CN115353729B - Non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material and preparation method and application thereof - Google Patents
Non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 68
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 27
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
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- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/166—Magnesium halide, e.g. magnesium chloride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a non-covalent bond cross-linked high-strength high-toughness plastic recyclable composite material, a preparation method and application thereof. The composite material provides high strength and high toughness through the synergistic effect of multiple non-covalent bonds. The composite material comprises the following raw materials in parts by weight (based on 100 parts by weight of the total weight of the composite material): 5.5-45 parts of polyurethane, 25-43 parts of polyphenol compounds, 5-8.5 parts of metal ion compounds and 25-43 parts of modified two-dimensional materials. The composite material has excellent mechanical properties, is plastic and recyclable, and can be used in the fields of aerospace, electronics, military, civil engineering and machinery.
Description
Technical Field
The invention belongs to the technical field of bionic design, and particularly relates to a non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material and a preparation method and application thereof.
Background
The mother-of-pearl existing in nature has excellent mechanical properties thanks to its internal well-known "brick-mud" type structure, and has a work of fracture about 3000 times that of calcium carbonate crystals as its basic component. The excellent mechanical property makes the brick-mud structure a bionic target of researchers in the microstructure design direction of modern high-performance synthetic materials, and many technologies are developed in the past decade to manufacture multifunctional imitation pearl layer materials, including freezing casting, layer-by-layer assembly, vacuum filtration, additive manufacturing, evaporation and the like. However, these techniques have some drawbacks, including long time consumption, complex equipment, and the like. Meanwhile, the bionic structural materials are limited to single morphology (sheet or block) and partial functional defects (such as self-repairing performance), and the requirements of human beings on high-performance materials are difficult to further meet.
In the breaking process, the simulated pearl layer material generates crack initiation after elastic deformation, then generates stable crack growth along an interface, and then generates crack deflection to enter an unstable crack growth stage, and finally generates breaking. Therefore, the energy dissipation purpose can be achieved by weakening the interface bonding strength of the material, micro holes and micro cracks in the composite material with weak interface bonding are more easily captured by main cracks, and the cracks can expand along the interface and deflect. The selection of weak interfacial bonds can effectively improve the fracture toughness of the material.
Non-covalent bonds such as hydrogen bonds, pi-pi conjugation, solvophobic effects, ion dipolar effects and the like are deep into the discipline fields such as biology, chemistry, materials, environment and the like. As weak bonds, these forces break easily under large deformations and dissipate energy, which can be introduced into the material as weak interfacial bonds, but the improvement of mechanical properties by a single weak bond is very limited. Therefore, in order to improve the mechanical property of the composite material and improve the transfer efficiency of the interlayer load, various acting forces and various synergistic effects are designed between the interfaces of the sheets.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention provides a non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material, and a preparation method and application thereof. According to the invention, polyurethane, a polyphenol compound, a metal ion compound and a modified two-dimensional material are blended by a one-pot method to prepare the high-strength high-toughness plastic recyclable composite material. The composite material provides high strength and high toughness through the synergistic effect of multiple non-covalent bonds.
The technical scheme is as follows: in order to achieve the above purpose, the invention adopts the following technical scheme:
the first object of the invention is to provide a non-covalent bond cross-linked high-strength high-toughness plastic recyclable composite material, which comprises polyurethane, a polyphenol compound, a metal ion compound and a modified two-dimensional material, wherein the modified two-dimensional material is an ellagic acid surface modified two-dimensional material.
According to the invention, ellagic acid and a two-dimensional material are mixed to be mutually stacked through pi-pi conjugation, and then two-dimensional sheets in the material extruded by an internal mixer are mutually extruded to form a cross-interlocking mortise-tenon structure, so that the obtained composite material provides high-strength and high-toughness performance through multiple non-covalent bond synergism.
