CN111825793A - Double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel and preparation method thereof - Google Patents
Double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
- 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
Abstract
The invention relates to a preparation method of a mussel-like high-adhesion hydrogel based on double-bonded eugenol crosslinking, wherein the hydrogel is obtained by crosslinking double-bonded eugenol by taking acrylamide as a main monomer, ammonium persulfate as an initiator and dopamine methacrylamide as a high-adhesion comonomer; the invention aims to solve the problems that the existing hydrogel has low adhesion strength in an underwater environment and a nonrenewable petroleum-based crosslinking agent is used. The preparation method comprises the following steps: (1) preparing dopamine methacrylamide; (2) preparing double-bonded eugenol; (3) and (3) preparing the double-bonded eugenol cross-linked mussel-like high-adhesion hydrogel. According to the invention, the underwater adhesion strength of the hydrogel is improved by introducing the dopamine methacrylamide high-adhesion comonomer, and the mechanical strength of the hydrogel is improved by using double-bonded eugenol as a biomass-based crosslinking agent, so that the mussel-like hydrogel with good mechanical strength and underwater adhesion is finally obtained.
Description
Technical Field
The invention belongs to the field of hydrogel and preparation thereof, and particularly relates to a preparation method of double-bonded eugenol crosslinked mussel-imitated high-adhesion hydrogel.
Background
Hydrogel is a material with excellent biocompatibility, has a three-dimensional cross-linked structure similar to extracellular matrix in a human body, has excellent physicochemical properties and biological properties such as certain strength, unique water absorption and retention capacity, controllable drug release, good biological adhesion and biocompatibility and the like, and is widely applied to the fields of wound dressings, drug controlled release materials, adhesives and the like. At present, the existing hydrogel adhesive has the defects of poor mechanical strength, poor adhesive property, obvious reduction of adhesive property in water environment and even loss of adhesive force, so that the application range of the hydrogel adhesive is greatly limited. Therefore, there is a strong need to improve the mechanical strength of hydrogels and to impart underwater adhesion thereto in order to expand the application fields of hydrogel adhesives.
In recent years, excessive use of petroleum-based resources has brought about serious problems of environmental pollution and resource exhaustion. Thus, the development of biomass-based crosslinking agents has received increasing attention from researchers. The eugenol as a biomass-based compound has the advantages of low cost and wide source. However, the allylic double bond contained in the eugenol is low in activity, and the phenolic hydroxyl group of the eugenol has a polymerization inhibition effect, so that the eugenol is difficult to perform self polymerization.
The adhesive protein of marine mussels has an ultra-strong underwater adhesion effect so that the marine mussels can be firmly adhered to the surfaces of various substrates. Research shows that the super-strong adhesive capacity of the mussel is related to 3, 4-Dihydroxyphenylalanine (DOPA) in adhesive protein secreted by byssus thereof, and the DOPA serving as a main functional group of the mussel adhesive protein can form interaction with different matrix materials to show very strong adhesive capacity. However, natural mussels have low content of adhesive protein and poor water solubility, and the direct extraction of adhesive protein is complicated and costly, and is difficult to apply and popularize.
Disclosure of Invention
For the problem that eugenol is difficult to self-polymerize, phenolic hydroxyl in eugenol can be converted into methacrylate groups with higher activity, so that double-bonded eugenol (ME) is introduced into a hydrogel system, and a rigid benzene ring on the structure of the double-bonded eugenol and two double bonds on the structure of the double-bonded eugenol are copolymerized with double bonds on acrylamide and dopamine methacrylamide structures respectively to endow the hydrogel with higher mechanical strength. The extraction operation of the adhesive protein of the natural mussel is complex and the cost is high, and the Dopamine Methacrylamide (DMA) with catechol groups and amino groups can be used as a precursor of the mussel adhesive protein by simulating the molecular structure of the mussel adhesive protein and is introduced into a Polyacrylamide (PAM) hydrogel system to endow the hydrogel with good underwater adhesion property. The structure of the prepared hydrogel is shown as the following formula, and the formula (1) is the structural formula (DMA-ME-PAM) of the hydrogel:
the invention provides a preparation method of double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel, which aims to solve the problems of poor mechanical strength, low bonding strength and obvious reduction and even loss of adhesion in a water environment of the conventional hydrogel adhesive. According to the method, double-bonded eugenol is used as a biomass crosslinking agent, and the hydrogel with good underwater bonding performance and mechanical strength is prepared by performing free radical copolymerization reaction on acrylamide and dopamine methacrylic anhydride under a neutral condition.
