CN111303511A - Polymer composite material containing micro-nano hybrid structure filler and preparation method thereof - Google Patents
Polymer composite material containing micro-nano hybrid structure filler and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polymer composite material containing a micro-nano hybrid structure filler and a preparation method thereof. According to the invention, a stable, perfect and efficient heat conduction network chain is constructed in a polymer matrix by adopting an organic-inorganic hybrid body consisting of multi-scale and multi-dimensional graphene nanosheets and magnesium salt whiskers, the heat conduction performance of the composite material is greatly improved under the condition of a lower filler addition amount, and meanwhile, the good melting processing performance is ensured. The composite material has the advantages that the composite material is reinforced and toughened by the hybrid structure filler, and the comprehensive mechanical property of the composite material is improved obviously. The method has the advantages of simple and easy production process, abundant raw material sources, safety, environmental protection and low production cost.
Description
Technical Field
The invention relates to a polymer composite material containing a micro-nano hybrid structure filler and a preparation method thereof, in particular to a polymer composite material with high melt strength, high heat conductivity coefficient and high mechanical property and a preparation method thereof, belonging to the field of functional polymer composite materials.
Background
In recent years, with the rapid development of microelectronic packaging technology and integration technology, the output power of electronic components is larger and smaller, and the high-temperature environment generated by heat accumulation causes the poor working stability and the reduced service life of the components. Therefore, the electronics industry has put higher demands on heat management systems, and the heat-conducting member must be able to diffuse heat out quickly to avoid the service life of the device from being damaged. Although the polymer heat conduction material has good comprehensive properties of light weight, impact resistance, corrosion resistance, thermal fatigue resistance, easy processing and forming and the like, most polymer materials are poor heat conductors, the intrinsic heat conduction coefficient is only 0.1-0.4W/m.K, and the requirement of rapid heat dissipation is difficult to meet. Therefore, how to effectively enhance the thermal conductivity of polymer materials has become a focus of attention for researchers in the field of materials and engineering.
Solid, thermally conductive carriers can be generally classified as electrons, photons, and phonons. The metal material exhibits high thermal conductivity because it contains a large amount of free electrons. Materials containing crystalline structures can accomplish heat conduction by thermal vibration of the grains, i.e. the phonon concept we describe; the heat conduction of the amorphous material mainly depends on the thermal vibration of randomly arranged atoms or molecules around a fixed position, and can also be explained by the concept of phonons; the glass and the single crystal with better transmission have obvious effect on heat conduction by photons at a certain temperature. The thermal conductivity of polymer materials has a positive correlation with molecular weight, degree of crosslinking, degree of crystallinity, degree of orientation, and ambient temperature.
The phonon free path of the polymer material is small, resulting in low thermal conductivity. The addition of carbon nanofillers (e.g., one-dimensional carbon nanotubes and two-dimensional graphene nanoplatelets) is an effective way to improve the thermal conductivity of polymers. In addition to the thermal conductivity of the matrix, the thermal conductivity of the composite depends on the intrinsic thermal conductivity of the filler, the state of dispersion and its interaction with the matrix. The thermal resistance of the composite material is mainly derived from the polymer matrix with low thermal conductivity: when the content of the heat-conducting filler is low, the filler can be uniformly dispersed but isolated from each other, a sea-island discrete structure is formed, and the contribution to improving the heat-conducting property of the composite material is small even if the heat-conducting coefficient of the filler is higher; only when the amount of the filler is increased to a certain critical value, the filler can be mutually overlapped to form a structure similar to a net or chain, namely a heat conduction net chain, so that the heat conductivity of the composite material can be rapidly improved. This was confirmed in the study by Yu et al (Advanced Materials 2008,20, 4740): the mixed filler (10 wt%) with the mass ratio of the single-walled carbon nanotube to the graphite flake being 3:1 is selected, the mutually overlapped heat conduction network chain can be constructed, the interface thermal resistance is reduced, and the heat conduction coefficient of the epoxy resin is improved to 1.75W/m.K, which is obviously higher than that of the composite material only added with the graphite nanosheet (1.49W/m.K) or the single-walled carbon nanotube (0.85W/m.K). However, the thermal conductivity of epoxy resin composites is still below 2W/m.K, and applications in the electronics industry may be limited.
