CN102634042A - PVA (polyvinyl alcohol) composite aquagel with bioactivity and preparation method thereof - Google Patents
PVA (polyvinyl alcohol) composite aquagel with bioactivity and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PVA (polyvinyl alcohol) composite aquagel with bioactivity and a preparation method thereof. The preparation method comprises the following steps: mixing a PVA water solution and a PEO (polyoxyethylene) solution, adding a Ca-ethanol suspension or calcium ethoxide solution, adding anhydrous alcohol containing H3PO4, freezing, and defreezing to obtain the PVA composite aquagel with bioactivity. The invention has the advantages of no biotoxicity of raw materials, low cost, mild reaction conditions, and safe and simple technique, and satisfies the environmental requirements; high number-average molecular weight PEO with favorable biocompatibility and lubricating property is introduced into a nano HA/PVA composite aquagel, so the high number-average molecular weight PEO molecular chain forms polymer brushes on the aquagel surface to lower the friction force of the aquagel surface; and thus, the material can be conveniently applied to joint prosthesis cartilage replacement materials.
Description
Technical field
The present invention relates to the bio-medical composition technical field, relate in particular to polyvinyl alcohol composite hydrogel of a kind of biologically active and preparation method thereof.
Background technology
Z 150PH (PVA) hydrogel is the cancellated water-soluble bloated body of hydrophilic polyethene alcohol macromole through the formation of crosslinked back; PVA hydrogel through certain processes moulding with it with its stable chemical property; Good physical and mechanical properties, be easy to moulding, have no side effect, with the tissue excellent biological compatibility, obtained many application.Especially at biomedical sector, the physical properties of utilizing PVA hydrogel class material more is used for like burn or trauma care, Cosmetics Surgery, slow releasing pharmaceutical carrier, artificial vitreous etc. near character such as biological tissue, the excellent perviousness to water molecules etc., suitable extendability, good snappinesies than all other men worker's synthetic materials.
In recent years; PVA hydrogel artificial cartilage implant material has caused people's attention, and the PVA hydrogel has structure similar with joint cartilage and performance, extrudes during its contained a large amount of moisture content pressurized and plays lubrication; Has lower frictional force; Avoid because the complication that the implant short term failure that causes of wearing and tearing and abrasive dust cause, therefore, the PVA hydrogel becomes ideal artificial articular cartilage equivalent material.But existing P VA hydrogel is from clinical medical certain distance that still has, the one, there is not biological activity, and poor during as cartilage prosthese implantation joint position with the bonding properties of bone substrate, influence fixing and repairing effect of cartilage; The 2nd, the physical strength of PVA hydrogel (like modulus of compression) is lower.For this reason, a lot of scientists attempt with biological active materials (like Win 40350, HA) and the PVA hydrogel compound, both can make the PVA hydrogel have certain biological activity (osteoinductive), can improve the physical strength of hydrogel again greatly.
Application number is that 02134218.0 Chinese invention patent application discloses a kind of biological activity Z 150PH/hydroxyapatite nano composite aquogel and preparation method thereof, and it is with Z 150PH preparing PVA aqueous solution behind refining purifying; With Ca (OH)
2After grinding is sieved, add pure absolute ethyl alcohol, heating and ultra-sonic dispersion obtain ethanol-calcium aaerosol solution; Two solution are mixed, add again and contain H
3PO
4Absolute ethyl alcohol, promptly obtain the high PVA/HA Nanometer composite hydrogel of even structure, mechanical property and biological activity through freezing-melt molding.
Though the introducing of HA can impel osseous tissue to the gel growth inside; Form firm biological bonding and synosteosis, effectively prevent to implant the cartilage material dislocation that is moved, improve the artificial cartilage prosthesis stability; But improved the skin friction force of artificial cartilage simultaneously, caused more wearing and tearing.How to improve PVA hydrogel physical strength, to give its bioactive while, still keeping the excellent low friction behavior of PVA hydrogel, at home and abroad be not well solved as yet at present.
Summary of the invention
For solving the defective that exists in the prior art, the present invention provides a kind of preparation method of polyvinyl alcohol composite hydrogel, and the HMW polyoxyethylene (PEO) that will have good biocompatibility and oilness is introduced in the nanometer HA/PVA composite aquogel.
