CN113831737A - Functionalized graphene nanosheet reinforced silicone rubber composite material and preparation method thereof - Google Patents
Functionalized graphene nanosheet reinforced silicone rubber composite material and preparation method thereof Download PDFInfo
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention belongs to the field of graphene reinforced silicone rubber composite materials, and particularly relates to a functionalized graphene nanosheet reinforced silicone rubber composite material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, forming an azaring structure on the surface of the graphene nanosheet through a 1, 3-dipolar cycloaddition reaction, wherein the azaring structure has a terminal containing a carboxyl group; s2, bonding APTMS on the graphene nanosheets through the introduced carboxyl groups to obtain functionalized graphene nanosheets; s3, mixing the functionalized graphene nano sheets in silicon rubber to obtain the functionalized graphene nano sheet reinforced silicon rubber composite material. The functionalized graphene nanosheet reinforced silicone rubber composite material provided by the invention has excellent mechanical properties and thermal properties.
Description
Technical Field
The invention belongs to the field of graphene reinforced silicone rubber composite materials, and particularly relates to a functionalized graphene nanosheet reinforced silicone rubber composite material and a preparation method thereof.
Background
Silicone Rubber (SR) is widely used in industry because of its excellent properties. Due to the excellent physical properties and chemical inertness of the silicone rubber, the silicone rubber shows adaptability in extreme environments (-100-300 ℃) and high resistance to ultraviolet rays, ozone and aging compared with other existing organic materials. However, the use of silicone rubbers is limited by their low mechanical properties and low surface energy.
Graphene was first isolated in 2004, a two-dimensional and monoatomic nanomaterial consisting of sp2Hybridized carbon atom. Graphene has excellent potential as a polymer composite reinforcement material due to its excellent mechanical, thermal and electrical properties. However, large-scale application of graphene is limited due to high cost and complicated production process of graphene.
Graphene Nanoplatelets (GNPs) are composed of multi-layer graphene, have a thickness range of about 100nm, and have received wide attention as an economically feasible substitute for graphene in large-scale applications. Graphene, typically in the form of Graphene Oxide (GO), and graphene nanoplatelets have both been investigated as reinforcing fillers to enhance the mechanical properties and thermal conductivity of silicone rubber composites. The reinforcing effect of the graphene or graphene nanosheet on the whole silicon rubber matrix depends on the dispersion level of the graphene or graphene nanosheet in the silicon rubber matrix and the interface adhesive force between the silicon rubber and the graphene or graphene nanosheet. In the latter case, the interfacial adhesion between the two is usually improved by modifying the surface of the filler, such as graphene oxide. Meanwhile, silane coupling agents such as (3-aminopropyl) triethoxysilane (APTES) and Vinyltrimethoxysilane (VTMS) are commonly used to react with graphene oxide or graphene nanoplatelets to enhance the compatibility of the graphene or graphene nanoplatelets with the silicone rubber matrix. However, the reaction degree of the silane coupling agent and graphene is relatively low by using the existing method, that is, the graphene is difficult to be functionalized, so that the thermal property and the mechanical property of the silicon rubber composite material enhanced by the functionalized graphene are difficult to meet the increasing industrial requirements.
Disclosure of Invention
In order to overcome the defects of the prior art, the technical problems to be solved by the invention are as follows: the thermal property and the mechanical property of the functional graphene nanosheet reinforced silicone rubber composite material are improved.
In order to solve the technical problem, the invention provides a preparation method of a functionalized graphene nanosheet reinforced silicone rubber composite material, which comprises the following steps:
s1, forming an azaring structure on the surface of the graphene nanosheet through a 1, 3-dipolar cycloaddition reaction, wherein the azaring structure has a terminal containing a carboxyl group;
s2, bonding APTMS on the graphene nanosheets through the introduced carboxyl groups to obtain functionalized graphene nanosheets;
s3, mixing the functionalized graphene nano sheets in silicon rubber to obtain the functionalized graphene nano sheet reinforced silicon rubber composite material.
Further provides the functional graphene nanosheet reinforced silicone rubber composite material prepared by the preparation method of the functional graphene nanosheet reinforced silicone rubber composite material.
