CN114790305B - 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 PDFInfo
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- CN114790305B CN114790305B CN202210577029.0A CN202210577029A CN114790305B CN 114790305 B CN114790305 B CN 114790305B CN 202210577029 A CN202210577029 A CN 202210577029A CN 114790305 B CN114790305 B CN 114790305B
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- C08L2201/12—Shape memory
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 invention prepares the nanocomposite material with polybutadiene-polystyrene-vinyl pyridine copolymer as a matrix by using carbon oxide nano onion as an additive and through simple solvent reaction, and the preparation process does not need pressurization or catalyst addition. The preparation method of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material is simple in process method, easy to operate, low in energy consumption, low in cost, mild and controllable in condition 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 construction, automobiles, maritime work, aviation, aerospace, medicine and the like.
Description
Technical Field
The invention belongs to the field of nano composite material preparation, and in particular relates to a carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material, and a preparation method and application thereof.
Background
The intelligent material is a novel functional material capable of sensing external excitation and completing corresponding judgment and specific response, and is one of important directions of development of new modern high-technology materials. The development significance of the intelligent material is mainly that the structural function integration and diversification of the material are realized, namely, the functions of sensing, feedback, information identification and accumulation, response, self-diagnosis, self-repair, self-adaption 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, 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 conventional rubber industry, polybutadiene is generally required to be crosslinked by a vulcanization process, and is difficult to recycle after aging due to vulcanization. Thermoplastic styrene shape memory polymers are thermoplastic elastomers prepared by block polymerization or graft polymerization of styrene and butadiene. The copolymer with shape memory function can be obtained by controlling the proportion of the comonomer, wherein the glass transition temperature of styrene and the like is high as a reversible phase, and the glass transition temperature of butadiene is low as a stationary phase. When the temperature exceeds 150 ℃, the two-phase structure can be melted, and the two-phase structure can be processed by processing and molding methods such as extrusion molding, injection molding and the like to obtain a product with a required shape, and the product with the shape memory function can be obtained by cooling the product to the room temperature. However, the long-term use of thermoplastic materials has the effect that the molecules are oriented in the direction of the external force, which results in a decrease or even complete loss of the memory properties of the material.
Poly (styrene-vinylpyridine) is a multifunctional polymer whose pyridine functionality is a six-membered heterocyclic ring containing a nitrogen atom that can form a bond by electrophilic attack, i.e., the pyridine functionality 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, 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 recycle and the like, the invention provides the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material and the preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
in one aspect, the invention provides a method for preparing a carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material, which comprises the following steps:
step one, mixing carbon nano onion and a first strong acid solution to prepare a suspension, adding a second strong acid solution under the stirring condition, cooling by ice water, and heating for reaction;
step two, dissolving the product (carbon nano onion oxide) 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-vinyl pyridine composite material.
In certain specific embodiments, in step one, the cooling is ice water bath cooling for 10-60 min.
In the first step, the heating reaction condition is that the heating reaction is carried out for 10 to 90 minutes at the temperature of between 60 and 100 ℃; preferably at 80℃for 30min.
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 to 4, more preferably 1:3, a step of;
preferably, the mass fraction of the concentrated sulfuric acid is more than or equal to 95%;
preferably, the mass fraction of the concentrated nitric acid is more than or equal to 65%.
In certain specific embodiments, step one further comprises post-treatment comprising dilution, standing, and centrifugation;
preferably, the time of the standing is 12 hours or more, more preferably 24 hours;
preferably, the centrifugal speed is 4000rpm or more;
preferably, the dilution, standing and centrifugation are repeated 2 to 4 times.
Specifically, the post-treatment is to add distilled water into the dispersion liquid obtained by the heating reaction for dilution, stand for more than 12 hours, and then centrifuge the dispersion liquid at a rotating speed of more than 4000 rpm; adding distilled water, standing, centrifuging and repeating for 2-4 times, and collecting black precipitate; the time of the standing is preferably 24 hours.
As a preferred embodiment, in the first step, the ratio relationship among the carbon nano onion, the first strong acid solution and the second strong acid solution is 10mg: 1-10 mL: 1-10 mL.
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, in the solution II, the mass ratio of the polybutadiene to the zinc acetate is 1 to 100:1, preferably 10:1, a step of;
preferably, the mass ratio of polybutadiene to polystyrene-vinylpyridine is 100:1 to 10.
In a preferred embodiment, in the third step, the evaporating 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 24 hours or more.
In still another aspect, the invention also provides the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material obtained by the preparation method.
