adapt to the needs of different application occasion.
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 utilizing inorganic salt recrystallization to prepare with in-situ compounding process, belongs to technical field of polymer materials.
Background technology
Hydrogel is a class High water cut but water insoluble, has the soft wet stock of three-dimensional net structure, because it has good biocompatibility, environmental sensitivity and environmental sound and be subject to extensive concern.Tempting application prospect is all demonstrated in fields such as agricultural, industry, biology and materials.But the hydrogel intensity that major part is traditional is all very poor, becomes the major cause limiting it and further develop.In recent years, due to PVA hydrogel there is stable chemical property, be easy to shaping, feature is medically the commonly employed prospect such as snappiness, wear-resisting and good histocompatibility, toxicity are little, 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, usually makes it have higher intensity containing collegen filament.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, etal.Strongfiberreinforcedhydrogelsforbiomedicalapplicat ions [C] //BioengineeringConference (NEBEC), 2011IEEE37thAnnualNortheast.IEEE, 2011:1-2.) urethane is prepared fibre-reinforced composite aquogel as fortifying fibre and polyethyleneglycol diglycidylether (PEGDGE), the hydrogel mechanical property obtained is than not significantly improving with fibre-reinforced hydrogel.But the preparation of polyurethane fiber is complicated, and the preparation of fiber and the shaping of hydrogel are proceed step by step, are subject to the impact of environmental factors, wayward.
US Patent No. 5422050 report a kind of fiber reinforcement hydrogel preparation method.Length, by being first configure PVA solution, is then 1mm by this patent, and diameter is that the PVA fiber of 16 μm adds PVA solution and fully mixes, then this mixing solutions is carried out freezing melting, obtains fibre-reinforced hydrogel.Also may there is the phenomenons such as deposition and maldistribution in PVA fiber in the preparation process of PVA hydrogel.
Summary of the invention
Mechanical strength in view of current hydrogel is general lower, the present invention's a kind of In-situ reaction staple fibre/hydrogel that utilized single stage method to prepare, provide a kind of inorganic salt recrystallization that utilizes and prepare the preparation method of short fiber reinforced hydrogel with in-situ compounding process, the method significantly improves the mechanical property of hydrogel.
In order to realize object of the present invention, contriver is studied and persistent exploration by lot of experiments, finally obtains following technical scheme:
A preparation method for In-situ reaction staple fibre/hydrogel, this preparation method comprises the steps:
Step 1: DMSO and deionized water are made into mixed solvent, then adds this mixed solvent by PVA, is placed in 90 ~ 95 DEG C of water bath with thermostatic control condensing refluxes 2 ~ 4 hours, dissolves completely to PVA, is made into the PVA solution that massfraction is 10 ~ 15%;
Step 2: inorganic salt are dissolved in deionized water and are made into the salts solution that massfraction is 15% ~ 40%, and add step (1) gained PVA solution, the mass ratio making inorganic salt and PVA in the mixing solutions of gained is 0.1 ~ 1:1, stirs and to be placed in 95 DEG C of vacuum drying ovens degassed 10 ~ 30 minutes;
Step 3: degassed complete after, solution is poured in mould, inserts-20 ~-40 DEG C of refrigeration chambers after freezing 10 ~ 24 hours, thaw at RT melting 2 ~ 4 hours after taking out, obtain the In-situ reaction staple fibre/hydrogel containing staple fibre.
Preferably, the preparation method of In-situ reaction staple fibre/hydrogel as above, in the mixed solvent wherein described in step (1), the massfraction of DMSO is 60% ~ 95%.
Preferably, the preparation method of In-situ reaction staple fibre/hydrogel as above, wherein said inorganic salt are selected from and are easy to crystallization from solution at low temperatures and the elongated inorganic salt of crystal formation.
Further preferably, the preparation method of In-situ reaction staple fibre/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, solvation can be played to PVA segment, form network structure more closely.
In above-mentioned preparation method, the performance of composite aquogel can be adjusted by the cycle number changing freezing melting, when the cycle number of freezing melting increases, inter-chain entanglement increases, namely intermolecular hydrogen chain effect can be more remarkable, the point that tangles increases, and forms finer and close three-dimensional net structure, thus affects the performance of hydrogel.
In above-mentioned preparation method, the performance of hydrogel can be adjusted by the consumption changing inorganic salt, 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 has an impact to the performance of hydrogel.
Above-mentioned preparation method, composite aquogel be prepared as in-situ compositing, In-situ reaction be material under certain condition, one or more wild phases are generated at intrinsic silicon by chemical reaction or physical action, thus 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 utilize freezing scorification make molecular chain by the physical action of Van der Waals force and hydrogen bond etc. combine closely formed tangle point and prepare PVA hydrogel, and inorganic salt are added wherein as a 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 the matrix material of a kind 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, compared with prior art, tool has the following advantages and marked improvement the preparation method of the bright staple fibre/hydrogel utilizing inorganic salt recrystallization to prepare with In-situ reaction related to of this law:
(1) this method can regulate the performance of composite short fiber/hydrogel easily by the consumption and kind changing inorganic salt, and Modulatory character is high;
(2) preparation process is simple, and raw material is easy to get and range of choice is large, easy to operate, has no side effect;
(3) obtained composite short fiber/hydrogel tensile strength, modulus of compression, tearing energies etc. are all higher than pure PVA hydrogel.
(4) hydrogel that this method obtains has excellent mechanical property, in the tissue repair such as cartilage, blood vessel, skin and twice-laid stuff, possess potential using value.
specific implementation method
The preparation method of the In-situ reaction staple fibre/hydrogel that 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 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 the PVA solution that massfraction is 6% ~ 15%;
Inorganic salt are dissolved in deionized water to be made into massfraction and to be the salts solution of 15% ~ 40% and to add above-mentioned PVA solution (mass ratio of inorganic salt and PVA is 0.1 ~ 1:1), solution stirring to be evenly placed in 95 DEG C of vacuum drying ovens degassed 10 ~ 30 minutes.
