CN110106712B - Mussel foot adhesion-simulated polymer-skeleton interface reinforcing agent and preparation method thereof - Google Patents
Mussel foot adhesion-simulated polymer-skeleton interface reinforcing agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer-skeleton adhesion and relates to a mussel foot adhesion-imitating polymer-skeleton interface reinforcing agent and a preparation method thereof, wherein the mussel foot adhesion-imitating polymer-skeleton interface reinforcing agent is prepared from the following components, by mass, 100 parts of a polar polymer, 0.05-50 parts of a nano filler, 0.01-10 parts of an amine compound, 0.01-10 parts of a polyphenol compound and 0.01-10 parts of a polyvalent metal salt. Based on the adhesion mechanism of mussel feet, the adhesion system of mussel foot-like protein is constructed by replacing expensive dopamine with cheap commercial polyphenolic compounds, amine compounds and polyvalent metal salts, so that the interfacial adhesion strength between polymer and skeleton is improved.
Description
Technical Field
The invention belongs to the technical field of polymer-skeleton adhesion, and particularly relates to a mussel foot adhesion-simulating polymer-skeleton interface reinforcing agent and a preparation method thereof.
Background
The skeleton structure can remarkably improve the mechanical and structural stability of polymer products, and can reduce the mechanical relaxation phenomenon (creep and stress relaxation) of the polymer products, so that the skeleton structure can be used as a structural member to replace a metal structural member, is favorable for the light weight of the products, and has wide application requirements in the fields of aerospace, automobiles, rail transit and the like.
The common polymer product framework materials comprise cord threads, cord fabrics, glass fibers, glass fiber cloth, carbon fibers, carbon fiber cloth, steel wires and the like, the framework materials not only have smooth microscopic surfaces, but also present physical/chemical inertness and have no strong physical/chemical action with a polymer matrix, the interface action between the polymer matrix and the framework is weaker due to the combined action of the two aspects, the polymer matrix and the framework are easy to delaminate under the action of external force, and external loads cannot be effectively transferred to the framework, so that the framework cannot play a role in reinforcement. Therefore, the backbone must be modified to increase the interfacial adhesion between the backbone and the polymer matrix.
In terms of adhesion, it is impressive that marine organisms such as mussels in nature can be firmly adsorbed on the surface of ships or rocks. Researches show that the mussel foot muscle protein responsible for adhesion mainly consists of a polydopamine chemical network structure and a catechol-ferric ion physical network structure. Accordingly, many scientists have successfully used dopamine chemistry in basic research for surface coatings, biomimetic mineralization and hydrogels [ chem. rev.,2014,114, 5057-. However, dopamine is expensive and is difficult to popularize in most commercial fields, including the field of polymer-matrix bonding according to the present invention.
Disclosure of Invention
In view of the above situation, the present invention aims to provide a mussel foot adhesion-imitating polymer-skeleton interface reinforcing agent and a preparation method thereof, wherein the polymer-skeleton interface reinforcing agent provided by the present invention is prepared from the following components: 100 parts by mass of polar polymer, 0.05-50 parts by mass of nano filler, 0.01-10 parts by mass of amine compound, 0.01-10 parts by mass of polyphenol compound and 0.01-10 parts by mass of polyvalent metal salt. The interface enhancer is based on the adhesion mechanism of mussel feet, and a mussel foot muscle protein adhesion promoting system is constructed by replacing expensive dopamine with cheap commercial polyphenol compounds, amine compounds and polyvalent metal salts. In the system, under the alkaline environment provided by the amine compound, on one hand, the polyphenol compound and the amine compound can generate Michael addition and Schiff base reaction to form a chemical network, and on the other hand, the polyphenol compound and the polyvalent metal ion can generate multi-coordination complexation to form a physical network, and the structure of the system is similar to that of the adhesive muscle protein secreted by mussel feet. On the basis, the strength of the interface reinforcing agent is improved on one hand, and the roughness of the framework is improved on the other hand through the introduction of the nano filler, so that the adhesive force between the polymer matrix and the framework is further increased.