The invention has the beneficial effects that: an azaring structure similar to a graphene structure is formed on the surface of a graphene nanosheet through 1, 3-dipolar ring addition reaction, and a carboxyl terminal of the azaring structure reacts with (3-aminopropyl) trimethoxysilane (APTMS) to enable APTMS to be bonded on the graphene nanosheet, at the moment, functional groups bonded on the surface of the graphene nanosheet respectively have the azaring structure similar to the graphene nanosheet structure and a silane structure similar to a silicon rubber structure, so that the bonding degree between the graphene nanosheet and silicon rubber can be effectively improved, and the mechanical property and the thermal property of the functionalized graphene nanosheet reinforced silicon rubber composite material can be further improved through synergistic interaction.
Drawings
Fig. 1 shows a schematic representation of the preparation of functionalized graphene nanoplatelets according to the present invention in a specific embodiment;
FIG. 2 is a TGA analysis graph of various samples according to embodiments of the present invention;
FIG. 3 shows XPS spectra of different samples according to embodiments of the present invention;
FIG. 4 shows a nuclear-scale spectrum of Si 2p in an embodiment of the present invention;
FIG. 5 shows a nuclear spectrum of C1s in an embodiment of the present invention;
FIG. 6 shows an XPS spectrum of f-GNP in a specific embodiment of the present invention;
FIG. 7 shows an XPS spectrum of f-GNP-Si in an embodiment of the present invention;
FIG. 8 shows Raman spectra of different samples according to embodiments of the present invention;
FIG. 9 shows an SEM image of GNPs in an embodiment of the present invention;
FIG. 10 shows an SEM image of f-GNP-Si according to an embodiment of the present invention;
FIG. 11 shows an EDS single spectrogram of GNP in an embodiment of the present invention;
FIG. 12 shows an EDS single spectrogram for f-GNP-Si in an embodiment of the present invention;
FIG. 13 is a graph of the elemental carbon distribution of f-GNP-Si in an embodiment of the present invention;
FIG. 14 is a graph of the elemental oxygen distribution of f-GNP-Si in an embodiment of the present invention;
FIG. 15 is a graph of the elemental silicon distribution of f-GNP-Si in an embodiment of the present invention;
FIG. 16 is a chart of DSC analysis of various samples in accordance with an embodiment of the present invention;
FIG. 17 is a graph of the Young's modulus change for various samples in accordance with the present invention;
FIG. 18 is a graph of the change in tensile strength for different samples in an embodiment of the present invention;
FIG. 19 is a graph of the change in elongation at break for different specimens in a specific embodiment of the present invention;
FIG. 20 is a cross-sectional SEM image of a fracture of a silicone rubber in an embodiment of the present invention;
FIG. 21 is an SEM image of a fracture cross-section of GNP (2phr)/SR in a specific embodiment of the present invention;
FIG. 22 is an SEM image of a fracture cross-section for f-GNP-Si (2phr)/SR in an embodiment of the present invention;
FIG. 23 is an SEM image of a fracture cross-section of GNP (5phr)/SR in a specific embodiment of the present invention;
FIG. 24 is an SEM image of a fracture cross-section for f-GNP-Si (5phr)/SR in a specific embodiment of the present invention;
FIG. 25 is a graph of the variation of thermal conductivity for different samples in accordance with one embodiment of the present invention;
FIG. 26 is a graph comparing thermal conductivity for different samples according to the present invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The preparation method of the functionalized graphene nanosheet reinforced silicone rubber composite material comprises the following steps:
s1, forming an azaring structure on the surface of the graphene nanosheet through a 1, 3-dipolar cycloaddition reaction, wherein the azaring structure has a terminal containing a carboxyl group;
s2, bonding APTMS on the graphene nanosheets through the introduced carboxyl groups to obtain functionalized graphene nanosheets;
s3, mixing the functionalized graphene nano sheets in silicon rubber to obtain the functionalized graphene nano sheet reinforced silicon rubber composite material.
With particular reference to fig. 1, wherein 1 represents graphene nanoplatelets; i represents a process of forming a nitrogen heterocyclic ring structure with a carboxyl terminal on the surface of the graphene nanosheet through a 1, 3-dipolar cycloaddition reaction, and reaction i is referred to as i hereinafter; 2 represents a graphene nanosheet with a nitrogen heterocyclic ring structure on the surface; ii represents a process of reacting APTMS with a carboxyl group to bond APTMS to the graphene nanoplatelets, and ii is hereinafter referred to as reaction ii; and 3 represents functional graphene nanosheets.