The technical scheme adopted by the invention is as follows:
the invention provides a mussel-imitated high-adhesion hydrogel which is environment-friendly, good in mechanical property and has underwater adhesion, and is prepared by using double-bonded eugenol as a biomass-based cross-linking agent and dopamine methacrylamide as a high-adhesion copolymerization functional monomer.
The hydrogel is obtained by free radical polymerization by using acrylamide as a main monomer, dopamine methacrylamide as a high-adhesion comonomer, double-bonded eugenol as a cross-linking agent and ammonium persulfate as an initiator.
Further, the method comprises the following steps:
mixing 10-30 parts of dopamine methacrylamide, 5-15 parts of double-bonded eugenol and 2400 parts of acetone solution in parts by mass, and fully stirring to obtain a solution A; dissolving 100-400 parts of acrylamide in 300-900 parts of neutral deionized water to obtain a solution B; and uniformly mixing the solution A and the solution B, adding 3-9 parts of ammonium persulfate, stirring for 30-60min, and fully reacting to obtain the ammonium persulfate/ammonium persulfate composite material.
The high-adhesion comonomer dopamine methacrylamide is obtained by introducing double-bond methacrylic anhydride into dopamine hydrochloride through amidation reaction.
The double-bonded eugenol is obtained by esterification reaction of biomass-based eugenol and methacrylic anhydride.
More specifically, the following steps may be included:
the method comprises the following steps: preparation of dopamine methacrylamide
According to the mass portion, 10-30 portions of sodium tetraborate and 4-12 portions of sodium bicarbonate are dissolved in 100 portions of deionized water and 300 portions of deionized water, then the mixture is placed in a reactor at 25 ℃, and N is introduced under the condition of good air tightness2Reacting for 30-60min, adding 5-15 parts of dopamine hydrochloride into a reactor, slowly dropwise adding a mixed solution of methacrylic anhydride and tetrahydrofuran (in the process, dropwise adding 1mol/L sodium hydroxide aqueous solution to control the pH to be more than 8.0), and continuously introducing N2Reacting for 14-18h, washing the generated suspension twice with ethyl acetate, then adjusting the pH to 1.0-3.0 with 6mol/L hydrochloric acid aqueous solution, extracting for 3 times with ethyl acetate, drying the three organic phases with anhydrous magnesium sulfate, filtering, adding the obtained filtrate into n-hexane for settling and stirring, standing overnight at 4 ℃, and drying in vacuum to obtain dopamine methacrylamide.
Step two: preparation of double-bonded eugenol
Adding 20-60 parts of eugenol into a reactor according to the mass fraction, and introducing N under the condition of good air tightness2Reacting for 2-3h to remove O2And moisture. Slowly dropping methacrylic anhydride into the reactor, gradually raising the temperature to 40-60 ℃, and continuously introducing N2And reacting for 24 hours. The product from the reactor was transferred to a beaker, to which was added 2 to 4 volumes of dichloromethane to dilute the product. And adding a sodium bicarbonate aqueous solution with the volume 4 times that of the product into the beaker to wash the product with water, and repeatedly washing for 5-6 times until no bubbles are generated in the beaker. The organic layer in the beaker was washed with 1.0mol/L aqueous sodium hydroxide solution, 0.5mol/L aqueous sodium hydroxide solution, and 1.0mol/L hydrochloric acid solution in this order. Adding excessive anhydrous magnesium sulfate to dry the product, filtering, distilling under reduced pressure, and drying in an oven at 40-80 ℃ overnight to obtain the double-bonded eugenol.
