CN117986484A - Intercalation polymerization modification method based on two-dimensional polymer, prepared polymer gel material and application - Google Patents
Intercalation polymerization modification method based on two-dimensional polymer, prepared polymer gel material and application Download PDFInfo
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Classifications
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
-
- 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
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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)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a two-dimensional polymer modification method, which comprises the following steps: adding a two-dimensional polymer containing hydrogen bonds into deionized water, and adding vinyl monomers to stir and blend to obtain a uniform transparent solution; and adding a redox initiator into the solution, and obtaining the polymer gel material through freezing, vacuumizing and nitrogen filling. The invention mixes the two-dimensional polymer containing hydrogen bond and vinyl monomer uniformly and then polymerizes, which solves the problem that the obtained material has defects caused by too strong acting force of the two-dimensional polymer and uneven blending; according to the invention, the vinyl monomer is introduced into the two-dimensional polymer for polymerization, which is equivalent to introducing the linear polymer into the two-dimensional polymer, so that the polymer of a two-dimensional and linear interpenetrating network is formed, and the problems of strength and toughness of the polymer gel material are effectively improved.
Description
Technical Field
The invention relates to the technical field of high polymers, in particular to an intercalation polymerization modification method based on a two-dimensional polymer, a prepared polymer gel material and application.
Background
Two-dimensional materials possess many excellent properties: the unique electronic property enables the electron mobility of the current carrying electron to be high and the quantum confinement effect to be achieved; the large specific surface area enables the catalyst to have stronger adsorption and catalysis performance; easy processing makes it suitable for flexible electronic devices and elastic materials. The two-dimensional material is considered to have great application prospect in the aspects of sensing equipment, proton exchange membranes, energy storage and the like. In the field of polymer science, the synthesis and application of two-dimensional polymers is also an emerging and very challenging frontier. A two-dimensional polymer is a planar lamellar macromolecule, typically a monolayer structure having a uniform atomic or molecular thickness, with structural units connected to one another in a plane by covalent bonds. Two-bit polymers can generally be divided into three categories: the two-dimensional polymer is formed by synthesizing a two-dimensional crystal through monomer molecule crystallization and carrying out polymerization reaction, a two-dimensional organic framework material constructed by taking polyvalent metal ions or polyfunctional organic molecules as nodes, and a two-dimensional polymer formed by forming a two-dimensional aggregate through organic monomer molecule self-assembly and polymerizing.
The research shows that amphiphilic molecules with proper geometric configuration and non-covalent interaction can be self-assembled into a supermolecule two-dimensional structure with regular shape in aqueous solution, and the two-dimensional structure is more stable after a two-dimensional polymer is generated through polymerization reaction. However, the compound has the defects of low mechanical strength, poor stability and the like when used for preparing materials. This may result from the lack of flexible segments within such two-dimensional materials for dissipating external forces and the mere thinness of the material due to the only hydrogen bonding forces.
Polymer modification has two main routes, polymer blend modification or ion-induced crosslinking enhancement. The polymer blending modification is a modification method for improving the performance of the original polymer by mixing two or more polymers together by adopting a chemical or physical method to form a multi-component polymer. For example, the authors in the Jian Z W,Julong J,Qifeng M,etal.Azo-Crosslinked Double-Network Hydrogels Enabling Highly Efficient Mechanoradical Generation[J].Journal of the American Chemical Society,2022,144(7) paper devised a dual network hydrogel formed by polymerization of two monomers, AMPS and AAM, which consists of two interpenetrating polymer networks with relative mechanical properties. One is a highly crosslinked brittle network and the other is a loosely crosslinked stretchable network, which results in a substantial breaking of the brittle network chemical bonds to help dissipate energy during loading under stress, while the soft network maintains the integrity of the gel while achieving enhanced toughening of the gel.