It should be noted that fig. 1 is only an exemplary structure of the nitrogen heterocyclic structure, and other nitrogen heterocyclic structures having a carboxyl terminal which can be formed by 1, 3-dipolar cycloaddition reaction are within the scope of the present application.
Further, the S1 is performed using a solvent-free reaction.
By adopting solvent-free reaction, the problem that the solvent is remained in the reaction i and the reaction ii and the reaction degree of the reaction i and the reaction ii is reduced can be effectively avoided.
Specifically, the solvent-free reaction is as follows: adding graphene nanosheets into a mixed solution of IDA (immunogenic acid) and PFA (paraformaldehyde) with ethanol as a solvent, stirring and mixing until the solvent is removed, heating the solid mixture to 180-250 ℃, and reacting for 5 hours.
Because the ethanol is volatile, the ethanol can be gradually volatilized in the stirring process of the graphene nanosheets and the mixed solution, and after the ethanol is completely removed, the residual solid mixture is subjected to heating reaction, so that a nitrogen heterocyclic structure with a carboxyl terminal is formed on the surface of the graphene nanosheets through 1, 3-dipolar ring addition reaction. In order to improve the volatilization efficiency of ethanol, the mixed solution may be gently heated during the stirring process.
Exemplary heating temperatures are 180 ℃, 200 ℃, 220 ℃ and 250 ℃.
Preferably, the heating temperature is 180 ℃.
Preferably, the molar ratio of IDA to PFA is 1: 5.
Further, the S3 specifically includes: adding the functionalized graphene nanosheet into chloroform, mixing under ultrasonic waves, adding the mixture into silicon rubber in a ratio of 0.5-5.0 phr, and curing for 24 hours after adding a curing agent to obtain the functionalized graphene nanosheet reinforced silicon rubber composite material.
It should be noted that phr represents parts per hundred of silicone rubber (parts per rounded rubber). For example, 0.5phr represents an addition of 0.5 parts per hundred parts of silicone rubber.
Illustratively, the functionalized graphene is added in an amount of 0.5phr, 1.0phr, 2.0phr, and 5.0 phr.
Preferably, the method also comprises the step of removing chloroform in the silicone rubber before adding the curing agent.
Specifically, chloroform, a solvent, may be removed by reacting the reaction of S3 in a vacuum oven (vacuum oven).
The curing agent may be any commercially available curing agent for silicone rubber.
The S3 specifically includes: adding the functionalized graphene nanosheet into chloroform (20mg/mL) for ultrasonic treatment for 1h, adding the obtained functionalized graphene nanosheet resuspension into silicon rubber, uniformly mixing, and removing the chloroform by using a vacuum furnace; and adding a curing agent to stir after the chloroform is removed, putting the mixture into a Teflon mold, degassing in vacuum, and curing at room temperature for 24 hours to obtain the functionalized graphene nanosheet reinforced silicone rubber composite material.
Preferably, the nitrogen heterocyclic structure is pyrrole-1-carboxylic acid.
The functionalized graphene nanosheet reinforced silicone rubber composite material is prepared by the preparation method of the functionalized graphene nanosheet reinforced silicone rubber composite material.
Preferably, the addition amount of the functionalized graphene nano-sheets is 2phr or 5 phr.
Compared with a silicon rubber material without the functionalized graphene nanosheets, when the addition amount of the functionalized graphene nanosheets is 2phr, the Young modulus of the functionalized graphene nanosheet reinforced silicon rubber composite material is reduced by 25%, and the toughness reinforcement of the functionalized graphene nanosheet reinforced silicon rubber composite material is shown; when the addition amount of the functionalized graphene nanosheets is 5phr, the thermal conductivity of the functionalized graphene nanosheet reinforced silicone rubber composite is enhanced by 150%, and the functionalized graphene nanosheet reinforced silicone rubber composite is shown to have high thermal conductivity.
