CN110563970A - microgel reinforced double-network hydrogel and preparation method thereof - Google Patents
microgel reinforced double-network hydrogel and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- 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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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
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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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
- C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
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Abstract
The invention discloses a microgel reinforced double-network hydrogel and a preparation method thereof, which solve the problem of uneven product performance of each batch caused by the difficulty in controlling the monomer molar ratio of a first network and a second network in the existing two-step method. The technical scheme of the invention is as follows: dissolving 2-acrylamide-2-methylpropanesulfonic acid, N-methylene bisacrylamide, potassium persulfate and acrylamide, reacting, taking out the formed first network hydrogel, drying and crushing the first network hydrogel into powder; and dissolving acrylamide, potassium persulfate and N, N-methylene bisacrylamide, mixing the ground hydrogel powder with the prepared monomer solution, and reacting at the temperature of 60 ℃ for 3 to obtain the microgel reinforced double-network hydrogel. The preparation method greatly shortens the swelling time of the single-network hydrogel, only needs a short time in the swelling process, and overcomes the defect that the specific shape cannot be formed due to the difficult peristalsis of the first-network hydrogel in the existing two-step method.
Description
Technical Field
The invention belongs to the field of hydrogel, and particularly relates to microgel reinforced double-network hydrogel and a preparation method thereof.
background
Hydrogels (hydrogels) are a class of water-based polymers, which are three-dimensional networks of hydrophilic high molecular polymers with chemically or physically cross-linked structures, and because of their hydrophilic cross-linked networks, hydrogels can absorb a large amount of water but are insoluble in water, and they can maintain a certain shape and three-dimensional spatial network structure in water and swell rapidly. Due to these unique structures, hydrogels are widely used in many fields such as medical treatment, medicine, tissue engineering, etc.
However, since the mechanical strength of the conventional hydrogel is insufficient to limit its application, researchers have developed novel high-strength hydrogels, such as a Topological (TP) hydrogel, a double-network (DN) hydrogel, a Macromolecular Microsphere Composite (MMC) hydrogel, and the like. Among them, the fact that the double-network hydrogel exhibits extremely high strength and toughness due to the contrast of network structures and effective energy dissipation by fracture has been one of the hot spots of research on high-strength hydrogels. Since the double-network (DN) hydrogel is usually obtained by a two-step method during synthesis, processes of swelling, diffusion and two-step initiated polymerization are involved during synthesis, the processes are complex and long-time consuming, the monomer molar ratio of the first network and the second network is difficult to control, so that the mechanical properties of each batch of products still have large difference, and the requirements on application fields are harsh due to the two-step synthesis of the double-network hydrogel.
Disclosure of Invention
The invention aims to provide the microgel reinforced double-network hydrogel and the preparation method thereof, the preparation method is simple, and the prepared hydrogel has excellent compression strength.
In order to achieve the above object, the present invention provides a method for preparing a microgel reinforced double-network hydrogel, comprising the following steps:
Dissolving 20 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 0.6 part by weight of potassium persulfate and 0.3 part by weight of acrylamide into 100 parts by weight of water, reacting at 60 ℃ for 3-7 hours, taking out the formed first network hydrogel, drying and crushing the first network hydrogel into powder. And dissolving 15 parts by weight of acrylamide, 0.05 part by weight of potassium persulfate and 0.017 part by weight of N, N-methylene bisacrylamide into 100 parts by weight of water, mixing the ground hydrogel powder with the prepared monomer solution in a mass ratio of 1: 41-45, and reacting at the temperature of 60 ℃ for 3 hours to obtain the microgel reinforced double-network hydrogel.
The microgel reinforced double-network hydrogel prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1) Compared with the existing two-step method, the swelling time of the single-network hydrogel is greatly shortened, the swelling process can be completed within 10 minutes, and the time for synthesizing the double-network hydrogel by the two-step method is shortened.
2) Compared with the existing two-step method, the method solves the problem of uneven product performance of each batch caused by the difficulty in controlling the monomer molar ratio of the first network and the second network in the existing two-step method.
