CN107603106B - Preparation method of acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel - Google Patents
Preparation method of acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel Download PDFInfo
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Abstract
The invention relates to a preparation method of acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel. The preparation method comprises the following steps: 1) dissolving acrylamide, acrylic acid, calcium chloride and polyvinyl alcohol in water according to the proportion and mixing: 2) adding a cross-linking agent and an initiator in sequence, performing argon oxygen-removing treatment, and adding a catalyst: 3) and (3) carrying out vacuum pumping and ultrasonic treatment on the obtained mixture solution, and then carrying out heating reaction to obtain the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel with a certain shape. The obtained hydrogel was frozen at-20 ℃ for 12h, then thawed at room temperature for 8h, and repeated freezing-thawing was carried out three times. The acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel prepared by the invention has higher tensile strength and compressive strength, and the water absorption expansion rate can be controlled by controlling the dosage of polyvinyl alcohol and calcium chloride. Has potential application in biomedicine, such as non-bearing artificial cartilage.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel.
Background
The hydrogel is a high polymer material with a three-dimensional network structure, can absorb water to expand but is insoluble in water, has good biocompatibility, and is widely applied to the fields of medicine, medical treatment, health care, tissue engineering and the like. The traditional organic crosslinking hydrogel obtained by single chemical crosslinking has low tensile strength and compressive strength, and the elongation at break of the hydrogel becomes lower with the increase of the dosage of the chemical crosslinking agent, so that the hydrogel becomes fragile under stress and compression. The mechanical strength of the hydrogel is poor, which limits its application.
In recent years, several methods for synthesizing high-strength hydrogel have appeared, such as topological hydrogel, hydrogel with double-network structure, graphene-doped nano-composite hydrogel, inorganic nano-material-doped composite hydrogel, and double-crosslinked hydrogel.
In recent years, chemical crosslinking and physical crosslinking doped hydrogel is in wide interest, because physical crosslinking is rapid, reversible and recoverable, and the hydrogel prepared through the coordination of physical crosslinking and chemical crosslinking doping has good mechanical properties.
The CN1005504166A patent discloses a polymer hydrogel containing sodium alginate-acrylamide, which is formed by graft copolymerization of amide groups of polyacrylamide and sodium alginate, and cross-linking and coordination of sodium alginate and multivalent ions to form a double-network hydrogel. The patent focuses on the fact that sodium alginate is used for adsorbing heavy metal ions, a tensile property test is not carried out, the compression test is carried out under the condition of dry balance weight, the compression test is not carried out under the condition of water content, and the compression property of hydrogel cannot be objectively shown. CN101111542A discloses a method of making covalently cross-linked vinyl polymer hydrogels. The freezing/unfreezing cycle of the PVA polymer in the freezing-unfreezing circulating solution leads to the formation of physical crosslinking, so that hydrogel with a three-dimensional network structure is formed, and pure PVA hydrogel does not have good tensile elongation and only has physical crosslinking, so that the PVA hydrogel does not have good toughness.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel doped with physical crosslinking and chemical crosslinking.
The present invention is realized in the following manner.
A preparation method of acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel is characterized by comprising the following steps:
1) dissolving acrylamide, acrylic acid, calcium chloride and polyvinyl alcohol in water according to a certain mass ratio to obtain a uniform mixed solution I;
2) adding a cross-linking agent and an initiator into the mixed solution I in sequence, and adding an accelerant after argon is used for removing oxygen to obtain a mixed solution II, wherein the mass ratio of the cross-linking agent to the initiator to the accelerant to the acrylamide is (0.0015-0.05): (0.025-0.01):0.0125: 1;
3) carrying out vacuumizing defoaming treatment and low-temperature ultrasonic treatment, sealing the obtained mixed solution II into a glass mold, heating in a water bath to 40-70 ℃, and carrying out heat preservation reaction for 1-8h to obtain the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel with a certain shape;
4) freezing the gel prepared in the step 3) at-20 ℃ for 12h, then thawing for 8h at room temperature, and repeatedly freezing and thawing for three times to obtain the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel;
in the scheme, the total concentration of acrylamide, acrylic acid, polyvinyl alcohol and calcium chloride in the mixed solution I is 21-28 wt%; the cross-linking agent is N, N' -methylene bisacrylamide and polyethylene glycol diacrylate (600); the initiator is ammonium persulfate and potassium persulfate; the accelerant is N, N, N ', N' -tetramethyl ethylene diamine; and introducing argon for bubbling for 0.5h, vacuumizing to remove bubbles, and then carrying out ultrasonic treatment for 0.5 h.
