CN115627039A - Double-filler system ternary fluororubber nanocomposite and preparation method thereof - Google Patents
Double-filler system ternary fluororubber nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of preparation of high polymer materials, in particular to a preparation method of a ternary fluororubber nanocomposite material of a double-filler system. The invention relates to a ternary fluororubber nanocomposite material of a double-filler system, which is prepared by taking ternary fluororubber as a matrix, aminated multi-walled carbon nanotubes (MWCNT-A) and multi-walled carbon nanotubes (MWCNT) as fillers and mixing, vulcanizing and two-stage vulcanizing through an open mill, wherein amino groups of the aminated multi-walled carbon nanotubes can participate in crosslinking of fluororubber molecular chains during vulcanization to form another crosslinking network except the fluororubber molecular chains, and the crosslinking network is an assisting force for improving the tensile strength of the composite material.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a ternary fluororubber nanocomposite material of a double-filler system and a preparation method thereof.
Background
The fluororubber is a synthetic polymer rubber (elastomer) containing fluorine atoms on carbon atoms of a main chain or a side chain, which belongs to special fluororubbers, and compared with other hydrocarbon rubbers, the fluororubber has the characteristics of strong electronegativity, high-bond-energy fluorine-carbon bonds (bond energy is as high as 465 kj/mol), small van der waals bond angle (1.32 angstroms) and the like, and the covalent radius of the fluorine atoms is small (0.64 angstroms, which is only about half of the length of the carbon-carbon bond (C-C) bond, so that the fluorine atoms play a role in shielding the carbon-carbon main chain, thereby protecting the carbon-carbon main chain, ensuring the stability of the carbon-carbon main chain, and the structure endows the fluororubber with good heat resistance, chemical medium aging resistance and weather aging resistance, good chemical inertness in solvents, hydrocarbons, acids and bases, and has the characteristics of low dielectric constant, low refractive index, low surface energy (oil and water repellency), low hygroscopicity, and the high-bond energy of the C-F bond is very favorable for improving oxidation resistance and hydrolysis resistance.
Patent CN202210723245.1 discloses a preparation method of fluororubber with high performance retention rate at high temperature. The preparation method of the fluororubber with high performance retention rate at high temperature provided by the invention is simple and easy to operate, and has low cost, and the prepared fluororubber has high performance retention rate at high temperature and good processability, and can be widely applied to the technical fields of aerospace, military industry, national defense, automobiles, petrochemical industry and the like. However, the preparation method relates to the use of solution, which easily causes environmental pollution, and the process contains vacuum environment and gas protection, so that the control of experimental conditions is very strict, and errors are easily caused.
Patent CN202210467957.1 discloses a preparation method of low compression stress relaxation fluororubber for battery sealing member. The fluororubber with low compression stress relaxation, excellent high temperature resistance, electrolyte resistance, acid and alkali resistance and chemical corrosion resistance is prepared by simple mechanical blending, and the sealing element prepared by the fluororubber has the advantages of high temperature resistance, electrolyte resistance, acid and alkali resistance, chemical corrosion resistance, good sealing reliability, long service life and the like. But the hardness and the wear resistance are low, and the sealing element is easy to wear in the using process, thereby shortening the service life.
Patent CN202210683998.4 provides a preparation method of a fluororubber composite material, which combines wollastonite with a needle-like structure and magnesium hydroxide with a sheet-like structure, and adds the wollastonite with a needle-like structure and the magnesium hydroxide into the fluororubber, so that the fluororubber can be continuously filled, and the thermal conductivity of the fluororubber can be further improved. However, the drying of water involved in the secondary mixing process, which is somewhat incomplete, will generate bubbles during vulcanization, thereby affecting the properties of the composite, and the tensile strength of the composite after combining the two inorganic fillers is low.
Patent CN202111417540.6 discloses an electrically conductive fluororubber for oil seal. The novel conductive fluororubber material for the oil seal is prepared by mixing modified ternary fluororubber raw rubber, carbon nano tubes, conductive carbon black, magnetic powder, graphite, dioctyl sebacate, an acid-absorbing agent, a release agent and a dispersing agent in parts by weight together in an internal mixer, and compared with the traditional conductive fluororubber material, the strength and the conductivity of the conductive fluororubber material are improved to a certain extent, and the prepared conductive fluororubber material is excellent in comprehensive mechanical properties. However, the method of mixing in an internal mixer cannot uniformly disperse various fillers such as carbon nanotubes, so that the fillers agglomerate in the fluororubber matrix, thereby affecting the performance of the fluororubber.
