CN115627039B - Ternary fluororubber nanocomposite material with double filler systems and preparation method thereof - Google Patents
Ternary fluororubber nanocomposite material with double filler systems and preparation method thereof Download PDFInfo
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- CN115627039B CN115627039B CN202211176357.6A CN202211176357A CN115627039B CN 115627039 B CN115627039 B CN 115627039B CN 202211176357 A CN202211176357 A CN 202211176357A CN 115627039 B CN115627039 B CN 115627039B
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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 with a double-filler system. According to the invention, ternary fluororubber is used as a matrix, an amino multi-wall carbon nano tube (MWCNT-A) and a multi-wall carbon nano tube (MWCNT) are used as fillers, and a dual-filler system ternary fluororubber nano composite material is prepared by mixing, vulcanizing and two-stage vulcanizing through an open mill, wherein amino groups of the amino multi-wall carbon nano tube can participate in crosslinking of fluororubber molecular chains during vulcanizing to become another crosslinking network except fluororubber molecular chains, and the crosslinking network becomes an assistance 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 with 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, and belongs to special fluororubber, compared with other hydrocarbon rubber, the fluororubber has the characteristics of strong electronegativity, fluorine-carbon bond containing high bond energy (bond energy is as high as 465 kj/mol), small Van der Waals bond angle (1.32 angstrom) and the like, and the covalent radius of the fluorine atoms is small (0.64 angstrom, which is only about half of the bond length of a carbon-carbon bond (C-C)), so that the fluorine atoms play a role of 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, good chemical inertness in solvents, hydrocarbons, acids and alkalis, low dielectric constant, low combustibility, low refractive index, low surface energy (oil and water repellency), and low hygroscopicity, and the high energy of the C-F bond is often beneficial to improving oxidation resistance and hydrolysis resistance in all the fluororubber, and the fluororubber is used as a main metal in the harsh synthetic rubber, and is commonly called a very good condition for the most severe synthetic rubber.
Patent CN202210723245.1 discloses a method for preparing fluororubber with higher retention rate of performance at high temperature. The preparation method of the fluororubber with higher performance retention rate at high temperature is simple and easy to operate, and low in cost, and the prepared fluororubber has higher 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 involves the use of solution, is easy to cause environmental pollution, contains vacuum environment and gas protection in the process, has very strict control on experimental conditions, and is easy to cause errors.
Patent CN202210467957.1 discloses a preparation method of low-compression stress relaxation fluororubber for battery sealing parts. Fluororubber with low compression stress relaxation, excellent high temperature resistance, electrolyte resistance, acid and alkali resistance and chemical corrosion resistance is prepared through simple mechanical blending, and the sealing element prepared from 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 has lower hardness and wear resistance, and is easy to wear in the use process of the sealing element, thereby shortening the service life.
Patent CN202210683998.4 provides a preparation method of a fluororubber composite material, and by combining wollastonite with a needle structure and magnesium hydroxide with a sheet structure, continuous filling of fluororubber can be realized, and the heat conducting property of fluororubber is further improved. However, the secondary mixing process involves drying of water, and a few dryness will be incomplete, which will generate bubbles during vulcanization, thereby affecting the properties of the composite material, and the tensile strength of the composite material after combining the two inorganic fillers is lower.
Patent CN202111417540.6 discloses a conductive fluororubber for oil seal. The modified ternary fluororubber raw rubber, the carbon nano tube, the conductive carbon black, the magnetic powder, the graphite and the dioctyl sebacate are mixed with the acid absorber, the release agent and the dispersing agent to be mixed in the internal mixer, so that the novel conductive fluororubber material for the oil seal is prepared. However, the method of mixing in an internal mixer cannot uniformly disperse various fillers such as carbon nanotubes, so that the fillers are agglomerated in a fluororubber matrix to influence the performance of fluororubber.
Patent CN202110800238.2 discloses a method for preparing low-resistivity fluororubber for automobile fuel pipeline system. After kneading and generating heat in an internal mixer, adding N990 carbon black, active magnesium oxide, carbon nano tubes, 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 out the sheet, 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 sheet after open mixing to obtain a mixed rubber; and (3) after the rubber compound is preformed, placing the rubber compound into a mould for moulding, and finally, carrying out secondary vulcanization. However, the fluororubber composite material added with various fillers has relatively reduced tensile strength and compression set, which is unfavorable for application in sealing elements.