3) compared with the existing two-step method, the method overcomes the defect that the existing two-step method cannot form a specific shape due to the fact that the first network hydrogel is difficult to creep, and can meet the requirements of some fields with harsh use requirements. Such as certain fields where the first network hydrogel cannot be made to swell in equilibrium due to field conditions or application fields where the double network hydrogel cannot be obtained by the existing two-step process.
Drawings
FIG. 1 is a compressive stress-strain curve of a microgel reinforced double-network hydrogel.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
Example 1
2.07g of 2-acrylamide-2-methylpropanesulfonic acid, 0.062g of N, N-methylenebisacrylamide, 0.027g of potassium persulfate and 0.029g of acrylamide are dissolved in 10mL of water and reacted at 60 ℃ for 3 hours, and the formed first network hydrogel is taken out, dried and smashed into powder. Then 15g of acrylamide, 0.05g of potassium persulfate and 0.017g of N, N-methylene bisacrylamide are dissolved in 100mL of water, the hydrogel powder obtained by grinding and the prepared monomer solution are mixed according to the proportion of 1:45, and the mixture reacts for 3 hours at the temperature of 60 ℃ to obtain the high-strength double-network hydrogel.
Example 2
2.07g of 2-acrylamide-2-methylpropanesulfonic acid, 0.062g of N, N-methylenebisacrylamide, 0.027g of potassium persulfate and 0.029g of acrylamide are dissolved in 10mL of water and reacted at 60 ℃ for 3 hours, and the formed first network hydrogel is taken out, dried and smashed into powder. Then 15g of acrylamide, 0.05g of potassium persulfate and 0.017g of N, N-methylene bisacrylamide are dissolved in 100mL of water, the hydrogel powder obtained by grinding and the prepared monomer solution are mixed according to the proportion of 1:41, and the mixture reacts for 3 hours at the temperature of 60 ℃ to obtain the high-strength double-network hydrogel.
Example 3
2.07g of 2-acrylamide-2-methylpropanesulfonic acid, 0.062g of N, N-methylenebisacrylamide, 0.027g of potassium persulfate and 0.029g of acrylamide are dissolved in 10mL of water and reacted at 60 ℃ for 3 hours, and the formed first network hydrogel is taken out, dried and smashed into powder. Then 15g of acrylamide, 0.05g of potassium persulfate and 0.017g of N, N-methylene bisacrylamide are dissolved in 100mL of water, the hydrogel powder obtained by grinding and the prepared monomer solution are mixed according to the proportion of 1:43, and the mixture reacts for 3 hours at the temperature of 60 ℃ to obtain the high-strength double-network hydrogel.
Example 4
2.07g of 2-acrylamide-2-methylpropanesulfonic acid, 0.062g of N, N-methylenebisacrylamide, 0.027g of potassium persulfate and 0.029g of acrylamide are dissolved in 10mL of water and reacted at 60 ℃ for 5 hours, and the formed first network hydrogel is taken out, dried and smashed into powder. Then 15g of acrylamide, 0.05g of potassium persulfate and 0.017g of N, N-methylene bisacrylamide are dissolved in 100mL of water, the hydrogel powder obtained by grinding and the prepared monomer solution are mixed according to the proportion of 1:41, and the mixture reacts for 3 hours at the temperature of 60 ℃ to obtain the high-strength double-network hydrogel.
Example 5
2.07g of 2-acrylamide-2-methylpropanesulfonic acid, 0.062g of N, N-methylenebisacrylamide, 0.027g of potassium persulfate and 0.029g of acrylamide are dissolved in 10mL of water and reacted at 60 ℃ for 7 hours, and the formed first network hydrogel is taken out, dried and smashed into powder. Then 15g of acrylamide, 0.05g of potassium persulfate and 0.017g of N, N-methylene bisacrylamide are dissolved in 100mL of water, the hydrogel powder obtained by grinding and the prepared monomer solution are mixed according to the proportion of 1:41, and the mixture reacts for 3 hours at the temperature of 60 ℃ to obtain the high-strength double-network hydrogel.