Patent CN202110800238.2 discloses a preparation method of low-resistivity fluororubber for automobile fuel pipe system. Kneading the ternary fluororubber in an internal mixer to generate heat, adding N990 carbon black, active magnesium oxide, a carbon nanotube, nano-scale surface silver-plated glass beads, calcium hydroxide and a release agent, and stirring and kneading; turning to an open mill for turning, thinning and discharging sheets, and then taking out and standing; then putting the mixture into an open mill again for mixing, adding bisphenol AF and a vulcanization accelerator, and discharging the mixture after open milling to obtain rubber compound; and (3) placing the rubber compound into a die for compression molding after performing, and finally performing two-stage vulcanization. However, the fluororubber composite material added with various fillers has relatively reduced tensile strength and compression set, and is not beneficial to the application in the aspect of sealing elements.
Patent CN201710620527.8 provides an automobile cooling tube, which is modified by adding nano elemental tungsten, nano graphite fiber and nano potassium feldspar on the basis of the original material of the automobile cooling tube, so as to improve the heat transfer effect of the automobile cooling tube. Although the heat transfer effect of the fluororubber is greatly improved by adding a plurality of fillers, the use amount of the fillers is too large, and the economic benefit is not high.
Patent CN202210388971.2 discloses a preparation method of a silicone filler modified fluororubber masterbatch. Dispersing the micro-nano silicon filler into a mixed solution of absolute ethyl alcohol and deionized water, adjusting the pH value after ultrasonic mixing, adding a modifier to realize organic bridging of the silicon filler and the fluororubber, and washing, centrifuging and drying a reaction product to obtain a modified silicon filler; the modified silicon filler and the fluororubber are mixed and then mixed, and the block material is divided into particles after mixing to obtain the silicon filler modified fluororubber master batch. However, in the preparation process, an organic solvent is required, the environment is easily polluted, the requirement of environmental protection cannot be met, and a large amount of deionized water solution is used, so that bubbles are easily formed in the fluororubber at high temperature, and the performance and the quality of the fluororubber are influenced.
Patent CN202210376077.3 discloses an oil-resistant easy-to-process fluorine-containing elastomer composition. The polyhexafluoropropylene oxide methyl pentafluoropropionate is obtained by refluxing, esterifying and dehydrating the polyhexafluoropropylene oxide methyl monomethanol and the pentafluoropropionic acid for 3 to 4 hours under the action of catalyst phosphoric acid. The invention achieves the purposes of softening the fluororubber and improving the fluidity, the demolding property and the roll separation property of the fluororubber by adding the fluoroalkyl ester with medium and low molecular weight into the fluororubber. The fluorine-containing elastomer has good solvent resistance, processing manufacturability, high temperature resistance, corrosion resistance and good mechanical strength. But the preparation process is complex, the requirement on the process is high, and a large amount of organic solvent is used, so that the method is easy to cause harm to human bodies and pollution to the environment.
Patent CN202210705213.9 provides a preparation process of a high temperature resistant special fluororubber. The high-temperature-resistant fluororubber composite material is obtained through simple mechanical blending, the problems that the fluororubber has poor low-temperature performance due to poor flexibility of a fluororubber molecular chain and high glass transition temperature are solved, a large amount of powder and organic solvent are added, the environment is easily polluted in the processing process, the health of an operator is harmed, and the value for improving the tensile property is not high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a ternary fluororubber nanocomposite with a double-filler system, and the technical scheme adopted by the invention is as follows:
a preparation method of a double-filler system ternary fluororubber nanocomposite comprises the following steps:
(1) Weighing the following raw materials in parts by weight:
100 parts of ternary fluororubber;
1-5 parts of an acid acceptor;
1-5 parts of an accelerator;
0.5-5 parts of octadecylamine;
1-10 parts of a multi-wall carbon nanotube;
1-10 parts of aminated multi-walled carbon nanotubes;
1-5 parts of a vulcanizing agent;
(2) Setting the roll temperature of an open mill to be 45-55 ℃, putting the fluororubber into the open mill, adding the premixed acid-absorbing agent and the accelerator into the open mill, uniformly mixing, and finally adding the octadecylamine, the multi-walled carbon nanotubes, the aminated multi-walled carbon nanotubes and the vulcanizing agent into the open mill, and uniformly mixing;
(3) After the composite material refined in the step (2) is cooled for a period of time, pressing the composite material into a rubber sheet by a flat vulcanizing machine;
(4) And (4) putting the rubber sheet prepared in the step (3) into an oven for secondary vulcanization to prepare the double-filler system ternary fluororubber nanocomposite.