In order to construct a relatively perfect heat-conducting network chain, xuRuijie et al, Guangdong industry university, discloses a heat-conducting insulating plastic containing a carbon nanotube filler with a special structure and a preparation method thereof (Chinese invention patent publication No. CN103554900B), and the adopted technical scheme is as follows: the preparation method comprises the steps of sequentially carrying out surface carboxylation, grafting and hydrolysis treatment on a compound of carbon black and a carbon nano tube to obtain the star-shaped heat-conducting filler with multiple heat-conducting points, wherein the carbon black is used as a core, the carbon nano tube is used as an outer extension, then stirring and uniformly mixing (2-6 parts) the star-shaped heat-conducting filler with multiple heat-conducting points with a polymer (100 parts), a coupling agent (1-3 parts), a lubricant (0.2-10 parts), an antioxidant (0.1-0.2 part) and inorganic powder (40-180 parts) such as metal oxide, nitride or carbide and the like at a high speed, extruding and granulating to obtain the insulating plastic with the heat-conducting coefficient of 4.1-8.4. This method has some significant disadvantages: the preparation process of the star-shaped carbon black-carbon nanotube heat-conducting filler with multiple heat-conducting points is very complicated and time-consuming, and a large amount of organic solvents such as strong acid, tetrahydrofuran, DCC and the like are required to be used; treatment in high concentration strong acid, which may damage the carbon nanotube structure and decrease the aspect ratio (CrystEngComm 2012,14, 4976; 4979.), leads to an increase in the thermal resistance of the carbon nanotube-matrix interface, which is not favorable for the formation of the thermal conductive network chain and the improvement of the thermal conductivity of the composite material (Composites Part A: Applied Science and Manufacturing 2016,82, 208; 213.); the addition amount of the heat-conducting filler is large (the mass ratio of the addition amount to the matrix in the best embodiment is 111:100), the processability of the polymer matrix is damaged, and the heat-conducting filler is particularly not suitable for producing products with high requirements on melt strength, such as fibers, pipes, films and the like.
Xudong et al of Anhui Ke polymer new materials Co., Ltd discloses a polyamide composite material, a preparation method and application thereof (Chinese invention patent publication No. CN103044902A), and the adopted technical scheme is as follows: the heat-conducting property of the polyamide (10-30 parts) composite material is improved by adding 0.1-10 parts of graphene/graphene oxide, 30-80 parts of inorganic filler, 0.2-3 parts of coupling agent, 0.2-1 part of antioxidant and 0.2-2 parts of lubricant in a matching manner. Besides the need to use high-cost graphene oxide, this method has some significant disadvantages: in a preferred embodiment, in order to obtain a high thermal conductivity (>5W/mW) of the composite material, more than 65 parts of inorganic thermal conductive filler is required to be added, and the mass part of the polyamide matrix is less than 25, which is likely to cause great difficulty in molding and processing the composite material and shaping a complex product.
The method comprises the steps of preparing a hybrid of graphene and a ceramic heat-conducting filler (the mass ratio of the graphene to the ceramic heat-conducting filler is 1: 2-1: 200) by electrostatic self-assembly, uniformly compounding the hybrid with polyvinylidene fluoride by a solution flocculation method, and carrying out in-situ reduction to obtain the heat-conducting composite material (Chinese patent publication No. CN 103183889A). Although this method achieves higher thermal conductivity than the conventional solvent blending method, it is only achieved around 0.45W/m (the content of the alumina-graphene hybrid is 20 wt%). Especially the high cost of graphene oxide, the complex surface treatment and the use of a large amount of solvent may adversely affect the industrial production of the method.
Therefore, in the conventional method, a large amount (> 50%) of graphite, metal or metal oxide is usually added into the composite material, and a large amount of interface defects are formed due to incompatibility of the matrix and the filler, so that the filler needs to be additionally subjected to surface modification by a coupling agent or the coupling agent is directly added in the composite process, but higher interface thermal resistance is formed, and the increase of the thermal conductivity is not facilitated. In addition, the traditional filler has low surface activity, an effective heat conduction network chain is difficult to construct in a polymer matrix, and the addition of a large amount of filler obviously damages the processing performance and the mechanical property of the material. This is especially true for graphene composite materials, because the specific gravities of graphene powder and polymer matrix are greatly different, and the molding processing of high-content graphene composite materials is still a great challenge.
Although graphene has extremely high thermal conductivity (about 5000W/m.K), means for controlling the stripping state and the dispersion form of graphene in the composite material are still lacked at present, and the improvement effect of the thermal conductivity and the mechanical property of the composite material is further influenced. On the other hand, limited by the preparation technology of the inorganic heat-conducting filler (for example, filler form, crystal structure and crystallinity control), the addition of the filler has poor effect of improving the heat-conducting performance of the composite material or the material performance is unstable and difficult to repeat, and the method has no guiding significance for the actual production of the heat-conducting composite material.
The magnesium salt whisker has rich raw material sources and high heat conductivity coefficient (30-500W/m.K), and is commonly used for improving the heat conductivity of polymers. However, the currently reported preparation method of magnesium salt whiskers has some significant drawbacks, for example, Dujuan et al, the university of Qinghua, discloses a method for preparing magnesium oxide whiskers by an alcohol-hydrothermal method (Chinese patent publication No. CN103088400A), but a large amount of alcohol additives (accounting for 20-80% of the total volume of the solution) is required, the obtained whiskers have uneven diameter distribution (0.62-1.49 μm), low length (14.8-25.1 μm), and uncertain surface activity; jiangyangli Zhizhi et al, the university of Shenyang theory of technology, discloses a method for preparing nano magnesium hydroxide whiskers by using basic magnesium sulfate whiskers (Chinese patent publication No. CN103849924A), but sulfuric acid and sodium hydroxide are needed, so that the production risk and the pollution of strong acid and strong base are easily caused, and the surface activity of whisker products is uncertain. The outstanding contribution of these whisker products to the improvement of thermal conductivity in polymer composites is also less reported in the prior art literature.
