CN114790305A - Carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material and preparation method and application thereof - Google Patents

Carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material and preparation method and application thereof Download PDF

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CN114790305A
CN114790305A CN202210577029.0A CN202210577029A CN114790305A CN 114790305 A CN114790305 A CN 114790305A CN 202210577029 A CN202210577029 A CN 202210577029A CN 114790305 A CN114790305 A CN 114790305A
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polybutadiene
polystyrene
vinylpyridine
composite material
solution
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CN114790305B (en
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谢芳
宫晓博
李联杰
阮超
吴迪
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Harbin Institute of Technology Weihai
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Harbin Institute of Technology Weihai
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

The invention belongs to the field of nano composite material preparation, and particularly discloses a carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material, and a preparation method and application thereof. The carbon oxide nano onion is used as an additive, the nano composite material taking the polybutadiene-polystyrene-vinylpyridine copolymer as the matrix is prepared through simple solvent reaction, and the preparation process does not need pressurization and does not need to add a catalyst. The process method for preparing the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material is simple, easy to operate, low in energy consumption, low in cost, mild and easy to control in conditions and low in equipment requirement, and the prepared composite material has the functions of self-repairing and shape memory. The invention has great promotion effect on the application of the intelligent composite material in the fields of building, automobile, maritime work, aviation, aerospace, medicine and the like.