Preferably, the acid acceptor is zinc oxide, the accelerator is triallyl isocyanurate, and the vulcanizing agent is 2, 5-dimethyl-2, 5-dihexane.
Preferably, in the step (3), the vulcanization pressure is 8-10MPa, the vulcanization temperature is 175-180 ℃, and the vulcanization time is 6-8 min.
Preferably, in the step (4), the secondary vulcanization temperature is 230-234 ℃ and the time is 1-3 h.
Preferably, the mass portion of the multi-wall carbon nano tube is 1-5.
Preferably, the aminated multi-wall carbon nanotube accounts for 1-5 parts by weight.
Also provides a double-filler system ternary fluororubber nanocomposite prepared by the preparation method.
The invention has the following beneficial effects: the fluororubber nanocomposite is prepared by taking ternary fluororubber as a matrix and aminated multi-walled carbon nanotubes (MWCNT-A) and multi-walled carbon nanotubes (MWCNT) as fillers, amino groups of the aminated multi-walled carbon nanotubes can participate in crosslinking of molecular chains of the fluororubber during vulcanization to form another crosslinking network except for the molecular chains of the fluororubber, and the crosslinking network becomes a force for improving the mechanical property of the composite material, so that the tensile strength, the elongation at break, the 100% stress at constant elongation and the hardness of the material have obvious advantages compared with a single filler system, and the synergistic effect of the MWCNT and the MWCNT-A is very obvious in the former three; in the aspect of thermal stability, the initial decomposition temperature of the composite material of the dual-filler system is reduced, which is related to a good heat conduction channel formed by the system, and besides, the carbon residue rate of the fluororubber is also influenced by the heat conduction channel of the dual-filler system, so that a compact carbon layer can be rapidly generated on the surface of the material, and the influence of external heat on the fluororubber is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is SEM pictures of (a) FKM/C-1, (b) FKM/C-3, (C) FKM/C-5, (d) FKM/C-7;
FIG. 2 is an FTIR spectrum of comparative example 1 (FKM/C-1), comparative example 2 (FKM/C-3), comparative example 3 (FKM/C-5) and example 1 (FKM/C-7);
FIG. 3 is (a) tensile strength, (b) elongation at break, (c) 100% stress at definite elongation, (d) hardness for comparative examples 1-3 and example 1;
FIG. 4 is the volumetric wear amounts of comparative examples 1-3 and example 1;
FIG. 5 is the conductivity of comparative examples 1-3 and example 1;
FIG. 6 shows (a) thermal conductivity, (b) Thermogravimetry (TG), (c) thermogravimetry (DTG) and (d) char yield of comparative examples 1-3 and example 1.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Comparative examples 1-3 and example 1:
samples were prepared according to the recipe of table 1, respectively, the preparation method was: setting the roll temperature at 50 ℃, putting the ternary fluororubber raw rubber into an open mill, then sequentially and uniformly adding premixed zinc oxide (ZnO) and triallyl isocyanurate (TAIC), and packaging in a triangular bag for 3 times; then adding octadecylamine, multi-walled carbon nanotubes (MWCNT), aminated multi-walled carbon nanotubes (MWCNT-A) and 2, 5-dimethyl-2, 5-dihexyl (biquintet) in sequence, beating in a triangular bag for 6 times, and refining to be uniform; the samples of comparative examples 1 to 3 and example 1 were numbered FKM/C-1, FKM/C-3, FKM/C-5, FKM/C-7 in this order, and left at room temperature for 24 hours.
And pressing the prepared sample into a rubber sheet by a flat vulcanizing machine, wherein the vulcanizing pressure is 10MPa, the vulcanizing temperature and time are 177 ℃, the vulcanizing time is 7 min, and then putting the rubber sheet into an oven for secondary vulcanization, wherein the vulcanizing temperature and time are 232 ℃, and the vulcanizing time is 2 h.