Example 1
The functionalized graphene nanosheet reinforced silicone rubber composite material is prepared by the following steps:
s1, preparing graphene nano-sheets (graphite nano-sheets) with equivalent diameter (equivalent diameter) of about 10 μm and surface area of 27m2Supplied by Nacional de Grafite, Brazil, hereinafter referred to as GNP) was added to a mixed solution of IDA and PFA in ethanol as a solvent, wherein the molar ratio of IDA to PFA was 1:5, gently heated and magnetically stirred until ethanol was completely removed, and then the solid was heated at 180 ℃ to mixReacting the mixture for 5h, washing the solid mixture after the reaction with ethanol, acetone and distilled water for several times, filtering and drying at 40 ℃ overnight under a vacuum condition to obtain graphene nanosheets (hereinafter, denoted by f-GNP) with a surface having a carboxyl-terminated pyrrolidine ring structure;
s2, adding 3.0g f-GNP into 200mL of chloroform for resuspension, adding 2.0mL of APTMS for stirring overnight at room temperature under a nitrogen atmosphere, washing the mixture obtained by stirring with chloroform and filtering in vacuum, and drying the filtered mixture in a vacuum furnace for overnight to obtain functionalized graphene nanosheets (hereinafter denoted by f-GNP-Si);
s3, resuspending f-GNP-Si with chloroform (20mg/mL), vacuum-treating for 1h, adding 2.0phr of the suspension into silicone rubber (Xiaometer RTV-4234-T4 available from East Coast Fibreglass Supplies), stirring uniformly with a three-roll mill (three-roll-mill), and removing the chloroform with a vacuum furnace; and after the chloroform is removed, adding a curing agent into the f-GNP-Si/silicone rubber composite material, mixing, putting into a Teflon mold, degassing in vacuum, and curing at room temperature for 24 hours to obtain the functionalized graphene nanosheet reinforced silicone rubber composite material.
Example 2
S1, adding graphene nanosheets (graphite nanosheets, with an equivalent diameter (equivalent diameter) of about 10 microns, a surface area of 27m2/g, provided by Nacional de Grafite, Brazil) into a mixed solution of IDA and PFA with ethanol as a solvent, wherein the molar ratio of IDA to PFA is 1:5, heating gently and electromagnetically stirring until ethanol is completely removed, heating the solid mixture at 180 ℃ for 5 hours to react, washing the reacted solid mixture with ethanol, acetone and distilled water for several times, filtering, and drying at 40 ℃ under a vacuum condition overnight to obtain carboxymethyl-pyrrolidine functionalized graphene nanosheets;
s2, adding 3.0g f-GNP into 200mL of chloroform for resuspension, adding 2.0mL of APTMS, stirring overnight at room temperature under the nitrogen atmosphere, washing a mixture obtained by stirring with chloroform, filtering in vacuum, and drying the filtered mixture in a vacuum furnace overnight to obtain a functionalized graphene nanosheet;
s3, resuspending f-GNP-Si with chloroform (20mg/mL), vacuum-treating for 1h, adding the suspension into silicone rubber (Xiaometer RTV-4234-T4, available from East Coast Fibreglass Supplies) according to 5.0phr, stirring uniformly with a three-roll mill (three-roll-mill), and removing the chloroform with a vacuum furnace; and after the chloroform is removed, adding a curing agent into the f-GNP-Si/silicone rubber composite material, mixing, putting into a Teflon mold, degassing in vacuum, and curing at room temperature for 24 hours to obtain the functionalized graphene nanosheet reinforced silicone rubber composite material.
Comparative example 1
The functionalized graphene nanosheet reinforced silicone rubber composite material is different from the silicone rubber composite material in example 1 in that: the GNPs were directly mixed with the silicone rubber, excluding the S1 and S2 steps.
Comparative example 2
The functionalized graphene nanosheet reinforced silicone rubber composite material is different from the silicone rubber composite material in example 1 in that: the f-GNPs were directly mixed with silicone rubber, excluding the S2 step.
Comparative example 3
The functionalized graphene nanosheet reinforced silicone rubber composite material is different from the silicone rubber composite material in example 1 in that: the GNP-APTMS (GNP directly bonded to APTMS) was directly mixed with the silicone rubber, excluding the S1 step.