Optionally, in one embodiment of the invention, the composite material comprises the following raw materials:
based on the total weight portion of the composite material,
alternatively, in one embodiment of the invention, the composite provides fracture strength and energy dissipation by non-covalent crosslinking. The tensile strength of the composite material is more than 400MPa, and the toughness is more than 20MJ/m 3 。
The non-covalent bond crosslinking comprises the electrostatic force action of the polyphenol compound and the modified two-dimensional material, the complexation of the polyphenol compound and metal ions and the hydrogen bond action of the polyphenol compound and polyurethane.
Alternatively, in one embodiment of the present invention, the polyphenol compound includes one or a combination of two or more of tannic acid, phytic acid, and gallic acid.
Alternatively, in one embodiment of the present invention, the polyphenol compound is preferably phytic acid.
Alternatively, in one embodiment of the present invention, the metal ions in the metal ion compound include Ca2 + 、Mg 2+ 、Fe 2+ 、Fe 3+ One or a combination of two or more of them.
Alternatively, in one embodiment of the present invention, the metal ion is preferably Ca 2+ 。
Alternatively, in one embodiment of the present invention, the metal ion compound is a chloride of the metal ion.
Alternatively, in one embodiment of the present invention, the two-dimensional material includes one or a combination of two or more of graphene oxide, graphene, montmorillonite, and a transition metal two-dimensional material (e.g., MXene).
Alternatively, in one embodiment of the present invention, the two-dimensional material is preferably graphene oxide.
The second object of the invention is to provide a preparation method of the non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material, wherein the composite material is obtained by blending polyurethane, a polyphenol compound, a metal ion compound and a modified two-dimensional material.
In the present invention, the composite provides fracture strength and energy dissipation through non-covalent crosslinking. Wherein, the non-covalent bond crosslinking comprises the electrostatic force action of the polyphenol compound and the modified two-dimensional material, the complexation of the polyphenol compound and metal ions and the hydrogen bond action of the polyphenol compound and polyurethane.
Alternatively, in one embodiment of the present invention, the composite material comprises 5.5 to 45 parts by weight of polyurethane, 25 to 43 parts by weight of polyphenol compound, 5 to 8.5 parts by weight of metal ion compound, and 25 to 43 parts by weight of modified two-dimensional material.
Optionally, in one embodiment of the present invention, the method specifically includes the following steps:
1) Blending the modified two-dimensional material, the polyphenol compound and the metal ion in water, and adjusting the pH value to 5-8.5, and obtaining an intermediate product after the reaction is finished;
2) And dripping the intermediate product into polyurethane solution under stirring, mixing, pressing into a mold for molding by mixing through an internal mixer after the reaction is finished, and drying to obtain the product.
On one hand, the invention firstly stacks ellagic acid and two-dimensional materials through pi-pi conjugation, and then the two-dimensional sheets in the materials extruded by an internal mixer are mutually extruded to form a cross-interlocking mortise-tenon structure, so that the composite material obtained by the invention provides high-strength and high-toughness performance through multiple non-covalent bond synergism.
On the other hand, the composite material obtained by the invention also has good plastic recoverability, firstly, the intermediate product prepared by the invention is blended with polyurethane to form a mud-like substance, so that the mud-like substance can be extruded by an internal mixer to obtain any shape, and has plasticity; secondly, the invention disperses the material in water again and repeats the steps to prepare new material, or the material after stretching and breaking is spliced again and a certain amount of water is dripped on the split, and the material is repaired after standing and volatilizing the water, so that the material has recoverability.
Alternatively, in one embodiment of the present invention, in step 1), the reaction conditions are 60-80℃water bath conditions for 20-24 hours.
Alternatively, in one embodiment of the invention, in step 2), the intermediate product is blended with dropwise into the polyurethane solution under stirring for 1-2 hours.
Alternatively, in one embodiment of the present invention, in step 2), the internal mixer mixes for 1-2 hours at 25-30 ℃, and the drying is performed for 20-24 hours at 40-80 ℃.