A kind of preparation method of polyvinyl alcohol composite hydrogel of biologically active comprises the steps:
(1) the PVA aqueous solution is mixed with PEO solution;
(2) in 80～90 ℃ of waters bath with thermostatic control, stir down, the absolute ethyl alcohol suspension-s of Ca or alcohol calcium solution are joined in the mixing solutions that step (1) obtains, stirred 1～10 hour;
(3) press Ca/P than 1.3～2.5: 1 mixed solution and dripping H to step (2) gained
3PO
4Ethanolic soln, after being added dropwise to complete, under 60～100 ℃, reacted 5～20 hours, the HA/PEO/PVA mixing solutions;
Described H
3PO
4Ethanolic soln in, H
3PO
4Mass percent concentration be 5～20%;
Described Ca/P is than being Ca and step (3) H in the step (2)
3PO
4In the mol ratio of P; Ca/P in people's bone is than near 1.67, thus select Ca/P than 1.3～2.5 with as far as possible near the ratio of the Ca/P in people's bone, the increase biocompatibility.
(4) step (3) gained HA/PEO/PVA mixing solutions is poured in the mould,, promptly obtained described polyvinyl alcohol composite hydrogel through 2～6 moulding of freeze-thaw.
In the said step (1), the mass ratio of the PVA aqueous solution and PEO solution is 1: 0.01～0.5, and the consumption of PEO is too much unsuitable, otherwise is prone to reduce the elasticity of composite aquogel.
In the said step (1), the polymerization degree of PVA is 1000～5000 in the PVA aqueous solution, and the degree of hydrolysis of PVA is 85～99%, and the massfraction of PVA is 5%～30%.
Solvent in the said step (1) in the PEO solution is water and terepthaloyl moietie, and the mass ratio of water and terepthaloyl moietie is 1: 0.1～0.3, and the PEO number-average molecular weight is about 1 * 10
5～8 * 10
6, the massfraction of PEO is 0.01～10% in the PEO solution.
The PEO molecular chain of high number-average molecular weight can form the polymer molecule brush in hydrogel surface; Reduce the frictional force of hydrogel surface, but the too high meeting of molecular weight makes PEO be crystal form, and the PEO viscosity in aqueous solution depends primarily on the concentration of solution; Take all factors into consideration, preferred number average molecular weight is about 1 * 10
5～8 * 10
6, massfraction is 0.01～10% PEO.
In the said step (2), the mass ratio of the mixing solutions that the absolute ethyl alcohol suspension-s of Ca or alcohol calcium solution and step (1) obtain is 0.05～0.5: 1.
In the said step (2), the absolute ethyl alcohol suspension-s of Ca is prepared as follows: with Ca (OH)
2Grinding is sieved, join in the absolute ethyl alcohol, ultra-sonic dispersion 20～100min, in 50～80 ℃ of heating 5～30min, massfraction is the absolute ethyl alcohol suspension-s of 1～30% Ca.
In the said step (2), alcohol calcium solution is prepared as follows: under 50～85 ℃, nitrogen protection, metal Ca puts in the absolute ethyl alcohol, stirring reaction 2～10 hours, massfraction is 1～30% alcohol calcium solution.
In the said step (3), H
3PO
4The mass ratio of mixed solution of ethanolic soln and step (2) gained be 0.05～0.5: 1.
The processing condition of freeze-thaw do in the said step (4); Step (3) gained mixing solutions is poured in the mould; Under-20～-60 ℃ temperature freezing 8～24 hours then; Fusion at room temperature 5～24 hours, freezing under-20～-60 ℃ temperature then, freeze-thaw is 2～6 times so repeatedly.
The tensile modulus of said composite aquogel increases with the number of times of freeze-thaw.When the number of times of freeze-thaw increases; Formation interchain and the intrachain hydrogen bond cohesion ability of tangling strengthens in the plural gel, and the stability of intergranule also obviously improves, and the network structure of gel is tightr; This just makes the network gap in the unit volume reduce; Simultaneously void structure reduces, thereby the tensile strength that causes gel increases with the number of times of freeze-thaw, so preferred freeze-thaw 2～6 times among the present invention.
The present invention also provides the polyvinyl alcohol composite hydrogel of the biologically active that obtains through method for preparing.
The present invention adopts the equal lifeless matter toxicity of raw material; Cost is low, reaction conditions gentleness, process safety, simple, compliance with environmental protection requirements; The high number-average molecular weight polyoxyethylene (PEO) that will have good biocompatibility and oilness is introduced in the nanometer HA/PVA composite aquogel; High number-average molecular weight PEO molecular chain forms the polymer molecule brush in hydrogel surface, reduces the frictional force of hydrogel surface, helps material and is applied in the artificial articular cartilage replacing material.