Ion-induced crosslinking refers to a method of linking polymer chains by means of charge attraction between positive and negative ions. In the preparation process of the hydrogel, different types of ion crosslinking structures can be formed through the number and arrangement of positive and negative ions, so that the mechanical property of the hydrogel is improved. For example, in Ji D,Park J M,Oh M S,et al.Superstrong,superstiff,and conductive alginate hydrogels[J].Nature Communications,2022,13(1):3019., the authors prepared hydrogels by calcium ion crosslinking recombination, dissolved sodium alginate salts (Alg) in distilled water and mixed with calcium sulfate slurry (CaSO 4) to give an Alg mixture of 2wt/vol (%). The anisotropic drying/shrinkage of Ca-Alg pregel and crosslinking/rehydration in Ca 2+ solution further improves the mechanical properties of the hydrogel and the high conductivity up to 2.2Ms/cm.
It is known from the prior art that various interactions, such as van der Waals forces, electrostatic forces, hydrogen bonding forces, etc., can occur during the mixing of the same type of polymers due to the presence of different structures and functional groups. These interactions can change the structure of the polymer chains at the molecular level, thereby changing the properties of the polymer gel material. In the previous researches, the mechanical properties of the two-dimensional polymer are often improved by directly blending polymers such as PEG, PEI and the like, and direct gel is often caused by too strong acting force between the added polymer and the two-dimensional polymer, so that a uniformly mixed sample is difficult to prepare. For example, a poly-L-lactic acid and nylon 11 (PLA/PA 11) polymer blend material that is poorly compatible in Yu X,Wang X,Zhang Z,et al.High-performance fully bio-based poly(lactic acid)/polyamide11(PLA/PA11)blends by reactive blending with multi-functionalized epoxy[J].Polymer Testing,2019,78:105980..
Disclosure of Invention
The technical problem to be solved by the invention is how to improve the mechanical properties of the two-dimensional polymer.
The invention solves the technical problems by the following technical means:
The first aspect of the invention provides an intercalation polymerization modification method based on a two-dimensional polymer, which comprises the following steps:
(1) Adding a two-dimensional polymer containing hydrogen bonds into deionized water, and adding vinyl monomers to stir to obtain a uniform transparent solution;
(2) And adding a redox initiator or a photoinitiator into the solution, and polymerizing under a nitrogen atmosphere to obtain the polymer gel material.
The beneficial effects are that: the invention mixes the two-dimensional polymer containing hydrogen bond and vinyl monomer uniformly and then polymerizes, which solves the problem that the obtained material has defects caused by too strong acting force of the two-dimensional polymer and uneven blending; according to the invention, the vinyl monomer is introduced into the two-dimensional polymer for polymerization, which is equivalent to introducing the linear polymer into the two-dimensional polymer, so that the polymer of a two-dimensional and linear interpenetrating network is formed, and the problems of strength and toughness of the polymer gel material are effectively improved.
Preferably, the structural general formula of the vinyl monomer is as follows:
R 1 = H or OH or COOH or SO 3 H or PO 4H;R2＝R5＝RR8 = H or CH 3,R3＝(CH2)n;R4 = H or OH or COOH or SO 3 H or PO 4 H or NH 2 or NHCH 3 or N (CH 3)2 or C 6H6;R6 = H or CH 3 or (CH 2)nCH3 or CH (CH 3)2 or CH 2)nOH;R7 = H or CH 3 or (CH 2)nCH3 or CH (CH 3)2 or (CH 2)n OH; N is greater than or equal to 1).
Preferably, the vinyl monomer contains an amino group or an amine group.
The beneficial effects are that: due to the hydrogen bonding action of the two-dimensional polymer surface, the molecular flexibility is weakened, the rigidity is increased, a flexible chain segment for dissipating external force is lacking, the flexible chain segment is introduced after vinyl monomers are added for polymerization, the amino or amine groups and carboxyl groups on the two-dimensional lamellar surface generate ionic bonding action, the amino or amine groups and carboxyl groups are promoted to be mutually close to each other, the cross-linking density between polymer layers is increased, the retention of water molecules is facilitated, and the water retention performance of the polymer gel material is improved.
Preferably, the mass ratio of the two-dimensional polymer to the vinyl monomer is 5:5-10.
Preferably, the stirring time is 1-2h; the stirring temperature was 30 ℃.
Preferably, the redox initiators are potassium persulfate and sodium thiosulfate pentahydrate.
Preferably, the photoinitiator is ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate.
Preferably, the photoinitiator is added in an amount of 2wt% of the vinyl monomer.