Step three: preparation of double-bonded eugenol crosslinked mussel-imitated high-adhesion hydrogel.
Dissolving 10-30 parts of dopamine methacrylamide and 5-15 parts of double-bonded eugenol in 800-2400 parts of acetone solution by mass percent, and fully stirring until the dopamine methacrylamide and the double-bonded eugenol are completely dissolved to obtain a solution A; dissolving 100-400 parts of acrylamide in 300-900 parts of neutral deionized water to obtain a solution B; and mixing the solution A and the solution B, uniformly stirring, adding 3-9 parts of ammonium persulfate, stirring for 30-60min, and fully reacting to obtain the double-bonded eugenol crosslinked mussel-imitated high-adhesion hydrogel.
In the first step, the volume ratio of the methacrylic anhydride to the tetrahydrofuran mixed solution is 1: 5.
In the second step, the mass ratio of the eugenol to the methacrylic anhydride is 2: 1.
In the third step, solvents of dopamine methacrylamide and double-bonded eugenol are anhydrous acetone; the reaction temperature is 60-80 ℃, and the reaction time is 3-4 h.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a preparation method of a double-bonded eugenol crosslinked mussel-like hydrogel, wherein a method for copolymerizing dopamine methacrylamide, double-bonded eugenol and acrylamide is adopted in the preparation process, the double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel can be obtained under mild conditions by adjusting the curing reaction conditions, and the used raw material acrylamide has the characteristics of low price, easiness in obtaining and wide application, and the preparation method is simple, the preparation conditions are mild, and the popularization and application prospects are realized.
(2) The double-bonded eugenol crosslinked mussel-like hydrogel prepared by the method utilizes good underwater adhesion of dopamine on one hand and reaction activity of unsaturated carbon-carbon double bonds in double-bonded eugenol on the other hand, so that the prepared hydrogel has good underwater adhesion and mechanical strength.
(3) The double-bonded eugenol crosslinked mussel-like hydrogel prepared by the invention can effectively regulate and control the adhesiveness and mechanical property of the gel by regulating the proportion of the adhesion functional monomer dopamine methacrylamide, the crosslinking agent double-bonded eugenol and a matrix acrylamide copolymerization system, and the hydrogel has better adhesiveness to aluminum plates, glass, polyethylene plastics, hardboards and birch boards in a water environment.
Detailed Description
The present invention will be described in detail with reference to specific embodiments. These examples are intended to further illustrate features and advantages of the present invention, and are not intended to limit the claims of the present invention.
The invention relates to a preparation method of double-bonded eugenol crosslinked mussel-imitated adhesive hydrogel, which takes acrylamide as a raw material, dopamine methacrylic anhydride as an adhesive functional monomer and double-bonded eugenol as a crosslinking agent to prepare the hydrogel with obviously improved underwater adhesive property and mechanical strength.
Example 1:
the method comprises the following steps: preparation of dopamine methacrylamide
Weighing 5g of sodium tetraborate and 2g of sodium bicarbonate, dissolving in 50mL of deionized water, placing in a reactor at 25 ℃, and introducing N under the condition of good air tightness2Reacting for 30min, adding 2.5g dopamine hydrochloride into the reactor, slowly dropwise adding a mixed solution of 2.35mL methacrylic anhydride and 11.75mL tetrahydrofuran (in the process, dropwise adding 1mol/L sodium hydroxide aqueous solution to control the pH to be more than 8.0), and continuously introducing N2The reaction was carried out for 16h, and the resulting suspension was washed with ethyl acetate twiceAdjusting the pH value to 1.0-3.0 by using 6mol/L hydrochloric acid aqueous solution, extracting for 3 times by using ethyl acetate, drying the three organic phases by using anhydrous magnesium sulfate, carrying out suction filtration, adding the obtained filtrate into n-hexane, settling and stirring, standing overnight at 4 ℃, and carrying out vacuum drying to obtain the dopamine methacrylamide.
