CN1586706A - Method for preparing quick temperature response semi-interpenetration network hydrogel - Google Patents
Method for preparing quick temperature response semi-interpenetration network hydrogel Download PDFInfo
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Abstract
The preparation process of semi-interpenetration network hydrogel with quick temperature response includes the following steps: dissolving the monomer and cross-linking agent in deionized water; adding polyeleectrolyte, electrolyte and initiator through stirring under inertial atmosphere for 5-10 min, reaction at 0-30 deg.c for 2-48 hr, and collecting semi-interpenetration network hydrogel with quick temperature response. The hydrogel has not only quick temperature response, but also great gel strength, and its response speed may be regulated via altering the consumption and molecular weight of the polyeleectrolyte and salt concentration in the reaction liquid. The hydrogel has 90 sec dehydration rate over 95 % at the temperature over its phase conversion point, can reach dehydration balance in 2 min, and has good pH response and thus expanded application range, especially in biological and medicine fields.
Description
Technical field
The present invention relates to a kind of preparation method of fast temperature response semi-interpenetrating network aqueous gel.
Background of invention
Intelligent aqueous gel capable is a most noticeable current hydrogel.Poly-N-isopropyl acrylamide (being called for short PNIPAAm) hydrogel is typical case's representative of this gellike.There is near volume phase transition temperature (VPTT is 32 ℃) in the PNIPAAm hydrogel, when environment temperature is lower than VPTT, and PNIPAAm hydrogel water absorption and swelling; When environment temperature was higher than VPTT, the PNIPAAm hydrogel acutely shrank and dehydration.Based on this thermally sensitive character of PNIPAAm hydrogel, fields such as it has been applied to, and controlled delivery of pharmaceutical agents discharges, the immobilization of enzyme and circulation absorbent.
But traditional PNIPAAm hydrogel speed of response is slower, has limited its application in some aspects greatly, as fields such as chemical sensor, artificial-muscle and chemical valves.Around the speed of response that improves the PNIPAAm hydrogel, the method that adopts mainly contains following several at present:
(1) by method of emulsion polymerization preparation micron or nano level PNIPAAm hydrogel microsphere.Because square being directly proportional of the linear size of response time of hydrogel and hydrogel, the size of dwindling hydrogel will significantly improve the speed of response of hydrogel.But require the hydrogel of large scale (more than the Centimeter Level) in the reality mostly, so the range of application of this method is comparatively limited.
(2) adopt synthetic macropore of pore former and super hole PNIPAAm hydrogel.For example Wang Xiao worker waits (CN1328063A, CN 1328067A) to add different-grain diameter CaCO in polymerisation
3Particle treats that gel forms after the salt acid rinse is removed CaCO
3Particle obtains the PNIPAAm hydrogel of loose structure; It carries out polymerisation in supercritical carbon dioxide in addition, and pressure makes carbon dioxide effusion in the gel in the reduction reactor after reaction finishes, and forms pore passage structure and help the hydrone turnover in gel network, thereby improved the respective rate of hydrogel.Though this method is simple, to equipment require too high.(Journal of Polymer Science such as Wu, Part A:PolymerChemistry, 1992,30:2121-2129) prepare macropore PNIPAAm hydrogel as pore former with hydroxypropyl cellulose, but polymerization must be carried out more than the hydroxypropyl cellulose phase transition temperature, the PNIPAAm hydrogel outward appearance of preparation is opaque, and intensity is relatively poor.
(3) prepare comb-type structure PNIPAAm hydrogel by monolithic design.(Nature such as Yoshida R for example, 1995,374:240-242) synthesized comb type grafting PNIPAAm hydrogel, owing in the PNIPAAm hydrogel network, there is free-moving PNIPAAm side chain, the hydrophobic effect of grafted chain produces a plurality of hydrophobic core when temperature raises, greatly strengthened the cross linked chain gathering, thereby the speed of response of gel is improved greatly.(Macromolecules such as KanekoY, 1998,31:6099-61050) hydrophilic PEO (PEO) is grafted on the PNIPAAm, when temperature raises, because the formation that adds compact surfaces layer in the affiliation destruction PNIPAAm hydrogel contraction process of hydrophily grafted chain PEO, make hydrone pass in and out gel easily, thereby improved the respective rate of gel.But this method more complicated, difficult in practice the application.