The second aspect of the invention provides a polymer gel material prepared by the intercalation polymerization modification method based on the two-dimensional polymer.
The beneficial effects are that: the polymer gel material of the invention has improved strength and toughness, and simultaneously has improved mechanical properties. The modification method is simple, short in period and easy to obtain materials, effectively simplifies the preparation steps of the polymer gel material, and is expected to be prepared and applied in a large scale.
In a third aspect the present invention provides the use of a polymer gel material as described above in a hydrogel.
The invention has the advantages that:
The invention mixes the two-dimensional polymer containing hydrogen bond and vinyl monomer uniformly and then polymerizes, which solves the problem that the obtained material has defects caused by too strong acting force of the two-dimensional polymer and uneven blending; the present invention uses an intercalation polymerization process in combination with a two-dimensional polymer substrate to improve polymer material properties, equivalent to uniformly blending linear polymers in a two-dimensional polymer. The two-dimensional sheet layers are not only provided with uniformly distributed ionic bonds, but also are increased with flexible chain segments, so that energy dissipation is facilitated when force is loaded, and the problems of strength and toughness of the polymer gel material are effectively improved.
Due to the hydrogen bonding action of the two-dimensional polymer surface, the flexibility of molecules is weakened, the rigidity is increased, an alkene monofunctional group monomer is added before polymerization, the amino group and the carboxyl group on the two-dimensional lamellar surface generate ionic bonding action, the amino group and the carboxyl group are promoted to be mutually close, the cross-linking density between polymer layers is increased, the retention of water molecules is facilitated, and the water retention performance of the polymer gel material is improved.
The polymer gel material of the invention has improved strength and toughness, and simultaneously has improved mechanical properties. The modification method is simple, short in period and easy to obtain materials, effectively simplifies the preparation steps of the polymer gel material, and is expected to be prepared and applied in a large scale.
Drawings
FIG. 1 is a schematic diagram of the hydrogen bonding forces of the two-dimensional polymer prepared in example 1;
FIG. 2 is a schematic diagram of a scanning electron microscope for preparing a two-dimensional polymer according to example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the two-dimensional polymer of example 2 before and after polymerization;
FIG. 4 is a Fourier infrared spectrum of the two-dimensional polymer of example 2 before and after polymerization;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the two-dimensional polymer of example 3 before and after polymerization;
FIG. 6 is a Fourier infrared spectrum of the two-dimensional polymer of example 3 before and after polymerization;
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the two-dimensional polymer of example 4 before and after polymerization;
FIG. 8 is a Fourier infrared spectrum of the two-dimensional polymer of example 4 before and after polymerization;
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of the two-dimensional polymer of example 5 before and after polymerization;
FIG. 10 is a Fourier infrared spectrum of the two-dimensional polymer of example 5 before and after polymerization;
FIG. 11 is a graph of mechanical properties of 5 polymer gel materials of example 8;
FIG. 12 is a graph showing the mechanical properties of the polymer gel materials prepared in examples 2 to 7;
FIG. 13 is a graph showing the water retention and evaporation rates of the polymer gel material and the water-absorbent polymer resin obtained in example 2 and comparative example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
The embodiment provides a preparation method of a two-dimensional polymer containing hydrogen bonds and the two-dimensional polymer, which concretely comprises the following steps:
(1) In this example, 12-aminododecanoic acid was reacted with acrylic acid to form the amphiphilic Monomer Acrylamide Dodecanoic Acid (MADA).
(2) Adding amphiphilic Monomer Acrylamide Dodecanoic Acid (MADA) into deionized water, then adding sodium hydroxide, oscillating, dissolving, mixing uniformly, and irradiating with a laser pen to obtain a visible Tyndall phenomenon, which indicates that a supermolecule solution is formed.
(3) Adding redox initiator potassium persulfate into the supermolecule solution, cooling, vacuumizing, filling nitrogen for 3 times, deoxidizing, performing free radical polymerization at 35 ℃, and dialyzing and freeze-drying to obtain the two-dimensional Polymer (PMADA).
The hydrogen bonding force predicted by the Material Studio in this example is shown in fig. 1, and the scanning electron microscope is shown in fig. 2.