Alternatively, in one embodiment of the present invention, in step 1), the pH is adjusted to any value between 5.5 and 8.5, such as ph=5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, etc.
Optionally, in one embodiment of the present invention, in step 1), preferably, the pH may be further adjusted to any value between 6 and 8.5, such as ph=6.0, 6.5, 7.0, 7.5, 8.0, 8.5, etc.
Alternatively, in step 1) of the present invention, blending in water means that all the raw materials may be mixed in water, and the specific amount of water is not limited and is within the scope of the present invention.
Optionally, in one embodiment of the present invention, the method specifically includes the following steps:
1) Blending the modified two-dimensional material, the polyphenol compound and the metal ion in water, adjusting the pH to 5-8.5, and then reacting for 20-24 hours under the water bath condition of 60-80 ℃ to obtain an intermediate product after the reaction is finished;
2) Dripping the intermediate product into polyurethane solution under stirring for blending for 1-2h, after the reaction is finished, mixing for 1-2h by an internal mixer at 25-30 ℃, pressing into a mould for molding, and placing the mould into an oven at 40-80 ℃ for drying for 20-24h to obtain the product.
The third object of the invention is to provide the non-covalent bond cross-linked high-strength high-toughness plastic recyclable composite material or the application of the preparation method thereof, which can be particularly applied to the fields of aerospace, electronics, military, civil engineering and machinery.
The invention has the beneficial technical effects that:
1) According to the invention, the energy dissipation effect is achieved by weakening the interface bonding strength of the material, and the interlayer load transfer efficiency is improved by utilizing the synergistic effect of a plurality of non-covalent bonds, and the mechanical property of the composite material is finally improved;
2) The preparation method has simple preparation steps, and the product is prepared by a one-pot method;
3) The composite material prepared by the invention has high strength and high toughness, and is plastic and recyclable;
4) The high-strength and high-toughness composite material prepared by the invention has wide application prospect in the fields of aerospace, electronics, military, civil engineering, machinery and the like.
Drawings
FIG. 1 is a schematic view of a mortise and tenon structure of extruded materials through an internal mixer;
fig. 2 is a schematic view of a "brick-mud" structure formed inside the material.
Detailed Description
The invention will be further described with reference to the drawings and examples. The invention will be better understood from the following examples. However, it will be readily understood by those skilled in the art that the specific material ratios, process conditions and results thereof described in the examples are illustrative of the present invention and should not be construed as limiting the invention described in detail in the claims.
In an embodiment of the invention, the preparation of the non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material comprises the following steps:
1) Blending the modified two-dimensional material, the polyphenol compound and the metal ion in water, and adjusting the pH value to 5-8.5, and obtaining an intermediate product after the reaction is finished;
2) And dripping the intermediate product into polyurethane solution under stirring, mixing, pressing into a mold for molding by mixing through an internal mixer after the reaction is finished, and drying to obtain the product.
In an embodiment of the present invention, the polyphenol compound includes one or a combination of two or more of tannic acid, phytic acid, gallic acid or any other polyphenol compound.
In an embodiment of the present invention, the metal ions include Ca2 + 、Mg 2+ 、Fe 2+ 、Fe 3+ One or a combination of two or more of them.
In the embodiment of the invention, the two-dimensional material comprises one or more than two of graphene oxide, graphene, montmorillonite and transition metal two-dimensional material (such as MXene).
In an embodiment of the invention, the modified two-dimensional material is an ellagic acid surface modified two-dimensional material.