According to the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel prepared by the scheme, acrylamide, acrylic acid and a cross-linking agent are cross-linked to form a hydrogel three-dimensional network, the shape of the hydrogel can be kept, and linear polyvinyl alcohol is inserted into the hydrogel; the carboxylic acid groups on the acrylic acid coordinate with calcium ions to form divalent crosslinks. By the freeze-thaw process, the polyvinyl alcohol forms microcrystalline regions, resulting in cross-linking between the polyvinyl alcohol.
The acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel prepared according to the scheme has high tensile strength and compressive strength. The water absorption expansion rate can be controlled by controlling the use amount of polyvinyl alcohol and calcium chloride. Has potential application in biology.
The acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel is acrylamide, a copolymer of acrylic acid is interpenetrated with polyvinyl alcohol, acrylic acid is coordinated with calcium ions to form divalent crosslinking and acrylamide, acrylic acid and a crosslinking agent are polymerized to form a hydrogel three-dimensional network, polyvinyl alcohol linear molecules are interpenetrated, microphase separation is carried out in the process of freezing and unfreezing to form crosslinking, bubbles of a mixed solution can be effectively removed in the step of vacuum defoaming treatment, stress defects in the hydrogel are reduced and even avoided, mechanical properties of the hydrogel are improved, meanwhile, oxygen in a reaction liquid can be removed by argon bubbling and vacuum defoaming, an initiation system is combined, the effective crosslinking process of acrylamide and acrylic acid is promoted, and the mechanical properties of the obtained hydrogel are improved.
The invention has the beneficial effects that:
1) the preparation process of the invention is simple, can be used for preparing hydrogel with various shapes, and has wide raw material source and low cost.
2) The prepared acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel has excellent mechanical properties such as higher tensile strength, compressive strength and recoverability through the coordination of chemical bonds and physical bonds.
3) In the step of bubble removal, bubbles in the mixed liquid are effectively removed through vacuumizing, ultrasonic treatment and argon bubbling, so that the formed hydrogel does not have stress defects, and the mechanical property of the hydrogel is effectively improved; meanwhile, oxygen in the solution can be effectively removed through argon bubbling and vacuum defoaming, and the polymerization of acrylamide, acrylic acid and a crosslinking agent can be effectively promoted.
4) The acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel has better biocompatibility.
5) The strength of the hydrogel lost after stress can be recovered by enhancing the physical crosslinking density through the freezing-thawing process, or the strength of the hydrogel can be recovered by soaking the hydrogel in an aqueous solution containing glutaraldehyde, and enabling the amido bond and the hydroxyl group of polyvinyl alcohol to react with the aldehyde group of the glutaraldehyde to form crosslinking so as to enhance the crosslinking density of the hydrogel.
The hydrogel of the invention is introduced with a chemical crosslinking network, and a physical crosslinking network coordinated by ionic bonds and polyvinyl alcohol form a crystallization micro-area through a freezing-unfreezing cyclic process so as to form the physical crosslinking network. The acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel has higher tensile strength and compressive strength. The water absorption expansion rate can be controlled by controlling the use amount of polyvinyl alcohol and calcium chloride. Has potential application in biological medicine, such as artificial cartilage, artificial muscle, etc.
Detailed Description
Six preferred embodiments of the invention are given below:
the following examples are not specifically described, and all reagents used are commercially available chemical reagents or industrial products; testing the tensile strength and the compressive strength of the hydrogel on a universal tensile machine, wherein the tensile rate is 100 mm/min; the compression rate was 5mm/min and the test temperature was 25 ℃.
Example one
Polyvinyl alcohol (PVA) and deionized water (DI) were added to a 250ml flask and heated at 90 ℃ for 2 hours to dissolve the PVA to form a homogeneous solution, which was then left to cool at room temperature for further use.
Acrylamide (AM), acrylic Acid (AC), PVA and calcium chloride (CaCl) were mixed at room temperature2) Adding the mixture into DI according to the mass ratio of 4:2:1:0.2 to obtain uniform mixed solution I, wherein AM, AC, PVA and CaCl are contained in the mixed solution2The total concentration of the components is 23.07 wt%, then N, N ' -methylene bisacrylamide is added in sequence, argon bubbling is carried out for 0.5h after dissolution, ammonium persulfate and N, N, N ', N ' -tetramethyl ethylenediamine are added and mixed evenly, wherein the mass ratio of the N, N ' -methylene bisacrylamide, the ammonium persulfate and the N, N, N ', N ' -tetramethyl ethylenediamine to the acrylamide and the acrylic acid monomer is 0.0014:0.0033:0.0083:1, then transferring the obtained solution into a glass mold, vacuumizing and ultrasonically processing, carrying out heat preservation reaction at 60 ℃ for 6h after sealing, freezing the obtained hydrogel at-20 ℃ for 12h after the reaction is finished, then standing and unfreezing for 8h at room temperature, repeating the freezing-unfreezing process for three times, thus obtaining the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel.