The two-dimensional polymer containing hydrogen bonds of the invention is not limited to PMADA, and can be prepared from other amphiphilic monomers. For example, a hydrogel having a self-healing function under the action of hydrogen bonding as mentioned in He M,Chen X,Liu D,et al.Two-dimensional self-healing hydrogen-bond-based supramolecular polymer film[J].Chinese Chemical Letters,2019,30(5):961-965. or a supramolecular hydrogel formed by hydrogen bonding as mentioned in Yue Y.Self-Assembled Liquid-Crystalline Membranes Form Supramolecular Hydrogels via Hydrogen Bonding[J].Macromolecular Rapid Communications,2017,38(7):1600762..
Example 2
The embodiment provides an intercalation polymerization modification method based on a two-dimensional polymer and a prepared polymer gel material, which comprises the following specific steps:
(1) 2D PMADA (100 mg, 0.356 mmol) obtained in example 1 was added to a10 mL polymerization bottle, and 1mL deionized water was added thereto, dimethylaminoethyl methacrylate (100 mg,0.636 mmol) was weighed, and the above solution was added and stirred for 1 hour at a stirring temperature of 30℃to obtain a uniform transparent polymer solution.
(2) The polymerization solution is vacuumized and filled with nitrogen for three times to remove oxygen, and a photoinitiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphonate (2 mol percent of monomers) is added into the polymerization solution under the nitrogen atmosphere, wherein the vertical distance between an ultraviolet lamp and the polymerization solution is 10cm, the ultraviolet lamp (390-405 nm) is used for illumination polymerization for 5 minutes, and the polymerization is dried for 48 hours.
This example characterizes the pre-and post-polymerization solutions by nuclear magnetic hydrogen spectroscopy 1 H NMR, as shown in fig. 3. From 1 HNMR, it is clear that the double bond peak of the polymer gel material prepared in this example disappeared after polymerization, confirming the completion of the polymerization reaction.
As shown in FIG. 4, the blend system before and after polymerization was further characterized by FTIR, and the completion of the polymerization reaction was further confirmed by comparing the carbon-carbon double bond peaks of dimethylaminoethyl methacrylate before and after polymerization at 1558cm -1, and by disappearing the double bond peaks after polymerization.
The polymer gel material prepared in this example was cast into a film, and then the mechanical properties were tested by an electronic universal tensile tester, and the results were shown as 2DP/DMAEMA in FIG. 12, with a breaking stress of up to 12MPa.
Placing the polymer gel material prepared in the embodiment on a surface dish, and weighing the initial weight; the weight of the polymer gel material is weighed every one hour under the constant temperature environment of 15 ℃, and the polymer gel material is put in place immediately after being weighed. The polymer gel material has a water retention rate and a water volatilization rate curve as shown in fig. 13, and the water volatilization rate is only between 0.4 and 1.3 percent. Compared with the unblended 2D PMADA, the water-retaining effect is improved, and the water-retaining effect is far higher than that of the super-high molecular water-absorbent resin (diaper raw material).
Example 3
The embodiment provides an intercalation polymerization modification method based on a two-dimensional polymer and a prepared polymer gel material, which comprises the following specific steps:
(1) 2D PMADA (100 mg,0.358 mmol) obtained in example 1 was added to a 10mL polymerization flask, and 1mL deionized water was added thereto, methyl methacrylate (100 mg,0.998 mmol) was weighed, and the above solution was added and stirred for 1 hour at a stirring temperature of 30℃to obtain a uniform transparent polymer solution.
(2) The polymerization solution is vacuumized and filled with nitrogen for three times to remove oxygen, and a photoinitiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphonate (2 mol percent of monomers) is added into the polymerization solution under the nitrogen atmosphere, wherein the vertical distance between an ultraviolet lamp and the polymerization solution is 10cm, the ultraviolet lamp (390-405 nm) is used for illumination polymerization for 5 minutes, and the polymerization is dried for 48 hours.
This example characterizes the pre-and post-polymerization solutions by nuclear magnetic hydrogen spectroscopy 1 H NMR, as shown in fig. 5. From 1 HNMR, it is clear that the double bond peak of the polymer gel material prepared in this example disappeared after polymerization, confirming the completion of the polymerization reaction.
