CN113201153B - Super-elastic heat-resistant anti-freezing composite hydrogel and preparation method thereof - Google Patents
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Abstract
The invention relates to a super-elastic heat-resistant anti-freezing composite hydrogel and a preparation method thereof, wherein the super-elastic heat-resistant anti-freezing composite hydrogel comprises the following raw materials in parts by weight: 0.2-10.0 parts of hydrophobic monomer, 5.0-10.0 parts of hydrophilic monomer acrylamide, 0.4-0.80 part of sodium chloride, 1.0-2.0 parts of surfactant cetyl trimethyl ammonium bromide, 2.0-10.0 parts of calcium chloride, 0.8-1.2 parts of cosolvent, 0.02-0.04 part of initiator, 0.02-0.04 part of tetramethyl ethylenediamine and 20.0-30.0 parts of deionized water. According to the embodiment of the invention, calcium chloride is added into the hydrogel formula, so that the prepared hydrogel has excellent freezing resistance, heat resistance, flame retardance and lasting mechanical stability, the problem that the hydrogel is easy to lose water in a freezing and drying environment below zero is effectively solved, the temperature range of hydrogel application is greatly expanded, and the hydrogel is advanced towards application diversification.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to a super-elastic heat-resistant anti-freezing composite hydrogel and a preparation method thereof.
Background
The hydrogel is a soft material which rapidly swells to equilibrium in water, can maintain the shape and three-dimensional network structure of the hydrogel, is insoluble in water, and has good elasticity and biocompatibility, thereby being used in drug delivery, tissue engineering,The sensor is widely applied in the fields of sensor construction and the like. In the last two decades, hydrophobically modified polyacrylamide hydrogels have been extensively studied. The hydrophobic association hydrogel is mainly based on intermolecular hydrophobic association effect, hydrophobic sequences are doped in a hydrophilic polymer acrylamide, and the hydrophobic association structural domains serve as physical crosslinking points in a network, so that a hydrophobic modified hydrogel three-dimensional network skeleton is constructed. Most of the hydrogels studied at present have difficulty in maintaining good mechanical properties even in a high-temperature or low-temperature environment because only 20-30 kJ. mol-1The weak hydrogen bonding of (a) inevitably vaporizes or crystallizes the liquid water. It is noted that the loss or freezing of water can cause the hydrogel to stiffen, thereby severely impairing its tensile, compressive and shear properties. In addition, conventional hydrogels gradually dehydrate and burn to ash after ignition, resulting in limited practical applications. How to maintain these excellent combinations of properties over a wide temperature range is a major challenge in designing high quality hydrogels with superior stretchability, long-term stability, excellent temperature and fire resistance, and self-healing properties.
Disclosure of Invention
Based on the above, the invention aims to provide a super-elastic heat-resistant anti-freezing composite hydrogel which has the advantages of super elasticity and strong moisture retention and anti-freezing properties.
A super-elastic heat-resistant anti-freezing composite hydrogel comprises the following raw materials in parts by weight: 0.2-10.0 parts of hydrophobic monomer, 5.0-10.0 parts of hydrophilic monomer acrylamide, 0.4-0.80 part of sodium chloride, 1.0-2.0 parts of surfactant cetyl trimethyl ammonium bromide, 2.0-10.0 parts of calcium chloride, 0.02-0.04 part of initiator, 0.02-0.04 part of tetramethyl ethylenediamine and 20.0-30.0 parts of deionized water.
According to the embodiment of the invention, calcium chloride is added into the hydrogel formula, on one hand, the coordination effect of calcium ions, amino groups in a Polyacrylamide (PAM) chain and hydroxyl groups in water is utilized to realize the super elasticity, moisture retention and frost resistance of the hydrogel: based on an energy dissipation mechanism, the reconstruction of chemical bonds can be rapidly carried out through stronger interaction between calcium metal ions and amino groups of a polymer chain; the dynamic equilibrium of the metal-ligand bond causes it to break and reform rapidly during stretching, thereby leading toThe polyacrylamide chains are unfolded and slide, so that the polyacrylamide chains have good elasticity, and the prepared hydrogel can be stretched to 136 times of the original length and is obviously superior to the elongation numerical value reported in the literature; ca2+And the complex bond is easy to form with hydroxyl (-OH) of an electron donor in water, so that a hydrated ion cluster with a stable structure is obtained, the water retention capacity of the prepared hydrogel is obviously enhanced by hydrated calcium ions, and the polyacrylamide chain is prevented from losing superelasticity.
