CN109400779B - Preparation method of phenolic hydroxyl self-polymerization hydrogel - Google Patents
Preparation method of phenolic hydroxyl self-polymerization hydrogel Download PDFInfo
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- CN109400779B CN109400779B CN201811201529.4A CN201811201529A CN109400779B CN 109400779 B CN109400779 B CN 109400779B CN 201811201529 A CN201811201529 A CN 201811201529A CN 109400779 B CN109400779 B CN 109400779B
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a preparation method of phenolic hydroxyl self-polymerization hydrogel, belonging to the technical field of biological materials; according to the invention, specific metal ions and organic matters containing phenolic hydroxyl groups are subjected to redox reaction to generate quinone radical free radicals, and meanwhile, the complexes formed by the specific metal ions and the organic matters containing phenolic hydroxyl groups are used for synergistically and efficiently catalyzing persulfate to generate hydroxyl free radicals, and finally, double bonds of double-bond compounds are opened to polymerize to form a hydrogel network; the metal ion-phenolic hydroxyl complex catalytic system can form hydrogel through self-catalysis by generating quinone radical, is different from the traditional chemical crosslinking process, enables a crosslinking network to be homogenized, provides a brand new theory and thought for the polymerization of the hydrogel, does not need to add a crosslinking agent, an auxiliary agent and auxiliary conditions, and has high gelling rate and good gelling effect.
Description
Technical Field
The invention relates to the technical field of biological materials, in particular to a preparation method of phenolic hydroxyl self-polymerization hydrogel.
Background
The hydrogel has good biocompatibility and water permeability, and hydrogel materials with different microstructures and performances can be obtained through artificial synthesis; these properties allow the hydrogel to find wide application in the biomedical field; however, the traditional double-bond hydrogel has difficulty in double-bond polymerization and needs to be completed under the action of a crosslinking agent, an auxiliary agent or auxiliary ultraviolet irradiation.
Secondly, the commonly used auxiliary agent NNNN-tetramethylethylenediamine for traditional hydrogel such as polyacrylamide polymerization has certain toxicity and pollutions to the environment, and polyacrylic acid polymerization needs a cross-linking agent and can be completed under the catalysis of ultraviolet light; on one hand, the double-bond hydrogel has the problems of difficult polymerization and complex conditions; on the other hand, the traditional hydrogel has more or less defects in the preparation process, so that the hydrogel cannot well meet the application of the existing biology and engineering.
Disclosure of Invention
The invention provides a preparation method of phenolic hydroxyl self-polymerization hydrogel capable of self-polymerizing synthetic gel without using a cross-linking agent and an auxiliary agent.
The technical scheme adopted by the invention is as follows:
a preparation method of phenolic hydroxyl self-polymerization hydrogel comprises the following steps:
step 1: adding a phenolic hydroxyl compound into a metal ion aqueous solution, wherein the molar ratio of the phenolic hydroxyl compound to the metal ion is 2-35: 1;
step 2: adding a double-bond compound solution with the mass concentration of 15-45% into the mixed solution obtained in the step 1, wherein the volume of the double-bond compound solution accounts for 15-30% of that of the mixed solution obtained in the step 1; uniformly stirring to obtain a mixed solution A;
and step 3: and (3) adding an initiator into the mixed solution A obtained in the step (2), uniformly mixing, and then carrying out self-polymerization to obtain the required hydrogel.
Further, the phenolic hydroxyl group-containing compound in step 1 is one of phenol, dopamine, resorcinol, catechol, tannic acid and lignin.
Further, the metal ion is one of ferric ion, cobalt ion, nickel ion, divalent silver ion, zirconium ion and strontium ion.
Further, the double-bond compound is one of acrylic acid, acrylamide, hydroxyethyl methacrylate, allyl alcohol, N-isopropyl acrylamide, vinyl pyrrolidone and 2-acrylamido-2-methylpropanesulfonic acid.
Further, the initiator is one of ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoic acid peroxide, benzoyl tert-butyl peroxide and methyl ethyl ketone peroxide.
Further, the self-polymerization reaction in the step 3 is carried out at the temperature of 4-50 ℃, and the reaction time is 5 s-1 min.
