CN113603993B - Preparation method of self-healing polymer-nano composite material - Google Patents
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- CN113603993B CN113603993B CN202110790545.7A CN202110790545A CN113603993B CN 113603993 B CN113603993 B CN 113603993B CN 202110790545 A CN202110790545 A CN 202110790545A CN 113603993 B CN113603993 B CN 113603993B
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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
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- C08K3/02—Elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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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
- C08K3/28—Nitrogen-containing compounds
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Abstract
The invention relates to a preparation method of a self-healing polymer-nano composite material, which comprises the steps of generating carbon quantum dots on a polymer substrate in situ, and extruding by a double screw to form the self-healing polymer-nano composite material. The composite material obtained by the method has excellent fluorescence, good mechanical strength and self-healing performance. Compared with the traditional flexible self-healing polymer, the self-healing behavior of the hard polymer is realized, and the application range of the polymer material is greatly expanded. Meanwhile, the preparation method is simple and easy to implement, and has strong popularization and application values.
Description
Technical Field
The invention relates to a preparation method of a polymer-nano composite material with excellent fluorescence, good mechanical strength and self-healing performance, and the self-healing material can be widely used for various engineering materials and prolongs the service life of the engineering materials. Meanwhile, the preparation method is simple and feasible and has innovation.
Technical Field
Nowadays, various high molecular polymer materials are being widely used in industrial products in our daily lives. However, a major disadvantage is that these engineering materials gradually age and degrade over time. Thus, self-healing polymer materials have attracted considerable attention from researchers. Many self-healing polymers have also been successfully prepared. However, at present, the reported self-healing polymers are flexible polymer materials prepared by polymerization reaction of monomers, and the flexible polymer self-healing materials have low strength and good ductility, and can be widely applied to electronic skins, photoelectric device displays and medical fields. Meanwhile, the traditional engineering plastics and engineering polymer materials need to have certain tensile strength, such as common polypropylene plastics, rubber tires, polyester materials and the like, and the self-healing of the traditional hard polymer materials is realized, so that the service life of the materials can be prolonged, the production cost is reduced, and the production efficiency is improved. And few researches on the self-healing material are reported at present. Based on the self-healing performance, the research on the self-healing performance of the hard engineering polymer material is carried out, and the method has great practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a self-healing polymer-nano composite material, and the self-healing polymer-nano composite material prepared by the method has excellent fluorescence and good mechanical strength, more importantly, the material achieves self-healing performance and is a hard self-healing polymer composite material different from the traditional flexible self-healing polymer. The added value of the material is greatly improved, and the method can be widely applied to the field of engineering materials.
The technical scheme of the invention is as follows: a preparation method of a self-healing polymer-nanometer material is characterized by comprising the following steps: carbon quantum dots are generated in situ on the polymer substrate, and the self-healing polymer-nano composite material is formed by double-screw extrusion. The method comprises the following specific steps:
the method comprises the following steps: compounding ingredients, namely fully and uniformly mixing the carbon quantum dot precursor powder with the polymer base material, or fully and uniformly mixing the carbon quantum dot precursor powder with the carbon nitride and the polymer base material;
step two: and extruding and granulating, namely performing in-situ generation of carbon quantum dots on the fully mixed composite material through a double-screw extruder, and forming the self-healing polymer-nano composite material through a granulator.
Preferably, the carbon quantum dot precursor powder is sodium alginate-urea, citric acid-urea or citrate-urea; wherein the mass fraction of urea in the carbon quantum dot precursor powder is 50-75%.
Preferably, carbon nitride is added when the carbon quantum dot precursor powder is mixed with the polymer base material, so that the healing performance of the obtained self-healing polymer-nano composite material is improved to a certain extent.
Preferably, the polymer substrate is polymethyl methacrylate or polyurethane.
Preferably, the mass ratio of the carbon quantum dot precursor powder to the polymer substrate is 0.01-0.5; the mass ratio of the carbon nitride to the polymer base material is 0.01-0.1.
The reaction temperature of the double-screw extruder is preferably 180-230 ℃.
Has the beneficial effects that:
1. the method can be used for simply, conveniently and rapidly preparing the carbon quantum dots, is simpler and more convenient compared with the traditional preparation method, and simultaneously realizes large-scale continuous preparation of the carbon quantum dots. The coupling with the polymer maintains the fluorescence properties of the carbon quantum dots themselves, and is also easy for subsequent processing.
2. The invention is innovative in that the carbon nitride is added into the polymer/carbon quantum dot self-healing composite material, and the end group of the carbon nitride is easier to form hydrogen bonds and covalent bonds, thereby further improving the self-healing performance of the material.
3. The self-healing performance of the hard polymer material is realized by a simple preparation method, and the original mechanical performance of the polymer is maintained, and meanwhile, the self-healing capacity of the hard polymer material is endowed. The application field of polymer products is enlarged, and the added value of the products is improved.