Detection example 1
Thermogravimetric analysis (TGA) is carried out on the functionalized graphene nanosheet reinforced silicone rubber composite material prepared in example 1 and comparative examples 1-3, the heating rate is carried out at 10 ℃/min, and the analysis result is shown in FIG. 2. Wherein the non-illustrated portion of each curve represents, from top to bottom, GNP (comparative example 1), f-GNP (comparative example 2), f-GNP-Si (example 1), and APTMS (comparative example 3), respectively; the inset in FIG. 2 is a high precision TGA curve for GNP, f-GNP-Si.
As can be seen from fig. 2, the GNP curve shows that comparative example 1 is a material with thermal stability, which has a weight loss (weight loss) of less than 2 wt% at 600 ℃. In contrast, the f-GNP and f-GNP-Si curves show that comparative example 2 and example 1 lose more than 18 wt% at 600 deg.C, mainly due to thermal decomposition of their functional groups at 600 deg.C. The f-GNP curve shows a separate degradation process starting from around 250 ℃, which may be related to the decomposition of the carboxymethyl pyrrolidine functional group. And two degradation processes are shown on the f-GNP-Si curve, wherein the degradation process below 200 ℃ is related to the thermal degradation of APTMS, and the degradation process starting at about 250 ℃ is related to the degradation of the functional groups remained on the pyrrolidine.
Detection example 2
XPS (X-ray Electron Spectroscopy) was performed on f-GNP-Si, f-GNP and GNP, respectively, to analyze the surface compositions, and the results are shown in FIG. 3. Wherein, each line segment of the non-illustrated part is f-GNP-Si, f-GNP and GNP from top to bottom in sequence.
The peaks around 284eV, 399eV, 531eV, and 102eV in the figure represent the binding energies of carbon, oxygen, nitrogen, and silicon, respectively, and the contents of the respective components are shown in Table 1. It was found that the oxygen content was below 2% for GNPs. It can be seen from Table 1 that the concentrations of nitrogen and oxygen atoms in both f-GNP and f-GNP-Si are increased. Wherein the nitrogen-oxygen ratio of the f-GNP and the f-GNP-Si is 0.6, the silicon-oxygen ratio of the f-GNP-Si is 0.3, and the silicon-nitrogen ratio is 0.5, which shows that the f-GNP and the f-GNP-Si have the expected functionalized structures.
TABLE 1
| C | O | N | Si | [N]:[O] | [Si]:[O] | [Si]:[N] | |
| GNP | 98.4 | 1.6 | - | - | - | - | - |
| f-GNP | 87.4 | 7.9 | 4.7 | - | 0.6 | - | - |
| f-GNP-Si | 76.8 | 12.5 | 7.2 | 3.5 | 0.6 | 0.3 | 0.5 |
Further, the results of core-level spectrum (core-level spectrum) analysis of Si 2p are shown in FIG. 4. The non-illustrated part of the curves show envelope, Si-O and Si-C, respectively, from top to bottom at around 102 eV.
The peaks corresponding to the values of the binding energy contributed by the Si-C and Si-O bonds, 101.6eV and 102.4eV, respectively, are shown from FIG. 4.
The C1s of GNP was further subjected to nuclear-scale spectral analysis, and the analysis results are shown in FIG. 5. The peak binding energy of C1s at 284.5eV (major contribution), 285.2eV, 286.1eV and 287.2eV is shown by C ═ C (sp) respectively2Bonded carbon), C-C (sp)3Bonded carbon), C-OH (alkoxy), and C ═ O (carbonyl). Among these, the broad weak peak at 291.1eV (broad bead peak) comes from the vibrational transition of pi-pi. The C1s nuclear-scale spectra of f-GNP (FIG. 6) and f-GNP-Si (FIG. 7) appear to be more asymmetric than the GNP spectra, which is related to the increased contributions of 284.5eV, 285.2eV, 286.1eV, and 287.2 eV. For C (═ O) O (carboxyl) derived from the carboxylic acid function, the contribution at 288.9eV in f-GNP appears insignificant, whereas for f-GNP-Si, the contribution appears to be a peak in binding energy at 283.3eV from the contribution of the C-Si bond, indicating that the carboxyl moiety in f-GNP has completely reacted with APTMS.
Detection example 3
Raman spectrum analysis was performed on f-GNP-Si, f-GNP and GNP, respectively, and the analysis results are shown in FIG. 8. Wherein the non-illustrated portion of the top-down curves are denoted f-GNP-Si, f-GNP, and GNP in that order.