Step two: preparation of double-bonded eugenol
Weighing 20g of eugenol, adding into a reactor, and introducing N under the condition of good air tightness2Reacting for 2h to remove O2And moisture. Weighing 10g of methacrylic anhydride, slowly dropping the methacrylic anhydride into the reactor, gradually increasing the temperature to 50 ℃, and continuously introducing N2And reacting for 24 hours. The product from the reactor was transferred to a beaker, where it was diluted by adding 2 times the volume of the product in dichloromethane. And adding a sodium bicarbonate aqueous solution with the volume 4 times that of the product into the beaker to wash the product with water, and repeatedly washing for 5-6 times until no bubbles are generated in the beaker. The organic layer in the beaker was washed with 1.0mol/L aqueous sodium hydroxide solution, 0.5mol/L aqueous sodium hydroxide solution, and 1.0mol/L hydrochloric acid solution in this order. And adding excessive anhydrous magnesium sulfate to dry the product, filtering, and carrying out reduced pressure distillation operation to obtain a pure product. The resulting pure product was placed in an oven at 50 ℃ and dried overnight to double bonded eugenol.
Step three: preparation of double-bonded eugenol crosslinked mussel-like adhesive hydrogel adhesive.
Weighing 0.5g of dopamine methacrylamide in the step one and 0.205g of double-bonded eugenol in the step two, dissolving in 8mL of acetone solution, fully stirring until the dopamine methacrylamide and the double-bonded eugenol are completely dissolved to obtain a solution A, dissolving 6.13g of acrylamide in 12mL of neutral deionized water to obtain a solution B, mixing the solution A and the solution B, uniformly stirring, adding 0.164g of ammonium persulfate, stirring for 30min, and placing the mixed solution at 60 ℃ for reaction for 3-4h to obtain the double-bonded eugenol crosslinked mussel adhesive hydrogel adhesive.
Example 2:
the method comprises the following steps: preparation of dopamine methacrylamide
10g of sodium tetraborate and 4g of sodium bicarbonate are weighed out and dissolved in 100mL of deionized water,placing in a reactor at 25 deg.C, introducing N under good air tightness230min, adding 5g dopamine hydrochloride into the reactor, slowly dropwise adding a mixed solution of 4.7mL methacrylic anhydride and 23.5mL tetrahydrofuran (in the process, dropwise adding 1mol/L sodium hydroxide aqueous solution to control the pH to be more than 8.0), and continuously introducing N2Reacting for 16h, washing the generated suspension twice with ethyl acetate, then adjusting the pH to 1.0-3.0 with 6mol/L hydrochloric acid aqueous solution, extracting for 3 times with ethyl acetate, drying the three organic phases with anhydrous magnesium sulfate, filtering, adding the obtained filtrate into n-hexane for settling and stirring, standing overnight at 4 ℃, and drying in vacuum to obtain dopamine methacrylamide.
Step two: preparation of double-bonded eugenol
Weighing 20g of eugenol, adding into a reactor, and introducing N under the condition of good air tightness2Reacting for 2h to remove O2And moisture. Weighing 10g of methacrylic anhydride, slowly dropping the methacrylic anhydride into the reactor, gradually increasing the temperature to 50 ℃, and continuously introducing N2And reacting for 24 hours. The stirring was stopped, the product from the reactor was transferred to a beaker, and the product was diluted by adding dichloromethane in a volume 2 times the volume of the product. And adding a sodium bicarbonate aqueous solution with the volume 4 times that of the product into the beaker to wash the product with water, and repeatedly washing for 5-6 times until no bubbles are generated in the beaker. The organic layer in the beaker was washed with 1.0mol/L aqueous sodium hydroxide solution, 0.5mol/L aqueous sodium hydroxide solution, and 1.0mol/L hydrochloric acid solution in this order. And adding excessive anhydrous magnesium sulfate to dry the product, filtering, and carrying out reduced pressure distillation operation to obtain a pure product. The resulting pure product was placed in an oven at 50 ℃ and dried overnight to double bonded eugenol.
Step three: preparation of double-bonded eugenol crosslinked mussel-like adhesive hydrogel adhesive.