On the other hand, the freezing/evaporating performance of water ligand molecules is obviously weakened due to the limitation of calcium central ions, so that the prepared gel material has excellent freezing resistance and heat resistance. The hyperelastic hydrogel modified by calcium chloride does not burn completely as quickly as the hydrophobic association hydrogel before modification when being threatened by naked fire, because liquid water molecules locked by calcium ions can quickly evaporate and absorb a large amount of heat, while the calcium chloride inorganic salt protective layer can avoid direct contact of combustible substances and oxygen, and the double protection mechanism ensures that the synthesized hydrogel has excellent flame retardant property; in addition, the polyacrylamide chains in the hydrogel, water and strong coordination bonds of calcium ions firmly fix the water in a polymer network, so that the high-quality hydrogel has excellent freezing resistance, heat resistance, flame retardance and lasting mechanical stability, the problem that the hydrogel is easy to lose water in a freezing and drying environment below zero degree is effectively solved, the temperature range of the hydrogel application is greatly expanded, and the hydrogel is advanced towards the application diversification direction.
Further, the hydrophobic monomer is n-alkyl methacrylate selected from cetyl methacrylate, stearyl methacrylate or behenyl methacrylate.
Further, the cosolvent is propanol, n-butanol, n-pentanol, n-hexanol or isopropanol. The addition of a co-solvent aids in the dissolution of the hydrophobic monomer.
Further, the initiator is a persulfate initiator selected from potassium persulfate, ammonium persulfate, or sodium persulfate.
In addition, the embodiment of the invention also provides a preparation method of the super-elastic heat-resistant anti-freezing composite hydrogel, which comprises the following specific operation steps:
s1, weighing the component materials according to the formula;
s2, adding sodium chloride and cetyl trimethyl ammonium bromide serving as a surfactant into deionized water with a part of formula amount, and stirring at room temperature until the sodium chloride and the cetyl trimethyl ammonium bromide are completely dissolved;
s3, adding calcium chloride into the deionized water with the rest formula amount for dissolving, then adding the calcium chloride into the solution obtained in the step S2, stirring until no bubbles are generated, continuously adding a hydrophobic monomer and a cosolvent, and stirring until a semitransparent solution is formed; then adding hydrophilic monomer acrylamide and an initiator, stirring until the solution is clear and transparent, then adding tetramethylethylenediamine, and uniformly mixing;
s4, pouring the solution prepared in the step S3 into a mold, and placing the mold in an oven to react for a certain time to obtain the super-elastic heat-resistant anti-freezing composite hydrogel.
Further, step S3 is performed at room temperature.
Further, in the step S4, the mold is placed in an oven at 45-55 ℃ for reaction for 10-14 h.
Further, the mold used in step S4 is a glass mold.
Compared with the heat-resistant and anti-freezing hydrogel prepared by the currently generally adopted secondary soaking solvent exchange method, the method disclosed by the embodiment of the invention is simpler and more efficient, the moisture-retaining molecules are uniformly distributed in the hydrogel network, the preparation operation process is simple and easy to realize, the requirement on equipment is low, the energy consumption is lower, and the method is suitable for large-scale production.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a scanning electron micrograph of hydrogels obtained in example 1 of the present invention and comparative example 1;
FIG. 2 is a stress-strain curve of hydrogels prepared according to examples 1-5 of the present invention and comparative example 1;
FIG. 3 is a schematic diagram showing the in-situ tensile test results of the composite hydrogel with a diameter of 6 mm and an effective length of 60-80 mm at a temperature of-40-50 ℃.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments of the present invention are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described herein, and it will be apparent to those of ordinary skill in the art that the present invention may be practiced without departing from the spirit and scope of the present invention, and therefore the present invention is not limited by the examples disclosed below.