In yet another aspect, the present invention provides the use of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material described above in the preparation of smart materials, in particular, in the preparation of self-healing materials, shape memory materials.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material provided by the invention has a self-repairing and shape memory function; by adjusting the raw material formula, the composite material meeting different application requirements can be synthesized, and has great application prospects in the fields of construction, automobiles, maritime work, aviation, aerospace, medicine and the like;
2. the rubber material generally needs to be improved in strength through vulcanization crosslinking, the zinc ions provided by soluble acetate-zinc acetate are salified with modified carboxylic acid groups on polybutadiene, and pyridine functional groups on polystyrene-vinylpyridine with certain alkalinity are attracted, so that metal coordination effect is achieved between the polybutadiene and the polystyrene-vinylpyridine to replace vulcanization crosslinking, the vulcanization process and a catalyst to be added in vulcanization are omitted, and the rubber (PB-COO - /Zn 2+ The PS-VP) and adding the carbon nano onion to prepare the composite material, so that the binding force of the composite material is enhanced, the multifunctional property of the composite material is provided, and the synthesis method has the characteristics of simple process, low energy consumption, mild and controllable condition, 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 low cost.
Drawings
FIG. 1 is a graph of the self-healing mechanism of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composites of examples 1-4.
FIG. 2 is a self-healing test of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite of example 2.
FIG. 3 is a tensile stress-strain plot of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite of example 1.
Detailed Description
The present invention will be described in detail by way of specific examples. The scope of the invention is not limited to this particular embodiment.
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
In the following examples:
carbon nano onions were purchased from Nanjing Mingchang new materials technology Co.
The mass fraction of the concentrated sulfuric acid is 95%.
The mass fraction of the concentrated nitric acid is 65%.
polystyrene-Vinylpyridine (Poly (4-Vinylpyridine-co-Styrene)) was purchased from Scientific Polymer Products company.
Example 1:
the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in this example was prepared by the following steps:
firstly, weighing 50mg of carbon nano onion and mixing with 35mL of concentrated sulfuric acid to prepare a suspension; adding 15mL of concentrated sulfuric acid and 25mL of concentrated nitric acid into the suspension under the condition of continuous stirring, cooling for 30min by adopting ice water, and heating to 80 ℃ for reaction for 30min to obtain a dispersion;
step two, adding 300mL of distilled water into the dispersion liquid obtained in the step one for dilution, and then standing for 12h; placing the rest diluted solution into a centrifuge for centrifugation, repeating the diluting and centrifuging processes for 2 times at 7500rpm, and collecting black solids to obtain carbon oxide nano-onions;
step three, dissolving 50mg of the 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 were dissolved in 20mL of toluene; thoroughly mixing the two solutions, standing, and adding 10mL (containing 500 mg) of polystyrene-vinylpyridine toluene solution with a concentration of 5% after layering the solutions 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 adopting a rotary evaporator, and 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 in example 1, except that: the dilution and centrifugation process in step two was repeated 4 times instead, the remainder being the same.
Example 3:
the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in this example is the same as in example 1, except that: the amount of the polystyrene-vinylpyridine used in the third step was changed to 250mg, and the remainder was the same.
Example 4:
the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material in this example is the same as in example 1, except that: step three, dissolving 50mg of the carbon 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 were dissolved in 20mL of toluene; the two solutions were mixed well, left to stand, and after the solutions had been layered, 10mL of a toluene solution of polystyrene-vinylpyridine (containing 500mg of polystyrene-vinylpyridine) was added at a concentration of 5%, to thereby form a gray mixed solution. The remainder being identical.
FIG. 1 is a graph showing the self-healing mechanism of the composites of examples 1-4: as can be seen from the figure, there is a large number of pyridine functional groups, carboxyl groups of carboxyl-terminated polybutadiene (PB-COO) provided by polystyrene-vinyl (PSVP) pyridine within the composite sample - ) And zinc ions (Zn) 2+ ) The constituted metal coordination bond, once cut, is re-constituted by the dynamic metal coordination bondAnd combining to form new metal coordination bonds so that the composite material completes the self-repairing process.