(4) utilize phase detachment technique to prepare non-homogeneous structure porous PNIPAAm hydrogel.(Langmuir such as Zhang for example, 2002,18:2538-2542) with the mixed solution of water and oxolane as reaction medium, the solubility property difference in mixed solution according to monomer N-N-isopropylacrylamide (NIPAAm) and poly-N-isopropyl acrylamide (PNIPAAm), in polymerisation is carried out, the poly-N-isopropyl acrylamide polymer that generates is not dissolved by reaction medium and separates out and be fixed in the whole gel network, make whole gel network crosslinked inhomogeneous, thereby cause and have more pore space structure in the gel network, the result has improved the respective rate of gel, but the difficult control of this non-homogeneous structure is difficult for using in practice.
By analyzing as can be seen, the existing advantage of above several method has limitation again, and requires gel not only to prepare simple possible, also require gel to have good comprehensive performances simultaneously in actual applications.
Summary of the invention
The technical issues that need to address of the present invention are the preparation methods that disclose a kind of fast temperature response semi-interpenetrating network aqueous gel, to overcome the above-mentioned defective that prior art exists.
The preparation method of fast temperature response hydrogel of the present invention may further comprise the steps:
(1) monomer and crosslinking agent are dissolved in the deionized water, the mass percent concentration of monomer is 7-20%, and the mass percent concentration of crosslinking agent is the 0.1-5% of monomer;
Said monomer is the N-N-isopropylacrylamide;
Said crosslinking agent is selected from N, N '-methylene-bisacrylamide or two acrylic acid glycol ester;
(2) add polyelectrolyte in above-mentioned solution, the mass percent concentration of polyelectrolyte is 0.1-20%;
Said polyelectrolyte is selected from sodium alginate, sanlose or polyacrylic acid, and molecular weight is 1.0 * 10
3-4.0 * 10
5
(3) add electrolyte in above-mentioned solution, electrolytical molar concentration is 0.01-5M, stirs 5-40 minute in inert atmosphere;
Said electrolyte is selected from sodium salt (NaCl, NaNO
3, Na
2SO
4) or sylvite (KCl, KNO
3, K
2SO
4);
(4) add initator, its mass percent is the 0.5-3% of monomer, and the addition of catalyst is the 0.2-6% of monomer mass, stirs 5-10 minute in inert atmosphere;
Said initator is selected from ammonium persulfate or potassium peroxydisulfate, and catalyst is selected from N, N, N ', N '-tetramethylethylenediamine or sodium hydrogensulfite;
(5) then above-mentioned solution was reacted 2-48 hour under 0-30 ℃ temperature, from product, collect fast temperature response semi-interpenetrating network aqueous gel of the present invention then.
In the present invention, with polyelectrolyte and N-N-isopropylacrylamide (NIPAAm) is raw material, with polyelectrolyte in salting liquid the strand conformation be changed to the basis, adopt the method for ipn technology in-situ polymerization, original position drilling in salting liquid to prepare the PNIPAAm hydrogel, its gel has not only fast that temperature-responsive also has gel strength preferably, and the concentration of salt is regulated in the consumption that its speed of response can be by polyelectrolyte, the size of molecular weight and the reactant liquor.