Description

Carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of nano composite materials, and particularly relates to a carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material as well as a preparation method and application thereof.
Background
The intelligent material is a novel functional material which can sense external excitation and complete corresponding judgment and specific response, and is one of important directions for the development of modern high-technology new materials. The development significance of the intelligent material is mainly to realize the structural function integration and diversification of the material, namely, the functions of sensing, feedback, information identification and accumulation, response, self-diagnosis, self-repair, self-adaptation and the like are realized through material design.
Polybutadiene rubber is one of synthetic rubbers, has the advantages of high elasticity, good low-temperature resistance, excellent wear resistance, good flexibility resistance, low heat generation and the like, and is widely applied to the fields of manufacturing industry, transportation, electronic communication, aerospace and the like. However, in the traditional rubber industry, polybutadiene generally needs to be used after being crosslinked through a vulcanization process, and is difficult to recycle once being aged due to vulcanization. Thermoplastic styrene shape memory polymers are thermoplastic elastomers prepared from styrene and butadiene by block or graft polymerization. The copolymer with the shape memory function can be obtained by controlling the proportion of the comonomer, wherein styrene and the like with high glass transition temperature are used as reversible phases, and butadiene with low glass transition temperature is used as a stationary phase. When the temperature exceeds 150 ℃, the two-phase structure can be melted, and can be processed by extrusion molding, injection molding and other processing molding methods to obtain a product with a required shape, and the product with the shape memory function can be obtained by cooling the product to room temperature. However, the long-term use of the thermoplastic material causes the molecules to be oriented along the direction of the external force action, which leads to the reduction of the memory performance of the material and even the complete loss of the memory performance.
Poly (styrene-vinylpyridine) is a multifunctional polymer whose pyridine function is a six-membered heterocyclic ring containing one nitrogen atom which can be bonded by electrophilic attack, i.e. the pyridine function has some basicity.
The carbon nano onion is a novel carbon nano material, has excellent physical and chemical properties such as high specific surface area, high conductivity, good structure and chemical stability, and has wide application prospects in the fields of electromagnetic shielding, energy conversion and storage, catalysis, lubrication and the like.
Disclosure of Invention
In order to overcome the defects that the existing polybutadiene-polystyrene shape memory material is single in function, easy to age, difficult to recover and recycle and the like, the invention provides a carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides a preparation method of a carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material, which comprises the following steps:
mixing carbon nano onion and a first strong acid solution to prepare a suspension, adding a second strong acid solution under the condition of stirring, cooling by using ice water, and heating for reaction;
step two, dissolving the product (carbon oxide nano onion) obtained in the step one and zinc acetate in a mixed solution of water and ethanol to obtain a solvent I; polybutadiene and zinc acetate are dissolved in toluene to obtain a solution II; mixing the solution I and the solution II, standing for layering, and adding a toluene solution of polystyrene-vinyl pyridine (poly (4-vinylpyridine-co-styrene));
and step three, evaporating the solvent and drying to obtain the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material.
In some specific embodiments, in the step one, the cooling is ice-water bath cooling for 10 to 60 min.
Preferably, in the first step, the heating reaction is carried out under the condition of heating to 60-100 ℃ for 10-90 min; preferably, the reaction is carried out at 80 ℃ for 30 min.
In a preferred embodiment, in the first step, the first strong acid solution is concentrated sulfuric acid;
preferably, the second strong acid solution is a mixed solution of concentrated sulfuric acid and concentrated nitric acid, and the mixing volume ratio is 1: 1-4, and more preferably 1: 3;
preferably, the mass fraction of the concentrated sulfuric acid is more than or equal to 95 percent;
preferably, the mass fraction of the concentrated nitric acid is more than or equal to 65 percent.
In certain specific embodiments, step one further comprises post-treatment comprising dilution, standing and centrifugation;
preferably, the standing time is more than 12 hours, and further preferably 24 hours;
preferably, the centrifugal rotation speed is more than 4000 rpm;
preferably, the dilution, standing and centrifugation are repeated 2-4 times.
Specifically, the post-treatment is to add distilled water into the dispersion liquid obtained by the heating reaction for dilution, to stand for more than 12 hours, and then to centrifuge the dispersion liquid at the rotating speed of more than 4000 rpm; adding distilled water, standing, centrifuging and repeating for 2-4 times, and collecting black precipitate; the time for the standing is preferably 24 hours.
In a preferred embodiment, in the first step, a ratio relationship among the carbon nano-onions, the first strong acid solution and the second strong acid solution is 10 mg: 1-10 mL: 1-10 mL.
In a preferable embodiment, in the second step, in the solution I, the mass ratio of the product obtained in the first step to zinc acetate is 1-10: 1.
in a preferred embodiment, in the second step, the mass ratio of the polybutadiene to the zinc acetate in the solution II is 1 to 100: 1, preferably 10: 1;
preferably, the mass ratio of polybutadiene to polystyrene-vinylpyridine is 100: 1 to 10.
In a preferred embodiment, in step three, the evaporation solvent is rotary evaporation.
Preferably, the drying is vacuum drying.
Specifically, the drying is drying in a vacuum drying oven. The solvent removed during the drying process comprises toluene, water, ethanol and acetic acid; the drying temperature is not particularly limited, but is generally 50 ℃ or higher; the drying time is determined by the drying temperature and is generally more than 24 h.
In another aspect, the invention also provides the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material prepared by the preparation method.