Further, the concentration of the phenolic hydroxyl compound-containing solution in the step 1 is 0.1-5 mol/L, and the concentration of the metal ions in the mixed solution in the step 1 is 0.1-10 mol/L.
Further, the addition amount of the initiator in the step 3 is 0.001-0.03 mg added in each liter of the mixed solution A.
The invention has the beneficial effects that:
(1) the invention can self-polymerize a compound containing double bonds, metal ions and an organic matter containing phenolic hydroxyl groups into glue only by using an initiator without other auxiliary conditions;
(2) the invention needs to use the cross-linking agent and the auxiliary agent, is green, convenient and quick, has the gelling time of between 3 and 20 seconds, and can rapidly gel at low temperature;
(3) the raw materials used in the invention, such as the organic matter containing phenolic hydroxyl, metal ions, the initiator and the monomer containing double bonds, have no toxicity and good biocompatibility.
Drawings
FIG. 1 is a graph showing the compressive stress-strain curves of examples 1-4 of the present invention with different mass of iron ions added.
FIG. 2 is a graph showing tensile stress-strain curves of examples 1 to 4 of the present invention with different amounts of iron ions added.
FIG. 3 is an SEM photograph of a hydrogel prepared in example 1 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Step 1: adding a phenolic hydroxyl compound into a metal ion aqueous solution, wherein the molar ratio of the phenolic hydroxyl compound to the metal ion is 2-35: 1;
the concentration of the phenolic hydroxyl compound-containing solution is 0.1-5 mol/L, and the concentration of metal ions in the mixed solution in the step 1 is 0.1-10 mol/L; the phenolic hydroxyl compound is one of phenol, dopamine, resorcinol, catechol, tannic acid and lignin; the metal ion is one of ferric ion, cobalt ion, nickel ion, divalent silver ion, zirconium ion and strontium ion.
Step 2: adding a double-bond compound solution with the mass concentration of 15-45% into the mixed solution obtained in the step 1, wherein the volume of the double-bond compound solution accounts for 15-30% of that of the mixed solution obtained in the step 1; uniformly stirring to obtain a mixed solution A;
the double-bond compound is one of acrylic acid, acrylamide, hydroxyethyl methacrylate, allyl alcohol, N-isopropyl acrylamide, vinyl pyrrolidone and 2-acrylamide-2-methylpropanesulfonic acid.
And step 3: adding an initiator into the mixed solution A obtained in the step 2, uniformly mixing, and then carrying out self-polymerization to obtain the required hydrogel;
the addition amount of the initiator is 0.001-0.03 mg added in each liter of the mixed solution A; the initiator is one of ammonium persulfate, potassium persulfate, hydrogen peroxide, benzoic acid peroxide, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide; the self-polymerization reaction is carried out at the temperature of 4-50 ℃, and the reaction time is 5 s-1 min.
Example 1
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.06g of ferric chloride hexahydrate, uniformly stirring, and standing for 10 s; adding 2.7ml of acrylic acid, stirring uniformly, adding 0.015g of ammonium persulfate, stirring uniformly, and standing to form the gel.
The hydrogel structure is shown in fig. 3, and it can be seen from the figure that the hydrogel has a uniform porous structure inside, a smooth sheet-like structure and good internal crosslinking distribution.
Example 2
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.10g of ferric chloride hexahydrate, uniformly stirring, and standing for 10 s; adding 2.7ml of acrylic acid, stirring uniformly, adding 0.015g of ammonium persulfate, stirring uniformly, and standing to form the gel.
Example 3
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.08g of ferric chloride hexahydrate, uniformly stirring, and standing for 10 s; adding 2.7ml of acrylic acid, stirring uniformly, adding 0.015g of ammonium persulfate, stirring uniformly, and standing to form the gel.
Example 4
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.04g of ferric chloride hexahydrate, uniformly stirring, and standing for 10 s; adding 2.7ml of acrylic acid, stirring uniformly, adding 0.015g of ammonium persulfate, stirring uniformly, and standing to form the gel.
Examples 1-4 the compressive properties of the hydrogels prepared are shown in figure 1 and the tensile properties in figure 2; in the figure, A is the hydrogel prepared in example 1, B is the hydrogel prepared in example 2, C is the hydrogel prepared in example 3, and D is the hydrogel prepared in example 4.