The patent CN201710620527.8 provides an automobile cooling pipe, which is modified by adding nano simple substance tungsten, nano graphite fiber and nano potassium feldspar on the basis of the original material of the automobile cooling pipe, so that the heat transfer effect of the automobile cooling pipe is improved. Although the heat transfer effect of the fluororubber is greatly improved by adding various 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 master batch. Dispersing micro-nano silicon filler in a mixed solution of absolute ethyl alcohol and deionized water, regulating the PH value after ultrasonic mixing, adding a modifier to realize organic bridging of the silicon filler and fluororubber, washing a reaction product, centrifuging and drying to obtain a modified silicon filler; the modified silicon filler and the fluororubber are mixed and then are mixed, lump materials are segmented after mixing to form particles, and the silicon filler modified fluororubber master batch is obtained, so that the master batch can not only overcome the problem of uneven dispersion of common fillers in rubber, but also improve the low temperature resistance and mechanical property, and has the advantages of simple production process, low cost and easy industrial production. However, in the preparation process, an organic solvent is required, so that the environment is easily polluted, the environment-friendly requirement cannot be met, and a large amount of deionized water solution is used, so that bubbles are easily formed in the fluororubber under the high-temperature condition, and the performance and quality of the fluororubber are affected.
Patent CN202210376077.3 discloses an oil resistant and processable fluoroelastomer composition. The poly (hexafluoropropylene oxide) methyl pentafluoropropionate is obtained through reflux esterification dehydration reaction of poly (hexafluoropropylene oxide) monomethyl alcohol and pentafluoropropionic acid for 3-4 hours under the action of catalyst phosphoric acid. According to the invention, the fluororubber is softened by adding the high-fluoroalkyl ester with medium and low molecular weight into the fluororubber, so that the fluidity, the demolding property and the roll-off property of the fluororubber are improved. The fluorine-containing elastomer has good solvent resistance, processing manufacturability, high temperature resistance, corrosion resistance and good mechanical strength. However, the preparation process is complex, the requirement on the process is high, and a large amount of organic solvents are used, so that the preparation process is easy to cause harm to human bodies and pollute the environment.
Patent CN202210705213.9 provides a preparation process of high-temperature-resistant special fluororubber. The high-temperature resistant fluororubber composite material is obtained through simple mechanical blending, the problem that fluororubber has poor low-temperature performance due to poor molecular chain flexibility and higher glass transition temperature of fluororubber is solved, but a large amount of powder and organic solvent are added, so that the environment is easily polluted in the processing process, the health of operators is endangered, and the value for improving the tensile property is low.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provide a preparation method of a double-filler system ternary fluororubber nanocomposite, which adopts the following technical scheme:
a preparation method of a ternary fluororubber nanocomposite with a double-filler system comprises the following steps:
(1) Weighing the following raw materials in parts by mass:
100 parts of ternary fluororubber;
1-5 parts of acid absorber;
1-5 parts of a promoter;
0.5-5 parts of octadecylamine;
1-10 parts of multi-wall carbon nano-tubes;
1-10 parts of aminated multi-wall carbon nano tube;
1-5 parts of vulcanizing agent;
(2) Setting the roller temperature of an open mill to be 45-55 ℃, putting fluororubber into the open mill, adding a premixed acid absorber and an accelerant into the open mill for uniform mixing, and finally adding octadecylamine, multi-wall carbon nanotubes, aminated multi-wall carbon nanotubes and a vulcanizing agent into the open mill for uniform 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 (3) placing the rubber sheet prepared in the step (3) into an oven for secondary vulcanization to prepare the ternary fluororubber nanocomposite with the double-filler system.
Preferably, the acid absorber is zinc oxide, the accelerator is triallyl isocyanurate, and the vulcanizing agent is 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide.
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 fraction of the multiwall carbon nanotubes is 1-5.
Preferably, the mass fraction of the aminated multi-wall carbon nano tube is 1-5.
The ternary fluororubber nanocomposite with the double-filler system is prepared by the preparation method.