Performance testing
1. Morphology of the composite Material
Shown as a-d in FIG. 1 are SEM images of a composite material (example 1) containing MWCNT and MWCNT-A, and MWCNT-A without carbon material (comparative example 1), and MWCNT-A (comparative example 2) and MWCNT-A, respectively. As can be seen, the fracture surface of example 1 is relatively flat, and the surface has only some particles of the auxiliary zinc oxide; both of the graphs (b) and (c) show a layered structure due to the presence of MWCNT and MWCNT-A, and a less flat fracture surface appears; in the case of two kinds of multi-walled carbon nanotubes, not only a distinct layered structure but also a more dense wrinkle pattern were observed, and the fracture surface was not as smooth as in example 1. In the three diagrams (b), (c) and (d), the composite material shows a few pores due to the addition of the unmodified multi-walled carbon nanotubes and the aminated multi-walled carbon nanotubes, as indicated by red circles in fig. 1.
2. Infrared analysis
Fourier infrared absorption spectroscopy can be used to analyze the structural composition of a substance or to determine its chemical groups. FIG. 2 shows the IR spectra of FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7. It can be seen that the baseline of FKM/C-3, FKM/C-5 and FKM/C-7 all have different degrees of tilt when two multi-walled carbon nanotubes are added into the composite material, especially the composite material FKM/C-7, and the infrared baseline has a higher degree of tilt after the filling of two multi-walled carbon nanotubes are superimposed. In figure 2, the number of composite materials is 893 cm -1 ，1127 cm -1 ，1393 cm -1 ，1692 cm -1 And 2963 cm -1 Near which there appears the corresponding characteristic infrared peak, respectively-CF 3 group, -CF 2-group, -CF-group, C = C bond and-C-H-group, of which 1692 cm -1 The infrared absorption peaks demonstrate that the dehydrofluorination and oxidation reactions of FKM have occurred during sulfidation. After two kinds of multi-wall carbon nanotubes are added, the fluororubber is 1259 cm -1 The infrared absorption peak of (C-C bond) is prominent, and is particularly remarkable in the FKM/C-7 composite material containing MWCNT and MWCNT-A dual fillers.
3. Tensile Properties
FIG. 3 shows the performance of the composite materials FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7 in tensile strength, elongation at break, 100% stress at break and hardness.
As shown in FIG. 3 (a), the tensile strengths of the composite materials are 8.2 MPa,10.0 MPa,12.1 MPa and 18.8 MPa, respectively. We have found that when multi-walled carbon nanotubes are added, a filler network is formed inside the composite material, so that a larger external force is required to break the composite material. Meanwhile, the amino group of the aminated multi-walled carbon nanotube can participate in the crosslinking of the fluororubber molecular chain during vulcanization to form another crosslinked network except the fluororubber molecular chain, and the formation of the crosslinked network is undoubtedly the assistance for improving the tensile strength of the composite material, so that the tensile strength of the MWCNT-A-containing composite material FKM/C-5 is higher than that of the MWCNT-A-containing composite material FKM/C-3. Compared with the composite material FKM/C-1 which is not filled with any multi-wall carbon nano tube, the tensile strength of the composite materials FKM/C-3, FKM/C-5 and FKM/C-7 is respectively improved by 20.7%,47.6% and 129.3%, and the tensile strength improvement rate (129.3%) of the composite material FKM/C-7 containing the MWCNT and MWCNT-A dual-filler system is far greater than the sum (20.7% +47.6% = 68.3%) of the tensile strength improvement rate of the composite material FKM/C-3 containing only MWCNT and the composite material FKM/C-5 containing only MWCNT-A by superposition calculation, which shows that the combined filling of the two carbon materials has a synergistic effect besides the superposition effect of the MWCNT and the MWCNT-A, so that the tensile strength of the composite material FKM/C-7 is greatly improved.