It can be seen from the figure that hydrogels with different iron ion contents have different compressive and tensile properties; the compression performance of the iron ions with lower concentration is poor, and the iron ions with higher concentration become brittle due to overlarge crosslinking density; the hydrogel prepared in example 1 exhibited the most excellent tensile properties; the compression performance is also the most excellent; the required mechanical properties can be obtained by adjusting the content of iron ions.
Example 5
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.09g of strontium nitrate, uniformly stirring, and standing for 10 s; adding 2.7ml of acrylic acid, stirring uniformly, adding 0.015g of ammonium persulfate, stirring uniformly, and standing to form the gel.
Example 6
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.06g of silver nitrate, uniformly stirring, and standing for 10 s; adding 2.7ml of acrylic acid, stirring uniformly, adding 0.015g of ammonium persulfate, stirring uniformly, and standing to form the gel.
Example 7
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.06g of nickel nitrate, uniformly stirring, and standing for 10 s; adding 2.7ml of acrylic acid, stirring uniformly, adding 0.015g of potassium persulfate, stirring uniformly, and standing to form the gel.
Example 8
Adding 0.003g of catechol into 7ml of aqueous solution containing 0.004g of nickel nitrate, uniformly stirring, and standing for 10 s; adding 2.6g of acrylamide, stirring uniformly, adding 0.015g of potassium persulfate, stirring uniformly, and standing to form the gel.
Example 9
Adding resorcinol 0.003g into 10ml of water solution containing cobalt nitrate 0.004g, stirring uniformly, and standing for 10 s; adding 2.6g of acrylic acid, stirring uniformly, adding 0.015g of potassium persulfate, stirring uniformly, and standing to form the gel.
Example 10
Adding 0.003g of tannic acid into 10ml of aqueous solution containing 0.06g of nickel nitrate, uniformly stirring, and standing for 10 s; adding 2.6ml of acrylic acid, stirring uniformly, adding 0.015g of potassium persulfate, stirring uniformly, and standing to form the gel.
Example 11
Adding 0.003g of dopamine into 10ml of aqueous solution containing 0.004g of ferric chloride hexahydrate, uniformly stirring, and standing for 10 s; adding 2.6g of acrylamide, stirring uniformly, adding 0.015g of potassium persulfate, stirring uniformly, and standing to form the gel.
Example 12
Adding resorcinol 0.003g into 10ml of water solution containing cobalt nitrate 0.06g, stirring uniformly, and standing for 10 s; adding 2.6ml of acrylic acid, stirring uniformly, adding 0.015g of sodium persulfate, stirring uniformly, and standing to form the gel.
Observing the color change of the solution in the reaction process, the solution added with ferric chloride is light orange, and can initially become dark green when dopamine is added and become orange after standing for a few seconds; the solution turned reddish-brown after the addition of acrylic acid.
According to the invention, specific metal ions and organic matters containing phenolic hydroxyl groups are subjected to redox reaction to generate quinone radical free radicals, and meanwhile, the complex formed by the specific metal ions and the organic matters containing phenolic hydroxyl groups is used for efficiently catalyzing persulfate to generate hydroxyl free radicals in a synergistic manner; finally opening the double bonds of the double-bond compound to polymerize to form a hydrogel network; the method is different from the traditional chemical crosslinking process, so that the crosslinking network is homogenized, and a brand new theory and thought are provided for the polymerization of the hydrogel; the self-polymerization glue can be formed by self-polymerizing only an initiator, a double-bond monomer, specific metal ions and an organic matter containing phenolic hydroxyl groups, other auxiliary conditions are not needed, a cross-linking agent and an auxiliary agent are not used, and the self-polymerization glue is green, convenient and quick. The gelling time is between 3 and 20 seconds, and the gel can be rapidly gelled under the condition of low temperature; the used reagents of the organic matter containing phenolic hydroxyl, the specific metal ions, the initiator and the double bond monomer are nontoxic and have good biocompatibility.