Disclosure of Invention
In view of the above, the invention aims to provide a polymer composite material containing a micro-nano hybrid structure filler and a preparation method thereof, which are used for solving the above defects in the existing heat-conducting composite material preparation technology and providing a heat-conducting graphene composite material capable of being applied to the fields of electronic industry, heat energy utilization and heat management. The invention adopts a multi-scale and multi-dimensional organic-inorganic hybrid of graphene nanosheets and magnesium salt whiskers to construct a stable, perfect and efficient heat conducting network chain in a polymer matrix, and has the advantages of simple and easy production process, abundant raw material sources, safety, environmental protection and low production cost.
The invention provides a polymer composite material containing a micro-nano hybrid structure filler, which consists of graphene nanosheets, magnesium salt whiskers and a polymer matrix.
According to the polymer composite material, the mass ratio of the graphene nanosheets to the magnesium salt whiskers is 1:20-10:1, and the mass ratio of the total addition amount of the graphene nanosheets to the magnesium salt whiskers to the polymer matrix is 10:90-50: 50.
According to the polymer composite material, the maximum radial dimension of the graphene nano sheet is 0.5-40 mu m, and the thickness of the graphene nano sheet is 1-20 nm.
According to the polymer composite material, the magnesium salt whisker is at least one of magnesium hydroxide whisker, magnesium carbonate whisker and magnesium oxide whisker.
Further, the diameter of the magnesium salt whisker is 1-10 μm, the length is 20-80 μm, and the length-diameter ratio>10, specific surface area>120m2/g。
According to the polymer composite material, the polymer matrix is at least one of polyethylene, polypropylene, polybutylene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyamide, polyphenylene sulfide, polycarbonate, polybutylene terephthalate or polyethylene terephthalate.
On the other hand, the invention also provides a preparation method of the polymer composite material containing the micro-nano hybrid structure filler, which comprises the following steps:
s1, preparation of magnesium carbonate/magnesium hydroxide whiskers: adding soluble carbonate or alkali into an aqueous solution dissolved with a stabilizer, and uniformly stirring to obtain a mixed solution A; simultaneously dissolving soluble magnesium salt in water to obtain a uniform solution B; under the stirring state, uniformly adding the solution B into the solution A to obtain a flocculent mixed solution C, mixing, standing for a period of time to enable insoluble magnesium salt crystals to nucleate, grow and precipitate, and separating and drying to obtain magnesium carbonate or magnesium hydroxide whiskers;
s2, preparing the magnesium oxide whisker: calcining the magnesium carbonate or magnesium hydroxide whiskers in a high temperature furnace to remove free water, bound water and CO2Obtaining magnesium oxide crystal whisker with high purity, high crystallinity and high specific surface area by using molecules;
s3, preparing the composite material: adding the graphene nanosheets and the magnesium salt whiskers containing the magnesium carbonate, the magnesium hydroxide and/or the magnesium oxide whiskers into a polymer matrix according to a certain proportion, and carrying out melt mixing through a double-screw extruder to obtain the high-thermal-conductivity composite material.
According to the preparation method, the mass ratio of the graphene nanosheets to the magnesium salt whiskers is 1:20-10:1, and the mass ratio of the total addition amount of the graphene nanosheets to the magnesium salt whiskers to the polymer matrix is 10:90-50: 50.
According to the preparation method, the stabilizer is one or more of polyethylene glycol, sodium dodecyl benzene sulfonate, fatty glyceride, polyethylene glycol p-isooctyl phenyl ether or carboxymethyl cellulose.
The mass ratio of the stabilizer to the water is 0.01:100-10: 100.
More preferably, the mass ratio of the stabilizer to water is 0.05:100 to 0.1: 100.
According to the preparation method of the invention, the soluble carbonate or alkali preferably contains CO3 2-Or OH-1More preferably at least one of sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.
Said dissolved CO3 2-Or OH-1The molar concentration of the ions in water is 0.05-10mol/L, the temperature of the solution is 20-40 ℃, and the full and uniform reaction is ensured in a stirring way.
According to the preparation method of the invention, the soluble magnesium salt used in the solution B is at least one of magnesium chloride, magnesium nitrate or magnesium sulfate.
Said dissolved Mg2+The molar concentration of the ions in water is 0.05-10mol/L, the temperature of the solution is 20-50 ℃, and the full and uniform reaction is ensured in a stirring way.
According to the preparation method of the invention, Mg in the solution C2+Ions with CO3 2-Or OH-1The concentration ratio of the ions is 1.1-0.8 or 0.6-0.4 respectively, the mixing temperature is normal temperature, and the full and uniform reaction is ensured in a stirring way.
Further, Mg in the C solution2+Ions with CO3 2-Or OH-1The concentration ratio of the ions is preferably 1 to 0.9 or 0.5 to 0.45, respectively.