The polar polymer is: one or more of phenolic resin, urea resin, melamine resin, epoxy resin, novolac epoxy resin, polyurethane, polyurea, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, chloroprene rubber, brominated butyl rubber, nitrile rubber, polyacrylic acid, polymethacrylic acid, polyvinyl acetate, acrylate rubber, fluororubber and derivatives thereof.
The nano filler is as follows: silicon dioxide, carbon black, fullerene, carbon nano tube, graphene, metal particles, metal compounds, calcium carbonate, boric acid, borate, borax, halloysite nano tube, hydroxyapatite, clay with the number of layers less than or equal to 20, graphite with the number of layers less than or equal to 20, boron nitride with the number of layers less than or equal to 20, black phosphorus with the number of layers less than or equal to 20 and one or more mixtures of derivatives thereof.
The amine compound is as follows: one or more mixtures of non-dopamine compounds having a primary amine group in the structure. For example, polyethyleneimine, ethylenediamine, γ -aminopropyltriethoxysilane, etc.
The polyphenol compound is: one or more of non-dopamine compounds with the number of phenolic hydroxyl groups more than or equal to 2 in the structure. Such as tea tannin, tannic acid, valonia extract, etc.
The polyvalent metal salt is: one or more mixtures of metal salts containing metal ions with the valence more than or equal to 2.
The preparation method of the polymer-framework interface reinforcing agent provided by the invention comprises the following steps:
1) dispersing the nano filler: dispersing the nano filler in a solvent A under a certain condition with the assistance of a phenolic auxiliary agent to obtain a dispersion liquid A;
2) dissolution of polar polymer: dispersing a polar polymer in a solvent B under a certain condition to obtain a dispersion liquid B, wherein the solvent A and the solvent B are the same or can be mutually soluble;
3) preparing an interface reinforcing agent: and mixing the dispersion liquid A and the dispersion liquid B under a certain condition, and then sequentially adding the multivalent metal salt and the amine compound for reaction to obtain the interface enhancer dispersion liquid.
The polymer-framework interface reinforcing agent can be used as an interface reinforcing agent of a rubber matrix-reinforcing framework, a thermoplastic plastic matrix-reinforcing framework and a thermosetting resin matrix-reinforcing framework, and the bonding strength of the interface between the polymer and the framework is obviously improved.
Compared with the prior art, the adhesion-promoting system with a mussel-like foot muscle protein structure is successfully constructed by replacing expensive dopamine with cheap commercial polyphenol compounds, amine compounds and polyvalent metal salts, and the adhesion strength between a polymer and a skeleton is remarkably improved through a synergistic effect of the three. Compared with commercial interface enhancers, the mussel-like foot adhesion system of the invention shows superior effect in improving polymer-skeleton adhesion.
Description of the drawings:
FIG. 1 is a scanning electron micrograph of an unmodified cord of example 1.
FIG. 2 is a scanning electron micrograph of a modified cord of the self-made interface enhancer of example 1.
FIG. 3 is a scanning electron micrograph of the unmodified cord of example 1 after it has been extracted from the tread rubber of a tire.
FIG. 4 is a scanning electron micrograph of the modified cord of the self-made interface enhancer of example 1 after being extracted from the tread rubber of a tire.
Detailed Description
The invention is explained in further detail below by means of specific embodiments with reference to the drawings. It is to be understood that the following examples are intended to illustrate the invention and are not intended to limit its scope.
Comparative example 1:
a polymer-backbone interface enhancer comprising the composition: 100 parts by mass of chloroprene rubber, 50 parts by mass of silicon dioxide, 10 parts by mass of polyethyleneimine and 5 parts by mass of cobalt chloride. The interface reinforcing agent is prepared by the following steps:
1) adding silicon dioxide into 100 parts by mass of water at 45 ℃ at 1000r/min, and stirring for 1h to prepare silicon dioxide dispersion liquid;
2) at the temperature of 60 ℃ and at the speed of 4500r/min, adding chloroprene rubber into 200 parts by mass of acetone, and stirring for 3 hours to prepare a chloroprene rubber solution;
3) firstly, stirring and mixing the prepared silicon dioxide dispersion liquid and the chloroprene rubber solution for 1h at the temperature of 25 ℃ and the speed of 1000 r/min; then, cobalt chloride and polyethyleneimine are sequentially added and stirred for 1 hour, and the polymer-framework interface enhancer dispersion liquid is prepared.