The beneficial effects of the invention are as follows: the fluororubber nanocomposite is prepared by taking ternary fluororubber as a matrix and taking an aminated multi-walled carbon nanotube (MWCNT-A) and a multi-walled carbon nanotube (MWCNT) as fillers, wherein amino groups of the aminated multi-walled carbon nanotube can participate in crosslinking of fluororubber molecular chains during vulcanization to become another crosslinking network except fluororubber molecular chains, and the crosslinking network becomes an aid for improving the mechanical properties of the composite, so that the tensile strength, the elongation at break, the 100% stretching stress and the hardness of the composite are obviously superior to those of a single filler system, and the synergistic effect of the MWCNT and the MWCNT-A is very obvious; in the aspect of thermal stability, the initial decomposition temperature of the composite material of the double-filler system is reduced, which is related to a good heat conduction channel formed by the system, besides, the carbon residue rate of the fluororubber is also influenced by the heat conduction channel of the double-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 invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a SEM photograph of (a) FKM/C-1, (b) FKM/C-3, (C) FKM/C-5, and (d) FKM/C-7;
FIG. 2 is a 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 shows (a) tensile strength, (b) elongation at break, (c) 100% tensile stress, and (d) hardness of comparative examples 1-3 and example 1;
FIG. 4 is the bulk attrition rates of comparative examples 1-3 and example 1;
FIG. 5 is the electrical conductivities of comparative examples 1-3 and example 1;
FIG. 6 is the thermal conductivity (a), (b) Thermogravimetric (TG), (c) thermogravimetric analysis (DTG) and (d) char yield of comparative examples 1-3 and example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Comparative examples 1-3 and example 1:
the samples were prepared according to the formulation of table 1, the preparation method was: setting the roller temperature to 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 triangulating for 3 times; then sequentially adding octadecylamine, multi-walled carbon nanotube (MWCNT), aminated multi-walled carbon nanotube (MWCNT-A) and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (Bifide-penta), triangulating for 6 times, and refining to uniformity; the samples of comparative examples 1-3 and example 1 were numbered FKM/C-1, FKM/C-3, FKM/C-5, FKM/C-7 in that order and left at room temperature for 24 hours.
Pressing the prepared sample into a rubber sheet by using a flat vulcanizing machine, wherein the vulcanizing pressure is 10MPa, the vulcanizing temperature and time are 177 ℃, the temperature is 7 minutes, and then, the rubber sheet is put into an oven for secondary vulcanization, and the vulcanizing temperature and time are 232 ℃ and 2 h.
Performance testing
1. Morphology of composite material
As shown in FIGS. 1 a-d, there are scanning electron micrographs of the composite material (example 1) containing neither the carbon material (comparative example 1) nor the MWCNT (comparative example 2), the MWCNT-A (comparative example 3), nor the MWCNT-A. It can be seen that the fracture surface of example 1 is relatively flat, and the surface only contains some particles of the auxiliary zinc oxide; whereas both (b) and (c) present a layered structure due to the presence of MWCNT and MWCNT-a, and a less flat fracture surface appears; in the case of the simultaneous presence of two multi-walled carbon nanotubes, not only the obvious layered structure was present, but also the denser wrinkled texture was present, and the fracture surface was not as smooth as in example 1. In the three figures (b), (c) and (d), the composite material has a small number of pores due to the addition of the unmodified multi-wall carbon nanotubes and the aminated multi-wall 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. The infrared spectra of FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7 are shown in FIG. 2. It can be seen from the figure that the base strings of FKM/C-3, FKM/C-5 and FKM/C-7 are inclined to different degrees when two kinds of multi-walled carbon nanotubes are added into the composite material, and especially the base strings of the composite material FKM/C-7 are inclined to a higher degree after the two kinds of multi-walled carbon nanotubes are stacked and filled. Several composite materials are shown in FIG. 2 at 893 cm -1 ，1127 cm -1 ，1393 cm -1 ，1692 cm -1 And 2963 cm -1 Corresponding infrared characteristic peaks appear nearby the positions, which are respectively-CF 3 groups, -CF 2-group, -CF-group, c=c bond and-C-H-group, wherein 1692 cm -1 The infrared absorption peak at this point demonstrates that FKM has undergone dehydrofluorination and oxidation reactions during vulcanization. When two multi-walled carbon nanotubes are added, the fluororubber is added in 1259 cm -1 The infrared absorption peaks at (C-C bonds) are prominent, especially in the composite FKM/C-7 containing both MWCNT and MWCNT-A double fillers.