Adopt document (Zhang J T et al.Colloid Polym Sci, 2003,281:582～589) disclosed method (size of the gel speed of response characterizes with the retention rate and the time relation of water in the gel) detects, the PNIPAAm hydrogel of the present invention preparation its more than phase transition temperature, in 90 seconds percentage of water loss can reach about 95%, just reached dehydration balance in 2 minutes, and traditional water gel percentage of water loss in 2 hours only is about 5%, 24 hours even longer time just can reach dehydration balance.Gel with this method preparation also has pH response preferably simultaneously, thereby has widened the range of application of gel, especially at biology and field of medicaments.In a word this method simple, be convenient to operation, be easy to controlled, good with the gel combination property that this method is synthesized.
The specific embodiment
Embodiment 1
With 9.2mmol (1.04g) monomer NIPAAm, 0.25mmol (0.039g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding the 0.26g molecular weight is 1.5 * 10
4Sodium alginate, 0.15g NaCl, stir and logical nitrogen 20 minutes.Add the 0.039g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 40 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Adopt document (Zhang J T et al.Colloid Polym Sci, 2003,281:582～589) disclosed method (size of the gel speed of response characterizes with the retention rate and the time relation of water in the gel) detects, the PNIPAAm hydrogel that is obtained its more than phase transition temperature, in 90 seconds percentage of water loss be just to reach dehydration balance in 95%, 2 minute.
Embodiment 2
With 11.5mmol (1.3g) monomer NIPAAm, 0.169mmol (0.026g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 2.9 * 10
5Sodium alginate 0.52g, NaCl 0.61g after stir and logical nitrogen 15 minutes.Add the 0.026g ammonium persulfate, stir, led to nitrogen 6 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 30 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24 h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Adopt document (Zhang J T et al.Colloid Polym Sci, 2003,281:582～589) disclosed method (size of the gel speed of response characterizes with the retention rate and the time relation of water in the gel) detects, the PNIPAAm hydrogel that is obtained its more than phase transition temperature, in 90 seconds percentage of water loss be just to reach dehydration balance in 96%, 2 minute.
Embodiment 3
17.25mmol (1.95g) monomer NIPAAm, the two acrylic acid glycol esters of 0.38mmol (0.0585g) crosslinking agent are dissolved in the 13ml deionized water, and adding molecular weight is 2.0 * 10
5Sanlose 0.16g, KCl 0.30g after stir and logical nitrogen 30 minutes.Add the 0.029g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 60 μ L mix the back and continued logical nitrogen 8 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Adopt document (Zhang J T et al.Colloid Polym Sci, 2003,281:582～589) disclosed method (size of the gel speed of response characterizes with the retention rate and the time relation of water in the gel) detects, the PNIPAAm hydrogel that is obtained its more than phase transition temperature, in 90 seconds percentage of water loss be just to reach dehydration balance in 96.1%, 2 minute.
Embodiment 4
With 13.8mmol (1.56g) monomer NIPAAm, 0.25mmol (0.039g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 1.5 * 10
4Sodium alginate 0.30g, Na
2SO
40.07g back stirring and logical nitrogen 20 minutes.Add the 0.039g ammonium persulfate, stir, led to nitrogen 10 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 80 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Adopt document (Zhang J T et al.Colloid Polym Sci, 2003,281:582～589) disclosed method (size of the gel speed of response characterizes with the retention rate and the time relation of water in the gel) detects, the PNIPAAm hydrogel that is obtained its more than phase transition temperature, in 90 seconds percentage of water loss be just to reach dehydration balance in 95.5%, 2 minute.
Embodiment 5
With 10.4mmol (1.17g) monomer NIPAAm, 0.114mmol (0.0176g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 2.9 * 10
5Sodium alginate 0.52g, NaCl 0.45g after stir and logical nitrogen 20 minutes.Add the 0.039g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 20 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Embodiment 6
With 9.2mmol (1.04g) monomer NIPAAm, 0.25mmol (0.039g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 0.6 * 10
4Sodium alginate 0.72g, 0.30g NaNO
3Back stirring and logical nitrogen 20 minutes.Add the 0.0208g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst sodium hydrogensulfite 0.0208g again and mixed the logical nitrogen of back continuation 8 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places 25 ℃ of water-baths reaction 48h, test tube is placed 45 ℃ of water-baths, shrink the back fully up to gel and take out, soaked 6 days with deionized water, refresh the water periodically to remove electrolyte in unreacted monomer and the reaction system, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate.