Weighing 1g of dopamine methacrylamide in the step one and 0.205g of double-bonded eugenol in the step two, dissolving in 15mL of acetone solution, fully stirring until the dopamine methacrylamide and the double-bonded eugenol are completely dissolved to obtain a solution A, dissolving 6.13g of acrylamide in 12mL of neutral deionized water to obtain a solution B, mixing the solution A and the solution B, uniformly stirring, adding 0.164g of ammonium persulfate, stirring for 30min, and placing the mixed solution at 60 ℃ for reaction for 3-4h to obtain the double-bonded eugenol crosslinked mussel-like adhesive hydrogel adhesive.
Example 3:
the method comprises the following steps: preparation of dopamine methacrylamide
Weighing 10g of sodium tetraborate and 4g of sodium bicarbonate, dissolving in 100mL of deionized water, placing in a reactor at 25 ℃, and introducing N under the condition of good air tightness230min, adding 5g dopamine hydrochloride into the reactor, slowly dropwise adding a mixed solution of 4.7mL methacrylic anhydride and 23.5mL tetrahydrofuran (in the process, dropwise adding 1mol/L sodium hydroxide aqueous solution to control the pH to be more than 8.0), and continuously introducing N2Reacting for 16h, washing the generated suspension twice with ethyl acetate, then adjusting the pH to 1.0-3.0 with 6mol/L hydrochloric acid aqueous solution, extracting for 3 times with ethyl acetate, drying the three organic phases with anhydrous magnesium sulfate, filtering, adding the obtained filtrate into n-hexane for settling and stirring, standing overnight at 4 ℃, and drying in vacuum to obtain dopamine methacrylamide.
Step two: preparation of double-bonded eugenol
Weighing 20g of eugenol, adding into a reactor, and introducing N under the condition of good air tightness2Reacting for 2h to remove O2And moisture. Weighing 10g of methacrylic anhydride, slowly dropping the methacrylic anhydride into the reactor, gradually increasing the temperature to 50 ℃, and continuously introducing N2And reacting for 24 hours. The stirring was stopped, the product from the reactor was transferred to a beaker, and the product was diluted by adding dichloromethane in a volume 2 times the volume of the product. And adding a sodium bicarbonate aqueous solution with the volume 4 times that of the product into the beaker to wash the product with water, and repeatedly washing for 5-6 times until no bubbles are generated in the beaker. The organic layer in the beaker was washed with 1.0mol/L aqueous sodium hydroxide solution, 0.5mol/L aqueous sodium hydroxide solution, and 1.0mol/L hydrochloric acid solution in this order. And adding excessive anhydrous magnesium sulfate to dry the product, filtering, and carrying out reduced pressure distillation operation to obtain a pure product. The resulting pure product was placed in an oven at 50 ℃ and dried overnight to double bonded eugenol.
Step three: preparation of double-bonded eugenol crosslinked mussel-like adhesive hydrogel adhesive.
Weighing 1g of dopamine methacrylamide in the step one and 0.4g of double-bonded eugenol in the step two, dissolving in 15mL of acetone solution, fully stirring until the dopamine methacrylamide and the double-bonded eugenol are completely dissolved to obtain a solution A, dissolving 6.13g of acrylamide in 12mL of neutral deionized water to obtain a solution B, mixing the solution A and the solution B, uniformly stirring, adding 0.164g of ammonium persulfate, stirring for 30min, and placing the mixed solution at 60 ℃ for reaction for 3-4h to obtain the double-bonded eugenol crosslinked mussel-like adhesive hydrogel adhesive.
Comparative example 1:
compared with example 1, the present comparative example is different from example 1 in that "dopamine methacrylamide" in the first step of example 1 is replaced by "dopamine hydrochloride which is not modified by double bonding", specifically, the first step of example 1 is omitted, and the third step is adjusted as follows: weighing 0.5g of dopamine hydrochloride and 0.205g of doubly-bonded eugenol, dissolving in 8mL of acetone solution, fully stirring until the dopamine hydrochloride and the doubly-bonded eugenol are completely dissolved to obtain solution A, dissolving 6.13g of acrylamide in 12mL of neutral deionized water to obtain solution B, mixing the solution A and the solution B, uniformly stirring, adding 0.164g of ammonium persulfate, stirring for 30min, and placing the mixed solution at 60 ℃ for reaction for 3-4h to obtain the doubly-bonded eugenol crosslinked mussel-like adhesive hydrogel adhesive.