3. Tensile Properties
The tensile strength, elongation at break, 100% elongation stress and hardness of the composites FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7 are shown in FIG. 3.
As shown in fig. 3 (a), the tensile strength of several composite materials is 8.2 MPa,10.0 MPa,12.1 MPa,18.8MPa, respectively. It has been found that when multiwall carbon nanotubes are added, a filler network is formed within the composite, such that a greater force is required to stretch the composite apart. At the same time, the amino groups of the aminated multiwall carbon nanotubes can participate in crosslinking of the fluororubber molecular chains during vulcanization, become another crosslinked network except the fluororubber molecular chains, and the formation of the crosslinked network certainly becomes an assisting force for improving the tensile strength of the composite material, so that the tensile strength of the composite material FKM/C-5 containing the MWCNT-A is higher than that of the composite material FKM/C-3 containing the MWCNT. Compared with the composite FKM/C-1 without filling any multi-wall carbon nano tube, the tensile strength of the composite 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 FKM/C-7 containing the MWCNT and MWCNT-A double-filler system is far greater than the sum of the tensile strength improvement rates (20.7% +47.6% = 68.3%) of the composite FKM/C-3 containing the MWCNT and the composite FKM/C-5 containing the MWCNT-A, 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 FKM/C-7 is greatly improved.
FIG. 3 (b) shows elongation at break of several composites, 344.0%,162.0%,218.0% and 148.0%, respectively. Therefore, when two multi-wall carbon nanotubes 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 bear stress when being stretched by external force, so that the breaking elongation of the composite material FKM/C-5 is reduced to a certain extent, and the reduction amplitude is smaller compared with that of the composite material FKM/C-3. The elongation at break of composite FKM/C-7 was reduced by 57.0% less than the sum of the elongation at break reductions of composite FKM/C-3 containing only MWCNT and composite FKM/C-5 containing only MWCNT-a (52.9% + 36.6% = 89.5%), indicating that synergy is also present in the elongation at break of the composite.
Fig. 3 (c) is the 100% tensile stress of several composites, with the most pronounced boosting effect of all properties. Wherein, the 100% stretching stress of the composite FKM/C-3 added with MWCNT is increased by 267.1%, the 100% stretching stress of the composite FKM/C-5 added with MWCNT-A is increased by 195.1%, and the 100% stretching stress of the composite FKM/C-7 added with MWCNT and MWCNT-A is increased by 680.5%, which is far greater than the 100% stretching stress increase rate of the composite FKM/C-3 and the composite FKM/C-5 (267.1% + 195.1% = 462.2%), thus it can be seen that the dual filler system of MWCNT and MWCNT-A can also exhibit excellent synergistic effect in terms of 100% stretching stress.
Shown in fig. 3 (d) are the hardness of the four composite materials. Compared with FKM/C-1 without adding the multi-wall carbon nano tube, the hardness of the composite material FKM/C-3, FKM/C-5 and FKM/C-7 is sequentially improved by 27.0%,24.6% and 46.8%, so that the hardness of the composite material is well improved by adding the two fillers simultaneously.
4. Wear resistance
The "abrasion" as used herein refers to a loss of a substance generated in a friction surface of a fluororubber sample due to a mechanical action such as friction force during friction. The abrasion resistance of the fluororubber is affected by various factors, such as frictional abrasion conditions during testing, and the test results obtained in the test have comparability and are not affected by the factors because all the test samples of the test are tested at the same room temperature under the same test conditions. In addition, the abrasion resistance of the fluororubber is also affected by the internal structure of the fluororubber, i.e., the crosslink density of the fluororubber. As shown in FIG. 4, the four composite materials have volume abrasion values of 124.1 and mm respectively 3 ，96.5 mm 3 ，93.1 mm 3 ，94.1 mm 3 . From experimental results, the addition of the MWCNT and the MWCNT-A can effectively reduce the volume abrasion of the composite material, wherein the MWCNT-A increases the crosslinking density of the composite material due to chemical crosslinking with the fluororubber molecular chain, thereby leading the volume abrasion of the composite material FKM/C-5 to be compared with that of the composite materialThe composite FKM/C-3 was lower. After the two multi-wall carbon nanotubes are combined, the wear resistance of the composite material is not greatly changed, which indicates that the volume abrasion of fluororubber can be reduced when the two carbon nano fillers are respectively added into the composite material under the action of friction force, but the synergistic effect of the two carbon nano fillers has little influence on the wear resistance of the composite material.