Preferably, in the embodiment of the invention, the modified two-dimensional material is subjected to drying treatment after being manufactured, because the original hydrogen bonds in the modified two-dimensional material (taking ellagic acid modified graphene oxide EGO as an example) are destroyed in consideration of the intervention of moisture, and instead, new hydrogen bonds formed by small molecular water and functional groups on the surface of graphene oxide GO are formed; the principle of forming the most hydrogen bonds shows that the water can fully replace the original hydrogen bond structure to form new hydrogen bonds, so that the original EGO hydrogen bond system is destroyed, and the water builds a new hydrogen bond system in the hydrogen bond system. However, under the dried condition, on the surface of the EGO, the hydrogen bond formed by the water molecules and related functional groups is instantaneously destroyed, and the water molecules return to the ambient atmosphere again; along with the extension of the drying time, the moisture is gradually dispersed into the ambient atmosphere, and the original hydrogen bond system is gradually repaired, so that the bond and the effect of EGO in the system can be fully exerted and utilized, and the mechanical property of the material is further improved.
Example 1
1) Based on 100 parts by weight of the total weight of the modified two-dimensional material, 10 parts by weight of graphene oxide and 90 parts by weight of ellagic acid are weighed. Ellagic acid was first dissolved in NaOH aqueous solution, after which graphene oxide was added and the pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in a water bath for 24h. And washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified graphene oxide.
2) Weighing 23 parts by weight of polyurethane, 35 parts by weight of phytic acid and CaCl 2 7 parts by weight of modified graphene oxide and 35 parts by weight of modified graphene oxide. Firstly, modified graphene oxide, phytic acid and CaCl are subjected to 2 Dispersing in deionized water, performing ultrasonic treatment for 10min, adjusting the pH to 8 by NaOH (1M), heating to 80 ℃ in a water bath, and reacting for 24h. And obtaining an intermediate product after the reaction is finished.
3) The intermediate product is added into polyurethane drop by drop and stirred for 1h at normal temperature. After the reaction is finished, the mixture is mixed for 1 hour by a 25 ℃ internal mixer, pressed into a die for molding, and placed in an 80 ℃ oven for drying, and the composite material 1 is obtained after 24 hours.
Example 2
1) Based on 100 parts by weight of the total weight of the modified two-dimensional material, 10 parts by weight of graphene oxide and 90 parts by weight of ellagic acid are weighed. Ellagic acid was first dissolved in NaOH aqueous solution, after which graphene oxide was added and the pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in a water bath for 24h. And washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified graphene oxide.
2) 28.5 parts of polyurethane, 32.5 parts of phytic acid, 26.5 parts of CaCl and 32.5 parts of modified graphene oxide are weighed. Firstly, modified graphene oxide, phytic acid and CaCl are subjected to 2 Dispersing in deionized waterUltrasonic for 10min, and adjusting pH to 8 by NaOH (1M), heating to 80deg.C in water bath, and reacting for 24 hr. And obtaining an intermediate product after the reaction is finished.
3) The intermediate product is added into polyurethane drop by drop and stirred for 1h at normal temperature. After the reaction is finished, the mixture is mixed for 1 hour by a 25 ℃ internal mixer, pressed into a die for molding, and placed in an 80 ℃ oven for drying, and the composite material 2 is obtained after 24 hours.
Example 3
1) Based on 100 parts by weight of the total weight of the modified two-dimensional material, 10 parts by weight of graphene oxide and 90 parts by weight of ellagic acid are weighed. Ellagic acid was first dissolved in NaOH aqueous solution, after which graphene oxide was added and the pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in a water bath for 24h. And washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified graphene oxide.
2) 39.5 parts of polyurethane, 27.5 parts of phytic acid, 25.5 parts of CaCl and 27.5 parts of modified graphene oxide are weighed. Firstly, modified graphene oxide, phytic acid and CaCl are subjected to 2 Dispersing in deionized water, performing ultrasonic treatment for 10min, adjusting the pH to 8 by NaOH (1M), heating to 80 ℃ in a water bath, and reacting for 24h. And obtaining an intermediate product after the reaction is finished.