FIG. 3 (b) is a graph of elongation at break for several composites, 344.0%,162.0%,218.0%, and 148.0%, respectively. Therefore, when two kinds of multi-wall carbon nano-tubes are added, the formed filler network structure promotes the rigidity of the composite material to be greatly improved, and meanwhile, the cross-linked network formed by the MWCNT-A and the FKM can help to bear stress when being stretched by external force, so that the elongation at break of the composite material FKM/C-5 is reduced to a small extent compared with the composite material FKM/C-3. The elongation at break of the composite material FKM/C-7 decreased by 57.0%, which was less than the sum of the elongation at break decreases of the composite material FKM/C-3 containing only MWCNT and the composite material FKM/C-5 containing only MWCNT-A (52.9% + 36.6% = 89.5%), indicating that a synergistic effect was also present in the elongation at break of the composite material.
Fig. 3 (c) is the 100% stress at definite elongation for several composites, the most significant enhancement of all properties. Among them, the 100% stress at definite time of the composite FKM/C-3 with MWCNT-A was increased by 267.1%, the 100% stress at definite time of the composite FKM/C-5 with MWCNT-A was increased by 195.1%, and the 100% stress at definite time of the composite FKM/C-7 with MWCNT and MWCNT-A was increased by 680.5%, which was much greater than the increase rate of the 100% stress at definite time of the composite FKM/C-3 and composite FKM/C-5 (267.1% + 195.1% = 462.2%), whereby it was found that the dual filler system of MWCNT and MWCNT-A could also exhibit excellent synergistic effect in terms of 100% stress at definite time.
The hardness of the four composite materials is shown in fig. 3 (d). Compared with FKM/C-1 without multi-wall carbon nano-tubes, the hardness of the composite materials FKM/C-3, FKM/C-5 and FKM/C-7 is improved by 27.0 percent, 24.6 percent and 46.8 percent in sequence, so that the hardness of the composite material is improved by simultaneously adding the two fillers.
4. Wear resistance
The term "abrasion" as used herein means a material loss occurring on the friction surface of the fluororubber sample due to a mechanical action such as a frictional force during the rubbing process. The abrasion resistance of the fluororubber is influenced by various factors, such as frictional wear conditions during testing, and because all sample tests in the experiment are carried out at the same room temperature and under the same test conditions, the test results obtained in the experiment have comparability and are not influenced by the factorsAnd (6) sounding. Furthermore, the abrasion resistance of fluororubbers is also affected by the internal structure of the fluororubber, i.e., the crosslink density of the fluororubber. FIG. 4 shows the volumetric wear rates of the four composite materials, respectively 124.1 mm 3 ，96.5 mm 3 ，93.1 mm 3 ，94.1 mm 3 . From experimental results, the addition of MWCNT and MWCNT-A can effectively reduce the volume abrasion amount of the composite material, wherein the MWCNT-A increases the crosslinking density of the composite material due to chemical crosslinking with a fluororubber molecular chain, so that the volume abrasion amount of the composite material FKM/C-5 is lower than that of the composite material FKM/C-3. After the two multi-wall carbon nano-tubes are combined, the wear resistance of the composite material is not greatly changed, which shows that under the action of friction force, the volume wear amount of the fluororubber can be reduced when the two carbon nano-fillers are respectively added into the composite material, but the synergistic effect of the two carbon nano-fillers has little influence on the wear resistance of the composite material.
5. Electric conductivity
FIG. 5 shows the conductivity of FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7, respectively. Compared with the fluororubber which is not filled with any carbon material, the conductivity of the MWCNT-containing composite material FKM/C-3 is improved by 8 orders of magnitude, the conductivity of the MWCNT-A-containing composite material FKM/C-5 is improved by 6 orders of magnitude, and the conductivity of the MWCNT-A-containing composite material FKM/C-7 is improved by 10 orders of magnitude; similar to the wear resistance, when two carbon fillers are added respectively, the conductivity of the fluororubber is improved to a certain extent, and when the two carbon fillers are added together, the conductivity of the FKM can be improved again, but the synergistic effect of the two carbon fillers is not obvious.
6. Thermal performance
As shown in FIG. 6 (a), the thermal conductivity of the four composite materials is 0.1941W/(m.K), 0.2352W/(m.K), 0.2385W/(m.K) and 0.2675W/(m.K). According to experimental results, the multi-walled carbon nanotube has excellent heat conduction performance, so that the heat conduction coefficient of the composite material can be greatly improved, wherein the heat conduction coefficient of the composite material FKM/C-3 containing MWCNT is increased by 21.2%, and the heat conduction coefficient of the composite material FKM/C-5 containing MWCNT-A is increased by 22.9%, so that the aminated and modified multi-walled carbon nanotube has more excellent heat conduction performance, the heat conduction performance of fluororubber can be better improved, and meanwhile, chemical crosslinking can be generated between the MWCNT-A and an FKM molecular chain, so that a second crosslinking network is formed, and the interior of the composite material has a more unobstructed heat conduction network. Meanwhile, the heat conductivity coefficient of the composite material FKM/C-7 added with the unmodified multi-wall carbon nano tube and the aminated multi-wall carbon nano tube is increased by 37.8 percent, and the composite material has better performance enhancement effect compared with the composite material only added with one multi-wall carbon nano tube.