Example 1
Adding 0.4g of sodium chloride (NaCl) and 1.0g of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into 20ml of deionized water, and stirring at room temperature for 20min until the components are completely dissolved; then adding 10ml of water solution containing 2.0g of calcium chloride, stirring until no bubbles are generated, continuously adding 254 mu L of hydrophobic monomer cetyl methacrylate and 1 ml of cosolvent n-butyl alcohol, and stirring for 5 hours at room temperature until uniform semitransparent solution is formed; then adding 5.0g of hydrophilic monomer acrylamide and 0.04g of initiator potassium persulfate, and stirring for 1 hour until the solution is clear and transparent; then adding 52 mu L of tetramethyl ethylenediamine, quickly pouring the prepared solution into a glass plate mould with the thickness of 200mm multiplied by 2mm, and placing the mould in an oven with the temperature of 50 ℃ for reaction for 12 hours to prepare the super-elastic heat-resistant anti-freezing composite hydrogel.
Example 2
Adding 0.4g of sodium chloride (NaCl) and 1.0g of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into 20ml of deionized water, and stirring at room temperature for 20min until the components are completely dissolved; then adding 10ml of water solution containing 4.0g of calcium chloride, stirring for 20min until no bubbles are generated, continuously adding 254 mu L of hydrophobic monomer cetyl methacrylate and 1 ml of cosolvent n-butyl alcohol, and stirring for 5h at room temperature until uniform semitransparent solution is formed; then adding 5.0g of hydrophilic monomer acrylamide and 0.04g of initiator potassium persulfate, and stirring for 1 hour until the solution is clear and transparent; then adding 52 mu L of tetramethyl ethylenediamine, quickly pouring the prepared solution into a glass plate mould with the thickness of 200mm multiplied by 2mm, and placing the mould in an oven with the temperature of 50 ℃ for reaction for 12 hours to prepare the super-elastic heat-resistant anti-freezing composite hydrogel.
Example 3
Adding 0.4g of sodium chloride (NaCl) and 1.0g of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into 20ml of deionized water, and stirring at room temperature for 20min until the components are completely dissolved; then adding 10ml of water solution containing 6.0g of calcium chloride, stirring for 20min until no bubbles are generated, continuously adding 254 mu L of hydrophobic monomer cetyl methacrylate and 1 ml of cosolvent n-butyl alcohol, and stirring for 5h at room temperature until uniform semitransparent solution is formed; then adding 5.0g of hydrophilic monomer acrylamide and 0.04g of initiator potassium persulfate, and stirring for 1 hour until the solution is clear and transparent; then adding 52 mu L of tetramethyl ethylenediamine, quickly pouring the prepared solution into a glass plate mould with the thickness of 200mm multiplied by 2mm, and placing the mould in an oven with the temperature of 50 ℃ for reaction for 12 hours to prepare the super-elastic heat-resistant anti-freezing composite hydrogel.
Example 4
Adding 0.4g of sodium chloride (NaCl) and 1.0g of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into 20ml of deionized water, and stirring at room temperature for 20min until the components are completely dissolved; then adding 10ml of water solution containing 8.0g of calcium chloride, stirring for 20min until no bubbles are generated, continuously adding 254 mu L of hydrophobic monomer cetyl methacrylate and 1 ml of cosolvent n-butyl alcohol, and stirring for 5h at room temperature until uniform semitransparent solution is formed; then adding 5.0g of hydrophilic monomer acrylamide and 0.04g of initiator potassium persulfate, and stirring for 1 hour until the solution is clear and transparent; then adding 52 mu L of tetramethyl ethylenediamine, quickly pouring the prepared solution into a glass plate mould with the thickness of 200mm multiplied by 2mm, and placing the mould in an oven with the temperature of 50 ℃ for reaction for 12 hours to prepare the super-elastic heat-resistant anti-freezing composite hydrogel.
