CN108948347B - Modified aromatic polyamide, temperature-sensitive hydrogel with two critical temperatures and preparation method thereof - Google Patents
Modified aromatic polyamide, temperature-sensitive hydrogel with two critical temperatures and preparation method thereof Download PDFInfo
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- CN108948347B CN108948347B CN201810618323.5A CN201810618323A CN108948347B CN 108948347 B CN108948347 B CN 108948347B CN 201810618323 A CN201810618323 A CN 201810618323A CN 108948347 B CN108948347 B CN 108948347B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
The invention discloses modified aromatic polyamide, temperature-sensitive hydrogel with two critical temperatures and a preparation method thereof. The preparation method of the modified aromatic polyamide comprises the steps of dissolving aromatic diamine, aromatic dicarboxylic acid and end group functionalized polyether in an organic solvent, stirring and reacting at 100-120 ℃ under a nitrogen atmosphere by taking calcium chloride as a catalyst, filtering and extracting a product solution to obtain the modified aromatic polyamide; wherein, the weight portion of aromatic diamine is 90-210 portions, the weight portion of aromatic dicarboxylic acid is 150-270 portions, and the weight portion of end group functional polyether is 0-50 portions. The temperature-sensitive hydrogel with two critical temperatures, which is prepared from the modified aromatic polyamide, has two critical temperatures, can detect and indicate a temperature range, and is an excellent intelligent temperature-sensitive switch material.
Description
Technical Field
The invention relates to the technical field of intelligent high polymer materials, in particular to modified aromatic polyamide, temperature-sensitive hydrogel with two critical temperatures and a preparation method thereof.
Background
The hydrogel is a gel in which water is used as a dispersion medium. The hydrogel is a cross-linked polymer with a part of hydrophobic groups and hydrophilic residues introduced into a water-soluble macromolecule with a reticular cross-linked structure, the hydrophilic residues are combined with water molecules to connect the water molecules in the reticular structure, and the hydrophobic residues swell when meeting water. Therefore, the hydrogel is soft due to the polymer network system, can keep a certain shape, and can absorb a large amount of water. Meanwhile, the hydrogel has high similarity with human tissues, so that the hydrogel has important potential application value in the fields of biological tissue engineering, simulated skin and the like. The crosslinking method of the hydrogel mainly comprises a physical crosslinking method and a chemical crosslinking method. The physical cross-linking method is mainly completed through hydrogen bonds, ionic bonds, hydrophobic acting force and intermolecular mutual winding action. Physically prepared gels are non-permanent and can change with changes in physical conditions. Chemical methods are through graft copolymerization and ionizing radiation crosslinking, etc.
Temperature sensitive hydrogels are a class of gel materials that can produce a corresponding change in functionality in response to a change in ambient temperature. Various natural or synthetic high molecular materials can be used for preparing the temperature-sensitive hydrogel. The natural polymer materials mainly comprise chitin/chitosan and derivatives thereof, hydroxymethyl cellulose, collagen, hyaluronic acid, gelatin, alginate and the like, and have certain advantages such as abundant reserves in the nature, easy acquisition, good biocompatibility, certain biodegradability, low antigenicity, no toxicity and the like, however, hydrogel prepared from the natural polymer materials is poor in mechanical properties and long in gelling time. The synthetic polymer material mainly comprises polyacrylic acids and derivatives thereof, polyacrylamide and derivatives thereof, polyvinyl alcohol, polyethylene glycol and the like. The synthesized polymer material has more varieties, can be modified by simple physical and chemical methods to meet different requirements, has better production repeatability and can be produced in large quantities.
The temperature-sensitive hydrogel has a great application prospect in intelligent temperature control switches. At present, most of temperature-sensitive hydrogels have only one low-temperature critical temperature. That is, there is a lowest critical transition temperature at which the volume changes, called the low temperature dissolution temperature, and when the ambient temperature is lower than the low temperature dissolution temperature, the temperature sensitive hydrogel is in a fluid liquid state. In practice, however, a smart responsive material with two critical temperatures, high and low, is often required to detect and ensure that an environment is always within a desired temperature range. Therefore, the preparation of hydrogel with two critical temperatures of high and low temperature is a problem to be solved urgently.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified aromatic polyamide, a temperature-sensitive hydrogel with two critical temperatures and a preparation method thereof.
Aromatic polyamides are an important polymeric material. The aromatic polyamide has a large number of symmetrical benzene rings and amide bonds in molecules and a large intermolecular force, so that the aromatic polyamide has extremely excellent physical and mechanical properties and liquid crystal behavior in a solution. The water-soluble aromatic polyamide is soluble in water, and a large number of hydrogen bonds exist between the molecules of the water-soluble aromatic polyamide, so that the hydrogel can be prepared by adjusting the concentration of the aromatic polyamide in water. Based on the above, the invention creatively provides that the water-soluble aromatic polyamide is used as a hydrogel precursor, and the hydrogel with two critical temperatures is prepared by modifying the water-soluble aromatic polyamide.