5. Conductivity of conductive material
The conductivities of FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7 are shown in FIG. 5, respectively. The conductivity of FKM/C-3 of the composite containing MWCNT-A was increased by 8 orders of magnitude, the conductivity of FKM/C-5 of the composite containing MWCNT-A was increased by 6 orders of magnitude, and the conductivity of FKM/C-7 of the composite containing MWCNT and MWCNT-A was increased by 10 orders of magnitude, compared with the fluororubber not filled with any carbon material; similar to the abrasion resistance, the conductivity of the fluororubber is improved to a certain extent when the two carbon fillers are added respectively, and the conductivity of the FKM can be improved again when the two carbon fillers are added together, but the synergistic effect of the two carbon fillers is not obvious.
6. Thermal performance
The thermal conductivities of the four composites are shown in FIG. 6 (a), 0.1941W/(mK), 0.2352W/(mK), 0.2385W/(mK) and 0.2675W/(mK), respectively. According to experimental results, the multi-wall carbon nano tube 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 the MWCNT is increased by 21.2%, and the heat conduction coefficient of the composite material FKM/C-5 containing the MWCNT-A is increased by 22.9%, so that the aminated and modified multi-wall carbon nano tube has more excellent heat conduction performance, the heat conduction performance of fluororubber can be better improved, and meanwhile, the MWCNT-A can be chemically crosslinked with FKM molecular chains to form a second crosslinked network, so that the composite material internally has a more smooth heat conduction network. The thermal conductivity coefficient of FKM/C-7 of the composite material added with the unmodified multi-wall carbon nano tube and the aminated multi-wall carbon nano tube is increased by 37.8%, and the composite material has better performance enhancement effect compared with the composite material added with only one multi-wall carbon nano tube.
FIGS. 6 (b) and (c) are TG and DTG, respectively, measured at temperatures ranging from 40℃to 600℃for four composites. Combining the two graphs of (b) (C), it can be seen that the initial decomposition temperatures of the composites FKM/C-1, FKM/C-3, FKM/C-5 and FKM/C-7 were 437.6 ℃,444.3 ℃,442.8 ℃ and 438.0 ℃, respectively. The addition of 5 parts of the composite material increases the initial decomposition temperature in terms of the amount of carbon material, which means that the addition of carbon material can increase the thermal stability of the composite material. However, when the amount of carbon material was increased to 10 parts, the initial decomposition temperature of the composite FKM/C-7 was rather lowered. This is because the heat transfer network formed by the multiwall carbon nanotubes in the composite accelerates heat transfer and pulls the elbows with their higher 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 heat stability of the composite material is improved; when 10 parts of carbon material is added, the heat conduction network formed by the multi-wall carbon nano tubes plays a main role, and the thermal stability of the composite material is reduced. In the same 5 parts of filler, the MWCNT-A increases the structural stability due to the formation of a new cross-linked network between the MWCNT-A and the molecular chain of FKM, and simultaneously improves the heat conduction channel of the composite FKM/C-5, thereby having the effect of accelerating heat transfer, enabling heat to quickly reach every position inside fluororubber, and reducing the thermal stability of the composite FKM/C-5.