Example 5
Adding 0.4g of sodium chloride (NaCl) and 1.0g of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into 20ml of deionized water, and stirring at room temperature for 20min until the components are completely dissolved; then adding 10ml of water solution containing 10.0g of calcium chloride, stirring for 20min until no bubbles are generated, continuously adding 254 mu L of hydrophobic monomer cetyl methacrylate and 1 ml of cosolvent n-butyl alcohol, and stirring for 5h at room temperature until uniform semitransparent solution is formed; then adding 5.0g of hydrophilic monomer acrylamide and 0.04g of initiator potassium persulfate, and stirring for 1 hour until the solution is clear and transparent; then adding 52 mu L of tetramethyl ethylenediamine, quickly pouring the prepared solution into a glass plate mould with the thickness of 200mm multiplied by 2mm, and placing the mould in an oven with the temperature of 50 ℃ for reaction for 12 hours to prepare the super-elastic heat-resistant anti-freezing composite hydrogel.
Comparative example 1
Adding 0.4g of sodium chloride (NaCl) and 1.0g of surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) into 20ml of deionized water, and stirring at room temperature for 20min until the components are completely dissolved; then 254 mu L of hydrophobic monomer cetyl methacrylate and 1 ml of cosolvent n-butyl alcohol are added, and the mixture is continuously stirred for 5 hours at room temperature until the solution is clear and transparent; then 5.0g of hydrophilic monomer acrylamide and 0.04g of initiator potassium persulfate were added and stirred for 1h until the solution was clear and transparent. Then 52. mu.L of tetramethylethylenediamine was added, and finally the prepared solution was poured into a glass plate mold of 200 mm. times.200 mm. times.2 mm, and the mold was placed in an oven at 50 ℃ to react for 12 hours to prepare a hydrophobically associating hydrogel.
Referring to FIG. 1, FIG. 1 is a scanning electron micrograph of hydrogels obtained in example 1 and comparative example 1 of the present invention. The examples 1 to 5 and comparative example 1 were taken out of the mold, cut with a cutter into dumbbell-shaped test pieces having a length of 75mm, a width of 4mm and a thickness of 2mm, and subjected to a tensile test with a universal tester (model: GP-6113A, Germany) at a test speed of 100 mm/min. Referring to FIG. 2, FIG. 2 is a stress-strain curve of the hydrogels prepared in examples 1-5 of the present invention and comparative example 1, from which it can be seen that the calcium chloride loaded superelastic hydrogel can be stretched to a higher strain before breaking than the conventional hydrophobically associating hydrogel. For acrylamide/calcium chloride mass ratio of 5: 2, the maximum strain at break can reach 4700 ± 10%, and it can self-recover to its original length within 1 hour by stress release. A transparent hydrogel with an acrylamide/calcium chloride mass ratio of 5:10 can even be stretched to more than 85 times its original length without breaking. In contrast, the maximum elongation of a conventional hydrophobically-associated hydrogel of similar dimensions is only 1000-3500%.
Referring to FIG. 3, FIG. 3 is a graph showing the in-situ tensile test results of the composite hydrogel having a diameter of 6 mm and an effective length of 60 to 80 mm at a temperature ranging from-40 to 50 ℃, wherein as shown in the graph, curve (I) shows that the initial tensile length of the original hydrogel without calcium chloride is 240% under an external force of 0.5N, but the tensile ratio rapidly decreases to 10% and the elasticity completely disappears even when the original hydrogel is left at room temperature for 8 hours. Curve (ii) represents an acrylamide/calcium chloride mass ratio of 5: the change of the tensile rate of the 10 hydrogel in a 50 ℃ forced air drying oven along with the time can find that the tensile curve under the action of 0.2N external force reaches balance in about 5 hours, and the mechanical property can still be kept at 67 percent after the hydrogel is treated at high temperature for 12 hours. Curve (III) shows the change in mechanical properties of the calcium chloride-loaded superelastic hydrogel at ambient temperature (65% relative humidity). Tests show that the value slightly fluctuates in the first 12 hours because the adsorption-desorption of the environmental moisture is not balanced yet, and then gradually becomes stable, and finally is stabilized at about 100%. The change in elongation of the calcium chloride loaded superelastic hydrogel at low temperature is shown in curve (IV), and the material is placed in a freezer at-40 ℃ for 24 hours without freezing, and the elasticity is completely retained.