FIGS. 6 (b) and (c) are TG and DTG measurements of the four composites, respectively, at temperatures ranging from 40 ℃ to 600 ℃. In the combination of the two graphs of (b) (C), it can be seen that the initial decomposition temperatures of the composite materials FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7 are 437.6 ℃,444.3 ℃,442.8 ℃ and 438.0 ℃ respectively. The initial decomposition temperature of the composite material increased with 5 parts of the carbon material, which means that the thermal stability of the composite material was improved by the addition of the carbon material. However, when the amount of the carbon material is increased to 10 parts, the initial decomposition temperature of the composite FKM/C-7 is rather lowered. This is because the heat conducting network formed by the multi-walled carbon nanotubes in the composite material accelerates the heat transfer and mutually brakes with the self-high heat resistance. Therefore, when 5 parts of carbon material is added, the heat resistance of the multi-wall carbon nano tube plays a main role, and the thermal stability of the composite material is improved; when 10 parts of carbon material is added, the heat conducting network formed by the multi-wall carbon nano-tube plays a main role, and the thermal stability of the composite material is rather reduced. In the same 5 parts of filler, MWCNT-A forms a new cross-linked network with the molecular chain of FKM, so that the structural stability is improved, and the heat conduction channel of the composite FKM/C-5 is more perfect, so that the heat transfer is accelerated, the heat can quickly reach every position in the fluororubber, and the thermal stability of the composite FKM/C-5 is reduced.
FIG. 6 (d) shows the carbon residue ratios of the four composites, which are 4.6%,14.2%,14.3% and 17.7%, respectively. Therefore, the addition of the carbon material can obviously improve the carbon residue rate of the fluororubber. Because the unmodified multi-walled carbon nanotube has excellent heat-conducting property, the heat can be quickly transferred in the internal structure of the fluororubber, so that a large number of carbon layers are accumulated on the surface of the composite material FKM/C-3 to isolate the external heat, and the carbon residue rate of the fluororubber is remarkably improved. After the multi-wall carbon nano tube is subjected to amination modification, the heat conductivity coefficient of the composite material FKM/C-5 is increased, rapid heating in the composite material accelerates carbonization of fluororubber, a compact carbon layer is formed on the surface of the composite material, and the influence degree of the internal rubber by external heat is reduced. And the composite material FKM/C-7 is added with 5 parts of MWCNT and 5 parts of MWCNT-A, even if the MWCNT-A can generate chemical crosslinking with fluororubber so as to enable the internal structure to be more stable, the heat conduction network formed by the carbon material is dominant under the condition of filling 10 parts of the carbon material as described in the initial decomposition temperature, so that the rapid heat transfer in the composite material not only reduces the initial decomposition temperature of the composite material FKM/C-7, but also enables the composite material to rapidly form a large number of compact carbon layers on the surface, and improves the carbon residue rate and the ablation resistance of the composite material FKM/C-7.