According to the preparation method, the standing time in S1 is 0.5-12h, the standing condition is 20-80 ℃, and the obtained insoluble magnesium salt is magnesium carbonate or magnesium hydroxide whisker.
Furthermore, the diameter of the magnesium carbonate or magnesium hydroxide whisker is 1-10 μm, and the length is 20-80 μm.
According to the preparation method, the equipment for calcination comprises a microwave high-temperature furnace, a high-temperature carbonization furnace, a medium-frequency induction high-temperature furnace or a muffle furnace, the high-temperature calcination temperature is 500-700 ℃, the calcination time is 30-360min, and the calcination environment is normal-pressure air.
According to the preparation method of the invention, the diameter of the magnesium oxide whisker in S2 is 1-10 μm, the length is 20-80 μm, and the length-diameter ratio>10, specific surface area>120m2/g。
According to the preparation method provided by the invention, the maximum radial dimension of the graphene nanosheet in S3 is 0.5-40 μm, and the thickness is 1-20 nm.
According to the preparation method of the invention, in the S3, the polymer matrix is at least one of polyethylene, polypropylene, polybutylene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyamide, polyphenylene sulfide, polycarbonate, polybutylene terephthalate, or polyethylene terephthalate.
According to the preparation method of the invention, the length-diameter ratio of the screw of the double-screw extruder in S3 is more than 15, and the temperature of melt blending is 150-380 ℃.
Compared with the prior art, the preparation method has the following advantages:
1) the method is safe, simple and convenient, has high whisker yield and is easy to produce in batch.
2) The graphene nanosheets and the micron-sized inorganic whiskers are used for constructing a multi-dimensional and multi-scale heat conduction network chain, the synergistic effect of the hybrid filler is remarkable, the heat conduction coefficient of the composite material is greatly improved, and the high heat conduction level (the heat conduction coefficient is more than 5W/m.K) is achieved under the condition of low addition amount.
3) No modifier, coupling agent or other auxiliary agent is used, so that the production cost and the process complexity are reduced, and the increase of the thermal resistance of the filler-matrix interface can be avoided.
4) The composite material has high melt index and melt strength and good processability, can be widely applied to conventional polymer processing methods such as hot-press molding, injection molding, film blow molding, pipe extrusion process and the like, and ensures the industrial production of the composite material.
5) The micro-nano hybrid filler has good reinforcing and toughening effects on the composite material, can obviously improve the comprehensive mechanical property of the composite material, and widens the application range of the high-thermal-conductivity composite material.
Drawings
Fig. 1 is a schematic diagram of a mechanism that magnesium salt whiskers and graphene nano-sheets with different sizes and dimensions construct a three-dimensional heat-conducting network chain in a polymer matrix.
FIG. 2 is a scanning electron microscope image of (a) low power and (b) high power of the magnesium oxide whisker of the invention.
FIG. 3 is an X-ray diffraction intensity curve of magnesium carbonate whiskers and magnesium oxide whiskers of the present invention.
FIG. 4 is a nitrogen isothermal adsorption and desorption curve of the magnesium oxide whisker.
FIG. 5 is a scanning electron microscope image of a conventional commercially available magnesium oxide particle in the prior art.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The invention provides a polymer composite material containing a micro-nano hybrid structure filler, which consists of graphene nanosheets, magnesium salt whiskers and a polymer matrix.
According to the polymer composite material, the mass ratio of the graphene nanosheets to the magnesium salt whiskers is 1:20-10:1, and the mass ratio of the total addition amount of the graphene nanosheets to the magnesium salt whiskers to the polymer matrix is 10:90-50: 50.
Specifically, the maximum radial dimension of the graphene nanosheet is 0.5-40 μm, and the thickness of the graphene nanosheet is 1-20nm, so that the heat conducting property of the composite material is fully improved, and the processability of the graphene composite material is ensured.
According to the polymer composite material, the magnesium salt whisker is at least one of magnesium hydroxide whisker, magnesium carbonate whisker and magnesium oxide whisker.
Specifically, the diameter of the magnesium salt whisker is 1-10 μm, the length is 20-80 μm, and the length-diameter ratio>10, specific surface area>120m2The/g can be used as an efficient modifier for improving the thermal conductivity of the composite material.
According to the polymer composite material, the polymer matrix is at least one of polyethylene, polypropylene, polybutylene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyamide, polyphenylene sulfide, polycarbonate, polybutylene terephthalate or polyethylene terephthalate.
A preparation method of a polymer composite material containing micro-nano hybrid structure filler comprises the following steps:
dissolving a proper amount of soluble carbonate or alkali and a stabilizer in water, and uniformly stirring to obtain a mixed solution A; dissolving soluble magnesium salt in water, and uniformly stirring to obtain a solution B; uniformly adding B into A under stirring at normal temperature to obtain uniform mixed solution C, mixing, standing, nucleating, growing and precipitating insoluble magnesium salt crystal, separating, and drying to obtain white magnesium carbonate whisker or magnesium hydroxide whisker flocculent precipitate;
the stabilizer used in the invention is one or more of polyethylene glycol, sodium dodecyl benzene sulfonate, fatty glyceride, polyethylene glycol p-isooctyl phenyl ether or carboxymethyl cellulose, and the mass ratio of the stabilizer to water is 0.01:100-10: 100; more preferably, the mass ratio of the stabilizer to water is 0.05:100 to 0.1: 100.