As shown in FIG. 6, the blend system before and after polymerization was further characterized by FTIR, and the completion of the polymerization reaction was confirmed by comparing the carbon-carbon double bond peaks at 1543cm -1 of methyl methacrylate before and after polymerization, and by disappearing the double bond peaks after polymerization.
The polymer gel material prepared in this example was cast into a film, and then the mechanical properties were tested by an electronic universal tensile tester, and the results were shown as 2DP/MMA in FIG. 12, with a breaking stress of 8.6MPa.
Example 4
The intercalation polymerization modification method based on the two-dimensional polymer and the prepared polymer gel material provided by the embodiment comprise the following specific steps:
(1) 2D PMADA (100 mg,0.358 mmol) obtained in example 1 was added to a 10mL polymerization flask, 1mL deionized water was added, butyl acrylate (100 mg,0.78 mmol) was weighed, the above solution was added and stirred for 1 hour, and the stirring temperature was 30℃to obtain a uniform transparent polymer solution.
(2) The polymerization solution is vacuumized and filled with nitrogen for three times to remove oxygen, and a photoinitiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphonate (2 mol percent of monomers) is added into the polymerization solution under the nitrogen atmosphere, wherein the vertical distance between an ultraviolet lamp and the polymerization solution is 10cm, the ultraviolet lamp (390-405 nm) is used for illumination polymerization for 5 minutes, and the polymerization is dried for 48 hours.
This example characterizes the pre-and post-polymerization solutions by nuclear magnetic hydrogen spectroscopy 1 H NMR, as shown in fig. 7. From 1 HNMR, it is clear that the double bond peak of the polymer gel material prepared in this example disappeared after polymerization, confirming the completion of the polymerization reaction.
As shown in FIG. 8, the blend system before and after polymerization was further characterized by FTIR, and the completion of the polymerization reaction was confirmed by comparing the carbon-carbon double bond peaks at 1561cm -1 of butyl acrylate before and after polymerization with the disappearance of the double bond peaks after polymerization.
The polymer gel material prepared in this example was cast into a film, and then the mechanical properties were tested by an electronic universal tensile tester, and the results were shown as 2DP/BA in FIG. 12, with a breaking stress of 3.6MPa.
Example 5
The embodiment provides an intercalation polymerization modification method based on a two-dimensional polymer and a prepared polymer gel material, which comprises the following specific steps:
(1) 2D PMADA (100 mg,0.358 mmol) obtained in example 1 was added to a10 mL polymerization bottle, and 1mL deionized water was added thereto, benzyl methacrylate (100 mg, 0.218 mmol) was weighed, and the above solution was added and stirred for 1 hour at a stirring temperature of 30℃to obtain a uniform transparent polymer solution.
(2) The polymerization solution is vacuumized and filled with nitrogen for three times to remove oxygen, and a photoinitiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphonate (2 mol percent of monomers) is added into the polymerization solution under the nitrogen atmosphere, wherein the vertical distance between an ultraviolet lamp and the polymerization solution is 10cm, the ultraviolet lamp (390-405 nm) is used for illumination polymerization for 5 minutes, and the polymerization is dried for 48 hours.
This example characterizes the pre-and post-polymerization solutions by nuclear magnetic hydrogen spectroscopy 1 H NMR, as shown in fig. 9. From 1 HNMR, it is clear that the double bond peak of the polymer gel material prepared in this example disappeared after polymerization, confirming the completion of the polymerization reaction.
As shown in FIG. 10, the blend system before and after polymerization was further characterized by FTIR, and the completion of the polymerization reaction was confirmed by comparing the carbon-carbon double bond peaks at 1545cm -1 of benzyl methacrylate before and after polymerization, and by disappearing the double bond peaks after polymerization.
The polymer gel material prepared in this example was cast into a film, and then the mechanical properties were tested by an electronic universal tensile tester, and the results were shown as 2DP/BZMA in FIG. 12, with a breaking stress of 1.8MPa.
Example 6
The embodiment provides an intercalation polymerization modification method based on a two-dimensional polymer and a prepared polymer gel material, which comprises the following specific steps:
(1) 2D PMADA (100 mg,0.358 mmol) obtained in example 1 was added to a 10mL polymerization bottle, 1mL of ethanol was added, styrene (100 mg,0.96 mmol) was weighed, the above solution was added and stirred for 1 hour at a stirring temperature of 30℃to obtain a uniform transparent polymer solution.