Comparative example 2:
this comparative example is compared to example 2, except that the dopamine methacrylamide component of example 2 was omitted and a double-bonded eugenol crosslinked polyacrylamide hydrogel was prepared. Specifically, the first step in embodiment 2 is omitted, and the third step is adjusted to: weighing 0.205g of double-bonded eugenol, dissolving in 15mL of acetone solution, fully stirring until the double-bonded eugenol is completely dissolved to obtain solution A, dissolving 6.13g of acrylamide in 12mL of neutral deionized water to obtain solution B, mixing the solution A with the solution B, uniformly stirring, adding 0.164g of ammonium persulfate, stirring for 30min, and reacting the mixed solution at 60 ℃ for 3-4h to obtain the double-bonded eugenol crosslinked polyacrylamide hydrogel.
Comparative example 3:
compared with the embodiment 3, the comparative example is different from the embodiment 3 in that the double bond eugenol of the cross-linking agent in the embodiment 3 is omitted, specifically, the step two in the embodiment 3 is omitted, and the step three is adjusted as follows: weighing 1g of dopamine methacrylamide, dissolving the dopamine methacrylamide in 15mL of acetone solution, fully stirring until the dopamine methacrylamide is completely dissolved to obtain solution A, dissolving 6.13g of acrylamide in 12mL of neutral deionized water to obtain solution B, mixing the solution A and the solution B, uniformly stirring, adding 0.164g of ammonium persulfate, stirring for 30min, and reacting the mixed solution at 60 ℃ for 3-4h to obtain the mussel-like adhesive hydrogel adhesive.
The hydrogel prepared in examples 1 to 3 and comparative examples 1 to 3 was subjected to the adhesion weight test: the results are shown in the attached Table 1 (mechanical properties of six hydrogels)
Attached table 1
Note: the hydrogel in the three embodiments has better adhesion to aluminum plates, glass, polyethylene plastics, hardboards and birch boards.
As can be seen from the attached Table 1, the hydrogel prepared by performing double-bonding modification on dopamine hydrochloride in example 1 has better comprehensive properties than the hydrogel prepared by using unmodified dopamine hydrochloride in comparative example 1;
compared with the comparative example 2 (dopamine methacrylamide is not used), the adhesive functional monomer dopamine methacrylamide is introduced into the hydrogel system, so that the toughness of the prepared hydrogel is obviously improved, and the hydrogel is endowed with good adhesion at room temperature and in a water environment;
example 3 compared with comparative example 3 (without using the cross-linking agent double-bonded eugenol), the introduction of the cross-linking agent double-bonded eugenol improves the cross-linking degree of the hydrogel system and improves the adhesive strength of the hydrogel to a certain extent.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel is characterized by comprising the following steps:
and (3) carrying out free radical polymerization reaction by using acrylamide as a main monomer, dopamine methacrylamide as a comonomer and double-bonded eugenol as a cross-linking agent to obtain the mussel-like high-adhesion hydrogel.
2. The method as claimed in claim 1, wherein the mass ratio of acrylamide, dopamine methacrylamide and double bonded eugenol is (100- & 400): (10-30): (5-15).
3. The method of claim 1, wherein the radical polymerization is a solution polymerization using an acetone-water mixed solvent.
4. The method of claim 1, comprising the steps of:
mixing 10-30 parts of dopamine methacrylamide, 5-15 parts of double-bonded eugenol and 2400 parts of acetone by mass, and fully stirring to obtain a solution A;
dissolving 100-400 parts of acrylamide in 300-900 parts of water to obtain a solution B;
and uniformly mixing the solution A and the solution B, adding 3-9 parts of ammonium persulfate, uniformly dispersing, and fully reacting under the condition of free radical polymerization.