The typical characteristic bands of graphite materials can be identified in all spectra: at 1330cm-1Left and right D wave band at 1580cm-1The sum of the left and right G wave bands is 2680cm-1Left and right 2D bands. Shows a prominent D band from both f-GNP and f-GNP-Si and approximately 1620cm-1At the shoulder of the G band (D' band), indicating sp associated with the covalent linking function3The bonds are all formed on the GNP surface.
Detection example 4
SEM analysis of GNP and f-GNP-Si is shown in FIGS. 9 and 10, respectively. As can be seen from the figure, the functionalization process results in an increase in the surface roughness of the graphene nanoplatelets.
EDS single spectrum (EDS single spectrum) analysis was further performed on GNP and f-GNP-Si, and the results are shown in FIGS. 11 and 12, respectively. The peaks for carbon and oxygen are shown in both fig. 11 and fig. 12, and additional peaks for nitrogen and silicon are also shown in fig. 12. This result was consistent with the XPS analysis in detection example 2.
EDS mapping analysis was further performed on f-GNP-Si, and the analysis results are shown in FIGS. 13, 14 and 15. In fig. 13, 14, and 15, the distributions of carbon, oxygen, and silicon elements are shown, respectively. The figure shows that the elements are evenly distributed in the sample.
Detection example 5
DSC (differential scanning calorimetry) analysis was performed according to the compositions in the items of Table 2, and the analysis results are shown in FIG. 16 and Table 2.
TABLE 2
χcCalculated according to the following formula:
wherein, χcRepresents the degree of crystallinity,. DELTA.HmThe melting enthalpy of 100% crystalline PDMS (polydimethylsiloxane) was 37.4J/g.
As can be seen from an analysis of FIG. 16 and Table 2, T is increased with the addition amounts of GNP and f-GNP-SimSlightly increased, which is associated with the limited mobility of the silicone rubber chains caused by the rigid filler. And, for f-GNP-Si material, T thereofmThe value is remarkable, and the silane functional group bonded on the surface of the f-GNP-Si can provide an active site and can perform more effective interaction with a silicon rubber chain, so that the T is improvedm。
And, regarding the crystallinity, the crystallinity of the silicone rubber composite material is continuously reduced along with the increase of the addition amount of GNP or f-GNP-Si in the silicone rubber, and the secondary phenomenon is that the addition of GNP and f-GNP-Si prevents the rearrangement of the silicone rubber chains in the crystallization process.
Detection example 6
Young modulus, tensile strength and elongation at break of the silicone rubber composite materials containing different amounts of added GNP and f-GNP-Si are respectively detected, and the detection results are respectively shown in FIGS. 17, 18 and 19.
It can be seen from the figure that the young's modulus of the silicone rubber composite shows a characteristic increase before 2phr and a decrease after 2phr with increasing addition of GNP due to the presence of aggregates (aggrerates) in the silicone rubber composite and to the poor interaction of the silicone rubber chains with GNP at the interface. The maximum improvement value of 25% at 2phr is shown with increasing f-GNP-Si addition compared to pure silicone rubber (neat SR). Therefore, the positive effect of doping f-GNP-Si into the silicone rubber matrix on the Young's modulus indicates that the functionalization of GNP plays an important role in improving the mechanical properties of the silicone rubber composite, can effectively improve the dispersibility of GNP in the silicone rubber medium, and improves the benign interaction between the silicone rubber chains and GNP at the interface. Furthermore, with increasing addition of GNP and f-GNP-Si in the silicone rubber composite, the elongation of the silicone rubber composite can be made to increase gradually, with a maximum at 2phr and a decreasing trend at 5 phr. It was further found that GNP or f-GNP-Si had no effect on the elongation at break of the silicone rubber composite.
Further, the results of SEM examination of fracture cross-section of SR (near), GNP (2phr)/SR and f-GNP-Si (2phr)/SR are shown in FIGS. 20, 21 and 22, respectively.