In addition, the hydrogels obtained in examples 1 to 5 and comparative example 1 were tested for flame resistance, and the results of the tests showed that they were freeze-dried to remove water and did not contain CaCl2The hydrogel can be completely combusted in only 45 seconds, contains water and does not contain CaCl2The hydrogel(s) burned within two thirds of 90 seconds, but due to the high enthalpy of evaporation of water (40.63 kJ. mol. at 100 ℃ C.)-1) And therefore there is no open flame throughout the combustion process. The calcium chloride-loaded composite hydrogel still shows excellent flame-retardant performance even after being placed in an environment with the relative humidity of 65% for two weeks, and burns for only 5mm within 90 seconds, accounting for about ten times of the total lengthAnd one-fourth.
According to the tests, the calcium chloride-loaded super-elastic hydrogel prepared by the invention has the advantages of large tensile strain, ultrahigh elasticity, dry and freeze resistance, flame retardance and the like, the change of the surfactant and the addition of the calcium chloride improve the tensile property of the hydrogel, endow the hydrogel with new moisture retention, freeze resistance and anti-combustion performance, solve the problem that the hydrogel is easy to lose water in freezing and drying environments below zero degree, and enable the application of the hydrogel to develop towards a more diversified direction.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (8)
1. The super-elastic heat-resistant anti-freezing composite hydrogel is characterized by comprising the following raw materials in parts by weight: 0.2-10.0 parts of hydrophobic monomer, 5.0-10.0 parts of hydrophilic monomer acrylamide, 0.4-0.80 part of sodium chloride, 1.0-2.0 parts of surfactant cetyl trimethyl ammonium bromide, 2.0-10.0 parts of calcium chloride, 0.8-1.2 parts of cosolvent, 0.02-0.04 part of initiator, 0.02-0.04 part of tetramethyl ethylenediamine and 20.0-30.0 parts of deionized water.
2. A superelastic heat resistant antifreeze composite hydrogel according to claim 1, wherein: the hydrophobic monomer is n-alkyl methacrylate selected from cetyl methacrylate, stearyl methacrylate or behenyl methacrylate.
3. The superelastic, heat-resistant, freeze-resistant composite hydrogel according to claim 1, wherein: the cosolvent is propanol, n-butanol, n-pentanol, n-hexanol or isopropanol.
4. The superelastic, heat-resistant, freeze-resistant composite hydrogel according to claim 1, wherein: the initiator is a persulfate initiator selected from potassium persulfate, ammonium persulfate or sodium persulfate.
5. A method for preparing the super elastic heat-resistant antifreeze composite hydrogel according to any claim 1 to 4, which comprises the following specific steps:
s1, weighing the component materials according to the formula;
s2, adding sodium chloride and cetyl trimethyl ammonium bromide serving as a surfactant into deionized water with a part of formula amount, and stirring at room temperature until the sodium chloride and the cetyl trimethyl ammonium bromide are completely dissolved;
s3, adding calcium chloride into the deionized water with the rest formula amount to dissolve, then adding the calcium chloride into the solution obtained in the step S2, stirring until no bubbles are generated, continuously adding a hydrophobic monomer and a cosolvent, and stirring until a semitransparent solution is formed; then adding hydrophilic monomer acrylamide and an initiator, stirring until the solution is clear and transparent, then adding tetramethylethylenediamine, and uniformly mixing;
s4, pouring the solution prepared in the step S3 into a mold, and placing the mold in an oven to react for a certain time to obtain the super-elastic heat-resistant anti-freezing composite hydrogel.
6. The method for preparing the superelastic heat-resistant antifreeze composite hydrogel according to claim 5, wherein the preparation method comprises the following steps: step S3 is performed at room temperature.
7. The method for preparing the superelastic heat-resistant antifreeze composite hydrogel according to claim 5, wherein the preparation method comprises the following steps: in the step S4, the mold is placed in an oven at 45-55 ℃ to react for 10-14 h.
8. The method for preparing the superelastic heat-resistant antifreeze composite hydrogel according to claim 5, wherein the preparation method comprises the following steps: the mold used in step S4 is a glass mold.
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