Drawings
Fig. 1 is a physical representation of the self-healing polymer-nanomaterial of example 1, wherein a is the particles after dicing and b is the morphology of the injection molded sample.
Fig. 2 shows the ir spectra of the self-healing polymer-nanomaterial of polymer substrate polymethylmethacrylate (a), example 1 (b) and example 5 (c).
FIG. 3 is a characterization of healing efficiency (tensile strength of material tested by universal testing machine) of the self-healing polymer-nanomaterial of example 5, where a is the original strength of the material and b is the strength of the material after healing.
The specific implementation mode is as follows:
example 1:
1. weighing citric acid and urea according to the mass ratio of 1.
2. And putting the uniformly mixed component A into a double-screw extruder for melting and mixing. Wherein the reaction temperature of the twin-screw extruder was set to 200 ℃. The rotating speed of a main machine of the twin-screw is set to be 15r/min, and the speed of the feeder is set to be 10r/min. And (3) after extrusion, bracing and cooling by adopting a water cooling mode, then feeding the material into a granulator for granulation, and setting the granulation speed to be parallel to the rotation speed of the screw so as to obtain carbon quantum dot/polymethyl methacrylate particles B (the infrared representation of the material is shown as B in the attached figure 2).
3. And (3) performing injection molding on the component B by using an injection machine (the appearance of the sample is shown as figure 1 (B)), breaking the sample in a liquid nitrogen cooling mode, immersing the sample in an ethanol solution of the carbon quantum dots (the composite material particles are directly dissolved in ethanol), taking out the sample after several seconds, and observing the self-healing phenomenon in a natural environment at normal temperature and normal pressure. The healing efficiency is characterized by the ratio of the tensile strength of the test material in the universal tester, both original and after healing.
Example 2:
1. weighing sodium alginate and urea according to the mass ratio of 1.
2. And putting the uniformly mixed component A into a double-screw extruder for melting and mixing. Wherein the reaction temperature of the twin-screw extruder was set at 230 ℃. The rotating speed of the double-screw main machine is set to be 15r/min, and the speed of the feeder is set to be 10r/min. And (3) after extrusion, bracing and cooling are carried out in a water cooling mode, then the extruded material enters a granulator for granulation, and the granulation speed is set to be parallel to the rotating speed of the screw, so that carbon quantum dot/polymethyl methacrylate particles B are obtained.
3. And the component B is subjected to injection molding by an injection machine, a sample is fractured in a liquid nitrogen cooling mode, is immersed in an ethanol solution (the composite material particles are directly dissolved in ethanol) of the carbon quantum dots, is taken out after several seconds, and is observed in a natural environment at normal temperature and normal pressure to represent the self-healing performance.
Example 3:
1. weighing zinc citrate and urea according to the mass ratio of 1.
2. And putting the uniformly mixed component A into a double-screw extruder for melting and mixing. Wherein the reaction temperature of the twin-screw extruder was set to 180 ℃. The rotating speed of the twin-screw main machine is set to be 15r/min, and the speed of the feeder is set to be 10r/min. And (3) bracing and cooling by adopting a water cooling mode after extrusion, then feeding the material into a granulator for granulation, and setting the granulation speed to be parallel to the rotating speed of the screw rod to obtain carbon quantum dot/polymethyl methacrylate particles B.
3. And the component B is subjected to injection molding by an injection machine, a sample is fractured in a liquid nitrogen cooling mode, the sample is immersed in an ethanol solution (composite material particles are directly dissolved in ethanol) of the carbon quantum dots, the sample is taken out after several seconds, the self-healing phenomenon is observed in a natural environment at normal temperature and normal pressure, and the self-healing performance is characterized.
Example 4:
1. weighing citric acid and urea according to a mass ratio of 1.
2. And putting the uniformly mixed component A into a double-screw extruder for melting and mixing. Wherein the melt temperature of the twin-screw extruder was set at 200 ℃. The rotating speed of the double-screw main machine is set to be 15r/min, and the speed of the feeder is set to be 10r/min. And (3) after extrusion, bracing and cooling are carried out in a water cooling mode, then the extruded material enters a granulator for granulation, and the granulation speed is set to be parallel to the rotating speed of the screw, so that carbon quantum dot/polymethyl methacrylate particles B are obtained.
3. And the component B is formed by injection molding through an injection machine, a sample is broken in a liquid nitrogen cooling mode, the sample is immersed in an ethanol solution of a carbon quantum dot (the composite material particle is directly dissolved in ethanol), and the pH value (pH =3 and pH = 10) of a solution medium is respectively adjusted by sulfuric acid and ammonia water. And taking out after several seconds, observing the self-healing phenomenon in a natural environment at normal temperature and normal pressure, and representing the self-healing performance.
