CN112480308B - Intelligent hydrogel and preparation method thereof - Google Patents
Intelligent hydrogel and preparation method thereof Download PDFInfo
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- CN112480308B CN112480308B CN202011346652.2A CN202011346652A CN112480308B CN 112480308 B CN112480308 B CN 112480308B CN 202011346652 A CN202011346652 A CN 202011346652A CN 112480308 B CN112480308 B CN 112480308B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 30
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 14
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 239000007788 liquid Substances 0.000 abstract description 16
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 Polydimethylsiloxane Polymers 0.000 description 4
- 238000003698 laser cutting Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
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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
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of material preparation, and particularly relates to an intelligent hydrogel and a preparation method thereof. The intelligent hydrogel is prepared by polymerizing hydroxyethyl methacrylate and acrylic acid through photoinitiation, is released to the surface of aqueous liquid, and can autonomously generate surface tension gradient difference on the water surface due to the water absorption process and the exchange phenomenon of hydrophilic and hydrophobic functional groups. The invention further widens the application range of the hydrogel, and is expected to be applied to the fields of biomedicine, soft robots, liquid drop transportation and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an intelligent hydrogel and a preparation method thereof.
Background
The marangoni effect means that the liquid will flow towards areas with low surface tension, since a liquid with high surface tension will pull more on the surrounding liquid than a liquid with low surface tension. There are two main ways of establishing a surface tension gradient: (1) is a gradient of surface tension induced by a temperature gradient; (2) is the gradient of surface tension induced by a concentration gradient.
The hydrogel is a gel having a three-dimensional network structure that swells by absorbing a large amount of water in water. Due to superior performances such as higher water content, biocompatibility, degradability, stimulation responsiveness and the like, the method has wide application prospect in the fields of drug controlled release, tissue engineering, environmental protection, optical modulation, soft robots and the like. However, the existing hydrogel does not have the capability of establishing a surface tension gradient by itself, and the novel intelligent hydrogel obtained in the invention can realize the purpose of automatically generating a surface tension gradient difference on the surface of an aqueous liquid through water absorption and hydrophilic and hydrophobic effects.
Disclosure of Invention
The invention aims to provide a novel intelligent hydrogel and a preparation method thereof. The intelligent hydrogel releases the surface of aqueous liquid, and the surface tension gradient difference can be automatically generated on the water surface due to the water absorption effect and the exchange phenomenon of hydrophilic and hydrophobic functional groups.
The novel intelligent hydrogel provided by the invention is formed by polymerizing hydroxyethyl methacrylate and acrylic acid.
The invention also provides a preparation method of the novel intelligent hydrogel, which comprises the following specific steps:
hydroxyethyl methacrylate, acrylic acid, a cross-linking agent and a photoinitiator are mixed into a precursor solution and irradiated to obtain the intelligent hydrogel which can generate surface tension gradient difference on a water-containing liquid surface.
In the present invention, the crosslinking agent is preferably ethylene glycol dimethacrylate.
In the present invention, the photoinitiator is preferably 2-hydroxy-2-methyl propiophenone.
In the invention, the volume ratio of the hydroxyethyl methacrylate, the acrylic acid, the cross-linking agent and the photoinitiator is set to 1 by taking the hydroxyethyl methacrylate as a base number, and the volume ratio of the acrylic acid to the acrylic acid is 0.2-1; the volume ratio range of the cross-linking agent ethylene glycol dimethacrylate to the cross-linking agent ethylene glycol dimethacrylate is 0.02-1; the volume ratio of the photoinitiator 2-hydroxy-2-methyl propiophenone to the photoinitiator is 0.2-0.6.
In the invention, the irradiation is carried out under an ultraviolet lamp, the wavelength of the ultraviolet light is 365 nanometers, and the irradiation time is preferably 5 seconds to 60 minutes.
The specific principle of the novel intelligent hydrogel provided by the invention for generating the surface tension gradient difference on the water-containing liquid surface is as follows:
the novel intelligent hydrogel is characterized in that after water absorption, due to the fact that the surface energy of the internal hydrophilic and hydrophobic functional groups is reduced, the hydrophobic functional groups which are originally towards the outside face towards the inside, and in the process, the novel intelligent hydrogel generates a surface tension gradient difference on the surface of water-containing liquid and is dynamically wetted.
Has the advantages that: the novel intelligent hydrogel and the preparation method thereof provided by the invention realize that the gradient difference of the surface tension can be constructed only by the hydrogel material above the uniform water-containing liquid level, thereby endowing the hydrogel material with a brand new intelligent performance. The novel intelligent hydrogel provided by the invention is simple in preparation method and applicable to industrial production, so that the novel intelligent hydrogel has practical application significance.
The invention has the originality that the novel intelligent hydrogel obtained by the photoinitiated polymerization method can generate surface tension gradient difference on the uniform water-containing liquid surface through the self water absorption effect without external stimulation, thereby providing potential possibility for the application of the novel intelligent hydrogel in the fields of swimming soft robots and the like.
Drawings
FIG. 1 is a flow chart for making a novel intelligent hydrogel.