3) The intermediate product is added into polyurethane drop by drop and stirred for 1h at normal temperature. After the reaction is finished, mixing for 1.5 hours by a 25 ℃ internal mixer, pressing into a die for molding, and placing the die into an 80 ℃ oven for drying for 24 hours to obtain the composite material 3.
Example 4
1) Based on 100 parts by weight of the total weight of the modified two-dimensional material, 10 parts by weight of graphene and 90 parts by weight of ellagic acid are weighed. Ellagic acid was first dissolved in NaOH aqueous solution, after which graphene was added and pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in water bath for 24h. And washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified graphene.
2) Weighing 12 parts by weight of polyurethane, 40 parts by weight of phytic acid and MgCl 2 8 parts by weight of modified graphene and 40 parts by weight of modified graphene. Firstly, modified graphene, phytic acid and MgCl 2 Dispersing in deionized water, performing ultrasonic treatment for 10min, adjusting the pH to 8.5 by NaOH (1M), and heating to 70 ℃ in a water bath for reaction for 22h. After the reaction is finished, the intermediate is obtainedAn intermediate product.
3) The intermediate product was added dropwise to the polyurethane and stirred at room temperature for 1.5h. After the reaction is finished, mixing for 1h by a 30 ℃ internal mixer, pressing into a mould for molding, pouring into the mould, and placing into a 60 ℃ oven for drying for 24h to obtain the composite material 4.
Example 5
1) 10 parts by weight of MXene and 90 parts by weight of ellagic acid are weighed based on 100 parts by weight of the total weight of the modified two-dimensional material. Ellagic acid was first dissolved in aqueous NaOH, after which MXene was added and the pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in a water bath for 24h. After the reaction, washing with water and placing in an oven at 80 ℃ for 24 hours to obtain the modified MXene.
2) Weighing 20.5 parts by weight of polyurethane, 36 parts by weight of phytic acid and FeCl 2 7.5 parts by weight of modified MXene36 parts by weight. Firstly, modified MXene, phytic acid and FeCl 2 Dispersing in deionized water, performing ultrasonic treatment for 10min, adjusting pH to 6 by NaOH (1M), heating to 60 ℃ in a water bath, and reacting for 24h. And obtaining an intermediate product after the reaction is finished.
3) The intermediate product is added into polyurethane drop by drop and stirred for 2h at normal temperature. After the reaction is finished, the mixture is mixed for 1 hour by a 30 ℃ internal mixer, pressed into a die for molding, and placed in an 80 ℃ oven for drying, and the composite material 5 is obtained after 20 hours.
Example 6
1) 10 parts by weight of montmorillonite and 90 parts by weight of ellagic acid are weighed according to 100 parts by weight of the total weight of the modified two-dimensional material. Ellagic acid was first dissolved in aqueous NaOH, after which montmorillonite was added and the pH was adjusted to 5 by HCl (1M) and heated to 80 ℃ in a water bath for 24h. Washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified montmorillonite.
2) Weighing 23 parts by weight of polyurethane, 35 parts by weight of phytic acid and CaCl 2 7 parts by weight of modified montmorillonite and 35 parts by weight of modified montmorillonite. Firstly, dispersing modified montmorillonite, phytic acid and CaCl2 in deionized water for 10min by ultrasonic treatment, adjusting the pH to 7 by NaOH (1M), and heating in a water bath to 70 ℃ for reaction for 22h. And obtaining an intermediate product after the reaction is finished.
3) The intermediate product is added into polyurethane drop by drop and stirred for 2h at normal temperature. After the reaction is finished, the mixture is mixed for 2 hours by a 25 ℃ internal mixer, pressed into a die for molding, and placed in a 40 ℃ oven for drying, and the composite material 6 is obtained after 24 hours.
Example 7
And (3) dropwise adding deionized water into the spliced part after the fracture surfaces of the fragments of the composite material 1 subjected to the tensile fracture test are spliced again, and standing until the material is dried to obtain the composite material 7.