Embodiment
Embodiment 1
(1) be 1750 with the 10g polymerization degree, degree of hydrolysis is that 95% PVA is dissolved in the 60g deionized water under 90 ℃.With the 0.15g number-average molecular weight is 2 * 10
6PEO add in the 2ml ethanol, add the 30g deionized water then preliminary the dispersion, stir dissolving down in 60 ℃.The PVA aqueous solution is mixed with PEO solution, fully stirred 10 hours, be mixed into transparent uniform solution until both.
(2) with Ca (OH)
2Grinding is sieved, and gets 1g, adds in the 10ml absolute ethyl alcohol, and ultra-sonic dispersion 30 minutes heats 5min under 70 ℃, make the absolute ethyl alcohol suspension-s of Ca.
(3) in 80 ℃ of waters bath with thermostatic control, under vigorous stirring, the suspension-s of (2) is added in the mixing solutions of (1), fully stir 4 hours to being uniformly dispersed.
(4) be 1.6 to get refining H by the Ca/P ratio
3PO
4, be mixed with concentration and be 10% H
3PO
4Ethanolic soln slowly drops in the mixed solution of (3), vigorous stirring, 90 ℃ of following reactions 12 hours, gets finely dispersed HA/PEO/PVA mixing solutions.
(5) mixing solutions is poured in the mould while hot, put into temperature and be-20 ℃ refrigerator-freezer, take out after 10 hours, room temperature was placed after 24 hours, put into temperature again and was-20 ℃ refrigerator-freezer 10 hours, and room temperature was placed 24 hours, promptly got polyvinyl alcohol composite hydrogel.
The tensile modulus 2.0MPa of composite aquogel, modulus of compression are 1.4MPa, and scanning electron microscopic observation HA is uniformly dispersed in matrix, and particle diameter is about between 100～400nm.When load was 14kPa, the frictional coefficient of composite aquogel was 0.65.As a comparison, the frictional coefficient that does not add the HA/PVA binary hydrogel of PEO is 0.8.
Embodiment 2
(1) be 6000 with the 6g polymerization degree, degree of hydrolysis is that 88% PVA is dissolved in the 64g deionized water under 90 ℃.With the 0.1g number-average molecular weight is 2 * 10
6PEO add in the 2ml ethanol, add the 30g deionized water then preliminary the dispersion, stir down in 60 ℃, fully dissolving.PVA solution is mixed with PEO solution, fully stirred 10 hours, be mixed into transparent uniform solution until both.
(2) with Ca (OH)
2Grinding is sieved, and gets 2g, adds the 10ml absolute ethyl alcohol, ultra-sonic dispersion 30 minutes, and heating 5min makes the Ca-alcohol suspension under 70 ℃.
(3) in 80 ℃ of waters bath with thermostatic control, under vigorous stirring, the suspension-s of (2) is added in the mixing solutions of (1), fully stir 4 hours to being uniformly dispersed.
(4) be 1.6 to get refining H by the Ca/P ratio
3PO
4, be mixed with concentration and be 15% H
3PO
4Ethanolic soln slowly drops in the mixed solution of (3), vigorous stirring, 90 ℃ of following reactions 12 hours, gets finely dispersed HA/PEO/PVA mixing solutions.
(5) mixing solutions is poured in the mould while hot, put into temperature and be-40 ℃ refrigerator-freezer, take out after 10 hours, room temperature was placed after 24 hours, put into temperature again and was-40 ℃ refrigerator-freezer 10 hours, and room temperature was placed 24 hours, promptly got polyvinyl alcohol composite hydrogel.
The tensile modulus 1.8MPa of composite aquogel, modulus of compression is 1.6MPa, when loading to 14kPa, the frictional coefficient of composite aquogel is 0.69.
Embodiment 3
(1) be 1750 with the 10g polymerization degree, degree of hydrolysis is that 95% PVA is dissolved in the 64g deionized water under 90 ℃.With the 0.15g number-average molecular weight is 8 * 10
5PEO add in the 2ml ethanol, add the 30g deionized water then preliminary the dispersion, stir down in 60 ℃, fully dissolving.PVA solution is mixed with PEO solution, fully stirred 10 hours, be mixed into transparent uniform solution until both.
(2) with Ca (OH)
2Grinding is sieved, and gets 0.5g, adds the 10ml absolute ethyl alcohol, ultra-sonic dispersion 30 minutes, and heating 5min makes the Ca-alcohol suspension under 70 ℃.
(3) in 80 ℃ of waters bath with thermostatic control, under vigorous stirring, the suspension-s of (2) is added in the mixing solutions of (1), fully stir 4 hours to being uniformly dispersed.