According to the national standard GB/T2942-2009, an average withdrawal force of 58.3N was measured, which is a small improvement over the untreated cord average withdrawal force of 47.2N, but is much lower than the average withdrawal force of 97.3N for the polyester cord treated with the commercial interface enhancer.
Comparative example 2:
a polymer-backbone interface enhancer comprising the composition: 100 parts of chloroprene rubber, 50 parts of silicon dioxide, 5 parts of tea tannin and 5 parts of cobalt chloride. The interface reinforcing agent is prepared by the following steps:
1) adding silicon dioxide into 100 parts by mass of water under the condition of 45 ℃ and 1000r/min and with the assistance of tea tannin, and stirring for 1h to prepare silicon dioxide dispersion liquid;
2) at the temperature of 60 ℃ and at the speed of 4500r/min, adding chloroprene rubber into 200 parts by mass of acetone, and stirring for 3 hours to prepare a chloroprene rubber solution;
3) firstly, stirring and mixing the prepared silicon dioxide dispersion liquid and the chloroprene rubber solution for 1h at the temperature of 25 ℃ and the speed of 1000 r/min; then, cobalt chloride was added and stirred for 1 hour to prepare a polymer-skeleton interface enhancer dispersion.
According to the national standard GB/T2942-2009, an average withdrawal force of 60.3N was measured, which is a small improvement over the untreated cord average withdrawal force of 47.2N, but still lower than the average withdrawal force of 97.3N for the polyester cord treated with the commercial interface enhancer.
Comparative example 3:
a polymer-backbone interface enhancer comprising the composition: 100 parts of chloroprene rubber, 50 parts of silicon dioxide, 10 parts of polyethyleneimine and 5 parts of tea tannin. The interface reinforcing agent is prepared by the following steps:
1) adding silicon dioxide into 100 parts by mass of water under the condition of 45 ℃ and 1000r/min and with the assistance of tea tannin, and stirring for 1h to prepare silicon dioxide dispersion liquid;
2) at the temperature of 60 ℃ and at the speed of 4500r/min, adding chloroprene rubber into 200 parts by mass of acetone, and stirring for 3 hours to prepare a chloroprene rubber solution;
3) firstly, stirring and mixing the prepared silicon dioxide dispersion liquid and the chloroprene rubber solution for 1h at the temperature of 25 ℃ and the speed of 1000 r/min; then, polyethyleneimine is added and stirred for 1h to prepare the polymer-skeleton interface enhancer dispersion liquid.
According to the national standard GB/T2942-2009, the average withdrawal force of the cord was measured to be 68.1N, which is a greater improvement than the untreated cord average withdrawal force of 47.2N, but still lower than the average withdrawal force of 97.3N for the polyester cord treated with the commercial interface enhancer.
Example 1:
a polymer-backbone interface enhancer comprising the composition: 100 parts of chloroprene rubber, 50 parts of silicon dioxide, 10 parts of polyethyleneimine, 5 parts of tea tannin and 5 parts of cobalt chloride. The interface reinforcing agent is prepared by the following steps:
1) adding silicon dioxide into 100 parts by mass of water under the condition of 45 ℃ and 1000r/min and with the assistance of tea tannin, and stirring for 1h to prepare silicon dioxide dispersion liquid;
2) at the temperature of 60 ℃ and at the speed of 4500r/min, adding chloroprene rubber into 200 parts by mass of acetone, and stirring for 3 hours to prepare a chloroprene rubber solution;
3) firstly, stirring and mixing the prepared silicon dioxide dispersion liquid and the chloroprene rubber solution for 1h at the temperature of 25 ℃ and the speed of 1000 r/min; then, cobalt chloride and polyethyleneimine are sequentially added, and the mixture is stirred and reacted for 1 hour to prepare the polymer-framework interface enhancer dispersion liquid.