In another aspect, the invention provides application of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in preparing an intelligent material, in particular application in preparing a self-repairing material and a shape memory material.
Compared with the prior art, the invention has the beneficial effects that:
1. the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material provided by the invention has self-repairing and shape memory functions; by adjusting the raw material formula, the composite material meeting different application requirements can be synthesized, and the composite material has a huge application prospect in the fields of buildings, automobiles, maritime work, aviation, aerospace, medicine and the like;
2. the invention uses soluble acetate-zinc acetate to provide zinc ions which form salt with carboxylic acid group modified on polybutadiene and attract pyridine functional group on polystyrene-vinylpyridine with certain alkalinity, thus having metal coordination effect between polybutadiene and polystyrene vinylpyridine to replace vulcanization crosslinking, omitting vulcanization process and catalyst added in vulcanization, and preparing rubber (PB-COO) with shape memory and self-repair effect - /Zn 2+ /PS-VP) with addition of carbonThe nano onion is used for preparing the composite material, so that the binding force of the composite material is enhanced, and the composite material is endowed with multiple functions, and the synthesis method has the characteristics of simple process, low energy consumption, mild and easily-controlled conditions, low requirement on equipment and the like;
3. the preparation method provided by the invention has the advantages of low raw material price, simple preparation method and lower cost.
Drawings
FIG. 1 is a self-healing mechanism diagram of the carbon oxide nano-onion/polybutadiene-polystyrene-vinylpyridine composites of examples 1-4.
Fig. 2 is a self-repair test chart of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in example 2.
FIG. 3 is a tensile stress-strain plot of the carbon oxide nano-onion/polybutadiene-polystyrene-vinylpyridine composite in example 1.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. The scope of the invention is not limited to the specific embodiments.
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples:
carbon nano-onions were purchased from Nanjing Mingchang New Material science and technology, Inc.
The mass fraction of the concentrated sulfuric acid is 95%.
The mass fraction of the concentrated nitric acid is 65 percent.
Polystyrene-vinyl pyridine (Poly (4-Vinylpyridine-co-Styrene)) was purchased from Scientific Polymer Products.
Example 1:
the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in the embodiment is prepared by the following steps:
step one, weighing 50mg of carbon nano-onion and 35mL of concentrated sulfuric acid, and mixing to prepare a suspension; adding 15mL of concentrated sulfuric acid and 25mL of concentrated nitric acid into the suspension under the condition of continuously stirring, cooling for 30min by using ice water, and heating to 80 ℃ for reaction for 30min to obtain a dispersion liquid;
step two, adding 300mL of distilled water into the dispersion liquid obtained in the step one for dilution, and then standing for 12 hours; placing the diluted solution after standing in a centrifuge for centrifugation, wherein the rotation speed of the centrifuge adopts 7500rpm, repeating the dilution and centrifugation processes for 2 times, and collecting black solids to obtain carbon oxide nano onions;
step three, dissolving 50mg of carbon oxide nano onion obtained in the step two and 10mg of zinc acetate in a mixed solution of 1mL of water and 1mL of ethanol; 5000mg of polybutadiene and 500mg of zinc acetate are dissolved in 20mL of toluene; fully mixing the two solutions, standing, adding 10mL (containing 500mg of polystyrene-vinylpyridine) of 5% polystyrene-vinylpyridine toluene solution after the solution is layered to form a gray mixed solution;
and step four, removing most of the solvent in the gray mixed solution obtained in the step three by using a rotary evaporator, then placing the obtained mixture in a vacuum drying oven for drying at 50 ℃ for 24 hours, and removing the residual solvent to obtain the gray-brown semitransparent carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material.
Example 2:
the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in this example is the same as example 1, except that: the dilution and centrifugation process in step two was repeated 4 times, the rest being the same.
Example 3:
the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in this example is the same as example 1, except that: the amount of polystyrene-vinylpyridine used in step three was changed to 250mg, the rest being the same.
Example 4:
the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in this example is the same as example 1, except that: step three, dissolving 50mg of carbon oxide nano onion obtained in the step two and 5mg of zinc acetate in a mixed solution of 1mL of water and 1mL of ethanol; 5000mg of polybutadiene and 250mg of zinc acetate are dissolved in 20mL of toluene; the two solutions were mixed well, left to stand, and after the solutions were layered, 10mL (containing 500mg of polystyrene-vinylpyridine) of a 5% polystyrene-vinylpyridine solution in toluene was added to form a gray mixed solution. The rest is the same.
FIG. 1 shows the self-healing mechanism of the composites of examples 1-4: as can be seen from the figure, a large number of pyridine functional groups provided by polystyrene-vinyl (PSVP) pyridine, carboxyl groups of carboxyl-terminated polybutadiene (PB-COO) exist in the composite sample - ) And zinc ion (Zn) 2+ ) Once the formed metal coordination bonds are cut off, the dynamic metal coordination bonds can be recombined to form new metal coordination bonds, so that the composite material can complete a self-repairing process.
Comparative example 1:
in this comparative example, the material prepared did not include carbon oxide nano-onions, and the preparation method was as follows:
preparing 5000mg of polybutadiene and 15mg of zinc acetate into a toluene solution; then 10mL of toluene solution of polystyrene-vinylpyridine with the concentration of 5% (containing 500mg of styrene-vinylpyridine) is added to form a milky white mixed solution;
removing most of the solvent in the milky white mixed solution obtained in the step one by adopting a rotary evaporator, then placing the obtained mixture in a vacuum drying oven for drying for 24 hours, and removing the residual solvent to obtain a yellowish-earthy translucent polybutadiene-polystyrene-vinylpyridine polymer material;
effect embodiment:
self-repairing performance test:
after the composite materials in the embodiments 1 to 4 and the comparative example 1 are completely cut off, the cuts are found to be completely healed after being placed side by side for 6-12 hours without applying external force, so that the composite material provided by the embodiment has the self-repairing performance. FIG. 2 shows the test chart during the self-healing process of example 2, from which it can be seen that the composite after the repair achieves complete healing. In addition, it was found in the experiment that the time required for the composite material of example 4 to completely heal was much longer than that of the composite materials of examples 1 to 3 and comparative example 1.
And (3) testing mechanical properties:
the mechanical properties of the composite material and the tensile stress-strain curve in the self-repairing process after the composite material is cut off are tested, and fig. 3 shows the test results in the example 1.
Testing the memory performance:
the composite materials in examples 1-4 and comparative example 1 are made into a rod-shaped sample, electrodes are added at two ends of the rod-shaped sample, the temperature of the sample in examples 1-4 is increased due to the heat effect generated by electrifying, the sample is softened, at the moment, the sample is bent into a U shape by external force, the temperature of the sample is reduced after the electrodes are removed, the sample can be kept in the U shape, when the two ends of the sample are electrified again, the shape of the sample is restored to the original rod shape, and the deformation of the sample in the shape recovery process can push the table tennis ball to move, wherein the distance for the composite material in example 3 to drive the table tennis ball to move is far less than that of the composite materials in examples 1-2 and example 4. After the composite material of the comparative example 1 is electrified, the temperature does not rise, the sample does not become soft, and the shape change and recovery cannot be realized by an electrified heating mode.
The embodiment, the comparative example and the effect embodiment prove that the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material provided by the invention has self-repairing and shape memory functions. The self-repairing time and the shape memory driving force of the prepared composite material can be controlled by adjusting the proportion of each component.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The preparation method of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material is characterized by comprising the following steps of:
mixing carbon nano onion and a first strong acid solution to prepare a suspension, adding a second strong acid solution under the condition of stirring, cooling, and heating for reaction;
step two, dissolving the product obtained in the step one and zinc acetate in a mixed solution of water and ethanol to obtain a solution I; polybutadiene and zinc acetate are dissolved in toluene to obtain a solution II; mixing the solution I and the solution II, standing for layering, and adding a toluene solution of polystyrene-vinylpyridine;
and thirdly, evaporating the solvent and drying to obtain the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material.
2. The preparation method according to claim 1, wherein in the first step, the heating reaction is carried out under conditions of heating to 60-100 ℃ for 10-90 min; preferably, the reaction is carried out at 80 ℃ for 30 min.
3. The method according to claim 1, wherein in the first step, the first strong acid solution is concentrated sulfuric acid;
preferably, the second strong acid solution is a mixed solution of concentrated sulfuric acid and concentrated nitric acid; the mixing volume ratio is 1: 1-4, and more preferably 1: 3;
preferably, the mass fraction of the concentrated sulfuric acid is more than or equal to 95 percent;
preferably, the mass fraction of the concentrated nitric acid is more than or equal to 65 percent.
4. The method of claim 1, wherein the first step further comprises post-treatment comprising dilution, standing and centrifugation;
preferably, the standing time is more than 12 hours, and further preferably 24 hours;
preferably, the rotation speed of the centrifugation is more than 4000 rpm;
preferably, the dilution, standing and centrifugation are repeated 2-4 times.
5. The method according to claim 1, wherein in the first step, the carbon nano-onion, the first strong acid solution and the second strong acid solution are mixed in a ratio of 10 mg: 1-10 mL: 1-10 mL.
6. The preparation method according to claim 1, wherein in the second step, in the solution I, the mass ratio of the product obtained in the first step to zinc acetate is 1-10: 1.
7. the preparation method according to claim 1, wherein in the second step, the mass ratio of the polybutadiene to the zinc acetate in the solution II is 1-100: 1, preferably 10: 1;
preferably, the mass ratio of polybutadiene to polystyrene-vinylpyridine is 100: 1 to 10.
8. The method according to claim 1, wherein in step three, the evaporation solvent is rotary evaporation;
preferably, the drying is vacuum drying.
9. The carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material obtained by the preparation method of any one of claims 1-8.
10. The application of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in the preparation of intelligent materials is characterized by being used in the preparation of self-repairing materials and shape memory materials.
CN202210577029.0A 2022-05-25 2022-05-25 Carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material and preparation method and application thereof Active CN114790305B (en)

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CN111171520A (en) * 2020-02-24 2020-05-19 中国石油大学(华东) Modified carbon nanotube reinforced shape memory epoxy resin composite material and preparation method thereof
CN111868146A (en) * 2018-01-11 2020-10-30 纳诺科尔有限公司 Composite materials comprising mechanical ligands
CN114230848A (en) * 2021-12-24 2022-03-25 湖南绿舟新型材料科技有限公司 Nano zinc oxide grafted polystyrene composite foam board material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180298154A1 (en) * 2014-11-11 2018-10-18 Nanocore Aps Design of composite materials with desired characteristics
CN111868146A (en) * 2018-01-11 2020-10-30 纳诺科尔有限公司 Composite materials comprising mechanical ligands
CN111171520A (en) * 2020-02-24 2020-05-19 中国石油大学(华东) Modified carbon nanotube reinforced shape memory epoxy resin composite material and preparation method thereof
CN114230848A (en) * 2021-12-24 2022-03-25 湖南绿舟新型材料科技有限公司 Nano zinc oxide grafted polystyrene composite foam board material and preparation method thereof

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