(4) be 1.5 to get refining H by the Ca/P ratio
3PO
4, be mixed with concentration and be 10% H
3PO
4Ethanolic soln slowly drops in the mixed solution of (3), vigorous stirring, 90 ℃ of following reactions 8 hours, gets finely dispersed HA/PEO/PVA mixing solutions.
(5) mixing solutions is poured in the mould while hot, put into temperature and be-20 ℃ refrigerator-freezer, take out after 10 hours, room temperature was placed after 24 hours, put into temperature again and was-20 ℃ refrigerator-freezer 10 hours, and room temperature was placed 24 hours, promptly got polyvinyl alcohol composite hydrogel.
The tensile modulus 1.6MPa of composite aquogel, modulus of compression is 1.1MPa, when loading to 14kPa, the frictional coefficient of composite aquogel is 0.63.
Embodiment 4
(1) be 2000 with the 10g polymerization degree, degree of hydrolysis is that 99% PVA is dissolved in the 60g deionized water under 95 ℃.With the 0.2g number-average molecular weight is 4 * 10
6PEO add in the 3ml ethanol, add the 30g deionized water then preliminary the dispersion, stir down in 60 ℃, fully dissolving.PVA solution is mixed with PEO solution, fully stirred 15 hours, be mixed into transparent uniform solution until both.
Under (2) 80 ℃ of nitrogen protections, the 1g calcium metal is put in the 10ml absolute ethyl alcohol, stirred 4 hours, get mass percent and be about 8% alcohol calcium solution.
(3) in 90 ℃ of waters bath with thermostatic control, under vigorous stirring, the solution that (2) are obtained is added in the mixing solutions of (1), fully stirs 6 hours to being uniformly dispersed.
(4) be 1.7 to get refining H by the Ca/P ratio
3PO
4, be mixed with concentration and be 10% H
3PO
4Ethanolic soln slowly drops in the mixed solution of (3), vigorous stirring and 90 ℃ of following reactions 10 hours, obtains finely dispersed HA/PEO/PVA mixing solutions.
(5) mixing solutions is poured in the mould while hot, put into temperature and be-30 ℃ refrigerator-freezer, take out after 10 hours, room temperature was placed after 24 hours, 4 times repeatedly, promptly got polyvinyl alcohol composite hydrogel.
The tensile modulus 2.8MPa of composite aquogel, modulus of compression are 2.13MPa, and scanning electron microscopic observation HA is uniformly dispersed in matrix, and particle diameter is about below the 100nm.When load was 14kPa, the frictional coefficient of composite aquogel was 0.61.
Embodiment 5
(1) be 1750 with the 6g polymerization degree, degree of hydrolysis is that 95% PVA is dissolved in the 60g deionized water under 95 ℃.With the 0.4g number-average molecular weight is 2 * 10
5PEO add in the 3ml ethanol, add the 20g deionized water then preliminary the dispersion, stir down in 50 ℃, fully dissolving.PVA solution is mixed with PEO solution, fully stirred 7 hours, be mixed into transparent uniform solution until both.
Under (2) 80 ℃ of nitrogen protections, the 2.5g calcium metal is put in the 10ml absolute ethyl alcohol, stirred 4 hours, get mass percent and be about 20% alcohol calcium solution.
(3) in 90 ℃ of waters bath with thermostatic control, under the vigorous stirring, the solution that (2) are obtained is added in the mixing solutions of (1), fully stirs 4 hours to being uniformly dispersed.
(4) be 2.0 to get refining H by the Ca/P ratio
3PO
4, be mixed with concentration and be 15% H
3PO
4Ethanolic soln slowly drops in the mixed solution of (3), vigorous stirring and 90 ℃ of following reactions 15 hours, obtains finely dispersed HA/PEO/PVA mixing solutions.
(5) mixing solutions is poured in the mould while hot, put into temperature and be-30 ℃ refrigerator-freezer, take out after 10 hours, room temperature was placed after 10 hours, 4 times repeatedly, promptly got polyvinyl alcohol composite hydrogel.
The tensile modulus 2.1MPa of composite aquogel, modulus of compression are 1.8MPa, and scanning electron microscopic observation HA is uniformly dispersed in matrix, and particle diameter is about below the 100nm.When load was 14kPa, the frictional coefficient of composite aquogel was 0.71.
Embodiment 6
(1) be 1750 with the 10g polymerization degree, degree of hydrolysis is that 95% PVA is dissolved in the 60g deionized water under 90 ℃.With the 0.2g number-average molecular weight is 2 * 10
6PEO add in the 3ml ethanol, add the 30g deionized water then preliminary the dispersion, stir down in 60 ℃, fully dissolving.PVA solution is mixed with PEO solution, fully stirred 10 hours, be mixed into transparent uniform solution until both.