FIG. 20 shows SR (neat) with a flat and smooth fracture surface; the white arrows in fig. 21 indicate weak interfacial bonding of GNPs to the silicone rubber matrix, in contrast to the fact that f-GNP-Si is shown in fig. 22 to be hardly distinguishable in the silicone rubber matrix, and a representative f-GNP-Si is shown by the white arrows, from which it can be seen that f-GNP-Si is incorporated into the silicone rubber matrix and does not exhibit significant cracking. This difference in morphology and improved filler-matrix interaction, in turn, contributes to the enhancement of the mechanical properties of the silicone rubber composite.
Further, the fracture cross-section SEM examination of GNP (5phr)/SR and f-GNP-Si (5phr)/SR was conducted, and the results are shown in FIGS. 23 and 24, respectively.
It can be seen from the figure that when the amount of GNP or f-GNP-Si added is 5phr, large GNP/f-GNP-Si agglomerates are shown in the fracture cross section of the silicone rubber composite, which is strongly correlated with the deterioration degree of the mechanical properties of the silicone rubber.
Detection example 7
Thermal conductivity coefficient detection is performed on the GNP/SR and the f-GNP-Si, the detection result is shown in FIG. 25, and the data is further compared with the existing silicone rubber composite material, and the comparison result is shown in FIG. 26.
The figure shows that as the addition of GNP or f-GNP-Si is gradually increased, the silicone rubber composite exhibits higher thermal conductivity to greater than 2phr (Φ ≈ 0.009), whereas at 5phr (Φ ≈ 0.02) the opposite behavior is shown, with f-GNP-Si exhibiting a 150% increase in thermal conductivity compared to GNP.
GNP-SR composite (k)c) The thermal conductivity of (b) can be predicted by means of a Lewis-Nielsen model (see Liu MF et al, Micromechanics of correlation of a graphene-based thermoplastic elastomer nanocomposite. composite Part A.2018; 110:84-92.)
In particular to
Wherein
In the formulae (1), (2) and (3), kmIs the thermal conductivity of the matrix, kfIs the thermal conductivity of the filler, phi is the volume fraction of the filler, phimFor maximum filler volume fraction, the parameter A is associated with a generalized Einstein coeffient (k)EMore specifically, A ═ kE-1, which depends on the shape of the fillers, the aspect ratio and their relative heat flow direction. Although A and phimThe values of (A) and (k) are unknown for graphite or other 2D fillers, so A and k are used in this experimentfAs fitting parameters. Phi is amAssuming a value of 0.52, this corresponds to a three-dimensional random packing of the filler in the polymeric matrix.
As can be seen from fig. 25, the Lewis-Nielsen model well followed the trend of the experimental results. Experimental results with 5phr of GNP-SR the deviation from the predicted values is related to the re-packing and agglomeration of the filler, which significantly reduces the aspect ratio of GNPs. And this parameter, because it depends on the shape and aspect ratio of the filler, decreases with decreasing GNP aspect ratio and results in a decrease in thermal conductivity.
FIG. 26 shows comparative experiments on thermal conductivity of GNP/SR and f-GNP-Si/SR in the present invention and silicone rubber composites in the prior art. In the legend, the GNP is referred to Mu QH et al, Thermal conductivity of graphite/silicone rubber preparation by solution interaction. Thermochim acta.2007; 462(1-2) 70-5; silicon coating to a graphene for enhancing thermal conductivity and electrical insulation of graphene/polydimethysiloxane nanocomposites, J Mater Sci Technol.2019, Shen CX et al; 35(1) 36-43; (iv) Enhancing the thermal, electrical, and mechanical properties of silicone rubber by addition of graphene nanoplatiles. Material design. 2015; 88:950-7.
APTES and VTMS functionalized GNP see Zhang GW et al, Effect of Functionalization of Graphene nanoplates on the Mechanical and Thermal Properties of Silicone Rubber composites materials, 2016; 9(2).
APTES-GO is described in Tang JJ et al Study on a novel composite coated base on PDMS coated with modified graphene oxide.J Coat Technol Res.2018; 15(2):375-83.
APTES-rGO is described in Zhong Y et al Preparation and thermal-mechanical properties of functionalized graphene/silicone rubber nanocomposites.201516th International Conference on electronic Packaging Technology (ICEPT)2015, 30-4.
VTMS-GO is described in Ma WS et al, Improving the thermal and mechanical properties of silicone polymers by interacting with functionalized graphene oxide.J. Mater Sci.2013; 48(15):5287-94.