The preparation method of the modified aromatic polyamide comprises the steps of dissolving aromatic diamine, aromatic dicarboxylic acid and end group functionalized polyether in an organic solvent, stirring and reacting at 100-120 ℃ under a nitrogen atmosphere by taking calcium chloride as a catalyst, filtering and extracting a product solution to obtain the modified aromatic polyamide;
wherein, the weight portion of aromatic diamine is 90-210 portions, the weight portion of aromatic dicarboxylic acid is 150-270 portions, and the weight portion of end group functional polyether is 0-50 portions.
Further, the reaction was stirred at 100 ℃ and 120 ℃ under a nitrogen atmosphere for 10 to 12 hours.
Further, the resultant solution was poured into methanol, filtered and extracted to obtain a modified aromatic polyamide.
Further, the aromatic diamine, the aromatic dicarboxylic acid and the end group functionalized polyether are dissolved in an organic solvent, and the mass concentration of the solute is 0.14-0.20 mg/mL.
Further, the aromatic diamine is one of p-phenylenediamine or sodium o-sulfonate p-phenylenediamine; the aromatic dicarboxylic acid is one of terephthalic acid or sodium o-sulfonate terephthalic acid and sodium-2-sulfonate terephthalic acid; the end group functionalized polyether is one or more of terminal amino polypropylene glycol, terminal carboxyl polyethylene glycol, terminal amino polyethylene glycol and terminal carboxyl polypropylene glycol, and the molecular weight is 200-2000; the organic solvent is nitrogen methyl pyrrolidone.
Further, by mass, 90-110 parts of aromatic diamine, 270 parts of aromatic dicarboxylic acid and 20-50 parts of end group functionalized polyether.
The invention also provides the modified aromatic polyamide prepared by the preparation method.
The invention also provides a temperature-sensitive hydrogel with two critical temperatures, which comprises the following components in parts by mass: 0.1-10 parts of modified aromatic polyamide and 100 parts of deionized water.
Wherein the modified aromatic polyamide is the modified aromatic polyamide according to any one of claims 1 to 8.
The invention also provides a preparation method of the temperature-sensitive hydrogel with two critical temperatures, which is characterized in that the temperature-sensitive hydrogel with two critical temperatures is obtained by mixing the modified aromatic polyamide and the deionized water, vigorously stirring for 2-10 hours at 60-90 ℃ until the modified aromatic polyamide and the deionized water are completely dissolved, and standing at the environment temperature of 25 ℃.
The temperature-sensitive hydrogel has two critical temperatures, can detect and indicate a temperature range, and is an excellent intelligent temperature-sensitive switch material.
Detailed Description
The present invention is described in detail below with reference to examples, and the description in this section is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
1.5g of terephthalic acid and 2.1g of sodium o-sulfonate p-phenylenediamine are dissolved in 25ml of nitrogen methyl pyrrolidone, 0.6g of anhydrous calcium chloride is added, the mixture is stirred and reacted for 10 hours at 110 ℃, and then the product solution is poured into methanol, filtered and extracted with methanol for 3 times to obtain the water-soluble aromatic polyamide.
0.1g of a water-soluble aromatic polyamide was mixed with 100g of deionized water, stirred at 60 ℃ for 10 hours, and then allowed to stand.
Example 2
2.7g of terephthalic acid, 0.9g of p-phenylenediamine and 0.5g of amino-terminated polypropylene glycol having a molecular weight of 2000 were dissolved in 25ml of N-methylpyrrolidone, 0.6g of anhydrous calcium chloride was added, and a reaction was carried out at 120 ℃ for 10 hours with stirring, after which the resultant solution was poured into methanol, filtered, and extracted with methanol 3 times to obtain a water-soluble aromatic polyamide.
1g of a water-soluble aromatic polyamide was mixed with 10g of deionized water, stirred at 90 ℃ for 2 hours, and then allowed to stand.
Example 3
2.5g of sodium o-sulfonate terephthalic acid, 1.0g of p-phenylenediamine and 0.3g of carboxyl-terminated polyethylene glycol with the molecular weight of 200 are dissolved in 25ml of nitrogen methyl pyrrolidone, 0.6g of anhydrous calcium chloride is added, the mixture is stirred and reacted for 12 hours at the temperature of 100 ℃, and then the product solution is poured into methanol, filtered and extracted with methanol for 3 times to obtain the water-soluble aromatic polyamide.
0.5g of water-soluble aromatic polyamide was mixed with 10g of deionized water, stirred at 80 ℃ for 6 hours, and then allowed to stand.
Example 4
2.7g of sodium 2-sulfonate terephthalate, 2.1g of sodium o-sulfonate p-phenylenediamine and 0.1g of terminal amino polyethylene glycol with the molecular weight of 1000 are dissolved in 25ml of nitrogen methyl pyrrolidone, 0.6g of anhydrous calcium chloride is added, the mixture is stirred and reacted for 10 hours at the temperature of 110 ℃, and then the product solution is poured into methanol, filtered and extracted for 3 times by the methanol to obtain the water-soluble aromatic polyamide.