The hydrogel obtained in this example was subjected to tensile and compressive tests, and the tensile strength, tensile elongation at break and compressive strength were 0.310MPa, 445.12% and 2.540MPa (compression set 87.98%) by means of a universal tensile tester.
Example two
The polyvinyl alcohol solution was prepared as in example 1.
AM, AC, PVA and CaCl at room temperature2Adding the mixture into DI according to the mass ratio of 1:5:1:1 to obtain uniform mixed solution I, wherein AM, AC, PVA and CaCl are contained in the mixed solution2The total concentration of the components is 25.00 wt%, then N, N '-methylene bisacrylamide is sequentially added, argon bubbling is carried out for 0.5h after dissolution, ammonium persulfate and N, N, N', N '-tetramethyl ethylenediamine are added and uniformly mixed, wherein the mass ratio of the N, N' -methylene bisacrylamide, the ammonium persulfate, the N, N, N ', N' -tetramethyl ethylenediamine, the acrylamide and the acrylic acid monomer is 0.0014:0.0033:0.0083:1, then the obtained solution is transferred into a glass mold, vacuumized and treated by ultrasonic waves, and the heat preservation reaction is carried out for 8h at 60 ℃ after sealing. The freezing-unfreezing process is the same as the first embodiment, and the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel is obtained.
The hydrogel obtained in this example was tested by a universal tensile machine tester to have a tensile strength of 66.67KPa, a tensile elongation of 416.47%, and a compressive strength of 11.120MPa (compression set of 89.60%).
EXAMPLE III
The polyvinyl alcohol solution was prepared as in example 1.
AM, AC, PVA and CaCl at room temperature2Adding the mixture into DI according to the mass ratio of 3:3:1:1 to obtain uniform mixed solution I, wherein AM, AC, PVA and CaCl are contained in the mixed solution2The total concentration of the components is 25.00 wt%, then N, N '-methylene bisacrylamide is sequentially added, argon bubbling is carried out for 0.5h after dissolution, ammonium persulfate and N, N, N', N '-tetramethyl ethylenediamine are added and uniformly mixed, wherein the mass ratio of the N, N' -methylene bisacrylamide, the ammonium persulfate and the N, N, N ', N' -tetramethyl ethylenediamine to the acrylamide monomer is 0.0015:0.005:0.0125:1, then the obtained solution is transferred into a glass mold, vacuumizing and ultrasonic treatment are carried out, heat preservation reaction is carried out for 6h at the temperature of 60 ℃ after sealing, the freezing-unfreezing process is the same as that of the first embodiment, and the acrylamide-polyvinyl alcohol is obtained-acrylic acid-calcium chloride tri-network composite hydrogel.
The hydrogel obtained in this example was tested by a universal tensile machine tester to have a tensile strength of 0.572MPa, a tensile elongation of 611.55%, and a compressive strength of 3.810MPa (compression set of 90.00%).
Example four
The polyvinyl alcohol solution was prepared as in example 1.
AM, AC, PVA and CaCl at room temperature2Adding the mixture into DI according to the mass ratio of 4:2:2:1 to obtain uniform mixed solution I, wherein AM, AC, PVA and CaCl are contained in the mixed solution2The total concentration of the components is 27.27 wt%, then N, N '-methylene-bisacrylamide is sequentially added, argon bubbling is carried out for 0.5h after dissolution, ammonium persulfate and N, N, N', N '-tetramethyl-ethylenediamine are added and uniformly mixed, wherein the mass ratio of the N, N' -methylene-bisacrylamide, the ammonium persulfate and the monomer of the N, N, N ', N' -tetramethyl-ethylenediamine to the monomer of the acrylamide is 0.0014:0.0033:0.0083:1, then the obtained solution is transferred into a glass mold, vacuum pumping and ultrasonic treatment are carried out, heat preservation reaction is carried out for 6h at the temperature of 60 ℃ after sealing, and the freezing-unfreezing process is the same as the first embodiment, thus obtaining the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel.
The hydrogel obtained in this example was tested by a universal tensile machine tester to have a tensile strength of 0.806MPa, a tensile elongation of 364.22%, and a compressive strength of 3.890MPa (compression set of 90.00%).