The prepared polymer-framework interface reinforcing agent dispersion liquid is coated on the surface of a polyester cord by dipping, and after the cord is dried, the cord and the tire tread rubber are vulcanized together. From a comparison of fig. 1 and 2, it was found that the surface of the unmodified cord was smooth, while the cord surface roughness after modification with the interface enhancer was significantly increased. According to the national standard GB/T2942-2009, the average withdrawal force of the cord was measured to be 163.7N, which is significantly improved compared with the average withdrawal force of 47.2N for the untreated cord and 97.3N for the polyester cord treated with the commercial interface enhancer. From comparison of fig. 3 and fig. 4, it is found that after the unmodified cord is extracted from the tire tread rubber, the surface is smooth and has no rubber, which indicates that the interface of the unmodified cord and the tire tread rubber is very weak, and the interface is firstly damaged in the extraction process, so that the applied load cannot be effectively transferred to the cord, and the extraction force is low; and after the cord thread modified by the self-made interface reinforcing agent is extracted from the tire tread rubber, a layer of tire tread rubber is attached to the surface of the cord thread, which shows that the interface between the modified cord thread and the tire tread rubber is very strong, external loading load can be effectively transferred to the cord thread in the extraction process, and fracture occurs in an interface layer near the cord thread, so that the extraction force is high. In addition, compared with comparative examples 1-3, the average drawing force of the cord of example 1 is greatly improved, which shows that the synergistic tackifying effect is achieved among the three components of the polyphenol compound, the amine compound and the multivalent metal salt.
Example 2:
a polymer-backbone interface enhancer comprising the composition: 100 parts of water-soluble polyurethane, 0.05 part of graphene oxide, 0.01 part of ethylenediamine, 0.01 part of tannic acid and 0.01 part of ferric chloride. The interface reinforcing agent is prepared by the following steps:
1) adding graphene oxide into 10 parts by mass of water under the assistance of tannic acid at the temperature of 25 ℃ and the speed of 3000r/min, and stirring for 3 hours to prepare a graphene dispersion liquid;
2) adding waterborne polyurethane into 100 parts by mass of water at 25 ℃ and 3000r/min, and stirring for 1h to prepare polyurethane dispersion;
3) firstly, stirring and mixing the prepared graphene dispersion liquid and polyurethane dispersion liquid for 5min at the temperature of 25 ℃ and under the condition of 3000 r/min; then, ferric trichloride and ethylenediamine are sequentially added, and stirring reaction is carried out for 30min, so as to obtain the polymer-skeleton interface enhancer dispersion liquid.
And dip-coating the prepared polymer-framework interface reinforcing agent dispersion liquid on the surface of the steel wire, and after the steel wire is dried, co-vulcanizing the steel wire and the tire bead rubber. According to the national standard GB/T3513-2001, the maximum withdrawal force of the steel wire was 1484.5N, while the average withdrawal force of the untreated steel wire was only 237.2N, and the average withdrawal force of the steel wire treated with the commercial interface enhancer was 1047.1N.
Example 3:
a polymer-backbone interface enhancer comprising the composition: 100 parts of phenolic resin, 1 part of montmorillonite nanosheet (one type of clay), 3 parts of halloysite nanotube, 5 parts of silicon dioxide, 3 parts of gamma-aminopropyltriethoxysilane, 10 parts of valonea extract and 10 parts of manganese sulfate. The interface reinforcing agent is prepared by the following steps:
1) under the conditions of 60 ℃ and 6000r/min and with the assistance of valonea extract, adding montmorillonite nanosheets, halloysite nanotubes and silicon dioxide into 20 parts by mass of water, and stirring for 15min to prepare montmorillonite nanosheet/halloysite nanotube/silicon dioxide nanofiller dispersion liquid;
2) adding phenolic resin into 50 parts by mass of ethanol at 25 ℃ at 500r/min, and stirring for 1h to prepare a phenolic resin solution;
3) firstly, stirring and mixing the prepared montmorillonite nanosheet/halloysite nanotube/silicon dioxide nanofiller dispersion liquid and phenolic resin solution for 1h at the temperature of 25 ℃ and at the speed of 300 r/min; then, manganese sulfate and gamma-aminopropyl triethoxysilane are added in sequence, and after stirring reaction for 3 hours, the polymer-framework interface enhancer dispersion liquid is prepared.