Comparative example 1:
in this comparative example, the materials prepared do not include oxidized carbon nano onions, and the preparation method is as follows:
step one, preparing a toluene solution from 5000mg of polybutadiene and 15mg of zinc acetate; then 10mL of a toluene solution of polystyrene-vinylpyridine (containing 500mg of styrene-vinylpyridine) having a concentration of 5% was added to form a milky white mixed solution;
removing most of the solvent in the milky white mixed solution obtained in the first step by adopting a rotary evaporator, and then placing the obtained mixture in a vacuum drying oven for drying for 24 hours, and removing the residual solvent to obtain a turkish semitransparent polybutadiene-polystyrene-vinylpyridine polymer material;
effect examples:
self-repairing performance test:
after the composite materials in examples 1 to 4 and comparative example 1 were completely cut, the cut was found to be completely healed after being placed side by side for 6 to 12 hours without external force, so that the composite material provided in this example had self-healing properties. Fig. 2 shows a test chart during the self-healing process of example 2, from which it can be seen that the composite material after healing achieved complete healing. In addition, the time required for the composite of example 4 to heal completely was found to be much longer in the experiments than in examples 1-3 and comparative example 1.
Mechanical property test:
the mechanical properties of the composite material and the tensile stress-strain curve in the self-repairing process after the composite material is cut are tested, and the test result in the embodiment 1 is shown in fig. 3, so that the mechanical properties of the composite material are gradually recovered along with time after the composite material is cut, and the mechanical properties are almost completely recovered after the composite material is self-repaired for 9 hours.
Memory performance test:
the composite materials in the examples 1-4 and the comparative example 1 are made into rod-shaped samples, electrodes are added to two ends of the rod-shaped samples, the temperature of the samples in the examples 1-4 is increased due to the heat effect generated by electrifying, the samples are softened, the samples are bent into a U shape by adopting external force, the temperature of the samples is reduced after the electrodes are removed, the samples can be kept in the U shape, when the two ends of the samples are electrified again, the shape of the samples can be restored to the original rod shape, and the deformation of the samples in the shape restoring process can push the table tennis balls to move, wherein the distance that the composite material in the example 3 drives the table tennis balls to move is far smaller than that of the composite materials in the examples 1-2 and the example 4. After the composite material of comparative example 1 is electrified, the temperature is not increased, the sample is not softened, and the shape change and recovery cannot be realized by an electrified heating mode.
The above examples, comparative examples and effect examples demonstrate 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 modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (16)
1. The preparation method of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material is characterized by comprising the following steps of:
step one, mixing carbon nano onion and a first strong acid solution to prepare a suspension, adding a second strong acid solution under the stirring condition, 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-vinyl pyridine;
evaporating the solvent and drying to obtain the carbon oxide nano onion/polybutadiene-polystyrene-vinyl pyridine composite material;
in the first step, the first strong acid solution is concentrated sulfuric acid; 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, mixing volume ratio is 1:1 to 4; the ratio relationship among the carbon nano onion, the first strong acid solution and the second strong acid solution is 10mg: 1-10 mL: 1-10 mL;
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, a step of; in the solution II, the mass ratio of the polybutadiene to the zinc acetate is 1-100: 1, a step of; the mass ratio of the polybutadiene to the polystyrene-vinyl pyridine is 100:1 to 10.
2. The method according to claim 1, wherein in the first step, the heating reaction is carried out under a condition of heating to 60 to 100 ℃ for 10 to 90 minutes.
3. The method according to claim 2, wherein in the first step, the heating reaction is carried out at 80℃for 30 minutes.
4. The method according to claim 1, wherein in the first step, the second strong acid solution is mixed by concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1: 3.
5. The method according to claim 1, wherein in the first step, the mass fraction of the concentrated sulfuric acid is not less than 95%.
6. The method according to claim 1, wherein in the first step, the mass fraction of the concentrated nitric acid is not less than 65%.
7. The method of claim 1, wherein step one further comprises post-treatment comprising dilution, standing, and centrifugation.
8. The method according to claim 7, wherein the standing time is 12 hours or longer.
9. The method of claim 8, wherein the time of resting is 24 hours.
10. The method according to claim 7, wherein the rotational speed of the centrifugation is 4000rpm or more.
11. The method of claim 7, wherein the diluting, standing and centrifuging are repeated 2 to 4 times.
12. 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 10:1.
13. the method according to claim 1, wherein in the third step, the evaporation solvent is rotary evaporation.
14. The method of claim 1, wherein the drying is vacuum drying.
15. The carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material obtained by the preparation method of any one of claims 1 to 14.
16. Use of the carbon oxide nano onion/polybutadiene-polystyrene-vinylpyridine composite material according to claim 15 for the preparation of smart materials, characterized in that it is used for the preparation of self-repairing materials, shape memory materials.
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| CN111868146A (en) * | 2018-01-11 | 2020-10-30 | 纳诺科尔有限公司 | Composite materials comprising mechanical ligands |
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| 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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