Example 5:
1. weighing carbon nitride, citric acid and urea according to a mass ratio of 2.
3. And putting the uniformly mixed component A into a double-screw extruder for melting and mixing. Wherein the melt temperature of the twin-screw extruder was set at 200 ℃. The rotating speed of the twin-screw main machine is set to be 15r/min, and the speed of the feeder is set to be 10r/min. And (3) after extrusion, bracing and cooling by adopting a water cooling mode, and then feeding the material into a granulator for granulation, wherein the granulation speed is set to be parallel to the screw rotation speed, so that carbon nitride/carbon quantum dots/polymethyl methacrylate particles B (the infrared characterization of the material is shown as c in the attached figure 2) are obtained.
3. And (3) injecting and molding the component B by an injection machine, breaking a sample in a liquid nitrogen cooling mode, immersing the sample in an ethanol solution (namely, composite material particles are directly dissolved in ethanol) of the carbon quantum dots for several seconds, taking out the sample, observing the self-healing phenomenon in a natural environment at normal temperature and normal pressure, and representing the self-healing performance (the performance test is shown in figure 3).
Example 6:
1. weighing carbon nitride, citric acid and urea according to the mass ratio of 3.
3. And putting the uniformly mixed component A into a double-screw extruder for melting and mixing. Wherein the melt temperature of the twin-screw extruder was set at 200 ℃. The rotating speed of the double-screw main machine is set to be 15r/min, and the speed of the feeder is set to be 10r/min. And (3) after extrusion, bracing and cooling by adopting a water cooling mode, then feeding the material into a granulator for granulation, and setting the granulation speed to be parallel to the rotating speed of the screw so as to obtain the carbon nitride/carbon quantum dots/polymethyl methacrylate particles B.
3. And the component B is subjected to injection molding by an injection machine, a sample is fractured in a liquid nitrogen cooling mode, the sample is taken out after being immersed in an ethanol solution (the composite material particles are directly dissolved in ethanol) of the carbon quantum dots for several seconds, and the self-healing phenomenon is observed in a natural environment at normal temperature and normal pressure to characterize the self-healing performance.
Example 7:
1. weighing carbon nitride, citric acid and urea according to the mass ratio of 3.
3. And putting the uniformly mixed component A into a double-screw extruder for melting and mixing. Wherein the melt temperature of the twin-screw extruder was set at 200 ℃. The rotating speed of the double-screw main machine is set to be 15r/min, and the speed of the feeder is set to be 10r/min. And (3) bracing and cooling by adopting a water cooling mode after extrusion, then entering a granulator for granulation, and setting the granulation speed to be parallel to the rotating speed of the screw rod to obtain the carbon nitride/carbon quantum dots/polyurethane particles B.
3. And the component B is subjected to injection molding by an injection machine, a sample is fractured in a liquid nitrogen cooling mode, the sample is taken out after being immersed in an ethanol solution (the composite material particles are directly dissolved in ethanol) of the carbon quantum dots for several seconds, and the self-healing phenomenon is observed in a natural environment at normal temperature and normal pressure to characterize the self-healing performance.
Claims (3)
1. Use of a self-healing polymer-nanocomposite material, characterized in that: breaking a self-healing polymer-nano composite material sample in a liquid nitrogen cooling mode, immersing the self-healing polymer-nano composite material sample in an ethanol solution of a carbon quantum point, taking out the self-healing polymer-nano composite material sample after several seconds, and self-healing the self-healing polymer-nano composite material sample in a natural environment at normal temperature and normal pressure; the self-healing polymer-nano composite material generates carbon quantum dots on a polymer substrate in situ, and the carbon quantum dots are extruded by a double screw to form the self-healing polymer-nano composite material; the method comprises the following specific steps:
the method comprises the following steps: compounding ingredients, namely fully and uniformly mixing the carbon quantum dot precursor powder and the polymer base material, or fully and uniformly mixing the carbon quantum dot precursor powder, the carbon nitride and the polymer base material; the carbon quantum dot precursor powder is sodium alginate-urea, citric acid-urea or citrate-urea; wherein the mass fraction of urea in the carbon quantum dot precursor powder is 50-75%; the polymer base material is polymethyl methacrylate or polyurethane;
step two: and extruding and pelletizing, namely enabling the fully mixed composite material to pass through a double-screw extruder to generate carbon quantum dots in situ, and forming the self-healing polymer-nano composite material through a pelletizer.
2. The use of claim 1, wherein: the mass ratio of the carbon quantum dot precursor powder to the polymer base material is 0.01-0.5; the mass ratio of the carbon nitride to the polymer base material is 0.01-0.1.
3. The use of claim 1, wherein: the reaction temperature of the double-screw extruder is 180-230 ℃.
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