Embodiment 7
With 12.65mmol (1.43g) monomer NIPAAm, 0.23mmol (0.058g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 2 * 10
5Polyacrylic acid 0.26g, 0.54g.KNO
3Back stirring and logical nitrogen 20 minutes.Add the 0.039g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 80 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Embodiment 8
With 9.2mmol (1.04g) monomer NIPAAm, 0.25mmol (0.039g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 2.9 * 10
5Sodium alginate 0.78g, KCl 0.15g after stir and logical nitrogen 20 minutes.Add the 0.039g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 40 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Embodiment 9
With 11.5mmol (1.3g) monomer NIPAAm, 0.169mmol (0.026g) _ N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 8 * 10
4Sodium alginate 0.19g, K
2SO
40.45g back stirring and logical nitrogen 20 minutes.Add the 0.039g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 40 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Embodiment 10
With 9.2mmol (1.04g) monomer NIPAAm, 0.25mmol (0.039g) N, N '-methylene-bisacrylamide is dissolved in the 13ml deionized water, and adding molecular weight is 2.9 * 10
5Sodium alginate 0.52g, NaCL 0.45g after stir and logical nitrogen 20 minutes.Add the 0.039g ammonium persulfate, stir, led to nitrogen 5 minutes, add catalyst n again, N, N ', N '-tetramethylethylenediamine 40 μ L mix the back and continued logical nitrogen 5 minutes, pour into rapidly then in the test tube that diameter is 10cm, after sealing places ice-water bath reaction 24h, test tube is placed 45 ℃ of water-baths, shrinking the back fully up to gel takes out, soaked 6 days with deionized water, refresh the water periodically, promptly obtain the fast PNIPAAm hydrogel of good springiness contraction rate to remove electrolyte in unreacted monomer and the reaction system.
Claims (7)
1. the preparation method of a fast temperature response semi-interpenetrating network aqueous gel is characterized in that, may further comprise the steps:
(1) monomer and crosslinking agent are dissolved in the deionized water, the mass percent concentration of monomer is 7-20%, and the mass percent concentration of crosslinking agent is the 0.1-5% of monomer;
Said monomer is the N-N-isopropylacrylamide;
(2) add polyelectrolyte in above-mentioned solution, the mass percent concentration of polyelectrolyte is 0.1-20%;
(3) add electrolyte in above-mentioned solution, electrolytical molar concentration is 0.01-5M, stirs 5-40 minute in inert atmosphere;
(4) add initator, its mass percent is the 0.5-3% of monomer, and the addition of catalyst is the 0.2-6% of monomer mass, stirs 5-10 minute in inert atmosphere;
(5) then above-mentioned solution was reacted 2-48 hour under 0-30 ℃ temperature, from product, collect fast temperature response semi-interpenetrating network aqueous gel of the present invention then.
2. method according to claim 1 is characterized in that said crosslinking agent is selected from N, N '-methylene-bisacrylamide or two acrylic acid glycol ester.
3. method according to claim 1 is characterized in that said polyelectrolyte is selected from sodium alginate, sanlose or polyacrylic acid.
4. method according to claim 1 is characterized in that said electrolyte is selected from NaCl, NaNO
3, Na
2SO
4, KCl, KNO
3Or K
2SO
4In a kind of.
5. method according to claim 1 is characterized in that said initator is selected from ammonium persulfate or potassium peroxydisulfate.
6. method according to claim 1 is characterized in that catalyst is selected from N, N, N ', N '-tetramethylethylenediamine or sodium hydrogensulfite.
7. method according to claim 3 is characterized in that, the polyelectrolyte molecules amount is 1.0 * 10
3-4.0 * 10
5
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