In the solution A obtained in the invention, the soluble carbonate or alkali preferably contains CO3 2-Or OH-1More preferably at least one of sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide, and CO is dissolved3 2-Or OH-1The molar concentration of ions in water is 0.05-10mol/L, the temperature of the solution is 20-40 ℃, and the full and uniform reaction is ensured in a stirring manner, so that the nucleation and growth of the whiskers are ensured.
In the solution B obtained by the invention, the soluble magnesium salt is at least one of magnesium chloride, magnesium nitrate or magnesium sulfate, and Mg is dissolved2+The molar concentration of the ions in water is 0.05-10mol/L, the temperature of the solution is 20-50 ℃, and the full and uniform reaction is ensured in a stirring way.
In the solution C obtained by the invention, the Mg2+Ions with CO3 2-Or OH-1The concentration ratio of ions is 1.1-0.8 or 0.6-0.4 respectively, so that Mg2+The ions are fully reacted, the mixing temperature is normal temperature, and the reaction is fully and uniformly ensured in a stirring mode.
Further, Mg in the C solution2+Ions with CO3 2-Or OH-1The concentration ratio of the ions is preferably 1 to 0.9 or 0.5 to 0.45, respectively.
In other embodiments of the polymer composite of the present invention, the standing time is 0.5 to 12 hours, the standing condition is 20 to 80 ℃, and the obtained insoluble magnesium salt is magnesium carbonate or magnesium hydroxide whisker, wherein the diameter of the magnesium carbonate or magnesium hydroxide whisker is 1 to 10 μm, and the length of the magnesium carbonate or magnesium hydroxide whisker is 20 to 80 μm.
Separating and drying the magnesium carbonate whisker precipitate and the magnesium hydroxide whisker precipitate, calcining in a high temperature furnace, and removing free water, bound water and CO2And (5) obtaining white fluffy magnesium oxide whiskers.
The equipment for calcining comprises a microwave high-temperature furnace, a high-temperature carbonization furnace, a medium-frequency induction high-temperature furnace or a muffle furnace, wherein the high-temperature calcining temperature is 500-700 ℃, the calcining time is 30-360min, and the calcining environment is normal-pressure air.
The magnesium oxide whisker obtained by the preparation method has the diameter of 1-10 mu m, the length of 20-80 mu m and the length-diameter ratio>10, specific surface area>120m2/g。
Adding graphene nanosheets and the magnesium salt whiskers into a polymer matrix according to a certain proportion, and melting and mixing the graphene nanosheets and the magnesium salt whiskers through a double-screw extruder to obtain the high-thermal-conductivity composite material, wherein the mass ratio of the graphene nanosheets to the magnesium salt whiskers is 1:20-10:1, and the mass ratio of the total addition amount of the graphene nanosheets to the magnesium salt whiskers to the polymer matrix is 10:90-50: 50.
The maximum radial dimension of the graphene nanosheet used in the invention is 0.5-40 μm, and the thickness is 1-20 nm.
The polymer matrix used in the invention is at least one of polyethylene, polypropylene, polybutylene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyamide, polyphenylene sulfide, polycarbonate, polybutylene terephthalate or polyethylene terephthalate.
The length-diameter ratio of the screw of the double-screw extruder used in the invention is more than 15, and the temperature of melt blending is 150-380 ℃.
Example 1
Dissolving 5kg of sodium carbonate and 50g of polyethylene glycol p-isooctyl phenyl ether in 50kg of water, and uniformly stirring to obtain a mixed solution A; simultaneously dissolving 4.5kg of magnesium chloride in 50kg of water, and uniformly stirring to obtain a solution B; and uniformly adding the B into the A under the stirring state at normal temperature to obtain a uniform mixed solution C, and standing for 6 hours at 25 ℃ after mixing to obtain flocculent precipitate of the white magnesium carbonate crystal whisker.
Centrifuging and drying the magnesium carbonate whisker precipitate, calcining at 700 deg.C for 0.5 hr, removing free water, bound water and CO2And (5) obtaining white fluffy magnesium oxide whiskers.
Uniformly mixing 1 part of graphene nanosheet, 20 parts of magnesium oxide whisker and 79 parts of Polyethylene (PE), melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PE composite material.
Example 2
Dissolving 53kg of sodium carbonate and 5kg of carboxymethyl cellulose in 50kg of water, and uniformly stirring to obtain a mixed solution A; simultaneously dissolving 59.2kg of magnesium nitrate in 50kg of water, and uniformly stirring to obtain a solution B; and uniformly adding the B into the A under the stirring state at normal temperature to obtain a uniform mixed solution C, and standing for 12 hours at 20 ℃ after mixing to obtain flocculent precipitate of the white magnesium carbonate crystal whisker.