1g of a water-soluble aromatic polyamide was mixed with 10g of deionized water, stirred at 90 ℃ for 2 hours, and then allowed to stand.
Example 5
2.3g of sodium 2-sulfonate terephthalate, 1.1g of p-phenylenediamine and 0.2g of carboxyl-terminated polypropylene glycol having a molecular weight of 600 were dissolved in 25ml of N-methylpyrrolidone, 0.6g of anhydrous calcium chloride was added, and a reaction was carried out with stirring at 110 ℃ for 10 hours, after which the resultant solution was poured into methanol, filtered, and extracted with methanol 3 times to obtain a water-soluble aromatic polyamide.
1g of a water-soluble aromatic polyamide was mixed with 10g of deionized water, stirred at 90 ℃ for 2 hours, and then allowed to stand.
Example 6
2.3g of sodium 2-sulfonate terephthalate, 0.9g of p-phenylenediamine and 0.3g of carboxyl-terminated polypropylene glycol with the molecular weight of 600 and 0.1g of amino-terminated polyethylene glycol with the molecular weight of 200 are dissolved in 25ml of azomethylpyrrolidone, 0.6g of anhydrous calcium chloride is added, the mixture is stirred and reacted for 10 hours at the temperature of 110 ℃, and then the product solution is poured into methanol, filtered and extracted with the methanol for 3 times to obtain the water-soluble aromatic polyamide.
1g of a water-soluble aromatic polyamide was mixed with 10g of deionized water, stirred at 90 ℃ for 2 hours, and then allowed to stand.
The hydrogel prepared by the invention has two critical temperatures, can be used for detecting the temperature range, and is a novel intelligent temperature control switch material.
Critical temperature measurement: and (3) placing the sample bottle containing the prepared hydrogel into an oil bath, heating the oil bath and observing the temperature of the oil bath and the state of the hydrogel under the liquid level of the heat-conducting oil in the sample bottle. The temperature at which the hydrogel dissolves to become a solution is its lower critical temperature and continued heating is its higher critical temperature when the solution becomes cloudy. Each sample was repeated 5 times, and the average was the result.
TABLE 1
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A temperature-sensitive hydrogel with two critical temperatures is characterized by comprising the following components in parts by mass: 0.1-10 parts of modified aromatic polyamide and 100 parts of deionized water;
the preparation method of the modified aromatic polyamide comprises the steps of dissolving aromatic diamine, aromatic dicarboxylic acid and end group functionalized polyether in an organic solvent, stirring and reacting at 100-120 ℃ under a nitrogen atmosphere by taking calcium chloride as a catalyst, filtering and extracting a product solution to obtain the modified aromatic polyamide;
wherein, the weight portion of aromatic diamine is 90-210, the weight portion of aromatic dicarboxylic acid is 150-270, and the weight portion of end group functional polyether is 0-50;
dissolving aromatic diamine, aromatic dicarboxylic acid and end group functionalized polyether in an organic solvent, wherein the mass concentration of a solute is 0.14-0.20 mg/mL;
the aromatic diamine is one of p-phenylenediamine or sodium o-sulfonate p-phenylenediamine; the aromatic dicarboxylic acid is one of terephthalic acid or sodium o-sulfonate terephthalic acid and sodium-2-sulfonate terephthalic acid; the end group functionalized polyether is one or more of terminal amino polypropylene glycol, terminal carboxyl polyethylene glycol, terminal amino polyethylene glycol and terminal carboxyl polypropylene glycol, and the molecular weight is 200-2000; the organic solvent is nitrogen methyl pyrrolidone;
the preparation method of the temperature-sensitive hydrogel with two critical temperatures is characterized in that the temperature-sensitive hydrogel with two critical temperatures is obtained by mixing the modified aromatic polyamide and deionized water, violently stirring for 2-10 hours at 60-90 ℃ until the modified aromatic polyamide and the deionized water are completely dissolved, and standing at the environment temperature of 25 ℃.
2. The temperature-sensitive hydrogel having two critical temperatures according to claim 1, wherein in the preparation method of the modified aromatic polyamide, the reaction is carried out at 100-120 ℃ under stirring in a nitrogen atmosphere for 10-12 hours.
3. The temperature-sensitive hydrogel having two critical temperatures according to claim 1, wherein in the method for producing the modified aromatic polyamide, the product solution is poured into methanol, filtered, and extracted to obtain the modified aromatic polyamide.
4. The temperature-sensitive hydrogel having two critical temperatures according to claim 1, wherein in the preparation method of the modified aromatic polyamide, 90 to 110 parts by mass of the aromatic diamine, 270 parts by mass of the aromatic dicarboxylic acid and 20 to 50 parts by mass of the terminal functionalized polyether are used.
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