In conclusion, the fluororubber nanocomposite prepared by using the ternary fluororubber as the matrix and using the aminated multi-walled carbon nanotube (MWCNT-A) and the multi-walled carbon nanotube (MWCNT) as the filler has the advantages that the tensile strength, the elongation at break, the 100% stress at definite elongation and the hardness are all increased, and the synergistic effect of the MWCNT and the MWCNT-A is more obvious in the former three parts; in the aspect of wear resistance, the two multi-walled carbon nanotubes can effectively reduce the volume wear loss of the fluororubber, and when the two carbon materials are combined, the wear resistance of the composite material is not greatly changed; in the aspect of thermal stability, the initial decomposition temperature of the dual-filler composite material is reduced, which is related to a good heat conduction channel formed by the system, and in addition, the carbon residue rate of the fluororubber is also influenced by the heat conduction channel of the dual-filler system, so that a compact carbon layer can be rapidly generated on the surface of a sample, and the influence of external heat on the fluororubber is reduced.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (7)
1. A preparation method of a double-filler system ternary fluororubber nano composite material is characterized by comprising the following steps:
(1) Weighing the following raw materials in parts by weight:
100 parts of ternary fluororubber;
1-5 parts of an acid acceptor;
1-5 parts of an accelerator;
0.5-5 parts of octadecylamine;
1-10 parts of a multi-wall carbon nanotube;
1-10 parts of aminated multi-walled carbon nanotubes;
1-5 parts of a vulcanizing agent;
(2) Setting the roll temperature of an open mill to be 45-55 ℃, putting ternary fluororubber into the open mill, adding the premixed acid-absorbing agent and the accelerator into the open mill, uniformly mixing, and finally adding the octadecylamine, the multi-walled carbon nanotube, the aminated multi-walled carbon nanotube and the vulcanizing agent into the open mill, and uniformly mixing;
(3) After the composite material refined in the step (2) is cooled for a period of time, pressing the composite material into a rubber sheet by using a flat vulcanizing machine;
(4) And (4) putting the rubber sheet prepared in the step (3) into an oven for secondary vulcanization to prepare the double-filler system ternary fluororubber nanocomposite.
2. The method for preparing the ternary fluororubber nanocomposite material with the dual filler system according to claim 1, wherein the method comprises the following steps: the acid absorbent is zinc oxide, the accelerator is triallyl isocyanurate, and the vulcanizing agent is 2, 5-dimethyl-2, 5-dihexyl.
3. The method for preparing the ternary fluororubber nanocomposite material with the dual filler system according to claim 1, wherein the method comprises the following steps: in the step (3), the vulcanization pressure is 8-10MPa, the vulcanization temperature is 175-180 ℃, and the vulcanization time is 6-8 min.
4. The preparation method of the ternary fluororubber nanocomposite material with the dual filler system according to claim 1, which is characterized by comprising the following steps: in the step (4), the secondary vulcanization temperature is 230-234 ℃, and the time is 1-3 h.
5. The method for preparing the ternary fluororubber nanocomposite material with the dual filler system according to claim 1, wherein the method comprises the following steps: the mass portion of the multi-wall carbon nano tube is 1-5.
6. The preparation method of the ternary fluororubber nanocomposite material with the dual filler system according to claim 1, which is characterized by comprising the following steps: the aminated multi-walled carbon nano-tube comprises 1-5 parts by mass.
7. The dual filler system ternary fluororubber nanocomposite prepared by the method for preparing a dual filler system ternary fluororubber nanocomposite according to any one of claims 1 to 6.
Priority Applications (1)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106633544A (en) * | 2016-11-17 | 2017-05-10 | 上海如实密封科技有限公司 | A fluororubber material used for sealing members resistant to high temperatures and high pressure and a preparing method thereof |
| US20170369660A1 (en) * | 2015-02-19 | 2017-12-28 | National Institute Of Advanced Industrial Science And Technology | Carbon nanotube-elastomer composite material, seal material and sealing material each produced using same, and method for producing carbon nanotube-elastomer composite material |
| CN112662095A (en) * | 2020-11-17 | 2021-04-16 | 温州大学 | Ternary fluororubber nanocomposite with three-crosslinking-network structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170369660A1 (en) * | 2015-02-19 | 2017-12-28 | National Institute Of Advanced Industrial Science And Technology | Carbon nanotube-elastomer composite material, seal material and sealing material each produced using same, and method for producing carbon nanotube-elastomer composite material |
| CN106633544A (en) * | 2016-11-17 | 2017-05-10 | 上海如实密封科技有限公司 | A fluororubber material used for sealing members resistant to high temperatures and high pressure and a preparing method thereof |
| CN112662095A (en) * | 2020-11-17 | 2021-04-16 | 温州大学 | Ternary fluororubber nanocomposite with three-crosslinking-network structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEI GAO，ET AL.: ""Improving thermal, electrical and mechanical properties of fluoroelastomer/amino-functionalized multi-walled carbon nanotube composites by constructing dual crosslinking networks"", 《COMPOSITE SCIENCE AND TECHNOLOGY》, vol. 162, pages 49 - 57 * |
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