Centrifuging and drying the magnesium carbonate whisker precipitate, calcining at 500 deg.C for 6 hr, removing free water, bound water and CO2And (5) obtaining white fluffy magnesium oxide whiskers.
And uniformly mixing 10 parts of graphene nanosheets, 1 part of magnesium oxide whiskers and 89 Parts of Polypropylene (PP), melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PP composite material.
Example 3
Dissolving 380g of potassium carbonate and 5g of polyethylene glycol in 50kg of water, and uniformly stirring to obtain a mixed solution A; dissolving 301g of magnesium sulfate in 50kg of water, and uniformly stirring to obtain a solution B; and uniformly adding the B into the A under the stirring state at normal temperature to obtain a uniform mixed solution C, and standing for 0.5 hour at 80 ℃ after mixing to obtain flocculent precipitate of the white magnesium carbonate crystal whisker.
Taking out the magnesium carbonate crystal whisker precipitate, calcining at 500 deg.C for 6 hr, removing free water, bound water and CO2Molecular to obtain white fluffy oxygenAnd (4) melting the magnesium whisker.
Uniformly mixing 15 parts of graphene nanosheets, 15 parts of magnesium carbonate whiskers, 15 parts of magnesium oxide whiskers and 55 parts of Polybutylene (PB), melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PB composite material.
Example 4
308.55g of potassium hydroxide and 5g of sodium dodecyl benzene sulfonate are dissolved in 50kg of water and are uniformly stirred to obtain a mixed solution A; dissolving 301g of magnesium sulfate in 50kg of water, and uniformly stirring to obtain a solution B; and uniformly adding the B into the A under the stirring state at normal temperature to obtain a uniform mixed solution C, and standing for 3 hours at 40 ℃ after mixing to obtain flocculent precipitate of the white magnesium hydroxide whisker.
Centrifuging and drying the magnesium hydroxide whisker precipitate, calcining at 600 deg.C for 3 hr, removing free water, bound water and CO2And (5) obtaining white fluffy magnesium oxide whiskers.
And (2) uniformly mixing 20 parts of graphene nanosheets, 10 parts of magnesium oxide whiskers and 70 parts of polyamide 6(PA6), melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PA6 composite material.
Example 5
Dissolving 30.9kg of potassium hydroxide and 800g of sodium dodecyl benzene sulfonate in 50kg of water, and uniformly stirring to obtain a mixed solution A; simultaneously dissolving 23.8kg of magnesium chloride in 50kg of water, and uniformly stirring to obtain a solution B; and uniformly adding the B into the A under the stirring state at normal temperature to obtain a uniform mixed solution C, and standing for 10 hours at 20 ℃ after mixing to obtain flocculent precipitate of the white magnesium hydroxide whisker.
Centrifuging and drying the magnesium hydroxide whisker precipitate, calcining at 550 deg.C for 3.5 hr, removing free water, bound water and CO2And (5) obtaining white fluffy magnesium oxide whiskers.
Uniformly mixing 10 parts of graphene nanosheets, 10 parts of magnesium hydroxide whiskers, 30 parts of magnesium oxide whiskers and 50 parts of acrylonitrile-butadiene-styrene copolymer (ABS), melting and mixing through a double-screw extruder, and extruding and granulating to obtain the ABS composite material.
Example 6
Dissolving 200g of sodium hydroxide and 5g of fatty acid monoglyceride in 50kg of water, and uniformly stirring to obtain a mixed solution A; meanwhile, 462.5g of magnesium nitrate is dissolved in 50kg of water and stirred uniformly to obtain a solution B; and uniformly adding the B into the A under the stirring state at normal temperature to obtain a uniform mixed solution C, and standing for 1 hour at 30 ℃ after mixing to obtain flocculent precipitate of the white magnesium hydroxide whisker.
Centrifuging and drying the magnesium hydroxide whisker precipitate, calcining at 500 deg.C for 2 hr, removing free water, bound water and CO2And (5) obtaining white fluffy magnesium oxide whiskers.
And uniformly mixing 5 parts of graphene nanosheets, 25 parts of magnesium oxide whiskers and 70 Parts of Polyphenylene Sulfide (PPS), melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PPS composite material.
Example 7
Dissolving 20kg of sodium hydroxide and 500g of polyethylene glycol p-isooctyl phenyl ether in 50kg of water, and uniformly stirring to obtain a mixed solution A; simultaneously dissolving 23.8kg of magnesium chloride in 50kg of water, and uniformly stirring to obtain a solution B; and uniformly adding the B into the A under the stirring state at normal temperature to obtain a uniform mixed solution C, and standing for 8 hours at 35 ℃ after mixing to obtain flocculent precipitate of the white magnesium hydroxide whisker.
Centrifuging and drying the magnesium hydroxide whisker precipitate, calcining at 700 deg.C for 2 hr, removing free water, bound water and CO2And (5) obtaining white fluffy magnesium oxide whiskers.