In order to test the compressive property of the prepared double-network hydrogel, the inventor performs the following analysis and test on the prepared double-network hydrogel, and the analysis result is as follows:
FIG. 1 shows the compressive stress-strain curve of the double-network hydrogel prepared in example 1. As is obvious from the figure, the gel has stronger compressive strength which reaches 36.5 MPa.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (2)
1. A preparation method of microgel reinforced double-network hydrogel is characterized by comprising the following steps:
The method comprises the following steps:
Dissolving 20 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 0.6 part by weight of N, N-methylenebisacrylamide, 0.3 part by weight of potassium persulfate and 0.3 part by weight of acrylamide into 100 parts by weight of water, reacting for 3-7 hours at the temperature of 60 ℃, taking out the formed first network hydrogel, drying and crushing the first network hydrogel into powder;
and dissolving 15 parts by weight of acrylamide, 0.05 part by weight of potassium persulfate and 0.017 part by weight of N, N-methylene bisacrylamide into 100 parts by weight of water, mixing the ground hydrogel powder with the prepared monomer solution in a mass ratio of 1: 41-45, and reacting at the temperature of 60 ℃ for 3 hours to obtain the microgel reinforced double-network hydrogel.
2. A microgel reinforced double-network hydrogel prepared by the preparation method of claim 1.
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| CN201911006582.3A CN110563970A (en) | 2019-10-22 | 2019-10-22 | microgel reinforced double-network hydrogel and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548454A (en) * | 2020-05-25 | 2020-08-18 | 湖北工业大学 | Preparation method of printable and formable high-strength body temperature release drug hydrogel |
| CN112608495A (en) * | 2020-11-10 | 2021-04-06 | 深圳大学 | Hydrogel composite material, preparation method and application |
| CN113480698A (en) * | 2021-08-02 | 2021-10-08 | 陕西科技大学 | Preparation method of microgel reinforced nano composite double-network hydrogel |
| CN114752080A (en) * | 2022-05-16 | 2022-07-15 | 西京学院 | Preparation method and application of hydrogel with interpenetrating network structure |
| CN116003686A (en) * | 2023-01-05 | 2023-04-25 | 中钢集团马鞍山矿山研究总院股份有限公司 | Preparation method of super-absorbent microgel particles for emergency stopping and slowing |
| CN116143970A (en) * | 2023-01-05 | 2023-05-23 | 中钢集团马鞍山矿山研究总院股份有限公司 | Emergency microgel particle material for quick plugging and water stopping |
-
2019
- 2019-10-22 CN CN201911006582.3A patent/CN110563970A/en active Pending
Non-Patent Citations (2)
| Title |
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| JUNJI SAITO, ET AL.: "Robust bonding and one-step facile synthesis of tough hydrogels with desirable shape by virtue of the double network structure", 《POLYMER CHEMISTRY》 * |
| LUYI WANG, ET AL.: "A strong and tough interpenetrating network hydrogel with ultrahigh compression resistance", 《SOFT MATTER》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548454A (en) * | 2020-05-25 | 2020-08-18 | 湖北工业大学 | Preparation method of printable and formable high-strength body temperature release drug hydrogel |
| CN111548454B (en) * | 2020-05-25 | 2023-01-20 | 湖北工业大学 | Preparation method of printable and formable high-strength body temperature release drug hydrogel |
| CN112608495A (en) * | 2020-11-10 | 2021-04-06 | 深圳大学 | Hydrogel composite material, preparation method and application |
| CN113480698A (en) * | 2021-08-02 | 2021-10-08 | 陕西科技大学 | Preparation method of microgel reinforced nano composite double-network hydrogel |
| CN114752080A (en) * | 2022-05-16 | 2022-07-15 | 西京学院 | Preparation method and application of hydrogel with interpenetrating network structure |
| CN116003686A (en) * | 2023-01-05 | 2023-04-25 | 中钢集团马鞍山矿山研究总院股份有限公司 | Preparation method of super-absorbent microgel particles for emergency stopping and slowing |
| CN116143970A (en) * | 2023-01-05 | 2023-05-23 | 中钢集团马鞍山矿山研究总院股份有限公司 | Emergency microgel particle material for quick plugging and water stopping |
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