FIG. 6 (d) shows the char yield of the four composites, 4.6%,14.2%,14.3% and 17.7%, respectively. Therefore, the carbon material can be added to obviously improve the carbon residue rate of the fluororubber. The unmodified multi-wall carbon nano tube has excellent heat conducting performance, so that heat can be quickly transferred in the inner structure of the fluororubber, a large amount of carbon layers are piled on the surface of the composite material FKM/C-3, the external heat is isolated, and the carbon residue rate of the fluororubber is remarkably improved. After the multi-wall carbon nano tube is aminated and modified, the thermal conductivity coefficient of the composite material FKM/C-5 is increased, the fluororubber is accelerated to carbonize by rapid heating in the composite material, and a compact carbon layer is formed on the surface of the composite material, so that the influence degree of external heat on the internal rubber is reduced. In the composite material FKM/C-7, 5 parts of MWCNT and 5 parts of MWCNT-A are added, so that even though the MWCNT-A can generate chemical crosslinking with fluororubber to enable the internal structure to be more stable, as described above, under the condition of 10 parts of carbon material filling, a heat conduction network formed by the carbon material is dominant, so that the rapid heat transfer inside 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 the carbon residue rate and ablation resistance of the composite material FKM/C-7 are improved.
In summary, the fluororubber nanocomposite prepared by using ternary fluororubber as a matrix and aminated multi-walled carbon nanotubes (MWCNT-A) and multi-walled carbon nanotubes (MWCNT) as fillers has increased tensile strength, elongation at break, 100% stretching stress and hardness, and the synergistic effect of the MWCNT and the MWCNT-A is more obvious in the former three materials; in the aspect of wear resistance, the volume abrasion of fluororubber can be effectively reduced by two multi-wall carbon nanotubes, and the wear resistance of the composite material is not greatly changed after the two carbon materials are combined; in the aspect of thermal stability, the initial decomposition temperature of the double-filler composite material is reduced, which is related to a good heat conduction channel formed by the system, besides, the carbon residue rate of the fluororubber is also influenced by the heat conduction channel of the double-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 foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (7)
1. The preparation method of the ternary fluororubber nanocomposite with the double-filler system is characterized by comprising the following steps of:
(1) Weighing the following raw materials in parts by mass:
100 parts of ternary fluororubber;
1-5 parts of acid absorber;
1-5 parts of a promoter;
0.5-5 parts of octadecylamine;
1-10 parts of multi-wall carbon nano-tubes;
1-10 parts of aminated multi-wall carbon nano tube;
1-5 parts of vulcanizing agent;
(2) Setting the roller temperature of an open mill to be 45-55 ℃, putting ternary fluororubber into the open mill, adding a premixed acid absorbent and an accelerant into the open mill for uniform mixing, and finally adding octadecylamine, multi-wall carbon nanotubes, aminated multi-wall carbon nanotubes and a vulcanizing agent into the open mill for uniform 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 (3) placing the rubber sheet prepared in the step (3) into an oven for secondary vulcanization to prepare the ternary fluororubber nanocomposite with the double-filler system.
2. The method for preparing the ternary fluororubber nanocomposite with the double filler system, according to claim 1, is characterized in that: the acid absorber is zinc oxide, the accelerator is triallyl isocyanurate, and the vulcanizing agent is 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide.
3. The method for preparing the ternary fluororubber nanocomposite with the double filler system, according to claim 1, is characterized in that: 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 method for preparing the ternary fluororubber nanocomposite with the double filler system, according to claim 1, is characterized in that: in the step (4), the second-stage vulcanization temperature is 230-234 ℃ and the time is 1-3 h.
5. The method for preparing the ternary fluororubber nanocomposite with the double filler system, according to claim 1, is characterized in that: the mass portion of the multiwall carbon nanotube is 1-5 portions.
6. The method for preparing the ternary fluororubber nanocomposite with the double filler system, according to claim 1, is characterized in that: the mass portion of the amination multiwall carbon nanotube is 1-5 portions.
7. The dual-filler system ternary fluororubber nanocomposite prepared by the preparation method of the dual-filler system ternary fluororubber nanocomposite as claimed in any one of claims 1 to 6.
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| 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 |
| 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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| WO2016133207A1 (en) * | 2015-02-19 | 2016-08-25 | 国立研究開発法人産業技術総合研究所 | Carbon nanotube-elastomer composite material, seal material and sealing material each produced using same, and method for producing carbon nanotube-elastomer composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| "Improving thermal, electrical and mechanical properties of fluoroelastomer/amino-functionalized multi-walled carbon nanotube composites by constructing dual crosslinking networks";Wei Gao，et al.;《Composite Science and Technology》;第162卷;第49-57页 * |
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