EXAMPLE five
The polyvinyl alcohol solution was prepared as in example 1.
AM, AC, PVA and CaCl at room temperature2Adding the mixture into DI according to the mass ratio of 2:4:1:1 to obtain uniform mixed solution I, wherein AM, AC, PVA and CaCl are contained in the mixed solution2The total concentration of the components is 25.00 wt%, then N, N '-methylene bisacrylamide is added in sequence, argon bubbling is carried out for 0.5h after dissolution, ammonium persulfate and N, N, N', N '-tetramethyl ethylenediamine are added and mixed uniformly, wherein the mass ratio of the N, N' -methylene bisacrylamide, the ammonium persulfate and the N, N, N ', N' -tetramethyl ethylenediamine to the acrylamide monomer is 0.0015:0.005:0.0125:1, then the obtained solution is transferred into a glass mold, vacuum pumping and ultrasonic processing are carried out,and (3) after sealing, keeping the temperature at 60 ℃ for reaction for 6h, and performing the same freezing-unfreezing process as in the first embodiment to obtain the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel.
The hydrogel obtained in this example was tested by a universal tensile machine tester to have a tensile strength of 0.337MPa, a tensile elongation of 744.86%, and a compressive strength of 3.620MPa (compression set of 90.01%).
EXAMPLE six
The polyvinyl alcohol solution was prepared as in example 1.
AM, AC, PVA and CaCl at room temperature2Adding the mixture into DI according to the mass ratio of 4:2:1:0.5 to obtain uniform mixed solution I, wherein AM, AC, PVA and CaCl are contained in the mixed solution2The total concentration of the components is 23.81 wt%, then N, N '-methylene bisacrylamide is sequentially added, argon bubbling is carried out for 0.5h after dissolution, ammonium persulfate and N, N, N', N '-tetramethyl ethylenediamine are added and uniformly mixed, wherein the mass ratio of the N, N' -methylene bisacrylamide, the ammonium persulfate and the N, N, N ', N' -tetramethyl ethylenediamine to the acrylamide monomer is 0.0015:0.005:0.0125:1, then the obtained solution is transferred into a glass mold, vacuum pumping and ultrasonic treatment are carried out, heat preservation reaction is carried out for 6h at the temperature of 60 ℃ after sealing, and the freezing-unfreezing process is the same as that of the first embodiment, so that the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel is obtained.
The tensile strength of the hydrogel obtained in this example was measured by a universal tensile machine tester to be 0.345 MPa. The elongation at break was 333.67%, the compressive strength obtained by subjecting the hydrogel obtained by freezing and thawing once to a compression test was 0.580MPa (compression set was 89.42%), and the compressive strength obtained by subjecting the hydrogel obtained by freezing and thawing three times to a compression test was 4.735MPa (compression set was 88.31%).
Claims (2)
1. A preparation method of acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel is characterized by comprising the following steps:
(1) dissolving acrylamide, acrylic acid, calcium chloride and polyvinyl alcohol in water according to a certain mass ratio to obtain a uniform mixed solution I;
(2) adding a cross-linking agent and an initiator into the mixed solution I in sequence, and adding an accelerant after argon is used for removing oxygen to obtain a mixed solution II, wherein the mass ratio of the cross-linking agent to the initiator to the accelerant to the acrylamide is (0.0015-0.05): (0.025-0.01) 0.0125: 1;
(3) carrying out vacuumizing defoaming treatment and low-temperature ultrasonic treatment, sealing the obtained mixed solution II into a glass mold, heating in a water bath to 40-70 ℃, and carrying out heat preservation reaction for 1-8h to obtain the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel with a certain shape;
(4) freezing the gel prepared in the step (3) at-20 ℃ for 12h, then thawing for 8h at room temperature, and repeatedly freezing and thawing for three times to obtain the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel.
2. The method for preparing the acrylamide-polyvinyl alcohol-acrylic acid-calcium chloride three-network composite hydrogel as claimed in claim 1, wherein the total concentration of the acrylamide, the acrylic acid, the polyvinyl alcohol and the calcium chloride in the mixed solution I is 21-28 wt%; the cross-linking agent is N, N' -methylene-bisacrylamide and polyethylene glycol diacrylate (600); the initiator is ammonium persulfate and potassium persulfate; the accelerant is N, N, N ', N' -tetramethyl ethylene diamine; bubbling for 0.5h by filling argon, vacuumizing to remove bubbles, and then carrying out ultrasonic treatment for 0.5 h.
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