(2) The polymerization solution was subjected to vacuum-nitrogen-filled circulation for three times to remove oxygen, and 2,4, 6-trimethylbenzoyl ethyl phenylphosphonate (2 mol% of monomer) as a photoinitiator was added to the polymerization solution under nitrogen atmosphere, and the polymerization solution was subjected to light polymerization by an ultraviolet lamp (390-405 nm) at a vertical distance of 10cm from the polymerization solution for 5 minutes and dried for 48 hours.
The polymer gel material prepared in this example was cast into a film, and then the mechanical properties were tested by an electronic universal tensile tester, and the results were shown as 2DP/SM in FIG. 12, with a breaking stress of 2.1MPa.
Example 7
The embodiment provides an intercalation polymerization modification method based on a two-dimensional polymer and a prepared polymer gel material, which comprises the following specific steps:
(1) 2D PMADA (100 mg,0.358 mmol) obtained in example 1 was added to a 10mL polymerization flask, 1mL deionized water was added, acrylamide (100 mg,1.124 mmol) was weighed, the above solution was added and stirred for 1 hour at a stirring temperature of 30℃to obtain a uniform transparent polymer solution.
(2) The polymerization solution is vacuumized and filled with nitrogen for three times to remove oxygen, and a photoinitiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphonate (2 mol percent of monomers) is added into the polymerization solution under the nitrogen atmosphere, wherein the vertical distance between an ultraviolet lamp and the polymerization solution is 10cm, the ultraviolet lamp (390-405 nm) is used for illumination polymerization for 5 minutes, and the polymerization is dried for 48 hours.
The polymer gel material prepared in the embodiment is poured into a film, and then the mechanical properties of the film are tested by an electronic universal tensile testing machine, and the result is shown as 2DP/AM in figure 12, and the breaking stress reaches 9.26Mpa.
Example 8
The embodiment provides an intercalation polymerization modification method based on a two-dimensional polymer and a prepared polymer gel material, which comprises the following specific steps:
(1) In this example, 2D PMADA (100 mg,0.358 mmol) obtained in example 1 was added to 510 mL polymerization bottles, and 1mL deionized water was added thereto, and dimethylaminoethyl methacrylate (120 mg,0768 mmol), (140 mg,0.896 mmol), (160 mg,1.024 mmol), (180 mg,1.152 mmol) and (200 mg,1.28 mmol) were weighed respectively, and sequentially added to the above solutions and stirred for 2 hours at a stirring temperature of 30℃to obtain 5 different polymerization liquids.
(2) The 5 different polymerization solutions are subjected to freezing, vacuumizing and nitrogen filling circulation for three times to remove oxygen, potassium persulfate (2 mg,0.0074 mmol) and sodium thiosulfate pentahydrate (2 mg, 0.0078 mmol) are added and stirred uniformly, polymerization is carried out for 12 hours at 30 ℃, and drying is carried out for 48 hours to obtain 5 polymer gel materials. This example designates the 5 different polymer gel materials as 2D PMADA100/DMAEMA120,2D PMADA100/DMAEMA140,2DPMADA100/DMAEMA160, and so on.
The 5 polymer gel materials prepared in this example were cast into films, and then the mechanical properties were tested by an electronic universal tensile tester, and the results are shown in fig. 11, in which the maximum strain of the polymer gel materials reaches 354%, the maximum breaking stress is 4.6MPa, and the strength decreases with the increase of the DMAEMA blending ratio.
Comparative example 1
The comparative example provides a polymer gel material, specifically as follows:
(1) Polymer gel material was prepared by adding example 1 preparation 2D PMADA (100 mg,0.358 mmol) to a 10mL polymerization flask, while adding 1mL deionized water. The polymer gel material of the comparative example was cast into a film, and then the mechanical properties were tested by an electronic universal tensile tester, and as shown in fig. 12, the polymer gel material blended without the addition of the vinyl monofunctional monomer was brittle and fragile, and the test performance was 1.4MPa.