Comparative example 1
1) Based on 100 parts by weight of the total weight of the modified two-dimensional material, 10 parts by weight of graphene oxide and 90 parts by weight of ellagic acid are weighed. Ellagic acid was first dissolved in NaOH aqueous solution, after which graphene oxide was added and the pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in a water bath for 24h. And washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified graphene oxide.
2) Weighing 23 parts by weight of polyurethane, 35 parts by weight of phytic acid and CaCl 2 7 parts by weight of modified graphene oxide and 35 parts by weight of modified graphene oxide. Firstly, modified graphene oxide, phytic acid and CaCl are subjected to 2 Dispersing in deionized water, performing ultrasonic treatment for 10min, adjusting pH to 5 by NaOH (1M), heating to 80 ℃ in a water bath, and reacting for 24h. And obtaining an intermediate product after the reaction is finished.
3) The intermediate product is added into polyurethane drop by drop and stirred for 1h at normal temperature. After the reaction is finished, the mixture is mixed for 1 hour by a 25 ℃ internal mixer, pressed into a die for molding, and placed in an 80 ℃ oven for drying, and the comparative material 1 is obtained after 24 hours.
Comparative example 2
1) Based on 100 parts by weight of the total weight of the modified two-dimensional material, 10 parts by weight of graphene oxide and 90 parts by weight of ellagic acid are weighed. Ellagic acid was first dissolved in NaOH aqueous solution, after which graphene oxide was added and the pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in a water bath for 24h. And washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified graphene oxide.
2) Weighing 45.5 parts by weight of phytic acid and CaCl 2 9 parts by weight of modified graphene oxide and 45.5 parts by weight of modified graphene oxide. Firstly, modified graphene oxide, phytic acid and CaCl are subjected to 2 Dispersing in deionized water, performing ultrasonic treatment for 10min, adjusting the pH to 8 by NaOH (1M), heating to 80 ℃ in a water bath, and reacting for 24h. Pouring into a mold after the reaction is finished and placing inOven-drying at 80 ℃ for 24 hours to obtain the comparative material 2.
Comparative example 3
1) Based on 100 parts by weight of the total weight of the modified two-dimensional material, 10 parts by weight of graphene oxide and 90 parts by weight of ellagic acid are weighed. Ellagic acid was first dissolved in NaOH aqueous solution, after which graphene oxide was added and the pH was adjusted to 5 by HCl (1M), heated to 80 ℃ in a water bath for 24h. And washing with water after the reaction is finished, and placing in an oven at 80 ℃ for 24 hours to obtain the modified graphene oxide.
2) Weighing 23 parts by weight of polyurethane, 35 parts by weight of phytic acid and CaCl 2 7 parts by weight of modified graphene oxide and 35 parts by weight of modified graphene oxide. Firstly, modified graphene oxide, phytic acid and CaCl are subjected to 2 Dispersing in deionized water, performing ultrasonic treatment for 10min, adjusting the pH to 8 by NaOH (1M), heating to 80 ℃ in a water bath, and reacting for 24h. And obtaining an intermediate product after the reaction is finished.
3) The intermediate product is added into polyurethane drop by drop and stirred for 1h at normal temperature. Pouring the mixture into a mold after the reaction is finished, and placing the mold in an oven at 80 ℃ for drying for 24 hours to obtain the contrast material 3.
Comparative example 4
1) 23 parts of polyurethane, 35 parts of phytic acid, 27 parts of CaCl and 35 parts of graphene oxide are weighed. Firstly, graphene oxide, phytic acid and CaCl2 are dispersed in deionized water for 10min, the pH is adjusted to 8 through NaOH (1M), and water bath heating is carried out to 80 ℃ for reaction for 24h. And obtaining an intermediate product after the reaction is finished.
2) The intermediate product is added into polyurethane drop by drop and stirred for 1h at normal temperature. After the reaction is finished, mixing by a 30 ℃ internal mixer, pressing into a die for molding, and placing in an 80 ℃ oven for drying for 24 hours to obtain the comparative material 4.