5. The method of claim 1, wherein said dopamine methacrylamide is obtained by introducing a double bond containing methacrylic anhydride into dopamine hydrochloride via an amidation reaction.
6. The method of claim 5, wherein said dopamine methacrylamide is obtained by a method comprising the steps of:
according to the mass portion, 10-30 portions of sodium tetraborate and 4-12 portions of sodium bicarbonate are dissolved in 100 portions of deionized water and 300 portions of deionized water, then the mixture is placed in a reactor at 25 ℃, and N is introduced under the condition of good air tightness2Reacting for 30-60 min; adding 5-15 parts of dopamine hydrochloride into the reactor, slowly dropwise adding the mixed solution of methacrylic anhydride and tetrahydrofuran, controlling the pH to be more than 8.0 in the process, and continuously introducing N2Reacting for 14-18 h; washing the generated suspension twice by using ethyl acetate, and then adjusting the pH to 1.0-3.0 by using 6mol/L hydrochloric acid aqueous solution; extracting with ethyl acetate for 3 times, drying the organic phase with anhydrous magnesium sulfate, and vacuum filtering; adding the obtained filtrate into n-hexane for settling and stirring, standing overnight at 4 ℃, and drying in vacuum to obtain the dopamine methacrylamide.
7. The method of claim 1, wherein the doubly-bonded eugenol is derived from the esterification of biomass-based eugenol with methacrylic anhydride.
8. The method of claim 7, wherein the doubly-bonded eugenol is obtained by a process comprising the steps of:
adding 20-60 parts of eugenol into a reactor according to the parts by weight, and introducing N under the condition of good air tightness2Reacting for 2-3h to remove O2And moisture; slowly dropping methacrylic anhydride into the reactor, gradually raising the temperature to 40-60 ℃, and continuously introducing N2Reacting for 24 hours; transferring the product into a beaker, and adding dichloromethane with the volume 2-4 times that of the product into the beaker for dilution; adding sodium bicarbonate water solution with the volume 4 times that of the product to wash the product with water, and repeating the washing until no bubbles are generated; washing the organic layer with 1.0mol/L sodium hydroxide aqueous solution, 0.5mol/L sodium hydroxide aqueous solution and 1.0mol/L hydrochloric acid solution in sequence; adding excessive anhydrous magnesium sulfate to dry the product, filtering, distilling under reduced pressure, drying in an oven at 40-80 deg.C overnight to obtain double bondAnd (4) dissolving eugenol.
9. The method of claim 1, comprising the steps of:
dissolving 10-30 parts of dopamine methacrylamide and 5-15 parts of double-bonded eugenol in 2400 parts of acetone solution by mass, and fully stirring until the dopamine methacrylamide and the double-bonded eugenol are completely dissolved to obtain a solution A; dissolving 100-400 parts of acrylamide in 300-900 parts of neutral deionized water to obtain a solution B; and mixing the solution A and the solution B, uniformly stirring, adding 3-9 parts of ammonium persulfate, stirring for 30-60min, and fully reacting at 60-80 ℃ for 3-4h to obtain the double-bonded eugenol crosslinked mussel-imitated high-adhesion hydrogel.