Acrylamide (AA) functionalized rGO is described in Lin SC et al Preparation of a graphene-silver nanowire hybrid/silicone rubber composite for thermal interface materials J Taiwan Inst Chem E.2016; 68:396-406.
MQ Silicone-rGO is described in Liang WJ et al, Reduced Graphene Oxide Embedded with MQ Silicone Resin Nano-Aggregates for Silicone Rubber Composites with Enhanced Thermal Conductivity and Mechanical Performance polymers.2018; 10(11).
In general, the GNP/SR and f-GNP-Si/SR composite materials provided by the invention have stronger competitive advantages in thermal conductivity under the same addition amount. And when the addition amount of the f-GNP-Si reaches 5phr, higher thermal conductivity enhancement is shown compared with other GNPs or other functionalized GNPs.
In summary, an aza-ring structure similar to the graphene structure is formed on the surface of the graphene nanosheet through a 1, 3-dipolar ring addition reaction, and a carboxyl terminal of the aza-ring structure reacts with (3-aminopropyl) trimethoxysilane (APTMS) to bond the APTMS to the graphene nanosheet, at this time, functional groups bonded to the surface of the graphene nanosheet respectively have an aza-ring structure similar to the graphene nanosheet structure and a silane structure similar to the silicon rubber structure, so that the degree of bonding between the graphene nanosheet and the silicon rubber can be effectively improved, and the mechanical property and the thermal property of the functionalized graphene nanosheet reinforced silicon rubber composite material can be further improved through a synergistic effect.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (9)
1. The preparation method of the functionalized graphene nanosheet reinforced silicone rubber composite material is characterized by comprising the following steps:
s1, forming an azaring structure on the surface of the graphene nanosheet through a 1, 3-dipolar cycloaddition reaction, wherein the azaring structure has a terminal containing a carboxyl group;
s2, bonding APTMS on the graphene nanosheets through the introduced carboxyl groups to obtain functionalized graphene nanosheets;
s3, mixing the functionalized graphene nano sheets in silicon rubber to obtain the functionalized graphene nano sheet reinforced silicon rubber composite material.
2. The method for preparing the functionalized graphene nanoplatelet reinforced silicone rubber composite according to claim 1, wherein the S1 is performed using a solvent-free reaction.
3. The method for preparing the functionalized graphene nanoplatelet reinforced silicone rubber composite material of claim 2, wherein the solvent-free reaction is: adding the graphene nanosheets into a mixed solution of IDA and PFA with ethanol as a solvent, stirring and mixing until the solvent is removed completely, heating the solid mixture to 180-250 ℃, and reacting for 5 hours.
4. The method for preparing the functionalized graphene nanoplatelet reinforced silicone rubber composite material according to claim 3, wherein the molar ratio of IDA to PFA is 1: 5.
5. The preparation method of the functionalized graphene nanoplatelet reinforced silicone rubber composite material according to claim 1, wherein S3 specifically is: adding the functionalized graphene nanosheet into chloroform, mixing under ultrasonic waves, adding the mixture into silicon rubber in a ratio of 0.5-5.0 phr, and curing for 24 hours after adding a curing agent to obtain the functionalized graphene nanosheet reinforced silicon rubber composite material.
6. The preparation method of the functionalized graphene nanoplatelet reinforced silicone rubber composite as recited in claim 5, further comprising the step of removing chloroform from the silicone rubber before adding the curing agent.
7. The method of preparing a functionalized graphene nanoplatelet reinforced silicone rubber composite of claim 1, wherein the nitrogen heterocyclic ring structure is pyrrole-1-carboxylic acid.
8. The functionalized graphene nanosheet reinforced silicone rubber composite material is characterized by being prepared by the preparation method of the functionalized graphene nanosheet reinforced silicone rubber composite material as claimed in any one of claims 1 to 7.
9. The functionalized graphene nanoplatelet reinforced silicone rubber composite of claim 8 wherein the functionalized graphene nanoplatelets are added in an amount of 2phr or 5 phr.
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Non-Patent Citations (1)
| Title |
|---|
| 任河等: ""硅烷改性石墨烯纳米片增强硅橡胶的研制"", 《有机硅材料》 * |
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