And (3) dipping the prepared polymer-framework interface reinforcing agent dispersion liquid on the surface of glass fiber cloth, drying the glass fiber cloth, and curing and molding the glass fiber cloth and epoxy resin to obtain the composite material. According to the national standard GB/T1843-2008, the cantilever beam impact strength of the composite material is 2880J/m, the cantilever beam impact strength of the composite material prepared by adopting untreated glass fiber cloth is only 1046J/m, and the cantilever beam impact strength of the composite material prepared by adopting the glass fiber cloth treated by the commercial interface reinforcing agent is 2387J/m.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the scope of the present invention is not limited thereto. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (4)
1. A mussel foot adhesion-simulating polymer-skeleton interface reinforcing agent is characterized by being prepared from the following components: 100 parts by mass of polar polymer, 0.05-50 parts by mass of nano filler, 0.01-10 parts by mass of amine compound, 0.01-10 parts by mass of polyphenol compound and 0.01-10 parts by mass of polyvalent metal salt, wherein the amine compound is one or a mixture of more than one non-dopamine compound containing primary amine group in the structure; the polyphenol compound is one or a mixture of more than one non-dopamine compound with the number of phenolic hydroxyl groups more than or equal to 2 in the structure; the polyvalent metal salt is one or a mixture of more of metal salts containing metal ions with the valence state more than or equal to 2; the polymer-framework interface reinforcing agent can be used as an interface reinforcing agent of a rubber matrix-reinforcing framework, a thermoplastic plastic matrix-reinforcing framework and a thermosetting resin matrix-reinforcing framework.
2. The polymer-matrix interface enhancer of claim 1, wherein the polar polymer is: one or more of phenolic resin, urea resin, melamine resin, epoxy resin, novolac epoxy resin, polyurethane, polyurea, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, chloroprene rubber, brominated butyl rubber, nitrile rubber, polyacrylic acid, polymethacrylic acid, polyvinyl acetate, acrylate rubber, fluororubber and derivatives thereof.
3. The polymer-matrix interface enhancer of claim 1, wherein the nanofiller is: silicon dioxide, carbon black, fullerene, carbon nano tube, graphene, metal particles, metal compounds, calcium carbonate, boric acid, borate, halloysite nano tube, hydroxyapatite, clay with the number of layers less than or equal to 20, graphite with the number of layers less than or equal to 20, boron nitride with the number of layers less than or equal to 20, black phosphorus with the number of layers less than or equal to 20 and one or more mixtures of derivatives of the black phosphorus and the black phosphorus.
4. A method of preparing a polymer-matrix interface enhancer according to any one of claims 1 to 3, comprising the steps of:
1) dispersing the nano filler: dispersing the nano filler in a solvent A under a certain condition with the assistance of a polyphenol compound to obtain a dispersion liquid A;
2) dissolution of polar polymer: dispersing a polar polymer in a solvent B under a certain condition to obtain a dispersion liquid B, wherein the solvent A and the solvent B are the same or can be mutually soluble;
3) Preparing an interface reinforcing agent: and mixing the dispersion liquid A and the dispersion liquid B under a certain condition, and then sequentially adding the multivalent metal salt and the amine compound for reaction to obtain the interface enhancer dispersion liquid.
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| CN113494025A (en) * | 2021-07-09 | 2021-10-12 | 江苏云睿汽车电器系统有限公司 | Polymer-skeleton interface nano reinforcing agent and preparation method thereof |
| CN113827768B (en) * | 2021-09-22 | 2022-12-09 | 苏州大学附属第二医院 | Preparation method of bionic scaffold carrying lysophosphatidic acid nanoparticles |
| CN114150508B (en) * | 2021-12-21 | 2022-10-14 | 中国科学院兰州化学物理研究所 | Functional liner fabric and preparation method thereof, liner fabric reinforced resin composite material and self-lubricating composite material |
| CN115353729B (en) * | 2022-09-05 | 2024-02-13 | 江南大学 | Non-covalent bond crosslinked high-strength high-toughness plastic recyclable composite material and preparation method and application thereof |
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