(2) Polymer gel material was prepared by adding example 1 preparation 2D PMADA (100 mg,0.358 mmol) to a 10mL polymerization flask, while adding 1mL deionized water. Placing the polymer gel material prepared in the comparative example on a surface dish, and weighing the initial weight; the weight of the polymer gel material is weighed every one hour under the constant temperature environment of 15 ℃, and the polymer gel material is put in place immediately after being weighed. Comparative example the polymer gel material prepared in example 2 and the polymer gel material prepared in comparative example were shown in FIG. 13, and the water retention rate and the water evaporation rate of the high molecular weight water-absorbent resin were set to be in the range of 4 to 5%.
(3) The comparative experiment procedure of the high molecular water-absorbent resin (diaper raw material) is as follows: 200mg of a high molecular weight water-absorbent resin was weighed, dispersed in 1g of deionized water, and placed on a dish, and the initial weight was weighed. The weight of the high molecular water-absorbent resin is weighed every one hour under the constant temperature environment of 15 ℃, and the high molecular water-absorbent resin is put back into the original position after being weighed.
The water retention rate and the water volatilization rate can be calculated according to the following formula:
W=m 2/m1 ×100%; w-material water retention rate, m 1 -initial mass of material before drying and m 2 -mass of hydrogel after drying;
M= (M 4-m3)/m5 X100%; M-moisture evaporation rate, M 3 -mass of material after drying, M 4 -mass of material before drying, M 5 -total amount of water in the material).
In summary, the invention utilizes a great amount of hydrogen bond donors and vinyl monomer hydrogen bond acceptors on the surface of the two-dimensional polymer sheet to generate interaction force, the hydrogen bonds connected with each other between polymers improve the miscibility and compatibility, and the intercalation polymerization modification method is used for solving the problems of too strong direct blending force and uneven miscibility between polymers. The mechanical properties of the polymer gel material are improved by polymerization after blending, which shows that the introduction of ionic bonds and the compatibility of blending between polymers are realized by the technical scheme of the invention, and the method becomes an effective strategy for modifying the two-dimensional polymer. The invention also discloses an amino-containing vinyl monomer added before polymerization, and the amino generates an ionic bond effect with carboxyl on the surface of the two-dimensional lamellar, so that the cross-linking density between polymer layers is increased, the retention of water molecules is facilitated, and the water retention performance of the polymer gel material is improved.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The intercalation polymerization modification method based on the two-dimensional polymer is characterized by comprising the following steps of:
(1) Adding a two-dimensional polymer containing hydrogen bonds into deionized water, and adding vinyl monomers to stir to obtain a uniform transparent solution;
(2) And adding a redox initiator or a photoinitiator into the solution, and polymerizing under a nitrogen atmosphere to obtain the polymer gel material.
2. The method of claim 1, wherein the vinyl monomer has the general structural formula:
Wherein R 1 = H or OH or COOH or SO 3 H or PO 4H;R2＝R5＝R8 = H or CH 3,R3＝(CH2)n;R4 = H or OH or COOH or SO 3 H or PO 4 H or NH 2 or NHCH 3 or N (CH 3)2 or C 6H6;R6 = H or CH 3 or (CH 2)nCH3 or CH (CH 3)2 or (CH 2)nOH;R7 = H or CH 3 or (CH 2)nCH3 or CH (CH 3)2 or (CH 2)n OH; N is not less than 1).
3. The method according to claim 2, wherein the vinyl monomer contains an amino group or an amine group.
4. The modification process according to claim 1, wherein the mass ratio of the two-dimensional polymer to the vinyl monomer is 5:5 to 10.
5. The modification process according to claim 1, wherein the stirring time is 1 to 2 hours; the stirring temperature was 30 ℃.
6. The modification process according to claim 1, wherein the redox initiator is potassium persulfate or sodium thiosulfate pentahydrate.
7. The method of claim 1, wherein the photoinitiator is ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate.
8. The method of claim 7, wherein the photoinitiator is added in an amount of 2wt% of the vinyl monomer.
9. The polymer gel material produced by the two-dimensional polymer-based intercalation polymerization modification method according to any one of claims 1 to 8.
10. Use of a polymer gel material according to claim 9 in a hydrogel.
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