Under (2) 80 ℃ of nitrogen protections, the 0.5g calcium metal is put in the 10ml absolute ethyl alcohol, stirred 4 hours, get mass percent and be about 4% alcohol calcium solution.
(3) in 80 ℃ of waters bath with thermostatic control, under vigorous stirring, the solution that (2) are obtained is added in the mixing solutions of (1), fully stirs 4 hours to being uniformly dispersed.
(4) be 1.5 to get refining H by the Ca/P ratio
3PO
4, be mixed with concentration and be 10% H
3PO
4Ethanolic soln slowly drops in the mixed solution of (3), vigorous stirring, 90 ℃ of following reactions 8 hours, gets finely dispersed HA/PEO/PVA mixing solutions.
(5) mixing solutions is poured in the mould while hot, put into temperature and be-45 ℃ refrigerator-freezer, take out after 10 hours, room temperature was placed after 15 hours, 5 times repeatedly, promptly got polyvinyl alcohol composite hydrogel.
The tensile modulus 1.8MPa of composite aquogel, modulus of compression is 1.06MPa, when loading to 14kPa, the frictional coefficient of composite aquogel is 0.59.
Claims (8)
1. the preparation method of the polyvinyl alcohol composite hydrogel of a biologically active is characterized in that, comprises the steps:
(1) the PVA aqueous solution is mixed with PEO solution;
(2) in 80～90 ℃ of waters bath with thermostatic control, stir down, the absolute ethyl alcohol suspension-s of Ca or alcohol calcium solution are joined in the mixing solutions that step (1) obtains, stirred 1～10 hour;
(3) press Ca/P than 1.3～2.5: 1 mixed solution and dripping H to step (2) gained
3PO
4Ethanolic soln, after being added dropwise to complete, under 60～100 ℃, reacted 5～20 hours, the HA/PEO/PVA mixing solutions;
(4) step (3) gained HA/PEO/PVA mixing solutions is poured in the mould,, promptly obtained described polyvinyl alcohol composite hydrogel through 2～6 moulding of freeze-thaw.
2. the preparation method of the polyvinyl alcohol composite hydrogel of biologically active as claimed in claim 1 is characterized in that, in the said step (1), the mass ratio of the PVA aqueous solution and PEO solution is 1: 0.01～0.5.
3. the preparation method of the polyvinyl alcohol composite hydrogel of biologically active as claimed in claim 1; It is characterized in that in the said step (1), the polymerization degree of PVA is 1000～5000 in the PVA aqueous solution; The degree of hydrolysis of PVA is 85～99%, and the massfraction of PVA is 5%～30%.
4. the preparation method of the polyvinyl alcohol composite hydrogel of biologically active as claimed in claim 1; It is characterized in that; Solvent in the step (1) in the PEO solution is water and terepthaloyl moietie, and the mass ratio of water and terepthaloyl moietie is 1: 0.1～0.3, and the number-average molecular weight of PEO is 1 * 10
5～8 * 10
6, the massfraction of PEO is 0.01～10% in the PEO solution.
5. the preparation method of the polyvinyl alcohol composite hydrogel of biologically active as claimed in claim 1; It is characterized in that; In the said step (2), the mass ratio of the mixing solutions that the absolute ethyl alcohol suspension-s of Ca or alcohol calcium solution and step (1) obtain is 0.05～0.5: 1.
6. the preparation method of the polyvinyl alcohol composite hydrogel of biologically active as claimed in claim 1 is characterized in that, in the step (3), and H
3PO
4The mass ratio of mixed solution of ethanolic soln and step (2) gained be 0.05～0.5: 1.
7. the preparation method of the polyvinyl alcohol composite hydrogel of biologically active as claimed in claim 1; It is characterized in that; The processing condition of freeze-thaw are in the said step (4): step (3) gained mixing solutions is poured in the mould, and under-20～-60 ℃ temperature freezing 8～24 hours then, fusion at room temperature 5～24 hours; Freezing under-20～-60 ℃ temperature then, freeze-thaw is 2～6 times so repeatedly.
8. the polyvinyl alcohol composite hydrogel of the biologically active for preparing like each described preparation method of claim 1～7.
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| CN107189295A (en) * | 2017-06-29 | 2017-09-22 | 倪群 | A kind of preparation method of hydrophobically modified hydroxyapatite polyvinyl alcohol composite material |
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