FIG. 2 is a photograph of a novel intelligent hydrogel.
FIG. 3 is a graph of the water absorption curve of the novel intelligent hydrogel as a function of time.
Fig. 4 is a photograph of the contact angle of the novel smart hydrogel as a function of time.
Detailed Description
The invention provides a novel intelligent hydrogel which is formed by polymerizing hydroxyethyl methacrylate and acrylic acid.
The invention provides a preparation method of the intelligent hydrogel, which comprises the following steps:
hydroxyethyl methacrylate, acrylic acid, a cross-linking agent and a photoinitiator are mixed into a precursor solution and irradiated to obtain the intelligent hydrogel.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
Hydroxyethyl methacrylate, acrylic acid, a cross-linking agent and a photoinitiator are mixed into a precursor solution. In the invention, the cross-linking agent is preferably ethylene glycol dimethacrylate, and the photoinitiator is preferably 2-hydroxy-2-methyl propiophenone. In the invention, the volume ratio of the hydroxyethyl methacrylate, the acrylic acid, the cross-linking agent and the photoinitiator is set to 1 by taking the hydroxyethyl methacrylate as a base number, and the volume ratio of the acrylic acid to the acrylic acid is 0.2-1; the volume ratio range of the cross-linking agent ethylene glycol dimethacrylate to the cross-linking agent ethylene glycol dimethacrylate is 0.02-1; the volume ratio of the photoinitiator 2-hydroxy-2-methyl propiophenone to the photoinitiator is 0.2-0.6. In the invention, the mixing process comprises the steps of mixing hydroxyethyl methacrylate and acrylic acid, then adding a cross-linking agent and a photoinitiator into the obtained mixed solution in sequence, shading the obtained precursor solution, and introducing high-purity nitrogen for 5 minutes until various components are fully and uniformly mixed and dissolved oxygen is removed; the nitrogen gas is introduced at a speed which is not specially limited, and all the components can be uniformly mixed and dissolved oxygen can be removed. The invention introduces nitrogen under the shading condition to avoid the failure of the photoinitiator under the sunlight.
After the mixing is completed, the obtained precursor solution is irradiated. The obtained precursor solution is placed in a Polydimethylsiloxane (PDMS) mould for irradiation, the irradiation is preferably carried out under an ultraviolet lamp, and the wavelength of the ultraviolet light is preferably 365 nm; the irradiation time is preferably 5 seconds to 60 minutes.
In the invention, the material of the mold is preferably polydimethylsiloxane, and the mold is preferably manufactured by adopting a laser cutting technology and a PDMS (polydimethylsiloxane) molding technology. In the invention, the preparation method of the mould comprises the following steps: designing and modeling the shape of the die by using AutoCAD software, and storing a modeling file in a dwg format; importing the dwg format modeling file into a laser cutting machine, and manufacturing an acrylic male die by taking an acrylic plate as a raw material; and manufacturing a mould on the male mould by adopting a PDMS (polydimethylsiloxane) molding process. In the invention, the PDMS mold is used for realizing ultraviolet curing forming of the solution. The invention has no special limitation on the specific processes of modeling, laser cutting of acrylic and PDMS molding, and can select conventional methods well known by the technicians in the field.
FIG. 1 is a flow chart of the preparation of the intelligent hydrogel autonomously moving on the water surface. As shown in the figure, according to the invention, 3D modeling is carried out on a mould by adopting AutoCAD software, then an acrylic male mould is manufactured by cutting an acrylic plate by laser, and a PDMS mould is manufactured by using a PDMS forming process; mixing hydroxyethyl methacrylate, acrylic acid, a cross-linking agent and a photoinitiator to obtain a precursor solution, and introducing high-purity nitrogen into the precursor solution for 5 minutes in a shading manner to obtain a prepared precursor solution; and placing the prepared precursor liquid in the PDMS mold, and irradiating under the ultraviolet light with the wavelength of 365 nanometers to obtain the intelligent hydrogel which autonomously moves on the water surface.
In the present invention, fig. 2 is a diagram of a novel intelligent hydrogel. Wherein 1 is the intelligent hydrogel.
The novel intelligent hydrogel prepared by the method is placed on the surface of an aqueous liquid, and the hydrogel can absorb water to swell. FIG. 3 is a graph of the change of mass swelling ratio curve with time during water absorption of the novel intelligent hydrogel. The mass swell ratio of the hydrogel rapidly increased from 0 to 0.08353 in the first 90 minutes of water exposure, then slowly increased to 0.09318 in the next 60 minutes, and gradually and slowly increased to equilibrium in the last 60 minutes to reach equilibrium mass swell ratio 0.09498.