10. A double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel obtainable by the process according to any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010672696.8A CN111825793B (en) | 2020-07-14 | 2020-07-14 | Double-bonded eugenol crosslinked mussel-imitated high-adhesion hydrogel and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159496A (en) * | 2020-10-13 | 2021-01-01 | 乐陵泰山人造草坪产业有限公司 | Synthetic method of artificial grass fiber surface modification functional gel |
| CN112409611A (en) * | 2020-11-17 | 2021-02-26 | 中国石油大学(华东) | Mussel bionic gel composition, self-repairing gel and plugging agent as well as preparation method and application of mussel bionic gel composition and self-repairing gel and plugging agent |
| CN113461979A (en) * | 2021-07-19 | 2021-10-01 | 吉林大学 | Preparation method of simulated mussel hydrogel catalytically crosslinked by hemoglobin |
| CN113648453A (en) * | 2021-08-12 | 2021-11-16 | 同济大学 | Conductive self-healing hydrogel with adhesiveness and preparation method thereof |
| CN114851546A (en) * | 2022-05-17 | 2022-08-05 | 中国科学院兰州化学物理研究所 | Application of 3D printing hydrogel and bionic adhesion device |
| CN115354490A (en) * | 2022-09-15 | 2022-11-18 | 深圳市歌中歌服饰有限公司 | Preparation method of fiber blended moisture-absorption and bacterium-inhibition fabric |
| CN115418854A (en) * | 2022-09-23 | 2022-12-02 | 深圳市恩裳纺织品有限公司 | High-elastic antibacterial fiber knitted fabric and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180118978A1 (en) * | 2015-05-26 | 2018-05-03 | Japan Science And Technology Agency | Catechol-containing adhesive hydrogel, composition for preparing adhesive hydrogel, and compositions each including said adhesive hydrogel |
| CN109651623A (en) * | 2018-11-20 | 2019-04-19 | 江汉大学 | Improve the method and gained polyacrylamide hydrogel of polyacrylamide hydrogel adhesion property |
| CN111072848A (en) * | 2019-12-31 | 2020-04-28 | 江西省科学院应用化学研究所 | Hydrogel with controllable viscosity and preparation method and application thereof |
-
2020
- 2020-07-14 CN CN202010672696.8A patent/CN111825793B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180118978A1 (en) * | 2015-05-26 | 2018-05-03 | Japan Science And Technology Agency | Catechol-containing adhesive hydrogel, composition for preparing adhesive hydrogel, and compositions each including said adhesive hydrogel |
| CN109651623A (en) * | 2018-11-20 | 2019-04-19 | 江汉大学 | Improve the method and gained polyacrylamide hydrogel of polyacrylamide hydrogel adhesion property |
| CN111072848A (en) * | 2019-12-31 | 2020-04-28 | 江西省科学院应用化学研究所 | Hydrogel with controllable viscosity and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YUEHONG ZHANG ET AL.: "Synthesis and Characterization of Methacrylated Eugenol as a Sustainable Reactive Diluent for a Maleinated Acrylated Epoxidized Soybean Oil Resin", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| 熊雄: "具有多巴结构单元的贻贝仿生组织粘合剂", 《中国博士学位论文全文数据库》 * |
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| CN112159496A (en) * | 2020-10-13 | 2021-01-01 | 乐陵泰山人造草坪产业有限公司 | Synthetic method of artificial grass fiber surface modification functional gel |
| CN112409611A (en) * | 2020-11-17 | 2021-02-26 | 中国石油大学(华东) | Mussel bionic gel composition, self-repairing gel and plugging agent as well as preparation method and application of mussel bionic gel composition and self-repairing gel and plugging agent |
| CN113461979A (en) * | 2021-07-19 | 2021-10-01 | 吉林大学 | Preparation method of simulated mussel hydrogel catalytically crosslinked by hemoglobin |
| CN113648453A (en) * | 2021-08-12 | 2021-11-16 | 同济大学 | Conductive self-healing hydrogel with adhesiveness and preparation method thereof |
| CN114851546A (en) * | 2022-05-17 | 2022-08-05 | 中国科学院兰州化学物理研究所 | Application of 3D printing hydrogel and bionic adhesion device |
| CN114851546B (en) * | 2022-05-17 | 2023-08-25 | 中国科学院兰州化学物理研究所 | Application of 3D printing hydrogel and bionic adhesion device |
| CN115354490A (en) * | 2022-09-15 | 2022-11-18 | 深圳市歌中歌服饰有限公司 | Preparation method of fiber blended moisture-absorption and bacterium-inhibition fabric |
| CN115354490B (en) * | 2022-09-15 | 2024-02-13 | 深圳市歌中歌服饰有限公司 | Preparation method of fiber blended moisture-absorption antibacterial fabric |
| CN115418854A (en) * | 2022-09-23 | 2022-12-02 | 深圳市恩裳纺织品有限公司 | High-elastic antibacterial fiber knitted fabric and preparation method thereof |
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