And (3) testing:
the products obtained in examples 1 to 3 and 7 of the present invention and comparative examples 1 to 4 were cut to prepare standard bars, and tensile properties were measured according to GB/T13022-1991, and the test results are shown in Table 1.
Table 1: technical index of examples and comparative examples
| Project | Tensile Strength/MPa | Fracture toughness/MJ/m 3 |
| Example 1 | 452 | 18.3 |
| Example 2 | 400 | 20.2 |
| Example 3 | 374 | 24.5 |
| Example 7 | 448 | 18.1 |
| Comparative example 1 | 90 | 15.6 |
| Comparative example 2 | 135 | 3.5 |
| Comparative example 3 | 353 | 15.1 |
| Comparative example 4 | 62 | 11.2 |
As can be seen from the data in table 1, the results of examples 1-3 show that the tensile strength of the composite material increases with the weight ratio of the modified graphene oxide, which demonstrates that the modified two-dimensional material provides strength to the composite material, while the pi-pi conjugation of the graphene oxide and ellagic acid in example 1 provides a way for the interlaminar slip of the material to occur when the material is stretched by external force, and when the material is subjected to external force, the two-dimensional lamellae and ellagic acid are dislocated with each other to dissipate energy, thereby further improving the toughness of the material;
it can be seen from example 7 that the composite material has self-repairing property, and the repaired material can still reach the previous mechanical standard. The self-repairing performance of the composite material is derived from metal complexation and hydrogen bonding in a system;
comparative examples 1-2 demonstrate the synergistic effect of multiple non-covalent bonds by controlling the presence of different non-covalent bonds, wherein the complexing ability of phytic acid to metal ions can be achieved by controlling the pH, so the pH of comparative example 1 is set to be 5; the presence of hydrogen bonds can be achieved by controlling the polyurethane content, so that comparative example 2 is set without polyurethane, so that the system lacks the hydrogen bonding effect between phytic acid and polyurethane, thereby illustrating the disadvantage of a single non-covalent bond. From the results, compared with the examples, the strength of the composite material is weakened due to single hydrogen bond or metal complexation in comparative examples 1-2, which shows that the mechanical properties of the material can be remarkably improved due to the synergistic effect of multiple non-covalent bonds;
comparative example 3 is an unmelted composite, with two-dimensional sheets of material built up in this way stacked on top of each other to form a typical "brick-mud" structure, as shown in fig. 2. In the embodiment of the invention, the two-dimensional sheets in the material extruded by the internal mixer are mutually extruded to form a mortise-tenon structure which is cross-interlocked, as shown in figure 1, compared with a planar structure under the same condition, the performance of the composite material with the mortise-tenon structure is improved to a certain extent, the improvement of the performance is attributed to different stress transmission paths, when in the planar structure, the stress is transmitted through polyurethane, and when in the mortise-tenon structure, the stress is transmitted through a harder two-dimensional material layer, so that the tensile strength of the composite material is effectively improved.
According to the invention, polyurethane, a polyphenol compound, a metal ion compound and a modified two-dimensional material are blended by a one-pot method to prepare the high-strength high-toughness plastic recyclable composite material. The composite material provides high-strength and high-toughness performance through the synergistic effect of multiple non-covalent bonds, and the whole preparation process is economical and feasible and environment-friendly. The preparation technology system is environment-friendly, safe and sanitary, has no organic pollution emission and solvent residue, and can be used in the fields of aerospace, electronics, military, civil engineering and machinery.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (17)
1. The non-covalent bond cross-linked high-strength high-toughness plastic recyclable composite material is characterized by comprising, by total weight of the composite material, 5.5-45 parts by weight of polyurethane, 25-43 parts by weight of polyphenol compounds, 5-8.5 parts by weight of metal ion compounds and 25-43 parts by weight of modified two-dimensional materials, wherein the modified two-dimensional materials are two-dimensional materials subjected to ellagic acid surface modification, and the two-dimensional materials comprise one or more of graphene oxide, graphene, montmorillonite and transition metal two-dimensional materials;
the preparation method of the composite material comprises the following steps:
1) Blending the modified two-dimensional material, the polyphenol compound and the metal ion compound in water, and adjusting the pH value to 5-8.5, and obtaining an intermediate product after the reaction is finished;
2) And dripping the intermediate product into polyurethane solution under stirring, mixing, pressing into a mold for molding by mixing through an internal mixer after the reaction is finished, and drying to obtain the product.