The change condition of the surface tension of the novel intelligent hydrogel along with time is represented by testing the dynamic contact angle of the novel intelligent hydrogel prepared by the method by using a sessile drop contact angle method. 2 microliter of water drops are dropped on the surface of the intelligent hydrogel, the initial contact angle is 103.1 degrees, and with the exchange phenomenon of water absorption and hydrophilic and hydrophobic functional groups, the contact angle is reduced to 88.3 degrees after 5 minutes; then, 2. mu.l of a drop was dropped onto the original position, and the contact angle immediately increased to 101.9 degrees, and after 5 minutes, the contact angle was again decreased to 89.6 degrees due to water absorption. The contact angle test results of dropping 2. mu.l of water drop every 5 minutes are shown in the photograph of FIG. 4. This result demonstrates that the smart hydrogels proposed by the present invention are able to build a surface tension gradient after exposure to water.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing an intelligent hydrogel precursor solution: mixing hydroxyethyl methacrylate and acrylic acid in a volume ratio of 1:0.4, and then adding a crosslinking agent ethylene glycol dimethacrylate, wherein the volume ratio of the crosslinking agent ethylene glycol dimethacrylate to the hydroxyethyl methacrylate is 0.02: 1; and finally adding a photoinitiator 2-hydroxy-2-methyl propiophenone, wherein the volume ratio of the photoinitiator to hydroxyethyl methacrylate is 0.5:1, shading and introducing high-purity nitrogen for 5 minutes to obtain a prepared precursor solution.
Manufacturing a mould: 3D modeling is carried out on the die by using AutoCAD software, and a modeling file is stored in a dwg format; importing the modeling file in the dwg format into a laser cutting machine, and cutting an acrylic plate by laser to manufacture an acrylic male die, wherein the protrusion is cylindrical, the diameter of the protrusion is 1 cm, and the height of the protrusion is 3 mm; and manufacturing a PDMS mold on the acrylic male mold by using a PDMS molding process.
Preparing intelligent hydrogel: and injecting the prepared precursor liquid into a PDMS mold, irradiating ultraviolet light above the PDMS mold, and irradiating for 1 minute by using an ultraviolet lamp with the wavelength of 365 nm to obtain the cured intelligent hydrogel. The intelligent hydrogel is cylindrical, the diameter of the intelligent hydrogel is 1 cm, and the thickness of the intelligent hydrogel is 3 mm. The intelligent hydrogel is released to the water surface, and the surface tension gradient can be automatically generated through the water absorption process.
Example 2
Following the protocol described in example 1, the only difference is: the volume ratio of acrylic acid to hydroxyethyl methacrylate was 1:1, and the volume ratio of the remaining material to hydroxyethyl methacrylate was the same as in example 1. The volume ratio of the crosslinking agent ethylene glycol dimethacrylate to the hydroxyethyl methacrylate is still 0.02: 1; the volume ratio of the photoinitiator 2-hydroxy-2-methyl propiophenone to the hydroxyethyl methacrylate is still 0.5: 1.
Example 3
Following the protocol described in example 1, the only difference is: the volume ratio of the crosslinking agent ethylene glycol dimethacrylate to hydroxyethyl methacrylate was 0.2:1, and the volume ratio of the remaining material to hydroxyethyl methacrylate was the same as in example 1. The volume ratio of acrylic acid to hydroxyethyl methacrylate is still 0.4: 1; the volume ratio of the photoinitiator 2-hydroxy-2-methyl propiophenone to the hydroxyethyl methacrylate is still 0.5: 1.
Example 4
The process described in example 1 is followed, with the difference that: the volume ratio of 2-hydroxy-2-methyl propiophenone to hydroxyethyl methacrylate was 0.4:1, and the volume ratio of the remaining material to hydroxyethyl methacrylate was the same as in example 1. The volume ratio of acrylic acid to hydroxyethyl methacrylate is still 0.4: 1; the volume ratio of the crosslinking agent ethylene glycol dimethacrylate to the hydroxyethyl methacrylate is still 0.02: 1.
The surface tension changes of the novel hydrogels of example 2, example 3 and example 4 were verified according to the protocol of example 1, and the results show that the novel smart hydrogels of example 2, example 3 and example 4 can also establish a surface tension gradient after being released to the water surface, and the results of the contact angle test all prove the conclusion.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. The preparation method of the intelligent hydrogel is characterized by comprising the following specific steps:
hydroxyethyl methacrylate, acrylic acid, a cross-linking agent and a photoinitiator are mixed into a precursor solution and irradiated to obtain intelligent hydrogel; the irradiation is carried out under an ultraviolet lamp, and the wavelength of the ultraviolet light is 365 nanometers; the irradiation time is 5 seconds to 60 minutes;
wherein the cross-linking agent is ethylene glycol dimethacrylate, and the photoinitiator is 2-hydroxy-2-methyl propiophenone; the volume ratio of the hydroxyethyl methacrylate, the acrylic acid, the cross-linking agent and the photoinitiator is set to 1 by taking the hydroxyethyl methacrylate as a base number, and the volume ratio of the acrylic acid to the acrylic acid is 0.2-1; the volume ratio range of the cross-linking agent ethylene glycol dimethacrylate to the cross-linking agent ethylene glycol dimethacrylate is 0.02-1; the volume ratio of the photoinitiator 2-hydroxy-2-methyl propiophenone to the photoinitiator is 0.2-0.6.
2. An intelligent hydrogel obtained by the method of claim 1.
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