B) freezing scorification prepares short fiber reinforced hydrogel, makes hydrogel and generated in-situ staple fibre single stage method compound
Above-mentioned solution degassed complete after, solution is poured in mould, inserts-20 ~-40 DEG C of refrigeration chambers after freezing 10 ~ 24 hours, take out thaw at RT melting 2 ~ 4 hours, obtain the In-situ reaction staple fibre/hydrogel containing staple fibre.
In-situ reaction staple fibre/the invention will be further described for hydrogel specific embodiment for the PVA hydrogel comparative example not having a composite short fiber below by and 3, but the present invention is not limited to this.
Comparative example
Step 1: mixed by 33gDMSO and 11ml deionized water, then 5gPVA is added mixed solvent, be placed in 90 ~ 95 DEG C of water bath with thermostatic control condensing refluxes 2 hours, dissolve completely to PVA, to be then placed in 95 DEG C of vacuum drying ovens degassed 30 minutes;
Step 2: degassed complete after, solution is poured in mould, inserts-25 DEG C of refrigeration chambers after freezing 20 hours, take out thaw at RT melting 2 hours, obtain pure PVA hydrogel.
Record: tensile strength is 0.95MPa, elongation at break is 419.6%, modulus of compression is 1.882MPa, tearing energy is 7.522J/m
2.
Embodiment 1
Step 1: 33gDMSO and 8.5ml deionized water is made into mixed solvent, then 5gPVA is added mixed solvent, is placed in 90 ~ 95 DEG C of water bath with thermostatic control condensing refluxes 2 hours, dissolves completely to PVA;
Step 2: by 0.5gNa
2hPO
4add above-mentioned PVA solution after mixing with 2.5ml deionized water, solution stirring to be evenly placed in 95 DEG C of vacuum drying ovens degassed 30 minutes;
Step 3: degassed complete after, solution is poured in mould, inserts-25 DEG C of refrigeration chambers after freezing 20 hours, take out thaw at RT melting 2 hours, obtain containing Na
2hPO
4the Na of 9%
2hPO
4/ PVA staple fibre composite aquogel.
Record that tensile strength is 1.37MPa, elongation at break is 561.27%, modulus of compression is 5.645MPa, tearing energy is 13.285J/m
2.
Embodiment 2
Step 1: 33gDMSO and 7ml deionized water is mixed, then 5gPVA is added 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 2.5gNa
2hPO
4add above-mentioned PVA solution after mixing with 4ml deionized water, solution stirring to be evenly placed in 95 DEG C of vacuum drying ovens degassed 30 minutes;
Step 3: degassed complete after, solution is poured in mould, inserts-25 DEG C of refrigeration chambers after freezing 20 hours, take out thaw at RT melting 2 hours, obtain containing Na
2hPO
4the Na of 33.3%
2hPO
4/ PVA staple fibre composite aquogel.
Record that tensile strength is 11.6MPa, elongation at break is 578.72%, modulus of compression is 9.526MPa, tearing energy is 16.918J/m
2.
Embodiment 3
Step 1: then 5gPVA is added mixed solvent by the mixing of 33gDMSO and 3ml deionized water, is placed in 90 ~ 95 DEG C of water bath with thermostatic control condensing refluxes 2 hours, dissolves completely to PVA;
Step 2: by 5gNa
2hPO
4add above-mentioned PVA solution after mixing with 8ml deionized water, solution stirring to be evenly placed in 95 DEG C of vacuum drying ovens degassed 30 minutes;
Step 3: degassed complete after, solution is poured in mould, inserts-25 DEG C of refrigeration chambers after freezing 20 hours, take out thaw at RT melting 2 hours, obtain containing Na
2hPO
4the Na of 50%
2hPO
4/ PVA staple fibre composite aquogel.
Record that tensile strength is 8.9MPa, elongation at break is 622.65%, modulus of compression is 11.507MPa, tearing energy is 29.591J/m
2.
The mechanical property of 4 kinds of hydrogels is as following table:
Can be found 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 in the trend increased.
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 in the trend increased.
Claims (2)
1. a preparation method for In-situ reaction staple fibre/hydrogel, this preparation method comprises the steps:
Step 1: DMSO and deionized water are made into mixed solvent, then adds this mixed solvent by PVA, is placed in 90 ~ 95 DEG C of water bath with thermostatic control condensing refluxes 2 ~ 4 hours, dissolves completely to PVA, is made into the PVA solution that massfraction is 10 ~ 15%;
Step 2: inorganic salt are dissolved in deionized water and are made into the salts solution that massfraction is 15% ~ 40%, and add step (1) gained PVA solution, the mass ratio making inorganic salt and PVA in the mixing solutions of gained is 0.1 ~ 1:1, stirs and to be placed in 95 DEG C of vacuum drying ovens degassed 10 ~ 30 minutes;
Step 3: degassed complete after, solution is poured in mould, inserts-20 ~-40 DEG C of refrigeration chambers after freezing 10 ~ 24 hours, thaw at RT melting 2 ~ 4 hours after taking out, obtain the In-situ reaction staple fibre/hydrogel containing staple fibre;
Described inorganic salt are following one or more: Potassium Persulphate, Sodium phosphate dibasic, ammonium acetate.
2. the preparation method of In-situ reaction staple fibre/hydrogel according to claim 1, is characterized in that: in the mixed solvent described in step (1), the massfraction of DMSO is 60% ~ 95%.
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