2. The non-covalent cross-linked high-strength high-toughness plastic recyclable composite according to claim 1, wherein the composite has a tensile strength of greater than 400MPa and a toughness of greater than 20MJ/m 3 。
3. The non-covalent cross-linked high-strength high-toughness plastic recyclable composite according to claim 1, wherein the polyphenolic compound comprises one or a combination of more than two of tannic acid, phytic acid, and gallic acid.
4. A non-covalent cross-linked high strength high toughness plastic recyclable composite according to claim 3, wherein the polyphenolic compound is phytic acid.
5. The non-covalent cross-linked high strength high toughness plastic recyclable composite according to claim 1, wherein the metal ions in the metal ion compound comprise Ca 2+ 、Mg 2+ 、Fe 2+ 、Fe 3+ One or a combination of two or more of them.
6. The non-covalent cross-linked high strength high toughness plastic recyclable composite according to claim 5, wherein the metal ion is Ca 2+ 。
7. The non-covalent cross-linked high strength, high toughness, plastic recyclable composite according to claim 1, wherein the metal ion compound is a chloride of the metal ion.
8. The non-covalent cross-linked high-strength high-toughness plastic recyclable composite according to claim 1, wherein the two-dimensional material is graphene oxide.
9. The non-covalent cross-linked high strength, high toughness, plastic recyclable composite according to claim 1, wherein in step 1), the pH is adjusted to 5.5 to 8.5.
10. The non-covalent cross-linked high strength, high toughness, plastic recyclable composite according to claim 9, wherein in step 1), the pH is adjusted to 6.0 to 8.5.
11. The non-covalent cross-linked high strength, high toughness, plastic recyclable composite according to claim 9, wherein in step 1), the pH is adjusted to 5.0.
12. The non-covalent cross-linked high strength, high toughness, plastic recyclable composite according to claim 9, wherein in step 1), the pH is adjusted to 8.0.
13. The non-covalent cross-linked high-strength high-toughness plastic recyclable composite according to claim 1, wherein in the step 1), the reaction condition is that the reaction is carried out for 20-24 hours under the water bath condition of 60-80 ℃.
14. The non-covalent cross-linked high-strength high-toughness plastic recyclable composite according to claim 1, wherein in the step 2), the intermediate product is dripped into the polyurethane solution under stirring to blend for 1-2h.
15. The non-covalent cross-linked high-strength high-toughness plastic recyclable composite according to claim 1, wherein in step 2), the internal mixer is used for mixing at 25-30 ℃ for 1-2h.
16. The non-covalent cross-linked high strength high toughness plastic recyclable composite according to claim 1, wherein in step 2), the drying is performed at 40-80 ℃ for 20-24 hours.
17. A non-covalent cross-linked high strength high toughness plastic recyclable composite as described in any one of claims 1-16 for use in aerospace, electronics, military, civil engineering and mechanical applications.
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| CN114085484A (en) * | 2021-11-26 | 2022-02-25 | 江南大学 | High-strength high-toughness composite material, preparation method and application |
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| CN102219211A (en) * | 2011-04-16 | 2011-10-19 | 华南理工大学 | Method for reducing and decorating graphene oxide by plant polyphenol and derivant thereof |
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