And uniformly mixing 15 parts of graphene nanosheets, 10 parts of magnesium hydroxide whiskers and 10 parts of magnesium oxide whiskers with 15 parts of PE and 50 parts of Polytetrafluoroethylene (PTFE), melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PTFE/PE composite material.
Comparative example 1
And uniformly mixing 40 parts of graphite and 60 parts of PE, melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PE composite material filled with graphite.
Comparative example 2
And uniformly mixing 40 parts of commercially available magnesium oxide particles and 60 parts of PP, melting and mixing through a double-screw extruder, and extruding and granulating to obtain the PP composite material filled with magnesium oxide.
Comparative example 3
After 20 parts of the magnesium oxide whisker, 25 parts of the magnesium carbonate whisker and 55 parts of PB prepared in example 1 were mixed uniformly, they were melt-mixed by a twin-screw extruder, and extruded and pelletized to obtain a PB composite material filled with a composite magnesium salt whisker.
Comparative example 4
And uniformly mixing 10 parts of graphene, 40 parts of commercially available magnesium oxide particles and 50 parts of ABS, melting and mixing through a double-screw extruder, and extruding and granulating to obtain the graphene/magnesium oxide particle filled ABS composite material.
Structural characterization and Performance testing
The microstructures of the magnesium oxide whiskers prepared in example 1 and the magnesium oxide particles used in comparative example 2 were observed by a field emission scanning electron microscope (fig. 2 and 5); the crystal structures of the magnesium carbonate whiskers and the magnesium oxide whiskers prepared in example 3 were characterized using an X-ray diffractometer (fig. 3); the specific surface area of the magnesium oxide whisker prepared in the example 1 is tested by a BET method and reaches 175m2In terms of/g (FIG. 4).
The processing performance, the heat conducting performance and the mechanical performance of the composite materials of the examples and the comparative examples are tested, and the performance evaluation method and the test standard are as shown in the following table 1:
melt index (MFR) test: the MFR value (g/10min) of the extruded composite pellets at 230 ℃ under a load of 2.16kg was measured by an MFR tester according to the melt index test standard of ASTM D1238 of the American society for testing materials. Since part of the engineering plastics have a melting point of 230 ℃ or higher, the MFR value cannot be measured.
Melt strength test: the measurements were carried out using a melt strength tester (Brabender rheomex single screw laboratory extruder equipped with capillary tubes and Gottfert "Rheotens" melt strength tester) according to the method described by Muke et al (Journal of Non-Newtonian fluid mechanics,2001,101, 77-93). The extruded composite melt is extruded by uniaxial stretching downward and is simultaneously pulled by two rollers which are arranged on a balance beam and move in opposite directions. The melt strand is drawn under such a force that the rollers accelerate uniformly until the melt strand breaksThe force to which the melt strand breaks is defined as the "melt strength".
The extruded, pelletized composite was dried at 100 ℃ for 1-2 hours and then test samples (each set of samples comprised 5 tensile test bars and 3 thermally conductive test panels) were molded using an injection molding machine equipped with a standard test bar mold.
Thermal conductivity test: the composites were evaluated for performance according to the ASTM E1461 standard for thermal conductivity testing, the german relaxation resistant LFA 447 model thermal conductivity meter. At least 3 replicates of each group were tested and the results averaged.
Mechanical Property test: the tensile properties of the composites were tested using a universal tensile machine (model 5900) from Instron, USA, according to the Plastic tensile Property test Standard from ASTM D638-2003, American society for testing materials. At least 3 replicates of each group were tested and the results averaged.
TABLE 1 test results of processability, thermal conductivity and mechanical properties of polymer composites
Fig. 1 shows a schematic mechanism diagram of building a three-dimensional heat-conducting network chain in a polymer matrix by adding magnesium oxide whiskers and graphene nano sheets with different sizes and dimensions, and the synergistic action mechanism is the theoretical basis of the patent.
FIGS. 2-4 show the morphological characteristics, crystal structure and surface activity of the magnesium salt whisker, and confirm that the preparation method provided by the patent can obtain regular structure, high crystallization and high surface activity (the specific surface area exceeds 170 m)2Per g) magnesium salt whiskers. By analyzing the test results of the composites obtained in examples 1-7 in table 1, the improvement of the thermal conductivity of the polymer by the magnesium salt whiskers and the graphene is very obvious. Taking the preferred example 3 as an example, the graphene/magnesium oxide crystalThe heat conductivity coefficient of the whisker/magnesium carbonate whisker/PB (15/15/15/55) composite material reaches 6.88W/m.K, is improved by 203 percent compared with the composite material (2.27W/m.K) only added with 45 parts of magnesium oxide whisker, and simultaneously has excellent processability (melt strength of 18cN) and mechanical property (tensile strength of 26.2 MPa). The thermal conductivity coefficients of the composite materials in the embodiments 3-7 with the graphene, the magnesium carbonate whisker, the magnesium oxide whisker or the magnesium hydroxide whisker synergistically improved are all larger than 5W/m.K, and the composite materials can widely meet the material requirements of heat energy utilization and electronic industry. In comparative examples 1 to 4 which do not contain the micro-nano hybrid structure, although the addition amounts of the fillers are all higher (40%, 45% and 50%, respectively), the thermal conductivity coefficients of the composite materials are all lower than 2.5W/m.K, and the damage to the processing performance and the mechanical performance is obvious.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
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 (16)
1. A polymer composite material containing a micro-nano hybrid structure filler is composed of graphene nanosheets, magnesium salt whiskers and a polymer matrix.