Claims (5)
1. A preparation method of phenolic hydroxyl self-polymerization hydrogel is characterized by comprising the following steps:
step 1: adding a phenolic hydroxyl compound into a metal ion aqueous solution, wherein the molar ratio of the phenolic hydroxyl compound to the metal ion is 2-35: 1;
step 2: adding a double-bond compound solution with the mass concentration of 15-45% into the mixed solution obtained in the step 1, wherein the volume of the double-bond compound solution accounts for 15-30% of that of the mixed solution obtained in the step 1; uniformly stirring to obtain a mixed solution A;
and step 3: adding an initiator into the mixed solution A obtained in the step 2, uniformly mixing, and then carrying out self-polymerization to obtain the required hydrogel; in the step 1, the phenolic hydroxyl compound is one of dopamine, resorcinol, catechol and tannic acid;
the metal ions are one of ferric ions, cobalt ions, nickel ions, divalent silver ions and strontium ions; the double-bond compound is one of acrylic acid and acrylamide.
2. The method of claim 1, wherein the initiator is one of ammonium persulfate and potassium persulfate.
3. The method for preparing the phenolic hydroxyl self-polymerized hydrogel according to claim 1, wherein the self-polymerization reaction in the step 3 is carried out at 4-50 ℃ for 5 s-1 min.
4. The method for preparing the phenolic hydroxyl self-polymerized hydrogel according to claim 1, wherein the concentration of the phenolic hydroxyl compound-containing solution in the step 1 is 0.1 to 5mol/L, and the concentration of the metal ions in the mixed solution in the step 1 is 0.1 to 10 mol/L.
5. The method for preparing the phenolic hydroxyl self-polymerized hydrogel according to claim 1, wherein the amount of the initiator added in the step 3 is 0.001-0.03 mg per liter of the mixed solution A.
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| CN112824439A (en) * | 2019-11-20 | 2021-05-21 | 山东百多安医疗器械股份有限公司 | Self-repairing antibacterial conductive hydrogel and preparation method thereof |
| CN111363072A (en) * | 2020-03-06 | 2020-07-03 | 西南交通大学 | Preparation method of hydrogel based on polyphenol-silver nanoenzyme with plasma effect |
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| CN112661981B (en) * | 2020-12-11 | 2022-08-02 | 齐鲁工业大学 | Multifunctional hydrogel triggered by lignin phenolic resin silver-loaded nanospheres and preparation method and application thereof |
| CN114276562B (en) * | 2020-12-14 | 2023-05-23 | 南京工业大学 | Method for preparing hydrogel based on metal coordination physical mixing and hydrogel |
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| CN114773508B (en) * | 2022-04-29 | 2023-10-24 | 南京邮电大学 | Supermolecule hydrogel and preparation and application thereof |
| CN114805858B (en) * | 2022-05-25 | 2024-05-28 | 浙江农林大学 | Wide-temperature-range high-strength conductive composite hydrogel and preparation method and application thereof |
| CN115850560B (en) * | 2022-12-14 | 2023-12-12 | 吉林大学 | Preparation method of molecularly imprinted hydrogel based on metal autocatalysis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015153996A1 (en) * | 2014-04-03 | 2015-10-08 | Micro Vention, Inc. | Embolic devices |
| CN107163185A (en) * | 2017-05-25 | 2017-09-15 | 华南理工大学 | It is a kind of can spontaneous driving dopamine gel driver and preparation method thereof and type of drive |
| CN108264611A (en) * | 2018-01-30 | 2018-07-10 | 江汉大学 | A kind of preparation method from the superpower hydrogel of adherency |
-
2018
- 2018-10-16 CN CN201811201529.4A patent/CN109400779B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015153996A1 (en) * | 2014-04-03 | 2015-10-08 | Micro Vention, Inc. | Embolic devices |
| CN107163185A (en) * | 2017-05-25 | 2017-09-15 | 华南理工大学 | It is a kind of can spontaneous driving dopamine gel driver and preparation method thereof and type of drive |
| CN108264611A (en) * | 2018-01-30 | 2018-07-10 | 江汉大学 | A kind of preparation method from the superpower hydrogel of adherency |
Non-Patent Citations (2)
| Title |
|---|
| "Marine bioinorganic materials: mussels pumping iron";Jonathan J Wilker;《Current Opinion in Chemical Biology》;20091228;第14卷(第2期);第276–283页 * |
| "木质素基聚丙烯酸多孔水凝胶的制备及性能研究";孙亚杰;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180515;B016-313 * |
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