2. The polymer composite material of claim 1, wherein the mass ratio of the graphene nanoplatelets to the magnesium salt whiskers is 1:20-10:1, and the mass ratio of the total addition amount of the graphene nanoplatelets to the magnesium salt whiskers to the polymer matrix is 10:90-50: 50.
3. The polymer composite of claim 1 or 2, wherein the graphene nanoplatelets have a maximum radial dimension of 0.5 to 40 μ ι η and a thickness of 1 to 20 nm.
4. The polymer composite according to any one of claims 1 to 3, wherein the magnesium salt whiskers are at least one of magnesium hydroxide whiskers, magnesium carbonate whiskers and magnesium oxide whiskers.
5. The polymer composite material according to any one of claims 1 to 4, wherein the magnesium salt whiskers have a diameter of 1 to 10 μm, a length of 20 to 80 μm, and an aspect ratio>10, specific surface area>120m2/g。
6. The polymer composite of any one of claims 1 to 5, wherein the polymer matrix is at least one of polyethylene, polypropylene, polybutylene, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyamide, polyphenylene sulfide, polycarbonate, polybutylene terephthalate, or polyethylene terephthalate.
7. A preparation method of a polymer composite material containing micro-nano hybrid structure filler comprises the following steps:
s1, preparation of magnesium carbonate/magnesium hydroxide whiskers: adding soluble carbonate or alkali into an aqueous solution dissolved with a stabilizer, and uniformly stirring to obtain a mixed solution A; simultaneously dissolving soluble magnesium salt in water to obtain a uniform solution B; under the stirring state, uniformly adding the solution B into the solution A to obtain a flocculent mixed solution C, mixing, standing for a period of time to enable insoluble magnesium salt crystals to nucleate, grow and precipitate, and separating and drying to obtain magnesium carbonate or magnesium hydroxide whiskers;
s2, preparing the magnesium oxide whisker: calcining the magnesium carbonate or magnesium hydroxide whiskers in a high temperature furnace to remove free water, bound water and CO2Obtaining magnesium oxide crystal whisker with high purity, high crystallinity and high specific surface area by using molecules;
s3, preparing the composite material: adding the graphene nanosheets and the magnesium salt whiskers containing the magnesium carbonate, the magnesium hydroxide and/or the magnesium oxide whiskers into a polymer matrix according to a certain proportion, and carrying out melt mixing through a double-screw extruder to obtain the high-thermal-conductivity composite material.
8. The preparation method of claim 7, wherein the mass ratio of the graphene nanoplatelets to the magnesium salt whiskers is 1:20-10:1, and the mass ratio of the total addition amount of the graphene nanoplatelets to the magnesium salt whiskers to the polymer matrix is 10:90-50: 50.
9. The method according to claim 7 or 8, wherein the stabilizer is one or more selected from polyethylene glycol, sodium dodecylbenzenesulfonate, fatty glyceride, polyethylene glycol p-isooctylphenyl ether, and carboxymethylcellulose.
10. The method according to claim 9, wherein the mass ratio of the stabilizer to water is 0.01:100 to 10:100, preferably 0.05:100 to 0.1: 100.
11. The method of any one of claims 7 to 10, wherein the soluble carbonate or base in the solution a preferably comprises CO3 2-Or OH-1More preferably at least one of sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.
12. The method of claim 11, wherein the dissolved CO is3 2-Or OH-1The molar concentration of the ions in water is 0.05-10mol/L, the temperature of the solution is 20-40 ℃, and the full and uniform reaction is ensured in a stirring way.
13. The method for preparing any one of polymer composite materials according to claims 7 to 12, wherein the soluble magnesium salt used in the solution B is at least one of magnesium chloride, magnesium nitrate or magnesium sulfate.
14. The method of claim 13, wherein Mg is dissolved2+The molar concentration of the ions in water is 0.05-10mol/L, the temperature of the solution is 20-50 ℃, and the full and uniform reaction is ensured in a stirring way.
15. The method of any one of claims 7 to 14, wherein the solution C contains Mg2+Ions with CO3 2-Or OH-1The molar concentration ratio of the ions is 1.1-0.8 or 0.6-0.4, preferably 1-0.9 or 0.5-0.45, respectively; the mixing temperature is normal temperature, and the reaction is ensured to be full and uniform in a stirring mode.
16. The method for preparing the polymer composite material according to any one of claims 7 to 15, wherein the standing time in S1 is 0.5 to 12 hours, the standing condition is 20 to 80 ℃, and the obtained insoluble magnesium salt is magnesium hydroxide or magnesium carbonate whiskers.
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